Chemical Arithmetic 1
Chapter
Chemistry is basically an experimental science. In it we study
physical and chemical properties of substance and measure it upto
possibility. The results of measurement can we reported in two steps,
(a) Arithmetic number, (b) Unit of measurement.
Every experimental measurement vary slightly from one another and
involves some error or uncertainty depending upon the skill of person
making the measurements and measuring instrument. The closeness of the
set of values obtained from identical measurement called precision and a
related term, refers to the closeness of a single measurement to its true
value called accuracy.
Significant figures
In the measured value of a physical quantity, the digits about the
correctness of which we are surplus the last digit which is doubtful, are
called the significant figures. Number of significant figures in a physical
quantity depends upon the least count of the instrument used for its
measurement.
(1) Common rules for counting significant figures Following are
some of the common rules for counting significant figures in a given
expression
Rule 1. All non zero digits are significant.
Example : x  1234 has four significant figures. Again x  189
has only three significant figures.
Rule 2. All zeros occurring between two non zero digits are
significant.
Example : x  1007 has four significant figures. Again
x  1.0809 has five significant figures.
Rule 3. In a number less than one, all zeros to the right of decimal
point and to the left of a non zero digit are not significant.
Example : x  0.0084 has only two significant digits. Again,
x  1.0084 has five significant figures. This is on account of rule 2.
Rule 4. All zeros on the right of the last non zero digit in the
decimal part are significant.
Example : x  0.00800 has three significant figures 8, 0, 0. The
zeros before 8 are not significant again 1.00 has three significant figures.
1
Chemical Arithmetic
Rule 5. All zeros on the right of the non zero digit are not
significant.
Example : x  1000 has only one significant figure. Again
x  378000 has three significant figures.
Rule 6. All zeros on the right of the last non zero digit become
significant, when they come from a measurement.
Example : Suppose distance between two stations is measured to be
3050 m. It has four significant figures. The same distance can be expressed
as 3.050 km or 3.050  10 5 cm . In all these expressions, number of
significant figures continues to be four. Thus we conclude that change in
the units of measurement of a quantity does not change the number of
significant figures. By changing the position of the decimal point, the
number of significant digits in the results does not change. Larger the
number of significant figures obtained in a measurement, greater is the
accuracy of the measurement. The reverse is also true.
(2) Rounding off : While rounding off measurements, we use the
following rules by convention
Rule 1. If the digit to be dropped is less than 5, then the preceding
digit is left unchanged.
Example : x  7.82 is rounded off to 7.8, again x  3.94 is
rounded off to 3.9.
Rule 2. If the digit to be dropped is more than 5, then the preceding
digit is raised by one.
Example : x = 6.87 is rounded off to 6.9, again x = 12.78 is rounded
off to 12.8.
Rule 3. If the digit to be dropped is 5 followed by digits other than
zero, then the preceding digit is raised by one.
Example : x = 16.351 is rounded off to 16.4, again x  6.758 is
rounded off to 6.8.
Rule 4. If digit to be dropped is 5 or 5 followed by zeros, then preceding
digit is left unchanged, if it is even.
Example : x = 3.250 becomes 3.2 on rounding off, again
x  12.650 becomes 12.6 on rounding off.
 2 Chemical Arithmetic
Rule 5. If digit to be dropped is 5 or 5 followed by zeros, then the (1) C.G.S. System : Length (centimetre), Mass (gram), Time (second)
preceding digit is raised by one, if it is odd. (2) M.K.S. System : Length (metre), Mass (kilogram), Time
Example : x = 3.750 is rounded off to 3.8, again x  16.150 is (second)
rounded off to 16.2. (3) F.P.S. System : Length (foot), Mass (pound), Time
(3) Significant figure in calculation (second)
(i) Addition and subtraction : In addition and subtraction the (4) S.I. System : The 11th general conference of weights and measures
following points should be remembered (October 1960) adopted International system of units, popularly known as the SI
units. The SI has seven basic units from which all other units are derived called
(a) Every quantity should be changed into same unit.
derived units. The standard prefixes which helps to reduce the basic units are now
(b) If a quantity is expressed in the power of 10, then all the widely used.
quantities should be changed into power of 10.
(c) The result obtained after addition or subtraction, the number of Dimensional analysis : The seven basic quantities lead to a number of
figure should be equal to that of least, after decimal point. derived quantities such as pressure, volume, force, density, speed etc. The
units for such quantities can be obtained by defining the derived quantity in
(ii) Multiplication and division
terms of the base quantities using the base units. For example, speed
(a) The number of significant figures will be same if any number is
multiplied by a constant. (velocity) is expressed in distance/time. So the unit is m / s or ms 1 . The
(b) The product or division of two significant figures, will contain unit of force (mass  acceleration) is kg ms 2 and the unit for
the significant figures equal to that of least.
acceleration is ms 2 .
Units for measurement
The chosen standard of measurement of a quantity which has
essentially the same nature as that of the quantity is called the unit of the
quantity. Following are the important types of system for unit,
Table 1.1 Seven basic S.I. units
Length Mass Time Temperature Electric Current Luminous Intensity Amount of
substance

metre (m) Kilogram (kg) Second (s) Kelvin (K) Ampere (A) Candela (Cd) Mole (mol)

Table 1.2 Derived Units

Physical quantity Unit Symbol

Area square metre m 2

Volume cubic metre m 3

Velocity metre per second ms –1

Acceleration metre per second square ms –2

Density kilogram per cubic metre kg m –3

Molar mass kilogram per mole kg mol –1

Molar volume cubic metre per mole m mol

3 –1

Molar concentration mole per cubic metre mol m –3

Force newton (N) kg m s –2

Pressure pascal (Pa) Nm –2

Energy work joule (J) kg m s , Nm

2 –2

Table 1.3 Standard prefixes use to reduce the basic units

Multiple Prefix Symbol Submultiple Prefix Symbol
10
24
yotta Y 10–1
deci d
1021
zetta Z 10–2
centi c
10
18
exa E 10–3
milli m
10 peta P 10 micro 
15 –6

1012
tera T 10–9
nano n
 Chemical Arithmetic 3

109
giga G 10 –12
pico p
106
mega M 10 –15
femto f
103
kilo k 10 –18
atto a
102
hecto h 10 –21
zeto z
101
deca da 10–24
yocto y

Table 1.4 Conversion factors

1 m = 39.37 inch 1 cal = 4.184 J 1 e.s.u. = 3.3356  10 C –10 1 mole of a gas = 22.4 L at STP

1 inch = 2.54 cm 1 eV = 1.602  10 J–19 1 dyne = 10 N

–5
1 mole a substance = N molecules 0

1 litre = 1000 mL 1 eV/atom =96.5 kJ mol –1

1 atm = 101325 Pa 1 g atom = N atoms 0

1 gallon (US) = 3.79 L 1 amu = 931.5016 MeV 1 bar = 1  10 N m

5 –2 t ( F) = 9/5 t ( C) + 32
o o

1 lb = 453.59237 g 1 kilo watt hour = 3600 kJ 1 litre atm = 101.3 J 1 g cm = 1000 kg m

–3 –3

1 newton =1 kg m s –2
1 horse power = 746 watt 1 year = 3.1536  10 s 7 1Å = 10 m –10

1 J = 1 Nm =1 kg m s2 –2
1 joule = 10 erg
7

1 debye (D) = 1  10 esu cm –18 1nm = 10 m –9

Laws of chemical combination
Various chemical reactions take place according to the certain laws,
known as the Laws of chemical combination.
(1) Law of conservation of mass : It was proposed by Lavoisier and
verified by Landolt. According to this law, Matter is neither created nor
destroyed in the course of chemical reaction though it may change from one
form to other. The total mass of materials after a chemical reaction is same
as the total mass before reaction.
(2) Law of constant or definite proportion : It was proposed by
Proust. According to this law, A pure chemical compound always contains
the same elements combined together in the fixed ratio of their weights
whatever its methods of preparation may be.
(3) Law of multiple proportion : It was proposed by Dalton and
verified by Berzelius. According to this law, When two elements A and B
combine to form more than one chemical compounds then different weights
of A, which combine with a fixed weight of B, are in proportion of simple
whole numbers.
(4) Law of equivalent proportion or law of reciprocal proportion : It
was proposed by Ritcher. According to this law, The weights of the two or
more elements which separately react with same weight of a third element
are also the weights of these elements which react with each other or in
simple multiple of them.
(5) Gay-Lussac’s law : It was proposed by Gay–Lussac and is
applicable only for gases. According to this law, When gases
combine, they do so in volumes, which bear a simple ratio to each
other and also to the product formed provided all gases are
measured under similar conditions. The Gay-Lussac’s law, was based
on experimental observation.
Important hypothesis
(1) Atomic hypothesis : Keeping in view various law of chemical
combinations, a theoretical proof for the validity of different laws was given
by John Dalton in the form of hypothesis called Dalton's atomic hypothesis.
Postulates of Dalton's hypothesis is as followes,
(i) Each element is composed of extremely small particles
called atoms which can take part in chemical combination.
(ii) All atoms of a given element are identical i.e., atoms of a
particular element are all alike but differ from atoms of other element.
(iii) Atoms of different elements possess different properties
(including different masses).
(iv) Atoms are indestructible i.e., atoms are neither created nor
destroyed in chemical reactions.
(v) Atoms of elements take part to form molecules i.e., compounds
are formed when atoms of more than one element combine.
(vi) In a given compound, the relative number and kinds of atoms
are constant.
(2) Modern atomic hypothesis : The main modifications made in
Dalton’s hypothesis as a result of new discoveries about atoms are,
(i) Atom is no longer considered to be indivisible.
(ii) Atoms of the same element may have different atomic weights.
e.g., isotopes of oxygen O16 , O17 , and O18 .
(iii) Atoms of different element may have same atomic weights. e.g.,
isobars Ca 40 and Ar 40 .
(iv) Atom is no longer indestructible. In many nuclear reactions, a
certain mass of the nucleus is converted into energy in the form of , 
and  rays.
(v) Atoms may not always combine in simple whole number ratios.
e.g., in sucrose (C12 H 22 O11 ) , the elements carbon, hydrogen and oxygen
are present in the ratio of 12 : 22 : 11 and the ratio is not a simple whole
number ratio.
(3) Berzelius hypothesis : “Equal volumes of all gases contain equal
number of atoms under same conditions of temperature and pressure”.
When applied to law of combining volumes, this hypothesis predicts that
atoms are divisible and hence it is contrary to Dalton's hypothesis.
(4) Avogadro’s hypothesis : “Equal volumes of all gases under similar
conditions of temperature and pressure contain equal number of
molecules.” Avogadro hypothesis has been found to explain as follows,
(i) Provides a method to determine the atomic weight of gaseous
elements.
(ii) Provides a relationship between vapour density (V.D.) and
molecular masses of substances.
Molecular mass  2  vapour density
 4 Chemical Arithmetic
(iii) It helps in the determination of mass of fixed volume of a Approximat e atomic mass
particular gas. Valency 
Equivalent mass
Mass of 1 ml gas = V.D.  0.0000897 gm. (ii) Vapour density method : It is suitable for elements whose
(iv) It also helps in the determination of molar volume at N.T.P. chlorides are volatile.

 V.D.  0.0000897 gm. gas has volume = 1 ml Valency of the element =

Molecular mass of chloride
Equivalent mass of chloride
2  V.D.(i.e., molecular mass) gm. has
2  Vapour density of chloride
1  2  V .D. =
volume  ml  22400 ml Equivalent mass of metal  35.5
V .D.  0.0000897
Atomic mass = Equivalent mass of metal  Valency
 Molar mass of a gas or its 1 mole occupies 22.4 L volume at
S.T.P. (iii) Specific heat method : It is suitable only for gases. The two
(v) It helps in determination of molecular formulae of gases and is types of specific heats of gases are C (at constant pressure) and C v (at
P

very useful in gas analysis. By knowing the molecular volumes of reactants constant volume). Their ratio is known as  whose value is constant (1.66
and products of reaction, molecular composition can be determined easily. for monoatomic, 1.40 for diatomic and 1.33 for triatomic gases).
Atomic, Molecular and Equivalent masses Molecular mass
Atomic mass of a gaseous element 
(1) Atomic mass : It is the average relative mass of atom of element Atomicity
as compared with an atom of carbon –12 isotope taken as 12. (iv) Isomorphism method : It is based on law of isomorphism which
Average mass of an atom states that compounds having identical crystal structure have similar
Atomic mass  constitution and chemical formulae.
1/12  Mass of an atom of C 12
Average atomic mass : If an elements exists in two isotopes having Example : K 2 SO 4 , K 2 CrO 4 and K 2 SeO 4
atomic masses ‘a’ and ‘b’ in the ratio m : n, then average atomic mass (valency of S, Cr, Se = 6),
(m  a)  (n  b)
= . Since the atomic mass is a ratio, it has no units and is ZnSO 4 . 7 H 2 O, MgSO4 .7 H 2 O, FeSO 4 . 7 H 2 O
m n
24
expressed in amu, 1 amu = 1.66  10 g . One atomic mass unit (amu) is (valency of Zn, Mg, Fe = 2).
1 (2) Molecular mass : Molecular mass of a molecule, of an element or
equal to th of the mass of an atom of carbon-12 isotope. a compound may be defined as a number which indicates how many times
12
1
Gram atomic mass (GAM) : Atomic mass of an element expressed in heavier is a molecule of that element or compound as compared with of
grams is called Gram atomic mass or gram atom or mole atom. 12
the mass of an atom of carbon–12. Molecular mass is a ratio and hence has
Mass of an element no units. It is expressed in a.m.u.
(i) Number of gram atoms =
GAM
Mass of one molecule of the substance
(ii) Mass of an element in gm. = No. of gm. atom  GAM Molecular mass 
1 / 12  Mass of one atom of C - 12
(iii) Number of atoms in 1 GAM = 6.02  10 23 Actual mass of one molecule = Mol. mass 1.66 10 24 gm.
 Number of atoms in a given substance
Molecular mass of a substances is the additive property and can be
Mass calculated by adding the atomic masses present in one molecule.
= No. of GAM  6.02  10 23 =  6.02  10 23
GAM Gram molecular mass (GMM) and Gram molar volume : Molecular
mass of an element or compound when expressed in gm. is called its gram
6 .02  10 23
molecular mass, gram molecule or mole molecule.
(iv) Number of atoms in 1gm of element =
Atomic mass
Mass of substances
Number of gm molecules =
GAM GMM
(v) Mass of one atom of the element (in gm.) 
6.02  10 23 Mass of substances in gm = No. of gm. molecules  GMM
Methods of determination of atomic mass Volume occupied by one mole of any gas at STP is called Gram
(i) Dulong and Pettit's method : According to Dulong and Pettit's molar volume. The value of gram molar volume is 22.4 litres. Volume of 1
law mole of any gas at STP = 22.4 litres
Atomic mass  Specific heat = 6.4 (approx.) Expression for mass and density
6.4 Mass of 11 .2 L of any gas at STP = V.D. of that gas in gm.
Atomic mass (approx.) =
Specific heat (in cals.) Mol.mass in gm.
Density of a gas at NTP =
This law is applicable to solid elements only except Be, B, C and Si 22400 ml
because their specific heat is variable with temperature.
Important generalisations
Atomic mass = Equivalent mass  Valency
Number of atoms in a substance
 Chemical Arithmetic 5
= Number of GMM  6.02  10  Atomicity
23

Formula mass
(iv) EM of a salt =
Number of electrons in given substance Total positive or negative charge
= Number of GMM  6.02  10  Number of electrons
23

(v) EM of an oxidising agent

Methods of determination of molecular mass
Formula mass
Following methods are used to determine molecular mass, 
Number of electrons gained per molecule or Total change in O.N.
(i) Diffusion method (For gases) : The ratio of rates of diffusion of
two gases is inversely proportional to the square root of their molecular Equivalent mass of common oxidising agent changes with the
masses. medium of the reaction.
Methods of determination of equivalent mass
r1 M2
 (i) Hydrogen displacement method : The mass of metal which
r2 M1
displaces 11200 ml of hydrogen at NTP from an acid, alkali or alcohol is the
(ii) Vapour density method (For gases only) : Mass of a fixed volume equivalent mass of the metal.
of the vapour is compared with the mass of the same volume of hydrogen
(a) Equivalent mass of metal
under same conditions. The ratio of these masses is called Vapour density
or Relative density. Mass of metal W
  1 .008   1 .008 g
Molecular mass  2  Vapour desity Mass of H 2 displaced M

(iii) Victor Meyer method (For volatile liquids or solids) (b) Equivalent mass of metal
It is based on Dalton's law of partial pressure and Avogadro's hypothesis Mass of metal W
(gram molar volume).  11200 = 11200
Vol.(ml) of H 2 displaced at STP V
22400 ml of vapours of a substance = Molecular mass of that
substance This method is useful for metals which can displace hydrogen from
(iv) Colligative property method (For non-volatile solids) acids or can combine with hydrogen (Mg, Zn, Na, Ca etc.)
Discussed in colligative properties of solutions. (ii) Oxide formation method : The mass of the element which
Average atomic mass and molecular mass combines with 8 grams of oxygen is the equivalent mass of the element.

 Ai X i Mass of metal
A (Average atomic mass) = (a) Equivalent mass of metal = 8
 X total Mass of oxygen

 Mi Xi (b) Equivalent mass of metal

M (Average molecular mass) =
 X total Mass of metal
=  5600
Where A1 , A2 , A3 ..... are atomic mass of species 1, 2, 3,…. etc. Vol. of O 2 at S.T.P. in ml
with % ratio as X1 , X 2 , X 3 ..... etc. Similar terms are for molecular masses. (iii) Chloride formation method : The mass of an element which
reacts with 35.5 gm. of chlorine is the equivalent mass of that element.
(3) Equivalent mass : The number of parts by mass of a substance
that combines with or displaces 1.008 parts by mass of hydrogen or 8.0 Mass of metal
parts of oxygen or 35.5 parts of chlorine is called its equivalent mass (EM). (a) Equivalent mass of metal   35.5
Mass of chlorine
On the other hand quantity of a substance in grams numerically equal to its
equivalent mass is called its gram equivalent mass (GEM) or gram (b) Equivalent mass of metal
equivalent.
Mass of metal
Mass of the substance in grams   11200
Number of GEM  Vol. of Cl 2 (in ml.) at STP
GEM of the substance
(iv) Neutralisation method : (For acids and bases).
Expressions for equivalent mass (EM)
W
(i) EM of an element 
Atomic mass Equivalent mass of acid (or base) 
Valency VN

Molecular mass Where ,

(ii) EM of an acid 
Basicity W = Mass of acid or base in gm.,
(Basicity of acid is the number of replaceable hydrogen atoms in one V = Vol. of base or acid in litre required for neutralisation
molecule of the acid).
N is Normality of base or acid
Molecular mass (v) Metal displacement method : It is based on the fact that one gm.
(iii) EM of a base 
Acidity equivalent of a more electropositive metal displaces one gm equivalent of a
less electropositive metal from its salt solution.
(Acidity of a base is the number of replaceable– OH groups in one
Mass of metal added Eq. mass of metal added
molecule of the base). 
Mass of metal displaced Eq. mass of metal displaced
 6 Chemical Arithmetic

W1 E Element % Relative no. of atoms = Simplest Empirical

 1
W2 E2 %/at. wt. Ratio Formula
(vi) Electrolytic method : The quantity of substance that reacts at Relative no. of atoms : Divide the percentage of each element
electrode when 1 faraday of electricity is passed is equal to its gram present in compound by its at. weight. This gives the relative no. of atoms
equivalent mass. of element in molecule.
Gram equivalent mass = Electrochemical equivalent  96500 Simplest ratio : Find out lowest value of relative no. of atoms and
The ratio of masses of two metals deposited by the same divide each value of relative no. of atoms by this value to estimate simplest
quantity of electricity will be in the ratio of their equivalent masses. ratio of elements.
W1 E It the simplest ratio obtained are not complete integers, multiply
 1
W2 E2 them by a common factor to get integer values of simplest ratio.
(vii) Double decomposition method Empirical formula : Write all constituent atoms with their respective
no. of atoms derived in simplest ratio. This gives empirical formula of
AB  CD  AD   CB compound.
Mass of compound AB Eq. mass of A  Eq. mass of B Molecular formula : Molecular formula  n  empirical formula

Mass of compound AD Eq. mass of A  Eq. mass of D where ' n' is the whole no. obtained by
Mass of salt taken (W1 ) Eq. mass of salt (E1 ) molecular weight of compound
or  n
Mass of ppt. obtained (W2 ) Eq. mass of salt in ppt. (E 2 ) empirical formula weight of compound
(viii) Conversion method : When one compound of a metal is
converted to another compound of the same metal, then Chemical stoichiometry
Mass of compound I (W1 ) E  Eq. mass of radical I Stoichiometry (pronounced “stoy-key om-e-tree”) is the calculation

Mass of compound II (W2 ) E  Eq. mass of radical II of the quantities of reactants and products involved in a chemical reaction.
That means quantitative calculations of chemical composition and reaction
(E = Eq. mass of the metal) are referred to as stoichiometry.
(ix) Volatile chloride method
Basically, this topic involves two types of calculations.
2  V.D. of Chloride 2  V.D.
Valency of metal   (a) Simple calculations (gravimetric analysis) and
Eq. mass of metal chloride E  35.5
2  V.D. of Chloride (b) More complex calculations involving concentration and volume
E   35.5 of solutions (volumetric analysis).
Valency
(x) Silver salt method (For organic acids) There is no borderline, which can distinguish the set of laws
applicable to gravimetric and volumetric analysis. All the laws used in one
108  Mass of silversalt are equally applicable to the other i.e., mole as well as equivalent concept.
Equivalent Mass of acid =  107
Mass of Ag metal But in actual practise, the problems on gravimetric involves simpler
reactions, thus mole concept is convenient to apply while volumetric
Molecular mass of acid = Equivalent mass of acid  Basicity reactions being complex and unknown (unknown simple means that it is
The mole concept not known to you, as it’s not possible for you to remember all possible
reactions), equivalent concept is easier to apply as it does not require the
One mole of any substance contains a fixed number
knowledge of balanced equation.
(6.022  10 ) of any type of particles (atoms or molecules or ions) and
23
(1) Gravimetric analysis : In gravimetric analysis we relate the
has a mass equal to the atomic or molecular weight, in grams. Thus it is
weights of two substances or a weight of a substance with a volume
correct to refer to a mole of helium, a mole of electrons, or a mole of Na  , of a gas or volumes of two or more gases.
meaning respectively Avogadro’s number of atoms, electrons or ions.
Problems Involving Mass-Mass Relationship
Weight(grams)
 Number of moles 
Weight of one mole (g/mole) Proceed for solving such problems according to the following
instructions,
Weight

Atomic or molecular weight (i) Write down the balanced equation to represent the chemical
change.
Percentage composition & Molecular formula
(ii) Write the number of moles below the formula of the reactants
(1) Percentage composition of a compound and products. Also write the relative weights of the reactants and products
Percentage composition of the compound is the relative mass of each of the (calculated from the respective molecular formula), below the respective
constituent element in 100 parts of it. If the molecular mass of a compound formula.
is M and B is the mass of an element in the molecule, then
(iii) Apply the unitary method to calculate the unknown factor (s).
Mass of element X
Percentage of element   100   100 Problems Involving Mass-Volume Relationship
Molecular mass M
For solving problems involving mass-volume relationship, proceed
(2) Determination of empirical formula : The empirical formula of a according to the following instructions,
molecule is determined using the % of elements present in it. Following
method is adopted. (i) Write down the relevant balanced chemical equations (s).
 Chemical Arithmetic 7
(ii) Write the weights of various solid reactants and products. (iii) Iodiometric titrations : This is a simple titration involving free
iodine. This involves the titration of iodine solution with known sodium
(iii) Gases are usually expressed in terms of volumes. In case the
volume of the gas is measured at room temperature and pressure (or under thiosulphate solution whose normality is N . Let the volume of sodium
conditions other than N.T.P.), convert it into N.T.P. by applying gas thiosulphate is V ml .
equation.
I 2  2 Na 2 S 2 O 3  2 NaI  Na 2 S 4 O6
(iv) Volume of a gas at any temperature and pressure can be
converted into its weight and vice-versa with the help of the relation, by n  2, n 1
g
PV   RT where g is weight of gas, M is mole. wt. of gas, R is Equivalents of I 2  Equivalent of Na 2 S 2 O 3
M
gas constant.  Equivalents of I 2  N  V  10 3
Calculate the unknown factor by unitary method.
N  V  10 3
Problems Based on Volume-Volume Relationship Moles of I 2 
2
Such problems can be solved according to chemical equation as,
 N  V  10 3 
(i) Write down the relevant balanced chemical equation. Mass of free I 2 in the solution    254  g .
 2 
(ii) Write down the volume of reactants and products below the
formula to each reactant and product with the help of the fact that 1 gm (iv) Iodometric titrations : This is an indirect method of estimation
molecule of every gaseous substance occupies 22.4 litres at N.T.P. of iodine. An oxidising agent is made to react with excess of solid KI . The
oxidising agent oxidises I  to I 2 . This iodine is then made to react with
(iii) In case volume of the gas is measured under particular (or
room) temperature, convert it to volume at NTP by using ideal gas Na 2 S 2 O 3 solution.
equation.
Oxidising Agent
Take the help of Avogadro’s hypothesis “Equal volume of different
gases under the similar conditions of temperature and pressure contain the ( A)  KI  I 2   2 NaI  Na 2 S 4 O 6
2 Na 2 S 2 O3

same number of molecules”.
(2) Volumetric analysis : It is a method which involves quantitative
determination of the amount of any substance present in a solution through
volume measurements. For the analysis a standard solution is required. (A
solution which contains a known weight of the solute present in known
volume of the solution is known as standard solution.)
Let the normality of Na 2 S 2 O 3 solution is N and the volume of
thiosulphate consumed to V ml .
Equivalent of A  Equivalent of I 2  Equivalents of Na 2 S 2 O 3
Equivalents of I 2 liberated from KI  N  V  10 3

To determine the strength of unknown solution with the help of N  V  10 3

known (standard) solution is known as titration. Different types of titrations Moles of I 2 liberated from KI 
2
are possible which are summerised as follows,
(i) Redox titrations : To determine the strength of oxidising agents  N  V  10 3 
Mass of I 2 liberated from KI    254  g .
or reducing agents by titration with the help of standard solution of  2 
reducing agents or oxidising agents.
(v) Precipitation titrations : To determine the anions like
Examples:
CN , AsO33  , PO43  , X  etc, by precipitating with AgNO3 provides


K 2 Cr2 O7  4 H 2 SO 4  K 2 SO 4  Cr2 (SO 4 )3  4 H 2 O  3[O] examples of precipitation titrations.

[2 FeSO 4  H 2 SO 4  O  Fe2 (SO 4 )3  H 2 O]  3
6 FeSO 4  K 2 Cr2 O7  7 H 2 SO 4  3 Fe(SO 4 )3  K 2 SO 4  Cr2 (SO 4 )3 7 H 2 O
2 KMnO4  3 H 2 SO 4  K 2 SO 4  2 MnSO 4  3 H 2 O  5[O]
[2 FeSO 4  H 2 SO 4  O  Fe2 (SO 4 )3  H 2 O]  5
10 FeSO 4  2 KMnO4  8 H 2 SO 4  5 Fe2 (SO 4 )3  K 2 SO 4  2 MnSO 4  8 H 2 O
Similarly with H 2 C 2 O4
2 KMnO4  3 H 2 SO 4  5 H 2 C2 O4 
K 2 SO 4  2 MnSO 4  8 H 2 O  10CO 2 etc.
(ii) Acid-base titrations : To determine the strength of acid or base
with the help of standard solution of base or acid.
Example: NaOH  HCl  NaCl  H 2 O
and NaOH  CH 3 COOH  CH 3 COONa  H 2 O etc.
NaCl  AgNO3  AgCl   NaNO 3
KSCN  AgNO3  AgSCN   KNO 3
End point and equivalence point : The point at which
titration is stopped is known as end point, while the point at which
the acid and base ( or oxidising and reducing agents ) have been
added in equivalent quantities is known as equivalence point . Since
the purpose of the indicator is to stop the titration close to the
point at which the reacting substances were added in equivalent
quantities, it is important that the equivalent point and the end
point be as close as possible.
Normal solution : A solution containing one gram equivalent
weight of the solute dissolved per litre is called a normal solution ;
e.g. when 40 g of NaOH are present in one litre of NaOH solution,
the solution is known as normal ( N ) solution of NaOH . Similarly, a
solution containing a fraction of gram equivalent weight of the
 8 Chemical Arithmetic
solute dissolved per litre is known as subnormal solution. For
example, a solution of NaOH containing 20 g (1/2 of g eq. wt.) of
NaOH dissolved per litre is a sub-normal solution. It is written as
N /2 or 0.5 N solution.
Formula used in solving numerical problems on volumetric analysis
(1) Strength of solution = Amount of substance in g litre1
(2) Strength of solution = Amount of substance in g moles litre1
(3) Strength of solution = Normality  Eq. wt. of the solute
= molarity  Mol. wt. of solute
Limiting reagent or reactant
In many situations, an excess of one or more substance is available
for chemical reaction. Some of these excess substances will therefore be left
over when the reaction is complete; the reaction stops immediately as soon
as one of the reactant is totally consumed.
The substance that is totally consumed in a reaction is called
limiting reagent because it determines or limits the amount of product. The
other reactant present in excess are called as excess reagents.
Let us consider a chemical reaction which is initiated by passing a
spark through a reaction vessel containing 10 mole of H and 7 mole of O .
2 2

Moles of solute
(4) Molarity
Volume in litre 2 H 2 (g)  O2 (g)  2 H 2O (v)

Wt. in gm
(5) Number of moles   M  V(inl) Moles before reaction 10 7 0
Mol.wt.
Moles after reaction 0 2 10
Volume in litres
 at NTP (only for gases) The reaction stops only after consumption of 5 moles of O as no
22.4 2

further amount of H is left to react with unreacted O . Thus H is a limiting

2 2 2

Wt. in gm  1000 reagent in this reaction.

(6) Number of millimoles 
mol. wt.

 Molarity Volume in ml.

(7) Number of equivalents

Wt. in gm
  x  No. of moles  Normality  Volume in litre
Eq. wt.  Law of conservation of mass does not hold good for nuclear
reactions.
(8) Number of milliequivalents (meq.)
 Law of definite proportions do not hold good for non-
Wt. in gm  1000
  normality  Volume in ml. stoichiometric compounds e.g., Wusitite Fe O. 0.95

Eq. wt.
 Law of definite proportions, law of multiple proportions and law of
(9) Normality  x  No. of millimoles reciprocal proportions do not hold good when same compounds is
obtained by using different isotopes of te same element e.g. H O
Strength in gm litre1
2

 x  Molarity  and D O.
2

Eq. wt.
 The term atom was introduced by Ostwald and the term molecule
Mol.wt. was introduced by Avogadro.
where x  , x = valency or change in oxi. Number.
Eq. wt.  The concept of element was introduced by Robert Boyle.
(10) Normality formula, N1 V1  N 2 V2  The number of atoms present in a molecule of a gaseous element is
called Atomicity.
Wt. of solvent
(11) % by weight   100  Both atomic mass and molecular mass are just rations and hence
Wt. of solution
have no units.
Wt. of solvent
(12) % by volume   100  1 mol of H O  22400 cc of H O (because it is a liquid). Instead,
2 2

Vol. of solution
1 mol of H O = 18cc of H O
2 2

Vol. of solvent (because density of H O = 1 g/cc)

(13) % by strength   100 2

Vol. of solution
 1 M H SO = 2NH SO .
2 4 2 4

(14) Specific gravity

 Minimum molecular mass of a macromolecular substance can be
Wt. of solution calculated by analysing it for one of the minar components.
  Wt. of 1 ml. of solution
Vol. of solution Minimum molecular mass is obtained when it is supposed that one
molecule of the macromolecule contains only one atom or molecule
Wt. of ionic solute
(15) Formality  of the minor component.
Formula Wt. of solute Vin l
Minimum molecular mass
(16) Mol. Wt. = V.D  2 (For gases only)
 Chemical Arithmetic 9

Atomic/molecular mass of minor component


Mass of minor component per gram of macromolec ule
 10 Chemical Arithmetic
13. In known elements, the maximum number is of
[CPMT 1985]
(a) Metals (b) Non-metals
(c) Metalloids (d) None of these
14. Which one of the following is not an element
(a) Diamond (b) Graphite
Significant figures, Units for measurement, (c) Silica (d) Ozone
Matter and Separation of mixture 15. A mixture of ZnCl 2 and PbCl 2 can be separated by

1. One fermi is [Haryana CEET 1994; DPMT 2004] [AFMC 1989]

(a) Distillation (b) Crystallization
(a) 10 13 cm (b) 10 15 cm
(c) Sublimation (d) Adding aceitic acid
(c) 10 10 cm (d) 10 12 cm 16. A mixture of methyl alcohol and acetone can be separated by
2. A picometre is written as (a) Distillation
(a) 10 9 m (b) 10 10 m (b) Fractional distillation
(c) 10 11 m (d) 10 12 m (c) Steam distillation
3. One atmosphere is equal to (d) Distillation under reduced pressure
(a) 101.325 K pa (b) 1013.25 K pa 17. In the final answer of the expression
(29.2  20.2) (1 .79  10 5 )
(c) 10 5 Nm (d) None of these . The number of significant figures
1 .37
4. Dimensions of pressure are same as that of
is [CBSE PMT 1994]
[CBSE PMT 1995]
(a) 1 (b) 2
(a) Energy (b) Force
(c) 3 (d) 4
(c) Energy per unit volume (d) Force per unit volume
18. 81.4 g sample of ethyl alcohol contains 0.002 g of water. The
5. The prefix 1018 is [Kerala MEE 2002] amount of pure ethyl alcohol to the proper number of
(a) Giga (b) Nano significant figures is
(c) Mega (d) Exa (a) 81.398 g (b) 71.40 g
6. Given the numbers : 161cm, 0.161cm, 0.0161 cm. The number (c) 91.4 g (d) 81 g
of significant figures for the three numbers are 19. The unit J Pa 1 is equivalent to
[CBSE PMT 1998]
(a) m 3 (b) cm 3
(a) 3, 4 and 5 respectively (b) 3, 3 and 3 respectively
(c) 3, 3 and 4 respectively (d) 3, 4 and 4 respectively (c) dm 3 (d) None of these
7. Significant figures in 0.00051 are 20. From the following masses, the one which is expressed nearest
to the milligram is
(a) 5 (b) 3
(a) 16 g (b) 16.4 g
(c) 2 (d) 4
(c) 16.428 g (d) 16.4284 g
8. Which of the following halogen can be purified by sublimation [Manipal PMT 2001]
21. The number of significant figures in 6.02  10 23 is
(a) F2 (b) Cl 2
(a) 23 (b) 3
(c) Br2 (d) I2 (c) 4 (d) 26
9. Difference in density is the basis of [Kerala MEE 2002] 22. The prefix zepto stands for [DPMT 2004]
(a) Ultrafiltration (b) Molecular sieving (a) 10 9 (b) 10 12
(c) Gravity Separation (d) Molecular attraction
(c) 10 15 (d) 10 21
10. Which of the following elements of matter would best convey
23. The significant figures in 3400 are [BHU 2004]
that there is life on earth
(a) 2 (b) 5
(a) Oxygen (b) Hydrogen
(c) 6 (d) 4
(c) Carbon (d) Iron
24. The number of significant figures in 6.0023 are
11. The compound which is added to table salt for maintaining
[Pb.CET 2001]
proper health is
(a) 5 (b) 4
(a) KCl (b) KBr
(c) 3 (d) 1
(c) NaI (d) MgBr2
25. Given P  0.0030m , Q  2.40m , R  3000m , Significant
12. Which of the following contains only one element figures in P, Q and R are respectively [Pb. CET 2002]
(a) Marble (b) Diamond
(a) 2, 2, 1 (b) 2, 3, 4
(c) Glass (d) Sand
(c) 4, 2, 1 (d) 4, 2, 3
 Chemical Arithmetic 11
26. The number of significant figures in 60.0001 is 9. Two elements X and Y have atomic weights of 14 and 16. They
[Pb. CET 2000] form a series of compounds A, B, C, D and E in which the same
(a) 5 (b) 6 amount of element X, Y is present in the ratio 1 : 2 : 3 : 4 : 5. If
(c) 3 (d) 2 the compound A has 28 parts by weight of X and 16 parts by
weight of Y, then the compound of C will have 28 parts weight
27. A sample was weighted using two different balances. The
of X and [NCERT 1971]
result’s were (i) 3.929 g (ii) 4.0 g. How would the weight of the
sample be reported (a) 32 parts by weight of Y (b) 48 parts by weight of Y
(a) 3.929 g (b) 3 g (c) 64 parts by weight of Y (d) 80 parts by weight of Y
(c) 3.9 g (d) 3.93 g 10. Carbon and oxygen combine to form two oxides, carbon
monoxide and carbon dioxide in which the ratio of the weights
Laws of chemical combination of carbon and oxygen is respectively 12 : 16 and 12 : 32. These
figures illustrate the
1. Which of the following pairs of substances illustrate the law of (a) Law of multiple proportions
multiple proportions [CPMT 1972, 78]
(b) Law of reciprocal proportions
(a) CO and CO2 (b) H 2 O and D2 O (c) Law of conservation of mass
(c) NaCl and NaBr (d) MgO and Mg(OH ) 2 (d) Law of constant proportions
11. A sample of calcium carbonate (CaCO 3 ) has the following
2. 1.0 g of an oxide of A contained 0.5 g of A. 4.0 g of another
oxide of A contained 1.6 g of A. The data indicate the law of percentage composition : Ca = 40%; C = 12%; O = 48%
(a) Reciprocal proportions (b) Constant proportions If the law of constant proportions is true, then the weight of
calcium in 4 g of a sample of calcium carbonate obtained from
(c) Conservation of energy (d) Multiple proportions
another source will be
3. Among the following pairs of compounds, the one that (a) 0.016 g (b) 0.16 g
illustrates the law of multiple proportions is
(c) 1.6 g (d) 16 g
(a) NH 3 and NCl 3 (b) H 2 S and SO 2 12. n g of substance X reacts with m g of substance Y to form p g of
(c) CuO and Cu 2 O (d) CS 2 and FeSO 4 substance R and q g of substance S. This reaction can be
represented as, X  Y  R  S . The relation which can be
4. The percentage of copper and oxygen in samples of CuO established in the amounts of the reactants and the products will be
obtained by different methods were found to be the same. This
(a) n  m  p  q (b) n  m  p  q
illustrates the law of [AMU 1982, 92]
(c) n  m (d) pq
(a) Constant proportions (b) Conservation of mass
(c) Multiple proportions (d) Reciprocal proportions 13. Which of the following is the best example of law of
conservation of mass [NCERT 1975]
5. Two samples of lead oxide were separately reduced to metallic
lead by heating in a current of hydrogen. The weight of lead (a) 12 g of carbon combines with 32 g of oxygen to form 44 g
from one oxide was half the weight of lead obtained from the of CO 2
other oxide. The data illustrates [AMU 1983] (b) When 12 g of carbon is heated in a vacuum there is no
(a) Law of reciprocal proportions change in mass
(b) Law of constant proportions (c) A sample of air increases in volume when heated at
(c) Law of multiple proportions constant pressure but its mass remains unaltered
(d) Law of equivalent proportions (d) The weight of a piece of platinum is the same before and
6. Chemical equation is balanced according to the law of after heating in air
[AMU 1984] 14. The law of multiple proportions is illustrated by the two
(a) Multiple proportion (b) Reciprocal proportion compounds [NCERT 1972]
(c) Conservation of mass (d) Definite proportions (a) Sodium chloride and sodium bromide
7. Avogadro number is (b) Ordinary water and heavy water
(a) Number of atoms in one gram of element (c) Caustic soda and caustic potash
(b) Number of millilitres which one mole of a gaseous (d) Sulphur dioxide and sulphur trioxide
substances occupies at NTP 15. In compound A, 1.00 g nitrogen unites with 0.57 g oxygen. In
(c) Number of molecules present in one gram molecular mass compound B, 2.00 g nitrogen combines with 2.24 g oxygen. In
of a substance compound C, 3.00 g nitrogen combines with 5.11 g oxygen.
(d) All of these These results obey the following law [CPMT 1971]
8. Different propartions of oxygen in the various oxides of (a) Law of constant proportion
nitrogen prove the [MP PMT 1985] (b) Law of multiple proportion
(a) Equivalent proportion (b) Multiple proportion (c) Law of reciprocal proportion
(c) Constant proportion (d) Conservation of matter (d) Dalton's law of partial pressure
 12 Chemical Arithmetic
16. Hydrogen combines with oxygen to form H 2 O in which 16 g 4. 1 amu is equal to
of oxygen combine with 2 g of hydrogen. Hydrogen also 1 1
(a) of C  12 (b) of O - 16
combines with carbon to form CH 4 in which 2 g of hydrogen 12 14
combine with 6 g of carbon. If carbon and oxygen combine (c) 1g of H 2 (d) 1.66  10 23 kg
together then they will do show in the ratio of
5. Sulphur forms the chlorides S 2 Cl 2 and SCl 2 . The equivalent
(a) 6 : 16 or 12 : 32 (b) 6 : 18
mass of sulphur in SCl 2 is
(c) 1 : 2 (d) 12 : 24
17. 2 g of hydrogen combine with 16 g of oxygen to form water [EAMCET 1985; Pb. CET 2001]
and with 6 g of carbon to form methane. In carbon dioxide 12 g (a) 8 g/mole (b) 16 g/mole
of carbon are combined with 32 g of oxygen. These figures (c) 64.8 g/mole (d) 32 g/mole
illustrate the law of 6. The sulphate of a metal M contains 9.87% of M. This sulphate
(a) Multiple proportions (b) Constant proportions is isomorphous with ZnSO 4 .7 H 2 O . The atomic weight of M
(c) Reciprocal proportions (d) Conservation of mass is [IIT 1991]
18. An element forms two oxides containing respectively 53.33 and (a) 40.3 (b) 36.3
36.36 percent of oxygen. These figures illustrate the law of (c) 24.3 (d) 11.3
(a) Conservation of mass (b) Constant proportions 7. When 100 ml of 1 M NaOH solution and 10 ml of
(c) Reciprocal proportions (d) Multiple proportions 10 N H 2 SO 4 solution are mixed together, the resulting solution
19. After a chemical reaction, the total mass of reactants and will be [DPMT 1982]
products [MP PMT 1989]
(a) Alkaline (b) Acidic
(a) Is always increased (b) Is always decreased
(c) Strongly acidic (d) Neutral
(c) Is not changed (d) Is always less or more
8. In chemical scale, the relative mass of the isotopic mixture of
20. A sample of pure carbon dioxide, irrespective of its source
oxygen atoms (O 16 , O 17 , O 18 ) is assumed to be equal to
contains 27.27% carbon and 72.73% oxygen. The data support
[AIIMS 1992] [Bihar MADT 1981]

(a) Law of constant composition (a) 16.002 (b) 16.00

(c) 17.00 (d) 11.00
(b) Law of conservation of mass
9. For preparing 0.1 N solution of a compound from its impure
(c) Law of reciprocal proportions
sample of which the percentage purity is known, the weight of
(d) Law of multiple proportions the substance required will be [MP PET 1996]
21. The law of definite proportions is not applicable to nitrogen (a) More than the theoretical weight
oxide because [EAMCET 1981]
(b) Less than the theoretical weight
(a) Nitrogen atomic weight is not constant
(c) Same as the theoretical weight
(b) Nitrogen molecular weight is variable (d) None of these
(c) Nitrogen equivalent weight is variable 10. 1 mol of CH 4 contains
(d) Oxygen atomic weight is variable
(a) 6.02  10 23 atoms of H
22. Which one of the following pairs of compounds illustrates the
law of multiple proportion [EAMCET 1989]
(b) 4 g atom of Hydrogen

(a) H 2O, Na 2O (b) MgO, Na 2O (c) 1.81  10 23 molecules of CH 4

(d) 3.0 g of carbon
(c) Na 2O, BaO (d) SnCl 2 , SnCl 4
11. In the reaction 2 Na2 S 2O3  I2  Na2 S 4 O6  2 NaI , the
Atomic, Molecular and Equivalent masses equivalent weight of Na 2 S 2 O 3 (mol. wt. = M) is equal to
(a) M (b) M / 2
1. Which property of an element is always a whole number
(c) M / 3 (d) M / 4
[MP PMT 1986]
12. When potassium permanganate is titrated against ferrous
(a) Atomic weight (b) Equivalent weight
ammonium sulphate, the equivalent weight of potassium
(c) Atomic number (d) Atomic volume permanganate is [CPMT 1988]
2. Which one of the following properties of an element is not (a) Molecular weight /10 (b) Molecular weight /5
variable [Bihar MADT 1981] (c) Molecular weight /2 (d) Molecular weight
(a) Valency (b) Atomic weight
13. Boron has two stable isotopes, 10 B (19%) and 11 B (81%). The
(c) Equivalent weight (d) All of these atomic mass that should appear for boron in the periodic table
3. The modern atomic weight scale is based on is [CBSE PMT 1990]
[MP PMT 2002] (a) 10.8 (b) 10.2
12 16
(a) C (b) O (c) 11.2 (d) 10.0
(c) H1 (d) C 13
 Chemical Arithmetic 13
14. What is the concentration of nitrate ions if equal volumes of 0.1 27. The atomic weights of two elements A and B are 40 and 80
M AgNO 3 and 0.1 M NaCl are mixed together respectively. If x g of A contains y atoms, how many atoms are
[CPMT 1983; NCERT 1985] present in 2x g of B
(a) 0.1 M (b) 0.2 M y y
(a) (b)
(c) 0.05 M (d) 0.25 M 2 4
15. Total number of atoms represented by the compound (c) y (d) 2y
CuSO4.5H2O is [BHU 2005]
28. Assuming fully decomposed, the volume of CO 2 released at
(a) 27 (b) 21
(c) 5 (d) 8 STP on heating 9.85g of BaCO 3 (Atomic mass of Ba=137)
16. 74.5 g of a metallic chloride contain 35.5 g of chlorine. The will be [CBSE PMT 2000]
equivalent weight of the metal is [CPMT 1986] (a) 0.84 L (b) 2.24 L
(a) 19.5 (b) 35.5 (c) 4.06 L (d) 1.12 L
(c) 39.0 (d) 78.0
29. If N A is Avogadro’s number then number of valence electrons
17. 7.5 grams of a gas occupy 5.8 litres of volume at STP the gas is
(a) NO (b) N 2 O in 4.2 g of nitride ions ( N 3 )

(c) CO (d) CO 2 (a) 2.4 N A (b) 4.2 N A

18. The number of atoms in 4.25 g of NH 3 is approximately (c) 1.6 N A (d) 3.2 N A
[CBSE PMT 1999; MH CET 2003] 30. The weight of 1  10 22 molecules of CuSO 4 .5 H 2 O is
(a) 1  10 23 (b) 2  10 23
[IIT 1991]
(c) 4  10 23 (d) 6  10 23 (a) 41.59 g (b) 415.9 g
19. One litre of a gas at STP weight 1.16 g it can possible be
(c) 4.159 g (d) None of these
[AMU 1992]
31. Rearrange the following (I to IV) in the order of increasing
(a) C2 H 2 (b) CO
masses and choose the correct answer from (a), (b), (c) and (d)
(c) O2 (d) CH 4 (Atomic mass: N=14, O=16, Cu=63).
20. The vapour density of a gas is 11.2. The volume occupied by I. 1 molecule of oxygen
11.2 g of the gas at ATP will be [Bihar CET 1995]
II. 1 atom of nitrogen
(a) 11.2 L (b) 22.4 L
(c) 1 L (d) 44.8 L III. 1  10 10 g molecular weight of oxygen
21. Equivalent weight of crystalline oxalic acid is IV. 1  10 10 g atomic weight of copper
[MP PMT 1995]
(a) 30 (b) 63 (a) II<I<III<IV (b) IV<III<II<I
(c) 53 (d) 45 (c) II<III<I<IV (d) III<IV<I<II
22. The equivalent weight of an element is 4. Its chloride has a V.D 32. 1.520 g of the hydroxide of a metal on ignition gave 0.995
59.25. Then the valency of the element is [BHU 1997] gm of oxide. The equivalent weight of metal is
(a) 4 (b) 3 [DPMT 1984]

(c) 2 (d) 1 (a) 1.520 (b) 0.995

(c) 19.00 (d) 9.00
23. 1.25 g of a solid dibasic acid is completely neutralised by 25 ml
of 0.25 molar Ba(OH ) 2 solution. Molecular mass of the acid is 33. How much coulomb charge is present on 1g ion of N 3 
(a) 100 (b) 150 (a) 5.2  10 6 Couloumb (b) 2.894  10 5 Couloumb
(c) 120 (d) 200 (c) 6.6  10 6 Couloumb (d) 8.2  10 6 Couloumb
24. The oxide of a metal has 32% oxygen. Its equivalent weight 34. Ratio of C p and C v of a gas X is 1.4, the number of atom of
would be [MP PMT 1985] the gas ‘X’ present in 11.2 litres of it at NTP will be
(a) 34 (b) 32 [CBSE 1999]
(c) 17 (d) 8 (a) 6.02  10 23 (b) 1.2  10 23
25. The mass of a molecule of water is [Bihar CEE 1995]
(c) 3.01  10 23 (d) 2.01  10 23
26 25
(a) 3  10 kg (b) 3  10 kg 35. If we consider that 1/6, in place of 1/12, mass of carbon atom is
26 26
(c) 1.5  10 kg (d) 2.5  10 kg taken to be the relative atomic mass unit, the mass of one mole
of a substance will [AIEEE 2005]
26. 1.24 gm P is present in 2.2 gm
(a) Decrease twice
(a) P4 S 3 (b) P2 S 2
(b) Increase two fold
(c) PS 2 (d) P2 S 4 (c) Remain unchanged
(d) Be a function of the molecular mass of the substance
 14 Chemical Arithmetic
36. What should be the equivalent weight of phosphorous acid, if (a) 21 (b) 54
P=31; O=16; H=1 (c) 27.06 (d) 2.086
(a) 82 (b) 41 49. One gram of hydrogen is found to combine with 80g of
(c) 20.5 (d) None of these bromine one gram of calcium valency=2 combines with 4g of
37. The number of molecule at NTP in 1 ml of an ideal gas will be bromine the equivalent weight of calcium is
(a) 6  10 23 (b) 2.69  10 19 (a) 10 (b) 20
(c) 40 (d) 80
(c) 2.69  10 23 (d) None of these
50. The equivalent weight of MnSO 4 is half its molecular weight
38. The specific heat of a metal is 0.16 its approximate atomic
weight would be when it is converted to [IIT 1988; CPMT 1994]
(a) 32 (b) 16 (a) Mn 2 O 3 (b) MnO 2
(c) 40 (d) 64
(c) MnO4 (d) MnO42 
39. The weight of a molecule of the compound C 60 H 122 is
51. 100 mL of PH3 on decomposition produced phosphorus and
[AIIMS 2000]
hydrogen. The change in volume is [MNR 1986]
(a) 1.4  10 21 g (b) 1.09  10 21 g
(a) 50 mL increase (b) 500 mL decrease
(c) 5.025  10 23 g (d) 16.023  10 23 g
(c) 900 mL decrease (d) Nil.
40. What is the weight of oxygen required for the complete
combustion of 2.8 kg of ethylene [CBSE PMT 1989] 52. 12 g of Mg (at. mass 24) on reacting completely with acid
(a) 2.8 kg (b) 6.4 kg gives hydrogen gas, the volume of which at STP would be
(c) 9.6 kg (d) 96 kg [CPMT 1978]
41. What volume of NH 3 gas at STP would be needed to prepare (a) 22.4 L (b) 11.2 L
100ml of 2.5 molal (2.5m) ammonium hydroxide solution (c) 44.8 L (d) 6 .1 L
(a) 0.056 litres (b) 0.56 litres
53. Which of the following has least mass [Pb. PET 1985]
(c) 5.6 litres (d) 11.2 litres
(a) 2 g atom of nitrogen (b) 3  10 23
atoms of C
42. If the density of water is 1 g cm 3 then the volume occupied
by one molecule of water is approximately [Pb. PMT 2004] (c) 1 mole of S (d) 7 .0 g of Ag
(a) 18 cm 3 (b) 22400 cm 3 54. How many mole of helium gas occupy 22.4 L at 0 o C at 1
(c) 6.02  10 23 cm 3 (d) 3.0  10 23 cm 3 atm. pressure [Kurukshetra CEE 1992; CET 1992]
(a) 0.11 (b) 0.90
43. Caffeine has a molecular weight of 194. If it contains 28.9% by
mass of nitrogen, number of atoms of nitrogen in one molecule (c) 1.0 (d) 1.11
of caffeine is 55. Volume of a gas at STP is 1.12  10 7 cc. Calculate the number
(a) 4 (b) 6 of molecules in it [BHU 1997]
(c) 2 (d) 3
(a) 3.01  10 20 (b) 3.01  1012
44. A 400 mg iron capsule contains 100 mg of ferrous fumarate,
(CHCOO ) 2 Fe . The percentage of iron pasent in it is (c) 3.01  10 23 (d) 3.01  10 24

approximately 56. 4 .4 g of an unknown gas occupies 2.24 L of volume at

(a) 33% (b) 25% standard temperature and pressure. The gas may be
(c) 14% (d) 8% [MP PMT 1995]
26
45. The element whose a atom has mass of 10.86  10 kg is (a) Carbon dioxide (b) Carbon monoxide
(a) Boron (b) Calcium (c) Oxygen (d) Sulphur dioxide
(c) Silver (d) Zinc 57. The number of moles of oxygen in 1 L of air containing 21%
46. The number of gram atoms of oxygen present in 0.3 gram mole oxygen by volume, in standard conditions, is
of (COOH ) 2 .2 H 2 O is
[CBSE PMT 1995; Pb. PMT 2004]
(a) 0.6 (b) 1.8 (a) 0.186 mol (b) 0.21 mol
(c) 1.2 (d) 3.6
(c) 2.10 mol (d) 0.0093 mol
47. A gaseous mixture contains CH 4 and C 2 H 6 in equimolecular
58. The number of molecules in 8.96 L of a gas at 0 o C and 1
proportion. The weight of 2.24 litres of this mixture at NTP is
(a) 4.6 g (b) 1.6 g atmosphere pressure is approximately [BHU 1993]

(c) 2.3 g (d) 23 g (a) 6.02  10 23

(b) 12.04  10 23

48. Vapour density of a metal chloride is 66. Its oxide contains (c) 18.06  10 23
(d) 24.08  10 22
53% metal. The atomic weight of the metal is
[Bihar MADT 1982]
 Chemical Arithmetic 15
59. The equivalent weight of a metal is 9 and vapour density of its (c) 6  10 23 (d) 12  10 23
chloride is 59.25. The atomic weight of metal is 6. The volume occupied by 4.4 g of CO 2 at STP is
[Pb. CET 2002]
[AFMC 1997, 2004; Pb. CET 1997, 2002]
(a) 23.9 (b) 27.3 (a) 22.4 L (b) 2.24 L
(c) 36.3 (d) 48.3 (c) 0.224 L (d) 0.1 L
60. The molecular weight of a gas is 45. Its density at STP is 7. The number of water molecules present in a drop of water
[Pb. PMT 2004] (volume 0.0018 ml) at room temperature is [DCE 2000]
(a) 22.4 (b) 11.2 (a) 6.023  10 19 (b) 1.084  10 18
(c) 5.7 (d) 2.0 (c) 4.84  10 17 (d) 6.023  10 23
61. Equivalent weight of a bivalent metal is 37.2. The molecular 8. One mole of calcium phosphide on reaction with excess of
weight of its chloride is [MH CET 2003] water gives [IIT 1999]
(a) 412.2 (b) 216 (a) One mole of phosphine
(c) 145.4 (d) 108.2 (b) Two moles of phosphoric acid
62. On reduction with hydrogen, 3.6 g of an oxide of metal left 3.2 (c) Two moles of phosphine
g of metal. If the vapour density of metal is 32, the simplest (d) One mole of phosphorus pentoxide
formula of the oxide would be 9. 19.7 kg of gold was recovered from a smuggler. How many
[DPMT 2004] atoms of gold were recovered (Au =197) [Pb. CET 1985]

(a) MO (b) M 2 O 3 (a) 100 (b) 6.02  10 23

(c) 6.02  10 24 (d) 6.02  10 25
(c) M 2O (d) M 2 O 5
10. The total number of protons in 10 g of calcium carbonate is
63. The number of molecules in 4.25 g of ammonia are ( N 0  6.023  10 23 )
[Pb. CET 2000]
(a) 1.5057  10 24 (b) 2.0478  10 24
(a) 0.5  10 23
(b) 1.5  10 23
(c) 3.0115  10 24 (d) 4.0956  10 24
(c) 3.5  10 23 (d) 1.8  10 32 11. The number of molecules in 16 g of methane is
The mole concept (a) 3.0  10 23 (b) 6.02  10 23
16 16
(c)  10 23 (d)  10 23
1. Which one of the following pairs of gases contains the same 6 .02 3 .0
number of molecules [EAMCET 1987] 12. Number of molecules in 100 ml of each of
(a) 16 g of O 2 and 14 g of N 2 O 2 , NH 3 and CO 2 at STP are [Bihar MADT 1985]
(b) 8 g of O 2 and 22 g of CO 2 (a) In the order CO 2  O2  NH 3
(c) 28 g of N 2 and 22 g of CO 2 (b) In the order NH 3  O 2  CO 2
(d) 32 g of O 2 and 32 g of N 2 (c) The same
2. Number of gm of oxygen in 32.2 g Na 2 SO 4 .10 H 2 O is (d) NH 3  CO 2  O 2
[Haryana PMT 2000] 13. The molecular weight of hydrogen peroxide is 34. What is the
(a) 20.8 (b) 22.4 unit of molecular weight [MP PMT 1986]
(c) 2.24 (d) 2.08 (a) g (b) mol
3. 250 ml of a sodium carbonate solution contains 2.65 grams of (c) g mol 1 (d) mol g 1
Na 2 CO 3 . If 10 ml of this solution is diluted to one litre, what
14. The number of water molecules in 1 litre of water is
is the concentration of the resultant solution (mol. wt. of [EAMCET 1990]
Na 2 CO 3 =106) [EAMCET 2001]
(a) 18 (b) 18  1000
(a) 0.1 M (b) 0.001 M (c) N A (d) 55.55 N A
4
(c) 0.01 M (d) 10 M 15. The number of electrons in a mole of hydrogen molecule is
4. A molar solution is one that contains one mole of a solute in [CPMT 1987]
[IIT 1986] (a) 6.02  10 23
(b) 12.046  10 23

(a) 1000 g of the solvent (b) One litre of the solvent

(c) 3.0115  10 23
(d) Indefinite
(c) One litre of the solution (d) 22.4 litres of the solution
16. The numbers of moles of BaCO 3 which contain 1.5 moles of
5. The number of oxygen atoms in 4.4 g of CO 2 is approx.
oxygen atoms is [EAMCET 1991]
[CBSE PMT 1990]
(a) 0.5 (b) 1
(a) 1.2  10 23 (b) 6  10 22
(c) 3 (d) 6.02  10 23
 16 Chemical Arithmetic
17. Which of the following is Loschmidt number (a) 40 (b) 60
(a) 6  10 23
(b) 2.69  10 19 (c) 8 (d) 10
(c) 3  10 23
(d) None of these 2. The percentage of nitrogen in urea is about [KCET 2001]

18. How many molecules are present in one gram of hydrogen (a) 46 (b) 85
[AIIMS 1982] (c) 18 (d) 28
(a) 6.02  10 23 (b) 3.01  10 23 3. If two compounds have the same empirical formula but
different molecular formula, they must have
(c) 2.5  10 23 (d) 1.5  10 23 [MP PMT 1986]
19. The total number of gm-molecules of SO 2 Cl 2 in 13.5 g of (a) Different percentage composition
sulphuryl chloride is [CPMT 1992] (b) Different molecular weights
(a) 0.1 (b) 0.2 (c) Same viscosity
(c) 0.3 (d) 0.4 (d) Same vapour density
20. The largest number of molecules is in [BHU 1997] 4. A compound (80 g) on analysis gave C = 24 g, H = 4 g, O =
(a) 34 g of water (b) 28 g of CO 2 32 g. Its empirical formula is [CPMT 1981]
(c) 46 g of CH 3 OH (d) 54 g of N 2 O5 (a) C2 H 2 O2 (b) C 2 H 2 O
21. The number of moles of sodium oxide in 620 g of it is (c) CH 2 O 2 (d) CH 2 O
[BHU 1992] 5. The empirical formula of a compound is CH 2 O. 0.0835 moles
(a) 1 mol (b) 10 moles
of the compound contains 1.0 g of hydrogen. Molecular
(c) 18 moles (d) 100 moles formula of the compound is
22. 2 g of oxygen contains number of atoms equal to that in (a) C 2 H 12 O 6 (b) C 5 H 10 O 5
[BHU 1992] (c) C 4 H 8 O8 (d) C 3 H 6 O 3
(a) 0 .5 g of hydrogen (b) 4 g of sulphur
6. The empirical formula of an acid is CH 2O2 , the probable
(c) 7 g of nitrogen (d) 2 .3 g of sodium
molecular formula of acid may be [AFMC 2000]
23. Molarity of liquid HCl with density equal to 1.17 g / cc is
(a) CH 2 O (b) CH 2O2
[CBSE PMT 2001]
(a) 36.5 (b) 18.25 (c) C 2 H 4 O2 (d) C3 H 6 O4
(c) 32.05 (d) 4.65 7. In which of the following pairs of compounds the ratio of C, H
24. How many atoms are contained in one mole of sucrose and O is same
(C12 H 22 O11 ) [Pb. PMT 2002]
(a) Acetic acid and methyl alcohol
(a) 45  6.02  10 23 atoms/mole (b) Glucose and acetic acid
(b) 5  6.62  10 23 atoms/mole (c) Fructose and sucrose
(c) 5  6.02  10 23 atoms/mole (d) All of these
(d) None of these
25. The number of molecules of CO2 present in 44g of CO2 is Chemical stoichiometry
[BCECE 2005]
1. How much of NaOH is required to neutralise 1500 cm 3 of 0.1
(a) 6.0  10 23
(b) 3  10 23
N HCl (Na = 23) [KCET 2001]
(c) 12  10 23 (d) 3  10 10
(a) 40 g (b) 4 g
26. A sample of phosphorus trichloride (PCl 3 ) contains 1.4 moles
(c) 6 g (d) 60 g
of the substance. How many atoms are there in the sample[Kerala PMT 2004]
2. How much water should be added to 200 c.c of semi normal
(a) 4 (b) 5.6
solution of NaOH to make it exactly deci normal
(c) 8.431  10 23 (d) 3.372  10 24
[AFMC 1983]
(e) 2.409  10 24 (a) 200 cc (b) 400 cc
27. The number of sodium atoms in 2 moles of sodium
(c) 800 cc (d) 600 cc
ferrocyanide is [BHU 2004]
3. 2.76 g of silver carbonate on being strongly heated yield a
(a) 12  10 23 (b) 26  10 23
residue weighing [Pb. CET 2003]
(c) 34  10 23 (d) 48  10 23
(a) 2.16 g (b) 2.48 g
(c) 2.64 g (d) 2.32 g
Percentage composition & Molecular formula

1. The percentage of oxygen in NaOH is [CPMT 1979]

 Chemical Arithmetic 17
4. In the reaction, 4 NH 3 (g)  5O 2 (g)  4 NO(g)  6 H 2 O(g) , (c) 80 grams (d) 320 grams
When 1 mole of ammonia and 1 mole of O 2 are made to react 13. What is the normality of a 1 M solution of H 3 PO4
to completion [AIIMS 1982]

(a) 1.0 mole of H 2 O is produced (a) 0.5 N (b) 1.0 N

(c) 2.0 N (d) 3.0 N
(b) 1.0 mole of NO will be produced
14. Normality of 2M sulphuric acid is [AIIMS 1992]
(c) All the oxygen will be consumed
(a) 2N (b) 4N
(d) All the ammonia will be consumed
N N
(c) (d)
5. Haemoglobin contains 0.33% of iron by weight. The molecular 2 4
weight of haemoglobin is approximately 67200. The number of
15. How many g of a dibasic acid (Mol. wt. = 200) should be
iron atoms (At. wt. of Fe = 56) present in one molecule of present in 100 ml of its aqueous solution to give decinormal
haemoglobin is [CBSE PMT 1998] strength [AIIMS 1992]
(a) 6 (b) 1 (a) 1 g (b) 2 g
(c) 4 (d) 2 (c) 10 g (d) 20 g
6. What quantity of ammonium sulphate is necessary for the 16. The solution of sulphuric acid contains 80% by weight
production of NH 3 gas sufficient to neutralize a solution H 2 SO 4 . Specific gravity of this solution is 1.71. Its normality
containing 292 g of HCl ? [HCl=36.5; (NH 4 )2 SO 4 =132; is about [CBSE 1991]

NH 3 =17] [CPMT 1992] (a) 18.0 (b) 27.9

(c) 1.0 (d) 10.0
(a) 272 g (b) 403 g
(c) 528 g (d) 1056 g 17. Mohr's salt is dissolved in dil. H 2 SO 4 instead of distilled
7. The percentage of P2 O 5 in diammonium hydrogen phosphate water to
(NH 4 ) 2 HPO4 is [CPMT 1992] (a) Enhance the rate of dissolution
(b) Prevent cationic hydrolysis
(a) 23.48 (b) 46.96
(c) 53.78 (d) 71.00 (c) Increase the rate of ionisation
(d) Increase its reducing strength
1
8. If 1 moles of oxygen combine with Al to form Al2 O 3 the 18. Acidified potassium permanganate solution is decolourised by
2
weight of Al used in the reaction is (Al=27) [EAMCET 1980] (a) Bleaching powder (b) White vitriol
(a) 27 g (b) 54 g (c) Mohr's salt (d) Microcosmic salt
(c) 49.5 g (d) 31 g 19. Approximate atomic weight of an element is 26.89. If its
equivalent weight is 8.9, the exact atomic weight of element
9. The percentage of Se in peroxidase anhydrous enzyme is 0.5% would be [DPMT 1984]
by weight (atomic weight=78.4). Then minimum molecular
(a) 26.89 (b) 8.9
weight of peroxidase anhydrous enzyme is
(c) 17.8 (d) 26.7
[CBSE PMT 2001]
20. Vapour density of a gas is 22. What is its molecular mass
(a) 1.568  10 4 (b) 1.568  10 3
[AFMC 2000]
(c) 15.68 (d) 3.136  10 4 (a) 33 (b) 22
10. H 2 evolved at STP on complete reaction of 27 g of (c) 44 (d) 11
Aluminium with excess of aqueous NaOH would be 21. Equivalent weight of KMnO4 acting as an oxidant in acidic
[CPMT 1991] medium is [CPMT 1990; MP PET 1999]
(a) 22.4 (b) 44.8 (a) The same as its molecular weight
(c) 67.2 (d) 33.6 litres (b) Half of its molecular weight

11. What is the % of H 2 O in Fe(CNS )3 .3 H 2O (c) One-third of its molecular weight

(d) One-fifth of its molecular weight
(a) 45 (b) 30
22. 0.16 g of dibasic acid required 25 ml of decinormal NaOH
(c) 19 (d) 25 solution for complete neutralisation. The molecular weight of
12. What weight of SO 2 can be made by burning sulphur in 5.0 the acid will be [CPMT 1989]

moles of oxygen (a) 32 (b) 64

(a) 640 grams (b) 160 grams (c) 128 (d) 256
 18 Chemical Arithmetic
23. To neutralise 20 ml of M / 10 sodium hydroxide, the volume [CPMT 1992]
of M / 20 hydrochloric acid required is (a) 0.6 g (b) 1.0 g
[Andhra MBBS 1980] (c) 1.5 g (d) 2.0 g
(a) 10 ml (b) 15 ml 32. In the preceeding question, the amount of Na 2CO 3 present in
(c) 20 ml (d) 40 ml the solution is [CPMT 1992]
24. Hydrochloric acid solutions A and B have concentration of 0.5 (a) 2.650 g (b) 1.060 g
N and 0.1 N respectively. The volume of solutions A and B
(c) 0.530 g (d) 0.265 g
required to make 2 litres of 0.2 N hydrochloric are
[KCET 1993]
33. How many ml of 1 (M) H 2 SO 4 is required to neutralise 10 ml
(a) 0.5 l of A + 1.5 l of B of 1 (M) NaOH solution
[MP PET 1998; MNR 1982; MP PMT 1987]
(b) 1.5 l of A + 0.5 l of B
(a) 2.5 (b) 5.0
(c) 1.0 l of A + 1.0 l of B
(c) 10.0 (d) 20.0
(d) 0.75 l of A + 1.25 l of B
34. Which of the following cannot give iodometric titrations
25. 5 ml of N HCl, 20 ml of N / 2 H 2 SO 4 and 30 ml of
[AIIMS 1997]
N / 3 HNO3 are mixed together and volume made to one litre.
3 2
(a) Fe (b) Cu
The normality of the resulting solution is [MNR 1991]
(a) N /5 (b) N / 10 (c) Pb2  (d) Ag 
(c) N / 20 (d) N / 40 35. KMnO4 reacts with ferrous ammonium sulphate according to
26. Under similar conditions of pressure and temperature, 40 ml of the equation
slightly moist hydrogen chloride gas is mixed with 20 ml of MnO4  5 Fe2   8 H   Mn2   5 Fe3   4 H 2O , here 10
ammonia gas, the final volume of gas at the same temperature
and pressure will be [CBSE PMT 1993] ml of 0.1 M KMnO4 is equivalent to [CPMT 1999]

(a) 100 ml (b) 20 ml (a) 20 ml of 0.1 M FeSO 4

(c) 40 ml (d) 60 ml
(b) 30 ml of 0.1 M FeSO 4
27. KMnO4 reacts with oxalic acid according to the equation,
(c) 40 ml of 0.1 M FeSO 4
2 MnO4  5 C2O42   16 H   2 Mn2   10CO 2  8 H 2O , here
20 ml of 0.1 M KMnO4 is equivalent to [CBSE PMT 1996] (d) 50 ml of 0.1 M FeSO 4

(a) 20 ml of 0.5 M H 2C2O4 (b) 50 ml of 0.1 M H 2C2O4 36. Ca(OH ) 2  H 3 PO4  CaHPO4  2 H 2 O the equivalent
(c) 50 ml of 0.5 M H 2C2O4 (d) 20 ml of 0.1 M H 2C2O4 weight of H 3 PO4 in the above reaction is [Pb. PMT 2004]

28. In order to prepare one litre normal solution of KMnO4 , how (a) 21 (b) 27
many grams of KMnO4 are required if the solution is used in (c) 38 (d) 49
acidic medium for oxidation [MP PET 2002] 37. The mass of BaCO 3 produced when excess CO 2 is bubbled
(a) 158 g (b) 31.6 g through a solution of 0.205 mol Ba(OH ) 2 is
(c) 790 g (d) 62 g [UPSEAT 2004]
29. What is the concentration of nitrate ions if equal volumes of 0.1
(a) 81 g (b) 40.5 g
M AgNO3 and 0.1 M NaCl are mixed together
(c) 20.25 g (d) 162 g
[NCERT 1981; CPMT 1983]
38. The amount of water that should be added to 500 ml of 0.5 N
(a) 0.1 N (b) 0.2 M
solution of NaOH to give a concentration of 10 mg per ml is
(c) 0.05 M (d) 0.25 M
30. 30 ml of acid solution is neutralized by 15 ml of a 0.2 N base. (a) 100 (b) 200
The strength of acid solution is [CPMT 1986] (c) 250 (d) 500
(a) 0.1 N (b) 0.15 N
39. Number of moles of KMnO 4 required to oxidize one mole of
(c) 0.3 N (d) 0.4 N
Fe(C 2 O 4 ) in acidic medium is [Haryana CEE 1996]
31. A solution containing Na 2CO 3 and NaOH requires 300 ml of
0.1 N HCl using phenolpthalein as an indicator. Methyl orange (a) 0.6 (b) 0.167
is then added to the above titrated solution when a further 25 ml (c) 0.2 (d) 0.4
of 0.2 N HCl is required. The amount of NaOH present in
40. A hydrocarbon contains 86% carbon, 488ml of the hydrocarbon
solution is (NaOH  40, Na 2CO3  106)
weight 1.68 g at STP. Then the hydrocarbon is an
 Chemical Arithmetic 19
(a) Alkane (b) Alkene (c) 18 g (d) 19 g
(c) Alkyne (d) Arene M
50. A solution of 10 ml FeSO 4 was titrated with
41. The ratio of amounts of H 2 S needed to precipitate all the metal 10
KMnO4 solution in acidic medium. The amount of
ions from 100 ml of 1 M AgNO 3 and 100 ml of 1 M
KMnO4 used will be [CPMT 1984]
CuSO 4 will be
(a) 5 ml of 0.1 M (b) 10 ml of 1.1 M
(a) 1:1 (b) 1:2
(c) 10 ml of 0.5 M (d) 10 ml of 0.02 M
(c) 2:1 (d) None of these
51. 1.12 ml of a gas is produced at STP by the action of 4.12 mg of
42. An electric discharge is passed through a mixture containing 50 alcohol, with methyl magnesium iodide. The molecular mass of
c.c. of O 2 and 50 c.c. of H 2 . The volume of the gases formed alcohol is [Roorkee 1992; IIT 1993]

(i) at room temperature and (ii) at 1100C will be (a) 16.0 (b) 41.2
(a) (i) 25 c.c. (ii) 50 c.c. (b) (i) 50 c.c. (ii) 75 c.c. (c) 82.4 (d) 156.0
(c) (i) 25 c.c. (ii) 75 c.c. (d) (i) 75 c.c. (ii) 75 c.c. 52. The simplest formula of a compound containing 50% of
43. 100 ml of 0.1 N hypo decolourised iodine by the addition of x g element X (atomic mass 10) and 50% of element Y (atomic
of crystalline copper sulphate to excess of KI. The value of ‘x’ mass 20) is [Roorkee 1994]

is (molecular wt. of CuSO 4 .5 H 2 O is 250) (a) XY (b) X 2Y

(a) 5.0 g (b) 1.25 g (c) XY 3 (d) X 2Y3

(c) 2.5 g (d) 4 g 53. A compound contains atoms of three elements in A, B and C. If
the oxidation number of A is +2, B is +5 and that of C is – 2, the
44. How many grams of caustic potash required to completely
possible formula of the compound is
neutralise 12.6 gm HNO 3
[CBSE PMT 2000]
(a) 22.4 KOH (b) 1.01 KOH (a) A 3 (BC 4 ) 2
(c) 6.02 KOH (d) 11.2 KOH
(b) A 3 (B 4 C)2
45. If isobutane and n-butane are present in a gas, then how much
oxygen should be required for complete combustion of 5 kg of (c) ABC 2
this gas (d) A 2 (BC 3 ) 2
(a) 17.9 kg (b) 9 kg
54. What will be the volume of CO 2 at NTP obtained on heating
(c) 27 kg (d) 1.8 kg 10 grams of (90% pure) limestone [Pb. CET 2001]
46. 16.8 litre gas containing H 2 and O 2 is formed at NTP on (a) 22.4 litre
electrolysis of water. What should be the weight of electrolysed (b) 2.016 litre
water
(c) 2.24 litre
(a) 5 g (b) 9 g (d) 20.16 litre
(c) 10 g (d) 12 g 55. The ratio of the molar amounts of H 2 S needed to precipitate
47. On electrical decomposition of 150 ml dry and pure O 2 , 10% the metal ions from 20mL each of 1M Cd (NO 3 )2 and
of O 2 gets changed to O, then the volume of gaseous mixture 0.5 M CuSO 4 is [CPMT 1997]
after reaction and volume of remaining gas left after passing in
(a) 1 : 1
turpentine oil will be
(b) 2 : 1
(a) 145 ml (b) 149 ml
(c) 1 : 2
(c) 128 ml (d) 125 ml
(d) Indefinite
48. What should be the weight of 50% HCl which reacts with 100 g
56. 12 g of Mg (at. mass 24) will react completely with acid to
of limestone
give [MNR 1985]
(a) 50% pure (b) 25% pure
(a) One mole of H 2
(c) 10% pure (d) 8% pure
(b) 1/2 mole of H 2
49. What should be the weight and moles of AgCl precipitate
obtained on adding 500ml of 0.20 M HCl in 30 g of (c) 2/3 mole of O 2
AgNO 3 solution? ( AgNO 3 = 170) (d) Both 1/2 mol of H 2 and 1/2 mol of O 2
(a) 14.35 g (b) 15 g
 20 Chemical Arithmetic
57. 1 .5 mol of O 2 combine with Mg to form oxide MgO . The (b) 22.4 L of CO 2 at STP
mass of Mg (at. mass 24) that has combined is (c) 0.44 g of CO 2
[KCET 2001] (d) None of these
(a) 72 g (b) 36 g 8. In a mole of water vapour at STP, the volume actually occupied
or taken by the molecules (i.e., Avogadro’s No.  Volume
(c) 48 g (d) 24 g of one molecule) is [Kerala EEE 2000]
58. 100 g CaCO3 reacts with 1litre 1 N HCl. On completion of (a) Zero
reaction how much weight of CO 2 will be obtain (b) Less than 1% of 22.4 litres
(c) About 10% of the volume of container
[Kerala CET 2005]
(d) 1% to 2% of 22.4 litres
(a) 5 .5 g (b) 11 g
(e) Between 2% to 5% of 22.4 litres
(c) 22 g (d) 33 g 9. If 10 21 molecules are removed from 200mg of CO 2 , then the
(e) 44 g number of moles of CO 2 left are [IIT 1983]

(a) 2.85  10 3 (b) 28.8  10 3

(c) 0.288  10 3 (d) 1.68  10 2
10. The set of numerical coefficient that balances the
equation K 2 CrO4  HCl  K 2 Cr2 O7  KCl  H 2 O is
[Kerala CEE 2001]
1. Mixture of sand and sulphur may best be separated by (a) 1, 1, 2, 2, 1 (b) 2, 2, 1, 1, 1
[Kerala CET 2001] (c) 2, 1, 1, 2, 1 (d) 2, 2, 1, 2, 1
(a) Fractional crystallisation from aqueous solution 11. One litre hard water contains 12.00 mg Mg 2  milli equivalent
(b) Magnetic method of washing soda required to remove its hardness is [
(c) Fractional distillation (a) 1 (b) 12.15
(d) Dissolving in CS 2 and filtering
(c) 1  10 3 (d) 12.15  10 3
2. Irrespective of the source, pure sample of water always yields 12. In standardization of using by
Na 2 S 2O3 K2Cr2O7
88.89% mass of oxygen and 11.11% mass of hydrogen. This is
explained by the law of [Kerala CEE 2002] iodometry, the equivalent weight of K2Cr2O7 is [IIT 2000]
(a) Conservation of mass (b) Constant composition (a) MW / 2 (b) MW / 3
(c) Multiple proportions (d) Constant volume (c) MW / 6 (d) MW / 1
3. Zinc sulphate contains 22.65% of zinc and 43.9% of water of 13. 3.92 g of ferrous ammonium sulphate crystals are dissolved in
crystallization. If the law of constant proportions is true, then 100 ml of water, 20 ml of this solution requires 18 ml of
the weight of zinc required to produce 20 g of the crystals will
KMnO4 during titration for complete oxidation. The weight of
be
(a) 45.3 g (b) 4.53 g KMnO4 present in one litre of the solution is
(c) 0.453 g (d) 453 g [Tamilnadu CET 2002]
4. 3 3
10 dm of N 2 gas and 10 dm of gas X at the same temperature (a) 3.476 g (b) 12.38 g
contain the same number of molecules. The gas X is (c) 34.76 g (d) 1.238 g
(a) CO (b) CO 2 14. A 100 ml solution of 0.1 n HCl was titrated with 0.2 N NaOH
solution. The titration was discontinued after adding 30 ml of
(c) H2 (d) NO NaOH solution. The remaining titration was completed by
5. The molar heat capacity of water at constant pressure is 75 adding 0.25 N KOH solution. The volume of KOH required for
JK 1 mol 1 . When 1.0 kJ of heat is supplied to 100 g of water completing the titration is [DCE 1999]

which is free to expand, the increases in temperature of water is (a) 70[CBSE

ml PMT 2003] (b) 32 ml
(a) 6.6 K (b) 1.2 K (c) 35 ml (d) 16 ml
(c) 2.4 K (d) 4.8 K 15. What volume of Hydrogen gas, at 273 K and 1 atm pressure
6. A compound possesses 8% sulphur by mass. The least will be consumed in obtaining 21.6 g of elemental boron
molecular mass is [AIIMS 2002] (atomic mass = 10.8) from the reduction of boron trichloride by
(a) 200 (b) 400 Hydrogen [AIEEE 2003]

(c) 155 (d) 355 (a) 22.4 L (b) 89.6 L

7. Which of the following contains maximum number of atoms (c) 67.2 L (d) 44.8 L
[JIPMER 2000] 16. The mass of 112 cm 3 of CH 4 gas at STP is
(a) 6.023  10 21
molecules of CO 2 [Karnataka CET 2001]
 Chemical Arithmetic 21
(a) 0.16 g (b) 0 .8 g Reason : Under similar conditions of temperature and
pressure all gases contain equal number of
(c) 0.08 g (d) 1 .6 g
molecules.
17. Complete combustion of 0.858 g of compound X gives 7. Assertion : One atomic mass unit (amu) is mass of an
2.63 g of CO 2 and 1.28 g of H 2 O . The lowest molecular atom equal to exactly one-twelfth the mass of
a carbon-12 atom.
mass X can have [Kerala MEE 2000]
Reason : Carbon-12 isotope was selected as standard.
(a) 43 g (b) 86 g
M
(c) 129 g (d) 172 g 8. Assertion : Molecular mass of A is if the molecular
4
18. In the following reaction, which choice has value twice that of mass of B is M.
the equivalent mass of the oxidising agent Reason : Vapour density of A four times that of B.
SO 2  H 2O  3 S  2 H 2O [DPMT 2000] 9. Assertion : Pure water obtained from different sources
such as, river, well, spring, sea etc. always
(a) 64 (b) 32 contains hydrogen and oxygen combined in
(c) 16 (d) 48 the ratio 1 : 8 by mass.
Reason : A chemical compound always contains
elements combined together in same
proportion by mass, it was discovered by
French chemist, Joseph Proust (1799).
10. Assertion : As mole is the basic chemical unit, the
concentration of the dissolved solute is
Read the assertion and reason carefully to mark the correct option out usually specified in terms of number of moles
of the options given below : of solute.
Reason : The total number of molecules of reactants
(a) If both assertion and reason are true and the reason is the
correct explanation of the assertion. involved in a balanced chemical equation is
(b) If both assertion and reason are true but reason is not the known as molecularity of the reaction.
correct explanation of the assertion. 11. Assertion : A certain element X, forms three binary
(c) If assertion is true but reason is false. compounds with chlorine containing
(d) If the assertion and reason both are false. 59.68%,68.95% and 74.75% chlorine
(e) If assertion is false but reason is true. respectively. These data illustrate the law of
multiple proportions.
1. Assertion : Volume of a gas is inversely proportional to
Reason : According to law of multiple proportions, the
the number of moles of a gas.
relative amounts of an element combining
Reason : The ratio by volume of gaseous reactants and with some fixed amount of a second element
products is in agreement with their mole in a series of compounds are the ratios of
ratio. [AIIMS 1995] small whole numbers.
2. Assertion : Molecular weight of oxygen is 16. 12. Assertion : Equivalent weight of Cu in CuO is 63.6
Reason : Atomic weight of oxygen is 16. and in Cu 2 O 31.8.
[AIIMS 1996] Reason : Equivalent weight of an element
3. Assertion : Atoms can neither be created nor destroyed. Atomic weight of the element

Reason : Under similar condition of temperature and Valency of the element
pressure, equal volume of gases does not 13. Assertion : Mass spectrometer is used for the
contain equal number of atoms. determination of isotopes.
[AIIMS 1994,2002] Reason : Isotopes are the atoms of same element
4. Assertion : One mole of SO 2 contains double the number of differing in mass numbers.
14. Assertion : Gases combine in simple ratio of their
molecules present in one mole of O 2 .
volume but, not always.
Reason : Molecular weight of SO 2 is double to that of Reason : Gases deviate from ideal behaviour.
O2 . 15. Assertion : Isomorphous substances form crystals of
same shape and can grow in saturated
5. Assertion : 1.231 has three significant figures.
solution of each other.
Reason : All numbers right to the decimal point are Reason : They have similar constitution and chemical
significant. formulae.
6. Assertion : 22.4 L of N 2 at NTP and 5.6 L O 2 at NTP 16. Assertion : Atomicity of oxygen is 2.
contain equal number of molecules.
 22 Chemical Arithmetic
Reason : 1 mole of an element contains 6.023  10 23 1 a 2 b 3 b 4 c 5 a
atoms. 6 b 7 a 8 c 9 d 10 c
17. Assertion : 1 amu equals to 1.66  10 24 g .
11 b 12 c 13 c 14 d 15 a
24 1 16 a 17 b 18 b 19 a 20 a
Reason : 1.66  10 g equals to th of mass of a
12
21 b 22 b 23 c 24 a 25 a
C 12 atom.
26 c 27 d

Percentage composition & Molecular formula

1 a 2 a 3 b 4 d 5 a
6 b 7 b

Significant figures, Units for measurement,

Matter and Separation of mixture Chemical stoichiometry

1 a 2 d 3 a 4 c 5 d 1 c 2 c 3 a 4 c 5 c

6 b 7 c 8 d 9 c 10 c 6 c 7 c 8 b 9 a 10 d

11 c 12 b 13 a 14 c 15 b 11 c 12 d 13 d 14 b 15 a

16 b 17 b 18 a 19 a 20 c 16 b 17 b 18 c 19 d 20 c

21 b 22 d 23 a 24 a 25 b 21 d 22 c 23 d 24 a 25 d

26 b 27 d 26 b 27 b 28 b 29 c 30 a
31 b 32 c 33 b 34 c 35 d
Laws of chemical combination 36 d 37 b 38 d 39 a 40 b
41 b 42 c 43 c 44 d 45 a
1 a 2 d 3 c 4 a 5 c
46 b 47 a 48 a 49 a 50 d
6 c 7 c 8 b 9 b 10 a
51 c 52 b 53 a 54 b 55 b
11 c 12 b 13 a 14 d 15 b
56 b 57 a 58 c
16 a 17 c 18 d 19 c 20 a
21 c 22 d
Critical Thinking Questions
Atomic, Molecular and Equivalent masses
1 d 2 b 3 b 4 a 5 c

1 c 2 b 3 a 4 a 5 b 6 b 7 b 8 b 9 a 10 d

6 c 7 d 8 b 9 a 10 b 11 a 12 c 13 a 14 d 15 c

11 a 12 b 13 a 14 c 15 b 16 c 17 a 18 b

16 c 17 a 18 d 19 a 20 a
Assertion & Reason
21 b 22 b 23 d 24 c 25 a
26 a 27 c 28 d 29 a 30 c 1 e 2 e 3 c 4 e 5 d
31 a 32 d 33 b 34 a 35 c 6 d 7 a 8 c 9 a 10 b
36 b 37 b 38 c 39 a 40 b 11 a 12 e 13 e 14 a 15 a
41 c 42 d 43 a 44 d 45 d 16 b 17 a
46 b 47 c 48 c 49 b 50 b
51 a 52 b 53 b 54 c 55 b
56 a 57 d 58 d 59 a 60 d
61 c 62 d 63 b

The mole concept

 Chemical Arithmetic 23
Significant figures, Units of measurement, 6. (c) As the given sulphate is isomorphous with ZnSO 4 .7 H 2 O
Matter and Separation of mixture its formula would be MSO 4 .7 H 2 O .m is the atomic
weight of M, molecular weight of MSO 4 .7 H 2 O
Force [MLT 2 ]  m  32  64  126  m  222
4. (c) Pressure    [ML1 T  2 ]
Area [L2 ] m
Hence % of M   100  9.87 (given) or
m  222
[ML2 T 2 ]
Energy per unit volume   [ML1 T  2 ] 100m  9.87m  222  9.87 or 90.13m  222  9.87
[L3 ]
222  9 .87
or m   24.3 .
(29.2  20.2) (1 .79  10 5 ) 9 .0  1 .79  10 5 90.13
17. (b) 
1 .37 1 .37
Least precise terms i.e., 9.0 has only two significant figures.
Hence, final answer will have two significant figures.
18. (a) Pure ethyl alcohol  81.4  0.002  81.398 .
19. (a) JPa–1; Unit of work is Joule and unit of pressure is Pascal.
Dimension of Joule i.e. work  F  L  MLT 2  L

 ML2 T 2 
1

1

Pa Pressure F
1 1 A

F
 MLT 1  
A
     
So, JPa–1  ML2 T 2  L2  L  L3 .

22. (d) 1 zepto  10 21

23. (a) As we know that all non zero unit are significant number.
Therefore significant figure is 2.
24. (a) Number of significant figures in 6.0023 are 5 because all
the zeroes stand between two non zero digit are counted
towards significant figures.
25. (b) Given P  0.0030m , Q  2.40m & R  3000m In
P(0.0030) initial zeros after the decimal point are not
significant. Therefore, significant figures in P(0.0030) are 2.
Similarly in Q(2.40) significant figures are 3 as in this case
final zero is significant. In R  (3000) all the zeroes are
significant hence, in R significant figures are 4.
26. (b) All the zeroes between two non zero digit are significatn.
Hence in 60.0001 significant figures is 6.
27. (d) Round off the digit at 2nd position of decimal 3.929
= 3.93.

Laws of chemical combination

12. (b) X Y ⇌ R S
ng mg pg qg

n  m  p  q by low of conservation of mass.

Atomic, Molecular and Equivalent masses

5. (b) The atomic weight of sulphur =32

In SCl 2 valency of sulphur =2
32
So equivalent mass of sulphur   16 .
2
 24 Chemical Arithmetic
7. (d) For NaOH, M  N  22.4gm of gas occupies 22.4L at S.T.P.
22.4
N1 V1  100ml  1 N  100ml(N )  11.2gm of gas occupies  11.2  11.2 L .
22.4
For H 2 SO 4 , N 2 V2  10ml  10 N  100ml(N ) Molecular weight
21. (b) Equivalent weight 
Hence, N 1 V1  N 2 V2 . Valency
COOH 126
10 . (b) 1 mole of CH 4 contains 4 mole of hydrogen atom i.e. 4g atom Molecular weight of |  2H 2O   63 .
C OOH 2
of hydrogen.
2  V .D 2  59.25
2 2.5 22. (b) Valency of the element  
11. (a) Na 2 SO 3  I 2  Na 2 S 4 O6  NaI E  35.5 4  35.5
118.50
n  2  0. 5  1  =3.
39.5
E
M

M
M W (gm)  1000
23. (d) Molarity 
n  factor 1 V (ml )  molecular weight
M 1 .25  1000
12. (b) E 0 .25 
5 25  molecular weight

10  19  81  11 190  891 1 .25  1000

13. (a) Atomic mass   
1081  Molecular weight   200 .
100 100 100 0 .25  25
24. (c) Let weight of metal oxide = 100 gm
 10.81 Weight of oxygen = 32gm
14. (c) 0.1M AgNO3 will react with 0.1 M NaCl to form  weight of metal  100  32  68 gm
0.1M NaNO 3 . But as the volume doubled, conc. of wt. of metal
Equivalent weight of oxide  8
0.1 wt. of oxygen
NO 3   0 .05 M .
2 68
  8  17 .
32
16. (c) wt. of metallic chloride  74.5
25 . (a) 6  10 23 molecules has mass  18 gm
wt. of chlorine = 35.5
18
 wt. of metal  74.5  35.5  39 1 molecules has mass   3  10 23 gm
6  10 23

Equivalent weight of metal 

weight of metal
 35.5  3  10 26 kg .
weight of chlorine 26. (a) Choice (a) is P4 S 3


39
 35.5  39 31  4
 gm P is present in 220 gm P4 S 3
35.5 (124 )
17. (a)  5.8L of gas has mass  7.5 gm 220
 1.24gm P is present in =  1 .24  2 .2 gm
124
7.5
 22.4L " " " =  22.4  28.96 x
5.8 27. (c) Number of moles of A 
40
So molecular weight = 29
x
So, molecular formula of compound is NO Number of atoms of A   Avogadro no.  y (say)
40
(d)  17gm NH 3 contains 6  10 23 molecules of NH 3 40y
18. Or x 
Avogadro no.
6  10 23 2x
 4.25 gm NH 3 contains =  4 .25 Number of moles of B 
17 80
Number of atoms of B
6  10 23  4 .25
 No. of atoms   4  6  10 23 .

2x
 Av.no. 
2

40 y
 Av.no.  y
17
80 80 Av.no.
19. (a)  1L of gas at S.T.P. weight 1.16g 28. (d) BaCO3  BaO  CO 2 
 22.4 L of gas at S.T.P. weight  22.4  1.16 Molecular weight of BaCO3  137  12  3  16 =197
 25.984  26  197gm produces 22.4L at S.T.P.
22.4
This molecular weight indicates that given compound is  9.85 gm produces  9 .85  1 .12 L at S.T.P.
C2 H 2 . 197
29. (a) 14 gm N 3  ions have  8 N A valence electrons
20 . (a) Molecular weight  2  V.D  2  11.2  22.4
 Chemical Arithmetic 25
8 N A  4 .2 Molecular weight of H 3 PO3  3  31  48  82
4.2gm of N 3  ions have   2.4 N A
14
Molecular weight 82
 Equivalent weight   = 41.
30 . (c) [  Molecular weight of CuSO 4 .5 H 2O Basicity 2
 63.5  32  64  90  249.5 ]
37. (b)  22400 ml at NTP has 6.023  10 23 molecule
6  10 23
molecules has weight  249.5 gm
6 .023  10 23
 1 ml at NTP has =
249.5  1  10 22
22400
1  10 22 molecules has weight 
6  10 23

 41.58  10 1 = 0.0002688  10 23  2.69  1019 .

 4.158 38. (c) Sp. heat × atomic wt.= 6.4
31. (a) (I) 1 molecule of oxygen 0.16 × atomic wt.= 6.4
6 .4
 6  10 23 molecule has mass  32 gm Atomic wt.   40 .
0 .16

 1 molecule of O 2 has mass 

32 39. (a) Molecular weight of C60 H122  12  60  122  1
6  10 23
 720  122  842
 5.3  10 23 gm
 6  10 23
molecule C60 H122 has mass = 842gm
(II) 1 atom of nitrogen
842
 1 molecule C60 H122 has mass
 2  6  10 23 atoms of N 2 has mass = 28gm 6  10 23

28  140.333  10 23 gm  1.4  10 21 gm .

 1 atom of N 2 has mass 
2  6  10 23 40 . (b) C2 H 4  2O2  2CO 2  2 H 2 O

 2.3  10 23 gm  28gm C 2 H 4 requires 64gm oxygen

64
(III) 1  10 10 g molecular weight of oxygen  2.8  10 3 gm C 2 H 4 requires =  2 .8  10 3 gm
28
g atomic weight  2  1  10 10  2  10 10 g  6.4  10 3 gm = 6.4kg.
(IV) 1  10 10 g atomic weight of copper 41. (c) 2.5 molal NH 4 OH means 2.5 moles of NH 3 in 1000 g

So, order of increasing masses II  I  III  IV . H 2 O (1000 cc of solution)

Hence, 100 cc solution of NH 3 requires = 0.25 mole
wt. of metal hydroxide EM  EOH 
32. (d) 
wt. of metal oxide EM  EO   0.25  22.4 L  5.6 L .
1 .520 x  17 M M
  42. (d) d  ; 1 or M = V; 18gm = 18ml
0 .995 x 8 V V
 1.520 x  1.520  8  0.995 x  0.995  17 6  10 23 molecule of water has volume =18 cc
1.520 x  12.160  0.995 x  16.915 18
1 molecule of water has volume 
or 0.525 x  4.755 6  10 23
 3  10 23 cm 3 .
4 .755
x 9. 43. (a) 100gm caffeine has 28.9gm nitrogen
0 .525
28.9
33. (b) One ion carries 3  1.6  10 19 coulomb 194gm caffeine has =  194  56.06 gm
100
Then 1 gm ion N 3  (1 mole) carries  No. of atoms in caffeine 
56.06
4.
14
 3  1.6  10 19  6.02  10 23
44. (d) Molecular weight of (CHCOO )2 Fe  170
 2.89  10 5 coulomb Fe present in 100 mg of (CHCOO )2 Fe
CP 56
34. (a)  1 .4 so, given gas is diatomic   100mg  32.9 mg
CV 170
This is present in 400 mg of capsule
11.2L  3.01  10 23 molecules 32.9
% of Fe in capsule   100  8 .2 .
 No. of atoms  3.01  10 23  2  6.023  10 23 atoms 400
26
36. (b) The acid is dibasic. 45 . (d) 1 atom has mass  10.86  10 kg
 26 Chemical Arithmetic

 10.86  10 23 gm 12  3  10 23
3  10 23 atoms of C has mass   6 gm
6.023  10 23 atoms has mass 6  10 23
(c) 1mole of S has mass = 32gm
= 10.86  10 23  6.023  10 23 = 65.40 gm
(d) 7.0 gm of Ag
This is the atomic weight of Zn.
So, lowest mass = 6gm of C.
46. (b)  1mole (COOH )2 . 2 H 2 O has 96gm oxygen
5 4. (c) 1mole of any gas at STP occupies 22.4 L.
 0.3 mole (COOH )2 . 2 H 2 O has 96  0.3  28.8 gm
55. (b)  22400 cc of gas at STP has 6  10 23 molecules
28.8
 No. of gram atoms of oxygen   1 .8 .
6  10 23  1 .12  10 7
16  1.12  10 7 of gas at STP has
47. (c) Equimolecular proportion means both gases occupied equal 22400
2 .24  .03  1014  3  1012 .
volume   1 .12 L
2 5 6. (a)  2.24L of gas has mass = 4.4gm
For CH 4 :
4.4
22.4L CH 4 has mass  16 gm  22.4L of gas has mass   22.4  44
2 .24
16
1.12L CH 4 has mass   1 .12  0 .8 gm . So given gas is CO 2 because CO 2 has molecular mass=44.
22.4
For C 2 H 6 5 7. (d) 1L of air =210 cc O 2
22.4L C 2 H 6 has mass = 30 gm 22400 cc = 1 mole
30 3 .0 1
1.12L C 2 H 6 has mass   1 .12  gm  1 .5 gm 210 cc   210  0.0093 .
22.4 2 22400
Total mass  1.5 gm  0.8 gm  2.3 gm . 5 8. (d)  22.4L of a gas at STP has no. of molecules
48. (c) Let wt. of metal oxide = 100 gm
 6.023  10 23
wt. of metal = 53gm
wt. of oxygen = 47gm  8.96L of a gas at STP has no. of molecules
wt. of metal 6 .02  10 23  8 .96
Equivalent weight of oxygen  8   2.408  10 23  24.08  10 22 .
wt. of oxygen 22.4
53 5 9. (a) Given equivalent weight of metal = 9

 8  9 .02 Vapour density of metal chloride = 59.25
47
2  V .D 2  66 132  molecular weight of metal chloride
Valency     2.96  3
E  35.5 9  35.5 44.5  2  V.D  2  59.25  118.5
 Atomic weight  Equivalentweight  Valency  valency of metal
 9.02  3  27.06 molecular weight of metal chloride

49. (b) One gram of hydrogen combines with 80 gm of bromine. equivalnet weight of metal  35.5
So, equivalent weight of bromine = 80 gm
118.5 118.5
 4gm of bromine combines with 1 gm of Ca Valency of metal    2.66
9  35.5 44.5
1
 80gm of bromine combines with =  80  20 . Therefore atomic weight of the metal
4
=equivalent weight  valency
2 4
50 . (b) Mn SO 4  Mn O2  9  2.66  23.9
Change of valency  4  2  2 molecular wt. of metal
60 . (d) The density of gas 
M volume
 Equivalent weight  .
2 45
  2 gm litre1
5 1. (a) 2 PH 3  2 P  3 H 2 22.4
(solid)
2ml 3ml 61. (c) Equivalent weight of bivalent metal = 37.2
100ml 150ml
 Atomic weight of metal  37.2  2  74.4
Increase in volume  150ml  100ml  50ml increase.
5 2. (b) Mg  2 HCl  MgCl2  H 2  Formula of chloride  MCl 2

 24g Mg evolves 22.4L H 2 at STP Hence, molecular weight of chloride

(MCl2 )  74.4  2  35.5  145.4
22.4
 12g Mg evolves H 2 at STP  12 62. (c) As we know that
24
=11.2L at STP. weight of metal
Equivalent weight  8
5 3. (b) (a) 2gm atom of nitrogen = 28gm weight of oxygen
(b) 6  10 23 atoms of C has mass  12 gm
 Chemical Arithmetic 27


32
 8  64  1.2  10 23 atoms.
0 .4 6. (b) 44g CO 2 occupies 22.4L at STP
mol. wt
Vapour density  22.4
2 4.4g CO 2 occupies   4 .4 = 2.24L.
44
Mol. wt  2  V.D  2  32  64
Mass g
mol. wt 64 7. (a) D ensity  ; 1 or g  ml
As we know that n   1 Volume ml
eq. wt 64
0.0018ml = 0.0018gm
Suppose, the formula of metal oxide be M 2 On . Hence the weight 0 .0018
No. of moles    1  10  4
formula of metal oxide  M 2 O . Molecular weight 18
63. (b) Molecular weight of NH 3 is 17  No. of water molecules = 6.023  10 23  1  10 4
According to the mole concept  6.023  1019 .
17 gm NH 3 has molecules  6.02  10 23 8. (c) Ca 3 P2  6 H 2 O  2 PH3  3Ca(OH)2

6 .02  10 23 9. (d) Amount of gold  19.7kg  19.7  1000 gm =19700 gm

 1 gm NH 3 has molecules 
17 19700
No. of moles   100
 4.25 gm NH 3 has molecules 197
 No. of atoms  100  6.023  10 23
6.02  10 23  4 .25
  1 .5  10 23 molecule
17  6.023  10 25 atoms.
10 . (c)  100 gm CaCO 3  6.023  10 23 molecules
The mole concept
6 .023  10 23
 10 gm CaCO 3 =  10
16 1 100
1. (a) 16g O 2 has no. of moles  
32 2  6.023  10 22 molecule
14 1 1 molecule of CaCO 3 = 50 protons
14g N 2 has no. of moles  
28 2
6.023  10 22 molecule of CaCO 3  50  6.023  10 22
No. of moles are same, so no. of molecules are same.
2. (b) Na 2 SO 4 . 10 H 2 O  2  23  32  4  16  10  18  3.0115  10 24

 46  32  64  180  322gm 11. (b) 16gm of CH 4 = 1mole  6.023  10 23 molecules.

12. (c) According to avogadro's hypothesis equal volumes of all gases
322gm Na 2 SO 4 .10 H 2 O contains = 224 gm oxygen under similar conditions of temperature and pressure contains
32.2gm Na 2 SO 4 .10 H 2 O contains equal no. of molecules.
M
32.2  224 14. (d) d (d = density, M= mass, V =volume)
=  22.4 gm V
322
Since d = 1
W (gm)  1000
3. (b) Molarity  So, M  V
molecular wt.  V(ml.)
18gm = 18ml
2.65  1000 18ml = N molecules (N = avogadro's no.)
  0 .1 M A A

106  250
NA
10ml of this solution is diluted to 1000 ml N1 V1  N 2 V2 1000ml   1000 = 55.555 N.
18 A

10  0.1  1000  x 15. (a) This is fact.

0.1  10 16. (a)  3 moles of oxygen is that in 1 mole of BaCO3
x  0 .001M .
1000  1.5 moles of oxygen is that in mole of BaCO3
4. (c) According to definition of molar solution  A molar solution is 1 1
one that contains one mole of a solute in one litre of the   1 .5   0 .5 .
3 2
solution.
17. (b) The no. of molecules present in 1ml of gas at STP is known as
5. (a) 44g of CO has 2  6  10 23 atoms of oxygen
2
Laschmidt number.
22400 ml of gas has total no. of molecules
12  10 23
4.4g of CO has =  4 .4
2
44  6.023  10 23
 28 Chemical Arithmetic

6 .023  10 23 25 . (a) wt of CO 2  44
1ml of gas has total no. of molecules 
22400 mol wt of CO 2  44
 2.69  1019 . wt. of CO 2
No. of molecule   6 .02  10 23
18. (b)  2gm of hydrogen  6.02  10 23 molecules mol wt of CO 2
 1gm of hydrogen
44
 6 .02  10 23  6.02  10 23
6 .02  10 23 44
  3 .01  10 23 molecule.
2 26. (c) No. of atoms in one molecule
19. (a) Molecular weight of SO 2 Cl 2 = no. of moles  6.022  10 23
 32  32  2  35.5 = 135 gm  1.4  6.022  10 23  8.432  10 23
 135 gm of SO 2 Cl 2 = 1gm molecule 27. (d) As we know that four sodium atom are present in sodium
1 ferrocyanide [ Na 4 Fe(CN )6 ]
 13.5 gm of SO 2 Cl 2   13.5  0 .1 .
135 Hence, number of Na atoms = No. of moles  number of
20 . (a) (a) 34gm of water atom  Avogadro’s number
 18gm H 2 O = 6.023  10 23 molecule 2  4  6.023  10 23  48  10 23

6 .023  10 23 Percentage composition & Molecular formula

 34gm H 2 O =  34
18
1. (a)  40 gm NaOH contains 16gm of oxygen
 11.37  10 23 mole
16
(b) 28gm of CO 2  100 gm of NaOH contains  100 =40% oxygen.
40
 44gm CO 2  6  10 23 molecules 2. (a) Urea- NH 2  CO  NH 2
 60 gm of urea contains 28gm of nitrogen
6  10 23
 28gm CO 2   28  3 .8  10 23 28
44  100 gm of urea contains  100  46.66 .
60
(c) 46gm of CH 3 OH 3. (b) Based on facts.
 32gm CH 3 OH  6  10 23 molecules 4. (d) C  24 gm , H  4 gm , O  32 gm
So, Molecular formula  C2 H 4 O2
6  10 23
 46gm CH 3 OH   46  8.625  10 23
32 So, Empirical formula  CH 2O
(Simplest formula).
(d)  108gm of N 2O5  6  10 23
molecules
5. (a)  0.0835 mole of compound contains 1 gm of hydrogen
6  10 23 1
 54gm of N 2 O5   54  3  10 23 molecules.  1gm mole of compound contain =  11.97
108 0 .0835
21. (b) Sodium oxide  Na 2 O =12gm of hydrogen.
Molecular weight = 46 +16 = 62 12 gm of H 2 is present in C 2 H12 O6
62gm of Na 2 O = 1 mole 6. (b) Empirical formula of an acid is CH 2O2
620gm of Na 2 O = 10 mole. (Empirical formula) n  Molecular formula
2 1 n = whole no. multiple i.e. 1,2,3,4..............
22. (b) 2gm of oxygen contains atom   mole If n  1 molecular formula CH 2O2 .
16 8
4 1 7. (b) Glucose - C 6 H 12 O6
also 4g of sulphur   mole.
32 8 Ratio of C, H and O  1 : 2 : 1
23. (c) Molarity = mole/litre In acetic acid CH 3  C  O  H
 1cc contains 1.17gm ||
O
1170gm
 1000 cc contains 1170 gm Ratio of C, H and O 1 : 2 : 1 .
Mol.wt.
1170 Chemical stoichiometry
  32.05mole / litre (Mol. wt. of HCl =36.5)
36.5
24. (a) 1 mole of sucrose contains 6.023  10 23 molecules W(gm)  1000
1. (c) N 
 1 molecule of sucrose has 45 atoms V  Eq.wt.
 6.023  10 23 molecule of sucrose has 1500 ml of 0.1N HCl = 150 ml (N)
45  6.023  10 23 atoms/mole
 Chemical Arithmetic 29
W(gm)  1000 150  40 (d) H 2 O  Al  NaOH  NaAlO2 
3
1 , W (gm )   6 gm . 10 . H2
150  40 1000 27 gm
3
2
22 .4 33 .6 L
1 1 2
2. (c) N 1 V1  N 2 V2 ;  200   V2 ; V2  1000ml
2 10 11. (c) In Fe(CNS )3 . 3 H 2 O
Volume of water added  1000  200  800ml . 3  18
% of H 2 O   100  19% .

3. (a) 2 Ag2CO 3  4 Ag  2CO 2  O2 284
12. (d) 5 S  5 O 2  5 SO 2 ; 5 O 2  5 SO 2 ; 5  64  320 gm .
2  276 gm 4  108 gm
13. (d) H 3 PO4 is tribasic so N  3 M  3  1  3 .
 2  276 gm of Ag2CO 3 gives 4  108 gm
14. (b) H 2 SO 4 is dibasic N  2 M  2  2  4 .
4  108
 1 gm of Ag2CO 3 gives 
2  276 15 . (a) For Dibasic acid E 
M 200
  100
2 2
 2.76 gm of Ag2CO 3 gives
W  1000
4  108  2.76 N
 2.16 gm E  V (in ml )
2  276
4. (c) 1 W  1000
  W  1gm .
10 100  100
4 NH 3(g )  5 O2(g )  4 NO( g)  6 H 2 O( g )
10  sp. gr. of the solution wt.% of solute Mol.wt.
t0 1 1 0 0 16. (b) N
Molecular wt. of solute Eq. wt.
t  t 1  4x 1  5x 4x 6x
10  1.71  80  98
Oxygen is limiting reagent N   27.9
98  49
1
So, X   0 .2 all oxygen consumed 18. (c) 2 KMnO4  3 H 2 SO 4 
5
Left NH 3  1  4  0.2  0.2 . K2 SO 4  2 MnSO4  3 H 2 O  [O]

5. (c)  100gm Hb contain = 0.33gm Fe 2 FeSO 4  H 2 SO 4  [O]  Fe2 (SO 4 )3  H 2 O]  5

[Mohrsalt]
67200  0 .33
 67200 gm Hb = gm Fe 2 KMnO4  10 FeSO 4  8 H 2 SO 4 
100
672  0 .33
gm atom of Fe = 4. K 2 SO 4  2 MnSO 4  5 Fe2 (SO 4 )3  8 H 2 O
56
6. (c) (NH 4 )2 SO 4  2 NH 3  2 HCl Mohr-salt reducing agent KMnO4 / H   oxidising agent
2(36 .5 )73 gm
132 19. (d) Atomic weight = Equivalent weight × Valency
73 g HCl  132 g(NH 4 )2 SO 4
292 g HCl  528 g(NH 4 )2 SO 4  26.89 
 8.9  3  26.7  Valency   3 .
 8.9 
7. (c) 2(NH 4 )2 HPO4  P2 O5
2(36 1  31  64 ) 264 62  80 142 20 . (c) MW  2  V.D.  2  22  44 .
wt. of P2 O 5 21. (d) 2 KMnO4  3 H 2 SO 4  K 2 SO 4  2 MnSO 4  3 H 2 O  5[O]
% of P2 O 5   100 7 2
wt of salt
Change by 5
142
  100  53.78% . Mol.wt.
264 Eq. wt. 
5
3
8. (b) 2 Al  O 2  Al2 O 3 22. (c) Dibasic acid NaOH; N 1 V1  N 2 V2
2
3 W 1 0 .16 25
According to equation mole of O 2 combines with 2 mole  1000   25 ;  1000 
2 E 10 E 10
Al . M  2  E  2  64  128 .
2 mole Al = 54gm 23. (d) NaOH HCl
9. (a) 0.5 gm Se  100 gm peroxidase anhydrous enzyme
1 1
100  78.4 N 1 V1  N 2 V2 ; 20    V ; V = 40 ml.
78.4gm Se   1.568  10 4 10 20
0 .5
24. (a) NV  N 1 V1  N 2 V2
Minimum m.w.  molecule at least contain one selenium.
0.2  2  0.5 x  0.1(2  x )
0. 4  0. 5 x  0. 2  0. 1 x
0.2  0.4 x
 30 Chemical Arithmetic
1 35 . (d) KMnO4  Mohr salt
x L  0.5 L
2 M1 V1 M 2 V2 0 .1  10 M 2 V2
 ;  ; M 2 V2  5 .
25 . (d) NV  N1V1  N 2 V2  N 3 V3 n1 n2 1 5

1 1 molecular weight
N  1000  1  5   20   30  5  10  10  25 36. (d) The equivalent weight of H 3 PO4 
2 3 2
N  mole wt of H 3 PO4 = 3 + 31 + 64 = 98
N  0 .025  .
40 98
  49
26. (b) NH 3(g )  HCl( g )  NH 4 Cl(s) 2
t0 20ml 40ml 0 37. (b) Ba(OH)2  CO 2  BaCO3  H 2O
t t 0 20 ml solid
Atomic wt. of BaCO3 = 137  12  16  3 = 197
Final volume = 20 ml .
wt. of substance
27. (b) KMnO4 Oxalic acid No. of mole 
mol wt.
M 1 V1 M 2 V2 20  0 .1 M 2 V2  1 mole of Ba(OH )2 gives 1 mole of BaCO3
 ;  ; M 2 V2  5 .
n1 n2 2 5
 205 mole of Ba(OH )2 will give .205 mole of BaCO3

28. (b) Acidic medium E 

M 158
  31.6 gm .  wt. of 0.205 mole of BaCO3 will be
5 5
.205  197  40.385 gm  40.5 gm
29. (c) 0.1 M AgNO3 will react with 0.1 M NaCl to form 0.1 M 38. (d) N1  0.5 N  10mg per mL
NaNO 3 . But as the volume is doubled, conc. of
10  10 3 gm
0 .1 N2   1000 =0.25 N
NO 3   0 .05 M 40  1
2
V1  500ml , V2  ?
30 . (a) Acid base
N1V1  N 2 V2 ; 0.5  500  0.25  V2
N 1 V1 = N 2 V2 ; N 1  30  0.2  15 ; N1  0.1 N
31. (b) (I) Phenopthalein indicate partial neutralisation of V2  1000mL final volume water added = 1000 – 500
= 500 mL.
Na 2 CO 3  NaHCO 3
39. (a) eq. of KMnO4 = eq. of Fe(C2 O4 )
Meq. of Na 2 CO 3 + Meq. of NaOH = Meq. of HCl
x 5  1 3
W W x  0.6
 1000   1000  NV
E E 40 . (b)
Element At.wt. Mole Ratio Empirical
(Suppose Na 2 CO 3  a gm , NaOH = b gm) formula
a b C =86% 12 7.1 1 CH
 1000   1000  300  0 .1 .....(1)
2

H =14% 1 14 2 Beleongs to
106 40
alkene Cn H 2n
(II) Methyl orange indicate complete neutralisation
HCl HCl 41. (b) AgNO3  2 Ag   S 2   Ag2 S
(H 2 S )
N 1 V1  N 2 V2 , 25  0.2  0.1  V2 so V2  50ml excess
 2 mole  1 mole [100×1 =100 millimole]
a b  100 miliimole  50 millimole H 2 S required
  1000   1000  350  0.1 .....(2)
53 40
CuSO 4  Cu 2  S 2   CuS
From (1) and (2) b =1gm. (H 2 S )
32. (c) From solution of (31)  1 mole  1 mole [100×1=100 millimole]
From equation (1)
 100 millimole  100 millimole H 2 S required
a  Na 2 CO 3  0.53 gm .
50 1
M1V1 M 2 V2 Ratio  .
33. (b) (H 2 SO 4 )  ( NaOH ) 100 2
n1 n2 42. (c) At room temperature 2 H 2(g)  O2(g)  2 H 2 O(l)
1  V1 1  10 t =0 50 ml 50 ml 0
 ; V1  5ml .
1 2 t =t 50 – 2x 50 – x 2x
34. (c) Atom in highest oxidation state can oxidize iodide to liberate =0 25 gases (50)liquid
I2 which is volumetrically measured by iodometric titration In this case H 2 is limiting reagent
using hypo.
x = 25 ml
2 I   I2
At 110°C 2 H 2(g)  O2(g)  2 H 2O(g) Vgas  75 ml
Pb2  Lowest oxidation state can not oxidise iodide to I2 . t =t 0 25 ml 50 ml
 Chemical Arithmetic 31
2 2 2 1 1.12 mL is obtained from 4.12 mg
43. (c) CuSO 4  2 KI  K 2 SO 4  CuI 2 ; 2 CuI 2  CuI 2  I2
 22400 mL will be obtained from
I2  2 Na 2 S 2O3  2 NaI  Na 2 S 4 O6
4 .12
Eq. wt. Of CuSO 4 .5 H 2O  Mol.wt.  250  22400 mg  84.2 g
1.12
100 ml of 0.1 N hypo  100 ml of 0.1 N CuSO 4 .5 H 2O 5 2. (b)
Element %(a) At.wt.(b) a/b Ratio
250  0 .1  100
  2 .5 gm X 50 10 5 2
100
Y 50 20 2.5 1
44. (d) HNO3  KOH  KNO 3  H 2O
Simplest formula  X 2 Y
12 . 6
 0.2 mole; HNO3  KOH
63 5 3. (a) A3 (BC4 )2  3  2  [5  (2  4 )]2  0 .
0.2 mole  0.2 mole 5 4. (b) CaCO 3  CaO  CO 2
0.2  56  11.2 gm . 10 gm
45 . (a) Isobutane and n-butane C4 H10  have same molecular 9
90% pure 9gm  mole
13 100
formula; C4 H10  O2  4 CO 2  5 H 2 O
2 CaCO 3  CO 2  0.09 mole
For 58gm of C4 H10 208 gm O 2 is required then for 5 kg of
At NTP Vol. CO 2  0.09  22.4  2.016 L .
5  208
C4 H10 O2   17.9 kg
58 55. (b) Cd 2  S 2   CdS
16.8 20×1= 20
46. (b) n   0 .75 mole of H 2 and O 2
22.4 Cu 2  S 2   CuS
0 .25 O2 20×0.5 =10
2 H 2 O  2 H 2  O2 0 .75 0 .25 H2
2:1 Ratio = 2 : 1
2 mole H 2 – 2 mole H 2 O
5 6. (b) Mg 2  H 2
0.5 mole H 2 – 0.5 mole H 2 O = 9gm.
12 gm 1
47. (a)  3ml (O)  1ml O 3 n  mole of H 2
24 gm 2
30ml (O)  10 ml O 3
1
5 7. (a) Mg  O 2  MgO
150  10 2
x  15ml 1mole
0 .5 mole
100
0.5 mole of oxygen react with 1 mole of Mg
V of O2  V of O3  135  10  145ml
Turpentine oil absorb ozone. 1 .5
1.5 mole of oxygen react with  3 mole
48. (a) 50% HCl itself means 50 gm HCl react with 100 gm sample 0 .5
50 24  3  72 gm .
% Purity   100  50% .
100 5 8. (c) CaCO 3  2 HCl  CaCl 2  CO 2  H 2 O
49. (a) AgNO3  HCl  AgCl  HNO3 100 g 2N 44 g

30 500  0 .2 100 g CaCO 3 with 2 N HCl gives 44 g CO 2

170 1000 100 g CaCO 3 with 1 N HCl gives 22 g CO 2
t =0 0.176 mole 0.1 mole limiting =14.345 gm
t =t 0.076 mole 0 0.1mole Critical Thinking Questions
50. (d) KMnO4 FeSO4
2. (b) H 2 O contains H and O in a fixed ratio by mass. It illustrates
M 1 V1 M 2 V2 n
= ; M1 V1  1 M 2 V2 the law of constant composition.
n1 n2 n2 3. (b) 100 g of ZnSO crystals are obtained from =22.65 g Zn
4

2 1 1 22.65
  10    0.2 1g of ZnSO crystals will be obtained from 
4
g Zn
10 10 5 100
1 22.65
20 g of ZnSO crystals obtained from   20  4 .53 g
For (d), M1V1  0 .02  10  4

100
5
4. (a) If same volume is occupied by the gas, the no. of molecules are
OR same, so no. of moles are same.
5 1. (c) ROH  CH 3 MgI  CH 4  Mg
I 1 mole of N 2 gas  2  14  28 gm
1 mol. 1 mol  22400 cc
 32 Chemical Arithmetic
1 mole of CO gas  12  16  28 gm M1 V1 M 2 V2  W  V
   1000   2
75 1 5 M V  5
5. (c) Heat capacity of water per gram   4 .17
18  W  1000  3 .92  1000 20
Q = mST  58  1000   18  392  1000  5 W=3.476gm/L.
 
1000  100  4.17  t 14. (d) Volume m of HCl neutralised by NaOH = (Caustic soda) = V1
1000
t  2 .4 K . N1V1  N 2 V2 ; 0.1  V1  0.2  30 ; V1  60ml
100  4 .17
6. (b)  8gm sulphur is present in 100 gm of substance V total (HCl ) = 100 ml
100 V1 = 60 ml
 32gm sulphur will present =  32  400 .
8 40 ml
40ml 0.1N HCl is now neutralised by KOH (0.25 N) 
7. (b) (a) 6.023  10 23
molecules of CO 2
(HCl ) N1V1  N 2 V2 (KOH)
No. of atoms  3  6.023  10 21 = 18.069  10 21 atoms
(b) 22.4L of CO 2 0.1  40  0.25  V2 ; V2  16ml .
15 . (c) BCl3  3[H ]  B  3 HCl
No. of atoms = 6.023  10 23  3  18.069  10 23 atoms
(c) 0.44gm of CO 2 3 21.6
BCl3  H 2  B  3 HCl ; B   2 mole
2 10.8
0.44 1
No. of moles    6.023  10 23 moles 3
44 100 B H2
2
 6.023  10 moles  3  6.023  10 atoms
21 21

3
18.069  10 21 atoms 1mole  mole ; 2 mole – 3 mole
2
8. (b) It is about 22.4L.
V  3  22.4  67.2 L .
9. (a) 200mg of CO 2 = 200  10 3  0.2 gm
W V W 112
16. (c) n  ;  ; W  0.08 gm .
44gm of CO 2 = 6  10 23 molecules M 22400 16 22400

6  10 23 12 WCO 2 12 2.63
0.2gm of CO 2 =  0 .2  0 .0272  10 23 17. (a) %C    100    100  83.6%
44 44 W 44 0.858

 2.72  10 21 molecule 2 WH 2 O 2 1 .28

%H    100    100  16.4%
18 W 18 .858
Now 10 21 molecule are removed.
Element
%(a) At.wt.(b) a/b Ratio
So remaining molecules  2.72  10 21  10 21 C 83.6 12 6.96 1 ×3
 10 21 (2.72  1) = 1.72  10 21 molecules H 16.4 1 16.4 2.3 7
Now, 6.023  10 23 molecules = 1mole C3 H7  12  3  7  43 gm .

1  1 .72  10 21 18. (b) SO 2  2 H 2 O  S  2 H 2 O2

1.72  10 21 molecules   0 .285  10  2 4 0
6 .023  10 23
M 64
 2.85  10 3 . EW    16 ; Twice 16  2  32
4 4
10 . (d) 2 K 2 Cr2 O 4  2 HCl  K 2 Cr2 O7  2 KCl  H 2 O
Assertion & Reason
11. (a) Meq of Mg 2  Meq of washing soda
W 24 1. (e) We know that from the reaction H 2  Cl2  2 HCl that the
1000  Mg 2 ; EW   12
E 2 ratio of the volume of gaseous reactants and products is in
3 agreement with their molar ratio. The ratio of
12  10
 1000  1 . H 2 : Cl2 : HCl volumes is 1 : 1 : 2 which is the same as
12
their molar ratio. Thus volume of gas is directly related to the
12. (c) K 2 Cr2 O7  4 H 2 SO 4  K 2 SO 4 Cr2 (SO 4 )3
number of moles. Therefore, the assertion is false but reason is
 12/two atom  6/two atom
Change by 6 true.
4 H 2 O  3[O]
2. (e) We know that molecular weight of substance is calculated by
Mol.wt. adding the atomic weight of atoms present in one molecules.
Eq. wt. 
6 We also know that molecular weight of oxygen (O2 ) =2x
13. (a) KMnO4 = Mohr salt (Atomic weight of oxygen)  2  16  32 a.m.u. Atomic
 Chemical Arithmetic 33
weight of oxygen is 16, because it is 16 times heavier than1/12 of
th

2 HCl  H 2  I2 (Bimolecular)
carbon atom. Therefore assertion is false but reason is true.
 Molarity and molecularity are used in different sense.
3. (c) According to Dalton's atomic theory atoms can neither be
11. (a) Both assertion and reason are true and reason is the correct
created nor destroyed and according to berzelius hypothesis,
explanation of assertion.
under similar condition of temperature and pressure equal
volumes of all gases contain equal no. of atom. Therefore 63.6 At.wt.
assertion is true but reason is false. 12. (e) Equivalent wt. of Cu in CuO =  =31.8
2 Valency
4. (e) One mole of any substance corresponding to 6.023  10 23 63.6
entities is respective of its weight. Equivalent wt. of Cu in Cu 2 O  =63.6
1
Molecular weight of SO 2  32  2  16  64 gm . (Valency of Cu =1).
13. (e) Mass spectrometer is the instrument used for the
Molecular weight of O2  16  2  32 gm . determination of accurate atomic mass and the relative
abundance of the isotopes.
 Molecular weight of SO 2 is double to that of O 2 .
14. (a) Both assertion and reason are true and reason is the correct
5. (d) 1.231 has four significant figures all no. from left to right are explanation of assertion.
counted, starting with the first digit that is not zero for 15 . (a) Example of isomorphous compounds are
calculating the no. of significant figure.
K2 SO 3 , K2CrO4 , K2 SeO 4 (valency of S, Cr, Se = 6) and
6. (d) Molar volume (at NTP) = 22.4 L
ZnSO 4 . 7 H 2O, MgSO4 . 7 H 2O, FeSO4 . 7 H 2O (valency
Now 22.4L of N 2  volume occupied by one mole of of Zn, Mg, Fe =2).

N 2  28 gm  6.023  10 23 molecules. 16. (b) No. of atoms present in a molecules of a gaseous element is
called atomicity.
Similarly, O2  2  16  32 gm , For example, O 2 has two atoms and hence its atomicity is 2.
32 gm  6.023  10 23 molecules = 22.4L
17. (a) 12gm of C-12 contain 6.023  10 23 atom
6 .023  10 23  5 .6 12
 22.4 L  6.023  10 23 or 5 .6 L    10  23  1.66  10  24 .
22.4 6.023

1
  6 .023  10 23
4

According to avagadro's hypothesis equal volume of all gases

contain equal no. of molecules under similar condition of
temperature and pressure.
7. (a) For universally accepted atomic mass unit in 1961, C-12
was selected as standard. However the new symbol used is ' v'
(unified mass) in place of amu.

M
8. (c) Vapour density of B  ,
2

M
Vapour density of A  4   2M
4
Molecular mass of A  2  2 M  4 M .
9. (a) Pure water always contains hydrogen and oxygen in the ratio
1 : 8 by mass. This is in accordance with the law of constant
composition.
10 . (b) The number of moles of a solute present in litre of solution is
known is as molarity ( M).
The total no. of molecules of reactants present in a balanced
chemical equation is known as molecularity. For example,
PCl5  PCl3  Cl2 (Unimolecular)
 34 Chemical Arithmetic

1. A m ixture of sand and iodine can be separated by 8. Crystals of which pair are isom orphous [MP PMT 1985]
[Kerala CEE 2002] (a) ZnSO 4 , SnSO 4 (b) MgSO4 , CaSO 4
(a) Cry stallisation (b) Sublim ation (c) ZnSO 4 , MgSO4 (d) PbSO4 , NiSO4
(c) Distillation (d) Fractional distillation
9. M is the m olecular weight of KMnO4 . The equiv alent
2. The elem ent sim ilar to carbon is
weight of KMnO 4 when it is conv erted into K 2 MnO4 is
(a) Mg (b) Mn
(a) M (b) M / 3
(c) Sn (d) Po
(c) M / 5 (d) M / 7
2. The law of m ultiple proportions was proposed by
10. An aqueous solution of 6.3 g of oxalic acid dihy drate is
[IIT 1992]
m ade up of to 2 50 ml. The v olum e of 0.1
(a) Lav oisier (b) Dalton
N NaOH required to com pletely neutralise 1 0 ml of this
(c) Proust (d) Gay -Lussac solution is [IIT 2001]
4. 1 L of N 2 com bines with 3 L of H 2 to form 2 L of (a) 4 0 ml (b) 2 0 ml
NH 3 under the sam e conditions. This illustrates the (c) 1 0 ml (d) 4 ml
(a) Law of constant composition 11. The normality of orthophosphoric acid hav ing purity of
70% by weight and specific gravity 1.54 would be[CPMT 1992]
(b) Law of m ultiple proportions
(a) 1 1 N (b) 2 2 N
(c) Law of reciprocal proportions
(c) 3 3 N (d) 4 4 N
(d) Gay -Lussac’s law of gaseous v olum es
12. The equivalent weight of phosphoric acid (H 3 PO4 ) in the
5. One sam ple of atmospheric air is found to hav e 0.03 % of
carbon dioxide and another sam ple 0.04 %. This is reaction, NaOH  H 3 PO4  NaH 2 PO4  H 2O is
ev idence that [A IIMS 1999; BHU 2005]
(a) The law of constant com position is not alway s true (a) 2 5 (b) 49
(b) The law of m ultiple proportions is true (c) 59 (d) 9 8
(c) Air is a com pound
13. Volume of 0.6 M NaOH required to neutralize 30 cm 3 of
(d) Air is a m ixture
0.4 M HCl is [KCET 1995]
6. One part of an elem ent A com bines with two parts of 3 3
(a) 30 cm (b) 20 cm
another B. Six parts of the element C com bine with four
parts of the element B. if A and C com bine together the
(c) 50 cm 3 (d) 45 cm 3
ratio of their weights will be governed by [A MU 1984]
(a) Law of definite proportion 14. One m ole of potassium dichrom ate com pletely oxidises
the following num ber of m oles of ferrous sulphate in
(b) Law of m ultiple proportion
acidic m edium [MP PET 1998]
(c) Law of reciprocal proportion (a) 1 (b) 3
(d) Law of conserv ation of m ass (c) 5 (d) 6
7. The m aximum amount of BaSO 4 precipitated on m ixing 15. The number of equivalents of Na 2 S 2O3 required for the
equal v olum es of BaCl2 (0.5 M) with H 2 SO 4 (1 M) will
volumetric estimation of one equivalent of Cu 2  is
correspond to [A IIMS 1997] [Kerala MEE 2000]
(a) 0.5 M (b) 1 .0 M (a) 1 (b) 2
(c) 1 .5 M (d) 2 .0 M (c) 3 /2 (d) 3

(SET -1)
 Chemical Arithmetic 35

1. (b) Iodine shows sublimation and hence v olatalizes on 10. (a) Oxalic acid NaOH
heating, the vapour condenses on cooling to give pure
N 1 V1  N 2 V2
iodine.
2. (c) Carbon and tin both are same group elements so have  W 1000 
sim ilarities in properties.  E  V   V1  N 2 V2
 
3. (b) Law of m ultiple proportions was proposed by Dalton 6.3 1000
and v erified by Berzelius.   10  0 .1  V V= 4 0ml.
63 250
4. (d) Gay - Lussac's law : The volumes of the reacting gases
and those of the gaseous products bear the sim ple 11. (a) 7 0% by weight 70 gm H 3 PO4  100 gm
ratio (also called the law of gaseous v olum es). solution/sam ple
5. (d) W 100 70  1000
V  N  11 N .
6. (c) The weights of two elements combining with a fixed d 1 .54 98  100 / 1.54
am ount of the third elem ent will bear the sam e
ratio(or sim ple m ultiple of it) in which they 12. (d) NaOH  H 3 PO4  NaH 2 PO4
(PO43 ) ( NaPO42 )
them selv es react.
7. (a) BaCl2  H 2 SO 4  BaSO4  2 HCl EW 
MW

98
.
no. of ionisableH  1
One m ole of BaCl2 reacts with one m ole of H 2 SO 4 .
13. (b) NaOH HCl
Hence 0.5 mole will react with 0.5 mole of H 2 SO 4
N1 V1  N 2 V2 ; 0.6  V1  0.4  30 ; V1  20ml .
i.e. BaCl2 is the limiting reagent.

8. (c) Isom orphous substance m olecules contain the sam e 14. (d) Cr2 O7  Cr 3  ; Fe   Fe  
n 1
num ber of atom s bonded in sim ilar fashion. n6
7 6 eq. of K2Cr2O7 = eq. of FeSO 4
9. (a) KMnO4  K 2 MnO4
1  6  x 1
Change in 0.5 per atom  7  6  1
15. (b) Cu 2   2 I   CuI 2 2CuI 2  Cu 2 I2  I2
 Equivalent weight of KMnO4
Molecular weight of KMnO4 M I2  2 Na 2S 2 O3  2 NaI  Na 2 S 4 O6
  M.
Change of 0.5 per atom 1
Cu 2   2 Na 2 S 2O3

***
 34 Chemical Arithmetic

1. A m ixture of sand and iodine can be separated by 8. Crystals of which pair are isom orphous [MP PMT 1985]
[Kerala CEE 2002] (a) ZnSO 4 , SnSO 4 (b) MgSO4 , CaSO 4
(a) Cry stallisation (b) Sublim ation (c) ZnSO 4 , MgSO4 (d) PbSO4 , NiSO4
(c) Distillation (d) Fractional distillation
9. M is the m olecular weight of KMnO4 . The equiv alent
2. The elem ent sim ilar to carbon is
weight of KMnO 4 when it is conv erted into K 2 MnO4 is
(a) Mg (b) Mn
(a) M (b) M / 3
(c) Sn (d) Po
(c) M / 5 (d) M / 7
2. The law of m ultiple proportions was proposed by
10. An aqueous solution of 6.3 g of oxalic acid dihy drate is
[IIT 1992]
m ade up of to 2 50 ml. The v olum e of 0.1
(a) Lav oisier (b) Dalton
N NaOH required to com pletely neutralise 1 0 ml of this
(c) Proust (d) Gay -Lussac solution is [IIT 2001]
4. 1 L of N 2 com bines with 3 L of H 2 to form 2 L of (a) 4 0 ml (b) 2 0 ml
NH 3 under the sam e conditions. This illustrates the (c) 1 0 ml (d) 4 ml
(a) Law of constant composition 11. The normality of orthophosphoric acid hav ing purity of
70% by weight and specific gravity 1.54 would be[CPMT 1992]
(b) Law of m ultiple proportions
(a) 1 1 N (b) 2 2 N
(c) Law of reciprocal proportions
(c) 3 3 N (d) 4 4 N
(d) Gay -Lussac’s law of gaseous v olum es
12. The equivalent weight of phosphoric acid (H 3 PO4 ) in the
5. One sam ple of atmospheric air is found to hav e 0.03 % of
carbon dioxide and another sam ple 0.04 %. This is reaction, NaOH  H 3 PO4  NaH 2 PO4  H 2O is
ev idence that [A IIMS 1999; BHU 2005]
(a) The law of constant com position is not alway s true (a) 2 5 (b) 49
(b) The law of m ultiple proportions is true (c) 59 (d) 9 8
(c) Air is a com pound
13. Volume of 0.6 M NaOH required to neutralize 30 cm 3 of
(d) Air is a m ixture
0.4 M HCl is [KCET 1995]
6. One part of an elem ent A com bines with two parts of 3 3
(a) 30 cm (b) 20 cm
another B. Six parts of the element C com bine with four
parts of the element B. if A and C com bine together the
(c) 50 cm 3 (d) 45 cm 3
ratio of their weights will be governed by [A MU 1984]
(a) Law of definite proportion 14. One m ole of potassium dichrom ate com pletely oxidises
the following num ber of m oles of ferrous sulphate in
(b) Law of m ultiple proportion
acidic m edium [MP PET 1998]
(c) Law of reciprocal proportion (a) 1 (b) 3
(d) Law of conserv ation of m ass (c) 5 (d) 6
7. The m aximum amount of BaSO 4 precipitated on m ixing 15. The number of equivalents of Na 2 S 2O3 required for the
equal v olum es of BaCl2 (0.5 M) with H 2 SO 4 (1 M) will
volumetric estimation of one equivalent of Cu 2  is
correspond to [A IIMS 1997] [Kerala MEE 2000]
(a) 0.5 M (b) 1 .0 M (a) 1 (b) 2
(c) 1 .5 M (d) 2 .0 M (c) 3 /2 (d) 3

(SET -1)
 Chemical Arithmetic 35

1. (b) Iodine shows sublimation and hence v olatalizes on 14. (d) Cr2 O7  Cr 3  ; Fe   Fe  
heating, the vapour condenses on cooling to give pure n 1
n6
iodine.
eq. of K2Cr2O7 = eq. of FeSO 4
2. (c) Carbon and tin both are same group elements so have
sim ilarities in properties. 1  6  x 1
3. (b) Law of m ultiple proportions was proposed by Dalton 15. (b) Cu 2 
 2 I  CuI 2 2CuI 2  Cu 2 I2  I2
and v erified by Berzelius.
4. (d) Gay - Lussac's law : The volumes of the reacting gases I2  2 Na 2S 2 O3  2 NaI  Na 2 S 4 O6
and those of the gaseous products bear the sim ple
ratio (also called the law of gaseous v olum es). Cu 2   2 Na 2 S 2O3

5. (d)
6. (c) The weights of two elements combining with a fixed
am ount of the third elem ent will bear the sam e
ratio(or sim ple m ultiple of it) in which they
them selv es react.
7. (a) BaCl2  H 2 SO 4  BaSO4  2 HCl

One m ole of BaCl2 reacts with one m ole of H 2 SO 4 .

Hence 0.5 mole will react with 0.5 mole of H 2 SO 4
i.e. BaCl2 is the limiting reagent.

8. (c) Isom orphous substance m olecules contain the sam e

num ber of atom s bonded in sim ilar fashion.
7 6
9. (a) KMnO4  K 2 MnO4

Change in 0.5 per atom  7  6  1

 Equivalent weight of KMnO4
Molecular weight of KMnO4 M
  M.
Change of 0.5 per atom 1

10. (a) Oxalic acid NaOH

N 1 V1  N 2 V2

 W 1000 
 E  V   V1  N 2 V2
 
6.3 1000
  10  0 .1  V V= 4 0ml.
63 250
11. (a) 7 0% by weight 70 gm H 3 PO4  100 gm

solution/sam ple
W 100 70  1000
V  N  11 N .
d 1 .54 98  100 / 1.54
12. (d) NaOH  H 3 PO4  NaH 2 PO4
(PO43 ) ( NaPO42 )

MW 98
EW   .
no. of ionisableH  1
13. (b) NaOH HCl
N1 V1  N 2 V2 ; 0.6  V1  0.4  30 ; V1  20ml .

***
 36 Structure of atom
John Dalton 1808, believed that matter is made up of extremely
minute indivisible particles, called atom which can takes part in chemical
reactions. These can neither be created nor be destroyed. However, modern
researches have conclusively proved that atom is no longer an indivisible
particle. Modern structure of atom is based on Rutherford’s scattering
experiment on atoms and on the concepts of quantization of energy.
Composition of atom
The works of J.J. Thomson and Ernst Rutherford actually laid the
foundation of the modern picture of the atom. It is now believed that the atom
consists of several sub-atomic particles like electron, proton, neutron, positron,
neutrino, meson etc. Out of these particles, the electron, proton and the neutron
are called fundamental subatomic particles and others are non-fundamental
particles.
Electron ( e )
–1
o
(1) It was discovered by J.J. Thomson (1897) and is negatively
charged particle. Electron is a component particle of cathode rays.
(2) Cathode rays were discovered by William Crooke's & J.J.
Thomson (1880) using a cylindrical hard glass tube fitted with two metallic
electrodes. The tube has a side tube with a stop cock. This tube was known
as discharge tube. They passed electricity (10,000V) through a discharge
tube at very low pressure ( 10 2 to 10 3 mm Hg) . Blue rays were
emerged from the cathode. These rays were termed as Cathode rays.
(3) Properties of Cathode rays
(i) Cathode rays travel in straight line.
(ii) Cathode rays produce mechanical effect, as they can rotate the
wheel placed in their path.
(iii) Cathode rays consist of negatively charged particles known as
electron.
(iv) Cathode rays travel with high speed approaching that of light
(ranging between 10 9 to 10 11 cm/sec)
(v) Cathode rays can cause fluorescence.
Table : 2.1 Comparison of mass, charge and specific charge of electron, proton and neutron
Chapter
2
Structure of atom
(vi) Cathode rays heat the object on which they fall due to transfer
of kinetic energy to the object.
(vii) When cathode rays fall on solids such as Cu, X  rays are
produced.
(viii) Cathode rays possess ionizing power i.e., they ionize the gas
through which they pass.
(ix) The cathode rays produce scintillation on the photographic
plates.
(x) They can penetrate through thin metallic sheets.
(xi) The nature of these rays does not depend upon the nature of gas
or the cathode material used in discharge tube.
(xii) The e/m (charge to mass ratio) for cathode rays was found to

be the same as that for an e (1.76  10 8 coloumb per
gm). Thus, the cathode rays are a stream of electrons.
(xiii) According to Einstein’s theory of relativity, mass of electron in
Rest mass of electron(m)
motion is, m  
[1  (u / c)2 ]
Where u = velocity of electron, c= velocity of light.
When u=c than mass of moving electron =.
Proton ( H , H , P)
1
1 +
(1) Proton was discovered by Goldstein and is positively charged
particle. It is a component particle of anode rays.
(2) Goldstein (1886) used perforated cathode in the discharge tube
and repeated Thomson's experiment and observed the formation of anode
rays. These rays also termed as positive or canal rays.
(3) Properties of anode rays
(i) Anode rays travel in straight line.
(ii) Anode rays are material particles.
(iii) Anode rays are positively charged.
 Structure of atom 37

Name of constant Unit Electron(e ) –

Proton(p )
+
Neutron(n)
Amu 0.000546 1.00728 1.00899
Mass (m) Kg 9.109 × 10 –31
1.673 × 10 –27
1.675 × 10 –27

Relative 1/1837 1 1

Coulomb (C) – 1.602 × 10 –19

+1.602 × 10 –19
Zero
Charge(e) Esu – 4.8 × 10 –10
+4.8 × 10–10
Zero
Relative –1 +1 Zero
Specific charge (e/m) C/g 1.76 × 10
8
9.58 × 10 4
Zero
Density Gram / cc 2.17  10 17 1.114  1014 1.5  10 14

 The atomic mass unit (amu) is 1/12 of the mass of an individual atom of 6 C 12 , i.e. 1.660  10 27 kg .
Table : 2.2 Other non fundamental particles
Particle Symbol Nature Charge esu Mass Discovered by
10–10 (amu)
Positron + + 4.8029 0.0005486 Anderson (1932)
e  , 1e 0 ,  
Neutrino  0 0 < 0.00002 Pauli (1933) and Fermi (1934)
Anti-proton – – 4.8029 1.00787 Chamberlain Sugri (1956) and Weighland (1955)
p
Positive mu meson + + 4.8029 0.1152 Yukawa (1935)

Negative mu meson – – 4.8029 0.1152 Anderson (1937)

Positive pi meson + + 4.8029 0.1514

Negative pi meson – – 4.8029 0.1514
 Powell (1947)
Neutral pi meson 0 0 0.1454
0

(iv) Anode rays may get deflected by external magnetic field. Atomic number, Mass number and Atomic species
(v) Anode rays also affect the photographic plate. (1) Atomic number or Nuclear charge
(i) The number of protons present in the nucleus of the atom is
(vi) The e/m ratio of these rays is smaller than that of electrons. called atomic number (Z).
(vii) Unlike cathode rays, their e/m value is dependent upon the (ii) It was determined by Moseley as,
nature of the gas taken in the tube. It is maximum when gas present in the   a(Z  b) or aZ  ab  s 1
tube is hydrogen.
Where,   X  ray’s frequency Z Fig. 2.1
(viii) These rays produce flashes of light on ZnS screen.
Z= atomic number of the metal a & b are constant.
Neutron ( n , N)
o
1
(iii) Atomic number = Number of positive charge on nucleus =
Number of protons in nucleus = Number of electrons in nutral atom.
(1) Neutron was discovered by James Chadwick (1932) according to
(iv) Two different elements can never have identical atomic number.
the following nuclear reaction,
(2) Mass number
4 Be 9  2 He 4  6 C 12  o n 1 Mass number (A) = Number of protons or Atomic number (Z) +
Number of neutrons or Number of neutrons = A – Z .
or 5 B 11  2 He 4  7 N 14  o n 1 (i) Since mass of a proton or a neutron is not a whole number (on
atomic weight scale), weight is not necessarily a whole number.
(2) Neutron is an unstable particle. It decays as follows, (ii) The atom of an element X having mass number (A) and atomic
number (Z) may be represented by a symbol, XA.
 1 H 1  1 e  0
1 0 0 Z
0n
neutron Proton electon antinutrino

Table: 2.3 Different types of atomic species

Atomic species Similarities Differences Examples
Isotopes (i) Atomic No. (Z) (i) Mass No. (A) (i) 11 H , 12 H , 13 H
(Soddy) (ii) No. of protons (ii) No. of neutrons
 38 Structure of atom

(iii) No. of electrons (iii) Physical properties (ii) 16 17 18

8 O, 8 O, 8 O
(iv) Electronic configuration
35 37
(v) Chemical properties (iii) 17 Cl, 17 Cl

(vi) Position in the periodic table

(i) Mass No. (A) (i) Atomic No. (Z) (i) 40 40
Ar, 19 K, 40
18 20 Ca
(ii) No. of nucleons (ii) No. of protons, electrons and
130
neutrons (ii) 52 Te , 130 130
54 Xe, 56 Ba
Isobars
(iii)Electronic configuration
(iv) Chemical properties
(v) Position in the perodic table.
No. of neutrons (i) Atomic No. (i) 30 31
Si, 15 32
P, 16 S
14
(ii) Mass No., protons and electrons.
39
(iii) Electronic configuration (ii) 19 K, 40
20 Ca
Isotones
(iv) Physical and chemical properties (iii) 3
H , 42 He
1
(v) Position in the periodic table.
13 14
(iv) 6 C, 7 N
Isotopic No. (i) At No., mass No., electrons, protons, (i) 92 U 235 , 90 Th 231
(N – Z) or (A – 2Z) neutrons.
Isodiaphers (ii) Physical and chemical properties. (ii) 19 K 39 , 9 F19
65
(iii) 29 Cu , 24 Cr 55
(i) No. of electrons At. No., mass No. (i) N 2 O, CO 2 , CNO  (22e  )
(ii) Electronic configuration
(ii) CO , CN  , N 2 (14 e  )
Isoelectronic species
(iii) H  , He, Li  , Be 2  (2e  )
(iv) P 3  , S 2 , Cl  , Ar, K  and Ca 2 (18 e  )

(i) No. of atoms (i) N 2 and CO

(ii) No. of electrons
(ii) CO 2 and N 2 O
(iii) Physical and chemical properties.
Isosters (iii) HCl and F2

(iv) CaO and MgS

(v) C 6 H 6 and B3 N 3 H 6

Electromagnetic radiations
(1) Light and other forms of radiant energy propagate without any measured is terms of centimeter(cm), angstrom(Å), micron(  ) or
medium in the space in the form of waves are known as electromagnetic nanometre (nm).
radiations. These waves can be produced by a charged body moving in a
magnetic field or a magnet in a electric field. e.g.   rays,   rays,
cosmic rays, ordinary light rays etc.

(2) Characteristics
Crest Wavelength
(i) All electromagnetic radiations travel with the velocity of light.
(ii) These consist of electric and magnetic fields components Vibrating
that oscillate in directions perpendicular to each other and source
perpendicular to the direction in which the wave is travelling.
Energy
(3) A wave is always characterized by the following five
characteristics,
(i) Wavelength : The distance between two nearest crests or nearest
troughs is called the wavelength. It is denoted by  (lambda) and is Trough
Fig. 2.2
 Structure of atom 39
incandescent object resolved through prism or spectroscope, it also gives
continuous spectrum of colours.
(ii) Line spectrum : If the radiation’s obtained by the excitation of a
substance are analysed with help of a spectroscope a series of thin bright
lines of specific colours are obtained. There is dark space in between two
1 Å  10 8 cm  10 10 m ; 1  10 4 cm  10 6 m ; consecutive lines. This type of spectrum is called line spectrum or atomic
spectrum..
1nm  10 7 cm  10 9 m ; 1cm  10 8 Å  10 4   10 7 nm
(2) Absorption spectrum : Spectrum produced by the absorbed
(ii) Frequency : It is defined as the number of waves which pass
radiations is called absorption spectrum.
through a point in one second. It is denoted by the symbol  (nu) and is
expressed in terms of cycles (or waves) per second (cps) or hertz (Hz). Hydrogen spectrum
(1) Hydrogen spectrum is an example of line emission spectrum or
  distance travelled in one second = velocity =c
atomic emission spectrum.
c
  (2) When an electric discharge is passed through hydrogen gas at
 low pressure, a bluish light is emitted.
(iii) Velocity : It is defined as the distance covered in one second by (3) This light shows discontinuous line spectrum of several isolated
the wave. It is denoted by the letter ‘c’. All electromagnetic waves travel sharp lines through prism.
with the same velocity, i.e., 3  1010 cm / sec . (4) All these lines of H-spectrum have Lyman, Balmer, Paschen,
c    3  1010 cm / sec Barckett, Pfund and Humphrey series. These spectral series were named by
the name of scientist discovered them.
(iv) Wave number : This is the reciprocal of wavelength, i.e., the
(5) To evaluate wavelength of various H-lines Ritz introduced the
number of wavelengths per centimetre. It is denoted by the symbol  (nu
following expression,
bar). It is expressed in cm 1 or m 1 .
1  1 1 
1     R 2  2 
   c  n1 n 2 

(v) Amplitude : It is defined as the height of the crest or depth of Where R is universal constant known as Rydberg’s constant its value
the trough of a wave. It is denoted by the letter ‘A’. It determines the is 109, 678 cm 1 .
intensity of the radiation.
The arrangement of various types of electromagnetic radiations in Plum pudding model of Thomson
the order of their increasing or decreasing wavelengths or frequencies is (1) He suggected that atom is a positively charged sphere having
known as electromagnetic spectrum. electrons embedded uniformly giving an overall picture of plum pudding.
Table: 2.4 Positively charged
Name Wavelength (Å) Frequency (Hz) + – + sphere
Radio wave
3  10 14  3  10 7 1  10 5  1  10 9 – + – +
–
Microwave Electron unifromly
3  10  6  10
7 6
1  10  5  10
9 11
+ –
+
embedded
Infrared (IR) –
6  10 6  7600 5  10 11  3.95  10 16 +
Visible 7600  3800 3.95  10 16
 7.9  10 14 Positive charge spreaded throughout the sphere

Ultraviolet (UV) 3800  150 (2) This model failed toFig.explain

2.3 the line spectrum of an element and
7.9  10 14
 2  10 16
the scattering experiment of Rutherford.
X-Rays 150  0.1 2  10 16  3  10 19
  Rays 0.1  0.01 3  10 19  3  10 20
Cosmic Rays 0.01- zero Rutherford's nuclear model
3  10 20  infinity
(1) Rutherford carried out experiment on the bombardment of thin
(10 mm) Au foil with high speed positively charged   particles emitted
–4

from Ra and gave the following observations based on this experiment,

(i) Most of the  particles passed without any deflection.
Atomic spectrum - Hydrogen spectrum
(ii) Some of them were deflected away from their path.
Atomic spectrum (iii) Only a few (one in about 10,000) were returned back to their
Spectrum is the impression produced on a photographic film when original direction of propagation.
the radiation (s) of particular wavelength (s) is (are) analysed through a Deflected
prism or diffraction grating. -particles
Types of spectrum
(1) Emission spectrum : Spectrum produced by the emitted radiation -rays
is known as emission spectrum. This spectrum corresponds to the radiation
+ve Nucleus
emitted (energy evolved) when an excited electron returns back to the
ground state.
(i) Continuous spectrum : When sunlight is passed through a prism, it
gets dispersed into continuous bands of different colours. If the light of an
Fig. 2.4 ZnS screen
 40 Structure of atom
(2) From the above observations he concluded that, an atom
consists of
(i) Nucleus which is small in size but carries the entire mass i.e.
contains all the neutrons and protons.
(ii) Extra nuclear part which contains electrons. This model was
similar to the solar system.
(3) Properties of the nucleus
(i) Nucleus is a small, heavy, positively charged portion of the atom
and located at the centre of the atom.
(ii) All the positive charge of atom (i.e. protons) are present in
nucleus.
(iii) Nucleus contains neutrons and protons, and hence these
particles collectively are also referred to as nucleons.
(iv) The size of nucleus is measured in Fermi (1 Fermi = 10 cm).
(v) The radius of nucleus is of the order of 1.5  10 13 cm. to
6.5  10 13 cm. i.e. 1 .5 to 6 .5 Fermi. Generally the radius of the
nucleus ( rn ) is given by the following relation,
rn  ro ( 1.4  10 13 cm)  A1 / 3
This exhibited that nucleus is 10 5 times small in size as
compared to the total size of atom.
(vi) The Volume of the nucleus is about 10 39 cm 3 and that of
atom is 10 24 3
cm , i.e., volume of the nucleus is 10 15
times that of an
atom.
15
(vii) The density of the nucleus is of the order of 10
10 8 tonnes cm 3 or 10 12 kg / cc . If nucleus is spherical than,
mass of the nucleus mass number
Density =  atom. However, in order to account for the stability of the atom he
volume of the nucleus 4
6 .023  10 23  r 3
3
(4) Drawbacks of Rutherford's model
(i) It does not obey the Maxwell theory of electrodynamics,
according to it “A small charged particle moving around an oppositely
charged centre continuously loses its energy”. If an electron does so, it
should also continuously lose its energy and should set up spiral motion
ultimately failing into the nucleus.
(ii) It could not explain the line spectra of H  atom and
discontinuous spectrum nature.
Planck's quantum theory
When black body is heated, it emits thermal radiation’s of different
wavelengths or frequency. To explain these radiations, max planck put
forward a theory known as planck’s quantum theory.
(i) The radiant energy which is emitted or absorbed by the black
body is not continuous but discontinuous in the form of small discrete
packets of energy, each such packet of energy is called a 'quantum'. In case
of light, the quantum of energy is called a 'photon'.
(ii) The energy of each quantum is directly proportional to the
frequency (  ) of the radiation, i.e.
hc
E   or E  hv 

Where, h Planck's constant = 6.62×10 –27
erg. sec. or
6.62  10 34 Joules sec .
(iii) The total amount of energy emitted or absorbed by a body
will be some whole number quanta. Hence E  nh , where n is an
integer.
Photoelectric effect
(1) When radiations with certain minimum frequency ( 0 ) strike
the surface of a metal, the electrons are ejected from the surface of the
metal. This phenomenon is called photoelectric effect and the electrons
emitted are called photo-electrons. The current constituted by
photoelectrons is known as photoelectric current.
(2) The electrons are ejected only if the radiation striking the
surface of the metal has at least a minimum frequency ( 0 ) called
Threshold frequency. The minimum potential at which the plate
photoelectric current becomes zero is called stopping potential.
–13
(3) The velocity or kinetic energy of the electron ejected depend
upon the frequency of the incident radiation and is independent of its
intensity.
(4) The number of photoelectrons ejected is proportional to the
intensity of incident radiation.
(5) Einstein’s photoelectric effect equation
According to Einstein,
Maximum kinetic energy of the ejected electron = absorbed energy
– threshold energy
1 1 1 
2
mv max  h   h  0  hc   
2    0 
Where,  0 and 0 are threshold frequency and threshold
3 wavelength.
g cm or
Bohr’s atomic model
Bohr retained the essential features of the Rutherford model of the
introduced the concept of the stationary orbits. The Bohr postulates are,
(1) An atom consists of positively charged nucleus responsible for
almost the entire mass of the atom (This assumption is retention of
Rutherford model).
(2) The electrons revolve around the nucleus in certain permitted
circular orbits of definite radii.
(3) The permitted orbits are those for which the angular
momentum of an electron is an intergral multiple of h / 2 where h is
the Planck’s constant. If m is the mass and v is the velocity of the
electron in a permitted orbit of radius r, then
nh
L  mvr  ; n  1 , 2, 3, …… 
2
Where L is the orbital angular momentum and n is the number
of orbit. The integer n is called the principal quantum number. This
equation is known as the Bohr quantization postulate.
(4) When electrons move in permitted discrete orbits they do not
radiate or lose energy. Such orbits are called stationary or non-radiating
orbits. In this manner, Bohr overcame Rutherford’s difficulty to account for
the stability of the atom. Greater the distance of energy level from the
nucleus, the more is the energy associated with it. The different energy
levels were numbered as 1,2,3,4 .. and called as K, L, M , N , …. etc.
(5) Ordinarily an electron continues to move in a particular
stationary state or orbit. Such a state of atom is called ground state.
When energy is given to the electron it jumps to any higher energy
level and is said to be in the excited state. When the electron jumps
from higher to lower energy state, the energy is radiated.
 Structure of atom 41
Advantages of Bohr’s theory  1 
2 2k 2me 4 Z 2  1 
(i) Bohr’s theory satisfactorily explains the spectra of species having   n2  n2 
ch3  1 2 
one electron, viz. hydrogen atom, He  , Li 2  etc.
1  1 1 
(ii) Calculation of radius of Bohr’s orbit : According to Bohr, radius This can be represented as    RZ 2  2  2 
of n orbit in which electron moves is
th
  1
n n 2 

 h2  n2 2 2 k 2 me 4
rn   2 2 . Where, R  ; R is known as Rydberg constant. Its
ch 3
 4 me k  Z
value to be used is 109678cm 1 .
Where, n  Orbit number, m  Mass number
9.1  10 31

kg , e  Charge on the electron 1.6  10 19   Z  Atomic
The negative sign in the above equations shows that the electron
and nucleus form a bound system, i.e., the electron is attracted towards the
number of element, k = Coulombic constant 9  10 9 Nm 2c 2   nucleus. Thus, if electron is to be taken away from the nucleus, energy has
to be supplied. The energy of the electron in n  1 orbit is called the
After putting the values of m,e,k,h, we get. ground state energy; that in the n  2 orbit is called the first excited state
energy, etc. When n   then E  0 which corresponds to ionized atom
n2
rn   0 .529 Å i.e., the electron and nucleus are infinitely separated H  H   e 
Z
(ionization).
(6) Spectral evidence for quantisation (Explanation for hydrogen spectrum
(iii) Calculation of velocity of electron on the basisof bohr atomic model)
1/2
2e 2 ZK  Ze 2  2 .188  10 8 Z (i) The light absorbed or emitted as a result of an electron changing
Vn  , Vn    ; Vn  cm. sec 1 orbits produces characteristic absorption or emission spectra which can be
nh  mr  n
recorded on the photographic plates as a series of lines, the optical
(iv) Calculation of energy of electron in Bohr’s orbit spectrum of hydrogen consists of several series of lines called Lyman,
Balmar, Paschen, Brackett, Pfund and Humphrey. These spectral series were
Total energy of electron = K.E. + P.E. of electron
named by the name of scientist who discovered them.
2 2 2
kZe kZe kZe
   (ii) To evaluate wavelength of various H-lines Ritz introduced the
2r r 2r following expression,
 2 2 mZ 2 e 4 k 2 1  1 1
Substituting of r, gives us E  Where, n=1, 2,     R 2  2 
n 2h2  c  n1 n 2 
3………. 
Putting the value of m, e, k, h,  we get 2 2me 4
Where, R is =  Rydberg's constant
Z2 ch 3
E  21.8  10 12  erg per atom
n2 It's theoritical value = 109,737 cm –1
and It's experimental value =
1
109,677.581cm
Z2
 21.8  10 19  J per atom(1 J  10 7 erg) This remarkable agreement between the theoretical and
n2
2
experimental value was great achievment of the Bohr model.
Z
E  13.6  eV per atom(1eV  1.6  10 -19 J ) (iii) Although H-atom consists of only one electron yet it's spectra
n2 consist of many spectral lines.
Z2 (iv) Comparative study of important spectral series of Hydrogen is
 13.6  k .cal / mole (1 cal = 4.18J)
n2 shown in following table.
(v) If an electron from n excited state comes to various energy
th

1312 2
or Z kJmol 1 n(n  1)
n2 states, the maximum spectral lines obtained will be = . n=
2
When an electron jumps from an outer orbit (higher energy) n 2 to principal quantum number.
an inner orbit (lower energy) n1 , then the energy emitted in form of As n=6 than total number of spectral lines =
radiation is given by 6(6  1) 30
  15.
2 2
2 2 k 2 me 4 Z 2  1 1 
E  En2  En1  
 n2  n2 
(vi) Thus, at least for the hydrogen atom, the Bohr theory accurately
h2  1 2  describes the origin of atomic spectral lines.
(7) Failure of Bohr model
 1 1 
 E  13.6 Z 2  2  2 eV / atom (i) Bohr theory was very successful in predicting and accounting the
 1
n n 2  energies of line spectra of hydrogen i.e. one electron system. It could not
explain the line spectra of atoms containing more than one electron.
1 E
As we know that E  h , c   and    , (ii) This theory could not explain the presence of multiple spectral
 hc lines.
 42 Structure of atom
(iii) This theory could not explain the splitting of spectral lines in (iv) This theory was unable to explain of dual nature of matter as
magnetic field (Zeeman effect) and in electric field (Stark effect). The explained on the basis of De broglies concept.
intensity of these spectral lines was also not explained by the Bohr atomic (v) This theory could not explain uncertainty principle. (vi) No
model. conclusion was given for the concept of quantisation of energy.
Table: 2.5

S.No. Spectral series Lies in the Transition n12n22 n12  max n2

region max   min   2 2 2
n2  n1 (n22 n12 )R R  min n 2  n1
(1) Lymen series Ultraviolet n1  1 n1  1 and n 2  2 n1  1 and n 2  
region 4
n 2  2,3,4....  4 1
 max   min  3
3R R

(2) Balmer series Visible region n1  2 n1  2 and n 2  3 n1  2 and n2  

n 2  3,4,5....  36 4 9
 max   min 
5R R 5
(3) Paschen series Infra red n=3
1 n1  3 and n 2  4 n1  3 and n 2  
region n 2  4,5,6....  16
144 9
 max   min  7
7R R
(4) Brackett series Infra red n1  4 n1  4 and n2  5 n1  4 and n 2  
region 25
n 2  5,6,7....  16  25 16
max   min  9
9R R

(5) Pfund series Infra red n1  5 n1  5 and n 2  6 n1  5 and n 2  

region 36
n 2  6,7,8....  25  36 25
 max   min  11
11R R
(6) Humphrey Far infrared n1  6 n1  6 and n 2  7 n1  6 and n 2  
series region 49
n 2  7,8....  36  49 36
 max   min  13
13 R R

Bohr–Sommerfeild’s model energy of photon (on the basis of Einstein’s mass energy

It is an extension of Bohr’s model. The electrons in an atom revolve relationship), E  mc 2

around the nuclei in elliptical orbit. The circular path is a special case of
hc h
ellipse. Association of elliptical orbits with circular orbit explains the fine Equating both  mc 2 or   which is same as de-
line spectrum of atoms.  mc
Broglie relation.  mc  p 
Dual nature of electron
(5) This was experimentally verified by Davisson and Germer by
(1) In 1924, the French physicist, Louis de Broglie suggested that if
observing diffraction effects with an electron beam. Let the electron is
light has both particle and wave like nature, the similar duality must be true
accelerated with a potential of V than the Kinetic energy is
for matter. Thus an electron, behaves both as a material particle and as a
wave. 1
mv 2  eV ; m 2 v 2  2eVm
(2) This presented a new wave mechanical theory of matter. 2
According to this theory, small particles like electrons when in motion
h
possess wave properties. mv  2eVm  P ;  
(3) According to de-broglie, the wavelength associated with a 2eVm
particle of mass m, moving with velocity v is given by the relation (6) If Bohr’s theory is associated with de-Broglie’s equation then
wave length of an electron can be determined in bohr’s orbit and relate it
h
 , where h = Planck’s constant. with circumference and multiply with a whole number
mv
2r
(4) This can be derived as follows according to Planck’s equation, 2r  n  or  
n
h.c  c
E  h     
   From de-Broglie equation,  
h
.
mv
 Structure of atom 43

h 2r nh (iii) If  2 is maximum than probability of finding e  is maximum

Thus  or mvr 
mv n 2 around nucleus and the place where probability of finding e  is maximum
(7) The de-Broglie equation is applicable to all material objects but is called electron density, electron cloud or an atomic orbital. It is different
it has significance only in case of microscopic particles. Since, we come from the Bohr’s orbit.
across macroscopic objects in our everyday life, de-broglie relationship has
(iv) The solution of this equation provides a set of number called
no significance in everyday life.
quantum numbers which describe specific or definite energy state of the
Heisenberg’s uncertainty principle electron in atom and information about the shapes and orientations of the
most probable distribution of electrons around the nucleus.
This principle states “It is impossible to specify at any given
Radial probability distribution curves : Radial probability is
moment both the position and momentum (velocity) of an electron”.
R  4r 2 dr 2 . The plats of R distance from nucleus as follows
h
Mathematically it is represented as , x . p 
4 14
12
Where x  uncertainty is position of the particle, 10 5 5
p  uncertainty in the momentum of the particle

4r2 dr 2

4r2 dr 2

4r2 dr 2
8 4 4
6 3 3
Now since p  m v 4 2 2
2 1 1
h h
So equation becomes, x . m v  or x  v  0 0 0
4 4m 2 4 6 8 2 4 6 8 2 4 6 8
0.53Å r(Å) 0.53Å 2.7Å r(Å) 2.1Å r(Å)
In terms of uncertainty in energy, E and uncertainty in time 1s 2s 2s
h Fig. 2.5
t, this principle is written as, E . t  Quantum numbers
4
Each orbital in an atom is specified by a set of three quantum
Schrödinger wave equation numbers (n, l, m) and each electron is designated by a set of four quantum
(1) Schrodinger wave equation is given by Erwin Schrödinger in numbers (n, l, m and s).
1926 and based on dual nature of electron. (1) Principle quantum number (n)
(2) In it electron is described as a three dimensional wave in the electric (i) It was proposed by Bohr and denoted by ‘n’.
field of a positively charged nucleus.
(ii) It determines the average distance between electron and nucleus,
(3) The probability of finding an electron at any point around the means it denotes the size of atom.
nucleus can be determined by the help of Schrodinger wave equation which
is, (iii) It determine the energy of the electron in an orbit where
electron is present.
2 2 2 8 2m (iv) The maximum number of an electron in an orbit
   (E  V )   0
x 2
y 2
z 2
h2
represented by this quantum number as 2n 2 . No energy shell in
Where x, y and z are the 3 space co-ordinates, m = mass of atoms of known elements possess more than 32 electrons.
electron, h = Planck’s constant, E = Total energy, V = potential energy of (v) It gives the information of orbit K, L, M, N------------.
electron,  = amplitude of wave also called as wave function,  = for an (vi) Angular momentum can also be calculated using principle
infinitesimal change. quantum number
(4) The Schrodinger wave equation can also be written as, (2) Azimuthal quantum number (l)
8 2m (i) Azimuthal quantum number is also known as angular
2   (E  V )   0
h 2 quantum number. Proposed by Sommerfield and denoted by ‘ l ’.

Where  = laplacian operator. (ii) It determines the number of sub shells or sublevels to which the
electron belongs.
(5) Physical significance of  and  2 (iii) It tells about the shape of subshells.
(i) The wave function  represents the amplitude of the (iv) It also expresses the energies of subshells s  p  d  f
electron wave. The amplitude  is thus a function of space co-ordinates (increasing energy).
and time i.e.   (x , y, z...... times)
(v) The value of l  (n  1) always. Where ‘n’ is the number of
(ii) For a single particle, the square of the wave function ( ) at 2 principle shell.
any point is proportional to the probability of finding the particle at that (vi) Value of l = 0 1 2 3…..(n-1)
point. Name of subshell = s p d f

Shape of subshell = Spheric Dumbbell Double Complex

al dumbbell
 44 Structure of atom
(vii) It represent the orbital angular momentum. Which is equal to (vii) Degenerate orbitals : Orbitals having the same energy are
h known as degenerate orbitals. e.g. for p subshell p x p y p z
l(l  1)
2
(viii) The number of degenerate orbitals of s subshell =0.
(viii) The maximum number of electrons in subshell  2(2l  1)
(4) Spin quantum numbers (s)
s  subshell 2 electrons d  subshell 10 electrons (i) It was proposed by Goldshmidt & Ulen Back and denoted by the
symbol of ‘s’.
p  subshell 6 electrons f  subshell 14 electrons.
(ii) The value of ' s' is  1/2 and - 1/2, which signifies the spin
(ix) For a given value of ‘n’ the total values of ‘l’ is always equal to
or rotation or direction of electron on it’s axis during movement.
the value of ‘n’.
(iii) The spin may be clockwise or anticlockwise.
(3) Magnetic quantum number (m)
(iv) It represents the value of spin angular momentum is equal to
(i) It was proposed by Zeeman and denoted by ‘m’.
h
s(s  1).
(ii) It gives the number of permitted orientation of subshells. 2
(iii) The value of m varies from –l to +l through zero.
(v) Maximum spin of an atom  1 / 2  number of unpaired
(iv) It tells about the splitting of spectral lines in the magnetic field electron.
i.e. this quantum number proves the Zeeman effect.
(vi) This quantum number is not the result of solution of
(v) For a given value of ‘n’ the total value of ’m’ is equal to n 2 . schrodinger equation as solved for H-atom.

(vi) For a given value of ‘l’ the total value of ‘m’ is equal to (2l  1).
Table : 2.6 Distribution of electrons among the quantum levels
Designation of Number of Orbitals in the subshell
n l m
orbitals
1 0 0 1s 1
2 0 0 2s 1

2 1 –1, 0, +1 2p 3
3 0 0 3s 1
3 1 –1, 0, +1 3p 3

3 2 –2, –1, 0, +1, +2 3d 5

4 0 0 4s 1

4 1 –1, 0, +1 4p 3

4 2 –2, –1, 0, +1, +2 4d 5

4 3 –3, –2, –1, 0, +1, +2, +3 4f 7

Shape of orbitals
(1) Shape of ‘s’ orbital (2) Shape of ‘p’ orbitals
(i) For ‘s’ orbital l=0 & m=0 so ‘s’ orbital have only one (i) For ‘p’ orbital l=1, & m=+1,0,–1 means there are three ‘p’ orbitals,
unidirectional orientation i.e. the probability of finding the electrons is same which is symbolised as p x , p y , p z .
in all directions.
(ii) The size and energy of ‘s’ orbital with increasing ‘n’ will be (ii) Shape of ‘p’ orbital is dumb bell in which the two lobes on
opposite side separated by the nodal plane.
1s  2s  3 s  4 s.
(iii) p-orbital has directional properties.
(iii) s-orbitals known as radial node or modal surface. But there is
no radial node for 1s orbital since it is starting from the nucleus. Z Z Z
Y Y Y

X X X

Px PY Pz

Fig. 2.7
1S 2S
Fig. 2.6
 Structure of atom 45

(3) Shape of ‘d’ orbital The orbital diagram does not represent a possible
(i) For the ‘d’ orbital l =2 then the values of ‘m’ are –2, –1, 0, +1, +2. arrangement of electrons
It shows that the ‘d’ orbitals has five orbitals as d xy , d yz , d zx , d x 2 y 2 , d z 2 . 1s
Because there are only two possible values of s, an orbital can hold
(ii) Each ‘d’ orbital identical in shape, size and energy. not more than two electrons.
(iii) The shape of d orbital is double dumb bell . (4) Hund’s Rule of maximum multiplicity
(iv) It has directional properties. This rule deals with the filling of electrons in the orbitals having
Z Z equal energy (degenerate orbitals). According to this rule,
Y Y
“Electron pairing in p, d and f orbitals cannot occur until each
orbitals of a given subshell contains one electron each or is singly occupied”.
X X
This is due to the fact that electrons being identical in charge, repel
each other when present in the same orbital. This repulsion can however be
dZX dXY minimised if two electrons move as far apart as possible by occupying
Z different degenerate orbitals. All the unpaired electrons in a degenerate set
Z Y
Y of orbitals will have same spin.
Z As we now know the Hund’s rule, let us see how the three electrons
X
are arranged in p orbitals.
X Z
Y The important point ot be remembered is that all the singly
occupied orbitals should have electrons with parallel spins i.e in the same
dYZ dX2–Y2 direction either-clockwise or anticlockwise.
2 px 2 py 2 pz 2 px 2 py 2 pz
X or
Electronic configurations of elements
d
z2
On the basis of the elecronic configuration principles the electronic
Fig. 2.8 configuration of various elements are given in the following table :
The above method of writing the electronic configurations is quite
(4) Shape of ‘f’ orbital cumbersome. Hence, usually the electronic configuration of the atom of any
(i) For the ‘f’ orbital l=3 then the values of ‘m’ are –3, –2, – element is simply represented by the notation.
1,0,+1,+2,+3. It shows that the ‘f’ orbitals have seven orientation as Number of
fx ( x 2  y 2 ) , fy( x 2  y 2 ) , fz ( x 2  y 2 ), fxyz , fz 3 , fyz 2 and fxz 2 . electrons
Present
(ii) The ‘f’ orbital is complicated in shape.
number of nlx symbol of
Rules for filling of electrons in various orbitals principal
subshell
shell
The atom is built up by filling electrons in various orbitals according Some Unexpected Electronic Configuration
to the following rules,
Some of the exceptions are important though, because they occur
(1) Aufbau’s principle with common elements, notably chromium and copper.
This principle states that the electrons are added one by one to the Cu has 29 electrons. Its excepted electronic configuration is
various orbitals in order of their increasing energy starting with the orbital
1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 2 3 d 9 but in reality the configuration is
of lowest energy. The increasing order of energy of various orbitals is
2 2 6 2 6 1 10
1s 2 s 2 p 3 s 3 p 4 s 3 d as this configuration is more stable. Similarly
1s  2s  2 p  3 s  3 p  4 s  3d  4 p  5 s  4 d  5 p  6 s  4 f
Cr has the configuration of 1s 2 2 s 2 sp 6 3 s 2 3 p 6 4 s 1 3d 5 instead of
 5d  6 p  7 s  5 f  6 d  7 p.........
1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 2 3 d 4 .
(2) (n+l) Rule
Factors responsible for the extra stability of half-filled and
In neutral isolated atom, the lower the value of (n + l) for an orbital, completely filled subshells,
lower is its energy. However, if the two different types of orbitals have the
(i) Symmetrical distribution : It is well known fact that symmetry
same value of (n + l), the orbitals with lower value of n has lower energy.
leads to stability. Thus the electronic configuration in which all the orbitals
(3) Pauli’s exclusion principle of the same subshell are either completely filled or are exactly half filled are
According to this principle “no two electrons in an atom will have more stable because of symmetrical distribution of electrons.
same value of all the four quantum numbers”. (ii) Exchange energy : The electrons with parallel spins present in
the degenerate orbitals tend to exchange their position. The energy released
If one electron in an atom has the quantum numbers n  1 , l  0 , during this exchange is called exchange energy. The number of exchanges
m  0 and s  1 / 2 , no other electron can have the same four that can take place is maximum when the degenerate orbtials (orbitals of
quantum numbers. In other words, we cannot place two electrons with the same subshell having equal energy) are exactly half-filled or completely. As a
same value of s in a 1s orbital. result, the exchange energy is maximum and so it the stability.
 46 Structure of atom

 When energy or frequency of scattered ray is lesser than the

 All lines in the visible region are of Balmer series but reverse is not
true i.e., all Balmer lines will not fall in visible region.
 A part of an atom up to penultimate shell is a kernel or atomic
core.
 If the energy supplied to hydrogen atom is less than 13.6 eV it will
awpt or absorb only those quanta which can take it to a certain higher
energy level i.e., all those photons having energy less than or more than a
particular energy level will not be absorbed by hydrogen atom, but if
energy supplied to hydrogen atom is more than 13.6eV then all photons
are absorbed and excess energy appear as kinetic energy of emitted
photo electron.
 No of nodes in any orbital  (n  l  1)
 No of nodal planes in an orbitals  l
 The d orbital which does not have four lobes is d z 2
 The d orbital whose lobes lie along the axis is d x 2 y 2
h
 Spin angular momentum  s(s  1)
2
n
 Total spin   ; where n is no of unpaired e 
2
 Magnetic moment  n(n  2) B.M. (Bohr magnetron) of n
unpaired e 
 Ion with unpaired electron in d or f orbital will be coloured.
 Exception of E.C. are Cr(24) , Cu(29) , Mo(42) , Ag(47) ,
W (74 ) , Au(79) .
incident ray, it is known as Compton effect.
 The instrument used to record solar spectrum is called
spectrometer or spectrograph developed by Bunsen and Kirchoff in 1859.
 The intensities of spectral lines decreases with increase in the value
of n . For example, the intensity of first Lyman line (2  1) is greater
than second line (3  1) and so on.
 In Balmer series of hydrogen spectrum the first line (3  2) is
also known as L line. The second line (4  2) is L  line. The line
from infinity energy shell is called limiting line.
Discovery and Properties of anode, cathode rays
neutron and Nuclear structure
1. A neutral atom (Atomic no. > 1) consists of
[CPMT 1982]
(a) Only protons
(b) Neutrons + protons
(c) Neutrons + electrons
(d) Neutron + proton + electron
2. The nucleus of the atom consists of
[CPMT 1973, 74, 78, 83, 84; MADT Bihar 1980;
DPMT 1982, 85; MP PMT 1999]

2r h (a) Proton and neutron

 No. of waves n  (where   )
 mv (b) Proton and electron
v (c) Neutron and electron
 No. of revolutions of e  per second is  .
2r (d) Proton, neutron and electron
 The solution of schrodinger wave equation gives principal, 3. The size of nucleus is of the order of
azimuthal and magnetic quantum numbers but not the spin quantum [CPMT 1982; MP PMT 1991]
number. 12 8
(a) 10 m (b) 10 m
 In the Rydberg formula, when n 2   the line produced is called
the limiting line of that series. (c) 10 15 m (d) 10 10 m
4. Positive ions are formed from the neutral atom by the
 Among various forms of visible light, violet colour has shortest
wavelength, highest frequency and highest energy. [CPMT 1976]
(a) Increase of nuclear charge
 Red coloured light has largest wavelength, least frequency and
lowest energy in visible light. (b) Gain of protons
(c) Loss of electrons
 Elements give line spectra. The line spectrum is characteristic of
the excited atom producing it. No two elements have identical line (d) Loss of protons
spectrum. 5. The electron is
 The line spectrum results from the emission of radiations from the [DPMT 1982; MADT Bihar 1980]
atoms of the elements and is therefore called as atomic spectrum.
(a)  -ray particle (b)  -ray particle
 Atoms give line spectra (known as atomic spectrum) and the molecules (c) Hydrogen ion (d) Positron
give band spectra (known as molecular spectrum).
6. Who discovered neutron
 The negative potential at which the photoelectric current becomes [IIT 1982; BITS 1988;CPMT 1977; NCERT 1974;
zero is called cut off potential or stopping potential.
MP PMT 1992; MP PET 2002]
 Structure of atom 47
(a) James Chadwick (b) William Crooks
(c) J.J. Thomson (d) Rutherford
7. The ratio of charge and mass would be greater for
[BHU 2005]
(a) Proton (b) Electron
(c) Neutron (d) Alpha
 48 Structure of atom

8. Magnitude of K.E. in an orbit is equal to [BCECE 2005] (a) Proton is nucleus of deuterium
(a) Half of the potential energy (b) Proton is ionized hy drogen m olecule
(b) Twice of the potential energy (c) Proton is ionized hy drogen atom
(c) One fourth of the potential energy (d) Proton is  -particle
(d) None of these 20. Cathode rays are made up of [A MU 1983]
9. The density of neutrons is of the order [NCERT 1980] (a) Positiv ely charged particles
(a) 10 3 kg / cc (b) 10 6 kg / cc (b) Negativ ely charged particles
(c) Neutral particles
(c) 10 9 kg / cc (d) 1011 kg / cc
(d) None of these
10. The discov ery of neutron becom es v ery late because
[CPMT 1987; AIIMS 1998] 21. Anode rays were discov ered by [DPMT 1985]
(a) Neutrons are present in nucleus (a) Goldstein (b) J. Stoney
(b) Neutrons are highly unstable particles (c) Rutherford (d) J.J. Thom son
(c) Neutrons are chargeless 22. The radius of an atom is of the order of
(d) Neutrons do not m ov e [A MU 1982; IIT 1985; MP PMT 1995]
11. The fundamental particles present in the nucleus of an (a) 10 10
cm (b) 10 13 cm
atom are [CPMT 1983, 84]
(a) Alpha particles and electrons (c) 10 15 cm (d) 10 8 cm
23. Neutron possesses [CPMT 1982]
(b) Neutrons and protons
(a) Positiv e charge (b) Negativ e charge
(c) Neutrons and electrons
(c) No charge (d) All are correct
(d) Electrons, neutrons and protons
24. Neutron is a fundamental particle carrying
12. The order of density in nucleus is
[CPMT 1990]
[NCERT 1981, CPMT 1981, 2003]
(a) A charge of + 1 unit and a m ass of 1 unit
(a) 10 8 kg / cc (b) 10 8 kg / cc (b) No charge and a m ass of 1 unit
(c) 10 9 kg / cc (d) 10 12 kg / cc (c) No charge and no m ass
13. Cathode rays are [JIPMER 1991; NCERT 1976] (d) A charg of –1 and a m ass of 1 unit
(a) Protons (b) Electrons 25. Cathode rays have [CPMT 1982]

(c) Neutrons (d)  -particles (a) Mass only (b) Charge only
(c) No m ass and charge (d) Mass and charge both
14. Number of neutron in C 12 is [BCECE 2005]
26. The size of nucleus is m easured in
(a) 6 (b) 7 [EA MCET 1988; CPMT 1994]
(c) 8 (d) 9 (a) am u (b) Angstrom
15. Heaviest particle is [DPMT 1983; MP PET 1999] (c) Ferm i (d) cm
(a) Meson (b) Neutron 27 . Which phrase would be incorrect to use
(c) Proton (d) Electron [A MU (Engg.) 1999]
16. Penetration power of prot on is (a) A m olecular of a com pound
[BHU 1985; CPMT 1982, 88] (b) A m olecule of an elem ent
(a) More than electron (b) Less than electron (c) An atom of an elem ent
(c) More than neutron (d) None (d) None of these
17. An elementary particle is [CPMT 1973] 28. Which one of the following pairs is not correctly m atched
(a) An elem ent present in a com pound [MP PET 2002]
(b) An atom present in an elem ent (a) Rutherford-Proton
(c) A sub-atom ic particle (b) J.J. Thom som -Electron
(d) A fragm ent of an atom (c) J.H. Chadwick-Neutron
18. The nucleus of helium contains (d) Bohr-Isotope
[CPMT 1972; DPMT 1982] 29. Proton was discov ered by [A FMC 2004]
(a) Four protons (a) Chadwick (b) Thom son
(b) Four neutrons (c) Goldstein (d) Bohr
(c) Two neutrons and two protons 30. The m inimum real charge on any particle which can exist
(d) Four protons and two electrons is
19. Which is correct statem ent about proton [RPMT 2000]
[CPMT 1979; MP PMT 1985; NCERT 1985; MP PET 1999] (a) 1.6  10 19 Coulomb (b) 1.6  10 10 Coulomb
 Structure of atom 49
(a) Atom ic weight (b) Atom ic num ber
(c) 4.8  10 10 Coulomb (d) Zero
(c) Equiv alent weight (d) Electron affinity
31. The nature of anode ray s depends upon 2. The nucleus of the element having atomic number 2 5 and
[MP PET 2004] atom ic weight 55 will contain
(a) Nature of electrode (b) Nature of residual gas [CPMT 1986; MP PMT 1987]
(c) Nature of discharge tube (d) All the abov e (a) 2 5 protons and 3 0 neutrons
32. One would expect proton to hav e v ery large (b) 2 5 neutrons and 3 0 protons
(c) 55 protons
[Pb. CET 2004]
(d) 55 neutrons
(a) Ionization potential (b) Radius
3. If W is atom ic weight and N is the atom ic num ber of an
(c) Charge (d) Hy dration energy elem ent, then [CPMT 1971, 80, 89]
33. The m ass of a m ol of proton and electron is (a) Num ber of e 1  W  N
(a) 6.023  10 23 g (b) 1.008 g and 0.55mg (b) Num ber of 0 n 1  W  N

(c) 9.1  10 28 kg (d) 2 gm (c) Num ber of 1 H 1  W  N

34. The average distance of an electron in an atom from its (d) Num ber of 0 n 1  N
nucleus is of the order of [MP PET 1996]
4. The total number of neutrons in dipositive zinc ions with
(a) 10 6 m (b) 10 6 m mass number 70 is [IIT 1979; Bih a r MEE 1997]

(c) 10 10 m (d) 10 15 m (a) 3 4 (b) 4 0

(c) 3 6 (d) 3 8
35. The mass of 1 mole of electrons is [Pb. CET 2004]
5. Which of the following are isoelectronic with one another
(a) 9.1  10 28 g (b) 1.008 mg [NCERT 1983; EAMCET 1989]

(c) 0.55 mg (d) 9.1  10 27
g (a) Na and Ne (b) K  and O
(c) Ne and O (d) Na  and K 
36. The ratio of specific charge of a proton and an  -particle
6. The num ber of electrons in one m olecule of CO 2 are
is
[IIT 1979; MP PMT 1994; RPMT 1999]
[MP PET 1999]
(a) 2 2 (b) 4 4
(a) 2 : 1 (b) 1 : 2
(c) 6 6 (d) 88
(c) 1 : 4 (d) 1 : 1
7. Chlorine atom differs from chloride ion in the num ber of
37 . Ratio of masses of proton and electron is [BHU 1998] [NCERT 1972; MP PMT 1995]
(a) Infinite (b) 1.8  10 3 (a) Proton (b) Neutron
(c) Electrons (d) Protons and electrons
(c) 1 .8 (d) None of these
8. CO has sam e electrons as or the ion that is isoelectronic
38. Splitting of signals is caused by [Pb. PMT 2000]
with CO is [CPMT 1984; IIT 1982;
(a) Proton (b) Neutron EA MCET 1990; CBSE PMT 1997]
(c) Positron (d) Electron (a) N 2 (b) CN 
39. The proton and neutron are collectiv ely called as
(c) O 2 (d) O 2
[MP PET 2001]
9. The m ass of an atom is constituted m ainly by
(a) Deutron (b) Positron
[DPMT 1984, 91; AFMC 1990]
(c) Meson (d) Nucleon
(a) Neutron and neutrino (b) Neutron and electron
40. Which of the following has the sam e m ass as that of an (c) Neutron and proton (d) Proton and electron
electron [A FMC 2002]
10. The atom ic num ber of an elem ent represents
(a) Photon (b) Neutron [CPMT 1983; CBSE PMT 1990; NCERT 1973; AMU 1984]
(c) Positron (d) Proton (a) Num ber of neutrons in the nucleus
41. What is the ratio of m ass of an electron to the m ass of a (b) Num ber of protons in the nucleus
proton (c) Atom ic weight of elem ent
[UPSEAT 2004] (d) Valency of elem ent
11. An atom has 2 6 electrons and its atomic weight is 56. The
(a) 1 : 2 (b) 1 : 1
num ber of neutrons in the nucleus of the atom will be
(c) 1 : 1 83 7 (d) 1 : 3 [CPMT 1980]
(a) 2 6 (b) 3 0
Atomic number, Mass number, Atomic species
(c) 3 6 (d) 56
12. The m ost probable radius (in pm) for finding the electron
1. The number of electrons in an atom of an element is equal
to its [BHU 1979] in He  is [A IIMS 2005]
 50 Structure of atom
(a) 0.0 (b) 52 .9 (b) The number of nucleons is double of the number of
(c) 2 6 .5 (d) 1 05.8 electrons
(c) The number of protons is half of the number of neutrons
13. The number of unpaired electrons in the Fe 2  ion is
(d) The number of nucleons is double of the atomic num ber
[MP PET 1989; KCET 2000]
(a) 0 (b) 4 24. Pick out the isoelectronic structures from the following
(c) 6 (d) 3 CH 3 H3O NH 3 CH 3 [IIT 1993]
I II III IV
14. A sodium cation has different num ber of electrons from
(a) I and II (b) I and IV
(a) O 2  (b) F 
(c) I and III (d) II, III and IV
(c) Li  (d) Al 3
25. Number of electrons in CONH 2 is [A MU 1988]
15. An atom which has lost one electron would be
[CPMT 1986] (a) 2 2 (b) 2 4
(a) Negativ ely charged (c) 2 0 (d) 2 8
(b) Positiv ely charged 26. The atomic number of an element having the valency shell
(c) Electrically neutral electronic configuration 4 s 2 4 p 6 is [MP PMT 1991]
(d) Carry double positiv e charge (a) 3 5 (b) 3 6
16. Num ber of electrons in the outermost orbit of the element (c) 3 7 (d) 3 8
of atomic num ber 15 is [CPMT 1988, 93]
27 . The present atom ic weight scale is based on
(a) 1 (b) 3 [EA MCET 1988; MP PMT 2002]
(c) 5 (d) 7
(a) C 12
(b) O 16
17. The atom ic weight of an elem ent is double its atom ic
num ber. If there are four electrons in 2 p orbital, the (c) H 1 (d) C 13
elem ent is [A MU 1983] 28. Isoelectronic species are [EA MCET 1989]
(a) C (b) N 
(a) K , Cl 
(b) Na , Cl 


(c) O (d) Ca
(c) Na, Ar (d) Na  , Ar
18. An atom has the electronic configuration of 1s 2 ,2 s 2 2 p 6 ,
29. If the atom ic weight of an element is 2 3 tim es that of the
3 s 2 3 p 6 3d 10 ,4 s 2 4 p 5 . Its atom ic weight is 80. Its atom ic lightest element and it has 1 1 protons, then it contains
num ber and the number of neutrons in its nucleus shall [EA MCET 1986; AFMC 1989]
be
(a) 1 1 protons, 2 3 neutrons, 1 1 electrons
[MP PMT 1987]
(b) 1 1 protons, 1 1 neutrons, 1 1 electrons
(a) 3 5 and 4 5 (b) 4 5 and 3 5
(c) 4 0 and 4 0 (d) 3 0 and 50 (c) 1 1 protons, 1 2 neutrons, 1 1 electrons
19. Which of the following particles has m ore electrons than (d) 1 1 protons, 1 1 neutrons, 2 3 electrons
neutrons 30. Which of the following oxides of nitrogen is isoelectronic
 with CO 2 [CBSE PMT 1990]
(a) C (b) F
(c) O 2
(d) Al 3 (a) NO 2 (b) N 2 O
20. Com pared with an atom of atomic weight 1 2 and atom ic (c) NO (d) N 2 O 2
num ber 6 , the atom of atom ic weight 1 3 and atom ic
31. The ratio between the neutrons in C and Si with respect
num ber 6 [NCERT 1971] to atom ic m asses 1 2 and 2 8 is [
(a) Contains m ore neutrons(b) Contains m ore electrons
(a) 2 : 3 (b) 3 : 2
(c) Contains m ore protons(d) Is a different elem ent
(c) 3 : 7 (d) 7 : 3
21. In the nucleus of 20 Ca 40 there are 32. The atom ic num ber of an elem ent is alway s equal to
[CPMT 1990; EAMCET 1991] [MP PMT 1994]
(a) 40 protons and 2 0 electrons (a) Atom ic weight div ided by 2
(b) 20 protons and 4 0 electrons (b) Num ber of neutrons in the nucleus
(c) 20 protons and 2 0 neutrons (c) Weight of the nucleus
(d) 20 protons and 4 0 neutrons (d) Electrical charge of the nucleus
22. Na  ion is isoelectronic with [CPMT 1990] 33. Which of the following is isoelectronic with carbon atom
2 [MP PMT 1994; UPSEAT 2000]
(a) Li  (b) Mg

(a) Na (b) Al 3 
(c) Ca 2 (d) Ba 2
23. Ca has atomic no. 2 0 and atomic weight 4 0. Which of the (c) O 2  (d) N 
following statem ents is not correct about Ca atom 34. CO 2 is isostructural with
[MP PET 1993] [IIT 1986; MP PMT 1986, 94, 95]
(a) The num ber of electrons is sam e as the num ber of (a) SnCl 2 (b) SO 2
neutrons
 Structure of atom 51
(c) HgCl2 (d) All the abov e 47 . The num ber of electrons in [19
40
K ]1 is
35. The hy dride ions (H  ) are isoelectronic with [CPMT 1997; AFMC 1999]
(a) 1 9 (b) 2 0
[A FMC 1995; Bihar MEE 1997]
(c) 1 8 (d) 4 0
(a) Li (b) He  48. The number of electrons and neutrons of an element is 1 8
(c) He (d) Be and 2 0 respectiv ely . Its m ass num ber is
[CPMT 1997; Pb. PMT 1999; MP PMT 1999]
36. The num ber of electrons in the nucleus of C 12 is
[A FMC 1995] (a) 1 7 (b) 3 7
(c) 2 (d) 3 8
(a) 6 (b) 1 2
49. Num ber of protons, neutrons and electrons in the
(c) 0 (d) 3
37 . An elem ent has electronic configuration 2 , 8, 1 8, 1 . If its elem ent 89
231
Y is [A FMC 1997]
atom ic weight is 6 3 , t hen how m any neutrons will be (a) 89, 2 3 1 , 89 (b) 89, 89, 2 4 2
present in its nucleus (c) 89, 1 4 2 , 89 (d) 89, 7 1 , 89
(a) 3 0 (b) 3 2 50. Be 2  is isoelectronic with [EA MCET 1998]
(c) 3 4 (d) 3 3 2 
(a) Mg (b) Na
38. The nucleus of the elem ent E 45 contains 
21 (c) Li (d) H 
(a) 4 5 protons and 2 1 neutrons 51. An isostere is [UPSEA T 1999]
(b) 2 1 protons and 2 4 neutrons (a) NO 2 and O 3 (b) NO 2 and PO43 
(c) 2 1 protons and 4 5 neutrons
(d) 2 4 protons and 2 1 neutrons (c) CO 2 , N 2 O, NO 3 (d) ClO4 and OCN 
39. Neutrons are found in atom s of all elem ents except in 52. Nitrogen atom has an atomic number of 7 and oxygen has
[MP PMT 1997] an atomic number 8. The total num ber of electrons in a
(a) Chlorine (b) Oxy gen nitrate ion will be [Pb. PMT 2000]
(a) 8 (b) 1 6
(c) Argon (d) Hy drogen
(c) 3 2 (d) 6 4
40. The m ass number of an anion, X 3  , is 14. If there are ten 53. If m olecular mass and atom ic m ass of sulphur are 2 56
electrons in the anion, the num ber of neutron s in the and 32 respectively, its atom icity is [RPET 2000]
nucleus of atom , X 2 of the elem ent will be (a) 2 (b) 8
[MP PMT 1999] (c) 4 (d) 1 6
(a) 1 0 (b) 1 4 54. The nitride ion in lithium nitride is com posed of
(c) 7 (d) 5 [KCET 2000]
41. Which of the following are isoelectronic species (a) 7 protons + 1 0 electrons
I  CH 3 , II  NH 2 , III  NH 4 , IV  NH 3 [CPMT 1999] (b) 1 0 protons + 1 0 electrons
(c) 7 protons + 7 protons
(a) I, II, III (b) II, III, IV (d) 1 0 protons + 7 electrons
(c) I, II, IV (d) I and II 55. The atomic number of an elem ent is 1 7 . The num ber of
42. The charge on the atom containing 1 7 protons, 1 8 orbitals containing electron pairs in its v alence shell is
neutrons and 18 electrons is [A IIMS 1996] [CPMT 2001]
(a) 1 (b) 2 (a) Eight (b) Six
(c) 1 (d) Zero (c) Three (d) Two
43. Number of unpaired electrons in inert gas is[CPMT 1996] 56. The atomic number of an element is 3 5 and mass number
(a) Zero (b) 8 is 81 . The number of electrons in the outer m ost shell is
(c) 4 (d) 1 8 [UPSEAT 2001]
44. In neutral atom , which particles are equiv alent (a) 7 (b) 6
[RPMT 1997] (c) 5 (d) 3
   
(a) p , e (b) e , e 57 . Which of the following is not isoelectronic[MP PET 2002]

(c) e , p 
(d) p , n  o
(a) Na  (b) Mg 2 
45. Nuclei tend to have m ore neutrons than protons at high (c) O 2  (d) Cl 
mass numbers because [Roor kee Qu a l ify in g 1998]
58. The charge of an electron is  1.6  10 19 C. The v alue of
(a) Neutrons are neutral particles 
(b) Neutrons hav e m ore m ass than protons free charge on Li ion will be
(c) More neutrons m inim ize the coulom b repulsion [A FMC 2002; KCET (Engg.) 2002]
19
(d) Neutrons decrease the binding energy (a) 3.6  10 C (b) 1  10 19 C
46. Which one of the following is not isoelectronic with O 2  (c) 1.6  10 19 C (d) 2.6  10 19 C
[CBSE PMT 1994] 59. Iso-electronic species is [RPMT 2002]
(a) N 3  (b) F  
(a) F , O 2 
(b) F , O
(c) Tl  (d) Na 
 52 Structure of atom

(c) F  , O  (d) F  , O 2 (b) 4 protons and 7 electrons

(c) 4 protons and 1 0 electrons
60. An elem ent hav e atom ic weight 4 0 and it’s electronic
(d) 1 0 protons and 7 electrons
configuration is 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 . Then its atom ic
number and number of neutrons will be [RPMT 2002] 73. Num ber of neutrons in heav y hy drogen atom is
(a) 1 8 and 2 2 (b) 2 2 and 1 8 [MP PMT 1986]

(c) 2 6 and 2 0 (d) 4 0 and 1 8 (a) 0 (b) 1

61. The nucleus of tritium contains [MP PMT 2002] (c) 2 (d) 3
(a) 1 proton + 1 neutron (b) 1 proton + 3 neutron 74. Which of the following is alway s a whole num ber
(c) 1 proton + 0 neutron (d) 1 proton + 2 neutron [CPMT 1976, 81, 86]
62. Which one of the following groupings represents a (a) Atom ic weight (b) Atom ic radii
collection of isoelectronic species [A IEEE 2003] (c) Equiv alent weight (d) Atom ic num ber
(a) Na  , Ca 2  , Mg 2  (b) N 3  , F  , Na 
Atomic models and Planck's quantum theory
(c) Be, Al 3  , Cl  (d) Ca 2  , Cs  , Br
63. Which of the following are isoelectronic and isostructural 1. Rutherford's experiment on scattering of particles showed
NO 3 , CO 32  , ClO3 , SO 3 [IIT Scr een in g 2003] for the first tim e that the atom has
(a) NO 3 , CO 32  (b) SO 3 , NO 3 [IIT 1981; NCERT 1981; CMC Vellore 1991;
CPMT 1984; Kurukshetra CEE 1998]
(c) ClO3 , CO 32  (d) CO 32  , SO 3
(a) Electrons (b) Protons
64. The number of electrons in Cl  ion is [MP PMT 2003] (c) Nucleus (d) Neutrons
(a) 1 9 (b) 2 0
2. Rutherford's scattering experiment is related to the size of
(c) 1 8 (d) 3 5 the
65. The number of neutron in tritium is [CPMT 2003]
[IIT 1983; MADT Bihar 1995; BHU 1995]
(a) 1 (b) 2
(c) 3 (d) 0 (a) Nucleus (b) Atom
66. Tritium is the isotope of [CPMT 2003] (c) Electron (d) Neutron
(a) Hy drogen (b) Oxy gen 3. Rutherford's alpha particle scattering experim ent
(c) Carbon (d) Sulpher ev entually led to the conclusion that[IIT 1986; RPMT 2002]
67 . The atomic number of an element is 3 5. What is the total (a) Mass and energy are related
num ber of electrons present in all the p-orbitals of the
ground state atom of that elem ent (b) Electrons occupy space around the nucleus
[EA MCET (Engg.) 2003] (c) Neutrons are buried deep in the nucleus
(a) 6 (b) 1 1 (d) The point of im pact with m atter can be precisely
(c) 1 7 (d) 2 3 determ ined
68. The nucleus of an element contain 9 protons. Its v alency
4. Bohr's m odel can explain [IIT 1985]
would be [MP PET 2004]
(a) 1 (b) 3 (a) The spectrum of hy drogen atom only
(c) 2 (d) 5 (b) Spectrum of atom or ion containing one electron only
69. The compound in which cation is isoelectronic with anion is
[UPSEAT 2004] (c) The spectrum of hy drogen m olecule
(a) NaCl (b) CsF (d) The solar spectrum
(c) NaI (d) K 2 S 5. When atoms are bombarded with alpha particles, only a
70. Which among the following species have the same number of few in m illion suffer deflection, others pass out
electrons in its outerm ost as well as penultim ate shell undeflected. This is because[MNR 1979; NCERT 1980; A FMC 19
[DCE 2004] (a) The force of repulsion on th e m oving alpha particle is
(a) Mg 2
(b) O 2 sm all
(b) The force of attraction on the alpha particle to the
(c) F  (d) Ca 2 
oppositely charged electrons is v ery sm all
7 1. Six protons are found in the nucleus of
[CPMT 1977, 80, 81; NCERT 1975, 78] (c) There is only one nucleus and large num ber of
electrons
(a) Boron (b) Lithium
(c) Carbon (d) Helium (d) The nucleus occupies m uch sm aller v olum e
com pared to the v olum e of the atom
72. The nitrogen atom has 7 protons and 7 electrons, the
3 6. Positronium consists of an electron and a positron (a
nitride ion ( N ) will hav e [NCERT 1977]
particle which has the sam e m ass as an electron, but
(a) 7 protons and 1 0 electrons opposite charge) orbiting round their com m on centre of
 Structure of atom 53
m ass. Calculate the value of the Rydberg constant for this (a) Positiv e ray analy sis
sy stem. (b)  -ray scattering experim ents
(a) R / 4 (b) R / 2 (c) X-ray analy sis
(c) 2 R (d) R (d) Discharge tube experim ents
15. Electron occupies the av ailable orbital singly before
7. When  -particles are sent through a thin m etal foil, most pairing in any one orbital occurs, it is [CBSE PMT 1991]
of them go straight through the foil because (one or m ore (a) Pauli's exclusion principle
are correct) [IIT 1984]
(b) Hund's Rule
(a) Alpha particles are m uch heav ier than electrons
(c) Heisenberg's principle
(b) Alpha particles are positiv ely charged
(b) Prout's hy pothesis
(c) Most part of the atom is em pty space 16. The wav elength of a spectral line for an electronic
(d) Alpha particles m ov e with high v elocity transition is inversely related to [IIT 1988]
8. When an electron jumps from L to K shell (a) The number of electrons undergoing the transition
[CPMT 1983] (b) The nuclear charge of the atom
(a) Energy is absorbed (c) The difference in the energy of the energy lev els
inv olv ed in the transition
(b) Energy is released
(d) The v elocity of the electron undergoing the transition
(c) Energy is som etim es absorbed and som etim es
17. When an electron drops from a higher energy lev el to a
released
low energy level, then [A MU 1985]
(d) Energy is neither absorbed nor released (a) Energy is em itted
9. When bery llium is bom barded with  -particles, (b) Energy is absorbed
extrem ely penetrating radiations which cannot be
(c) Atom ic num ber increases
deflected by electrical or m agnetic field are giv en out.
These are (d) Atom ic num ber decreases
[CPMT 1983] 18. Dav isson and Germ er's experim ent showed that
(a) A beam of protons (b)  -ray s [MA DT Bihar 1983]
(a)  -particles are electrons
(c) A beam of neutrons (d) X-ray s
(b) Electrons com e from nucleu s
10. Which one of the following is not the characteristic of
Planck's quantum theory of radiation [A IIMS 1991] (c) Electrons show wav e nature
(a) The energy is not absorbed or em itted in whole (d) None of the abov e
num ber or m ultiple of quantum 19. When an electron jum ps from lower to higher orbit, its
(b) Radiation is associated with energy energy [MA DT Bi h a r 1982]
(a) Increases (b) Decreases
(c) Radiation energy is not em itted or absorbed conti -
nuously but in the form of sm all packets called (c) Rem ains the sam e (d) None of these
quanta 20. Experimental ev idence for the existence of the a tom ic
nucleus com es from [CBSE PMT 1989]
(d) This m agnitude of energy associated with a quantum
is proportional to the frequency (a) Millikan's oil drop experim ent
(b) Atom ic em ission spectroscopy
11. The spectrum of He is expected to be sim ilar to
(c) The m agnetic bending of cathode ray s
[A IIMS 1980, 91; DPMT 1983; MP PMT 2002]
(d) Alpha scattering by a thin m etal foil
(a) H (b) Li  21. Which of the following statem ents does not form part of
Bohr's m odel of the hydrogen atom [CBSE PMT 1989]
(c) Na (d) He 
(a) Energy of the electrons in the orbit is quantized
12. Energy of orbit [DPMT 1984, 91]
(b) The electron in the orbit nearest the nucleus has the
(a) Increases as we m ov e away from nucleus
lowest energy
(b) Decreases as we m ov e away from nucleus
(c) Electrons rev olv e in different orbits around the
(c) Rem ains sam e as we m ov e away from nucleus nucleus
(d) None of these (d) The position and velocity of the electrons in the orbit
13. Bohr m odel of an atom could not account for cannot be determ ined sim ultaneously
(a) Em ission spectrum 22. When  -particles are sent through a tin m etal foil, m ost
(b) Absorption spectrum of them go straight through the foil as [EA MCET 1983]
(c) Line spectrum of hy drogen (a)  -particles are m uch heav ier than electrons
(d) Fine spectrum
(b)  -particles are positiv ely charged
14. Existence of positively charged nucleus was established by
(c) Most part of the atom is em pty space
[CBSE PMT 1991]
 54 Structure of atom

(d)  -particles m ov e with high v elocity 2 2 m 4 e 2 z 2 2 2 me 2 z 2

(a) E n   (b) E n  
23. The energy of second Bohr orbit of the hydrogen atom is – n2h2 n2h2
3 2 8 kJ mol–1, hence the energy of fourth Bohr orbit would be
2 me z
2 4 2
2m 2 e 2 z 4
[CBSE PMT 2005] (c) E n   (d) E n  
n2h2 n2h2
(a) – 4 1 kJ mol–1 (b) –1 3 1 2 kJ mol–1
33. Who m odified Bohr's theory by introducing ellipt ical
(c) –1 6 4 kJ mol–1 (d) – 82 kJ mol–1
orbits for electron path [CBSE PMT 1999; A FMC 2003]
24. When an electron rev olv es in a stationary orbit then (a) Hund (b) Thom son
[MP PET 1994] (c) Rutherford (d) Som m erfield
(a) It absorbs energy 34. Bohr's radius can have [DPMT 1996]
(b) It gains kinetic energy
(a) Discrete v alues (b) ve v alues
(c) It em its radiation
(c) ve v alues (d) Fractional v alu es
(d) Its energy rem ains constant 35. The first use of quantum theory to explain the structure of
25. A m ov ing particle m ay hav e wav e m otion, if atom was made by[IIT 1997; CPMT 2001; J&K CET 2005]
(a) Its m ass is v ery high (a) Heisenberg (b) Bohr
(b) Its v elocity is negligible (c) Planck (d) Einstein
(c) Its m ass is negligible 36. An electronic transition from 1s orbital of an atom causes
(d) Its m ass is v ery high and v elocity is negligible [JIPMER 1997]
26. The postulate of Bohr theory that electrons jum p from (a) Absorption of energy
one orbit to the other, rather than flow is according to (b) Release of energy
(a) The quantisation concept (c) Both release or absorption of energy
(b) The wav e nature of electron (d) Unpredictable
(c) The probability expression for electron 37 . In an element going away from nucleus, the energy of
(d) Heisenberg uncertainty principle particle [RPMT 1997]
27 . The frequency of an electrom agnetic radiation is (a) Decreases (b) Not changing
2  10 Hz . What is its wav elength in m etres
6
(c) Increases (d) None of these
(Velocity of light  3  10 8 ms 1 ) 38. The  -particle scattering experim ent of Rutherford
concluded that [Or issa JEE 1997]
(a) 6.0  10 14
(b) 1.5  10 4
(a) The nucleus is m ade up of protons and neutrons
(c) 1.5  10 2
(d) 0.66  10 2 (b) The number of electrons is exactly equal to number of
28. What is the packet of energy called [A FMC 2005] protons in atom
(a) Electron (b) Photon (c) The positive charge of the atom is concentrated in a
(c) Positron (d) Proton v ery sm all space
29. The energy of an electron in n th orbit of hydrogen atom is (d) Electrons occupy discrete energy lev els
[MP PET 1999] 39. Wavelength associated with electron m otion [BHU 1998]
13 .6 13 .6 (a) Increases with increase in speed of electron
(a) eV (b) eV (b) Rem ains sam e irrespectiv e of speed of electron
n4 n3
13 .6 13 .6 (c) Decreases with increase in speed of e 
(c) eV (d) eV (d) Is zero
n2 n
40. The elem ent used by Rutherford in his famous scattering
30. If wav elength of photon is 2.2  10 11 m, h  6.6  10 34 J- experim ent was [KCET 1998]
sec, then m om entum of photon is [MP PET 1999] (a) Gold (b) Tin
(a) 3  10 23 kg ms 1 (b) 3.33  10 22 kg ms 1 (c) Silv er (d) Lead
41. If electron falls from n  3 to n  2 , then emitted energy
(c) 1.452  10 44 kg ms 1 (d) 6.89  10 43 kg ms 1 is
31. The expression for Bohr's radius of an atom is [A FMC 1997; MP PET 2003]
[MP PMT 1999] (a) 10.2eV (b) 12.09eV
n2h2 n2h2 (c) 1.9 eV (d) 0.65eV
(a) r  (b) r  42. The radius of the nucleus is related to the m ass num ber
4 me z
2 4 2
4 2 me 2 z
A by [
n2h2 n2h2
(c) r  (d) r  (a) R  R o A 1/2
(b) R  R o A
4 2 me 2 z 2 4 2 m 2 e 2 z 2
(c) R  R o A 2
(d) R  R o A 1 / 3
32. The energy of an electron revolving in n th Bohr's orbit of
an atom is given by the expression [MP PMT 1999] 43. The specific charge of proton is 9.6  10 6 C kg 1 then for an
 -particle it will be [MH CET 1999]
 Structure of atom 55
(a) 38.4  10 7 C kg 1 (b) 19.2  10 7 C kg 1 54. Rutherford’s  -particle scattering experiment proved that
atom has [MP PMT 2001]
(c) 2.4  10 7 C kg 1 (d) 4.8  10 7 C kg 1 (a) Electrons (b) Neutron
44. In hy drogen spectrum the different lines of Ly m an series (c) Nucleus (d) Orbitals
are present is [UPSEA T 1999] 55. Wav elength of spectral line em itted is inv ersely
(a) UV field (b) I R field proportional to [
(a) Radius (b) Energy
(c) Visible field (d) Far I R field
(c) Velocity (d) Quantum num ber
45. Which one of the following is considered as the m ain
postulate of Bohr’s m odel of atom [A MU 2000] 56. The energy of a radiation of wavelength 8000 Å is E1 and
(a) Protons are present in the nucleus energy of a radiation of wavelength 16000 Å is E 2 . What
(b) Electrons are rev olv ing around the nucleus is the relation between these two [Kerala CET 2005]
(c) Centrifugal force produced due to the rev olv ing (a) E1  6 E 2 (b) E1  2E 2
electrons balances the force of attraction between the (c) E1  4 E 2 (d) E1  1 / 2 E2
electron and the protons
(e) E1  E 2
(d) Angular momentum of electron is an integral multiple of
h 57 . The form ation of energy bonds in solids are in accordance
with [DCE 2001]
2
(a) Heisenberg’s uncertainty principle
46. The electronic energy levels of the hydrogen atom in the
(b) Bohr’s theory
Bohr’s theory are called [A MU 2000]
(c) Ohm ’s law
(a) Ry dberg lev els (b) Orbits
(d) Rutherford’s atom ic m odel
(c) Ground states (d) Orbitals 58. The frequency of y ellow light having wavelength 600 nm
47 . The energy of a photon is calculated by [Pb. PMT 2000] is
(a) E  h (b) h  E [MP PET 2002]
E h (a) 5.0  10 Hz14
(b) 2.5  10 Hz
7
(c) h  (d) E 
  (c) 5.0  10 7 Hz (d) 2.5  10 14 Hz
48. Visible range of hy drogen spectrum will contain the 59. The v alue of the energy for the first excited state of
following series [RPET 2000] hy drogen atom will be [MP PET 2002]
(a) Pfund (b) Ly m an (a)  13.6 eV (b)  3.40 eV
(c) Balm er (d) Brackett (c)  1.51 eV (d)  0.85 eV
49. Radius of the first Bohr’s orbit of hy drogen atom is 60. Bohr m odel of atom is contradicted by [MP PMT 2002]
[RPET 2000]
(a) Pauli’s exclusion principle
(a) 1 .06 Å (b) 0 .22 Å (b) Planck quantum theory
(c) Heisenberg uncertainty principle
(c) 0 .28 Å (d) 0 .53 Å
(d) All of these
50. In Balm er ser ies of hy drogen atom spectrum which
61. Which of the following is not true in Rutherford’s nuclear
electronic transition causes third line [MP PMT 2000]
m odel of atom [Or issa JEE 2002]
(a) Fifth Bohr orbit to second one (a) Protons and neutrons are present inside nucleus
(b) Fifth Bohr orbit to first one (b) Volum e of nucleus is v ery sm all as com pared to
(c) Fourth Bohr orbit to second one v olum e of atom
(d) Fourth Bohr orbit to first one (c) The num ber of protons and neutrons are alway s
51. Energy of electron of hydrogen atom in second Bohr orbit equal
is (d) The num ber of electrons and protons are alway s
[MP PMT 2000] equal
(a)  5.44  10 19 J (b)  5.44  10 19 kJ 62. The em ission spectrum of hydrogen is found to satisfy the
expression for the energy change. E (in joules) such
(c)  5.44  10 19 cal (d)  5.44  10 19 eV
 1 1 
52. If change in energy (E)  3  10 8 J , h  6.64  10 34 J - s that E  2 .18  10 2  2  J where n 1 = 1, 2 , 3 ….. and
 n1 n2 
and c  3  10 8 m/s, then wavelength of the light is n 2 = 2 , 3 , 4 ……. The spectral lines correspond to Paschen
[CBSE PMT 2000] series to [UPSEA T 2002]
(a) 6.36  10 Å3
(b) 6.36  10 5 Å (a) n1  1 and n 2  2, 3, 4
8
(c) 6.64  10 Å (d) 6.36  10 18 Å (b) n1  3 and n 2  4, 5, 6
53. The radius of first Bohr’s orbit for hydrogen is 0.53 Å. The
radius of third Bohr’s orbit would be [MP PMT 2001] (c) n1  1 and n 2  3, 4, 5
(a) 0.7 9 Å (b) 1 .59 Å (d) n1  2 and n 2  3, 3, 5
(c) 3 .1 8 Å (d) 4 .7 7 Å
(e) n1  1 and n 2  infinity
 56 Structure of atom
63. The ratio between kinetic energy and the total energy of 74. The wav elength of the radiation em itted, when in a
the electrons of hydrogen atom according to Bohr’s m odel hy drogen atom electron falls from infinity to stationary
is state 1 , would be (Ry dberg constant  1.097 10 7 m 1 )
[Pb. PMT 2002]
[A IEEE 2004]
(a) 2 : 1 (b) 1 : 1 (a) 4 06 nm (b) 1 92 nm
(c) 1 : – 1 (d) 1 : 2
(c) 91 nm (d) 9.110 8 nm
64. Energy of the electron in Hy drogen atom is giv en by
[A MU (Engg.) 2002] 75. In Bohr’s m odel, atomic radius of the first orbit is  , the
131.38 131.33 radius of the 3 rd orbit, is [MP PET 1997; Pb. CET 2001]
(a) En   kJ mol 1 (b) En   kJ mol 1 (a)  / 3 (b) 
n2 n
1313.3 313.13 (c) 3 (d) 9
(c) En   kJ mol 1 (d) En   kJ mol 1
n 2
n 2 76. According to Bohr’s principle, the relation between
65. Ratio of radii of second and first Bohr orbits of H atom principle quantum number (n) and radiu s of orbit is [BHU 2004]
[BHU 2003] (a) r  n (b) r  n 2
(a) 2 (b) 4 1 1
(c) 3 (d) 5 (c) r  (d) r  2
n n
66. The frequency corresponding to transition n  2 to n  1 77. The ionisation potential of a hydrogen atom is –1 3 .6 eV.
in hydrogen atom is [MP PET 2003] What will be the energy of the atom corresponding to
(a) 15.66  10 10 Hz (b) 24.66  10 14 Hz n2
[Pb. CET 2000]
(c) 30.57  10 14 Hz (d) 40.57  10 24 Hz
(a) –3 .4 eV (b) –6.8 eV
67 . The m ass of a photon with a wav elength equal to
(c) –1 .7 eV (d) – 2 .7 eV
1.54  10 8 cm is [Pb. PMT 2004] 7 8. The energy of electron in hy drogen atom in its grounds
(a) 0.8268  10 34 kg (b) 1.2876  10 33 kg state is –13.6 eV. The energy of the level corresponding to
the quantum number equal to 5 is [Pb. CET 2002]
(c) 1.4285  10 32 kg (d) 1.8884  10 32 kg (a) –0.54 eV (b) – 0.85 eV
68. Splitting of spectral lines under the influence of m agnetic (c) – 0.64 eV (d) – 0.4 0 eV
field is called [MP PET 2004] 79. The positive charge of an atom is [A FMC 2002]
(a) Zeem an effect (b) Stark effect (a) Spread all ov er the atom
(c) Photoelectric effect (d) None of these (b) Distributed around the nucleus
69. The radius of electron in the first excited state of (c) Concentrated at the nucleus
hy drogen atom is [MP PMT 2004] (d) All of these
(a) a0 (b) 4a0 80. A metal surface is exposed to solar radiations [DPMT 2005]
(c) 2a0 (d) 8a0 (a) The em itted electrons hav e energy less than a
m aximum value of energy depending upon frequency
70. The ratio of area cov ered by second orbital to the first of incident radiations
orbital is [A FMC 2004] (b) The em itted electrons hav e energy less than
(a) 1 : 2 (b) 1 : 1 6 m aximum value of energy depending upon intensity
(c) 8 : 1 (d) 1 6 : 1 of incident radiation
7 1. Tim e taken for an electron to com plete one rev olution in (c) The em itted electrons hav e zero energy
the Bohr orbit of hydrogen atom is [Ker a l a PMT 2004] (d) The em itted electrons have energy equal to energy of
4 2 mr 2 nh photos of incident light
(a) (b) 81. Which of the following transitions hav e m inim um
nh 4 2 mr wav elength [DPMT 2005]
(c)
nh
(d)
h (a) n4  n1 (b) n 2  n1
4 2 mr 2 2mr
(c) n4  n 2 (d) n3  n1
72. The radius of which of the following orbit is sam e as that
of the first Bohr's orbit of hy drogen atom Dual nature of electron
[IIT Screening 2004]
(a) He  (n  2) (b) Li 2 (n  2) 1. De broglie equation describes the relationship of wavelengt h
2 3
(c) Li (n  3) (d) Be (n  2) associated with the motion of an electron and its[MP PMT
1986]
73. The frequency of radiation em itted when the electron falls
from n  4 to n  1 in a hy drogen atom will be (Giv en (a) Mass (b) Energy
18 1 (c) Mom entum (d) Charge
ionization energy of H  2.18  10 J atom and
34 2. The wav e nature of an electron was first giv en by
h  6.625  10 Js ) [CBSE PMT 2004]
[CMC V ellore 1991; Pb. PMT 1998; CPMT 2004]
(a) 3.08  1015 s 1 (b) 2.00  1015 s 1 (a) De-Broglie (b) Heisenberg
(c) 1.54  1015 s 1 (d) 1.03  1015 s 1 (c) Mosley (d) Som m erfield
 Structure of atom 57
3. Am ong the following for which one m athem atical 13. The de-Broglie wavelength associated with a particle of
expression  
h
stands m ass 10 6 kg m ov ing with a v elocity of 10 ms 1 , is
p [A IIMS 2001]
(a) De Broglie equation (b) Einstein equation 22 29
(a) 6.63  10 m (b) 6.63  10 m
(c) Uncertainty equation (d) Bohr equation
4. Which one of the following explains light both as a stream (c) 6.63  10 31 m (d) 6.63  10 34 m
of particles and as wav e m otion 14. What is the de-Broglie wav elength associated with the
[A IIMS 1983; IIT 1992; UPSEAT 2003] hydrogen electron in its third orbit [A MU (En gg.) 2002]
(a) Diffraction (b)   h / p (a) 9.96  10 10 cm (b) 9.96  10 8 cm
(c) Interference (d) Photoelectric effect
(c) 9.96  10 4 cm (d) 9.96  10 8 cm
5. In which one of the following pairs of experim ental
observ ations and phenom enon does the experim ental 15. If the v elocity of hy drogen m olecule is 5  10 4 cm sec 1 ,
observation correctly account for phenomenon [Ade-Broglie
then its IIMS 1983] wavelength is [MP PMT 2003]
Experimental observa t ion Ph en om en on (a) 2 Å (b) 4 Å
(a) X -ray spectra Charge on the nucleus (c) 8 Å (d) 1 00 Å
(b)  -particle scattering Quantized electron orbit 16. A 2 00g golf ball is m oving with a speed of 5 m per hour.
(c) Em ission spectra The quantization of energy The associated wav e length is (h  6.625  10 34 J - sec)
(d) The photoelectric effect The nuclear atom [MP PET 2003]
6. Which of the following expressions giv es the de-Broglie (a) 10 10 m (b) 10 20 m
relationship[MP PMT 1996, 2004; MP PET /PMT 1998]
 h (c) 10 30 m (d) 10 40 m
(a) h  (b)  
mv mv 17. A cricket ball of 0.5 kg is m ov ing with a v elocity of
m v 100 m / sec . The wavelength associated with its m otion is
(c)   (d)  
hv mh [DCE 2004]
7. de-Broglie equation is (a) 1 / 100cm (b) 6.6  10 34 m
[MP PMT 1999; CET Pune 1998]
(c) 1.32  10 35 m (d) 6.6  10 28 m
(a) n  2d sin (b) E  hv 18. Dual nature of particles was proposed by [DCE 2004]
h (a) Heisenberg (b) Lowry
(c) E  mc 2 (d)  
mv (c) de-Broglie (d) Schrodinger
19. Calculate de-Broglie wavelength of an electron trav elling
8. The de-Broglie wavelength of a particle with m ass 1 gm at 1% of the speed of light [DPMT 2004]
and velocity 100m / sec is[CBSE PMT 1999; EA MCET 1997;
(a) 2.73  10 24 (b) 2.42  10 10
A FMC 1999; AIIMS 2000]
33 (c) 242.2  10 10 (d) None of these
(a) 6.63  10 m (b) 6.63  10 34 m 20. Which is the correct relationship between wavelength and
(c) 6.63  10 35 m (d) 6.65  10 35 m m omentum of particles [Pb. PMT 2000]
9. Minimum de-Broglie wavelength is associated with [RPMT h h
1999] (a)   (b)  
P P
(a) Electron (b) Proton
h P
(c) CO 2 m olecule (d) SO 2 m olecule (c) P  (d) h 
 
10. The de-Broglie wav elength associated with a m aterial 21. The de-Broglie equation applies [MP PMT 2004]
particle is [JIPMER 2000] (a) To electrons only
(a) Directly proportional to its energy (b) To neutrons only
(b) Directly proportional to m om entum (c) To protons only
(c) Inv ersely proportional to its energy (d) All the m aterial object in m otion
(d) Inv ersely proportional t o m om entum
Uncertainty principle and Schrodinger wave
11. An electron has kinetic energy 2.8  10 23 J . de-Broglie equation
wav elength will be nearly
(m e  9.1  10 31 kg ) [MP PET 2000] 1. The uncertainty principle was enunciated by
4 7 [NCERT 1975; Bihar MEE 1997]
(a) 9.28  10 m (b) 9.28  10 m
(a) Einstein (b) Heisenberg
(c) 9.28  10 8 m (d) 9.28  10 10 m (c) Rutherford (d) Pauli
12. What will be de-Broglie wavelength of an electron m ov ing 2. According to heisenberg uncertainty principle
with a velocity of 1.2  10 ms 5 1
[MP PET 2000] [A MU 1990; BCECE 2005]
h
(a) 6.068  10 9 (b) 3.133  10 37 (a) E  mc 2 (b) x  p 
4
(c) 6.626  10 9 (d) 6.018  10 7
 58 Structure of atom
h h (c) Heisenberg, Planck (d) Planck, Heisenberg
(c)   (d) x  p 
p 6 12. The uncertainty in m om entum of an electron is
3. “The position and velocity of a sm all particle like electron 1  10 5 kg  m / s . The uncertainty in its position will be
cannot be simultaneously determined.” This statement is ( h  6.62  10 34 kg  m 2 / s )
[NCERT 1979; BHU 1981, 87]
[A FMC 1998; CBSE PMT 1999; JIPMER 2002]
(a) Heisenber g uncertainty principle
(b) Principle of de Broglie's wav e nature of electron (a) 1.05  10 28 m (b) 1.05  10 26 m
(c) Pauli's exclusion principle (c) 5.27  10 30 m (d) 5.25  10 28 m
(d) Aufbau's principle 13. The uncertainty in the position of a m oving bullet of m ass
h 1 0 gm is 10 5 m . Calculate the uncertainty in its v elocity
4. In Heisenberg's uncertainty equation x  p  ; p
4 [DCE 1999]
stands for 28 28
(a) 5.2  10 m / sec (b) 3.0  10 m / sec
(a) Uncertainty in energy
(b) Uncertainty in v elocity (c) 5.2  10 22 m / sec (d) 3  10 22 m / sec
(c) Uncertainty in m om entum h
14. The equation x .p  shows [MP PET 2000]
(d) Uncertainty in m ass 4
5. Which one is not the correct relation in the following (a) de-Broglie relation
E (b) Heisenberg’s uncertainty principle
(a) h  (b) E  mc 2 (c) Aufbau principle
v
(d) Hund’s rule
h h 15. Which quantum number is not related with Schrodinger
(c) x  p  (d)  
4 mv equation [RPMT 2002]
6. The m aximum probability of finding an electron in the (a) Principal (b) Azim uthal
d xy orbital is [MP PET 1996] (c) Magnetic (d) Spin
(a) Along the x-axis 16. Uncertainty in position of a 0.2 5 g particle is 10 5 .
(b) Along the y-axis Uncertainty of velocity is (h  6.6  10 34 Js) [A IEEE 2002]

(c) At an angle of 45 o from the x and y-axes (a) 1.2  10 34 (b) 2.1  10 29
(d) At an angle of 90 o from the x and y-axes (c) 1.6  10 20
(d) 1.7  10 9
17. The uncertainty in m om entum of an electron is
7. Sim ultaneous determ ination of exact position and
m omentum of an electron is [BHU 1979] 1  10 5 kg m / s . The uncertainity in its position will be
(a) Possible (h  6.63  10 34 Js) [Pb. CET 2000]
(b) Im possible (a) 5.28  10 30
m (b) 5.25  10 28 m
(c) Som etim es possible som etim es im possible (c) 1.05  10 m 26
(d) 2.715  10 30 m
(d) None of the abov e 18. According to Heisenberg’s uncertainty principle, the
8. If uncertainty in the position of an electron is zero, the product of uncertainties in position and v elocities for an
uncertainty in its m om entum would be [CPMT 1988] electron of m ass 9.1  10 31 kg is [
h 3 2 1 5 2 1
(a) Zero (b)  (a) 2.8  10 m s (b) 3.8  10 m s
2 5 2 1
(c) 5.8  10 m s (d) 6.8  10 6 m 2 s 1
h
(c)  (d) Infinite 19. For an electron if the uncertainty in v elocity is  , the
2
uncertainty in its position (x ) is given by [DPMT 2005]
9. The possibility of finding an electron in an orbital was
hm 4
conceiv ed by [MP PMT 1994] (a) (b)
4 hm 
(a) Rutherford (b) Bohr
h 4 m
(c) Heisenberg (d) Schrodinger (c) (d)
4m  h . 
10. Uncertainty principle gav e the concept of
20. Orbital is [DPMT 2005]
(a) Probability
(a) Circular path around the nucleus in which the
(b) An orbital electron rev olv es
(c) Phy sical m eaning of  the  2 (b) Space around the nucleus where the probability of
finding the electron is m axim um
(d) All the abov e
(c) Am plitude of electrons wav e
11. The uncertainty principle and the concept of wave nature (d) None of these
of m atter was proposed by ...... and ...... respectiv ely
[MP PET 1997]
Quantum number, Electronic configuration
(a) Heisenberg, de Broglie (b) de-Broglie, Heisenberg
 Structure of atom 59
and Shape of orbitals 1
(c) 5, 1, 1,  (d) 6, 0, 0, 
1
2 2
1. Be's 4 th electron will hav e four quantum num bers 10. The correct ground state electronic configuration of
[MNR 1985] chromium atom is[IIT 1989, 94; MP PMT 1993; EA MCET 1997;
n l m s ISM Dh anbad 1994; AFMC 1997; Bihar MEE 1996;
(a) 1 0 0 + 1 /2 MP PET 1995, 97; CPMT 1999; Kerala PMT 2003]
(b) 1 1 +1 + 1 /2 (a) [ Ar] 3d 5 4 s 1 (b) [ Ar] 3d 4 4 s 2
(c) 2 0 0 – 1 /2
(d) 2 1 0 + 1 /2 (c) [ AR]3d 6 4 s 0 (d) [ Ar]4 d 5 4 s 1
2. The quantum number which specifies the location of an 11. 2 p orbitals have [NCERT 1981; MP PMT 1993, 97]
electron as w ell as energy is [DPMT 1983] (a) n  1, l  2 (b) n  1, l  0
(a) Principal quantum num ber
(c) n  2, l  1 (d) n  2, l  0
(b) Azim uthal quantum num ber
(c) Spin quantum num ber 12. Electronic configuration of H  is [CPMT 1985]
(d) Magnetic quantum num ber (a) 1s 0 (b) 1s 1
3. The shape of an orbital is given by the quantum number
(c) 1s 2 (d) 1s 1 2 s 1
[NCERT 1984; MP PMT 1996]
13. The quantum numbers for the outerm ost electron of an
(a) n (b) l
(c) m (d) s 1
elem ent are given below as n  2, l  0, m  0, s   . The
4. In a given atom no two electrons can have the same values 2
for all the four quantum num bers. This is called atom s is [EA MCET 1978]
[BHU 1979; A MU 1983; EAMCET 1980, 83; (a) Lithium (b) Bery llium
MA DT Bihar 1980; CPMT 1986, 90, 92; NCERT 1978, 84; (c) Hy drogen (d) Boron
RPMT 1997; CBSE PMT 1991; MP PET 1986, 99] 14. Principal quantum num ber of an atom represents
(a) Hund's rule [EA MCET 1979; IIT 1983; MNR 1990;UPSEAT 2000, 02]
(b) Aufbau's principle (a) Size of the orbital
(c) Uncertainty principle (b) Spin angular m om entum
(d) Pauli's exclusion principle (c) Orbital angular m om entum
5. Nitrogen has the electronic configuration (d) Space orientation of the orbital
1s 2 ,2 s 2 2 p 1x 2 p 1y 2 p 1z and not 1s 2 ,2 s 2 2 p x2 2 p 1y 2 p z0 which is 15. An elem ent has the electronic configuration
determ ined by 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 2 . Its v alency electrons are
[DPMT 1982, 83, 89; MP PMT/PET 1988; EAMCET 1988] [NCERT 1973]
(a) Aufbau's principle (b) Pauli's exclusion (a) 6 (b) 2
principle (c) 3 (d) 4
(c) Hund's rule (d) Uncertainty principle 16. The m agnetic quantum num ber specifies
6. Which one of the following configuration represents a [MNR 1986; BHU 1982; CPMT 1989, 94;
noble gas [CPMT 1983,
MP89, 93;1999;
PET NCERT 1973;
AFMC MPAMU
1999; PMT (Engg.)
1989; 1999]
DPMT 1984]
(a) Size of orbitals (b) Shape of orbitals
2 2 6 2
(a) 1s ,2 s 2 p ,3 s (b) 1s ,2 s 2 p ,3 s1
2 2 6
(c) Orientation of orbitals (d) Nuclear stability
(c) 1s 2 ,2 s 2 2 p 6 (d) 1s 2 ,2 s 2 sp6 ,3 s 2 3 p 6 ,4 s 2 17. Which of the following sets of quantum num bers
represent an impossible arrangement[IIT 1986; MP PET 1995]
7. The electronic configuration of silver atom in ground state
is n l m ms
[CPMT 1984, 93] 1
(a) 3 2 –2 (+ )
(a) [Kr]3d 10
4s 1
(b) [ Xe] 4 f 5 d 6 s
14 10 1
2

(c) [Kr] 4 d 5 s10 1

(d) [Kr] 4 d 9 5 s 2 1
(b) 4 0 0 (–)
2
8. Principal, azimuthal and m agnetic quantum numbers are
respectively related to [CPMT 1988; A IIMS 1999] 1
(c) 3 2 –3 (+ )
(a) Size, shape and orientation 2
(b) Shape, size and orientation 1
(d) 5 3 0 (–)
(c) Size, orientation and shape 2
(d) None of the abov e 18. If n  3 , then the v alue of ' l' which is incorrect
9. Correct set of four quantum numbers for valence electron [CPMT 1994]
of rubidium (Z = 3 7 ) is (a) 0 (b) 1
[IIT 1984; JIPMER 1999; UPSEAT 2003]
(c) 2 (d) 3
1 1 19. Which orbital is dum b-bell shaped
(a) 5, 0, 0,  (b) 5, 1, 0, 
2 2 [MP PMT 1986; MP PET/PMT 1998]
 60 Structure of atom
(a) s -orbital (b) p -orbital [MNR 1988; UPSEAT 1999, 2000; Kerala PMT 2003]
(a) Principal quantum num ber
(c) d -orbital (d) f -orbital
(b) Azim uthal quantum num ber
20. The total number of unpaired electrons in d - orbitals of
atom s of element of atomic number 29 is [CPMT 1983] (c) Magnetic quantum num ber
(d) Spin quantum num ber
(a) 1 0 (b) 1
(c) 0 (d) 5 32. A com pletely filled d -orbital (d 10 ) [MNR 1987]
21. The shape of 2 p orbital is (a) Spherically symmetrical
[CPMT 1983; NCERT 1979] (b) Has octahedral sy m m etry
(a) Spherical (b) Ellipsoidal (c) Has tetrahedral sy m m etry
(c) Dum b-bell (d) Py ram idal (d) Depends on the atom
22. The m agnetic quantum number for a n electron when the 33. If m agnetic quantum number of a given atom represented
v alue of principal quantum num ber is 2 can hav e by –3 , then what will be its principal quantum num ber
[CPMT 1984] [BHU 2005]
(a) 3 v alues (b) 2 v alues (a) 2 (b) 3
(c) 9 v alues (d) 6 v alues (c) 4 (d) 5
23. Which one is the correct outer configuration of chromium 34. The total number of orbitals in an energy level designated
[A IIMS 1980, 91; BHU 1995] by principal quantum number n is equal to
[A IIMS 1997; J&K CET 2005]
(a)     
(a) 2n (b) 2n 2
(b)   
(c) n (d) n 2
(c)       35. The number of orbitals in the fourth principal quantum
(d) num ber will be
     
(a) 4 (b) 8
24. The following has zero valency [DPMT 1991] (c) 1 2 (d) 1 6
(a) Sodium (b) Bery llium 36. Which set of quantum numbers are not possible from the
(c) Alum inium (d) Kry pton following
25. The number of electrons in the valence shell of calcium is
1
[IIT 1975] (a) n  3, l  2, m  0, s  
(a) 6 (b) 8 2
(c) 2 (d) 4 (b) n  3, l  2, m  2, s  
1
26. The valence electron in the carbon atom are [MNR 1982] 2
(a) 0 (b) 2 1
(c) n  3, l  3, m  3, s  
(c) 4 (d) 6 2
27 . For the dum b-bell shaped orbital, the v alue of l is 1
[CPMT 1987, 2003] (d) n  3, l  0, m  0, s  
2
(a) 3 (b) 1 37 . The four quantum number for the valence shell electron
(c) 0 (d) 2 or last electron of sodium (Z = 11) is [MP PMT 1999]
28. Chrom ium has the electronic configuration 4 s1 3d 5 1
(a) n  2, l  1, m  1, s  
rather than 4 s 2 3d 4 because 2
(a) 4 s and 3 d hav e the sam e energy 1
(b) n  3, l  0, m  0, s  
(b) 4 s has a higher energy than 3 d 2
(c) 4 s 1 is m ore stable than 4 s 2 1
(c) n  3, l  2, m  2, s  
(d) 4 s 1 3d 5 half-filled is m or e stable than 4 s 2 3d 4 2
1
29. The electronic configuration of calcium ion (Ca 2  ) is (d) n  3, l  2, m  2, s  
[CMC V ellore 1991] 2
38. The explanation for the presence of three unpaired
(a) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 ,4 s 2 electrons in the nitrogen atom can be giv en by
(b) 1s 2 ,2 s 2 sp 6 ,3 s 2 3 p 6 ,4 s 1 [NCERT 1979; RPMT 1999; DCE 1999, 2002;
2 2 6
(c) 1s ,2 s 2 p ,3 s 3 p 3d
2 6 2 CPMT 2001; MP PMT 2002; Pb. PMT / CET 2002]
2 2 6 2 6 5 (a) Pauli's exclusion principle
(d) 1s ,2 s sp ,3 s 3 p 3d
2 2 6 2 6 0
(b) Hund's rule
(e) 1s ,2 s 2 p ,3 s 3 p ,4 s (c) Aufbau's principle
30. The structure of external m ost shell of inert gases is (d) Uncertainty principle
[JIPMER 1991]
2 3 2 6 39. The m axim um energy is present in any electron at
(a) s p (b) s p
(a) Nucleus
1 2
(c) s p (d) d 10 s 2 (b) Ground state
31. The two electrons in K sub-shell will differ in (c) First excited state
 Structure of atom 61
(d) Infinite distance from the nucleus 1
(b) n  4 , l  0, m  0, s  
40. The electron density between 1s and 2 s orbital is 2
(a) High (b) Low 1
(c) Zero (d) None of these (c) n  3, l  1, m  1, s  
2
41. For ns orbital, the magnetic quantum number has v alue
1
(a) 2 (b) 4 (d) n  4 , l  2, m  1, s  
2
(c) – 1 (d) 0
53. The angular m omentum of an electron depends on
42. The m axim um num ber of electrons that can be
(a) Principal quantum num ber
accom m odated in the M th shell is (b) Azim uthal quantum num ber
(a) 2 (b) 8 (c) Magnetic quantum num ber
(c) 1 8 (d) 3 2 (d) All of these
43. For a giv en value of quantum num ber l , the num ber of 54. The electronic configuration of copper ( 29 Cu ) is
allowed v alues of m is giv en by
[DPMT 1983; BHU 1980; AFMC 1981;
(a) l  2 (b) 2l  2
CBSE PMT 1991; MP PMT 1995]
(c) 2l  1 (d) l  1
(a) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 9 ,4 s 2
44. The num ber of radial nodes of 3 s and 2 p orbitals are
respectively. [IIT -JEE 2005] (b) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 10 ,4 s1
(a) 2 , 0 (b) 0, 2
(c) 1s 2 .2 s 2 2 p 6 ,3 s 2 3 p 6 ,4 s 2 4 p 6
(c) 1 , 2 (d) 2 , 1
45. Which of the sub-shell is circular (d) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 10
(a) 4 s (b) 4 f 55. The num ber of orbitals in 2 p sub-shell is
(c) 4 p (d) 4 d [NCERT 1973; MP PMT 1996]
(a) 6 (b) 2
46. Which electronic configuration for oxy gen is correct
according to Hund's rule of m ultiplicity (c) 3 (d) 4
56. The number of orbitals in d sub-shell is [MNR 1981]
(a) 1s 2 ,2 s 2 2 p x2 2 p 1y 2 p 1z (b) 1s 2 ,2 s 2 2 p x2 2 p y2 2 p z0
(a) 1 (b) 3
(c) 1s 2 ,2 s 2 2 p x3 2 p 1y 2 p z0 (d) None of these (c) 5 (d) 7
47 . If v alue of azimuthal quantum number l is 2 , then total 57 . A sub-shell l  2 can take how m any electrons
possible v alues of m agnetic quantum num ber will be [NCERT 1973, 78]
(a) 7 (b) 5 (a) 3 (b) 1 0
(c) 3 (d) 2 (c) 5 (d) 6
48. The ty pe of orbitals present in Fe is 58. Pauli's exclusion principle states that
(a) s (b) s and p [MNR 1983; A MU 1984]
(c) s, p and d (d) s, p, d and f (a) Two electrons in the same atom can hav e the sam e
energy
49. The shape of d xy orbital will be
(b) Two electrons in the sam e atom cannot hav e the
(a) Circular (b) Dum b-bell sam e spin
(c) Double dum b-bell (d) Trigonal (c) The electrons tend to occupy different orbitals as far
50. In any atom which sub-shell will have the highest energy as possible
in the following (d) Electrons tend to occupy lower energy orbitals
(a) 3 p (b) 3 d preferentially
(c) 4 s (d) 3 s (e) None of the abov e
51. Which electronic configuration is not observ ing the 59. For d electrons, the azim uthal quantum num ber is
( n  l ) rule
[MNR 1983; CPMT 1984]
(a) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 1 ,4 s 2 (a) 0 (b) 1
2 2 6 2 6 7 2
(b) 1s ,2 s sp ,3 s 3 p 3d ,4 s (c) 2 (d) 3
2 2 6 2 6 5
(c) 1s ,2 s 2 p ,3 s 3 p 3d ,4 s
1
60. For p -orbital, the m agnetic quantum number has v alue
2 2 6 2 6 8
(d) 1s ,2 s 2 p ,3 s 3 p 3d ,4 s
2 (a) 2 (b) 4 , – 4
(c) – 1 , 0, + 1 (d) 0
52. The four quantum numbers of the outermost orbital of K
(atomic no. =19) are [MP PET 1993, 94] 61. For n  3 energy level, the number of possible orbitals (all
1 kinds) are [BHU 1981; CPMT 1985; MP PMT 1995]
(a) n  2, l  0, m  0, s  
2 (a) 1 (b) 3
(c) 4 (d) 9
 62 Structure of atom
62. Which of the following ions is not hav ing the 72. In a potassium atom, electronic energy lev els are in the
configuration of neon following order [EA MCET 1979; DPMT 1991]

(a) F  (b) Mg 2 (a) 4 s  3d (b) 4 s  4 p

(c) 4 s  3d (d) 4 s  3 p
(c) Na  (d) Cl 
63. Elem ents upto atomic number 103 have been synthesized 73. Fe (atom ic num ber = 2 6) atom has the electronic
and studied. If a newly discov ered elem ent is found to arrangement [NCERT 1974; MNR 1980]
have an atomic number 106, its electronic configuration (a) 2 , 8, 8, 8 (b) 2 , 8, 1 6
will be (c) 2 , 8,1 4 , 2 (d) 2 , 8, 1 2 , 4
[A IIMS 1980]
74. Cu 2  will hav e the following electronic configuration
(a) [Rn]5 f ,6 d ,7 s
14 4 2
(b) [Rn]5 f ,6 d 1 ,7 s 2 7 p 3
14
[MP PMT 1985]

(c) [Rn]5 f ,6 d ,7 s
14 6 0
(d) [Rn]5 f ,6 d ,7 s
14 5 1
(a) 1s ,2 s 2 p ,3 s 3 p 3d
2 2 6 2 6 10

64. Ions which have the sam e electronic configuration are (b) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 9 ,4 s 1
those of
(a) Lithium and sodium (b) Sodium and potassium (c) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 9
(c) Potassium and calcium (d) Oxy gen and chlorine (d) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 10 ,4 s 1
65. When the azim uthal quantum num ber has a v alue of 75. Which one is the electronic con figuration of Fe 2
l  0 , the shape of the orbital is [MP PET 1995]
[MA DT Bihar 1982; AIIMS 1989]
(a) Rectangular (b) Spherical
(a) 1s ,2 s 2 p ,3 s 3 p 3d 6
2 2 6 2 6
(c) Dum bbell (d) Unsy m m etrical
66. The m agnetic quantum number for v alency electrons of (b) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 4 ,4 s 2
sodium is [CPMT 1988; MH CET 1999]
(c) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 5 ,4 s 1
(a) 3 (b) 2
(d) None of these
(c) 1 (d) 0
76. How m any electrons can be fit into the orbitals that
67 . The electronic configuration of an elem ent with atom ic
number 7 i.e. nitrogen atom is [CPMT 1982, 84, 87] com prise the 3 rd quantum shell n  3
[MP PMT 1986, 87; Orissa JEE 1997]
(a) 1s 2 ,2 s 1 ,2 p x3 (b) 1s 2 ,2 s 2 2 p x2 2 p1y (a) 2 (b) 8
(c) 1s 2 ,2 s 2 2 p 1x 2 p 1y 2 p 1z (d) 1s 2 ,2 s 2 2 p 1x 2 p y2 (c) 1 8 (d) 3 2
77. Which element is represented by the following electronic
68. In a m ulti-electron atom, which of the following orbitals configuration [MP PMT 1987]
described by the three quantum m em bers will hav e the
sam e energy in the absence of m agnetic and electric fields 2p
[A IEEE 2005] 2s   
(1 ) n  1, l  0, m  0 (2 ) n  2, l  0, m  0 1s 
(3 ) n  2, l  1, m  1 (4 ) n  3, l  2, m  0 
(5) n  3, l  2, m  0 (a) Nitrogen (b) Oxy gen
(a) (1 ) and (2 ) (b) (2 ) and (3 ) (c) Fluorine (d) Neon
(c) (3 ) and (4 ) (d) (4 ) and (5) 7 8. If the v alue of azim uthal quantum num ber is 3 , the
possible v alues of m agnetic quantum num ber would be
69. Which of the following represents the electronic
[MP PMT 1987; RPMT 1999; AFMC 2002; KCET 2002]
configuration of an elem ent with atom ic num ber 1 7
[A MU 1982] (a) 0, 1 , 2 , 3 (b) 0, – 1 , – 2 , – 3
(c) 0,  1 ,  2 ,  3 (d)  1 ,  2 ,  3
2 2 6
(a) 1s ,2 s 2 p ,3 s 3 p 1 6
(b) 1s ,2 s 2 p ,3 s 2 3 p 4 ,4 s1
2 2 6
79. Kry pton (36 Kr) has the electronic configuration (18 Ar)
(c) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 5 (d) 1s 2 ,2 s 2 2 p 6 ,3 s 1 3 p 4 ,4 s 2
4 s 2 ,3d 10 ,4 p 6 . The 37 th electron will go into which one of
70. The shape of s -orbital is [NCERT 1978I] the following sub-lev els
(a) Py ram idal (b) Spherical [CBSE PMT 1989; CPMT 1989; EAMCET 1991]
(c) Tetrahedral (d) Dum b-bell shaped (a) 4 f (b) 4 d
7 1. When 3 d orbital is com plete, the new electron will enter (c) 3 p (d) 5 s
the
[EA MCET 1980; MP PMT 1995] 1
80. If an electron has spin quantum num ber of  and a
2
(a) 4 p -orbital (b) 4 f -orbital
m agnetic quantum number of 1 , it cannot be presented
(c) 4 s -orbital (d) 4 d -orbital in an [CBSE PMT 1989; UPSEA T 2001]
 Structure of atom 63
(a) d -orbital (b) f -orbital (c) Cs  (d) K 
(c) p -orbital (d) s -orbital 93. The order of filling of electrons in the orbitals of an atom
will be [
81. The azim uthal quantum num ber is related to
(a) 3d, 4 s, 4 p, 4 d, 5 s (b) 4 s, 3d, 4 p, 5 s, 4 d
[BHU 1987, 95]
(a) Size (b) Shape (c) 5 s, 4 p, 3d, 4 d, 5 s (d) 3d, 4 p, 4 s, 4 d, 5 s
(c) Orientation (d) Spin 94. The quantum number which m ay be designated by s, p, d
82. The total number of electrons that can be accomm odated and f instead of number is BHU 1980]
in all the orbitals having principal quantum number 2 and
azimuthal quantum number 1 is [CPMT 1971, 89, 91] (a) n (b) l
(a) 2 (b) 4 (c) m l (d) m s
(c) 6 (d) 8 95. Which of the following represents the correct sets of the
83. Electronic configuration of C is [CPMT 1975] four quantum num bers of a 4 d electron
[MNR 1992; UPSEAT 2001; J&K CET 2005]
(a) 1s 2 ,2 s 2 2 p 2 (b) 1s 2 ,2 s 2 2 p 3
1
(a) 4 , 3, 2, (b) 4 , 2 , 1 , 0
(c) 1s 2 ,2 s 2 (d) 1s 2 ,2 s 2 2 p 6 2
84. There is no difference between a 2 p and a 3 p orbital 1 1
(c) 4 , 3,  2,  (d) 4 , 2, 1, 
regarding [BHU 1981] 2 2
(a) Shape (b) Size 96. Which of the following statem ents is not correct for an
(c) Energy (d) Value of n electron that has the quantum numbers n  4 and m  2
[MNR 1993]
85. The electronic configuration of chrom ium is
[MP PMT 1993; MP PET 1995; BHU 2001; BCECE 2005]
1
(a) The electron m ay have the quantum num ber s  
2
(a) [ Ne ]3 s 2 3 p 6 3d 4 ,4 s 2 (b) [ Ne ]3 s 2 3 p 6 3d 5 ,4 s 1
(b) The electron m ay have the quantum num ber l  2
(c) [ Ne ]3 s 2 3 p 6 ,4 s 2 4 p 4 (d) [ Ne ]3 s 2 3 p 6 3d 1 ,4 s 2 4 p 3 (c) The electron m ay have the quantum num ber l  3
86. The shape of p -orbital is [MP PMT 1993] (d) The electron m ay hav e the quantum num ber
l  0, 1, 2, 3
(a) Elliptical (b) Spherical
97 . The set of quantum num bers not applicable for an
(c) Dum b-bell (d) Com plex geom etrical electron in an atom is [MNR 1994]
87 . The electronic configuration (outerm ost) of Mn 2 ion (a) n  1, l  1, m l  1, m s  1 / 2
(atom ic num ber of Mn  25 ) in its ground state is (b) n  1, l  0, m l  0, m s  1 / 2
[MP PET 1993]
(c) n  1, l  0, m l  0, m s  1 / 2
(a) 3 d 5 ,4 s 0 (b) 3 d 4 ,4 s 1
(d) n  2, l  0, m l  0, m s  1 / 2
(c) 3 d 3 ,4 s 2 (d) 3d 2 ,4 s 2 4 p 2
98. Correct configuration of Fe 3 [2 6] is
88. The principal quantum number represents [CPMT 1991]
[CPMT 1994; BHU 1995; KCET 1992]
(a) Shape of an orbital
(b) Distance of electron from nucleus (a) 1s ,2 s 2 p ,3 s 3 p 6 3d 5
2 2 6 2

(c) Num ber of electrons in an orbit (b) 1s 2 ,2 s 2 sp 6 ,3 s 2 3 p 6 3d 3 ,4 s 2

(d) Num ber of orbitals in an orbit (c) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 6 ,4 s 2
89. When the azim uthal quantum num ber has a v alue of
l  1 , the shape of the orbital is [MP PET 1993] (d) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 5 ,4 s 1
(a) Unsy m m etrical (b) Spherically symmetrical 99. Azim uthal quantum number for last electron of Na atom
(c) Dum b-bell (d) Com plicated is
[BHU 1995]
90. How m any electrons can be accommodated in a sub-shell
(a) 1 (b) 2
for which n  3, l  1 [CBSE PMT 1990]
(c) 3 (d) 0
(a) 8 (b) 6 100. A 3 p orbital has [IIT 1995]
(c) 1 8 (d) 3 2 (a) Two spherical nodes
91. For azim uthal quantum num ber l  3 , the m axim um (b) Two non-spherical nodes
num ber of electrons will be [CBSE PMT 1991;
(c) One spherical and one non -spherical nodes
EA MCET 1991; RPMT 2002; CBSE PMT 2002]
(d) One spherical and two non -spherical nodes
(a) 2 (b) 6
101. All electrons on the 4 p sub-shell m ust be characterized
(c) 0 (d) 1 4
by the quantum number(s) [MP PET 1996]
92. An ion has 1 8 electrons in the outerm ost shell, it is
1
[CBSE PMT 1990] (a) n  4 , m  0, s   (b) l  1
2
 4
(a) Cu (b) Th
 64 Structure of atom
1
(c) l  0, s   (d) s  
1 (c) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 4
2 2
(d) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 1 3d 3
102. The electronic configuration of the elem ent of atom ic
num ber 2 7 is 110. Which of the following configuration is correct for iron
[CBSE PMT 1999]
(a) 1s , 2 s 2 p , 3 s 3 p , 4 s () 4 p ()()() 5 s ()
2 2 6 2 6
(a) 1s 2 s 2 p 3 s 3 p 3d
2 2 6 2 6 5

(b) 1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 3d ()()(), 4 s () 4 p ()

(b) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 2 3d 5
(c) 1s , 2 s 2 p , 3 s 3 p , 3d ()()()(), 4 s ()
2 2 6 2 6
(c) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 2 3d 7
(d) 1s , 2 s 2 p , 3 s 3 p , 3d ()()()()() 4 s ()
2 2 6 2 6
(d) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 2 3d 6
103. When the value of the principal quantum number n is 3 , 111. Which of the following set of quantum numbers belong to
the permitted values of the azimuthal quantum num bers highest energy [CPMT 1999]
l and the m agnetic quantum num bers m , are
1
l m (a) n  4 , l  0, m  0, s  
2
0 0
1
(a) 1  1, 0,  1 (b) n  3, l  0, m  0, s  
2
2  2,1, 0,  1,2
1
1 1 (c) n  3, l  1, m  1, s  
2
(b) 2  2, 1,  1 1
(d) n  3, l  2, m  1, s  
3  3,2, 1,  2,3 2
0 0 112. Which quantum number will determine the shape of the
(c) 1 1, 2, 3 subshell [CPMT 1999; Pb. PMT 1998]
2  3,  2, 1,  2,3 (a) Principal quantum num ber
(b) Azim uthal quantum num ber
1 0, 1
(c) Magnetic quantum num ber
(d) 2 0, 1, 2
(d) Spin quantum num ber
3 0, 1, 2, 3
113. For the n  2 energy level, how many orbitals of all kinds
104. The number of possible spatial orientations of an electron are possible [Bih a r CEE 1995]
in an atom is giv en by its
(a) 2 (b) 3
(a) Spin quantum num ber
(c) 4 (d) 5
(b) Spin angular m om entum
(c) Magnetic quantum num ber 114. Which one is in the ground state [DPMT 1996]
(d) Orbital angular m om entum

105. Which of the following sets of orbitals m ay degenerate
(a)   
(a) 2 s, 2 p x , 2 p y (b) 3 s, 3 p x ,3d xy

(c) 1s, 2 s, 3 s (d) 2 p x , 2 p y , 2 p z
106. The set of quantum num bers n  3, l  0, m  0, s  1 / 2 (b)   
belongs to the elem ent 
(a) Mg (b) Na 
(c) Ne (d) F (c)   
107 . An electron has principal quantum num ber 3 . The

num ber of its (i) sub-shells and (ii) orbitals would be
respectiv ely 
[MP PET 1997] (d)   
(a) 3 and 5 (b) 3 and 7 
(c) 3 and 9 (d) 2 and 5
2 115. When the principal quantum number (n  3) , the possible
108. What is the electronic configuration of Cu (Z  29) of
least position [MP PET /PMT 1998; MP PET 2001] v alues of azim uthal quantum num ber ( l ) is
[Bihar MEE 1996; KCET 2000]
(a) [ Ar] 4 s 3d
1 8
(b) [ Ar] 4 s 2 3d 10 4 p 1
(a) 0, 1 , 2 , 3 (b) 0, 1 , 2
(c) [ Ar] 4 s 1 3d 10 (d) [ Ar] 3 d 9 (c) – 2 , – 1 , 0, 1 , 2 (d) 1 , 2 , 3
(e) 0, 1
109. The correct electronic configuration of Ti(Z  22) atom is
116. Which statem ent is not correct for n  5 , m  3
[MP PMT 1999]
2 2 6 2 6 2 2 [CPMT 1996]
(a) 1s 2 s 2 p 3 s 3 p 4 s 3d
1
2 2 6 2 6 4 (a) l  4 (b) l  0, 1, 3; s  
(b) 1s 2 s 2 p 3 s 3 p 3d 2
 Structure of atom 65
(c) l  3 (d) All are correct (c) [ Xe]4 s 3 5 d 5 6 s 2 (d) [ Xe]4 f 6 5 d 2 6 s 2
117 . 2 2
1s 2 s 2 p 3 s 6 1
shows configuration of [CPMT 1996] 125. An e  has m agnetic quantum number as 3 , what is its
(a) Al 3
in ground state (b) Ne in excited state principal quantum number [BHU 1998]

(c) Mg in excited state (d) None of these (a) 1 (b) 2
(c) 3 (d) 4
118. Fiv e v alence electrons of p 15 are labelled as
126. The number of quantum numbers required to describe an
AB X Y Z electron in an atom com pletely is [CET Pu n e 1998]
3s 3p (a) 1 (b) 2
1 (c) 3 (d) 4
If the spin quantum of B and Z is  , the group of
2 127 . The electronic configuration 1s 2 2 s 2 2 p 1x 2 p 1y 2 p 1z
electrons with three of the quantum num ber sam e are
[A FMC 1997; Pb. PMT 1999; CBSE PMT 2001; AIIMS 2001]
[JIPMER 1997]
(a) Oxy gen (b) Nitrogen
(a) AB, XYZ , BY (b) AB
(c) Hy drogen (d) Fluorine
(c) XYZ, AZ (d) AB, XYZ
128. Which one of the following set of quantum numbers is not
119. Electronic configuration of Sc 21 is [BHU 1997] possible for 4 p electron [EA MCET 1998]
(a) 1s 2 s 2 p 3 s 3 p 4 s 3d
2 2 6 2 6 2 1
1
(a) n  4 , l  1, m  1, s  
2 2 6
(b) 1s 2 s 2 p 3 s 3 p 4 s 3d 2 6 1 2 2
1
(c) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 0 3d 3 (b) n  4 , l  1, m  0, s  
2
(d) 1s 2 2 s 2 2 p 6 3 s 2 3 p 2 4 s 2 3d 2
1
120. If n  l  6 , then total possible num ber of subshells (c) n  4 , l  1, m  2, s  
2
would be [RPMT 1997]
1
(a) 3 (b) 4 (d) n  4 , l  1, m  1, s  
2
(c) 2 (d) 5
129. Which of the following orbital is not possible[RPMT 1999]
121. An electron hav ing the quantum num bers (a) 3 f (b) 4 f
1 (c) 5 f (d) 6 f
n  4, l  3, m  0 , s   would be in the orbital
2 130. Which set of quantum numbers for an electron of an atom
[Or issa JEE 1997] is not possible [RPMT ; DCE 1999]
(a) n  1, l  0, m  0, s  1 / 2
(a) 3 s (b) 3 p
(b) n  1, l  1, m  1, s  1 / 2
(c) 4 d (d) 4 f (c) n  1, l  0, m  0, s  1 / 2
122. Which of the following sets of quantum num bers is not (d) n  2, l  1, m  1, s  1 / 2
allowed [Or issa JEE 1997]
131. Electronic configuration of ferric ion is [RPET 2000]
1
(a) n  1, l  0, m  0, s   (a) [ Ar] 3 d 5
(b) [ Ar] 3 d 7
2
(c) [ Ar] 3 d 3
(d) [ Ar] 3 d 8
1
(b) n  1, l  1, m  0, s   132. What is the m aximum number of electrons which can be
2
accom modated in an atom in which the highest principal
1 quantum num ber value is 4 [MP PMT 2000]
(c) n  2, l  1, m  1, s  
2 (a) 1 0 (b) 1 8
(c) 3 2 (d) 54
1 133. Which of the following electronic configurations is not
(d) n  2, l  1, m  0, s  
2 possible
[CPMT 2000]
123. For which of the following sets of four quantum numbers,
2 2 6
an electron will have the highest energy [CBSE PMT 1994] (a) 1s 2 s
2 2
(b) 1s 2 s 2 p
10 2 2
n l m s (c) 3d 4s 4 p (d) 1s 2 2 s 2 2 p 2 3 s 1
(a) 3 2 1 + 1 /2 134. The electronic configuration of an elem ent is
(b) 4 2 1 + 1 /2 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 5 4 s1 . This represents its
(c) 4 1 0 –1 /2 [IIT Screening 2000]
(a) Excited state (b) Ground state
(d) 5 0 0 –1 /2
(c) Cationic form (d) Anionic form
124. The electronic configuration of gadolinium (atom ic no. 135. Which of the following set of quantum num bers is
64) is [CBSE PMT 1997]
possible
8 9 2 7 1 2 [A IIMS 2001]
(a) [ Xe]4 s 5 d 6 s (b) [ Xe]4 s 5 d 6 s
 66 Structure of atom
1 (a) Hund’s rule
(a) n  3; l  2; m  2 and s  
2 (b) Aufbau’s principle
1 (c) Pauli’s exclusion principle
(b) n  3; l  4 ; m  0 and s   (d) Heisenberg’s uncertainty principle
2
145. Which of the following has maximum energy
1
(c) n  4 ; l  0; m  2 and s   [A IIMS 2002]
2 3s 3p 3d
1
(d) n  4 ; l  4 ; m  3 and s   (a)
2
136. Which of the following set of quantum num ber is not 3s 3p 3d
v alid
[A IIMS 2001] (b)
(a) n  1, l  2 (b) 3  2, m  1
(c) m  3, l  0 (d) 3  4, l  2 3s 3p 3d
(c)
137 . Which one pair of atom s or ions will hav e sam e
configuration [JIPMER 2001]
(a) F  and Ne (b) Li  and He  3s 3p 3d
 (d)
(c) Cl and Ar (d) Na and K
138. Which of the following sets of quantum num ber is not 146. The total m agnetic quantum num bers for d-orbital is
possible [MP PET 2001] given by [
1 (a) 2 (b) 0,  1 ,  2
(a) n  3; l  2; m  0; s  
2 (c) 0, 1 , 2 (d) 5
1
(b) n  3; l  0; m  0; s   147 . The outer electronic structure 3 s 2 3 p 5 is possessed by
2 [Pb. PMT 2002; Pb. CET 2001]
1 (a) Cl (b) O
(c) n  3; l  0; m  1; s  
2 (c) Ar (d) Br
1 148. Which of the following set of quantum num ber is not
(d) n  3; l  1; m  0; s  
2 possible [Pb. PMT 2002]
139. Which of the following set of quantum numbers is correct n l m1 m2
for the 19th electron of chromium [DCE 2001]
(a) 3 2 1 + 1 /2
n l m s
(b) 3 2 1 – 1 /2
(a) 3 0 0 1 /2
(c) 3 2 1 0
(b) 3 2 –2 1 /2 (d) 5 2 –1 + 1 /2
(c) 4 0 0 1 /2 149. The configuration 1s 2 , 2 s 2 2 p 5 , 3 s 1 shows[Pb. PMT 2002]
(d) 4 1 –1 1 /2
(a) Excited state of O 2
140. When the v alue of azim uthal quantum num ber is 3 , (b) Excited state of neon
magnetic quantum number can have values[DPMT 2001] (c) Excited state of fluorine
(a) + 1 , 0, – 1
(d) Ground state of fluorine atom
(b) + 2 , + 1 , 0, – 1 , – 2
150. The quantum num ber ‘m’ of a free gaseous atom is
(c) – 3 , – 2 , – 1 , – 0, + 1 , + 2 , + 3 associated with [A IIMS 2003]
(d) + 1 , – 1
(a) The effectiv e v olum e of the orbital
141. The quantum num bers n  2, l  1 represent [A FMC 2002]
(b) The shape of the orbital
(a) 1 s orbital (b) 2 s orbital (c) The spatial orientation of the orbital
(c) 2 p orbital (d) 3 d orbital
(d) The energy of the orbital in the absence of a m agnetic
142. The m agnetic quantum num ber of v alence electron of field
sodium (Na) is [RPMT 2002]
151. Correct statement is [BHU 2003]
(a) 3 (b) 2
(c) 1 (d) 0 (a) K  4 s , Cr  3d 4 s , Cu  3d 4 s
1 4 2 10 2

143. Azimuthal quantum number defines [A IIMS 2002]

(b) K  4 s 2 , Cr  3d 4 4 s 2 , Cu  3d 10 4 s 2
(a) e/m ratio of electron
(b) Spin of electron (c) K  4 s 2 , Cr  3d 5 4 s 1 , Cu  3d 10 4 s 2
(c) Angular m om entu m of electron
(d) K  4 s 1 , Cr  3d 5 4 s 1 , Cu  3d 10 4 s 1
(d) Magnetic m om entum of electron
144. Quantum numbers of an atom can be defined on the basis 152. Number of orbitats in h sub-shell is [BHU 2003]
of [A IIMS 2002] (a) 1 1 (b) 1 5
 Structure of atom 67
(c) 1 7 (d) 1 9 (a) Heisenberg’s principle
153. Electronic configuration (b) Hund’s rule
1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 3d 5 , 4 s 1 represents [CPMT 2003] (c) Aufbau principle
(d) Pauli exclusion principle
(a) Ground state (b) Excited state
162. The electronic configuration of elem ent with atom ic
(c) Anionic state (d) All of these number 24 is [Pb. CET 2004]
154. Which of the following sets is possible for quantum
num bers (a) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 4 ,4 s 2
[RPET 2003] (b) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 10
(a) n  4, l  3, m  2, s  0 (c) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 6
1 (d) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 5 4 s 1
(b) n  4 , l  4 , m  2, s  
2 163. The m axim um num ber of electrons in p -orbital with
(c) n  4 , l  4 , m  2, s  
1 n  5, m  1 is [Pb. CET 2003]
2 (a) 6 (b) 2
(d) n  4 , l  3, m  2, s  
1 (c) 1 4 (d) 1 0
2 164. Num ber of two electron can have the sam e v alues of ……
155. For principle quantum number n  4 the total number of quantum num bers [UPSEA T 2004]
orbitals having l  3 [A IIMS 2004] (a) One (b) Two
(a) 3 (b) 7 (c) Three (d) Four
(c) 5 (d) 9 165. The number of orbitals present in the shell with n  4 is
156. The num ber of 2 p electrons hav ing spin quantum [UPSEAT 2004]
num ber s  1 / 2 are [KCET 2004] (a) 1 6 (b) 8
(c) 1 8 (d) 3 2
(a) 6 (b) 0
166. Which of the following electronic configuration is not
(c) 2 (d) 3
possible
157 . Which of the following sets of quantum num bers is [MHCET 2003]
correct for an electron in 4 f orbital [A IEEE 2004]
(a) 1s 2 s2 2
(b) 1s ,2 s 2 p 6
2 2
1
(a) n  4 , l  3, m  1, s  
2 (c) [ Ar] 3d 10 ,4 s 2 4 p 2 (d) 1s 2 ,2 s 2 2 p 2 ,3 s 1
1 167 . p x orbital can accom m odate
(b) n  4 , l  4 , m  4 , s  
2 [MNR 1990; IIT 1983; MADT Bihar 1995; BCECE 2005]
1 (a) 4 electrons
(c) n  4 , l  3, m  4 , s  
2 (b) 6 electrons
1 (c) 2 electrons with parallel spins
(d) n  3, l  2, m  2, s  
2 (d) 2 electrons with opposite spins
158. Consider the ground state of (Z  24) . The num bers of 168. The m axim um num ber of electrons that can be
electrons with the azimuthal quantum numbers, l  1 and accom m odated in ' f ' sub shell is
2 are, respectiv ely [A IEEE 2004] [CPMT 1983, 84; MP PET/PMT 1988; BITS 1988]
(a) 1 6 and 4 (b) 1 2 and 5 (a) 2 (b) 8
(c) 1 2 and 4 (d) 1 6 and 5 (c) 3 2 (d) 1 4
159. The four quantum num bers of the v alence electron of 169. The number of electrons which can be accom m odated in
potassium are [DPMT 2004] an orbital is [DPMT 1981; A FMC 1988]
1 1 (a) One (b) Two
(a) 4 , 1 , 0 and (b) 4 , 0, 1 and
2 2 (c) Three (d) Four
1 1 170. The num ber of electrons in the atom which has 2 0
(c) 4 , 0, 0 and  (d) 4 , 1 , 1 and protons in the nucleus[CPMT 1981, 93; CBSE PMT 1989]
2 2
(a) 2 0 (b) 1 0
160. Which of the following electronic configuration is not
possible according to Hund’s rule (c)a l3a0PMT 2004]
[Ker (d) 4 0
(a) 1s 2 2 s 2 (b) 1s 2 2 s 1 171. The m aximum number of electrons accommodated in 5 f
orbitals are [MP PET 1996]
(c) 1s 2 2 s 2 2 p 1x 2 p 1y 2 p 1x (d) 1s 2 2 s 2 2 p x2
(a) 5 (b) 1 0
(e) 1s 2 2 s 2 2 p x2 2 p 1y 2 p 1z (c) 1 4 (d) 1 8
161. The ground state term sy m bol for an electronic state is 172. The m aximum number of electrons in an atom with l  2
governed by [UPSEA T 2004] and n  3 is [MP PET /PMT 1998]
 68 Structure of atom
(a) 2 (b) 6 (a) 6 (b) 4
(c) 1 2 (d) 1 0 (c) 3 (d) 1
173. The configuration 1s 2 2 s 2 2 p 5 3 s 1 shows [A IIMS 1997] 185. 3d 10 4 s 0 electronic configuration exhibits by
(a) Ground state of fluorine atom (a) Zn   (b) Cu  
(b) Excited state of fluorine atom (c) Cd   (d) Hg  
(c) Excited state of neon atom 186. Which of the following m etal ions will hav e m axim um
(d) Excited state of ion O 2 number of unpaired electrons [CPMT 1996]

174. For sodium atom the number of electrons with m  0 will (a) Fe 2 (b) CO 2
be [RPMT 1999] (c) Ni 2 (d) Mn 2
(a) 2 (b) 7 187 . Which of the m etal ion will hav e highest num ber of
(c) 9 (d) 8 unpaired electrons
175. The number of electrons that can be accom m odated in (a) Cu  (b) Fe 2 
dz 2 orbital is [Ku r u ksh et r a CEE (c) Fe 3  (d) Co 2 
2002]
188. The m axim um num ber of unpaired electron can be
(a) 1 0 (b) 1 present in d orbitals are
(c) 4 (d) 2 (a) 1 (b) 3
(c) 5 (d) 7
176. Num ber of unpaired electrons in 1s 2 2 s 2 2 p 3 is
189. The m olecule hav ing one unpaired electron is
[CPMT 1982; MP PMT 1987; BHU 1987; (a) NO (b) CO
CBSE PMT 1990; CET Pune 1998; AIIMS 2000]
(c) CN  (d) O 2
(a) 2 (b) 0
190. A filled or half-filled set of p or d -orbitals is spherically
(c) 3 (d) 1
sy m m etric. Point out the species which has spherical
177. Total number of unpaired electrons in an atom of atom ic
sy m m etry [NCERT 1983]
num ber 2 9 is [CPMT 1984, 93]
(a) Na (b) C
(a) 1 (b) 3
(c) 4 (d) 2 (c) Cl  (d) Fe
191. The atom of the element having atomic number 14 should
17 8. The num ber of unpaired electrons in 1s 2 , 2 s 2 2 p 4 is hav e [A MU 1984]
[NCERT 1984; CPMT 1991; MP PMT 1996, 2002] (a) One unpaired electron (b) Two unpaired electrons
(a) 4 (b) 2 (c) Three unpaired electrons (d)Four unpaired electrons
(c) 0 (d) 1 192. An atom has 2 electrons in K shell, 8 electrons in L shell
179. The m axim um num ber of electrons that can be and 6 electrons in M shell. The num ber of s -electrons
accom m odated in a 3 d subshell is present in that elem ent is [CPMT 1989]
(a) 2 (b) 1 0 (a) 6 (b) 5
(c) 6 (d) 1 4 (c) 7 (d) 1 0
180. The m aximum number of electrons which each sub-shell 193. The num ber of unpaired electrons in carbon atom in
can occupy is [Pb. CET 1989] excited state is [MNR 1987]
(a) 2n 2 (b) 2n (a) One (b) Two
(c) 2(2l  1) (d) (2l  1) (c) Three (d) Four
181. Num ber of unpaired electrons in the ground state of 194. Maxim um num ber of electrons present in ' N ' shell is
bery llium atom is [EA MCET 1984]
(a) 2 (b) 1 (a) 1 8 (b) 3 2
(c) 0 (d) All the abov e (c) 2 (d) 8
182. How m any unpaired electrons are present in Ni 2  cation 195. The number of d electrons in Fe 2 (atom ic num ber of
(atom ic num ber = 2 8) [IIT 1981; MNR 1984; Fe  26 ) is not equal to that of the [MNR 1993]
MP PMT 1995; Kerala PMT 2003] (a) p -electrons in Ne (At. No.= 1 0)
(a) 0 (b) 2
(b) s -electrons in Mg (At. No.= 1 2 )
(c) 4 (d) 6
(c) d -electrons in Fe
183. The number of unpaired electrons in an O 2 m olecule is
[MNR 1983] (d) p -electrons in Cl  (At. No. of Cl = 1 7 )
(a) 0 (b) 1 4
196. A transition m etal X has a configuration [ Ar]3 d in its
(c) 2 (d) 3 3 oxidation state. Its atomic number is[EA MCET 1990]
184. The number of unpaired electrons in a chrom ic ion Cr 3  (a) 2 5 (b) 2 6
(atomic number = 24) is [MNR 1986; CPMT 1992] (c) 2 2 (d) 1 9
 Structure of atom 69
197 . The total num ber of electrons present in all the p - (c) Pauli's exclusion principle
orbitals of brom ine are [MP PET 1994] (d) Uncertainty principle
(a) Fiv e (b) Eighteen 208. According to Aufbau's principle, which of the three
(c) Sev enteen (d) Thirty fiv e 4 d , 5 p and 5 s will be filled with electrons first[MA DT Bi h a r 19
198. Which of the following has the m axim um num ber of (a) 4 d
unpaired electrons [IIT 1996]
(b) 5 p
(a) Mg 2  (b) Ti 3  (c) 5 s
(c) V 3  (d) Fe 2  (d) 4 d and 5 s will be filled sim ultaneously
199. Which of the following has m ore unpaired d -electrons 209. The energy of an electron of 2 p y orbital is [A MU 1984]
[CBSE PMT 1999]
(a) Greater than that of 2 p x orbital
(a) Zn  (b) Fe 2 
(b) Less than that of 2 p x orbital
(c) N 3  (d) Cu 
(c) Equal to that of 2 s orbital
200. Maximum electrons in a d -orbital are [CPMT 1999]
(d) Sam e as that of 2 p z orbital
(a) 2 (b) 1 0
210. Which of the following principles/rules lim its the
(c) 6 (d) 1 4
maximum number of electrons in an orbital to two[CBSE PMT 198
201. The num ber of unpaired electrons in Fe 3  (Z  26) are (a) Aufbau principle
[KCET 2000] (b) Pauli's exclusion principle
(a) 5 (b) 6 (c) Hund's rule of m axim um m ultiplicity
(c) 3 (d) 4 (d) Heisenberg's uncertainty principle
202. How m any unpaired electrons are present in cobalt [ Co] 211. The electrons would go to lower energy lev els first and
m etal [RPMT 2002] then to higher energy lev els according to which of the
(a) 2 (b) 3 following
(c) 4 (d) 7 [BHU 1990; MP PMT 1993]
203. The num ber of unpaired electrons in nitrogen is (a) Aufbau principle
[Pb. CET 2002] (b) Pauli's exclusion principle
(a) 1 (b) 3 (c) Hund's rule of m axim um m ultiplicity
(c) 2 (d) None of these (d) Heisenberg's uncertainty principle
212. Energy of atomic orbitals in a particular shell is in the
204. Which of the following has the least energy
order
(a) 2 p (b) 3 p [A FMC 1990]
(c) 2 s (d) 4 d (a) s  p  d  f (b) s  p  d  f
205. Pauli's exclusion principle states that [CPMT 1983, 84] (c) p  d  f  s (d) f  d  s  p
(a) Nucleus of an atom contains no negativ e charge
213. Aufbau principle is not satisfied by [MP PMT 1997]
(b) Electrons m ove in circular orbits around the nucleus
(a) Cr and Cl (b) Cu and Ag
(c) Electrons occupy orbitals of lowest energy
(d) All the four quantum numbers of two electrons in an (c) Cr and Mg (d) Cu and Na
atom cannot be equal 214. Which of the following explains the sequence of filling the
206. For the energy lev els in an atom , which one of the electrons in different shells [A IIMS 1998; BHU 1999]
following statements is correct [A IIMS 1983] (a) Hund's rule (b) Octet rule
(a) There are sev en principal electron energy lev els (c) Aufbau principle (d) All of these
(b) The second principal energy lev el can hav e four sub- 215. Aufbau principle is obey ed in which of the following
energy levels and contains a maximum of eight electrons electronic configurations [A FMC 1999]
(c) The M energy lev el can hav e m axim um of 3 2 (a) 1s 2 2 s 2 2 p 6 (b) 1s 2 3 p 3 3 s 2
electrons
(c) 1s 2 3 s 2 3 p 6 (d) 1s 2 2 s 2 3 s 2
(d) The 4 s sub-energy level is at a higher energy than
216. Following Hund’s rule which elem ent contains six
the 3 d sub-energy lev el
unpaired electron [RPET 2000]
207 . The statem ents [A IIMS 1982]
(a) Fe (b) Co
(i) In filling a group of orbitals of equal energy , it is
(c) Ni (d) Cr
energetically preferable to assign electrons to em pty
orbitals rather than pair them into a particular 217 . Electron enters the sub-shell for which (n  l) v alue is
orbital. m inim um . This is enunciated as
(ii) When two electron s are placed in two different [RPMT 2000]
orbitals, energy is lower if the spins are parallel. (a) Hund’s rule
are v alid for (b) Aufbau principle
(a) Aufbau principle (c) Heisenberg uncertainty principle
(b) Hund's rule (d) Pauli’s exclusion principle
 70 Structure of atom
218. The atom ic orbitals are progressiv ely filled in order of (a) F  (b) Oxy gen atom
increasing energy . This principle is called as
[MP PET 2001] (c) Mg (d) N 
(a) Hund’s rule (b) Aufbau principle 2. Atom s consists of protons, neutrons and electrons. If the
(c) Exclusion principle (d) de-Broglie rule m ass of neutrons and electrons were m ade half and two
219. The correct order of increasing energy of atom ic orbitals tim es respectively to their actual masses, then the atomic
is m ass of 6 C 12 [NCERT 1982]
[MP PET 2002] (a) Will rem ain approxim ately the sam e
(a) 5 p  4 f  6 s  5 d (b) 5 p  6 s  4 f  5 d (b) Will becom e approxim ately two tim es
(c) 4 f  5 p  5 d  6 s (d) 5 p  5d  4 f  6 s (c) Will rem ain approxim ately half
220. The orbital with maximum energy is [CPMT 2002] (d) Will be reduced by 2 5%
(a) 3 d (b) 5p 3. The increasing order (lowest first) for the v alues of e / m
(c) 4 s (d) 6 d (charge/m ass) for [IIT 1984]
221. p-orbitals of an atom in presence of m agnetic field are (a) e, p, n,  (b) n, p, e, 
[Pb. PMT 2002]
(c) n, p, , e (d) n, , p, e
(a) Two fold degenerate (b) Non degenerate
(c) Three fold degenerate (d) None of these 4. The electronic configuration of a dipositive metal M 2  is
222. Orbital angular momentum for a d-electron is[MP PET 2003] 2 , 8, 14 and its atomic weight is 56 a.m.u. The num ber of
neutrons in its nuclei would be
6h 6h
(a) (b) [MNR 1984, 89; Kerala PMT 1999]
2 2
(a) 3 0 (b) 3 2
12h 12 h
(c) (d) (c) 3 4 (d) 4 2
2 2
223. Number of nodal centres for 2s orbital [RPET 2003] 5. The ratio of the energy of a photon of 2000 Å wavelength
(a) 1 (b) 0 radiation to that of 4000 Å radiation is
(c) 4 (d) 3 [IIT 1986; DCE 2000; JIPMER 2000]
224. The orbital angular m om entum of an electron in 2 s - (a) 1 /4 (b) 4
orbital is [MP
(c)PET
1 /22004] (d) 2
1 h h 6. Discov ery of the nucleus of an atom was due to the
(a) (b)
2 2 2 experiment carried out by [CPMT 1983; MP PET 1983]
h (a) Bohr (b) Mosley
(c) 2 (d) Zero
2 (c) Rutherford (d) Thom son
225. The m aximum num ber of electrons present in an orbit 7. In a Bohr's m odel of atom when an electron jum ps from
l  3 , is [Pb. PMT 2004] n  1 to n  3 , how m uch energy will be em itted or
(a) 6 (b) 8 absorbed [CBSE PMT 1996]
(c) 1 0 (d) 1 4
(a) 2.15  10 11 erg (b) 0.1911  10 10 erg
226. Number of unpaired electrons in Mn 4  is [DPMT 2005]
(a) 3 (b) 5 (c) 2.389  10 12 erg (d) 0.239  10 10 erg
(c) 6 (d) 4 8. The nucleus of an atom can be assum ed to be spherical.
227 . Which of the following sequence is correct as per Aufbau The radius of the nucleus of m ass number A is giv en by
principle [DPMT 2005] 1.25  10 13  A1 / 3 cm Radius of atom is one Å . If the
(a) 3 s  3d  4 s  4 p (b) 1s  2 p  4 s  3d m ass num ber is 64 , then the fraction of the atom ic
(c) 2 s  5 s  4 p  5 d (d) 2 s  2 p  3d  3 p volume that is occupied by the nucleus is [NCERT 1983]
228. Electronic configuration of deuterium atom is (a) 1.0  10 3 (b) 5.0  10 5
[J&K CET 2005]
(c) 2.5  10 2 (d) 1.25  10 13
(a) 1s 1 (b) 2s 2 9. The energy of an electron in the first Bohr orbit of
(c) 2s 1 (d) 1s 2 H atom is 13.6 eV . The possible energy v alue(s) of the
excited state(s) for electrons in Bohr orbits to hy drogen
is(are)
[IIT 1998; Orissa JEE 2005]
(a) 3.4 eV (b) 4.2eV
(c) 6.8 eV (d) 6.8 eV
10. The energy of the electron in the first orbit of He  is
1. Which of the following atom s and ions are isoelectronic  871.6  10 20 J . The energy of the electron in the first
i.e. hav e the sam e num ber of electrons with the neon orbit of hydrogen would be[Roor kee Qu a l ify i n g 1998]
atom
[NCERT 1978] (a)  871.6  10 20 J (b)  435.8  10 20 J
 Structure of atom 71

(c)  217.9  10 20 J (d)  108.9  10 20 J 21. Which of the following electron transition in a hy drogen
atom will require the largest am ount of energy
11. The total number of v alence electrons in 4.2 gm of N 3 [UPSEAT 1999, 2000, 01]
ion is ( N A is the Av ogadro's number) [CBSE PMT 1994] (a) From n  1 to n  2 (b) From n  2 to n  3
(a) 1.6 N A (b) 3.2 N A (c) From n   to n  1 (d) From n  3 to n  5
(c) 2.1 N A (d) 4.2 N A 22. In Bohr series of lines of hy drogen spectrum , the third
line from the red end corresponds to which one of the
12. The Bohr orbit radius for the hy drogen atom (n  1) is following inter-orbit jumps of the electron for Bohr orbits
approximately 0.530 Å . The radius for the first excited in an atom of hy drogen [A IEEE 2003]
state (n  2) orbit is [CBSE PMT 1998; BHU 1999] (a) 3  2 (b) 5  2
(a) 0.13 Å (b) 1.06 Å (c) 4  1 (d) 2  5
(c) 4.77 Å (d) 2.12 Å 23. The v alue of Planck’s constant is 6.63  10 34 Js. The
v elocity of light is 3.0  10 8 ms 1 . Which value is closest to
13. The frequency of a wave of light is 12  10 14 s 1 . The wav e
number associated with this light is [Pb. PMT 1999] the wavelength in nanometres of a quantum of lig ht with
frequency of 8  10 15 s 1 [CBSE PMT 2003]
(a) 5  10 7 m (b) 4  10 8 cm 1
(a) 3  10 7
(b) 2  10 25
(c) 2  10 7 m 1 (d) 4  10 4 cm 1
14. The series lim it for Balm er series of H-spectra is (c) 5  10 18 (d) 4  10 1
[A MU (Engg.) 1999] 24. As electron m oves away from the nucleus, its potential
energy [UPSEA T 2003]
(a) 3 800 (b) 4 2 00
(a) Increases (b) Decreases
(c) 3 6 4 6 (d) 4 000
(c) Rem ains constant (d) None of these
15. The ionization energy of hydrogen atom is 13.6 eV . The
energy required to excite the electron in a hydrogen atom
from the ground state to the first excited state is
(Avogadro’s constant = 6.022 × 10 23) [BHU 1999]

(a) 1.69  10 20 J (b) 1.69  10 23 J

(c) 1.69  10 23 J (d) 1.69  10 25 J
Read the assertion and reason carefully to m ark the correct
16. The energy required to dislodge electron from excited option out of the options giv en below :
isolated H-atom, IE1  13.6 eV is [DCE 2000]
(a) I f both assertion and reason are true and the reason is
(a)  13.6 eV (b)  13.6 eV the correct explanation of the assertion.
(b) I f both assertion and reason are true but reason is not
(c)  13.6 and  3.4 eV (d)  3.4 eV the correct explanation of the assertion.
(c) I f assertion is true but reason is false.
17. The num ber of nodal planes in a p x is (d) I f the assertion and reason both are false.
[IIT Screening 2000] (e) I f assertion is false but reason is true.
(a) One (b) Two 1. Assertion : The position of an electron can be
(c) Three (d) Zero determined exactly with the help of an
18. The third line in Balm er series corresponds to an electron m icroscope.
electronic transition between which Bohr’s orbits in Reason : The product of uncertainty in the
hy drogen m easurement of its m om entum and the
[MP PMT 2001] uncertainty in the m easurem ent of the
position cannot be less than a finite limit.
(a) 5  3 (b) 5  2
[NDA 1999]
(c) 4  3 (d) 4  2 2. Assertion : A spectral line will be seen for a
19. Which of the following has m aximum number of unpaired 2 p x  2 p y transition.
electron (atomic number of Fe 26) [MP PMT 2001]
Reason : Energy is released in the form of wav e of
(a) Fe (b) Fe (II) light when the electron drops from
(c) Fe (III) (d) Fe (IV) 2 p x  2 p y orbital. [A IIMS 1996]
20. The frequency of one of the lines in Paschen series of
3. Assertion : The cation energy of an electron is largely
hy drogen atom is 2.340  10 11 Hz. The quantum num ber determ ined by its principal quantum
n 2 which produces this transition is [DPMT 2001] num ber.
(a) 6 (b) 5 Reason : The principal quantum num ber n is a
m easure of the m ost probable distance of
(c) 4 (d) 3 finding the electron around the nucleus.
[A IIMS 1996]
 72 Structure of atom

4. Assertion : Nuclide 30
Al13 is less stable than 40
Ca 20 Reason : Num ber of orbitals in a shell equals to
2n .
Reason : Nuclides having odd num ber of protons 17. Assertion : Energy of the orbitals increases as
and neutrons are generally unstable
[IIT 1998] 1s  2 s  2 p  3 s  3 p  3d  4 s  4 p
5. Assertion : The atoms of different elem ents hav ing  4 d  4 f  ......
sam e m ass number but different atom ic Reason : Energy of the electron depends
num ber are known as isobars com pletely on principal quantum
Reason : The sum of protons and neutrons, in the num ber.
isobars is always different [A IIMS 2000] 18. Assertion : Splitting of the spectral lines in the
6. Assertion : Two electrons in an atom can hav e the presence of m agnetic field is known as
sam e values of four quantum num bers. stark effect.
Reason : Two electrons in an atom can be present Reason : Line spectrum is sim plest for hy drogen
in the sam e shell, sub-shell and orbital atom .
and have the same spin [A IIMS 2001] 19. Assertion : Thom son’s atom ic m odel is known as
7. Assertion : The v alue of n for a line in Balm er series ‘raisin pudding’ m odel.
of hy drogen spectrum having the highest Reason : The atom is v isualized as a pudding of
wav e length is 4 and 6 . positiv e charge with electrons (raisins)
Reason : For Balm er series of hydrogen spectrum , em bedded in it.
the v alue n1  2 and n2  3 , 4 , 5. 20. Assertion : Atom ic orbital in an atom is designated
by n, l, m l and m s .
[A IIMS 1992]
Reason : These are helpful in designating electron
8. Assertion : Absorption spectrum conists of som e
present in an orbital.
bright lines separated by dark spaces.
21. Assertion : The transition of electrons n3  n 2 in H
Reason : Em ission spectrum consists of dark lines.
[A IIMS 2002] atom will em it greater energy than
n4  n3 .
9. Assertion : A resonance hybrid is always m ore stable
than any of its canonical structures. Reason : n 3 and n 2 are closer to nucleus tan n 4 .
Reason : This stability is due to delocalization of 22. Assertion : Cathode rays are a stream of  -particles.
electrons. [A IIMS 1999]
Reason : They are generated under high pressure
10. Assertion : Cathode ray s do not trav el in straight and high v oltage.
lines.
23. Assertion : In case of isoelectronic ions the ionic size
Reason : Cathode ray s penetrate through thick increases with the increase in atom ic
sheets [A IIMS 1996] num ber.
11. Assertion : Electrons revolving around the nucleus Reason : The greater the attraction of nucleus,
do not fall into the nucleus because of greater is the ionic radius.
centrifugal force.
Reason : Rev olv ing electrons are planetary
electrons.
[A IIMS 1994]
12. Assertion : Threshold frequency is a character istic
for a m etal.
Reason : Threshold frequency is a m axim um
frequency required for the ejection of Discovery and Properties of anode, cathode rays
electron from the m etal surface.
neutron and Nuclear structure
13. Assertion : The radius of the first orbit of hy drogen
atom is 0.52 9 Å.
1 d 2 a 3 c 4 c 5 b
Reason : Radius for each circular orbit
(rn )  0.52 9 Å (n 2 / Z) , where n  1 ,2 ,3 6 a 7 b 8 a 9 d 10 c

and Z  atom ic num ber. 11 b 12 d 13 b 14 a 15 b

14. Assertion : 3 d z 2 orbital is spherically sy m m etrical. 16 b 17 c 18 c 19 c 20 b

Reason : 3 d z 2 orbital is the only d -orbital which 21 a 22 d 23 c 24 b 25 d

is spherical in shape. 26 c 27 b 28 d 29 c 30 a
15. Assertion : Spin quantum number can have the value 31 b 32 d 33 b 34 c 35 c
+ 1 /2 or –1 /2 .
36 a 37 b 38 a 39 d 40 c
Reason : (+ ) sign here signifies the wave function.
16. Assertion : Total number of orbitals associated with 41 c
principal quantum num ber n  3 is 6.
 Structure of atom 73
Atomic number, Mass number, Atomic species 1 b 2 b 3 a 4 c 5 c
6 c 7 b 8 d 9 d 10 a
1 b 2 a 3 b 4 b 5 a
11 a 12 c 13 a 14 b 15 d
6 a 7 c 8 b 9 c 10 b
16 b 17 a 18 c 19 c 20 b
11 b 12 c 13 b 14 c 15 c
16 c 17 c 18 a 19 c 20 a Quantum number, Electronic configuration
21 c 22 b 23 c 24 d 25 b and Shape of orbitals
26 b 27 a 28 a 29 c 30 b
1 c 2 a 3 b 4 d 5 c
31 c 32 d 33 d 34 c 35 c
6 c 7 c 8 a 9 a 10 a
36 c 37 c 38 b 39 d 40 c
11 c 12 c 13 a 14 a 15 d
41 b 42 c 43 a 44 c 45 b
16 c 17 c 18 d 19 b 20 c
46 c 47 d 48 a 49 c 50 c
21 c 22 a 23 c 24 d 25 c
51 a 52 c 53 b 54 a 55 c
26 c 27 b 28 d 29 e 30 b
56 a 57 d 58 c 59 a 60 a
31 d 32 a 33 c 34 d 35 d
61 d 62 b 63 a 64 c 65 b
36 c 37 b 38 b 39 d 40 c
66 a 67 c 68 a 69 d 70 d
41 d 42 c 43 c 44 a 45 a
71 c 72 a 73 b 74 d
46 a 47 b 48 c 49 c 50 b
Atomic models and Planck's quantum theory 51 c 52 b 53 b 54 b 55 c
56 c 57 b 58 e 59 c 60 c
1 c 2 a 3 b 4 b 5 d
6 b 7 c 8 b 9 c 10 a 61 d 62 d 63 d 64 c 65 b

11 b 12 a 13 d 14 b 15 b 66 d 67 c 68 d 69 c 70 b
16 c 17 a 18 c 19 a 20 d 71 a 72 c 73 c 74 c 75 a
21 d 22 c 23 d 24 d 25 c 76 c 77 c 78 c 79 d 80 d
26 a 27 c 28 b 29 c 30 a 81 b 82 c 83 a 84 a 85 b
31 b 32 c 33 d 34 b 35 b
86 c 87 a 88 b 89 c 90 b
36 a 37 c 38 c 39 c 40 a
91 d 92 a 93 b 94 b 95 d
41 c 42 d 43 d 44 a 45 d
96 d 97 a 98 a 99 d 100 c
46 b 47 a 48 c 49 d 50 a
51 a 52 c 53 d 54 c 55 b 101 b 102 d 103 a 104 c 105 d
56 b 57 b 58 a 59 b 60 c 106 a 107 c 108 d 109 a 110 d
61 c 62 b 63 c 64 c 65 b 111 d 112 b 113 c 114 b 115 b
66 b 67 c 68 a 69 b 70 d 116 a 117 c 118 b 119 a 120 a
71 a 72 d 73 a 74 c 75 d
121 d 122 b 123 b 124 b 125 d
76 b 77 a 78 a 79 c 80 a
126 d 127 b 128 c 129 a 130 b
81 a
131 a 132 c 133 d 134 b 135 a
Dual nature of electron 136 a 137 c 138 c 139 c 140 c
141 c 142 d 143 c 144 c 145 b
1 c 2 a 3 a 4 b 5 c
146 d 147 a 148 c 149 b 150 c
6 b 7 d 8 a 9 d 10 d
151 d 152 a 153 a 154 d 155 b
11 c 12 c 13 b 14 b 15 b
156 d 157 a 158 b 159 c 160 d
16 c 17 c 18 c 19 b 20 a
161 c 162 d 163 b 164 c 165 a
21 d
166 d 167 d 168 d 169 b 170 a
171 c 172 d 173 c 174 b 175 d
Uncertainty principle and Schrodinger wave
equation 176 c 177 a 178 b 179 b 180 c
 74 Structure of atom

181 c 182 b 183 c 184 c 185 a 10. (c) This is because chargeless particles do not undergo
any deflection in electric or m agnetic field.
186 d 187 c 188 c 189 a 190 c
11. (b) Neutron and proton found in nucleus.
191 b 192 a 193 d 194 b 195 d 13. (b) Cathode ray s are m ade up of negativ ely charged
196 a 197 c 198 d 199 b 200 b particles (electrons) which are deflected by both the
electric and m agnetic fields.
201 a 202 b 203 b 204 c 205 d 15. (b) Mass of neutron is greater than that of proton, m eson
206 b 207 b 208 c 209 d 210 b and electron.
Mass of neutron = mass of proton + m ass of electron
211 a 212 a 213 b 214 c 215 a
16. (b) Proton is 1 837 (approx 1800) times heav ier than an
216 d 217 b 218 b 219 b 220 d 1
electron. Penetration power 
221 b 222 b 223 a 224 d 225 d mass
226 a 227 b 228 a 18. (c) Nucleus of helium is 2 He 4 m ean 2 neutrons and 2
protons.
Critical Thinking Questions 19. (c) Proton is the nucleus of H  atom ( H  atom dev oid
of its electron).
1 a 2 d 3 d 4 a 5 d 20. (b) Cathode ray s are m ade up of negativ ely charged
6 c 7 b 8 d 9 a 10 c particles (electrons, e  )
11 a 12 d 13 d 14 c 15 b 26. (c) Size of nucleus is m easured in Fermi (1 Ferm i
16 d 17 a 18 b 19 c 20 b  10 15 m) .
21 a 22 a 23 d 24 a 27 . (b) A m olecule of an elem ent is a incorrect statem ent.
The correct statement is “an element of a m olecule”.
Assertion & Reason

1 d 2 d 3 a 4 a 5 c
6 d 7 e 8 d 9 a 10 e
11 b 12 c 13 a 14 d 15 c
16 d 17 c 18 e 19 a 20 e
21 b 22 d 23 d

Discovery and Properties of anode, cathode rays

neutron and Nuclear structure

1. (d) Neutrons and protons in the nucleus and electrons in

the extranuclear region.
2. (a) It consists of proton and neutron and these are also
known as nucleones.
15
3. (c) Radius of nucleus ~ 10 m.
4. (c) Positiv e ions are formed from the neutral atom by the
loss of electrons.
5. (b) The  -ray particle constitute electrons.
6. (a) Jam es Chadwick discov ered neutron (0 n1 ) .
7. (b) Charge/m ass for
2 1 1
n  0,   , p  and e 
4 1 1 / 1837
11
9. (d) The density of neutrons is of the order 10 kg / cc.
 Structure of atom 75
29. (c) Proton is represented by p having charge +1 discovered in 1988 12. (c) Most probable radius = a / Z 0

by Goldstein. where a = 52.9 pm. For helium ion, Z = 2.

0

31. (b) The nature of anode rays depends upon the nature of residual 52 . 9
gas. r =
mp
= 26.45 pm.
2
32. (d) H  (proton) will have very large hydration energy due to its
very small ionic size 13. (b) Four unpaired electron are present in the Fe 2  ion
2
1 Fe 26  [ Ar] 3d 6 ,4 s 0
Hydration energy 
Size 14. (c) Na  has 10 electron and Li  has 2 electron so these are
33. (b) Mass of a proton  1.673  10 24 g different number of electron from each other.
16. (c) P15  2, 8, 5
 Mass of one mole of proton
 9.1  10 24  6.02  10 23  10.07  10 1  1.008 g 17. (c) 8O  1s 2 2 s 2 2 p 4

Mass of a electron  9.1  10 28 g 18. (a) 35 Br

80
 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 10 4 s 2 4 p 5
 Mass of one mole of electron A  80 , Z  35 , N  ?
 9.1  10 28
 6.02  10 23
 54.78  10 5
g  0.55 mg . N  A  Z  80  35  45
35. (c) One mole of electron = 6.023 × 10 electron 23
atomic number (Proton) is 35 and no. of neutron is 45.
Mass of one electron = 9.1 × 10 gm –28

19. (c) 16 O   have more electrons than neutron

8
Mass of one mole of electrons
p  8, e  10, n  8 .
= 6.023 × 10 23  9.1  10 28 gm = 5.48  10 4 gm
20. (a) A 12 and X 13 both are isotopes but have different no. of
= 5.48  10 4  1000 mg = 0.548 gm  0.55 mg .
6 6
neutrons.
36. (a) Charge on proton  1 unit, charge on  particle = + 2 units, 2 : A12 , For A have p  6, e  6 and n  6 and
6
1.
37. (b) m p / me ~ 1837 ~ 1.8  10 3 . 6 X 13 , For B have p  6, e  6 and n  7

38. (a) Splitting of signals is caused by protons attached to adjacent 21. (c) P  20, mass no. (A) = 40
carbon provided these are not equivalent to the absorbing N  A–P = 40  20  20
proton.
39. (d) Nucleus consists of proton and neutron both are called as P  N  20.
nucleon.
22. (b) Electrons in Na   11  1  10
40. (c) Positron (1e 0 ) has the same mass as that of an electron
Electrons in Mg2   12  2  10
(1e ) .
0
40
23. (c) 20 Ca has 20 proton, 20 neutron.
1
41. (c) Electron time lighter than proton so their mass ratio 24. (d) CH 3  6  3  1  8e ,
1837
will be 1 : 1837
H 3 O   3  8  1  10e  ,

Atomic number, Mass number, Atomic species NH 3  7  3  10e  , CH 3  6  3  1  10e 

1. (b) The number of electrons in an atom is equal to its atomic 25. (b)  CONH 2  6  8  7  2  1 (from other atom to form
number i.e. number of protons. covalent bond) = 24.
2. (a) No. of protons = Atomic no. = 25 and no. of neutron = 55 – 26. (b) Complete E.C.  [ Ar]18 3d 10 4 s 2 4 p 6 .
25 = 30.
3. (b) No. of neutrons = mass number – no. of protons. = W – N. Hence no. of e   no. of protons  36  Z .
4. (b) 30 Zn 70 , Zn 2  has No. of Neutrons = 70 – 30 = 40. 28. (a) K   1s 2 2 s 2 2 p 6 3 s 2 3 p 6

5. (a) Na  and Ne are isoelectronic which contain 10 electrons. Cl   1s 2 2 s 2 2 p 6 3 s 2 3 p 6 .

6. (a) One molecule of CO 2 have 22 electrons. 29. (c) Mass no.  At. Wt.
Mass no. = no. of protons + no. of neutrons
7. (c) Cl and Cl  differs in number of electrons. Cl has 17 e 
At. no. = no. of protons.
while Cl  has 18 e  .
30. (b) N 2O  14  8  22
8. (b) CO and CN  are isoelectronic.
CO  6  8  14 and CN   6  7  1  14 . CO 2  6  16  22.
9. (c) Mass of an atom is due to nucleus (neutron + proton). 31. (c) Neutron in 12
 6, , Neutrons in 28
Si  14
6 C 14
10. (b) Atomic number is defined as the number of protons in the
nucleus. Ratio = 6 : 14 = 3 : 7.

11. (b) X 56 A  P  N  Z  N  E  N 33. (d) N 7  1s 2 2 s 2 2 p 3

26

N  A  E  56  26  30 N   1s 2 2 s 2 2 p 2
 76 Structure of atom
C  1s 2 2 s 2 2 p 2 . 62. (b) N 3  , F  and Na  (These three ions have e   10 , hence
they are isoelectronic)
34. (c) O  C  O, linear structure 180 o angle
63. (a) NO 3 and CO 32  consist of same electron and show same
Cl  Hg  Cl, linear structure 180 o angle. isostructural.
35. (c) H   1s 2 and He   1s 2 . 64. (c) Atomic number of chlorine 17 and in Cl  ion total no. of
36. (c) In the nucleus of an atom only proton and neutrons are electron =18.
present. 65. (b) Tritium (H 13 ) has one proton and two neutron.
63
37. (c) Cu 29 Number of neutrons = atomic mass – atomic number = 63
67. (c) X 35  1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 2 3d 10 4 s 2 4 p 5
– 29 = 34.
38. (b) 21 Protons and 24 Neutrons are present in nucleus and element Total no. of e  is all p–orbitals  6  6  5  17 .
is Sc. 68. (a) Since its nucleus contain 9 proton so its. atomic number is 9
40. (c) 14
, n  14  7  7 and its electronic configuration is 2, 7. So it require one more
7 X
electron to complete its octet. Hence its valency is 1.
42. (c) Cl  have 17 proton, 18 neutron and 18 electron. 69. (d) K 2 S formed by K  and S 2  ion. We know that atomic
43. (a) Number of unpaired electrons in inert gas is zero because they
have full filled orbitals. number of K is 19 and in K  ion its atomic number would be
44. (c) Electrons and Protons are same in neutral atom. 18 similarly atomic number of S is 16 and in form S 2  ion its
48. (d) No. of proton and no. of electron = 18 [ Ar1836 ] and No. of atomic number would be 18 so the K  and S 2  are
neutron = 20 isoelectronic with each other in K 2 S .
Mass number = P + N = 18  20  38. 70. (d) 20 Ca  2, 8, 8, 2
Ca 2   2, 8, 8
231
49. (c) In Xe 89 number of protons and electrons is 89 and No. of
neutrons = A – Z = 231 – 89 = 142. Hence, Ca 2  has 8 electrons each in outermost and
51. (a) NO 2 and O 3 are isostere. The number of atoms in these penultimate shell.
71. (c) Atomic no. of C = 6 so the number of protons in the nucleus =
( 3) and number of electrons (24 ) are same. 6
52. (c) Number of electrons in nitrogen = 7 and number of electron is
72. (a) No. of P  Z  7; No. of electrons in N 3   7  3  10.
oxygen = 8 we know that formula of nitrate ion is NO 3 we
2
also know that number of electron 73. (b) Heavy hydrogen is 1 D .Number of neutrons = 1
= (1 × Number of electrons in nitrogen) 74. (d) Atomic number is always whole number.
+ (3 × number of electrons in oxygen) + 1
= (1 × 7) + (3 × 8) + 1 = 32. Atomic models and Planck's quantum theory
Molecular mass 256
53. (b) Atomicity =   8  S8 . 2. (a) The central part consisting whole of the positive charge and
Atomic mass 32 most of the mass caused by nucleus, is extremely small in size
compared to the size of the atom.
54. (a) In case of N 3  , p  7 and c  10
3. (b) Electrons in an atom occupy the extra nuclear region.
55. (c) Chlorine Cl 17  [Ne ] 4. (b) According to the Bohr model atoms or ions contain one
3s 2
3p 5
electron.
5. (d) The nucleus occupies much smaller volume compared to the
volume of the atom.
7. (c) -particles pass through because most part of the atom is
empty.
Three electron pair
56. (a) Bromine consists of outer most electronic configuration 8. (b) An electron jumps from L to K shell energy is released.
[ Ar] 3d 10 4 s 2 4 p 5 . 9. (c) Neutron is a chargeless particles, so it does not deflected by
electric or magnetic field.
57. (d) Na   1s 2 2 s 2 2 p 6 10. (a) Energy is always absorbed or emitted in whole number or
multiples of quantum.
Mg  1s 2 2 s 2 2 p 6
++

11. (b) Both He and Li  contain 2 electrons each.

18. (c) During the experimental verification of de-Broglie equation,
O 2   1s 2 2 s 2 2 p 6
Davisson and Germer confirmed wave nature of electron.
Cl   1s 2 2 s 2 2 p 6 3 s 2 3 p 6 19. (a) Increases due to absorption of energy and it shows absorption
spectra.
60. (a) Ar1840 = atomic number 18 and no. of Neutron in case of 20. (d) Rutherford -Scattering experiment.
21. (d) It represents Heisenberg’s uncertainty principle.
Ar22
Neutron = Atomic mass – Atomic number E4 22 4 1 E 328
23. (d)  2   ; E4  2   82 kJ / mol.
 40  18  22 E2 4 16 4 4 4
61. (d) Nucleus of tritium contain [H 13 ] c 3  10 8
27. (c) When c     than     1 .5  10 2 m
p 1 , e 1 , n  2  2  10 6
 Structure of atom 77
28. (b) According to quantum theory of radiation, a hot body emits  12.1567  10 8 m
radiant energy not continuously but discontinuously in the
form of small packets of energy called quanta or photons. 3  10 8
c
34
v   24.66  1014 Hz .
h 6 .6  10  12.567  10 8
30. (a) p   3  10 23 kgms 1
 2 .2  10 11 h h
67. (c) We know that   ;  m
n 2h2 mv m
34. (b) Bohr’s radius  . Which is a positive quantity.
4 2 me 2 z The velocity of photon (v) = 3  10 8 m sec 1
40. (a) Gold used by Rutherford in scatting experiment.   1.54  10 8 cm  1.54  10 10 meter
 1 1  6 .626  10 34 Js
41. (c) E  E3  E2  13.6  2  2   1 .9 eV m
 (2) (3)  1 .54  10 10 m  3  10 8 m sec 1
42. (d) R  R 0 ( 1.4  10 13 cm)  A 1 / 3  1.4285  10 32 kg .
q 1q  1 68. (a) The spliting of spectral line by the magnetic field is called
43. (d)        9 .6  10 7  4 .8  10 7 C kg 1 Zeeman effect.
 m  2  m  p 2
69. (b) r  n 2 (excited state n  2 )
44. (a) According to Hydrogen spectrum series.
r  4a 0
45. (d) The electron can move only in these circular orbits where the
h 70. (d) rn  n 2 : An  n 4
angular momentum is a whole number multiple of or it
2 A 2 n 24 2 4 16
is quantised.  4  4   16 : 1
A1 n1 1 1
46. (b) Generally electron moving in orbits according to Bohr‘s
principle. 4 2 mr 2
47. (a) According to the planck’s law that energy of a photon is 71. (a) It will take
nh
directly proportional to its frequency i.e. E  h
49. (d) Bohr’s radius of the hydrogen atom n2
72. (d) rH  0 .529 Å
n 2  0.529Å z
r  ; where z = Atomic number, For hydrogen ; n  1 and z  1 therefore
z
n = Number of orbitals rH  0.529 Å
2 .172  10 18  2 .172  10 18 For Be 3  : Z  4 and n  2 Therefore
51. (a) E 
n2 22
0 .529  2 2
19
 5.42  10 J . rBe 3    0 .529 Å .
4
hc hc
52. (c) E  or   2
13.6 Z eff
 E 73. (a) Eionisation  E  En  eV
n2
6 .64  10 34  3  10 8
  6 .64  10 8 Å  13.6 Z 2 13.6 Z 2 
3  10 8 =   
2
53. (d) rn  r1  n 2  n 2 n12 
r3  0.53  3 2  0.53  9  4.77 Å 13.6  1 2 13.6  1 2
E  h   ; h  13.6  0.85
54. (c) According to Rutherford an atom consists of nucleus which is (1)2 (4 )2
small in size but carries the entire mass (P+ N ).
55. (b) Wavelength of spectral line emitted is inversely proportional to  h  6.625  10 34
1 13.6  0 .85
energy   .   1.6  10 19 = 3.08  10 15 s 1 .
E 6 .625  10 34
1 1 1 1 1 
56. (b) E  ; E1  ; E2  74. (c)
1
 R 2  2 
 8000 16000   n1 n 2 
E1 16000
  2  E1  2 E2 1 1 1 
E2 8000  1 .097  10 7 m 1  2  2 
 1  
c3  10 8 ms 1
58. (a)     5 .0  1014 Hz .    91  10 9 m
 600  10  9 m
13.6 13.6 13.6 We know 10 9  1 nm So   91nm
59. (b) E eV    3.40 eV
n2 22 4 75. (d) r  n 2
r2 (2)2 For I orbit   1
st

65. (b) Bohr radius   2  4.

r1 (1) For III orbit =   3 2  9
rd

1 So it will 9  .
1 1  1 1 
66. (b) v   R  2  2   109678     82258.5 76. (b) Bohr suggest a formulae to calculate the radius and energy of
  n1 n 2  1 4  each orbit and gave the following formulae
  1.21567  10 5 cm or   12.1567  10 6 cm
 78 Structure of atom

n2h2 h 6 .63  10 34

rn     6 .63  10  29 m
4 2 kme 4 Z mv 10 6  10
Where except n 2 , all other unit are constant so rn  n 2 . 15. (b) According to de–Broglie
 E0 h 6 .62  10 20 erg. sec
77. (a) Energy of an electron E   
n2 mv 2
 5  10 4 cm / sec
For energy level (n  2) 6 .023  10 23
13.6 13.6 6 .62  10 27  6 .023  10 23
E   3 .4 eV .  cm  4  10 8 cm  4 Å .
(2) 2
4 2  5  10 4
78. (a) Energy of ground stage (E 0 ) = 13.6 eV and energy level = h 6 .625  10 34
5 16. (c)    10  30 m .
mv 5
13.6 13.6 13.6 0 .2 kg 
E5  eV  =  0 .54 eV . 60  60 ms 1
n2 52 25
17. (c) From de Broglie equation
79. (c) Positive charge of an atom is present in nucleus.
81. (a) For n4  n1 , greater transition, greater the energy difference, h 6 .62  10 34
 = = 1.32  10 35 m .
lesser will be the wavelength. mv 0 .5  100
18. (c) Dual nature of particle was proposed by de-broglie who gave
Dual nature of electron the following equation for the wavelength.
h
h h h 
1. (c) According to de-Broglie equation   or or . mv
mv p mc 19. (b) One percent of the speed of light is
h h h  1 
4. (b)   or or de-Broglie equation. v  1
 (3 .00  10 ms ) = 3.00  10 ms
8 6 1
p mv mc
 100 
5. (c) Emission spectra of different  accounts for quantisation of
energy. Momentum of the electron (p ) = m 
6. (b) According to de-Broglie equation = (9.11  10 31 kg ) (3.00  10 6 ms 1 )
h h h
 , p  mv ,   ,   = 2.73  10 24 kg ms 1
mv p mc
The de-broglie wavelength of this electron is
 h 
7. (d) According to de-Broglie    .
 mv  h 6 .626  10 34
 
p 2 .73  10  24 kgms 1
h 6 .63  10 34
8. (a)    6 .63  10  33 m
mv 10  3  100   2.424  10 10 m .
h 1 20. (a) We know that the correct relationship between wavelength and
9. (d)   . For same velocity   . h
mv m momentum is   . Which is given by de-Broglie.
SO 2 molecule has least wavelength because their molecular p
mass is high. 21. (d) De-broglie equation applies to all the material object in motion.
h
10. (d) de-Broglie equation is   . Uncertainty principle and Schrodinger wave
p
11. (c) Formula for de-Broglie wavelength is
equation
h h 1 2eV 1. (b) The uncertainty principle was enunciated by Heisenberg.
 or    eV  mv 2 or  
p mv 2 m 2. (b) According to uncertainty principle, the product of uncertainties
of the position and momentum, is x  p  h / 4 .
h 6 .62  10 34
  h
2meV 2  9 .1  10  31  2 .8  10  23 5. (c) x  p  is not the correct relation. But correct
4
8
  9.28  10 meter . h
Heisenberg’s uncertainty equation is x  p  .
h 4
12. (c)  , p  mv 7. (b) According to the Heisenberg’s uncertainty principle momentum and
p
exact position of an electron can not be determined simultaneously.
h 6 .62  10 34 h
  8. (d) x. p  , if  x  0 then p   .
mv 9 .1  10  31  1 .2  10 5 4
  6.626  10 9 m . 12. (c) According to x  p 
h
4
13. (b) Mass of the particle (m)  10 6 kg and velocity of the particle
h 6 .62  10 34
(v)  10 ms 1 x    5.27  10 30 m .
p  4 1  10 5  4  3 .14
 Structure of atom 79
13. (a) Uncertainty of moving bullet velocity 10. (a) 3d subshell filled with 5 electrons (half-filled) is more stable
h 6 .625  10 34 than that filled with 4 electrons. 1, 4 s electrons jumps into
v  
4  m  v 4  3 .14  .01  10 5 3 d subshell for more sability.
28 (c) In 2p – orbital, 2 denotes principal quantum number (n) and
 5.2  10 m/sec . 11.
h p denotes azimuthal quantum number (l  1) .
14. (b) x .p  This equation shows Heisenberg’s uncertainty
4 12. (c) Electronic configuration of H  is 1s 2 . It has 2 electrons in
principle. According to this principle the product of uncertainty extra nuclear space.
in position and momentum of particle is greater than equal to
h 13. (a) The electronic configuration must be 1s 2 2 s 1 . Hence, the
. element is lithium (z  3).
4
15. (d) Spin quantum number does not related with Schrodinger 14. (a) Principal quantum no. tells about the size of the orbital.
equation because they always show 1 / 2 , 1 / 2 value. 15. (d) An element has the electronic configuration
h h 1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 2 , (Si) . It’s valency electrons are four.
16. (b) According to x  m  v  ; v 
4 x  m  4 16. (c) The magnetic quantum number specifies orientation of orbitals.
6 .6  10 34 17. (c) If l  2, m  3. (e to e ) .
 5
 2 .1  10  29 m / s
10  0 .25  3 .14  4 18. (d) If n  3 then l  0, 1, 2 but not 3.
h
17. (a) Uncertainity in position x  20. (c) Atomic number of Cu is 29  ( Ar) 4 s 1 3d 10 .
4  p
6 .63  10 34 21. (c) The shape of 2 p orbital is dumb-bell.
  5.28  10 30 m .
4  3 .14  (1  10 5 ) 22. (a) When the value of n  2 , then l  1 and the value of
18. (c) Given that mass of electron  9.1  10 31
kg m  1, 0,  1 i.e. 3 values.
34 2 1
Planck’s constant  6.63  10 kg m s 23. (c) Cr24  ( Ar) 3d 5 4 s 1 electronic configuration because half filled
h orbital are more stable than other orbitals.
h
By using x  p  ; x  v  m  24. (d) Kr has zero valency because it contains 8 electrons in
4 4
outermost shell.
where : x = uncertainity in position
25. (c) 2 electron in the valence shell of calcium Ca 20  (2, 8, 8, 2) .
v = uncertainity in velocity
h 27. (b) Value of l  1 means the orbital is p (dumb-bell shape).
x  v 
4  m 28. (d) Cr has Ar4 s 1 3d 5 electronic configuration because half
34
6 .63  10 filled orbital are more stable than other orbitals.
  5.8  10 5 m 2 s 1 .
4  3 .14  9 .1  10 31 31. (d) The two electrons will have opposite spins.
33. (c) If m = –3, then l = 3, for this value n must be 4.
Quantum number, Electronic configuration
and Shape of orbitals 2n 2
34. (d) No. of electrons  2n 2 hence no. of orbital   n2 .
2
3. (b) The shape of an orbital is given by azimuthal quantum number 2n 2
'l' . 35. (d) No. of electrons  2n 2 hence no. of orbital   n2 .
2
5. (c) Hund’s rule states that pairing of electrons in the orbitals of a
36. (c) If n  3 then l  0 to n  1 & m  l to l
subshell (orbitals of equal energy) starts when each of them is
singly filled. 37. (b) Na 11  2, 8, 1  1s 2 , 2 s 2 2 p 6 , 3 s 1
2 2 6
6. (c) 1s , 2 s , 2 p represents a noble gas electronic configuration. n  3, l  0, m  0, s  1 / 2
7. (c) The electronic configuration of Ag in ground state is 38. (b) Hund’s rule states that pairing of electrons in the orbitals of a
[Kr] 4 d 10 5 s 1 . subshell (orbitals of equal energy) starts when each of them is
singly filled.
8. (a) n, l and m are related to size, shape and orientation
respectively. 39. (d) As a result of attraction, some energy is released. So at infinite
distance from the nucleus energy of any electron will be
9. (a) Electronic configuration of Rb(37 ) is maximum. For bringing electrons from  to the orbital of
any atom some work has to be done be electrons hence it bill
1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 10 4 s 2 4 p 6 5 s 1 loose its energy for doing that work.
So for the valence shell electron (5 s 1 ) 40. (c) This space is called nodal space where there is no possibility of
oressene of electrons.
1 (d) For s orbital l  0 m  0 .
n  5, l  0, m  0 , s   41.
2
42. (c) For M th shell, n  3; so maximum no. of electrons in M th
shell  2n 2  2  3 2  18 .
 80 Structure of atom
43. (c) m  l to l including zero. 67. (c) N  1s 2 ,2 s 2 2 p1x , 2 p1y , 2 p1z . Hund’s rule states that pairing
7
44. (a) Number of radial nodes = (n  l  1) of electrons in the orbitals of a subshell (orbitals of equal
For 3s: n = 3, l = 0 energy) starts when each of them is singly filled.
(Number of radial node = 2) 68. (d) (4) and (5) belong to d -orbital which are of same energy.
For 2p: n =2, l = 1 69. (c) Atomic no. 17 is of chlorine.
(Number of radial node = 0) 70. (b) The s-orbital has spherical shape due to its non- directional
nature.
45. (a) It consists only s orbital which is circular.
71. (a) According to the Aufbau’s principle the new electron will enter
46. (a) Hund’s rule states that pairing of electrons in the orbitals of a
subshell (orbitals of equal energy) starts when each of them is in those orbital which have least energy. So here 4 p -orbital
singly filled. has least energy then the others.
47. (b) If value of l is 2 then m  2,  1, 0,  1,  2 . m  l to l 72. (c) According to Aufbau’s principle.
including zero. 73. (c) 1s 2 2 s 2 2 p 6 ,3 s 2 3 p 6 ,4 s 2 3d 6  2, 8, 14, 2 .
(5 values of magnetic quantum number)
74. (c) Ground state of Cu 29  1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 10 4 s1
48. (c) s, p, d orbitals present in Fe
Cu 2   1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 9 .
Fe26  1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 , 4 s 2 3d 6
50. (b) According to Aufbau rule. 76. (c) No. of electrons in 3 rd shell = 2n 2 = 2 (3) 2  18
51. (c) 3d subshell filled with 5 electrons (half-filled) is more stable 77. (c) F9  1s 2 2 s 2 2 p 5
than that filled with 4 electrons. 1, 4 s electrons jumps into
3 d subshell for more sability. 78. (c) When l  3 then
m  3,  2,  1, 0,  1,  2,  3 . m  l to l including
52. (b) K19  1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 , 4 s 1
zero.
for 4 s1 electrons. 80. (d) m  1 is not possible for s orbital (l  0).
1 84. (a) Both 2p and 3p-orbitals have dumb-bell shape.
n  4, l  0, m  0 and s   .
2 85. (b) 3d subshell filled with 5 electrons (half-filled) is more stable
54. (b) 3d subshell filled with 5 electrons (half-filled) is more stable than that filled with 4 electrons. 1, 4 s electrons jumps into
than that filled with 4 electrons. 1, 4 s electrons jumps into 3 d subshell for more sability.
3 d subshell for more sability. 86. (c) The shape of 2 p orbital is dumb-bell.
55. (c) It has 3 orbitals p x , p y , p z .
87. (a) 25 Mn  [ Ar] 3d 5 4 s 2 -2 electrons Mn 2   [ Ar] 3d 5 4 s 0
57. (b) If l  2 then it must be d orbital which can have 10
electrons. 89. (c) For p-orbital, l  1 means dumb-bell shape.
59. (c) for d orbital l  2 . 91. (d) l  3 means f subshell maximum number of e in f subshell = –

14.
60. (c) m  l to l including zero.
93. (b) As per Aufbau principle.
61. (d) When n  3 shell, the orbitals are n 2  3 2  9 .
94. (b) l  0 is s, l = 1is p and l  2 is d and so on hence s p d may
No. of electrons  2n 2 be used in state of no..
2n 2 1
Hence no. of orbital   n2 . 95. (d) For 4 d, n  4, l  2, m  2,1,0,1,2, s   .
2 2
62. (d) Configuration of Ne = 1s 2 2 s 2 2 p 6 96. (d) m cannot be greater than l ( 0, 1).

(a) For n  1, l  0.
2 2 6
F = 1s 2 s 2 p 97.

Na  = 1s 2 2 s 2 2 p 6 99. (d) Na 11  1s 2 2 s 2 p 6 3 s 2
Mg   = 1s 2 2 s 2 2 p 6 1
n  3, l  0, m  0 and s   .
 2 2 6 2 6 2
Cl = 1s 2 s 2 p 3 s 3 p .
102. (d) According to Aufbau’s rule.
63. (d) Unh106  [Rn] 5 f 14 , 6 d 5 , 7 s 1
105. (d) 2 p x , 2 p y , 2 p z sets of orbital is degenerate.
 
64. (c) K and Ca have the same electronic configuration
106. (a) Mg12 have 1s 2 2 s 2 2 p 6 3 s 2 electronic configuration
(1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 )
1
65. (b) For s-orbital, l  0. n  3, l  0, m  0, s   .
2
66. (d) 3s 1 is valency electrons of Na for this
1
n  3, l  0, m  0, s 
2
 Structure of atom 81
107. (c) The principle quantum number n  3 . Then azimuthal 146. (d) m  (2l  1) for d orbital l  2 m  (2  2  1)  5 .
quantum number l  3 and number of orbitals 147. (a) The atomic number of chlorine is 17 its configuration is
 n 2  3 2  9 . 3 and 9 1s 2 2 s 2 2 p 6 3 s 2 3 p 5
108. (d) 29 Cu  [ Ar] 3d 10 4 s 1 , Cu 2  [ Ar] 3d 9 .4 s 0 . 148. (c) n l m1 m2
Ground state of Cu 29
 1s 2 s 2 p 3 s 3 p 3 d 4 s
2 2 6 2 6 10 1
3 2 1 0
2
Cu  1s , 2 s 2 p ,3 s 3 p 3 d .
2 2 6 2 6 9 This set (c) is not possible because spin quantum number
1
110. (d) 1s 2 s 2 2 p 6 3 s 2 3 p 6 4 s 2 3d 6
2
it shows electronic values   .
2
configuration of Iron.
149. (b) The ground state of neon is 1s 2 2 s 2 2 p 6 on excitation an
111. (d) Orbitals are 4 s, 3 s, 3 p and 3 d . Out of these 3d has highest
energy. electron from 2 p jumps to 3 s orbital. The excited neon

113. (c) For the n  2 energy level orbitals of all kinds are possible configuration is 1s 2 2 s 2 2 p 5 3 s 1 .
2n , 2 2  4 . 152. (a) s p d f g h
l=0 1 2 3 4 5
114. (b) n  2 than no. of orbitals  n 2 , 2 2  4 Number of orbitals  5  2  1  11
118. (b) For both A & B electrons s  1 / 2 & 1 / 2 respectively, 153. (a) It is the ground state configuration of chromium.
n  3, l  0, m  0 155. (b) n  4  1s 2 , 2 s 2 , 2 p 6 , 3 s 2 , 3 p 6 , 3d 10 , 4 s 2 , 4 p 6 , 4 d 10 , 4 f 14
119. (a) According to Aufbau’s rule. So l  (n  1)  4  1  3 which is f orbit contain 7 orbital.
120. (a) Possible number of subshells would be (6s, 5p, 4d). 156. (d) 2p have contain maximum 6 electron out of which there are 3
121. (d) For f orbital l  3 . are of + 1/2 spin and 3 are of – 1/2 spin
123. (b) 4d-orbital have highest energy in given data.  
   +1/2 –1/2
125. (d) If m  3, l  3 and n  4.
157. (a) For 4f orbital electron, n  4
127. (b) N 714  1s 2 2 s 2 2 p 1x 2 p 1y 2 p 1z . l  3 (Because 0, 1, 2, 3)
128. (c) m can't be greater than l. s, p, d, f
130. (b) n  1 and m  1 not possible for s-orbitals. m = + 3, + 2, +1, 0, – 1, – 2, – 3
s = +1/2
131. (a) Fe 26  [ Ar] 3d 6 4 s 2
158. (b) Cr  1s 2 , 2 s 2 , 2 p 6 , 3 s 2 , 3 p 6 , 3 d 5 , 4 s1
Fe 3   [ Ar] 3d 5 4 s 0 .
24
l 1 l 1 l  2
132. (c) Maximum number of electron (We know that for p the value of l  1 and for d , l  2)
 2n 2 (where n  4 )  2  4 2  32 .
For l  1 total number of electron = 12
133. (d) When 2p orbital is completely filled then electron enter in the
For l  2 total number of electron = 5.
3s. The capacity of 2p orbital containing e  is 6. So
159. (c) Atomic number of potassium is 19 and hence electronic
1s 2 , 2 s 2 2 p 2 3 s 1 is a wrong electronic configuration the
configuration will be 1s 2 , 2 s 2 , 2 p 6 , 3 s 2 , 3 p 6 , 4 s1
write is 1s 2 2 s 2 2 p 3 .
Hence for 4 s1 electron value of Quantum number are
134. (b) This electronic configuration is Cr (chromium element) in the
ground state Principal quantum number n  4
 1s 2 s 2 p 3 s 3 p 3 d 4 s
2 2 6 2 6 5 1 Azimuthal quantum number l  0
Magnetic quantum number m  0
137. (c) No. of electron are same (18) in Cl  and Ar .
Spin quantum number s  1 / 2
138. (c) For s-subshell l  0 then should be m  0.
160. (d) According to Hund's rule electron first fill in unpaired form in
139. (c) 19 electron of chromium is 4 s1
th
vacant orbital then fill in paired form to stabilized the molecule
n  4 , l  0, m  0, s  
1 by which 1s 2 ,2 s 2 ,2 p x2 is not possible. According to Hund's
2 rule. Because 2 p x , py , p z have the same energy level so
140. (c) The value of m is – l to l including zero so for l = 3, m would electron first fill in unpaired form not in paired form so it
be –3, –2, –1, 0, +1, +2, +3.
should be 1s 2 , 2 s 2 , 2 p1x ,2 p1y .
141. (c) l  1 is for p orbital.
161. (c) It is governed by Aufbau principle.
142. (d) Magnetic quantum number of sodium ( 3 s1 ) final electron is m 162. (d) The electronic configuration of atomic number
= 0.
24  1s 2 , 2 s 2 , 2 p 6 , 3 s 2 ,3 p 6 ,3d 5 , 4 s1
143. (c) Generally azimuthal quantum number defines angular
momentum. 163. (b) The maximum number of electron in any orbital is 2.
 82 Structure of atom
164. (c) According to pauli principle 2 electron does not have the same
value of all four quantum number. They have maximum same
value are 3.
192. (a) Shell = K, L, M = 1s 2 2 s 2 2 p 6 3 s 2 3 p 4
165. (a) Number of orbitals  n 2  4 2  16 .
Hence the number of s electron is 6 in that element.
166. (d) We know from the Aufbau principle, that 2p orbital will be
filled before 3s orbital. Therefore, the electronic configuration 193. (d) C 6  1s 2 , 2 s 2 2 p 2 (Ground state)
1s 2 , 2 s 2 , 2 p 2 , 3 s1 is not possible.
 1s 2 2 s1 2 Px1 2 p1y 2 p1z (Excited state)
167. (d) Each orbital may have two electrons with opposite spin.
In excited state no. of unpaired electron is 4.
168. (d) Maximum no. of electrons in a subshell  2(2l  1) for f-
194. (b) Max. no. of electrons in N-shell n  4 
subshell, l = 3 so 14 electrons accommodated in f -subshell.
169. (b) Each orbital has atleast two electron.  2n2  2  4 2  32 .
170. (a) Nucleus of 20 protons atom having 20 electrons. 195. (d) 26 Fe  [ Ar] 3d 6 , 4 s 2
174. (b) For m  0 , electron must be in s-orbital. Fe2   [ Ar] 3d 6 , 4 s0
176. (c) In this type of electronic configuration the number of unpaired
electrons are 3. Number of d-electrons = 6
=3 17 Cl  [ Ne ] 3 s 2 , 3 p 5
1s 2s 2p Cl   [ Ne ] 3 s 2 , 3 p 6
177. (a) Atomic number of Cu is 29 so number of unpaired electrons is
1 Number of p-electrons = 6.
4 s1 3d 10 196. (a) Electrons in the atom  18  4  3  25 i.e. Z  25 .
Cu  (Ar) 197. (c) The atomic number of bromine is 35 and the electronic
configuration of Br is
1s 2 2s 2 2p4 Br35  1s 2 , 2 s 2 , 2 p 6 , 3 s 2 , 3 p 6 , 3d 10 , 4 s 2 , 4 p 5
178. (b) O8 
total electron present in p-orbitals of Br is –
Unpaired electron 2 p 6  3 p 6  4 p 5  17.
181. (c) Be 4  1s , 2 s = (Ground state)
2 2

198. (d) Fe 2  has 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 6 configuration with 4

Number of unpaired electrons in the ground state of Beryllium unpaired electron.
atom is zero.
182. (b) Two unpaired electrons are present in 199. (b) Fe 2  [ Ar] 3d 6 4 s 0

Ni   (z  28) cation =4

Ni28  [ Ar]
Fe 2  consist of maximum 4 unpaired electrons.
3d 8 4s 0

201. (a) Fe 3  (z  26)

183. (c) O 2  1s 2 2 s 2 2 p 6 3 s 2 3 p 4
Fe 3   [ Ar] 3d 5 4 s 0
3s 2 3p4
=5
3d 4s
2 Unpaired electrons
3
184. (c) Cr24  ( Ar) 3d 5
4 s 1 but Cr24  ( Ar) 3d 4 s 3 0
Total no. of unpaired electron=5

185. (a) Zn 30  [ Ar] 3d 10 4 s 2 202. (b) Co 27  [ Ar] 3d 7 4 s 2

Zn    [ Ar] 3d 10 4 s 0 3d 7

186. (d) Mn 2 ion will have five (maximum) unpaired electrons

3 unpaired electron are present in cobalt metal.
[Ar] 203. (b) According to Hund's rule, the pairing of electrons will not
occur in any orbital of a subshell unit and unless, all the
3d 5 4s available of it have one electron each.
3 Electronic configuration of
187. (c) Fe ion will have five (maximum) unpaired electrons.
N 14  1 s 2 , 2 s 2 , 2 p x 2 p y 2 p z
1 1 1
190. (c) Due to full filled d-orbital Cl  has spherical symmetry. 7

191. (b) Atomic number 14 leaving 2 unpaired electron Hence it has 3 unpaired electron in 2p-orbital.

14 Si  1s 2 s 2 p 3 s 3 p
2 2 6 2 2 204. (c) 2 s orbital have minimum energy and generally electron filling
increases order of energy according to the Aufbau’s principle.

1s 2s 2p 3s 3p
 Structure of atom 83
205. (d) According to Pauli’s exclusion principle no two electrons in the 1
same atom can have all the set of four quantum numbers (iii) Proton  1
identical. 1
206. (b) The second principal shell contains four orbitals viz 1
(iv) electron   1837 .
2 s, 2 p x , 2 p y and 2 p z . 1 / 1837
207. (b) Follow Hund’s multiplicity rules. 4. (a) Metal is 56 M 2  (2, 8, 14) than n  A  Z
208. (c) According to the Aufbau’s principle, electron will be first enters
in those orbital which have least energy. So decreasing order of  56  26  30 .
energy is 5 p  4 d  5 s. 5. (d) E  hv  h
c
i.e. E 
1
210. (b) No two electrons in an atom can have identical set of all the  
four quantum numbers. E1  4000
 2   2.
212. (a) In particular shell, the energy of atomic orbital increases with E2 1 2000
the value of l .
6. (c) Rutherford discovered nucleus.
214. (c) Aufbau principle explains the sequence of filling of orbitals in
increasing order of energy. 7. (b) According to Bohr’s model E  E1  E3
215. (a) According to Aufbau principle electron are filling increasing 2 .179  1011
order of energy. Therefore the electronic configuration  2 .179  10 11 
9
1s 2 2 s 2 2 p 6 obeys Aufbau principle.
8
  2 .179  10 11  1.91  10 11  0.191  10 10 erg
216. (d) Electronic configuration of the Cr24 is [ Ar] 4 s1 3d 5 or 9
=6 Since electron is going from n  1 to n  3 hence energy is
absorbed.
3d 4s
8. (d) Radius of nucleus  1.25  10 13  A1 / 3 cm
217. (b) According to the Aufbau principle electron filling minimum to
higher energy level.
 1.25  10 13  64 1 / 3  5  10 13 cm
219. (b) According to Aufbau principle electron are filled in various
atomic orbital in the increasing order of energy Radius of atom = 1Å  10 8 cm.
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f <
5 d < 6p < 7 s . Volume of nucleus (4 / 3) (5  10 13 )3

220. (d) According to Aufbau’s rule. Volume of atom (4 / 3) (10  8 )3
222. (b) We know that for d-electron l  2.  1.25  10 13 .
h h
  l(l  1) ;   2 (2  1) 13.6
2 2 9. (a) Values of energy in the excited state  eV
n2
h h 13.6
  2 (2  1) ;  6 .   3 .4 eV in which n  2, 3, 4 etc.
2 2 4
223. (a) Number of nodal centre for 2 s orbitals ( n  1)  2  1  1 .
10. (c) E1 He   E1 H  z 2
224. (d) Since s-orbital have l  0
 871.6  10 20  E1 H  4
h h
Angular momentum = l (l  1)  = 0 0 .
2 2 E1 H  217.9  10 20 J
225. (d) Azimuthal quantum number (l) = 3 shows the presence of f
orbit, which contain seven orbitals and each orbital have 2 11. (a) 42g of N 3 ions have 16 N A valence electrons 4.2g of N 3
electrons. Hence 7  2  14 electrons. 16 N A
ion have   4 .2  1 .6 N A .
227. (b) According to Aufbau principle. 42
228. (a) Atomic number of deuterium = 1; 1 D2  1s1 12. (d) Ist excited state means n  2

Critical Thinking Questions r  r0  2 2  0.53  4  2.12 Å

13. (d) Frequency   12  1014 s 1 and velocity of light

1. (a) F  have the same number of electrons with the neon atom.
c  3  10 cm s 1 . We know that the wave number
10
2. (d) No change by doubling mass of electrons however by reducing
mass of neutron to half total atomic mass becomes 6  3 v 12  1014
   4  10 4 cm 1
instead of 6  6 . Thus reduced by 25%. c 3  1010
e 0 14. (c) The last line in any series is called series limit. Series limit for
3. (d) for (i) neutron  0 Balmer series is 3646 Å.
m 1
13.6 13.6
(ii)   particle 
2
 0.5 15. (b) E   3.4 eV
4 n2 4
 84 Structure of atom
We know that energy required for excitation E  E 2  E1 6. (d) We know from the Pauli exclusion principle, that two electrons
in the same atom can not have same value of all four quantum
 3.4  (13.6)  10.2 eV numbers. This means each electron in an atom has only one set
Therefore energy required for excitation of electron per atom of values for n, l, m and s . Therefore both the Assertion and
10.2 Reason are false.
  1.69  10  23 J 7. (e) We know that the line in Balmer series of hydrogen spectrum the
6.02  10 23
highest wavelenght or lowest energy is between n1  2 and
17. (a) The number of nodal plane are present in a p x is one or no.
n 2  3 . And for Balmer series of hydrogen spectrum, the value of
of nodal place = l
n1  2 and n 2  3,4,5 . Therefore the Assertion is false but the
for p x orbital l = 1
Reason is true.
8. (d) We know that Absorption spectrum is produced when white
x light is passed through a substance and transmitted light is
analysed by a spectrograph. The dark spaces corresponds to the
Nodal plane light radiation absorbed by the substance. And emission
18. (b) In Balmer series of hydrogen atomic spectrum which electronic spectrum is produced by analysing the radiant energy emitted
by an excited substance by a spectrograph. Thus discontinuous
transition causes third line O  L , n2  5  n1  2
spectra consisting of a series of sharp lines and separated by
1 1 1  dark bands are obtained. Therefore both the Assertion and
20. (b)    RH  2  2  Reason are false.
  n1 n2  9. (a) We know that a resonance hybrid or the actual molecule is
always more stable than any of its canonical structures which is
1 1 1 
  R H  2  2   n2  3 for Paschen series. also called hypothetical or imaginary structures. This stability is
  3 n2  due to delocalization of electrons and is measured in terms of
resonance energy or delocalization energy, it is defined as the
1 1  difference in internal energy of the resonance hybrid and the
21. (a) E 2  2 most stable canonical structure. Therefore both the Assertion
 n2 n1  and Reason are true and the Reason is a correct explantion of
c 3  10 8 the Assertion.
23. (d)     3 .75  10 8 10. (e) We know that cathode rays cast shadows of solid objects placed
v 8  1015
in their path. During experiment performed on these rays,
 3.75  10 8  10 9 nm  4  101 nm . fluorescene (flash of light) is observed in the region, outside
the shadow. This shows that cathode rays travel in straight
Assertion & Reason lines. We also known that cathode rays penetrate through a
thin sheet of metals but are stopped by thick sheets. Therefore
both Assertion and Reason are false.
1. (d) The assertion is false but the reason is true exact position and
exact momentum of an electron can never be determined as 11. (b) We know that electrons are revolving around the nucleus at
according to Hesenberg’s uncertainity principle even with the high speed in circular paths. The centrifugal force (which arises
due to rotation of electrons) acting outwards, balances the
help of electron microscope because when e  beam of electrostatic force of attraction (which arises due to attraction
electron microscope strikes the target e  of atom, the impact between electrons and nucleus). This prevent the electron from
falling into the nucleus. We also know that Rutherford’s model
causes the change in velocity of e  thus attempt to locate the of atom is comparable to the “solar system”. The nucleeus
e  changes ultimately, the momentum & position of e  . represent the sun whereas revolving electrons represent the
h planets revolving around the sun. Thus revolving electron are
x .p   0.57 ergs sec/ gm. also called planetary electrons. Therefore both Assertion and
4 Reason are true but Reason is not a correct explanation of
2. (d) Both assertion and reason are false. 2 p x and 2 p y orbitals Assertion.
are degenerate orbitals, i.e., they are of equal energy and hence 12. (c) Assertion is true but Reason is false. Threshold frequency is a
no possibility of transition of electron. minimum frequency required for the emission of electrons
from the metal surface.
3. (a) We know that principal quantum number represent the main
energy level or energy shell. Since each energy level is 13. (a) Both assertion and reason are true and reason is the correct
associated with a definite amount of energy, this quantum explanation of assertion.
number determines to a large extent te energy of an electron. It n2h2 n2
also determines the average distance of an electron around the Radius, r   0 .529 Å. rn also increases
nucleus. Therefore both Assertion and Reason are true and the 4e mZ
2
Z
Reason is a correct explanation of the Assertion. indicating a greater separation between the orbit and the
nucleus.
4. (a) It is observed that a nucleus which is made up of even number
of nucleons (No. of n & p ) is more stable than nuclie which 14. (d) Both assertion and Reason are false. Only s -orbital is
consist of odd number of nucleons. If number of neutron or spherically symmertrical. Shape of different d orbitals is as
proton is equal to some numbers i.e., 2,8, 20, 50, 82 or 126 below.
(which are called magic numbers), then these passes extra 15. (c) Assertion is true but reason is false. Spin angular momentum
stability. of the electron, a vector quantity, can have two orientations
5. (c) The assertion that the isobars are the atoms of different (represented by + and – sign) relative to a chosen axis. These
elements having same mass number but different atomic two orientation are distinguished by the spin quantum number
number, is correct but reason is false because atomic mass is 1 1
m s equals to  or  . These are called the two spin
sum of number of neutron and protons which should be same 2 2
for isobars.
 Structure of atom 85
states of the electron and are normaly represented by the two
arrows  (spin up) and  (spin down) respectively.
16. (d) Both assertion and reason are false. Total number of orbitals
associated with Principal quantum number n  3 is 9. One
3 s orbital + three 3 p orbital + five 3 d orbitals. 
Therefore there are a total number of nine orbitals. Number of
orbitals in a shell equals to n 2 .
17. (c) Assertion is true but reason is false. The order
1s  2s  2 p  3 s  3 p  3d  .... is true for the energy of
an electron in a hydrogen atom and is solely determined by
Principal quantum number. For multielectron system energy
also depends on azimuthal quantum number. The stability of
an electron in a multi electron atom is the net result of the
attraction between the electron and the uncleus and the
repulsion between the electron and the rest of the electron
present. Energies of different subshell (azimuthal quantum
number) present within the same principal shell are found to
be in order of s  p  d  f .
18. (e) Assertion is false but reason is true. Splitting of the spectral
lines in the presence of a magnetic field is known as Zeeman
effect or in electric field it is known as stark effect. The
splitting of spectral lines is due to different orientations which
the orbitals can have in the presence of magnetic field.
19. (a) Both assertion and reason are true and reason is the correct
explanation of assertion.
20. (e) Assertion is false but reason is true. Atomic orbital is
designated by n, l and m l while state of an electron in an
atom is specified by four quantum numbrs n, l, m l and m s .
21. (b) Both assertion and reason are true but reason is not the
correct explanation of assertion. The difference between the
energies of adjacent energy levels decreases as we move away
from the nucleus. Thus in H atom
E2  E1  E3  E2  E4  E3 ......
22. (d) Both assertion and reason are false. Cathode rays are stream of
electrons. They are generated through gases at low pressure
and high voltage.
23. (d) Both assertion and reason are false. In case of isoelectronic, i.e.,
ions, having the same number of electrons and different
nuclear charge, the size decreases with increase in atomic
number.
Ion At. No. No. of electrons Ionic radii
Na+ 11 10 0.95Å
Mg2+ 12 10 0.65Å
Al3+ 13 10 0.50Å
 86 Structure of atom

1. The correct set of quantum numbers for the unpaired electron of (c) n  2; l  1; m  0l s  1 / 2
chlorine atom is [IIT 1989; MP PET 2004]
n l m (d) n  4 ; l  3; m  2; s  1 / 2

(a) 2 1 0 8. The uncertainty in the position of an electron ( mass =

(b) 2 1 1 9.1  10 28 g) moving with a velocity of 3.0  10 4 cm s 1
(c) 3 1 1 accurate upto 0.001% will be
(d) 3 0 0 h
(Use in the uncertainty expression, where
2. The orbital diagram in which the Aufbau's principle is violated is 4 [IIT 1988; AMU 1999]

2s 2px 2 py 2 pz h  6.626  10 27 erg  s ) [CBSE PMT 1995]

(a) 1.92cm (b) 7.68 cm

(a)   
(c) 5.76cm (d) 3.84 cm
(b)    
9. The orbital angular momentum of an electron in s orbital is
(c)     [IIT 1996; AIEEE 2003; MP PET 2004]
(d)     1 h
(a)  . (b) Zero
3. The mass of neutron is nearly 2 2
[MNR 1988; UPSEAT 1999, 2000, 02] h h
(c) (d) 2.
(a) 10 23
kg (b) 10 24 kg 2 2
10. Values of the four quantum numbers for the last electron in the
(c) 10 26 kg (d) 10 27 kg
atom are n  4, l  1, m  1 and s  1 / 2 . Atomic number of
4. Which electronic level would allow the hydrogen atom to absorb a the atom will be
photon but not to emit a photon
(a) 22 (b) 32
[IIT 1984; CPMT 1997]
(c) 33 (d) 36
(a) 3s (b) 2p
11. The atomic weight of an element is 39. The number of neutrons in
(c) 2s (d) 1s its nucleus is one more than the number of protons. The number of
protons, neutrons and electrons respectively in its atom would be[MP PMT 1997
5. Which of the following is not correct for electron distribution in the
ground state [AIIMS 1982] (a) 19, 20, 19 (b) 19, 19, 20

4s 3d (c) 20, 19, 19 (d) 20, 19, 20

12. The electrons identified by quantum numbers n and l (i)
(a) Co (Ar)      
n  4, l  1 (ii) n  4, l  0 (iii) n  3, l  2 (iv) n  3, l  1
(b) Ni(Ar)       can be placed in order of increasing energy from the lowest to
highest, as [IIT 1999]
(c) Cu (Ar)      
(a) (iv) < (ii) < (iii) <(i)
(d) Zn(Ar)       (b) (ii) < (iv) < (i) < (iii)
6. If electron, hydrogen, helium and neon nuclei are all moving with (c) (i) < (iii) < (ii) < (iv)
the velocity of light, then the wavelengths associated with these (d) (iii) < (i) < (iv) < (ii)
particles are in the order [MP PET 1993]
13. Ground state electronic configuration of nitrogen atom can be
(a) Electron > hydrogen > helium > neon represented by [IIT 1999]
(b) Electron > helium > hydrogen > neon
(a)     
(c) Electron < hydrogen < helium < neon
(d) Neon < hydrogen < helium < electron (b)     
7. From the given sets of quantum numbers the one that is inconsistent
with the theory is [IIT Screening 1994]
(c)     
(a) n  3; l  2; m  3; s  1 / 2

(b) n  4 ; l  3; m  3; s  1 / 2
 Structure of atom 87

(d)      (c) 10 20 (d) 6.02  10 20

18. Which of the following have the same number of unpaired electrons
in ‘d’ orbitals [Roorkee 2000]
14. Which of the following statements (s) is (are) correct
(a) Cr (b) Mn
[IIT 1998]
(c) Fe 3+
(d) Co 3+

5 1
(a) The electronic configuration of Cr is [ Ar] 3d 4 s (Atomic 19. The quantum numbers + 1/2 and – 1/2 for the electron spin
represent [IIT Screening 2001]
no. of Cr  24 )
(a) Rotation of the electron in clockwise and anticlockwise
(b) The magnetic quantum number may have a negative value direction respectively
(c) In silver atom, 23 electrons have a spin of one type and 24 of (b) Rotation of the electron in anticlockwise and clockwise
the opposite type (Atomic no. of Ag  47 ) direction respectively
(c) Magnetic moment of the electron pointing up and down
(d) The oxidation state of nitrogen in HN 3 is 3 respectively
15. The position of both an electron and a helium atom is known within (d) Two quantum mechanical spin states which have no classical
1.0nm and the momentum of the electron is known within analogue
50  10 26 kg ms 1 . The minimum uncertainty in the 20. The de-Broglie wavelength of a tennis ball of mass 60 g moving with
a velocity of 10 metres per second is approximately
measurement of the momentum of the helium atom is
[CBSE PMT 1998; AIIMS 2001] (a) 10 33 metres (b) 10 31 metres

(a) 50kg ms 1 (b) 60 kg ms 1 (c) 10 16 metres (d) 10 25 metres

21. Which of the following are isoelectronic and isostructural
(c) 80  10 26 kg ms 1 (d) 50  10 26 kg ms 1
NO 3 , CO 32  , ClO3 , SO 3 [IIT Screening 2003]
16. Which of the following pair of orbitals posses two nodal planes [RPMT 2000]
(a)  2
NO 3 , CO 3 (b) SO 3 , NO 3
(a) p xy , d x 2 y 2 (b) d xy , d zx
(c) ClO3 , CO 32  (d) CO 32  , SO 3
(c) p xy , d zx (d) d z 2 , d x 2 y 2 22. The total number of electrons present in all the s-orbitals, all the p-
orbitals and all the d-orbitals of cesium ion are respectively
17. The number of atoms in 0.004 g of magnesium are
(a) 8, 26, 10 (b) 10, 24, 20
[AFMC 2000]
(c) 8, 22, 24 (d) 12, 20, 22
(a) 4  10 20
(b) 8  10 20

(SET -2)

1. (c) Electronic configuration of Cl is

3s 2 3p So for the unpaired electron (3 p1z ) :

1
[ Ne ] 3 s 2 3 p 5 or [Ne ] n  3, l  1, m  1, S  
2
3 p 2 x 3p 2 y 3p 1 z
 88 Structure of atom
2. (b) According to Aufbau principle the orbitals of lower energy (2s) 1
should be fully filled before the filling of orbital of higher 14. (a,b,c) The oxidation state of nitrogen in HN 3 is  .
energy starts. 3

3. (d) Mass of neutron  1.675  10 27 kg . 1

HN 3 : 1  3 x  0  3 x  1 or x 
4. (d) 1s-orbital is of lowest energy. Absorption of photon can raise 3
the electron in higher energy state but emission is not possible.
15. (d) The product of uncertainties in the position and the
5. (c) The correct electronic configuration
momentum of a sub atomic particle  h/4 . Since x is
Cu 29  [ Ar], 4 s1 3d 10
same for electron and helium so p must be same for both
the particle i.e. 50  10 26 kg ms 1 (given).
1
6. (a)   , m e  m H  m He  m Ne . 16. (b) d xy and d zx has two modal planes.
m
7. (a) When l  2, m  3 . 17. (c) No. of atoms in magnesium =
0 .004
 6 .023  10 23 =10 20

24
8. (a) p  m  v
18. (a,b,c) Cr , Mn and Fe3  have 5 unpaired electron in d-
0 .001 orbitals.
p  9.1  10  28  3.0  10 4 
100 24 Cr  3d 5 4 s1  5

P  2.73  10 24 25 Mn  3d 5 4 s 2  5

h 6 .626  10 27 26 Fe3   3d 5 4 s 0  5

Hence x  
p  4 2 .73  10  28  4  3 .14 19. (a,d) Both statement are correct.
h 6 .63  10 34
x  1.92 cm. 20. (a)    10  33 m
mv 60  10  3  10
9. (b) For 2s orbital, l = 0; azimuthal quantum number is not show
21. (a) NO 3 and CO 32  consist of same electron and show same
angular momentum for the 2 s orbitals.
isostructural.
h 22. (b) (Cs 35 )  1s 2 , 2 s 2 , 2 p 6 ,3 s 2 ,3 p 6 ,3d 10 ,4 s 2
Angular momentum  l(l  1) 0.
2
4 p 6 ,4 d 10 ,5 s 2 ,5 p 6 ,6 s1
10. (d) Atomic number is 36 and element is Kr .
Cs   1s 2 , 2 s 2 ,2 p 6 , 3 s 2 ,3 p 6 ,3d 10 , 4 s 2 ,
11. (a) 39
K 19 , P  19 , E  19 , N  20
4 p 6 ,4 d 10 , 5 s 2 ,5 p 6
12. (a) (i) 4 p (ii) 4 s (iii) 3d (iv) 3 p order of increasing energy is
Total no. of e  in s-orbitals  10
3 p  4 s  3d  4 p.
Total no. of e  in p-ortbitals  24
13. (a,d) According to Hund’s principle.
Total no. of e  in d-ortbitals  20 .

***
 Chemical Bonding 89

Chapter

3
Chemical Bonding

Atoms of different elements excepting noble gases donot have Some other examples are: MgCl , CaCl , MgO, Na S, CaH , AlF , NaH,
2 2 2 2 3

complete octet so they combine with other atoms to form chemical bond. KH, K 2O , KI, RbCl, NaBr, CaH etc. 2

The force which holds the atoms or ions together within the molecule is
called a chemical bond and the process of their combination is called (1) Conditions for formation of electrovalent bond
Chemical Bonding. It depends on the valency of atoms. (i) The atom which changes into cation (+ ive ion) should possess 1,
2 or 3 valency electrons. The other atom which changes into anion (–ve
Cause and Modes of chemical combination ion) should possess 5, 6 or 7 electrons in the valency shell.
Chemical bonding takes place due to acquire a state of minimum (ii) A high difference of electronegativity (about 2) of the two atoms
energy and maximum stability and to convert atoms into molecule to is necessary for the formation of an electrovalent bond. Electrovalent bond
acquire stable configuration of the nearest noble gas. We divide atoms into is not possible between similar atoms.
three classes,
(iii) There must be overall decrease in energy i.e., energy must be
(1) Electropositive elements which give up one or more electrons released. For this an atom should have low value of Ionisation potential and
easily. They have low ionisation potentials. the other atom should have high value of electron affinity.
(2) Electronegative elements, which can gain electrons. They have (iv) Higher the lattice energy, greater will be the case of forming an ionic
higher value of electronegativity. compound. The amount of energy released when free ions combine together to
(3) Elements which have little tendency to lose or gain electrons. K
form one mole of a crystal is called lattice energy (U). Lattice energy    ;
r r
Different types of bonds are formed from these types of atoms.
r   r  is internuclear distance.
Atoms involved Type
The energy changes involved in the formation of ionic compounds
A+B Electrovalent
from their constituent elements can be studied with the help of a
B+B Covalent thermochemical cycle called Born Haber cycle.
A+A Metallic
Electrons deficient molecule or ion Coordinate
Na(s) 1
(Lewis acid) and electrons rich + Cl 2 (g)
2 H
molecule or ion (Lewis base) H
f
sub 1/2Hdiss.
H and electronegative element (F, Hydrogen
Na(g) Cl (g) Na Cl (s)
+ –

N,O) (Crystal)
+IE – e– – EA +e
–
–U
Electrovalent bond Na  (g) + Cl  (g) (Lattice energy)
An electrovalent bond is formed when a metal atom transfers one or
more electrons to a non-metal atom. (Born Haber Cycle)
According to Hess's law of constant heat summation, heat of
 
 
       formation of an ionic solid is net resultant of the above changes.
Na   Cl    Na    Cl   or Na  Cl 
       H f  H Subl. 
1
H diss.  IE  EA  U
2
 90 Chemical Bonding
(2) Characteristics of electrovalent compounds (ii) Diamond, Carborandum (SiC), Silica (SiO ), AlN etc. have giant
2

(i) Electrovalent compounds are generally crystalline is nature. The three dimensional network structures; therefore have exceptionally high
constituent ions are arranged in a regular way in their lattice. melting points otherwise these compounds have relatively low melting and
boiling points.
(ii) Electrovalent compounds possess high melting and boiling
(iii) In general covalent substances are bad conductor of electricity.
points. Order of melting and boiling points in halides of sodium and oxides
Polar covalent compounds like HCl in solution conduct electricity. Graphite
of II group elements is as,
nd

NaF  NaCl  NaBr  NaI, MgO  CaO  BaO
(iii) Electrovalent compounds are hard and brittle in nature.
(iv) Electrovalent solids do not conduct electricity. While
electrovalent compounds in the molten state or in solution conduct
electricity.
(v) Electrovalent compounds are fairly soluble in polar solvents and
insoluble in non-polar solvents.
(vi) The electrovalent bonds are non-rigid and non-directional. Thus
these compound do not show space isomerism e.g. geometrical or optical
isomerism.
(vii) Electrovalent compounds furnish ions in solution. The chemical
reaction of these compounds are known as ionic reactions, which are fast.
   
K  Cl   Ag NO 3  Ag Cl   K NO 3
(Precipitate )
(viii) Electrovalent compounds show isomorphism.
(ix) Cooling curve of an ionic compound is not smooth, it has two
break points corresponding to time of solidification.
(x) Ionic compounds show variable electrovalency due to unstability
can conduct electricity in solid state since electrons can pass from one layer
to the other.
(iv) These compounds are generally insoluble in polar solvent like
water but soluble in non-polar solvents like benzene etc. some covalent
compounds like alcohol, dissolve in water due to hydrogen bonding.
(v) The covalent bond is rigid and directional. These compounds,
thus show isomerism (structural and space).
(vi) Covalent substances show molecular reactions. The reaction
rates are usually low.
(vii) The number of electrons contributed by an atom of the element
for sharing with other atoms is called covalency of the element. Covalency
= 8 – [Number of the group to which element belongs]. The variable
covalency of an element is equal to the total number of unpaired electrons
in s, p and d-orbitals of its valency shell.
  The element such as P, S, Cl, Br, I have vacant d-orbitals in their
valency shell. These elements show variable covalency by increasing the
number of unpaired electrons under excited conditions. The electrons from
paired orbitals get excited to vacant d-orbitals of the same shell.
Four elements, H, N, O and F do not possess d-orbitals in their
valency shell. Thus, such an excitation is not possible and variable valency is
not shown by these elements. This is reason that NCl exists while NCl does
3 5

not.
of core and inert pair effect.
(3) The Lewis theory : The tendency of atoms to achieve eight
Covalent bond electrons in their outermost shell is known as lewis octet rule.
Lewis symbol for the representative elements are given in the
Covalent bond was first proposed by Lewis in 1916. The bond
following table,
formed between the two atoms by mutual sharing of electrons so as to
1 2 13 14 15 16 17
complete their octets or duplets (in case of elements having only one shell)
Group IA IIA IIIA IVA VA VIA VIIA
is called covalent bond or covalent linkage. A covalent bond between two
similar atoms is non-polar covalent bond while it is polar between two Lewis X X     
symbol X X  X  X X 
different atom having different electronegativities. Covalent bond may be    

single, double or a triple bond. We explain covalent bond formation by (4) Failure of octet rule : There are several stable molecules known
Lewis octet rule. in which the octet rule is violated i.e., atoms in these molecules have
Chlorine atom has seven electrons in the valency shell. In the number of electrons in the valency shell either short of octet or more than
formation of chlorine molecule, each chlorine atom contributes one electron octet.
and the pair of electrons is shared between two atoms. both the atoms BeF2 , BF3 , AlH3 are electron- deficients (Octet incomplete) hence
acquire stable configuration of argon.
are Lewis acid.
 **  
    In PCl5 , P has 10 electrons in valency shell while in SF6 , S has 12
 Cl   Cl *
*
  Cl * Cl  or Cl  Cl
 
**
( 2 , 8 , 7 ) ( 2, 8 , 7 )
 electrons in valence shell. Sugden introduced singlet linkage in which one
( 2, 8 , 8 ) ( 2, 8 , 8 )
electron is donated (Instead of one pair of electrons) to the electron
Some other examples are : H 2 S , NH 3 , HCN , PCl3 , PH3, deficient atom so that octet rule is not violated. This singlet is represented
as (⇁). Thus, PCl5 and SF6 have structures as,
C2 H 2 , H 2 , C2 H 4 , SnCl 4 , FeCl3 , BH3 , graphite, BeCl 2 etc.
(1) Conditions for formation of covalent bond
Cl Cl F F
(i) The combining atoms should be short by 1, 2 or 3 electrons in Cl P Cl F S F
the valency shell in comparison to stable noble gas configuration.
Cl F F
(ii) Electronegativity difference between the two atoms should be (5) Construction of structures for molecules and poly atomic ions :
zero or very small. The following method is applicable to species in which the octet rule is not
(iii) The approach of the atoms towards one another should be violated.
accompanied by decrease of energy. (i) Determine the total number of valence electrons in all the atoms
(2) Characteristics of covalent compounds present, including the net charge on the species (n ). 1

(i) These exist as gases or liquids under the normal conditions of (ii) Determine n = [2 × (number of H atoms) + 8 × (number of
2

temperature and pressure. Some covalent compounds exist as soft solids. other atoms)].
 Chemical Bonding 91
(iii) Determine the number of bonding electrons, n , which equals n 3 2
Examples : CO, N O, H O , N O , N O , N O , HNO , NO 3 , SO , SO ,
– n . No. of bonds equals n /2. 2 2 2 2 3 2 4 2 5 3 2 3

SO 42  , SO 22  ,
1 3

(iv) Determine the number of non-bonding electrons, n , which H SO ,

2 4
H 3 PO4 , H 4 P2O7 ,
4

equals n – n . No. of lone pairs equals n /2.

1 3
(v) Knowing the central atom (you’ll need to know some chemistry
here, math will not help!), arrange and distribute other atoms and n /2
4
H 3 PO3 , Al2Cl6 (Anhydrous), O3 , SO 2Cl2 , SOCl 2 , HIO3 , HClO4 ,
HClO3 , CH 3 NC , N 2 H 5 , CH 3 NO 2 , NH 4 , [Cu(NH 3 )4 ]2 etc.
Characteristics of co-ordinate covalent compound
3

bonds. Then complete octets using n /2 lone pairs. 4

(1) Their melting and boiling points are higher than purely covalent
(vi) Determine the ‘formal charge’ on each atom. compounds and lower than purely ionic compounds.
(vii) Formal Charge = [valence electrons in atom) – (no. of bonds) – (2) These are sparingly soluble in polar solvent like water but readily
(no. of unshared electrons)] soluble in non-polar solvents.
(viii) Other aspects like resonance etc. can now be incorporated. (3) Like covalent compounds, these are also bad conductors of
electricity. Their solutions or fused masses do not allow the passage to
Illustrative examples electricity.
(i) CO 32  ; n1  4  (6  3)  2  24 [2 added for net charge] (4) The bond is rigid and directional. Thus, coordinate compounds
show isomerism.
n 2 = (2 × 0) + (8 × 4) = 32 (no. H atom, 4 other atoms (1’C’ and 3
‘O’) Dipole moment
n 3 = 32 – 24 = 8, hence 8/2 = 4 bonds “The product of magnitude of negative or positive charge (q) and
the distance (d) between the centres of positive and negative charges is
n 4 = 24 – 8 = 16, hence 8 lone pairs. called dipole moment”.
Since carbon is the central atom, 3 oxygen atoms are to be arranged  = Electric charge  bond length
around it, thus, As q is in the order of 10 esu and d is in the order of 10 cm,  is in
–10 –8

the order of 10 esu cm. Dipole moment is measured in “Debye” (D) unit.
–18

O
| 1D  10 18 esu cm = 3.33  10 30 coulomb metre (In S.I. unit).
O  C  O , but total bonds are equal to 4. Dipole moment is indicated by an arrow having a symbol ( )
O pointing towards the negative end. Dipole moment has both magnitude and
| direction and therefore it is a vector quantity.
Hence, we get O  C  O . Now, arrange lone pairs to complete Symmetrical polyatomic molecules are not polar so they do not have
.. any value of dipole moment.
.O :
. | .. H
octet : O  C  O : F
..
O C O C
(ii) CO 2 ; n = 4 + (6 × 2 ) = 16 1
B H H
F F
n = (2 × 0) + (8 × 3) = 24
2 H
n = 24 – 16 = 8, hence 4 bonds
3
 = 0 due to symmetry
n = 16 – 8 = 8, hence 4 lone-pairs
4 Unsymmetrical polyatomic molecules always have net value of dipole
Since C is the central atom, the two oxygen atoms are around to be moment, thus such molecules are polar in nature. H O, CH Cl, NH , etc are 2 3 3

arranged it thus the structure would be; O – C – O, but total no. of bonds polar molecules as they have some positive values of dipole moments
Cl .
=4
Thus, O = C = O. After arrangement of lone pairs to complete
O N C
.. .. .. ..
octets, we get, : O  C  O : and thus final structure is : O  C  O : H H H H H H
Water
Co-ordinate covalent or Dative bond  = 1.84D H H
This is a special type of covalent bond where the shared pair of Ammonia Methyl chloride
electrons are contributed by one species only but shared by both. The atom  = 1.46D  = 1.86D
which contributes the electrons is called the donor (Lewis base) while the   0 due to unsymmetry
other which only shares the electron pair is known as acceptor (Lewis acid). (1) Dipole moment is an important factor in determining the
geometry of molecules.
This bond is usually represented by an arrow (  ) pointing from donor to Table : 3.1 Molecular geometry and dipole moment
the acceptor atom. General Molecular geometry Dipole Example
BF molecule, boron is short of two electrons. So to complete its
3
formula moment
octet, it shares the lone pair of nitrogen in ammonia forming a dative bond. AX Linear May be HF, HCl

non zero

 Linear Zero
H

 F  H  F  H
AX 2 CO 2 ,CS 2
       
F Bent or V-shape Non zero
  | | H 2O, NO 2
H * N **  B 
 F

 H * N 
 B 
 F   H  N  B  F
          | | AX 3 Triangular planar Zero BF3

H  F  H 
 F 

H F Pyramidal Non zero
NH 3 , PCl3
   T-shape Non zero
Formation of a co-ordinate ClF3
bond between NH3 and BF3
AX 4 Tetrahedral Zero CH 4 ,CCl 4
 92 Chemical Bonding
Square planar Zero XeF4 (8) Between two sub shells of same energy level, the sub shell more
See saw Non zero directionally concentrated shows more overlapping. Bond energy :
SF4 ,TeCl 4
2s  2s < 2s  2 p < 2 p  2 p
AX 5 Trigonal bipyramidal Zero PCl5
Square pyramidal Non zero (9) s -orbitals are spherically symmetrical and thus show only head
BrCl5 on overlapping. On the other hand, p -orbitals are directionally
AX 6 Octahedral Zero SF6 concentrated and thus show either head on overlapping or lateral
Distorted octahedral Non zero overlapping.Overlapping of different type gives sigma () and pi () bond.
XeF6
AX 7 Pentagonal bipyramidal Zero IF7 Sigma () bond Pi () bond
It results from the end to end It result from the sidewise (lateral)
(2) Every ionic compound having some percentage of covalent
overlapping of two s-orbitals or overlapping of two p-orbitals.
character according to Fajan's rule. The percentage of ionic character in
two p-orbitals or one s and one p-
compound having some covalent character can be calculated by the
orbital.
following equation.
Stronger Less strong
Observed 
The % ionic character   100 . Bond energy 80 kcals Bond energy 65 kcals
Theoretica l 
More stable Less stable
(3) The trans isomer usually possesses either zero dipole moment or Less reactive More reactive
very low value in comparison to cis–form
Can exist independently Always exist along with a -bond
H  C  Cl H  C  Cl
|| || The electron cloud is symmetrical The electron cloud is above and
H  C  Cl Cl  C  H about the internuclear axis. below the plane of internuclear
axis.
Fajan’s rule
The magnitude of polarization or increased covalent character Hybridization
depends upon a number of factors. These factors are,
The concept of hybridization was introduced by Pauling and Slater.
(1) Small size of cation : Smaller size of cation greater is its
Hybridization is defined as the intermixing of dissimilar orbitals of the same
polarizing power i.e. greater will be the covalent nature of the bond.
atom but having slightly different energies to form same number of new
(2) Large size of anion : Larger the size of anion greater is its
orbitals of equal energies and identical shapes. The new orbitals so formed
polarizing power i.e. greater will be the covalent nature of the bond.
are known as hybrid orbitals.
(3) Large charge on either of the two ions : As the charge on the
ion increases, the electrostatic attraction of the cation for the outer Characteristics of hybridization
electrons of the anion also increases with the result its ability for forming (1) Only orbitals of almost similar energies and belonging to the
the covalent bond increases. same atom or ion undergoes hybridization.
(4) Electronic configuration of the cation : For the two ions of the (2) Hybridization takes place only in orbitals, electrons are not
same size and charge, one with a pseudo noble gas configuration (i.e. 18
involved in it.
electrons in the outermost shell) will be more polarizing than a cation with
noble gas configuration (i.e., 8 electron in outer most shell). (3) The number of hybrid orbitals produced is equal to the number
of pure orbitals, mixed during hybridization.
Valence bond theory or VBT
(4) In the excited state, the number of unpaired electrons must
It was developed by Heitler and London in 1927 and modified by
correspond to the oxidation state of the central atom in the molecule.
Pauling and Slater in 1931.
(5) Both half filled orbitals or fully filled orbitals of equivalent
(1) To form a covalent bond, two atoms must come close to each
energy can involve in hybridization.
other so that orbitals of one overlaps with the other.
(2) Orbitals having unpaired electrons of anti spin overlaps with (6) Hybrid orbitals form only sigma bonds.
each other. (7) Orbitals involved in  bond formation do not participate in
(3) After overlapping a new localized bond orbital is formed which hybridization.
has maximum probability of finding electrons. (8) Hybridization never takes place in an isolated atom but it occurs
(4) Covalent bond is formed due to electrostatic attraction between only at the time of bond formation.
radii and the accumulated electrons cloud and by attraction between spins (9) The hybrid orbitals are distributed in space as apart as possible
of anti spin electrons. resulting in a definite geometry of molecule.
(5) Greater is the overlapping, lesser will be the bond length, more (10) Hybridized orbitals provide efficient overlapping than
will be attraction and more will be bond energy and the stability of bond overlapping by pure s, p and d-orbitals.
will also be high.
(11) Hybridized orbitals possess lower energy.
(6) The extent of overlapping depends upon: Nature of orbitals
involved in overlapping, and nature of overlapping. How to determine type of hybridization : The structure of any
molecule can be predicted on the basis of hybridization which in turn can
(7) More closer the valence shells are to the nucleus, more will be
be known by the following general formulation,
the overlapping and the bond energy will also be high.
1
H  (V  M  C  A)
2
 Chemical Bonding 93
Where H = Number of orbitals involved in hybridization viz. 2, 3, 4, O O O
5, 6 and 7, hence nature of hybridization will be sp, sp , sp , sp d, sp d , sp d
2 3 3 3 2 3 3

| || |
respectively. C  C  C
V = Number electrons in valence shell of the central atom, // \ / \ / \\

O O O O 
O O
M = Number of monovalent atom
C = Charge on cation, 2 11
Bond order   1.33
A = Charge on anion 3

Resonance Bond characteristics

The phenomenon of resonance was put forward by Heisenberg to (1) Bond length
explain the properties of certain molecules. “The average distance between the centre of the nuclei of the two
In case of certain molecules, a single Lewis structure cannot explain bonded atoms is called bond length”.
all the properties of the molecule. The molecule is then supposed to have
many structures, each of which can explain most of the properties of the It is expressed in terms of Angstrom (1 Å = 10 10 m) or picometer
molecule but none can explain all the properties of the molecule. The actual (1pm = 10 12 m).
structure is in between of all these contributing structures and is called
resonance hybrid and the different individual structures are called In an ionic compound, the bond length is the sum of their ionic
resonating structures or canonical forms. This phenomenon is called radii ( d  r  r ) and in a covalent compound, it is the sum of their
resonance.
covalent radii (e.g., for HCl, d  rH  rCl ).
To illustrate this, consider a molecule of ozone O3 . Its structure
Factors affecting bond length
can be written as
. . .. .. (i) The bond length increases with increase in the size of the atoms.
O .O. O
For example, bond length of H  X are in the order,
. O. . .. .. . . . HI  HBr  HCl  HF .
.O O.
.O. . .O . . (c ) . . .
. . .. . O
(a ) (b )
..
(ii) The bond length decreases with the multiplicity of the bond.
As a resonance hybrid of above two structures (a) and (b. For Thus, bond length of carbon–carbon bonds are in the order,
simplicity, ozone may be represented by structure (c), which shows the C CC CC –C.
resonance hybrid having equal bonds between single and double. (iii) As an s-orbital is smaller in size, greater the s-character shorter
Resonance is shown by benzene, toluene, O , allenes
3
(>C = C = is the hybrid orbital and hence shorter is the bond length.
C<), CO, CO , CO 3 , SO , NO, NO while it is not shown by H O , H O, NH ,
2 3 2 2 2 2 3
For example, sp 3 C – H  sp 2 C – H  sp C – H
CH , SiO .
4 2

As a result of resonance, the bond lengths of single and double bond (iv) Polar bond length is usually smaller than the theoretical non-
in a molecule become equal e.g. O–O bond lengths in ozone or C–O bond polar bond length.
lengths in CO 32 – ion. (2) Bond energy

The resonance hybrid has lower energy and hence greater stability “The amount of energy required to break one mole of bonds of a
than any of the contributing structures. particular type so as to separate them into gaseous atoms is called bond
dissociation energy or simply bond energy”. Greater is the bond energy,
Greater is the number of canonical forms especially with nearly
same energy, greater is the stability of the molecule. stronger is the bond. Bond energy is usually expressed in kJ mol –1 .
Difference between the energy of resonance hybrid and that of the Factors affecting bond energy
most stable of the resonating structures (having least energy) is called
resonance energy. Thus, (i) Greater the size of the atom, greater is the bond length and less
is the bond dissociation energy i.e. less is the bond strength.
Resonance energy = Energy of resonance hybrid – Energy of the
most stable of resonating structure. (ii) For the bond between the two similar atoms, greater is the
In the case of molecules or ions having resonance, the bond order multiplicity of the bond, greater is the bond dissociation energy.
changes and is calculated as follows, (iii) Greater the number of lone pairs of electrons present on the
bonded atoms, greater is the repulsion between the atoms and hence less is
Total no. of bonds between two atoms in all the structures the bond dissociation energy.
Bond order 
Total no. of resonating structures
(iv) The bond energy increases as the hybrid orbitals have greater
amount of s orbital contribution. Thus, bond energy decreases in the
In benzene 
 following order, sp  sp 2  sp 3
(v) Greater the electronegativity difference, greater is the bond
double bond  singlebond 2  1 polarity and hence greater will be the bond strength i.e., bond energy,
Bond order    1.5 H  F  H  Cl  H  Br  H  I ,
2 2
In carbonate ion
 94 Chemical Bonding
(vi) Among halogens Cl – Cl > F – F > Br – Br > I – I, (Decreasing In case the central atom remains the same, bond angle increases
order of bond energy) Resonance increases bond energy. with the decrease in electronegativity of the surrounding atom.
(3) Bond angle PCl3 PBr3 PI3 , AsCl3 AsBr3 AsI3
In case of molecules made up of three or more atoms, the average Bond angle 100 o 101.5 o 102 o 98.4 o 100.5 o 101o
angle between the bonded orbitals (i.e., between the two covalent bonds) is
known as bond angle . Valence shell electron pair repulsion theory (VSEPR )
Factors affecting bond angle The basic concept of the theory was suggested by Sidgwick and
Powell (1940). It provides useful idea for predicting shapes and geometries
(i) Repulsion between atoms or groups attached to the central atom
of molecules. The concept tells that, the arrangement of bonds around the
may increase or decrease the bond angle.
central atom depends upon the repulsion’s operating between electron
(ii) In hybridisation as the s character of the s hybrid bond pairs(bonded or non bonded) around the central atom. Gillespie and
increases, the bond angle increases. Nyholm developed this concept as VSEPR theory.
The main postulates of VSEPR theory are
Bond type sp3
sp 2
sp
(1) For polyatomic molecules containing 3 or more atoms, one of the
Bond angle 109º28 120° 180° atoms is called the central atom to which other atoms are linked.
(2) The geometry of a molecule depends upon the total number of
(iii) By increasing lone pair of electron, bond angle decreases valence shell electron pairs (bonded or not bonded) present around the
approximately by 2.5%. central atom and their repulsion due to relative sizes and shapes.
(3) If the central atom is surrounded by bond pairs only. It gives the
CH NH HO
4 3 2
symmetrical shape to the molecule.
Bond angle 109º 107 o
105 o
(4) If the central atom is surrounded by lone pairs (lp) as well as
bond pairs (bp) of e  then the molecule has a distorted geometry.
(iv) If the electronegativity of the central atom decreases, bond angle (5) The relative order of repulsion between electron pairs is as
decreases. follows : lp – lp > lp – bp > bp – bp.
A lone pair is concentrated around the central atom while a bond
H 2O  H 2S  H 2 Se  H 2 Te pair is pulled out between two bonded atoms. As such repulsion becomes
Bond angle 104.5 o 92.2 o 91.2 o 89.5 o greater when a lone pair is involved.

Table : 3.2 Geometry of Molecules/Ions having bond pair as well as lone pair of electrons
No. of bond No. of lone
Type of Hybridi- Expected
pairs of pairs of Bond angle Actual geometry Examples
mole-cule zation geometry
electron electrons
V-shape, Bent,
AX 3 2 1 sp 2 < 120 o
Trigonal planar
Angular
SO , SnCl , NO
2 2 2
–

V-shape,
AX 4 2 2 sp 3 < 109 28 o
Tetrahedral
Angular
H O, H S, SCl , OF , NH , ClO
2 2 2 2 2
– –

AX 4 3 1 sp 3 < 109 28 o

Tetrahedral Pyramidal NH , NF , PCl, PH, AsH, ClO , H O
3 3 3 3 3
–

3 3
+

Trigonal Irregular
AX 5 4 1 sp 3 d < 109 28 o

bipyramidal tetrahedron
SF , SCl , TeCl
4 4 4

Trigonal
AX 5 3 2 sp 3 d 90 o

bipyramidal
T-shaped ICl , IF , ClF
3 3 3

Trigonal
AX 5 2 3 sp 3 d 180 o

bipyramidal
Linear XeF , I , ICl2 3
– –

Square
AX 6 5 1 sp 3 d 2 < 90 o
Octahedral
pyramidal
ICl , BrF , IF
5 5 5

3 2
AX 6 4 2 sp d – Octahedral Square planar XeF , ICl 4
–

Pentagonal Distorted
AX 7
6 1 sp d 3 3 –
pyramidal octahedral
XeF 6

(2) Molecular orbitals are the energy states of a molecule in which

Molecular orbital theory or MOT the electrons of the molecule are filled just as atomic orbitals are the energy
Molecular orbital theory was given by Hund and Mulliken in 1932. states of an atom in which the electrons of the atom are filled.
The main ideas of this theory are, (3) In terms of probability distribution, a molecular orbital gives
the electron probability distribution around a group of nuclei just as an
(1) When two atomic orbitals combine or overlap, they lose their atomic orbital gives the electron probability distribution around the single
identity and form new orbitals. The new orbitals thus formed are called nucleus.
molecular orbitals.
(4) Only those atomic orbitals can combine to form molecular
orbitals which have comparable energies and proper orientation.
 Chemical Bonding 95
(5) The number of molecular orbitals formed is equal to the number Increasing energy (for electrons > 14)
of combining atomic orbitals.
(b)  1s,  1s,  2 s,  * 2 s,  2 p y ,  2 p x ,
*
(6) When two atomic orbitals combine, they form two new orbitals
called bonding molecular orbital and antibonding molecular orbital.
 * 2pz
(7) The bonding molecular orbital has lower energy and hence
greater stability than the corresponding antibonding molecular orbital. Increasing energy (for electrons  14)
(8) The bonding molecular orbitals are represented by  ,  etc, (12) Number of bonds between two atoms is called bond
whereas the corresponding antibonding molecular orbitals are represented order and is given by

by  * ,  * etc.  N  NA 
Bond order   B 
(9) The shapes of the molecular orbitals formed depend upon the  2 
type of combining atomic orbitals. where N B  number of electrons in bonding MO.
(10) The filling of molecular orbitals in a molecule takes place in
N A  number of electrons in antibonding MO.
accordance with Aufbau principle, Pauli's exclusion principle and Hund's
rule. The general order of increasing energy among the molecular orbitals For a stable molecule/ion, N B  N A
formed by the elements of second period and hydrogen and their general
electronic configurations are given below. (13) Bond order  Stability of molecule  Dissociation energy 
1
(11) Electrons are filled in the increasing energy of the MO which is .
in order Bond length
(14) If all the electrons in a molecule are paired then the substance
(a)  1s,  *1s,  2 s,  * 2 s,  2 p x ,  2 p y  * 2 py ,  * 2 p x is a diamagnetic on the other hand if there are unpaired electrons in the
molecule, then the substance is paramagnetic. More the number of unpaired
 2 pz ,  * 2 pz electron in the molecule greater is the paramagnetism of the substance.
*  (2pz)
*(2pz)
2p 2p
2p 2p *(2py) *(2px)
*(2py) *(2px)
 (2py)  (2px)
 (2pz)
Increasing energy

 (2py)  (2px)
Increasing energy

 (2pz)
2s *(2s) 2s
2s *(2s) 2s

 (2s)
 (2s)

1s *(1s) 1s
1s *(1s) 1s

 (1s)
 (1s)
Atomic Molecular Atomic
Atomic Molecular Atomic orbitals orbitals orbitals
orbitals orbitals orbitals
Molecular orbital energy level diagram obtained by the overlap of 2s and 2pz
Molecular orbital energy level diagram atomic orbitals after mixing
(Applicable for elements with Z > 7) (Applicable for elements with Z < 7)
Hydrogen bonding (ii) Hydrogen bond in alcohol and water molecules
In 1920, Latimer and Rodebush introduced the idea of “hydrogen (2) Intramolecular hydrogen bond (Chelation)
bond”.
Intramolecular hydrogen bond is formed between the hydrogen atom
For the formation of H-bonding the molecule should contain an and the highly electronegative atom (F, O or N) present in the same
atom of high electronegativity such as F, O or N bonded to hydrogen atom molecule. Intramolecular hydrogen bond results in the cyclisation of the
and the size of the electronegative atom should be quite small. molecules and prevents their association. Consequently, the effect of
Types of hydrogen bonding intramolecular hydrogen bond on the physical properties is negligible.
(1) Intermolecular hydrogen bond : Intermolecular hydrogen bond is For example : Intramolecular hydrogen bonds are present in
formed between two different molecules of the same or different molecules such as o-nitrophenol, o-nitrobenzoic acid, etc.
substances. O H
(i) Hydrogen bond between the molecules of hydrogen fluoride. | |
C C
O
H O
O
H
O O
N H
N O
| | Salicyldehyde
O O (o-hydroxy benzaldehyde)
Ortho nitrophenol Ortho nitrobenzoic acid
 96 Chemical Bonding

(5) As the compounds involving hydrogen bonding between

The extent of both intramolecular and intermolecular hydrogen
different molecules (intermolecular hydrogen bonding) have higher boiling
bonding depends on temperature.
points, so they are less volatile.
Effects of hydrogen bonding
(6) The substances which contain hydrogen bonding have higher
Hydrogen bond helps in explaining the abnormal physical properties viscosity and high surface tension.
in several cases. Some of the properties affected by H-bond are given below,
(7) Explanation of lower density of ice than water and maximum
(1) Dissociation : In aqueous solution, hydrogen fluoride dissociates density of water at 277K : In case of solid ice, the hydrogen bonding gives
and gives the difluoride ion (HF2 ) instead of fluoride ion (F  ) . This is rise to a cage like structure of water molecules as shown in following figure.
As a matter of fact, each water molecule is linked tetrahedrally to four other
due to H-bonding in HF. This explains the existence of KHF2 . H-bond
water molecules. Due to this structure ice has lower density than water at
formed is usually longer than the covalent bond present in the molecule
273K. That is why ice floats on water. On heating, the hydrogen bonds
(e.g. in H O, O–H
2
bond = 0.99 Å but H-bond = 1.77 Å).
start collapsing, obviously the molecules are not so closely packed as they
(2) Association : The molecules of carboxylic acids exist as dimers are in the liquid state and thus the molecules start coming together
because of the hydrogen bonding. The molecular masses of such compounds resulting in the decrease of volume and hence increase of density. This goes
are found to be double than those calculated from their simple formulae.
on upto 277K. After 277 K, the increase in volume due to expansion of the
For example, molecular mass of acetic acid is found to be 120.
liquid water becomes much more than the decrease in volume due to
(3) High melting and boiling point : The compounds having breaking of H-bonds. Thus, after 277 K , there is net increase of
hydrogen bonding show abnormally high melting and boiling points. volume on heating which means decrease in density. Hence density of water
The high melting points and boiling points of the compounds is maximum 277 K .
(H 2 O, HF and NH 3 ) containing hydrogen bonds is due to the fact that
0.90 Å
H
some extra energy is needed to break these bonds. (99 pm)
1.77 Å
O (177 pm)
(4) Solubility : The compound which can form hydrogen bonds with
the covalent molecules are soluble in such solvents. For example, lower H H H
alcohols are soluble in water because of the hydrogen bonding which can O Vacant spaces
O
take place between water and alcohol molecules as shown below,
H H H H
     
H  O .......... ...... H  O .......... ..... H  O O O

H H H H
C2 H 5 H C2 H 5
O O
The intermolecular hydrogen bonding increases solubility of the
H H H H
compound in water while, the intramolecular hydrogen bonding decreases.
O O
O H – O …… H – O – H H H
H

O Cage like structure of H2O in the ice

N
ON=O
|
O
o- Nitrophenol
p- Nitrophenol

Due to chelation, – OH group is not – OH group available to form

available to form hydrogen bond with hydrogen bond with water, hence it
water hence it is sparingly soluble in is completely soluble in water.
water.
 98 Chemical Bonding

Electrovalent bonding
1. Which forms a crystal of NaCl
[CPMT 1972; NCERT 1976; DPMT 1996]
(a) NaCl molecules (b) Na  and Cl  ions
(c) Na and Cl atoms (d) None of the above
 A chemical bond is expected to be formed when the energy of the 2. When sodium and chlorine reacts then [NCERT 1973]
aggregate formed is about 40 kJ mole lower than the separate
–1 (a) Energy is released and ionic bond is formed
particles. (b) Energy is released and a covalent bond is formed
(c) Energy is absorbed and ionic bond is formed
 Formation of a chemical bond is always an exothermic process. (d) Energy is absorbed and covalent bond is formed
3. Which one is least ionic in the following compounds
 Lattice energies of bi-bivalent solids > bi-univalent solids > uni- [CPMT 1976; BHU 1998]
univalent solids. For example, lattice energy of (a) AgCl (b) KCl
Mg 2  O 2  (3932 kJ mole 1 )  Ca 2  (F  )2 (2581 kJ mole 1 )  (c) BaCl2 (d) CaCl 2
  1 4. The electronic configuration of four elements L, P, Q and R are
Li F (1034 kJ mole ) .
given in brackets
 When co-ordination number increases, the coulombic forces of   
L 1s 2 , 2 s 2 2 p 4 ; Q 1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 5 
P 1s , 2 s 2 p , 3 s ; R 1s , 2 s 2 p , 3s 
attraction increases and hence stability increases. 2 2 6 1 2 2 6 2

 Ionic solids have negative vapour pressure. The formulae of ionic compounds that can be formed between these
elements are [NCERT 1983]
 As a general rule, atomic crystals are formed by the lighter (a) L2 P, RL, PQ and R2 Q (b) LP , RL, PQ and RQ
elements of the middle columns of the periodic table.
(c) P2 L, RL, PQ and RQ2 (d) LP , R2 L, P2Q and RQ
 FeCl3 is more covalent than FeCl2 because polarising power of 5. Electrovalent compound's [MP PMT 1984]
3 2 (a) Melting points are low
Fe is more than that of Fe . Similarly SnCl 4 is more
(b) Boiling points are low
covalent than SnCl 2 . (c) Conduct current in fused state
(d) Insoluble in polar solvent
 Boron forms the maximum number of electron deficient 6. A electrovalent compound is made up of
compounds than any other elements in the periodic table. [CPMT 1978, 81; MNR 1979]
(a) Electrically charged molecules
 Roughly each lone pair decreases the bond angle by 2.5°. (b) Neutral molecules
(c) Neutral atoms
 Greater the number of the lone pairs at the two bonding atoms, (d) Electrically charged atoms or group of atoms
greater is the repulsion between them and weaker is the bond. 7. Electrovalent bond formation depends on
(a) Ionization energy (b) Electron affinity
 The actual number of s- and p-electrons present in the outermost (c) Lattice energy (d) All the three above
shell of the element is called maximum covalency of that atom. 8. In the following which substance will have highest boiling point [NCERT 1973; M
(a) He (b) CsF
 The hydrogen bonds are tetrahedral in their directions and not
planar. (c) NH 3 (d) CHCl 3
9. An atom of sodium loses one electron and chlorine atom accepts one
 The hydrogen bond is stronger in HF and persists even in vapour electron. This result the formation of sodium chloride molecule. This
state. Such bonds account for the fact that gaseous hydrogen type of molecule will be
fluoride is largely polymerised into the molecular species [MP PMT 1987]
H 2 F2 , H 3 F3 , H 4 F4 , H 5 F5 and H 6 F6 . (a) Coordinate (b) Covalent
(c) Electrovalent (d) Matallic bond
 Hydrogen bonding is strongest when the bonded structure is 10. Formula of a metallic oxide is MO. The formula of its phosphate
stabilised by resonance. will be [CPMT 1986, 93]
(a) M 2 PO4 2 (b) M PO4 
 Critical temperature of water is higher than that of O 2 because
(c) M 2 PO4 (d) M 3 PO4 2
H 2 O molecule has dipole moment.
11. From the following which group of elements easily forms cation
(a) F, Cl, Br (b) Li, Na, K
(c) O, S , Se (d) N , P, As
12. Which type of compounds show high melting and boiling points
(a) Electrovalent compounds
(b) Covalent compounds
 Chemical Bonding 99
(c) Coordinate compounds 23. In the transition of Zn atoms to Zn   ions there is a decrease in
(d) All the three types of compounds have equal melting and the [CPMT 1972]
boiling points (a) Number of valency electrons
13. Lattice energy of an ionic compound depends upon
(b) Atomic weight
[AIEEE 2005]
(c) Atomic number
(a) Charge on the ion only
(d) Equivalent weight
(b) Size of the ion only
24. Phosphate of a metal M has the formula M 3 PO4 2 . The formula
(c) Packing of ions only
(d) Charge on the ion and size of the ion for its sulphate would be
14. In the given bonds which one is most ionic [CPMT 1973; MP PMT 1996]
[EAMCET 1980] (a) MSO 4 (b) M SO 4 2
(a) Cs  Cl (b) Al  Cl (c) M 2 SO 4 3 (d) M 3 SO 4 2
(c) C  Cl (d) H  Cl
25. The molecular formula of chloride of a metal M is MCl 3 . The
15. Element x is strongly electropositive and y is strongly
formula of its carbonate would be [CPMT 1987]
electronegative. Both element are univalent, the compounds formed
from their combination will be [IIT 1980] (a) MCO 3 (b) M 2 CO 3 3
(a) x y  (b) x  y (c) M 2 CO 3 (d) M CO 3 2
(c) x y (d) x y 26. Sodium chloride easily dissolves in water. This is because
16. In the formation of NaCl from Na and Cl [CPMT 1985] [NCERT 1972; BHU 1973]
(a) Sodium and chlorine both give electrons (a) It is a covalent compound
(b) Sodium and chlorine both accept electrons (b) Salt reacts with water
(c) Sodium loses electron and chlorine accepts electron (c) It is a white substance
(d) Sodium accepts electron and chlorine loses electron (d) Its ions are easily solvated
17. Which of the following is an electrovalent linkage 27. When NaCl is dissolved in water the sodium ion becomes
[CPMT 1974; DPMT 1984, 91; AFMC 1988] [NCERT 1974; CPMT 1989; MP PMT 1999]
(a) CH 4 (b) MgCl2 (a) Oxidized (b) Reduced
(c) SiCl4 (d) BF3 (c) Hydrolysed (d) Hydrated
18. Electrovalent compounds do not have [CPMT 1991] 28. Solid NaCl is a bad conductor of electricity since
(a) High M.P. and Low B.P. (b) High dielectric constant [AFMC 1980]
(c) High M.P. and High B.P. (d) High polarity (a) In solid NaCl there are no ions
19. Many ionic crystals dissolve in water because (b) Solid NaCl is covalent
[NCERT 1982]
(a) Water is an amphiprotic solvent (c) In solid NaCl there is no motion of ions
(b) Water is a high boiling liquid (d) In solid NaCl there are no electrons
(c) The process is accompanied by a positive heat of solution 29. Favourable conditions for electrovalency are
(d) Water decreases the interionic attraction in the crystal (a) Low charge on ions, large cation, small anion
lattice due to solvation (b) High charge on ions, small cation, large anion
20. The electronic structure of four elements A, B, C, D are (c) High charge on ions, large cation, small anion
(A) 1s 2 (B) 1s 2 , 2 s 2 2 p 2 (d) Low charge on ions, small cation, large anion
30. The sulphate of a metal has the formula M 2 SO 4 3 . The formula
(C) 1s 2 , 2 s 2 2 p 5 (D) 1s 2 , 2 s 2 2 p 6
for its phosphate will be
The tendency to form electrovalent bond is largest in [DPMT 1982; CPMT 1972; MP PMT 1995]
[MNR 1987, 95] (a) M HPO4 2 (b) M 3 PO4 2
(a) A (b) B
(c) M 2 PO4 3 (d) MPO4
(c) C (d) D
21. Chloride of metal is MCl 2 . The formula of its phosphate will be 31. Ionic bonds are usually formed by combination of elements with [CBSE PMT 199
[CPMT 1979]
(a) High ionisation potential and low electron affinity
(a) M 2 PO4 (b) M 3 PO4 2 (b) Low ionisation potential and high electron affinity
(c) M 2 PO4 3 (d) MPO4 (c) High ionisation potential and high electron affinity
(d) Low ionisation potential and low electron affinity
22. The phosphate of a metal has the formula MPO4 . The formula of 32. Molten sodium chloride conducts electricity due to the presence of
its nitrate will be [CPMT 1971; MP PMT 1996] (a) Free electrons
(a) MNO 3 (b) M 2 NO 3 2 (b) Free ions
(c) M NO 3 2 (d) M NO 3 3 (c) Free molecules
(d) Atoms of sodium and chlorine
 100 Chemical Bonding

33. The phosphate of a metal has the formula MHPO4 . The formula 45. Out of the following, which compound will have electrovalent
bonding
of its chloride would be
[NCERT 1974; CPMT 1977] (a) Ammonia (b) Water
(a) MCl (b) MCl 2 (c) Calcium chloride (d) Chloromethane
46. The force which holds atoms together in an electrovalent bond is
(c) MCl 3 (d) M 2 Cl 3
(a) Vander Waal's force
34. A number of ionic compounds e.g. AgCl, CaF2 , BaSO 4 are (b) Dipole attraction force
insoluble in water. This is because [NCERT 1984] (c) Electrostatic force of attraction
(a) Ionic compounds do not dissolve in water (d) All the above
(b) Water has a high dielectric constant 47. The main reaction during electrovalent bond formation is
(c) Water is not a good ionizing solvent (a) Redox reaction (b) Substitution reaction
(d) These molecules have exceptionally high alternative forces in (c) Addition reaction (d) Elimination reaction
the lattice
48. Electrovalent compounds are [CPMT 1996]
35. What is the nature of chemical bonding between Cs and F
(a) Good conductor of electricity
[MP PMT 1987; CPMT 1976]
(b) Polar in nature
(a) Covalent (b) Ionic
(c) Coordinate (d) Metallic (c) Low M.P. and low B.P.
36. Which one of the following compound is ionic (d) Easily available
[MNR 1985] 49. Ionic compounds do not have [RPMT 1997]

(a) KCl (b) CH 4 (a) Hard and brittle nature

(b) High melting and boiling point
(c) Diamond (d) H2
(c) Directional properties
37. Which of the following compound has electrovalent linkage (d) Soluble in polar solvents
[CPMT 1983, 84, 93] 50. Highest melting point would be of [RPMT 1999]
(a) CH 3 Cl (b) NaCl (a) He (b) CsCl
(c) CH 4 (d) Cl 2 (c) NH 3 (d) CHCl 3
38. An ionic compound is generally a [MADT Bihar 1981] 51. What is the effect of more electronegative atom on the strength of
(a) Good electrolyte (b) Weak electrolyte ionic bond [AMU 1999]
(c) Non-electrolyte (d) Neutral (a) Decreases (b) Increases
39. What metals combine with non-metals, the metal atom tends to [AMU 1982]
(c) Decreases slowly (d) Remains the same
(a) Lose electrons
52. An element X with the electronic configuration 1s 2 , 2 s 2 2 p 6 , 3 s 2
(b) Gain electrons
would be expected to form the chloride with the formula
(c) Remain electrically neutral
(a) XCl 3 (b) XCl 2
(d) None of these
40. Chemical formula for calcium pyrophosphate is Ca 2 P2 O7 . The (c) XCl (d) X 2 Cl
formula for ferric pyrophosphate will be [NCERT 1977] 53. Two element have electronegativity of 1.2 and 3.0. Bond formed
(a) Fe3 (P2 O7 )3 (b) Fe4 P4 O14 between them would be [CPMT 1982; DCE 2000]
(a) Ionic (b) Polar covalent
(c) Fe4 (P2 O7 )3 (d) Fe3 PO4 (c) Co-ordinate (d) Metallic
41. Among the bonds formed by a chlorine atom with atoms of 54. Which of the following is least ionic [MP PET 2002]
hydrogen, chlorine, sodium and carbon, the strongest bond is
(a) C 2 H 5 Cl (b) KCl
formed between [EAMCET 1988; MP PMT 1993]
(a) H  Cl (b) Cl  Cl (c) BaCl2 (d) C 6 H 5 N  H 3 Cl 
(c) Na  Cl (d) C  Cl 55. Which type of bonding exists in Li 2 O and CaF2 respectively
42. Which of the following is least soluble [CPMT 1989] [RPET 2000]
(a) BeF2 (b) SrF2 (a) Ionic, ionic (b) Ionic, covalent
(c) Covalent, ionic (d) Coordinate, ionic
(c) CaF2 (d) MgF2
56. An atom with atomic number 20 is most likely to combine
43. Which of the following halides has maximum melting point chemically with the atom whose atomic number is
(a) NaCl (b) NaBr [BHU 2000]
(c) NaI (d) NaF (a) 11 (b) 14
44. The high melting point and insolubility in organic solvents of (c) 16 (d) 10
sulphanilic acid are due to its ...... structure. [IIT 1994] 57. Bond formed in crystal by anion and cation is
(a) Simple ionic (b) Bipolar ionic [CBSE PMT 2000]
(c) Cubic (d) Hexagonal (a) Ionic (b) Metallic
 Chemical Bonding 101
(c) Covalent (d) Dipole (c) 6 (d) 10
58. Atoms or group of atoms which are electrically charged are known 3. The electronic
[UPSEATconfiguration
2001] of four elements are given in brackets
(a) Anions (b) Cations   
L 1s 2 , 2 s 2 2 p 1 ; M 1s 2 , 2 s 2 2 p 5 
(c) Ions (d) Atoms
59. Which one is the strongest bond [Pb. PMT 2001] Q 1s , 2 s
2 2
 
2 p 6 , 3 s1 ; R 1s 2 , 2 s 2 2 p 2 
(a) Br – F (b) F–F The element that would most readily form a diatomic molecule is
[NCERT 1983]
(c) Cl – F (d) Br – Cl
(a) Q (b) M
60. The interionic attraction depends on interaction of
(c) R (d) L
[Kerala CET (Med.) 2002]
4. In covalency [CPMT 1974, 76, 78, 81; AFMC 1982]
(a) Solute-Solute (b) Solvent-Solvent (a) Electrons are transferred
(c) The charges (d) Molecular properties (b) Electrons are equally shared
61. Which of the following compounds is ionic (c) The electron of one atom are shared between two atoms
[UPSEAT 2002] (d) None of the above
5. Which compound is highest covalent
(a) KI (b) CH 4
(a) LiCl (b) LiF
(c) Diamond (d) H 2 (c) LiBr (d) LiI
62. Which of the following pairs of species has same electronic 6. The nature of bonding in graphite is
configuration [UPSEAT 2002] [DPMT 1986; CPMT 1986]
(a) Covalent (b) Ionic
(a) Zn 2  and Ni 2  (b) Co 3 and Ni 4  (c) Metallic (d) Coordinate
(c) Co 2  and Ni 2  (d) Ti 4  and V 3  7. Which of the following substances has giant covalent structure
[DPMT 1985, 86; NCERT 1975]
63. The energy that opposes dissolution of a solvent is
[CPMT 2002]
(a) Iodine crystal (b) Solid CO 2
(a) Hydration energy (b) Lattice energy (c) Silica (d) White phosphorus
(c) Internal energy (d) Bond energy 8. With which of the given pairs CO resembles 2
[BHU 2005]
(a) HgCl , C H (b) HgCl , SnCl
64. Which of the following has highest melting point 2 2 2 2 4

[RPET 2003] (c) C H , NO

2 2 2
(d) N O and NO 2 2

9. The electron pair which forms a bond between two similar non-
(a) BeCl 2 (b) MgCl2 metallic atoms will be [IIT 1986]
(c) CaCl 2 (d) BaCl2 (a) Dissimilar shared between the two
(b) By complete transfer from one atom to other
65. Which of the following statements is not true for ionic compounds [RPET 2003]
(c) In a similar spin condition
(a) High melting point (d) Equally shared in between the two
(b) Least lattice energy 10. For the formation of covalent bond, the difference in the value of
(c) Least solubility in organic compounds electronegativities should be [EAMCET 1982]
(d) Soluble in water (a) Equal to or less than 1.7 (b) More than 1.7
66. Electrolytes are compound containing [MADT Bihar 1981] (c) 1.7 or more (d) None of these
11. Which type of bond is formed between similar atoms
(a) Electrovalent bond (b) Covalent bond
(a) Ionic (b) Covalent
(c) Coordinate bond (d) Hydrogen bond (c) Coordinate (d) Metallic
67. Which of the following hydrides are ionic [Roorkee 1999] 12. Covalent compounds are generally ...... in water
(a) CaH 2 (b) BaH 2 [CPMT 1987]
(a) Soluble (b) Insoluble
(c) SrH 2 (d) BeH 2 (c) Dissociated (d) Hydrolysed
68. Which of the following conduct electricity in the fused state 13. Which one is the electron deficient compound [AIIMS 1982]
[Roorkee 2000] (a) ICl (b) NH 3
(a) BeCl 2 (b) MgCl2 (c) BCl3 (d) PCl3
(c) SrCl 2 (d) BaCl2 14. Which among the following elements has the tendency to form
covalent compounds
(a) Ba (b) Be
Covalent bonding
(c) Mg (d) Ca
1. The valency of sulphur in sulphuric acid is [NCERT 1974] 15. Silicon has 4 electrons in the outermost orbit. In forming the bonds
(a) 2 (b) 4 (a) It gains electrons (b) It loses electrons
(c) 6 (d) 8 (c) It shares electrons (d) None of these
2. The number of electrons involved in the bond formation of 16. Which of the following occurs when two hydrogen atoms bond with
N 2 molecule each others
(a) Potential energy is lowered
[IIT 1980; CPMT 1983, 84, 85; CBSE PMT 1992]
(b) Kinetic energy is lowered
(a) 2 (b) 4
 102 Chemical Bonding
(c) Electronic motion ceases (a) LiCl  NaCl  BeCl 2 (b) BeCl 2  NaCl  LiCl
(d) Energy is absorbed
(c) NaCl  LiCl  BeCl 2 (d) BeCl 2  LiCl  NaCl
17. A bond with maximum covalent character between non-metallic
elements is formed [NCERT 1982] 27. Bond energy of covalent O  H bond in water is
(a) Between identical atoms [EAMCET 1982]
(b) Between chemically similar atoms (a) Greater than bond energy of H  bond
(c) Between atoms of widely different electronegativities
(b) Equal to bond energy of H  bond
(d) Between atoms of the same size
(c) Less than bond energy of H  bond
18. Amongst the following covalent bonding is found in
(d) None of these
[CPMT 1973]
(a) Sodium chloride (b) Magnesium chloride 28. Solid CH 4 is [DPMT 1983]

(c) Water (d) Brass (a) Molecular solid (b) Ionic solid
19. Indicate the nature of bonding in diamond (c) Pseudo solid (d) Does not exist
[EAMCET 1980; BHU 1996; KCET 2000] 29. A covalent bond is likely to be formed between two elements which
(a) Covalent (b) Ionic (a) Have similar electronegativities
(c) Coordinate (d) Hydrogen (b) Have low ionization energies
20. Octet rule is not valid for the molecule (c) Have low melting points
[IIT 1979; MP PMT 1995] (d) Form ions with a small charge
(a) CO 2 (b) H 2O 30. The bond between two identical non-metal atoms has a pair of
electrons [CPMT 1986]
(c) CO (d) O 2
(a) Unequally shared between the two
21. Which of the following compounds are covalent (b) Transferred fully from one atom to another
[IIT 1980; MLNR 1982] (c) With identical spins
(a) H2 (b) CaO (d) Equally shared between them
(c) KCl (d) Na 2 S 31. The valency of phosphorus in H 3 PO4 is [DPMT 1984]

22. Indicate the nature of bonding in CCl 4 and CaH 2 (a) 2 (b) 5
(c) 4 (d) 1
[NCERT 1973]
32. Which of the following substances has covalent bonding
(a) Covalent in CCl 4 and electrovalent in CaH 2
[AMU 1985]
(b) Electrovalent in both CCl 4 and CaH 2 (a) Germanium (b) Sodium chloride
(c) Covalent in both CCl 4 and CaH 2 (c) Solid neon (d) Copper
33. The covalency of nitrogen in HNO 3 is [CPMT 1987]
(d) Electrovalent in CCl 4 and covalent in CaH 2
(a) 0 (b) 3
23. If the atomic number of element X is 7, the best electron dot
(c) 4 (d) 5
symbol for the element is [NCERT 1973; CPMT 2003]
34. Hydrogen chloride molecule contains a [CPMT 1984]
(a) X . (b) . X .
(a) Covalent bond (b) Double bond
. ..
(c) . X : (d) : X . (c) Coordinate bond (d) Electrovalent bond
. ..
35. As compared to covalent compounds, electrovalent compounds
24. Which is the most covalent [AFMC 1982] generally have
(a) C O (b) C  Br [CPMT 1990, 94; MP PMT 1997]

(c) CS (d) C  F (a) Low melting points and low boiling points
25. The covalent compound HCl has the ionic character as (b) Low melting points and high boiling points
[EAMCET 1980] (c) High melting points and low boiling points
(a) The electronegativity of hydrogen is greater than that of (d) High melting points and high boiling points
chlorine
36. The interatomic distances in H 2 and Cl 2 molecules are 74 and
(b) The electronegativity of hydrogen is equal to that of chlorine
198 pm respectively. The bond length of HCl is
(c) The electronegativity of chlorine is greater than that of
[MP PET 1993]
hydrogen
(a) 272 pm (b) 136 pm
(d) Hydrogen and chlorine are gases
(c) 124 pm (d) 248 pm
26. The correct sequence of increasing covalent character is represented
by [CBSE PMT 2005] 37. On analysis, a certain compound was found to contain iodine and
oxygen in the ratio of 254 gm of iodine and 80 gm of oxygen.
 Chemical Bonding 103
The atomic mass of iodine is 127 and that of oxygen is 16. Which of (e) M3 A
the following is the formula of the compound [CPMT 1981]
47. The table shown below gives the bond dissociation energies (E diss )
(a) IO (b) I2 O
for single covalent bonds of carbon (C) atoms with element
(c) I5 O 2 (d) I2 O5 A, B, C and D. Which element has the smallest atoms[CBSE PMT 1994]
38. Ionic and covalent bonds are present in Bond E diss (kJ mol 1 )
[CBSE PMT 1990; MNR 1990; KCET 2000; UPSEAT 2001]
CA 240
(a) CCl 4 (b) CaCl 2
CB 328
(c) NH 4 Cl (d) H 2O C C 276
39. Highest covalent character is found in [EAMCET 1992] CD 485
(a) CaF2 (b) CaCl 2 (a) A (b) B
(c) C (d) D
(c) CaBr2 (d) CaI 2
48. If a molecule X 2 has a triple bond, then X will have the electronic
40. Among the following which property is commonly exhibited by a
configuration [CET Pune 1998]
covalent compound [MP PET 1994]
(a) High solubility in water (a) 1s 2 2 s 2 2 p 5 (b) 1s 2 2 s 2 2 p 3
(b) High electrical conductance (c) 1s 2 2 s 1 (d) 1s 2 2 s 2 2 p 1
(c) Low boiling point
49. Which of the following compounds does not follow the octet rule for
(d) High melting point electron distribution [CET Pune 1998]
41. Atoms in the water molecule are linked by [MP PAT 1996] (a) PCl5 (b) PCl 3
(a) Electrovalent bond
(c) H 2O (d) PH 3
(b) Covalent bond
(c) Coordinate covalent bond 50. The valency of A  3 and B  2 , then the compound is
(d) Odd electron bond [Bihar MEE 1997]
(a) A2 B3 (b) A3 B2
42. Which is the correct electron dot structure of N 2 O molecule
[MP PET 1996] (c) A3 B3 (d) A2 B2
.. .. (e) None of these
(a) : N  N  O (b) : N  N   O :  51. The number of electrons shared by each outermost shell of N 2 is
.. ..
.. .. .. .. (a) 2 (b) 3
(c) N N O (d) : N  N  O : (c) 4 (d) 5
.. .. .. 52. Which of the following substances when dissolved in water will give
43. A covalent bond between two atoms is formed by which of the a solution that does not conduct electricity
following [MP PMT 1996] [JIPMER 1999]
(a) Electron nuclear attraction (a) Hydrogen chloride (b) Potassium hydroxide
(b) Electron sharing (c) Sodium acetate (d) Urea
53. Which of the following atoms has minimum covalent radius
(c) Electron transfer
[DPMT 2000]
(d) Electrostatic attraction
(a) B (b) C
44. The electronic configuration of a metal M is (c) N (d) Si
2 2 6 1
1s , 2 s 2 p , 3 s . The formula of its oxides will be 54. Boron form covalent compound due to [Pb. PMT 2000]
[MP PET/PMT 1998] (a) Small size (b) Higher ionization energy
(a) MO (b) M 2O (c) Lower ionization energy (d) Both (a) and (b)
55. Two elements X and Y have following electron configurations
(c) M 2 O3 (d) MO 2
45. Which of the following statements regarding covalent bond is not X  1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 , 4 s 2
true [MP PET/PMT 1998]
and Y  1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6
(a) The electrons are shared between atoms
(b) The bond is non-directional The compound formed by combination of X and Y is
(c) The strength of the bond depends upon the extent of [DPMT 2001]
overlapping (a) XY5 (b) X 2 Y5
(d) The bond formed may or may not be polar
(c) X 5 Y3 (d) XY 2
46. If the electronic configuration of M  2, 8, 3 and that of
56. Covalent compounds have low melting point because
A  2, 8, 7, the formula of the compound is
[KCET 2002]
[Bihar MEE 1996]
(a) Covalent bond is less exothermic
(a) M 2 A3 (b) MA 2
(b) Covalent molecules have definite shape
(c) M2 A (d) MA3 (c) Covalent bond is weaker than ionic bond
 104 Chemical Bonding
(d) Covalent molecules are held by weak Vander Waal’s force of (a) 8 (b) 5
attraction (c) 6 (d) 7
57. p and n-type of semiconductors are formed due to 70. Hydrogen atoms are held together to form hydrogen molecules by
[UPSEAT 2002] (a) Hydrogen bond (b) Ionic bond
(c) Covalent bond (d) Dative bond
(a) Covalent bonds (b) Metallic bonds
71. Strongest bond is [AFMC 1987]
(c) Ionic bonds (d) Co-ordinate bond
(a) C  C (b) C  H
58. Which of the following is Lewis acid [RPET 2003]
(c) C  N (d) C  O
(a) BF3 (b) NH 3 72. The major binding force of diamond, silicon and quartz is
[Kerala CET (Med.) 2002]
(c) PH 3 (d) SO 2 (a) Electrostatic force (b) Electrical attraction
(c) Co-valent bond force (d) Non-covalent bond force
59. Among the species : CO 2 , CH 3 COO  , CO , CO 3 2  , HCHO
73. Multiple covalent bonds exist in a molecule of [NCERT 1973]
which has the weakest carbon- oxygen bond
(a) H2 (b) F2
[Kerala PMT 2004]
(c) C2 H 4 (d) N2
(a) CO 2 (b) CH 3 COO 
74. Which of the following does not obey the octet rule
2
(c) CO (d) CO 3 [EAMCET 1993]
(e) HCHO (a) CO (b) NH 3
60. Valency of sulphur in Na 2 S 2 O 3 is [DPMT 1984] (c) H 2O (d) PCl5
(a) Two (b) Three 75. Which of the following statements is correct for covalent bond
(c) Four (d) Six (a) Electrons are shared between two atoms
61. The acid having O  O bond is (b) It may be polar or non-polar
[IIT JEE Screening 2004] (c) Direction is non-polar
(a) H 2 S 2 O3 (b) H 2 S 2 O6 (d) Valency electrons are attracted
76. Among CaH 2 , NH 3 , NaH and B2 H 6 , which are covalent
(c) H 2 S 2 O8 (d) H 2 S 4 O6
hydride [Orissa JEE 2005]
62. The following salt shows maximum covalent character (a) NH 3 and B2 H 6 (b) NaH and CaH 2
[UPSEAT 2004]
(c) NaH and NH 3 (d) CaH 2 and B2 H 6
(a) AlCl3 (b) MgCl2
(c) CsCl (d) LaCl 3 Co-ordinate or Dative bonding
63. Which type of bond is present in H 2 S molecule 1. Which species has the maximum number of lone pair of electrons
[MHCET 2003; Pb CET 2001] on the central atom? [IIT 2005]
(a) Ionic bond (b) Covalent bond (a) [ClO ]3
(b) XeF 4

(c) Co-ordinate (d) All of three (c) SF (d) [I ]

4 3

64. H 2 S is more acidic than H 2 O , due to [BVP 2004] 2. A simple example of a coordinate covalent bond is exhibited by [
(a) O is more electronegative than S (a) C2 H 2 (b) H 2 SO 4
(b) O  H bond is stronger than S  H bond
(c) NH 3 (d) HCl
(c) O  H bond is weaker than S  H bond
(d) None of these 3. The bond that exists between NH 3 and BF3 is called
65. Which of the following has covalent bond [AFMC 1982; MP PMT 1985; MNR 1994;
[AFMC 1988; DCE 2004]
KCET 2000; MP PET 2001; UPSEAT 2001]
(a) Na 2 S (b) AlCl3
(a) Electrovalent (b) Covalent
(c) NaH (d) MgCl2 (c) Coordinate (d) Hydrogen
66. The following element forms a molecule with eight its own weight 4. Which of the following does not have a coordinate bond
atoms [MHCET 2004] [MADT Bihar 1984]
(a) Si (b) S (a) SO 2 (b) HNO 3
(c) Cl (d) P
(c) H 2 SO 3 (d) HNO 2
67. In H 2 O2 , the two oxygen atoms have
(a) Electrovalent bond (b) Covalent bond 5. Coordinate covalent compounds are formed by
(c) Coordinate bond (d) No bond [CPMT 1990, 94]
68. Carbon has a valency of 2 in CO and 4 in CO 2 and CH 4 . Its (a) Transfer of electrons (b) Sharing of electrons
(c) Donation of electrons (d) None of these process
valency in acetylene C 2 H 2  is [NCERT 1971]
6. In the coordinate valency [CPMT 1989]
(a) 1 (b) 2 (a) Electrons are equally shared by the atoms
(c) 3 (d) 4
(b) Electrons of one atom are shared with two atoms
69. Number of electrons in the valence orbit of nitrogen in an ammonia
molecule are [MH CET 2004] (c) Hydrogen bond is formed
 Chemical Bonding 105
(d) None of the above [DPMT 1985]
7. Which of the following contains a coordinate covalent bond (a) BF3 (b) CCl 4
[MNR 1990; IIT 1986]
(c) BeCl 2 (d) All of these
(a) N 2 O5 (b) BaCl 2
3. Which molecule has the largest dipole moment
(c) HCl (d) H 2O [CPMT 1991]
8. A coordinate bond is formed when an atom in a molecule has (a)PMTHCl
[CBSE 1992] (b) HI
(a) Electric charge on it (c) HBr (d) HF
(b) All its valency electrons shared 4. The unequal sharing of bonded pair of electrons between two atoms
(c) A single unshared electron in a molecule causes [EAMCET 1986]
(d) One or more unshared electron pair (a) Dipole
9. Which has a coordinate bond [RPMT 1997] (b) Radical formation
(a) SO 32  (b) CH 4 (c) Covalent bond
(d) Decomposition of molecule
(c) CO 2 (d) NH 3
5. Which of the following will show least dipole character
10. The compound containing co-ordinate bond is [NCERT 1975; Kurukshetra CEE 1998]
[AFMC 1999; Pb. CET 2002]
(a) Water (b) Ethanol
(a) O3 (b) SO 3
(c) Ethane (d) Ether
(c) H 2 SO 4 (d) All of these 6. Which of the following molecules will show dipole moment
11. The number of dative bonds in sulphuric acid molecules is [NCERT 1972, 74; DPMT 1985]
[MP PET 2002] (a) Methane (b) Carbon tetrachloride
(a) 0 (b) 1 (c) Chloroform (d) Carbon dioxide
(c) 2 (d) 4 7. Which of the following compounds possesses the dipole moment[NCERT 1978; E
12. Which of the following compounds has coordinate (dative) bond [RPET 2003]
(a) Water (b) Boron trifluoride
(a) CH 3 NC (b) CH 3 OH (c) Benzene (d) Carbon tetrachloride
(c) CH 3 Cl (d) NH 3 8. Which bond angle  would result in the maximum dipole moment
for the triatomic molecule YXY [AIIMS 1980]
13. The structure of orthophosphoric acid is [KCET 2003]
(a)   90 o (b)   120 o
O
H
 |
(c)   150 o (d)   180 o
(a) H O  P O H (b) O  P  O  H 9. Which of the following would have a permanent dipole moment[CBSE PMT 2005
| |
O O (a) BF3 (b) SiF4
| |
H H (c) SF4 (d) XeF4

O 10. Carbon tetrachloride has no net dipole moment because of

H [IIT 1982, 83; MP PMT 1985, 91; EAMCET 1988;
|  AMU 1999]
(c) O  P OH (d) H O P  O
| (a) Its planar structure
H (b) Its regular tetrahedral structure
14. What is the nature of the bond between B and O in (c) Similar sizes of carbon and chlorine atoms
(C 2 H 5 )2 OBH 3 [Orissa JEE 2003] (d) Similar electron affinities of carbon and chlorine
11. The molecule which has the largest dipole moment amongst the
(a) Covalent (b) Co-ordinate covalent following [MNR 1983]
(c) Ionic bond (d) Banana shaped bond
(a) CH 4 (b) CHCl 3
15. Sulphuric acid provides a example of
[Kerala CET (Med.) 2002] (c) CCl 4 (d) CHI 3
(a) Co-ordinate bonds 12. Positive dipole moment is present in
(b) Non-covalent compound [MNR 1986; MP PET 2000]
(c) Covalent and co-ordinate bond (a) CCl 4 (b) C 6 H 6
(d) Non-covalent ion
(c) BF3 (d) HF
Dipole moment 13. The polarity of a covalent bond between two atoms depends upon
(a) Atomic size (b) Electronegativity
1. Which molecules has zero dipole moment (c) Ionic size (d) None of the above
[AIIMS 1980, 82, 91; Roorkee 2000; MH CET 2001] 14. Pick out the molecule which has zero dipole moment
(a) H 2O (b) CO 2 [CPMT 1989; EAMCET 1993; MP PMT 1999]
(a) NH 3 (b) H 2O
(c) HF (d) HBr
2. In the following which one have zero dipole moment (c) BCl 3 (d) SO 2
 106 Chemical Bonding
15. Zero dipole moment is present in [DPMT 1986; IIT 1987] (c) Sulphur dioxide (d) Water
(a) NH 3 (b) H 2O 
28. N 2 is less reactive than CN due to [UPSEAT 2003]
(c) cis 1, 2-dichloroethene (d) trans 1, 2-dichloroethene (a) Presence of more electrons in orbitals
16. Which of the following is the most polar [AFMC 1988] (b) Absence of dipole moment
(a) CCl 4 (b) CHCl 3 (c) Difference in spin quantum no
(c) CH 3 OH (d) CH 3 Cl (d) None of these

17. Which one has minimum (nearly zero) dipole moment 29. In a polar molecule, the ionic charge is 4.8  10 10 e.s.u. If the
[IIT Screening 1994; CBSE PMT 1996] inter ionic distance is one Å unit, then the dipole moment is
(a) Butene-1 (b) cis butene-2 (a) 41.8 debye (b) 4.18 debye
(c) trans butene-2 (d) 2-methyl-1-propene (c) 4.8 debye (d) 0.48 debye
18. Which one of the following is having zero dipole moment 30. Which of the following is a polar compound
[RPMT 1997; EAMCET 1988; MNR 1991]
[Pb. CET 2000]
(a) CCl 4 (b) CH 3 Cl
(a) HCl (b) H 2 Se
(c) CH 3 F (d) CHCl 3
(c) CH 4 (d) HI
19. Which of the following molecules does not possess a permanent
dipole moment [CBSE PMT 1994] 31. Which of the following has no dipole moment
(a) H 2 S (b) SO 2 [DCE 2002]

(c) CS 2 (d) SO 3 (a) CO 2 (b) SO 3

20. Which of the following has zero dipole moment (c) O3 (d) H 2O
[CPMT 1997; AFMC 1998; CBSE PMT 2001]
32. Which of the following is non-polar [DCE 2002]
(a) CH 2 Cl 2 (b) CH 4
(a) PCl5 (b) PCl3
(c) NH 3 (d) PH 3
(c) SF6 (d) IF7
21. Fluorine is more electronegative than either boron or phosphorus.
What conclusion can be drawn from the fact that BF3 has no 33. Identify the non-polar molecule in the set of compounds given :
HCl, HF, H 2 , HBr [UPSEAT 2004]
dipole moment but PF3 does
[Pb. PMT 1998] (a) H2 (b) HCl
(a) BF3 is not spherically symmetrical but PF3 is (c) HF, HBr (d) HBr
(b) BF3 molecule must be linear 34. Dipole moment is shown by [IIT 1986]
(c) The atomic radius of P is larger than the atomic radius of B (a) 1, 4-dichlorobenzene
(d) The BF3 molecule must be planar triangular (b) cis 1, 2-dichloroethene
22. Which molecule does not show zero dipole moment (c) trans 1, 2-dichloroethene
[RPET 1997, 99]
(d) trans 1, 2-dichloro-2-pentene
(a) BF3 (b) NH 3 35. If HCl molecule is completely polarized, so expected value of dipole
(c) CCl 4 (d) CH 4 moment is 6.12D (deby), but experimental value of dipole moment is
1.03D. Calculate the percentage ionic character [Kerala CET 2005]
23. The dipole moment of HBr is 1.6  10 30 cm and interatomic (a) 17 (b) 83
spacing is 1Å. The % ionic character of HBr is
[MP PMT 2000] (c) 50 (d) Zero
(a) 7 (b) 10 (e) 90
(c) 15 (d) 27
24. Non-polar solvent is [RPET 2000] Polarisation and Fajan's rule
(a) Dimethyl sulphoxide (b) Carbon tetrachloride
(c) Ammonia (d) Ethyl alcohol 1. BF3 and NF3 both molecules are covalent, but BF3 is non-polar
25. Which shows the least dipole moment and NF3 is polar. Its reason is
[UPSEAT 2001; DPMT 1982]
[CPMT 1989; NCERT 1980]
(a) CCl 4 (b) CHCl 3
(a) In uncombined state boron is metal and nitrogen is gas
(c) CH 3 CH 2 OH (d) CH 3 COCH 3
(b) B  F bond has no dipole moment whereas N  F bond has
26. Which molecule has zero dipole moment [UPSEAT 2001] dipole moment
(a) H 2 O (b) AgI (c) The size of boron atom is smaller than nitrogen
(c) PbSO 4 (d) HBr (d) BF3 is planar whereas NF3 is pyramidal
27. The dipole moment is zero for the molecule 2. Which one is polar molecule among the following
[IIT 1989; MP PMT 2002]
(a) Ammonia (b) Boron trifluoride (a) CO 2 (b) CCl 4
 Chemical Bonding 107
(c) H 2O (d) CH 4 (c) Na  (d) Ca 2 
3. If the electron pair forming a bond between two atoms A and B is 15. Maximum covalent character is associated with the compound [RPMT 1999]
not in the centre, then the bond is [AIIMS 1984] (a) NaI (b) MgI2
(a) Single bond (b) Polar bond (c) AlCl3 (d) AlI3
(c) Non-polar bond (d)  bond 16. Polarisibility of halide ions increases in the order
4. Which of the following liquids is not deflected by a non-uniform [DCE 1999]
electrostatic field [NCERT 1978] (a) F  , I  , Br  , Cl  (b) Cl  , Br  , I  , F 
(a) Water (b) Chloroform
(c) I  , Br  , Cl  , F  (d) F  , Cl  , Br  , I 
(c) Nitrobenzene (d) Hexane
17. According to Fajan’s rule, covalent bond is favoured by
5. Which of the following is non-polar [EAMCET 1983]
[AIIMS 1999]
(a) H2S (b) NaCl (a) Large cation and small anion
(c) Cl 2 (d) H 2 SO 4 (b) Large cation and large anion
(c) Small cation and large anion
6. Polarization is the distortion of the shape of an anion by an
(d) Small cation and small anion
adjacently placed cation. Which of the following statements is
18. Which of the following statements is correct [AMU 1999]
correct [NCERT 1982]
(a) Maximum polarization is brought about by a cation of high (a) SF4 is polar and non-reactive
charge (b) SF6 is non-polar and very reactive
(b) Minimum polarization is brought about by a cation of
(c) SF6 is a strong fluorinating agent
low radius
(c) A large cation is likely to bring about a large degree of (d) SF4 is prepared by fluorinating SCl 2 with NaF
polarization 19. Choose the correct statement [RPMT 2000]
(d) A small anion is likely to undergo a large degree of polarization (a) Amino polarisation is more pronounced by highly charged
7. The bonds between P atoms and Cl atoms in PCl5 are likely to cation
be [MP PMT 1987] (b) Small cation has minimum capacity to polarise an anion.
(a) Ionic with no covalent character (c) Small anion has maximum polarizability
(d) None of these
(b) Covalent with some ionic character
(c) Covalent with no ionic character 20. The ICl molecule is [DPMT 2001]
(d) Ionic with some metallic character (a) Purely electrovalent
8. Two electrons of one atom A and two electrons of another atom B (b) Purely covalent
are utilized to form a compound AB. This is an example of (c) Polar
[MNRwith negative end on iodine
1981]
(a) Polar covalent bond (b) Non-polar covalent bond (d) Polar with negative end on chlorine
(c) Polar bond (d) Dative bond 21. Which of the following is a polar compound [AIIMS 2001]
(a) HF (b) HCl
9. In which of the following molecule is the covalent bond most polar [AMU 1985; MP PET 2001]
(c) HNO 3 (d) H 2 SO 4
(a) HI (b) HBr
22. Which of the following has zero dipole moment
(c) HCl (d) H 2
[MP PMT 2002]
10. Amongst ClF3 , BF3 and NH 3 molecules the one with non- (a) ClF (b) PCl 3
planar geometry is [MP PMT 1999]
(c) SiF4 (d) CFCl 3
(a) ClF3 (b) NH 3
23. Which of the following compounds has least dipole moment
(c) BF3 (d) None of these [RPET 2003]
11. Which of the following possesses highest melting point (a) PH 3 (b) CHCl 3
[CPMT 1999] (c) NH 3 (d) BF3
(a) Chlorobenzene (b) o-dichlorobenzene
24. Pauling’s electronegativity values for elements are useful in
(c) m-dichlorobenzene (d) p-dichlorobenzene predicting [UPSEAT 2004]
12. The polar molecule among the following is (a) Polarity of bonds in molecules
[Orissa JEE 1997] (b) Position of elements in electrochemical series
(a) CCl 4 (b) CO 2 (c) Co-ordination number
(d) Dipole moment of various molecules
(c) CH 2 Cl 2 (d) CH 2  CH 2
25. Amongst LiCl, RbCl, BeCl 2 and MgCl2 the compounds with the
13. Which of the following have both polar and non-polar bonds [AIIMS 1997]
greatest and the least ionic character, respectively, are [UPSEAT 2002]
(a) C 2 H 6 (b) NH 4 Cl
(a) LiCl and RbCl (b) RbCl and BeCl 2
(c) HCl (d) AlCl3
14. Which of the following has a high polarising power (c) RbCl and MgCl2 (d) MgCl2 and BeCl 2
[CET Pune 1998] 26. Bond polarity of diatomic molecule is because of
2 3 [UPSEAT 2002]
(a) Mg (b) Al
 108 Chemical Bonding
(a) Difference in electron affinities of the two atoms (b) Sidewise overlap of orbitals takes place
(b) Difference in electronegativities of the two atoms (c) End to end overlap of orbitals takes place
(c) Difference in ionisation potential (d) None of the above
(d) All of these 11. The number of sigma and pi bonds in 1-butene-3-yne are
[IIT 1989]
Overlaping-  and - bonds (a) 5 sigma and 5 pi (b) 7 sigma and 3 pi
(c) 8 sigma and 2 pi (d) 6 sigma and 4 pi
1. Triple bond in ethyne is formed from 12. The most acidic compound among the following is
[MP PMT 1990; NCERT 1979; EAMCET 1978; AMU 1985; [MP PET 1993]
CPMT 1988; MADT Bihar 1982; MH CET 2000] (a) CH 3 CH 2 OH (b) C 6 H 5 OH
(a) Three sigma bonds
(c) CH 3 COOH (d) CH 3 CH 2 CH 2 OH
(b) Three pi bonds
(c) One sigma and two pi bonds 13. Which of the following is not correct [CBSE PMT 1990]
(d) Two sigma and one pi bond (a) A sigma bond is weaker than  bond
2. The bond in the formation of fluorine molecule will be (b) A sigma bond is stronger than  bond
[MP PMT 1987] (c) A double bond is stronger than a single bond
(a) Due to s  s overlapping (d) A double bond is shorter than a single bond
(b) Due to s  p overlapping 14. Strongest bond formed, when atomic orbitals
(a) Maximum overlap (b) Minimum overlap
(c) Due to p  p overlapping
(c) Overlapping not done (d) None of them
(d) Due to hybridization 15. The p  p orbital overlapping is present in the following molecule
3. Which type of overlapping results the formation of a  bond
(a) Hydrogen (b) Hydrogen bromide
[DPMT 1981]
(c) Hydrogen chloride (d) Chlorine
(a) Axial overlapping of s  s orbitals
16. In N 2 molecule, the atoms are bonded by
(b) Lateral overlapping of p  p orbitals
[MP PET 1996; UPSEAT 2001]
(c) Axial overlapping of p  p orbitals
(a) One , Two  (b) One , One 
(d) Axial overlapping of s  p orbitals
(c) Two , One  (d) Three  bonds
4. The number and type of bonds between two carbon atoms in
calcium carbide are [AIEEE 2005] 17. In which of following there exists a p  d bonding
(a) One sigma, one pi (b) One sigma, two pi [AFMC 2001]
(c) Two sigma, one pi (d) Two singma, two pi (a) Diamond (b) Graphite
5. In a double bond connecting two atoms, there is a sharing of (c) Dimethyl amine (d) Trisilylamine
[CPMT 1977, 80, 81; NCERT 1975; 18. Number of bonds in SO 2 [DCE 2001]
Bihar MEE 1980; MP PET 1999]
(a) Two  and two 
(a) 2 electrons (b) 1 electron
(c) 4 electrons (d) All electrons (b) Two  and one 
6. Strongest bond is [DPMT 1990] (c) Two , two  and one lone pair
(a) C  C (b) C  C (d) None of these
(c) C  C (d) All are equally strong 19. Which of the following has p  d bonding [CBSE 2002]
7.  bond is formed [JIPMER 2002] (a) NO 3 (b) CO 32
(a) By overlapping of atomic orbitals on the axis of nuclei
(b) By mutual sharing of pi electron (c) BO 33 (d) SO 32
(c) By sidewise overlapping of half filled p-orbitals 20. Number of sigma bonds in P4 O10 is [AIEEE 2002]
(d) By overlapping of s-orbitals with p-orbitals (a) 6 (b) 7
8. The double bond between the two carbon atoms in ethylene consists (c) 17 (d) 16
of [NCERT 1981; EAMCET 1979]
(a) Two sigma bonds at right angles to each other
Hybridisation
(b) One sigma bond and one pi bond
(c) Two pi bonds at right angles to each other 1. Which molecule is not linear [CPMT 1994]
(d) Two pi bonds at an angle of 60 o to each other (a) BeF2 (b) BeH 2
9. In the series ethane, ethylene and acetylene, the C  H bond (c) CO 2 (d) H 2O
energy is [NCERT 1977]
(a) The same in all the three compounds 2. The bond angle in water molecule is nearly or Directed bonds in
(b) Greatest in ethane water forms an angle of
[NCERT 1980; EAMCET 1981; MNR 1983, 85;
(c) Greatest in ethylene
AIIMS 1982; CPMT 1989; MP PET 1994, 96;
(d) Greatest in acetylene
MP PET/PMT 1998]
10. In a sigma bond
(a) Sidewise as well as end to end overlap of orbitals take place (a) 120 o (b) 180 o
 Chemical Bonding 109

(c) 109 o 28 ' (d) 104 o 30' 12. The mode of hybridisation of carbon in CO 2 is [CPMT 1991]
2
3. The central atom in a molecule is in sp hybrid state. The shape of (a) sp (b) sp 2

molecule will be [MP PMT 1987; CBSE PMT 1989]

(c) sp 3 (d) None of these
(a) Pyramidal (b) Tetrahedral
(c) Octahedral (d) Trigonal planar 13. In which of the following the central atom does not use sp 3 hybrid
4. Which molecule is linear orbitals in its bonding [MNR 1992]
[MP PMT 1984; IIT 1982, 88; EAMCET 1993;
CBSE PMT 1992; MP PET 1995; RPMT 1997] (a) BeF3  (b) OH 3
(a) NO 2 (b) ClO2 (c) NH 2  (d) NF3
(c) CO 2 (d) H 2S 14. XeF2 involves hybridisation [DPMT 1990]
5. Which of the following molecules has trigonal planer geometry [CBSE PMT 2005]
3 3
(a) sp (b) sp d
(a) IF3 (b) PCl3
3 2
(c) NH 3 (d) BF3 (c) sp d (d) None of these
15. Which of the following hybridisation results in non-planar orbitals
6. A sp3 hybridized orbital contains
[DPMT 1984; BHU 1985; CPMT 1976] (a) sp 3 (b) dsp 2
1 1 sp 2
(a) s  character (b) s  character (c) (d) sp
4 2
16. Octahedral molecular shape exists in .......... hybridisation
2 3
(c) s  character (d) s  character [DPMT 1990]
3 4 3 3 2
(a) sp d (b) sp d
7. Structure of ammonia is
[MP PMT 1987, 89, 91; CPMT 1975, 82; 3 3
(c) sp d (d) None of these
RPMT 1999; JIPMER 2002]
17. The electronic structure of molecule OF2 is a hybrid of
(a) Trigonal (b) Tetrahedral
(c) Pyramidal (d) Trigonal pyramidal (a) sp (b) sp 2
8. The bond angle in ethylene is [CPMT 1987]
(c) sp 3 (d) sd 3
o o
(a) 180 (b) 120
18. Percentage of s-character in sp 3 hybrid orbital is
(c) 109 o (d) 90 o
(a) 25 (b) 50
9. Compound formed by sp3 d hybridization will have structure (c) 66 (d) 75
[BHU 1982; RPMT 1999] 19. Shape of XeF4 molecule is
(a) Planar (b) Pyramidal [BHU 1987; AFMC 1992; CET Pune 1998;
(c) Angular (d) Trigonal bipyramidal Roorkee Qualifying 1998; DCE 2002]
10. Which of the following formula does not correctly represent the (a) Linear (b) Pyramidal
bonding capacity of the atom involved
(c) Tetrahedral (d) Square planar
[CBSE PMT 1990]
20. For which of the following hybridisation the bond angle is maximum
 H 
 |  F F (a) sp 2 (b) sp
(a) H  P  H  (b) 3
 |  O (c) sp (d) dsp 2
 H 
21. The C  H bond distance is the longest in [MNR 1990]
O O (a) C2 H 2 (b) C 2 H 4
(c) ON (d) H C C
(c) C 2 H 4 Br2 (d) C 6 H 6
OH OH
22. The nature of hybridization in CH 2 Cl  CH 2 Cl for carbon is
11. Which of the following statement is not correct
[AIIMS 1983] (a) sp (b) sp 2
(a) Hybridization is the mixing of atomic orbitals prior to their
combining into molecular orbitals (c) sp 3 (d) sp 2 d
23. Shape of methane molecule is [MNR 1983]
(b) sp 2 hybrid orbitals are formed from two p atomic orbitals
(a) Tetrahedral (b) Pyramidal
and one s atomic orbital
(c) Octahedral (d) Square planer
(c) d 2 sp 3 hybrid orbitals are directed towards the corners of a 24. Which one amongst the following possesses an sp hybridized
regular octahedron carbon in its structure [CBSE PMT 1989]
(d) dsp 3 hybrid orbitals are all at 90 o to one another (a) CH 2  C.Cl  CH  CH 2
 110 Chemical Bonding

(b) C.Cl 2  C.Cl 2 35. In the following molecule, the two carbon atoms marked by asterisk
(*) possess the following type of hybridized orbitals
(c) CH 2  C  CH 2
H 3 C  C *  C *  CH 3 [NCERT 1984]
(d) CH 2  CH  CH  CH 2
(a) sp 3 orbital (b) sp 2 orbital
25. Which of the following is the correct electronic formula of chlorine
molecule [CPMT 1971] (c) sp orbital (d) s orbital
.. .. .. .. 36. The bond angle in carbon tetrachloride is approximately
(a) : Cl : Cl : (b) : Cl  : : Cl  : [MNR 1981; MP PMT 1987]
.. .. .. ..
o o
(a) 90 (b) 109
.. .. .. ..
o
(c) : Cl : Cl : (d) : Cl : : Cl : (c) 120 (d) 180 o
37. When two pairs of electrons are shared, bond is
26. In XeF4 hybridization is [MNR 1979]
3 2 3
(a) Single covalent bond (b) Double covalent bond
(a) sp d (b) sp
(c) Dative bond (d) Triple bond
(c) sp 3 d (d) sp 2 d 38. The nature of hybridization in the NH 3 molecule is
27. In HCHO, ' C' has hybridization [AIIMS 1987] [EAMCET 1982]
2
(a) sp (b) sp
(a) sp (b) sp 2
(c) sp 3 (d) sp 3 d
(c) sp 3 (d) All the above
39. Which one of the following compounds has bond angle as nearly
28. Which has the shortest C  C bond length 90 o [MP PMT 1985]
[NCERT 1982; CPMT 1989]
(a) NH 3 (b) H2S
(a) C 2 H 5 OH (b) C 2 H 6
(c) H 2O (d) CH 4
(c) C2 H 2 (d) C 2 H 4
40. In ethene, the bond angle(s) is/are
29. The hybridization of Ag in the linear complex Ag NH 3 2  is 
[CPMT 1985; BHU 1981] [CPMT 1976; AMU 1984; MP PMT 1985]
o
(a) 109 28 ' (b) 120 o
(a) dsp 2 (b) sp
(c) 180 o (d) Different
(c) sp 2 (d) sp 3
41. Structure formula of H 2 O 2 is [CPMT 1993]
30. Experiment shows that H 2 O has a dipole moment while CO 2 has
H
not. Point out the structures which best illustrate these facts [DPMT 1984; NCERT 1983; CPMT 1984]
(a) O O
O
(a) (b) O  C  O ; H  O  H H
O  C  O; H H
(b) H  O  O  H (straight line)
(c) C ; H – H – O (d) O H
|| | H'
O O C O ; O  H
(c) OO
31. Which species do not have sp 3 hybridization H
[DPMT 1985]
Where H  O  O  O  O  H '  101.5 o and all the four
(a) Ammonia (b) Methane
atoms are in the same plane
(c) Water (d) Carbon dioxide
H'
32. As compared to pure atomic orbitals, hybrid orbitals have
(a) Low energy (b) Same energy (d) OO
(c) High energy (d) None of these H
33. The compound 1, 2-butadiene has Where H  O  O  O  O  H '  97 o and the angle
[IIT 1983; MP PMT 1996]
(a) Only sp hybridized carbon atoms between H  O  O plane and O  O  H ' plane is 101 o
42. Number of shared electrons in between carbon-carbon atoms in
(b) Only sp 2 hybridized carbon atoms ethylene molecule is [MADT Bihar 1983]

(c) Both sp and sp 2 hybridized carbon atoms (a) 2 (b) 4

(c) 6 (d) 3
(d) sp, sp2 and sp 3 hybridized carbon atoms 43. The structural formula of a compound is
34. The number of unpaired electrons in O 2 molecule is CH 3  CH  C  CH 2 . The type of hybridization at the four
[MNR 1983; Kerala PET 2002] carbons from left to right are [CBSE PMT 1989]
(a) 0 (b) 1 (a) sp 2 , sp, sp 2 , sp 3 (b) sp 2 , sp 3 , sp 2 , sp
(c) 2 (d) 3
 Chemical Bonding 111

(c) sp 3 , sp 2 , sp, sp 2 (d) sp 3 , sp 2 , sp 2 , sp 2 55. In diborane, the H  B  H bond angle is 120 o . The
44. Acetate ion contains [AMU 1983]
hybridization of boron is likely to be
[BHU 1981; CBSE PMT 1999]
(a) One C, O single bond and one C, O double bond 2
(a) sp (b) sp
(b) Two C, O single bonds
(c) sp 3 (d) dsp 2
(c) Two C, O double bonds
56. The number of shared pairs of electrons in propane is
(d) None of the above [BHU 1981]
45. The two carbon atoms in acetylene are (a) 2 (b) 4
[AMU 1984; MADT Bihar 1982]
(c) 6 (d) 10
3
(a) sp hybridized (b) sp 2 hybridized 57. s-character in sp hybridised orbitals are
(c) sp hybridized (d) Unhybridized 1 1
46. Among the following compounds which is planar in shape (a) (b)
3 2
[AMU 1992]
1 2
(a) Methane (b) Acetylene (c) (d)
4 3
(c) Benzene (d) Isobutene
47. In methane the bond angle is [AMU 1983] 58. The two types of bonds present in B 2 H 6 are covalent and
[IIT 1994]
(a) 180 o (b) 90 o
(a) Three centre bond (b) Hydrogen bond
(c) 120 o (d) 109 o (c) Two centre bond (d) None of the above
48. The angle between sp 2 orbitals in ethylene is 59. In the compound CH 3 OCl, which type of orbitals have been
[BHU 1987, 95; AMU 1985] used by the circled carbon in bond formation
[MP PET 1994]
(a) 90 o (b) 120 o
3 2
(a) sp (b) sp
(c) 180 o (d) 109.5 o
(c) sp (d) p
49. The species in which the central atom uses sp 2 hybrid orbitals in
60. The correct order of the O  O bond length in O 2 , H 2 O 2 and
its bonding is [IIT 1988]
O 3 is [CBSE PMT 1995]
(a) PH 3 (b) NH 3
(a) O2  O3  H 2 O2 (b) O 3  H 2 O 2  O 2
(c) H3C  (d) SbH 3
(c) H 2 O2  O3  O2 (d) O 2  H 2 O 2  O 3
50. Carbon atoms in diamond are bonded to each other in a
configuration [CPMT 1981] 61. The structure of PF5 molecule is
(a) Tetrahedral (b) Planar [AFMC 1995; JIPMER 2001]
(c) Linear (d) Octahedral (a) Tetrahedral (b) Trigonal bipyramidal
51. Which of the following molecules can central atom said to adopt (c) Square planar (d) Pentagonal bipyramidal
sp 2 hybridization [CBSE PMT 1989; MP PET 1994] 62. Which of the following hybridisation has maximum s-characters

(a) BeF2 (b) BCl 3 (a) sp 3 (b) sp 2

(c) sp (d) None of these
(c) C2 H 2 (d) NH 3
In Cu NH 3 4  SO 4 , ; Cu has following hybridization
63. The PCl5 molecule is a result of the hybridisation of
52.
[MP PET 1995; DCE 2000; MP PMT 2002]
[AIIMS 1988; UPSEAT 2001]
2 2
(a) sp d (b) sp 3 d
(a) dsp 2 (b) sp 3
(c) spd 3 (d) sp 2 d 3
(c) sp 2 (d) sp 3 d 2
64. Hybridisation involves [MP PMT 1996]
53. The hybridization of carbon atoms in C  C single bond of (a) Addition of an electron pair
HC  C  CH  CH 2 is [IIT 1991; MP PET 1995] (b) Mixing up of atomic orbitals
(a) sp 3  sp 3 (b) sp 2  sp 3 (c) Removal of an electron pair
(d) Separation of orbitals
(c) sp  sp 2 (d) sp 3  sp 65. The geometry of sulphur trioxide molecule is
54. The compound in which C * 3
uses sp hybrids for bond formation (a) Tetrahedral (b) Trigonal planar
is [IIT 1989] (c) Pyramidal (d) Square planar
  66. The shapes of BCl 3 , PCl3 and ICl 3 molecules are all
(a) HCOOH (b) ( NH 2 )2 CO
(a) Triangular (b) Pyramidal
 
(c) ( NH 3 )3 COH HgCl2 (d) CH 3 CHO (c) T  shaped (d) All above are incorrect
67. In benzene molecule all C  C bond lengths are equal because
 112 Chemical Bonding
(a) All carbon atoms are equivalent (a) SnCl 2 (b) HCl
(b) All carbon atoms are sp 2 hybridised (c) CO 2 (d) HgCl 2
(c) All C  C bonds in benzene, have same order 79. Which one of the following statements is true for ammonium ion [
(d) All C  C bonds are single covalent bond (a) All bonds are ionic
68. Which one is false in the following statements
(b) All bonds are coordinate covalent
[MP PET 1997]
2
(c) H atoms are situated at the corners of a square
(a) Each carbon in ethylene is in sp hybridisation
(d) H atoms are situated at the corners of a tetrahedron
(b) Each carbon in acetylene is in sp 3 hybridisation
80. The bond angle in sp 2 hybridisation is [RPMT 1997]
2
(c) Each carbon in benzene is in sp hybridisation
(a) 180 o (b) 120 o
3
(d) Each carbon in ethane is in sp hybridisation
(c) 90 o (d) 109 o 2'
69. Out of the following hybrid orbitals, the one which forms the bond 81. The correct order towards bond angle is [RPMT 1997]
at angle 120 o , is [MP PMT 1997]
(a) sp  sp  sp
2 3

(a) d 2 sp 3 (b) sp 3
(b) sp 2  sp  sp 3
(c) sp 2 (d) sp
(c) sp 3  sp 2  sp
70. As the p  character increases, the bond angle in hybrid orbitals
formed by s and atomic orbitals [MP PMT 1997] (d) Bond angle does not depend on hybridisation
(a) Decreases (b) Increases 82. The geometry and the type of hybrid orbital present about the
(c) Doubles (d) Remains unchanged central atom in BF3 is [IIT 1998; BHU 2001]

71. sp 3 hybridization leads to which shape of the molecule (a) Linear, sp (b) Trigonal planar, sp 2
[MP PET/PMT 1998]
(c) Tetrahedral, sp 3 (d) Pyramidal, sp 3
(a) Tetrahedron (b) Octahedron
(c) Linear (d) Plane triangle 83. In graphite, electrons are [CBSE PMT 1997]

72. Which of the following will be octahedral [MP PET 1999] (a) Localised on every third C atom
 (b) Present in antibonding orbital
(a) SF6 (b) BF4
(c) Localised on each C atom
(c) PCl5 (d) BO 33  (d) Spread out between the structure
73. The hybrid orbitals used by central atoms in BeCl 2 , BCl 3 and 84. The ammonium ion is [CET Pune 1998]
CCl 4 molecules are respectively [MP PMT 1999] (a) Tetrahedral (b) Trigonal pyramidal
(c) Square planar (d) Square pyramidal
(a) sp 2 , sp 3 and sp (b) sp , sp 2 and sp 3 85. In sp hybridisation, shape is [Bihar MEE 1997]
3 2 2 3
(c) sp , sp and sp (d) sp , sp and sp (a) Angular (b) Tetrahedral
74. The structure of H 2 O 2 is [CBSE PMT 1999; AFMC 2003] (c) Bipyramidal (d) Linear
(e) None of these
(a) Planar (b) Non-planar
(c) Spherical (d) Linear 86. When the hybridisation state of carbon atom changes from sp 3 to
75. Which of the following is isoelectronic as well as has same structure sp 2 to sp, the angle between the hybridised orbitals
as that of N 2 O [CPMT 1999]
[AIIMS 1998]
(a) N3H (b) H 2O (a) Decreases gradually (b) Increases gradually
(c) NO 2 (d) CO 2 (c) Decreases considerably (d) All of these

76. CCl 4 has the hybridisation [DPMT 1996] 87. The structure and hybridisation of Si(CH 3 )4 is
[CBSE PMT 1996]
(a) sp 3 d (b) dsp 2
2
(a) Bent, sp (b) Trigonal, sp
(c) sp (d) sp 3
77. Compound having planar symmetry is [DPMT 1996] (c) Octahedral, sp 3 d (d) Tetrahedral, sp 3
(a) H 2 SO 4 (b) H 2O 88. The type of hybridisation of boron in diborane is
[BHU 1999]
(c) HNO 3 (d) CCl 4 2
(a) sp - hybridisation (b) sp - hybridisation
78. Which of the following compounds is not linear
3
[CPMT 1996] (c) sp - hybridisation (d) sp 3 d 2 - hybridisation
89. Which compound does not possess linear geometry
 Chemical Bonding 113
[RPET 1999] 101. The bond angle is minimum in
(a) CH 2  CH 2 (b) HC  CH [Pb. PMT 2001; MP PET 2003; UPSEAT 2004]
(a) H 2 Te (b) H 2 Se
(c) BeCl 2 (d) CO 2
(c) H 2O (d) H 2S
90. Which of the following molecule does not show tetrahedral shape [RPET 1999]
102. The correct order of hybridization of the central atom in the
(a) CCl 4 (b) SiCl 4
following species NH 3 [PtCl4 ]2  , PCl5 and BCl 3 is
(c) SF4 (d) CF4
[IIT Screening 2001; BHU 2005]
91. Pyramidal shape would be of [RPET 1999] 2 3 2
(a) dsp , dsp , sp and sp (b) 3
sp3 , dsp2 , dsp3 , sp2
(a) NO 3 (b) H 2O
(c) dsp 2 , sp 2 , sp 3 , dsp 3 (d) dsp 2 , sp 3 , sp 2 , dsp 3
(c) H3O (d) NH 4 103. Which of the following pairs has same structure [BHU 2001]
92. What is the correct mode of hybridization of the central atom in the (a) PH 3 and BCl 3 (b) SO 2 and NH 3
following compounds : NO 2 , SF4 , PF6  (c) PCl5 and SF6 (d) NH 4 and SO 42 
[AMU 1999] 104. The smallest bond angle is found in [AIIMS 2001]
(a) 2 3
sp , sp , d sp 2 3
(b) 3
sp , sp d , sp d3 2 3 2 (a) IF7 (b) CH 4
(c) BeF2 (d) BF3
(c) sp, sp 3 d, sp 3 d 2 (d) sp, sp 2 , sp 3
105. Which of the following is not linear [DCE 2001]
93. The hybridization in PF3 is [DCE 2000]
(a) CO 2 (b) ClO2
(a) sp 3 (b) sp 2
(c) I 3 (d) None of these
3 2 3
(c) dsp (d) d sp 106. Which of the following is not tetrahedral [MP PMT 2001]
94. Which of the following molecule is linear [MP PMT 2000] (a) SCl 4 (b) SO 42 
(a) SO 2 (b) NO 2 (c) Ni(CO )4 (d) NiCl 42 
(c) NO 2 (d) SCl 2 107. As the s-character of hybridisation orbital increases, the bond angle [BHU 2002;
(a) Increases (b) Decreases
95. The geometry of the molecule with sp 3 d 2 hybridised central atom (c) Becomes zero (d) Does not change
is [NCERT 1981; AFMC 1982; RPMT 2000] 108. The shape of IF7 molecule is
(a) Square planar (b) Trigonal bipyramidal [AFMC 2002; MHCET 2003]
(c) Octahedral (d) Square pyramidal (a) Octahedral (b) Pentagonal bipyramidal
96. The bond angle in PH 3 is [RPMT 2000] (c) Trigonal bipyramidal (d) Tetrahedral
(a) Much less than NH 3 109. A completely filled d orbital (d 10 ) [UPSEAT 2002]
(a) Spherically symmetrical
(b) Equal to that of NH 3
(b) Has octahedral symmetry
(c) Much greater than NH 3 (c) Has tetrahedral symmetry
(d) Depends on the atom
(d) Slightly greater than NH 3
110. Which has sp 3 hybridization of central atom
97. Which of the following has tetrahedral structure
[UPSEAT 2002]
[CPMT 2000]
(a) PCl 3 (b) SO 3
(a) CO 3 (b) NH 4
(c) BF3 (d) NO 3
(c) K 4 [Fe(CN )6 ] (d) None of these 111. In which of the following species is the interatomic bond angle is
98. The single, double and triple bond lengths of carbon in carbon 109 o 28  [AIEEE 2002]
dioxide are respectively [AIIMS 2000] 1 
(a) NH 3 , (BF4 ) (b) (NH 4 ) , BF3
(a) 1.15, 1.22 and 1.10 Å (b) 1.22, 1.15 and 1.10 Å
(c) 1.10, 1.15 and 1.22 Å (d) 1.15, 1.10 and 1.22 Å (c) NH 3 , BF4 (d) (NH 2 )1 , BF3

99. Shape of BF3 molecule is [CPMT 2000; Pb. CET 2002] 112. A square planar complex is formed by hybridisation of which atomic
orbitals [AIEEE 2002]
(a) Linear (b) Planar (a) s, p x , p y , d yz (b) s, p x , p y , d x 2 y 2
(c) Tetrahedral (d) Square pyramidal
(c) s, p x , p y , d z 2 (d) s, p y , p z , d xy
100. In the complex [SbF5 ] 2  , sp 3 d hybridization is present.
Geometry of the complex is [Pb. PMT 2000] 113. In benzene, all the six C – C bonds have the same length because
(a) Square (b) Square pyramidal of [MP PET 2002]
(c) Square bipyramidal (d) Tetrahedral (a) Tautomerism (b) sp 2 hybridisation
 114 Chemical Bonding
(c) Isomerism (d) Inductive effect (c) SO 3 (d) NO 3
1
114. The bond energies of H  H and Cl – Cl are 430 kJ mol and 125. Which of the following has a linear structure [MP PMT 2004]
1
242 kJ mol respectively, H t for HCl is 91 kJ mol . The bond
-1
(a) CCl 4 (b) C2 H 2
energy of HCl will be [MP PET 2003]
(c) SO 2 (d) C2 H 4
(a) 427 kJ (b) 766 kJ
(c) 285 kJ (d) 245 kJ 126. In a regular octahedral molecule, MX 6 , the number X  M  X
bonds at 180° is [CBSE PMT 2004]
115. Which of the following has dsp 2 hybridization
(a) Six (b) Four
[MP PET 2003] (c) Three (d) Two
(a) NiCl 42  (b) SCl 4 127. sp3 d 2 hybrid orbitals are [MP PET 2004]
(c) NH 4 (d) PtCl42  (a) Linear bipyramidal (b) Pentagonal
(c) Trigonal bipyramidal (d) Octahedral
116. Which one of the following is a planar molecule
[EAMCET 2003] 128. In an octahedral structure, the pair of d orbitals involved in d 2 sp3
hybridization is [CBSE PMT 2004]
(a) NH 3 (b) H3O
(a) d x 2 , d xz (b) d xy , d yz
(c) BCl 3 (d) PCl 3
(c) d x 2 y 2 , dz 2 (d) d xz , d x 2  y 2
117. Which one of the following is a correct set with respect to molecule,
hybridisation and shape [EAMCET 2003] 129. The correct order of bond angles (smallest first) in
(a) BeCl 2 , sp 2 , linear H 2 S , NH 3 , BF3 and SiH 4 is [AIEEE 2004]
(a) H 2 S  NH 3  SiH4  BF3
(b) BeCl 2 , sp 2 , triangular planar
(b) NH 3  H 2 S  SiH4  BF3
(c) BCl 3 , sp 2 , triangular planar
(c) H 2 S  SiH4  NH 3  BF3
(d) BCl 3 , sp 3 , tetrahedral H 2 S  NH 3  BF3  SiH4
(d)
118. Which of the following compounds doesn’t have linear structure [RPET 1997, 2003]
130. Which one of the following has the regular tetrahedral structure
(a) CO 2 (b) SO 2
(a) BF4 (b) SF4
(c) BeCl 2 (d) C 2 H 2
(c) XeF4 (d) Ni(CN )4 2 
119. Which of the following bonds require the largest amount of bond
energy to dissociate the atom concerned (Atomic no. : B  5, S  16, Ni  28, Xe  54 )
[UPSEAT 2003] 131. The states of hybridazation of boron and oxygen atoms in boric acid
(a) H – H bond in H 2 (b) C – C bond in CH 4 (H 3 BO3 ) are respectively [AIEEE 2004]

(c) N  N bond in N 2 (d) O  O bond in O 2 (a) sp 3 and sp 2 (b) sp 2 and sp 3

(e) C – C bond in ethane (c) sp 2 and sp 2 (d) sp 3 and sp 3
120. The percentage s-character of the hybrid orbitals in methane,
ethene and ethyne are respectively [KCET 2003] 132. The hybridisation in BF3 molecule is [Pb. PMT 2004]
(a) 25, 33, 50 (b) 25, 50, 75 (a) sp (b) sp 2
(c) 50, 75, 100 (d) 10, 20, 40
(c) sp 3 (d) sp3 d
121. Arrange the hydra-acids of halogens in increasing order of acidity [Orissa JEE 2003]
(a) HF  HCl  HBr  HI (b) HI  HBr  HCl  HF 133. Among the compounds, BF3 , NCl 3 , H 2 S , SF4 and BeCl 2 ,
identify the ones in which the central atom has the same type of
(c) HF  HBr  HI  HCl (d) HF  HI  HBr  HCl hybridisation [Kerala PMT 2004]
122. Which one has sp  hybridisation
2
[MP PMT 2004] (a) BF3 and NCl 3 (b) H 2 S and BeCl 2
(a) CO 2 (b) N 2O
(c) BF3 , NCl 3 and H 2 S (d) SF4 and BeCl 2
(c) SO 2 (d) CO
123. Among the following compounds the one that is polar and has (e) NCl 3 and H 2 S
central atom with sp  hybridization is
2
134. The molecule of CO 2 has 180° bond angle. It can be explanid on
[MP PMT 2004; IIT 1997] the basis of [AFMC 2004]
(a) H 2 CO 3 (b) BF3
(a) sp 3 hybridisation (b) sp 2 hybridisation
(c) SiF4 (d) HClO2
124. The molecule which is pyramid shape is (c) sp hybridisation (d) d 2 sp3 hybridisation
[MP PMT 2004; EAMCET 1985; IIT 1989]
135. sp 3 hybridisation is found in
(a) PCl3 (b) CO 32 
[Pb. CET 2003; Orissa JEE 2005]
 Chemical Bonding 115

(a) CO 32  (b) BF3 (c) d 2 sp 3 or sp 3 d 2 (d) d 3 sp 2 or d 2 sp 3

146. The valency of carbon is four. On what principle it can be explained
(c) NO 3 (d) NH 3 in a better way
136. Which set hydridisation is correct for the following compounds[Pb. CET 2003] (a) Resonance (b) Hybridization
(c) Electron transfer (d) None of the above
NO 2 , SF4 PF6
147. Hybridization is due to the overlapping of
2 3 [MADT Bihar 1983]
(a) sp , sp , sp
(a) Orbitals of different energy levels
(b) sp , sp 3 d , sp 3 d 2 (b) Orbitals of different energy content
(c) Orbitals of same energy content
(c) sp 2 , sp 3 , d 2 sp 3 (d) None of the above
(d) sp 3 , sp 3 d 2 , sp 3 d 2 148. If a molecule MX 3 has zero dipole moment, the sigma bonding
orbital used by M are
137. The state of hybridisation of B in BCl 3 is [IIT 1981; MP PMT 1994; Kerala PMT 2004]
[Pb. CET 2000; BHU 2004] (a) sp d  hybrid
3
(b) sp  hybrid
(a) sp (b) sp 2 (c) sp d  hybrid
3 2
(d) sp 2  hybrid
(c) sp 3 (d) sp 2 d 2 149. The linear structure is assumed by [IIT 1991]

(a) SnCl 2 (b) NCO
138. The hybrid state of sulphur in SO 3 molecule is [DCE 2004]
(c) CS 2 (d) NO 2
(a) sp 3 d (b) sp 3
150. Hybridisation of central atom in NF3 is [Orissa JEE 2005]
(c) sp 3 d 2 (d) sp 2
(a) sp3 (b) sp
139. Which of the following molecules has pyramidal shape
2
[DCE 2004; J&K CET 2005] (c) sp (d) dsp2
151. The pair having similar geometry is [J&K CET 2005]
(a) PCl3 (b) SO 3
(a) PCl3 , NH 3 (b) BeCl 2 , H 2O
(c) CO 32  (d) NO 3
(c) CH 4 , CCl 4 (d) IF5 , PF5
140. The hybrdization of IF7 is [Pb. CET 2001] 3
152. The d-orbital involved in sp d hybridisation is
(a) sp d 3 3
(b) 2
sp d [J&K CET 2005]
(a) d x 2 y 2 (b) d xy
(c) d 2 sp 3 (d) sp 3
(c) dz 2 (d) d zx
141. In which compound, the hydrogen bonding is the strongest in its
`
liquid phase [Pb. CET 2001]
Resonance
(a) HF (b) HI
(c) CH 4 (d) PH 3 1. Which one in the following is not the resonance structure of CO 2
142. Geometry of ammonia molecule and the hybridization of nitrogen 
(a) OCO (b) O  C  O
involved in it are [MH CET 2004]
(a) sp 3 -hybridization and tetrahedral geometry (c)  O  C  O  (d) O  C  O
2. Which of the following molecule contains one pair of non-bonding
(b) sp 3 -hybridization and distorted tetrahedral geometry electrons
(c) sp 2 -hybridization and triangular geometry (a) CH 4 (b) NH 3
(d) None of these (c) H 2O (d) HF
143. Be in BeCl 2 undergoes [MH CET 2004] 3. Resonance is due to [NCERT 1981; Kurukshetra CEE 1998]
(a) Diagonal hybridization (a) Delocalization of sigma electrons
(b) Trigonal hybridization (b) Delocalization of pi electrons
(c) Tetrahedral hybridization
(c) Migration of H atoms
(d) No hybridization
(d) Migration of protons
144. Which of the following is non-linear molecule [DCE 2003]
4. Resonating structures have different [AMU 1983]
(a) CO 3 (b) CO 2
(a) Atomic arrangements (b) Electronic arrangements
(c) CS 2 (d) BeCl 2 (c) Functional groups (d) Alkyl groups
145. The trigonal bipyramidal geometry results from the hybridisation[UPSEAT 2004]
5. In the cyanide ion, the formal negative charge is on
(a) dsp 3 or sp 3 d (b) dsp 2 or sp 2 d [AMU 1984]
 116 Chemical Bonding
(a) C (c) PF3 (d) NH 3
(b) N 4. Which has the least bond angle [NCERT 1973;
(c) Both C and N DPMT 1990; CBSE PMT 1990; UPSEAT 2003]
(d) Resonate between C and N (a) NH 3 (b) BeF2
6. Which does not show resonance [CPMT 1990] (c) H 2O (d) CH 4
(a) Benzene (b) Aniline
5. In compound X , all the bond angles are exactly 109 o 28 ' , X is
(c) Ethyl amine (d) Toluene
(a) Chloromethane (b) Iodoform
7. The enolic form of acetone contains
(c) Carbon tetrachloride (d) Chloroform
[IIT 1990; Bihar MEE 1997]
6. The shape of SO 42  ion is
(a) 9 sigma bonds, 1 pi bond and 2 lone pairs
[CPMT 1982; DPMT 1983, 84, 96; Bihar MEE 1997]
(b) 8 sigma bonds, 2 pi bonds and 2 lone pairs
(a) Square planar (b) Tetrahedral
(c) 10 sigma bonds, 1 pi bond and 1 lone pair (c) Trigonal bipyramidal (d) Hexagonal
(d) 9 sigma bonds, 2 pi bonds and 1 lone pair 7. Which of the following molecules has one lone pair of electrons on
8. Point out incorrect statement about resonance the central atom
[EAMCET 1980; AMU 1982; MNR 1989]
[MP PET 1997]
(a) H 2O (b) NH 3
(a) Resonance structures should have equal energy
(b) In resonance structures, the constituent atoms should be in the (c) CH 4 (d) PCl5
same position 8. Of the following compounds, the one having a linear structure is[NCERT 1981; CP
(c) In resonance structures, there should not be the same number MP PMT 1985; AIIMS 1996]
of electron pairs (a) NH 2 (b) CH 4
(d) Resonance structures should differ only in the location of (c) C2 H 2 (d) H 2O
electrons around the constituent atoms 9. XeF6 is
9. The number of possible resonance structures for CO 32  is (a) Octahedral (b) Distorted octahedral
[MP PMT 2000] (c) Planar (d) Tetrahedral
(a) 2 (b) 3 10. Which has maximum bond angle [CPMT 1993]
(c) 6 (d) 9 (a) CHF3
10. Resonance hybrid of nitrate ion is [RPET 2000]
1/ 2
(b) CHCl 3
(a) O ........ N ........O 1/ 2 (b) 2 / 3
O ........ N ........O 2 / 3
  (c) CHBr3
 
O 1/ 2 O 2 / 3 (d) All have maximum bond angle
11. Of the following species the one having a square planar structure is
 [NCERT 1981; MP PMT 1994]
1/ 3
(c) O ........ N ........O 1/3 (d) 2 / 3
O ...... N ......
O2 / 3
  (a) NH 4 (b) BF4
 
O 1/3 O2 / 3 (c) XeF4 (d) SCl 4
12. In which of the following is the angle between the two covalent
11. CO 32  anion has which of the following characteristics
bonds greatest
[Roorkee 1999] [NCERT 1975; AMU 1982; MNR 1987;
(a) Bonds of unequal length IIT 1981; CPMT 1988; MP PMT 1994]
(b) sp 2 hybridization of C atom (a) CO 2 (b) CH 4
(c) Resonance stabilization
(c) NH 3 (d) H 2O
(d) Same bond angles
13. As the s-character of hybridized orbital decreases, the bond angle
VSEPR Theory (a) Decreases (b) Increases
(c) Does not change (d) Becomes zero
The structure of Cu H 2 O 4  ion is

1. 14. XeF2 molecule is [BHU 1982]
[NCERT 1983; MP PMT 1983] (a) Linear (b) Triangular planar
(a) Square planar (b) Tetrahedral (c) Pyramidal (d) Square planar
(c) Distorted rectangle (d) Octahedral
15. Of the following sets which one does NOT contain isoelectronic
2. The bond angle in PH 3 would be expected to be close to species [AIEEE 2005]
(a) 90 o (b) 105 o (a) PO43  , SO 42  , ClO4 (b) CN  , N 2 , C 22 
(c) 109 o (d) 120 o
(c) SO 32  , CO 32  , NO 3 (d) BO33  , CO 32  , NO 3
3. In which molecule are all atoms coplanar [MP PMT 1994]
16. A molecule which contains unpaired electrons is
(a) CH 4 (b) BF3
 Chemical Bonding 117
[NCERT 1982] (b) C 2 H 2  NH 3  H 2 O  CH 4
(a) Carbon monoxide (b) Molecular nitrogen
(c) NH 3  H 2 O  CH 4  C 2 H 2
(c) Molecular oxygen (d) Hydrogen peroxide
(d) H 2 O  NH 3  CH 4  C 2 H 2
17. H 2 O is [MADT Bihar 1983]
28. Which compound has bond angle nearly to 90
(a) A linear triatomic molecule [Pb. PMT 2001]
(b) A bent (angular) triatomic molecule (a) H 2O (b) H 2S
(c) Both of these (c) NH 3 (d) CH 4
(d) None of these 29. A lone pair of electrons in an atom implies [KCET 2002]
18. Bond angle between two hybrid orbitals is 105 .% s-orbital o (a) A pair of valence electrons not involved in bonding
character of hybrid orbital is [MP PMT 1986] (b) A pair of electrons involved in bonding
(a) Between 20  21% (b) Between 19  20% (c) A pair of electrons
(d) A pair of valence electrons
(c) Between 21  22% (d) Between 22  23%
30. The bond angle of water is 104.5 o due to [CPMT 2002]
19. The bond angle between H  O  H in ice is closest to
(a) Repulsion between lone pair and bond pair
[CPMT 1989; UPSEAT 2002]
o o (b) sp 3 hybridization of O
(a) 120 28 ' (b) 60
(c) Bonding of H 2 O
(c) 90 o (d) 105 o
20. Which of the following molecules does not have a linear (d) Higher electronegativity of O
arrangement of atoms [CBSE PMT 1989] 31. The correct sequence of decrease in the bond angle of the following
hybrides is [MP PET 2002]
(a) H 2 S (b) C 2 H 2
(a) NH 3  PH 3  AsH 3  SbH 3
(c) BeH 2 (d) CO 2
(b) NH 3  AsH 3  PH 3  SbH 3
21. BCl 3 is a planar molecule while NCl 3 is pyramidal, because [CBSE PMT 1995]
(c) SbH 3  AsH 3  PH 3  NH 3
(a) BCl 3 has no lone pair of electrons but NCl 3 has a lone pair
of electrons (d) PH 3  NH 3  AsH 3  SbH 3
(b) B  Cl bond is more polar than N  Cl bond 32. Central atom of the following compound has one lone pair of electrons and
(c) Nitrogen atom is smaller than boron atom three bond pairs of electrons [JIPMER 2002]
(d) N  Cl bond is more covalent than B  Cl bond (a) H 2S (b) AlCl3
22. The isoelectronic pair is [AIIMS 2005] (c) NH 3 (d) BF3
(a) Cl 2 O, ICl2 (b) ICl2 ,ClO2
33. Among KO 2 , AlO2 , BaO2 and NO 2 unpaired electron is
(c) IF2 , I3 (d) ClO2 , CIF2 present in [MP PET 2003]
23. According to VSEPR theory, the most probable shape of the (a) NO 2 and BaO2 (b) KO 2 and AlO2
molecule having 4 electron pairs in the outer shell of the central
atom is [MP PET 1996, 2001] (c) KO 2 only (d) BaO2 only
(a) Linear (b) Tetrahedral 34. True order of bond angle is [RPET 2003]
(c) Hexahedral (d) Octahedral (a) H 2 O  H 2 S  H 2 Se  H 2 Te
24. The molecular shapes of SF4 , CF4 and XeF4 are
(b) H 2 Te  H 2 Se  H 2 S  H 2 O
[AIEEE 2005]
(a) The same with 2, 0 and 1 lone pairs of electrons on the central (c) H 2 S  H 2 O  H 2 Se  H 2 Te
atom, respectively
(d) H 2 O  H 2 S  H 2 Te  H 2 Se
(b) The same with 1, 1 and 1 lone pair of electrons on the central
atoms, respectively 35. Which of the following has not a lone pair over the central atom
(c) Different with 0, 1 and 2 lone pairs of electrons on the central (a) NH 3 (b) PH 3
atom, respectively
(d) Different with 1, 0 and 2 lone pairs of electrons on the central (c) BF3 (d) PCl 3
atom, respectively 36. In BrF3 molecule,the lone pairs occupy equatorial positions to
25. Which of the following species is planar [JIPMER 1997] minimize [CBSE PMT 2004]
(a) CO 32  (b) NH 2 (a) Lone pair- lone pair repuilsion and lone pair-bond pair
repulsion
(c) PCl 3 (d) None of these
(b) Lone pair- lone pair repulsion only
26. The shape of CH 3 species is [RPET 1999] (c) Lone pair- bond pair repulsion only
(a) Tetrahedral (b) Square planar (d) Bond pair- bond pair repulsion only
(c) Trigonal planar (d) Linear 37. H 2 O is dipolar, whereas BeF2 is not. It is because
27. Which of the following is the correct reducing order of bond-angle [BHU 2000] [CBSE PMT 1989; 2004]
(a) NH 3  CH 4  C 2 H 2  H 2 O
(a) H 2 O is linear and BeF2 is angular
 118 Chemical Bonding

(b) H 2 O is angular and BeF2 is linear (a) O2 (b) O22

(c) The electornegativity of F is greater than that of O
(c) O21 (d) O21
(d) H 2 O involves hydrogen bonding whereas BeF2 is a discrete
5. The bond order is maximum in
molecule
[AIIMS 1983, 85; CBSE PMT 1994; MP PET 2002]
38. Maximum bond angle is present in [BVP 2004]
(a) O2 (b) O21
(a) BCl 3 (b) BBr3
(c) O21 (d) O22
(c) BF3 (d) Same for all
6. Which of the following compounds of boron does not exist in the
39. The shape of a molecule of NH 3 , in which central atoms contains free form
lone pair of electron, is [MHCET 2003] (a) BCl 3 (b) BF3
(a) Tetrahedral (b) Planar trigonal
(c) Square planar (d) Pyramidal (c) BBr3 (d) BH 3
40. The largest bond angle is in [DCE 2002; MNR 1984] 7. Molecular orbital theory was developed mainly by
(a) AsH3 (b) NH 3 [BHU 1987; Pb. CET 2003]
(c) H 2O (d) PH 3 (a) Pauling (b) Pauling and Slater
(c) Mulliken (d) Thomson
41. The bond angle in ammonia molecule is [EAMCET 1980]
8. The bond order of a molecule is given by [NCERT 1984]
(a) 91 8 
o
(b) 93 3' o
(a) The difference between the number of electrons in bonding
(c) 106 o 45' (d) 109 o 28' and antibonding orbitals
42. Which of the following gives correct arrangement of compounds (b) Total number of electrons in bonding and antibonding orbitals
involved based on their bond strength (c) Twice the difference between the number of electrons in
[BHU 2005] bonding and antibonding electrons
(a) HF > HCl > HBr > HI (d) Half the difference between the number of electrons in bonding
(b) HI > HBr > HCl > HF and antibonding electrons
(c) HF > HBr > HCl > HI 9. Oxygen molecule is paramagnetic because
(d) HCl > HF > HBr > HI [NCERT 1984; IIT 1984]
43. Which one has a pyramidal structure [CBSE PMT 1990] (a) Bonding electrons are more than antibonding electrons
(b) Contains unpaired electrons
(a) CH 4 (b) NH 3
(c) Bonding electrons are less than antibonding electrons
(c) H 2O (d) CO 2 (d) Bonding electrons are equal to antibonding electrons
44. Among the following the pair in which the two species are not 10. Which one is paramagnetic from the following
isostructural is [CBSE PMT 2004] [IIT 1989; CBSE PMT 1995]

(a) BH 4 and NH 4 (b) PF6 and SF6 (a) O 2 (b) NO

(c) SiF4 and SF4 (d) IO3 and XeO 3 (c) Both (a) and (b) (d) CN 
45. The maximum number of 90° angles between bond pair-bond pair 11. The bond order in N 2 ion is [Pb. CET 2004]
of electrons is observed in [AIEEE 2004] (a) 1 (b) 2
(a) dsp 2 hybridization (b) sp 3 d hybridization (c) 2.5 (d) 3
12. Out of the following which has smallest bond length
(c) dsp3 hybridization (d) sp 3 d 2 hybridization
[RPMT 1997]
(a) O2 (b) O 2
Molecular orbital theory
(c) O 2 (d) O 22 
1. Bond order is a concept in the molecular orbital theory. It depends
13. Which of the following molecule is paramagnetic
on the number of electrons in the bonding and antibonding orbitals.
[CPMT 1980; RPET 1999;MP PMT 1999; RPMT 2000]
Which of the following statements is true about it ? The bond order[AIIMS 1980]
(a) Chlorine (b) Nitrogen
(a) Can have a negative quantity
(c) Oxygen (d) Hydrogen
(b) Has always an integral value 14. Which molecule has the highest bond order
(c) Can assume any positive or integral or fractional value
(a) N 2 (b) Li 2
including zero
(d) Is a non zero quantity (c) He 2 (d) O 2
2. The bond order of NO molecule is [MP PET 1996] 15. The molecular electronic configuration of H 2 ion is

 1s 2  x 1s 2
(a) 1 (b) 2
(c) 2.5 (d) 3 (a)  1s 2 (b)
3. When two atomic orbitals combine they form
(a) One molecular orbital (b) Two molecular orbital
2

(c)  1s   x 1s 
1
(d)  1s 
3

16. The paramagnetic nature of oxygen molecule is best explained on

(c) Three molecular orbital (d) Four molecular orbital the basis of [BHU 1996]
4. Which of the following species is the least stable (a) Valence bond theory (b) Resonance
 Chemical Bonding 119
(c) Molecular orbital theory (d) Hybridization (c) Equal to that of 2 s orbital
17. In which case the bond length is minimum between carbon and
nitrogen (d) Double that of 2 s orbital
(a) CH 3 NH 2 (b) C 6 H 5 CH  NOH 29. In the electronic structure of acetic acid, there are
[AMU 1983]
(c) CH 3 CONH 2 (d) CH 3 CN
(a) 16 shared and 8 unshared electrons
18. Which one of the following species is diamagnetic in nature
[AIEEE 2005] (b) 8 shared and 16 unshared electrons
(c) 12 shared and 12 unshared electrons
(a) He 2 (b) H 2

(d) 18 shared and 6 unshared electrons

(c) H 2 (d) H 2 30. Which of the following does not exist on the basis of molecular
19. Which one of the following oxides is expected exhibit paramagnetic orbital theory [AFMC 1990; MP PMT 1996]
behaviour [CBSE PMT 2005]
(a) H 2 (b) He 2
(a) CO 2 (b) SO 2
(c) ClO2 (d) SiO2 (c) He 2 (d) Li 2
20. The bond order in N 2 molecule is 31. In P4 O10 , the number of oxygen atoms attached to each
[CBSE 1995; Pb. PMT 1999; MP PET 1997] phosphorus atom is [IIT 1995]
(a) 1 (b) 2 (a) 2 (b) 3
(c) 3 (d) 4
(c) 4 (d) 2.5
21. Which one is paramagnetic and has the bond order 1/2
[NCERT 1983] 32. Of the following statements which one is correct
(a) O2 (b) N2 (a) Oxygen and nitric oxide molecules are both paramagnetic
because both contain unpaired electrons
(c) F2 (d) H 2
(b) Oxygen and nitric oxide molecules are both diamagnetic
22. When two atoms of chlorine combine to form one molecule of because both contain no unpaired electrons
chlorine gas, the energy of the molecule [AMU 1982]
(c) Oxygen is paramagnetic because it contains unpaired electrons,
(a) Greater than that of separate atoms
while nitric oxide is diamagnetic because it contains no
(b) Equal to that of separate atoms unpaired electrons
(c) Lower than that of separate atoms
(d) None of the above statement is correct (d) Oxygen is diamagnetic because it contains no unpaired
23. An atom of an element A has three electrons in its outermost shell electrons, while nitric oxide is paramagnetic because it contains
and that of B has six electrons in the outermost shell. The formula an unpaired electron
of the compound between these two will be 33. According to the molecular orbital theory, the bond order in C 2
[CPMT 1974, 84; RPMT 1999] molecule is
(a) A3 B4 (b) A2 B3 (a) 0 (b) 1
(c) A3 B2 (d) A2 B (c) 2 (d) 3
24. The bond order of individual carbon-carbon bonds in benzene is 34. [IIT 1980]orbital configuration of a diatomic molecule is
The molecular
(a) One (b) Two
(c) Between 1 and 2 (d) One and two alternately   2 py2
 1s 2  * 1s 2  2 s 2  * 2 s 2  2 p x2 
  2 pz
2
25. PCl5 exists but NCl 5 does not because
[EAMCET 1977; MP PET/PMT 1988] Its bond order is
(a) Nitrogen has no vacant d-orbitals
(a) 3 (b) 2.5
(b) NCl 5 is unstable
(c) 2 (d) 1
(c) Nitrogen atom is much smaller
(d) Nitrogen is highly inert 35. The difference in energy between the molecular orbital formed and
26. Paramagnetism is exhibited by molecules the combining atomic orbitals is called
[NCERT 1979; MP PET 2002] (a) Bond energy (b) Activation energy
(a) Not attracted into a magnetic field (c) Stabilization energy (d) Destabilization energy
(b) Containing only paired electrons
(c) Carrying a positive charge 36. According to molecular orbital theory, the paramagnetism of O 2
(d) Containing unpaired electrons molecule is due to presence of [MP PMT 1997]
27. Which one of the following is paramagnetic [DPMT 1985] (a) Unpaired electrons in the bonding  molecular orbital
(a) H 2O (b) NO 2 (b) Unpaired electrons in the antibonding  molecular orbital

(c) SO 2 (d) CO 2 (c) Unpaired electron in the bonding  molecular orbital

(d) Unpaired electrons in the antibonding  molecular orbital
28. The energy of a 2 p orbital except hydrogen atom is
[AMU 1983] 37. The bond order in O 2 is [MP PET 1999; BHU 2001]

(a) Less than that of 2 s orbital (a) 2 (b) 2.5

(b) More than that of 2 s orbital (c) 1.5 (d) 3
 120 Chemical Bonding
38. Which of the following is paramagnetic [MP PET 1999] 50. The number of antibonding electron pairs in O 22  molecular ion on

(a) O2 (b) CN the basis of molecular orbital theory is
[Pb. PMT 2000]
(c) CO (d) NO  (a) 4 (b) 3
39. If N x is the number of bonding orbitals of an atom and N y is the (c) 2 (d) 5
number of antibonding orbitals, then the molecule/atom will be 51. The bond order of He 2 molecule ion is
stable if [DPMT 1996] [Pb. PMT 2000; Pb CET 2001]
(a) Nx  Ny (b) Nx  Ny (a) 1 (b) 2
1 1
(c) Nx  Ny (d) Nx  Ny (c) (d)
2 4
40. Which of the following molecular orbitals has two nodal planes 52. Which one does
[KCET not exhibit paramagnetism
1996] [DPMT 2000]
(a)  2s (b)  2 p y (a) ClO2 (b) ClO2
(c) NO 2 (d) NO
(c)  * 2py (d)  * 2 p x
53. In which of the following pairs the two molecules have identical
41. The number of nodal planes ' d ' orbital has [KCET 1996] bond order [MP PMT 2000]
(a) Zero (b) One (a) N 2 , O 22  (b) N 2 O 2
,

(c) Two (d) Three

(c) N 2
O2 (d) O 2 N2
42. Atomic number of an element is 26. The element shows , ,

54. The bond order is not three for [MP PMT 2001]
[CPMT 1996]
(a) Ferromagnetism (b) Diamagnetism (a) N 2 (b) O 22 
(c) Paramagnetism (d) None of these (c) N2 (d) NO 
43. What is correct sequence of bond order [BHU 1997]
55. In H 2 O 2 molecule, the angle between the two O – H planes is
(a) O 2  O 2  O2 (b) O 2  O2  O 2
(a) 90 o (b) 101 o
(c) O 2  O 2  O 2 (d) O 2  O 2  O 2 (c) 103 o (d) 105 o
44. Which bond is strongest [RPMT 1997]
56. Which of the following molecule has highest bond energy
[AIIMS 2002]
(a) FF (b) Br  F
(a) F  F (b) C – C
(c) Cl  F (d) I  F (c) N – N (d) O – O
45. Which of the following is not paramagnetic [AIIMS 1997] 57. Which of the following species would be expected paramagnetic
(a) S 2
(b) N2 
(a) Copper crystals (b) Cu 

(c) Cu (d) H2
(c) O 2 (d) NO
58. Which of the following is correct for N 2 triple bond
46. Which one of the following molecules is paramagnetic
[CPMT 2002]
[Pb. PMT 1998]
(a) 3s (b) 1p, 2s
(a) CO 2 (b) SO 2 (c) 2p, 1s (d) 3p
(c) NO (d) H 2O 59. In which of the following pairs molecules have bond order three and
are isoelectronics [MP PET 2003]
47. N 2 and O 2 are converted into monoanions N 2 and O 2
(a) CN  , CO (b) NO  , CO 
respectively, which of the following statements is wrong

[CBSE PMT 1997] (c) CN  , O 2 (d) CO, O 2
(a) In N 2 , the N  N bond weakens 60. Which of the following is paramagnetic [MP PET 2003]
(b) In O 2 , the O  O bond order increases (a) O 2 (b) CN 
(c) In O 2 , bond length increases (c) CO (d) N2
61. How many bonding electron pairs are there in white phosphorous
(d) N 2 becomes diamagnetic
(a) 6 (b) 12
48. With increasing bond order, stability of a bond (c) 4 (d) 8
[CET Pune 1998] ˆ P bond angle in the
62. The atomicity of phosphorus is X and the PP
(a) Remains unaltered (b) Decreases
molecule is Y. What are X and Y [EAMCET 2003]
(c) Increases (d) None of these
(a) X = 4, Y = 90 o (b) X = 4, Y = 60 o
49. Which is not paramagnetic [DCE 1999, 2000]
(c) X = 3, Y = 120 o (d) X = 2, Y = 180 o
(a) O2 (b) O 2
(c) O 22  (d) O 2
 Chemical Bonding 121
63. From elementary molecular orbital theory we can give the electronic (b) Bond length in NO is greater than in NO 
configuration of the singly positive nitrogen molecular ion N 2 as [UPSEAT 2003]
(c) Bond length in NO  is greater than in NO
 
(a)  (1s)  (1s)  (2 s)  (2 s)  (2 p)  (2 p)
2 2 2 2 4 1 (d) Bond length is unpredictable
73. Which of the following is diamagnetic [BVP 2004]
(b)  (1s)2  (1s)2  (2 s)2  (2 s)2  (2 p)1 (2 p)3
(a) Oxygen molecule (b) Boron molecule
(c)  (1s)2  (1s)2  (2 s)2  (2 p)2  (2 p)4 (c) N 2 (d) None
 
(d)  (1s)  (1s)  (2 s)  (2 s)  (2 p)  (2 p)
2 2 2 2 2 2
74. Bond energies in NO, NO 
and NO  are such as
64. The paramagnetic property of the oxygen molecule due to the
presence of unpaired electorns present in [Pb. CET 2004]
 
[Kerala PMT 2004] (a) NO  NO  NO (b) NO  NO  NO 


(a) ( 2 p x ) and ( 2 p x )
1 * 1

(c) NO  NO  NO (d) NO   NO   NO


75. Which of the following is paramagnetic [UPSEAT 2004]

( 2 p x )1 and ( 2 p y )
1
(b)
(a) B 2 (b) C 2
(c) ( * 2 p y )1 and ( * 2 p z )1
(c) N2 (d) F2
(d) ( * 2 p y )1 and ( 2 p y )1 76. The paramagnetic molecule at ground state among the following is[UPSEAT 200
(e) ( * 2 p z )1 and ( 2 p z )1 (a) H 2 (b) O 2

65. In PO43  ion, the formal charge on each oxygen atom and (c) N 2 (d) CO
77. Which has the highest bond energy [DCE 2002]
P  O bond order respectively are [DPMT 2004]
(a) F2 (b) Cl 2
(a) 0.75, 1.25 (b) 0.75, 1.0
(c) Br2 (d) I2
(c) 0.75, 0.6 (d) 3, 1.25
78. In O 2 ,
O 2 and O 22
molecular species, the total number of
66. The bond order in CO 32  ion between C  O is
antibonding electrons respectively are [DCE 2003]
[Pb. PMT 2004]
(a) 7, 6, 8 (b) 1, 0, 2
(a) Zero (b) 0.88
(c) 1.33 (d) 2 (c) 6, 6, 6 (d) 8, 6, 8
79. Which of the following is not paramagnetic [DCE 2002]
67. The bond order of O 2 is the same as in [CPMT 2004]
(a) O2 (b) O 22 
(a) N 2 (b) CN 
(c) O 22  (d) O 2

(c) CO (d) NO 80. Which of the following species have maximum number of unpaired
68. Bond order of O 2 is [DPMT 2004] electrons [AIIMS 1983]

(a) 2 (b) 1.5 (a) O2 (b) O 2

(c) 3 (d) 3.5 (c) O 2 (d) O 22 
69. The total number of electron that takes part in forming bonds in
81. The correct order in which the O – O bond length increases in the
N 2 is [MP PET 2004] following is [BHU 2000; CBSE PMT 2005]
(a) 2 (b) 4 (a) H 2 O2  O2  O3 (b) O2  H 2 O2  O3
(c) 6 (d) 10
(c) O2  O3  H 2 O2 (d) O3  H 2 O2  O2
70. The bond length the species O2 , O2 and O 2 are in the order of 82. Correct[MP PETof2004]
order bond length is [Orissa JEE 2005]

(a) O2  O2  O2 (b) O2  O2  O2 (a) CO 32   CO 2  CO (b) CO 2  CO  CO 32 

(c) O2  O2  O2 (d) O2  O2  O2 (c) CO  CO 2  CO 32  (d) None of these
71. According to molecular orbital theory which of the following 83. Which of the following is paramagnetic [DPMT 2005]
statement about the magnetic character and bond order is correct (a) N 2 (b) C 2
regarding O 2 [IIT JEE Screening 2004] (c) N 2 (d) O22 
(a) Paramagnetic and bond order< O 2 84. Among the following molecules which one have smallest bond angle[Orissa JEE 2
(b) Paramagnetic and bond order> O 2 (a) NH 3 (b) PH3
(c) H 2O (d) H 2 Sc
(c) Dimagnetic and bond order< O 2
(e) H 2S
(d) Dimagnetic and bond order> O 2

72. The bond order in NO is 2.5 while that in NO  is 3. Which of the Hydrogen bonding
following statements is true for these two species
1. In the following which bond will be responsible for maximun value
[AIEEE 2004]
of hydrogen bond
(a) Bond length in NO  is equal to that in NO (a) O  H (b) N  H
 122 Chemical Bonding

(c) S  H (d) F  H 13. The pairs of bases in DNA are held together by
2. In which of the following hydrogen bond is present [NCERT 1978; DPMT 1985; CBSE PMT 1992]
(a) H 2 (b) Ice (a) Hydrogen bonds (b) Ionic bonds
(c) Sulphur (d) Hydrocarbon (c) Phosphate groups (d) Deoxyribose groups
3. In the following which has highest boiling point
14. Water has high heat of vaporisation due to [AFMC 1982]
[MP PMT 1989; RPMT 1997]
(a) HI (b) HF (a) Covalent bonding (b) H  bonding
(c) HBr (d) HCl (c) Ionic bonding (d) None of the above
4. Which contains hydrogen bond [MP PMT 1989] 15. In which of the following compounds does hydrogen bonding occur
(a) HF (b) HCl (a) SiH 4 (b) LiH
(c) HBr (d) HI
(c) HI (d) NH 3
5. Contrary to other hydrogen halides, hydrogen fluoride is a liquid
because [MP PMT 1990; AMU 1983; EAMCET 1980] 16. Which among the following compounds does not show hydrogen
(a) Size of F atom is small bonding [MP PMT 1989]
(a) Chloroform (b) Ethyl alcohol
(b) HF is a weak acid
(c) Acetic acid (d) Ethyl ether
(c) HF molecule are hydrogen bonded 17. Acetic acid exists as dimer in benzene due to [CPMT 1982]
(d) Fluorine is highly reactive
(a) Condensation reaction
6. In the following which species does not contain sp3 hybridization [DPMT 1985]
(b) Hydrogen bonding
(a) NH 3 (b) CH 4 (c) Presence of carboxyl group
(d) Presence of hydrogen atom at   carbon
(c) H 2O (d) CO 2
18. Which one among the following does not have the hydrogen bond [
7. As a result of sp hybridization, we get [IIT 1984]
UPSEAT 2001]
(a) Two mutual perpendicular orbitals (a) Phenol (b) Liquid NH 3
(b) Two orbitals at 180 o (c) Water (d) Liquid HCl
(c) Four orbitals in tetrahedral directions 19. The bond that determines the secondary structure of a protein is[NCERT 1984; M
(d) Three orbitals in the same plane (a) Coordinate bond (b) Covalent bond
8. The reason for exceptionally high boiling point of water is (c) Hydrogen bond (d) Ionic bond
[DPMT 1986; NCERT 1976; AMU 1984; EAMCET 1979;
20. HCl is a gas but HF is a low boiling liquid. This is because
MP PMT 1993; AIIMS 1996; KCET 2001; CPMT 2003]
[NCERT 1984; MP PMT 2001]
(a) Its high specific heat
(a) H  F bond is strong
(b) Its high dielectric constant
(b) H  F bond is weak
(c) Low ionization of water molecules
(c) Molecules aggregate because of hydrogen bonding
(d) Hydrogen bonding in the molecules of water
9. Which concept best explains that o-nitrophenol is more volatile than (d) HF is a weak acid
p-nitrophenol 21. The relatively high boiling point of HF is due to
[AIIMS 1980, 82; Kurukshetra CEE 1998; MP PET 2002] [NCERT 1984]
(a) Resonance (b) Hyperconjugation (a) Hydrogen bonding
(c) Hydrogen bonding (d) Steric hindrence (b) Covalent bonding
10. Which contains strongest H  bond (c) Unshared electron pair on F
[IIT 1986; MP PET 1997, 2003; UPSEAT 2001, 03] (d) Being a halogen acid
(a) O  H..... S (b) S  H..... O 22. Water is liquid due to [MADT Bihar 1983]

(c) F  H..... F (d) F  H..... O (a) Hydrogen bonding (b) Covalent bond
11. Which of the following compound can form hydrogen bonds (c) Ionic bond (d) Vander Waals forces
[NCERT 1978; MP PMT 1997] 23. The maximum possible number of hydrogen bonds in which an
H 2 O molecule can participate is
(a) CH 4 (b) NaCl
[MP PMT 1986; MNR 1991; IIT 1992;MP PET 1999]
(c) CHCl 3 (d) H 2O (a) 1 (b) 2
12. Of the following hydrides which has the lowest boiling point (c) 3 (d) 4
[CBSE PMT 1987] 24. Hydrogen bonding is maximum in
(a) NH 3 (b) PH 3 [IIT 1987; MP PMT 1991; MP PET 1993, 2001;
MNR 1995; CPMT 1999; KCET (Med.) 2002]
(c) SbH 3 (d) AsH 3
(a) Ethanol (b) Diethyl ether
 Chemical Bonding 123
(c) Ethyl chloride (d) Triethyl amine 35. Ethanol and dimethyl ether form a pair of functional isomers. The
25. The hydrogen bond is strongest in boiling point of ethanol is higher than that of dimethyl ether due to
the presence of [AIIMS 1998]
[BHU 1987; CBSE PMT 1990, 92]
(a) Hydrogen bonding in ethanol
(a) Water (b) Ammonia
(b) Hydrogen bonding in dimethyl ether
(c) Hydrogen fluoride (d) Acetic acid
(c) CH 3 group in ethanol
26. The high boiling point of ethanol (78.2 o C) compared to dimethyl
(d) CH 3 group in dimethyl ether
ether (23.6 o C) , though both having the same molecular formulae
36. Which of the following hydrogen bonds are strongest in vapour
C 6 H 6 O , is due to [MP PMT 1993]
phase [AMU 1999]
(a) Hydrogen bonding
(a) HF    HF (b) HF    HCl
(b) Ionic bonding
(c) HCl    HCl (d) HF    HI
(c) Coordinate covalent bonding
(d) Resonance 37. Which of the following shows hydrogen bonding
[CPMT 2000]
27. Methanol and ethanol are miscible in water due to
[CPMT 1989] (a) NH 3 (b) P
(a) Covalent character (c) As (d) Sb
(b) Hydrogen bonding character 38. The boiling point of a compound is raised by [DPMT 2001]
(c) Oxygen bonding character (a) Intramolecular hydrogen bonding
(d) None of these (b) Intermolecular hydrogen bonding
28. B.P. of H 2 O (100 o C) and H 2 S (42 o C) explained by (c) Covalent bonding
(a) Vander Waal's forces (b) Covalent bond (d) Ionic covalent
(c) Hydrogen bond (d) Ionic bond 39. The boiling point of water is exceptionally high because
29. Strength of hydrogen bond is intermediate between [KCET 2001]
[DPMT 1991] (a) Water molecule is linear
(a) Vander Waal and covalent (b) Water molecule is not linear
(b) Ionic and covalent (c) There is covalent bond between H and O
(c) Ionic and metallic (d) Water molecules associate due to hydrogen bonding
(d) Metallic and covalent 40. NH 3 has a much higher boiling point than PH 3 because
30. In which of the following compounds intramolecular hydrogen bond
[UPSEAT 2002; MNR 1994]
is present [MP PET 1994]
(a) Ethyl alcohol (b) Water (a) NH 3 has a larger molecular weight
(c) Salicylaldehyde (d) Hydrogen sulphide (b) NH 3 undergoes umbrella inversion
31. Hydrogen bonding is formed in compounds containing hydrogen
and [MP PET 1995] (c) NH 3 forms hydrogen bond
(a) Highly electronegative atoms (d) NH 3 contains ionic bonds whereas PH 3 contains covalent
(b) Highly electropositive atoms bonds
(c) Metal atoms with d-orbitals occupied 41. Which one has the highest boiling point [MP PET 2002]
(d) Metalloids (a) Acetone (b) Ethyl alcohol
32. Which of the following compounds in liquid state does not have (c) Diethyl ether (d) Chloroform
hydrogen bonding [MP PMT 1996]
42. Which of the following compounds has the highest boiling point
(a) H 2O (b) HF
(a) HCl (b) HBr
(c) NH 3 (d) C 6 H 6 (c) H 2 SO 4 (d) HNO 3
33. Compounds showing hydrogen bonding among HF, NH 3 , H 2 S 43. Which of the following has minimum melting point
and PH 3 are [UPSEAT 2003]
(a) CsF (b) HCl
(a) Only HF, NH 3 and PH 3
(c) HF (d) LiF
(b) Only HF and NH 3 44. Hydrogen bond energy is equal to [UPSEAT 2003]
(c) Only NH 3 , H 2 S and PH 3 (a) 3 – 7 cals (b) 30 – 70 cals
(d) All the four (c) 3 – 10 kcals (d) 30 – 70 kcals
34. The high density of water compared to ice is due to 45. H 2 O is a liquid while H 2 S is gas due to [BHU 2003]
[CBSE PMT 1997; BHU 1999; AFMC 2001]
(a) Covalent bonding
(a) Hydrogen bonding interactions
(b) Dipole-dipole interactions (b) Molecular attraction
(c) Dipole-induced dipole interactions (c) H – bonding
(d) Induced dipole-induced dipole interactions (d) H – bonding and molecular attraction
 124 Chemical Bonding
46. H – bonding is maximum in [BHU 2003] (a) Overlapping valency orbitals
(a) C 6 H 5 OH (b) C 6 H 5 COOH (b) Mobile valency electrons
(c) Delocalized electrons
(c) CH 3 CH 2 OH (d) CH 3 COCH 3 (d) Highly directed bonds
47. Select the compound from the following which dissolves in water 8. In melting
[IIT lattice,
1980] structure of solid [CPMT 1982]
(a) Remains unchanged (b) Changes
(a) CCl 4 (b) CS 2
(c) Becomes compact (d) None of the above
(c) CHCl 3 (d) C2 H 5 OH 9. Which of the following has the highest melting point
[CPMT 1994]
48. When two ice cubes are pressed over each other, they unit to form
one cube. Which of the following force is responsible for holding (a) Pb (b) Diamond
them together [NCERT 1978] (c) Fe (d) Na
(a) Vander Waal's forces 10. In the formation of a molecule by an atom [AFMC 1995]
(b) Hydrogen bond formation (a) Attractive forces operate
(c) Covalent attraction (b) Repulsive forces operate
(c) Both attractive and repulsive forces operate
(d) Dipole–dipole attraction
(d) None of these
49. Which is the weakest among the following types of bond
11. Which has weakest bond [RPMT 1997]
[NCERT 1979; MADT Bihar 1984]
(a) Diamond (b) Neon (Solid)
(a) Ionic bond (b) Metallic bond
(c) KCl (d) Ice
(c) Covalent bond (d) Hydrogen bond 12. Which of the following exhibits the weakest intermolecular forces[AIIMS 1999; BH
50. H-bond is not present in [BCECE 2005] (a) He (b) HCl
(a) Water (b) Glycerol (c) NH 3 (d) H 2O
(c) Hydrogen fluoride (d) Hydrogen Sulphide 13. Glycerol has strong intermolecular bonding therefore it is
[RPET 2000]
Types of bonding and Forces in solid (a) Sweet (b) Reactive
(c) Explosive (d) Viscous
1. In a crystal cations and anions are held together by
14. Among the following the weakest one is
[EAMCET 1982] [Pb. PMT 2004; CPMT 2002]
(a) Electrons (b) Electrostatic forces (a) Metallic bond (b) Ionic bond
(c) Nuclear forces (d) Covalent bonds (c) Van der Waal's force (d) Covalent bond
2. In the following metals which one has lowest probable interatomic 15. Lattice energy of alkali metal chlorides follows the order
forces [MP PMT 1990] [DPMT 2004]

(a) Copper (b) Silver (a) LiCl  NaCl  KCl  RbCl  CsCl
(c) Zinc (d) Mercury (b) CsCl  NaCl  KCl  RbCl  LiCl
3. In solid argon, the atoms are held together by (c) LiCl  CsCl  NaCl  KCl  RbCl
[NCERT 1981; MP PET 1995] (d) NaCl  LiCl  KCl  RbCl  CsCl
(a) Ionic bonds (b) Hydrogen bonds 16. In the following which molecule or ion possesses electrovalent,
covalent and co-ordinate bond at the same time
(c) Vander Waals forces (d) Hydrophobic forces
4. Which one is the highest melting halide [AIIMS 1980] (a) HCl (b) NH 4

(a) NaCl (b) NaBr (c) Cl  (d) H 2 O2

(c) NaF (d) NaI 17. Both ionic and covalent bond is present in the following
5. The enhanced force of cohesion in metals is due to [MNR 1986; MP PMT 2004]
[NCERT 1972]
(a) CH 4 (b) KCl
(a) The covalent linkages between atoms
(b) The electrovalent linkages between atoms (c) SO 2 (d) NaOH
(c) The lack of exchange of valency electrons 18. The formation of a chemical bond is accompanied by
(d) The exchange energy of mobile electrons [MP PET 1995]
6. Which one of the following substances consists of small discrete (a) Decrease in energy
molecules [CPMT 1987]
(b) Increase in energy
(a) NaCl (b) Graphite
(c) Neither increase nor decrease in energy
(c) Copper (d) Dry ice
(d) None of these
7. Which of the following does not apply to metallic bond
[CBSE PMT 1989]
19. Chemical bond implies [KCET 2002]
 Chemical Bonding 125
(a) Attraction [UPSEAT 2001]
(b) Repulsion (a) N 2 H 5 (b) BaCl2
(c) Neither attraction nor repulsion
(c) HCl (d) H 2O
(d) Both (a) and (b)
20. Which of the following statements is true [AIEEE 2002] 6. Which combination is best explained by the co-ordinate covalent
(a) HF is less polar than HBr bond [JIPMER 2001; CBSE PMT 1990]
(b) Absolutely pure water does not contain any ions (a) H   H 2O (b) Cl + Cl
(c) Chemical bond formation take place when forces of attraction
1
overcome the forces of repulsion (c) Mg  O2 (d) H 2  I2
2
(d) In covalency transference of electron takes place
Which of the following statements is true about Cu NH 3 4 SO 4
7. Arrange the following compounds in order of increasing dipole
21. moment.[CPMT 1988]

(a) It has coordinate and covalent bonds (I) Toluene (II) m  dichlorobenzene
(b) It has only coordinate bonds (III) o  dichlorobenzene (IV) p  dichlorobenzene
(c) It has only electrovalent bonds [IIT 1996]
(d) It has electrovalent, covalent and coordinate bonds (a) I  IV  II  III (b) IV  I  II  III
22. Blue vitriol has
(c) IV  I  III  II (d) IV  II  I  III
(a) Ionic bond (b) Coordinate bond
8. The correct order of dipole moment is [Roorkee 1999]
(c) Hydrogen bond (d) All the above
(a) CH 4  NF3  NH 3  H 2 O
23. The number of ionic, covalent and coordinate bonds in NH 4 Cl
are respectively [MP PMT 1999] (b) NF3  CH 4  NH 3  H 2 O
(a) 1, 3 and 1 (b) 1, 3 and 2 (c) NH 3  NF3  CH 4  H 2 O
(c) 1, 2 and 3 (d) 1, 1 and 3
(d) H 2 O  NH 3  NF3  CH 4
24. Covalent molecules are usually held in a crystal structure by
9. Which of the following has the highest dipole moment
[MP PET 1995]
[AIIMS 2002]
(a) Dipole-dipole attraction
H CH 3
(b) Electrostatic attraction H | |
(a) CO (b) C  C
(c) Hydrogen bonds H | |

(d) Vander Waal's attraction CH 3 H

CH 3 H Cl CH 3
| | | |
(c) CC (d) C  C
| | | |
CH 3 H CH 3 Cl
10. Which of the following arrangement of molecules is correct on the
basis of their dipole moments [AIIMS 2002]
1. The values of electronegativity of atoms A and B are 1.20 and 4.0 (a) BF3  NF3  NH 3 (b) NF3  BF3  NH 3
respectively. The percentage of ionic character of A – B bond is [MP PET 2003]
(c) NH 3  BF3  NF3 (d) NH 3  NF3  BF3
(a) 50 % (b) 43 %
11. The type of hybrid orbitals used by the chlorine atom in ClO 2 is
(c) 55.3 % (d) 72.24%
(a) sp 3 (b) sp 2
2. O 22  is the symbol of ….. ion [EAMCET 2003]
(c) sp (d) None of these
(a) Oxide (b) Superoxide 12. Among the following species, identify the isostructural pairs,
(c) Peroxide (d) Monoxide NF3 , NO 3 , BF3 , H 3 O  , HN 3 [IIT 1996]
3. The number of electrons that are paired in oxygen molecule is [IIT 1995]
(a) [ NF3 , NO 3 ] and [BF3 , H 3 O ]

(a) 7 (b) 8
(b) [ NF3 , HN 3 ] and [ NO 3 , BF3 ]
(c) 14 (d) 16
(c) [ NF3 , H 3 O  ] and [ NO 3 , BF3 ]
4. When N 2 goes to N 2 , the N  N bond distance ..... and when
(d) [ NF3 , H 3 O  ] and [HN 3 , BF3 ]
O 2 goes to O 2 , the O  O bond distance .......
13. In the compound CH 2  CH  CH 2  CH 2  C  CH , the
[IIT 1996]
C2  C3 bond is of the type [IIT 1999]
(a) Decrease, increase (b) Increase, decrease
(c) Increase, increase (d) None of these (a) sp  sp 2 (b) sp 3  sp 3
5. Which of the following contains a coordinate covalent bond
 126 Chemical Bonding

(c) sp  sp 3 (d) sp 2  sp 3 (d) Isoelectronic and weak field ligands

24. The number of S – S bonds in sulphur trioxide trimer S 3 O 9 is [
14. The correct order of increasing C O bond length of (a) Three (b) Two
CO , CO 32  , CO 2 is [IIT 1999] (c) One (d) Zero
25. Strongest intermolecular hydrogen bond is present in the following
(a) CO 32   CO 2  CO (b) CO 2  CO 32   CO molecules pairs [IIT 1981; DCE 2000]
(a) SiH 4 and SiF
(c) CO  CO 32   CO 2 (d) CO  CO 2  CO 32 
O
15. In the dichromate dianion [IIT 1999] ||
(b) CH 3  C  CH 3 and CHCl 3
(a) 4 Cr  O bonds are equivalent
O O
(b) 6 Cr  O bonds are equivalent || ||
(c) H  C  OH and CH 3  C  OH
(c) All Cr  O bonds are equivalent
(d) H 2 O and H 2 O 2
(d) All Cr  O bonds are non-equivalent
26. A compound contains atoms X , Y , Z. The oxidation number of
16. Bond length of ethane (I), ethene (II), acetylene (III) and benzene
(IV) follows the order [CPMT 1999] X is  2, Y is + 5 and Z is  2 . Therefore, a possible formula
of the compound is [CPMT 1988]
(a) I  II  III  IV (b) I  II  IV  III
(c) I  IV  II  III (d) III  IV  II  I (a) XYZ 2 (b) X 2 YZ 3 2

17. Hybridisation state of chlorine in ClF3 is [RPET 1999] (c) X 3 YZ 4 2 (d) X 3 Y 4 Z 2

(a) sp 3 (b) sp 3 d 27. Bonds present in CuSO 4 .5 H 2 O is [IIT 1983; DCE 2001]
(a) Electrovalent and covalent
(c) sp 3 d 2 (d) sp 3 d 3
(b) Electrovalent and coordinate
18. Molecular shapes of SF4 , CF4 and XeF4 are
(c) Electrovalent, covalent and coordinate
[IIT Screening 2000]
(a) The same with 2, 0 and 1 lone pairs of electrons respectively (d) Covalent and coordinate
(b) The same, with 1, 1 and 1 lone pairs of electrons respectively 28. The ionization of hydrogen atom would give rise to
(c) Different, with 0, 1 and 2 lone pairs of electrons respectively [UPSEAT 2001]
(d) Different, with 1, 0 and 2 lone pairs of electrons respectively
(a) Hybrid ion (b) Hydronium ion
19. Structure of IF4 and hybridization of iodine in this structure are[UPSEAT 2001]
(c) Proton (d) Hydroxyl ion
(a) sp 3 d , Linear 29. Which can be described as a molecule with residual bonding
(b) sp 3 d 2 , T-shaped capacity [JIPMER 2000]
(a) BeCl 2 (b) NaCl
(c) sp3 d , Irregular tetrahedral
(d) sp 3 d 2 , Octahedral (c) CH 4 (d) N2
20. In which of the following the central atom does not use sp hybrid 3

orbitals in its bonding [UPSEAT 2001, 02]

(a) BeF3 (b) OH 3
(c) NH 2 (d) NF3
21. The magnetic moment of K 3 [Fe(CN )6 ] is found to be 1.7 B.M.
How many unpaired electron (s) is/are present per molecule Read the assertion and
[Orissa JEEreason
2003] carefully to mark the correct option out of
(a) 1 (b) 2 the options given below :
(c) 3 (d) 4 (a) If both assertion and reason are true and the reason is the correct
explanation of the assertion.
22. N 2 and O 2 are converted into monocations N 2 and O 2 (b) If both assertion and reason are true but reason is not the correct
respectively. Which is wrong [CBSE PMT 1997] explanation of the assertion.
(a) In N 2 , the N  N bond weakens (c) If assertion is true but reason is false.
(d) If the assertion and reason both are false.
(b) In O 2 , the O  O bond order increases
(e) If assertion is false but reason is true.
(c) In O 2 , paramagnetism decreases
1. Assertion : Water is a good solvent for ionic compounds but
(d) N 2 becomes diamagnetic poor one for covalent compounds.
23. The common features among the species CN  , CO and NO  are Reason : Hydration energy of ions releases sufficient
[IIT Screening 2001] energy to overcome lattice energy and break
(a) Bond order three and isoelectronic hydrogen bonds in water, while covalent bonded
(b) Bond order three and weak field ligands compounds interact so weakly that even Vander
(c) Bond order two and -acceptors
 Chemical Bonding 127
Wall's forces between molecules of covalent 16. Assertion : The crystal structure gets stabilized even though
compounds cannot be broken. [AIIMS 1996] the sum of electron gain enthalpy and ionization
enthalpy is positive.
2. Assertion : The atoms in a covalent molecule are said to
share electrons, yet some covalent molecules are Reason : Energy is absorbed during the formation of
polar. crystal lattice.
17. Assertion : Order of lattice energy for same halides are as
Reason : In a polar covalent molecule, the shared electrons
spend more time on the average near one of the LiX  NaX  KX .
atoms. [AIIMS 1996] Reason : Size of alkaline – earth metal increases from Li
3. Assertion : Diborane is electron deficient to K .
Reason : There are no enough valence electrons to form 18. Assertion : Born-Haber cycle is based on Hess’s law.
the expected number of covalent bonds[AIIMS 2001] Reason : Lattice enthalpy can be calculated by Born-
4. Assertion : A resonance hybrid is always more stable than Haber cycle.
any of its canonical structures 19. Assertion : Bond energy has order like
Reason : This stability is due to delocalization of electrons[AIIMS 1999] C C  C  C  C  C .
5. Assertion : All F  S  F angle in SF4 greater than 90° but Reason : Bond energy increases with increase in bond
order.
less than 180°
20. Assertion : Electron affinity refers to an isolated atom’s
Reason : The lone pair-bond pair repulsion is weaker than
attraction for an additional electron while
bond pair-bond pair repulsion
electronegativity is the ability of an element to
[AIIMS 2004]
attract electrons towards itself in a shared pair of
O electrons.
6. Assertion : The electronic structure of O 3 is
O O Reason : Electron affinity is a relative number and
electronegativity is experimentally measurable.
O 21. Assertion : Geometry of SF4 molecule can be termed as
Reason : structure is not allowed because
O O distorted tetrahedron, a folded square or see saw.
octet around cannot be expanded. Reason : Four fluorine atoms surround or form bond with
[IIT 1998] sulphur molecule.
7. Assertion : Bond order can assume any value number 22. Assertion : BF3 has greater dipole moment than H 2 S .
including zero
Reason : Fluorine is more electronegative than sulphur.
Reason : Higher the bond order, shorter is bond length
and greater is bond energy 23. Assertion : The bond between two identical nonmetal atoms
has a pair of electrons with identical spin.
[AIIMS 1999]
8. Assertion : Ortho nitrophenol molecules are associated due to the Reason : Electrons are transferred fully from one atom to
presence of intermolecular hydrogen bonding while another.
paranitrophenol involves intramolecular, hydrogen 24. Assertion : B molecule is diamagnetic.
2

bonding Reason : The highest occupied molecular orbital is of 

Reason : Ortho nitrophenol is more volatile than the para type. [AIIMS 2005]
nitrophenol [AIIMS 1999] 25. Assertion : The nearly tetrahedral arrangement of the
9. Assertion : Nitrogen molecule diamagnetic. orbitals about the oxygen atom allows each water
Reason : N 2 molecule have unpaired electrons. molecule to form hydrogen bonds with as many
as four neighbouring water molecules.
10. Assertion : Ice is less dense than liquid water.
Reason : In ice each molecule forms four hydrogen bonds
Reason : There are vacant spaces between hydrogen as each molecule is fixed in the space.
bonded water molecules in ice.
26. Assertion : The bond order of helium is always zero.
11. Assertion : Water is liquid but H 2 S is a gas.
Reason : The number of electrons in bonding molecular
Reason : Oxygen is paramagnetic. orbital and antibonding molecular orbital is
12. Assertion : Iodine is more soluble in water then in carbon equal.
tetrachloride.
Reason : Iodine is a polar compound.
13. Assertion : o and p -nitrophenols can be separated by
steam distillation.
Reason : o -nitrophenol have intramolecular hydrogen
bonding while p -nitrophenol exists as
associated molecules. Electrovalent bonding
14. Assertion : The fluorine has lower reactivity.
1 b 2 a 3 a 4 c 5 c
Reason : F  F bond has low bond dissociation energy.
15. Assertion :  is strong while  is a weak bond. 6 d 7 d 8 b 9 c 10 d
Reason : Atoms rotate freely about  bond. 11 b 12 a 13 d 14 a 15 a
16 c 17 b 18 a 19 d 20 c
 128 Chemical Bonding

21 b 22 d 23 a 24 a 25 b Polarisation and Fajan’s rule

26 d 27 d 28 c 29 a 30 d
1 d 2 c 3 b 4 d 5 c
31 b 32 b 33 b 34 d 35 b
6 a 7 b 8 a 9 c 10 b
36 a 37 b 38 a 39 a 40 c
11 d 12 c 13 b 14 b 15 d
41 c 42 b 43 d 44 b 45 c
16 d 17 c 18 b 19 a 20 d
46 c 47 a 48 b 49 c 50 b
21 a 22 c 23 d 24 a 25 b
51 b 52 b 53 a 54 a 55 a
26 b
56 c 57 a 58 c 59 a 60 c
61 a 62 b 63 d 64 d 65 b
Overlaping -  and - bonds
66 a 67 abc 68 bd

1 c 2 c 3 b 4 b 5 c
Covalent bonding
6 c 7 c 8 b 9 d 10 c
1 c 2 c 3 B 4 b 5 d 11 b 12 c 13 a 14 a 15 d
6 a 7 c 8 a 9 d 10 a 16 a 17 d 18 c 19 d 20 d
11 b 12 b 13 c 14 b 15 c
16 a 17 a 18 c 19 a 20 b Hybridisation
21 a 22 a 23 c 24 c 25 c
1 d 2 d 3 d 4 c 5 d
26 c 27 a 28 a 29 a 30 d
6 a 7 c 8 b 9 d 10 d
31 b 32 a 33 d 34 a 35 d
11 d 12 a 13 a 14 b 15 a
36 b 37 d 38 c 39 d 40 c
16 b 17 c 18 a 19 d 20 b
41 b 42 b 43 b 44 b 45 b
21 c 22 c 23 a 24 c 25 a
46 d 47 d 48 b 49 a 50 a
26 a 27 b 28 c 29 b 30 a
51 b 52 d 53 c 54 d 55 d
31 d 32 a 33 d 34 c 35 c
56 d 57 a 58 a 59 d 60 a
36 b 37 b 38 c 39 b 40 b
61 c 62 a 63 b 64 b 65 b
41 d 42 b 43 c 44 a 45 c
66 b 67 b 68 d 69 b 70 c
46 c 47 d 48 b 49 c 50 a
71 c 72 c 73 cd 74 ad 75 ab
51 b 52 a 53 c 54 c 55 c
76 a
56 d 57 b 58 a 59 b 60 c

Co-ordinate or Dative bonding 61 b 62 c 63 b 64 b 65 b

66 a 67 c 68 b 69 c 70 a
1 d 2 b 3 c 4 d 5 c
71 a 72 a 73 b 74 b 75 d
6 b 7 a 8 d 9 a 10 d
76 d 77 c 78 a 79 d 80 b
11 c 12 a 13 a 14 b 15 c
81 c 82 b 83 d 84 a 85 d

Dipole moment 86 b 87 d 88 c 89 a 90 c
91 c 92 c 93 a 94 b 95 c
1 b 2 d 3 d 4 a 5 c 96 a 97 b 98 b 99 b 100 b
6 c 7 a 8 a 9 c 10 b 101 a 102 b 103 d 104 a 105 b
11 b 12 d 13 b 14 c 15 d 106 a 107 a 108 b 109 b 110 a
16 c 17 c 18 a 19 c 20 b 111 a 112 b 113 b 114 d 115 d
21 d 22 b 23 b 24 b 25 a 116 c 117 c 118 b 119 c 120 a
26 b 27 b 28 b 29 c 30 a 121 a 122 c 123 a 124 a 125 b
31 a 32 c 33 a 34 bd 35 a 126 c 127 d 128 c 129 c 130 a
131 b 132 b 133 e 134 c 135 d
 Chemical Bonding 129

136 b 137 b 138 d 139 a 140 a 6 d 7 b 8 d 9 c 10 c

141 a 142 b 143 a 144 a 145 a 11 d 12 b 13 a 14 b 15 d
146 b 147 c 148 d 149 bcd 150 a 16 d 17 b 18 d 19 c 20 c
151 ac 152 a 21 a 22 a 23 d 24 a 25 c
26 a 27 b 28 c 29 a 30 c
Resonance 31 a 32 b 33 d 34 a 35 a
36 a 37 a 38 b 39 d 40 c
1 d 2 b 3 b 4 b 5 b
41 a 42 c 43 b 44 c 45 c
6 c 7 a 8 c 9 b 10 c
46 b 47 d 48 b 49 d 50 d
11 abcd

Types of bonding and Forces in solid

VSEPR Theory
1 b 2 d 3 c 4 c 5 d
1 a 2 a 3 b 4 c 5 c
6 d 7 d 8 b 9 b 10 c
6 b 7 b 8 c 9 b 10 a
11 d 12 a 13 d 14 c 15 a
11 c 12 a 13 a 14 a 15 c
16 b 17 d 18 a 19 d 20 c
16 c 17 b 18 d 19 d 20 a
21 d 22 d 23 a 24 d
21 a 22 d 23 b 24 d 25 a
26 c 27 b 28 b 29 a 30 a Critical Thinking Question
31 a 32 c 33 c 34 a 35 c
36 b 37 b 38 d 39 d 40 b 1 d 2 c 3 c 4 b 5 a

41 c 42 a 43 b 44 c 45 d 6 a 7 b 8 a 9 a 10 d
11 a 12 c 13 d 14 d 15 b
Molecular orbital theory 16 c 17 b 18 d 19 c 20 a
21 a 22 d 23 a 24 d 25 c
1 a 2 c 3 b 4 b 5 c
26 c 27 c 28 c 29 a
6 d 7 c 8 b 9 c 10 b
11 c 12 b 13 c 14 a 15 c Assertion & Reason
16 c 17 d 18 b 19 c 20 c
1 a 2 a 3 a 4 a 5 c
21 d 22 c 23 b 24 c 25 a
6 b 7 b 8 e 9 c 10 a
26 d 27 b 28 b 29 a 30 c
11 b 12 d 13 a 14 e 15 c
31 c 32 a 33 c 34 a 35 c
16 c 17 c 18 b 19 a 20 c
36 d 37 b 38 a 39 a 40 c
21 b 22 e 23 d 24 d 25 a
41 c 42 a 43 b 44 a 45 a
26 a
46 c 47 b 48 c 49 c 50 a
51 c 52 b 53 a 54 a 55 a
56 c 57 c 58 c 59 a 60 a
61 a 62 b 63 a 64 c 65 a
66 c 67 a 68 a 69 c 70 a
71 b 72 b 73 d 74 c 75 a
76 b 77 b 78 a 79 c 80 a
81 c 82 a 83 c 84 d

Hydrogen bonding

1 d 2 b 3 b 4 a 5 c
 Chemical Bonding 133
24. (a) M 3 (PO4 )2 means M is divalent so formula of its sulphate is
MSO 4 .
25. (b) As the molecular formula of chloride of a metal M is MCl3 , it
is trivalent so formula of its carbonate will be M 2 (CO 3 )3 .
26. (d) Sodium chloride is electrovalent compound so it dissolves in
Electrovalent bonding water which is a polar solvent.
27. (d) When sodium chloride is dissolved in water, the sodium ion is
  hydrated.
1. (b) NaCl is ionic crystal so it is formed by Na and Cl ions.
30. (d) Yet the formula of sulphate of a metal (M) is M 2 (SO 4 )3 , it is
2. (a) Bond formation is always exothermic. Compounds of sodium
are ionic. M 3  ion so formula of its phosphate would be MPO4 .
3. (a) According to Fajan’s rule ionic character is less. 32. (b) Molten sodium chloride conducts electricity due to the
4. (c) Valencies of L, Q, P and R is – 2, – 1, + 1 and + 2 respectively so presence of free ions.
they will form P2 L, RL, PQ and RQ 2 . 33. (b) The phosphate of a metal has the formula MHPO4 it means
5. (c) Electrovalent compounds are good conductor of heat and metal is divalent so its chloride would be MCl 2 .
electricity in molten state or in aqueous solution. 34. (d)
7. (d) Electrovalent bond formation depends on ionization energy of 35. (b) Cs is highly electropositive while F is highly
cation, electron affinity of anion and on lattice energy. electronegative so they will form ionic bond.
8. (b) Because CsF is electrovalent compound. 37. (b) Na is highly electropositive while Cl is highly
electronegative so they will form ionic bond.
9. (c) NaCl is formed by electrovalent bonding. 38. (a) Ionic compounds are good conductors of heat and electricity so
10. (d) Valency of metal is + 2 by formula MO so its phosphate would they are good electrolyte.
be M 3 (PO4 )2 because valency of [PO4 ] is – 3. 39. (a) Metal tends to lose electrons due to low ionization energy.
40. (c) As the formula of calcium pyrophosphate is Ca 2 P2 O7 means
11. (b) Li, Na and K are alkali metals with low ionization energy and
one electron in their outermost shell so they will form cation valency of pyrophosphate radical is – 4 so formula of ferric
easily. pyrophosphate is Fe4 P2 O7 3 .
12. (a) Melting point and boiling point of electrovalent compounds are 41. (c) M  X bond is a strongest bond so between Na  Cl is a
high due to strong electrostatic force of attraction between the strongest bond.
ions. 42. (b) The solubility order is :
13. (d) The value of lattice energy depends on the charges present on BeF2  MgF2  CaF2  SrF2 so SrF2 is least soluble.
the two ions and distance between them. It shell be high if 43. (d) NaF has maximum melting point, melting point decreases of
charges are high and ionic radii are small. sodium halide with increase in size of halide their bond energy
14. (a) Cs is more electropositive. get lower.
15. (a) X loses electron, Y gains it. 44. (b) Sulphanilic acids have bipolar structure so their melting point
is high and insoluble in organic solvents.
 
16. (c) Formation of NaCl occurs by Na ion and Cl ion . 45. (c) CaCl 2 will have electrovalent bonding because calcium is
17. (b) MgCl2 has electrovalent linkage because magnesium is electropositive metal while chlorine is electronegative so they
will combined with electrovalent bond.
electropositive metal while chlorine is electronegative.
47. (a) Electrovalent bond is formed by losing electrons from one atom
18. (a) Electrovalent compounds generally have high m.pt and high and gaining electron by other atom i.e. redox reaction.
b.pt due to stronger coulombic forces of attractions. 48. (b) Electrovalent compound are polar in nature because they are
19. (d) Water is a polar solvent so it decreases the interionic attraction formed by ions.
in the crystal lattice due to solvation. 50. (b) CsCl has ionic bonding.
20. 2 2 5
(c) Element C has electronic structure 1s , 2 s 2 p , it requires 51. (b) As soon as the electronegativity increases, ionic bond strength
increases.
only one electron to complete its octet and it will form anion
52. (b) This X element is a second group element so its chloride will
so it will form electrovalent bond.
be XCl 2 .
21. (b) Since the chloride of a metal is MCl 2 therefore metal ‘M’
53. (a) When electronegativity difference is from 1.7 to 3.0. This bond
must be divalent i.e. M 2 . As a result the formula of its is called as ionic bond.
phosphate is M 3 (PO4 )2 . 54. (a) Ethyl chloride is an organic compound so it will be covalent.
55. (a) Lithium oxide and calcium fluoride show ionic characters.
22. (d) In MPO4 the oxidation state of M is +3. Hence, the formula
57. (a) Generally cation and anion form ionic bond.
of nitrate is M ( NO 3 )3 . 58. (c) Those atoms which contain +ve and –ve sign are known as ion.
23. (a) Ion is formed by gaining or losing electrons. To form cation 59. (a) Generally Br-F contain maximum electronegativity difference
electron are lost from the valency shell, so Zn atoms to Zn  compare to other compound.
ions there is a decrease in the no. of valency electron. 61. (a) Due to greater electronegativity difference.
3d 4s

4s
 134 Chemical Bonding

31. (b) Valency of phosphorus in H 3 PO4 is supposed ‘x’ then

62. (b) Co 3   3d 6 4 s 0 , 3  x 8  0, x 5  0 , x  5.
33. (d) (1)  x  3(2)  0  1  x  6  0  x  6  1  5 .
34. (a) HCl molecule has covalent bond.
Ni 4   3d 6 4 s 0 , 35. (d) Electrovalent compounds have high melting point and high
64. (d) BaCl2 contain higher ionic character. boiling point.
66. (a) Electrolytes are compound which get dissociated into their ion 36. (b) Middle length of H 2  74 pm
in water so it contains electrovalent bond.
74
67. (abc) CaH 2 , BaH2 , SrH 2 are ionic hydride. Length of H   37 pm
2
68. (bcd) Generally MgCl2 , SrCl 2 , BaCl2 are ionic compounds so Middle length of Cl 2  198 pm
they conduct electricity in fused state.
198
Length of Cl   99 pm
Covalent bonding 2
Bond length of HCl = Length of H + Length of Cl
2. (c) In N 2 molecule each Nitrogen atom contribute 3 e  so total = 37 + 99 = 136 pm
no. of electron’s are 6. 254
37. (d) Compound has 254 gm of I 2 means  2 mole, while
3. (b) Non-metals readily form diatomic molecules by sharing of 127
electrons. Element M (1s 2 2 s 2 2 p 5 ) has seven electrons in its 80
80 gm O 2 means  5 mole so they will form compound
valence shell and thus needs one more electron to complete its 16
octet. Therefore, two atoms share one electron each to form a I2 O5 .
diatomic molecule (M 2 )
38. (c) NH 4 Cl has covalent as well as ionic bond.
.. .. .. ..
: M ..M :  : M : M :  H 
.. .. .. ..  | 
 H  N  H  Cl 


5. (d) Covalent character depend on the size of cation and anion.  | 

 
6. (a) In graphite all carbon atoms are sp 2 -hybridised and have  H 
covalent bond. 39. (d) Covalent character increases when we come down a group so
7. (c) Silica has tendency to form long chain covalent structure such CaI2 will have highest covalent character.
as carbon so it has giant covalent structure. 41. (b) In water molecule three atom are linked by covalent bond.
8. (a) All have linear structure. O
Structure is
O = C = O, Cl – Hg – Cl, HC  CH H H
9. (d) Similar atoms form covalent bond. ..
10. (a) Covalent bond forms when electronegativity difference of two 42. (b) : N  N   O : or N  N  O.
..
atom is equal to 1.7 or less than 1.7
44. (b) The electronic configuration of Na (Z  11) is
11. (b) Similar atoms form covalent bond.
12. (b) Water is a polar solvent while covalent compounds are non- 1s 2 , 2 s 2 2 p 6 , 3 s1 . The oxide of Na is Na 2 O .
polar so they usually insoluble in water. 45. (b) Covalent bond is directional.
13. (c) BCl 3 is electron deficient compound because it has only ‘6’ 47. (d) Bond dissociation energy decreases with increase in size. So D
electrons after forming bond. is smallest.
14. (b) Due to its small size and 2 electrons in s-orbital Be forms 48. (b) Molecule X is nitrogen because nitrogen molecule has triple
covalent compound. bond. It’s configuration will be 1s 2 , 2 s 2 2 p 3 .
18. (c) H 2 O will formed by covalent bonding. 49. (a) PCl5 does not follow octet rule, it has 10 electrons in its
21. (a) Two identical atoms are joined with covalent bond so H 2 will valence shell.
be covalent. 50. (a) The compound will be A2 B3 (By criss cross rule).
23. (c) Element ‘X’ has atomic no. 7 so its electronic configuration will 51. (b) Each nitrogen share 3 electrons to form triple bond.
. 52. (d) Urea solution does not conduct electricity because it is a
be 2, 5. So its electron dot symbol would be : X . covalent compound.
.
24. (c) C-S will be most covalent. Covalent character depend on the 54. (d) Due to the small size and higher ionization energy, boron
size of cation and anion. forms covalent compound.
25. (c) HCl has ionic character yet it has covalent compound because 58. (a) BF 3 contain 6 electron so it is lewis acid.
electronegativity of chlorine is greater than that of hydrogen. 59. (d) Among the given species. The bond dissociation energy of
26. (c) Order of polarising power Be   Li   Na  C  O bond is minimum in case of CO 32  by which
Hence order of covalent character BeCl 2  LiCl  NaCl .
 Chemical Bonding 135

C  O bond become more weaker in CO 32  or the bond

order of CO 32  (1.33) is minimum so the bond become weaker.
60. (a) Valency of Na 2 S 2 O3 is supposed to be x, then
2  2 x  ( 6)  0 , 2 x  4  0 , x  2 .
O O
|| ||
61. (c) H  O  S  O  O  S  O  H (Marshall acid)
|| ||
O O
62. (a) Among the given choice Al is least electropositive therefore, the
bond between Al and Cl will be least ionic or most covalent or
the difference in electronegativeity of two atom is less than 1.8. 2. (b) H 2 SO 4 has co-ordinate covalent bond.
O
63. (b) Electronic configuration of 16 S 32  1s 2 ,2 s 2 ,2 p 6 ,3 s 2 ,3 p 4 . In 
the last orbit it has only 6 electron. So it require 2 electron to H O  SO H

complete its octet, therefore it share 2 electron with two O
hydrogen atom and forms 2 covalent bond with it.
3. (c) NH 3 has lone pair of electron while BF3 is electron
64. (b) The acidity of hydrides of VI group elements increase from top
deficient compound so they form a co-ordinate bond.
to bottom as the bond strength X  H decrease from top to NF3  BF3
bottom
H 2 O  H 2 S  H 2 Se  H 2 Te 4. (d) HNO 2 does not have co-ordinate bond. Structure is
H O  N  O .
65. (b) We know that Al 3 cation is smaller than Na  (because of 7. (a) Structure of N 2 O5 is O  N  O  N  O .
greater nuclear change) According to Fajan's rule, small cation  
3  O O
polarise anion upto greater extent. Hence Al polarise Cl
ion upto greater extent, therefore AlCl3 has covalent bond 9. (a) SO 32  has one coordinate bond.  O  S  O 

between Al and Cl atoms. O
66. (b) Sulphur has the second highest catenation property after 10. (d) Co-ordinate bond is a special type of covalent bond which is
formed by sharing of electrons between two atoms, where both
carbon. Its molecule has eight atom bonded together (i.e. S 8 ) the electrons of the shared pair are contributed by one atom.
67. (b) H 2 O 2 has open book structure. Since this type of sharing of electrons exits in O 3 , SO 3 and
O H 2 SO 4 . Therefore all these contains coordinate bond.
H 
O 12. (a) CH 3 N  C contain dative bond.
H 13. (a) H 3 PO4 is orthophosphoric acid.
69. (b) The electronic configuration of nitrogen is
O
N  1s 2 , 2 s 2 , 2 p 3 
7
H O  PO  H
It has 5 electrons in valency shell, hence in ammonia molecule |
it complete its octet by sharing of three electron with three H O
|
atom, therefore it has 8 electrons in its valence shell in H
ammonia molecule 15. (c) Sulphuric acid contain, covalent and co-ordinate bond.
.. ..
H   N   H or H  N  H Dipole moment
. |
 H
H 1. (b) CO 2 is a symmetrical molecule so its dipole moment is
71. (c) Multiple bonds have more bond energy so C  N will be the zero.
strongest. 2. (d) These all have zero dipole moment.
72. (c) Diamond, silicon and quartz molecule bounded by covalent 3. (d) HF has largest dipole moment because electronegativity
bond. difference of both is high so it is highly polar.
73. (cd) C 2 H 4 and N 2 has multiple bonds. 5. (c) Due to its symmetrical structure.
6. (c) Chloroform has 3 chlorine atom and one hydrogen atom
74. (ad) CO has only 6 electrons while PCl5 has 10 electrons after attached to the carbon so it is polarised and it will show dipole
sharing so both don’t follow octet rule. moment.
76. (a) Among these, NaH and CaH 2 are ionic hydrides and B2 H 6 8. (a) The dipole moment of two dipoles inclined at an angle  is
and NH 3 are covalent hydrides. given by the equation   X 2  Y 2  2 XY cos
cos 90  0 . Since the angle increases from 90  180 , the
Co-ordinate or Dative bonding value of cos becomes more and more – ve and hence
resultant decreases. Thus, dipole moment is maximum when
1. (d)   90 .
– F F

Cl Xe
O
O F F
O

F
F
 136 Chemical Bonding

9. (c) Due to distorted tetrahedral geometry SF4 has permanent 1.03

  100  16.83%  17%
dipole moment F 6.12
F
: S Polarisation and Fajan's rule
F
F 1. (d) BF3 is planar while NF3 is pyramidal due to the presence of
10. (b) CCl 4 has no net dipole moment because of its regular lone pair of electron on nitrogen in NF3 .
tetrahedral structure.
2. (c) H 2 O is a polar molecule due to electronegativity difference of
12. (d) H-F is polar due to difference of electronegativity of hydrogen
and fluorine so it shows positive dipole moment. hydrogen and oxygen.
14. (c) BCl 3 has zero dipole moment because of its trigonal planar 3. (b) When electronegativity difference is more between two joined
atoms then covalent bond becomes polar and electron pair
geometry. forming a bond don’t remain in the centre.
16. (c) Dipole moment of CH 3 OH is maximum in it. 4. (d) Hexane has symmetrical structure so does not have polarity.
20. (b) CH 4 have regular tetrahedron so its dipole moment is zero. 5. (c) When two identical atoms form a bond, bond is non-polar.
22. (b) Ammonia have some dipole moment. 6. (a) According to Fajan’s rule, polarisation of anion is influenced by
charge and size of cation more is the charge on cation, more is
23. (b) Charge of e   1.6  10 19 polarisation of anion.
Dipole moment of HBr  1.6  10 30 8. (a) When two atoms shares two electrons it is an example of
covalent bond. This covalent bond may be polar or may be
Inter atomic spacing  1Å  1  10 10 m non-polar depends on the electronegativity difference. In given
% of ionic character in example formula is AB. So it is polar.

dipolemoment of HBr  100 9. (c) HCl is most polar due to high electronegativity of Cl.
HBr 
inter spacing distance q 10. (b) NH 3 has sp 3 hybridised central atom so it is non planar.

1 .6  10 30 11. (d) p-dichloro benzene have highest melting point.

  100
1 .6  10 19  10 10 13. (b) NH 4 Cl has both types of bonds polar and non polar
 10 30  10 29  100  10 1  100  0.1  100  10% 
 H 
25. (a) Carbon tetrachloride has a zero dipole moment because of its  | 
regular tetrahedral structure.  H  N|  H  Cl 
 
27. (b) BF3 has zero dipole moment.  H 

29. (c) Given ionic charge  4.8  10 10 e.s.u. and ionic distance 14. (b) Greater the charge of cation more will be its polarising power
8
(according to Fajan’s rule).
 1 A  10 cm we know that dipole moment = ionic charge
15. (d) AlI3 Aluminiumtriiodide shows covalent character. According
× ionic distance  4.8  10 10  10 8
to Fajan’s rule.
 4.8  10 8 e.s.u. per cm  4.8 debye. 16. (d) As the size of anion increases, polarity character increases.
30. (a) Higher is the difference in electronegativity of two covalently 20. (d) Due to the electronegativity difference.
bonded atoms, higher is the polarity. In HCl there is high
difference in the electronegativity of H and Cl atom so it is a 21. (a) We know that greater the difference in electronegativity of two
polar compound. atoms forming a covalent bond. More is its polar nature. In HF
there is a much difference in the electronegatives of hydrogen
31. (a) Linear molecular has zero dipole moment CO 2 has linear and flourine. Therefore (HF) is a polar compound.
structure so it does not have the dipole moment O  C  O . 22. (c) Silicon tetrafloride has a centre of symmetry.
32. (c) SF6 is symmetrical and hence non polar because its net dipole 23. (d) BF3 have zero dipole moment.
moment is zero.
25. (b) According to Fajan’s rule largest cation and smallest anion form
33. (a) Polarity create due to the difference in electronegativity of both ionic bond.
atom in a molecule except H 2 all other molecule have the 26. (b) Polarity character is due to the difference in electronegativity of
different atom so they will have the polarity while H 2 will be two atoms or molecule.
non polar.
Overlaping-  and - bonds
34. (bd) cis isomer shows dipole moment while that of trans is
zero or very low value. Trans 1, 2 di-chloro-2-pentene will
also show dipole moment due to unsymmetry.  
1. (c)
35. (a) % of ionic character H–C C–H
Experiment al value of dipole moment
=
Expected value of dipole moment 2.  molecule formation p-p orbitals take part in bond
(c) In fluorine
formation.
 Chemical Bonding 137
3. (b) -bond is formed by lateral overlapping of unhybridised p-p 1
orbitals. 5. (d) No. of e pair  3 
–
[3  3] =0
2
C F
No. of e pair  3 +0
–
120°
4. (b) Ca 1 and 2
F B 120°
C
5. (c) In a double bond connecting two atom sharing of 4 electrons 120° F
take place as in H 2 C  CH 2 . No. of atom bonded to the central atom  3
6. (c) C  C is a multiple bond so it is strongest. In case of 3, 3 geometry is Trigonal planar.
9. (d) As the bond order increases, C  H bond energy also 6. (a) In sp 3 –hybridisation each sp 3 hybridised orbital has 1/4 s-
increases so it will be greatest in acetylene because its B.O. is 3. character.
H H
| | 8. (b) In ethylene both Carbon atoms are sp 2 - hybridised so 120 o .
11. (b) H C  C  C  C
| 9. (d) Structure of sp 3 d hybridized compound is Trigonal
  H bipyramidal.
16. (a) O
N N ||
10. (d) In H  C  C  O  H the asterisked carbon has a valency of
 *
17. (d) We know that trisilylamine is sp 2 –hybridized therefore
p  d bonding is possible due to the availability of vacant 5 and hence this formula is not correct.
d-orbitals with silicon. 11. (d) dsp 3 hybrid orbitals have bond angles 120 o , 90 o .
18. (c)
13. (a) In BeF3 , Be is not sp 3 –hybridised it is sp 2 hybridised.

S 17. (c) In molecule OF2 oxygen is sp 3 hybridised.

2, 2 bond and one lone pair. 18. (a) In sp 3 hybrid orbitals s-character is 1/4 means 25%.th

.. ..
:O :O 19. (d) XeF4 molecule has ‘Xe’ sp 3 d 2 hybridised and its shape is
.. .. square planar.
19. (d) : O  S  O : 5 atoms has 12 electrons in its outermost 20. (b) The bond angle is maximum for sp hybridisation because two
||

O: sp hybridised orbitals lies at angle of 180 o .

..
21. (c) C 2 H 4 Br2 has all single bonds so C  H bond distance is
shell. One (S  O) bond will be (p-p)  bond while two
the largest.
(S  O) bond will be (p-d)  bond.
23. (a) In methane molecule C is sp 3 hybridised so its shape will be
20. (d) Structure of P4 O10 is
tetrahedral.
O
3 2 1
24. (c) In compound CH 2  C  CH 2 the second carbon sp-
P
O
hybridised.
O
.. ..
O 25. (a) : Cl   Cl : is the correct electronic formula of Cl 2 molecule
.. ..
O P P O
O because each chlorine has 7 electrons in its valence shell.
26. (a) XeF4 has sp 3 d 2 hybridisation, its shape is square planar.
O O
P 27. (b) In HCHO, carbon is sp 2 hybridized
H
O |
Each phosphorus is attached to 4 oxygen atoms. H  C2  O
sp
Hybridisation 28. (c) Because of the triple bond, the carbon-carbon bond distance in
ethyne is shortest.
1. (d) H 2 O is not linear because oxygen is sp 3 hybridised in
29. (b) The hybridisation of Ag in complex [ Ag (NH 3 )2 ] will be sp
H 2O .
because it is a Linear complex.
2. (d) O 30. (a) Structure of CO 2 is linear O  C  O while that of H 2 O
95.7 pm
(104.5) o O
H H is i.e. bent structure so in CO 2 resultant dipole
H H
4. (c) CO 2 has sp – hybridization and is linear. moment is zero while that of H 2 O has some value.

31. (d) CO 2 is not sp 3 hybridised, it is sp hybridised.

 138 Chemical Bonding
32. (a) As compare to pure atomic orbitals, hybrid orbitals have low 70. (a) As p-character increases the bond angle decreases.
energy. 1
In sp - p-character , bond angle - 180 o
sp 2 sp sp 2 sp 3 2
33. (d) CH 2  C  CH – CH 3 1, 2-butadiene.
2
In sp 2 - p-character , bond angle - 120 o
36. (b) CCl 4 is sp 3 hybridised so bond angle will be approximately 3
109 o . 3
In sp 3 - p-character , bond angle - 109 o
40. 2
(b) Ethene has sp hybridised carbon so bond angles are 120 . o 4

O 71. (a) sp 3 -hybridization called tetrahedral because it provides

tetrahedral shape to the molecule.
44. (a) Acetate ion is CH 3 C i.e. one C  O single bond
O  72. (a) S-atom in SF6 has sp 3 d 2 hybridisation. So, the structure of
and one C  O double bond. SF6 will be octahedral.

46. (c) Benzene has all carbons sp 2 hybridised and planar in shape. 74. (b) Structure of H 2 O 2 is non-planar. It has open book structure.

47. (d) In methane C is sp 3 hybridized and bond angle is 109 o . 75. (d) Structure of N 2 O is similar to CO 2 both have linear
structure.
H H H
| | | 78. (a) SnCl 2 is V–shaped.
56. (d) H  C C C H
| | |
79. (d) In NH 4 nitrogen is sp 3 hybridised so 4 hydrogen situated
H H H
at the corners of a tetrahedron.
There are 10 shared pairs of electrons.
81. (c) Increasing order of bond angle is sp 3  sp 2  sp .
58. (a) The diborane molecule has two types of B – H bond : 109  120  180 

(i) B  H t – It is a normal covalent bond. 84. (a) NH 4 3

has sp –hybridized nitrogen so its shape is tetrahedral.
(ii) B  H b – It is a three centred bond. 86. (b) Bond angle increases with change in hybridisation in following
Hb order sp 3  sp 2  sp .
Ht Ht
88. (c) In Diborane boron shows sp 3 –hybridization.
B B
Ht 89. (a) Alkene does not show linear structure but it has planar
Ht
Hb structure due to sp 2 –hybridisation.
3
61. (b) PF5 involves sp d hybridization and hence has trigonal 90. (c) Generally SF4 consist of 10 electrons, 4 bonding electron pair
bipyramidal structure.
and one lone pair of electron, hence it shows sp 3 d
1 hybridization.
62. (c) s-character in sp   100  50%
2 92. (c) Atom/Ion Hybridisation
1 NO 2 sp
s-character in sp 2   100  33.3%
3
SF4 sp 3 d with one lone pair of electron
1
s-character in sp   100  25%3
PF6 sp 3 d 2
4
Hence, maximum s-character is found in sp-hybridisation. 93. (a) PF3 consist of three bonding pair electrons and one lone pair
of electron hence it shows sp 3 – hybridization.
3
63. (b) The molecule of PCl5 has sp d hybridisation, structure is
trigonal bipyramidal.
94. (b) NO 2 shows sp–hybridization. So its shape is linear.
64. (b) Merging (mixing) of dissimilar orbitals of different energies to
form new orbitals is known as hybridisation and the new 95. (c) Generally octahedral compound show sp 3 d 2 – hybridization.
orbital formed are known as hybrid oribitals. They have similar
energy. 96. (a) In fifth group hydride bond angle decreases from top to
bottom
65. (b) In SO 3 sulphur is sp 2 hybridized so its shape will be
NH 3  PH3  AsH3  SbH 3  BiH3 .
trigonal planar.
66. (a) These all are triangular with sp 2 hybridization. 97. (b) Generally NH 4 shows sp 3 hybridization.
67. (c) Bond length depends upon bond order and in benzene all 98. (b) We know that single, double and triple bond lengths of carbon
C  C bonds have same bond order. in carbon dioxide are 1.22 Å,1.15 Å and 1.10Å respectively.
68. (b) In C2 H 2 each carbon has sp -hybridization 99. (b) It shows sp 2 –hybridization so it is planar.
H  C  C H 101. (a) Bond angle of hydrides decreases down the group.
sp sp
 Chemical Bonding 139

102. (b) Hybridization of N in NH 3 is sp 3 that of Pt in [PtCl4 ]2 125. (b) There is sp hybridization in C 2 H 2 so it has the linear
2 3 structure.
is dsp that P in PCl5 is sp d and that of B in BCl 3 is
126. (c) In octahedral molecule six hybrid orbitals directed towards the
sp 2 . corner of a regular octahedron with a bond angle of 90°.

103. (d) NH 4 and SO 42  both show sp 3 –hybridization and X

tetrahedral structure. X X
104. (a) It is shows sp 3 d 3 –hybridization. Hence the bond angle is M
about 72 o .
according to thisX geometry, the number
X of X  M  X bond
107. (a) s-character increases with increase in bond angle. at 180° must be three. X
Hybridization s% Angle
127. (d) sp3 d 2 hybrid orbital have octahedral shape
sp 50 180 o
33.3 128. (c) In the formation of d 2 sp3 hybrid orbitals two (n  1)d orbitals
sp 2 120 o
of e.g., set [i.e., (n  1) dz 2 and (n  1)dx 2  y 2 orbitals] one
sp 3 25 109.28 o
ns and three np [ np x , npy and np z ] orbitals combine
sp d 3 1 20 90 o and 120 o 2 3
together and form six d sp hybrid orbitals.
3 3
108. (b) IF7 molecule show sp d –hybridization. 129. (c) The correct order of bond angle (Smallest first) is

110. (a) PCl3 contain three bonding and one lone pair electron. Hence H 2 S  NH 3  SiH4  BF3

shows sp 3 –hybridization. 92.6  107  10928'  120

H N
111. (a) Ammonia and (BF4 )1 shows sp 3 –hybridization. H
H 107°
2
92.6°
112. (b) For square planar geometry hybridization is dsp involving S H H
s, p x , p y and d x 2  orbital.
y2 H
F
113. (b) All carbon atoms of benzene consist of alternate single and
109° 28'
double bond and show sp 2 hybridization. 120°
Si
B
H H
116. (c) BCl 3 molecule show sp 2 –hybridization and planar F F
structure. H

117. (c) BCl 3 Boron trichloride molecule show sp 2 –hybridization and trigonal 130. (a) F –
2–
planar structure. NC CN
118. (b) SO 2 molecule shows sp 2 –hybridization and bent structure. Ni B F

119. (c) Due to multiple bonding in N 2 molecule. F

NC CN F
120. (a) % of s-character in
100 100 Square planar Regular tetrahedral
CH 4   25 , C 2 H 4   33 ,
3
(sp ) 4 2
(sp ) 3
F F F F
100
C2 H 2   50
( sp ) 2 S F Xe
121. (a) Acidic character increases when we come down a group, so HI F F
is the strongest acid. F
122. (c) SO 2 has sp 2 hybridization have the V shape structure See saw shaped Square planar
131. (b)
( 120) due to 2 lone pair of electron over S atom. CO 2 H ··
O
and N 2 O have the sp hybridization.
··

123. (a) In H 2 CO 3 and BF3 central atom are in sp 2 hybridization

but in H 2 CO 3 due to the ionic character of O  H bond it B
will be polar (High electronegativity of oxygen).
H ··
O
sp2 ··
O sp3
H
sp 3
·· ··
124. (a) Due to sp 3 hybridization and presence of lone pair of electron
on p atom PCl3 are of pyramidal shape like that of NH 3 . 132. (b) In the formation of BF3 molecule, one s and 2p orbital
hybridise. Therefore it is sp 2 hybridization.
 140 Chemical Bonding

133. (e) In NCl 3 and H 2 S the central atom of both (N and S) are in I  [ Xe] 5 s 2 ,5 p 5 hence
5s 5p 5d
sp 3 hybridization state
I in ground state
·· ··
N S

··
5s 5p 5d
107° 92.5° I in excited state
Cl H H
Cl Cl
while in BF3 and NCl 3 central atoms are in sp 2 and
and I F7 in excited
sp 3 hybridization respectively. In H 2 S and BeCl 2 central state
F F F I F F F
atom are in sp 3 and sp 2 hybridization In BF3 , NCl 3 & 3 2
IF shows sp d hybridization. So, sp
7
itsd structure is pentagonal 3 3

H 2 S central atom are in sp 2 , sp 3 & sp 3 hybridization bipyramidal.

141. (a) Compound containing highly electronegative element (F, O, N)
and in the central atom are in sp 3 and sp hybridization. attached to an electropositive element (H) show hydrogen
bonding. Fluorine (F) is highly electronegative and has smaller
Cground state  2 s 2 ,2 p x 1 py1 ; Cexcited state  2 s1 ,2 p x py p z
1 1 1
134. (c)
size. So hydrogen fluoride shows the strongest hydrogen
Oground state  2 s 2 ,2 p x p y p z
2 1 1 bonding in the liquid phase.

In the formation of CO 2 molecule, hybridization of orbitals of 142. (b) In the ammonia molecule N atom is sp 3  hybridized but due
carbon occur only to a limited extent involving only one s and one to the presence of one lone pair of e  (i.e. due to greater
p orbitals there is thus sp hybridisation of valence shell orbitals of
the carbon atom resulting in the formation of two sp hybrid L p  b p repulsion) it has distorted tetrahedral (or pyramidal)
orbitals. geometry.
Oxygen atom in
ground state
sp – p N
 bonded p – p
Carbon atom in H H
H
excited state
4 Be  1s ,2 s ,2 p
2 2 0
143. (a)
sp – p p – p
 bonded Be in ground state
Oxygen atom in
ground state 1s 2s 2p
3
135. (d) In NH 3 , N undergoes sp hybridization. Due to the presence Be in excited state
of one lone pair, it is pyramidal in shape.
136. (b) NO 2 SF4 PF6 BeCl2
sp sp 3 d sp 3 d 2
Cl Cl
137. (b) The configuration of 5B  1s 2 , 2 s 2 2 p 1
sp hybridisation
B in ground state (Linear diagonal hybridization)
144. (a) Except CO 3 other choice CO 2 , CS 2 and BeCl 2 have
1s 2s 2p sp  hybridization and shows the linear structure while
B in excited state CO 3 have sp3 hybridization and show the non linear
1s 2s 2p structure because sp3 generate tetrahedral structure.
In BCl3 state
145. (a) dsp3 or sp3 d hybridization exhibit trigonal bipyramidal
1s 2s 2p geometry e.g., PCl 5

Cl Cl Cl
sp2hybridisation Cl Cl
2
138. (d) In SO 3 molecule, S atom remains sp hybrid, hence it has
Cl P sp3d2 (Trigonal bipyramidal)
trigonal planar structure O

Cl Cl
S

O O 146. (b) Carbon has only two unpaired electrons by its configuration
139. (a) In PCl3 molecule, phosphorous is sp 3  hybridised but due but hybridization is a concept by which we can explain its
to presence of lone pair of electron, it has pyramidal structure valency 4.
147. (c) Hybridization is due to overlapping of orbitals of same energy
content.
P
140. (a) The electronic configuration of
Cl Cl Cl
 Chemical Bonding 141

148. (d) MX 3 show the sp 2 hybridization in which 3sp 2 hybridized 9. (b) XeF6 is distorted Octahedral. It has sp 3 d 3 hybridisation
orbital of M bonded by 3 X from  bond and having the with lone pair of electron on Xe, so its shape is distorted.
10. (a)
zero dipole moment. 5s 5p 5d
11. (c) Xe ground state
149. (bcd) SnCl 2 has V–shaped geometry.
Xe double excitation 5s 5p 5d
150. (a) NF3 is predominantly covalent in nature and has pyramidal
structure (the central atom is sp 3 hybridised) with a lone pair
5s 5p 5d
of electrons in the fourth orbital. XeF4
151. (ac) PCl3 , NH 3  Pyramidal. sp 3 d 2 - hybridization
CH 4 , CCl 4  Tetrahedral. 12. (a) CO 2 has bond angle 180 o .
13. (a) As the s-character of hybridized orbitals decreases the bond
152. (a) dsp 3 or sp 3 d : one s  three p  one d (d z 2 ) . angle also decreases
In sp 3 hybridisation: s-character 1/4, bond angle 109 o
Resonance
In sp 2 hybridisation: s-character 1/3, bond angle 120 o
1. (d) Choice (a), (b), (c) are the resonance structures of CO 2 . In sp hybridisation: s-character 1/2, bond angle 180 o
2. (b) In NH 3 nitrogen has one lone pair of electron. 14. (a) XeF2 molecule is Linear because Xe is sp hybridised.

5. (b) In CN ion formal negative charge is on nitrogen atom due 15. (c) SO 42  has 42 electrons; CO 32  has 32 electrons; NO 3 has
to lone pair of electrons. 32 electrons.
 
 16. (c) Molecular oxygen contains unpaired electron so it is
 O H
| paramagnetic (according to MOT).
7. (a) CH 3  C  CH 2 has 9, 1 and 2 lone pairs. 17. (b) Structure of H 2 O is a bent structure due to repulsion of lone
8. (c) In resonance structure there should be the same number of pair of oxygen.
electron pairs.
18. (d) Bond angle between two hybrid orbitals is 105 o it means
9. (b) There are three resonance structure of CO 32  ion.
orbitals are sp 3 hybridised but to lone pair repulsion bond
O O O
angle get changed from 109 o to 105 o . So its % of s-
C C C character is between 22-23%.

O O O O 
O O 22. (d) Number of electrons in ClO2–
(I) (II) (III)
= 7 + 6 + 6 + 1 = 20
11. (abcd) It has all the characteristics.
Number of electrons in ClF2+ = 7+7+7 – 1=20.
23. (b) Central atom having four electron pairs will be of tetrahedral
shape.
VSEPR Theory F ..
F F F F
2. (a) The bond angle in PH 3 would be expected to be close to
24. (d) S. . C Xe
90 o . (The bond angle H  P  H in PH 3 is 93 o ) F F F F F
3. (b) In BF3 molecule Boron is sp 2 hybridised so its all atoms are F F ..
co-planar. 26. (c) It shows sp 2 –hybridization and show trigonal planar
4. (c) Due to lp  lp repulsions, bond angle in H 2 O is lower structure.
(104 o .5 o ) than that in NH 3 (107 o ) and CH 4 (109 o 28 ) . 28. (b) H 2 S show bond angle nearly 90 o .
BeF2 on the other hand, has sp-hybridization and hence has a 31. (a) Bond angle of hydrides is decreases top to bottom in the group.
bond angle of 180 . o NH 3  PH3  AsH3  SbH 3
5. (c) Compound is carbontetrachloride because CCl 4 has sp 3 – 32. (c)
hybridization 4 orbitals giving regular tetrahedron geometry. In N Three bond pair and one lone pair of electron.
others the geometry is little distorted inspite of sp 3
hybridization due to different atoms on the vertices of H H H
tetrahedron.
6. (b) SO 42  ion is tetrahedral since hybridization of S is sp 3 . 33. (c) Unpaired electrons are present in KO 2 while others have
paired electron
7. (b) NH 3 molecule has one lone pair of electrons on the central
atom i.e. Nitrogen. NO 2 = 22 electrons ; BaO2 = 72 electrons
8. (c) C 2 H 2 has linear structure because carbons are sp-hybridised AlO2  30 electrons ; KO 2  35 electrons
o
and lies at 180 . 34. (a) Bond angle decreases from H 2 O to H 2 Te .
 142 Chemical Bonding

35. (c) BF3 does not contain lone pair of electron.

Molecular orbital theory
36. (b) Bent T-shaped geometry in which
both lone pairs occupy the
F No. of bonding e   No. of antibonding e 
.. equatorial position of the trigonal 2. (c) B.O. 
bipyramidal here 2
Br F (l p  l p ) repulsion = 0 8 3 5
   2 .5 .
2 2
.. (lp  b p ) repulsion = 4 and 3. (b) One bonding M.O. and one anti-bonding M.O.
F
(b p  b p ) repulsion =2 4. (b) O 22  is least stable.
37. (b) The overall value of the dipole moment of a polar molecule
depends on its geometry and shape i.e., vectorial addition of 5. (c) B.O. of O 2 is 2, B.O. of O 21 is 1.5, B.O. of O 21 is 2.5 and of
dipole moment of the constituent bonds water has angular
structure with bond angle 105° as it has dipole moment. O 22  is 1.
However BeF2 is a linear molecule since dipole moment 6. (d) Hydride of boron does not exist in BH 3 form. It is stable as its
summation of all the bonds present in the molecule cancel each
dimer di borane (B2 H 6 ) .
other.
10. (c) O 2 (2  8  1  17) has odd number of electrons and hence
it is paramagnetic. All the remaining molecules/ions, i.e.,
O F Be F CN  (6  7  1  14) diamagnetic
38. (d) H BF3 , all of these have same structure i.e.
H3 , BBr3 and
BCl NO(7  8  15) has odd number of electrons and hence it is
2
trigonal planar ( sp hybridization) Hence bond angle is same paramagnetic.
for all of them (i.e., equal to 120°) No. of N b  No. of N a 5
11. (c) B.O.    2 .5 .
39. (d) We know that molecule of ( NH 3 ) has maximum repulsion 2 2
due to lone pair of electron. Its shape is pyramidal and is 12. (b) Bond order of O 2 is highest so its bond length is smallest.
sp3 hybridization. 13. (c) Oxygen is paramagnetic due to the presence of two unpaired
40. (b) :O: .. electron :
H 105° H N O 2   (1s)2   (1s)2  (2 s)2   (2 s)2
H H
107°
 (2 p x )2  (2 p y )2  (2 p x )2   (2 p y )1   (2 p z )1
.. . .H
As 17. (d) In CH 3 CN bond order between C and N is 3 so its bond
P
H H length is minimum.
H H
18. (b)
H
H Less than 107°
As the electronegativity of central atom decreases bond angle is He 2 H2 H 2 H 2
decreases  (1s)    
 NH 3 has largest bond angle. *
 (1s)  
41. (c) In NH 3 , sp 3 -hybridization is present but bond angle is 1 1 1
B.O. 1
106 o 45  because Nitrogen has lone pair of electron according 2 2 2
to VSEPR theory due to bp-lp repulsion bond angle decreases Magnetic
P D P P
from 109 o 45' to 106 o 45  . nature
42. (a) Bond strength decreases as the size of the halogen (P = Paramagnetic, D = Diamagnetic)
increases from F to I.
19. (c) Due to unpaired e  ClO2 is paramagnetic.
43. (b) NH 3 has pyramidal structure, yet nitrogen is sp 3 hybridised.
20. (c) The Bond order in N 2 molecule is 3, N  N Here,
This is due to the presence of lone pair of electron.
3 N b  2  4  2  8 and N a  2
44. (c) SiF4 has symmetrical tetrahedral shape which is due to sp
hybridization of the central sulphur atom in its excited state  B.O.  ( 8  2) / 2  3.
configuration. SF4 has distorted tetrahedral or Sea- Saw 1
21. (d) H 2 has the bond order , it has only one electron so it will
geometry which arise due to sp3 d hybridization of central 2
sulphur atom and due to the presence of lone pair of electron be paramagnetic.
in one of the equatorial hybrid orbital. 22. (c) When bond forms between two atom then their energy get
45. (d) lower than that of separate atoms because bond formation is
an exothermic process.
O 23. (b) Valency of A is 3 while that of B is 2 so according to Criss
O Cross rule the formula of the compound between these two
O
will be A2 B3 .
dsp2 hybridization sp3d hybridization sp3d2 hybridization 24. (c) Due to resonance bond order of C  C bonds in benzene is
(Four 90° angles (Six 90° angle (Twelve 90° angle between 1 and 2.
between bond pair between bond pair between bond pair
and bond pair) and bond pair) and bond pair)
 Chemical Bonding 143
25. (a) Nitrogen does not have vacant ‘d’-orbitals so it can’t have +5 55. (a) H 2 O 2 contain bond angle between two O  H planes about
oxidation state i.e. the reason PCl5 exists but NCl 5 does
90 o .
not. 56. (c) Nitrogen molecule has highest bond energy due to presence of
26. (d) Molecules having unpaired electrons show paramagnetism. triple bond.
27. (b) NO 2 has unpaired electrons so it would be paramagnetic.
57. (c) Cu 2  [ Ar18 ] 3d 9 4 s 0 it has one unpaired electron so it is
30. (c) Helium molecule does not exist as bond order of He 2  0 . paramagnetic.
31. (c) Structure of P4 O10 is 59. (a) CN   14 electrons ; CO =14 electrons
O 1 6
B.O. = [10  4 ]   3 .
P 2 2
1 5
O O 60. (a) B.O. = [10  5]   2 .5 , paramagnetic
2 2
O
P O P
O P
O 61. (a) P P
P
O O
64. (c) The paramagnetic property in oxygen came through unpaired
P
electron which can be explained by molecular orbital theory.
Each phosphorus is attached to 4Ooxygen atoms. Antibonding
N  Na 8  4
33. (c) B.O. of carbon  b  2. 2px*
2 2
N  N a 10  4
34. (a) B.O.  b  3.
2 2
N  Na 8  3 5 2pz* 2py*
37. (b) B.O.  b    2.5 .
2 2 2
38. (a) Electronic configuration of O2 is
O2   (1s)2   (1s)2  (2 s)2   (2 s)2  (2 p x )2  (2 p y )2 Px Py Pz Px Py Pz

 (2 p z )2   (2 p y )1   (2 p z )1
The molecule has two unpaired electrons So, it is paramagnetic
 2 p y has two nodal planes.
*
40. (c)
So 2 unpaired of electron present in  2 p y* and  2 p *z .
42. (a) Element with atomic number 26 is Fe. It is a ferromagnetic.
43. (b) Correct Sequence of bond order is Total number of bonds between atoms
65. (a) Bond order  2Px bonding
O 2  O 2  O 22 Total number of resonating structure
B.O – 2.5 2 1.5 5
44. (a) Due to small bond length.   1 .25
4
45. (a) S 2 have all paired electrons so it is diamagnetic. 66. (c) We know that carbonate ion has following resonating
46. (c) NO has 15 electrons. structures
47. (b) In the conversion of O 2 into O 2 bond order decreases. – O O – O
49. (c) O 22  does not have any unpaired electron so it is diamagnetic. C=O  C–O  – C – O–
– O – O O
50. (a) O 22  consist of four antibonding electron pair [1s and 2s have
two antibonding and 2 p x 2 p y have two antibonding electron Total number of bonds between atoms
Bond order 
pair]. Total number of resonating structure
51. (c) The electron’s distribution in molecular orbitals is 1s 2 , 2 s 1 1 1  2 4
   1 .33 .
2 1 1 3 3
B.O.    0 .5 .
2 2 67. (a) O 2 (15e  )  K : K * ( 2 s)2 ( * 2 s)2 ( 2 p x )2
52. (b) ClO2 has all paired electrons hence it does not show ( 2 p y )2 ( 2 p z )2 ( * 2 p y )1 ( * 2 p z )0
paramagnetism.
1
1 Hence, bond order  (10  5)  2 .5
53. (a) B.O.  [ N b  N a ] 2
2
1 6 1 6 N 2 (13e  )  KK * ( 2 s)2 ( * 2 s)2 ( 2 p x )2
N 2  [10  4 ]   3 ; O 22   [10  4 ]   3 .
2 2 2 2 ( 2 p y )2 ( 2 p z )1
 1 1 5
54. (a) B.O. for N 2 = [ N b  N a ] = [9  4 ]   2 .5 . 1
2 2 2 Hence, bond order  (9  4 )  2 .5 .
2
68. (a) Electronic configuration of O 2 is
 144 Chemical Bonding

O 2  ( 1s)2 ( * 1s)2 ( 2 s)2 ( * 2 s)2 ( * 2 s)2 ( 2 p z )2 So only B 2 exist unpaired electron and show the
paramagnetism.
( 2 p x2   2 p y2 ) ( * 2 p 1x  *
2 p 1y )
 2 py 2  * 2 py1
Hence bond order  N b  N a   [10  6]  2 .
1 1
76. (b) O2   1s 2 ,  * 1s 2 ,  2 s 2 ,  * 2 s 2 ,  2 p x 2
2 2
 2 pz 2  * 2 pz 2
69. (c) Nitrogen form triple bond N  N
In which 6 electron take part. So two unpaired electron found in O 2 at ground stage by
70. (a) As bond order increase bond length decrease the bond order of which it shows paramagnetism.
species are
77. (b) Due to greater electron affinity Cl 2 has the highest bond
number of bonding electron - Number of a.b. electron
 energy.
2 78. (a) Molecular orbital electronic configuration of these species are :
10  6
For O 2  2 ; O2 (17 e  )   1s 2 * 1s 2 ,  2 s 2 * 2 s 2 ,  2 p x 2 ,  2 p y 2 ,
2
10  5  2 p z 2 ,  * 2 p y 2 * 2 p z 1
O 2   2 .5
2
O2 (16 e )   1s 2 * 1s 2 ,  2 s 2 * 2 s 2 ,  2 p x 2 ,  2 p y 2 ,
10  7
O 2   1 .5
2  2 p z 2 * 2 p y 1 * 2 p z 1
So, bond order O 2  O 2  O 2 and bond length are
O22  (18 e )   1s 2 * 1s 2 ,  2 s 2 * 2 s 2 ,  2 p x 2 ,  2 p y 2 ,
O 2  O2  O 2 .
 2 p z 2 * 2 p y 2 * 2 p z 2
 2py 2  * 2py1
Hence number of antibonding electrons are 7,6,and 8
71. (b) O 2 :  1s 2 ,  * 1s 2 ,  2 s 2 ,  * 2 s 2 ,  2 p x 2 respectively.
 2pz 2  * 2pz1
79. (c) Species with unpaired electrons is paramagnetic O 2 has 2
10  6
Bond order   2.0 unpaired electrons, O 2 has one unpaired, O 22  has zero
2
(Two unpaired electrons in antibonding molecular unpaired electrons, O 22  has one unpaired.
orbital)
2  2 py  2 py
2 * 1 80. (a) O 2 has 2 unpaired electron while O 2 and O 2 has one each
O 2 :  1s 2 ,  * 1s 2 ,  2 s 2 ,  * 2 s 2 ,  2 p x  2 *
 2 pz  2 pz unpaired electrons while O 22  does not have any unpaired
0

10  5 electron.
Bond order   2 .5
2 81. (c) H OOH ,O  O  O,O  O
(One unpaired electron in antibonding molecular orbital so it is
O O
paramagnetic)
72. (b) Higher the bond order, shorter will be the bond length, thus O O O O
NO  having the higher bond order that is 3 as compared to
Due to resonance in O 3 O  O bond length will be in b/w
NO having bond order 2 so NO  has shorter bond length.
O  O and O  O .
73. (d) Oxygen molecule (O 2 ) boron molecule (B 2 ) and N 2 ion, all  
of them have unpaired electron, hence they all are 82. (a) From valency bond theory, bond order in CO, i.e. : C  O : is
paramagnetic.
3, that of O  C  O is 2 while that of CO 32  ion is 1.33.
 
74. (c) Bond order of NO , NO and NO are 3, 2 .5 and 2 Since the bond length increases as the bond order decreases,
respectively, bond energy  bond order
i.e. CO  CO 2  CO 32  .
75. (a) Paramagnetic property arise through unpaired electron. B 2
molecule have the unpaired electron so it show paramagnetism. 83. (c) N 2 : KK (2 s)2  * (2 s)2  (2 p x )2  (2 py )2  (2 p z )2

B2   1s 2 * 1s 2 ,  2 s 2 * 2 s 2 ,  2 p x 1   2 p y 1 (diamagnetic)
(2 unpaired electron) C2 : KK (2 s)  * (2 s)  (2 p x )  (2 py )
2 2 2 2
(diamagnetic)
C 2   1s  1s ,  2 s  2 s ,  2 p x . 2 p y
2 * 2 2 * 2 2 2
N 2 : KK (2 s)2  * (2 s)2  (2 p x )2  (2 py )2  (2 p z )2
(No unpaired electron)
(paramagnetic)
N 2   1s 2 * 1s 2 ,  2 s 2 * 2 s 2 ,  2 p x 2 ,  2 p y 2 2 p z 2
(No unpaired electron) O22  : KK (2 s)  * (2 s)  (2 p z )  (2 p x )  (2 py )2
2 2 2 2

F2  s 2 ,  *1s 2 ,  2 s 2 ,  * 2 s 2 ,  2 p x 2 ,  2 p y 2 ,  2 p z 2 ,  * (2 p x )2  * (2 py )2 (diamagnetic)
(No unpaired electron)
84. (d) NH 3  107, PH3  93, H 2O  104.5
 * 2 py 2 , * 2 pz 2 H 2 Se  91, H 2 S  92.5
 Chemical Bonding 145

Hydrogen bonding 47. (d) C 2 H 5 OH will dissolve in water because it forms hydrogen
bond with water molecule.
1. (d) Hydrogen bonding will be maximum in F-H bond due to 48. (b) In ice cube all molecules are held by inter molecular hydrogen
greater electronegativity difference. bond.
2. (b) Ice has hydrogen bonding. 49. (d) Hydrogen bonding is developed due to inter atomic attraction
3. (b) H – F has highest boiling point because it has hydrogen so it is the weakest.
bonding.
6. (d) CO 2 is sp-hybridised Types of bonding and Forces in solid
7. (b) sp-hybridization gives two orbitals at 180 o with Linear 1. (b) In electrovalent crystal has cation and anion are attached by
structure. electrostatic forces.
8. (d) Hydrogen bonding increases the boiling point of compound. 2. (d) Mercury has very weak interatomic forces so it remains in
9. (c) o-Nitrophenol has intramolecular hydrogen bonding but p- liquid state.
Nitrophenol has intermolecular hydrogen bonding so boiling 3. (c) The melting and boiling points of argon is low hence, in solid
point of p-Nitrophenol is more than o-Nitrophenol. argon atoms are held together by weak Vander Waal’s forces.
10. (c) The strongest hydrogen bond is in hydrogen fluoride because 4. (c) NaF is the strongest ionic crystal so its melting point would be
the power of hydrogen bond  electronegativity of atom and highest.
1 9. (b) Diamond is the hardest substance it’s melting point would be
electronegativity  highest.
atomic size
10. (c) Bond is formed by attractive and repulsive forces of both the
So fluorine has maximum electronegativity and minimum
atoms.
atomic size.
12. (a) Generally zero group elements are linked by the Vander Waal’s
11. (d) H 2 O can form hydrogen bonds rest CH 4 and CHCl 3 are force. Hence these show weakest intermolecular forces.
organic compound having no oxygen while NaCl has itself 13. (d) Glycerol has a three OH group hence it is viscous in nature.
intraionic attraction in the molecule. 14. (c) Vander waal's forces is the weakest force of attraction.
12. (b) PH 3 has the lowest boiling point because it does not form 16. (b) NH 4 contain all three types of bond in its structure
Hydrogen bond.

14. (b) Hydrogen bonding increases heat of vaporisation.  H 
15. (d) Only NH 3 forms H-bonds.  | 
 H  N  H 
22. (a) Water molecule has hydrogen bonding so molecules get  |

dissociated so it is liquid.  H 
23. (d) In case of water, five water molecules are attached together 17. (d) In NaOH covalent bond is present in O  H bond while
through four hydrogen bonding. ionic bond is formed between OH  and Na  .
25. (c) Hydrogen bond is strongest in hydrogen fluoride. 18. (a) Bond formation is an exothermic reaction so there is decrease
28. (c) Boiling point of H 2 O is more than that of H 2 S because in energy of product.
22. (d) Blue vitriol is CuSO 4 . 5 H 2 O and it has all types of bonds.
H 2 O forms hydrogen bonding while H 2 S does not.

 H 
30. (c)  Interamolecular H-bonding.  | 
O H 23. (a)  H  N  H  Cl 
  |

C O
 H 
31. (a) HydrogenHbond is formed when hydrogen is attached with the
atom which is highly electronegative and having small radius. Ionic bond = 1, Covalent bond = 3
34. (a) Water is dense than ice because of hydrogen bonding Co-ordinate bond = 1.
interaction and structure of ice.
35. (a) Ethanol have hydrogen bonding so its boiling point is higher Critical Thinking Questions
than its isomer dimethyl ether.
1. (d) We know that ionic characters
36. (a) A compound having maximum electronegative element will
form strong Hydrogen bond.  16 [EA  EB ]  3.5  [EA  EB ]2
37. (a) Due to electronegativity difference of N 2 and H 2 , NH 3 or ionic characters = 72.24%
form hydrogen bond. 3. (c) Configuration of O 2 molecule is
38. (b) Intermolecular hydrogen bonding compound contain more b.p.
compare to intramolecular hydrogen bonding compound. [ (1s)2   (1s)2  (2 s)2  * (2 s)2  (2 p x )2  (2 p y )2
39. (d) Water molecule contain hydrogen bonding.
 (2 p z )2   (2 p x )1   (2 p y )1 ]
40. (c) It contain intermolecular hydrogen bonding.
41. (b) Ethyl alcohol has a intermolecular hydrogen bond. No. of pair are 7 so total no. of paired electrons are 14.
43. (b) HCl contain weak covalent bond.  
45. (c) Due to intermolecular hydrogen bonding water molecules come 6. (a) H  O :  H  H  O  H
| |
close to each other and exist in liquid state.
H H
46. (b) Due to greater resonance stabilization.
7. (b) The correct order of increasing dipole moment is
 146 Chemical Bonding
p-dichlorobenzene < Toluene < m-dichlorobenzene < o- 27. (c) CuSO 4 .5 H 2 O has electrovalent, covalent and coordinate
dichlorobenzene.
bonds.
8. (a) The dipole moment of CH 4  0 D,
 O 
NF3  0.2 D, NH 3  1.47 D and H 2 O  1.85 D . 2
    

Therefore the correct order of the dipole moment is

Cu O  S  O . 5 H 2O .

 
CH 4  NF3  NH 3  H 2O .  O 
10. (d) Ammonia molecule is more basic than nitrogen trifluoride and
Boron trifluoride because ammonia molecule easily gives lone Assertion & Reason
pair of electron.
1. (a) Solubility in water depends on hydration energy and lattice
11. (a) Chlorine atom in ClO2 is sp 3 hybridised but its shape is energy.
angular. 2. (a) Polarity in covalent bond developed due to shifting of electrons
 towards one of the bonded atoms.
12. (c) [ NF3 and H 3 O ] are pyramidal while [ NO 3 and BF3 ]
are planar. Hence answer (c) is correct. 5. (c) SiF4 have sp 3 hybridization & shape of regular tetrahedral
13. (d) CH 2  CH  CH 2  CH 2  C  CH where the bond angle of
F
sp 2 sp 3 F  S  F are found
hybridised
109.5 o which is
  109.5o
14. (d) B.O. in CO i.e., : C  O : is 3, that of O  C  O is 2 while greater than 90 o
but
that of CO 32  ion is 1.33. Since the bond length increases as less than 180 o . S
Repulsion sequence are F
the bond order decreases i.e. CO  CO 2  CO 32 . Thus
Lp  Lp  Lp  Bp  Bp  Bp F
option (d) is correct. F
so assertion are true
15. (b) Dichromate dianion has following structure
but the reason are false.
2
 O O  9. (c) N 2 molecule is diamagnetic. The diamagnetic character is due
   
O  Cr  O  Cr  O  to the presence of paired electron N 2 molecule does not
 
  contain any unpaired electron. Thus, assertion is coorect but
 O O  the reason is false.
6, Cr  O bonds are equivalent. 10. (a) It is correct that during formation of Ice from water there are
17. (b) ClF3 is a [ AB 3 ] type of molecule because it consist of three vacant spaces between hydrogen bonded molecules of Ice. Ice
has a cage like structure. Due to this reason Ice is less dense
bonding pair and two lone pair of electrons hence this than liquid water. hence both assertion & reason are true &
compound shows sp 3 d hybridization. reason are the correct explanation of assertion.
11. (b) Water is liquid while H 2 S is gas because oxygen is of small
20. (a) BeF3 does not show sp 3 –hybridization because this
size & more electronegative in comparision to sulphur. Hence
compound is not formed. water molecules exist as associated molecules to form liquid
21. (a) K 3 [Fe(CN )6 ] state due to hydrogen bonding H 2 S does not have hydrogen
Fe26  4 s 2 3d 6 bonding & can’t associated hence it is gas.
12. (d) Iodine is more soluble in CCl 4 than in H 2 O because iodine
Fe 3   3d 5 4 s 0
is non polar & thus it dissolve in CCl 4 because like dissolves
like.
=
13. (a) o & p -nitrophenols can be separated by steam distillation
      because o -nitrophenol is steam volatile. Here, both assertion &
reason are correct & reason is correct explanation of assertion.
14. (e) Fluorine is highly reactive F  F bond has low bond
Unpaired electron d 2sp 3 –hybridization dissociation energy. Here assertion is false but reason is true.

22. (d) N 2 has one unpaired electron so it would be paramagnetic. 15. (c) It is true that sigma ( ) bond is stronger than pi ( ) bond but
23. (a) Each of the species has 14 electron so isoelectronic and shows the reason that there is free rotation of atoms is false.
bond order 3. 16. (c) Energy is released in the formation of the crystal lattice. It is
1 1 6 qualitative measure of the stability of an ionic compound so
B.O.  [ N b  N a ]  [10  4 ]   3 . assertion is true & reason are false.
2 2 2
17. (c) Li, Na & K are alkali metals & not alkaline earth metal so,
24. (d) O O
O size of alkali metal increases So. Assertion is true & reason are
S S
false.
O O 18. (b) Hess’s law states that the enthalpy of a reaction is the same,
O whether it takes place in a single step or in more than one
O S O step. In born haber cycle the formation of an cycle ionic
compound may occur either by direct combination of the
Trimer of SO 3 . O element or by a stepwise process involving vaporization of
elements, conversion of the gaseous atoms into ions & the
combination of the gaseous ions to form the ionic solid.
 Chemical Bonding 147
19. (a) With increase in bond order, bond length decreases & hence bond
energy increases so both assertion & reason are true & reason are
the correct explanation of assertion.
20. (c) Electron affinity is experimentally measurable while
electronegativity is a relative number so assertion is true but
reason are false.
21. (b) Assertion & reason both are correct but reason is not the
correct explanation of assertion sulphur has five electrons pairs
whose arrangement should be trigonal bipyramidal according
to VSEPR theory. Two structure are possible
F
.. F | F
FS F :S
F | F
F
(a) (b)
Lone pair in the axial Lone pair in the equatorial
position (three l.p – b.p position (two L.p – b.p
repulsion at 90o) repulsion)
22. (e) BF3 has zero dipole moment because of its structure.
F
F  B    0
F
H 2 S has two lone pairs on sulphur atom & hence. It has
irregular shape.
Thus it possess dipole moment. So assertion is false but reason
are true.
23. (d) Both assertion & reason are false because pairs of electron will
have different spins. Electrons are equally shared between
them.
24. (d) In B2, total number of electrons = 10
B  (1s) *(1s ) (2s) *(2s) (2p ) (2p )
2
2 2 2 2

x
1

y
1

Presence of unpaired electron shows the paramagnetic nature.

The highest occupied molecular orbital is of -type.
25. (a) Both assertion & reason are true & reason is the correct
explanation of the assertion because. At any given instant, at
room temperature each water molecules forms hydrogen bonds
with other water molecules. The H 2 O molecules are in
continuous motion. So hydrogen bonds are constantly & rapidly
broken & formed. In Ice H 2 O molecules are however fixed in
the space lattice.
26. (a) Both assertion & reason are true & reason is the correct
explanation of assertion, because helium molecule is formed by
linking two helium atoms. both have 1s orbitals. These will
combine to form two molecular orbitals  ( 1s ) &  * ( 1s )
four available electrons are accommodated as  (1s)2 &
 * (1s)2 .
 Chemical Bonding 149

NH 4 
1. Nature of the bond formed between two elements depends on the
(c) H3O (d)
(a) Oxidation potential (b) Electronegativity
(c) Ionization potential (d) Electron affinity 12. The dipole moment of chlorobenzene is 1.73 D. The dipole moment
of p -dichlorobenzene is expected to be
2. Two elements X and Y have following electronic configurations
[CPMT 1991]
X  1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 , 4 s 2 and (a) 3.46 D (b) 0.00 D
Y  1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 5 . The expected compound formed by (c) 1.73 D (d) 1.00 D
13. Polarization of electrons in acrolein may be written as
combination of X and Y is [BHU 1990]
[IIT 1988]
(a) XY 2 (b) X 5Y2    
(c) X 2 Y5 (d) XY 5 (a) C H 2  CH  C H  O (b) C H 2  CH  CH  O

3. Electricity do not pass through ionic compounds    

(c) C H 2  C H  CH  O (d) C H 2  CH  CH  O
(a) In solution (b) In solid state
(c) In melted state (d) None of these 14. The order of dipole moments of the following molecules is
[Roorkee 2000]
4. From the following which compound on heating readily sublimes
(a) CHCl 3  CH 2 Cl 2  CH 3 Cl  CCl 4
(a) NaCl (b) MgCl2
(b) CH 2 Cl 2  CH 3 Cl  CHCl 3  CCl 4
(c) BaCl2 (d) AlCl3
(c) CH 3 Cl  CH 2 Cl 2  CHCl 3  CCl 4
5. Which one in the following contains ionic as well as covalent bond [IIT 1979; CPMT 1983; DPMT 1983]
(a) CH (b) H (d) CH 2 Cl 2  CHCl 3  CH 3 Cl  CCl 4
4 2

(c) KCN (d) KCl 15. The electronegativity of C, H , O, N and S are 2.5, 2.1, 3.5, 3.0
6. The solution of sugar in water contains and 2.5 respectively. Which of the following bond is most polar
[NCERT 1972; MP PET 2000] (a) O  H (b) S  H
(a) Free atoms (c) N  H (d) C  H
(b) Free molecules 16. Which of the following bond has the most polar character
(c) Free ions [DPMT 1982; CBSE PMT 1992; CPMT 1999]
(d) Free atoms and free molecules (a) C O (b) C  Br
7. In which of the following reactions, there is no change in the valency (c) CS (d) C  F
[NCERT 1974; CPMT 1971, 78]
17. The geometry of H 2 S and its dipole moment are [IIT 1999]
(a) 4 KClO3  3 KClO4  KCl
(a) Angular and non-zero (b) Angular and zero
(b) SO 2  2 H 2 S  2 H 2 O  3 S (c) Linear and non-zero (d) Linear and zero
(c) BaO2  H 2 SO 4  BaSO 4  H 2 O 2 18. How many  and  bonds are there in the molecule of
tetracyanoethylene
(d) 2 BaO  O 2  2 BaO2
N C CN
8. The octet rule is not followed in [BHU 1981] CC
N C CN
(a) F2 (b) NaF [NCERT 1980; MP PMT 1986, 95;Orissa JEE 1997]
(c) CaF2 (d) BF3 (a) Nine  and nine  (b) Five  and nine 
9. Sodium chloride is an ionic compound whereas hydrogen chloride is (c) Nine  and seven  (d) Five  and eight 
a gas because [KCET 2002] 
19. The shape of H 3 O ion is [EAMCET 1993; CPMT 2001]
(a) Sodium is reactive
(b) Covalent bond is weaker than ionic bond (a) Linear (b) Angular
(c) Hydrogen chloride is a gas (c) Trigonal planar (d) Triangular pyramidal
(d) Covalent bond is stronger than ionic bond 20. The hybridization in sulphur dioxide is[IIT 1986; DPMT 1990]
10. Which one of the following molecules has a coordinate bond (a) sp[CPMT 1988, 94] (b) sp 3
(a) NH 4 Cl (b) AlCl3
(c) sp 2 (d) dsp 2
(c) NaCl (d) Cl 2 21. The number and type of bonds between two carbon atoms in
11. Co-ordinate bond is absent in [RPMT 2002] CaC 2 are [IIT 1996]
(a) BH 4 (b) CO 32 (a) One sigma ( ) and one pi ( ) bonds
 150 Chemical Bonding
(b) One sigma ( ) and two pi ( ) bonds (a) 3 (b) 2
(c) 1 (d) 1/2
(c) One sigma ( ) and one and a half pi ( ) bonds
(d) One sigma ( ) bond 28. In the process, O 2  O 22  e the electron lost is from
[Orissa JEE 2002]
22. Which of the following resonating structures of N 2 O is the most
(a) Bonding -orbital (b) Antibonding -orbital
contributing [Roorkee Qualifying 1998]
(a) N  N  O (b) N  N  O (c) 2 p z orbital (d) 2 p x orbital
(c) N  N O (d) NN O 29. The maximum number of hydrogen bonds formed by a water
molecule in ice is
23. The hybridization of atomic orbitals of nitrogen in NO 2 , NO 3 , [MP PET 1993; AFMC 2002;UPSEAT 1999, 2001, 02]
and NH 4 are [IIT Screening 2000] (a) 4 (b) 3
(c) 2 (d) 1
(a) sp, sp 3 and sp 2 respectively
30. Hydrogen bonding is not present in
2 3 [AIIMS 1998; MP PET/PMT 1998]
(b) sp, sp and sp respectively
(a) Glycerine
(c) sp 2 , sp and sp 3 respectively (b) Water
(d) sp 2 , sp 3 and sp respectively (c) Hydrogen sulphide
24. The molecule having one unpaired electron is (d) Hydrogen fluoride
[IIT 1985; MP PMT 1989] 31. The bonds in K 4 [Fe (CN )6 ] are [EAMCET 1991]
(a) NO (b) CO (a) All ionic
(c) CN  (d) O 2 (b) All covalent
(c) Ionic and covalent
25. The geometry of ClO3 , according to valence shell electron pair
(d) Ionic, covalent and coordinate covalent
repulsion (VSEPR) theory will be
32. In which of the following ionic, covalent and coordinate bonds are
[KCET 1996; MP PET 1997]
present [UPSEAT 2002]
(a) Planar triangle (b) Pyramidal
(a) Water
(c) Tetrahedral (d) Square planar
(b) Ammonia
26. Which of the following halogens has the highest bond energy [CPMT 1988]
(c) Sodium cyanide
(a) F2 (b) Cl 2
(d) Potassium bromide
(c) Br2 (d) I2

27. What bond order does O 22  have [Pb. PMT 2001]

(SET -3)
1. (b) If the two elements have similar electronegativities,the bond 3. (b) Ionic compounds can’t pass electricity in solid state because
between them will be covalent, while a large difference in they don’t have mobile ion in solid state.
electronegativities leads to an ionic bond. 4. (d) AlCl3 sublimes readily on heating.
2. (a) From electronic configuration valencies of X and Y are + 2 and
..
–1 respectively so formula of compound is XY 2 . 5. (c) Structure of KCN is [K  (C   N )] .
 Chemical Bonding 151
6. (b) Sugar is an organic compound which is covalently bonded so in 27. (c) O 22  have bond order one
water it remains as free molecules.
2 6 2 6 1 2
B.O.  [10  8 ]   1 .
7. (c) In the reaction BaO2  H 2 SO 4  BaSO 4  H 2 O valency 2 2
is not changing. 28. (b) Electron lost from antibonding  orbital.
8. (d) BF3 does not have octet, it has only six electrons so it is 29. (a) In ice each water molecule forms four hydrogen bond through
which each water molecule is tetrahedrally attached with other
electron deficient compound.
water molecule.
9. (b) NaCl is a ionic compound because it consists of more
elelctronegativity difference compare to HCl. H
10. (a) NH 4 Cl has a coordinate bond besides covalent and ionic O
 H H H
 H 
 |  O O
bonds  H  N  H  Cl 
 |
 H H H H
 H 
O O
O
| H H H H
11. (b)  O  C  O has covalent bonds only.
12. (b) Due to symmetry dipole moment of p-dichloro benzene is zero. O O
13. (d) H H H H
14. (d) CCl 4 has zero dipole moment because of symmetric O O
tetrahedral structure. CH 3 Cl has slightly higher dipole 30. (c) Hydrogen bonding H which have F, O, or
H is present in molecules
moment which is equal to 1.86D. Now CH 3 Cl has less N atoms.
31. (d) Structure of K 4 [Fe(CN )6 ] is
electronegativity then CH 2 Cl 2 . But CH 2 Cl 2 has greater
4
dipole moment than CHCl 3 .  
 CN 
15. (a) More the difference in electronegativity of atoms. Bond C  N 
between them will be more polar.  C  N 
4K  Fe 
16. (d) C  F bond has the most polar character due to difference of
 
their electronegativity.  C  N C  N 
CN
17. (a) H 2 S has angular geometry and have some value of dipole  
moment. 32. (c) Sodium cyanide contain ionic, covalent and coordinate bond.

N   C C 

N
 

18. (a) C 

C

  
N 

C C 

N

9 and 9 bonds.
19. (d) H 3 O  has sp 3 hybridization and its shape is triangular
pyramidal due to lone pair on oxygen.
20. (c) SO 2 molecule has sp 2 hybridisation.
C
***
21. (b) In Ca two carbons are joined with 1 and 2 bonds.
C
22. (a) In N 2 O molecule N  N  O structure is most contributed.
23. (b) The shape of NO 2 , NO 3 and NH 4 are linear trigonal
planar and tetrahedral respectively. Thus the hybridization of
atomic orbitals of nitrogen in these species are sp, sp 2 and
sp 3 respectively.
24. (a) NO has one unpaired electron with Nitrogen.
..
: N :: O :
. ..
..

25. (b) O  Cl  O
|
O
26. (b) Bond energy of Cl 2 is highest among all halogen molecule.
Bond energies of F2 , Cl2 , Br2 , I2 are 37, 58, 46 and 36 Kcal
mol 1 respectively.
 152 Solution and Colligative properties

Chapter

4
Solution & Colligative properties

“A solution is a mixture in which substances are intermixed so (1) Percentage : It refers to the amount of the solute per 100 parts of
intimately that they can not be observed as separate components”. The the solution. It can also be called as parts per hundred (pph). It can be
dispersed phase or the substance which is to be dissolved is called solute, expressed by any of following four methods,
while the dispersion medium in which the solute is dispersed to get a (i) Weight to weight percent
homogenous mixture is called the solvent. Wt. of solute
% w/w   100
Solubility Wt. of solution
“Solubility of a substance may be defined as the amount of solute Example : 10% Na 2 CO 3 solution w/w means 10 g of Na 2 CO 3
dissolved in 100gms of a solvent to form a saturated solution at a given is dissolved in 100 g of the solution. (It means 10 g Na 2 CO 3 is
temperature”. A saturated solution is a solution which contains at a given
dissolved in 90 g of H 2 O )
temperature as much solute as it can hold in presence of dissolveding
solvent. Any solution may contain less solute than would be necessary to (ii) Weight to volume percent
saturate it. Such a solution is known as unsaturated solution. When the Wt. of solute
solution contains more solute than would be necessary to saturate it then it % w/v   100
Volume of solution
is termed as supersaturated solution.
Example : 10% Na 2 CO 3 (w/v) means 10 g Na 2 CO 3 is
Kinds of solutions
dissolved in 100 cc of solution.
All the three states of matter (gas, liquid or solid) may behave either
(iii) Volume to volume percent
as solvent or solute. Depending on the state of solute or solvent, mainly
there may be following nine types of binary solutions. Vol. of solute
% v/v   100
Solvent Solute Example Vol. of solution
Gas Gas Mixture of gases, air. Example : 10% ethanol (v/v) means 10 cc of ethanol dissolved in
Gas Liquid Water vapours in air, mist.
100 cc of solution.
Gas Solid Sublimation of a solid into a gas, smoke.
Liquid Gas CO2 gas dissolved in water (aerated drinks). (iv) Volume to weight percent
Liquid Liquid Mixture of miscible liquids, e.g., alcohol in water. Vol. of solute
Liquid Solid Salt in water, sugar in water. % v/w   100
Wt. of solution
Solid Gas Adsorption of gases over metals; hydrogen over
palladium. Example : 10% ethanol (v/w) means 10 cc of ethanol dissolved in
Solid Liquid Mercury in zinc, mercury in gold, CuSO4.5H2O. 100 g of solution.
Solid Solid Homogeneous mixture of two or more metals
(alloys), e.g., copper in gold, zinc in copper. (2) Parts per million (ppm) and parts per billion (ppb) : When a
Among these solutions the most significant type of solutions are solute is present in trace quantities, it is convenient to express the
those which are in liquid phase and may be categorised as, (1) Solid in concentration in parts per million and parts per billion. It is the number of
liquid solutions, (2) Liquid in liquid solutions and (3) Gas in liquid parts of solute per million (10 6 ) or per billion (10 9 ) parts of the
solutions. solution. It is independent of the temperature.
Methods of expressing concentration of solution mass of solutecomponent
ppm   10 6
Concentration of solution is the amount of solute dissolved in a Total mass of solution
known amount of the solvent or solution. The concentration of solution can
be expressed in various ways as discussed below,
 Solution and Colligative properties 153

mass of solutecomponent (xi) If W g of an acid is completely neutralised by V ml of base of

ppb   10 9
Total mass of solution normality N
(3) Strength : The strength of solution is defined as the amount of Wt. of acid VN

solute in grams present in one litre (or dm 3 ) of the solution. It is g eq. wt. of acid 1000
expressed in g/litre or (g / dm 3 ) . Wt. of base Vol. of acid  N of acid
Similarly, 
Mass of solutein grams g eq. wt. of base 1000
Strength 
Volume of solutionin litres (xii) When Va ml of acid of normality N a is mixed with Vb ml
(4) Normality (N) : It is defined as the number of gram equivalents of base of normality N b
(equivalent weight in grams) of a solute present per litre of the solution.
Unit of normality is gram equivalents litre . Normality changes with
–1
(a) If Va N a  Vb N b (Solution neutral)
temperature since it involves volume. When a solution is diluted x times, (b) If Va N a  Vb N b (Solution is acidic)
its normality also decreases by x times. Solutions in term of normality
generally expressed as, (c) If Vb N b  Va N a (Solution is basic)

N  Normal solution; 5 N  Penta normal, Va N a  Vb N b

(xiii) Normality of the acidic mixture 
(Va  Vb )
10 N  Deca normal; N / 2  semi normal
Vb N b  Va N a
N / 10  Deci normal; N / 5  Penti normal (xiv) Normality of the basic mixture 
(Va  Vb )
N / 100 or 0.01 N  centinormal,
No. of meq * of solute
(xv) N 
N / 1000 or 0.001= millinormal Vol. of solutionin ml
Mathematically normality can be calculated by following formulas, (* 1 equivalent = 1000 milliequivalent or meq.)
(5) Molarity (M) : Molarity of a solution is the number of moles of
Number of g.eq. of solute the solute per litre of solution (or number of millimoles per ml. of solution).
(i) Normality ( N ) 
Volume of solution(l) Unit of molarity is mol/litre or mol/dm For example, a molar (1 M ) solution
3

Weight of solutein g. of sugar means a solution containing 1 mole of sugar (i.e., 342 g or
(ii) N  6.02  10 23 molecules of it) per litre of the solution. Solutions in term of
g. eq. weight of solute Volume of solution(l)
molarity generally expressed as,
Wt. of soluteper litreof solution 1 M = Molar solution, 2 M = Molarity is two,
(iii) N 
g eq. wt. of solute M
or 0.5 M = Semimolar solution,
Wt. of solute 1000 2
(iv) N  
g.eq. wt. of solute Vol. of solutionin ml M
or 0.1 M = Decimolar solution,
10
Percent of solute 10
(v) N  , M
g eq. wt. of solute or 0.01 M = Centimolar solution
100
Strength in g l -1 of solution M
(vi) N  or 0.001 M = Millimolar solution
g eq. wt. of solute 1000
Wt%  density  10  Molarity is most common way of representing the concentration
(vii) N  of solution.
Eq. wt.
1
(viii) If volume V1 and normality N 1 is so changed that new  Molarity is depend on temperature as, M 
T
normality and volume N 2 and V2 then,  When a solution is diluted (x times), its molarity also decreases
N 1 V1  N 2 V2 (Normality equation) (by x times)
Mathematically molarity can be calculated by following formulas,
(ix) When two solutions of the same solute are mixed then normality
No. of moles of solute( n)
of mixture (N ) is (i) M  ,
Vol. of solutionin litres
N 1 V1  N 2 V2
N Wt. of solute(in gm) per litreof solution
V1  V2 (ii) M 
Mol.wt. of solute
(x) Vol. of water to be added i.e., (V2  V1 ) to get a solution of
Wt. of solute(in gm) 1000
normality N 2 from V1 ml of normality N 1 (iii) M  
Mol.wt. of solute Vol. of solutionin ml.
 N  N2  No. of millimoles of solute
V2  V1   1  V1
 (iv) M 
 N2  Vol. of solutionin ml
Percent of solute 10
(v) M 
Mol.wt. of solute
 154 Solution and Colligative properties

Strength in gl-1 of solution 10  solubility

(vi) M  (vi) m 
Mol.wt. of solute Mol.wt. of solute
10  Sp. gr. of the solution Wt.% of the solute 1000  wt.% of solute(x )
(vii) M  (vii) m 
Mol.wt. of the solute (100  x )  mol. wt. of solute
(viii) If molarity and volume of solution are changed from M 1 , V1
1000  Molarity
(viii) m 
to M 2 , V2 . Then, (1000  sp. gravity) (Molarity Mol.wt. of solute)
M 1 V1  M 2 V2 (Molarity equation) Relation between molarity (M) and molality (m)
(ix) In balanced chemical equation, if n 1 moles of reactant one Molarity
Molality (m) =
react with n 2 moles of reactant two. Then, Molarity molecular mass
Density 
M 1 V1 M V 1000
 2 2
n1 n2 Molality density
Molarity (M) 
Molality molecular mass
(x) If two solutions of the same solute are mixed then molarity (M) 1
of resulting solution. 1000
M 1 V1  M 2 V2 (7) Formality (F) : Formality of a solution may be defined as the
M number of gram formula masses of the ionic solute dissolved per litre of the
(V1  V2 )
solution. It is represented by F . Commonly, the term formality is used to
(xi) Volume of water added to get a solution of molarity M 2 from express the concentration of the ionic solids which do not exist as molecules
V1 ml of molarity M 1 is but exist as network of ions. A solution containing one gram formula mass
of solute per litre of the solution has formality equal to one and is called
 M  M2  formal solution. It may be mentioned here that the formality of a solution
V2  V1   1  V1
 changes with change in temperature.
 M2 
Relation between molarity and normality Number of gram formula masses of solute
Formality (F)=
Molecular mass Volume of solutionin litres
Normality of solution = molarity 
Equivalent mass Mass of ionic solute(g)
=
Normality  equivalent mass = molarity  molecular mass (gm. formula mass of solute) (Volume of solution(l))
Molecular mass W B (g) WB (g)  1000
For an acid, = Basicity Thus, F  or
Equivalent mass GFM  V (l) GFM  V (ml )
So, Normality of acid = molarity  basicity. (8) Mole fraction (X) : Mole fraction may be defined as the ratio of
Molecular mass number of moles of one component to the total number of moles of all the
For a base, = Acidity components (solvent and solute) present in the solution. It is denoted by
Equivalent mass
the letter X . It may be noted that the mole fraction is independent of the
So, Normality of base = Molarity  Acidity. temperature. Mole fraction is dimensionless. Let us suppose that a solution
(6) Molality (m) : It is the number of moles or gram molecules of contains the components A and B and suppose that W A g of A and
the solute per 1000 g of the solvent. Unit of molality is mol / kg . For WB g of B are present in it.
example, a 0 .2 molal (0.2m ) solution of glucose means a solution
WA
obtained by dissolving 0.2 mole of glucose in 1000 gm of water. Molality Number of moles of A is given by, n A  and
MA
(m) does not depend on temperature since it involves measurement of
weight of liquids. Molal solutions are less concentrated than molar solution. WB
the number of moles of B is given by, n B 
Mathematically molality can be calculated by following formulas, MB
where M A and M B are molecular masses of A and B
Number of moles of the solute
(i) m   1000 respectively.
Weight of the solvent in grams
Total number of moles of A and B  n A  n B
Strength per 1000 grams of solvent nA
(ii) m  Mole fraction of A , X A 
Molecular mass of solute n A  nB
No. of gm moles of solute nB
(iii) m  Mole fraction of B , X B 
Wt. of solvent in kg n A  nB
The sum of mole fractions of all the components in the solution is
Wt. of solute 1000 always one.
(iv) m  
Mol.wt. of solute Wt. of solvent in g nA nB
XA  XB   1.
n A  nB n A  nB
No. of millimoles of solute
(v) m  Thus, if we know the mole fraction of one component of a binary
Wt. of solvent in g solution, the mole fraction of the other can be calculated.
 Solution and Colligative properties 155
Relation between molality of solution (m) and mole fraction of the (3) Purity of liquid : Pure liquid always has a vapour pressure
solute (X ).
A
greater than its solution.
m Raoult’s law : When a non-volatile substance is dissolved in a
XA 
55.5  m liquid, the vapour pressure of the liquid (solvent) is lowered. According
(9) Mass fraction : Mass fraction of a component in a solution is the to Raoult’s law (1887), at any given temperature the partial vapour
mass of that component divided by the total mass of the solution. For a pressure (p ) of any component of a solution is equal to its mole
A

solution containing w A gm of A and w B gm of B fraction (X ) multiplied by the vapour pressure of this component in the
A

wA wB pure state ( p 0A ) . That is, p A  p 0A  X A

Mass fraction of A  ; Mas fraction of B 
w A  wB w A  wB The vapour pressure of the solution (Ptotal) is the sum of the
It may be noted that molality, mole fraction, mass fraction etc. are partial pressures of the components, i.e., for the solution of two volatile
preferred to molarity, normality, etc. because the former involve the weights liquids with vapour pressures p A and p B .
of the solute and solvent where as later involve volumes of solutions.
Temperature has no effect on weights but it has significant effect on
Ptotal  p A  p B  (p 0A  X A )  (p B0  X B )
volumes.
(10) Demal unit (D) : The concentrations are also expressed in Alternatively, Raoult’s law may be stated as “the relative lowering of
“Demal unit”. One demal unit represents one mole of solute present in one vapour pressure of a solution containing a non-volatile solute is equal to the
litre of solution at 0 o C . mole fraction of the solute in the solution.”
Colligative properties Relative lowering of vapour pressure is defined as the ratio of
lowering of vapour pressure to the vapour pressure of the pure solvent. It is
Certain properties of dilute solutions containing non-volatile solute determined by Ostwald-Walker method.
do not depend upon the nature of the solute dissolved but depend only
Thus according to Raoult’s law,
upon the concentration i.e., the number of particles of the solute present in
the solution. Such properties are called colligative properties. The four well w
known examples of the colligative properties are, p0  p n m
 
(1) Lowering of vapour pressure of the solvent. p0 nN w W

(2) Osmotic pressure of the solution. m M
(3) Elevation in boiling point of the solvent. where, p  Vapour pressure of the solution
(4) Depression in freezing point of the solvent.
Since colligative properties depend upon the number of solute p 0  Vapour pressure of the pure solvent
particles present in the solution, the simple case will be that when the n  Number of moles of the solute
solute is a non-electrolyte. In case the solute is an electrolyte, it may split to
a number of ions each of which acts as a particle and thus will affect the N  Number of moles of the solvent
value of the colligative property. w and m  weight and mol. wt. of solute
Each colligative property is exactly related to other, Relative lowering
W and M  weight and mol. wt. of the solvent.
of vapour pressure, elevation in boiling point and depression in freezing
point are directly proportional to osmotic pressure. Limitations of Raoult’s law
Lowering of vapour pressure  Raoult’s law is applicable only to very dilute solutions.

The pressure exerted by the vapours above the liquid surface in  Raoult’s law is applicable to solutions containing non-volatile
equilibrium with the liquid at a given temperature is called vapour pressure solute only.
of the liquid. The vapour pressure of a liquid depends on,  Raoult’s law is not applicable to solutes which dissociate or
(1) Nature of liquid : Liquids, which have weak intermolecular forces, associate in the particular solution.
are volatile and have greater vapour pressure. For example, dimethyl ether Ideal and Non-Ideal solution
has greater vapour pressure than ethyl alcohol.
(2) Temperature : Vapour pressure increases with increase in
temperature . This is due to the reason that with increase in
temperature more molecules of the liquid can go into vapour phase.

Table: 4.1 Ideal and non-ideal solutions

Non-ideal solutions
Ideal solutions
Positive deviation from Raoult's law Negative deviation from Raoult's law
1. Obey Raoult's law at every range of 1. Do not obey Raoult's law. 1. Do not obey Raoult's law.
concentration.
2. H mix  0; neither heat is evolved nor 2. H mix  0. Endothermic dissolution; heat 2. H mix  0. Exothermic dissolution; heat is
absorbed during dissolution. is absorbed. evolved.
3. Vmix  0; total volume of solution is 3. Vmix  0. Volume is increased after 3. Vmix  0. Volume is decreased during
equal to sum of volumes of the dissolution. dissolution.
components.
 156 Solution and Colligative properties

4. P  p A  p B  p 0A X A  p B0 X B i.e., 4. p A  p 0A X A ; p B  p B0 X B 4. p A  p 0A X A ; p B  p B0 X B

p A  p 0A X A : p B  p B0 X B  p A  p B  p 0A X A  p B0 X B  p A  p B  p 0A X A  p B0 X B

5. A  A, A  B, B  B interactions should be 5. A  B attractive force should be weaker 5. A  B attractive force should be greater
same, i.e., 'A' and 'B' are identical in shape, size than A  A and B  B attractive forces. than A  A and B  B attractive forces.
and character. 'A' and 'B' have different shape, size and 'A' and 'B' have different shape, size and
character. character.
6. Escaping tendency of 'A' and 'B' should be 6. 'A' and 'B' escape easily showing higher 6. Escaping tendency of both components 'A'
same in pure liquids and in the solution. vapour pressure than the expected value. and 'B' is lowered showing lower vapour
pressure than expected ideally.
Examples: Examples: Examples:
Dilute solutions; Acetone +ethanol Acetone + aniline;
benzene + toluene: acetone + CS 2 : acetone + chloroform;
n-hexane + n-heptane; water + methanol; CH 3 OH  CH 3 COOH ;
chlorobenzene + bromobenzene;
water + ethanol; H 2O  HNO3
ethyl bromide + ethyl iodide;
CCl 4  toluene; chloroform + diethyl ether;
n-butyl chloride + n-butyl bromide
CCl 4  CHCl 3 ; water + HCl;
acetic acid + pyridine;
acetone + benzene;
chloroform + benzene
CCl 4  CH 3 OH ;
cyclohexane + ethanol

Graphical representation of ideal and non-ideal solutions

Ideal solution Positive deviation Negative deviation
Total vapour pressure
p°A P=pA + pB p°A p°A Total vapour pressure

PA=p0A XA p°B p°B p°B

Vapour pressure

Vapour pressure

Vapour pressure

PB=p0B XB
Ideal
Ideal

XA = 1 Mole fraction XA = 0 XA = 1 Mole fraction XB = 1 XA = 1 Mole fraction XA = 0

XB = 0 XB = 1
Azeotropic mixture
Azeotropes are defined as the mixtures of liquids which boil at
constant temperature like a pure liquid and possess same composition of
components in liquid as well as in vapour phase. Azeotropes are also called
constant boiling mixtures because whole of the azeotropes changes into
vapour state at constant temperature and their components can not be
separated by fractional distillation. Azeotropes are of two types as described
below,
(1) Minimum boiling azeotrope : For the solutions with positive
deviation there is an intermediate composition for which the vapour
pressure of the solution is maximum and hence, boiling point is minimum.
At this composition the solution distills at constant temperature without
change in composition. This type of solutions are called minimum boiling
azeotrope. e.g.,
H 2O  C2 H5 OH, H 2O  C2 H5 CH 2OH
CHCl 3  C 2 H 5 OH , (CH 3 )2 CO  CS 2
(2) Maximum boiling azeotrope : For the solutions with negative
deviations there is an intermediate composition for which the vapour
pressure of the solution is minimum and hence, boiling point is maximum.
At this composition the solution distill`s at constant temperature without
the change in composition. This type of solutions are called maximum
boiling azeotrope. e.g.,
XB = 0 XA= 0 XB = 0 XB = 1
H 2 O  HCl, H 2 O  HNO 3 , H 2 O  HClO4
Osmosis and Osmotic pressure of the solution
(1) Osmosis : The flow of solvent from pure solvent or from solution
of lower concentration into solution of higher concentration through a
semi-permeable membrane is called Osmosis. Osmosis may be divided in
following types,
(i) Exo-Osmosis : The outward osmotic flow of water from a cell
containing an aqueous solution through a semi-permeable membrane is
called as Exo-osmosis. For example, egg (after removing hard shell) placed
in conc. NaCl solutions, will shrink due to exo-osmosis.
(ii) Endo-osmosis : The inward flow of water into the cell containing
an aqueous solution through a semi-permeable membrane is called as endo-
osmosis. e.g., an egg placed in water swells up due to endo-osmosis.
(iii) Reverse osmosis : If a pressure higher than osmotic pressure is
applied on the solution, the solvent will flow from the solution into the pure
solvent through the semi-permeable membrane. Since here the flow of
solvent is in the reverse direction to that observed in the usual osmosis, the
process is called reverse osmosis.
Differences between osmosis and diffusion
Osmosis Diffusion
In osmosis movement of molecules In diffusion there is no role of semi-
 Solution and Colligative properties 157
takes place through a semi-permeable permeable membrane. In the above relations,  = Osmotic pressure; d = Density of solution
membrane. at temperature T; R = Universal gas constant; M = Mol. Mass of solute;
It involves movement of only solvent It involves passage of solvent as well as Kb = Molal elevation constant of solvent; K f = Molal depression
molecules from one side to the other. solute molecules from one region to
the other. constant of solvent
Osmosis is limited to solutions only. Diffusion can take place in liquids, (v) Isotonic, Hypertonic and Hypotonic solutions
gases and solutions. (a) Isotonic or iso-osmotic solutions : Two solutions of different
Osmosis can be stopped or reversed by Diffusion can neither be stopped nor substances having same osmotic pressure at same temperature are known
applying additional pressure on the reversed as isotonic solutions.
solution side.
For isotonic solutions,  1   2 Primary Condition …..(i)
(2) Osmotic pressure ()
Also, C1  C2
The osmotic pressure of a solution at a particular temperature may
be defined as the excess hydrostatic pressure that builds up when the n1 n2
solution is separated from the solvent by a semi-permeable membrane. It is or 
V1 V2 Secondary Conditions
denoted by .
or w1 w2
or  …..(ii)
Osmotic pressure may be defined as the excess pressure which must m1 V1 m 2 V2
be applied to a solution in order to prevent flow of solvent into the solution
through the semi-permeable membrane. Eq. (ii) holds good only for those solutes which neither possess the
tendency to get associate nor dissociate in solution, e.g.,
or
Osmotic pressure is the excess pressure which must be applied to a Urea and glucose are isotonic then,  1   2 and C1  C2
given solution in order to increase its vapour pressure until it becomes
equal to that of the solution. Urea and NaCl are isotonic then,  1   2 but C1  C2
(dissociate)
(i) Measurements of osmotic pressure : Following methods are used
for the measurement of osmotic pressure, Urea and Benzoic acid are isotonic then,  1   2 but C1  C2
(associate)
(a) Pfeffer’s method, (b) Morse and Frazer’s method, (c)
Berkeley and Hartley’s method, (d) Townsend’s negative pressure method, (b) Hypertonic and hypotonic solution : The solution which has
(e) De Vries plasmolytic method. more osmotic pressure than the other solution is called as hypertonic
(ii) Determination of molecular mass of non-volatile solute from solution and the solution which has lesser osmotic pressure than the other
osmotic pressure () : The osmotic pressure is a colligative property. For a is called as hypotonic solution.
given solvent the osmotic pressure depends only upon the molar The flow of solvent is always from lower osmotic pressure to higher
concentration of solute but does not depend upon its nature. The following osmotic pressure i.e. from hypotonic to hypertonic solution.
relation relates osmotic pressure to the number of moles of the solute,
According to Boyle Van't Hoff law (at conc. temp.) Elevation in b.pt. of the solvent (Ebullioscopy)
 C .....(i) Boiling point of a liquid may be defined as the temperature at which
According to Gaylussac Van't Hoff law (at conc. temp.) its vapour pressure becomes equal to atmospheric pressure, i.e., 760 mm.
Since the addition of a non-volatile solute lowers the vapour pressure of the
 T .....(ii)
solvent, solution always has lower vapour pressure than the solvent and
From equation (i) and (ii) hence it must be heated to a higher temperature to make its vapour
  CT ,   CRT (Van't Hoff equation) pressure equal to atmospheric pressure with the result the solution boils at
a higher temperature than the pure solvent. Thus sea water boils at a
n  n w RT  w
 RT  C   ;    n   higher temperature than distilled water. If T is the boiling point of the
b

V  V  m V  m  solvent and T is the boiling point of the solution, the difference in the boiling
Here, C = concentration of solution in moles per litre point (T or  T ) is called the elevation of boiling point.
b

R = gas constant ; T = temperature

T  Tb  Tb or T
n = number of moles of solute ; V = volume of solution
m = molecular weight of solute ; w = weight of solute Elevation in boiling point is determined by Landsberger’s method
(iii) Conditions for getting accurate value of molecular mass are, and Cottrell’s method. Study of elevation in boiling point of a liquid in
which a non-volatile solute is dissolved is called as ebullioscopy.
(a) The solute must be non-volatile.
(b) The solution must be dilute. Important relations concerning elevation in boiling point
(c) The solute should not undergo dissociation or association in the (1) The elevation of boiling point is directly proportional to the
solution. lowering of vapour pressure, i.e., Tb  p 0  p
(iv) Relation of osmotic pressure with different colligative properties
: Osmotic pressure is related to relative lowering of vapour pressure, (2) Tb  Kb  m
elevation of boiling point and depression of freezing point according to the
following relations, where K b  molal elevation constant or ebullioscopic constant of
 PAo  PA  dRT dRT the solvent; m  Molality of the solution, i.e., number of moles of solute
(a)    
 M (b)   Tb  per 1000 g of the solvent; Tb  Elevation in boiling point
 PAo  1000  Kb
1000  K b  w 1000  K b  w
(c)   Tf 
dRT (3) Tb  or m 
1000  K f m W Tb  W
 158 Solution and Colligative properties
where, K b is molal elevation constant and defined as the elevation
in b.pt. produced when 1 mole of the solute is dissolved in 1 kg of the
solvent.
w and W are the weights of solute and solvent and m is the
molecular weight of the solute.
0 .002(T0 )2
(4) Kb 
lV
where T 0  Normal boiling point of the pure solvent; lV  Latent
heat of evaporation in cal / g of pure solvent; K b for water is
1
0.52 deg  kg mol .
Depression in f.pt. of the solvent (Cryoscopy)
Freezing point is the temperature at which the liquid and the solid
states of a substance are in equilibrium with each other or it may be
defined as the temperature at which the liquid and the solid states of a
substance have the same vapour pressure. It is observed that the freezing
point of a solution is always less than the freezing point of the pure solvent.
Thus the freezing point of sea water is low than that of pure water. The
depression in freezing point (T or Tf ) of a solvent is the difference
in the freezing point of the pure solvent (Ts ) and the solution (Tsol . ) .
Ts  Tsol  Tf or T
NaCl or CaCl 2 (anhydrous) are used to clear snow on roads.
They depress the freezing point of water and thus reduce the temperature
of the formation of ice.
Depression in freezing point is determined by Beckmann’s method
and Rast’s camphor method. Study of depression in freezing point of a
liquid in which a non-volatile solute is dissolved in it is called as cryoscopy.
Important relations concerning depression in freezing point.
(1) Depression in freezing point is directly proportional to the
lowering of vapour pressure. Tf  p 0  p
(2) Tf  K f  m
where K f  molal depression constant or cryoscopic constant;
m  Molality of the solution (i.e., no. of moles of solute per 1000 g of the
solvent); Tf  Depression in freezing point
1000  K f  w 1000  K f  w
(3) Tf  or m 
m W Tf  W
where K f is molal depression constant and defined as the
depression in freezing point produced when 1 mole of the solute is dissolved
in 1kg of the solvent. w and W are the weights of solute and solvent
and m is the molecular weight of the solute.
R(T0 )2 0 .002(T0 )2
(4) K f   normal values for unassociated molecules.
l f 1000 lf
where T0  Normal freezing point of the solvent; l f  Latent heat
of fusion/g of solvent; K f for water is 1.86 deg  kg mol 1
Colligative properties of electrolytes
The colligative properties of solutions, viz. lowering of vapour
pressure, osmotic pressure, elevation in b.p. and depression in freezing
point, depend on the total number of solute particles present in solution.
Since the electrolytes ionise and give more than one particle per formula
unit in solution, the colligative effect of an electrolyte solution is always
greater than that of a non-electrolyte of the same molar concentration. All
colligative properties are used for calculating molecular masses of non-
volatile solutes. However osmotic pressure is the best colligative property
for determining molecular mass of a non-volatile substance.
Colligative properties are depending on following factory
(1) Colligative properties  Number of particles
 Number of molecules
(in case of non-electrolytes)
 Number of ions
(In case of electrolytes)
 Number of moles of solute
 Mole fraction of solute
(2) For different solutes of same molar concentration, the magnitude
of the colligative properties is more for that solution which gives more
number of particles on ionisation.
(3) For different solutions of same molar concentration of different
non-electrolyte solutes, the magnitude of the colligative properties will be
same for all.
(4) For different molar concentrations of the same solute, the
magnitude of colligative properties is more for the more concentrated
solution.
(5) For solutions of different solutes but of same percent strength,
the magnitude of colligative property is more for the solute with least
molecular weight.
(6) For solutions of different solutes of the same percent strength,
the magnitude of colligative property is more for that solute which gives
more number of particles, which can be known by the knowledge of
molecular weight and its ionisation behaviour.
Abnormal molecular masses
Molecular masses can be calculated by measuring any of the
colligative properties. The relation between colligative properties and
molecular mass of the solute is based on following assumptions.
(1) The solution is dilute, so that Raoult’s law is obeyed.
(2) The solute neither undergoes dissociation nor association in
solution.
In case of solutions where above assumptions are not valid we find
discrepencies between observed and calculated values of colligative
properties. These anomalies are primarily due to
(i) Association of solute molecules.
(ii) Dissociation of solute molecules.
(i) Association of solute molecules : Certain solutes in solution are
found to associate. This eventually leads to a decrease in the number of
molecular particles in the solutions. Thus, it results in a decrease in the
values of colligative properties.
1
Colligative property 
molecular mass of solute
therefore, higher values are obtained for molecular masses than
(ii) Dissociation of solute molecules : A number of electrolytes
dissociate in solution to give two or more particles (ions). Therefore, the
number of solute particles, in solutions of such substances, is more than the
expected value. Accordingly, such solutions exhibit higher values of
colligative properties. Since colligative properties are inversely proportional
to molecular masses, therefore, molecular masses of such substances as
calculated from colligative properties will be less than their normal values.
Van’t Hoff’s factor (i) : In 1886, Van’t Hoff introduced a factor ‘i’
called Van’t Hoff’s factor, to express the extent of association or dissociation
of solutes in solution. It is ratio of the normal and observed molecular
masses of the solute, i.e.,
 Solution and Colligative properties 159

Normal molecular mass

i
Observed molecular mass
In case of association, observed molecular mass being more than the
normal, the factor i has a value less than 1. But in case of dissociation, the
Van’t Hoff’s factor is more than 1 because the observed molecular mass has
a lesser value than the normal molecular mass. In case there is no
dissociation the value of ‘i’ becomes equal to one.
Since colligative properties are inversely proportional to molecular
masses, the Van’t Hoff’s factor may also be written as,
Observed value of colligative property
i
Calculated value of colligative property
assuming no association or dissociation
No. of particles after association or dissociation
i
No. of particles before association or dissociation
Introduction of the Van’t Hoff factor modifies the equations for the
colligative properties as follows,
PAo  PA
Relative lowering of vapour pressure   iXB
PAo
Elevation of boiling point, Tb  ikb m
Depression in freezing point, Tf  ikf m

inRT
Osmotic pressure,   ;   iCRT
V
From the value of ‘i’, it is possible to calculate degree of dissociation
or degree of association of substance.
Degree of dissociation () : It is defined as the fraction of total
molecules which dissociate into simpler molecules or ions.
i1
 ; m= number of particles in solution
m 1
Degree of association () : It is defined as the fraction of the total
number of molecules which associate or combine together resulting in the
formation of a bigger molecules.
i 1
 ; m = number of particles in solution.
1/m 1
 160 Solution and Colligative properties

Solubility
1. The solubility of a gas in water depends on [MP PET 2002]
(a) Nature of the gas (b) Temperature
(c) Pressure of the gas (d) All of the above
2. Which of the following is not correct for D2 O
[Orissa JEE 2002]
 A supersaturated solution is metastable. (a) Boiling point is higher than H 2 O
 Dissolution of gases in liquid is always exothermic because (b) D2 O reacts slowly than H 2 O
S  ve (non favourable factor) and in order to have (c) Viscosity is higher than H 2 O at 25 o
G  ve (spontaneous process), H has to be –ve.
(d) Solubility of NaCl in it is more than H 2 O
 1 M aqueous solution is more concentrated than 1 m aqueous 3. The statement “ The mass of a gas dissolved in a given mass of a
solution. solvent at any temperature is proportional to the pressure of the gas
above the solvent” is [AMU 2002]
 Substances having high V.P. (e.g., petrol) evaporate more quickly (a) Dalton’s Law of Partial Pressures
than substances having low V.P. (e.g., motor oil). (b) Law of Mass Action
(c) Henry’s Law
 Babo’s law : The lowering in vapour pressure of a solution caused (d) None of these
by addition of an non-volatile solute is called as Babo’s law. 4. Which is correct about Henry’s law [KCET 2002]
(a) The gas in contact with the liquid should behave as an ideal
 Konowaloff’s rule : In case of a binary solution, at a fixed gas
(b) There should not be any chemical interaction between the gas
temperature, the vapour phase is richer in that component whose
and liquid
addition causes increase in total vapour pressure of the solution i.e., (c) The pressure applied should be high
vapour phase is always richer in the more volatile component. (d) All of these
5. The statement “If 0.003 moles of a gas are dissolved in 900 g of
 When a non-volatile solute is added to the solvent, V.P. decrease, water under a pressure of 1 atmosphere, 0.006 moles will be
B.P. increase, F.P. decrease. dissolved under a pressure of 2 atmospheres”, illustrates [JIPMER 1999]
(a) Dalton’s law of partial pressure
 Ethylene glycol is commonly added to car radiators to depress the (b) Graham’s law
freezing point of water. It is known as antifreeze. (c) Raoult’s law
(d) Henry’s law
 NaCl or CaCl2 (anhydrous) are used to clear snow on roads. It 6. The solution of sugar in water contains [BHU 1973]
depresses the freezing point of water and reduce the temperature (a) Free atoms (b) Free ions
at which ice is expected to be formed. (c) Free molecules (d) Free atom and molecules

 Plasmolysis : When a plant cell is placed in a hypertonic solution, Method of expressing concentration of solution
the fluid from the plant cell comes out and the cell shrinks. This
phenomenon is called plasmolysis and is due to osmosis. 1. 25 ml of 3.0 M HNO 3 are mixed with 75 ml of

 Bursting of red blood cells when placed in water is due to osmosis. 4.0 M HNO3 . If the volumes are additive, the molarity of the final
mixture would be [DPMT 1986; MH CET 2001]
 Gelatinous Cu 2 [Fe(CN )6 ] and gelatinous Ca3 (PO4 )2 are (a) 3.25 M (b) 4.0 M
artificial semipermeable membranes. (c) 3.75 M (d) 3.50 M
2. The amount of anhydrous Na 2 CO 3 present in 250 ml of 0.25 M
 Semipermeable membrane of Cu 2 [Fe(CN )6 ] dose not work in
solution is [DPMT 2001]
non aqueous solutions because it get dissolved in non aqueous (a) 6.225 g (b) 66.25 g
solvents. (c) 6.0 g (d) 6.625 g
3. Dilute one litre 1 molar H 2 SO 4 solution by 5 litre water, the
 Osmotic coefficient (g) is the ratio of van’t Hoff factor (i) to the no.
normality of that solution is [DPMT 1983]
of ions furnished by one molecule of the electrolyte (N).
(a) 0.2 N (b) 5 N
i.e., g  i / N .
(c) 10 N (d) 0.33 N
4. If 5.85 gms of NaCl are dissolved in 90 gms of water, the mole
fraction of NaCl is
[CMC Vellore 1991; MP PMT 1994; AFMC 1998]
(a) 0.1 (b) 0.2
(c) 0.3 (d) 0.01
(e) 0.0196
5. The molarity of 0.006 mole of NaCl in 100ml solution is
 Solution and Colligative properties 161
[Bihar MEE 1996] (a) Normality (b) Molarity
(a) 0.6 (b) 0.06 (c) Mole fraction (d) Mass percentage
(c) 0.006 (d) 0.066 (e) Molality
(e) None of these
20. The normality of 2.3 M H 2 SO 4 solution is [KCET 2000]
6. 9 .8 g of H 2 SO 4 is present in 2 litres of a solution. The molarity
(a) 2.3 N (b) 4.6 N
of the solution is [EAMCET 1991; MP PMT 2002]
(c) 0.46 N (d) 0.23 N
(a) 0.1M (b) 0.05 M
21. The molarity of a solution made by mixing 50ml of conc. H 2 SO 4
(c) 0.2 M (d) 0.01M
(36N) with 50 ml of water is [MP PMT 2001]
7. What will be the molarity of a solution containing 5 g of sodium
(a) 36 M (b) 18 M
hydroxide in 250 ml solution (c) 9 M (d) 6 M
[MP PET 1999; BHU 1999; KCET 1999;
22. 171 g of cane sugar (C12 H 22 O11 ) is dissolved in 1 litre of water.
AIIMS 2000; Pb. CET 2000]
(a) 0.5 (b) 1.0 The molarity of the solution is [MP PMT 2001]
(c) 2.0 (d) 0.1 (a) 2.0 M (b) 1.0 M
8. The normality of 0.3 M phosphorus acid (H 3 PO3 ) is (c) 0.5 M (d) 0.25 M
[IIT 1999; AIIMS 2000] 23. The volumes of 4 N HCl and 10 N HCl required to make 1 litre
(a) 0.1 (b) 0.9 of 6 N HCl are [Kerala PMT 2004]
(c) 0.3 (d) 0.6 (a) 0.75 litre of 10 N HCl and 0.25 litre of 4 N HCl
9. Which of the following has maximum number of molecules
(b) 0.25 litre of 4 N HCl and 0.75 litre of 10 N HCl
[CBSE PMT 2002]
(c) 0.67 litre of 4 N HCl and 0.33 litre of 10 N HCl
(a) 16 gm of O 2 (b) 16 gm of NO 2
(d) 0.80 litre of 4 N HCl and 0.20 litre of 10 N HCl
(c) 7 gm of N 2 (d) 2 gm of H 2 (e) 0.50 litre of 4 N HCl and 0.50 litre of 10 N HCl
10. Molarity is expressed as [JIPMER 1991; CBSE PMT 1991] 24. Which statement is true for solution of 0.020 M H 2 SO 4
(a) Gram/litre (b) Moles/litre [DPMT 2001]
(c) Litre/mole (d) Moles/1000 gms
11. 20 ml of HCl solution requires 19.85 ml of 0.01 M NaOH (a) 2 litre of the solution contains 0.020 mole of SO 42 
solution for complete neutralization. The molarity of HCl solution (b) 2 litre of the solution contains 0.080 mole of H 3 O 
is [MP PMT 1999]
(a) 0.0099 (b) 0.099 (c) 1 litre of the solution contains 0.020 mole H 3 O 
(c) 0.99 (d) 9.9 (d) None of these
12. How much of NaOH is required to neutralise 1500 cm 3 of 0.1 N 25. 10 litre solution of urea contains 240g urea. The active mass of urea
HCl (At. wt. of Na =23) [KCET 2001] will be [KCET 2000]
(a) 4 g (b) 6 g (a) 0.04 (b) 0.02
(c) 40 g (d) 60 g (c) 0.4 (d) 0.2
13. If 5.85 g of NaCl (molecular weight 58.5) is dissolved in water and 26. 5 ml of N HCl, 20 ml of N/2 H 2 SO 4 and 30 ml of N/3 HNO are
the solution is made up to 0.5 litre, the molarity of the solution will be[AMU 1999; Pb PMT 2000; AFMC 2001]
3

mixed together and volume made to one litre. The normally of the
(a) 0.2 (b) 0.4 resulting solution is [Kerala CET (Med.) 2003]
(c) 1.0 (d) 0.1
14. A mixture has 18g water and 414g ethanol. The mole fraction of N N
(a) (b)
water in mixture is (assume ideal behaviour of the mixture) 5[MP PMT 2000] 10
(a) 0.1 (b) 0.4 N N
(c) 0.7 (d) 0.9 (c) (d)
20 40
15. The number of molecules in 4.25 g of ammonia is approximately [CBSE PMT 2002]
N
(a) 0.5  10 23
(b) 1.5  10 23 (e)
25
(c) 3.5  10 23
(d) 2.5  10 23
27. The amount of K 2 Cr2 O7 (eq. wt. 49.04) required to prepare 100
16. The largest number of molecules is in [Kurukshetra CEE 1998] ml of its 0.05 N solution is [JIPMER 2002]
(a) 25 g of CO 2 (b) 46 g of C 2 H 5 OH (a) 2.9424 g (b) 0.4904 g
(c) 36 g of H 2 O (d) 54 g of N 2 O5 (c) 1.4712 g (d) 0.2452 g
28. With increase of temperature, which of these changes
17. If 1 M and 2.5 litre NaOH solution is mixed with another 0.5 M and
[AIEEE 2002]
3 litre NaOH solution, then molarity of the resultant solution will be[CBSE PMT 2002]
(a) Molality
(a) 1.0 M (b) 0.73 M
(b) Weight fraction of solute
(c) 0.80 M (d) 0.50 M
(c) Fraction of solute present in water
18. When a solute is present in trace quantities the following expression
is used [Kerala CET (Med.) 2002] (d) Mole fraction
(a) Gram per million (b) Milligram percent 29. 25ml of a solution of barium hydroxide on titration with a 0.1molar
solution of hydrochloric acid gave a litre value of 35 ml. The
(c) Microgram percent (d) Nano gram percent molarity of barium hydroxide solution was
(e) Parts per million [AIEEE 2003]
19. When the concentration is expressed as the number of moles of a (a) 0.07 (b) 0.14
solute per litre of solution it known as
(c) 0.28 (d) 0.35
[Kerala CET (Med.) 2002]
 162 Solution and Colligative properties

30. 2.0 molar solution is obtained , when 0.5 mole solute is dissolved in 43. Molar solution
[MP PMTmeans
2003] 1 mole of solute present in
(a) 250 ml solvent (b) 250 g solvent [BCECE 2005]
(c) 250 ml solution (d) 1000 ml solvent (a) 1000g of solvent (b) 1 litre of solvent
31. How many gram of HCl will be present in 150 ml of its 0.52 M (c) 1 litre of solution (d) 1000g of solution
solution [RPET 1999] 44. What will be the molality of a solution having 18 g of glucose (mol.
(a) 2.84 gm (b) 5.70 gm wt. = 180) dissolved in 500 g of water
(c) 8.50 gm (d) 3.65 gm [MP PET/PMT 1998; CBSE PMT 2000; JIPMER 2001]
32. The number of moles present in 2 litre of 0.5 M NaOH is (a) 1m (b) 0 .5 m
[MH CET 2001]
(c) 0 .2 m (d) 2m
(a) 0.5 (b) 0.1
(c) 1 (d) 2 45. A solution of Al2 (SO 4 )3 {d  1.253 gm / ml} contain 22% salt by
33. 36g water and 828g ethyl alcohol form an ideal solution. The mole weight. The molarity, normality and molality of the solution is
fraction of water in it, is [MP PMT 2003] (a) 0.805 M, 4.83 N, 0.825 M
(a) 1.0 (b) 0.7 (b) 0.825 M, 48.3 N, 0.805 M
(c) 0.4 (d) 0.1
(c) 4.83 M, 4.83 N, 4.83 M
34. What will be the normality of a solution containing 4.9 g. H 3 PO4 (d) None
dissolved in 500 ml water [MP PMT 2003]
46. Which of the following should be done in order to prepare
(a) 0.3 (b) 1.0
0.40 M NaCl starting with 100 ml of 0.30 M NaCl (mol.wt.
(c) 3.0 (d) 0.1
of NaCl  58.5 ) [BIT 1992]
35. 3.0 molal NaOH solution has a density of 1.110 g/ml. The molarity of
the solution is [BVP 2003] (a) Add 0.585 g NaCl (b) Add 20 ml water
(a) 3.0504 (b) 3.64
(c) Add 0.010ml NaCl (d) Evaporate 10ml water
(c) 3.05 (d) 2.9732
36. Which of the following modes of expressing concentration is 47. Which of the following solutions has the highest normality
independent of temperature [IIT 1988; CPMT 1999; [JIPMER 1991]
CBSE PMT 1992, 95; MP PMT 1992; AIIMS 1997, 2001] (a) 8 gm of KOH / litre (b) N phosphoric acid
(a) Molarity (b) Molality (c) 6 gm of NaOH / 100 ml (d) 0.5 M H 2 SO 4
(c) Formality (d) Normality 48. What volume of 0 .8 M solution contains 0.1 mole of the solute
37. The molality of a solution is [MP PMT 1996]
(a) 100 ml (b) 125 ml
(a) Number of moles of solute per 1000 ml of the solvent
(c) 500 ml (d) 62.5 ml
(b) Number of moles of solute per 1000 gm of the solvent
49. Hydrochloric acid solution A and B have concentration of
(c) Number of moles of solute per 1000 ml of the solution 0.5 N and 0.1 N respectively. The volumes of solutions A and
(d) Number of gram equivalents of solute per 1000 ml of the B required to make 2 litres of 0.2 N HCl are
solution [KCET 1993]
38. The number of molecules in 16 gm of methane is (a) 0 .5 l of A  1.5 l of B
[MP PET/PMT 1998] (b) 1 .5 l of A  0.5l of B
(a) 3.0  10 23
(b) 6.02  10 23
(c) 1 .0 l of A  1.0 l of B
16 16 (d) 0.75 l of A  1.25l of B
(c)  10 23 (d)  10 23
6 .02 3.0 50. Conc. H 2 SO 4 has a density of 1.98 gm/ml and is 98% H 2 SO 4
39. The number of moles of a solute in its solution is 20 and total by weight. Its normality is [MP PET 2002]
number of moles are 80. The mole fraction of solute is (a) 2 N (b) 19.8 N
[MP PMT 1997] (c) 39.6 N (d) 98 N
(a) 2.5 (b) 0.25 51. The mole fraction of the solute in one molal aqueous solution is [CBSE PMT 200
(c) 1 (d) 0.75 (a) 0.027 (b) 0.036
40. The normality of a solution of sodium hydroxide 100 ml of which (c) 0.018 (d) 0.009
contains 4 grams of NaOH is [CMC Vellore 1991] N
52. With 63 gm of oxalic acid how many litres of solution can be
(a) 0.1 (b) 40 10
(c) 1.0 (d) 0.4 prepared [RPET 1999]
41. Two solutions of a substance (non electrolyte) are mixed in the (a) 100 litre (b) 10 litre
following manner 480 ml of 1.5M first solution + 520 mL of 1.2M (c) 1 litre (d) 1000 litre
second solution. What is the molarity of the final mixture [AIEEE 2005] 53. Molarity of 0.2 N H 2 SO 4 is [KCET 2005]
(a) 1.20 M (b) 1.50 M
(a) 0.2 (b) 0.4
(c) 1.344 M (d) 2.70 M (c) 0.6 (d) 0.1
42. The normal amount of glucose in 100ml of blood (8–12 hours 54. 10.6 grams of a substance of molecular weight 106 was dissolved in
after a meal) is [BHU 1981] 100ml . 10ml of this solution was pipetted out into a 1000ml
(a) 8 mg (b) 80 mg flask and made up to the mark with distilled water. The molarity of the
resulting solution is [EAMCET 1998]
(c) 200 mg (d) 800 mg
(a) 1 . 0M (b) 10 2 M
 Solution and Colligative properties 163
[EAMCET 1987]
(c) 10 3 M (d) 10 4 M
(a) 0.1M (b) 0.2 M
55. The mole fraction of water in 20% aqueous solution of H 2 O 2 is [EAMCET 1993]
(c) 0.3 M (d) 0.4 M
77 68 66. Which of the following concentration factor is affected by change in
(a) (b)
68 77 temperature [DCE 2002]
20 80 (a) Molarity (b) Molality
(c) (d) (c) Mole fraction (d) Weight fraction
80 20 67. The distribution law is applied for the distribution of basic acid
56. Mole fraction (X ) of any solution is equal to between [UPSEAT 2001]
No. of moles of solute (a) Water and ethyl alcohol
(a) (b) Water and amyl alcohol
Volume of solutionin litre
(c) Water and sulphuric acid
No. of gram equivalent of solute (d) Water and liquor ammonia
(b)
Volume of solutionin litre 68. Which is heaviest [CBSE PMT 1991]
No. of moles of solute (a) 25 gm of mercury
(c) (b) 2 moles of water
Mass of solvent in kg
(c) 2 moles of carbon dioxide
No. of moles of any constituent
(d) (d) 4 gm atoms of oxygen
Total no. of moles of all constituents
69. The molarity of a solution of Na 2 CO 3 having 10.6 g / 500ml of
57. When WB gm solute (molecular mass M B ) dissolves in WA gm
solution is [AFMC 1992; DCE 2000]
solvent. The molality M of the solution is (a) 0.2 M (b) 2 M
WB MB WB 1000
(a)  (b)  (c) 20 M (d) 0.02 M
W A 1000 MB WA
70. On passing H 2 S gas through a solution of Cu  and Zn 2 ions,
W A 1000 WA  M B
(c)  (d) CuS is precipitated first because [AMU 2001]
WB MB WB  1000 (a) Solubility product of CuS is equal to the ionic product of ZnS
58. Normality (N ) of a solution is equal to (b) Solubility product of CuS is equal to the solubility product of
No. of moles of solute ZnS
(a) (c) Solubility product of CuS is lower than the solubility product
Volume of solutionin litre of ZnS
No. of gram equivalent of solute (d) Solubility product of CuS is greater than the solubility product
(b)
Volume of solutionin litre of ZnS
No. of moles of solute 71. The number of moles of solute per kg of a solvent is called its[DPMT 1983; IIT 19
(c) (a) Molarity (b) Normality
Mass of solvent in kg
(c) Molar fraction (d) Molality
(d) None of these 72. 1.0 gm of pure calcium carbonate was found to require 50 ml of
59. The volume strength of 1.5 N H 2 O 2 solution is dilute HCl for complete reaction. The strength of the HCl
[CBSE PMT 1997; BHU 2002] solution is given by [CPMT 1986]
(a) 4.8 (b) 5.2 (a) 4 N (b) 2 N
(c) 8.8 (d) 8.4 (c) 0.4 N (d) 0.2 N
60. How many gm of H 2 SO 4 is present in 0.25 gm mole of 73. Molecular weight of glucose is 180. A solution of glucose which
H 2 SO 4 [CPMT 1990] contains 18 gms per litre is [AFMC 1978]
(a) 24.5 (b) 2.45 (a) 2 molal (b) 1 molal
(c) 0.25 (d) 0.245 (c) 0.1 molal (d) 18 molal
61. 20 g of hydrogen is present in 5 litre vessel. The molar 74. 0.5 M of H 2 SO 4 is diluted from 1 litre to 10 litre, normality of
concentration of hydrogen is [DPMT 2000] resulting solution is [AFMC 2005]
(a) 4 (b) 1 (a) 1 N (b) 0.1 N
(c) 3 (d) 2 (c) 10 N (d) 11 N
62. To prepare a solution of concentration of 0.03 g/ml of AgNO3 , 75. If one mole of a substance is present in 1 kg of solvent, then
what amount of AgNO3 should be added in 60 ml of solution [AFMC 2005] [CPMT 1996]
(a) 1.8 (b) 0.8 (a) It shows molar concentration
(c) 0.18 (d) None of these (b) It shows molal concentration
63. How many grams of dibasic acid (mol. wt. 200) should be present in (c) It shows normality
100ml of its aqueous solution to give decinormal strength[AIIMS 1992; CBSE PMT (d)
1999; ItAFMC 1999;
shows strength gm / gm
KCET 2000; CPMT 2001]
(a) 1g (b) 2g 76. The molality of 90% H 2 SO 4 solution is
(c) 10 g (d) 20 g [density=1.8 gm/ml] [MP PMT 2004]
(a) 1.8 (b) 48.4
64. The weight of pure NaOH required to prepare 250cm 3 of (c) 9.18 (d) 94.6
0.1 N solution is [KCET 1991; Kerala PMT 2004]
77. The volume of water to be added to 100cm 3 of 0.5 N H 2 SO 4 to get
(a) 4 g (b) 1 g
decinormal concentration is [KCET (Engg.) 2001]
(c) 2 g (d) 10 g
(a) 400 cm 3 (b) 500 cm 3
65. If 20ml of 0.4 N NaOH solution completely neutralises 40ml
of a dibasic acid. The molarity of the acid solution is (c) 450 cm 3 (d) 100 cm 3
 164 Solution and Colligative properties

78. If 25 ml of 0.25 M NaCl solution is diluted with water to a volume (c) 0.3 (d) 0.4
of 500ml the new concentration of the solution is 92. The weight of H 2C2O4 . 2 H 2O required to prepare 500ml of
[UPSEAT 2000, 01]
(a) 0.167 M (b) 0.0125 M 0.2 N solution is [EAMCET 1991]
(c) 0.833 M (d) 0.0167 M (a) 126 g (b) 12.6 g
79. 10 grams of a solute is dissolved in 90 grams of a solvent. Its mass (c) 63 g (d) 6 .3 g
percent in solution is
(a) 0.01 (b) 11.1 93. In a solution of 7.8 gm benzene C 6 H 6 and 46.0 gm toluene
(c) 10 (d) 9 (C6 H 5 CH 3 ) , the mole fraction of benzene in this solution is
80. What is the molality of a solution which contains 18 g of glucose
(a) 1/6 (b) 1 / 5
(C6 H12 O6 ) in 250 g of water [UPSEAT 2001]
(c) 1/2 (d) 1 / 3
(a) 4.0 m (b) 0.4 m
(c) 4.2 m (d) 0.8 m 94. A solution contains 25% H 2 O , 25%C 2 H 5 OH and
81. Calculate the molality of 1 litre solution of 93% 50% CH 3 COOH by mass. The mole fraction of H 2 O would be
H 2 SO 4 (weight/volume). The density of the solution is 1.84 g (a) 0.25 (b) 2.5
/ml [UPSEAT 2000] (c) 0.503 (d) 5.03
(a) 10.43 (b) 20.36
95. A 5 molar solution of H 2 SO 4 is diluted from 1 litre to 10 litres.
(c) 12.05 (d) 14.05
What is the normality of the solution [AFMC 2005]
82. Volume of water needed to mix with 10 ml 10N HNO 3 to get 0.1 N (a) 0.25 N (b) 1 N
HNO 3 [UPSEAT 2003] (c) 2 N (d) 7 N
(a) 1000 ml (b) 990 ml 96. Molarity of a solution containing 1g NaOH in 250ml of solution
(c) 1010 ml (d) 10 ml is [EAMCET 1990]
83. The sum of the mole fraction of the components of a solution is (a) 0.1M (b) 1 M
(a) 0 (b) 1
(c) 2 (d) 4 (c) 0.01 M (d) 0.001 M
84. Increasing the temperature of an aqueous solution will cause 97. What is molarity of a solution of HCl which contains 49% by
[IIT Screening 1993] weight of solute and whose specific gravity is 1.41
(a) Decrease in molality (b) Decrease in molarity [CPMT 2001; CBSE PMT 2001]
(c) Decrease in mole fraction (d) Decrease in % w/w (a) 15.25 (b) 16.75
85. 1000 gms aqueous solution of CaCO 3 contains 10 gms of (c) 18.92 (d) 20.08
carbonate. Concentration of the solution is [CPMT 1985] 98. NaClO solution reacts with H 2 SO 3 as,
(a) 10 ppm (b) 100 ppm NaClO  H 2 SO 3  NaCl  H 2 SO 4 . A solution of NaClO
(c) 1000 ppm (d) 10000 ppm used in the above reaction contained 15g of NaClO per litre. The
86. 3.65 gms of HCl is dissolved in 16.2 gms of water. The mole fraction normality of the solution would be [AMU 1999]
of HCl in the resulting solution is [EAMCET 2003] (a) 0.8 (b) 0.6
(a) 0.4 (b) 0.3 (c) 0.2 (d) 0.33
(c) 0.2 (d) 0.1
87. An aqueous solution of glucose is 10% in strength. The volume in 99. A solution contains 1.2046  10 24 hydrochloric acid molecules in
which 1 gm mole of it is dissolved will be one dm 3 of the solution. The strength of the solution is [KCET 2004]
[AIIMS 1992; Pb. CET 2004] (a) 6 N (b) 2 N
(a) 18 litre (b) 9 litre (c) 4 N (d) 8 N
(c) 0.9 litre (d) 1.8 litre 1
100. 10 N and N solution is called
88. The concentration of an aqueous solution of 0.01M CH 3 OH 10
solution is very nearly equal to which of the following (a) Decinormal
[BITS 1992]and decanormal solution
(a) 0.01% CH 3 OH (b) 0.01m CH 3 OH (b) Normal and decinormal solution
(c) Normal and decanormal solution
(c) x CH 3 OH  0.01 (d) 0.99 M H 2O
(d) Decanormal and decinormal solution
(e) 0.01 N CH 3 OH 101. When 7.1gm Na 2 SO 4 (molecular mass 142) dissolves in
89. When 1.80 gm glucose dissolve in 90 gm of H 2 O , the mole 100 ml H 2 O , the molarity of the solution is
fraction of glucose is [AFMC 2000] [CBSE PMT 1991; MP PET 1993, 95]
(a) 0.00399 (b) 0.00199 (a) 2.0 M (b) 1.0 M
(c) 0.0199 (d) 0.998 (c) 0.5 M (d) 0.05 M
90. 6.02  10 20 molecules of urea are present in 100 ml of its solution. 102. Molarity of 4% NaOH solution is [EAMCET 1987]
The concentration of urea solution is [AIEEE 2004] (a) 0.1M (b) 0.5 M
(a) 0.02 M (b) 0.01 M (c) 0.01M (d) 1.0 M
(c) 0.001 M (d) 0.1 M 103. When 6 gm urea dissolve in 180 gm H 2 O . The mole fraction of
(Avogadro constant, N A  6.02  10 mol )
23 1 urea is [CPMT 1988]
10 10 . 1
91. The number of moles of SO 2 Cl 2 in 13.5 gm is [CPMT 1994] (a) (b)
10 . 1 10
(a) 0.1 (b) 0.2
 Solution and Colligative properties 165
10 . 1 0 .1 (c) 0.33 (d) None of these
(c) (d)
0 .1 10 . 1 117. A solution of CaCl 2 is 0.5 mol / litre, then the moles of chloride
104. The normality of 10% (weight/volume) acetic acid is ion in 500ml will be [MP PMT 1986]
[CPMT 1983] (a) 0.25 (b) 0.50
(a) 1 N (b) 10 N (c) 0.75 (d) 1.00
(c) 1.7 N (d) 0.83 N
118. What is the molarity of H 2 SO 4 solution, that has a density 1.84
105. Unit of mole fraction is [BHU 1998, 2005]
(a) Moles/litre (b) Moles/litre 2
gm/cc at 35 o C and contains solute 98% by weight
(c) Moles–litre (d) Dimensionless [AIIMS 2001]
106. Normality of 2 M sulphuric acid is (a] 4.18 M (b) 8.14 M
[AIIMS 1991, 92; Pb. CET 2002] (c) 18.4 M (d) 18 M
(a) 2 N (b) 4 N 119. A certain aqueous solution of FeCl 3 (formula mass =162) has a
(c) N / 2 (d) N / 4 density of 1.1 g / ml and contains 20.0% FeCl3 . Molar
107. Molar concentration (M ) of any solution = concentration of this solution is [Pb. PMT 1998]
No. of moles of solute (a) 0.028 (b) 0.163
(a) (c) 1.27 (d) 1.47
Volume of solutionin litre
120. If 0.50 mol of CaCl 2 is mixed with 0.20 mol of Na 3 PO4 , the
No. of gram equivalent of solute
(b) maximum number of moles of Ca 3 (PO4 )2 which can be formed,
Volume of solutionin litre
is [Pb. PMT 1998]
No. of moles of solute
(c) (a) 0.70 (b) 0.50
Mass of solvent in kg
(c) 0.20 (d) 0.10
No. of moles of any constituent 121. An X molal solution of a compound in benzene has mole fraction
(d)
Total no. of moles of all constituents of solute equal to 0.2. The value of X is
108. If 5.0 gm of BaCl2 is present in 10 6 gm solution, the [KCET 1996; DCE 2001]
(a) 14 (b) 3.2
concentration is
(c) 4 (d) 2
(a) 1 ppm (b) 5 ppm
(c) 50 ppm (d) 1000 ppm 122. Molecular weight of urea is 60. A solution of urea containing 6 g
109. 1 Molar solution contains [DPMT 2002] urea in one litre is [BHU 1996, 99]
(a) 1000g of solute (b) 1000g of solvent (a) 1 molar (b) 1.5 molar
(c) 1 litre of solvent (d) 1 litre of solution (c) 0.1 molar (d) 0.01 molar
110. To neutralise completely 20 mL of 0.1 M aqueous solution of 123. The molar solution of sulphuric acid is equal to
[MP PET 1999]
phosphorous acid (H 3 PO3 ), the volume of 0.1 M aqueous KOH
solution required is [AIEEE 2004] (a) N solution (b) 2 N solution
(a) 40 mL (b) 20 mL (c) N / 2 solution (d) 3 N solution
(c) 10 mL (d) 60 mL 124. The weight of sodium carbonate required to prepare 500 ml of a
111. On dissolving 1 mole of each of the following acids in 1 litre water, semi- normal solution is [JIPMER 1999]
the acid which does not give a solution of strength 1 N is [MPgPET 1993]
(a) 13.25 (b) 26.5 g
(c) 53 g (d) 6.125 g
(a) HCl (b) Perchloric acid
125. 200ml of a solution contains 5.85 g dissolved sodium chloride.
(c) HNO 3 (d) Phosphoric acid
The concentration of the solution will be (Na  23; Cl  35.5) [MP PMT 1999
112. How many grams of NaOH will be required to neutralize 12.2 (a) 1 molar (b) 2 molar
grams of benzoic acid [MP PMT 1999]
(c) 0.5 molar (d) 0.25 molar
(a) 40 gms (b) 4 gms 126. Molarity of a solution prepared by dissolving 75.5 g of pure KOH in
(c) 16 gms (d) 12.2 gms 540 ml solution is [BHU 1999]
(a) 3.05 M (b) 1.35 M
113. 10ml of conc. H 2 SO 4 (18 molar) is diluted to 1 litre. The
(c) 2.50 M (d) 4.50 M
approximate strength of dilute acid could be [JIPMER 1991]
127. Which one of the following is an extensive property
(a) 0.18 N (b) 0.09 N
[KCET 1998]
(c) 0.36 N (d) 1800 N
(a) Molar volume (b) Molarity
114. The normality of 10 lit. volume hydrogen peroxide is
(c) Number of moles (d) Mole fraction
[Kerala CET (Med.) 2003]
(a) 0.176 (b) 3.52 128. Addition of conc. HCl to saturated BaCl2 solution precipitates
(c) 1.78 (d) 0.88 BaCl2 ; because [AMU 2000]
(e) 17.8
(a) It follows from Le Chatelier’s principle
115. Essential quantity of ammonium sulphate taken for preparation of 1
molar solution in 2 litres is (b) Of common-ion effect
(a) 132 gm (b) 264 gm (c) Ionic product (Ba  ), (Cl  ) remains constant in a saturated
solution
(c) 198 gm (d) 212 gm
(d) At constant temperature, the product (Ba 2 ), (Cl  )2 remains
116. In a mixture of 1 gm H 2 and 8 gm O 2 , the mole fraction of
constant in a saturated solution
hydrogen is [Orissa JEE 2002]
(a) 0.667 (b) 0.5
 166 Solution and Colligative properties

129. How much water is needed to dilute 10 ml of 10 N hydrochloric acid (c) 1.96 gm (d) 19.6 gm
to make it exactly decinormal (0.1 N)
141. If 18 gm of glucose (C 6 H 12 O6 ) is present in 1000 gm of an
[EAMCET 1982]
(a) 990 ml (b) 1000 ml aqueous solution of glucose, it is said to be [CPMT 1986]
(c) 1010 ml (d) 100 ml (a) 1 molal (b) 1.1 molal
130. The formula weight of H 2 SO 4 is 98. The weight of the acid in (c) 0.5 molal (d) 0.1 molal
400ml of 0.1M solution is [EAMCET 1987] 142. The number of moles of KCl in 1000 ml of 3 molar solution is
(a) 2.45 g (b) 3.92 g (a) 1 (b) 2
(c) 4.90 g (d) 9 .8 g (c) 3 (d) 1.5
131. The molarity of pure water is 143. The unit of molality is [Pb. CET 2003]
[CPMT 1974, 88, 90; CMC Vellore 1991; RPET 1999; (a) Mole per litre (b) Mole per kilogram
NCERT 1974, 76; MP PMT 1999; AMU 2002] (c) Per mole per litre (d) Mole litre
(a) 55.6 (b) 5.56
144. A solution contains 1 mole of water and 4 mole of ethanol. The mole
(c) 100 (d) 18 fraction of water and ethanol will be
132. The molarity of a 0.2 N Na 2 CO 3 solution will be (a) 0.2 water + 0.8 ethanol
[MP PMT 1987; Pb. CET 2004] (b) 0.4 water + 0.6 ethanol
(a) 0.05 M (b) 0.2 M
(c) 0.6 water + 0.8 ethanol
(c) 0.1 M (d) 0.4 M
(d) 0.8 water + 0.2 ethanol
133. How many moles of water are present in 180 g of water
[JIPMER 1991; DPMT 1982; Manipal MEE 1995]
(a) 1 mole (b) 18 mole
Colligative properties
(c) 10 mole (d) 100 mole
1. The magnitude of colligative properties in all colloidal dispersions is
134. If we take 44 g of CO 2 and 14 g of N 2 what will be mole ….than solution [AMU 1999]
fraction of CO 2 in the mixture [KCET 1990] (a) Lower (b) Higher
(a) 1/5 (b) 1/3 (c) Both (d) None
(c) 2/3 (d) 1/4 2. Equimolar solutions in the same solvent have [AIEEE 2005]
135. What is the volume of 0.1 N HCl required to react completely
(a) Same boiling point but different freezing point
with 1 .0 g of pure calcium carbonate
(b) Same freezing point but different boiling point
(Ca  40, C  12 and O  16) [KCET 1998]
(c) Same boiling and same freezing points
(a) 150 cm 3 (b) 250 cm 3 (d) Different boiling and different freezing points
(c) 200 cm 3 (d) 100 cm 3 3. Which of the following is a colligative property
[AFMC 1992; CBSE PMT 1992; MP PMT 1996, 2003]
136. The amount of NaOH in gms in 250 cm 3 of a
(a) Osmotic pressure (b) Boiling point
0.100 M NaOH solution would be (c) Vapour pressure (d) Freezing point
(a) 4 gm (b) 2 gm 4. The colligative properties of a solution depend on
(c) 1 gm (d) 2.5 gm [CPMT 1984; MP PMT 1993; UPSEAT 2001; Kerala PMT 2002]
137. 4.0 gm of NaOH are contained in one decilitre of solution. Its (a) Nature of solute particles present in it
molarity would be
(b) Nature of solvent used
(a) 4 M (b) 2 M
(c) Number of solute particles present in it
(c) 1 M (d) 1.5 M
(d) Number of moles of solvent only
138. When 90 gm of water is mixed with 300 gm of acetic acid. The total 5. Which of the following is not a colligative property
number of moles will be
[BHU 1982; CPMT 1988; DPMT 1985; MP PET 1999]
(a) 5 (b) 10
(a) Osmotic pressure
(c) 15 (d) 20
(b) Elevation in B.P.
139. A molal solution is one that contains one mole of a solute in
(c) Vapour pressure
[NCERT 1983; DPMT 1983; CPMT 1985; IIT 1986;
(d) Depression in freezing point
MP PMT 1987; EAMCET 1990; MP PET 1994, 99]
6. Which of the following is not a colligative property
(a) 1000 gm of the solvent
[MP PET 2001; CPMT 2001; Pb. CET 2001]
(b) One litre of the solvent
(a) Optical activity
(c) One litre of the solution (b) Elevation in boiling point
(d) 22.4 litres of the solution (c) Osmotic pressure
140. What weight of ferrous ammonium sulphate is needed to prepare (d) Lowering of vapour pressure
100 ml of 0.1 normal solution (mol. wt. 392)
7. Colligative properties of a solution depends upon
[CPMT 1983]
[MP PMT 1994, 2002]
(a) 39.2 gm (b) 3.92 gm
(a) Nature of both solvent and solute
 Solution and Colligative properties 167
(b) The relative number of solute and solvent particles (a) Directly proportional to the mole fraction of the solvent
(c) Nature of solute only (b) Inversely proportional to the mole fraction of the solute
(d) Nature of solvent only (c) Inversely proportional to the mole fraction of the solvent
8. Which is not a colligative property (d) Directly proportional to the mole fraction of the solute
[CPMT 1984; BHU 1982; Manipal MEE 1995] 7. When a substance is dissolved in a solvent the vapour pressure of
(a) Refractive index the solvent is decreased. This results in
(b) Lowering of vapour pressure [NCERT 1981]
(c) Depression of freezing point (a) An increase in the b.p. of the solution
(d) Elevation of boiling point (b) A decrease in the b.p. of the solvent
9. Which of the following is a colligative property (c) The solution having a higher freezing point than the solvent
[BHU 1990; NCERT 1983; MP PMT 1983; DPMT 1981, 83; (d) The solution having a lower osmotic pressure than the solvent
MP PET/PMT 1998; AIIMS 1999; Pb. CET 2000] 8. If P o and P are the vapour pressure of a solvent and its solution
(a) Surface tension (b) Viscosity respectively and N 1 and N 2 are the mole fractions of the solvent
(c) Osmotic pressure (d) Optical rotation and solute respectively, then correct relation is
10. Colligative properties are used for the determination of (a) P  P o N1 (b) P  Po N2
[Kerala CET (Engg.) 2002]
(a) Molar Mass (c) P o  P N 2 (d) P  P o (N1 / N 2 )
(b) Equivalent weight 9. An aqueous solution of methanol in water has vapour pressure
(c) Arrangement of molecules (a) Equal to that of water
(d) Melting point and boiling point (b) Equal to that of methanol
(c) More than that of water
(d) Both (a) and (b)
(d) Less than that of water
11. What does not change on changing temperature
10. The pressure under which liquid and vapour can coexist at
[DCE 2001] equilibrium is called the
(a) Mole fraction (b) Normality (a) Limiting vapour pressure
(c) Molality (d) None of these (b) Real vapour pressure
(c) Normal vapour pressure
Lowering of vapour pressure (d) Saturated vapour pressure
11. Which solution will show the maximum vapour pressure at 300 K
1. Vapour pressure of CCl 4 at 25 o C is 143mm of Hg 0.5 gm (a) 1 M C 12 H 22 O11 (b) 1 M CH 3 COOH
of a non-volatile solute (mol. wt. = 65) is dissolved in
100 ml CCl 4 . Find the vapour pressure of the solution (Density of (c) 1 M NaCl 2 (d) 1 M NaCl
12. The relative lowering of the vapour pressure is equal to the ratio
CCl 4  1.58 g / cm 2 ) [CBSE PMT 1998] between the number of
(a) 141.43 mm (b) 94.39 mm [EAMCET 1991; CBSE PMT 1991]
(a) Solute moleules and solvent molecules
(c) 199.34 mm (d) 143.99 mm
(b) Solute molecules and the total molecules in the solution
2. For a solution of volatile liquids the partial vapour pressure of each (c) Solvent molecules and the total molecules in the solution
component in solution is directly proportional to (d) Solvent molecules and the total number of ions of the solute
(a) Molarity (b) Mole fraction
(c) Molality (d) Normality 13. 5cm 3 of acetone is added to 100 cm 3 of water, the vapour
3. “The relative lowering of the vapour pressure is equal to the mole pressure of water over the solution
fraction of the solute.” This law is called (a) It will be equal to the vapour pressure of pure water
[MP PET 1997, 2001] (b) It will be less than the vapour pressure of pure water
(a) Henry's law (b) Raoult's law (c) It will be greater than the vapour pressure of pure water
(c) Ostwald's law (d) Arrhenius's law (d) It will be very large
14. At 300 K, when a solute is added to a solvent its vapour pressure
4. The relative lowering of vapour pressure produced by dissolving 71.5 over the mercury reduces from 50 mm to 45 mm. The value of
g of a substance in 1000 g of water is 0.00713. The molecular weight mole fraction of solute will be
of the substance will be (a) 0.005 (b) 0.010
[DPMT 2001] (c) 0.100 (d) 0.900
(a) 18.0 (b) 342 15. A solution has a 1 : 4 mole ratio of pentane to hexane. The vapour
(c) 60 (d) 180 pressure of the pure hydrocarbons at 20°C are 440 mmHg for
pentane and 120 mmHg for hexane. The mole fraction of pentane in
5. When mercuric iodide is added to the aqueous solution of potassium
the vapour phase would be
iodide, the [IIT 1987]
[CBSE PMT 2005]
(a) Freezing point is raised (a) 0.549 (b) 0.200
(b) Freezing point is lowered (c) 0.786 (d) 0.478
(c) Freezing point does not change 16. Benzene and toluene form nearly ideal solutions. At 20°C, the
(d) Boiling point does not change vapour pressure of benzene is 75 torr and that of toluene is 22 torr.
The parial vapour pressure of benzene at 20°C for a solution
6. Vapour pressure of a solution is containing 78g of benzene and 46g of toluene in torr is [AIEEE 2005]
[EAMCET 1988; MP PET 1994] (a) 50 (b) 25
 168 Solution and Colligative properties

(c) 37.5 (d) 53.5 (c) 20 (d) 180

17. The vapour pressure lowering caused by the addition of 100 g of 28. “Relative lowering in vapour pressure of solution containing non-
sucrose(molecular mass = 342) to 1000 g of water if the vapour volatile solute is directly proportional to mole fraction of solute”.
pressure of pure water at 25 o C is 23.8 mm Hg Above statement is [AFMC 2004]
[RPET 1999] (a) Henry law (b) Dulong and Petit law
(a) 1.25 mm Hg (b) 0.125 mm Hg (c) Raoult's law (d) Le-Chatelier's principle
(c) 1.15 mm Hg (d) 00.12 mm Hg 29. An ideal solution was obtained by mixing methanol and ethanol. If
18. Which of the following is incorrect [J & K 2005] the partial vapour pressure of methanol and ethanol are
(a) Relative lowering of vapour pressure is independent 2.619 kPa and 4.556 kPa respectively, the composition of the
(b) The vapour pressure is a colligative property vapour (in terms of mole fraction) will be
(c) Vapour pressure of a solution is lower than the vapour
[Pb. PMT 1998]
pressure of the solvent
(d) The relative lowering of vapour pressure is directly (a) 0.635 methanol, 0.365 ethanol
propertional to the original pressure (b) 0.365 methanol, 0.635 ethanol
19. Among the following substances the lowest vapour pressure is (c) 0.574 methanol, 0.326 ethanol
exerted by (d) 0.173 methanol, 0.827 ethanol
(a) Water (b) Mercury
30. The vapour pressure of two liquids P and Q are 80 and 600 torr,
(c) Kerosene (d) Rectified spirit respectively. The total vapour pressure of solution obtained by
20. According to Raoult's law the relative lowering of vapour pressure of mixing 3 mole of P and 2 mole of Q would be
a solution of volatile substance is equal to
[CBSE PMT 2005]
[CBSE PMT 1995; BHU 2001]
(a) Mole fraction of the solvent (a) 140 torr (b) 20 torr
(b) Mole fraction of the solute (c) 68 torr (d) 72 torr
(c) Weight percentage of a solute 31. The vapour pressure of benzene at a certain temperature is
(d) Weight percentage of a solvent 640 mm of Hg . A non-volatile and non-electrolyte solid weighing
21. When a substance is dissolved in a solvent, the vapour pressure of 2.175 g is added to 39.08 g of benzene. The vapour pressure of
the solvent is decreased. This results in
[MP PMT 1983; NCERT 1981] the solution is 600mm of Hg . What is the molecular weight of
(a) An increase in the boiling point of the solution solid substance
(b) A decrease in the boiling point of solvent [CBSE PMT 1999; AFMC 1999]
(c) The solution having a higher freezing point than the solvent (a) 49.50 (b) 59.6
(d) The solution having a lower osmotic pressure than the solvent (c) 69.5 (d) 79.8
22. The vapour pressure of a liquid depends on 32. Which one of the following is the expression of Raoult's law
(a) Temperature but not on volume p  ps n ps  p N
(b) Volume but not on temperature (a)  (b) 
p nN p N n
(c) Temperature and volume
(d) Neither on temperature nor on volume p  ps N ps  p N  n
(c)  (d) 
23. Which one of the statements given below concerning properties of ps N n ps N
solutions, describes a colligative effect [AIIMS 2003]
p  vapour pressure of pure solvent
(a) Boiling point of pure water decreases by the addition of ethanol
(b) Vapour pressure of pure water decreases by the addition of p s  vapour pressure of the solution
nitric acid n  number of moles of the solute
(c) Vapour pressure of pure benzene decreases by the addition of
naphthalene N  number of moles of the solvent
(d) Boiling point of pure benzene increases by the addition 33. Which has maximum vapour pressure [DPMT 2001]
of toluene (a) HI (b) HBr
24. The atmospheric pressure is sum of the (c) HCl (d) HF
[Kerala CET (Med.) 2002] 34. When a non-volatile solute is dissolved in a solvent, the relative
(a) Pressure of the biomolecules lowering of vapour pressure is equal to
(b) Vapour pressure of atmospheric constituents [BHU 1979; IIT 1983]
(c) Vapour pressure of chemicals and vapour pressure of volatiles (a) Mole fraction of solute
(d) Pressure created on to atmospheric molecules (b) Mole fraction of solvent
25. The vapour pressure of pure liquid A is 0.80 atm. On mixing a non- (c) Concentration of the solute in grams per litre
volatile B to A, its vapour pressure becomes 0.6 atm. The mole
fraction of B in the solution is [MP PET 2003]
(d) Concentration of the solute in grams 100 ml
(a) 0.150 (b) 0.25 35. 60 gm of Urea (Mol. wt 60) was dissolved in 9.9 moles, of water. If
(c) 0.50 (d) 0.75 the vapour pressure of pure water is Po , the vapour pressure of
26. Lowering of vapour pressure is highest for [BHU 1997] solution is [DCE 2000]
(a) Urea (b) 0.1M glucose (a) 0.10 Po (b) 1.10 Po
(c) 0.1 M MgSO4 (d) 0.1 M BaCl2 (c) 0.90 Po (d) 0.99 Po
27. An aqueous solution of glucose was prepared by dissolving 18 g of
glucose in 90 g of water. The relative lowering in vapour pressure is 36. The vapour pressure of water at 20 o C is 17.54 mm. When 20g of
[KCET 2002] a non-ionic, substance is dissolved in 100g of water, the vapour
(a) 0.02 (b) 1
 Solution and Colligative properties 169
pressure is lowered by 0.30 mm. What is the molecular weight of 1. Which of the following liquid pairs shows a positive deviation from
the substances [UPSEAT 2001] Raoult's law
(a) 210.2 (b) 206.88 [MP PET 1993; UPSEAT 2001; AIEEE 2004]
(c) 215.2 (d) 200.8 (a) Water-nitric acid (b) Benzene-methanol
37. In an experiment, 1 g of a non-volatile solute was dissolved in 100 g (c) Water-hydrochloric acid (d) Acetone-chloroform
of acetone (mol. mass = 58) at 298K. The vapour pressure of the 2. Which one of the following is non-ideal solution
solution was found to be 192.5 mm Hg. The molecular weight of the
solute is (vapour pressure of acetone = 195 mm Hg) (a) Benzene + toluene
[CPMT 2001; CBSE PMT 2001; Pb CET 2002] (b) n -hexane + n -heptane
(a) 25.24 (b) 35.24 (c) Ethyl bromide + ethyl iodide
(c) 45.24 (d) 55.24 (d) CCl 4  CHCl 3
38. How many grams of CH 3 OH should be added to water to
3. A non ideal solution was prepared by mixing 30 ml chloroform and
prepare 150 ml solution of 2 M CH 3 OH [CBSE PMT 1994] 50 ml acetone. The volume of mixture will be [Pb. CET 2003]
(a) 9.6 (b) 2.4 (a) > 80 ml (b) < 80 ml
(c) 9.6  10 3
(d) 2.4  10 3 (c) = 80 ml (d)  80 ml
39. The vapour pressure of a solvent decreased by 10mm of mercury, 4. Which pair from the following will not form an ideal solution
when a non-volatile solute was added to the solvent. The mole (a) CCl 4  SiCl4 (b) H 2 O  C 4 H 9 OH
fraction of the solute in the solution is 0.2. What should be the mole
fraction of the solvent, if decrease in the vapour pressure is to be (c) C 2 H 5 Br  C 2 H 5 I (d) C6 H 14  C7 H 16
20 mm of mercury 5. An ideal solution is that which [MP PMT 1996]
[CBSE PMT 1998] (a) Shows positive deviation from Raoult's law
(a) 0.8 (b) 0.6 (b) Shows negative deviation from Raoult's law
(c) 0.4 (d) 0.2
(c) Has no connection with Raoult's law
40. For a dilute solution, Raoult's law states that
(d) Obeys Raoult's law
[CPMT 1987; BHU 1979; IIT 1985; MP PMT 2004;
MNR 1988; AMU 2002] 6. Which one of the following mixtures can be separated into pure
components by fractional distillation [CPMT 1987]
(a) The lowering of vapour pressure is equal to mole fraction of
solute (a) Benzene – toluene (b) Water – ethyl alcohol
(b) The relative lowering of vapour pressure is equal to mole (c) Water – nitric acid (d) Water – hydrochloric acid
fraction of solute 7. All form ideal solutions except [DPMT 1983; MP PET 1997]
(c) The relative lowering of vapour pressure is proportional to the (a) C 2 H 5 Br and C 2 H 5 I (b) C 6 H 5 Cl and C 6 H 5 Br
amount of solute in solution
(d) The vapour pressure of the solution is equal to the mole (c) C 6 H 6 and C 6 H 5 CH 3 (d) C 2 H 5 I and C 2 H 5 OH
fraction of solvent
8. Which property is shown by an ideal solution
41. The vapour pressure of a solvent A is 0.80 atm When a non-volatile
[MP PET 2002]
substance B is added to this solvent its vapour pressure drops to 0.6
atm. What is mole fraction of B in solution (a) It [MP
follows
PMTRaoult's
2000, 01]law (b) H mix  0
(a) 0.25 (b) 0.50
(c) Vmix  0 (d) All of these
(c) 0.75 (d) 0.90
42. Determination of correct molecular mass from Raoult's law is 9. When two liquid A and B are mixed then their boiling points
applicable to becomes greater than both of them. What is the nature of this
solution
(a) An electrolyte in solution
(a) Ideal solution
(b) A non-electrolyte in a dilute solution
(b) Positive deviation with non ideal solution
(c) A non-electrolyte in a concentrated solution (c) Negative deviation with non ideal solution
(d) An electrolyte in a liquid solvent (d) Normal solution
43. If two substances A and B have PA0 : PB0  1 : 2 and have mole 10. In mixture A and B components show –ve deviation as
[AIEEE 2002]
fraction in solution 1 : 2 then mole fraction of A in vapours [DPMT 2005]
(a) 0.33 (b) 0.25 (a) Vmix  0
(c) 0.52 (d) 0.2 (b) H mix  0
44. A dry air is passed through the solution, containing the 10 gm of (c) A-B interaction is weaker than A-A and B-B interaction
solute and 90 gm of water and then it pass through pure water. (d) A-B interaction is strong than A-A and B-B interaction
There is the depression in weight of solution wt by 2.5 gm and in 11. In which case Raoult's law is not applicable
weight of pure solvent by 0.05 gm. Calculate the molecular weight
of solute [Kerala CET 2005] (a) 1M NaCl (b) 1 M urea
(a) 50 (b) 180 (c) 1 M glucose (d) 1 M sucrose
(c) 100 (d) 25 12. A solution that obeys Raoult's law is [EAMCET 1993]
(e) 51 (a) Normal (b) Molar
(c) Ideal (d) Saturated
Ideal and Non-ideal solution 13. An example of near ideal solution is
(a) n -heptane and n -hexane
 170 Solution and Colligative properties

(b) CH 3 COOH  C5 H 5 N [JIPMER 1997]

(a) S mix  0 (b) H mix  0
(c) CHCl 3  (C 2 H 5 )2 O
(c) It obeys Raoult's law (d) Vmix  0
(d) H 2 O  HNO 3
26. Which of the following does not show negative deviation from
14. A mixture of liquid showing positive deviation in Raoult's law is Raoult’s law [MP PMT 2001]
(a) (CH 3 )2 CO  C 2 H 5 OH (b) (CH 3 )2 CO  CHCl 3 (a) Acetone-Chloroform (b) Acetone-Benzene
(c) (C 2 H 5 )2 O  CHCl 3 (d) (CH 3 )2 CO  C6 H 5 NH 2 (c) Chloroform-Ether (d) Chloroform-Benzene
27. A mixture of benzene and toluene forms [MP PMT 1993]
15. All form ideal solution except [UPSEAT 2001]
(a) An ideal solution (b) Non-ideal solution
(a) C2 H 5 Br and C 2 H 5 I (b) C 2 H 5 Cl and C6 H 5 Br (c) Suspension (d) Emulsion
(c) C6 H 6 and C6 H 5 CH 3 (d) C 2 H 5 I and C2 H 5 OH 28. Which of the following is an ideal solution
16. Formation of a solution from two components can be considered as (a) Water + ethanol
[CBSE PMT 2003]
(b) Chloroform + carbon tetrachloride
(i) Pure solvent  separated solvent molecules H 1
(c) Benzene + toluene
(ii) Pure solute  separated solute molecules H 2 (d) Water + hydrochloric acid
(iii) Separated solvent and solute molecules  solution H 3 29. When ethanol mixes in cyclohexane; cyclohexane reduces the
Solution so formed will be ideal if intermolecular forces between ethanol molecule. In this, liquid pair
(a) H soln  H 3  H1  H 2 shows
(a) Positive deviation by Raoult's law
(b) H soln  H1  H 2  H 3 (b) Negative deviation by Raoult's law
(c) H soln  H1  H 2  H 3 (c) No deviation by Raoult's law
(d) Decrease in volume
(d) H soln  H1  H 2  H 3 30. Liquids A and B form an ideal solution [AIEEE 2003]
17. Identify the mixture that shows positive deviation from Raoult’s law [Kerala CET (Engg.)
(a) 2002]
The enthalpy of mixing is zero
(a) CHCl 3  (CH 3 )2 CO (b) (CH 3 )2 CO  C6 H 5 NH 2 (b) The entropy of mixing is zero
(c) The free energy of mixing is zero
(c) CHCl 3  C6 H 6 (d) (CH 3 )2 CO  CS 2
(d) The free energy as well as the entropy of mixing are each zero
(e) C6 H 5 N  CH 3 COOH
18. When acetone is added to chloroform, then hydrogen bond is Azeotropic mixture
formed between them.These liquids show
(a) Positive deviation from Raoult's law 1. The azeotropic mixture of water (b. p.100 o C) and
(b) Negative deviation from Raoult's law o o
HCl (b. p. 85 C) boils at 108.5 C . When this mixture is
(c) No deviation from Raoult's law
distilled it is possible to obtain [IIT 1981]
(d) Volume is slightly increased
19. Which of the following is true when components forming an ideal (a) Pure HCl
solution are mixed [AMU 2000] (b) Pure water
(a) H m  Vm  0 (b) H m  Vm (c) Pure water as well as pure HCl
(c) H m  Vm (d) H m  Vm  1 (d) Neither HCl nor H 2 O in their pure states
20. The liquid pair benzene-toluene shows [MP PET 1995] 2. An azeotropic solution of two liquids has boiling point lower than
(a) Irregular deviation from Raoult's law either when it [NCERT 1978; IIT 1981]
(b) Negative deviation from Raoult's law (a) Shows a negative deviation from Raoult's law
(c) Positive deviation from Raoult's law
(b) Shows no deviation from Raoult's law
(d) Practically no deviation from Raoult's law
21. The solution which shows negative or positive deviation by Raoult's (c) Shows positive deviation from Raoult's law
law, is called (d) Is saturated
(a) Ideal solution (b) Real solution 3. A liquid mixture boils without changing constituent is called
(c) Non-ideal solution (d) Colloidal solution [DPMT 1982; CPMT 1987]
22. Which of the following does not show positive deviation from (a) Stable structure complex
Raoult’s law [MP PMT 2000]
(a) Benzene-Chloroform (b) Binary liquid mixture
(b) Benzene-Acetone (c) Zeotropic liquid mixture
(c) Benzene-Ethanol (d) Azeotropic liquid mixture
(d) Benzene-Carbon tetrachloride 4. Azeotropic mixture are [CPMT 1982]
23. Which of the following mixture shows positive deviation by ideal (a) Constant temperature boiling mixtures
behaviour
(b) Those which boils at different temperatures
(a) CHCl 3  (CH 3 )2 CO (b) C6 H 6  C6 H 5 CH 3
(c) Mixture of two solids
(c) H 2 O  HCl (d) CCl 4  CHCl 3 (d) None of the above
24. Which property is not found in ideal solution 5. A mixture of two completely miscible non-ideal liquids which distil
(a) PA  PAo  X A (b) H mix  0 as such without change in its composition at a constant temperature
as though it were a pure liquid. This mixture is known as
(c) Vmix  0 (d) All of these
(a) Binary liquid mixture (b) Azeotropic mixture
25. Which of the following is not correct for ideal solution
 Solution and Colligative properties 171
(c) Eutectic mixture (d) Ideal mixture 10. Two solutions A and B are separated by semi- permeable membrane.
If liquid flows form A to B then [MH CET 2000]

Osmosis and Osmotic pressure of the solution (a) A is less concentrated than B
(b) A is more concentrated than B
1. If 3 gm of glucose (mol. wt. 180) is dissolved in 60 gm of water at (c) Both have same concentration
15 o C . Then the osmotic pressure of this solution will be (d) None [MP of
PMTthese
1986]
(a) 0.34 atm (b) 0.65 atm 11. A 5% solution of canesugar (mol. wt. =342) is isotonic with 1%
solution of a substance X . The molecular weight of X is [
(c) 6.57 atm (d) 5.57 atm
(a) 34.2 (b) 171.2
2. The concentration in gms per litre of a solution of cane sugar
(M  342) which is isotonic with a solution containing 6 gms of (c) 68.4 (d) 136.8
12. Which of the following colligative properties can provide molar mass
urea (M  60) per litre is of proteins (or polymers or colloids) with greater precision[Kerala PMT 2004]
[Orissa PMT 1989] (a) Relative lowering of vapour pressure
(a) 3.42 (b) 34.2 (b) Elevation of boiling point
(c) 5.7 (d) 19 (c) Depression in freezing point
3. Osmotic pressure is 0.0821 atm at temperature of 300 K . Find (d) Osmotic pressure
concentration in mole/litre [Roorkee 1990] (e) Rast's method
(a) 0.033 (b) 0.066 13. The average osmotic pressure of human blood is 7.8 bar at 37 o C .
(c) 0.33  10 2 (d) 3 What is the concentration of an aqueous NaCl solution that could be
used in the blood stream [AIIMS 2004]
4. Osmotic pressure of a solution containing 0.1 mole of solute per litre
(a) 0.16 mol / L (b) 0.32 mol / L
at 273 K is (in atm) [CPMT 1988]
0 .1 (c) 0.60 mol / L (d) 0.45 mol / L
(a)  0 .08205  273 (b) 0.1  1  0.08205  273
1 14. A solution of sucrose(molar mass = 342 g/mol) is prepared by
dissolving 68.4 g of it per litre of the solution, what is its osmotic
1 0.1 273
(c)  0 .08205  273 (d)  pressure (R = 0.082 lit. atm. k 1 mol 1 ) at 273k
0 .1 1 0 .08205 [UPSEAT 2001]
5. A solution contains non-volatile solute of molecular mass M p . (a) 6.02 atm (b) 4.92 atm
Which of the following can be used to calculate molecular mass of (c) 4.04 atm (d) 5.32 atm
the solute in terms of osmotic pressure (m = Mass of solute, V = 15. Blood has been found to be isotonic with [CPMT 1994]
Volume of solution and  = Osmotic pressure) (a) Normal
[CBSE saline solution
PMT 2002]

m   m  RT (b) Saturated NaCl solution

(a) Mp    VRT (b) Mp   
  V  (c) Saturated KCl solution
(d) Saturated solution of a 1 : 1 mixture of NaCl and KCl
m   m 
(c) Mp    (d) Mp    RT 16. If 20 g of a solute was dissolved in 500 ml of water and osmotic
 V  RT V pressure of the solution was found to be 600 mm of Hg at 15 o C,
6. The osmotic pressure of a 5% (wt/vol) solution of cane sugar at then molecular weight of the solute is
150 o C is [AMU 1999] [BHU 2004]
(a) 2.45 atm (b) 5.078 atm (a) 1000 (b) 1200
(c) 3.4 atm (d) 4 atm (c) 1400 (d) 1800
17. The osmotic pressure of 0.4% urea solution is 1.66 atm and. that of
7. The relationship between osmotic pressure at 273 K when 10 g a solution of suger of 3.42 % is 2.46 atm. When both the solution
glucose (P1 ),10 g urea (P2 ) and 10 g sucrose (P3 ) are dissolved are mixed then the osmotic pressure of the resultant solution will be[MP PMT 19
in 250ml of water is [CBSE PMT 1996]
(a) 1.64 atm (b) 2.46 atm
(c) 2.06 atm (d) 0.82 atm
(a) P1  P2  P3 (b) P3  P1  P2
18. Blood is isotonic with [DCE 2000]
(c) P2  P1  P3 (d) P2  P3  P1 (a) 0.16 M NaCl (b) Conc. NaCl
8. In osmosis [DPMT 1985] (c) 50 % NaCl (d) 30 % NaCl
(a) Solvent molecules move from higher concentration to lower 19. Which inorganic precipitate acts as semipermeable membrane or
concentration The chemical composition of semipermeable membrane is[CPMT 1984, 90; MP PM
(b) Solvent molecules move from lower to higher concentration (a) Calcium sulphate (b) Barium oxalate
(c) Nickel phosphate (d) Copper ferrocyanide
(c) Solute molecules move from higher to lower concentration
(d) Solute molecules move from lower to higher concentration 20. The osmotic pressure of 1 m solution at 27 o C is [CPMT 1999]
9. Semipermeable membrane is that which permits the passage of[BHU 1979; CPMT 1977, 90; atm
(a) 84,2.46 MP PMT 1994] (b) 24.6 atm
(a) Solute molecules only (c) 1.21 atm (d) 12.1 atm
(b) Solvent molecules only 21. Osmotic pressure of a solution can be measured quickly and
accurately by [JIPMER 1991; CPMT 1983]
(c) Solute and solvent molecules both
(a) Berkeley and Hartley's method
(d) Neither solute nor solvent molecules
 172 Solution and Colligative properties

(b) Morse's method (a) 8.4 atm (b) 0.48atm

(c) Pfeffer's method (c) 4.8 atm (d) 4.0 atm
(d) De Vries method 33. Diffusion of solvent through a semi permeable membrane is called
22. The solution in which the blood cells retain their normal form are (a) Diffusion (b) Osmosis
with regard to the blood [CBSE PMT 1991]
(c) Active absorption (d) Plasmolysis
(a) Isotonic (b) Isomotic
34. Solutions having the same osmotic pressure under a given set of
(c) Hypertonic (d) Equinormal conditions are known as [BHU 1979; EAMCET 1979;
23. The osmotic pressure of a solution is given by the relation CPMT 1990; MP PMT 1999; AFMC 1999, 2001]
[CPMT 1983, 84, 87, 93, 94] (a) Hypertonic (b) Hypotonic
RT CT (c) Normal (d) Isotonic
(a) P (b) P
C R 35. At low concentrations, the statement that equimolal solutions under a
given set of experimental conditions have equal osmotic pressure is
RC P
(c) P (d)  RT true for [EAMCET 1979; BHU 1979]
T C (a) All solutions
24. The osmotic pressure of a solution is directly proportional to (b) Solutions of non-electrolytes only
(a) The molecular concentration of solute (c) Solutions of electrolytes only
(b) The absolute temperature at a given concentration (d) None of these
(c) The lowering of vapour pressure 36. Which one of the following would lose weight on exposure to
(d) All of the above atmosphere [NCERT 1975]
25. What would happen if a thin slice of sugar beet is placed in a (a) Concentrated H 2 SO 4
concentrated solution of NaCl [CMC Vellore 1986]
(b) Solid NaOH
(a) Sugar beet will lose water from its cells
(c) A saturated solution of CO 2
(b) Sugar beet will absorb water from solution
(c) Sugar beet will neither absorb nor lose water (d) Anhydrous sodium carbonate
(d) Sugar beet will dissolve in solution 37. The molecular weight of NaCl determined by osmotic pressure
method will be
26. The osmotic pressure of a dilute solution is given by
(a) Same as theoritical value
[MP PMT 1987]
(b) Higher than theoritical value
(a) P  Po x (b) V  nRT (c) Lower than theoritical value
P Po  P (d) None of these
(c) P  Po N 2 (d)  38. The osmotic pressure of solution increases, if
Po Po
[CPMT 1985, 87, 91]
27. Which statement is wrong regarding osmotic pressure (P), volume (a) Temperature is decreased
(V) and temperature (T) [MP PMT 1985]
(b) Solution concentration is increased
1 (c) Number of solute molecules is increased
(a) P if T is constant
V (d) Volume is increased
(b) P  T if V is constant 39. At the same temperature, following solution will be isotonic
[MP PMT 1985]
(c) P  V if T is constant
(a) 3.24 gm of sucrose per litre of water and 0.18 gm glucose per
(d) PV is constant if T is constant litre of water
28. Isotonic solutions have [DPMT 1984; MP PMT 1986] (b) 3.42 gm of sucrose per litre and 0.18 gm glucose in 0.1 litre
(a) Equal temperature (b) Equal osmotic pressure water
(c) Equal volume (d) Equal amount of solute (c) 3.24 gm of sucrose per litre of water and 0.585 gm of sodium
29. Which of the following associated with isotonic solutions is not chloride per litre of water
correct [AMU 2002] (d) 3.42 gm of sucrose per litre of water and 1.17 gm of sodium
(a) They will have the same osmotic pressure chloride per litre of water
(b) They have the same weight concentrations 40. The osmotic pressure of a decinormal solution of BaCl2 in water
(c) Osmosis does not take place when the two solutions are is
separated by a semipermeable membrane (a) Inversely proportional to its celsius temperature
(d) They will have the same vapour pressure (b) Inversely proportional to its absolute temperature
30. Isotonic solution have the same (c) Directly proportional to its celsius temperature
[EAMCET 1979; JIPMER 1991, 2002; (d) Directly proportional to its absolute temperature
AFMC 1995; MP PMT 2002] 41. Blood cells will remain as such in [CPMT 2004]
(a) Density (b) Molar concentration
(a) Hypertonic solution (b) Hypotonic solution
(c) Normality (d) None of these
(c) Isotonic solution (d) None of these
31. A 0.6% solution of urea (molecular weight = 60) would be isotonic
with [NCERT 1982; DCE 2002] 42. The osmotic pressure of a dilute solution is directly proportional to
the [MP PMT 1987]
(a) 0.1M glucose (b) 0.1M KCl
(a) Diffusion rate of the solute
(c) 0.6% glucose solution (d) 0.6% KCl solution (b) Ionic concentration
32. The value of osmotic pressure of a 0.2 M aqueous solution at 293K (c) Elevation of B.P.
is [AMU 2002]
 Solution and Colligative properties 173
(d) Flow of solvent from a concentrated to a dilute solution 52. If molecular weight of compound is increased then sensitivity is
43. The osmotic pressure in atmospheres of 10% solution of canesugar decreased in which of the following methods
[DCE 2001]
at 69 o C is [AFMC 1991]
(a) Elevation in boiling point(b) Viscosity
(a) 724 (b) 824
(c) Osmosis (d) Dialysis
(c) 8.21 (d) 7.21
53. If solubility of NaCl at 20 o C is 35 gm per 100 gm of water.
44. Which of the following molecules would diffuse through a cell
membrane [NCERT 1978] Then on adding 50 gm of NaCl to the same volume at same
temperature the salt remains undissolved is
(a) Fructose (b) Glycogen
(a) 15 gm (b) 20 gm
(c) Haemoglobin (d) Catalase
(c) 50 gm (d) 35 gm
45. Two solutions of KNO 3 and CH 3 COOH are prepared separately. 54. Which of the following associated with isotonic solution is not
Molarity of both is 0 .1 M and osmotic pressures are P1 and P2 correct
respectively. The correct relationship between the osmotic pressures is (a) They will have the same osmotic pressure
[CPMT 1983, 84; Pb CET 2004] (b) They have the same weight concentration
(a) P2  P1 (b) P1  P2 (c) Osmosis does not take place when the two solutions are
separated by a semipermeable membrane
P1 P2 (d) They will have the same vapour pressure
(c) P1  P2 (d) 
P1  P2 P1  P2 55. If osmotic pressure of a solution is 2 atm at 273 K , then at
46. The osmotic pressure of a dilute solution of a non-volatile solute is 546 K [JIPMER 1999] pressure is
, the osmotic
(a) Directly proportional to its temperature on the centigrade scale (a) 0.5 atm (b) 1 atm
(b) Inversely proportional to its temperature on the Kelvin scale (c) 2 atm (d) 4 atm
(c) Directly proportional to its temperature on the Kelvin scale 56. In osmosis reaction, the volume of solution
(d) Inversely proportional to its temperature on the centigrade (a) Decreases slowly (b) Increases slowly
scale (c) Suddenly increases (d) No change
47. Osmotic pressure of a urea solution at 10 o C is 500 mm . 57. As a result of osmosis the volume of solution
Osmotic pressure of the solution become 105.3 mm. When it is [JIPMER 2000]

diluted and temperature raised to 25 o C. The extent of dilution is (a) Increases

[MP PET 2004] (c) Decreases
(a) 6 Times (b) 5 Times (c) Remains constant (d) Increases or decreases
(c) 7 Times (d) 4 Times 58. A solution of urea contain 8.6 gm/litre (mol. wt. 60.0). It is isotonic
with a 5% solution of a non-volatile solute. The molecular weight of
48. If a 0.1M solution of glucose (mol. wt. 180) and 0.1 molar the solute will be [MP PMT 1986]
solution of urea (mol. wt. 60) are placed on the two sides of a (a) 348.9 (b) 34.89
semipermeable membrane to equal heights, then it will be correct to (c) 3489 (d) 861.2
say [CBSE PMT 1992]
59. One mole each of urea, glucose and sodium chloride were dissolved
(a) There will be no net movement across the membrane in one litre of water Equal osmotic pressure will be produced by
(b) Glucose will flow across the membrane into urea solution solutions of [MH CET 1999]
(a) Glucose and sodium chloride
(c) Urea will flow across the membrane into glucose solution
(b) Urea and glucose
(d) Water will flow from urea solution into glucose solution (c) Sodium chloride and urea
49. At constant temperature, the osmotic pressure of a solution (d) None of these
[CPMT 1986] 60. Which of the following aqueous solutions produce the same osmotic
(a) Directly proportional to the concentration pressure [Roorkee 1999]
(b) Inversely proportional to the concentration (a) 0.1 M NaCl solution
(b) 0.1 M glucose solution
(c) Directly proportional to the square of the concentration
(c) 0.6 g urea in 100 ml solution
(d) Directly proportional to the square root of the concentration (d) 1.0 g of a non-electrolyte solute (X) in 50 ml solution (Molar
50. The solution containing 4.0 gm of a polyvinyl chloride polymer in mass of X = 200)
1 litre of dioxane was found to have an osmotic pressure 61. Which of the following aqueous solutions are isotonic (R  0.082
6.0  10 4 atmosphere at 300 K , the value of R used is 0.082 atm K 1 mol 1 ) [Roorkee Qualifying 1998]
litre atmosphere mole 1k 1 . The molecular mass of the polymer (a) 0.01 M glucose
was found to be [NCERT 1978]
(b) 0.01 M NaNO 3
(a) 3.0  10 2 (b) 1.6  10 5
(c) 500 ml solution containing 0 .3 g urea
(c) 5.6  10 4 (d) 6.4  10 2
(d) 0.04 N HCl
51. Solvent molecules pass through the semipermeable membrane is
called
[CPMT 1983; MP PMT 1987; RPET 2000; DCE 2004] Elevation of boiling boint of the solvent
(a) Electrolysis (b) Electrophoresis
(c) Cataphoresis (d) Osmosis 1. The latent heat of vapourisation of water is 9700 Cal / mole and
if the b.p. is 100 o C , ebullioscopic constant of water is
 174 Solution and Colligative properties
[CBSE PMT 1989] 10. If for a sucrose solution elevation in boiling point is 0.1°C then what
o o will be the boiling point of NaCl solution for same molal
(a) 0.513 C (b) 1.026 C
concentration [BHU 1998, 2005]
o
(c) 10.26 C (d) 1.832 o C (a) 0.1°C (b) 0.2°C
2. The molal elevation constant of water  0.52 o C . The boiling point (c) 0.08°C (d) 0.01°C
of 1.0 molal aqueous KCl solution (assuming complete dissociation of 11. The molal elevation constant is the ratio of the elevation in B.P. to
KCl ), therefore, should be [BHU 1987]
(a) Molarity (b) Molality
(a) 100.52 o C (b) 101.04 o C (c) Mole fraction of solute (d) Mole fraction of solvent
(c) 99.48 o C (d) 98.96 o C
12. The molal boiling point constant for water is 0.513 o C kg mol 1 .
3. The rise in the boiling point of a solution containing 1.8 gram of
When 0.1 mole of sugar is dissolved in 200ml of water, the
glucose in 100 g of a solvent in 0.1 o C . The molal elevation solution boils under a pressure of one atmosphere at
constant of the liquid is [CPMT 1999]
(a) 0.01 K / m (b) 0.1 K / m (a) 100.513 o C (b) 100.0513 o C

(c) 1K /m (d) 10 K / m (c) 100.256 o C (d) 101.025 o C

13. Value of gas constant R is [AIEEE 2002]
4. If 0.15 g of a solute dissolved in 15 g of solvent is boiled at a
temperature higher by 0.216 o C than that of the pure solvent. (a) 0.082 litre atm (b) 0.987 cal mol K 1 1

The molecular weight of the substance (molal elevation constant for (c) 8.3 J mol 1 K 1 (d) 83 erg mol 1 K 1
the solvent is 2.16 o C ) is 14. The temperature, at which the vapour pressure of a liquid becomes
[CBSE PMT 1999; BHU 1997] equal to the atmospheric pressure is known as
(a) 1.01 (b) 10 [Pb. PMT 2000]
(c) 10.1 (d) 100 (a) Freezing point (b) Boiling point
5. Pressure cooker reduces cooking time for food because (c) Absolute temperature (d) None of these
[MP PMT 1987; NCERT 1975; CPMT 1991; AIEEE 2003]
15. The elevation in boiling point of a solution of 13.44g of CuCl in 1kg of
(a) Heat is more evenly distributed in the cooking space water using the following information will be
2

(b) Boiling point of water involved in cooking is increased

(Molecular weight of CuCl = 134.4 and K = 0.52 K molal) 1

(c) The higher pressure inside the cooker crushes the food material
2 b

[IIT 2005]
(d) Cooking involves chemical changes helped by a rise in (a) 0.16 (b) 0.05
temperature
(c) 0.1 (d) 0.2
6. Which of the following statements is correct for the boiling point of
solvent containing a dissolved solid substance 16. When 10g of a non-volatile solute is dissolved in 100 g of benzene, it
[NCERT 1972, 74] raises boiling point by 1o C then molecular mass of the solute is
(K b for benzene =2.53k-m ) –1
[BHU 2002]
(a) Boiling point of the liquid is depressed
(b) Boiling point of the liquid is elevated (a) 223 g (b) 233 g
(c) 243 g (d) 253 g
(c) There is no effect on the boiling point
(d) The change depends upon the polarity of liquid 17. An aqueous solution containing 1g of urea boils at 100.25 o C . The
aqueous solution containing 3 g of glucose in the same volume will
7. When a substance is dissolved in a solvent, the vapour pressure of boil at (Molecular weight of urea and glucose are 60 and 180
solvent decreases. It brings [BHU 2004] respectively)
(a) A decrease in boiling point of solution [CBSE PMT 2000]
(b) An increase in boiling point of the solution (a) 100.75 Co
(b) 100.5 C o

(c) A decrease in freezing point of the solution o

(c) 100.25 C (d) 100 o C
(d) An increase in freezing point of the solution 18. When common salt is dissolved in water
8. Elevation in boiling point was 0.52 o C when 6 gm of a [CBSE PMT 1988; MP PET 1995; DCE 2000]
(a) Melting point of the solution increases
compound X was dissolved in 100 gm of water. Molecular weight
(b) Boiling point of the solution increases
of X is (K b for water is 0.52 per 1000 gm of water)
(c) Boiling point of the solution decreases
[CPMT 1989] (d) Both melting point and boiling point decreases
(a) 120 (b) 60 19. During the evaporation of liquid [DCE 2003]
(c) 180 (d) 600 (a) The temperature of the liquid will rise
9. If the solution boils at a temperature T1 and the solvent at a (b) The temperature of the liquid will fall
(c) May rise or fall depending on the nature
temperature T2 the elevation of boiling point is given by
(d) The temperature remains unaffected
[MP PET 1996] 20. At higher altitudes the boiling point of water lowers because
(a) T1  T2 (b) T1  T2 [NCERT 1972; CPMT 1994; J & K 2005]
(a) Atmospheric pressure is low
(c) T2  T1 (d) T1  T2 (b) Temperature is low
 Solution and Colligative properties 175
(c) Atmospheric pressure is high 7. What is the freezing point of a solution containing 8.1 g HBr in
(d) None of these 100 g water assuming the acid to be 90% ionised (K f for water
21. The elevation in boiling point for one molal solution of a solute in a
solvent is called [MH CET 2001]  1.86 K mole 1 )
(a) Boiling point constant (b) Molal elevation constant [BHU 1981; Pb CET 2004]
(c) Cryoscopic constant (d) None of these
(a) 0.85 C o
(b)  3.53 o C
22. A solution of 1 molal concentration of a solute will have maximum
boiling point elevation when the solvent is (c) 0o C (d)  0.35 o C
[MP PMT 2000] 8. If K f value of H 2 O is 1.86. The value of T f for 0.1m solution
(a) Ethyl alcohol (b) Acetone of non-volatile solute is
(c) Benzene (d) Chloroform (a) 18.6 (b) 0.186
23. Mark the correct relationship between the boiling points of very (c) 1.86 (d) 0.0186
dilute solutions of BaCl2 (t1 ) and KCl (t 2 ) , having the same
9. 1% solution of Ca(NO 3 )2 has freezing point
molarity [CPMT 1984, 93]
[DPMT 1982, 83; CPMT 1977]
(a) t1  t 2 o
(a) 0 C (b) Less than 0 o C
(b) t1  t 2
(c) Greater than 0 o C (d) None of the above
(c) t2  t1 10. A solution of urea (mol. mass 56g mol ) boils at 100.18°C at the
–1

atmospheric pressure. If K f and K b for water are 1.86 and 0.512K

(d) t 2 is approximately equal to t1
kg mol respectively the above solution will freeze at [CBSE PMT 2005]
–1

(a) – 6.54°C (b) 6.54°C

Depression of freezing point of the solvent (c) 0.654°C (d) –0.654°C
11. The molar freezing point constant for water is 1.86 o C mole 1 . If
1. Molal depression constant for water is 1.86 o C . The freezing point
of a 0.05 molal solution of a non-electrolyte in water is 342 gm of canesugar (C12 H 22 O11 ) are dissolved in 1000 gm of
[MNR 1990; MP PET 1997] water, the solution will freeze at
[NCERT 1977; CPMT 1989; Roorkee 2000; DCE 2004]
(a)  1.86 o C (b)  0.93 o C
(a)  1.86 C o
(b) 1.86 o C
(c)  0.093 o C (d) 0.93 o C
(c)  3.92 C o
(d) 2.42o C
2. The amount of urea to be dissolved in 500 ml of water (K =18.6 K
12. An aqueous solution of a non-electrolyte boils at 100.52 o C . The
mole 1 in 100g solvent) to produce a depression of 0.186 o C freezing point of the solution will be
in freezing point is [MH CET 2000]
(a) 0o C (b)  1.86 o C
(a) 9 g (b) 6 g
o
(c) 3 g (d) 0.3 g (c) 1.86 C (d) None of the above
3. The maximum freezing point falls in [MP PMT 1986] 13. The freezing point of one molal NaCl solution assuming NaCl
to be 100% dissociated in water is (molal depression constant = 1.86)
(a) Camphor (b) Naphthalene
[CPMT 1985; BHU 1981; MP PMT 1997; UPSEAT 2001]
(c) Benzene (d) Water
(a)  1.86 C o
(b)  3.72o C
4. Which one of the following statements is FALSE
[AIEEE 2004] (c)  1.86 o C (d)  3.72o C
(a) The correct order of osmotic pressure for 0.01 M aqueous 14. Heavy water freezes at [CPMT 1993]
solution of each compound is (a) 0o C (b) 3.8 o C
BaCl2  KCl  CH 3 COOH  sucrose.
(c) 38 o C (d)  0.38 o C
(b) The osmotic pressure ( ) of a solution is given by the 15. After adding a solute freezing point of solution decreases to – 0.186.
equation   MRT where M is the molarity of the solution. Calculate Tb if K f  1.86 and Kb  0.521 .
(c) Raoult's law states that the vapour pressure of a component [Orissa JEE 2002, 04; MP PET/PMT 1998; AIEEE 2000]
over a solution is proportional to its mole fraction. (a) 0.521 (b) 0.0521
(d) Two sucrose solutions of same molality prepared in different (c) 1.86 (d) 0.0186
solvents will have the same freezing point depression. 16. Given that T f is the depression in freezing point of the solvent in
5. Solute when dissolved in water [MADT Bihar 1981] a solution of a non-volatile solute of molality m , the quantity
(a) Increases the vapour pressure of water  T f 
lim  is equal to
m 0  m 
(b) Decreases the boiling point of water
 
(c) Decreases the freezing point of water
[IIT 1994; UPSEAT 2001]
(d) All of the above (a) Zero (b) One
6. The freezing point of a solution prepared from 1.25 gm of a non- (c) Three (d) None of the above
electrolyte and 20 gm of water is 271.9 K . If molar depression 17. The freezing point of 1 percent solution of lead nitrate in water will
be
constant is 1.86 K mole 1 , then molar mass of the solute will be[AFMC 1998; CPMT 1999] [NCERT 1971, 72; CPMT 1972; JIPMER 1991]
(a) 105.7 (b) 106.7 (a) Below 0 C o
(b) 0 o C
(c) 115.3 (d) 93.9
 176 Solution and Colligative properties

(c) 1o C (d) 2 o C Colligative properties of electrolyte

18. What is the effect of the addition of sugar on the boiling and
freezing points of water [Kerala CET (Med.) 2003]
1. If O.P. of 1 M of the following in water can be measured, which one
(a) Both boiling point and freezing point increases will show the maximum O.P.
(b) Both boiling point and freezing point decreases [NCERT 1975; CPMT 1977; JIPMER 2001]
(c) Boiling point increases and freezing point decreases
(a) AgNO3 (b) MgCl2
(d) Boiling point decreases and freezing point increases
19. During depression of freezing point in a solution the following are (c) (NH 4 )3 PO4 (d) Na 2 SO 4
in equilibrium [IIT Screening 2003]
2. Which of the following solution in water possesses the lowest
(a) Liquid solvent, solid solvent vapour pressure [BHU 1996]
(b) Liquid solvent, solid solute (a) 0.1 (M) NaCl (b) 0.1 (N ) BaCl2
(c) Liquid solute, solid solute
(d) Liquid solute solid solvent (c) 0.1 (M) KCl (d) None of these
20. 1.00 gm of a non-electrolyte solute dissolved in 50 gm of benzene 3. Which of the following solutions in water will have the lowest
lowered the freezing point of benzene by 0.40 K. K f for benzene is vapour pressure [Roorkee 2000]
5.12 kg mol . Molecular mass of the solute will be
–1
[DPMT 2004] (a) 0.1 M, NaCl (b) 0.1 M, Sucrose
(c) 0.1 M, BaCl2 (d) 0.1 M Na 3 PO4
(a) 256 g mol 1 (b) 2.56 g mol 1
4. The vapour pressure will be lowest for [CPMT 2004]
(c) 512  10 3 g mol 1 (d) 2.56  10 4 g mol 1 (a) 0.1 M sugar solution (b) 0.1 M KCl solution
21. 0.440 g of a substance dissolved in 22.2 g of benzene lowered the (c) 0.1 M Cu (NO 3 )2 solution (d) 0.1 M AgNO3 solution
freezing point of benzene by 0.567 o C . The molecular mass of the
5. Osmotic pressure of 0.1 M solution of NaCl and Na 2 SO 4 will
substance (K f  5.12 o C mol 1 ) be [AFMC 1978]
[BHU 2001; CPMT 2001] (a) Same
(a) 178.9 (b) 177.8 (b) Osmotic pressure of NaCl solution will be more than
(c) 176.7 (d) 175.6 Na 2 SO 4 solution
22. Which of the following aqueous molal solution have highest freezing
point [UPSEAT 2000, 01, 02; MNR 1988] (c) Osmotic pressure of Na 2 SO 4 solution will be more than
(a) Urea (b) Barium chloride NaCl
(c) Potassium bromide (d) Aluminium sulphate (d) Osmotic pressure of NaSO 4 will be less than that of NaCl
23. Which will show maximum depression in freezing point when solution
concentration is 0.1M
6. Which of the following solutions has highest osmotic pressure
[IIT 1989; MNR 1990; UPSEAT 2000; 03; BCECE 2005]
(a) NaCl (b) Urea (a) 1 M NaCl (b) 1 M urea
(c) Glucose (d) K 2 SO 4 (c) 1 M sucrose (d) 1 M glucose
7. Which one has the highest osmotic pressure
24. The freezing point of a 0.01M aqueous glucose solution at 1
[CBSE PMT 1991; DPMT 1991; MP PET 1994]
atmosphere is  0.18 o C . To it, an addition of equal volume of
0.002 M glucose solution will; produce a solution with freezing point (a) M / 10 HCl (b) M / 10 urea
of nearly [AMU 1999]
(c) M / 10 BaCl2 (d) M / 10 glucose
(a)  0.036 o C (b)  0.108 o C
8. In equimolar solution of glucose, NaCl and BaCl2 , the order of
(c)  0.216 o C (d)  0.422 o C osmotic pressure is as follow
25. What should be the freezing point of aqueous solution containing [CPMT 1988, 93; MP PMT/PET 1988; MP PET 1997, 2003]
17 gm of C 2 H 5 OH in 1000 gm of water (water K f = 1.86 (a) Glucose  NaCl  BaCl2
deg  kg mol 1 [MP PMT 1986] (b) NaCl  BaCl2  Glucose
(a)  0.69 C o
(b)  0.34 C
o
(c) BaCl2  NaCl  Glucose
(c) 0.0 o C (d) 0.34 o C (d) Glucose  BaCl2  NaCl
26. In the depression of freezing point experiment, it is found that the[IIT 1999]
9. The osmotic pressure of which solution is maximum (consider that
(a) Vapour pressure of the solution is less than that of pure deci-molar solution of each 90% dissociated)
solvent [MP PMT 2003]
(b) Vapour pressure of the solution is more than that of pure (a) Aluminium sulphate
solvent (b) Barium chloride
(c) Only solute molecules solidify at the freezing point (c) Sodium sulphate
(d) Only solvent molecules solidify at the freezing point (d) A mixture of equal volumes of (b) and (c)
27. Calculate the molal depression constant of a solvent which has
10. At 25 o C , the highest osmotic pressure is exhibited by 0.1M
freezing point 16.6 o C and latent heat of fusion 180.75 Jg 1 .[Orissa JEE 2005] solution of [CBSE PMT 1994; AIIMS 2000]
(a) 2.68 (b) 3.86 (a) CaCl 2 (b) KCl
(c) 4.68 (d) 2.86t6 (c) Glucose (d) Urea
 Solution and Colligative properties 177
11. Which of the following will have the highest boiling point at 1 atm (a) AlCl3  KNO 3  Glucose
pressure [MP PET/PMT 1998]
(a) 0.1 M NaCl (b) 0.1M sucrose (b) Glucose  KNO 3  AlCl3

(c) 0.1M BaCl2 (d) 0.1M glucose (c) Glucose  AlCl3  KNO 3
12. Which one of the following would produce maximum elevation in (d) AlCl3  Glucose  KNO 3
boiling point
23. Which of the following will have the highest F.P. at one atmosphere
[MP PMT 1985; CPMT 1990; NCERT 1982]
[BHU 1982; MP PMT 1987, MP PET/PMT 1988]
(a) 0.1 M glucose
(b) 0.2 M sucrose (a) 0.1M NaCl solution (b) 0.1M sugar solution
(c) 0.1 M barium chloride (c) 0.1M BaCl2 solution (d) 0.1M FeCl3 solution
(d) 0.1 M magnesium sulphate
13. 24. CPMT
Which of the following solutions will have the highest boiling point[DPMT 1991; Which
1991] of the following will produce the maximum depression in
freezing point of its aqueous solution
(a) 1% glucose (b) 1% sucrose
[MP PMT 1996]
(c) 1% NaCl (d) 1% CaCl 2
(a) 0.1M glucose
14. Which one of the following aqueous solutions will exhibit highest
boiling point [AIEEE 2004] (b) 0.1M sodium chloride
(a) 0.015 M urea (b) 0.01 M KNO 3 (c) 0.1M barium chloride
(c) 0.01 M Na 2 SO 4 (d) 0.015 M glucose (d) 0.1M magnesium sulphate
25. Which of the following has the lowest freezing point
15. Which of the following aqueous solutions containing 10 gm of solute
in each case has highest B.P. [UPSEAT 2004]
(a) 0.1 m sucrose (b) 0.1 m urea
(a) NaCl solution (b) KCl solution
(c) Sugar solution (d) Glucose solution (c) 0.1 m ethanol (d) 0.1 m glucose
16. 0.01 molar solutions of glucose, phenol and potassium chloride were 26. Which of the following has minimum freezing point
prepared in water. The boiling points of [Pb. PMT 1999]
(a) Glucose solution = Phenol solution = Potassium chloride (a) 0.1M K 2 Cr2 O7 (b) 0.1 M NH 4 Cl
solution
(b) Potassium chloride solution > Glucose solution > Phenol (c) 0.1 M BaSO 4 (d) 0.1 M Al2 (SO 4 )3
solution
27. Which of the following 0.10 m aqueous solution will have the
(c) Phenol solution > Potassium chloride solution > Glucose
solution lowest freezing point [CBSE PMT 1997]
(d) Potassium chloride solution > Phenol solution > Glucose (a) Al2 (SO 4 )3 (b) C 5 H 10 O5
solution
17. Which one has the highest boiling point [CBSE PMT 1990]
(c) KI (d) C12 H 22 O11
(a) 0.1 N Na 2 SO 4 (b) 0.1 N MgSO4 28. For 0.1 M solution, the colligative property will follow the order

(c) 0.1M Al2 (SO 4 )3 (d) 0.1M BaSO4 (a) NaCl  Na 2 SO 4  Na 3 PO4
18. Which of the following solutions boils at the highest temperature (b) [AMU2001]
NaCl Na 2 SO 4  Na 3 PO4
(a) 0.1 M glucose (b) 0.1 M NaCl (c) NaCl  Na 2 SO 4  Na 3 PO4
(c) 0.1 M BaCl2 (d) 0.1 M Urea
(d) NaCl  Na 2 SO 4  Na 3 PO4
19. 0.01M solution each of urea, common salt and Na 2 SO 4 are
29. Which of the following will have the lowest vapour pressure
taken, the ratio of depression of freezing point is
[Roorkee 1990] (a) 0.1M KCl solution
(a) 1 : 1 : 1 (b) 1 : 2 : 1 (b) 0.1M urea solution
(c) 1 : 2 : 3 (d) 2 : 2 : 3
(c) 0.1M Na 2 SO 4 solution
20. Which has the minimum freezing point [CPMT 1991]
(a) One molal NaCl solution (d) 0.1M K 4 Fe(CN )6 solution
(b) One molal KCl solution
(c) One molal CaCl 2 solution Abnormal molecular mass
(d) One molal urea solution
1. The Van't Hoff factor will be highest for
21. Which of the following has lowest freezing point
(a) Sodium chloride (b) Magnesium chloride
[NCERT 1981]
(c) Sodium phosphate (d) Urea
(a) 0 .1 M aqueous solution of glucose
2. Which of the following salt has the same value of Van't Hoff factor
(b) 0 .1 M aqueous solution of NaCl i as that of K 3 [Fe(CN )6 ]
(c) 0 .1M aqueous solution of ZnSO 4 [CBSE PMT 1994; AIIMS 1998]

(d) 0 .1 M aqueous solution of urea (a) Al2 (SO 4 )3 (b) NaCl

22. The freezing points of equimolar solutions of glucose, KNO 3 and (c) Na 2 SO 4 (d) Al(NO 3 )3
AlCl3 are in the order of [AMU 2000] 3. When benzoic acid dissolve in benzene, the observed molecular mass
is
 178 Solution and Colligative properties

(a) 244 (b) 61 14. The observed osmotic pressure of a solution of benzoic acid in
(c) 366 (d) 122 benzene is less than its expected value because
[CET Pune 1998]
4. The ratio of the value of any colligative property for KCl solution
to that for sugar solution is nearly [MP PMT 1985] (a) Benzene is a non-polar solvent
(a) 1 (b) 0.5 (b) Benzoic acid molecules are associated in benzene
(c) 2.0 (d) 3 (c) Benzoic acid molecules are dissociated in benzene
(d) Benzoic acid is an organic compound
5. Van't Hoff factor of Ca(NO 3 )2 is [CPMT 1997]
15. The experimental molecular weight of an electrolyte will always be
(a) 1 (b) 2 less than its calculated value because the value of Van't Hoff factor
(c) 3 (d) 4 “i” is [MP PMT 1993]
6. Dry air was passed successively through a solution of 5 gm of a (a) Less than 1 (b) Greater than 1
solute in 80 gm of water and then through pure water. The loss in (c) Equivalent to one (d) Zero
16. The molecular mass of acetic acid dissolved in water is 60 and when
weight of solution was 2.50 gm and that of pure solvent dissolved in benzene it is 120.This difference in behaviour of
0.04 gm . What is the molecular weight of the solute CH 3 COOH is because [AMU 2000]
[MP PMT 1986] (a) Water prevents association of acetic acid
(a) 70.31 (b) 7.143 (b) Acetic acid does not fully dissolve in water
(c) 714.3 (d) 80 (c) Acetic acid fully dissolves in benzene
7. The Van’t Hoff factor calculated from association data is (d) Acetic acid does not ionize in benzene
always...than calculated from dissociation data
17. The correct relationship between the boiling points of very dilute
[JIPMER 2000]
solutions of AlCl3 (t1 ) and CaCl 2 (t 2 ) , having the same molar
(a) Less (b) More concentration is [CPMT 1983]
(c) Same (d) More or less
(a) t1  t 2 (b) t1  t 2
8. If  is the degree of dissociation of Na 2 SO 4 , the Vant Hoff's
factor (i) used for calculating the molecular mass is (c) t 2  t1 (d) t 2  t1
[AIEEE 2005] 18. The Van't Hoff factor for sodium phosphate would be
(a) 1   (b) (a) 1 (b) 2
(c) 1  2 (d) 1  2 (c) 3 (d) 4
9. Van't Hoff factor i 19. The molecular weight of benzoic acid in benzene as determined by
depression in freezing point method corresponds to
Normal molecular mass
(a)  (a) Ionization of benzoic acid
Observed molecular mass (b) Dimerization of benzoic acid
Observed molecular mass (c) Trimerization of benzoic acid
(b) 
Normal molecular mass (d) Solvation of benzoic acid
(c) Less than one in case of dissociation
(d) More than one in case of association
10. Which of the following compounds corresponds Van't Hoff factor
' i' to be equal to 2 for dilute solution [NCERT 1978]
(a) K 2 SO 4 (b) NaHSO 4
(c) Sugar (d) MgSO4
1. On adding solute to a solvent having vapour pressure 0.80 atm,
11. The Van't Hoff factor i for a 0.2 molal aqueous solution of urea is vapour pressure reduces to 0.60 atm. Mole fraction of solute is
(a) 0.2 (b) 0.1 (a) 0.25 (b) 0.75
(c) 1.2 (d) 1.0 (c) 0.50 (d) 0.33
12. One mole of a solute A is dissolved in a given volume of a solvent. 2. A solution containing 30 gms of non-volatile solute in exactly 90 gm
The association of the solute take place according to nA ⇄ ( A)n . water has a vapour pressure of 21.85 mm Hg at 25 o C . Further 18
gms of water is then added to the solution. The resulting solution
The Van't Hoff factor i is expressed as
has a vapour pressure of 22.15 mm Hg at 25 o C . Calculate the
[MP PMT 1997]
molecular weight of the solute [UPSEAT 2001]
x (a) 74.2 (b) 75.6
(a) i 1 x (b) i  1 
n (c) 67.83 (d) 78.7
x 3. Vapour pressure of a solution of 5 g of non- electrolyte in 100 g
1 x 
(c) i n (d) i  1 of water at a particular temperature is 2985 N / m 2 . The vapour
1
13. Acetic acid dissolved in benzene shows a molecular weight of pressure of pure water is 3000 N / m 2 . The molecular weight of
[MP PET 1993, 02]
the solute is [IIT Screening 1993]
(a) 60 (b) 120
(a) 60 (b) 120
(c) 180 (d) 240
(c) 180 (d) 380
 Solution and Colligative properties 179
4. Azeotropic mixture of HCl and water has 14. An aqueous solution of a weak monobasic acid containing 0.1 g in
[AFMC 1997; JIPMER 2002] 21.7g of water freezes at 272.813 K. If the value of K f for water is
(a) 84% HCl (b) 22.2% HCl 1.86 K/m, what is the molecular mass of the monobasic acid [AMU 2002]
(c) 63% HCl (d) 20.2% HCl (a) 50 g/mole (b) 46 g/mole
(c) 55 g/mole (d) 60 g/mole
5. The osmotic pressure at 17 o C of an aqueous solution containing
1.75 g of sucrose per 150 ml solution is 15. K f of 1,4-dioxane is 4.9 mol 1 for 1000 g. The depression in
[BHU 2001] freezing point for a 0.001 m solution in dioxane is
[DPMT 2001]
(a) 0.8 atm (b) 0.08 atm
(a) 0.0049 (b) 4.9 + 0.001
(c) 8.1 atm (d) 9.1 atm (c) 4.9 (d) 0.49
6. A 1.2 of solution of NaCl is isotonic with 7.2 of solution of glucose. 16. How many litres of CO 2 at STP will be formed when 100ml of
Calculate the van’t Hoff’s factor of NaCl solution
0.1 M H 2 SO 4 reacts with excess of Na 2 SO 3
[UPSEAT 2001]
[EAMCET 1998]
(a) 2.36 (b) 1.50 (a) 22.4 (b) 2.24
(c) 1.95 (d) 1.00 (c) 0.224 (d) 5.6
7. 0 .6 g of a solute is dissolved in 0.1 litre of a solvent which 17. A solution is obtained by dissolving 12 g of urea (mol.wt.60) in a
litre of water. Another solution is obtained by dissolving 68.4 g of
develops an osmotic pressure of 1.23 atm at 27 o C . The molecular cane sugar (mol.wt. 342) in a litre of water at are the same
mass of the substance is [BHU 1990] temperature. The lowering of vapour pressure in the first solution is
[CPMT 2001]
(a) 149.5 g mole 1 (b) 120 g mole 1 (a) Same as that of 2 solution
nd

(b) Nearly one-fifth of the 2 solution

nd

(c) 430 g mole 1 (d) None of these (c) Double that of 2 solution
nd

8. The boiling point of a solution of 0.1050 gm of a substance in 15.84 (d) Nearly five times that of 2 solution
nd

gram of ether was found to be 100 o C higher than that of pure

ether. What is the molecular weight of the substance [Molecular
elevation constant of ether per 100 g = 21.6] [UPSEAT 2001]
(a) 144.50 (b) 143.18
(c) 140.28 (d) 146.66
9. Boiling point of chloroform was raised by 0.323 K, when 0.5143 g of
anthracene was dissolved in 35 g of chloroform. Molecular mass of Read the assertion and reason carefully to mark the correct option out of
anthracene is the options given below :
( K b for CHCl 3 = 3.9 kg mol )–1
[Pb PMT 2000] (a) If both assertion and reason are true and the reason is the correct
(a) 79.42 g/mol (b) 132.32 g/mol explanation of the assertion.
(c) 177.42 g/mol (d) 242.32 g/mol
(b) If both assertion and reason are true but reason is not the correct
explanation of the assertion.
10. The boiling point of water ( 100 o C ) becomes 100.52 o C , if 3 (c) If assertion is true but reason is false.
grams of a nonvolatile solute is dissolved in 200ml of water. The (d) If the assertion and reason both are false.
molecular weight of solute is (e) If assertion is false but reason is true.
( K b for water is 0.6 K  m ) [AIIMS 1998] 1. Assertion : One molal aqueous solution of urea contains
1 60 g of urea in 1kg (1000 g) water.
(a) 12.2 g mol (b) 15.4 g mol
1 Reason : Solution containing one mole of solute in
(c) 17.3 g mol (d) 20.4 g mol
1000 g solvent is called as one molal solution.
11. Normal boiling point of water is 373 K (at 760mm). Vapour
pressure of water at 298 K is 23 mm. If the enthalpy of evaporation 2. Assertion : If 100 cc of 0.1 N HCl is mixed with 100 cc of
is 40.656 kJ/mole, the boiling point of water at 23 mm pressure will
0.2 N HCl , the normality of the final solution
be [CBSE PMT 1995]
(a) 250 K (b) 294 K will be 0.30.
(c) 51.6 K (d) 12.5 K Reason : Normalities of similar solutions like HCl can be
12. A 0.2 molal aqueous solution of a weak acid (HX) is 20% ionised. added.
The freezing point of this solution is (Given K f  1.86 o C / m for 3. Assertion : If a liquid solute more volatile than the solvent is
added to the solvent, the vapour pressure of the
water) [IIT 1995]
solution may increase i.e., p s  p o .
(a)  0.31o C (b)  0.45 o C
Reason : In the presence of a more volatile liquid solute,
(c)  0.53 o C (d)  0.90 o C only the solute will form the vapours and solvent
13. A 0.001 molal solution of [Pt(NH 3 )4 Cl 4 ] in water had a freezing will not.
point depression of 0.0054 o C . If K f for water is 1.80, the 4. Assertion : Azeotropic mixtures are formed only by non-
ideal solutions and they may have boiling points
correct formulation for the above molecule is either greater than both the components or less
[Kerala CET (Med.) 2003] than both the components.
(a) [Pt(NH 3 )4 Cl 3 ] Cl (b) [Pt(NH 3 )4 Cl] Cl2 Reason : The composition of the vapour phase is same as
that of the liquid phase of an azeotropic mixutre.
(c) [Pt(NH 3 )4 Cl 2 ]Cl 3 (d) [Pt(NH 3 )4 Cl 4 ]
 180 Solution and Colligative properties
5. Assertion : Molecular mass of polymers cannot be calculated 21. Assertion : Increasing pressure on pure water decreases its
using boiling point or freezing point method. freezing point.
Reason : Polymers solutions do not possess a constant Reason : Density of water is maximum at 273 K.
boiling point or freezing point. [AIIMS 2003]
6. Assertion : The molecular weight of acetic acid determined
by depression in freezing point method in
benzene and water was found to be different.
Reason : Water is polar and benzene is non-polar.
7. Assertion : Ca   and K  ions are responsible for
maintaining proper osmotic pressure balance in
the cells of organism.
Reason : Solutions having the same osmotic pressure are Solubility
called isotonic solutions.
8. Assertion : Reverse osmosis is used in the desalination of sea 1 d 2 d 3 c 4 b 5 d
water.
6 c
Reason : When pressure more than osmotic pressure is
applied, pure water is squeezed out of the sea
water through the membrane. Method of expressing concentration of solution
9. Assertion : Camphor is used as solvent in the determination
of molecular masses of naphthalene, anthracene 1 c 2 d 3 d 4 e 5 b
etc.
Reason : Camphor has high molal elevation constant. 6 b 7 a 8 d 9 d 10 b
10. Assertion : Elevation in boiling point and depression in 11 a 12 b 13 a 14 a 15 b
freezing point are colligative properties.
16 c 17 b 18 e 19 b 20 b
Reason : All colligative properties are used for the
calculaltion of molecular masses. 21 c 22 c 23 c 24 b 25 c
11. Assertion : An increase in surface area increases the rate of 26 d 27 d 28 c 29 a 30 c
evaporation.
Reason : Stronger the inter-molecular attractive forces, 31 a 32 c 33 d 34 a 35 d
fast is the rate of evaporation at a given 36 b 37 b 38 b 39 b 40 c
temperature. [AIIMS 2002]
12. Assertion : The boiling and melting points of amides are 41 c 42 b 43 c 44 c 45 a
higher than corresponding acids. 46 ac 47 c 48 b 49 a 50 c
Reason : It is due to strong intermolecular hydrogen
bonding in their molecules. [AIIMS 2002] 51 c 52 b 53 d 54 b 55 b
13. Assertion : The freezing point is the temperature at which 56 d 57 b 58 b 59 c 60 a
solid crystallizers from solution.
61 d 62 a 63 a 64 b 65 a
Reason : The freezing point depression is the difference
between that temperature and freezing point of 66 a 67 c 68 c 69 a 70 d
pure solvent. [AIIMS 2000]
71 d 72 c 73 c 74 b 75 b
14. Assertion : On adding NaCl to water its vapour pressure
increases. 76 c 77 a 78 b 79 c 80 b
Reason : Addition of non-volatile solute increases the 81 d 82 b 83 b 84 b 85 d
vapour pressure. [AIIMS 1996]
15. Assertion : Molar heat of vaporisation of water is greater 86 d 87 d 88 e 89 b 90 b
than benzene. 91 a 92 d 93 a 94 c 95 a
Reason : Molar heat of vaporisation is the amount of heat
required to vaporise one mole of liquid at constant 96 a 97 c 98 d 99 b 100 d
temperature. [AIIMS 1996] 101 c 102 d 103 d 104 c 105 d
16. Assertion : Ice melts faster at high altitude.
106 b 107 a 108 b 109 d 110 a
Reason : At high altitude atmospheric pressure is high. [AIIMS 1997]
17. Assertion : Molecular mass of benzoic acid when determined 111 d 112 b 113 c 114 c 115 b
by colligative properties is found high. 116 a 117 b 118 c 119 c 120 d
Reason : Dimerisation of benzoic acid. [AIIMS 1998]
18. Assertion : Use of pressure cooker reduces cooking time. 121 b 122 c 123 b 124 a 125 c
Reason : At higher pressue cooking occurs faster. 126 c 127 c 128 c 129 a 130 b
[AIIMS 2000]
131 a 132 c 133 c 134 c 135 c
19. Assertion : CCl 4 and H 2 O are immiscible.
136 c 137 c 138 b 139 a 140 b
Reason : CCl 4 is a polar solvent. [AIIMS 2002]
141 d 142 c 143 b 144 a
20. Assertion : Isotonic solution do not show the phenomenon
of osmosis.
Reason : Isotonic solutions have equal osmotic pressure. Colligative properties
[AIIMS 2002]
 Solution and Colligative properties 181
1 a 2 c 3 a 4 c 5 c 11 b 12 c 13 c 14 b 15 a

6 a 7 b 8 a 9 c 10 a 16 d 17 c 18 b 19 b 20 a

11 ac 21 b 22 c 23 b

Lowering of vapour pressure Depression of freezing point of the solvent

1 a 2 b 3 b 4 d 5 b 1 c 2 c 3 a 4 d 5 c
6 a 7 a 8 a 9 c 10 b 6 a 7 b 8 b 9 b 10 d
11 a 12 b 13 b 14 c 15 d
11 a 12 b 13 b 14 b 15 b
16 a 17 b 18 d 19 b 20 b
16 d 17 a 18 c 19 a 20 a
21 a 22 a 23 b 24 b 25 b
26 d 27 a 28 c 29 b 30 d 21 a 22 a 23 d 24 c 25 a

31 c 32 a 33 c 34 a 35 c 26 ad 27 b

36 b 37 c 38 a 39 b 40 b
41 a 42 b 43 d 44 c Colligative properties of electrolyte

Ideal and Non-ideal solution 1 c 2 b 3 d 4 c 5 c

6 a 7 c 8 c 9 a 10 a
1 b 2 d 3 b 4 b 5 d
6 a 7 d 8 d 9 c 10 b 11 c 12 c 13 d 14 c 15 a

11 a 12 c 13 a 14 a 15 d 16 d 17 c 18 b 19 c 20 c

16 b 17 d 18 b 19 a 20 d 21 b 22 a 23 b 24 c 25 c
21 c 22 a 23 d 24 d 25 a 26 d 27 a 28 b 29 d
26 b 27 a 28 c 29 a 30 a

Azeotropic mixture Abnormal molecular mass

1 d 2 c 3 d 4 a 5 b 1 c 2 a 3 a 4 c 5 c

6 a 7 a 8 c 9 a 10 d
Osmosis and Osmotic pressure of the solution
11 d 12 c 13 b 14 b 15 b
1 c 2 b 3 c 4 a 5 b 16 b 17 b 18 d 19 b
6 b 7 c 8 b 9 b 10 a
11 c 12 d 13 b 14 b 15 a Critical Thinking Questions
16 b 17 c 18 a 19 d 20 b
21 a 22 a 23 d 24 d 25 a 1 a 2 c 3 c 4 d 5 a
26 b 27 c 28 b 29 b 30 b 6 c 7 b 8 b 9 c 10 c
31 a 32 c 33 b 34 d 35 b
11 b 12 b 13 b 14 d 15 a
36 c 37 c 38 c 39 b 40 d
16 c 17 a
41 c 42 b 43 c 44 a 45 c
46 c 47 b 48 a 49 a 50 b
Assertion & Reason
51 d 52 d 53 a 54 b 55 d
56 b 57 d 58 a 59 b 60 bcd
1 a 2 e 3 c 4 b 5 c
61 ac
6 a 7 d 8 a 9 c 10 b

Elevation of boiling point of the solvent 11 c 12 a 13 b 14 d 15 b

16 d 17 a 18 a 19 c 20 b
1 a 2 b 3 c 4 d 5 b
21 c
6 b 7 b 8 b 9 b 10 b
 182 Solution and Colligative properties

n1 1 1
Mole fraction of water     0 .1
n1  n 2 1  9 10

Method of expressing concentration of solution

1. (c) M1 V1  M 2 V2  MV
w w
2. (d) M ; 0 .25  ; w  6.625 gm
m  V (l) 106  0 .25
3. (d) N 1 V1  N 2 V2
2 1  N 2  6
N 2  0.33
5 .85
4. (e) 5.85 g NaCl = mole  0 .1 mol
58.5
90
90 g H 2 O  moles  5 moles
18
0.1
mole fraction of NaCl =  0 .0196 .
5  0 .1
n 0 .006
5. (b) M   0 .06
V (l) 0 .1
W  1000 9.8  1000
6. (b) M    0.05 M
mol. mass  Volume in ml. 98  2000
W 1000 5  1000
7. (a) M    0.5 M
m.wt . Volume in ml. 40  250
8. (d) Basicity of H 3 PO3 is 2.
Hence 0.3 M H 3 PO3  0.6 N .
9. (d) 2 gm. Hydrogen has maximum number of molecules than
others.
11. (a) M1V1  M 2 V2
0.01  19.85  M 2  20
M 2  0.009925 ; M  0.0099 .
12. (b) 1500 cm 3 of 0.1 N HCl have number of gm equivalence
N  V1 1500  0 .1
 1   0.15
1000 1000
 0.15 gm. equivalent of NaOH  0.15  40  6 gm.
w 5 .85
13. (a) M   0.2 M
m. wt .  volume in litre 58.5  0 .5
14. (a) Molecular weight of C 2 H 5 OH  24  5  16  1  46
Molecular mass of H 2 O  18
414
414g of C 2 H 5 OH has  9 mole
46
18
18g of H 2O has   1 mole
18
 Solution and Colligative properties 185
15. (b) 17 gm NH 3 = 1 mole. 20
39. (b) Mole fraction of solute   0 .25 .
80
6 .02  10 23  4 .25
Molecules of NH 3   1 .5  10 23 w  1000 4  1000
17 40. (c) N   1.0 N .
m.wt .  Volume in ml 40  100
17. (b) (2.5  1  3  0.5)  M 3  5.5
41. (c) M1 V1  M 2 V2  M 3 V3 ;
4
or 2.5  1.5  M 3  5.5 or M 3   0 .73 M. 1.5  480  1.2  520  M  1000
5 .5
(b) Normality of 2.3 M H 2 SO 4  M  Valency 720  624
20. M  1.344 M .
1000
 2. 3  2  4. 6 N
18  1000
21. (c) N 1 V1  N 2 V2 , 36  50  N 2  100 44. (c) m  0 .2 m
180  500
36  50
N2   18 ; 18 N H 2 SO 4  9 M H 2 SO 4 . %  10  d 22  10  1.253
100 45. (a) Molarity    0 .805 M .
GMM 342
w 171
22. (c) Molarity    0.5 M . %  10  d 22  10  1 .253
m.wt.  volume in litre 342  1 Normality    4 .83 N
GEM 342 / 6
23. (c) N 1 V1  N 2 V2  NV
22  1000
4 x  10(1  x )  6  1 ; 6 x  4 ; x  0.66 Molality   0 .825m
342(100  22)
24. (b) [H 3 O  ]  2  0.02  0.04 M 100  0 .3
46. (a) 100 ml. of 0.30M   0 .03 mole of NaCl
 1000
 2 litre solution contains 0.08 mole of H 3 O .
25. (c)  10 litre of urea solution contains 240 gm of urea 100  0 .4
100 ml of 0.40M   0 .04 mole of NaCl
240 1000
 Active mass   0.4 .
60  10 Moles of NaCl to be added  0.04  0.03  0.01 mole
26. (d) NV  N 1 V1  N 2 V2  N 3 V3 = 0.585 gm
6  1000
or, 1000 N  1  5 
1 1
 20   30 or N 
1
. 47. (c) N  1 .5 N
2 3 40 40  100
It is show highest normality than others.
N  eq .wt .  V (ml ) 0.05  49.04  100
27. (d) W    0.2452. n 0.1
1000 1000 48. (b) M  0 .8   V  125 ml .
29. (a) For HCl M  N  0.1 V (l) V (l)
N 1 V1  N 2 V2 ; 25  N 1  0.1  35 50. (c) Strength of H 2 SO 4  98  19.8 g / litre
0 .1  35 0.1  35 S 98  19.8
N1  ; M   0 .07 . S  eq . wt .  N ; N    39.6
25 25  2 eq . wt . 49
30. (c) We know that 51. (c) W  1000 gm (H 2 O) ; n  1 mole
Number of moles of solute
Molarity  W 1000
Volume of solutionin litre N   55.55
M 18
0.5
 2.0  n 1
Volume of solutionin litre x Solute =  = 0.018.
n  N 1  55.55
 Volume of solution in litre
53. (d) Normality of acid = molarity  basicity
0 .5
  0.250litre 250 ml. i.e., 0.2=molarity  2
2 .0
 Molarity = 0.2/2 = 0.1
w w
31. (a) M ; 0 .52  ; w  2.84 gm 80
m  V (l) 36.5  0 .15
n n 55. (b) Mole fraction of H 2 O =
18 =
68
.
32. (c) M ; 0.5  ; n 1
80 20 77
V (l) 2

33. (d) N
W 828
  18, n 
w 36
 2
18 34
M 46 m 18 1 .5  100
59. (d) Volume strength   8 .82.
n 2 2 17
x H 2O     0 .1
nN 2  18 20 w
60. (a) n ; w  n  m  0.25  98  24.5 gm
w  1000 98 m
34. (a) N , E  32.6
E  volume in ml. 3 Mole 20 2
61. (d) Molar concentration [H 2 ]    2.
4 .9  1000 V in litre 5
N   0.3 N .
32.6  500
 186 Solution and Colligative properties

62. (a) Amount of AgNO3 added in 60 ml of solution 84. (b) An increases in temperature increase the volume of the
solution and thus decreases its molarity.
 60  0.03  1.8 g
85. (d) 10 3 parts of CaCO 3 has number of parts = 10
w w
63. (a) N  0 .1   w  1 gm
E  V (l) 100  0.1 10 6 parts of CaCO 3 has number of parts
w w 10
64. (b) N  0 .1   w  1 gm   10 6  10,000 ppm .
E  V (l) 40  0 .25 10 3
n
65. (a) 20  0.4  40  N or N  0 .2 or M 
0.2
 0.1 M . 86. (d) X 
2 nN
w  1000 10.6  1000 w 3.65 W 16.2
69. (a) M   0.2 M . n   0.1, N    0 .9
m. wt .  Volume in ml. 106  500 m 36.5 M 18
0.1
72. (c) M.eq. of HCl = M.eq. of CaCO 3 X  0 .1 .
0.1  0.9
1 1  1000
N  50   1000 ; N   0.4 N 87. (d) 10% glucose solution means 10 g 
10
mole in 100 cc.
50 50  50 180
18 i.e., 0.1 litre
73. (c) molality   0.1 molal .
180 0 .1  180
Hence 1 mole will be present in =1.8 litre.
74. (b) Molarity of H 2 SO 4  0.5 10
88. (e) For methyl alcohol N = M.
Normality of H 2 SO 4 (N1 )  0.5  2  1
n
N1V1  N 2 V2 89. (b) Mole fraction of glucose =
nN
1 0 .01
1  1  N 2  10 or N 2   0 .1 N . =  0 .00199
10 0 .01  5
76. (c) The density of solution  1.8 gm / ml 6 .02  10 20
90. (b) Mole of urea   10  3 moles
Weight of one litre of solution  1800 gm 6 .02  10 23
1800  90 10 3
 Weight of H 2 SO 4 in the solution  =1620gm Conc. of solution (in molarity)   1000  0 .01 M .
100 100
 Weight of solvent  1800  1620  180 gm 91. (a) Gram molecule of SO 2 Cl 2 = 135
1620 100 w 13.5
 Molality    9 .18 n   0 .1 .
98 180 m 135
77. (a) Suppose the total volume of water = x 92. (d) 1000 ml of 1 N oxalic solution = 63 g
500 ml of 0.2 N oxalic acid solution
100cm  0.5 N  x  0.1 N
3
63
100  0.5 =  500  0.2  6 .3 g .
x   500cm 3 1000
0 .1
Therefore the volume of water added 7 .8
78 1
 Total volume – 100cm 3  500  100  400cm 3 . 93. (a) Mole fraction at C 6 H 6   .
7 .8 46 6

0 .25  25 78 92
78. (b) M 1 V1  M 2 V2 , M 2   0.0125 .
500 nH 2 O
94. (c) X H 2 O 
wt . of the solute(g) n H 2 O  nC 2 H 5 OH  nCH 3 COOH
79. (c) % by wt .   100
wt . of the solutiong 95. (a) M1V1  M 2 V2


10
 100  10 i.e. 5  1  M 2  10  M 2  0.5
90  10
0.5
w 18  1000 Normality of the solution   0 .25.
80. (b) Molality   1000   0.4 m 2
m W 180  250
w  1000 1  1000
w  1000 96. (a) M   0 .1 M .
81. (d) Molality (m )   14.05 . m  Volume in ml. 40  250
mW
w  1000
82. (b) N 1 V1  N 2 V2 98. (d) N  0.33 N .
eq . wt .  volume in ml.
10  10  0.1 (10  V )
1 .2046  10 24
10  10 99. (b) Mole of HCl   2 mole
V  10  1000  10  990 ml. 6 .023  10 23
0 .1 Normality = molarity  basidity or acicity  2  1  2 N
83. (b) Sum of mole fraction is always 1.
 Solution and Colligative properties 187
1 X
100. (d) 10 N  Deca - normal , N = Deci-normal. 121. (b)  0.2
10 1000
X
w  1000 7 .1  1000 78
101. (c) Molarity  =  0 .5 M .
ml wt.  Volume ml. 142  100 6
122. (c) C  0 .1 molar.
4  10 60
102. (d) M  1M .
40 123. (b) Molar solution of sulphuric acid is equal to 2N because it is
show dibasic nature.
6
n 0 .1 w  1000 106
103. (d) Mole fraction X   60  . 124. (a) N eq . wt .   53
nN 6 180 10 . 1 eq . wt .  volume in ml . 2

60 18 0 .5  53  500
w  13.25 .
w  1000 10  1000 1000
104. (c) N    1.66 N .
Eq.wt .  Volume 60  100 5.85  1000
125. (c) Molar concentration =  0.5 Molar .
106. (b) N  M  bosicity ; N  2  2  4 . 58.5  200
5  10 6 w  1000 75.5  1000
108. (b) Concentration  = 5 ppm. 126. (c) M    2 .50 M
10 6 m.wt .  V in ml 56  540
110. (a) H 3 PO3 is a dibasic acid 129. (a) N 1 V1  N 2 V2
N 1 V1 (acid)  N 2 V2 (base) 10  10  0.1 × Volume of new solution
0.1  2  20  0.1  1  V2 Volume of water = 1000 – 10 = 990 ml.
M  m . w t.  V 0.1  98  400
0 .1  2  20 130. (b) W   3.92 g .
 V2   40 ml 1000 1000
0 .1  1
1000
111. (d) H 3 PO4 ⇌ H   H 2 PO4 131. (a) Molarity of pure water   55.6 M .
18
H 2 PO4 ⇌ H   HPO42 N 0.2
132. (c) M   0 .1 M
HPO42  ⇌ H   PO43  2 2
Phosphoric acid does not give 1N strength. 180
133. (c) Moles of water   10 mole.
112. (b) C6 H 5 COOH  NaOH  C6 H 5 COONa  H 2 O 18
w 12.2 44
  4 gms. n CO 2 44 2
40 122 134. (c) Mole fraction of CO    .
n CO 2  n N 2 44 14
2

3
113. (c) (H 2 SO 4 ) N 1 V1 = N 2 V2 (dilute acid) 
44 28
N 2  (10  36) / 1000  0.36 N . w w4
136. (c) M  0 .1   w  1gm
1 m  V (l) 40  1
114. (c) H 2O2  H 2O  O2
2 w  1 litre 4 1
137. (c) M  1M .
1 M H 2 O 2 solution  2 N  34 gm / litre 11.2 m. wt .  Volume litre 40  0 .1
2  10 w1 w 2 90 300
So Normality   1 .75 138. (b) Number of moles =     10
11.2 m 1 m 2 18 60
115. (b) Weight = molarity × m.wt.× v = 1  132  2  264 gm. 139. (a) The number of moles of solute dissolved in 1000 gm of the
w 1 solvent is called molal solution.
n 0.1  100  392
116. (a) Mole fraction   m  2  0 .667 . 140. (b) w   3.92 g
nN w W 1 8 1000
 
m M 2 32 18 1
141. (d)   0 .1 molal.
118. (c) 98% H 2 SO 4 means 98g H 2 SO 4 in 100g solution. 180  1 10
100 n n
cc  54.3 cc ; 98 g H 2 SO 4  1 mol 142. (c) M  3   n  3 moles.
1 .84 V (l) 1
1 143. (b) The unit of molality is mole per kilogram.
Hence molarity   1000  18.4 M
54.3 144. (a) 0.2 water + 0.8 ethanol; X A  mole fraction of water,
120. (d) 3 CaCl 2  2 Na 3 PO4  Ca 3 (PO4 )2  6 NaCl X B  mole fraction of ethanol
 Mole of Na 3 PO4  3 mole of CaCl 2  1 mole N1 N2
XA  , XB 
Ca 3 (PO4 )2 N1  N 2 N 2  N1
 0.2 mole of Na 3 PO4  0.3 mole of CaCl 2 = 0.1 mole of  Mole fraction of water = 0.2 and ethanol = 0.8.
Ca 3 (PO4 )2 .
Colligative properties
 188 Solution and Colligative properties
3. (a) Osmotic pressure is colligative property. 0 .8  0 .6
5. (c) Vapour pressure is not colligative property. xB   0 .25 .
0 .8
Lowering of vapour pressure P 0  Ps
26. (d)  molality (1 -   x   y  ) the value of
P0
P  Ps
0
wM 0 .5  154 P 0  Ps is maximum for BaCl2 .
1. (a)   143   143
P 0
mW 65  158
P 0  Ps 18  18
 143  1.03  141.97 mm . 27. (a)   0 .02 .
P0 180  90
w
P 0  Ps 3 2
m 71.5 m 30. (d) PT  PP0 X P  PQ0 X Q ; PT  80   60 
4. (d)  or 0 .00713  5 5
P0 w W

71.5 1000

m M m 18 PT  48  24  72 torr .
m  180 w
5. (b) HgI2 although insoluble in water but shows complex P 0  Ps m W w 640  600
31. (c)    
formation with KI and freezing point is decreases. P 0 w W M m 640
6. (a) For solutions containing non-volatile solutes, the Raoult’s law 
m M
may be stated as at a given temperature, the vapour pressure
of a solution containing non-volatile solute is directly w M 40 2.175  78 2.175  78 640
    ;m 
proportional to the mole fraction of the solvent. m W 640 m  39.08 39.08 40
7. (a) Vapour pressure 
1 m  69.45 .
Boiling point 33. (c) The lower is boiling point more is vapour pressure; boiling
When vapour pressure decreases then b.pt. increases. point order, HCl  HBr  HI  HF
9. (c) Methanol has low boiling point than H 2 O P 0  Ps n P 0  Ps 1
Lower is boiling point of solvent more is vapour pressure. 35. (c) 0
   9.9 P 0  9 .9 Ps  P 0
P N P0 9 .9
11. (a) Sucrose will give minimum value of P .
8.9 0
P  P 0  Ps 8.9 P 0  9.9 Ps  Ps  P  0.90 P 0
9.9
Ps  P 0  P is maximum. 38. (a) 1000 ml of CH 3 OH requires methanol = 32 g.
12. (b) The relative lowering of the vapour pressure of dilute solution
150 ml of 2 M CH 3 OH requires methanol
is equal to the mole fraction of the solute molecule present in
the solution. 32
13. (b) Acetone solution has vapour pressure less than pure water.   150  2  9 .6 g .
1000
1 4
15. (d) PT  Pp0 x p  Ph0 x h = 440   120  39. (b)  P 0  Ps  P 0  mole fraction solute
5 5
88 10  P 0  0.2 ; 20  P 0  n  n  0.4  N  0.6 .
= 88  96 = 184 ; Pp0 x p  y p PT ;  yp 40. (b) According to the Raoult’s law for the non-volatile solute the relative
184
lowering of vapour pressure of a solution containing a non-volatile is
y p  0.478 equal to the mole fraction of the solute.
78 43. (d) Relationship between mole fraction of a component in the
78 vapour phase and total vapour pressure of an ideal solution.
16. (a) P = PBo X B ;  PB   75 ;  P = 50 torr
78 46 x A .PA0
B B

PA
 yA  
78 92 Ptotal x A .PA0  x B .PB0
17. (b) Given molecular mass of sucrose = 342
1 1 1 1
100     0 .2
Moles of sucrose   0 .292 mole 1 1  2  2 1  4 5
342
44. (c) Lowering in weight of solution  solution pressure
1000
Moles of water N   55.5 moles and Lowering in weight of solvent  P 0  Ps
18
Vapour pressure of pure water P 0  23.8 mm Hg (  p 0  vapour pressure of pure solvent)
According to Raoult’s law p 0  ps Lowering in weight of solvent
P n P 0.292 
   ps Lowering in weight of solution
P0 n  N 23.8 0.292  55.5
23.8  0.292 p 0  ps w  M
P   0.125 mm Hg. 
55.792 ps m W
18. (d) According to Raoult's law, the relative lowering in vapour 0 .05 10  18 2  2.5 2  250
pressure of a dilute solution is equal to mole fraction of the   m   100
2.5 90  m 0 .05 5
solute present in the solution.
21. (a) When vapour pressure of solvent decreases, then the boiling Ideal and Non-ideal solution
point of solvent increases.
25. (b) According to Raoult’s Law
1. (b) In solution showing positive type of deviation the partial
P 0  Ps pressure of each component of solution is greater than the
 x B (Mole fraction of solute) vapour pressure as expected according to Raoult’s law.
P0
 Solution and Colligative properties 189
In solution of methanol & benzene methanol molecules are held P2  P1  P3 .
together due to hydrogen bonding as shown below.
8. (b) In the osmosis solvent molecule move from lower concentration
CH 3 CH 3 CH 3 to higher concentration.
| | | 10. (a) Osmosis occur from dilute solution to concentrate solution.
   O — H    O — H    O — H     Therefore solution A is less concentrated than B.
On adding benzene, the benzene molecules get in between the
5 1000 50
molecule of methanol thus breaking the hydrogen bonds. As 11. (c) Molar concentration of cane sugar   
the resulting solution has weak intermolecular attraction, the 342 100 342
escaping tendency of alcohol & benzene molecule from the 1 1000 10
solution increases. Consequently the vapour pressure of the Molar concentration of X =  
solution is greater than the vapour pressure as expected from m 100 m
Raoult’s law. 10 50
3. (b) Chloroform & acetone form a non-ideal solution, in which  or m  68.4 .
m 342
A..... B type interaction are more than A...... A & B...... B 12. (d) Osmotic pressure method is especially suitable for the
type interaction due to H -bonding. Hence, the solution shows, determination of molecular masses of macromolecules such as
negative deviation from Raoult’s Law i.e., protein & polymer because for these substances the value of
Vmix  ve ; H mix  ve other colligative properties such as elevation in boiling point or
depression in freezing point are too small to be measured on
 total volume of solution = less than (30 + 50 ml) the other hand osmotic pressure of such substances are
or  80 ml measurable.
 7.8
4. (b) H 2 O and C 4 H 9 OH do not form ideal solution because 13. (b)   C R T ; C    0  31 mol / litre
R T  082  310
there is hydrogen bonding between H 2 O and C 4 H 9 OH .
14. (b)   CRT
6. (a) Aromatic compound generally separated by fractional
distillation. e.g. Benzene + Toluene. w  R  T 68.4  0.0821  273
  = 4.92 atm
7. (d) C 2 H 5 I and C 2 H 5 OH do not form ideal solution. mV 342
n m / MRT
19. (a) For the ideal solution H mix and Vmix  0 . 16. (b)   RT 
V V
25. (a) For the ideal solution S mix is not equal to zero.
600 20  0.0821  288  1000
 ; M  1200
Azeotropic mixture 760 500  M
1 .66  2.46
17. (c)   2 .06 atm
1. (d) Azeotropic mixture is constant boiling mixture, it is not 2
possible to separate the components of azeotropic mixture by 19. (d) Copper ferrocyanide ppt. acts as a semipermeable membrane.
boiling. 20. (b) Osmotic pressure = CRT where C = 1 m
3. (d) Azeotropic mixture is a mixture of two liquids which boils at
on particular temperature like a pure liquid and distils over in   CRT  1  0.0821  300  24.6 atm
the same composition. P
23. (d) P  CRT or  RT
C
Osmosis and Osmotic pressure of the solution
 P 0  Ps  dRT
24. (d)   CRT or    
3  1000  P0  M
1. (c)   CRT   0.0821  288  6.56 atm .  
180  60 31. (a) Isotonic solutions are those which have same concentration.
w1 w2 32. (c)   CRT  0.2  0.0821  293  4.81 atm.
2. (b) Isotonic solution =  35. (b) Equal osmotic pressure only applicable of non-electrolytes
m 1 V1 m 2 V2
solution at low concentration.
w1 6 342  6 38. (c) As soon as the solute molecules increases the osmotic pressure
    34.2 . of solution increase.
342  1 60  1 60
41. (c) Living cells shrinks in hypertonic solution (plasmolysis) while
 0.0821 bursts in hypotonic solution (endosmosis). There is no. effect
3. (c)   CRT , C    0.33  10  2 . when living cells are kept in isotonic solution.
RT 0.821  300
w 0 .1 43. (c) V  nRT
4. (a)   RT   0 .0821  273 w RT 10 0.821  (273  69)
m 1    = 8.21 atm.
m V 342 0 .1
n  m  RT
5. (b)   RT  M P    45. (c) KNO 3 dissociates completely while CH 3 COOH dissociates
V V 
to a small extent. Hence, P1  P2 .
5 1 50
6. (b) C    1000  mol/l 47. (b) V  n RT
342 100 342
50 500 V1 nR  283 V 1
  0.082  423  5 .07 atm  ; 1  so V2  5V1
342 105.3 V2 nR  298 V2 5
w 1
7. (c) P R.T since wvT are constant thus P 
mv m
 190 Solution and Colligative properties
48. (a) There is no net movement of the solvent through the So, i = 3
semipermeable membrane between two solution of equal T = 3  0.52  0.1 = 0.156  0.16
concentration. b

K  w  1000
w 16. (d) Tb  b
50. (b) V  RT m W
m
K b  w  1000 2.53  10  1000
4 m   253 g .
 6  10  4  1   0.0821  300 ; m  1.64  10 5 . Tb  W 1  100
m
18. (b) Common salt is non-volatile and rises the b.pt.
52. (d) According to the dialysis process molecular weight increases
but sensitivity decreases. 19. (b) In the process of evaporation, high energy molecules leave the
surface of liquid, hence average kinetic energy and
55. (d)   T ; if T is doubled  is also doubled. consequently the temperature of liquid falls.
56. (b) Osmosis reaction are takes place in increases the volume. 20. (a) The boiling occurs at lowers temperature if atmospheric
58. (a) For two non-electrolytic solution if isotonic, C1  C 2 pressure is lower than 76cm Hg.
23. (b) BaCl2 furnishes more ions than KCl and thus shows
8 .6 5  1000
   m  348.9 higher boiling point T1  T2 .
60  1 m . wt .  100
59. (b) Both urea and glucose are non-electrolytes but NaCl being
electrolyte ionises. Depression of freezing point of the solvent

1. (c) Tf  K f  molality  1.86  0.05  0.093 °C

Elevation of boiling point of the solvent
Thus freezing point = 0 – 0.093 =  0.093 o C .
M1 RT02 18  1 .987  (373)2
1. (a) Kb    0.513 o C 100  K  w 100  18.6  w
1000 H V 1000  9700 2. (c) T f  0.186 
m W 60  500
2. (b) Tb  imkb  0.52  1  2  1.04 .
w  3g
 Tb  100  1.04  101.04 o C .
3. (a) Camphor has the maximum value of K f ( 39.7) .
Tb 0 .1  100
3. (c) Kb   1K /m .
m 1 .8 4. (d) The extent of depression in freezing point varies with the
 1000 number of solute particles for a fixed solvent only and it is a
180
characteristics feature of the nature of solvent also. So for two
K  w  1000 2 .16  0 .15  1000 different solvents the extent of depression may vary even if
4. (d) m b  = 100 .
Tb  W 0 .216  15 number of solute particles be dissolved.
5. (b) Due to higher pressure inside the boiling point elevated. K f  1000  w 1 .86  1000  1 .25
6. (b) Dissolution of a non-volatile solute raises the boiling pt. of a 6. (a) Molar mass  
liquid. T f  W 20  1 .1
7. (b) As we know that
 105.68  105.7 .
1
Boiling point  7. (b) HBr ⇌ H   Br 
vapour pre ssure of liquid (1  )  
Hence, on decreasing vapour pressure, boiling point will
increase. Total = 1 +   i  1    1  0.9  1.9
100  K b  w 100  5 .2  6 8.1 1000
8. (b) Tb   0 .52  T f  i K f  m  1.9  1.86    3.53 o C
m W m  100 81 100
100  5 .2  6 T f  3.53 o C .
m  60 .
0.52  100
8. (b) T f  K f  m  1.86  0.1  0.186 .
10. (b) Elevation in a boiling point is a colligative property as it
depends upon the number of particles. 9. (b) Freezing point is lowered on addition of solute in it..
∆T  n
b 10. (d) Tb  0.18 ; Tb  mK b
For sucrose, n = 1, ∆T = 0.1°C b
0 .18 mK b 0 .18  1 .86
For NaCl, n = 2, ∆T = 0.2°C  ;  T f ; T f  0.653
T f
b

11. (b) Tb  Kb  m or Kb  Tb / m m Kf 0 .512

 0.1  T 0  Ts  0.653 ; T 0  Ts  0.653 ; Ts  0  0.653 o C .

12. (c) Tb  K b  m  0.513    1000 
 200   342 
11. (a) T f  1 .86     1 .86 ;  T f  1.86 C .
o o

 0.2565 C , Tb  100 . 256 C

o o
 342 
15. (a) T = i.K .m
b b
12. (b) Tb  Kb  m i.e. 0.52  0.52  m
CuCl  Cu +
2
2+
2Cl Tf  K f  m  1.86  1  1.86 ; T f  1.86 o C .
1 0 0
13. (b) For NaCl i  2
(1)  2
T f  2 K f m  2  1.86  1  3.72
i = 1 + 2
Assuming 100% ionization
 Solution and Colligative properties 191
Ts  T  T f  0  3.72  3.72C 6. (a) NaCl gives maximum ion hence it will show highest osmotic
pressure.
15. (b) T f  K f  m  0.186  1.86  m
8. (c) BaCl2  Ba2   2Cl   3 ion
So m  0.1 , Put the value of m in Tb  Kb  m
NaCl  Na   Cl   2 ion
Tb  0.521  (0.1)  0.0521 Glucose  No ionisation
17. (a) Dissolution of a non-volatile solute lowers the freezing pt. of  BaCl2  NaCl  Glucose
the solution H 2 O.
9. (a) Al2 (SO 4 )3 gives maximum osmotic pressure because it is
K f  1000  w 5 .12  1000  1 gives 5 ion.
20. (a) By using, m  
T f  WSolvent (gm) 0 .40  50 10. (a) Highest osmotic pressure is given by solution which produce
maximum number of ions i.e. CaCl2 .
 256 gm / mol
11. (c) BaCl2 gives maximum ion. Hence, its shows highest boiling
Hence, molecular mass of the solute  256 gm mol 1 point.
K f  w  1000 5.12  0.440  1000 12. (c) BaCl2 gives maximum ion. Hence, its boiling point is
21. (a) m   178.9
T f  W 0.567  22.2 maximum.
13. (d) CaCl 2 gives maximum ion hence it shows highest boiling
22. (a) KBr  K   Br   2 ions
point.
BaCl2  Ba 2   2Cl   3 inos 14. (c) Elevation in boiling point is a colligative property which
depends upon the number of solute particles. Greater the
Al2 (SO 4 )3  2 Al 3   3 SO 42   5 ions number of solute particle in a solution higher the extent of
 urea is not ionise hence it is shows highest freezing point. elevation in boiling point.

23. (d) NaCl  Na   Cl   2 ions Na 2 SO 4  2 Na   SO 42

15. (a) NaCl contain highest boiling point than other’s compound.
K 2 SO 4  2 K   SO 42   3 ions
16. (d) KCl  C6 H 5 OH  C6 H 12 O6
K 2 SO 4 give maximum ion in solution so it shows maximum Boiling point decreasing order 
depression in freezing point. Potassium chloride is ionic compound and phenol is formed
K f  1000  w phenoxide ion hence it is shows greater boiling point then
24. (c) T f   0 .216 Co
glucose.
m W
17. (c) Al2 (SO 4 )3 gives maximum ion hence it will show highest
1000  1.86  17
25. (a) T f   0.69 o C boiling point.
46  1000
18. (b) NaCl is a more ionic compare to BaCl2 , glucose and urea
T f  0  0.69  0.69 o C solution.
26. (ad) The depression of freezing point is less than that of pure 19. (c) Urea = 1 ; Common salt = 1 ; Na 2 SO 4  3
solvent and only solvent molecules solidify at the freezing point. Ratio = 1 : 2 : 3
RTf2 20. (c) CaCl 2 gives maximum ion hence it has minimum freezing
27. (b) Kf  , R  8.314 JK 1mol 1
1000  L f point.
21. (b) NaCl gives maximum ion hence it shows lowest freezing point
Tf  273  16.6  289.6 K ; L f  180.75 Jg 1 23. (b) Lesser the number of particles in solution. Lesser the
depression in freezing point, i.e. higher the freezing point.
8.314  289.6  289.6
Kf  24. (c) BaCl2 gives maximum ion hence it shows maximum
1000  180.75
depression in freezing point.
Colligative properties of electrolyte 26. (d) We know that lowering of freezing point is a colligative
property which is directly proportional to the number of
particles formed by one mole of compound therefore 0.1M
1. (c) (NH 4 )3 PO4 gives maximum ion. Hence, its osmotic pressure Al2 (SO 4 )3 solution will have minimum freezing point.
is maximum.
27. (a) Al2 (SO 4 )3 gives maximum ion hence its gives lowest
2. (b) BaCl2 gives maximum ion hence it is shows lowest vapour
freezing point.
pressure. 28. (b) Colligative property in decreasing order
3. (d) Na 3 PO4 consist of maximum ions hence it show lowest vapour Na 3 PO4  Na 2 SO 4  NaCl
pressure.
Na 3 PO4  3 Na   PO43   4
Na 3 PO4  3 Na   PO43   4 ion.
4. (c) Vapour pressure of a solvent is lowered by the presence of Na 2 SO 4  2 Na   SO 42   3
solute in it. Lowering in vapour pressure is a colligative
property i.e., it depends on the no. of particles present in the NaCl  Na   Cl   2
solution. Cu (NO 3 )2 give the maximum no. of ions. (i.e., 3) so 29. (d) K 4 [Fe(CN )6 ] gives maximum ion. Hence it have lowest
it causes the greatest lowering in vapour pressure of water. vapour pressure.
5. (c) Na2 SO 4 have more osmotic pressure than NaCl solution
because Na2 SO 4 gives 3 ions.
Abnormal Molecular Mass
 192 Solution and Colligative properties

1. (c) Na 3 PO4 gives maximum four ion it is show highest Vant’s 4. (d) It is known that azeotropic mixture of HCl and water 20.2%
haff factor. HCl .
2. (a) K 4 [Fe(CN )6 ] dissociates as 4 K   [Fe(CN )6 ]4  , thus 1 1 .75
n
molecule dissociates into five particles in the similar way 5. (a)   CRT  RT  342  0 .0821  290
Al2 (SO 4 )3 also gives five particles per molecule. V 150
3. (a) Benzoic acid in benzene undergoes association through 1000
intermolecular hydrogen bonding.  0.8095  0.81 atm .
experiment al C.P. 6. (c) Vant hoff factor of NaCl about 1.95 because it will be ionise
4. (c) vont’s Hoff factor (i )  into two ions.
Calculated C.P.
 1    x  y , for KCl it is = 2 and for sugar it is equal NaCl ⇌ Na   Cl 
to 1. wRT 0.6  0.082  300
7. (b) m    120
5. (c) Ca(NO 3 )2  Ca 2   2 NO 3 it gives three ions hence the PV 1.23  0.1
Van’t Hoff factor = 3. K  w  1000
8. (b) m  b  143.18
5  18  2 .5 Tb  W
6. (a) m   70.31
0 .04  80 9. (c) Here: Tb  0.323 K
8. (c) Na 2 SO 4 ⇌ 2 Na   SO 42 w  0.5143 g weight of Anthracene.
Mol. before diss. 1 0 0
W  35 g weight of chloroform
Mol. after diss 1   2 1
K b  Molal elevation constant (3.9 K  Kg / mol)
Exp.C.P.
i  1    2    1  2 Kb  w  1000 3 .9  0 .5143  1000
Normal C.P. m 
W  Tb 0 .323  35
10. (d) MgSO4 dissociates to give 2 ions.
 177.42 g / mol
11. (d) Urea does not give ion in the solution.
13. (b) Molecular weight of CH 3 COOH  60 10. (c) First boiling point of water = 100 o C
Hence the molecular weight of acetic acid in Final boiling point of water = 100.52 o
benzene  2  60  120 . w  3 g , W  200 g , Kb  0.6 kg 1
17. (b) AlCl3 furnishes more ions than CaCl 2 and thus shows Tb  100.52  100  0.52 o C
higher boiling point i.e. t1  t 2 . K b  w  1000
m
18. (d) Na 3 PO4  3 Na  
PO33  . Tb  W
0.6  3  1000 1800
19. (b) Benzoic acid dimerises due to strong hydrogen bonding.    17.3 gmol 1 .
0.52  200 104
Critical Thinking Questions 11. (b) Applying clausius clapeytron equation
P H V  T2  T1 
log 2   
P o  Ps n P1 2 .303 R  T1  T2 
1. (a)  ; P o  0.80, Ps  0.60
P o
nN 760 40656  373  T1 
log   373T 

n

0 .2
 0 .25 . 23 2 .303  8 .314  
n  N 0 .8 This gives T1  294.4 K .
2. (c) We have,
12. (b) Tf  molality K f  (1   )
p 0  21.85 30  18
 , for I case .....(i)   0.2 , Molality = 0.2, K f  1.86
21.85 90  m
wt. of solvent  90  18  108 gm Tf  0.2  1.2  1.86  0.4464 o

p 0  22.15 30  18 Freezing point =  0.45 o C .

 , for II case .....(ii) 13. (b) T f  imk f ; 0.0054  i  1.8  0.001
22.15 108  m
By eq. (1) p m0  21.85m  21.85  6  131.1 i  3 so it is [Pt(NH 3 )4 Cl]Cl 2 .
K f  w  1000
By eq. (2) p m0  22.15m  22.15  5  110.75 14. (d) m   60 g / mole .
T f  W
0.30m = 20.35
15. (a) T  K f  Molality  4.9  0.001  0.0049 K
20.35
m  67.83 16. (c) Na 2 CO 3  H 2 SO 4  Na 2 SO 4  CO 2 HO
0 .30
98 gm (2 mole ) 1 mole 1 mole
W2 5
0 .02  22.4
P o  Ps M 2 = 3000  2985 M2 0.02   0 .224 .
3. (c)   or M 2  180 2
Po W1 3000 100
M1 18
 Solution and Colligative properties 193
17. (a) We know that in the first solution number of the moles of urea abnormally high. This is because dimerisation of benzoic takes
Mass of urea 1 12 1 place in solution resulting high molecular mass. Therefore,
     0 .2 and assertion and reason are true and reason is correct explanation.
m.wt. of urea V 60 1
In second solution the number of moles of cane sugar 18. (a) It is fact that use of pressure cooker reduces cooking time
Mass of cane sugar 68.4 1 because at higher pressure over the liquid due to cooker lid,
    0 .2 . the liquid boils at higher temperature and cooking occurs
m.wt. of cane sugar 342 1 faster.

Assertion & Reason 19. (c) The assertion that CCl 4 & H 2 O are immiscible is true
because CCl 4 is non-polar liquid while water is polar hence
1. (a) Molecular weight of urea (NH 2CONH 2 ) assertion is true and reason is false.
 14  2  12  16  14  2  60 20. (b) It is true that isotonic solution doesn’t show the phenomenon
Weight 60 of osmosis. Isotonic solution are those solution which have
Number of moles   1 same osmotic pressure. Here both assertion and reason are
molecular weight 60 true but reason is not correct explanation.
2. (e) If 100 cc of 0.1 N HCl is mixed with 100 cc of 0.2 N HCl , the
normality of the final solution will be 0.15.
N1V1  N 2 V2  N 3 V3 i.e., 0.1  100  0.2  100
0.3  100
 N 3  200 or N 3   0 .15
200
3. (c) Both the solute and solvent will form the vapour but vapour
phase will become richer in the more volatile component.
4. (b) Non-ideal solutions with positive deviation i.e., having more
vapour pressure than expected, boil at lower temperature while
those with negative deviation boil at higher temperature than
those of the components.
5. (c) The polymer solutions possess very little elevation in boiling
point or depression in freezing point.
6. (a) Depression in freezing point is a colligative property which
depends upon the number of particles. The number of particles
are different in case of benzene and water that is why
molecular weight of acetic acid determined by depression in
freezing point method is also different.

7. (d) Sodium ion, Na  and potassium ion, K  are responsible for

maintaining proper osmotic pressure balance inside and outside
of the cells of organisms.
8. (a) If a pressure larger than the osmotic pressure is applied to the
solution side, the pure solvent flows out of the solution
through semi-permeable membrane and this phenomenon is
called as reverse osmosis.
9. (c) Camphor has high molal depression constant.
10. (b) Elevation in boiling point and depression in freezing point are
colligative properties because both depend only on the number
of particles (ions or molecules) of the solute in a definite
amount of the solvent but not on the nature of the solute.
12. (a) The boiling point and melting point are higher due to presence
of the intermolecular hydrogen bonding.
14. (d) If a non-volatile solute is added to water its vapour pressure
always decreases. Therefore, both assertion and reason are
false.

15. (b) We know that heat of vaporisation of water at 100 o C is

40.6 kJ and that of benzene is 31kJ at 80 o C . The
amount of heat required to vaporise one mole of liquid at
constant temperautre is known as heat of vapourisation
therefore, both assertion and reason are true but reason is nat
the correct explanation of assertion.
16. (d) See melts slowly at high altitude because melting is favoured at
a high pressure at high altitude the atmospheric pressure is
low and so ice melts slowly.
17. (a) Colligative properties are the properties of solutions containing
non volatile solute. It is correct that malecular mass of benzoic
acid when determined by colligative properties is found
 194 Solution and Colligative properties

1. The 2 N aqueous solution of H 2 SO 4 contains 9. The O.P. of equimolar solution of Urea, BaCl2 and AlCl3 , will
be in the order [DCE 2000]
(a) 49 gm of H 2 SO 4 per litre of solution
(a) AlCl3  BaCl2  Urea
(b) 4.9 gm of H 2 SO 4 per litre of solution
(b) BaCl2  AlCl3  Urea
(c) 98 gm of H 2 SO 4 per litre of solution
(c) Urea  BaCl2  AlCl3
(d) 9.8 gm of H 2 SO 4 per litre of solution

2. The amount of KMnO4 required to prepare 100 ml of 0.1 N (d) BaCl2  Urea  AlCl3
solution in alkaline medium is [CPMT 1986]
10. The osmotic pressure of a 5% solution of cane sugar at 150 o C is
(a) 1.58 gm (b) 3.16 gm (mol. wt. of cane sugar = 342)
(c) 0.52 gm (d) 0.31 gm [CPMT 1986; Manipal MEE 1995]
3. What weight of hydrated oxalic acid should be added for complete (a) 4 atm (b) 3.4 atm
neutralisation of 100ml of 0.2 N  NaOH solution ? [MP PMT 1997]
(c) 5.07 atm (d) 2.45 atm
(a) 0.45 g (b) 0.90 g 11. Which one of the following pairs of solutions can we expect to be
isotonic at the same temperature [NCERT 1982]
(c) 1.08 g (d) 1.26 g
(a) 0.1M urea and 0.1M NaCl
4. A 500 g tooth paste sample has 0 .2 g fluoride concentration.
What is the concentration of F in terms of ppm level (b) 0.[AIIMS
1M urea
1992]and 0.2 M MgCl2
(a) 250 (b) 200 (c) 0.1M NaCl and 0.1M Na 2 SO 4
(c) 400 (d) 1000
(d) 0.1M Ca(NO 3 )2 and 0.1M Na 2 SO 4
5. To 5.85 gm of NaCl one kg of water is added to prepare of
solution. What is the strength of NaCl in this solution (mol. wt. of 12. Which of the following would have the highest osmotic pressure
(assume that all salts are 90% dissociated)
NaCl  58.5 ) [CPMT 1990; DPMT 1987]
[NCERT 1982]
(a) 0.1 Normal (b) 0.1 Molal
(c) 0.1 Molar (d) 0.1 Formal (a) Decimolar aluminium sulphate
(b) Decimolar barium chloride
6. The degree of dissociation of Ca(NO 3 )2 in a dilute aqueous
(c) Decimolar sodium sulphate
solution containing 14g of the salt per 200g of water 100 o C is 70
(d) A solution obtained by mixing equal of (b) and (c) and filtering
percent. If the vapour pressure of water at 100 o C is 760 cm.
Calculate the vapour pressure of the solution 13. Which solution will have the highest boiling point
[UPSEAT 2000] [NCERT 1981]
(a) 746.3 mm of Hg (b) 757.5 mm of Hg (a) 1% solution of glucose in water
(c) 740.9 mm of Hg (d) 750 mm of Hg (b) 1% solution of sodium chloride in water
7. The vapour pressure of pure benzene at a certain temperature is 200 (c) 1% solution of zinc sulphate in water
mm Hg. At the same temperature the vapour pressure of a solution
containing 2g of non-volatile non-electrolyte solid in 78g of benzene is (d) 1% solution of urea in water
195 mm Hg. What is the molecular weight of solid 14. [UPSEAT
The boiling point2001]
of a solution of 0.11 gm of a substance in 15 gm of
(a) 50 (b) 70 ether was found to be 0.1o C higher than that of the pure ether.
(c) 85 (d) 80 The molecular weight of the substance will be (Kb  2.16) [MP PET 2002]
8. Which one of the following non-ideal solutions shows the negative
deviation (a) 148 (b) 158

(a) CH 3 COCH 3  CS 2 (b) C6 H 6  CH 3 COCH 3 (c) 168 (d) 178

15. The boiling point of benzene is 353.23 K. When 1.80 gm of a
(c) CCl 4  CHCl 3 (d) CH 3 COCH 3  CHCl 3 nonvolatile solute was dissolved in 90 gm of benzene, the boiling
point is raised to 354.11 K. the molar mass of the solute is
 Solution and Colligative properties 195

[Kb for benzene = 2.53 K mol ] –1

[DPMT 2004] 18. When 0.01 mole of sugar is dissolved in 100 g of a solvent, the
depression in freezing point is 0.40 o . When 0.03 mole of glucose
(a) 5.8 g mol 1
is dissolved in 50 g of the same solvent, the depression in freezing
point will be
(b) 0.58 g mol 1
(a) 0.60 o (b) 0.80 o
(c) 58 g mol 1
(c) 1.60 o (d) 2.40 o
1
(d) 0.88 g mol 19. The freezing point of equimolal aqueous solution will be highest for

16. The boiling point of 0.1 molal aqueous solution of urea is (a) C 6 H 5 NH 3 Cl  (aniline hydrochloride)
100.18 o C at 1 atm. The molal elevation constant of water is
(b) Ca(NO 3 )2
(a) 1.8 (b) 0.18
(c) La(NO 3 )3
(c) 18 (d) 18.6
(d) C 6 H 12 O6 (glucose)
17. The freezing point of a solution containing 4.8 g of a compound in
60 g of benzene is 4.48. What is the molar mass of the 20. The Van't Hoff factor of the compound K 3 Fe(CN )6 is
1
compound (K f  5.1 km ) , (freezing point of benzene = 5.5 C )
o
[AFMC 2000]
(a) 1 (b) 2
(a) 100 (b) 200 (c) 3 (d) 4
(c) 300 (d) 400
 196 Solution and Colligative properties

(SET -4)

1. (c) Wt. of H 2 SO 4 per litre  N  eq. mass  2  49 = 98g. 13. (b) NaCl and ZnSO 4 gives 2 ions but NaCl is more ionic

2. (a) In alkaline medium KMnO4 act as oxidant as follows. than ZnSO 4 .

2 KMnO4  2 KOH  2 K 2 MnO4  H 2 O  (O) Kb  w  1000

14. (b) m 
Tb  W
Hence its eq .wt . = m. wt .  158
Kb  2.16, w  0.11, W  15 g, Tb  0.1
Mass 1
Now, Normality   2.16  0.11  1000
Eq. mass V(L) m  158.40 ~ 158 .
0.1  15
100 15. (c) The elevation (Tb ) in the boiling point
mass  0.1  158  g  1.58 g.
1000
 354.11K  353.23 K  0.88 K
3. (d) For complete neutralization equivalent of oxalic acid =
equivalent of NaOH = Substituting these values in expression

w NV w 0.2  100 K b  1000  w

    w  1.26 gm . M Solute 
eq . wt 1000 63 1000 Tb  W

0.2 Where, w  weight of solute, W  weight of solvent

4. (c) F  ions in PPm =  10 6  400
500 2.53  1.8  1000
M solute   58 gm mol 1
5. (b) 5.85 g NaCl = 0.1 mol as it present in 1 kg of 0.88  90

water ; molality 
wt .

5 .85
=0.1molal Hence, molar mass of the solute  58 gm mol 1
m wt .  l 58.5  1
0 .18
6. (a) 16. (a) Kb   1 .8
0 .1
P o  Ps n P o  Ps w  M K f  1000  w 5.1  1000  4.8
7. (d)  ;   80 17. (d) m    400 .
P o
nN Po m W W  T f 60  1 .02

8. (d) CH 3 COCH 3  CHCl 3 is non ideal solution which shown 18. (d) T f  mk f
negative deviation. 0.01  1000
0.40  kf  kf  4
9. (a) The particle come of AlCl3 solution will be maximum due to 100
ionisation less in BaCl2 and minimum in urea again T f  mk f

0 .03  1000
AlCl3  Al 3   3Cl   4  4
50
BaCl2  Ba 2   2Cl   3  2.4
19. (d) La(NO 3 )3 will furnish four ions and thus will develop more
More the number of particles in solution more is the osmotic lowering in freezing point whereas glucose gives only one
pressure a colligative properties. particle and thus minimum lowering in freezing point.
5  0.0821  1000  423 20. (d) K 3 [Fe(CN )6 ]  3 K   [Fe(CN )6 ]3  .
10. (c)   5.07 atm .
342  100
11. (d) Osmotic pressure is a coligative properties equimolar solution
of Ca(NO 3 )2 and Na 2 SO 4 will produce same number of
solute particles.

CaNO 3 ⇌ Ca 2   2NO 3

Na 2 (SO 4 ) ⇌ 2 Na   SO 42 

12. (a) Al2 (SO 4 )3 Deci-molar gives maximum ion. Hence, its
***
osmotic pressure is maximum.
 Solid State 197

Chapter

5
Solid State

Silica occurs in crystalline as well as amorphous states. Quartz is a

The solids are the substances which have definite volume and
typical example of crystalline silica. Quartz and the amorphous silica differ
definite shape. In terms of kinetic molecular model, solids have regular
considerably in their properties.
order of their constituent particles (atoms, molecules or ions). These
particles are held together by fairly strong forces, therefore, they are present Quartz Amorphous silica
at fixed positions. The properties of the solids not only depend upon the It is crystalline in nature It is light (fluffy) white powder
nature of the constituents but also on their arrangements.
All four corners of SiO 44  The SiO 44  tetrahedra are randomly
Types and Classification of solids tetrahedron are shared by others to joined, giving rise to polymeric chains,
give a network solid sheets or three-dimensional units
(1) Types of solids It has high and sharp melting point It does not have sharp melting point
Solids can be broadly classified into following two types, (1710°C)

(i) Crystalline solids/True solids, (3) Diamond and graphite

(ii) Amorphous solids/Pseudo solids
Crystalline solids
They have long range order.
They have definite melting point
They have a definite heat of fusion
They are rigid and incompressible
They are given cleavage i.e. they
break into two pieces with plane
surfaces
They are anisotropic because of these
substances show different property in
different direction
There is a sudden change in volume
when it melts.
These possess symmetry
These possess interfacial angles.
Amorphous solids
They have short range order.
Not have definite melting point
Not have definite heat of fusion
Not be compressed to any appreciable
extent
They are given irregular cleavage i.e.
they break into two pieces with irregular
surface
They are isotropic because of these
substances show same property in all
directions
There is no sudden change in volume on
melting.
Not possess any symmetry.
Not possess interfacial angles.
Diamond and graphite are tow allotropes of carbon. Diamond and
graphite both are covalent crystals. But, they differ considerably in their
properties.
Diamond Graphite
It occurs naturally in free state It occurs naturally, as well as
manufactured artificially
It is the hardest natural substance It is soft and greasy to touch
known.
It has high relative density (about 3.5) Its relative density is 2.3
It is transparent and has high It has black in colour and opaque
refractive index (2.45)
It is non-conductor of heat and Graphite is a good conductor of heat
electricity. and electricity
It burns in air at 900°C to give CO2 It burns in air at 700°C to give CO2
It occurs as octahedral crystals It occurs as hexagonal crystals

(2) Crystalline and amorphous silica (SiO2 )

(4) Classification of crystalline solids
Table : 5.1 Some characteristics of different types of crystalline solids
Types of Constituents Bonding Examples Physical M.P. B.P. Electrical
Solid Nature Conductivity
 198 Solid State
Ionic Positive and Coulombic NaCl, KCl, CaO, MgO, Hard but High (≃1000K) High (≃2000K) Conductor
negative ions LiF, ZnS, BaSO4 and brittle (in molten state
network K2SO4 etc. and in aqueous
systematically solution)
arranged
Covalent Atoms connected in Electron SiO2 (Quartz), Hard Very high (≃4000K) Very high Insulator except
covalent bonds sharing SiC, C (diamond), Hard graphite
(≃5000K)
C(graphite) etc. Hard
Molecular Polar or non-polar (i) Molecular I2,S , P , CO , CH ,
8 4 2 4
Soft Low Low Insulator
molecules interactions CCl etc.
(intermolecu-
4
(≃300K to 600K) (≃ 450 to 800 K)
lar forces) Insulator
Starch, sucrose, Soft Low Low
(ii) Hydrogen
water, dry ice or
bonding
drycold (solid CO2) (≃400K) (≃373K to 500K)
etc.
Metallic Cations in a sea of Metallic Sodium , Au, Cu, Ductile High High Conductor
electrons magnesium, metals malleable
and alloys (≃800K to 1000 K) (≃1500K to 2000K)
Atomic Atoms London Noble gases Soft Very low Very low Poor thermal and
dispersion electrical
force conductors
(iii) Centre of symmetry : It is an imaginary point in the crystal that
Crystallography any line drawn through it intersects the surface of the crystal at equal
distance on either side. Y
“The branch of science that deals with the study of structure,
geometry and properties of crystals is called crystallography”.
(1) Symmetry in Crystal : A crystal possess following three types of Centre of
symmetry, symmetry of a
cubic crystal
(i) Plane of symmetry : It is an imaginary plane which passes
through the centre of a crystal can divides it into two equal portions which
are exactly the mirror images of each other. X

Z Fig. 5.3
Only simple cubic system have one centre of symmetry. Other
system do not have centre of symmetry.
The total number of planes, axes and centre of symmetries possessed
Plane of symmetry Rectangular plane of Diagonal plane by a crystal is termed as elements of symmetry.
symmetry of symmetry
A cubic crystal possesses total 23 elements of symmetry.
Fig. 5.1
(ii) Axis of symmetry : An axis of symmetry or axis of rotation is an Plane of symmetry ( 3 + 6) =9
imaginary line, passing through the crystal such that when the crystal is
Axes of symmetry ( 3 + 4 + 6) = 13
rotated about this line, it presents the same appearance more than once in
one complete revolution i.e., in a rotation through 360°. Suppose, the same Centre of symmetry (1) =1
appearance of crystal is repeated, on rotating it through an angle of 360°/n, Total symmetry = 23
around an imaginary axis, is called an n-fold axis where, n is known as the (2) Laws of crystallography : Crystallography is based on three
order of axis. By order is meant the value of n in 2 / n so that rotation fundamental laws.
through 2 / n, gives an equivalent configuration. (i) Law of constancy of interfacial angles : This law states that angle
between adjacent corresponding faces is inter facial angles of the crystal of a
particular substance is always constant inspite of different shapes and sizes
and mode of growth of crystal. The size and shape of crystal depend upon the
conditions of crystallisation. This law is also known as Steno's Law.

Axis of two fold symmetry Axis of three f old symmetry

Fig. 5.4. Constancy of interfacial angles

Axis of four fold symmetry
(ii) Law of rational indices : This law states that the ratio of
intercepts of different faces of a crystal with the three axes are constant and
can be expressed by rational numbers that the intercepts of any face of a
crystal along the crystallographic axes are either equal to unit intercepts
(i.e., intercepts made by unit cell) a, b, c or some simple whole number
multiples of them e.g., na, n' b, n''c, where n, n' and n'' are simple whole
numbers. The whole numbers n, n' and n'' are called Weiss indices. This law
was given by Hauy.
Fig. 5.2 Axis of six fold symmetry
 Solid state 199
(iii) Law of constancy of symmetry : According to this law, all A three dimensional group of lattice points which when repeated in
crystals of a substance have the same elements of symmetry is plane of space generates the crystal called unit cell.
symmetry, axis of symmetry and centre of symmetry. The unit cell is described by the lengths of its edges, a, b, c (which
Miller indices : Planes in crystals are described by a set of integers are related to the spacing between layers) and the angles between the edges,
(h, k and l) known as Miller indices. Miller indices of a plane are the ,  ,  . Space
Lattice
reciprocals of the fractional intercepts of that plane on the various
crystallographic axes. For calculating Miller indices, a reference plane, known
c
as parametral plane, is selected having intercepts a, b and c along x, y and

z-axes, respectively. Then, the intercepts of the unknown plane are given 
with respect to a, b and c of the parametral plane.
 b Unit
Thus, the Miller indices are : a
Cell

a Unit cell Space lattice & unit cell

h Fig. 5.5
Types of units cells
intercept of the plane along x - axis
A units cell is obtained by joining the lattice points. The choice of
b lattice points to draw a unit cell is made on the basis of the external
k
intercept of the plane along y - axis geometry of the crystal, and symmetry of the lattice. There are four
c different types of unit cells. These are,
l (1) Primitive or simple cubic (sc) : Atoms are arranged only at the
intercept of the plane along z - axis corners of the unit cell.
The distance between the parallel planes in crystals are designated (2) Body centred cubic (bcc) : Atoms are arranged at the corners
and at the centre of the unit cell.
as d hkl . For different cubic lattices these interplanar spacing are given by (3) Face centred cubic (fcc) : Atoms are arranged at the corners and
the general formula, at the centre of each faces of the unit cell.
(4) Side centered : Atoms are arranged at the centre of only one set
a
d(hkl )  of faces in addition to the atoms at the corner of the unit cell.
h2  k 2  l2 Formation of crystal and Crystal systems
Where a is the length of cube side while h, k and l are the Miller The crystals of the substance are obtained by cooling the liquid (or
indices of the plane. the melt) of the solution of that substance. The size of the crystal depends
When a plane is parallel to an axis, its intercept with that axis is upon the rate of cooling. If cooling is carried out slowly, crystals of large
taken as infinite and the Miller will be zero. size are obtained because the particles (ions, atoms or molecules) get
sufficient time to arrange themselves in proper positions.
Negative signs in the Miller indices is indicated by placing a bar on
the intercept. All parallel planes have same Miller indices. Atoms of molecules    cluster 
Dissolved

dissolved

dissolved embryo  nucleus  crystal

(unstable)

Space lattice and Unit cell (If loosing units dissolves as embryo and if gaining unit grow as a
crystals).
Crystal is a homogeneous portion of a crystalline substance, Bravais (1848) showed from geometrical considerations that there
composed of a regular pattern of structural units (ions, atoms or molecules) can be only 14 different ways in which similar points can be arranged. Thus,
by plane surfaces making definite angles with each other giving a regular there can be only 14 different space lattices. These 14 types of lattices are
geometric form. known as Bravais Lattices. But on the other hand Bravais showed that there
A regular array of points (showing atoms/ions) in three dimensions are only seven types of crystal systems.
is commonly called as a space lattice, or lattice.
Each point in a space lattice represents an atom or a group of
atoms.
Each point in a space lattice has identical surroundings throughout.
Table : 5.2 Bravais lattices corresponding to different crystal systems
Crystal system Space lattice Examples
Cubic Simple : Lattice points at the eight Body centered : Points at the eight Face centered : Points at the Pb, Hg, Ag,
corners of the unit cells. corners and at the body centred. eight corners and at the six
ab c, face centres. Au, Cu , ZnS ,
diamond, KCl , CsCl,
      90 o c
NaCl, Cu 2O, CaF2
  and alums. etc.
 b
a
Tetragonal Simple : Points at the eight corners of Body centered : Points at the eight corners and at the body centre SnO 2 , TiO 2 ,
the unit cell.
ab c , ZnO 2 , NiSO 4
      90 o c ZrSiO 4 . PbWO4 ,
white Sn etc.
 
 b
a
 200 Solid State
Orthorhombic (Rhombic) Simple: Points at the End centered : Also called side Body centered : Face centered: Points at KNO 3 , K2 SO 4 ,
eight corners of the centered or base centered. Points at the eight the eight corners and at
ab c, unit cell. Points at the eight corners and corners and at the the six face centres. PbCO 3 , BaSO 4 ,
      90 o at two face centres opposite to body centre rhombic sulphur,
each other. MgSO 4 . 7 H 2O etc.
c
 

b
a
Rhombohedral Simple : Points at the eight corners of the unit cell NaNO 3 , CaSO 4 ,
or Trigonal calcite, quartz,
ab c, As, Sb , Bi etc.
      90 
Hexagonal Simple : Points at the twelve corners of the unit cell or Points at the twelve corners of the hexagonal prism ZnO , PbS , CdS ,
out lined by thick line. and at the centres of the two hexagonal faces.
ab c , HgS , graphite, ice,
Mg, Zn, Cd etc.
    90 o

  120 o

Monoclinic Simple : Points at the eight corners of the unit cell End centered : Point at the eight corners and at two Na 2 SO 4 .10 H 2 O,
face centres opposite to the each other.
ab c, Na 2 B4 O7 .10 H 2 O,
    90 o ,   90 o
CaSO 4 .2 H 2 O,
monoclinic sulphur etc.

Triclinic Simple : Points at the eight corners of the unit cell. CaSO 4 .5 H 2O,
ab c, K 2 Cr2 O7 , H 3 BO3
      90 o
etc.

(2) Co-ordination number (C.N.) : It is defined as the number of

nearest neighbours or touching particles with other particle present in a
crystal is called its co-ordination number. It depends upon structure of the
crystal.
Analysis of cubic system For simple cubic system C.N. = 6.
(1) Number of atoms in per unit cell For body centred cubic system C.N. = 8
The total number of atoms contained in the unit cell for a simple For face centred cubic system C.N. = 12.
cubic called the unit cell content.
(3) Density of the unit cell ( ) : It is defined as the ratio of mass
n n f ni per unit cell to the total volume of unit cell.
The simplest relation can determine for it is, c  
8 2 1 ZM
Where n c  Number of atoms at the corners of the cube=8

a3 N 0
n f  Number of atoms at six faces of the cube = 6 Where Z = Number of particles per unit cell
n i  Number of atoms inside the cube = 1 M = Atomic mass or molecular mass
Cubic unit cell nc nf ni Total atom in N 0  Avogadro number (6.023  10 23 mol 1 )
per unit cell
Simple cubic (sc) 8 0 0 1 a  Edge length of the unit cell= a pm  a  10 10 cm
body centered cubic (bcc) 8 0 1 2
a 3  volume of the unit cell
Face centered cubic (fcc) 8 6 0 4
ZM
i.e.   g / cm 3
a  N 0  10 30
3
 Solid state 201
1 1
The density of the substance is same as the density of the unit cell.
4 2
(4) Packing fraction (P.F.) : It is defined as ratio of the volume of the
unit cell that is occupied by spheres of the unit cell to the total volume of
the unit cell. 3

Let radius of the atom in the packing = r

Edge length of the cube = a
Fig. 5.6. Square close packing
Volume of the cube V = a 3
(ii) Hexagonal close packing : In which the spheres in every second
4 3
Volume of the atom (spherical)   r row are seated in the depression between the spheres of first row. The
3 spheres in the third row are vertically aligned with spheres in first row. The
4 3 similar pattern is noticed throughout the crystal structure. In this
r Z
Z arrangement each sphere is in contact with six other spheres.
Packing density   3 3
V a 11 2
Structure r related to Volume of the Packing density % of void
a atom () 6 3

Simple cubic a 3  100–52 = 5 4

r 4 a  0 .52
2   6
48%
3 2
Face-centred 100 – 74
2
a 3
r 4  a 
cubic     0 .74 = 26% Fig. 5.7. Hexagonal close packing
2 2
3  6 (2) Close packing in three dimensions : In order to develop three
2 2 
Body- 100 – 68 dimensional close packing, let us retain the hexagonal close packing in the
3a  3a 
3
3 first layer. For close packing, each spheres in the second layer rests in the
centred r 4  0 .68 = 32%
4  
8
cubic 3  4  hollow at the centre of three touching spheres in the layer as shown in
 
figure. The spheres in the first layer are shown by solid lines while those in
X-ray study of crystal structure second layer are shown by broken lines. It may be noted that only half of
the triangular voids in the first layer are occupied by spheres in the second
Study of internal structure of crystal can be done with the help of X-
layer (i.e., either b or c). The unoccupied hollows or voids in the first layer
rays. The distance of the constituent particles can be determined from
are indicated by (c) in figure.
diffraction value by Bragg’s equation.
n  2d sin a
a a aa a
where,  = Wave length of X-rays, n = order of reflection,
  Angle of reflection, d = Distance between two parallel surfaces b b b
a
a a a
The above equation is known as Bragg’s equation or Bragg’s law. c c c
The reflection corresponding to n = 1 (for a given family of planes) is called
first order reflection; the reflection corresponding to n = 2 is the second a a a a a
order reflection and so on. Thus by measuring n (the order of reflection of
the X-rays) and the incidence angle , we can know d/. Fig. 5.8. Close packing in three dimensions
d n There are two alternative ways in which species in third layer can be

 2 sin arranged over the second layer,
From this, d can be calculated if  is known and vice versa. In X-ray (i) Hexagonal close packing : The third layer lies vertically above the
reflections, n is generally set as equal to 1. Thus Bragg’s equation may first and the spheres in third layer rest in one set of hollows on the top of
alternatively be written as
the second layer. This arrangement is called ABAB …. type and 74% of the
  2 d sin = 2 d sin hkl
available space is occupied by spheres. This arrangement is found in
Where d denotes the perpendicular distance between adjacent planes
hkl
Be, Mg, Zn, Cd, Sc, Y, Ti, Zr, Tc, Ru.
with the indices hkl. A

A
Close packing in crystalline solids
A
In the formation of crystals, the constituent particles (atoms, ions or B
B
molecules) get closely packed together. The closely packed arrangement is
A B
that in which maximum available space is occupied. This corresponds to a
state of maximum density. The closer the packing, the greater is the stability B
of the packed system.
A A
(1) Close packing in two dimensions : The two possible arrangement A
of close packing in two dimensions.
(i) Square close packing : In which the spheres in the adjacent row
lie just one over the other and show a horizontal as well as vertical Fig. 5.9. Hexagonal close packing (hcp) in three dimensions
alignment and form square. In this arrangement each sphere is in contact (ii) Cubic close packing : The third layer is different from the first
with four spheres. and the spheres in the third layer lie on the other set of hollows marked ‘C’
 202 Solid State
in the first layer. This arrangement is called ABCABC….. type and in this also (2) Tetrahedral void : A tetrahedral void is developed when triangular
74% of the available space is occupied by spheres. The cubic close packing voids (made by three spheres in one layer touching each other) have contact
has face centred cubic (fcc) unit cell. This arrangement is found in Cu, Ag, with one sphere either in the upper layer or in the lower layer.
Au, Ni, Pt, Pd, Co, Rh, Ca, Sr.
B B

The number of tetrahedral voids

Fig. 5.13. is double
Tetrahedral the number of spheres in
void
C
the crystal structure.
A
B
r
 0 .225
A
R
where, r is the radius of the tetrahedral void or atom
C C
occupying tetrahedral void.
R is the radius of spheres forming tetrahedral void.
Fig. 5.10. Cubic close packing (ccp or fcc) in three dimensions
(iii) Body centred cubic : This arrangement of spheres (or atoms) is (3) Octahedral void : This type of void is surrounded by six closely
not exactly close packed. This structure can be obtained if spheres in the packed spheres, i.e. it is formed by six
first layer (A) of close packing are slightly opened up. As a result none of spheres.
these spheres are in contact with each other. The second layer of spheres The number of octahedral voids is
(B) can be placed on top of the first layer so that each sphere of the second equal to the number of spheres.
layer is in contact with four spheres of the layer below it. Successive
r
building of the third will be exactly like the first layer. If this pattern of  0 .414
building layers is repeated infinitely we get an arrangement as shown in R
Fig. 5.14. Octahedral void
figure. This arrangement is found in Li, Na, K, Rb, Ba, Cs, V, Nb, Cr, Mo, Fe. (4) Cubic void : This type of void
is formed between 8 closely packed
A A spheres which occupy all the eight corner of
A A A A
A A cube.
B B B
B r
A A A A  0 .732
A
R
B B Fig. 5.15. Cubic void
B
A A
A The decreasing order of the size of the various voids is,
A A A A
Cubic > Octahedral > Tetrahedral > Trigonal
Fig. 5.11. Body centred cubic (bcc) close packing in three dimensions
Ionic radii and Radius ratio
Table : 5.3 Comparison of hcp, ccp and bcc
(1) Ionic radii : X-ray diffraction or electron diffraction techniques
Property hcp ccp bcc provides the necessary information regarding unit cell. From the dimensions
Arrangement of Close packed Close packed Not close of the unit cell, it is possible to calculate ionic radii.
packing packed
Type of AB AB A... ABC ABC A... AB AB A... Let, cube of edge length 'a' having cations and anions say NaCl
packing structure.
Available space 74% 74% 68% Then, rc  ra  a / 2
occupied Cl–
Coordination 12 12 8 where rc and ra are radius
number of cation and anion.
a/2
Malleability and Less malleable, Malleable and Radius of Cl 
ductility hard, brittle ductile 90°
(a / 2)2  (a / 2)2 a Na+ Cl–
Interstitial sites in close packing  
2 4 a/2
Even in the close packing of spheres, there is left some empty space Fig. 5.16. Radii of chloride ion
between the spheres. This empty space in the crystal lattice is called site or For bcc lattice say CsCl.
void or hole. Voids are of following types, 3a
rc  ra 
(1) Trigonal void : This site is formed when three spheres lie at the 2
vertices of an equilateral triangle. Size of the trigonal site is given by the
(2) Radius ratio : Ionic compounds occur in crystalline forms. Ionic
following relation,
Triogonal compounds are made of cations and anions. These ions are arranged in
r  0.155 R three dimensional array to form an aggregate of the type (A B ) . Since, the
void
+ –

r = Radius of the spherical Coulombic forces are non-directional, hence the structures of such crystals
trigonal void
R = Radius of closely packed spheres
Fig. 5.12
 Solid state 203

are mainly governed by the ratio of the radius of cation (r ) to that of 0.155 – 0.225 3 Planar triangle
anion (r ). The ratio r to r (r / r ) is called as radius ratio. 0.225 – 0.414 4 Tetrahedral

r 0.414 – 0.732 6 Octahedral

Radius ratio 
r 0.732 – 0.999 or 1 8 Body-centered cubic

Effect of temperature and Pressure on C.N.

On applying high pressure NaCl structure having 6 : 6 co-
ordination changes to CsCl structure having 8 : 8 co-ordination. Thus,
r+/r– = 0.414 r+/r– < 0.414
r+/r– > 0.732 increase in pressure increases the co-ordination number.
Coordination number Coordination number Similarly, CsCl structure on heating to about 760 K, changes to
increases from 6 to 8 decreases from 6 to 4
NaCl structure. In other words, increase of temperature decreases the co-
ordination number.
Fig. 5.17. Effect of radius ratio on co-ordination number
Table : 5.4 Limiting Radius ratios and Structure Pressure
NaCl CsCl
(6 : 6 ) Temp (8 : 8)
Limiting radius ratio (r )/(r )
+ –
C.N. Shape
< 0.155 2 Linear

Structure of ionic crystals

Table : 5.5 Types of ionic crystal with description
Crystal structure Brief description Examples Co-ordination Number of formula
type number units per unit cell
Type AB It has fcc arrangement in which Cl  ions Halides of Li, Na, K, Rb, AgF, Na   6 4
Rock salt (NaCl) occupy the corners and face centres of a cube AgBr, NH Cl, NH Br, NH I etc.
4 4 4

type 
Cl   6
while Na ions are present at the body and
edge of centres.
Zinc blende (ZnS) It has ccp arrangement in which S 2  ions CuCl , CuBr, CuI, AgI, BeS Zn 2   4 4
type
form fcc and each Zn 2  ion is surrounded S 2  4
2
tetrahedrally by four S ions and vice versa.
Type AB 2
It has arrangement in which Ca 2  ions form BaF2 , BaCl2 , SrF2 Ca 2   8 4
Fluorite (CaF ) type fcc with each Ca 2  ions surrounded by 8 F  SrCl2 , CdF2 , PbF2 F  4
2


ions and each F ions by 4Ca ions. 2+

Antifluorite type Here negative ions form the ccp arrangement Na 2 O Na   4 4

so that each positive ion is surrounded by 4
negative ions and each negative ion by 8 O2  8
positive ions
Caesium chloride It has the bcc arrangement with Cs  at the CsCl, CsBr, CsI, CsCN , Cs   8 1
(CsCl) type  TlCl, TlBr, TlI and TlCN
body centre and Cl ions at the corners of a Cl   8
cube or vice versa.

electron deficient bond formed by the release of an electron is called a hole.

Defects or Imperfections in solids
Any deviation from the perfectly ordered arrangement constitutes a
defect or imperfection. These defects sometimes called thermodynamic
defects because the number of these defects depend on the temperature.
(1) Electronic imperfections : Generally, electrons are present in fully
occupied lowest energy states. But at high temperatures, some of the
electrons may occupy higher energy state depending upon the temperature.
For example, in the crystals of pure Si or Ge some electrons are released
thermally from the covalent bonds at temperature above 0 K. these
electrons are free to move in the crystal and are responsible for electrical
conductivity. This type of conduction is known as intrinsic conduction. The
In the presence of electric field the positive holes move in a direction
opposite to that of the electrons and conduct electricity. The electrons and
holes in solids gives rise to electronic imperfections.
(2) Atomic imperfections/point defects : When deviations exist from
the regular or periodic arrangement around an atom or a group of atoms in
a crystalline substance, the defects are called point defects. Point defect in a
crystal may be classified into following three types.
(i) Stoichiometric defects : The compounds in which the number of
positive and negative ions are exactly in the ratios indicated by their
chemical formulae are called stoichiometric compounds. The defects do not
 204 Solid State A+ B– A+ B– A+ B– A+ B–

disturb the stoichiometry (the ratio of numbers of positive and negative A+

ions) are called stoichiometric defects. These are of following types, B– A+ B– A+ B– A+ B– A+
(a) Interstitial defect : This type of defect is caused due to the
presence of ions in the normally vacant interstitial sites in the crystals.
(b) Schottky defect : This type of defect when equal number of A+ B– A+ B– A+ e– A+ B–
cations and anions are missing from their lattice sites so that the electrical Fig. 5.20. Metal excess defect Fig. 5.21. Metal excess defect
neutrality is maintained. This type of defect occurs in highly ionic due to extra cation due to anion vacancy
compounds which have high co-ordination number and cations and anions
of similar sizes. e.g., NaCl, KCl, CsCl and KBr etc. Consequences of Metal excess defects
(c) Frenkel defect : This type of defect arises when an ion is missing The crystals with metal excess defects are generally coloured due to
from its lattice site and occupies an interstitial position. The crystal as a the presence of free electrons in them.
whole remains electrically neutral because the number of anions and cations The crystals with metal excess defects conduct electricity due to the
remain same. Since cations are usually smaller than anions, they occupy presence of free electrons and are semiconductors. As the electric transport
interstitial sites. This type of defect occurs in the compounds which have is mainly by “excess” electrons, these are called n-type (n for negative)
low co-ordination number and cations and anions of different sizes. e.g., semiconductor.
ZnS, AgCl and AgI etc. Frenkel defect are not found in pure alkali metal
halides because the cations due to larger size cannot get into the interstitial The crystals with metal excess defects are generally paramagnetic
due to the presence of unpaired electrons at lattice sites.
sites. In AgBr both Schottky and Frenkel defects occur simultaneously.
When the crystal is irradiated with white light, the trapped electron
A+ B– A+ B– A+ B– A+ B– absorbs some component of white light for excitation from ground state to
A+
the excited state. This gives rise to colour. Such points are called F-centres.
(German word Farbe which means colour) such excess ions are
B+ A– A+ B– A+ B– A+ accompanied by positive ion vacancies. These vacancies serve to trap holes
in the same way as the anion vacancies trapped electrons. The colour
centres thus produced are called V-centres.
B– A+ B– B– A+ B–
(c) Metal deficiency defect by cation vacancy : In this a cation is
Fig. 5.18. Schottky defect Fig. 5.19. Frenkel defect missing from its lattice site. To maintain electrical neutrality, one of the
Consequences of Schottky and Frenkel defects nearest metal ion acquires two positive charge. This type of defect occurs in
compounds where metal can exhibit variable valency. e.g., Transition metal
Presence of large number of Schottky defect lowers the density of compounds like NiO, FeO, FeS etc.
the crystal. When Frenkel defect alone is present, there is no decrease in (d) By having extra anion occupying interstitial site : In this, an extra
density. The closeness of the charge brought about by Frenkel defect tends anion is present in the interstitial position. The extra negative charge is
to increase the dielectric constant of the crystal. Compounds having such balanced by one extra positive charge on the adjacent metal ion. Since
defect conduct electricity to a small extent. When electric field is applied, an anions are usually larger it could not occupy an interstitial site. Thus, this
ion moves from its lattice site to occupy a hole, it creates a new hole. In this structure has only a theoretical possibility. No example is known so far.
way, a hole moves from one end to the other. Thus, it conducts electricity A+ B– A+ B–
across the crystal. Due to the presence of holes, stability (or the lattice Cation vacancy
energy) of the crystal decreases.
B– B– A+
(ii) Non-stoichiometric defects : The defects which disturb the
stoichiometry of the compounds are called non-stoichiometry defects. These Metal having higher
charge
defects are either due to the presence of excess metal ions or deficiency of A+ B– A2
+
B–
metal ions.
(a) Metal excess defects due to anion vacancies : A compound may B– A+ B– A+
have excess metal anion if a negative ion is absent from its lattice site,
leaving a ‘hole’, which is occupied by electron to maintain electrical Fig. 5.22
neutrality. This type of defects are found in crystals which are likely to Consequences of metal deficiency defects
possess Schottky defects. Anion vacancies in alkali metal halides are reduced Due to the movement of electron, an ion A changes to A ions. Thus,
+ +2

by heating the alkali metal halides crystals in an atmosphere of alkali metal the movement of an electron from A ion is an apparent of positive hole and
+

vapours. The ‘holes’ occupy by electrons are called F-centres (or colour
centres).
(b) Metal excess defects due to interstitial cations : Another way in
which metal excess defects may occur is, if an extra positive ion is present
in an interstitial site. Electrical neutrality is maintained by the presence of
an electron in the interstitial site. This type of defects are exhibit by the
crystals which are likely to exhibit Frenkel defects e.g., when ZnO is heated,
it loses oxygen reversibly. The excess is accommodated in interstitial sites,
with electrons trapped in the neighborhood. The yellow colour and the
electrical conductivity of the non-stoichiometric ZnO is due to these
trapped electrons.
the substances are called p-type semiconductor
(iii) Impurity defect : These defects arise when foreign atoms are
present at the lattice site (in place of host atoms) or at the vacant
interstitial sites. In the former case, we get substitutional solid solutions
while in the latter case, we get interstitial solid solution. The formation of
the former depends upon the electronic structure of the impurity while that
of the later on the size of the impurity.
Properties of solids
Some of the properties of solids which are useful in electronic and
magnetic devices such as, transistor, computers, and telephones etc., are
summarised below,
 Solid state 205
(1) Electrical properties : Solids are classified into following classes Examples, Nb 3 Ge alloy (Before 1986)
depending on the extent of conducting nature.
La1.25 Ba0.15 CuO 4 (1986)
(i) Conductors : The solids which allow the electric current to pass
through them are called conductors. These are further of two types; Metallic
YBa 2 Cu 3 O7 (1987)
conductors and electrolytic conductors. The electrical conductivity of these
solids is high in the range 10 4  10 6 ohm 1 cm 1 . Their conductance Following are the important applications of superconductivity,
decrease with increase in temperature.
(a) Electronics, (b) Building supermagnets,
(ii) Insulators : The solids which do not allow the current to pass
(c) Aviation transportation, (d) Power transmission
through them are called insulators. e.g., rubber, wood and plastic etc. the
electrical conductivity of these solids is very low i.e., “The temperature at which a material enters the superconducting
10 12
 10 22 1
ohm cm 1
. state is called the superconducting transition temperature, (Tc ) ”.
Superconductivity was also observed in lead (Pb) at 7.2 K and in tin (Sn) at
(iii) Semiconductors : The solids whose electrical conductivity lies 3.7K. The phenomenon of superconductivity in other materials such as
between those of conductors and insulators are called semiconductors. The polymers and organic crystals. Examples are
conductivity of these solid is due to the presence of impurities. e.g. Silicon
(SN) , polythiazyl, the subscript x indicates a large number of
and Germanium. Their conductance increase with increase in temperature. x

variable size.
The electrical conductivity of these solids is increased by adding impurity.
This is called Doping. When silicon is doped with P (or As, group 5 th
(TMTSF) PF , where TMTSF is tetra methyl tetra selena fulvalene.
2 6

elements), we get n-type semiconductor. This is because P has five valence

(2) Magnetic properties : Based on the behavior of substances when
electrons. It forms 4 covalent bonds with silicon and the fifth electron placed in the magnetic field, there are classified into five classes.
remains free and is loosely bound. This give rise to n-type semiconductor
because current is carried by electrons when silicon is doped with Ga (or in
In/Al, group 3 elements) we get p-type semiconductors.
rd

Superconductivity : When any material loses its resistance for

electric current, then it is called superconductor, Kammerlingh Onnes (1913)
observed this phenomenon at 4K in mercury. The materials offering no
resistance to the flow of current at very low temperature (2-5K) are called
superconducting materials and phenomenon is called superconductivity.
Table : 5.6 Magnetic properties of solids
Properties Description Alignment of Magnetic Dipoles Examples Applications
Diamagnetic Feebly repelled by the magnetic fields. Non-metallic All paired electrons TiO2, V2O5, NaCl, C6H6 Insulator
elements (excepts O2, S) inert gases and species with (benzene)
paired electrons are diamagnetic
Paramagnetic Attracted by the magnetic field due to the presence Electronic
O2 , Cu 2  , Fe3  , TiO, appliances
of permanent magnetic dipoles (unpaired electrons).
In magnetic field, these tend to orient themselves Ti2O3 , VO, VO2 , CuO
parallel to the direction of the field and thus, produce
magnetism in the substances. At least one unpaired electron
Ferromagnetic Permanent magnetism even in the absence of Dipoles are aligned in the same Fe, Ni, Co, CrO2 CrO2 is used in
magnetic field, Above a temperature called Curie direction audio and video
temperature, there is no ferromagnetism. tapes

Antiferromagnetic This arises when the dipole alignment is zero due to MnO, MnO2, Mn2O, FeO, –
equal and opposite alignment. Fe2O3; NiO, Cr2O3, CoO,
Co3O4,
Ferrimagnetic This arises when there is net dipole moment Fe3O4, ferrites –

(3) Dielectric properties : A dielectric substance is that which does
not allow the electricity to pass through them but on applying the electric
field, induced charges are produced on its faces. In an insulator, the
electrons are strongly held by the individual atoms. When an electric field is
applied polarization takes place because nuclei are attracted to one side and
the electron cloud to the other side. As a result, dipoles are created. Such
type of crystals shows the following properties,
(i) Piezoelectricity : In some of the crystals, the dipoles may align
themselves is an ordered way so as to give some net dipole moment. When
mechanical stress is applied in such crystals so as to deform them,
electricity is produced due to the displacement of ions. The electricity thus
produced is called piezoelectricity and the crystals are called piezoelectric
crystals. Examples, Quartz, Rochelle’s salt ( sod. pot. tartarate). Piezoelectric
crystals act as mechanical-electric transducer. These crystals are used as
pick-ups in record players where they produce electric signals by application
of pressure.
(ii) Pyroelectricity : On heating, some polar crystals produce a small
electric current. The electricity thus produced is called pyroelectircity.
(iii) Ferroelectricity : In some of the piezoelectric crystals, a
permanent alignment of the dipoles is always there even in the absence of
the electric field, however, on applying field the direction of polarization
changes. This phenomenon is called ferroelectricity and the crystals as
 206 Solid State
ferroelectric crystal. Example, Potassium hydrogen phosphate (KH 2 PO4 ) , 5. Value of heat of fusion of NaCl is
Barium titanate (BaTiO3 ) . (a) Very low
(iv) Antiferroelectricity : In some crystals, the dipoles in (b) Very high
alternate polyhedra point up and down so that the crystals does not (c) Not very low and not very high
possess any net dipole moment. Such crystals are said to be (d) None of the above
antiferroelectric. Example, Lead zirconate (PbZrO3 ) . Ferroelectrics 6. Piezoelectric crystals are used in
are used in the preparation of small sized capacitors of high (a) TV (b) Radio
capacitance. Pyroelectric infrared detectors are based on such (c) Record player (d) Freeze
substances. These can be used in transistors, telephone, computer 7. Which of the following is true for diamond
etc. [AFMC 1997]
(a) Diamond is a good conductor of electricity
(b) Diamond is soft
(c) Diamond is a bad conductor of heat
(d) Diamond is made up of C, H and O

8. NaCl is an example of
 The reverse of crystallization is the melting of the solid.
(a) Covalent solid (b) Ionic solid
 The slower the rate of formation of crystal, the bigger is the crystal. (c) Molecular solid (d) Metallic solid
 The hardness of metals increases with the number of electrons
available for metallic bonding. Thus Mg is harder than sodium.
 Isomorphism is applied to those substances which are not only
similar in their crystalline form, but also possess an equal number
of atoms united in the similar manner. The existence of a
substance in more than one crystalline form is known as
polymorphism.

Properties and Types of solid

1. The three states of matter are solid, liquid and gas. Which of the
following statement is/are true about them
[AIIMS 1991]
(a) Gases and liquids have viscosity as a common property
(b) The molecules in all the three states possess random
translational motion
(c) Gases cannot be converted into solids without passing through
the liquid phase
(d) Solids and liquids have vapour pressure as a common property
2. A pure crystalline substance, on being heated gradually, first forms a
turbid looking liquid and then the turbidity completely disappears.
This behaviour is the characteristic of substances forming [BHU 2000]
(a) Isomeric crystals (b) Liquid crystals
(c) Isomorphous crystals (d) Allotropic crystals
3. Which of the following is ferroelectric compound
[AFMC 1997]
(a) BaTiO3 (b) K 4 [Fe(CN )6 ]
(c) Pb2 O 3 (d) PbZrO3
4. Solid CO 2 is an example of
(a) Molecular crystal (b) Ionic crystal
(c) Covalent crystal (d) Metallic crystal
 208 Solid state
9. Amorphous substances show (c) Pseudo solids (d) Molecular solids
(A) Short and long range order 22. To get a n- type semiconductor, the impurity to be added to silicon
(B) Short range order should have which of the following number of valence electrons [KCET (Engg.)
(C) Long range order (a) 1 (b) 2
(D) Have no sharp M.P. (c) 3 (d) 5
(a) A and C are correct (b) B and C are correct 23. Which of the following is non-crystalline solid
(c) C and D are correct (d) B and D are correct (a) CsCl (b) NaCl
10. The characteristic features of solids are [AMU 1994] (c) CaF2 (d) Glass
(a) Definite shape 24. The lustre of a metal is due to [AFMC 1998]
(b) Definite size (a) Its high density (b) Its high polishing
(c) Definite shape and size (c) Its chemical inertness (d) Presence of free electrons
(d) Definite shape, size and rigidity 25. A crystalline solid have [DCE 2001]
11. Which one of the following is a good conductor of electricity (a) Long range order (b) Short range order
[MP PMT 1994; AFMC 2002]
(c) Disordered arrangement (d) None of these
(a) Diamond (b) Graphite
26. Crystalline solids are [Pb. PMT 1999]
(c) Silicon (d) Amorphous carbon
(a) Glass (b) Rubber
12. A crystalline solid [Kerala CET (Med.) 2003]
(c) Plastic (d) Sugar
(a) Changes abruptly from solid to liquid when heated
27. Davy and Faraday proved that [Kerala CET (Med.) 2002]
(b) Has no definite melting point
(a) Diamond is a form of carbon
(c) Undergoes deformation of its geometry easily
(d) Has an irregular 3-dimensional arrangements (b) The bond lengths of carbon containing compounds are always
equal
(e) Softens slowly
(c) The strength of graphite is minimum compared to platinum
13. Diamond is an example of
[MP PET/PMT 1998; CET Pune 1998]
(d) Graphite is very hard
(a) Solid with hydrogen bonding 28. Which one of the following metal oxides is antiferromagnetic in
nature [MP PET 2002]
(b) Electrovalent solid
(c) Covalent solid (a) MnO2 (b) TiO2
(d) Glass (c) VO2 (d) CrO 2
14. The solid NaCl is a bad conductor of electricity since 29. In graphite, carbon atoms are joined together due to
[AIIMS 1980]
[AFMC 2002]
(a) In solid NaCl there are no ions (a) Ionic bonding (b) Vander Waal’s forces
(b) Solid NaCl is covalent (c) Metallic bonding (d) Covalent bonding
(c) In solid NaCl there is no velocity of ions 30. Which of the following is not correct for ionic crystals
(d) In solid NaCl there are no electrons [Orissa JEE 2002]
15. The existence of a substance in more than one solid modifications is (a) They possess high melting point and boiling point
known as or Any compound having more than two crystal structures (b) All are electrolyte
is called
[MP PMT 1993; MP PET 1999] (c) Exhibit the property of isomorphism
(a) Polymorphism (b) Isomorphism (d) Exhibit directional properties of the bond
(c) Allotropy (d) Enantiomorphism 31. Which of the following is a molecular crystal
16. Which is not a property of solids [MP PET 1995] (a) SiC (b) NaCl
(a) Solids are always crystalline in nature (c) Graphite (d) Ice
(b) Solids have high density and low compressibility 32. Quartz is a crystalline variety of [Pb. PMT 2000]
(c) The diffusion of solids is very slow
(a) Silica (b) Sodium silicate
(d) Solids have definite volume
17. Which solid will have the weakest intermolecular forces (c) Silicon carbide (d) Silicon
(a) Ice (b) Phosphorus 33. Which type of solid crystals will conduct heat and electricity
(c) Naphthalene (d) Sodium fluoride [RPET 2000]
18. Dulong and Petit’s law is valid only for [KCET 2004] (a) Ionic (b) Covalent
(a) Metals (b) Non-metals (c) Metallic (d) Molecular
(c) Gaseous elements (d) Solid elements 34. Which of the following is an example of covalent crystal solid
19. Which of the following is an example of metallic crystal solid (a) Si (b) NaF
(a) C (b) Si (c) Al (d) Ar
(c) W (d) AgCl 35. Which of the following is an example of ionic crystal solid
20. Under which category iodine crystals are placed among the following (a) Diamond (b) LiF
(a) Ionic crystal (b) Metallic crystal (c) Li (d) Silicon
(c) Molecular crystal (d) Covalent crystal 36. Which one is an example of amorphous solid
21. Among solids the highest melting point is established by (a) Glass (b) Salt
[Kerala CET (Med.) 2002] (c) Cesium chloride (d) Calcium fluoride
(a) Covalent solids (b) Ionic solids 37. Silicon is [MHCET 2004]
 Solid state 209
(a) Semiconductor (b) Insulator 7. How many space lattices are obtainable from the different crystal
(c) Conductor (d) None of these systems [MP PMT 1996; MP PET/PMT 1998]
38. Which of the following statements about amorphous solids is (a) 7 (b) 14
incorrect [KCET 2004] (c) 32 (d) 230
(a) They melt over a range of temperature 8. Example of unit cell with crystallographic dimensions
(b) They are anisotropic a  b  c,     90 o ,   90 o is [AFMC 1998]
(c) There is no orderly arrangement of particles (a) Calcite (b) Graphite
(d) They are rigid and incompressible (c) Rhombic sulphur (d) Monoclinic sulphur
39. The ability of a given substance to assume two or more crystalline 9. In a face-centered cubic lattice, a unit cell is shared equally by how
structure is called [DCE 2004] many unit cells [CBSE PMT 2005]
(a) Amorphism (b) Isomorphism (a) 8 (b) 4
(c) Polymorphism (d) Isomerism (c) 2 (d) 6
40. Glass is 10. The maximum radius of sphere that can be fitted in the octahedral
(a) Supercooled liquid (b) Crystalline solid hole of cubical closed packing of sphere of radius r is
(c) Amorphous solid (d) Liquid crystal (a) 0.732 r (b) 0.414 r
(c) 0.225 r (d) 0.155 r
11. The unit cell of a NaCl lattice
Crystallography and Lattice
(a) Is body centred cube (b) Has 3 Na  ions
1. The correct statement in the following is [MP PET 1997] (c) Has 4 NaCl units (d) Is electrically charged
(a) The ionic crystal of AgBr has Schottky defect r
12. For tetrahedral coordination number, the radius ratio c is[KCET 2000]
(b) The unit cell having crystal parameters, a  b  c, ra 

    90 o ,   120 o is hexagonal (a) 0.732  1.000 (b) 0.414  0.732

 (c) 0.225  0.414 (d) 0.155  0.225
(c) In ionic compounds having Frenkel defect the ratio is 13. What type of lattice is found in potassium chloride crystal

[MP PMT 1996]
high
(a) Face centred cubic (b) Body centred cubic
(d) The coordination number of Na  ion in NaCl is 4 (c) Simple cubic (d) Simple tetragonal
2. Which of the following is correct [DPMT 1997]
14. The three dimensional graph of lattice points which sets the pattern
Crystal Axial distance Axial angles Examples for the whole lattice is called
system
(a) Space lattice (b) Simple lattice
(a) Cubic a b=c == Cu, KCl
(c) Unit cell (d) Crystal lattice
90 o

15. Crystals can be classified into ...... basic crystal habits

(b) Monoclinic a b=c === PbCrO , 2 [MP PMT 1994]
90 o PbCrO 4 (a) 3 (b) 7
(c) Rhombohedra a=b=c == CaCO , HgS 3
(c) 14 (d) 4
l 90 o 16. How many molecules are there in the unit cell of sodium chloride [MP PMT 1996
(a) 2 (b) 4
(d) Triclinic a=b=c = K Cr O ,
(c) 6 (d) 8
2 2 7

90 o CuSO . 4

5H O 2
17. In a crystal, the atoms are located at the position of
[AMU 1985]
3. Tetragonal crystal system has the following unit cell dimensions[MP PMT 1993]
(a) Maximum P.E. (b) Minimum P.E.
(a) a  b  c and       90 o (c) Zero P.E. (d) Infinite P.E.
18. The total number of lattice arrangements in different crystal systems
(b) a  b  c and       90 o is [KCET (Engg.) 2001]
(c) a  b  c and       90 o (a) 3 (b) 7
(c) 8 (d) 14
(d) a  b  c and     90 o ,   120 o 19. Monoclinic crystal has dimension [DCE 2000]
4. Rhombic sulphur has the following structure (a) a  b  c,     90,   90
(a) Open chain (b) a  b  c,       90
(b) Tetrahedral
(c) a  b  c,       90
(c) Puckered 6-membered ring
(d) Puckered 8-membered ring (d) a  b  c,       90
5. Space lattice of CaF2 is [MP PMT 1993] 20. The low solubility of BaSO 4 in water can be attributed to
(a) Face centred cubic [CBSE PMT 1991]
(b) Body centred cubic (a) High lattice energy (b) Dissociation energy
(c) Simple cubic (c) Low lattice energy (d) Ionic bond
(d) Hexagonal closed packing 21. Bravais lattices are of [MP PMT 1997]
6. For cubic coordination the value of radius ratio is (a) 8 types (b) 12 types
(a) 0.732  1.000 (b) 0.225  0.414 (c) 14 types (d) 9 types
(c) 0.000  0.225 (d) 0.414  0.732
 210 Solid state
22. The structure of TlCl is similar to CsCl. What would be the (c) 14 and 9 (d) 2 and 4
radius ratio in TlCl 7. An AB 2 type structure is found in [AIIMS 2002]
(a) 0.155  0.225 (b) 0.225  0.414
(a) NaCl (b) Al2 O 3
(c) 0.414  0.732 (d) 0.732  1.000
23. Structure similar to zinc blende is found in (c) CaF2 (d) N 2O
(a) AgCl (b) NaCl 8. Potassium crystallizes with a [MP PET/PMT 1998]
(c) CuCl (d) TlCl (a) Face-centred cubic lattice
(b) Body-centred cubic lattice
24. The structure of Na 2 O crystal is
(c) Simple cubic lattice
(a) CsCl type (b) NaCl type (d) Orthorhombic lattice
(c) ZnS type (d) Antifluorite 9. If the number of atoms per unit in a crystal is 2, the structure of
25. Structure of ZnS is crystal is
(a) Body centred cubic (b) Face centred cubic (a) Octahedral
(c) Simple cube (d) Fluorite structure (b) Body centred cubic bcc
26. The crystal system of a compound with unit cell dimensions (c) Face centred cubic fcc
a  0.387 , b  0.387 and c  0.504nm and     90 o (d) simple cubic
and   120 o is [AIIMS 2004] 10. The intermetallic compound LiAg crystallizes in cubic lattice in
(a) Cubic (b) Hexagonal which both lithium and silver have coordination number of eight.
(c) Orthorhombic (d) Rhombohedral The crystal class is
27. The number of tetrahedral voids in the unit cell of a face centered [CBSE PMT 1997]
cubic lattice of similar atoms is [Kerala PMT 2004] (a) Simple cube (b) Body-centred cube
(a) 4 (b) 6 (c) Face-centred cube (d) None of these
(c) 8 (d) 10 11. The number of octahedral sites per sphere in a fcc structure is [MP PMT 2000,
28. An fcc unit cell of aluminium contains the equivalent of how many (a) 8 (b) 4
atoms [DCE 2003] (c) 2 (d) 1
(a) 1 (b) 2 12. Hexagonal close packed arrangement of ions is described as
(c) 3 (d) 4 [MP PMT 1994]
(a) ABC ABA (b) ABC ABC
Crystal packing (c) ABABA (d) ABBAB
13. An example of a body cube is [AIIMS 1996]
1. If ‘Z’ is the number of atoms in the unit cell that represents the (a) Sodium (b) Magnesium
closest packing sequence    A B C A B C   , the number (c) Zinc (d) Copper
of tetrahedral voids in the unit cell is equal to 14. An example of fluorite structure is
[AIIMS 2005]
(a) NaF (b) SrF2
(a) Z (b) 2 Z
(c) Z/2 (d) Z/4 (c) AlCl3 (d) SiF4
2. The close packing represents ABC ABC...... order of 15. In which of the following crystals alternate tetrahedral voids are
(a) Body centred cubic packing occupied? [IIT 2005]
(b) Face centred cubic packing (a) NaCl (b) ZnS
(c) CaF (d) Na O
(c) Simple cubic packing 2 2

16. Which of the following contains rock salt structure

(d) Hexagonal cubic closed packing
3. The arrangement ABC ABC ABC ….. is referred as (a) SrF2 (b) MgO
[MP PET 2001] (c) Al 2 O 3 (d) All
(a) Octahedral close packing (b) Hexagonal close packing
17. In the fluorite structure, the coordination number of Ca 2  ion is
(c) Tetragonal close packing (d) Cubic close packing
(a) 4 (b) 6
4. The number of close neighbour in a body-centred cubic lattice of
identical sphere is [MP PET 2001] (c) 8 (d) 3
(a) 8 (b) 6 18. The ratio of close-packed atoms to tetrahedral holes in cubic close
packing is [Pb. PMT 1998]
(c) 4 (d) 2
(a) 1 : 1 (b) 1 : 2
5. The number of equidistant oppositely charged ions in a sodium
(c) 1 : 3 (d) 2 : 1
chloride crystal is [MP PET 2001]
(a) 8 (b) 6 19. A solid is made of two elements X and Z . The atoms Z are in
CCP arrangement while the atom X occupy all the tetrahedral
(c) 4 (d) 2 sites. What is the formula of the compound
6. Na and Mg crystallize in BCC and FCC type crystals respectively, [UPSEAT 2004]
then the number of atoms of Na and Mg present in the unit cell (a) XZ (b) XZ2
of their respective crystal is
(c) X2Z (d) X 2 Z3
[AIEEE 2002]
(a) 4 and 2 (b) 9 and 14
 Solid state 211
20. An ionic compound has a unit cell consisting of A ions at the (c) In between 0.41 and 0.22
corners of a cube and B ions on the centres of the faces of the cube. (d) Less than 0.22
The empirical formula for this compound would be [CBSE PMT 2004; AIEEE 6.
2005] The number of spheres contained (i) in one body centred cubic unit
(a) AB (b) A 2 B cell and (ii) in one face centred cubic unit cell, is
(a) In (i) 2 and in (ii) 4 (b) In (i) 3 and in (ii) 2
(c) AB 3 (d) A3 B
(c) In (i) 4 and in (ii) 2 (d) In (i) 2 and in (ii) 3
21. The vacant space in the bcc unit cell is
(a) 32% (b) 23% 7. CsBr crystal has bcc structure. It has an edge length of 4 .3 Å.
(c) 26% (d) None of these The shortest interionic distance between Cs  and Br  ions is[IIT 1995]
22. The number of octahedral voids in a unit cell of a cubical closest
packed structure is (a) 1 .86 Å (b) 3 .72 Å
(a) 1 (b) 2
(c) 4 (d) 8 (c) 4.3 Å (d) 7 .44 Å
23. In the closest packed structure of a metallic lattice, the number of 8. In octahedral holes (voids)
nearest neighbours of a metallic atom is (a) A simple triangular void surrounded by four spheres
[JIPMER 2002]
(b) A bi-triangular void surrounded by four spheres
(a) Twelve (b) Four
(c) A bi-triangular void surrounded by six spheres
(c) Eight (d) Six
(d) A bi-triangular void surrounded by eight spheres
24. In the rock salt structure, the number of formula units per unit cell
is equal to 9. Bragg's law is given by the equation [MP PMT 1995, 2002]
(a) 1 (b) 2 (a) n  2 sin (b) n  2d sin
(c) 3 (d) 4  d
25. Hexagonal close packing is found in crystal lattice of (c) 2n  d sin (d) n  sin
2 2
[MH CET 2002]
10. The number of atoms in 100 g of an fcc crystal with density
(a) Na (b) Mg
d  10 g / cm 3 and cell edge equal to 100 pm, is equal to[CBSE PMT 1994; K
(c) Al (d) None of these
26. Which ion has the largest radius from the following ions (a) 4  10 25 (b) 3  10 25
(a) Na  (b) Mg 2  (c) 2  10 25 (d) 1  10 25
(c) Al 3  (d) Si 4  11. In the crystals of which of the following ionic compounds would you
expect maximum distance between centres of cations and anions[CBSE PMT 1998
(a) LiF (b) CsF
Mathematical analysis of cubic system and
(c) CsI (d) LiI
Bragg’s equation
12. The number of unit cells in 58.5 g of NaCl is nearly
1. The formula for determination of density of unit cell is [MP PMT 2000, 01]
a3  N o NM (a) 6  10 20
(b) 3  10 22
(a) g cm  3 (b) g cm  3
NM a3  N o (c) 1.5  10 23
(d) 0.5  10 24
a M
3
M  No 13. How many unit cells are present in a cube-shaped ideal crystal of
(c) g cm  3 (d) g cm  3 NaCl of mass 1.00 g [Atomic masses: Na  23, Cl  35.5] [AIEEE 2003]
N  No a N3

2. Potassium fluoride has NaCl type structure. What is the distance (a) 2.57  10 21 unit cells (b) 5.14  10 21 unit cells
between K  and F  ions if cell edge is a cm
(c) 1.28  10 21 unit cells (d) 1.71  10 21 unit cells
(a) 2a cm (b) a / 2 cm
14. In the Bragg’s equation for diffraction of X- rays, n
(c) 4 a cm (d) a / 4 cm represents for [MP PMT 2000]
3. An element occurring in the bcc structure has 12.08  10 23 unit (a) Quantum number (b) An integer
cells. The total number of atoms of the element in these cells will be[MP PET 1994](c) Avogadro’s numbers (d) Moles
(a) 24.16  10 23 (b) 36.18  10 23 15. In a face centred cubic cell, an atom at the face contributes to the
(c) 6.04  10 23 (d) 12.08  10 23 unit cell
4. If an atom is present in the centre of the cube, the participation of [Karnataka (Engg./Med.) 2000; AFMC 2001]
that atom per unit cell is (a) 1/4 part (b) 1/8 part
1 (c) 1 part (d) 1/2 part
(a) (b) 1
4 16. The interionic distance for cesium chloride crystal will be
1 1 [MP PET 2002]
(c) (d)
2 8 a
(a) a (b)
5. For an ionic crystal of the general formula AX and coordination 2
number 6, the value of radius ratio will be
[MP PMT 1993] 3a 2a
(a) Greater than 0.73 (c) (d)
2 3
(b) In between 0.73 and 0.41
 212 Solid state
17. Sodium metal crystallizes as a body centred cubic lattice with the Crystal structure and Coordination number
cell edge 4.29 Å. What is the radius of sodium atom
[AIIMS 1999]
1. A solid has a structure in which 'W ' atoms are located at the
8 7
(a) 1.857  10 cm (b) 2.371  10 cm corners of a cubic lattice ' O ' atoms at the centre of edges and
' Na ' atoms at the centre of the cube. The formula for the
(c) 3.817  10 8 cm (d) 9.312  10 7 cm compound is [KCET 1996]
18. For an ionic crystal of the type AB, the value of (limiting) radius (a) NaW O2 (b) NaW O3
ratio is 0.40. The value suggests that the crystal structure should be
(a) Octahedral (b) Tetrahedral (c) Na 2 W O3 (d) NaW O4
(c) Square planar (d) Plane triangle 2. Potassium crystallizes in a bcc lattice, hence the coordination
19. Potassium has a bcc structure with nearest neighbour distance number of potassium in potassium metal is
3 [KCEE 1993]
4 .52 Å. Its atomic weight is 39. Its density (in kg m ) will be [AIIMS 1991]
(a) 0 (b) 4
(a) 454 (b) 804 (c) 6 (d) 8
(c) 852 (d) 908 3. Body centered cubic lattice has a coordination number of
r  [AIIMS 1996; MP PMT 2002]
20. If the value of ionic radius ratio  c  is 0.52 in an ionic (a) 4 (b) 8
 ra 
(c) 12 (d) 6
compound, the geometrical arrangement of ions in crystal is
(a) Tetrahedral (b) Planar 4. A compound is formed by elements A and B. This crystallizes in
(c) Octahedral (d) Pyramidal the cubic structure when atoms A are the corners of the cube and
21. The number of atoms/molecules contained in one face centred atoms B are at the centre of the body. The simplest formula of the
cubic unit cell of a monoatomic substance is compounds is
[KCET 1993; CBSE PMT 2000; Kerala PMT 2002]
[CPMT 1989, 94; CBSE PMT 1989, 96; NCERT 1990;
MP PET 1993; KCET 1999] (a) AB (b) AB 2
(a) 1 (b) 2 (c) A2 B (d) AB 4
(c) 4 (d) 6
22. The number of atoms/molecules contained in one body centered 5. Coordination number for Cu is [AMU 1982]
cubic unit cell is (a) 1 (b) 6
(a) 1 (b) 2 (c) 8 (d) 12
(c) 4 (d) 6 6. In the crystal of CsCl, the nearest neighbours of each Cs ion are[MP PET 199
23. It the distance between Na  and Cl  ions in sodium chloride (a) Six chloride ions (b) Eight chloride ions
crystal is X pm, the length of the edge of the unit cell is [KCET 2004] (c) Six Cs ions (d) Eight Cs ions
(a) 4X pm (b) X/4 pm 7. In a cubic structure of compound which is made from X and Y,
(c) X/2 pm (d) 2X pm where X atoms are at the corners of the cube and Y at the face
centres of the cube. The molecular formula of the compound is [AIIMS 2000]
24. The edge of unit cell of FCC Xe crystal is 620 pm . The radius of
(a) X 2 Y (b) X 3 Y
Xe atom is [MP PET 2004]
(a) 219.25 Pm (b) 235.16 Pm (c) XY 2 (d) XY 3
(c) 189.37 Pm (d) 209.87 Pm 8. Ferrous oxide has a cubic structure and each edge of the unit cell is
25. In orthorhombic, the value of a, b and c are respectively 5.0 Å. Assuming density of the oxide as 4.0 g  cm 3 , then the
4.2 Å, 8.6 Å and 8.3 Å . given the molecular mass of the solute is number of Fe2  and O 2  ions present in each unit cell will be [MP PET 2000
155 gm mol 1 and that of density is 3.3 gm / cc , the number of (a) Four Fe2  and four O 2 
formula units per unit cell is (b) Two Fe 2  and four O 2 
[Orrisa JEE 2005]
(c) Four Fe2  and two O 2 
(a) 2 (b) 3
(c) 4 (d) 6 (d) Three Fe 2  and three O 2 
26. A metal has bcc structure and the edge length of its unit cell is 9. Which of the following statements is not true about NaCl
3.04 Å . The volume of the unit cell in cm 3 will be structure [DCE 2001]
[Orrisa JEE 2005] (a) Cl  ions are in fcc arrangement
23
(a) 1.6  10 cm
21 3
(b) 2.81  10 cm 3
(b) Na  ions has coordination number 4
(c) 6.02  10 23 cm 3 (d) 6.6  10 24 cm 3
(c) Cl  ions has coordination number 6
27. In face centred cubic unit cell edge length is [DPMT 2005]
(d) Each unit cell contains 4 NaCl molecules
4 4
(a) r (b) r 10. In CsCl structure, the coordination number of Cs  is
3 2
[MP PMT 2001]

3 (a) Equal to that of Cl , that is 6
(c) 2r (d) r
2 (b) Equal to that of Cl  , that is 8
(c) Not equal to that of Cl  , that is 6
 Solid state 213

(d) Not equal to that of Cl  , that is 8 (a) 6 (b) 8

(c) 1 (d) 4
11. In a solid ‘AB’ having the NaCl structure, ‘A’ atoms occupy the
corners of the cubic unit cell. If all the face-centered atoms along 24. In CsCl lattice the coordination number of Cs  ion is
one of the axes are removed, then the resultant stoichiometry of the (a) 2 (b) 4
solid is [IIT Screening 2001]
(c) 8 (d) 12
(a) AB 2 (b) A 2 B
25. Crystal structure of NaCl is [NCERT 1982; BHU 1995]
(c) A4 B3 (d) A3 B4
(a) fcc (b) bcc
12. In solid CsCl each Cl is closely packed with how many Cs [MP PET 2003] (c) Both (a) and (b) (d) None
(a) 8 (b) 6
(c) 10 (d) 2 26. In NaCl lattice the coordination number of Cl  ion is
(a) 2 (b) 4
13. In A  B  ionic compound, radii of A  and B  ions are 180 pm
(c) 6 (d) 8
and 187 pm respectively. The crystal structure of this compound
27. In zinc blende structure the coordination number of Zn 2  ion is
will be
(a) 2 (b) 4
(a) NaCl type (b) CsCl type
(c) 6 (d) 8
(c) ZnS type (d) Similar to diamond
14. In which of the following substances the carbon atom is arranged in 28. Coordination number of Na  ion in rock salt is
a regular tetrahedral structure [NCERT 1978] [BVP 2004]
(a) Diamond (b) Benzene (a) 12 (b) 4
(c) Graphite (d) Carbon black (c) 8 (d) 6
15. The coordination number of a metal crystallizing in a hexagonal 29. The number of Cl  ions around one Na  in NaCl crystal
close packed structure is lattice is [MP PET 1996; BVP 2004]
[NCERT 1978; IIT 1999]
(a) 12 (b) 4
(a) 4 (b) 12
(c) 8 (d) 6
(c) 8 (d) 6
30. The number of atoms present in unit cell of a monoatomic
16. The structure of MgO is similar to NaCl. What would be the substance of simple cubic lattice is [Pb. PMT 2004]
coordination number of magnesium (a) 6 (b) 3
(a) 2 (b) 4 (c) 2 (d) 1
(c) 6 (d) 8 31. The coordination number of a metal crystallizing in a hexagonal
17. How many chloride ions are there around sodium ion in sodium close packed chep structure is [MP PMT 2004]
chloride crystal [NCERT 1979, 80; CPMT 1988; (a) 12 (b) 8
BHU 1982, 87; MP PET 1995, 99]
(c) 4 (d) 6
(a) 3 (b) 8
32. Which of the following statement(s) is(are) correct
(c) 4 (d) 6 [IIT 1998]
18. Most crystals show good cleavage because their atoms, ions or (a) The coordination number of each type of ion in CsCl crystal
molecules are [CBSE PMT 1991] is 8
(a) Weakly bonded together
(b) A metal that crystallizes in bcc structure has a coordination
(b) Strongly bonded together number of 12
(c) Spherically symmetrical (c) A unit cell of an ionic crystal shares some of its ions with other
(d) Arranged in planes unit cells
19. An example of a non-stoichiometric compound is (d) The length of the unit cell in NaCl is 552 pm
[NCERT 1983]
(rNa   95 pm; rCl   181 pm)
(a) Al 2 O 3 (b) Fe3 O 4
33. The co-ordination number of Na  in NaCl is
(c) NiO2 (d) PbO
[Orrisa JEE 2005]
20. If the radius ratio is in the range of 0.731  1, then the (a) 6 (b) 8
coordination number will be (c) 4 (d) 1
(a) 2 (b) 4 34. In the calcium fluoride structure the co-ordination number of the
(c) 6 (d) 8 cation and anions are respectively [J & K 2005]
21. If the radius ratio is in the range of 0.414  0.732, then the (a) 6, 6 (b) 8, 4
coordination number will be (c) 4, 4 (d) 4, 8
(a) 2 (b) 4
(c) 6 (d) 8 Defects in crystal
22. What is the coordination number of sodium in Na 2 O
1. Certain crystals produce electric signals on application of pressure.
[AIIMS 2003] This phenomenon is called [BHU 2005]
(a) 6 (b) 4 (a) Pyroelectricity (b) Ferroelectricity
(c) 8 (d) 2 (c) Peizoelectricity (d) Ferrielectricity
23. The ratio of cationic radius to anionic radius in an ionic crystal is 2. Which defect causes decrease in the density of crystal
greater than 0.732. Its coordination number is [KCET 2000, 05]
[KCET 2003] (a) Frenkel (b) Schottky
 214 Solid state
(c) Interstitial (d) F  centre (a) Increases (b) Decreases
3. The correct statement regarding F  centre is (c) Does not change (d) Changes
(a) Electron are held in the voids of crystals 14. Point defects are present in [MP PMT 1997]
(a) Ionic solids (b) Molecular solids
(b) F  centre produces colour to the crystals
(c) Amorphous solids (d) Liquids
(c) Conductivity of the crystal increases due to F  centre 15. If a non-metal is added to the interstitial sites of a metal then the
(d) All metal becomes [DCE 2001]
4. Doping of silicon (Si) with boron (B) leads to (a) Softer (b) Less tensile
[UPSEAT 2004] (c) Less malleable (d) More ductile
(a) n -type semiconductor (b) p -type semiconductor 16. In AgBr crystal, the ion size lies in the order Ag   Br  . The
(c) Metal (d) Insulator AgBr crystal should have the following characteristics
5. If NaCl is doped with 10 3 mol % SrCl2 , then the (a) Defectless (perfect) crystal
concentration of cation vacancies will be (b) Schottky defect only
(c) Frenkel defect only
(a) 1  10 3 mol% (b) 2  10 3 mol% (d) Both Schottky and Frenkel defects
(c) 3  10 3 mol% (d) 4  10 3 mol% 17. Frenkel and Schottky defects are [BHU 2003]
6. In the laboratory, sodium chloride is made by burning the sodium in (a) Nucleus defects (b) Non-crystal defects
the atmosphere of chlorine which is yellow in colour. The cause of (c) Crystal defects (d) None of these
yellow colour is 18. Which one of the following is the most correct statement
 (a) Brass is an interstitial alloy, while steel is a substitutional alloy
(a) Presence of Na ions in the crystal lattice
(b) Brass is a substitutional alloy, while steel is an interstitial alloy
(b) Presence of Cl  ions in the crystal lattice (c) Brass and steel are both substitutional alloys
(c) Presence of electron in the crystal lattice (d) Brass and steel are both interstitial alloys
(d) Presence of face centered cubic crystal lattice 19. The flame colours of metal ions are due to [KCET 2003]
7. Frenkel defect is caused due to [MP PET 1994] (a) Frenkel defect (b) Schottky defect
(a) An ion missing from the normal lattice site creating a vacancy (c) Metal deficiency defect (d) Metal excess defect
(b) An extra positive ion occupying an interstitial position in the 20. Which one of the following crystals does not exhibit Frenkel defect [MP PET 200
lattice (a) AgBr (b) AgCl
(c) An extra negative ion occupying an interstitial position in the (c) KBr (d) ZnS
lattice 21. In a solid lattice the cation has left a lattice site and is located at an
(d) The shift of a positive ion from its normal lattice site to an interstitial position, the lattice defect is
interstitial site [AIIMS 1982, 1991; DCE 2002; J & K 2005]
8. Which one of the following has Frenkel defect (a) Interstitial defect (b) Valency defect
[MP PMT 2000]
(c) Frenkel defect (d) Schottky defect
22. When electrons are trapped into the crystal in anion vacancy, the
(a) Sodium chloride (b) Graphite defect is known as [BHU 2005]
(c) Silver bromide (d) Diamond (a) Schotky defect (b) Frenkel defect
9. Schottky defect generally appears in [DCE 2004] (c) Stoichiometric defect (d) F-centres
(a) NaCl (b) KCl 23. Schottky defect defines imperfection in the lattice structure of a [AIIMS 2002]
(c) CsCl (d) All of these (a) Solid (b) Liquid
(c) Gas (d) Plasma
10. Schottky defect in crystals is observed when
[CBSE PMT 1998; KCET 2002]
(a) Density of crystal is increased
(b) Unequal number of cations and anions are missing from the
lattice
(c) An ion leaves its normal site and occupies an interstitial site
(d) Equal number of cations and anions are missing from the
lattice 1. Amorphous solids are
11. Ionic solids, with Schottky defects, contain in their structure (a) Solid substance in real sense
[CBSE PMT 1994] (b) Liquid in real sense
(a) Equal number of cation and anion vacancies (c) Supercooled liquid
(b) Anion vacancies and interstitial anions (d) Substance with definite melting point
(c) Cation vacancies only 2. Silicon is found in nature in the form of [MH CET 2002]
(d) Cation vacancies and interstitial cations (a) Body centered cubic structure
12. The following is not a function of an impurity present in a crystal[MP PET 1995] (b) Hexagonal close-packed structure
(c) Network solid
(a) Establishing thermal equilibrium
(d) Face centered cubic structure
(b) Having tendency to diffuse
3. A match box exhibits [MP PET 1993, 95]
(c) Contributing to scattering
(a) Cubic geometry (b) Monoclinic geometry
(d) Introducing new electronic energy levels (c) Orthorhombic geometry (d) Tetragonal geometry
13. Due to Frenkel defect, the density of ionic solids 4. Which has no rotation of symmetry [Orrisa JEE 2004]
[MP PET 1996; MP PMT 2002] (a) Hexagonal (b) Orthorhombic
 Solid state 215
(c) Cubic (d) Triclinic Na  Cl  Na  Cl  Na  Cl 
5. Which of the following molecules has three-fold axis of symmetry[UPSEAT 2004]
(a) NH 3 (b) C2 H 4 Cl   Cl  Na   Na 
(c) CO 2 (d) SO 2 Na  Cl   Cl  Na  Cl 
  
6. Which one possess a antifluorite structure Cl Na Cl Na   Na 
(a) Interstitial defect
(a) Na 2 O (b) MgO
(b) Schottky defect
(c) Fe 2 O 3 (d) Al 2 O 3 (c) Frenkel defect
7. Which one of the following is the biggest ion [MP PET 1993] (d) Frenkel and Schottky defects
(a) Al 3
(b) Ba 2 18. Which of the following is a three dimensional silicate
[MHCET 2003]
(c) Mg 2 (d) Na  (a) Mica (b) Spodumene
8. The edge length of face centred unit cubic cell is 508 pm. If the (c) Zeolite (d) None of these
(e) 12
radius of the cation is 110 pm, the radius of the anion is
[CBSE PMT 1998]
(a) 285 pm (b) 398 pm
(c) 144 pm (d) 618 pm
9. An element (atomic mass 100 g / mol) having bcc structure has
unit cell edge 400 pm. Then density of the element is Read the assertion and reason carefully to mark the correct option out of
[CBSE PMT 1996; AIIMS 2002] the options given below :
(a) 10.376 g / cm 3 (b) 5.188 g / cm 3 (a) If both assertion and reason are true and the reason is the correct
3 3
explanation of the assertion.
(c) 7.289 g / cm (d) 2.144 g / cm (b) If both assertion and reason are true but reason is not the correct
10. If the pressure on a NaCl structure is increased, then its explanation of the assertion.
coordination number will [AFMC 2000] (c) If assertion is true but reason is false.
(a) Increase (b) Decrease (d) If the assertion and reason both are false.
(c) Remain the same (d) Either (b) or (c) (e) If assertion is false but reason is true.
11. The pyknometric density of sodium chloride crystal is
1. Assertion : Diamond is a precious stone.
2.165  10 3 kg m 3 while its X-rays density is
Reason : Carbon atoms are tetrahedrally arranged in
2.178  10 3 kg m 3 . The fraction of unoccupied sites in sodium diamond. [AIIMS 1994 ]
chloride crystal is [CBSE PMT 2003] 2. Assertion : In crystal lattice, the size of the cation is larger in
3 a tetrahedral hole than in an octahedral hole.
(a) 5.96  10 (b) 5.96
Reason : The cations occupy more space than anions in
(c) 5.96  10 2 (d) 5.96  10 1 crystal packing. [AIIMS 1996]
12. Which of the following statements is correct for CsBr3 3. Assertion : Crystalline solids have short range order.
[IIT 1996] Reason : Amorphous solids have long range order.
(a) It is a covalent compound [AIIMS 1999]
(b) It contains Cs 3  and Br  ions 4. Assertion : In any ionic solid (MX) with Schottky defects, the
(c) It contains Cs  and Br3 ions number of positive and negative ions are same.
Reason : Equal number of cation and anion vacancies are
(d) It contains Cs  , Br  and lattice Br2 molecule present.
13. In which compound 8 : 8 coordination is found [IIT Screening 2001]
[EAMCET 1984] 5. Assertion : Space or crystal lattice differ in symmetry of the
(a) CsCl (b) MgO arrangement of points.
(c) Al 2 O 3 (d) All of these Reason : n  2d sin , is known as Bragg’s equation.
14. If the coordination of Ca 2  in CaF2 is 8, then the coordination 6. Assertion : In close packing of spheres, a tetrahedral void is
surrounded by four spheres whereas an
number of F  ion would be octahedral void is surrounded by six spheres.
(a) 3 (b) 4 Reason : A tetrahedral void has a tetrahedral shape
(c) 6 (d) 8 whereas an octahedral void has an octahedral
15. For some crystals, the radius ratio for cation and anion is 0.525, its shape.
coordination number will be 7. Assertion : Cyclic silicates and chain silicates have the same
(a) 2 (b) 4 general molecular formula.
(c) 6 (d) 8
Reason : In cyclic silicates, three corners of each SiO4
16. The basic building unit of all silicates is [UPSEAT 2002]
tetrahedron are shared while in chain silicates
(a) SiO 4 square planar (b) [SiO 4 ]4  tetrahedron only two are shared with other tetrahedra.
(c) SiO 4 octahedron (d) SiO 4 linear 8. Assertion : The presence of a large number of Schottky
17. What type of crystal defect is indicated in the diagram below defects in NaCl lowers its density.
[AIEEE 2004]
 216 Solid state

Reason : In NaCl , there are approximately 10 6 Mathematical analysis of cubic system and
Schottky pairs per cm 3 at room temperature. Bragg’s equation
9. Assertion : Anion vacancies in alkali halides are produced by
heating the alkali halide crystals with alkali metal 1 b 2 b 3 a 4 b 5 b
vapour.
Reason : Electrons trapped in anion vacancies are referred 6 a 7 b 8 c 9 b 10 a
to as F -centres.
11 c 12 c 13 a 14 b 15 d
10. Assertion : Electrical conductivity of semiconductors
increases with increasing temperature. 16 c 17 a 18 b 19 d 20 c
Reason : With increase in temperature, large number of
electrons from the valence band can jump to the 21 c 22 b 23 d 24 a 25 c
conduction band. 26 b 27 b
11. Assertion : On heating ferromagnetic or ferrimagnetic
substances, they become paramagnetic.
Reason : The electrons change their spin on heating. Crystal structure and Coordination number
12. Assertion : Lead zirconate is a piezoelectric crystal.
Reason : Lead zirconate crystals have no dipole moment. 1 b 2 d 3 b 4 a 5 d

6 b 7 d 8 a 9 b 10 b

11 d 12 a 13 b 14 a 15 b

16 c 17 d 18 d 19 b 20 d

21 c 22 b 23 b 24 c 25 a
Type of solid and Their properties
26 c 27 b 28 d 29 d 30 d

1 a 2 b 3 a 4 a 5 b 31 a 32 acd 33 a 34 b
6 c 7 c 8 b 9 d 10 d
11 b 12 a 13 c 14 c 15 a Defects in crystal
16 a 17 a 18 d 19 c 20 c
1 c 2 b 3 d 4 d 5 a
21 b 22 d 23 d 24 d 25 a
26 d 27 a 28 a 29 d 30 d 6 c 7 d 8 c 9 d 10 d

31 d 32 a 33 c 34 a 35 b 11 a 12 a 13 c 14 a 15 b

36 a 37 a 38 b 39 c 40 ac 16 c 17 c 18 c 19 d 20 c

21 c 22 d 23 a
Crystallography and Lattice

1 b 2 c 3 b 4 d 5 a Critical Thinking Questions

6 a 7 b 8 d 9 d 10 b
1 c 2 c 3 c 4 d 5 a
11 c 12 c 13 a 14 c 15 b
6 a 7 b 8 c 9 b 10 a
16 b 17 b 18 b 19 a 20 a
11 a 12 c 13 a 14 b 15 c
21 c 22 d 23 c 24 d 25 b
26 b 27 c 28 d 16 b 17 b 18 c

Crystal packing Assertion & Reason

1 b 2 b 3 d 4 a 5 b 1 b 2 d 3 d 4 a 5 b

6 d 7 c 8 b 9 b 10 b 6 c 7 c 8 b 9 b 10 a
11 d 12 c 13 a 14 b 15 b 11 a 12 c
16 b 17 c 18 b 19 c 20 c
21 a 22 c 23 a 24 d 25 b
26 a
 218 Solid state
35. (b) LiF is an example of ionic crystal solid, in which constituent
particles are positive (Li  ) and negative (F  ) ions.
36. (a) Amorphous solids neither have ordered arrangement (i.e. no
definite shape) nor have sharp melting point like crystals, but
when heated, they become pliable until they assume the
properties usually related to liquids. It is therefore they are
regarded as super-cooled liquids.
Properties and Types of solids 37. (a) Silicon is a semiconductor because it is a thermal active and its
conductivity increased with increasing temperature.
1. (a) Both gases and liquids possess fluidity and hence viscosity 38. (b) Amorphous solids are isotropic, because of these substances
molecules in the solid state do not have translational motion. show same properties in all directions.
39. (c) Polymorphism is a ability of a substances which show two or
2. (b) It is a characteristic of liquid crystal. more crystalline structure
3. (a) BaTiO3 is a ferroelectric compound. 40. (ac) Amorphous solids neither have ordered arrangement (i.e. no
definite shape) nor have sharp melting point like crystals, but
5. (b) The value of heat of fusion of NaCl is very high due to fcc when heated, they become pliable until they assume the
arrangement of its ions. properties usually related to liquids. It is therefore they are
6. (c) Piezoelectric crystals are used in record player. regarded as super-cooled liquids.
8. (b) NaCl is a ionic solid in which constituent particles are
positive ( Na  ) and negative (Cl  ) ions. Crystallography and Lattice
9. (d) Amorphous solids have short range order but no sharp in
melting point. 1. (b) A crystal system is hexagonal if its unit cell having a  b  c
10. (d) Solids have definite shape, size and rigidity. axial ratio and     90,   120 axial angles.
12. (a) In crystalline solid there is perfect arrangement of the constituent 2. (c) Rhombohedral crystal system
particles only at 0K. As the temperature increases the chance that a a  b  c ,       90 o
lattice site may be unoccupied by an ion increases. As the number
of defects increases with temperature solid change in liquid. ex – NaNO 3 , CaSO 4 , calcite CaCO 3 , HgS
13. (c) Diamond is a covalent solid in which constituent particles are 3. (b) Tetragonal system has the unit cell dimension
atoms. a  b  c,      90 .
14. (c) Solid NaCl is a bad conductor of electricity because ions are 5. (a) Space lattice of CaF2 is face centred cubic.
not free to move.
15. (a) The existence of a substance in more than one crystalline form 6. (a) For body centred cubic arrangement co-ordination number is 8
is known as polymorphism. and radius ratio (r / r ) is 0.732  1.000 .
16. (a) Solids are also non-crystalline in nature. 7. (b) There are 14 Bravais lattices (space lattices).
17. (a) Ice has the lowest melting point out of the given solids, hence 8. (d) Monoclinic sulphur is an example of Monoclinic crystal system.
it has the weakest intermolecular forces. 10. (b) r  0.414 r .
19. (c) All metals and some alloys are metallic crystal.
11. (c) Each unit cell of NaCl contains 4 NaCl units.
20. (c) Iodine crystals are molecular crystals, in which constituent
particles are molecules having interparticle forces are Vander 12. (c) For tetrahedral arrangement co-ordination number is 4 and
Waal’s forces. radius ratio (r / r ) is 0.225  0.414 .
21. (b) Ionic solids have highest melting point due to strong 13. (a) Face-centred cubic lattice found in KCl and NaCl .
electrostatic forces of attraction.
14. (c) Definition of unit cell.
22. (d) For n-type, impurity added to silicon should have more than 4
valence electrons. 16. (b) In NaCl (rock salt) : Number of Na  ions  12 (at edge
23. (d) Glass is an amorphous solid. 1
centers)   1 (at body centre) 1  4 . Number of
25. (a) Crystalline solids have regular arrangement of constituent 4
particles, sharp melting points and are anisotropic. 1 1
Cl  ions  8 (at corners)   6 (at face centre)   4 .
26. (d) Sugar is a crystalline solid while glass, rubber and plastic are 8 2
amorphous solids. Thus 4 formula units per unit cell.
28. (a) MnO2 is antiferromagnetic. 17. (b) Lowest potential energy level provides stable arrangement.
18. (b) The seven basic crystal lattice arrangements are :- Cubic,
29. (d) Graphite is sp 2 hybridised and a covalent crystal. Tetragonal, Orthorhombic, Monoclinic, Hexagonal,
Rhombohedral and Triclinic.
30. (d) Ionic crystals exhibit non-directional properties of the bond.
19. (a) The conditions for monoclinic crystal system.
31. (d) Ice is a molecular crystal in which the constituent units are
molecules and the interparticle forces are hydrogen bonds. 20. (a) High lattice energy of BaSO 4 causes low solubility of
32. (a) Quartz is a covalent crystal having a framework of silicates or BaSO 4 in water.
silica, i.e. a three dimensional network when all the four oxygen 21. (c) 14 kinds of Bravais lattices (space lattices) are possible in a
atoms of each of SiO4 tetrahedron are shared. crystal.
33. (c) Metallic crystals are good conductor of heat and current due to 22. (d) Radius ratio in TlCl is 0.732 – 1.000 and co-ordination number
free electrons in them. is 8 and arrangement is body centred cubic.
34. (a) Silicon is a covalent crystal in which constituent particles are 23. (c) Zinc blende (ZnS ) has fcc structure and is an ionic crystal
atoms. having 4 : 4 co-ordination number.
 Solid state 219

24. (d) Na 2 O has antifluorite ( A2 B) type structure. 21. (a) In bcc structure 68% of the available volume is occupied by
spheres. Thus vacant space is 32%.
25. (b) Zinc blende (ZnS ) has fcc structure and is an ionic crystal 22. (c) Number of atoms in the cubic close packed structure = 8.
having 4 : 4 co-ordination number. 1
Number of octahedral voids   8  4 .
1 2
28. (d)  8 (at corners)  1
8 23. (a) Co-ordination number in HCP and CCP arrangement is 12
1 while in bcc arrangement is 8.
 6 (at face centre)  3 24. (d) In NaCl (rock salt) : Number of Na  ions  12 (at edge
2
1
Z  1  3  4 (total no. of atoms) centers)   1 (at body centre) 1  4 . Number of Cl  ions
4
Crystal packing 1 1
 8 (at corners)   6 (at face centre)   4 . Thus 4
8 2
1. (b) Number of tetrahedral voids in the unit cell formula units per unit cell.
25. (b) Co-ordination number in HCP =12
= 2  number of atoms = 2Z.
Co-ordination number in Mg is also = 12
2. (b) The system ABC ABC…… is also referred to as face-centred
cubic or fcc. 26. (a) All are the iso-electronic species but Na  has low positive
3. (d) It represents ccp arrangement. charge so have largest radius.
4. (a) BCC has a coordination number of 8.
5. (b) In rock salt structure the co-ordination number of Na  : Cl  Mathematical analysis of cubic system and
is 6 : 6 . Bragg’s equation
6. (d) The bcc cell consists of 8 atoms at the corners and one atom at
centre. N  mol . wt.( M )
1. (b) Density of unit cell  g cm  3
 1 V ( a 3 )  avogadro no. (N o )
 n  8    1  2 .
 8
1
The fcc cell consists of 8 atoms at the eight corners and one 2. (b) Distance between K  and F    length of the edge
atom at each of the six faces. This atom at the face is shared by 2
two unit cells. 3. (a) There are two atoms in a bcc unit cell.
1  1 So, number of atoms in 12.08  10 23 unit cells
 n  8   6    4 .
8  2  2  12.08  10 23  24.16  10 23 atom .
7. (c) AB2 type of structure is present in CaF2 4. (b) bcc structure has one atom shared by 1 unit cell.
2  2 
 AB2 ⇌ A  2 B ; CaF2 ⇌ Ca  2 F 5. (b) The structural arrangement of co-ordination number ‘6’ is
8. (b) Potassium (K) has bcc lattice. octahedral and its radius ratio is 0.414  0.732 . The
9. (b) Number of atoms per unit cell in bcc system = 2. example of octahedral is KCl and NaCl .
10. (b) In body centred cubic, each atom/ion has a coordination 6. (a) The number of spheres in one body centred cubic and in one
number of 8. face centred cubic unit cell is 2 and 4 respectively.
11. (d) Number of octahedral sites = Number of sphere in the packing. 7. (b) Closest approach in bcc lattice
 Number of octahedral sites per sphere  1 . 1 1 3
12. (c) ABAB …… is hexagonal close packing.  of body diagonal   3 a   4 .3  3 .72 Å .
2 2 2
13. (a) Sodium (Na ) is a body cube.
14. (b) SrF2 has fluorite (CaF2 ) type structure.   a 3  N 0  10 30
10. (a) M
15. (b) In ZnS structure, sulphide ions occupy all FCC lattice points z
while Zn ions are present in alternate tetrahedral voids.
10  (100)  (6 .02  10 23 )  10 30
2+
3
16. (b) MgO contains rock salt (NaCl) structure.   15.05
4
17. (c) CaF2 (fluorite) has fcc structure with 8 : 4 coordination
6.02  1023
number. No. of atoms in 100 g   100  4  1025 .
18. (b) Every constituent has two tetrahedral voids. In ccp lattice 15.05
atoms
1 1 11. (c) Cs  and I  have largest sizes.
8 6  4
8 2 12. (c) 58.5 g NaCl  1 mole  6.02  10 23 Na  Cl units.
 Tetrahedral void  4  2  8 , One unit cell contains 4 Na  Cl  units. Hence number of unit
Thus ratio  4 : 8 :: 1 : 2 .
19. (c) Tetrahedral sites one double comparable to octahedral sites cell present
then ratio of X and Z respectively 2 : 1 since formula of the 6 .02  10 23
compound X 2 Z .   1.5  10 23 .
4
20. (c) A atoms are at eight corners of the cube. Therefore, the no. of
1
8 13. (a)  6.023  10 23  1.029  10 22
A atoms in the unit cell =  1 . B atoms are at the face 58.5
8
centre of six faces. Therefore, its share in the unit cell = A unit cell contains 4 Na  ion and 4 Cl  ions
6
 3 . The formula is AB . 1 .029  10 22
2
3
Unit cell   2.57  10 21 unit cell.
4
 220 Solid state
14. (b) Bragg’s equation is n  2d sin 4. (a) A atoms are at eight corners of the cube. Therefore, the
where n is an integer i.e. 1, 2, 3, 4 etc. 8
number of A atoms in the unit cell   1 , atoms B per unit
15. (d) Face centred cubic structure contribute of 1/8 by each atom 8
present on the corner and 1/2 by each atom present on the cell = 1. Hence the formula is AB.
face. 5. (d) Co-ordination number for Cu is 12.
16. (c) As CsCl is body-centred, d  3a / 2 . 6. (b) Each Cs  in CsCl is surrounded by eight Cl  and each
3a 3  4 .29 Cl  in CsCl is surrounded by eight Cs  .
17. (a) Radius of Na (if bcc lattice)   7. (d) X atoms are at eight corners of the cube. Therefore, the
4 4
8
number of X atoms in the unit cell   1 .
 1.8574 Å  1.8574  10 8 cm 8
18. (b) The crystals in which radius ratio value is found between Y atoms are at the face centre of six faces. Therefore, its share
0.225  0.414 shows tetrahedral crystal structure. 6
in the unit cell   3 . The formula is XY 3 .
3 2d 2  4.52 2
19. (d) For bcc, d  a or a    5.219 Å  522 pm 8. (a) Let the units of ferrous oxide in a unit cell  n , molecular weight
2 3 1.732
of ferrous oxide (FeO)  56  16  72 g mol 1 ,
ZM 2  39
  72  n
a 3  N 0  10 30 (522)3  (6 .023  10 23 )  10 30 weight of n units 
6 .023  10 23
 0.91 g / cm 3  910 kg m 3
Volume of one unit  (lengthof corner )3
20. (c) The value of ionic radius ratio is 0.52 which is between
0.414  0.732, then the geometrical arrangement of ions in  (5 Å)3  125  10 24 cm 3
crystal is octahedral. wt.of cell 72  n
Density  , 4.09 
21. (c) The number of atoms present in sc, fcc and bcc unit cell are 1, volume 6.023  10 23  125  10 24
4, 2 respectively.
3079.2  10 1
22. (b) The number of atoms present in sc, fcc and bcc unit cell are 1, n  42.7  10 1  4.27  4
4, 2 respectively. 72
23. (d) Cl  Na  Cl  9. (b) In NaCl crystal Na  ions has coordination number 6.
10. (b) Cl  ions in CsCl adopt BCC type of packing.
x 11. (d) There were 6 A atoms on the face-centres removing face-
centred atoms along one of the axes means removal of 2 A
a a = 2x atoms.
a 620 Now, number of A atoms per unit cell
24. (a) r ; r  219.25 Pm
1 1
2 2 2 2  8  4 3
V  N0 d 8 2
(face  centred)
25. (c) Z (corners )
M Number of B atoms per unit cell
4 .2  8 .6  8 .3  10 24  6 .023  10 23  3.3  12 
1
+ 14
  3.84  4 4
155 (edge centred) ( body centred )
26. (b) Volume of unit cell  a 3 Hence the resultant stoichiometry is A3 B4
 (3.04  10 8 cm)3  2.81  10 23 cm 3 12. (a) In Cs  Cl  crystal co-ordination number of each ion is 8.
27. (b) In FCC 180
13. (b) r / r   0 .962 which lies in the range of
4 r  2a 187
4r 0.732  1.000 , hence co-ordination number = 8 i.e. the
a
2 structure is CsCl type.
14. (a) In diamond, C-atoms are arranged in a regular tetrahedral
structure.
Crystal structure and Coordination number 15. (b) In hcp, co-ordination no. is 12.
1 16. (c) Mg has 6 co-ordination number (fcc structure).
1. (b) In a unit cell, W atoms at the corner  8 1
8 17. (d) In NaCl crystal every Na  ion is surrounded by 6 Cl  ion and

O atoms at the centre of edges 

1
 12  3 every chloride ion is surrounded by 6 Na  ion.
4 18. (d) Crystals show good cleavage because their constituent particles
Na atoms at the centre of the cube = 1 are arranged in planes.
W : O : Na  1 : 3 : 1, hence formula  NaW O3 19. (b) Fe3 O4 is a non-stoichiometric compound because in it the
2. (d) For bcc lattice, co-ordination number is 8. ratio of the cations to the anions becomes different from that
3. (b) Body centered cubic lattice has a co-ordination number 8. indicated by the chemical formula.
20. (d) The radius ratio for co-ordination number 4, 6 and 8 lies in
between the ranges [0.225  0.414], [0.414  0.732] and
[0.732  1] respectively.
 Solid state 221
21. (c) The radius ratio for co-ordination number 4, 6 and 8 lies in 16. (c) AgBr exhibits Frenkel defect due to large difference in the
between the ranges [0.225  0.414], [0.414  0.732] and
size of Ag  and Br  ions.
[0.732  1] respectively. 17. (c) Both are stoichiometric crystalline defects.
22. (b) In Na 2 O, each oxide ions (O 2 ) is co-ordinated to 8 Na  18. (c) Brass, Cu  80%, Zn  20% substitutional alloy.
ions and each Na  ion to 4 oxide ions. Hence it has 4 : 8 co- Steel is an interstitial alloy because it is an alloy of Fe with C, C
ordination. atoms occupy the interstitial voids of Fe crystal.
23. (b) When radius ratio between 0.732  1, then co-ordination 19. (d) In metal excess defect when holes created by missing of anions
are occupied by electrons, there sites are called F-centres and
number is 8 and structural arrangement is body-centred cubic. are responsible for colour in the crystal.
24. (c) Each Cs  is surrounded by eight Cl  ions in CsCl crystal 20. (c) KBr exhibits Schottky defect and not Frenkel defect.
lattice because its co-ordination number is 8 : 8. 21. (c) When cation shifts from lattice to interstitial site, the defect is
25. (a) NaCl has fcc arrangement of ions. called Frenkel defect.
26. (c) Each Na  is surrounded by six Cl  ions in NaCl crystal 22. (d) F-centres are the sites where anions are missing and instead electrons
lattice because its co-ordination number is 6 : 6. are present. they are responsible for colour.
27. (b) Zinc blende (ZnS ) has fcc structure and is an ionic crystal Critical Thinking Questions
having 4 : 4 co-ordination number.
30. (d) In a simple cubic structure 1. (c) Amorphous solids neither have ordered arrangement (i.e. no
1 definite shape) nor have sharp melting point like crystals, but
z   8 (atoms one at a corners) when heated, they become pliable until they assume the
8
properties usually related to liquids. It is therefore they are
z 1 regarded as super-cooled liquids.
31. (a) Co-ordination number in hcp structure is 12.
2. (c) Silicon due to its catenation property form network solid.
32. (acd) A metal that crystallizes in bcc structure has a co-ordination
number of 8. 3. (c) Orthorhombic geometry has abc and
33. 
(a) In sodium chloride, each Na ion is surrounded by six Cl        90 . The shape of match box obey this
geometry.
ions and each Cl  ion is surrounded by six Na  ions. Thus,
both the ions have coordination number six. 4. (d) In a triclinic crystal has no notation of symmetry.
34. (b) The Ca 2  ions are arranged in (ccp) arrangement, i.e. Ca 2  5. (a) In NH 3 molecule, the original appearance is repeated as a
ions are present at all corners and tat the centre of each face of result of rotation through 120 o . Such as axis is said to be an
the cube. the fluoride ions occupy all the tetrahedral sites. This axis of three-fold symmetry or a triad axis.
is 8 : 4 arrangement i.e., each Ca 2  ion is surrounded by
6. (a) Na 2 O has antifluorite ( A2 B) type structure.
8 F  ions and each F  ion by four Ca 2  ions.
7. (b) Cationic radius increases down the group and decreases along
the period.
Defects in crystal
8. (c) Distance between centres of cation and anion
d 508
1. (c) When polar crystal is subjected to a mechanical stress,    254 pm
electricity is produced – a case of piezoelectricity. Reversely, if 2 2
electric field is applied, mechanical stress is developed.
rc  ra  254 pm or 110  ra  254 or ra  144 pm
Piezoelectric crystal acts as a mechanical electrical transductor.
2. (b) More is the Schottky defect in crystal more is the decrease in nM
density. 9. (b) 
a 3  N 0  10  30
3. (d) All the given statements are correct about F-centres.
5. (a) As each Sr 2 ion introduces one cation vacancy, therefore 2  100
  5.188 g/cm 3
concentration of cation vacancies = mol % of SrCl 2 added. (400)  (6 .02  10 23 )  10 30
3

High pressure
6. (c) Yellow colour on heating NaCl in presence of Na is due to 10. (a) NaCl structure CsCl structure
(6 : 6 co.  ord. ) 760 K (8 : 8 co.  ord. )
presence of electrons in anion vacancies (F-centres).
7. (d) Frenkel’s defect is due to shift of an ion from the normal lattice
site (Creating a vacancy) and occupy interstitial spaces. 11. (a) Difference  2.178  10  2.165  10 3  0.013  10 3
3

8. (c) AgBr exhibits Frenkel defect due to large difference in the 0 .013  10 3
Fraction unoccupied   5.96  10 3
size of Ag  and Br  ions. 2 .178  10 3
9. (d) Schottky defects occurs in highly ionic compounds which have 12. (c) CsBr3 consist of Cs  and Br3 ions.
high co-ordination number ex. NaCl, KCl, CsCl .
10. (d) Schottky defect is due to missing of equal number of cations 13. (a) Each Cs  is surrounded by eight Cl  ions in CsCl crystal
and anions. lattice because its co-ordination number is 8 : 8.
11. (a) Schottky defect is due to missing of equal number of cations 14. (b) In each CaF2 each calcium cation is surrounded by eight
and anions. fluoride anions in a body centred cubic arrangement. Each
12. (a) Impurity present in a crystal does not establish thermal fluoride ion is in contact with four calcium ions. Thus CaF2
equilibrium.
13. (c) Since no ions are missing from the crystal as a whole, there is has 8 : 4 co-ordination number.
no effect on density. 15. (c) The radius ratio for co-ordination number 4, 6 and 8 lies in
15. (b) On adding non-metal in metal the metal becomes less tensile. between the ranges [0.225  0.414], [0.414  0.732] and
[0.732  1] respectively.

O O

Si O

O
 222 Solid state
16. (b)

17. (b) In this diagram, equal number of cations ( Na  ) and anions

(Cl  ) are missing, so it, shows schottky defect.
18. (c) Zeolite is a three dimensional silicate because of in the silicates
all the four oxygen atoms at (SiO4 )4 tetrahedra are shared
with other tetrahedra, vesulting in a three dimensional
network.

Assertion & Reason

1. (b) It is true that in the dimond structure, carbon atoms are

arranged in tetrahedrally ( sp 3 hybridized) but it is not the
correct explanation of assertion.
2. (d) Tetrahedral holes are smaller in size than octahedral
holes. Cations usually occupy less space than anions.
3. (d) Crystalline solids have regular arrangement of constituent
particles and are anisotropic whereas amorphous solids have no
regular arrangement and are isotropic.
4. (a) Schottky defect is due to missing of equal number of cations and
anions.
5. (b) Space or crystal lattice is a regular repeating arrangement of
points in space and forms the basis of classification of all
structures.
6. (c) Tetrahedral void is so called because it is surrounded by four
spheres tetrahedrally while octahedral void is so called because
it is surrounded by six spheres octahedrally.
7. (c) Two corners per tetrahedron one shared in both the cases.
8. (b) When an atom or an ion is missing from its normal lattice site,
a lattice vacancy or defect is created, which is called schottky
defect. Due to missing density of crystal will be lowered.
9. (b) On heating, the metal atoms deposit on the surface and finally
they deffuse into the crystal and after ionisation the alkali metal
ion occupies cationic vacancy where as electron occupies
anionic vacancy.
10. (a) In case of semiconductors, the gap between valence band and
the conduction band is small and there fore some of the
electrons may jump from valence band to conduction band and
thus on increasing temperature conductivity is also increased.
11. (a) All magnetically ordered solids (ferromagnetic and
antiferromagnetic solids) transform to the paramagnetic state
at high temperature due to the randomisation of spins.
12. (c) In piezoelectric crystals, the dipoles may align them selves in an
ordered manner such that there is a net dipole moment in the
crystal.
 Solid State 223

1. Particles of quartz are packed by 7. The second order Bragg's diffraction of X  rays with   1 Å
(a) Electrical attraction forces
from a set of parallel planes in a metal occurs at an angle of 60 o .
(b) Vander Waal's forces The distance between the scattering planes in the crystal is[CBSE PMT 1998; AFM
(c) Covalent bond forces
(a) 0.575 Å (b) 1 .00 Å
(d) Strong electrostatic attraction forces
2. Crystals of covalent compounds always have [BHU 1984] (c) 2 .00 Å (d) 1 .15 Å
(a) Atoms as their structural units 8. The edge length of the unit cell of NaCl crystal lattice is
(b) Molecules as structural units 552 pm. If ionic radius of sodium ion is 95 pm, what is the
(c) Ions held together by electrostatic forces ionic radius of chloride ion [KCET 1998]

(d) High melting points (a) 190 pm (b) 368 pm

3. Wax is an example of
(c) 181 pm (d) 276 pm
(a) Ionic crystal (b) Covalent crystal
(c) Metallic crystal (d) Molecular crystal 9. The ionic radii of Rb  and I  are 1.46 Å and 2.16Å. the most
probable type of structure exhibited by it is
4. Among the following which crystal will be soft and have low melting
[UPSEAT 2004]
point
(a) Covalent (b) Ionic (a) CsCl type (b) ZnS type

(c) Metallic (d) Molecular (c) NaCl type (d) CaF2 type
5. In zinc blende structure, zinc atom fill up 10. The coordination number of a cation occupying a tetrahedral hole is
(a) All octahedral holes (a) 6 (b) 8
(b) All tetrahedral holes (c) 12 (d) 4
(c) Half number of octahedral holes 11. If a electron is present in place of anion in a crystal lattice, then it is
(d) Half number of tetrahedral holes called

6. Which ion has the lowest radius from the following ions (a) Frenkel defect
[Kurukshetra CEE 1998] (b) Schottky defect
(c) Interstitial defects
(a) Na  (b) Mg 2 
(d) F  centre
(c) Al 3  (d) Si 4 

(SET -5)
 224 Solid State
1. (c) Quartz is a covalent solid in which constituent particles are 10. (d) The co-ordination number of a cation occupying a tetrahedral
atoms which are held together by covalent bond forces. hole is 4.
11. (d) When electrons are trapped in anion vacancies, these are called
2. (a) Constituent particles of covalent compounds are atoms. F-centres.
3. (d) Iodine crystals are molecular crystals, in which constituent
particles are molecules having interparticle forces are Vander
Waal’s forces.
4. (d) Molecular crystals are soft and have low melting point.

5. (d) In zinc blende (ZnS ) half number of tetrahedral holes are

filled by zinc atoms.

6. (d) All are the iso-electronic species but Si 4  has high positive
charge so have lowest radius.

7. (d) 2d sin  n or 2  d  sin 60  2  1 Å

or 2  d  0.8660  2

or d  1.15 Å (sin 60  3 / 2 or 0.8660) .

***

8. (c) Distance between centres of Na  and Cl 

rNa   rCl   276 pm or 95  rCl   276 pm

or rCl   276  95  181 pm

rc  1 .46
9. (c)   0 .676
ra  2 .16

It permits co-ordination number 6 and octahedral structure of

type NaCl .
 Gaseous State 225

Chapter

6
Gaseous state

The state of matter in which the molecular forces of attraction 1 m 3  10 3 dm 3  10 6 cm 3  10 6 mL  10 3 L

between the particles of matter are minimum, is known as gaseous state. It
is the simplest state and shows great uniformity in behaviour. (3) Mass : (i) The mass of a gas can be determined by weighing the
container in which the gas is enclosed and again weighing the container
Characteristics of gases after removing the gas. The difference between the two weights gives the
(1) Gases or their mixtures are homogeneous in composition. mass of the gas.
(2) Gases have very low density due to negligible intermolecular (ii) The mass of the gas is related to the number of moles of the gas
forces. i.e.
(3) Gases have infinite expansibility and high compressibility.
Mass in grams m
(4) Gases exert pressure. moles of gas (n)  
Molar mass M
(5) Gases possess high diffusibility.
(6) Gases do not have definite shape and volume like liquids. (4) Temperature : (i) Gases expand on increasing the temperature. If
(7) Gaseous molecules move very rapidly in all directions in a random temperature is increased twice, the square of the velocity (v 2 ) also
manner i.e., gases have highest kinetic energy. increases two times.
(8) Gaseous molecules collide with one another and also with the walls
of container with perfectly elastic collisions. (ii) Temperature is measured in centigrade degree ( o C) or celsius
(9) Gases can be liquified, if subjected to low temperatures (below degree with the help of thermometers. Temperature is also measured in
critical) or high pressures. Fahrenheit (F ).
o

(10) Thermal energy of gases >> molecular attraction. (iii) S.I. unit of temperature is kelvin (K) or absolute degree.
(11) Gases undergo similar change with the change of temperature K  o C  273
and pressure. In other words, gases obey certain laws known as gas laws.
C F o  32
o
Measurable properties of gases (iv) Relation between F and o C is 
5 9
(1) The characteristics of gases are described fully in terms of four
parameters or measurable properties : (5) Pressure : (i) Pressure of the gas is the force exerted by the gas
per unit area of the walls of the container in all directions. Thus, Pressure
(i) The volume, V, of the gas.
Force( F) Mass(m )  Acceleration(a)
(ii) Its pressure, P (P)  
(iii) Its temperature, T Area( A) Area(a)
(iv) The amount of the gas (i.e., mass or number of moles). (ii) Pressure exerted by a gas is due to kinetic energy
(2) Volume : (i) Since gases occupy the entire space available to 1
(KE  mv 2 ) of the molecules. Kinetic energy of the gas molecules
them, the measurement of volume of a gas only requires a measurement of 2
the container confining the gas. increases, as the temperature is increased. Thus, Pressure of a gas 
(ii) Volume is expressed in litres (L), millilitres (mL) or cubic Temperature (T).
centimetres (cm 3 ) or cubic metres (m 3 ) . (iii) Pressure of a pure gas is measured by manometer while that of
a mixture of gases by barometer.
(iii) 1L  1000 mL ; 1 mL  10 3 L ; 1 L  1 dm 3  10 3 m 3 (iv) Commonly two types of manometers are used,
(a) Open end manometer; (b) Closed end manometer
 226 Gaseous State
(v) The S.I. unit of pressure, the pascal (Pa), is defined as 1
newton per metre square. It is very small unit.

1Pa  1 Nm 2  1 kg m 1 s 2

(vi) C.G.S. unit of pressure is dynes cm 2 .

(vii) M.K.S. unit of pressure is kgf / m 2 . The unit kgf / cm 2 T1< T2< T3
sometime called ata (atmosphere technical absolute). PV T3
(viii) Higher unit of pressure is bar, KPa or MPa. T2
1 bar  10 5 Pa  10 5 Nm 2  100 KNm 2  100 KPa T1 log P

(ix) Several other units used for pressure are,

Name Symbol Value
bar bar O O
1bar  10 Pa 5 (4) At constantP mass and temperature densitylogof1/Va gas is directly
atmosphere atm proportional to its pressure and inversely proportional to its volume.
1 atm  1.01325  10 5 Pa
1  mass 
Torr Torr 101325 Thus, d  P   V  d 
1 Torr  Pa  133.322 Pa V  
760
d1 P V
mm Hg or  1  2  .......  K
millimetre of 1 mm Hg  133.322 Pa d 2 P2 V1
mercury
(5) At altitudes, as P is low d of air is less. That is why
(x) The pressure relative to the atmosphere is called gauge pressure. mountaineers carry oxygen cylinders.
The pressure relative to the perfect vacuum is called absolute pressure.
Charle's law
Absolute pressure = Gauge pressure + Atmosphere pressure.
(xi) When the pressure in a system is less than atmospheric (1) French chemist, Jacques Charles first studied variation of volume
pressure, the gauge pressure becomes negative, but is frequently designated with temperature, in 1787.
and called vacuum. For example, 16 cm vacuum will be (2) It states that, “The volume of a given mass of a gas is directly
76  16 proportional to the absolute temperature ( o C  273) at constant
 1.013  0 .80 bar .
76 pressure”.
(xii) If ‘h’ is the height of the fluid in a column or the difference in Thus, V  T at constant pressure and mass
the heights of the fluid columns in the two limbs of the manometer, d is the
density of the fluid or V  KT  K(t( o C)  273.15) , (where k is constant),

(Hg  13.6  10 3 Kg / m 3  13.6 g / cm 3 ) and g is the gravity, then K

V V V
or 1  2  K (For two or more gases)
pressure is given by, Pgas  Patm  h dg T T1 T2

(xiii) Two sets of conditions are widely used as 'standard' values for (3) If t  0 o C , then V  V0
reporting data.
hence, V0  K  273.15
Condition T P V (Molar volume)
m

S.T.P./N.T.P. 273.15 K 1 atm 22.414 L V0

 K
S.A.T.P .
*
298.15 K 1 bar 24.800 L 273.15
* Standard ambient temperature and pressure. V0  t 
V [t  273.15]  V0 1    V0 [1   v t]
Boyle's law 273.15  273 . 15 
(1) In 1662, Robert Boyle discovered the first of several relationships
where  v is the volume coefficient,
among gas variables (P, T, V).
(2) It states that, “For a fixed amount of a gas at constant V  V0 1
temperature, the gas volume is inversely proportional to the gas pressure.” v    3 .661  10  3 o C 1
tV0 273.15
Thus, P  1 / V at constant temperature and mass
or P  K / V (where K is constant) Thus, for every 1 o change in temperature, the volume of a gas
or PV  K or P1 V1  P2 V2  K (For two or more gases) 1  1 
changes by   of the volume at 0 o C .
(3) Graphical representation of Boyle's law : Graph between P and V 273.15  273 
at constant temperature is called isotherm and is an equilateral (or
rectangular) hyperbola. By plotting P versus 1 / V , this hyperbola can be (4) Graphical representation of Charle's law : Graph between V and
converted to a straight line. Other types of isotherms are also shown below, T at constant pressure is called isobar or isoplestics and is always a straight
line. A plot of V versus t( o C) at constant pressure is a straight line cutting
T3
the temperature axis at  273.15 o C . It is the lowest possible
T2
T1< T2< T3 temperature.
P P T1

T3
T2 T1< T2< T3
T1
O O
V or 1/d 1/V or d
 Gaseous State 227

1/d or V

1/d
or V
Avogadro's law
22.4 L mol–1 = V0
(1) According to this law, “Equal volumes of any two gases at the
O same temperature and pressure contain the same number of molecules.”
T(k) –273.15o C C
0o t C)
(o
(5) At constant mass and pressure density of a gas is inversely Thus, V  n (at constant T and P)
proportional to it absolute temperature. or V  Kn (where K is constant)
1 1  mass  V1 V2
Thus, d    V  d  or   .......  K
T V   n1 n 2

d1 T2 V2 Example, 2 H 2 (g) O 2 (g)  2 H 2 O(g)

or    ......  K 2 moles 1 mole 2 moles
d 2 T1 V1 2 volumes 1 volume 2 volumes
2 litres 1 litre 2 litres
(6) Use of hot air balloons in sports and meteorological observations 1 litre 1 / 2 litre 1 litre
1n litre 1 / 2 n litre 1n litre
is an application of Charle's law.
(2) One mole of any gas contains the same number of molecules
Gay-Lussac's law (Amonton's law)
(Avogadro's number  6.02  10 23 ) and by this law must occupy the
(1) In 1802, French chemist Joseph Gay-Lussac studied the variation same volume at a given temperature and pressure. The volume of one mole
of pressure with temperature and extende the Charle’s law so, this law is
of a gas is called molar volume, V which is 22.4 L mol 1 at S.T.P. or
also called Charle’s-Gay Lussac’s law.
m

(2) It states that, “The pressure of a given mass of a gas is directly
proportional to the absolute temperature ( o C  273) at constant
volume.”
Thus, P  T at constant volume and mass
N.T.P.
(3) This law can also express as, “The molar gas volume at a given
temperature and pressure is a specific constant independent of the nature
of the gas”.
Thus, Vm  specific constant  22.4 L mol 1 at S.T.P. or N.T.P.

or P  KT  K(t(o C)  273.15) (where K is constant)

Ideal gas equation
(1) The simple gas laws relating gas volume to pressure, temperature
P P P
K or 1  2  K (For two or more gases) and amount of gas, respectively, are stated below :
T T1 T2
1 1
Boyle's law : P or V  (n and T constant)
(3) If t  0 C , then P  P0
o V P
Charle's law : VT (n and P constant)
Hence, P0  K  273.15
Avogadro's law : V  n (T and P constant)
P0 If all the above law's combines, then
 K
273.15 nT
V
P0  t  P
P [t  273.15]  P0 1   P0 [1  t]
273.15  273.15  nRT
or V ( R  Ideal gas constant)
where  P is the pressure coefficient, P
or PV  nRT
P  P0 1
P    3.661  10  3 o C 1 This is called ideal gas equation. R is called ideal gas constant. This
tP0 273.15 equation is obeyed by isothermal and adiabatic processes.
(2) Nature and values of R : From the ideal gas equation,
Thus, for every 1 o change in temperature, the pressure of a gas
PV Pressure  Volume
1  1  R 
changes by   of the pressure at 0 o C . nT mole  Temperatur e
273.15  273 
Force
(4) This law fails at low temperatures, because the volume of the  Volume
Area Force  Length
gas molecules be come significant.  
mole  Temperatur e mole  Temperatur e
(5) Graphical representation of Gay-Lussac's law : A graph between
Work or energy
P and T at constant V is called isochore.  .
mole  Temperatur e
V1< V2< V3< V4
V1 R is expressed in the unit of work or energy mol 1 K 1 .
V2
V3 Since different values of R are summarised below :
P V4
P R  0.0821 L atm mol 1 K 1

O O T
T(k)
 228 Gaseous State

 8.3143 joulemol 1 K 1 (S.I. unit) Thus, Ptotal  P1  P2  P3  .........

 8.3143 Nm mol 1 K 1 Where P1 , P2 , P3 ,...... are partial pressures of gas number 1, 2, 3

.........
 8.3143 KPa dm 3 mol 1 K 1 (2) Partial pressure is the pressure exerted by a gas when it is
1 1 present alone in the same container and at the same temperature.
 8.3143 MPacm mol 3
K
Partial pressure of a gas
 5.189  10 19 eV mol 1 K 1 Number of moles of the gas (n1 )  PTotal
(P1 )   Mole fraction ( X 1 )  PTotal
1 1 Total number of moles (n) in the mixture
 1.99 cal mol K
(3) If a number of gases having volume V1 , V2 , V3 ...... at pressure
(3) Gas constant, R for a single molecule is called Boltzmann
constant (k) P1 , P2 , P3 ........ are mixed together in container of volume V, then,

R 8.314  10 7 P1 V1  P2 V2  P3 V3 .....
k  ergs mole 1 degree 1 PTotal 
N 6 .023  10 23 V

 1.38  10 16 ergsmol 1 degree 1 RT

or  (n1  n 2  n 3 .....) ( PV  nRT )
V
23 1 1
or 1.38  10 joulemol degree RT
or  n ( n  n1  n 2  n3 .....)
(4) Calculation of mass, molecular weight and density of the gas by V
gas equation (4) Applications : This law is used in the calculation of following
m relationships,
PV  nRT  RT
M (i) Mole fraction of a gas (X 1 ) in a mixture of gas
 mass of the gas (m )  Partial pressure of a gas (P1 )
 n   
 Molecular weight of the gas (M )  PTotal
mRT Partial pressure of a gas (P1 )
 M (ii) % of a gas in mixture   100
PV PTotal
PM  m (iii) Pressure of dry gas collected over water : When a gas is
d  d   collected over water, it becomes moist due to water vapour which exerts its
RT  V
own partial pressure at the same temperature of the gas. This partial
dT M M perssure of water vapours is called aqueous tension. Thus,
or  ,  Constant
P R R Pdry gas  Pmoist gas or PTotal  Pwater vapour
(  M and R are constant for a particular gas)
or Pdry gas  Pmoist gas  Aqueous tension (Aqueous tension is
dT d T d T
Thus, or 1 1  2 2 = Constant directly proportional to absolute temperature)
P P1 T2 (iv) Relative humidity (RH) at a given temperature is given by,
(For two or more different temperature and pressure) Partial pressure of water in air
(5) Gas densities differ from those of solids and liquids as, RH  .
Vapour pre ssure of water
(i) Gas densities are generally stated in g/L instead of g / cm 3 . (5) Limitations : This law is applicable only when the component
(ii) Gas densities are strongly dependent on pressure and gases in the mixture do not react with each other. For example, N 2 and
temperature as, d  P  1 / T O 2 , CO and CO 2 , N 2 and Cl 2 , CO and N 2 etc. But this law is not
Densities of liquids and solids, do depend somewhat on temperature, applicable to gases which combine chemically. For example, H 2 and Cl 2 ,
but they are far less dependent on pressure.
(iii) The density of a gas is directly proportional to its molar mass. CO and Cl 2 , NH 3 , HBr and HCl, NO and O 2 etc.
No simple relationship exists between the density and molar mass for liquid (6) Another law, which is really equivalent to the law of partial
and solids. pressures and related to the partial volumes of gases is known as Law of
molar mass partial volumes given by Amagat. According to this law, “When two or more
(iv) Density of a gas at STP  gases, which do not react chemically are kept in a closed vessel, the total
22.4 volume exerted by the mixture is equal to the sum of the partial volumes of
28 individual gases.”
d ( N 2 ) at STP   1 .25 g L1 ,
22.4 Thus, VTotal  V1  V2  V3  ......
32
d (O 2 ) at STP   1 .43 g L1 Where V1 , V2 , V3 ,...... are partial volumes of gas number 1, 2, 3.....
22.4
Graham's law of diffusion and Effusion
Dalton's law of partial pressures
(1) Diffusion is the process of spontaneous spreading and
(1) According to this law, “When two or more gases, which do not intermixing of gases to form homogenous mixture irrespective of force of
react chemically are kept in a closed vessel, the total pressure exerted by the gravity. While Effusion is the escape of gas molecules through a tiny hole
mixture is equal to the sum of the partial pressures of individual gases.” such as pinhole in a balloon.
 Gaseous State 229

 All gases spontaneously diffuse into one another when they are (1) Kinetic theory was developed by Bernoulli, Joule, Clausius,
brought into contact. Maxwell and Boltzmann etc. and represents dynamic particle or microscopic
model for different gases since it throws light on the behaviour of the
 Diffusion into a vacuum will take place much more rapidly than
particles (atoms and molecules) which constitute the gases and cannot be
diffusion into another place.
seen. Properties of gases which we studied earlier are part of macroscopic
 Both the rate of diffusion of a gas and its rate of effusion depend model.
on its molar mass. Lighter gases diffuses faster than heavier gases. The gas (2) Postulates
with highest rate of diffusion is hydrogen.
(i) Every gas consists of a large number of small particles called
(2) According to this law, “At constant pressure and temperature,
molecules moving with very high velocities in all possible directions.
the rate of diffusion or effusion of a gas is inversely proportional to the
square root of its vapour density.” (ii) The volume of the individual molecule is negligible as compared
to the total volume of the gas.
1
Thus, rate of diffusion (r)  (T and P constant) (iii) Gaseous molecules are perfectly elastic so that there is no net loss of
d kinetic energy due to their collisions.
For two or more gases at constant pressure and temperature,
(iv) The effect of gravity on the motion of the molecules is
r1 d2 negligible.

r2 d1 (v) Gaseous molecules are considered as point masses because they
(3) Graham's law can be modified in a number of ways as, do not posses potential energy. So the attractive and repulsive forces
between the gas molecules are negligible.
(i) Since, 2  vapour density (V.D.) = Molecular weight
(vi) The pressure of a gas is due to the continuous bombardment on
r d2 d2  2 M2 the walls of the containing vessel.
then, 1   
r2 d1 d1  2 M1 (vii) At constant temperature the average K.E. of all gases is same.
where, M 1 and M 2 are the molecular weights of the two gases. (viii) The average K.E. of the gas molecules is directly proportional
to the absolute temperature.
Volume of a gas diffused
(ii) Since, rate of diffusion (r)  (3) Kinetic gas equation : On the basis of above postulates, the
Time taken for diffusion
following gas equation was derived,
r1 V /t w /t d2
then,  1 1  1 1  1
r2 V2 / t 2 w 2 / t 2 d1 PV  2
mnu rms
3
(a) When equal volume of the two gases diffuse, i.e. V1  V2 where, P = pressure exerted by the gas
r1 t 2 d2 V = volume of the gas
then,  
r2 t1 d1 m = average mass of each molecule
(b) When volumes of the two gases diffuse in the same time, i.e. n = number of molecules
t1  t 2 u = root mean square (RMS) velocity of the gas.
(4) Calculation of kinetic energy
r1 V d2
then,  1  We know that,
r2 V2 d1
(iii) Since, r  p (when p is not constant) 1
K.E. of one molecule  mu 2
2
r1 P M2  P 
then,  1  r  
 M  K.E. of n molecules 
1 3 1
mnu 2  PV ( PV  mnu 2 )
r2 P2 M1 
2 2 3
(4) Rate of diffusion and effusion can be determined as,
(i) Rate of diffusion is equal to distance travelled by gas per unit 3
n = 1, Then K.E. of 1 mole gas  RT ( PV  RT )
time through a tube of uniform cross-section. 2
(ii) Number of moles effusing per unit time is also called rate of 3
diffusion.   8.314  T  12.47 T Joules .
2
(iii) Decrease in pressure of a cylinder per unit time is called rate of
effusion of gas. Average K.E.per mole 3 RT 3
   KT
(iv) The volume of gas effused through a given surface per unit time N (Avogadro number ) 2 N 2
is also called rate of effusion.
 R 
(5) Applications : Graham's law has been used as follows, K   Boltzmann constant 
(i) To determine vapour densities and molecular weights of gases.  N 
(ii) To prepare Ausell’s marsh gas indicator, used in mines. This equation shows that K.E. of translation of a gas depends only
(iii) Atmolysis : The process of separation of two gases on the basis on the absolute temperature. This is known as Maxwell generalisation. Thus
of their different rates of diffusion due to difference in their densities is average K.E.  T.
called atmolysis. It has been applied with success for the separation of
isotopes and other gaseous mixtures. If T  0 K (i.e.,  273.15 o C) then, average K.E. = 0. Thus,
absolute zero (0K) is the temperature at which molecular motion ceases.
Kinetic theory of gases
Molecular collisions
 230 Gaseous State
(1) The closest distance between the centres of two molecules taking (2) According to Maxwell, at a particular temperature the
part in a collision is called molecular or collision diameter (). The distribution of speeds remains constant and this distribution is referred to
molecular diameter of all the gases is nearly same lying in the order of as the Maxwell-Boltzmann distribution and given by the following
expression,
10 8 cm .
3/2
dn0  M  2
 4   .e  Mu / 2 RT
.u 2 dc
n  2RT 


where, dn0  Number of molecules out of total number of
Molecular diameter molecules n, having velocities between c and c  dc , dn0 / n  Fraction of
(2) The number of collisions taking place in unit time per unit the total number of molecules, M = molecular weight, T = absolute
volume, called collision frequency (z). 2
(i) The number of collision made by a single molecule with other temperature. The exponential factor e  Mu / 2 RT is called Boltzmann factor.
molecules per unit time are given by, Z A  2 2 u av. n (3) Maxwell gave distribution curves of molecular speeds for CO 2
where n is the number of molecules per unit molar volume, at different temperatures. Special features of the curve are :
(i) Fraction of molecules with two high or two low speeds is very small.
Avogadro number( N 0 ) 6 .02  10 23 3 (ii) No molecules has zero velocity.
n  m
Vm 0 .0224 (iii) Initially the fraction of molecules increases in velocity till the
(ii) The total number of bimolecular collision per unit time are given peak of the curve which pertains to most probable velocity and thereafter it
1 falls with increase in velocity.
by, Z AA   2 u av. n 2 Ump
2
300 K (T1) T1<T2<T3
(iii) If the collisions involve two unlike molecules, the number of
bimolecular collision are given by, Ump

Fraction of molecules
1/2 Uav
2  (M A  M B )  Urms U
  AB 8RT
mp
Z AB 
 MAMB 
1500 K (T2) 1800 K (T3)
 A  B
where,  AB 
2
Molecular speed
M A , M B are molecular weights (M  mN 0 ) (4) Types of molecular speeds or Velocities
(i) Root mean square velocity (u ) : It is the square root of the mean
(iv) (a) At particular temperature; Z  p 2 rms

of the squares of the velocity of a large number of molecules of the same

(b) At particular pressure; Z  T 3 / 2 gas.
(c) At particular volume; Z  T 1 / 2 u12  u 22  u 32  ..... u n2
(3) During molecular collisions a molecule covers a small distance u rms 
n
before it gets deflected. The average distance travelled by the gas molecules
between two successive collision is called mean free path (). 3 PV 3 RT 3 RT 3kT 3P
u rms     
Average distance travelled per unit time( u av ) (mN 0 )  M (mN 0 )  M M m d
 .
No. of collisionsmade by singlemolecule per unit time (Z A ) R
u av 1
where k = Boltzmann constant 
  N0
2 2 u avr.n 2n  2
(a) For the same gas at two different temperatures, the ratio of
T
(4) Based on kinetic theory of gases mean free path,   . Thus, u1 T1
P RMS velocities will be, 
u2 T2
(i) Larger the size of the molecules, smaller the mean free path, i.e.,
1 (b) For two different gases at the same temperature, the ratio of

(radius)2 u1 M2
RMS velocities will be, 
(ii) Greater the number of molecules per unit volume, smaller the u2 M1
mean free path.
(iii) Larger the temperature, larger the mean free path. (c) RMS velocity at any temperature t o C may be related to its
(iv) Larger the pressure, smaller the mean free path. 3 P(273  t)
value at S.T.P. as, u t  .
(5) Relation between collision frequency (Z) and mean free path () 273d
u (ii) Average velocity (v av ) : It is the average of the various velocities
is given by, Z  rms
 possessed by the molecules.

Molecular speeds or velocities v1  v 2  v 3  ...... v n 8 RT 8 kT

v av  ; v av  
(1) At any particular time, in the given sample of gas all the n M m
molecules do not possess same speed, due to the frequent molecular (iii) Most probable velocity ( mp ) : It is the velocity possessed by
collisions with the walls of the container and also with one another, the
molecules move with ever changing speeds and also with ever changing maximum number of molecules of a gas at a given temperature.
direction of motion.
 Gaseous State 231

2 RT 2 PV 2P (iii) Z  1 , the gas is more compressible than expected from ideal

 mp    behaviour and shows negative deviation, usually at low P i.e. PV  RT .
M M d
(5) Relation between molecular speeds or velocities, (iv) Z  1 for H 2 and He at all pressure i.e., always shows
positive deviation.
(i) Relation between u rms and v av : v av  0.9213  urms
(v) The most easily liquefiable and highly soluble gases (NH 3 , SO 2 )
or urms  1.085  v av
show larger deviations from ideal behaviour i.e. Z  1 .
(ii) Relation between  mp and u rms :  mp  0.816  urms
(vi) Some gases like CO 2 show both negative and positive
or urms  1.224   mp deviation.
(iii) Relation between  mp and v av : v av  1.128   mp (6) Causes of deviations of real gases from ideal behaviour : The
ideal gas laws can be derived from the kinetic theory of gases which is
(iv) Relation between  mp , v av and u rms based on the following two important assumptions,
 mp : v av : u rms (i) The volume occupied by the molecules is negligible in
comparison to the total volume of gas.
2 RT 8 RT 3 RT (ii) The molecules exert no forces of attraction upon one another. It
: : is because neither of these assumptions can be regarded as applicable to
M M M
real gases that the latter show departure from the ideal behaviour.
8
2 : : 3 Vander Waal's equation

(1) To rectify the errors caused by ignoring the intermolecular forces
1.414 : 1.595 : 1.732
of attraction and the volume occupied by molecules, Vander Waal (in 1873)
1 : 1.128 : 1.224 i.e.,  mp  v av  urms modified the ideal gas equation by introducing two corrections,
Real and Ideal gases (i) Volume correction (ii) Pressure correction
(2) Vander Waal's equation is obeyed by the real gases over wide
(1) Gases which obey gas laws or ideal gas equation (PV  nRT ) at
range of temperatures and pressures, hence it is called equation of state for
all temperatures and pressures are called ideal or perfect gases. Almost all the real gases.
gases deviate from the ideal behaviour i.e., no gas is perfect and the concept
of perfect gas is only theoretical. (3) The Vander Waal's equation for n moles of the gas is,
(2) Gases tend to show ideal behaviour more and more as the  2 
P  n a  [V  nb]  nRT
temperature rises above the boiling point of their liquefied forms and the  V 2 
pressure is lowered. Such gases are known as real or non ideal gases. Thus,  Volume correction for
Pressure correction finite size of molecules
a “real gas is that which obeys the gas laws under low pressure or high for molecular attraction
temperature”. a and b are Vander Waal's constants whose values depend on the
(3) The deviations can be displayed, by plotting the P-V isotherms of nature of the gas. Normally for a gas a  b .
real gas and ideal gas.
H2 (i) Constant a : It is a indirect measure of magnitude of attractive
forces between the molecules. Greater is the value of a, more easily the gas
He
can be liquefied. Thus the easily liquefiable gases (like
SO 2  NH 3  H 2 S  CO 2 ) have high values than the permanent gases
PV (like N 2  O 2  H 2  He) .
Z 
nRT
O2 Units of 'a' are : atm. L2 mol 2 or atm. m 6 mol 2 or
N2 4 2
CH4
N m mol (S.I. unit).
CO2 (ii) Constant b : Also called co-volume or excluded volume,
P
(4) It is difficult to determine quantitatively the deviation of a real 4 
b  4 N 0 v  4 N 0  r 3 
gas from ideal gas behaviour from the P-V isotherm curve as shown above. 3 
Compressibility factor Z defined by the equation, It's value gives an idea about the effective size of gas molecules.
PV  ZnRT or Z  PV / nRT  PVm / RT Greater is the value of b, larger is the size and smaller is the compressible
volume. As b is the effective volume of the gas molecules, the constant value
is more suitable for a quantitative description of the deviation from
of b for any gas over a wide range of temperature and pressure indicates
ideal gas behaviour.
that the gas molecules are incompressible.
(5) Greater is the departure of Z from unity, more is the deviation
from ideal behaviour. Thus, when Units of 'b' are : L mol 1 or m 3 mol 1 (S.I. unit)
(i) Z  1 , the gas is ideal at all temperatures and pressures. In case (iii) The two Vander Waal's constants and Boyle's temperature (TB )
o
of N 2 , the value of Z is close to 1 at 50 C . This temperature at which a are related as,
a
real gas exhibits ideal behaviour, for considerable range of pressure, is TB 
known as Boyle's temperature or Boyle's point (TB ) . bR
(4) Vander Waal's equation at different temperature and pressures
(ii) Z  1 , the gas is less compressible than expected from ideal (i) When pressure is extremely low : For one mole of gas,
behaviour and shows positive deviation, usual at high P i.e. PV  RT .
 232 Gaseous State

 a  a ab (v) Kammerlingh Onnes equation : It is the most general or

 P  2  (V  b)  RT or PV  RT   Pb  2 satisfactory expression as equation expresses PV as a power series of P at a
 V  V V given temperature.
(ii) When pressure is extremely high : For one mole of gas,
PV Pb Pb PV  A  BP  CP 2  DP3  ......
PV  RT  Pb ; 1 or Z  1  Here coefficients A, B, C etc. are known as first, second and third
RT RT RT
etc. virial coefficients.
where Z is compressibility factor.
(iii) When temperature is extremely high : For one mole of gas, (a) Virial coefficients are different for different gases.
PV  RT . (b) At very low pressure, first virial coefficient, A = RT.
(iv) When pressure is low : For one mole of gas, (c) At high pressure, other virial coefficients also become important
and must be considered.
 a  a ab
 P  2  (V  b)  RT or PV  RT  Pb   2 The critical state
 V  V V
PV a a (1) A state for every substance at which the vapour and liquid states
or 1 or Z  1  are indistinguishable is known as critical state. It is defined by critical
RT VRT VRT temperature and critical pressure.
(v) For hydrogen : Molecular mass of hydrogen is small hence value
(2) Critical temperature (T ) of a gas is that temperature above
of 'a' will be small owing to smaller intermolecular force. Thus the terms c

which the gas cannot be liquified however large pressure is applied. It is

a ab
and 2 may be ignored. Then Vander Waal's equation becomes, 8a
V V given by, Tc 
27 Rb
PV Pb (3) Critical pressure (P ) is the minimum pressure which must be
PV  RT  Pb or 1 c

RT RT applied to a gas to liquify it at its critical temperature. It is given by,

Pb a
or Z  1  Pc 
RT 27b 2
In case of hydrogen, compressibility factor is always greater than (4) Critical volume (V ) is the volume occupied by one mole of the
c

one. substance at its critical temperature and critical pressure. It is given by,
(5) Merits of Vander Waal's equation Vc  3b
(i) The Vander Waal's equation holds good for real gases upto (5) Critical compressibility factor (Z )
c
is given by,
moderately high pressures. Pc Vc 3
Zc    0 .375
(ii) The equation represents the trend of the isotherms representing RTc 8
the variation of PV with P for various gases.
A gas behaves as a Vander Waal’s gas if its critical compressibility
(iii) From the Vander Waal's equation it is possible to obtain
factor (Z c ) is equal to 0.375. A substance is the gaseous state below Tc is
expressions of Boyle's temperature, critical constants and inversion
temperature in terms of the Vander Waal's constants 'a' and 'b'. called vapour and above Tc is called gas.
(iv) Vander Waal's equation is useful in obtaining a 'reduced
equation of state' which being a general equation of state has the advantage
Degrees of freedom of a gaseous molecule
that a single curve can be obtained for all gases when the equation if (1) The motion of atoms and molecules is generally described in
graphically represented by plotting the variables. terms of the degree of freedom which they possess.
(6) Limitations of Vander Waal's equation (2) The degrees of freedom of a molecule are defined as the
(i) This equation shows appreciable deviations at too low independent number of parameters required to describe the state of the
temperatures or too high pressures. molecule completely.
(ii) The values of Vander Waal's constants a and b do not remain (3) When a gaseous molecule is heated, the energy supplied to it
constant over the entire ranges of T and P, hence this equation is valid only may bring about three kinds of motion in it, these are,
over specific range of T and P. (i) The translational motion (ii) The rotational motion
(7) Other equations of state : In addition to Vander Waal's equation, (iii) The vibrational motion.
there are also equations of state which have been used to explain real This is expressed by saying that the molecule possesses translational,
behaviour of gases are, rotational and vibrational degrees of freedom.
  (4) For a molecule made up of N atoms, total degrees of freedom =
a
(i) Clausius equation :  P  2 
(V  b)  RT . Here 'c' is 3N. Further split up of these is as follows,
 T (V  c)  Translational Rotational Vibrational
another constant besides a, b and R. For linear molecule : 3 2 3N – 5
 a  For non-linear molecule : 3 3 3N – 6
(ii) Berthelot equation :  P   (V  b)  RT .
 TV 2  Specific and Molar heat capacity of gases
RT a c (1) Specific heat (or specific heat capacity) of a substance is the
(iii) Wohl equation : P   
(V  b) V (V  b) V 2 quantity of heat (in calories, joules, kcal, or kilo joules) required to raise the
RT temperature of 1g of that substance through 1 o C . It can be measured at
(iv) Dieterici equation : P  .e a / RTV . constant pressure (c p ) and at constant volume (c v ) .
V b
The expression is derived on the basis of the concept that molecules (2) Molar heat capacity of a substance is the quantity of heat
near the wall will have higher potential energy than those in the bulk. required to raise the temperature of 1 mole of the substance by 1 o C .
 Gaseous State 233

 Molar heat capacity = Specific heat capacity  Molecular weight,
i.e.,
Cv  cv  M and C p  c p  M .
(3) Since gases upon heating show considerable tendency towards
expansion if heated under constant pressure conditions, an additional energy
has to be supplied for raising its temperature by 1 o C relative to that
required under constant volume conditions, i.e.,
C p  Cv or C p  Cv  Work done on expansion, PV( R)
where, C p  molar heat capacity at constant pressure; Cv 
molar heat capacity at constant volume.
(4) Some useful relations of C and C
p v
(iii) Liquid chlorine is used for bleaching and disinfectant purposes.
(iv) Liquid air is an important source of oxygen in rockets and jet-
propelled planes and bombs.
(v) Compressed oxygen is used for welding purposes.
(vi) Compressed helium is used in airships.
(5) Joule-Thomson effect : When a real gas is allowed to expand
adiabatically through a porous plug or a fine hole into a region of low
pressure, it is accompanied by cooling (except for hydrogen and helium
which get warmed up).
Cooling takes place because some work is done to overcome the
intermolecular forces of attraction. As a result, the internal energy decreases
and so does the temperature.

(i) C p  Cv  R  2 calories 8.314 J Ideal gases do not show any cooling or heating because there are no
intermolecular forces of attraction i.e., they do not show Joule-Thomson
3 3 effect.
(ii) C v  R (for monoatomic gas) and C v   x (for di and
2 2 During Joule-Thomson effect, enthalpy of the system remains
polyatomic gas), where x varies from gas to gas. constant.
Cp
(iii)   (Ratio of molar capacities) Joule-Thomson coefficient.   (T / P)H .
Cv
(iv) For monoatomic gas Cv  3 calories whereas, For cooling,   ve (because dT and dP will be ve )
C p  Cv  R  5 calories For heating   ve (because dT  ve , dP  ve ) .
5
Cp R For no heating or cooling   0 (because dT  0) .
(v) For monoatomic gas, ( )   2  1 .66 .
Cv 3 (6) Inversion temperature : It is the temperature at which gas shows
R
2 neither cooling effect nor heating effect i.e., Joule-Thomson coefficient
7   0 . Below this temperature, it shows cooling effect and above this
Cp R
temperature, it shows heating effect.
(vi) For diatomic gas ( )   2  1 .40
Cv 5
R Any gas like H 2 , He etc, whose inversion temperature is low
2
would show heating effect at room temperature. However, if these gases are
Cp 8R
(vii) For triatomic gas ( )    1 .33 just cooled below inversion temperature and then subjected to Joule-
Cv 6R Thomson effect, they will also undergo cooling.
Liquefaction of gases
(1) A gas may be liquefied by cooling or by the application of high
pressure or by the combined effect of both. The first successful attempt for
liquefying gases was made by Faraday.
(2) Gases for which the intermolecular forces of attraction are small
such as H 2 , N 2 , Ar and O 2 , have low values of Tc and cannot be
liquefied by the application of pressure are known as “permanent gases”  If the number of molecules present in 1 c.c. of the gas or vapour
while the gases for which the intermolecular forces of attraction are large, at S.T.P., then that is called loschmidt number. Its value is 2.687
such as polar molecules NH 3 , SO 2 and H 2 O have high values of Tc  10 per c.c.
19

and can be liquefied easily.  CO > SO > SO > PCl is order of rate of diffusion.
(3) Methods of liquefaction of gases : The modern methods of cooling
2 2 3 3

the gas to or below their Tc and hence of liquefaction of gases are done by  Vapour density is independent of temperature and has no unit
while absolute density is dependent of temperature and has unit
Linde's method and Claude's method. of gm –1

(i) Linde's method : This process is based upon Joule-Thomson

effect which states that “When a gas is allowed to expand adiabatically from  The isotherms of CO were first studied by Andrews. 2

a region of high pressure to a region of extremely low pressure, it is  1 Cal = 4.2 Joule, 1 Kcal = 4200 Joule
accompained by cooling.”
(ii) Claude's method : This process is based upon the principle that  The gas which has least mean free path has maximum value of a, is
when a gas expands adiabatically against an external pressure (as a piston in easily liquefied and has maximum value of T . b

an engine), it does some external work. Since work is done by the molecules
at the cost of their kinetic energy, the temperature of the gas falls causing  T<T <T
c b i

cooling.  For critical constants, compression factor Z is < 1.

(iii) By adiabatic demagnetisation.
(4) Uses of liquefied gases : Liquefied and gases compressed under a high  Boyle’s law and Avogadro’s law are applicable under limiting
pressure are of great importance in industries. condition. This limiting condition is P  0.
(i) Liquid ammonia and liquid sulphur dioxide are used as
refrigerants.  T = 0.296 T ; T = 6.75 T
c b i c

(ii) Liquid carbon dioxide finds use in soda fountains.

 234 Gaseous State

 Mean free path increases if H is replaced by He.

2
 Gaseous State 235
(a) 1.5 lit. (b) 2.8 lit.
(c) 11.2 lit. (d) 22.4 lit.
12. Pressure of a gas in a vessel can be measured by
(a) Barometer (b) Manometer
(c) Stalgometer (d) All the baove
13. Volume occupied by a gas at one atmospheric pressure and 0 o C is
Characteristics and Measurable properties of gases V mL. Its volume at 273 K will be
[Bihar MADT 1982]
1. Which one of the following statements is not correct about the three (a) V ml (b) V/2 ml
states of matter i.e. solid, liquid and gaseous
(c) 2 V (d) None of these
(a) Molecules of a solid possess least energy whereas those of a 14. Which one of the following statements is wrong for gases
gas possess highest energy
[CBSE PMT 1999]
(b) The density of solid is highest whereas that of gases is lowest
(a) Gases do not have a definite shape and volume
(c) Gases like liquids possess definite volumes (b) Volume of the gas is equal to the volume of the container
(d) Molecules of a solid possess vibratory motion confining the gas
2. The temperature and pressure at which ice, liquid water and water (c) Confined gas exerts uniform pressure on the walls of its
vapour can exist together are container in all directions
(a) 0 o C, 1 atm (b) 2o C, 4.7 atm (d) Mass of the gas cannot be determined by weighing a container
in which it is enclosed
(c) 0 o C, 4.7 mm (d)  2o C, 4.7 mm 15. Which of the following exhibits the weakest intermolecular forces [AIIMS 2000]
3. Which of the following is true about gaseous state (a) NH 3 (b) HCl
(a) Thermal energy = Molecular attraction (c) He (d) H 2O
(b) Thermal energy >> Molecular attraction 16. N 2 is found in a litre flask under 100kPa pressure and O 2 is
(c) Thermal energy << Molecular attraction
found in another 3 litre flask under 320 kPa pressure. If the two
(d) Molecular forces >> Those in liquids
flasks are connected, the resultant pressures is
4. Kinetic energy of molecules is highest in
[Kerala PMT 2004]
(a) Gases (b) Solids (a) 310 kPa (b) 210 kPa
(c) Liquids (d) Solutions (c) 420 kPa (d) 365 kPa
5. Which of the following statement is correct (e) 265 kPa
(a) In all the three states the molecules possess random
translational motion Ideal gas equation and Related gas laws
(b) Gases cannot be converted into solids without passing through
liquid state 1. If P, V, T represent pressure, volume and temperature of the gas,
(c) One of the common property of liquids and gases is viscosity the correct representation of Boyle's law is
(d) According to Boyle's law V/P is constant at constant T [BIT Ranchi 1988]
3 1
6. A volume of 1 m is equal to (a) V (at constant P) (b) PV  RT
3 T
(a) 1000 cm (b) 100 cm 3
(c) V  1 / P (at constant T) (d) PV  nRT
(c) 10 dm 3 (d) 10 6 cm 3 2. At constant temperature, in a given mass of an ideal gas
7. Which one of the following is not a unit of pressure [CBSE PMT 1991]
(a) Newton (b) Torr (a) The ratio of pressure and volume always remains constant
(c) Pascal (d) Bar (b) Volume always remains constant
(c) Pressure always remains constant
8. 1o C rise in temperature is equal to a rise of
(d) The product of pressure and volume always remains constant
(a) 1o F (b) 9 / 5o F 3. Air at sea level is dense. This is a practical application of
(c) 5 / 9 F o
(d) 33 F o [Kerala CEE 2000]
(a) Boyle's law (b) Charle's law
9. Which of the following relations for expressing volume of a sample
is not correct (c) Avogadro's law (d) Dalton's law

(a) 1L  10 3 ml (b) 1 dm 3  1 L 4. If 20 cm 3 gas at 1 atm. is expanded to 50 cm 3 at constant T, then

what is the final pressure [CPMT 1988]
(c) 1 L  10 3 m 3 (d) 1L  10 3 cm 3 1 1
(a) 20  (b) 50 
10. One atmosphere is numerically equal to approximately 50 20
(a) 10 6 dynes cm 2 (b) 10 2 dynes cm 2 1
(c) 1  50 (d) None of these
20
(c) 10 4 dynes cm 2 (d) 10 8 dynes cm 2
5. Which of the following statement is false [BHU 1994]
o
11. 2gm of O 2 at 27 C and 760mm of Hg pressure has volume[BCECE 2005] (a) The product of pressure and volume of fixed amount of a gas
is independent of temperature
 236 Gaseous state
(b) Molecules of different gases have the same K.E. at a given (d) Curve for V1 has a greater slope than that for V2
temperature
16. Two closed vessels of equal volume containing air at pressure P1
(c) The gas equation is not valid at high pressure and low
temperature and temperature T1 are connected to each other through a narrow
(d) The gas constant per molecule is known as Boltzmann constant tube. If the temperature in one of the vessels is now maintained at
6. Which of the following graphs represent Boyle's law T1 and that in the other at T2 , what will be the pressure in the
vessels
P PV 2 P1T1 T1
(a) (b)
(a) (b) T1  T2 2 P1T2
V P 2 P1T2 2 P1
(c) (d)
PV PV T1  T2 T1  T2
17. “One gram molecule of a gas at N.T.P. occupies 22.4 litres.” This fact
(c) (d) was derived from [CPMT 1981, 1995]
V P (a) Dalton's theory
7. Densities of two gases are in the ratio 1 : 2 and their temperatures
are in the ratio 2 : 1, then the ratio of their respective pressures is[BHU 2000] (b) Avogadro's hypothesis
(c) Berzelius hypothesis
(a) 1 : 1 (b) 1 : 2
(d) Law of gaseous volume
(c) 2 : 1 (d) 4 : 1
18. In a closed flask of 5 litres, 1.0 g of H 2 is heated from 300 to 600
8. At constant pressure, the volume of fixed mass of an ideal gas is
directly proportional to [EAMCET 1985]
K. which statement is not correct [CBSE PMT 1991]
(a) Pressure of the gas increases
(a) Absolute temperature (b) Degree centigrade
(b) The rate of collision increases
(c) Degree Fahrenheit (d) None (c) The number of moles of gas increases
9. Which of the following expression at constant pressure represents (d) The energy of gaseous molecules increases
Charle's law [AFMC 1990] 19. Which one of the following statements is false
1 1 [Manipal PMT 1991]
(a) V (b) V
T T 2
(a) Avogadro number  6.02  10 21

(c) V T (d) V  d (b) The relationship between average velocity (v ) and root mean
10. Use of hot air balloons in sports and meteorological obsevations is square velocity (u) is v  0.9213 u
an application of [Kerala MEE 2002] (c) The mean kinetic energy of an ideal gas is independent of the
(a) Boyle's law (b) Newtonic law pressure of the gas
(c) Kelvin's law (d) Charle's law (d) The root mean square velocity of the gas can be calculated by
the formula (3 RT / M )1 / 2
11. A 10 g of a gas at atmospheric pressure is cooled from 273o C to
20. The compressibility of a gas is less than unity at STP. Therefore [IIT 2000]
0 o C keeping the volume constant, its pressure would become (a) Vm  22.4 litres (b) Vm  22.4 litres
(a) 1/2 atm (b) 1/273 atm
(c) Vm  22.4 litres (d) Vm  44.8 litres
(c) 2 atm (d) 273 atm
12. Pressure remaining the same, the volume of a given mass of an ideal 21. In the equation of sate of an ideal gas PV  nRT , the value of the
gas increases for every degree centigrade rise in temperature by universal gas constant would depend only on
definite fraction of its volume at [KCET 2005]
[CBSE PMT 1989] (a) The nature of the gas
(b) The pressure of the gas
(a) 0 o C (b) Its critical temperature
(c) The units of the measurement
(c) Absolute zero (d) Its Boyle temperature
(d) None of these
13. A certain sample of gas has a volume of 0.2 litre measured at 1 atm.
22. In the ideal gas equation, the gas constant R has the dimensions of[NCERT 1982
pressure and 0 o C . At the same pressure but at 273o C , its (a) mole-atm K –1
(b) litre mole
volume will be [EAMCET 1992, 93; BHU 2005] (c) litre-atm K mole –1 –1
(d) erg K –1

(a) 0.4 litres (b) 0.8 litres

23. In the equation PV  nRT , which one cannot be the numerical
(c) 27.8 litres (d) 55.6 litres
value of R [BIT 1987]
14. 400 cm 3 of oxygen at 27 o C were cooled to  3 o C without
(a) 8.31  107 erg K 1mol 1
change in pressure. The contraction in volume will be
(a) 40 cm 3 (b) 30 cm 3 (b) 8.31  107 dyne cm K 1mol 1
(c) 44.4 cm 3 (d) 360 cm 3 (c) 8.31 JK 1mol 1
15. The pressure p of a gas is plotted against its absolute temperature T
for two different constant volumes, V1 and V2 . When V1  V2 , (d) 8.31 atm. K 1mol 1
the 24. Which one of the following indicates the value of the gas constant R[EAMCET 19
(a) Curves have the same slope and do not intersect (a) 1.987 cal K mol
–1 –1
(b) 8.3 cal K mol –1 –1

(b) Curves must intersect at some point other than T  0 (c) 0.0821 lit K mol
–1 –1
(d) 1.987 Joules K mol –1 –1

(c) Curve for V2 has a greater slope than that for V1 25. The constant R is [Orissa 1990]
(a) Work done per molecule
 Gaseous State 237
(b) Work done per degree absolute 37. 16 g of oxygen and 3 g of hydrogen are mixed and kept at 760 mm
(c) Work done per degree per mole pressure and 0 o C . The total volume occupied by the mixture will
(d) Work done per mole be nearly [Vellore CMC 1991]
26. Select one correct statement. In the gas equation, PV  nRT [CBSE PMT 1992] (a) 22.4 litres (b) 33.6 litres
(a) n is the number of molecules of a gas (c) 448 litres (d) 44800 ml
(b) V denotes volume of one mole of the gas 38. Pure hydrogen sulphide is stored in a tank of 100 litre capacity at
(c) n moles of the gas have a volume V 20 o C and 2 atm pressure. The mass of the gas will be [CPMT 1989]
(d) P is the pressure of the gas when only one mole of gas is (a) 34 g (b) 340 g
present (c) 282.4 g (d) 28.24 g
27. The correct value of the gas constant R is close to 39. At N.T.P. the volume of a gas is found to be 273 ml. What will be
[CBSE PMT 1992] the volume of this gas at 600 mm Hg and 273o C
(a) 0.082 litre-atmopshere K [CPMT 1992]
(b) 0.082 litre-atmosphere K 1 mol 1 (a) 391.8 mL (b) 380 ml
(c) 691.6 ml (d) 750 ml
(c) 0.082 litre- atmosphere1 K mole 1 40. One litre of a gas weighs 2 g at 300 K and 1 atm pressure. If the
pressure is made 0.75 atm, at which of the following temperatures
(d) 0.082 litre1 atmosphere1 K mol will one litre of the same gas weigh one gram
[CBSE PMT 1992]
28. S.I. unit of gas constant R is [CPMT 1994] (a) 450 K (b) 600 K
(a) 0.0821 litre atm K mole
–1 –1 (c) 800 K (d) 900 K
(b) 2 calories K mole
–1 –1
41. A wheather balloon filled with hydrogen at 1 atm and 27 o C has
(c) 8.31 joule K mole
–1 –1 volume equal to 12000 litres. On ascending it reaches a place where
(d) None the temperature is  23o C and pressure is 0.5 atm. The volume of
the balloon is
29. Gas equation PV  nRT is obeyed by [BHU 2000]
[CBSE PMT 1991]
(a) Only isothermal process (b) Only adiabatic process (a) 24000 litres (b) 20000 litres
(c) Both (a) and (b) (d) None of these (c) 10000 litres (d) 12000 litres
30. For an ideal gas number of moles per litre in terms of its pressure P,
gas constant R and temperature T is 42. The density of a gas at 27 o C and 1 atm is d. Pressure remaining
[AIEEE 2002] constant at which of the following temperatures will its density
(a) PT/R (b) PRT become 0.75 d [CBSE PMT 1992]
(c) P/RT (d) RT/P (a) 20 o C (b) 30 o C
31. If two moles of an ideal gas at 546 K occupy a volume of 44.8 litres, (c) 400 K (d) 300 K
the pressure must be
[NCERT 1981; JIPMER 1991] 43. A sample of gas occupies 100 ml at 27 o C and 740 mm pressure.
(a) 2 atm (b) 3 atm When its volume is changed to 80 ml at 740 mm pressure, the
(c) 4 atm (d) 1 atm temperature of the gas will be
[Vellore CMC 1991]
32. How many moles of He gas occupy 22.4 litres at 30 o C and one o o
atmospheric pressure [KCET 1992] (a) 21.6 C (b) 240 C
(a) 0.90 (b) 1.11 (c)  33 C o
(d) 89.5 o C
(c) 0.11 (d) 1.0 44. The total pressure exerted by a number of non-reacting gases is
33. Volume of 0.5 mole of a gas at 1 atm. pressure and 273 K is equal to the sum of the partial pressures of the gases under the
[EAMCET 1992] same conditions is known as [CPMT 1986]
(a) 22.4 litres (b) 11.2 litres (a) Boyle's law (b) Charle's law
(c) 44.8 litres (d) 5.6 litres (c) Avogadro's law (d) Dalton's law
34. At 0 o C and one atm pressure, a gas occupies 100 cc. If the 45. “Equal volumes of all gases at the same temperature and pressure
pressure is increased to one and a half-time and temperature is contain equal number of particles.” This statement is a direct
increased by one-third of absolute temperature, then final volume of consequence of [Kerala MEE 2002]
the gas will be (a) Avogadro’s law (b) Charle's law
[DCE 2000] (c) Ideal gas equation (d) Law of partial pressure
(a) 80 cc (b) 88.9 cc 46. If three unreactive gases having partial pressures PA , PB and PC
(c) 66.7 cc (d) 100 cc and their moles are 1, 2 and 3 respectively then their total pressure
35. Correct gas equation is [CBSE PMT 1989; CPMT 1991] will be [CPMT 1994]
(a)
V1T2 V2 T1
 (b)
P1V1 T
 1 PA  PB  PC
P1 P2 P2 V2 T2 (a) P  PA  PB  PC (b) P 
6
P1T2 P2 V2 V1V2 PA  PB  PC
(c)  (d)  P1 P2
V1 T2 T1T2 (c) P (d) None
3
36. Two separate bulbs contain ideal gases A and B. The density of gas 47. Dalton's law of partial pressure will not apply to which of the
A is twice that of gas B. The molecular mass of A is half that of gas following mixture of gases [Bihar MADT 1981]
B. The two gases are at the same temperature. The ratio of the
pressure of A to that of gas B is (a) H 2 and SO 2 (b) H 2 and Cl 2
[BHU 1994] (c) H 2 and CO 2 (d) CO 2 and Cl 2
(a) 2 (b) 1/2
(c) 4 (d) 1/4
 238 Gaseous state
48. Which of the following mixtures of gases does not obey Dalton's law (a) 4 (b) 1/4
of partial pressure (c) 16 (d) 1/16
[CBSE PMT 1996: Kerala PMT 2000] 60. If rate of diffusion of A is 5 times that of B, what will be the density
(a) O 2 and CO 2 (b) N 2 and O 2 ratio of A and B [AFMC 1994]
(a) 1/25 (b) 1/5
(c) Cl 2 and O 2 (d) NH 3 and HCl
(c) 25 (d) 4
49. To which of the following gaseous mixtures is Dalton's law not 61. The densities of two gases are in the ratio of 1 : 16. The ratio of their
applicable rates of diffusion is [CPMT 1995]
(a) Ne  He  SO 2 (b) NH 3  HCl  HBr (a) 16 : 1 (b) 4 : 1
(c) O2  N 2  CO 2 (d) N 2  H 2  O2 (c) 1 : 4 (d) 1 : 16
50. Equal amounts of two gases of molecular weight 4 and 40 are 62. At constant volume and temperature conditions, the rate of diffusion
mixed. The pressure of the mixture is 1.1 atm. The partial pressure of D A and DB of gases A and B having densities  A and  B are
the light gas in this mixture is related by the expression [IIT 1993]
[CBSE PMT 1991] 1/2 1/2
(a) 0.55 atm (b) 0.11 atm      
(c) 1 atm (d) 0.12 atm (a) DA   DB  A  (b) DA   DB  B 
 B    A
51. Rate of diffusion of a gas is [IIT 1985; CPMT 1987]
1/2 1/2
(a) Directly proportional to its density    
(c) DA  DB  A  (d) DA  DB  B 
 B   A 
(b) Directly proportional to its molecular mass
(c) Directly proportional to the square root of its molecular mass
63. Atmolysis is a process of
(d) Inversely proportional to the square root of its molecular mass (a) Atomising gas molecules
52. Which of the following gas will have highest rate of diffusion (b) The breaking of atoms to sub-atomic particles
[Pb. CET Sample paper 1993; CPMT 1990] (c) Separation of gases from their gaseous mixture
(a) NH 3 (b) N2 (d) Changing of liquids to their vapour state
64. A bottle of ammonia and a bottle of dry hydrogen chloride
(c) CO 2 (d) O2 connected through a long tube are opened simultaneously at both
53. Which of the following relationship is correct, where r is the rate of ends, the white ammonium chloride ring first formed will be[IIT 1988]
diffusion of a gas and d is its density [CPMT 1994] (a) At the centre of the tube
(b) Near the hydrogen chloride bottle
(a) r  1/d (b) r  d
(c) Near the ammonia bottle
(c) r  d (d) r  d (d) Throughout the length of the tube
54. According to Grahman's law at a given temperature, the ratio of the 65. Which of the following pairs will diffuse at the same rate through a
rates of diffusion rA / rB of gases A and B is given by [IIT 1998] porous plug [EAMCET 1990]
(a) CO, NO 2 (b) NO 2 , CO 2
(a) (PA / PB )(M A / M B )1 / 2
(c) NH 3 , PH3 (d) NO C2 H 6
(b) (M A / M B )(PA / PB )1 / 2 66. If 4 g of oxygen diffuse through a very narrow hole, how much
hydrogen would have diffused under identical conditions [CPMT 1971]
(c) (PA / PB )(M B / M A )1 / 2 (a) 16 g (b) 1 g
1/ 2 (c) 1/4 g (d) 64 g
(d) (M A / M B )(PB / PA )
67. A gas diffuse at a rate which is twice that of another gas B. The
(where P and M are the pressures and molecular weights of gases A ratio of molecular weights of A to B is [EAMCET 1986]
and B respectively) (a) 1.0 (b) 0.75
55. The ratio of the rate of diffusion of a given element to that of (c) 0.50 (d) 0.25
helium is 1.4. The molecular weight of the element is 68. Two grams of hydrogen diffuse from a container in 10 minutes. How
[Kerala PMT 1990] many grams of oxygen would diffuse through the same container in
(a) 2 (b) 4 the same time under similar conditions [MNR 1980]
(c) 8 (d) 16 (a) 0.5 g (b) 4 g
56. g
A gas diffuse 1/5 times as fast as hydrogen. Its molecular weight is[CPMT 1992; Bihar(c)CEE61982] (d) 8 g
(a) 50 (b) 25 69. The rate of diffusion of methane at a given temperature is twice that
of X. The molecular weight of X is
(c) 25 2 (d) 50 2 [MNR 1995; Kerala CEE 2001]
57. The molecular weight of a gas which diffuses through a porous plug (a) 64.0 (b) 32.0
at 1/6th of the speed of hydrogen under identical conditions is[EAMCET 1990] (c) 40.0 (d) 80.0
(a) 27 (b) 72 70. X ml of H 2 gas effuses through a hole in a container in 5 seconds.
(c) 36 (d) 48 The time taken for the effusion of the same volume of the gas
58. Molecular weight of a gas that diffuses twice as rapidly as the gas specified below under identical condition is
with molecular weight 64 is [EAMCET 1994] [IIT 1996]
(a) 16 (b) 8 (a) 10 seconds : He (b) 20 seconds : O 2
(c) 64 (d) 6.4 (c) 25 seconds : CO (d) 55 seconds : CO 2
59. The densities of hydrogen and oxygen are 0.09 and 1.44 g L1 . If 71. At what temperature, the rate of effusion of N 2 would be 1.625
the rate of diffusion of hydrogen is 1 then that of oxygen in the same
units will be [RPMT 1994] times that of SO 2 at 50 o C [CBSE PMT 1996]
 Gaseous State 239
(a) 110 K (b) 173 K 83. A closed vessel contains equal number of nitrogen and oxygen
(c) 373 K (d) 273 K molecules at a pressure of P mm. If nitrogen is removed from the
system then the pressure will be
72. Given the reaction C(s)  H 2O(l)  CO(g)  H 2 (g) calculate the
[MP PMT 1985]
volume of the gases produced at STP from 48.0 g of carbon
(a) P (b) 2P
(a) 179.2 L (b) 89.6 L
(c) 44.8 L (d) 22.4 L (c) P / 2 (d) P 2
73. 4.4 g of a gas at STP occupies a volume of 2.24 L, the gas can be[Haryana CEET
84. 2000]
If the four tubes of a car are filled to the same pressure with
(a) O 2 (b) CO N 2 , O2 , H 2 and Ne separately, then which one will be filled first[Manipal PMT
(c) NO 2 (d) CO 2 (a) N2 (b) O 2
74. Under what conditions will a pure sample of an ideal gas not only (c) H2 (d) Ne
exhibit a pressure of 1 atm but also a concentration of 1 mole
85. Which of the following gas mixture is not applicable for Dalton’s law
litre 1 of partial pressure [Pb. CET 2002]
(R  0.082 litreatm mol 1 deg 1 ) [CBSE PMT 1993] (a) SO 2 and Cl 2 (b) CO 2 and N 2
(a) At STP
(c) CO and CO 2 (d) CO and N 2
(b) When V  22.4 litres
86. At what pressure a quantity of gas will occupy a volume of 60 ml ,
(c) When T  12 K
if it occupies a volume of 100ml at a pressure of 720mm ?
(d) Impossible under any conditions (while temperature is constant) : [Pb. CET 2000]
75. There are 6.02  10 22 molecules each of N 2 , O2 and H 2 which (a) 700 mm (b) 800 mm
are mixed together at 760 mm and 273 K. The mass of the mixture (c) 100 mm (d) 1200 mm
in grams is [Pb. PMT 1997]
(a) 6.2 (b) 4.12 87. At constant temperature and pressure which gas will diffuse first
(c) 3.09 (d) 7 H 2 or O 2 ? [Pb. CET 2000]
76. Volume of 4.4 g of CO 2 at NTP is [Pb. CET 1997] (a) Hydrogen
(a) 22.4 L (b) 44.8 L (b) Oxygen
(c) 2.24 L (d) 4.48 L (c) Both will diffuse in same time
77. The energy of an ideal gas depends only on its (d) None of the above
(a) Pressure (b) Volume 88. When a jar containing gaseous mixture of equal volumes of CO 2
(c) Number of moles (d) Temperature and H 2 is placed in a solution of sodium hydroxide, the solution
78. A bottle of cold drink contains 200 ml liquid in which CO 2 is 0.1 level will [Pb. CET 2001]
molar. Suppose CO 2 behaves like an ideal gas, the volume of the (a) Rise (b) Fall
dissolved CO 2 at STP is [CBSE PMT 1991] (c) Remain constant (d) Become zero
(a) 0.224 litre (b) 0.448 litre 89. At S.T.P. 1g CaCO 3 on decomposition gives CO 2
(c) 22.4 litre (d) 2.24 litre [Pb. CET 2000]
79. The vapour density of a gas is 11.2. The volume occupied by 11.2 g of (a) 22.4 litre (b) 2.24 litre
this gas at N.T.P. is (c) 0.224 litre (d) 11.2 litre
[MNR 1982; CBSE PMT 1991] 90. At NTP, the density of a gas, whose molecular weight is 45 is
(a) 1 L (b) 11.2 L [Pb. CET 2001, 03]
(c) 22.4 L (d) 20 L (a) 44.8 gm/litre (b) 11.4 gm/litre
80. A pre-weighed vessel was filled with oxygen at N.T.P. and weighted. (c) 2 gm/ litre (d) 3 gm/litre
It was then evacuated, filled with SO 2 at the same temperature 91. What is the ratio of diffusion rate of oxygen and hydrogen
and pressure, and again weighted. The weight of oxygen will be[NCERT 1989] [Pb. CET 2003]
(a) 1 : 4 (b) 4 : 1
(a) The same as that of SO 2
(c) 1 : 8 (d) 8 : 1
1 92. The maximum number of molecules is present in
(b) that of SO 2
2 [CBSE PMT 2004]
(a) 0.5 g of H 2 gas (b) 10 g of O 2 gas
(c) Twice that of SO 2
(c) 15 L of H 2 gas at STP (d) 5 L of N 2 gas at STP
(d) One fourth that of SO 2
93. One litre oxygen gas at STP will weigh [Pb. CET 2004]
81. Five grams each of the following gases at 87 o C and 750 mm (a) 1.43 g (b) 2.24 g
pressure are taken. Which of them will have the least volume[MNR 1991] (c) 11.2 g (d) 22.4 g
(a) HF (b) HCl 94. How will you separate mixture of two gases [AFMC 2004]
(c) HBr (d) HI (a) Fractional distillation technique
82. Who among the following scientists has not done any important (b) Grahams law of diffusion technique
work on gases [Bihar MADT 1980] (c) Osmosis
(d) Chromatography
(a) Boyle (b) Charles
95. The rate of diffusion of hydrogen gas is
(c) Avogadro (d) Faraday [MH CET 2003; Pb. CET 2000]
(a) 1.4 times to He gas (b) Same as He gas
 240 Gaseous state
(c) 5 times to He gas (d) 2 times to He gas
96. Hydrogen diffuses six times faster than gas A . The molar mass of 1. Postulate of kinetic theory is [EAMCET 1980]
gas A is [KCET 2004] (a) Atom is indivisible
(a) 72 (b) 6 (b) Gases combine in a simple ratio
(c) 24 (d) 36 (c) There is no influence of gravity on the molecules of a gas
97. At what pressure will a quantity of gas, which occupies 100 ml at (d) None of the above
2. According to kinetic theory of gases, [EAMCET 1980]
a pressue of 720 mm , occupy a volume of 84 ml [DPMT 2004]
(a) There are intermolecular attractions
(a) 736.18 mm (b) 820.20 mm
(b) Molecules have considerable volume
(c) 784.15 mm (d) 857.14 mm
(c) No intermolecular attractions
98. Containers A and B have same gases. Pressure, volume and
(d) The velocity of molecules decreases after each collision
temperature of A are all twice that of B, then the ratio of
3. In deriving the kinetic gas equation, use is made of the root mean
number of molecules of A and B are [AFMC 2004] square velocity of the molecules because it is
(a) 1 : 2 (b) 2 [Bihar MADT 1980]
(c) 1 : 4 (d) 4 (a) The average velocity of the molecules
99. A mixture of NO 2 and N 2 O4 has a vapour density of 38.3 at (b) The most probable velocity of the molecules
300 K . What is the number of moles of NO 2 in 100 g of the (c) The square root of the average square velocity of the molecules
mixture [Kerala PMT 2004] (d) The most accurate form in which velocity can be used in these
(a) 0.043 (b) 4.4 calculations
(c) 3.4 (d) 3.86 4. Kinetic energy of a gas depends upon its[Bihar MADT 1982]
(e) 0.437 (a) Molecular mass (b) Atomic mass
100. A cylinder of 5 litres capacity, filled with air at NTP is connected (c) Equivalent mass (d) None of these
with another evacuated cylinder of 30 litres of capacity. The
resultant air pressure in both the cylinders will be [BHU 2004]
5. The kinetic theory of gases perdicts that total kinetic energy of a
(a) 10.8 cm of Hg (b) 14.9cm of Hg gaseous assembly depends on [NCERT 1984]
(c) 21.8 cm of Hg (d) 38.8 cm of Hg (a) Pressure of the gas
101. A certain mass of gas occupies a volume of 300 c.c. at 27 C and 620 (b) Temperature of the gas
mm pressure. The volume of this gas at 47 o C and 640 mm (c) Volume of the gas
pressure will be [MH CET 2003] (d) Pressure, volume and temperature of the gas
(a) 400 c.c. (b) 510 c.c. 6. According to kinetic theory of gases, the energy per mole of a gas is
(c) 310 c.c. (d) 350 c.c. equal to [EAMCET 1985]
102. What will be the volume of the mixture after the reaction? (a) 1.5 RT (b) RT
NH 3  HCl  NH 4 Cl [BVP 2004] (c) 0.5 RT (d) 2.5 RT
1.5 litre
4 litre (solid) 7. Internal energy and pressure of a gas per unit volume are related as[CBSE PMT
(a) 0.5 litre (b) 1 litre 2 3
(c) 2.5 litre (d) 0.1 litre (a) P  E (b) P  E
3 2
103. The pressure and temperature of 4dm 3 of carbon dioxide gas are
doubled. Then the volume of carbon dioxide gas would be[KCET 2004] 1
(c) P  E (d) P  2 E
(a) 2 dm 3 (b) 3dm 3 2
8. The translational kinetic energy of an ideal gas depends only on its
(c) 4 dm 3 (d) 8 dm 3 (a) Pressure (b) Force
104. If the absolute temperature of an ideal gas become double and (c) Temperature (d) Molar mass
pressure become half, the volume of gas would be 9. Helium atom is two times heavier than a hydrogen molecule at 298
[Kerala CET 2005] K, the average kinetic energy of helium is [IIT 1982]
(a) Remain unchange (b) Will be double (a) Two times that of a hydrogen molecule
(c) Will be four time (d) will be half (b) Same as that of a hydrogen molecule
(e) Will be one fourth (c) Four times that of a hydrogen molecule
105. At what temperature, the sample of neon gas would be heated to (d) Half that of a hydrogen molecule
double of its pressure, if the initial volume of gas is/are reduced to 10. Which of the following is valid at absolute zero
[Pb. CET 1985]
15% at 75 o C [Kerala CET 2005]
(a) Kinetic energy of the gas becomes zero but the molecular
o o
(a) 319 C (b) 592 C motion does not become zero
(c) 128 C o
(d) 60 o C (b) Kinetic energy of the gas becomes zero and molecular motion
also becomes zero
(e) 90 o C (c) Kinetic energy of the gas decreases but does not become zero
106. Equation of Boyle's law is [DPMT 2005] (d) None of the above
dP dV dP dV 11. The average K.E. of an ideal gas in calories per mole is
(a)  (b)  approximately equal to [EAMCET 1989]
p V P V
(a) Three times the absolute temperature
d2P dV d2P d 2V (b) Absolute temperature
(c)  (d)  (c) Two times the absolute temperature
P dT P dT
(d) 1.5 times the absolute temperature
12. According to kinetic theory of gases, for a diatomic molecule
Kinetic molecular theory of gases and [MNR 1991]
Molecular collisions
 Gaseous State 241
(a) The pressure exerted by the gas is proportional to the mean (a) 298 K (b) 273 K
velocity of the molecules (c) 193 K (d) 173 K
(b) The pressure exerted by the gas is proportional to the root 21. Ratio of C p and Cv of a gas 'X' is 1.4. The number of atoms of the
mean square velocity of the molecules
(c) The root mean square velocity is inversely proportional to the gas 'X' present in 11.2 litres of it at N.T.P. is
temperature [CBSE PMT 1989]
(d) The mean translational kinetic energy of the molecules is (a) 6.02  10 23
(b) 1.2  10 24
proportional to the absolute temperature
(c) 3.01  10 23
(d) 2.01  10 23
13. At STP, 0.50 mol H 2 gas and 1.0 mol He gas
22. The density of air is 0.00130 g/ml. The vapour density of air will be[DCE 2000]
[CBSE PMT 1993, 2000]
(a) 0.00065 (b) 0.65
(a) Have equal average kinetic energies
(c) 14.4816 (d) 14.56
(b) Have equal molecular speeds
(c) Occupy equal volumes 23. At 100 o C and 1 atm, if the density of liquid water is 1.0 g cm 3
(d) Have equal effusion rates and that of water vapour is 0.0006 g m 3 , then the volume
14. Which of the following expressions correctly represents the occupied by water molecules in 1 litre of steam at that temperature
relationship between the average molar kinetic energy, K.E. , of CO is [IIT 2000]
and N 2 molecules at the same temperature (a) 6 cm 3 (b) 60 cm 3
[CBSE PMT 2000]
(c) 0.6 cm 3 (d) 0.06 cm 3
(a) KE CO  KE N 2
24. The ratio  for inert gases is [AFMC 1990]
(b) KE CO  KE N 2 (a) 1.33 (b) 1.66
(c) 2.13 (d) 1.99
(c) KE CO  KE N 2 25. The density of neon will be highest at [CBSE PMT 1990]
(d) Cannot be predicted unless the volumes of the gases are given
(a) S.T.P. (b) 0 o C, 2 atm
15. Indicate the correct statement for a 1-L sample of N 2 (g) and
CO 2 (g) at 298 K and 1 atm pressure (c) 273o C, 1 atm (d) 273o C, 2 atm
26. Absolute zero is defined as the temperature
(a) The average translational KE per molecule is the same in N 2
[CBSE PMT 1990]
and CO 2 (a) At which all molecular motion ceases
(b) The rms speed remains constant for both N 2 and CO 2 (b) At which liquid helium boils
(c) At which ether boils
(c) The density of N 2 is less than that of CO 2
(d) All of the above
(d) The total translational KE of both N 2 and CO 2 is the same 27. Consider the following statements :
16. With increase of pressure, the mean free path (1) Joule-Thomson experiment is isoenthalpic as well as adiabatic.
[Pb. CET 1985] (2) A negative value of  JT (Joule Thomson coefficient
(a) Decreases (b) Increases corresponds to warming of a gas on expansion.
(c) Does not change (d) Becomes zero (3) The temperature at which neither cooling nor heating effect is
17. Which one of the following statements is NOT true about the effect observed is known as inversion temperature.
of an increase in temperature on the distribution of molecular Which of the above statements are correct
speeds in a gas [AIEEE 2005] (a) 1 and 2 (b) 1 and 3
(a) The most probable speed increases (c) 2 and 3 (d) 1, 2 and 3
(b) The fraction of the molecules with the most probable speed 28. Vibrational energy is [Pb. CET 1985]
increases (a) Partially potential and partially kinetic
(c) The distribution becomes broader (b) Only potential
(d) The area under the distribution curve remains the same as (c) Only kinetic
under the lower temperature (d) None of the above
18. If P, V, M, T and R are pressure, volume, molar mass, temperature 29. At the same temperature and pressure, which of the following gases
and gas constant respectively, then for an ideal gas, the density is will have the highest kinetic energy per mole
given by [CBSE PMT 1989, 91] [MNR 1991]
RT P (a) Hydrogen (b) Oxygen
(a) (b) (c) Methane (d) All the same
PM RT
30. Dimensions of pressure are the same as that of
M PM [CBSE PMT 1995]
(c) (d)
V RT (a) Energy (b) Force
19. An ideal gas will have maximum density when [CPMT 2000] (c) Energy per unit volume (d) Force per unit volume
(a) P  0.5 atm, T  600 K 31. The density of a gas An is three times that of a gas B. if the
molecular mass of A is M, the molecular mass of B is
(b) P  2 atm, T  150 K [CPMT 1987]
(c) P  1 atm, T  300 K
(a) 3 M (b) 3M
(d) P  1.0 atm, T  500 K
(c) M /3 (d) M/ 3
20. If the inversion temperature of a gas is  80 o C , then it will
produce cooling under Joule-Thomson effect at Molecular speeds
 242 Gaseous state

1. The ratio of root mean square velocity to average velocity of gas 3P 3 PV

(a) (b)
molecules at a particular temperature is [IIT 1981] d M
(a) 1.086 : 1 (b) 1 : 1.086
3 RT
(c) 2 : 1.086 (d) 1.086 : 2 (c) (d) All the above
2. Which is not true in case of an ideal gas [CBSE PMT 1991]
M
(a) It cannot be converted into a liquid 12. Root mean square velocity of a gas molecule is proportional to[CBSE PMT 1990]
(b) There is no interaction between the molecules (a) m1 / 2 (b) m 0
(c) All molecules of the gas move with same speed (c) m 1 / 2 (d) m
(d) At a given temperature, PV is proportional to the amount of 13. At constant volume, for a fixed number of moles of a gas, the
the gas pressure of the gas increases with increase in temperature due to[IIT 1992]
3. The ratio among most probable velocity, mean velocity and root (a) Increase in the average molecular speed
mean square velocity is given by [CBSE PMT 1993] (b) Increased rate of collision amongst molecules
(c) Increase in molecular attraction
(a) 1 : 2 : 3 (b) 1 : 2 : 3 (d) Decrease in mean free path
14. Molecular velocities of the two gases at the same temperature are
(c) 2 : 3 : 8 / (d) 2 : 8 / : 3
u1 and u 2 . Their masses are m1 and m 2 respectively. Which of
4. Which of the following has maximum root mean square velocity at
the following expressions is correct
the same temperature [Manipal PMT 2002]
[BHU 1994]
(a) SO 2 (b) CO 2 m1 m2
(a)  (b) m1u1  m 2u2
(c) O2 (d) H2 u12 u 22
5. The temperature at which RMS velocity of SO 2 molecules is half m1 m 2
(c)  (d) m1u12  m 2u22
that of He molecules at 300 K is [NTSE 1991] u1 u2
(a) 150 K (b) 600 K 15. The temperature of the gas is raised from 27 o C to 927 o C , the
(c) 900 K (d) 1200 K root mean square velocity is [CBSE PMT 1994]
6. At 27 o C , the ratio of rms velocities of ozone to oxygen is (a) 927 / 27 times the earlier value
[EAMCET 1992] (b) Same as before
(c) Halved
(a) 3/5 (b) 4/3 (d) Doubled
16. The ratio between the root mean square velocity of H at 50 K and
(c) 2/3 (d) 0.25 2

that of O 2 at 800 K is [IIT 1996]

7. The average kinetic energy of an ideal gas per molecule in SI units at
(a) 4 (b) 2
25 o C will be [CBSE PMT 1996] (c) 1 (d) 1/4
21 21 17. The root mean square velocity of an ideal gas at constant pressure
(a) 6.17  10 kJ (b) 6.17  10 J varies density (d) as [IIT 2000]
(c) 6.17  10 20 J (d) 7.16  10 20 J (a) d2 (b) d
8. At what temperature the RMS velocity of SO 2 be same as that of (c) d (d) 1 / d
18. Consider a mixture of SO 2 and O 2 kept at room temperature.
O 2 at 303 K [KCET 2001]
Compared to the oxygen molecule, the SO 2 molecule will hit the
(a) 273 K (b) 606 K
wall with
(c) 303 K (d) 403 K (a) Smaller average speed (b) Greater average speed
9. Among the following gases which one has the lowest root mean (c) Greater kinetic energy (d) Greater mass
square velocity at 25 o C [EAMCET 1983] 19. The rms speed of N 2 molecules in a gas is u. If the temperature is
(a) SO 2 (b) N2 doubled and the nitrogen molecules dissociate into nitrogen atoms,
the rms speed becomes
(c) O2 (d) Cl 2 (a) u / 2 (b) 2u
10. The root mean square velocity of an ideal gas in a closed container (c) 4u (d) 14u
20. Choose the correct arrangement, where the symbols have their usual
of fixed volume is increased from 5  10 4 cm s 1 to meanings
10  10 4 cm s 1 . Which of the following statement correctly (a) u  u p  urms (b) urms  u  u p
explains how the change is accomplished (c) u p  u  urms (d) u p  urms  u
[Pb. CET 1986] 21. The ratio of most probable velocity to that of average velocity is [JEE Orissa 200
(a) By heating the gas, the temperature is doubled (a)  / 2 (b) 2 / 
(b) By heating the gas, the pressure is quadrupled (i.e. made four
times) (c)  /2 (d) 2 / 
(c) By heating the gas, the temperature is quadrupled 22. The r.m.s. velocity of a certain gas is v at 300 K . The
(d) By heating the gas, the pressure is doubled temperature, at which the r.m.s. velocity becomes double
[Pb. CET 2002]
11. The rms velocity at NTP of the species can be calculated from the
expression [EAMCET 1990] (a) 1200 K (b) 900 K
(c) 600 K (d) 150 K
23. The r.m.s. velocity of a gas depends upon [DCE 2002]
(a) Temperature only
 Gaseous State 243
(b) Molecular mass only
(b) 100 o C and 2 atmospheric pressure
(c) Temperature and molecular mass of gas
(d) None of these (c)  100 o C and 5 atmospheric pressure
24. What is the pressure of 2 mole of NH 3 at 27 o C when its (d) 500 o C and 1 atmospheric pressure
volume is 5 litre in vander Waal’s equation (a = 4.17, b = 0.03711)[JEE Orissa7.2004] The temperature at which the second virial coefficient of real gas is
(a) 10.33 atm (b) 9.33 atm zero is called [AFMC 1993]
(c) 9.74 atm (d) 9.2 atm
25. The root mean square velocity of one mole of a monoatomic having (a) Critical temperature
(b) Eutetic point
molar mass M is U rms . The relation between the average kinetic
(c) Boiling point
energy (E) of the U rms is (d) Boyle's temperature
[IIT-JEE Screening 2004] 8. When is deviation more in the behaviour of a gas from the ideal gas
3E 2E equation PV  nRT
(a) U rms  (b) U rms 
2M 3M [DPMT 1981; NCERT 1982; CBSE PMT 1993]
(a) At high temperature and low pressure
2E E
(c) U rms  (d) U rms  (b) At low temperature and high pressure
M 3M (c) At high temperature and high pressure
26. Ratio of average to most probable velocity is (d) At low temperature and low high pressure
[Orissa JEE 2005]
(a) 1.128 (b) 1.224 9. Vander Waal's constants 'a' and 'b' are related with..... respectively[RPMT 1994]
(c) 1.0 (d) 1.112 (a) Attractive force and bond energy of molecules
(b) Volume and repulsive force of molecules
27. If the vrms is 30R1 / 2 at 27 o C then calculate the molar mass of
(c) Shape and repulsive forces of molecules
gas in kilogram. [DPMT 2005]
(a) 1 (b) 2 (d) Attractive force and volume of the molecules
(c) 4 (d) 0.001 10. Gas deviates from ideal gas nature because molecules
[CPMT 1996]
Real gases and Vander waal’s equation (a) Are colourless
(b) Attract each other
1. The Vander Waal's equation explains the behaviour of (c) Contain covalent bond
[DPMT 1981] (d) Show Brownian movement
(a) Ideal gases (b) Real gases 11. The Vander Waal's equation reduces itself to the ideal gas equation
(c) Vapour (d) Non-real gases at [Kerala MEE 2001; CBSE PMT 2002]
2. Gases deviate from the ideal gas behaviour because their molecules[NCERT 1981]
(a) Possess negligible volume (a) High pressure and low temperature
(b) Have forces of attraction between them (b) Low pressure and low temperature
(c) Are polyatomic (c) Low pressure and high temperature
(d) Are not attracted to one another (d) High pressure and high temperature
3. The compressibility factor of a gas is defined as Z  PV / RT . The 12. The compressibility factor for an ideal gas is [IIT 1997]
compressibility factor of ideal gas is (a) 1.5 (b) 1.0
[Pb. CET 1986]
(a) 0 (b) Infinity (c) 2.0 (d) 
(c) 1 (d) –1 13. When an ideal gas undergoes unrestrained expansion, no cooling
4. In Vander Waal's equation of state for a non-ideal gas, the term that occurs because the molecules [IIT 1984, 89]
accounts for intermolecular forces is (a) Are above the inversion temperature
[CBSE PMT 1990; IIT 1988] (b) Exert no attractive force on each other
(a) (V  b) (b) (RT )1 (c) Do work equal to loss in kinetic energy
 a  (d) Collide without loss of energy
(c) P  2  (d) RT 14. A gas is said to behave like an ideal gas when the relation
 V 
PV / T  constant . When do you expect a real gas to behave like
5. Vander Waal's equation of state is obeyed by real gases. For n moles
of a real gas, the expression will be an ideal gas
[IIT 1992; Pb. CET 1986; DPMT 1986] [IIT 1999; CBSE PMT 1990; CPMT 1991]
 P na   V  (a) When the temperature is low
(a)   2    RT (b) When both the temperature and pressure are low
n V  n b 
(c) When both the temperature and pressure are high
 a 
(b)  P  2  (V  b)  nRT (d) When the temperature is high and pressure is low
 V  15. A real gas most closely approaches the behaviour of an ideal gas at[KCET 1992]
 na  (a) 15 atm and 200 K (b) 1 atm and 273 K
(c)  P  2  (nV  b)  nRT
 V  (c) 0.5 atm and 500 K (d) 15 atm and 500 K
 n 2a  16. The temperature at which real gases obey the ideal gas laws over a
(d)  P  2  (V  nb)  nRT wide range of pressure is called
 V 
 [AFMC 1993; IIT 1981, 94]
6. Any gas shows maximum deviation from ideal gas at (a) Critical temperature
[CPMT 1991] (b) Boyle temperature
(a) 0 o C and 1 atmospheric pressure (c) Inversion temperature
 244 Gaseous state
(d) Reduced temperature (b) Its molecules are relatively smaller in size
17. At low pressure, the Vander Waal's equation is reduced to (c) It solidifies before becoming a liquid
(d) Forces operative between its molecules are negligible
pVm ap pVm b
(a) Z 1 (b) Z 1 p 4. However great the pressure, a gas cannot be liquefied above its
RT RT RT RT
(a) Boyle temperature
pVm a (b) Inversion temperature
(c) pVm  RT (d) Z 1
RT RT (c) Critical temperature
18. At high temperature and low pressure, the Vander Waal's equation (d) Room temperature
is reduced to 5. An ideal gas obeying kinetic theory of gases can be liquefied if[CBSE PMT 1995]
  (a) Its temperature is more than critical temperature Tc
(a)  p  a  (Vm )  RT
 2 (b) Its pressure is more than critical pressure Pc
 Vm 
(c) Its pressure is more than Pc at a temperature less than Tc
(b) pVm  RT
(d) It cannot be liquefied at any value of P and T
(c) p(Vm  b)  RT 6. The Vander Waal's parameters for gases W, X, Y and Z are
Gas a (atm L mol )
2 –2
b (L mol ) –1–11–1–14545454

 a 
(d)  p  2  (Vm  b)  RT W 4.0 0.027
 Vm 
 X 8.0 0.030
Y 6.0 0.032
19. When helium is allowed to expand into vacuum, heating effect is
observed. Its reason is that [CPMT 1987]
Z 12.0 0.027
Which one of these gases has the highest critical temperature
(a) Helium is an ideal gas
(a) W (b) X
(b) Helium is an inert gas (c) Y (d) Z
(c) The inversion temperature of helium is very low 7. The Vander Waal's constant 'a' for the gases O2 , N 2 , NH 3 and
(d) The boiling point of helium is the lowest among the elements
CH 4 are 1.3, 1.390, 4.170 and 2.253 L2 atm mol 2 respectively.
20. In van der Waal’s equation of state of the gas law, the constant ‘ b ’ The gas which can be most easily liquefied is
is a measure of [AIEEE 2004] [IIT 1989]
(a) Volume occupied by the molecules (a) O2 (b) N2
(b) Intermolecular attraction (c) NH 3 (d) CH 4
(c) Intermolecular repulsions 8. A gas can be liquefied [AFMC 2005]
(d) Intermolecular collisions per unit volume (a) Above its critical temperature
21. In which molecule the vander Waal’s force is likely to be the most (b) At its critical temperature
important in determining the m.pt. and b.pt. (c) Below its critical temperature
(d) At any temperature
[DPMT 2000]
9. Which of the following is correct for critical temperature
(a) H2S (b) Br2 (a) It is the highest temperature at which liquid and vapour can
coexist
(c) HCl (d) CO (b) Beyond the critical temperature, there is no distinction between
22. Pressure exerted by 1 mole of methane in a 0.25 litre container at the two phases and a gas cannot be liquefied by compression
300K using vander Waal's equation (given (c) At critical temperature (Tc ) the surface tension of the system
1  2.253 atml 2 mol 2 , b  0.0428 litmol 1 ) is is zero
[Orissa JEE 2005] (d) At critical temperature the gas and the liquid phases have
different critical densities
(a) 82.82 atm (b) 152.51 atm
10. A gas has a density of 2.68 g / L at stp. Identify the gas
(c) 190.52 atm (d) 70.52 atm
(a) NO 2 (b) Kr
Critical state and Liquefaction of gases (c) COS (d) SO 2
11. Weight of 112 ml of oxygen at NTP on liquefaction would be[DPMT 1984]
1. Which set of conditions represents easiest way to liquefy a gas[NCERT 1983] (a) 0.32 g (b) 0.64 g
(a) Low temperature and high pressure (c) 0.16 g (d) 0.96 g
(b) High temperature and low pressure
(c) Low temperature and low pressure
(d) High temperature and high pressure
2. Adiabatic demagnetisation is a technique used for
[BHU 1984]
(a) Adiabatic expansion of a gas
(b) Production of low temperature
(c) Production of high temperature 1. As the temperature is raised from 20 o C to 40 o C the average
kinetic energy of neon atoms changes by a factor of which of the
(d) None following [AIEEE 2004]
3. An ideal gas can't be liquefied because [CBSE PMT 1992]
o (a) 313/293 (b) (313 / 293)
(a) Its critical temperature is always above 0 C
 Gaseous State 245
(c) 1/2 (d) 2 11. If C1, C2 , C3 ...... represent the speeds of n1, n2 , n3 ..... molecules,
2. A gas is found to have a formula [CO] x . If its vapour density is 70, then the root mean square speed is [IIT 1993]
the value of x is [DCE 2004] 1/2
 n1C12  n2 C 22  n3 C32  ..... 
(a) 2.5 (b) 3.0 (a)  
(c) 5.0 (d) 6.0  n1  n2  n3  ..... 
 
3. Which of the given sets of temperature and pressure will cause a gas
to exhibit the greatest deviation from ideal gas behavior [DCE 2003] (n1C12  n2C22  n3 C32  .....) 1 / 2
(b)
n1  n2  n3  .....
(a) 100 o C and 4 atm (b) 100 o C and 2 atm
(c)  100 o C and 4 atm (d) 0 o C and 2 atm (n1C12 )1 / 2 (n2C22 )1 / 2 (n3 C32 )1 / 2
(c)    ......
4. The molecular weight of O 2 and SO 2 are 32 and 64 respectively. n1 n2 n3
1/2
If one litre of O 2 at 15 o C and 750 mm pressure contains 'N'  (n1C1  n2 C2  n3 C3  ....) 2 
(d)  
molecules, the number of molecules in two litres of SO 2 under the  (n1  n2  n3  ....) 
same conditions of temperature and pressure will be [CBSE 1990; MNR 1991]
12. 50 ml of hydrogen diffuses out through a small hole from a vessel in
(a) N /2 (b) N 20 minutes. The time needed for 40 ml of oxygen to diffuse out is[CBSE PMT 19
(c) 2N (d) 4N (a) 12 min (b) 64 min
5. What is the relationship between the average velocity (v), root mean (c) 8 min (d) 32 min
square velocity (u) and most probable velocity (a) 13. At what temperature will the average speed of CH 4 molecules have
[AFMC 1994] the same value as O 2 has at 300 K
(a)  : v : u :: 1 : 1.128 : 1.224 [CBSE PMT 1989]
(b)  : v : u :: 1.128 : 1 : 1.224 (a) 1200 K (b) 150 K
(c) 600 K (d) 300 K
(c)  : v : u :: 1.128 : 1.224 : 1
14. A sample of O 2 gas is collected over water at 23 o C at a
(d)  : v : u :: 1.124 : 1.228 : 1
barometric pressure of 751 mm Hg (vapour pressure of water at
6. Consider the following statements : For diatomic gases, the ratio
23 o C is 21 mm Hg). The partial pressure of O 2 gas in the
C p / Cv is equal to
sample collected is [CBSE PMT 1993]
(1) 1.40 (lower temperature) (a) 21 mm Hg (b) 751 mm Hg
(2) 1.66 (moderate temperature) (c) 0.96 atm (d) 1.02 atm
(3) 1.29 (higher temperature)
15. In an experiment during the analysis of a carbon compound, 145 l
which of the above statements are correct
of H 2 was collected at 760 mm Hg pressure and 27 o C
(a) 1, 2 and 3 (b) 1 and 2
(c) 2 and 3 (d) 1 and 3 temperature. The mass of H 2 is nearly
7. The compressibility factor for an ideal gas is [MP PET 2004] [MNR 1987]
(a) 1.5 (b) 1.0 (a) 10 g (b) 12 g
(c) 2.0 (d)  (c) 24 g (d) 6 g
8. The compressibility factor of a gas is less than 1 at STP. Its molar 16. The volume of 1 g each of methane (CH 4 ) , ethane (C2 H 6 ) ,
volume Vm will be [MP PET 2004]
propane (C3 H 8 ) and butane (C4 H10 ) was measured at 350 K
(a) Vm  22.42 (b) Vm  22.42 and 1 atm. What is the volume of butane [NCERT 1981]

(c) Vm  22.42 (d) None (a) 495 cm 3 (b) 600 cm 3

9. If some moles of O 2 diffuse in 18 sec and same moles of other gas (c) 900 cm 3 (d) 1700 cm 3
diffuse in 45 sec then what is the molecular weight of the unknown 17. The ratio of the rate of diffusion of helium and methane under
gas [CPMT 1988] identical condition of pressure and temperature will be [IIT 2005]
45 2 18 2 (a) 4 (b) 2
(a)  32 (b)  32
18 2 45 2 (c) 1 (d) 0.5
18. At what temperature in the celsius scale, V (volume) of a certain
18 2 45 2
(c) (d) mass of gas at 27 o C will be doubled keeping the pressure
45  32
2
18  32
2
constant [Orissa 1993]
10. The ratio of rates of diffusion of SO 2 , O2 and CH 4 is o o
(a) 54 C (b) 327 C
[BHU 1992]
(c) 427 o C (d) 527 o C
(a) 1: 2 :2 (b) 1 : 2 : 4
19. Pressure of a mixture of 4 g of O 2 and 2 g of H 2 confined in a
(c) 2 : 2 :1 (d) 1 : 2 : 2
bulb of 1 litre at 0 o C is [AIIMS 2000]
(a) 25.215 atm (b) 31.205 atm
 246 Gaseous state
(c) 45.215 atm (d) 15.210 atm 8. Assertion : 1/4 of the gas is expelled if air present in an
th

20. If pressure becomes double at the same absolute temperature on 2 open vessel is heated from 27 o C to 127 o C .
L CO 2 , then the volume of CO 2 becomes Reason : Rate of diffusion of a gas is inversely
proportional to the square root of its molecular
[AIIMS 1992]
mass.
(a) 2 L (b) 4 L 9. Assertion : Compressibility factor for hydrogen varies with
(c) 25 L (d) 1 L pressure with positive slope at all pressures.
Reason : Even at low pressures, repulsive forces dominate
21. Volume of the air that will be expelled from a vessel of 300 cm 3 hydrogen gas. [AIIMS 2005]
when it is heated from 27 o C to 37 o C at the same pressure will 10. Assertion : vander Waal’s equation is applicable only to non-
be ideal gases.
(a) 310 cm 3 (b) 290 cm 3 Reason : Ideal gases obey the equation PV  nRT .
(c) 10 cm 3
(d) 37 cm 3 11. Assertion : Pressure exerted by gas in a container with
increasing temperature of the gas.
22. 300 ml of a gas at 27 o C is cooled to  3 o C at constant Reason : With the rise in temperature, the average speed
pressure, the final volume is of gas molecules increases.
[NCERT 1981, MP PMT 1992] [AIIMS 1995]
(a) 540 ml (b) 135 ml 12. Assertion : Gases do not settle to the bottom of container.
(c) 270 ml (d) 350 ml Reason : Gases have high kinetic energy.
[AIIMS 1997]
13. Assertion : A mixture of He and O 2 is used for
respiration for deep sea divers.
Reason : He is soluble in blood. [AIIMS 1998]

Read the assertion and reason carefully to mark the correct option out of 14. Assertion : Wet air is heavier than dry air.
the options given below : Reason : The density of dry air is more than density of
(a) If both assertion and reason are true and the reason is the correct water. [AIIMS 1999]
explanation of the assertion. 15. Assertion : All molecules in a gas have some speed.
(b) If both assertion and reason are true but reason is not the correct
explanation of the assertion. Reason : Gas contains molecules of different size and
(c) If assertion is true but reason is false. shape. [AIIMS 2001]
(d) If the assertion and reason both are false. 16. Assertion : Effusion rate of oxygen is smaller than nitrogen.
(e) If assertion is false but reason is true.
Reason : Molecular size of nitrogen is smaller than oxygen.[AIIMS 200
1. Assertion : Plot of P Vs. 1 / V (volume) is a straight line.
Reason : Pressure is directly proportional to volume.
2. Assertion : Jet aeroplane flying at high altitude need
pressurization of the cabin.
Reason : Oxygen is not present at higher altitude.
3. Assertion : 1 mol of H 2 and O 2 each occupy 22.4 L of
volume at 0 o C and 1 bar pressure. Characteristics and Measurable properties of gases
Reason : Molar volume for all gases at the same
temperautre and pressure has the same volume. 1 c 2 c 3 b 4 a 5 c
4. Assertion : Pressure exerted by a mixture of reacting gases is
equal to the sum of their partial pressures. 6 d 7 a 8 b 9 c 10 a
Reason : Reacting gases react to form a new gas having 11 a 12 b 13 a 14 d 15 c
pressure equal to the sum of both.
5. Assertion : Greater the value of Vander Waal’s constant ' a' 16 e
greater is the liquefaction of gas.
Reason : ' a' indirectly measures the magnitude of Ideal gas equation and Related gas laws
attractive forces between the molecules.
6. Assertion : Carbondioxide has greater value of root mean
1 c 2 d 3 a 4 a 5 a
square velocity  rms than carbon monoxide.
Reason :  rms is directly proportional to molar mass. 6 bc 7 a 8 a 9 c 10 d
11 a 12 a 13 a 14 a 15 c
7. Assertion : 4.58 mm and 0.0098 o C is known to be triple
point of water. 16 c 17 b 18 c 19 a 20 b
Reason : At this pressure and temperature all the three
states i.e., water, ice and vapour exist 21 c 22 c 23 d 24 a 25 c
simultaneously.
26 c 27 b 28 c 29 c 30 c
 Gaseous State 247

31 a 32 a 33 b 34 b 35 b 21 b 22 a

36 c 37 d 38 c 39 c 40 a
41 b 42 c 43 c 44 d 45 a

46 a 47 b 48 d 49 b 50 c
51 d 52 a 53 a 54 c 55 a
56 a 57 b 58 a 59 b 60 a

61 b 62 d 63 c 64 b 65 d
66 b 67 d 68 a 69 a 70 b

71 c 72 a 73 d 74 c 75 a

76 c 77 d 78 b 79 b 80 b

81 d 82 d 83 c 84 c 85 a

86 d 87 a 88 a 89 c 90 c

91 a 92 c 93 a 94 b 95 a

96 a 97 d 98 b 99 e 100 a

101 c 102 c 103 c 104 c 105 a

106 a

Kinetic molecular theory of gases and

Molecular collisions

1 d 2 c 3 d 4 d 5 b

6 a 7 a 8 c 9 b 10 b

11 a 12 d 13 a 14 a 15 acd

16 a 17 b 18 d 19 b 20 d

21 a 22 d 23 c 24 b 25 b

26 a 27 d 28 a 29 d 30 c
31 c

Molecular speeds

1 a 2 c 3 d 4 d 5 d

6 c 7 b 8 b 9 d 10 b

11 d 12 c 13 a 14 d 15 d

16 c 17 d 18 d 19 b 20 b

21 c 22 a 23 c 24 b 25 c

26 a 27 d

Real gases and Vander waal’s equation

1 b 2 b 3 c 4 c 5 d
6 c 7 d 8 b 9 d 10 b
11 c 12 b 13 b 14 d 15 c
16 b 17 a 18 b 19 c 20 a
 Gaseous State 249

P = 100 kPa , P1  ? , V = 1 litre , V1  4 litre

Critical state and Liquefaction of gases
applying Boyle's law PV  P1V1
100  1 = P1  4 ; P1  25
1 a 2 b 3 d 4 c 5 d
If P2 is the pressure of O 2 gas in the mixture of O 2 and
6 d 7 c 8 c 9 abc 10 c
N 2 then, 320  3 = P2  4 ; P2  240
11 c
Hence, Total pressure P  P1  P2  25  240
 265 kPa
Critical Thinking Questions
Ideal gas equation and Related gas laws
1 a 2 c 3 c 4 c 5 a
1
6 d 7 b 8 b 9 a 10 a 1. (c) Boyle's law is V  at constant T
P
11 a 12 b 13 b 14 c 15 b
1
2. (d) According to Boyle's law V 
16 a 17 b 18 b 19 a 20 d P
21 c 22 c Constant
V ; VP = Constant.
P
Assertion & Reason 3. (a) At sea level, because of compression by air above the proximal
layer of air, pressure increases hence volume decreases i.e.
density increases. It is Boyle’s law.
1 c 2 c 3 a 4 d 5 a
4. (a) At constant T , P1V1  P2 V2
6 d 7 a 8 b 9 a 10 b 20
1  20  P2  50 ; P2  1
11 a 12 a 13 c 14 e 15 d 50
5. (a) P.V = constant at constant temperature. As temperature
16 c
changes, the value of constant also changes.
6. (b,c)According to Boyle's Law PV = constant, at constant
temperature either P increases or V increases both (b) & (c)
may be correct.
d1 1 T1 2 P1 V2 T1 T .d
7. (a)  ,      1 1
d 2 2 T2 1 P2 V1 T2 T2 .d 2
P1 2 1 1
 . 
P2 1 2 1
Characteristics and Measurable properties of gases o
8. (a) Absolute temperature is temperature measured in Kelvin ,
1. (c) Gases do not have definite shape and volume. Their volume is expressed by T
equal to the volume of the container. 11. (a) T1  273o C  273  273o K  546o K
2. (c) All the three phases of water can coexist at 0 o C & 4.7 mm T2  0 o C  273  0 o C  273o K
pressure.
3. (b) It is characteristic of gases i.e. Thermal energy >> molecular P1  1 ; P2  ?
attraction According to Gay-Lussac’s law
4. (a) In gases, molecular attraction is very less and intermolecular
P1 P2 PT 1  273 o K 1
spaces are large hence kinetic energy of gases is highest.   P2  1 2  atm; atm.
5. (c) Gases and liquids, both can flow and posses viscosity. T1 T2 T1 546 o K 2
7. (a) Newton is unit of force. 12. (a) Vt  Vo (1   v t)
C o F o  32
8. (b)   (V2  V1 )  V  Vo(t 2  t1 )
5 9
if t2  t1  1o then V  Vo
9. (c) 1 L  10 3 m 3  10 3 cm 3  1dm 3  10 3 ml .
10. (a) 1 atm = 10 6 dynes cm -2
For every 1o C increase in temperature, the volume of a given
12. (b) Barometer is used to measure atmospheric pressure of mixture mass of an ideal gas increases by a definite fraction
of gases. Staglometer is used to measure surface tension. Only 1
of Vo . Here Vo is volume at 0 o C temperature.
manometer is used to measure pressure of pure gas in a vessel. 273.15
13. (a) 0 o C is equivalent to 273o K i.e. conditions are same so V1 T1 T 546 o K
volume will be V ml. 13. (a)   V2  2 V1   0 .2 L  0 .4 L.
14. (d) The mass of gas can be determined by weighing the container, V2 T2 T1 273o K
filled with gas and again weighing this container after removing T2 270 o K
the gas. The difference between the two weights gives the mass 14. (a) V2  .V1  .400cm 3  360cm 3
of the gas. T1 300 o K
15. (c) Nobel gases has no intermolecular forces due to inertness. contraction  V1  V2  400  360  40cm 3
16. (e) Total volume of two flasks = 1+ 3 = 4
If P1 the pressure of gas N 2 in the mixture of N 2 and 15. (c) At constant volumes P  T
nR
O 2 then P = constant T; PV = nRT  P  T
V
 250 Gaseous State
nR P1 V1 P2 V2 PV T
slope = m   V2  V1 35. (b)   1 1  1
V T1 T P2 V2 T2
m1 V2
  m1  m 2 is curve for V has a greater slope than 36. (c) d a  2d b ; 2 M a  M b
2

m 2 V1 m m RT dRT
for V PV  nRT  RT ; P  . 
1
M V M M
P1 P1 P P
16. (c)    Pa d a M b 2d b 2 M a
T1 T1 T1 T2    4
Pb d b M a db Ma
2 P1  T  T2  2 P1 (T1 T2 ) 2 P1 T2
 P  1 ; P 
  37. (d) n of O2 
16 1

T1  1 2 
T T T (
1 1T  T 2 ) T1  T2 32 2
18. (c) At constant V of a definite mass 3
P1 P2 P1 300 1 n of H 2 
    i.e. pressure increases 2
T1 T2 P2 600 2 3 1
and on increasing temperature energy of molecules increases so  2
Total no. of moles =
2 2
the rate of collisions also increases and number of moles
nRT 2  .082  273
remains constant because there is neither addition nor V   44.8 lit = 44800 ml
removal of gas in the occurring. P 1
19. (a) Avogadro number = 6.0224  10 23
PV m
38. (c) n 
PV RT M
20. (b) Compressibility =  1 at STP (as given)
nRT MPV 34  2  100
nRT  PV R = 0.821 m   282.4 gm
RT 0.082  293
N  0.0821  273  1Vm T = 273 K o

PV T 760 546
39. (c) V2  1 1 1    273  691.6 ml.
22.41 litres Vm P=1 T1 P2 600 273
n=1 P1V1 P2 V2 P V m
21. (c) The value of universal gas constant can be expressed in 40. (a)   T2  2 2 T1 1
different units and its value would depend only on the units of n1T1 n2 T2 P1 V1 m2
the measurement. 0 .75 1 2
22. (c) PV = nRT     300 o K  450 o K
1 1 1
PV
R  litre . atm. K mole –1 –1
P1 T2 1 250
nT 41. (b) V2  .V1    12000lit.  20000lit.
23. (d) (atm. K mol ) is not a unit of R
-1 –1 P2 T1 0.5 300
24. (a) 8.31 J.K mol -1 –1
42. (c) At constant pressure
1 cal = 4.2 J. m
8 .31 V  nT  T
 cal.K 1mol 1 = 1.987 cal K mol –1 –1 M
4 .2 V1 m1 T1 T V m d 300 o K 0 .75 d
n P   1  1  2  2  
30. (c) PV = nRT   V2 m 2 T2 T2 m1 V2 d1 T2 d
V RT
300
nRT 2  0 .0821  546 T2   400 o K
31. (a) P    2 atm. 0 .75
V 44.8 l
P1 V1 P2 V2 PV 740 80
P1 V1 P2 V2 PVT 43. (c)   T2  2 2  T1    300
32. (a)   n 2  2 2 1 n1 T1 T2 P1 V1 740 100
n1 T1 n 2 T2 P1 V1 T2
 240o K  33o C
at STP n1  one mole. at T  273o  30 o  303o K 47. (b) Because H 2 & Cl 2 gases may react with each other to
P = 1 atm.
1
P2  1 atm produce HCl gas hence Dalton's law is not applicable.
V = 22.4 lt
1
V2  22.4 48. (d) Because HCl & NH 3 gases may react to produce NH 4 Cl
T = 273 K
1
o
gas. Dalton's Law is applicable for non reacting gas mixtures.
1 22.4 273 49. (b) NH 3 and HCl & HBr is a reacting gas mixture to
n2     1  0.9 moles
1 22.4 303 produce NH 4 Cl & NH 4 Br so Dalton's law is not applicable.
nRT 0 .5  0.082  273 K o
m
33. (b) V    11.2lit 50. (c) No. of moles of lighter gas 
P 1 4
P1 V1T2 m
34. (b) V2   P1  P ; T1  273o K No. of moles of heavier gas 
P2 T1 40
3 T 4 m m 11m
P2  P ; T2  T1  1   273 o K Total no. of moles   
2 3 3 4 40 40
2 P 4 273 800 m
V2     100cc  cc  88.888 cc 10
3 P 3 273 9 Mole fraction of lighter gas  4 
= 88.9 cc 11m 11
40
 Gaseous State 251

10 x 2 1
Partial pressure due to lighter gas  Po    gm.  .5 gm
11 10 10  4 2
10 69. (a) rCH 4  2rg
 1 .1   1atm.
11 2
 rCH 
52. (a) m. wt. of NH 3  17 ; m.wt. of N 2  28 M g  M CH 4  4   16  2 2  64
 rg 
m.wt. of CO 2  44 ; m.wt. of O2  32  
beacuse NH 3 is lightest gas out of these gases 1 Volume effused V
70. (b) r  r  
M time taken t
 1 
r   V 1
 MolecularWeight   for same volumes (V constant)
t M
rg M He r 2 He 4 4 t1 M1
55. (a)   M g  M He . 2  2
 2 t M 
rHe Mg r g (1 .4 ) 1 .96 t2 M2
Note : 1.4  2  t He  t H 2
M He
5
4
 5 2 s.
1 M H2 2
56. (a) rg  .rH 2
5
32
 rH 
2 tO 2  t  5  20 s
Mg 2
  2   (5)2  25 ; M g  2  25  50
M H2  rg  28 44
2
tCO  5  5 14 s ; tCO 2  5  5 22 s
1  rH  2 2
57. (b) rg  rH ; M g  M H 2 . 2   2  6 2  2  36  72
rN 2 TN 2 M So 2 TN 2
6 2  rg  71. (c) 
Vrms N 2
 .  
64
58. (a) M1  64 ; r2  2r1 rSO 2 Vrms SO 2 TSO 2 M N2 323 28
2
r  1 TN 2 16
M 2  M 1  1   64   16 1 .625  .
 2
r 4 323 7

0 09 (1 .625)2  323  7

dH 1 1 TN 2   373o K
59. (b) rO  rH 1   16
dO 1 .44 16 4
72. (a) C  H 2O  COg   H 2g 
2
r 
2
d 1 1 12 gm  1mol  1mol
60. (a) ra  5rb ; a   b     
d b  ra  5 25 12 gm C produces 2mole of gases (1mole CO & 1 mole of H ) 2

48
61. (b)
d1

1 r
; 1 
d2
 16 
4 48 gm C may produce  2  4  2  8 mole
d 2 16 r2 d1 1 12
 22.4  8 L gases  179.2 L gas.
1 1
DA B  B  2  B 2 mRT 4 .4  .082  273
62. (d)    ;  D A  DB   73. (d) Molecular weight =  = 44
A  A   1  2 .24
 A
PV
DB 
63. (c) Gases may be separated by this process because of different rates of So the gas should be CO 2
diffusion due to difference in their densities. 74. (c) PV  nRT
64. (b) NH 4 Cl ring will first formed near the HCl bottle because n n
P  RT   C  P  CRT
rate of diffusion of NH 3 is more than that of HCl because V V
M NH 3 : M HCl  17 : 36.5) . SO NH 3 will reach first to the P 1
T   12o K
HCl bottle & will react there with HCl to form NH 4 Cl CR 1  .821
ring 75. (a) 6.02  10 22 molecules of each N 2 , O2 and H 2
65. (d) Because both NO and C2 H 6 have same molecular weights 6 .02  10 22
M NO  M C 2 H 6  30  and rate of diffusion  molecular

6 .02  10 23
moles of each
weight. Weight of mixture = weight of 0.1 mole N 2  weight of 0.1
2
M A  rB  r 1 1 1 mole H 2 + weight of 0.1 mole of O2
67. (d)     rA  2rB  B   2   .25
M B  rA  rA 2 (2) 4  (28  0.1)  (2  0.1)  (32  0.1)  6.2 gm
2gm xgm 76. (c) M.wt of CO 2 = 12+16+16 = 44
68. (a) rH  if rO 
10 min 10 min Volume of 44 gm of CO 2 at NTP = 22.4 litre
M H2 2 2 22 .4
rO  rH  1 gm of CO 2 at NTP =
M O2 10 32 44
 252 Gaseous State
4.4 gm of CO 2 at N.T.P In 1l of H2 maximum number of molecules


22.4
 4 .4 litre  2.24 litre 6 .023  10 23

44 22.4
78. (b) No. of moles of CO 2 present in 200 ml solution In 15l of H2 maximum number of molecules
200 6 .023  10 23
= molarity  Volume (in lt.)  0 .1   .02   15  4.03  10 23 molecules.
1000 22.4
Volume of 0.02 mole of CO 2  22.4  .02lt.  0.448lit. 93. (a) 22.4 l O2 at S.T.P.  32 gm of O 2
79. (b) Molecular weight = V.d.  2 = 11.2  2 = 22.4 32
Volume of 22.4 gm Substance of NTP = 22.4 litre 1l O 2 at S.T.P.   1 .43 gm of O 2
22.4
22.4
1 gm substance at NTP = litre 95 (a) We know that molecular mass of hydrogen M1  2 and that
22.4
11.2 gm substance of NTP = 11.2 litre of helium M 2  4 , we also know that Graham's law of
M . wt . of O2 M 32 1 diffusion
80. (b)  1  
M . wt . of SO 2 M2 64 2 r1 M2 4
   2  1 .4 ; r1  1.4 m
1 r2 M1 2
The weight of oxygen will be that of SO 2
2 rA MH r 2
81. (b) For HI has the least volume because of greater molecular 96. (a)   
rH MA 6r MA
1
weight V  M A  6  6  2  72 g
M
83. (c) Since no. of molecules is halved so pressure should also be 97. (d) Given that:
halved. V1  100ml, P1  720mm , V2  84 ml, P2  ?
84. (c) H 2 will be filled first because of lower molecular weight By using P1V1  P2 V2 [According to the Boyle's law]
85. (a) Mixture of SO 2 and Cl 2 are reacted chemically and forms P1 V1 720  100
P2    857.142
SO 2 Cl 2 . That is why mixture of these gases is not applicable V2 84
for Dalton's law. Hence, P2  857.14 mm
86. (d) According to Boyle's law
98. (b) According to gas law
P1V1  P2 V2  P1  60  720  100
PV
720  100 PV  nRT , n 
P1   1200mm RT
60
P1 V1
1
87. (a) Rate of diffusion  nA RT1 n A P1 V1 T
Molecular Mass  ;   2
nB P V
2 2 nB T1 P2 V2
that is why H 2 gas diffuse first RT2
88. (a) Solution level will rise, due to absorption of CO 2 by sodium n A 2 P  2V T n 2
  ; A 
hydroxide. nB 2T PV n B 1
2 NaOH  CO 2  Na 2 CO 3  H 2 O 99. (e) No. of molecules  2  V.d
89. (c) CaCo 3 ˆ CaO  CO 2 
 2  38.3  76.3
(40 12 16 3 ) 100 gm 22 .4 litre
wt. of NO 2  x
 At S.T.P. 100 g CaCO 3 produce= 22.4 litreof CO 2 So that wt. of N 2O4  100  x
22.4 x 100  x 100 2 x  100  x 100
 At S.T.P. 1 g CaCO 3 produce =  .224 litre of    
100 Hence,
46 92 76.6 92 76.6
CO 2
20.10
Molecularwt . Of Metal 45 x = 20.10, no. of mole. of NO 2   0 .437
90. (c) The density of gas   46
Volume 22 .4 100. (a) Given that
= 2 gmlitre 1 P1  76cm of Hg (Initial pressure at N.T.P.)

91. (a) M1  32 g for O 2 , M 2  2 g for H 2 P2  ? , V1  5litre, V2  30  5  35litres

According to Boyle's law
r1 M2 r1 2 1 1 P1V1  P2 V2 ; 76  5  P2  35
 ;   
r2 M1 r2 32 16 4 76  5
P2   P2  10.8 cm of Hg
92. (c) In 22.4 l of H2 maximum number of molecules 35
101. (c) Given initial volume V1   300cc , initial temperature
 6.023  10 23

T1   27o C  300 K , initial pressure P1   620mm , final

 Gaseous State 253

temperature T2  47 o C  320 K and final pressure 12. (d) All molecules of an ideal gas show random motion. They collide
with each other and walls of container during which they lose
P2   640mm .We know from the general gas equation or gain energy so they may not have same kinetic energy
P1 V1 P2 V2 620  300 640  V2 always.
    V2  310cc 13. (a) For same temperature kinetic energies of H 2 & He molecules
T1 T2 300 320
will be same because kinetic energy depends only on
102. (c) NH 3  HCl  NH 4 Cl temperature.
4 litre 1.5litre 14. (a) For same temp. kinetic energies would be equal for all
HCl is a limiting compound. That's why 1.5litre of HCl molecules, what ever their molecular weights will be, it doesn't
matter.
reacts with 1.5litre of NH 3 and forms NH 4 Cl . Thus (4 -
15. (a,c,d)Kinetic energies per molecule will be same because it is
1.5) 2.5litre NH 3 remains after the reaction. proportional to absolute temperature only.
P1 V1 P2 V2 P1  4 2 P1  V2 dN2 MN2 28
103. (c)  ;    i.e. dN 2  dCO 2
T1 T2 T1 2T1 d CO 2 M CO 2 44
8  2  V2 so V2  4dm 3 Total translational kinetic energy will also be same because at
104. (c) P1  P, V1  V, T1  T same temperature & pressure number of molecules present in
same volume would be same (according to Avogadro's Law)
P
P2 , V2  ? , T2  T 16. (a) On increasing pressure, the volume decreases and density
2 increases. So molecules get closer to each other hence mean
According to gas equation free path also decreases.
P1 V1 P2 V2 PV PV2 17. (b) Most probable velocity increase and fraction of molecule
 or  possessing most probable velocity decrease.
T1 T2 T 2T
 V2  4 V m
18. (d) PV  nRT  RT
M
105. (a) P1  P, V1  V, T1  273  75  348 K
m PM
85    density
P2  2 P, V2  , T2  ? V RT
100
P  V 2 P  85 V 348  2  85 P P
  T2  19. (b) d  the value of is maximum for (b)
398 T2  100 100 T T

 T2  591.6 K  318.6 o C 20. (d) If inversion temperature is 80 o C  193o K then the

temperature, at which it will produce cooling under Joule
106. (a) Boyle's law  PV = constant Thomson’s effect, would be below inversion temperature except
On differentiating the equation,
173o K all other values given as
d(PV)  d(C)  PdV  VdP  0
CP
dP dV 21. (a) Since  1 .4 , the gas should be diatomic.
 VdP  PdV   . CV
P V
1
Kinetic molecular theory of gases If volume is 11.2 lt then, no. of moles =
2
and Molecular collisions
1
 no. of molecules =  Avagadro’s No.
2
3
4. (d) Kinetic energy  RT no. of atoms = 2  no. of molecules
2
3 1
5. (b) K.E = RT it means that K.E depends upon T (absolute 2  Avagadro’s No.
2 2
temperature) only.  6.0223  10 23
3 3
7. (a) KE  RT  PV 22. (d) Density =
M
2 2 V
2 E 2 v.d  2
P 
3 V
for unit volume (V = 1)  P  E
3 d M  V.d  2
V
(c) Tr. K. E. 
3 RT d V
8. it means that the Translational Kinetic V .d 
2 2
energy of Ideal gas depends upon temperature only. 0.00130  22400
V .d   14.56 gm 1
E He THe 2
9. (b)  so energies will be same for
EH2 TH 2 23. (c) Volume of steam = 1lt = 10 3 cm 3
 m  d.V
He & H 2 at same temperature.
mass of 10 3 cm 3 steam = density  Volume
3 3
11. (a) K. E.  .RT  .2 .T  R  2calK1mol 1 =
0 .0006 gm
 10 3 cm 3  0.6 gm
2 2 cm 3
K. E.  3T
 254 Gaseous State
Actual volume occupied by H 2 O molecules is equal to volume 3 KT 1 
1

of water of same mass 12. (c) Vrms  i.e. Vrms   (m ) 2

Molecularweight m
 Actual volume of H 2 O molecules in 6 gm steam
13. (a) When average speed of molecule is increased due to increase in
= mass of steam/density of water
temperature then the change in momentum during collision
= 0.6 gm /1 gm/cm  0.6 cm 33
between wall of container and molecules of gas also increases.
CP 5 U1 m 2 T1
24. (b) r    1 .66 (For Monoatomic as He, Ne , Ar ) 14. (d)  .  T1  T2
CV 3 U2 m1 T2
25. (b) The density of neon will be highest at 0 o C 2 atm according 2
U1 m2
P   m1U1 2  m 2U2 2
to d  U2
2
m1
T
3 T2 1200
29. (d) K.E. per mole  RT 15. (d) U2  U1  U1  U1  2
2 T1 300
so all will have same K.E. at same temperature. r.m.s. velocity will be doubled.
30. (c)  W  P.dV  E
 Energy per unit volume = P UH 2 TH 2 M O2 50 32
16. (c)  .  . 1
d M 3d M M UO 2 MH2 TH 2 2 800
31. (c) d  M  1  1 ;  ; M2  .
d2 M 2 d M2 3
3 RT 3 PV 3P 1
17. (d) U    U 
Molecular speeds M M d d
U1 n1T1 nT 1 1
3 RT 8 RT Vrms 3 19. (b)    
1. (a) Vrms  , Vav  ;  U2 n2 T2 2n  2 T 4 2
M M Vav 8
U2  2U1  2U
66 1 .086
  2 RT
56 1
21. (c)
Vmp
 M  
3. (d) most probable velocity : mean velocity : V rms
Vav 8 RT 2


2 RT
:
8 RT
:
3 RT
 2:
8
: 3
M
M M M  3 RT
22. (a) Vrms   Vrms  T
3 RT 1 M
4. (d) Vrms   Vrms  at same T
M M Given V1  V , T1  300 K , V2  2V , T2  ?
2
because H 2 has least molecular weight so its r.m.s. velocity V1 T1  V  300
 ;     T2  300  4  1200 K
should be maximum. V2 T2  2 V  T2
 n 2a 
(b)  P  2 V  nb   nRT
U SO 2 1 M He TSO 2 4 TSO 2
5. (d)    . 24.
U He 2 M SO 2 THe 64 300  V 
 
 P  (2)  4 .17 5  2  .03711  2  .0821  300
2
4 TSO 2 1
  ; TSO 2  1200o K  2 
64 300 4  (5 ) 
UO 3 M O2 2  .0821  300 4 .7  2 2
6. (c)  
32

2 P   10  0.66  9.33atm
UO 2 M O3 48 3 5  2  .03711 52
26. (a) Average speed : most probable speed
7. (b) Average kinetic energy per molecule
8 RT 2 RT 8
3 3 :  : 2  1.128 : 1.
 KT   1.38  10  23  300 J = 6.17  10 21 J M M 
2 2
3 RT
U SO 2 M O 2 TSO 2 32  TSO 2 27. (d) v rms 
8. (b)   1 M
UO2 M SO 2 TO 2 64  303
3 RT 3 R  300
30 2 R   30  30 R 
32  TSO 2 M M
1  TSO 2  606
64 303 3  300
 M 1 gm  0.001 kg .
9. (d) Among these Cl 2 has the highest molecular weight so it will 30  30
posses lowest root mean square velocity.

T1  5  10 4
2
 Real gases and Vander waal’s equation
10. (b)
U1

T1
   1
U2 T2 T2  10  10 4 
 4 2. (b) Because molecules of real gases have intermolecular forces of
attraction so the effective impact on the wall of container is
 Gaseous State 255

a  0.16 gm of O 2
diminished. Pressure of real gas is reduced by factor hence
v2
behaviour of real gas deviate from ideal behaviour. Critical Thinking Questions
PV 1. (a) Average kinetic energy  (T Kelvin)
3. (c) Z  for ideal gas PV = RT so Z = 1
RT K. E2 T2 40  273 313
PV (Factor)   
12. (b) Z ; for ideal gas PV = RT; so Z = 1 K. E1 T1 20  273 293
RT 2. (c) M. wt. = V.d.  2
13. (b) Ideal gas has no attractive force between the particles
m.wt . 40
14. (d) PV = nRT is a ideal gas equation it is allowed when the = 70  2 = 140  x   5
temperature is high and pressure is low. wt .of [CO ] 12  16 
16. (b) At Boyle temperature real gas is changed into ideal gas 3. (c) Gas deviate from ideal gas behaviour to real gas (according to
17. (a) When pressure is low Vander Waal's at low temperature and high pressure)
 a  4. (c) At same temperature and pressure, equal volumes have equal
 P  2 V  b   RT number of molecules. If 1lit. of oxygen consists N molecules
 V 
then at same temperature and pressure 1 lit of SO 2 will
a ab PV a
or PV  RT  Pb   2 or 1 consists N molecules. So 2 lit. of SO 2 will contain 2 N
V V RT VRT
molecules.
a  PV  5. (a) Vav : Vrms : V = V : U :
Z   Z most probable

VRT  RT 
8 RT 3 RT 2 RT
18. (b) At high temperature and low pressure, Vander Waal’s equation : :
is reduced to ideal gas equation. M M M
PV = nRT
8
PV = RT (For 1 mole of gas)  :V :U  2 : : 3  1 : 1.128 : 1.224
20. (a) Vander waal's constant for volume correction b is the measure 
of the effective volume occupied by the gas molecule. Cp
 2  6. (d) ratio for diatomic gases is 1.40 at lower temperature &
22. (a)  P  n a  (V  nb)  nRT Cv
 V 2 
 1.29 at higher temperature so the answer is 'd'.
 2.253  7. (b) PV  nRT (For ideal gas)
P   (0 .25  0 .0428)  0 .0821  300 PV
 0.25  0.25  Z  1 (For ideal gas)
nRT
or (P  36.048)(0.2072)  24.63
8. (b) If Z  1 then molar volume is less than 22.4 L
 P  36.048  118.87  P  82.82 atm. x x
9. (a) rO 2  mole / sec  rg  mol / sec
18 45
Critical state and Liquefaction of gases 2
 rO  2
  32 x  45   32  45
2

2. (b) A diabatic demagnetisation is a technique of liquefaction of M g  MO 2  2

 rg   18 x  18 2
gases in which temperature is reduced.  
3. (d) An ideal gas can’t be liquefied because molecules of ideal gas 1 1 1
have not force of attraction between them. 10. (a) rSO 2 : rO2 : rCH 4  : :
4. (c) At above critical temperature, substances are existing in M SO 2 O2 CH 4
gaseous state, since gas cannot be liquefied above it.
1 1
5. (d) Absence of inter molecular attraction ideal gas cannot be  
liquefied at any volume of P and T. 64 : 32 : 16 4 : 2 :1
6. (d) For Z gas of given gases, critical temperature is highest 1 1 1 2 2 2
8a 8  12 : : ; : : ; 1: 2 :2
Tc   Tc   1603.98 K 2 2 1 2 2 1
27 Rb 27  .0821  .027 1/2
7. (c) Value of constant a is greater than other for NH 3 that’s why  n c 2  n2 c 22  n3 c32  .... 
11. (a) Root mean square speed   1 1  .
NH 3 can be most easily liquefied.  n1  n2  n3  ...... 
8. (c) The temperature below which the gas can be liquefied by the 40
application of pressure alone is called critical temperature. 12. (b) If 40 ml O 2 will diffuse in t min. then. rO2 
t
M
10. (c) d   M  d V 50 M H2 50 2 50 1
V rH   rO  rH 2   .
M  2.68  22.4 at N.T.P.  V  22.41 20 M O2 20 32 20 4
M  60.03 gm 40 50 40  80
 t   60 min.
m. wt of COS  12  16  32  60 t 80 50
11. (c) 22400 ml is the volume of O 2 at N.T.P =32gm of O 2 TCH 4 M O2
Vav CH 4
32 13. (b)  . 1
1ml is the volume of O 2 at NTP = Vab O2 TO 2 M CH 4
22400
TCH 4 32
32 .  1 ; TCH 4  150 o K
112 ml is the volume of O 2 at NTP =  112 300 16
22400
14. (c) Pressure of O 2 (dry) = 751-21 = 730 mm Hg
 256 Gaseous State
730 V1 V2 V1
  0 .96 atm 8. (b)  (Initial fraction  1 when temperature is
760 T1 T2 V2
PV 1  145 V1 300 3
15. (b) PV  nRT , n    5.8  6 mole . 27 o C . At 127 o C the new fraction is   
RT 0.082  3 V2 400 4
nRT m RT 1 0.82  350
16. (a) V   .    0.495lit. air expelled  1 
3 1

P M P 58 1 4 4
= 495 cm 3

9. (a) In case of H , compressibility factor increases with the pressure.

2

rHe M CH 4 16 At 273 K, Z > 1 which shows that it is difficult to compress the

17. (b)  = 2 gas as compared to ideal gas. In this case repulsive forces
rCH 4 M He 4
dominate.
V1 T1 TV 2V 10. (b) In real gases, the intermolecular forces of attraction and the
18. (b)   T2  1 2  300 o K,  600 o K
V2 T2 V1 V volume occupied by the gas molecules cannot be neglected.
11. (a) When the temperature increase, the average speed of gas
T2  600o K  (600  273)o C  327o C molecules increases and by this increase the pressure of gas is
4 also increases.
19. (a) no. of moles of O2   0 .125 12. (a) It is correct that gases do not settle to the bottom of container
32 and the reason for this is that due to higher kinetic energy of
2 gaseous molecules they diffuse.
no. of moles of H 2  1 13. (c) The assertion, that a mixture of helium and oxygen is used for
2
deep sea divers, is correct. The He is not soluble in blood.
total no. of moles = 1  0.125  1.125 Therefore, this mixture is used.
nRT 1.125  0.082  273 14. (e) Dry air is heavier than wet air because the density of dry air is
P   25.184 atm. more than water.
V 1
15. (d) All molecule of a gas have different speed. Therefore, they move
P1  V P 2 by its own speed.
20. (d)  , 1  2 
P2 2 V2 P1 1 16. (c) Assertion is true but reason is false because of effusion rate
1
2L 2  (Molecular weight) but it does not depend on
 ; V2  1L M
V2 1
molecular size.
V2 T2
21. (c) 
V1 T1

T2 310 o K
 V2  V1   300 cm 3  310 cm 3
T1 300 o K
T2 270 o K
22. (c) V2  .V1   300ml  270ml
T1 300 o K

Assertion & Reason

1. (c) Pressure is inversly proportional to volume (Boyle’s law).
1
p (n, T constant).
V
2. (c) The air pressure decreases with increase in altitude. So the
partial pressure of Oxygen is not sufficient for breathing at
higher altitude and thus pressurization is needed.
3. (a) At a given temperature and pressure the volume of a gas is
directly proportional to the amount of gas Vn (P and T
constant).
4. (d) According to Dalton’s law of partial pressure, the pressure
exerted by a mixture of non – interacting gases is equal to the
sum of their partial pressures (pressure exerted by individual
gases in mixture) PTotal  P1  P2  P3 … (T and V constant).
Both the gases if non-interacting would spread uniformly to
occupy the whole volume of the vessel.
5. (a) Considering the attractive force pressure in ideal gas equation
an2
(PV = nRT) is correct by introducing a factor of where a
V2
is a vander waal’s constant.
3 RT
6. (d) rms  is inversly related to molecular mass.
M
Therefore, rms (CO )  rms (CO 2 ).
 Gaseous State 257

1. Same mass of CH 4 and H 2 is taken in container. The partial 7. Which of the following volume (V) – temperature (T) plots
represents the behaviour of one mole of an ideal gas at one
pressure caused by H 2 is [IIT 1989; CPMT 1996] atmospheric pressure [IIT Screening 2002]
V(L) V(L)
(a) 8 / 9 (b) 1 / 9
(36.8 L (28.6 L
(c) 1 / 2 (d) 1 (22.4 L 373 K) (22.4 L 373 K)
273 K) 273 K)
2. The following graph illustrates [JIPMER 2000]
(a) (b)
T(K) T(K)
V(L) V(L)
V
(30.6 L
(22.4 L 373 K) (22.4 L
273 K) 273 K)
(14.2 L
Temp. (oC) (c) (d) 373 K)
(a) Dalton's law (b) Charle's law
T(K) T(K)
(c) Boyle's law (d) Gay-Lussac's law 8. If the average velocity of N 2 molecule is 0.3 m / s at 27 o C ,
then the velocity will be 0.6 m / s at [Pb. CET 2001]
3. If the pressure and absolute temperature of 2 litres of CO 2 are
doubled, the volume of CO 2 would become (a) 1200 K (b) 600 K
(c) 400 K (d) 1800 K
[CBSE PMT 1991]
9. Equal volumes of two gases which do not react together are
(a) 2 litres (b) 4 litres enclosed in separate vessels. Their pressures at 100 mm and 400
(c) 5 litres (d) 7 litres mm respectively. If the two vessels are joined together, then what
will be the pressure of the resulting mixture (temperature remaining
4. What is kinetic energy of 1 g of O 2 at 47 o C constant) [CBSE PMT 1981]
[Orissa JEE 2004] (a) 125 mm (b) 500 mm
(c) 1000 mm (d) 250 mm
(a) 1.24  10 J 2
(b) 2.24  10 J 2

10. A gas of volume 100 cc is kept in a vessel at pressure 10 4 Pa

(c) 1.24  10 3 J (d) 3.24  10 2 J
maintained at temperature 24 o C . If now the pressure is increased
5. The root mean square speeds at STP for the gases H 2 , N 2 , O2 to 10 5 Pa, keeping the temperature constant, then the volume of
and HBr are in the order the gas becomes [AFMC 1992]
[Pb. CET 1994; CBSE PMT 1991] (a) 10 cc (b) 100 cc
(a) H 2  N 2  O2  HBr (c) 1 cc (d) 1000 cc
11. If a gas is expanded at constant temperature [IIT 1986]
(b) HBr  O2  N 2  H 2 (a) The pressure increases
(b) The kinetic energy of the molecules remains the same
(c) H 2  N 2  O2  HBr
(c) The kinetic energy of the molecules decreases
(d) HBr  O2  H 2  N 2 (d) The number of molecules of the gas increases
6. By what ratio the average velocity of the molecule in gas change 12. The rate of diffusion of SO 2 and O 2 are in the ratio
o
when the temperature is raised from 50 to 200 C [Assam JET 1991; EAMCET 1980]
[DCE 2003] (a) 1: 2 (b) 1 : 32
(a) 1.21 / 1 (b) 1.46 / 1 (c) 1 : 2 (d) 1 : 4
(c) 1.14 / 1 (d) 4 / 1

(SET -6)
 Gaseous State 259

N CH 4 = number of moles of CH 4 
m V1 T1 T 22.4  373
1. (a) 7. (c)   V2  V1 . 2   30.6 L
16 V2 T2 T1 273
m
N H 2 = number of moles of H 2  3 RT
2 8. (a) Vrms  ; Vrms  T
fraction partial pressure of H 2 is M

m m Given, V1  V , T1  300 K
nH2 2 8
H2    2  V2  2V , T2  ?
n H 2  n CH 4 m m 9m 9
 2
2 16 16 V1 T1  V  300
2. (b) According to Charle's Law V  T     
V2 T2  2V  T2
Vt  Vo  Vot
compare it with Y = C + mx T2  300  4  1200 K
PV T P 2T 9. (d) When two vessels are joined together, the volume will be
3. (a) V 2  1 1 . 2   2lt   2lt doubled hence effective pressure will be halved
T1 P2 2 P T
P1  P2 100  400
4. (a) K.E. 
3 3 1
nRT    8.314  320 J . P   250mm
2 2 32 2 2
 1.24  10 2 J 10. (a) P1 V1  P2 V2 at constant T
1
5. (b) Vrms  10 4.100  10 5  V2
m
V2  10 cc
1 1 1 1
U H 2 : U N 2 : U O2 : U HBr  : : : is
2 20 32 81 11. (b) Kinetic energy will also remain constant if Temperature is
constant.
UHB r  UO2  UN 2  UH 2
rSO 2 M O2 32 1
6. (c) T1  150  273  423 K ; T2  50  273  323 K 12. (a)   
rO2 M SO 2 64 2
(Vav )1 T1 423 1 .14
Hence,   
(Vav )2 T2 323 1

***
 Nuclear Chemistry 259

Chapter

7
Nuclear Chemistry

“The branch of chemistry which deals with the study of composition applying electric and magnetic fields. When these radiation were subjected
of atomic nucleus and the nuclear transformations is known as nuclear to electric or magnetic field, these were split into three types ,  and  –
chemistry”. rays.
The common examples of nuclear processes are radioactivity, Characteristics of radioactive rays
artificial transmutations, nuclear fission and nuclear fusion. The nuclear is -Ray -Ray -Ray
also an important aspect of chemistry because the energies involved in some Charge and mass : It carries +2 It carries -1 charge and It has no charge
of these are million times greater than those in ordinary chemical reactions. charge and 4 unit mass. no mass. and negligible
mass.
Radioactivity
Identity : Helium nuclei or High energy
“Radioactivity is a process in which nuclei of certain elements Electron  1e 0 raditons.
undergo spontaneous disintegration without excitation by any external helium ion 2 He 4 or He2+.
means.’’ and the elements whose atoms disintegrate and emit radiations are Action of magnetic field : Deflected to anode. Not deflected.
called radioactive elements. Deflected towards the cathode.
Henry Becquerel (1891) observed the spontaneous emission of Velocity : 1/10th to that of light. Same as that of light. Same as that of
light.
invisible, penetrating rays from potassium uranyl sulphate
Ionizing power : Very high Low nearly 100 times to Very low.
K 2 UO2 (SO4 )2 , which influenced photographic plate in dark and were nearly 100 times to that of - that of -rays.
able to produce luminosity in substances like ZnS. rays.
Later on, M.M. Curie and her husband P. Curie named this Effect on ZnS plate : They Very little effect. Very little effect.
cause luminescence.
phenomenon of spontaneous emission of penetrating rays as, Radioactivity.
Penetrating power : Low 100 times that of - 10 times that of -
Curies also discovered a new radioactive element Radium from particles. particles.
pitchblende (an ore of U i.e. U3 O8 ) which is about 3 million times more Range : Very small. More than -particles. More
radioactive than uranium. Now a days about 42 radioactive elements are Nature of product : Product Product obtained by the There is no change
known. obtained by the loss of 1 - loss of 1 -particle has in the atomic
particle has atomic number atomic number more by number as well as
The radioactivity may be broadly classified into two types, less by 2 units and mass 1 unit, without any in mass number.
(1) If a substance emits radiations by itself, it is said to possess number less by 4 units. change in mass number.
natural radioactivity.
(2) If a substance starts emitting radiations on exposure to rays
Theory of radioactivity disintegration
from some natural radioactive substance, the phenomenon is called induced Rutherford and Soddy, in 1903, postulated that radioactivity is a
or artificial radioactivity. nuclear phenomenon and all the radioactive changes are taking place in the
Radioactivity can be detected and measured by a number of devices nucleus of the atom. They presented an interpretation of the radioactive
like ionisation chamber, Geiger Muller counter, proportional counter, flow processes and the origin of radiations in the form of a theory known as
counter, end window counter, scintillation counter, Wilson cloud chamber, theory of radioactive disintegration. The main points of this theory are,
electroscope, etc. (1) The atomic nuclei of the radioactive elements are unstable and
Nature and characteristics of radioactive emissions liable to disintegrate any moment.
The phenomenon of radioactivity arises because of the decay of (2) The disintegration is spontaneous, i.e., constantly breaking. The
unstable nuclei or certain element. rate of breaking is not affected by external factors like temperature,
Photographic plate pressure, chemical combination etc.
The nature of the radiations emitted
from a radioactive substance was

investigated by Rutherford (1904) by
 

Radioactive
Lead block substance

Fig. 7.1
 260 Nuclear Chemistry
(3) During disintegration, atoms of new elements called daughter To determine the number of - and - particles emitted during the
elements having different physical and chemical properties than the parent nuclear transformation. It can be done in following manner,
elements come into existence. a
c X  bd Y  x 42 He  y 1 e 0
(4) During disintegration, either alpha or beta particles are emitted
from the nucleus. ab
a  b  4 x or x  .....(i)
The disintegration process may proceed in one of the following two 4
ways, c  d  2x  y .....(ii)
(i) -particle emission : When an -particle (2 He ) is emitted 4 where x = no. of -emitted, y = no. of -emitted
from the nucleus of an atom of the parent element, the nucleus of the new substituting the value of x from eq. (i) in eq. (ii) we get
element, called daughter element possesses atomic mass or atomic mass ab a  b 
c d  2  y ; y  d   c
number less by four units and nuclear charge or atomic number less by 2  4   2 
units because -particle has mass of 4 units and nuclear charge of two
units. Radioactive disintegration series
Parent element -α Daughter element

The phenomenon of natural radioactivity continues till stable nuclei
Atomic mass : W W 4
are formed. All the nuclei from the initial element to the final stable
Atomic number : Z Z 2 element constitute a series known as disintegration series. Further we know
(ii) -particle emission : -particle is merely an electron which has that mass numbers change only when -particles are emitted (and not
negligible mass. Whenever a beta particle is emitted from the nucleus of a when -particles are emitted) causing the change in mass of 4 units at each
radioactive atom, the nucleus of the new element formed possesses the step. Hence the mass numbers of all elements in a series will fit into one of
same atomic mass but nuclear charge or atomic number is increased by 1 the formulae. 4n, 4 n  1 , 4 n  2 and 4 n  3 , hence there can be only
unit than the parent element. Beta particle emission is due to the result of four disintegration series.
decay of neutron into proton and electron. 0 n1  1 p1  1e 0 4n 4n + 1 4n + 2 4n + 3
n 58 59 59 58
The electron produced escapes as a beta-particle-leaving proton in Parent element 232
90 Th 94 Pu 241 92 U
238
92 U
235
the nucleus.
Half life (yrs) 10
1.39  10 10 4.5  10 9 7.07  10 8
Parent element
-β
 Daughter element
Atomic mass : W W Half life (yrs) 13.5
Atomic number : Z Z 1 1.39  10 10 2.2  10 6 4.5  10 9

(iii) -ray emission : -rays are emitted due to secondary effects. The Name of series Thorium Neptunium Uranium Actinium
(Natural) (Artificial) (Natural) (Natural)
excess of energy is released in the form of -rays. Thus -rays arise from End product 208
energy re-arrangements in the nucleus. As -rays are short wavelength 82 Pb 83 Bi 209 82 Pb
206
82 Pb
207

electromagnetic radiations with no charge and no mass, their emission from n 52 52 51 51

a radioactive element does not produce new element. Number of lost  6  8  8  7
particles
Special case : If in a radioactive transformation 1 alpha and 2 beta-  4  5  6  4
particles are emitted, the resulting nucleus possesses the same atomic Nuclear structure and Nuclear forces
number but atomic mass is less by 4 units. A radioactive transformation of
this type always produces an isotope of the parent element. According to an earlier hypothesis, the nucleus is considered as
α W 4 β W 4 β W 4 being composed of two building blocks, proton's and neutron's, which are
Z A W

 Z 2 B 
 Z 1 C 
 ZD collectively called nucleons. The forces, which hold the nucleons together
A and D are isotopes. means stronger proton – proton, neutron – neutron and even proton –
neutron attractive forces, exist in the nucleus. These attractive forces are
Group displacement law called nuclear forces. Nuclear forces operate only within small distance of
Soddy, Fajans and Russell (1911-1913) observed that when an - about 1  10 15 m or 1 fermi (1 fermi = 10 13 cm ) and drops rapidly to
particle is lost, a new element with atomic number less by 2 and mass
number less by 4 is formed. Similarly, when -particle is lost, new element zero at a distance of 1  10 13 cm. These are referred to as short range
with atomic number greater by 1 is obtained. The element emitting then  forces. Nuclear forces are nearly 10 21 times stronger than electrostatic
forces.
or -particle is called parent element and the new element formed is called
daughter element. The above results have been summarized as, Yukawa in 1935, put forward a postulate that neutrons and protons
(1) When an -particle is emitted, the new element formed is are held together by very rapid exchange of nuclear particles called Pi-
displaced two positions to the left in the periodic table than that of the mesons (-mesons have mass equal to 275 times of the mass of an electron
parent element (because the atomic number decreases by 2). and a charge equal to +1, 0 or –1. These are designated as   and  + 0 –

(2) When a -particle is emitted, the new element formed is respectively). The nuclear force which is used in rapid exchange of Pi-
displaced one position to the right in the periodic table than that of the mesons between nucleons are also called exchange forces.
parent element (because atomic number increased by 1). The binding forces between unlike nucleons (p and n) are explained
(3) When a positron is emitted, the daughter element occupies its by the oscillation of a charged -meson ( or   ) +

position one group to the left of the parent element in periodic table.
Group displacement law should be applied with great care especially (a) p1  n 2 n1     n 2 n1  p 2
in the case of elements of lanthanide series (57 to 71), actinide series (89 to 
(b) p1  n 2 n1    p 2 n1  p 2
103), VIII group (26 to 28; 44 to 46; 76 to 78), IA and IIA groups.
Binding forces between like nucleons (p - p or n - n) result from the
exchange of neutral mesons ( ) as represented below.
0

(a) p1 p 2   0 or p1   0 p2
(b) n1 n 2   0 or n1   0 n2
Nuclear stability
Nuclides can be grouped on the basis of nuclear stability, i.e. stable
and unstable nucleus. The most acceptable theory about the atomic nuclear
stability is based upon the fact that the observed atomic mass of all known
isotopes (except hydrogen) is always less from the sum of the weights of
protons and neutrons present in it. Electron (- particle) from a radioactive
nucleus may be regarded as derived from a neutron in the following way,
Neutron  Proton  Electron
Similarly, photons are produced from internal stresses within the
nucleus.
The stability of nucleus may be discussed in terms of any one of the
following,
(1) Nuclear Binding Energy and Mass defect : It is observed that
atomic mass of all nuclei (except hydrogen) is different from the sum of
masses of protons and neutrons. The difference is termed mass defect.
Mass defect = Total mass of nucleons – obs. atomic mass
The mass defect is converted into energy. This energy is
called the binding energy. This is the energy required to break the
nucleus into is constituents (p and n).
Binding energy = Mass defect 931MeV
The stability of the nucleus is explained on the value of binding
energy per nucleon and not on the basis of total binding energy . Binding
energy per nucleon is maximum (8.7 MeV) in the case of iron (56). The
value of binding energy per nucleon can be increased either by fusion of
lighter nuclei or fission of heavier nuclei.
Value of binding energy predicts the relative stability of the different
isotopes of an element. If the value of binding energy is negative, the
product nucleus or nuclei will be less stable than the reactant nucleus. Thus
the relative stability of the different isotopes of an element can be predicted
by the values of binding energy for each successive addition of one neutron
to the nucleus.
2 He
3
 0 n1 2 He 4  20.5 MeV
4
 0 n1  2 He 5  0.8 MeV
2 He
Therefore, 2 He
4
is more stable than 2 He
3
and 2 He
5
. or by K-electron capture.
(2) Packing fraction : The difference of actual isotopic mass and the
mass number in terms of packing fraction is defined as,
Actual isotopicmass  Mass number
Packing fraction   10 4
Mass number
The value of packing fraction depends upon the manner of packing
of the nucleons with in the nucleus. Its value can be negative, positive or
even zero. A negative packing fraction generally indicates stability of the
nucleus.
In general, lower the packing fraction, greater is the binding energy
per nucleon and hence greater is the stability. The relatively low packing
fraction of He, C and O implies their exceptional stability, packing fraction
is least for Fe (negative) and highest for H (+78).
(3) Magic number : Nucleus of atom, like extra-nuclear electrons,
also has definite energy levels (shells).
Nuclei with 2, 8, 20, 28, 50, 82 or 126 protons or neutrons have
been found to be particularly stable with a large number of isotopes. These
numbers, commonly known as Magic numbers are defined as the number of
Nuclear Chemistry 261
nucleons required for completion of the energy levels of the nucleus.
Nucleons are arranged in shells as two protons or two neutrons (with
paired spins) just like electrons arranged in the extra-nuclear part. Thus the
following nuclei 2 He 4 , 8 O16 ,20 Ca 40 and 82 Pb208 containing protons 2,
8, 20 and 82 respectively (all magic numbers) and neutrons 2, 8, 20 and 126
respectively (all magic numbers) are the most stable.
Magic numbers for protons : 2, 8, 20, 28, 50, 82,114
Magic numbers for neutrons : 2, 8, 20, 28, 50, 126, 184, 196
When both the number of protons and number of neutrons are
magic numbers, the nucleus is very stable. That is why most of the
radioactive disintegration series terminate into stable isotope of lead (magic
number for proton = 82, magic number for neutron = 126). Nuclei with
nucleons just above the magic numbers are less stable and hence these may
emit some particles to attain magic numbers.
(4) Neutron-proton ratio or causes of radioactivity It has been
found that the stability of nucleus depends upon the neutron to proton
ratio (n/p). If we plot the number of neutrons against number of protons
for nuclei of various elements, it has been observed that most of the stable
(non-radioactive) nuclei lie in a belt shown by shaded region in figure this is
called stability belt or stability zone. The nuclei whose n/p ratio does not lie
in the belt are unstable and undergo spontaneous radioactive disintegration.
Stability belt
Neutron rich
Neutron number
nuclei
n/p=1
(n)
Proton rich
nuclei
20 40 60 80 100 120
It has been observed that, Atomic number (p)
Fig. 7.2
(i) n / p ratio for stable nuclei lies quite close to unity for elements
with low atomic numbers (20 or less) but it is more than one for nuclei
having higher atomic numbers. Nuclei having n / p ratio either very high or
low undergo nuclear transformation.
(ii) When n / p ratio is higher than required for stability, the nuclei
have the tendency to emit   rays i.e., a neutron is converted into a
proton.
(iii) When n / p ratio is lower than required for stability, the nuclei
increase the ratio, either by emitting   particle or by emitting a position
Rate of radioactive decay
“According to the law of radioactive decay, the quantity of a radio-
element which disappears in unit time (rate of disintegration) is directly
proportional to the amount present.”
The law of radioactive decay may also be expressed mathematically.
Suppose N be the number of atoms of the radioactive element
0
present at the commencement of observation, t  0 and after time t, the
number of atoms remaining unchanged is N t . The rate of disintegration
 dN t  dN t
  dt  at any time t is directly proportional to N. Then,  dt = N
 
where  is a radioactive constant or decay constant.
Various forms of equation for radioactive decay are,
N t  N 0 e t ; log N 0  log N t  0.4343 t
N0 t 2 .303 N
log  ;  log 0
Nt 2 .303 t Nt
 262 Nuclear Chemistry
This equation is similar to that of first order reaction, hence we can
say that radioactive disintegration are examples of first order reactions.
However, unlike first order rate constant (K), the decay constant () is
independent of temperature.
Rate of decay of nuclide is independent of temperature, so its energy
of activation is zero.
(1) Half-life period (T or t ) : The half-life period of a radioelement
1/2 1/2
is defined, as the time required by a given amount of the element to decay
to one-half of its initial value.
0 .693
t1 / 2 
 (c) which is defined as that amount of any radioactive material which gives
Now since  is a constant, we can conclude that half-life period of a
particular radioelement is independent of the amount of the radioelement.
In other words, whatever might be the amount of the radioactive element
present at a time, it will always decompose to its half at the end of one half-
life period.
Let the initial amount of a radioactive substance be N 0
Amount of radioactive substance left after n half-life periods
n
1
N    N0
2
Total time T  n  t1 / 2 where n is a whole number.
(2) Average-life period (T) : Since total decay period of any element
is infinity, it is meaningless to use the term total decay period (total life
period) for radioelements. Thus the term average life is used.
Sum of livesof the nuclei
Average life (T) 
Total number of nuclei
Average life (T) of an element is the inverse of its decay constant,
1
i.e., T  , Substituting the value of  in the above equation,

t1 / 2
T  1 .44 t1 / 2
0 .693
Thus, Average life (T)  1.44  Half life(T1 / 2 )  2  t1 / 2
Thus, the average life period of a radioisotope is approximately
under-root two times of its half life period.
(3) Activity of population or specific activity : It is the measure of
radioactivity of a radioactive substance. It is defined as ' the number of
radioactive nuclei, which decay per second per gram of radioactive isotope.'
Mathematically, if 'm' is the mass of radioactive isotope, then
Rate of decay N Avogadro number
Specific activity    
m m Atomic mass in g
where N is the number of radioactive nuclei which undergoes
disintegration.
(4) Radioactive equilibrium : Suppose a radioactive element A
disintegrates to form another radioactive element B which in turn
disintegrates to still another element C.
A  B  C
B is said to be in radioactive equilibrium with A if its rate of
formation from A is equal to its rate of decay into C.
It is important to note that the term equilibrium is used for
reversible reactions but the radioactive reactions are irreversible, hence it is
preferred to say that B is in a steady state rather than in equilibrium state.
N A  B T A t 1 / 2  A
At a steady state,   
N B  A T B t1 / 2 B
Thus at a steady state (at radioactive equilibrium), the amounts
(number of atoms) of the different radioelements present in the reaction
series are inversely proportional to their radioactive constants or directly
proportional to their half-life and also average life periods.
(5) Units of radioactivity : The standard unit in radioactivity is curie
3.7  1010 disintegration’s per second (dps), i.e.,1c = Activity of 1g of
Ra226  3.7  1010 dps
The millicurie (mc) and microcurie (c) are equal to 10 3 and
10 6 curies i.e. 3.7  10 7 and 3.7  10 4 dps respectively.
1c  10 3 mc  10 6 c ; 1c  3.7  1010 dps
1mc  3.7  107 dps ; 1c  3.7  10 4 dps
But now a day, the unit curie is replaced by rutherford (rd) which is
defined as the amount of a radioactive substance which undergoes
10 6 dps. i.e., 1 rd  10 6 dps . The millicurie and microcurie
correspondingly rutherford units are millirutherford (mrd) and
microrutherford (rd) respectively.
1 c  3.7  1010 dps  37  10 3 rd
1 mc  3.7  107 dps  37 rd
1 c  3.7  10 4 dps  37 mrd
However, in SI system the unit of radioactivity is Becquerel (Bq)
1 Bq = 1 disintegration per second = 1 dps = 1rd,
10 6 Bq  1 rd , 3.7  1010 Bq  1 c
(6) The Geiger-Nuttal relationship : It gives the relationship between
decay constant of an - radioactive substance and the range of the -
particle emitted.
log  A  B log R
Where R is the range or the distance which an -particle travels
from source before it ceases to have ionizing power. A is a constant which
varies from one series to another and B is a constant for all series. It is
obvious that the greater the value of  the greater the range of the -
particle.
Artificial transmutation of elements
The conversion of one element into another by artificial means, i.e.,
by means of bombarding with some fundamental particles, is known as
artificial transmutation. The phenomenon was first applied on nitrogen
whose nucleus was bombarded with -particles to produce oxygen.
14
 2 He 4  8 O17  1 H 1
7N
Nitrogen isotope Alpha particle Oxygen isotope Proton
The element, which is produced, shows radioactivity, the
phenomenon is known as Induced radioactivity. The fundamental particles
which have been used in the bombardment of different elements are,
-particle : 2 He 4 ; Proton : 1 H 1
Deutron : 1 H 2 or 1 D 2 ; Neutron : 0 n1
 Nuclear Chemistry 263

Since -particles, protons and deutrons carry positive charge, they
are repelled by the positively charged nucleus and hence these are not good
projectiles. On the other hand, neutrons, which carry no charge at all, are
the best projectiles. Cyclotron is the most commonly used instrument for
accelerating these particles. The particles leave the instrument with a
velocity of about 25,000 miles per second. A more recent accelerating
instrument is called the synchrotron or bevatron. It is important to note
that this instrument cannot accelerate the neutrons, being neutral.
When a target element is bombarded with neutrons, product
depends upon the speed of neutrons. Slow neutrons penetrate the nucleus
while a high-speed neutron passes through the nucleus.
92 U
238
 0n
1
 92 U 239 ; 92 U 238 
slow speed high speed
Thus slow neutrons, also called thermal neutrons are more effective
in producing nuclear reactions than high-speed neutrons.
Alchemy : The process of transforming one element into other is
known as alchemy and the person involved in such experiments is called
alchemist. Although, gold can be prepared from lead by alchemy, the gold
obtained is radioactive and costs very high than natural gold.
(i) Transmutation by -particles
(a) , n type
4 Be 9 ( , n) 6 C12 i.e. 4 Be
9
 2 He 4  6 C12  0 n1
Pu239 (, n) 96 Cm 242 i.e. Pu239  2 He 4  94 Cm 242  0 n1
94 94
4 Be 9 (, n) 4 Be 8 i.e., 4 Be 9    4 Be 8  0 n1
Synthetic elements : Elements with atomic number greater than 92
i.e. the elements beyond uranium in the periodic table are not found in
nature like other elements. All these elements are prepared by artificial
transmutation technique and are therefore known as transuranic elements
or synthetic elements.
Nuclear fission and Nuclear fusion
(1) Nuclear fission : The splitting of a heavier atom like that of
uranium – 235 into a number of fragments of much smaller mass, by
suitable bombardment with sub-atomic particles with liberation of huge
0n
1
 92 U 237  20 n1 amount of energy is called Nuclear fission. Hahn and Startsman discovered
that when uranium-235 is bombarded with neutrons, it splits up into two
relatively lighter elements.
92 U
235
 0 n 1  56 Ba140  36 Kr 93  3 0 n 1 + Huge amount of energy
Spallation reactions are similar to nuclear fission. However, they
differ by the fact that they are brought by high energy bombarding particles
or photons.
Elements capable of undergoing nuclear fission and their fission
products. Among elements capable of undergoing nuclear fission, uranium is
the most common. The natural uranium consists of three isotopes, namely
U 234 (0.006%) , U 235 (0.7%) and U 238 (99.3%) . Of the three isomers

(b) , p type of uranium, nuclear fission of U 235 and U 238 are more important.
19
(, p) 10 Ne 22 ie. 9 F19  2 He 4  10 Ne 22  1 H 1 Uranium-238 undergoes fission by fast moving neutrons while U 235
9F
undergoes fission by slow moving neutrons; of these two, U 235 fission is of
7 N 14
(, p) 8 O 17 i.e., 7 N 14  2 He 4  8 O17  1 H 1
much significance. Other examples are Pu 239 and U 233 .
(c) ,  type
Uranium-238, the most abundant (99.3%) isotope of uranium,
26 Fe59 (,  ) 29 Cu 63 i.e., 26 Fe59  2 He 4  29 Cu 63  1e 0 although itself does not undergo nuclear fission, is converted into
(ii) Transmutation by protons plutonium-239.
(a) p, n type
92 U
238
 0 n1  92 U 239 ; 92 U
239
 92 NP 239  1e 0
15 P 31 (p, n) 16 S 31 i.e., 15 P 31  1 H 1  16 S 31  0 n1
(b) p,  type 93 Np 238  94 Pu239  1e 0

6C (p,  ) 7 N 13 i.e., 6 C12  1 H 1  N 13  

12
Which when bombarded with neutrons, undergo fission to emit
(c) p, d type three neutrons per plutonium nucleus. Such material like U-238 which
themselves are non-fissible but can be converted into fissible material (Pu-
4 Be 9 (p, d ) 4 Be 8 i.e., 4 Be
9
 1 H 1  4 Be 8  1 H 2 239) are known as fertile materials.
(d) p,  type Nuclear chain reaction : With a small lump of U 235 , most of the
8 O ( p,  ) 7 N i.e., 8 O  1 H  7 N  2 He
16 31 16 1 13 4
neutrons emitted during fission escape but if the amount of U 235 exceeds a
(iii) Transmutation by neutrons few kilograms (critical mass), neutrons emitted during fission are absorbed by
(a) n,p type adjacent nuclei causing further fission and so producing more neutrons. Now
since each fission releases a considerable amount of energy, vast quantities
13 Al 27 (n, p) 12 Mg 27 i.e., 13 Al 27  0 n1  12 Mg 27  1 H 1 of energy will be released during the chain reaction caused by U 235
(b) n, type fission. Uranium
8O
16
(n, ) 12 Mg 27 i.e., 8 O16  0 n1  6 C13  2 He 4
E Neutron
(c) n,  type
92 U
238
(n, ) 92 U 239 i.e., 92 U
238
 0 n1  92 U 238  
3E
(d) n, type
8O
18
(n,  ) 9 F19 i.e., 8O
18
 0 n1  9 F19  1e 0
9E
(iv) Transmutation by deutrons
(a) d,p type
3 Li
6
(d, p) 3 Li7 i.e., 3 Li 6  1 H 2  3 Li7  1 H 1 Fig. 7.3
Atomic bomb : An atomic bomb is based upon the process of that
75
32 As (d , p) 32 As
76
i.e., 32 As
75
 1 H 2  32 As76  1 H 1
nuclear fission in which no secondary neutron escapes the lump of a fissile
(v) Transmutation by -radiations material for which the size of the fissile material should not be less than a
(a) , n type minimum size called the critical size. There is accordingly a sudden release
 264 Nuclear Chemistry
of a tremendous amount of energy, which represents an explosive force
much greater than that of the most powerful TNT bomb. In the world war
II in 1945 two atom bombs were used against the Japanese cities of
Hiroshima and Nagasaki, the former contained U-235 and the latter
contained Pu-239.
Atomic pile or Nuclear reactor : It is a device to obtain the nuclear
energy in a controlled way to be used for peaceful purposes. The most
common reactor consists of a large assembly of graphite (an allotropic form
of carbon) blocks having rods of uranium metal (fuel). Many of the
neutrons formed by the fission of nuclei of 92 U 235 escape into the
graphite, where they are very much slow down (from a speed of about
6000 or more miles/sec to a mile/sec) and now when these low speed
neutrons come back into the uranium metal they are more likely to cause
additional fissions. Such a substance like graphite, which slow down the
neutrons without absorbing them is known as a moderator. Heavy water,
D O is another important moderator where the nuclear reactor consists of
2
rods of uranium metal suspended in a big tank of heavy water (swimming
pool type reactor). Cadmium or boron are used as control rods for
absorbing excess neutrons.
Plutonium from a nuclear reactor : For such purposes the fissile
material used in nuclear reactors is the natural uranium which consists
mainly (99.3%) of U-238. In a nuclear reactor some of the neutrons
produced in U-235 (present in natural uranium) fission converts U-238 to a
long-lived plutonium isotope, Pu-239 (another fissionable material).
Plutonium is an important nuclear fuel. Such reactors in which neutrons
produced from fission are partly used to carry out further fission and partly
used to produce some other fissionable material are called Breeder reactors.
Nuclear reactors in India : India is equipped with the five nuclear
reactors, namely
(i) Apsara (1952) (ii) Cirus (1960)
(iii) Zerlina (1961) (iv) Purnima (1972) and R-5
Purnima uses plutonium fuel while the others utilize uranium as fuel.
(2) Nuclear fusion : “Oposite to nuclear fission, nuclear fusion is
defined as a process in which lighter nuclei fuse together to form a heavier
nuclei. However, such processes can take place at reasonable rates only at
very high temperatures of the order of several million degrees, which exist
only in the interior of stars. Such processes are, therefore, called
Thermonuclear reactions (temperature dependent reactions). Once a fusion
reaction initiates, the energy released in the process is sufficient to maintain
the temperature and to keep the process going on.
4 1H 1  2 He
4
 2 1e 0  Energy
Hydrogen Helium Positron
This is not a simple reaction but involves a set of the thermonuclear
reactions, which take place in stars including sun. In other words, energy of
sun is derived due to nuclear fission.
Controlled nuclear fusion : Unlike the fission process, the fusion
process could not be controlled. Since there are estimated to be some 1017
pounds of deuterium ( 1 H 2 ) in the water of the earth, and since each
pound is equivalent in energy to 2500 tonnes of coal, a controlled fusion
reactor would provide a virtually inexhaustible supply of energy.
Hydrogen bomb : Hydrogen bomb is based on the fusion of
hydrogen nuclei into heavier ones by the thermonuclear reactions with
release of enormous energy.
As mentioned earlier the above nuclear reactions can take place only
at very high temperatures. Therefore, it is necessary to have an external
source of energy to provide the required high temperature. For this
purpose, the atom bomb, (i.e., fission bomb) is used as a primer, which by
exploding provides the high temperature necessary for successful working of
hydrogen bomb (i.e., fusion bomb). In the preparation of a hydrogen bomb,
a suitable quantity of deuterium or tritium or a mixture of both is enclosed
in a space surrounding an ordinary atomic bomb. The first hydrogen bomb
was exploded in November 1952 in Marshall Islands; in 1953 Russia exploded
a powerful hydrogen bomb having power of 1 million tonnes of TNT
A hydrogen bomb is far more powerful than an atom bomb. Thus if it
is possible to have sufficiently high temperatures required for nuclear fusion,
the deuterium present in sea (as D O) is sufficient to provide all energy
2
requirements of the world for millions of years. The first nuclear reactor was
assembled by Fermi in 1942.
Difference between Nuclear fission and fusion
Nuclear fission Nuclear fusion
The process occurs only in the nuclei of The process occurs only in the nuclei
heavy elements. of light elements.
The process involves the fission of the The process involves the fission of the
heavy nucleus to the lighter nuclei. lighter nuclei to heavy nucleus.
The process can take place at ordinary The process takes place at higher
temperature.
temperature ( 10 8 o C) .
The energy liberated during this process The energy liberated during the
is high process is comparatively low
(200 MeV per fission) (3 to 24 MeV per fusion)
Percentage efficiency of the energy Percentage efficiency of the energy
conversion is comparatively less. conversion is high (four times to that
of the fission process).
The process can be controlled for useful The process cannot be controlled.
purposes.
Application of radioactivity
Radioisotopes find numerous applications in a variety of areas such as
medicine, agriculture, biology, chemistry, archeology, engineering and industry.
(1) Age determination : The age of earth has been determined by
uranium dating technique as follows. Samples of uranium ores are found to
contain Pb 206 as a result of long series of - and -decays. Now if it is
assumed that the ore sample contained no lead at the moment of its
formation, and if none of the lead formed from U 238 decay has been lost
then the measurement of the Pb 206 / U 238 ratio will give the value of time
t of the mineral.
No. of atoms of Pb 206
 e  t 1
No. of atoms of U 238 left
where  is the decay constant of uranium-238
Alternatively,
2 .303 Initial amount of U 238
t log
 Amount of U 238 in the mineral present till date
Similarly, the less abundant isotope of uranium, U 235 eventually decays
to Pb 207 ; Th 232 decays to Pb 208 and thus the ratios of Pb 207 / U 235 and
Pb 208 / Th 232 can be used to determine the age of rocks and minerals.
14
6C (half-life 5760 years) was used by Willard Libby (Nobel
lauret) in determining the age of carbon-bearing materials (e.g. wood,
animal fossils, etc.) Carbon-14 is produced by the bombardment of nitrogen
atoms present in the upper atmosphere with neutrons (from cosmic rays).
N 14  0 n1  6 C14  1 H 1
7
Thus carbon-14 is oxidised to CO 2 and eventually ingested by
plants and animals. The death of plants or animals puts an end to the intake
of C 14 from the atmosphere. After this the amount of C 14 in the dead
tissues starts decreasing due to its disintegration.
6C
14
 7 N 14  1e 0
It has been observed that on an average, one gram of radioactive
carbon emits about 12 -particles per minute. Thus by knowing either the
amount of C-14 or the number of -particles emitted per minute per gram
of carbon at the initial and final (present) stages, the age of carbon material
can be determined by using the following formulae.

2 .303 N 2 .303 N The increased pace of synthesis and use of radio isotopes has led to
 log 0 or t  log 0
t Nt  Nt
where t = Age of the fossil,  = Decay constant, N 0 = Initial radioactivity
(in the fresh wood), N t = Radioactivity in the fossil
The above formula can be modified as,
2 .303 Initial ratio of C 14 / C 12 (in fresh wood)
t log
 C 14 / C 12 ratio in the old wood
Similarly, tritium 1 H 3 has been used for dating purposes.
(2) Radioactive tracers (use of radio–isotopes) : A radioactive isotope
can be easily identified by its radioactivity. The radioactivity can, therefore
act as a tag or label that allows studying the behaviour of the element or
compounding which contains this isotope. An isotope added for this
purpose is known as isotopic tracer. The radioactive tracer is also known as
an isotopic tracer. The radioactive tracer is also known as an indicator
because it indicates the reaction. Radioisotopes of moderate half-life periods
are used for tracer work. The activity of radioisotopes can be detected by
means of electroscope, the electrometer or the Geiger-Muller counter.
Tracers have been used in the following fields,
(i) To diagnose many diseases : For example, Arsenic – 74 tracer is
used to detect the presence of tumours, Sodium – 24 tracer is used to
detect the presence of blood clots and Iodine –131 tracer is used to study
the activity of the thyroid gland. It should be noted that the radioactive
isotopes used in medicine have very short half-life periods.
(ii) In agriculture : The use of radioactive phosphorus 32 P in
fertilizers has revealed how phosphorus is absorbed by plants. This study
has led to an improvement in the preparation of fertilizers. 14 C is used to
study the kinetics of photo synthesis.
(iii) In industry : Radioisotopes are used in industry to detect the
leakage in underground oil pipelines, gas pipelines and water pipes.
Radioactive carbon has been used as a tracer in studying mechanisms
involved in many reactions of industrial importance such as alkylation,
polymerization, catalytic synthesis etc.
(iv) In analysis : Several analytical procedures can be used employing
radioisotopes as tracers.
(a) A small amount of radioactive isotope is mixed with the inactive
substance and the activity is studied before and after adsorption. Fall in
activity gives the amount of substance adsorbed.
(b) The solubility of lead sulphate in water may be estimated by
mixing a known amount of radioactive lead with ordinary lead.
(c) Ion exchange process of separation is readily followed by
measuring activity of successive fractions eluted from the column.
(d) By labelling oxygen of the water, mechanism of ester hydrolysis
has been studied.
(e) The efficiency of analytical procedures may be measured by
adding a known amount of radio-isotopes to the sample before analysis
begins. After the completion, the activity is again determined. The
comparison of activity tells about the efficiency of separation.
(3) Use of  rays :  rays are used for disinfecting food grains and
for preserving food stuffs. Onions, potatoes, fruits and fish etc., when
irradiated with  rays, can be preserved for long periods. High yielding
disease resistant varieties of wheat, rice, groundnut, jute etc., can be
developed by the application of nuclear radiations. The  rays radiations are
used in the treatment of cancer. The  radiations emitted by cobalt –60
can burn cancerous cells. The  radiations are used to sterilize medical
instruments like syringes, blood transfusion sets. etc. These radiations make
the rubber and plastics objects heat resistant.
Hazards of radiations
Nuclear Chemistry 265
increased concern about the effect of radiations on matter, particularly in
biological systems. The accident of Chernobyl occurred in 1986 in USSR is no
older when radioisotopes caused a hazard there. The nuclear radiations (alpha,
beta, gamma as well as X-rays) possess energies far in excess of ordinary bond
energies and ionisation energies. Consequently, these radiations are able to
break up and ionise the molecules present in living organisms if they are
exposed to such radiations. This disrupts the normal functions of living
organisms. The damage caused by the radiations, however, depends upon the
radiations received. The resultant radiation damage to living system can be
classified as,
(1)Somatic or pathological damage : This affects the organism during
its own life time. It is a permanent damage to living civilization produced in
body. Larger dose of radiations cause immediate death whereas smaller
doses can cause the development of many diseases such as paralysis, cancer,
leukaemia, burns, fatigue, nausea, diarrhoea, gastrointestinal problems etc.
some of these diseases are fatal. Many scientists presently believe that the
effect of radiations is proportional to exposure, even down to low exposures.
This means that any amount of radiation causes some finite risk to living
civilization.
(2) Genetic damage : As the term implies, radiations may develop
genetic effect. This type of damage is developed when radiations affect genes
and chromosomes, the body's reproductive material. Genetic effects are more
difficult to study than somatic ones because they may not become apparent
for several generations.
 The particle like mesons, positron, neutrino, etc, about 20 in
number are created by stresses in nucleus but do not exist as
component of nucleus.
 Highest degree of radioactivity is shown by radium.
 The nuclear forces are not governed by inverse square law.
 About 42 radioactive nuclides (Z > 82) occur in nature. Each of these
gives stable end product of an isotope of lead.
 The half life is independent of physical or chemical state of a
radioactive element.
 The average life of the natural radioactive element vary from 10 s 10
–6 10
years or more.
 It has been observed that fusion of 45 mg of hydrogen produce as
much energy as obtained from one ton of coal.
 Beryllium has been found to be the best moderator as it occupies small
space and have low absorption cross-section.
 The total life span of a radioactive element is infinite.
 The  - radiation of total energy 1.02 MeV, emitted when a positron
and an electron interact are known as annilation radiation.
 Nuclear Chemistry 267
10. Which can be used for carrying out nuclear reaction
[AFMC 2003]
(a) Uranium – 238 (b) Neptunium – 239
(c) Thorium – 232 (d) Plutonium – 239
11. On comparing chemical reactivity of C 12 and C 14 , it is revealed
that
Nucleus (Stability and Reaction) (a) C 12 is more reactive (b) C 14 is more reactive
(c) Both are inactive (d) Both are equally active
1. Nucleons are [CPMT 1982]
(a) Protons and electrons 12. The radionucleide 90234
Th undergoes two successive  -decays
(b) Protons and neutrons followed by one  -decay. The atomic number and the mass
number respectively of the resulting radionucleide are [
(c) Electrons and neutrons
(a) 92 and 234 (b) 94 and 230
(d) Electrons, protons and neutrons
(c) 90 and 230 (d) 92 and 230
2. A deutron contains [NCERT 1982; CPMT 1994]
13. Hydrogen and deuterium differ in [CPMT 1980]
(a) A neutron and a positron (a) Reactivity with oxygen (b) Reactivity with chlorine
(b) A neutron and a proton (c) Melting point (d) Reducing action
(c) A neutron and two protons 14. A nuclear reaction must be balanced in terms of
(d) A proton and two neutrons (a) Only energy (b) Only mass
3. The nucleus of radioactive element possesses (c) Mass and energy (d) None of these
(a) Low binding energy (b) High binding energy 15. In the following nuclear reaction, the other product is
(c) Zero binding energy (d) High potential energy 52 Te
130
1 H 2 53 I131  ? [MP PET 1991]
4. On bombarding 7 N 14 with  -particles, the nuclei of the product (a) Positron (b) Alpha particle
formed after the release of a proton will be or In nuclear reaction (c) One neutron (d) Proton
7N
14
 2 He  Z X  1 H , the term Z X represents[NCERT 1979;16.MP PMT
4 A 1 A
The1989;
reaction 5 B 4 Be 1 e
8
MNR 1995; 8 0
is due to [MP PMT 1991]
MP PET 1996; BHU 1996] (a) Loss of  -particles (b) Loss of  -particles
17 18
(a) 8O (b) 9F (c) Loss of positron (d) Electron loss
17. Positronium is the name given to an atom-like combination formed
(c) 9 F 17 (d) 8 O 18 between [NCERT 1980; JIPMER 1991]
5. Nuclear energy is based on the conversion of (a) A positron and a proton
(a) Protons into neutrons (b) A positron and a neutron
(b) Mass into energy (c) A positron and  -particle
(c) Neutrons into protons (d) A positron and an electron
(d) Uranium into radium 18. An electrically charged atom or a group of atoms is known as [

6. Positron has nearly the same weight as that of (a) A meson (b) A proton
[NCERT 1975; JIPMER 1991; BHU 1995]
(c) An ion (d) A cyclotron
19. The charge on positron is equal to the charge on which one of the
(a)  -particle (b) Proton
following [NCERT 1977]
(c) Neutron (d) Electron
(a) Proton (b) Electron
7. In the reaction 3 Li 6  (?)  2 He 4  1 H 3 . The missing particle (c)  -particle (d) Neutron
is [CPMT 1983, 84]
20. In the nuclear reaction 12 Mg 24  2 He 4  0 n1  ? The product
(a) Electron (b) Neutron
nucleus is [BHU 1987]
(c) Proton (d) Deutron
27 27
(a) Al (b) Si
8. The 6 C 14 in upper atmosphere is generated by the nuclear 13 14

reaction [MP PET 1993] (c) Al 28 (d) Mg 25

13 12

(a) N 14  1 H 1  6 C 14  1 e
0
 1H1 21. 14
is formed from 7 N 14 in the upper atmosphere by the
6C
7

(b) N 14  6 C 14  0 action of the fundamental particle [Orissa JEE 2002]

7 1 e
(a) Positron (b) Neutron
(c) 7 N 14  0 n 1  6 C 14  1 H 1 (c) Electron (d) Proton
22. In the nuclear reaction
(d) N 14  1 H 3  0 n 1  6 C 14  2 He 4
82 Pb 206  x 2 He 4  y 1 
7 238 0
92 U

9. Deuterons when bombarded on a nuclide produce 18 Ar 38 and the value of x and y are respectively ……..
neutrons. The target is [CPMT 1982, 87] [Orissa JEE 2002]
(a) 8, 6 (b) 6, 4
35
(a) 17 Cl (b) 19 K 27 (c) 6, 8 (d) 8, 10
23. If an isotope of hydrogen has two neutrons in its atom, its atomic
(c) 17 Cl
37
(d) 19 K 39 number and atomic mass number will respectively be
 268 Nuclear Chemistry
[CBSE 1992] The value of n will be [MP PMT 1999]
(a) 2 and 1 (b) 3 and 1 (a) 3 (b) 4
(c) 1 and 1 (d) 1 and 3 (c) 5 (d) 6
24. Which one of the following nuclear transformation is (n, p ) type [AIIMS 1980, 83]
34. The introduction of a neutron into the nuclear composition of an
(a) 3 Li7  1 H 1  4 Be 7  0 n1 atom would lead to a change in [MNR 1995]
(a) The number of the electrons also
(b) 33 As  2 He  35 Br  0 n
75 4 78 1
(b) The chemical nature of the atom
(c) 83 Bi209  1 H 2  84 Po 210  0 n1 (c) Its atomic number
(d) Its atomic weight
(d) 21 Sc  0 n  20 Ca  1 H
45 1 45 1

25. What is X in the following nuclear reaction 35. The composition of tritium ( 1 H 3 ) is

N 14  1 H 1 8 O 15  X [AIIMS 1983; MP PET 1997] [Manipal MEE 1995; DPMT 1982,96]
7
(a) 1 electron, 1 proton, 1 neutron
0 1
(a) 1 e (b) 0n (b) 1 electron, 2 protons, 1 neutron
(c)  (d) 1 e
0 (c) 1 electron, 1 proton, 2 neutrons
(d) 1 electron, 1 proton, 3 neutrons
26. In the reaction 93 Np 239 94 Pu 239 + (?), the missing particle
is [MNR 1987] 36. Identify ' X ' in 16 S 32  X  15 P 30  2 He 4
(a) Proton (b) Positron (a) 1H
1
(b) 1D
2

(c) Electron (d) Neutron

(c) 0n
1
(d) e 
27. According to the nuclear reaction 4 Be  2 He 4 6 C 12  0 n 1 ,
37. In terms of energy 1 a. m.u. is equal to
mass number of (Be ) atom is
[MP PET/PMT 1998]
[AFMC 2002]
(a) 100 J (b) 931.1 MeV
(a) 4 (b) 9
(c) 7 (d) 6 (c) 931.1 kcal (d) 10 7 erg
28. Which of the following nuclides has the magic number of both 38. Positron is [AIIMS 1997]
protons and neutrons [EAMCET 1989] (a) Electron with +ve charge
(a) 50 Sn 115 (b) 82 Pb 206 (b) A helium nucleus
(c) A nucleus with two protons
(c) Pb 208 (d) Sn 118
82 50 (d) A nucleus with one neutron and one proton
29. In the carbon cycle, from which hot stars obtain their energy, the   
14 39. X  Y   Z   W
6C nucleus is
In the above sequence of reaction, the elements which are isotopes
(a) Completely converted into energy of each other are [JIPMER 1997]
(b) Regenerated at the end of the cycle
(a) X and W (b) Y and Z
(c) Combined with oxygen to form carbon monoxide
(d) Broken up into its constituents protons and neutrons (c) X and Z (d) None of these
30. The atomic mass of lead is 208 and atomic number is 82. The 40. Stable nuclides are those whose n/p ratio is [MP PMT 1993]
atomic mass of bismuth is 209 and atomic number is 83. The ratio (a) n/ p 1 (b) n / p  2
of n/p in the atom is [EAMCET 1982]
(c) n / p  1 (d) n / p  1
(a) Higher of lead (b) Higher of bismuth
41. Neutrino has [NCERT 1981]
(c) Same (d) None of these
(a) Charge +1, mass 1 (b) Charge 0, mass 0
31. Which of the following is an n, p reaction [BHU 1995]
(c) Charge – 1, mass 1 (d) Charge 0 , mass 1
(a) 5C
13
 1 H 1  6 C 14 42. Which one of the following nuclear reaction is correct
[CPMT 1997]
(b) N 14  1 H 1  8 O 15  
  v
7
(a) 6C
13
1 H 7 N
1 13

(c) 13 Al 27  0 n1  12 Mg 27  1 H 1
(b) 11 Na 23  1 H 1  10 Ne 20  2 He 4
(d) 92 U
235
 0 n1  54 Xe 140  38 Sr 93  3 0 n1
(c) 13 Al 23  0 n 1  11 Na 23  e 0
32. Which one of the following statements is incorrect
[MP PET 1997] (d) None of these
(a) Mass defect is related with binding energy 43. Formation of nucleus from its nucleons is accompanied by
[NCERT 1975; RPET 2000]
(b) ‘Meson’ was discovered by Yukawa
(a) Decrease in mass (b) Increase in mass
(c) The size of the nucleus is of the order of 10 12  10 13 cm (c) No change of mass (d) None of them
(d) Magnetic quantum number is a measure of ‘orbital angular 44. A particle having the same charge and 200 times greater mass than
momentum’ of the electron that of electron is
33. In the sequence of following nuclear reactions (a) Positron (b) Proton
   n 
92 X
238

 Y   Z   L 84 M 218
(c) Neutrino (d) Meson
 Nuclear Chemistry 269
45. The positron is [AFMC 1997] 58. In the reaction, Po  
 Pb 
 Bi, if Bi, belongs to
0 0
(a) 1 e (b) 1 e group 15, to which Po belongs [DCE 2000]
1 1
(a) 14 (b) 15
(c) 1H (d) 0n (c) 13 (d) 16
46. Which of the following is the most stable atom 59. In the nuclear reaction 9
Be( p,  ) X , the X is
4
[AFMC 1997]
[MP PMT 2000]
(a) Bi (b) Al 4 6
(a) 2 He (b) 3 Li
(c) U (d) Pb
7 8
47. The positron is discovered by [RPMT 1997] (c) 3Li (d) Be 4
(a) Pauling (b) Anderson 60. Which of the following does not contain number of neutrons equal to
(c) Yukawa (d) Segar 40
that of 18 Ar [MP PMT 2000]
48. The nucleus of an atom is made up of X protons and Y neutrons. 41 43
For the most stable and abundant nuclei (a) 19 K (b) 21 Sc
[NCERT 1980] 40 42
(c) 21 Sc (d) 20 Ca
(a) X and Y are both even (b) X and Y are both odd

(c) X is even and Y is odd (d) X is odd and Y is even 61. Nuclear reactivity of Na and Na is same because both have
49. Atom A possesses higher values of packing fraction than atom B. (a) Same electron and proton
The relative stabilities of A and B are (b) Same proton and same neutron
(a) A is more stable than B (c) Different electron and proton
(b) B is more stable than A (d) Different proton and neutron
(c) A and B both are equally stable 62. Which of the following is the heaviest metal
[MH CET 2001]
(d) Stability does not depend on packing fraction
(a) Hg (b) Pb
50. How many neutrons are present in the nucleus of Ra (c) Ra (d) U
[CPMT 1980]
63. In the following reaction, x will be 29 Cu
64
28 Ni64  x
(a) 88 (b) 226
(c) 140 (d) 138 (a) A proton (b) An electron
51. In a nuclear explosion, the energy is released in the form of (c) A neutron (d) A positron
64. Which one out of the following statements is not correct for ortho
[CPMT 1994]
and para hydrogen [Orissa JEE 2002]
(a) Kinetic energy (b) Electrical energy (a) They have different boiling point
(c) Potential energy (d) None of these (b) Ortho form is more stable than para form
52. In equation 11 Na
23
1 H 1 12 Mg23  x , x represents (c) They differ in the spin of their protons
[MP PMT 1990; MP PET 1999] (d) The ratio of ortho to para hydrogen increases with increase in
temperature and finally pure ortho form is obtained
(a) Neutron (b) Deutron
(c)  -particle (d) Positron 65. For the nuclear reaction, 12 Mg  1 D
24 2
   ? , the missing
53. Which of the following atomic mass of uranium is the most nucleide is [Kurukshetra CEE 2002]
radioactive [AFMC 1997] 22 23
(a) 11 Na (b) 11 Na
(a) 238 (b) 235
23 26
(c) 226 (d) 248 (c) 12 Mg (d) 12 Mg
54. Which of the following particle is emitted in the reaction
66. ZX
M
 2 He 4 15 P 30  0 n 1 . Then [KCET 2002]
13 Al
27
 2 He 4 14 P 30  ..... [DCE 1999]
(a) Z  12, M  27 (b) Z  13, M  27
1 0
(a) 0n (b) 1 e
(c) Z  12, M  17 (d) Z  13, M  28
1 2
(c) 1H (d) 1H
67. An element 96 X emits 4 and 5  particles to form new
227
55. Which of the following sub-atomic particles is not present in an
atom [JIPMER 1999] element Y. Then atomic number and mass number of Y are
(a) Neutron (b) Proton (a) 93; 211 (b) 211; 93
(c) Electron (d) Positron (c) 212; 88 (d) 88; 211
56. Electromagnetic radiation with maximum wave length is 68. Meson was discovered [MH CET 2004]
[DCE 2000; UPSEAT 2000] (a) Yukawa (b) Austin
(a) Ultraviolet ray (b) Radiowave (c) Moseley (d) Einstein
(c) X-ray (d) Infrared
57. Neutrons are obtained by [JIPMER 1999]
Radioactivity and ,  and - rays
(a) Bombardment of Ra with -particles
(b) Bombardment of Be with -particles 1. Which of the following does not contain material particles
(c) Radioactive disintegration of uranium [BHU 2002]
(d) None of these (a) Alpha rays (b) Beta rays
(c) Gamma rays (d) Canal rays
2. Radioactive substances emit -rays, which are
 270 Nuclear Chemistry
[Orissa JEE 2002] (a) More than -rays (b) More than -rays
(a) + ve charged particle (b) – ve charged particle
(c) Less than -rays (d) None of these
(c) Massive particle (d) Packet of energy
3. Which statement is incorrect [CPMT 1982] 16. -particle is emitted in radioactivity by
(a)  -rays have more penetrating power than  -rays [AIEEE 2002; MP PMT 2004]

(b)  -rays have less penetrating power than  -rays (a) Conversion of proton to neutron
(b) Form outermost orbit
(c)  -rays have less penetrating power than  -rays
(c) Conversion of neutron to proton
(d)  -rays have more penetrating power than  -rays
(d) -particle is not emitted
4. The velocity of  -rays is approximately [CPMT 1982]
17.  -rays have [CPMT 1973, 78; NCERT 1977]
(a) Equal to that of the velocity of light
(b) 1/10 of the velocity of light (a) Positive charge
(c) 10 times more than the velocity of light (b) Negative charge
(d) Uncomparable to the velocity of light (c) No charge
5. The radiations having high penetrating power and not affected by (d) Sometimes positive charge and sometimes negative charge
electrical and magnetic field are [Kerala CET 1992] 18. X-rays are produced due to [JIPMER 2002]
(a) Alpha rays (b) Beta rays (a) Bombarding of electrons on solids
(c) Gamma rays (d) Neutrons (b) Bombarding of -particle on solids
6. Alpha particles are ...... times heavier (approximately) than neutrons [CPMT 1971]
(c) Bombarding of -rays on solids
(a) 2 (b) 4
(d) Bombarding of neutron on solids
1 19. Choose the element which is not radioactive [CPMT 1988]
(c) 3 (d) 2
2 (a) Cm (b) No
235
7. Uranium 92 U on bombardment with slow neutrons produces[CPMT 1982] (c) Mo (d) Md
(a) Deutrons (b) Fusion reaction 20. A magnet will cause the greatest deflection of
[MP PMT 1991]
(c) Fission reaction (d) Endothermic reaction
(a)  -rays (b)  -rays
8. -particles can be detected using [AIIMS 2005]
(a) Thin aluminum sheet (b) Barium sulphate (c)  -rays (d) Neutrons
(c) Zinc sulphide screen (d) Gold foil 21. Of the following radiations, the one most easily stopped by air is [MP PMT 1991
9. Alpha rays consist of a stream of [BHU 1979] (a)  -rays (b)  -rays
(c)  -rays (d) X-rays
(a) H  (b) He 2
(c) Only electrons (d) Only neutrons 22. Uranium ultimately decays into a stable isotope of
[MP PET 1995]
10. Which is the correct statement [CPMT 1971]
(a) Radium (b) Carbon
(a) Isotopes are always radioactive
(c) Lead (d) Neptunium
(b)  -rays are always negatively charged particles 23. Which leaves no track on Wilson cloud chamber
(c)  -rays are always negatively charged particles [AFMC 1988]
(d)  -rays can be deflected in magnetic field (a) Electrons (b) Protons
11. The  -particle is identical with (c)  -particles (d) Neutrons
[CPMT 1972, 82, 86; BHU 1984; 24. Which has the least penetrating power [CPMT 1994]
MP PMT 1990, 91, 93; MP PET 1999] (a)  -rays (b)  -rays
(a) Helium nucleus (c)  -rays (d) X -rays
(b) Hydrogen nucleus 25. There exists on  -rays
(c) Electron [MP PMT 1996; Pb. PMT 2004; EAMCET 2004]
(d) Proton (a) Positive charge
12. If by mistake some radioactive substance gets inside the human (b) Negative charge
body, then from the point of view of radiation damage, the most
harmful will be the one which emits (c) No charge
[DPMT 1986]
(d) Sometimes positive charge, sometimes negative charge
 -rays 26. Which is not emitted by radioactive substance
(a) (b) Neutrons
[AIIMS 1997]
(c)  -particles (d)  -particles (a)  -rays (b)  -rays
13. Radioactivity was discovered by (c) Positron (d) Proton
[CPMT 1983, 88; DPMT 1982; AMU 1983; 27. The radiations from a naturally occurring radio element, as seen
MADT Bihar 1982] after deflection in a magnetic field in one direction, are
(a) Henry Becquerel (b) Rutherford [IIT 1984; MP PMT 1986;
(c) J. J. Thomson (d) Madam Curie MP PET/PMT 1988 JIPMER 1999]
14. Which of the following is radioactive element [CPMT 1988] (a) Definitely -rays (b) Definitely -rays
(a) Sulphur (b) Polonium (c) Both  and -rays (d) Either  or -rays
(c) Tellurium (d) Selenium 226
28. The 88 Ra is [AIIMS 2001]
15. Penetrating power of -particle is [MP PMT 2002]
 Nuclear Chemistry 271
(a) n-mesons (b) u-mesons (c) 0.0018 amu (d) 1.8 amu
(c) Radioactive (d) Non-radioactive (e) 18 amu
29. During -decay [UPSEAT 2001]
(a) An atomic electron is ejected Causes of radioactivity
(b) An electron which is already present with in the nucleus is and Group displacement law
ejected
(c) A neutron in the nucleus decays emitting an electron 1. Am 241 and 234
belong respectively to
95 90 Th
(d) A part of binding of the nucleus is converted into an electron [MP PMT 1999]
30. The element californium belongs to the family of
(a) 4 n and 4 n  1 radioactive disintegration series
[UPSEAT 2002]
(a) Actinide series (b) Alkali metal family (b) 4 n  1 and 4 n  2 radioactive disintegration series
(c) Alkaline earth family (d) Lantanide series (c) 4 n  1 and 4 n  3 radioactive disintegration series
31. Which of the following is not deflected by magnetic field (d) 4 n  1 and 4 n radioactive disintegration series
[MP PMT 2001] 2. Group displacement law states that the emission of  or 
(a) Deuteron (b) Positron particles results in the daughter element occupying a position, in the
(c) Proton (d) Photon periodic table, either to the left or right of that of the parent
element. Which one of the following alternatives gives the correct
32. Which of the following can be used to convert 14
7 N into 17
8 O [MP PMT 2001] position of the daughter element
(a) Deuteron (b) Proton On emission of  particles On emission of  particles

(c) -particle (d) Neutron (a) 2 groups to the right 1 group to the right
33. The amount of energy, which is required to separate the nucleons (b) 2 groups to the right 1 group to the left
from a nucleus. The energy is called (c) 2 groups to the left 1 group to the left
[UPSEAT 2001] (d) 2 groups to the left 1 group to the right
(a) Binding energy (b) Lattice energy 3. The nuclides (A nuclide is the general name for any nuclear species)
12 56
(c) Kinetic energy (d) None of these 6 C , 26 Fe and 92 U 238 have 12, 56 and 238 nucleons
34. What happens when -particle is emitted respectively in the nuclei. The total number of nucleons in a nucleus
is equal to [NCERT 1975]
[CBSE PMT 1989; JIPMER 2002]
(a) The total number of neutrons in the nucleus
(a) Mass number decreases by 12 unit, atomic number decreases by
4 unit (b) The total number of neutrons in the atom
(b) Mass number decreases by 4 unit, atomic number decreases by (c) The total number of protons in the nucleus
2 unit (d) The total number of protons and neutrons in the nucleus
(c) Only mass number decreases 4. Radioactivity is due to [DPMT 1983, 89; AIIMS 1988]
(d) Only atomic number decreases (a) Stable electronic configuration
35. The charge on gamma rays is (b) Unstable electronic configuration
[Pb. PMT 2004; EAMCET 2004] (c) Stable nucleus
(a) Zero (b) +1 (d) Unstable nucleus
(c) –1 (d) +2 5. Radioactive disintegration differs from a chemical change in being [MNR 1991]
36. A nuclear reaction is accompanied by loss of mass equivalent to (a) An exothermic change
0.01864 amu . Energy liberated is (b) A spontaneous process
[DCE 2002] (c) A nuclear process
(a) 931 MeV (b) 186.6 MeV (d) A unimolecular first order reaction
6. 238
U emits 8 -particles and 6 -particles. The neutron/proton
(c) 17.36 MeV (d) 460 MeV 92
ratio in the product nucleus is
37. Nuclear theory of the atom was put forward by [AIIMS 2005]
[KCET 2004] (a) 60/41 (b) 61/40
(a) Rutherford (b) Aston (c) 62/41 (d) 61/42
(c) Neils Bohr (d) J.J. Thomson 7. The element with atomic number 84 and mass number 218 change
38. Decrease in atomic number is observed during [IIT 1998] to other element with atomic number 84 and mass number 214. The
(a) Alpha emission (b) Beta emission number of  and  -particles emitted are respectively [CPMT 1989]
(c) Positron emission (d) Electron capture (a) 1, 3 (b) 1, 4
39. Calculate mass defect in the following reaction (c) 1, 2 (d) 1, 5

1H
2
1 H 3 1 He 4 0 n1 8. A radium 88 Ra 224 isotope, on emission of an  -particle gives
rise to a new element whose mass number and atomic number will
(Given : mass H 2  2.014, H 3  3.016, He  4.004, be
n  1.008 amu ) [Kerala CET 2005] [CPMT 1980; EAMCET 1985; MP PMT 1993]
(a) 220 and 86 (b) 225 and 87
(a) 0.018 amu (b) 0.18 amu
(c) 228 and 88 (d) 224 and 86
 272 Nuclear Chemistry

9. 89 Ac 231 gives 82 Pb 207 after emission of some  and  - 19. After losing a number of  and -particles. 92 U
238
is changed to
particles. The number of such  and  -particles are respectively[MP PMT 1993; UPSEAT
82 Pb
2001]
206
. The total number of -particles lost in this process is[UPSEAT 1999, 2000
(a) 5, 6 (b) 6, 5 (a) 10 (b) 5
(c) 7, 5 (d) 5, 7 (c) 8 (d) 32
10. The number of  and  - particles emitted in the nuclear reaction 20. Which element is the end product of each natural radioactive series[MP PMT 199
90 Th
228
83 Bi212 are respectively (a) Sn (b) Bi
[MNR 1992; MP PMT 1993; AFMC 1998, 2001; (c) Pb (d) C
MH CET 1999; UPSEAT 2000, 01; AMU 2001; CPMT 2002] 21. 27
Al is a stable isotope. 29
Al is expected to disintegrate by
13 13
(a) 4, 1 (b) 3, 7 [IIT 1996; UPSEAT 2001]
(c) 8, 1 (d) 4, 7
(a)  -emission (b)  -emission
11. The number of neutrons in the parent nucleus which gives N 14 on (c) Positron emission (d) Proton emission
 -emission and the parent nucleus is
22. An isotope Y A X undergoes a series of m alpha and n beta
[EAMCET 1985; MNR 1992;
X 32
Kurukshetra CEE 1998; UPSEAT 2000, 01] disintegration to form a stable isotope Y 10 B . The values of
14 12 m and n are respectively [MP PET 1995]
(a) 8, C (b) 6, C
(a) 6 and 8 (b) 8 and 10
(c) 4 , C 13 (d) None of these (c) 5 and 8 (d) 8 and 6
23. During a  -decay the mass of the atomic nucleus
12. After the emission of  -particle from the atom 92 X 238 , the
[MP PET 1996]
number of neutrons in the atom will be
(a) Decreases by one unit (b) Increases by one unit
[MNR 1993; UPSEAT 1999, 2001, 02]
(c) Decreases by two units (d) Remains unaffected
(a) 138 (b) 140
24. Which one of the following notations shows the product incorrectly [MP PET/PM
(c) 144 (d) 150
13. When a radioactive element emits an electron the daughter element (a) 242
96 Cm ( , 2n) 97
243
Bk (b) 10
5 B ( , n) 13
7 N
formed will have [EAMCET 1988; MP PET 1994] 14
(c) 7 N (n, p) 14
6 C (d) 28
14
29
Si (d, n) 15 P
(a) Mass number one unit less
(b) Atomic number one unit less 25. An atom has mass number 232 and atomic number 90. How many
 -particles should it emit after emission of two  -particles, so
(c) Mass number one unit more
that the new element's atom has mass number 212 and atomic
(d) Atomic number one unit more number 82
14. If the amount of radioactive substance is increased three times, the (a) 4 (b) 5
number of atoms disintegrated per unit time would [MP PMT 1994]
(c) 6 (d) 3
(a) Be double (b) Be triple
26. After the emission of one  -particle followed by one   particle
(c) Remain one third (d) Not change
from the atom of 92 X 238 , the number of neutrons in the atom will
15.  -particles are emitted from the atom
be [CBSE PMT 1995]
(a) Due to disintegration of neutron
(a) 142 (b) 146
(b) Due to disintegration of proton (c) 144 (d) 143
(c) Due to removal of electron from K shell 27. A nuclide of an alkaline earth metal undergoes radioactive decay by
(d) Due to removal of electron from outermost orbit emission of the   particles in succession. The group of the
periodic table to which the resulting daughter element would belong
16. Nd (Z  60) is a member of group -3 in periodic table. An isotope is [CBSE PMT 2005]
of it is  -active. The daughter nuclei will be a member of (a) Gr.14 (b) Gr.16
(a) Group -3 (b) Group - 4 (c) Gr.4 (d) Gr.6
(c) Group -1 (d) Group - 2 28. Which one of the following is not correct [MP PMT 1997]
17. Number of neutrons in a parent nucleus X , which gives N 14
3 Li  1 H  4 Be  0 n
7 1 7 1
7 (a)
nucleus after two successive  emissions would be
(b) 21 Sc
45
 0 n1  20 Ca 45  0 n1
[CBSE PMT 1998; MP PMT 2003]
(a) 9 (b) 8 (c) 33 As 75  2 He 4  35 Br 78  0 n1
(c) 7 (d) 6
(d) 83 Bi209  1 H 2  84 Po 210  0 n1
18. The disintegration of an isotope of sodium.
24
12 Mg  1 e shown is due to
24 0 29. The end product of (4 n  2) radioactive disintegration series is
11 Na
[MP PET 1997; Pb. PMT 1998; BHU 2000]
[AMU (Engg.) 2000]
208
(a) The emission of -radiation (a) 82 Pb (b) 82 Pb 206
(b) The formation of a stable nuclide (c) 207
(d) 210
82 Pb 83 Bi
(c) The fall in the neutron : proton ratio
(d) None of these
 Nuclear Chemistry 273
30. The element Th belongs to thorium series. Which of the following
90
232

41. Whenever the parent nucleus emits a -particle, the daughter element
will act as the end product of the series is shifted in the periodic table [NCERT 1984]
[BHU 2005] (a) One place to the right
(a) 82
Pb 208
(b) Bi82
209

(b) One place to the left

(c) Pb
82
206
(d) Pb 82
207

(c) Two places to the right

31. On bombarding 8 O 16 with deutrons, the nuclei of the product (d) Two places to the left
formed will be [NCERT 1978] 42. In the nuclear reaction 92 U 238  82 Pb 206 , the number of alpha
(a) 9 F 18
(b) 9 F 17 and beta particles decayed are
[DPMT 1983; MNR 1985; Roorkee Qualifying 1998]
(c) 8 O 17 (d) 7 N 14 (a) 4 , 3  (b) 8 , 6 
32. An element with atomic number 84 and mass number 218 loses one
(c) 6 , 4  (d) 7 , 5 
 -particle and two  -particles in three successive stages, the
resulting element will have 43. Atomic number after a  -emission from a nucleus having atomic
[NCERT 1979; CPMT 1990] number 40, will be [BHU 1981]
(a) At. no. 84 and mass number 214 (a) 36 (b) 39
(b) At. no. 82 and mass number 214 (c) 41 (d) 44
(c) At. no. 84 and mass number 218 44. A certain nuclide has a half-life period of 30 minutes. If a sample
(d) At. no. 82 and mass number 218 containing 600 atoms is allowed to decay for 90 minutes, how many
33. Group displacement law was given by [DPMT 1984] atoms will remain [NCERT 1978]
(a) Becquerel (b) Rutherford (a) 200 atoms (b) 450 atoms
(c) Soddy and Fajan (d) Madam Curie (c) 75 atoms (d) 500 atoms
34. How many alpha particles are emitted in the nuclear transformation 45. The reaction which disintegrates neutron is or neutron is emitted
84 Po
215
82 Pb 211 [CPMT 1993] (which completes first)
[IIT 1988; MP PMT 1991; KCET 2005]
(a) 0 (b) 1
(c) 2 (d) 3 (a) 96 Am 240
 2 He  97 Bk
4 244
 1e 0
35. If uranium (mass no. 238 and atomic no. 92) emits  -particle, the
product has mass number and atomic number (b) 15 P 30  14 Si 30  1e 0
[CPMT 1984, 90, 93, 94; MNR 1991; IIT 1981]
(a) 234, 90 (b) 236, 92 (c) 6C
12
 1 H 1  7 N 13
(c) 238, 90 (d) 236, 90 (d) Al27  2 He 4  15 P 30
13
36. Initial mass of a radioactive element is 40 g. How many grams of it
would be left after 24 years, if its half-life period is 8 years [MP PMT 1985]
46. If 92 U 236 nucleus emits one  -particle, the remaining nucleus
(a) 2 (b) 5 will have
(c) 10 (d) 20 [MP PMT 1976, 80; BHU 1985; CPMT 1980]
37. What is the symbol for the nucleus remaining after 20 Ca
42 (a) 119 neutrons and 119 protons
(b) 142 neutrons and 90 protons
undergoes  -emission [MNR 1987; UPSEAT 2000, 02]
(c) 144 neutrons and 92 protons
42 42
(a) 21 Ca (b) 20 Sc (d) 146 neutrons and 90 protons
42 41 47.  -rays have high ionization power because they possess
(c) 21 Sc (d) 21 Sc
[CPMT 1982]
38. When a radioactive nucleus emits an  -particle, the mass of the (a) Lesser kinetic energy
atom [NCERT 1973, 82]
(b) Higher kinetic energy
(a) Increases and its at. number decreases (c) Lesser penetrating power
(b) Decreases and its at. number decreases (d) Higher penetrating power
(c) Decreases and its at. number increases 48. When radium atom which is placed in II group, loses an  -
(d) Remains same and its at. number decreases particle, a new element is formed which should be placed in group[CPMT 1979,
24
39. A photon of hard gamma radiation knocks a proton out of 12 Mg (a) Second (b) First
nucleus to form [AIEEE 2005] (c) Fourth (d) Zero
(a) The isotope of parent nucleus 49. Starting from radium, the radioactive disintegration process
(b) The isobar of parent nucleus terminates when the following is obtained [CPMT 1979]
23
(a) Lead (b) Radon
(c) The nuclide 11 Na (c) Radium A (d) Radium B
(d) The isobar of 23
Na 50. The appreciable radioactivity of uranium minerals is mainly due to[NCERT 1980]
11
(a) An uranium isotope of mass number 235
40. 84 Pb 210  82 Pb 206  2 He 4 . From the above equation, (b) A thorium isotope of mass number 232
deduce the position of polonium in the periodic table (lead belongs (c) Actinium
to group IV A) [AIIMS 1980] (d) Radium
(a) II A (b) IV B
(c) VI B (d) VI A 51. After losing a number of  and  -particles, 92 U
238
changed to
206
82 Pb . The total number of particles lost in this process is[MNR 1985]
 274 Nuclear Chemistry
(a) 14 (b) 5 (a) 209
(b) 209
82 Pb 83 Bi
(c) 8 (d) 32
208 206
52. When an radioactive element emits an alpha particle, the daughter (c) 82 Pb (d) 82 Pb
element is placed in the periodic table
63. All the nuclei from the initial element to the final element constitute a
[MP PET 1991; MADT Bihar 1981] series which is called [Kerala (Med.) 2002]
(a) Two positions to the left of the parent element (a) g-series (b) b-series
(b) Two positions to the right of the parent element
(c) b-g series (d) Disintegration series
(c) One position to the right of the parent element
(d) In the same position as the parent element 64. The number of neutrons in the parent nucleus which gives N 14 on 
53. If the quantity of a radioactive element is doubled, then its rate of – emission is [Pb.CET 2004]
disintegration per unit time will be (a) 7 (b) 14
[NCERT 1972, 92; MP PET 1989] (c) 6 (d) 8
(a) Unchanged 65. The nuclear binding energy for Ar (39.962384 amu) is: (given mass
(b) Reduced to half of proton and neutron are 1.007825 amu and 1.008665 amu
respectively) [Pb.CET 2002]
(c) Increased by 2 times
(a) 343.81 MeV (b) 0.369096 MeV
(d) Doubled
54. The number of  and  -particles emitted during the transformation of (c) 931 MeV (d) None of these
232
90 Th to 82 P 208 are respectively 66. The number   and  - particles emitted respectively during the
[MNR 1978; NCERT 1984;CPMT 1989; transformation of 232 208
90 Th to 82 Pb is
RPET 1999; MP PMT 2001; KCET 2003]
(a) 4, 2 (b) 2, 2 [Kerala PMT 2004]
(c) 8, 6 (d) 6, 4 (a) 3, 6 (b) 6, 3
55. The atomic number of a radioactive element increases by one unit in (c) 4, [EAMCET
6 1997] (d) 6, 4
(a) Alpha emission (b) Beta emission (e) 6, 8
(c) Gamma emission (d) Electron capture 67. Consider the following nuclear reactions, 238
92 M  yx N  2 42 He
56. The end product of (4 n  1) radioactive disintegration series is[MP PMT 1999] x
y N  BA L  2  
209 210
(a) 83 Bi (b) 84 Po
The number of neutrons in the element L is [AIEEE 2004]
(c) 82 Pb 208 (d) 82 Pb 207 (a) 140 (b) 144
(c) 142 (d) 146
57. When a  -particle emits from the atom of an element, then
[MP PET 1990]
68. The number of   and   particles emitted when a radioactive
(a) Atomic number increases by two units element 90 E 232 changes into 86 G
220
will be
(b) Atomic number increases by three units [MP PET 2004]
(c) Atomic number decreases by one unit (a) 5 and 4 (b) 2 and 3
(d) Atomic number increases by one unit (c) 3 and 2 (d) 4 and 1
58. The number of -particles emitted in radioactive change 69. The disintegration constant of radium with half-life 1600 years is [MHCET 2004]
92 U
238
82 Pb 206  2 He 4 is [KCET 2000] (a) 2.12  10 4 year 1 (b) 4.33  10 4 year 1
(a) 2 (b) 4 (c) 3.26  10 3 year 1 (d) 4.33  10 12 year 1
(c) 6 (d) 10
70. The number of  and   particles emitted in the nuclear reaction
59. If half-life of a certain radioactive nucleus is 1000 s, the
disintegration constant is [MP PET 2001] 92 U
238
90 Th 234 91 Pa234 are respectively
[Pb.CET 2001]
(a) 6.93  10 2 s 1 (b) 6.93  10 4 s
(a) 1 and 1 (b) 1 and 2
(c) 6.93  10 4 s 1 (d) 6.93  10 3 s (c) 2 and 1 (d) 2 and 2
60. Radioactivity of naptunium stops when it is converted to 71. In which radiation mass number and atomic number will not change [JEE Orissa
[JIPMER 2001]
(a)  (b) 
(a) Bi (b) Rn
(c) Th (d) Pb (c)  (d)  and 2 
61. The highest binding energy per nucleon will be for 72. Disintegration constant for a radioactive substance is 0.58 hr 1 . Its
[AIIMS 2001] half-life period [BHU 2004]
(a) Fe (b) H 2 (a) 8.2 hr (b) 5.2 hr
(c) 1.2 hr (d) 2.4 hr
(c) O 2 (d) U
73. A radioactive nucleus will not emit [DPMT 2005]
62. In the Thorium series, 90 Th 232 loses total of 6 -particles and 4 (a) Alpha and beta rays simultaneously
-particles in ten stages. The final isotope produced in the series is[MP PET 2001] (b) Beta and gamma rays simultaneously
(c) Gamma and alpha rays
 Nuclear Chemistry 275
(d) Gamma rays only (c) 20 minutes (d) 15 minutes
2   10. In radioactive decay which one of the following moves the fastest [MP PET/PMT
X 
   Z X
180 A
74. 72 . Z and A are [DPMT 2005]
(a) 69, 172 (b) 172, 69 (a)  -particle (b)  -particle
(c) 180, 70 (d) 182, 68 (c)  -rays (d) Positron
75. Loss of a beta particle is equivalent to [J & K 2005] 11. The half-life of a radionuclide is 69.3 minutes. What is its average
(a) Increase of one neutron only life (in minutes)
(b) Decrease of one neutron only (a) 100 (b) 10 2
(c) Both (a) and (b) (c) (69.3)1 (d) 0.693  69.3
(d) None of these
12. 10 gm of a radioactive substance is reduced to 1.25 gm after 15
Rate of decay and Half-life days. Its 1kg mass will reduce (in how many days) to 500 gm in
(a) 500 days (b) 125 days
1. The half-life period of a radioactive substance is 8 years. After 16 (c) 25 days (d) 5 days
years, the mass of the substance will reduce from starting 16.0 g 13. A radioactive isotope having a half-life of 3 days was received after
to [MP PMT 1999] 12 days. It was found that there were 3 gm of the isotope in the
(a) 8 .0 g (b) 6 .0 g container. The initial weight of the isotope when packed was
[NCERT 1980; CPMT 1999; KCET 2000; Pb.CET 2001]
(c) 4 .0 g (d) 2.0 g (a) 12 gm (b) 24 gm
2. The atomic mass of an element is 12.00710 amu. If there are 6 (c) 36 gm (d) 48 gm
neutrons in the nucleus of the atom of the element, the binding
energy per nucleon of the nucleus will be 14. C 14 is radioactive. The activity and the disintegration product are
[MP PMT 1999] (a)  -active, 7 N 14 (b)  - active, 7 Be
10

(a) 7.64 MeV (b) 76.4 MeV

(c) 764 MeV (d) 0.764 MeV (c) Positron active, 5B
14
(d)  - active, C 14

( e  =0.00055 amu, p =1.00814 amu, n =1.00893 amu) 15. Radioactivity of a radioactive element remains
1
of the original
3. Half-life period of a metal is 20 days. What fraction of metal does 10
remain after 80 days [BHU 1996] radioactivity after 2.303 seconds. The half-life period is
(a) 1 (b) 1/16 (a) 2.303 (b) 0.2303
(c) 1/4 (d) 1/8 (c) 0.693 (d) 0.0693
16. A radioactive substance has t1 / 2 60 minutes. After 3 hrs, what
4. In the radioactive decay 92 X 232  89 Y 220 , how many  and  -
percentage of radioactive substance will remain
particles are ejected from X to form Y [BHU 1995]
[CBSE 1999]
(a) 50% (b) 75%
(a) 3 and 3  (b) 5 and 3  (c) 25% (d) 12.5%
(c) 3 and 5  (d) 5 and 5  17. A freshly prepared radioactive source of half-life 2 hours emits
5. Which of the following does not take place by  - decay radiations of intensity which is 64 times the permissible safe level.
The minimum time after which it would be possible to work safely
[MP PMT 1996] with this source is
(a) 92 U
238
 90 Th 234
(b) 90 Th 232
 88 Ra 228 [IIT 1988]
(a) 6 hours (b) 12 hours
(c) Ra 226  86 Rn 222 (d) Bi 213  84 Po 213
88 83 (c) 24 hours (d) 128 hours
6. 1 .0 g of a radioactive isotope was found to reduce to 125 mg after 18. During a negative  -decay [MNR 1990; IIT 1985]
24 hours. The half-life of the isotope is [MP PET 1996] (a) An atomic electron is ejected
(a) 8 hours (b) 24 hours
(b) An electron which is already present within the nucleus is
(c) 6 hours (d) 4 hours ejected
7. A radioactive element decays at such a rate that after 15 minutes (c) A neutron in the nucleus decays emitting an electron
only 1/10 of the original amount is left. How many more minutes will
be needed when only 1/100 of the original amount will be left (d) A part of the binding energy of the nucleus is converted into
an electron
(a) 1.5 minutes (b) 15.0 mintues
(c) 16.5 minutes (d) 30 minutes 19. The decay constant of a radioactive sample is '  ' . The half-life and
mean life of the sample are respectively
8. The radioactive decay of 35 X 88 by a beta emission produces an [MNR 1990; IIT 1989]
unstable nucleus which spontaneously emits a neutron. The final
product is [MNR 1995; CBSE 2001] 1 ln 2 ln 2 1
(a) , (b) ,
   
(a) 37 X 88 (b) 35 Y 89
1  1
(c) Z 88 (d) 36 W
87 (c)  ln 2, (d) ,
34
 ln 2 
9. What is the half-life of a radioactive substance if 75% of a given
amount of the substance disintegrates in 30 minutes 20. The half-life of a radio isotope is 20 hours. After 60 hours, how
much amount will be left behind
(a) 7.5 minutes (b) 25 minutes
[MP PMT 1991]
 276 Nuclear Chemistry
(a) 1/8 (b) 1/4 33. If the half-life period of a first order reaction is 138.6 minutes, then the
(c) 1/3 (d) 1/2 value of decay constant for the reaction will be
[MH CET 1999]
21. Half-life period of a zero order reaction is
(a) 5 minute –1
(b) 0.5 minute –1

[AMU (Engg.) 1999]

(c) 0.05 minute –1
(d) 0.005 minute –1

(a) Inversely proportional to the concentration

34. Half-life of 10 gm of radioactive substance is 10 days. The half-life
(b) Independent of the concentration
(c) Directly proportional to the initial concentration of 20 gm is [CPMT 1996]
(d) Directly proportional to the final concentration (a) 10 days (b) 20 days
22. If 12 g of sample is taken, and 6 g of a sample decays in 1 hr. The (c) 25 days (d) Infinite
amount of sample showing decay in next hour is 35. 8 gm of the radioactive isotope, cesium-137 were collected on
[AMU (Engg.) 1999] February 1 and kept in a sealed tube. On July 1, it was found that
(a) 3 g (b) 1 g only 0.25 gm of it remained. So the half-life period of the isotope
(c) 2 g (d) 6 g is [KCET 1989]
23. What will be half-life period of a nucleus if at the end of 4.2 days, (a) 37.5 days (b) 30 days
N  0.798 N 0 [MP PET 2000] (c) 25 days (d) 50 days
36. The half-life of radium (226) is 1620 years. The time taken to
(a) 15 days (b) 10 days convert 10 grams of radium to 1.25 grams is
(c) 12.83 days (d) 20 days [MP PET 1994; UPSEAT 2001]
24. If 2.0 g of a radioactive substance has half-life of 7 days. The half-life (a) 810 years (b) 1620 years
of 1 g sample is [MP PET 2000] (c) 3240 years (d) 4860 years
(a) 7 days (b) 14 days 37. Half-life of a radioactive substance is 120 days. After 480 days, 4 gm
(c) 28 days (d) 35 days will be reduced to [EAMCET 1993]
(a) 2 (b) 1
25. The half-life of 90
38 Sr is 20 years. If its sample having initial activity (c) 0.5 (d) 0.25
of 8000 dis/min is taken, what would be its activity after 80 years [MP PMT 2000]
38. The half-life of Co 60 is 7 years. If one gm of it decays, the
(a) 500 dis/min (b) 800 dis/min
amount of the substance remaining after 28 years is
(c) 1000 dis/min (d) 1600 dis/min [EAMCET 1992]
24
26. 11 Na half-life is 15 hours. On heating it will (a) 0.25 gm (b) 0.125 gm
(a) Reduce (b) Remain unchanged (c) 0.0625 gm (d) 0.50 gm
(c) Depend on temperature (d) Become double 39. A radioactive isotope decays at such a rate that after 96 minutes
27. In a radioactive decay, an emitted electron comes from 1
[CBSE 1994; Pb. PET 1999] only th of the original amount remains. The half-life of this
8
(a) Nucleus of the atom
nuclide in minutes is [KCET 1992]
(b) Inner orbital of the atom
(a) 12 (b) 24
(c) Outermost orbit of the atom
(c) 32 (d) 48
(d) Orbit having principal quantum number one
28. What is the value of decay constant of a compound having half-life
40. C  14 has a half-life of 5760 years. 100mg of a sample
time T1 / 2  2.95 days [AFMC 1997] containing C  14 is reduced to 25mg in
[Bihar CEE 1992; AMU 2002; MHCET 1999]
(a) 2.7  10 5 s 1 (b) 2.7  10 6 s 1 (a) 11520 years (b) 2880 years
(c) 2.7  10 6 s 1 (d) 3  10 5 s 1 (c) 1440 years (d) 17280 years
29. What kind of radioactive decay does not lead to the formation of a 41. Half-life of a radioactive element is 100 yrs. The time in which it
daughter nucleus that is an isobar of the parent nucleus disintegrates to1999]
[JIPMER 50% of its mass, will be
(a) -rays (b) -rays [MP PMT 1995]
(c) Positron (d) Electron capture (a) 50 yrs (b) 200 yrs
(c) 100 yrs (d) 25 yrs
30. The half-life of 6 C 14 if its K or  is 2.31  10 4 is
42. The average life period of a radioactive element is the reciprocal of
[BHU 1999] its [MP PET 1995]
(a) 2  10 2 yrs (b) 3  10 3 yrs (a) Half-life period
(b) Disintegration constant
(c) 3.5  10 4 yrs (d) 4  10 3 yrs (c) Number of atoms present at any time
31. A radioactive isotope has a half-life of 10 days. If today 125 mg is (d) Number of neutrons
left over, what was its original weight 40 days earlier [KCET 2005] 43. The half-life period of a radioactive element is 30 minutes. One
(a) 2g (b) 600 mg sixteenth of the original quantity of the element will remain
(c) 1 g (d) 1.5 g unchanged after [CPMT 1983; MP PMT 1994]
16 (a) 60 minutes (b) 120 minutes
32. The binding energy of 8O is 127 MeV. Its binding energy per
(c) 70 minutes (d) 75 minutes
neutron is [MH CET 1999]
44. For a radioactive substance with half-life period 500 years, the time
(a) 0.794 MeV (b) 1.5875 MeV for complete decay of 100 milligram of it would be
(c) 7.94 MeV (d) 15.875 MeV [MADT Bihar 1984]
(a) 1000 years (b) 100  500 years
 Nuclear Chemistry 277
(c) 500 years (d) Infinite time (d) 1/16 of the original amount
45. A substance of which one gram is taken, after half-life time what 56. The radioactivity due to C 14 isotope (half-life 6000 years) of a
fraction of it is left ? [MADT Bihar 1983] sample of wood from an ancient tomb was found to be nearly half
1 1 that of fresh wood, the tomb is therefore about
(a) (b)
4 8 [NCERT 1980, 81; MP PET 1989]
1 1 (a) 3000 years old (b) 6000 years old
(c) (d) (c) 9000 years old (d) 1200 years old
2 32
57. The decay of a radioactive element follows first order kinetics, as a
46. The half-life of the radio element 83 Bi210 is 5 days. Starting with result [NCERT 1982]
20 g of this isotope, the amount remaining after 15 days is [BHU 1987]
(a) Half-life period = constant / k , where k is the decay constant
(a) 10 g (b) 5 g (b) Rate of decay is independent of temperature
(c) 2.5 g (d) 6.66 g (c) Rate can be changed by changing chemical conditions
47. In radioactive decay of X into Y below, Z Y m is (d) The element will be completely transformed into a new element
after expiry of two half-life period
3 
6 X 14   Z Y m 58. Half-life of a radioactive substance which disintegrates by 75 % in 60
15 17 minutes, will be [MP PMT 2002]
(a) 6 Y (b) 7 Y
(a) 120 min (b) 30 min
14
(c) 9 Y (d) 8 Y 14 (c) 45 min (d) 20 min
48. 75% of the first order reaction was completed in 32 minutes. When 59. 87.5% decomposition of a radioactive substance complete in 3 hours.
was 50% of the reaction completed What is the half-life of that substance [MP PMT 2003]
[MNR 1983; MP PET 1997; EAMCET 1998] (a) 2 hours (b) 3 hours
(a) 24 minutes (b) 16 minutes (c) 90 minutes (d) 1 hours
(c) 8 minutes (d) 4 minutes 60. Tritium undergoes radioactive decay giving
49. If 2 .0 g of a radioactive isotope has a half-life of 20 hr, the half-life [CPMT 1976; NCERT 1978]
of 0 .5 g of the same substance is (a)  -particles (b)  -particles
[MP PMT 1990; MNR 1992] (c) Neutrons (d) None of these
(a) 20 hr (b) 80 hr 61. Given that a radioactive species decays according to exponential law
(c) 5 hr (d) 10 hr
N  N 0 e t . The half-life of the species is
50. Radioactive lead 82 Pb 201 has a half-life of 8 hours. Starting from
[Kerala (Med.) 2003]
one milligram of this isotope, how much will remain after 24 hours [MP PMT 1990]
(a)  (b) No
(a) 1 / 2 mg (b) 1 / 3 mg
(c) /ln 2 (d) ln 2/
(c) 1 / 8 mg (d) 1 / 4 mg
62. Half-life of a radioactive disintegration (A  B) having rate
51. The half-life of 92 U 238 is 4.5  10 9 years. After how many years, constant 231 sec 1 is [CPMT 1988]
238
the amount of 92 U will be reduced to half of its present
(a) 3.0  10 2 sec (b) 3.0  10 3 sec
amount [CPMT 1990; MP PET 1999]
(c) 3.3  10 2 sec (d) 3.3  10 3 sec
(a) 9.0  10 9 years (b) 13.5  10 9 years
63. The amount of 53 I 128 t1 / 2  25 minutes) left after 50 minutes
(c) 4.5  10 9 years (d) 4.5  10 4.5 years
will be [AIIMS 1982; DPMT 1982, 83]
52. Radium has atomic weight 226 and a half-life of 1600 years. The
(a) One – half (b) One – third
number of disintegrations produced per second from 1 gm are[BHU 1990]
(c) One – fourth (d) Nothing
(a) 4.8  10 10 (b) 9.2  10 6 64. If 3/4 quantity of a radioactive element disintegrates in two hours,
its half-life would be [MP PMT 1989; CPMT 1984]
(c) 3.7  10 10
(d) Zero
(a) 1 hour (b) 45 minutes
53. The half-life of a radioactive element is 6 months. The time taken to
(c) 30 minutes (d) 15 minutes
reduce its original concentration to its 1/16 value is
[MP PET 1991] 65. Radioactive decay is a [MP PMT 1989, 97]
(a) 1 year (b) 16 years (a) Second order reaction (b) First order reation
(c) 2 years (d) 8 years (c) Zero order reaction (d) Third order reaction
54. In the case of a radio isotope the value of T1 / 2 and  are identical 66. The half-life of a radioactive element depends upon
[EAMCET 1980]
in magnitude. The value is [KCET 2002]
(a) The amount of the element
(a) 0.693 (b) (0.693)1 / 2 (b) The temperature
(c) 1/0.693 (d) (0.693)2 (c) The pressure
55. A radioactive element has half-life of one day. After three days, the (d) None of these
amount of the element left will be 67. The activity of radio isotope changes with [MNR 1986]
[MNR 1985; UPSEAT 2000, 01; MH CET 2002] (a) Temperature (b) Pressure
(a) 1/2 of the original amount (c) Chemical environment (d) None of these
(b) 1/4 of the original amount 68. A certain nuclide has a half-life of 25 minutes. If one starts with 100
(c) 1/8 of the original amount g of it, how much of it will remain at the end of 100 minutes
 278 Nuclear Chemistry
(a) 1.0 g (b) 4.0 g (a) 0.30 sec (b) 0.60 sec
(c) 6.25 g (d) 12.50 g (c) 3.3 sec (d) Data is insufficient
69. If U 235 is bombarded with neutrons, atom will split into 81. T1 / 2 of C 14 isotope is 5770 years. time after which 72% of
[CPMT 1981] isotope left is [Orissa JEE 2005]
(a) Sr + Pb (b) Cs + Rb (a) 2740 years (b) 274 years
(c) Kr + Cd (d) Ba + Kr (c) 2780 years (d) 278 years
70. If 8.0 of a radioactive isotope has a half-life of 10 hrs. The half-life of 2.0 82. A radioactive substance takes 20 min to decay 25%. How much time
g of the same substance is [UPSEAT 2001] will be taken to decay 75% [Orissa JEE 2005]
(a) 2.5 hrs. (b) 5 hrs. (a) 96.4 min (b) 68 min
(c) 10 hrs. (d) 40 hrs. (c) 964 min (d) 680 min
71. If the disintegration constant is 6.93  10 6 , then half-life of 83. A radioactive sample is emitting 64 times radiations than non
14
hazardous limit. if its half life is 2 hours, after what time it becomes
6C will be [KCET 2001] non-hazardous [DPMT 2005]
(a) 10 2 yrs (b) 10 3 yrs (a) 16 hr (b) 12 hr
(c) 8 hr (d) 4 hr
(c) 10 4 yrs (d) 10 5 yrs
84. If 8.0 g of a radioactive substance has a half-life of 10 hrs., the half
72. The decay constant of Ra 226 is 1.37  10 11 sec 1 . A sample of life of 2.0 g of the same substance is [J & K 2005]
Ra 226 having an activity of 1.5 millicurie will contain ...... atoms (a) 2.6 hr (b) 5 hr
(c) 10 hr (d) 40 hr
(a) 4.1  1018 (b) 3.7  1017
(c) 2.05  1015 (d) 4.7  1010 Artificial transmutation
73. Amount of 53 I
128
(t1 / 2  25 min) left after 75 minutes is 1. The age of most ancient geological formation is estimated by
[DCE 2002] [NCERT 1981; MP PET/PMT 1988; CBSE 1989;
(a) 1/6 (b) 1 / 4 MP PET 1997; MP PMT 2002]
(c) 1 / 8 (d) 1 / 9 (a) Potassium – Argon method
74. The half-life of a radioisotope is four hours. If the initial mass of the (b) Carbon – 14 dating method
isotope was 200 g, the mass remaining after 24 hours undecayed is (c) Radium
[AIEEE –2004]
Silicon method
(a) 3.125 g (b) 2.084 g (d) Uranium – Lead method
(c) 1.042 g (d) 4.167 g
2. The equation 3 Li 6  1 H 2  2 2 He 4  energy represents
14
75. An artificial radioactive isotope gave 7 N after two successive (a) Synthesis of helium (b) Transmutation of element
  particle emissions. The number of neutrons in the parent (c) Fusion reaction (d) Nuclear fission
nucleus must be [KCET 2004] 3. The phenomenon of radioactivity arises from the
(a) 9 (b) 14 [Kerala (Med.) 2002]
(c) 5 (d) 7 (a) Binary fission
76. If the half-life of an isotope X is 10 years, its decay constant is (b) Nuclear fusion
[DCE 2004]
(c) Stable nuclei
1 1
(a) 6.932 yr (b) 0.6932 yr (d) Decay of unstable nuclei
4. The first artificial disintegration of an atomic nucleus was achieved
(c) 0.06932 yr 1 (d) 0.006932 yr 1 by [Kerala (Engg.) 2002]
77. A radioactive isotope decays at such a rate that after 192 minutes (a) Geiger (b) Wilson
only 1 / 16 of the original amount remains. The half-life of the (c) Madame curie (d) Rutherford
radioactive isotope is
(e) Soddy
[Kerala CET 2004]
5. Artificial elements have been prepared by bombardment reactions in
(a) 32 min (b) 48 min high energy accelerators. What is the mass number of the element X
(c) 12 min (d) 24 min produced in the following nuclear reaction
  
78. In the given reaction, 92 U
235

( A) 
(B) 
(C) 95 Cf  7 N 105 X  4 0 n
249 15 1
[AMU (Engg.) 2002]
isotope are (a) 261 (b) 264
[Pb. CET 2000] (c) 260 (d) 257
235
(a) A and C (b) 92 U and C 6. Radioactive carbon dating was discovered by
(c) A and B (d) A, B and C [MP PET 2001]
79. Rate constant for a reaction is  . Average life is representative by (a) W.F. Libby
[Orissa JEE 2004] (b) G.N. Lewis
(c) J. Willard Gibbs (d) W. Nernst
(a) 1/ (b) In2 / 
7. The nuclear reaction
 0 .693
(c) (d) 63
29 Cu  42 He 17
37
Cl  14 11 H  16 10 n is referred to as
2 
[MP PET 2002]
80. For a reaction, the rate constant is 2.34 sec 1 . The half-life period (a) Spallation reaction (b) Fusion reaction
for the reaction is
(c) Fission reaction (d) Chain reaction
 Nuclear Chemistry 279
8. The carbon dating is based on [MP PMT 2001] (a) Nuclear fission
(a) 15
C (b) 14
C (b) Nuclear fusion
6 6
(c) Artificial transmutation
13 11
(c) 6 C (d) 6 C (d) Spontaneous disintegration
9. A possible material for use in the nuclear reactors as a fuel is 22. Which of the following is used as a moderator in a nuclear reactor
[DPMT 1986] (a) D2 O (b) N 2O
(a) Thorium (b) Zirconium
(c) H 2O (d) NaOH
(c) Beryllium (d) Plutonium
10. Heavy water freezes at [UPSEAT 2001]
23. The fuel of atomic pile is [NCERT 1973; AFMC 1989]
(a) Thorium (b) Sodium
(a) 0C (b) 3.8C
(c) Uranium (d) Petroleum
(c) 38C (d)  0.38C 24. Atom bomb is based on the principle of
11. To determine the masses of the isotopes of an element which of the [CPMT 1982; BHU 1985]
following techniques is useful (a) Nuclear fusion
[NCERT 1978; MNR 1979]
(b) Nuclear fission
(a) The acceleration of charged atoms by an electric field and their
subsequent deflection by a variable magnetic field (c) Radioactivity
(b) The spectroscopic examination of the light emitted by (d) Fusion and fission both
vaporised elements subjected to electric discharge 25. Who observed that when the nucleus of uranium atom was
(c) The photographing of the diffraction patterns which arise when bombarded with fast moving neutrons, it becomes so very unstable
X-rays are passed through crystals that it is immediately broken into two nuclei of nearly equal mass
(d) The bombardment of metal foil with alpha particles besides other fragments
12. The radioisotope, tritium (13 H ) has a half-life of 12.3 years. If the (a) J.J. Thomson (b) Chadwick
initial amount of tritium is 32 mg. How many milligrams of it would (c) Einstein (d) Hahn and Strassmann
remain after 49.2 years [CBSE 2003] 26. When a radioactive substance is subjected to vacuum, the rate of
(a) 8 mg (b) 1 mg disintegration per second
(c) 2 mg (d) 4 mg [DPMT 1985; NCERT 1972]
13. Neutron is used as a [CPMT 1988] (a) Increases considerably
(a) Reducing agent (b) Moderator (b) Increases only if the products are gaseous
(c) Tracer (d) In biological programme (c) Is not affected
14. Hydrogen bomb is based on the phenomenon of (d) Suffers a slight decrease
[EAMCET 1980; CPMT 1984, 96;
MP PMT 1993, 95, 2002; RPET 1999] 27. A radio isotope will not emit [KCET 2002]
(a) Nuclear fission (b) Nuclear fusion (a) Gamma and alpha rays simultaneously
(c) Nuclear explosion (d) Disintegration (b) Gamma rays only
15. In the nuclear reactors the speed of the neutrons is slowed down by [CPMT
(c) Alpha and1983,
beta84]
rays simultaneously
(a) Heavy water (b) Ordinary water (d) Beta and gamma rays simultaneously
(c) Zinc rods (d) Molten caustic soda
56
16. By which law, energy produced in nuclear reaction is given 28. What is the packing fraction of 26 Fe
[MP PET 2000] (Isotopic mass = 55.92066) [JIPMER 2002]
(a) Graham’s law (b) Charle’s law
(c) Gas Lussac’s Law (d) Einstein’s law (a) 14.167 (b) 173.90
17. If two light nuclei are fused together in nuclear reaction the average (c) 14.187 (d) 73.90
energy per nucleon [Pb. PMT 2001] 29. The energy released in an atom bomb explosion is mainly due to
(a) Increases (b) Cannot be determined
(a) Release of neutrons
(c) Remains same (d) Decreases
14
(b) Release of electrons
18. A wood piece is 11460 years old. What is the fraction of C activity left (c) Greater mass of products than initial material
14
in the piece? (Half-life period of C is 5730 years) (d) Lesser mass of products than initial material
[MP PMT 2000] 30. C 14 is [KCET 2002]
(a) 0.12 (b) 0.25
(a) A natural radioactive isotope
(c) 0.50 (d) 0.75
19. When nuclear energy is intended to be harnessed for generation of (b) A natural non-radioactive isotope
electricity, potentially destructive neutron released in a nuclear (c) An artificial radioactive isotope
reactor are absorbed by (d) An artificial non-radioactive isotope
[MH CET 2001]
31. A radioactive isotope has a half-life of 10 years. What percentage of the
(a) Long rods of Cd (b) Heavy water original amount of it remain after 20 years
(c) Cubical blocks of steel (d) Both (a) and (c) [KCET 2001]
20. The proper rays for radiocarbon dating are [MP PET 2002]
(a) 0 (b) 12.5
(a) UV-rays (b) IR-rays
(c) 8 (d) 25
(c) Cosmic rays (d) X-rays
32. In a chain reaction, uranium atom gets fissioned forming two
21. 1H
2
 1 H 2  2 He 3  0 n1 . Above nuclear reaction is called different materials. The total weight of these put together is
[UPSEAT 2001] (a) More than the weight of parent uranium atom
 280 Nuclear Chemistry
(b) Less than the weight of parent uranium atom 45. Liquid sodium finds use in nuclear reactors. Its function is
(c) More or less depends upon experimental conditions (a) To collect the reaction products
(d) Neither more nor less (b) To act as a heat exchanger or coolant
33. A substance used as a moderator in nuclear reactors is (c) To absorb the neutrons in order to control the chain reaction
[MP PET 1995] (d) To act as a moderator which slows down the neutrons
(a) Cadmium (b) Uranium-235 46. Which is least effective for artificial transmutation
(c) Lead (d) Heavy water [DPMT 2000]
34. Equation 37
 1 H  18 Ar  0 n is
2 38 1 (a) Deuterons (b) Neutrons
17 Cl [MP PMT 1989]
(c) -particles (d) Protons
(a) Nuclear fission
(b) Nuclear fusion 47. A piece of wood was found to have C 14 /C 12 ratio 0.7 times that in
(c) Transformation of chlorine a living plant. The time period when the plant died is (Half-life of
(d) Synthesis of argon C 14  5760 yrs) [Pb. PMT 1999]
35. 1.0 gm radioactive sodium on decay becomes 0.25 gm in 16 (a) 2770 yrs (b) 2966 yrs
hours. How much time 48 gm of same radioactive sodium will (c) 2980 yrs (d) 3070 yrs
need to become 3.0 gm 48. When a slow neutron goes sufficiently close to a U 235 nucleus,
(a) 48 hours (b) 32 hours then the process which takes place is [AFMC 2000]
(c) 20 hours (d) 16 hours (a) Fusion of U 235 (b) Fission of U 235
36. Large energy released in an atomic bomb explosion is mainly due to [CPMT
(c) 1972, 73, 81,
Fusion of 90]
neutron (d) First (a) then (b)
(a) Products having a lesser mass than initial substance
49. Al 28 when radiated by suitable projectile gives P 31 and
(b) Conversion of heavier to lighter atoms 13 15

(c) Release of neutrons neutron. The projectile used is

(d) Release of electrons [MP PMT/PET 1988; CPMT 1985, 82]
(a) Proton (b) Neutron
37. The reaction 1H
2
 1 H 3  2 He 4  0 n1  energy represents (c) Alpha particle (d) Deuteron
[MP PMT 1990; CPMT 1990; KCET 1992] 50. Which of the following statements about radioactivity of an element
(a) Nuclear fission is incorrect
(b) Nuclear fusion (a) It is a nuclear property
(c) Artificial disintegration (b) It does not involve any rearrangement of electrons
(d) Transmutation of element (c) Its rate is affected by change in temperature and/or pressure
38. Carbon-14 dating method is based on the fact that (d) It remains unaffected by the presence of other element or
[CBSE 1997] elements chemically combined with it
(a) Carbon-14 fraction is the same in all objects 51. Radioactive iodine is being used to diagnose the disease of
(b) Carbon-14 is highly insoluble [MP PET 1996]
(c) Ratio of carbon-14 and carbon-12 is constant (a) Bones (b) Kidneys
(d) All of these (c) Blood cancer (d) Thyroid
39. Half-life period of a radioactive element is 10.6 yrs. How much time 52. C  14 is used in carbon dating of dead objects because
will it take in its 99% decomposition [DPMT 1996]
[RPET 1999]
(a) 7046 yrs (b) 7.046 yrs (a) Its half-life is 10 3 years
(c) 704.6 yrs (d) 70.4 yrs (b) Its half-life is 10 4 years
40. Deuterium resembles hydrogen in chemical properties but reacts (c) It [JIPMER
is found2001]
in nature abundantly and in definite ratio
(a) More vigorously than hydrogen (d) It is found in dead animals abundantly
(b) Faster than hydrogen 53. A radioactive element resembling iodine in properties is
(c) Slower than hydrogen [Kurukeshetra CEE 1998]
(d) Just as hydrogen (a) Astatine (b) Lead
41. Which of the following is heavy water [AFMC 1997] (c) Radium (d) Thorium
54. For artificial transmutation of nuclei, the most effective one is
(a) H 2 O18 (b) H 2 O16
[MP PMT 1996]
(c) H 2 O3 (d) D2 O (a) Proton (b) Deuteron
(c) Helium nuclei (d) Neutron
42. D2 O is used in [CPMT 1997]
55. Which of the following cannot be accelerated [KCET 2005]
(a) Industry (b) Nuclear reactor
(a)  -particle (b)  -particle
(c) Medicine (d) Insecticide
(c) Protons (d) Neutrons
43. India conducted an underground nuclear test at
[KCET 1998]
56. For the fission reaction
(a) Tarapur (b) Narora 92 U
235
 0 n1  56 Ba40  y E x  2 0 n1
(c) Pokhran (d) Pushkar The value of x and y will be
44. Energy required to separate neutron and proton from the nucleus is
called [RPMT 1999] (a) x  93 and y  34 (b) x  92 and y  35
(a) Bond energy (b) Nuclear energy (c) x  89 and y  44 (d) x  94 and y  36
(c) Chemical energy (d) Radiation energy 57. Heavy water is used as
 Nuclear Chemistry 281
[Bihar MEE 1996; UPSEAT 1999, 2000, 02] (a) Lubricant
(a) Control rods (b) Moderator (b) Moderator to slow down neutrons
(c) Fuel (d) Coolant (c) Fuel
(e) None of these (d) Liner of the reactor
58. Unit for radioactive constant is [MP PET 1990] 70. The modern basis of atomic weight is
(a) Time -1 (b) Time [MP PET 1989; CPMT 1993]
1 1
(c) Mole  time (d) Time  mole (a) Isotope H  1.000
1
(b) Oxygen = 16.000
59. Which of the following is used in dating archeological findings or In (c) Isotope O  16.000
16
(d) Isotope C 12  12.000
a method of absolute dating of fossils a radioactive element is used.
It is 71. Which radioactive carbon has been helpful in understanding the
mechanism of photosynthesis in plants
[CPMT 1983, 85; NCERT 1978; BHU 1981;
14 13
MP PMT 1993; AFMC 1997] (a) 6C (b) 6C
235 14
(a) 92 U (b) 6C (c) 12
(d) 15
6C 6C
(c) 6 C 12 (d) 20 Ca 40 72. Artificial transmutation was discovered by [Pb.CET 2003]
60. A radioactive isotope has a half-life of 20 days. If 100 gm of the (a) Pauli (b) Rutherford
substance is taken, the weight of the isotope remaining after 40 days (c) Soddy (d) Curie
is [NCERT 1979] 73. Which of the following is an example of nuclear fusion
(a) 25 gm (b) 2.5 gm [MP PMT 1989; DCE 2004]
(c) 60 gm (d) 40 gm (a) 2
 1 H  2 He  energy
2 4
1H
61. In a fission reaction the nucleus of an element
[NCERT 1977] (b) 92 U
235
 o n1  56 Ba141  36 Kr 92  30 n1  energy
(a) Loses only some elementary nuclear particles from another
nucleus (c) 13 Al 27  1 H 1  12 Mg 24  2 He 4
(b) Captures some elementary nuclear particles from another (d) None of these
nucleus
(c) Breaks up into several smaller nuclei 74. The radioactivity isotope 60
27 Co which is used in the treatment of

(d) Breaks up into two smaller nuclei with the loss of same cancer can be made by (n, p) reaction. For this reaction the target
elementary nuclear particles nucleus is [CBSE PMT 2004]
62. The huge amount of energy which is released during atomic fission (a) 60
28 Ni (b) 60
27 Co
is due to [CPMT 1990]
59 59
(a) Loss of mass (b) Loss of electrons (c) 28 Ni (d) 27 Co
(c) Loss of protons (d) Loss of  -particles 75. Fusion bomb involves [AFMC 2004]
63. The measure of binding energy of a nucleus is the (a) Combination of lighter nuclei into bigger nucleus
[CPMT 1982; Kurukshetra CEE 1998] (b) Destruction of heavy nucleus into smaller nuclei
(a) Mass defect (b) Energy of protons
(c) Combustion of oxygen
(c) Energy of neutrons (d) Total energy of nucleons
(d) Explosion of TNT
64. The first controlled artificial disintegration of an atomic nucleus was
achieved by [BHU 1987] 76. The element used for dating the ancient remains is
(a) Geiger (b) Wilson [AFMC 2004]
(c) Cockcroft (d) Rutherford (a) Ni (b) C-14
65. Artificial radioactivity was first discovered by (c) C-12 (d) Rd
[CPMT 1972; BHU 1984; KCET 1999]
77. If radium and chlorine combine to from radium chloride the
(a) Seaberg (b) Rutherford compound is [Kerala PMT 2004]
(c) Einstein (d) Irene Curie & Juliot
(a) No longer radioactive
66. The half-life period of a radioactive element is 140 days. After 560
days, one gram of the element will reduce to (b) Twice as radioactive as radium
[CPMT 1989; IIT 1986; EAMCET 1992; (c) Half as radioactive as radium
MP PET 1997; UPSEAT 1999]
(d) As radioactive as radium
(a) 1/2g (b) 1 / 4 g
(e) Thrice as radioactive as radium
(c) 1/8 g (d) 1 / 16 g 78. Which of the following is an example of nuclear fission
67. A device used for the measurement of radioactivity is [Pb. CET 2002]
[BHU 1979]
(a) Mass spectrometer (b) Cyclotron (a) 1H
2
 1 H  2 He  
2 4

(c) Nuclear reactor (d) G.M. counter (b) A  B  C  energy

68. In a nuclear reactor, chain reaction is controlled by introducing [EAMCET 1984]
(a) Iron rod (b) Cadmium rod (c) 92 U
235
 0 n1  56 Ba141  36 Kr 92  3 0 n1  energy
(c) Graphite rod (d) Platinum rod
(d) Al 27  2 He 4  15 P 30  0 n1
69. In atomic reactors, graphite is used as a 13

[NCERT 1980; MP PET 1989]

 282 Nuclear Chemistry

79. The C 14 to C 12 ratio in a wooden article is 13% that of the fresh (a) 53 I131 (b) 15 P 32
wood. Calculate the age of the wooden article. Given that the half-
60 2
life of C 14 is 5770 years [Pb.CET 2004]
(c) 27 Co (d) 1H

(a) 16989 years (b) 16858 years 8. Elements having different nuclear charge but the same mass number
are called [NCERT 1974; MP PMT 1991;
(c) 15675 years (d) 17700 years CBSE PMT 1991; CPMT 1989; EAMCET 1992]
80. Hydrogen bomb is based on the principle of [AIEEE 2005] (a) Isotopes (b) Isobars
(a) Nuclear fission (b) Natural radioactivity (c) Isomers (d) Isotones
(c) Nuclear fusion (d) Artificial radioactivity 9. Which isotope on bombardment with  -particles will give 8O
17

81. Match List –I and List-II and choose right one by using code given and 1 H 1 [NCERT 1983]
in list [Kerala CET 2005]
16 14
List – I List –II (a) 8O (b) 7 N
Nuclear reactor Used substance
(c) 7 N 15 (d) 6C
14
Component
1. Moderator (A) Uranium 10. Emission of  -particle by an atom of an element results in the
2. Control rods (B) Graphite formation of its [BHU 1979; DPMT 1985; KCET 1999]
3. Fuel rods (C) Boron (a) Isotope (b) Isomer
4. Coolent (D) Lead (c) Isomorph (d) Isobar
(E) Sodium 11. Radioactive isotopes that have an excessive neutron/proton ratio
Code : generally exhibit
1 2 3 4 (a) e  emission (b) 2 He
4
emission
(a) B A C E
(b) B C A E (c) e  emission (d) K -electron capture
(c) C B A E 12. Atomic weights of carbon, nitrogen and oxygen are 12, 14 and 16
(d) C D A B respectively. An atom of atomic weight 14 and nuclear charge + 6 is
an isotope of
(e) D C B A (a) Oxygen (b) Carbon
(c) Nitrogen (d) None of these
Isotopes-Isotones and Nuclear isomers 13. Isotopes of an element have [MNR 1985]
(a) Similar chemical properties but different physical properties
1. Substances which have identical chemical properties but differ in (b) Similar chemical and physical properties
atomic weights are called (c) Similar physical properties but different chemical properties
[EAMCET 1980, 83; DPMT 1985; MNR 1982]
(d) Different chemical and physical properties
(a) Isothermals (b) Isotopes
14. Whose number is common in isotopes [AIIMS 1988]
(c) Isentropus (d) Elementary particles
(a) Proton (b) Neutron
2. Tritium is an isotope of [DPMT 1985]
(c) Proton and neutron (d) Nucleon
(a) Hydrogen (b) Titanium
15. In the following radioactive transformation
(c) Tantalum (d) Tellurium   
R  X  Y  Z ; the nuclei R and Z are
3. O – 18 isotope of oxygen will have [CPMT 1972, 79]
[BHU 1987]
(a) 18 protons
(a) Isotopes (b) Isobars
(b) 9 protons and 9 neutrons
(c) Isomers (d) Isotones
(c) 8 neutrons and 10 protons
16. Which one of the following pairs represents isobars
(d) 10 neutrons and 8 protons
[CPMT 1988]
4. Which of the following is an isobaric pair [CPMT 1987, 93]
3 4
13 (a) He and He
(a) 6C , 7 N 13 (b) 6C
13
, 7 N 14 2 2

24 25
(b) Mg and Mg
(c) 7 N 14 , 8 O15 (d) 7 N 13 , 8 O15 12 12

40 40
5. Isotopes are atoms having the same (c) 19 K and 20 Ca
[EAMCET 1978, 79; MP PMT 1980; CPMT 1973; 39 40
BHU 2001; AFMC 2003] (d) 19 K and 19 K
(a) Atomic mass (b) Mass number 17. Nuclei of isotopes differ in [CPMT 1986, 90; MP PMT 1987]
(c) Atomic number (d) Number of neutrons (a) The number of protons
6. Successive emission of an  -particle and two  -particles by an (b) The number of neutrons
atom of an element results in the formation of its (c) The number of protons and neutrons both
[MP PMT/PET 1988; BHU 1979] (d) None of these
(a) Isobar (b) Isomorph 18. An isotope of ‘parent’ is produced, when its nucleus loses
(c) Isotope (d) Isomer [CPMT 1987; MP PET 1991]
7. In treatment of cancer, which of the following isotope is used[DPMT 1985; BHU 1995;
(a)KCET  -particle
One1999; AMU 1999;
Pb.CET 2001; MP PET 2002; Kurukshetra CET 2002]
(b) One  -particle
 Nuclear Chemistry 283

(c) One  and two  -particles First isotope Second isotope

(a) 34 36
(d) One  and two  - particles
(b) 44 46
19. Which of the following isotopes is likely to be most stable
(c) 45 47
[EAMCET 1982]
(d) 79 81
71 66
(a) 30 Zn (b) 30 Zn 31. Isotopes are those which contain [RPMT 1997]
64 (a) Same number of neutrons
(c) 30 Zn (d) None of these
(b) Same physical properties
20. Which of the following statement is false
(c) Same chemical properties
[Manipal MEE 1995]
(d) Different atomic mass
35 37
(a) In chlorine gas, the ratio of Cl and Cl is 1 : 3 32. An element ' A' emits an  -particle and forms ' B'.' A' and ' B'
(b) The hydrogen bomb is based on the principle of nuclear fusion are [DPMT 1990]
(c) The atom bomb is based on the principle of nuclear fission (a) Isotopes (b) Isobars
(d) The penetrating power of a proton is less than that of an (c) Isotones (d) Isodiasphere
electron 33. Which of the following properties are different for neutral atoms of
21. Isotones are elements having isotopes of the same element
[Bihar MEE 1996; Bihar CEE 1995] [EAMCET 1987; NCERT 1971; CPMT 1976; MP PET 1994]
(a) Same mass number but different neutrons (a) Mass
(b) Same atomic number but different neutrons (b) Atomic number
(c) Same atomic number, mass number and neutrons (c) General chemical reactions
(d) Different atomic and mass number but same neutrons (d) Number of electrons
22. Isobaric atoms may contain 34. The isotope U 235 decays in a number of steps to an isotope of
92
 0
(a) Same number of p and different number of n lead 82 Pb 207 . The groups of particles emitted in this process will
0 
(b) Same number of n and different number of p be [MP PMT 1987]

(c) Same number of both p  and n 0 (a) 4 , 7  (b) 6 , 4 

(c) 7 , 4  (d) 10 , 8 
(d) Different numbers of both p  and n 0
35. Addition of two neutrons in an atom A would [AMU 1984]
23. 20 X 40 and 21 X 40 are [CPMT 1996]
(a) Change the chemical nature of A
(a) Isobars (b) Isotopes
(c) Isotones (d) Isostereomers (b) Produce an isobar of A
24. Which property is different for neutral atoms of the two isotopes of (c) Produce an isotope of A
the same element [JIPMER 2001] (d) Produce another element
(a) Number of protons (b) Atomic number 36. Atomic weight of the isotope of hydrogen which contains 2 neutrons
(c) Number of neutrons (d) None of these is the nucleus would be [CPMT 1980]
25. Which of the following species is isotonic with 86 (a) 2 (b) 3
37 Rb
(c) 1 (d) 4
[BHU 2001]
84 85
37. If a radioactive isotope with atomic number A and mass number M
(a) 36 Kr (b) 37 Rb emits an  -particle, the atomic number and mass number of that
new isotope will become
(c) 38 Sr 87 (d) 39 Y 89
[NCERT 1980]
26. The maximum sum of the number of neutrons and protons in an (a) A – 2, M – 4 (b) A – 2, M
isotope of hydrogen is [Pb. PMT 2001]
(c) A, M – 2 (d) A – 4, M – 2
(a) 4 (b) 5
(c) 6 (d) 3 38. Which character is different of the two isotopes of an element[NCERT 1971; EAM
35 37 (a) Atomic mass (b) Atomic number
27. Difference in 17 Cl and 17 Cl is of [AFMC 2000]
(c) Number of electrons (d) Number of protons
(a) Atomic number (b) Number of protons
(c) Number of neutrons (d) Number of electrons 39. The symbol of an isotope is 32 X 65 , this reveals that
28. Which of the following is an isotonic pair [MP PET 1991]
[AMU (Engg.) 2000] (a) Its atomic number is 32 and atomic weight is 65
(a) 40
19 K, 40
20 Ca (b) 39
19 K, 40
20 Ca
(b) Its atomic number is 65
33
(c) It has 65 electrons
(c) Ar, 40
18 Ar (d) 40
Ar, 4020 Ca
18 18 (d) It has 32 neutrons
29. 6 C 11 and 5 B 11 are referred as [NCERT 1978] 40. Two atoms have the same atomic mass but different atomic
numbers. Such atoms are called as
(a) Nuclear isomers (b) Isobars
[NCERT 1971, 76; IIT 1983]
(c) Isotopes (d) Fission products
(a) Isotopes (b) Isobars
30. The atomic number of bromine is 35 and its atomic weight is 79.
(c) Isomer (d) Isoelectronic
Two isotopes of bromine are present in equal amounts. Which of
the following statements represents the correct number of neutrons[NCERT41.1983] 18 Ar 40 , 20 Ca 40 and 19 K 40 are
 284 Nuclear Chemistry
[MNR 1983; DPMT 1991; EAMCET 1992; (c) CN and CO (d) NO 2 and CO 2
RPMT 1997; Pb.CET 2000]
55. Which of the following are pairs of isotopes
(a) Isomers (b) Isotopes [Bihar CEE 1982]
(c) Isobars (d) Isotones 2  3 3 4 
(a) 1H and 1H (b) 1H and 2H
42. Atoms in hydrogen gas have preponderance of
[CPMT 1972] (c) 3
2 He and 4
2 He (d) 12
6 C and 14
7 N
(a) 1
atoms 56. Which among the following isotope is not found in natural uranium
1H
234 235
(b) Deuteron atoms (a) 92 U (b) 92 U
(c) Tritium atoms (c) 238
(d) 239
92 U 92 U
(d) All the three (a), (b) and (c) are in equal proportion
76
43. Positron emission results from the transformation of one nuclear 57. An isotone of 32 Ge is (one or more are correct)
proton into neutron. The isotope thus produced possesses [MP PMT 1990] [IIT 1984; MADT Bihar 1995; MP PMT 1995]
(a) Same mass number (b) Higher nuclear charge 77 77
(a) 32 Ge (b) 33 As
(c) Intense radioactivity (d) No radioactivity
77 78
44. An isotope of oxygen has mass number 18. Other isotopes of oxygen (c) 34 Se (d) 34 Se
will have the same
[MP PMT 1985; MADT Bihar 1981]
(a) Mass number (b) Atomic weight
(c) Number of neutrons (d) Number of protons
45. Two nuclei which are not identical but have the same number of
nucleons represent
(a) Isotopes (b) Isobars
(c) Isotones (d) None of the three 23
1. 11 Na is the more stable isotope of Na. Find out the process by
46. The  -decay of 11 Na
24
produces an isotope of which 24
11 Na can undergo radioactive decay
[NCERT 1978] [IIT Screening 2003]
(a) Mg (b) Na (a) 
 emission (b)  emission
(c) Al (d) Ne

47. Isotopes differ in [NCERT 1973] (c)  emission (d) K electron capture
(a) Number of protons (b) Valency 2. Oxygen contains 90% of O and 10% of O 18 . Its atomic mass is
16

(c) Chemical reactivity (d) Number of neutrons (a) 17.4 (b) 16.2
48. The isobars are atoms with the same number of (c) 16.5 (d) 17
[DPMT 1982; CPMT 1994] 3. The missing particle in the reaction,
(a) Protons (b) Neutrons 235
U  1
n  Ba 146
 ...  3 1
n is [DPMT 2001]
92 0 56 0
(c) Protons and neutrons (d) Nucleons
87 89
49. Radioactive isotope of hydrogen is (a) 32 Ge (b) 35 Br
[MP PMT 2001; MPPET 2003] 87 86
(c) 36 Kr (d) 35 Br
(a) Tritium (b) Deuterium
(c) Para hydrogen (d) Ortho hydrogen 4. Sulphur-35 (34.96903 amu) emits a   particle but no   rays,
50. Isotopes of same elements have the same number of the product is chlorine-35 (34.96885 amu). The maximum energy
[BHU 1984; DPMT 1983; CPMT 1972, 78; AFMC 2000, 01] emitted by the   particle is
(a) Protons (b) Neutrons [DPMT 2004]
(c) Deutrons (d) None (a) 0.016767 MeV (b) 1.6758 MeV
(c) 0.16758 MeV (d) 16.758 MeV
51. In chlorine gas, ratio of Cl 35 and Cl 37 is 5. A radioactive substance has a constant activity of 2000
[BHU 1984; CPMT 1977, 80] disintegration/minute. The material is separated into two fractions,
(a) 1 : 3 (b) 3 : 1 one of which has an initial activity of 1000 disintegrations per
(c) 1 : 1 (d) 1 : 4 second while the other fraction decays with t1 / 2 = 24 hours. The
52. An ordinary oxygen contains [NCERT 1977] total activity in both samples after 48 hours of separation is
(a) Only O  16 isotopes (a) 2000 (b) 1250
(c) 1000 (d) 1500
(b) Only O  17 isotopes
6. How many alpha particles are emitted per second by 1 microgram of
(c) A mixture of O  16 and O  18 isotopes radium
(d) A mixture of O – 16, O  17 and O  18 isotopes (a) 3.62  10 4 / sec (b) 0.362  10 4 / sec
53. Isotopes were discovered by [AMU 1983; AFMC 1995]
(c) 362  10 4 / sec (d) 36.2  10 4 / sec
(a) Aston (b) Soddy
7. If 1 microgram of radium has disintegrated for 500 years, how many
(c) Thomson (d) Millikan alpha particles will be emitted per second
54. Which of the following are iso-electronic [CBSE 2002]
(a) 2.92  10 4 / sec (b) 292  10 4 / sec
(a) CO 2 and NO (b) SO 2 and CO 2
 Nuclear Chemistry 285
[EAMCET 1991]
(c) 0.292  10 4 / sec (d) 29.2  10 4 / sec
(a) 600 gm (b) 1000 gm
8. A radioactive nucleide X decays at the rate of 1.00  10 5
disintegration s 1 g 1 . Radium decays at the rate of 3.70  10 10 (c) 1250 gm (d) 2000 gm
1 1 1
disintegration s g . The activity of X in millicuries g 19. The half-life of 6 C 14 , if its decay constant is 6.31  10 4 is
1
(m ci g ) is [MP PET 2001] [CBSE PMT 2001]

(a) 0.027 (b) 0.270  10 5 (a) 1098 yrs (b) 109.8 yrs
(c) 0.00270 (d) 0.000270 (c) 10.98 yrs (d) 1.098 yrs
235 20. A radioactive sample has a half-life of 1500 years.A sealed tube
9. If 92 U nucleus absorbs a neutron and disintegrates in
containing 1 gm of the sample will contain after 3000 years[MNR 1994; UPSEAT
94
54 Xe 139 , 38 Sr and X, then what will be the product X
(a) 1 gm of the sample
[CBSE 2002]
(a) -particle (b) -particle (b) 0.5 gm of the sample
(c) 2-neutrons (d) 3-neutrons (c) 0.25 gm of the sample
10. The half-life of a radioactive isotope is 3 hours. Value of its
disintegration constant is [BHU 2002] (d) 0.00 gm of the sample
(a) 0.231 per hr (b) 2.31 per hr 21. The half-life of a radioactive isotope is three hours. If the initial mass
(c) 0.2079 per hr (d) 2.079 per hr of the isotope were 256 g, the mass of it remaining undecayed after
11. The activity of carbon-14 in a piece of an ancient wood is only 12.5%. 18 hours would be
If the half-life period of carbon-14 is 5760 years, the age of the piece [AIEEE 2003]
of wood will be (log 2  0.3010) (a) 4.0 g (b) 8.0 g
[MP PMT 1999] (c) 12.0 g (d) 16.0 g
(a) 17.281  10 2
years (b) 172.81  10 2
years 15
22. th of a radioactive sample decays in 40 days half-life of the
(c) 1.7281  10 years 2
(d) 1728.1  10 years 2 16
sample is [DCE 2001]
12. The radium and uranium atoms in a sample of uranium mineral are
(a) 100 days (b) 10 days
in the ratio of 1 : 2.8  10 6 . If half-life period of radium is 1620
years, the half-life period of uranium will be (c) 1 day (d) log e 2 days
[MP PMT 1999]
23. A radioactive element with half-life 6.5 hrs has 48  1019 atoms.
(a) 45.3  10 9 years (b) 45.3  10 10 years Number of atoms left after 26 hrs
(c) 4.53  10 9 years (d) 4.53  10 10 years [BHU 2003]
13. Half-life of radium is 1580 yrs. Its average life will be (a) 24  10 19
(b) 12  10 19

[AIIMS 1999; AFMC 1999; CPMT 1999]

(c) 3  10 19
(d) 6  1019
(a) 2.5  10 3 yrs (b) 1.832  10 3 yrs
24. The half-life of 1 gm of radioactive sample is 9 hours. The
(c) 2.275  10 3 yrs (d) 8.825  10 2 yrs radioactive decay obeys first order kinetics. The time required for
the original sample to reduce to 0.2 gm is
14. 8 gms of a radioactive substance is reduced to 0 .5 g after 1 hour. [AMU (Engg.) 2002]
The t1 / 2 of the radioactive substance is [DCE 2000] (a) 15.6 hours (b) 156 hours
(a) 15 min (b) 30 min (c) 20.9 hours (d) 2.09 hours
(c) 45 min (d) 10 min 25. The half-life period of a radioactive substance is 140 days. After how
15. A first order nuclear reaction is half completed in 45 minutes. How much time 15 g will decay from 16 g sample of it
long does it need 99.9% of the reaction to be completed [KCET 2001] [AFMC 2002]
(a) 5 hours (b) 7.5 hours (a) 140 days (b) 560 days
(c) 10 hours (d) 20 hours (c) 280 days (d) 420 days
16. Number of --particles emitted per second by a radioactive element 26. Percentage of a radioactive element decayed after 20 sec when half-
falls to 1/32 of its original value in 50 days. The half-life-period of life is 4 sec [BHU 2003]
this elements is [AMU 2001] (a) 92.25 (b) 96.87
(a) 5 days (b) 15 days (c) 50 (d) 75
(c) 10 days (d) 20 days 27. Consider an -particle just in contact with a 92 U 238 nucleus.
17. What is the half-life of a radioactive substance if 87.5% of any given Calculate the coulombic repulsion energy (i.e. the height of the
amount of the substance disintegrates in 40 minutes [Kerala CET 1996] coulombic barrier between U 238 and alpha particle) assuming that
(a) 160 min (b) 10 min the distance between them is equal to the sum of their radii[UPSEAT 2001]
(c) 20 min (d) 13 min 20 sec
(a) 23.8517× 10 4 eV
18. A radioactive isotope has a t1 / 2 of 10 days. If today 125 gm of it is
left, what was its weight 40 days earlier (b) 26.147738  10 4 eV
 286 Nuclear Chemistry

(c) 25.3522  10 4 eV Reason : Nuclides of the same element of different mass

numbers are called isotopes of that element.
(d) 20.2254  10 4 eV
3. Assertion : The activity of 1 g pure uranium-235 will be
28. The half-life period of Pb 210 is 22 years. If 2 gm of Pb 210 is greater than the same amount present as U3 O8 .
taken, then after 11 years how much of Pb 210 will be left
Reason : In the combined state, the activity of the
[KCET 2001]
radioactive element decreases.
(a) 1.414 gm (b) 2.428 gm
4. Assertion : Nuclear forces are called short range forces.
(c) 3.442 gm (d) 4.456 gm
Reason : Nuclear forces operate over very small distance
29. A wood specimen from an archeological centre shows a 14 6 C
activity of 5.0 counts/min/gm of carbon. What is the age of the i.e., 10 15 m or 1 fermi.
specimen (t1 / 2 for 14 5. Assertion : An example of K-capture is
6 C is 5000 years) and a freshly cut wood gives

15 counts/min/gm of carbon 133
56 Ba  e 133
55 Cs  X  ray.
[AMU (Engg.) 2002]
Reason : The atomic number decreases by one unit as
(a) 5.78  10 4 years (b) 9.85  10 4 years result of K-capture.
(c) 7.85  10 3 years (d) 0.85  10 4 years 6. Assertion : Radioactive heavy nuclei decay by a series of
11   and / or   emission, to form a stable
30. 92 U
235
 n  fission product+neutron  3.20  10 J. The
isotope of lead.
235
energy released when 1 g of 92 U undergoes fission is
Reason : Radioactivity is a physical phenomenon.
[CBSE PMT 1997]
7. Assertion : Actinium series is so called because it starts with
(a) 12.75  10 8 kJ (b) 18.60  10 9 kJ an isotope of actinium.
(c) 8.21  10 7 kJ (d) 6.55  10 6 kJ Reason : Actinium is formed in the nature as such and is
31. The triad of nuclei that is isotonic is not formed from the disintegration of any other
[IIT 1988; DCE 2000;MP PMT 2004] radioisotope.

(a) 14 15 17 8. Assertion : For maximum stability N/P ratio must be equal

6C , 7N , 9F
to 1.
12
(b) 6C , 7 N 14 , 9 F 19
Reason : Loss of   and   particles has no role in
(c) 6C
14
, 7N 14
, 9F 17 N/P ratio.
14
9. Assertion : The neutrons are better initiators of nuclear
(d) 6C , 7 N 14 , 9 F 19
reactions, than the protons, deutrons or -
32. The relative abundance of two isotopes of atomic weight 85 and 87 particles of the same energy.
is 75% and 25% respectively. The average atomic weight of element Reason : Neutrons are uncharged particles and hence, they
is [DCE 2003]
are not repelled by positively charged nucleus.
(a) 75.5 (b) 85.5
10. Assertion : Breeder reactor produces fissile Pu239 from
(c) 40.0 (d) 86.0 94
non-fissile uranium.
Reason : A breeder reactor is one that produces more
fissionable nuclei that it consumes.
11. Assertion : The activation energies for fusion reactions are
very low.
Read the assertion and reason carefully to mark the correct option out of Reason : They require very low temperature to overcome
the options given below : electrostatic repulsion between the nuclei.
(a) If both assertion and reason are true and the reason is the correct 12. Assertion : The archeological studies are based on the
explanation of the assertion. radioactive decay of carbon-14 isotope.
(b) If both assertion and reason are true but reason is not the correct
explanation of the assertion. Reason : The ration of C-14 to C-12 in the animals and
(c) If assertion is true but reason is false. plants is same as that in the atmosphere.
(d) If the assertion and reason both are false. 13. Assertion : Photochemical smog is produce by nitrogen
(e) If assertion is false but reason is true.
oxides.
1. Assertion : Mass number of an atom is equal to total Reason : Vehicular pollution is a major sources of nitrogen
number of nucleons present in the nucleus. oxides.
Reason : Mass number defines the identity of an atom. 14. Assertion : A nuclear binding energy per nucleon is in the
1 order 9
4 Be 73 Li 42 He .
2. Assertion : 1H , 1 H 2 and 1 H 3 are isotopes of hydrogen.
 Nuclear Chemistry 287
Reason : Binding energy per nuclear increases linearly 21 a 22 c 23 d 24 b 25 c
with difference in number of neutrons and
26 d 27 d 28 c 29 c 30 a
protons.
15. Assertion : Nuclear fission is always accompanied by release 31 d 32 c 33 a 34 b 35 a
of energy. 36 c 37 a 38 acd 39 a
Reason : Nuclear fission is a chain process.
[AIIMS 1994] Causes of radioactivity and Group displacement law
16. Assertion : Protones are more effective than neutrons of
equal energy in causing artificial disintegration of 1 b 2 d 3 d 4 d 5 c
atoms.
6 c 7 c 8 a 9 b 10 a
Reason : Neutrons are neutral they penetrate the nucleus.[AIIMS 1998]
11 a 12 c 13 d 14 b 15 a
17. Assertion : A beam of electrons deflects more than a beam
of  -particles in an electric field. 16 a 17 a 18 a,b,c 19 c 20 c
Reason : Electrons possess negative charge while  - 21 b 22 d 23 d 24 a 25 b
particles possess positive charge. 26 d 27 b 28 b 29 b 30 a
[AIIMS 2002]
31 a 32 a 33 c 34 b 35 a
22 22
18. Assertion : Na emits a position giving Mg .
11 12 36 b 37 c 38 b 39 c 40 d

Reason : In  emission neutron is transformed into 41 a 42 b 43 c 44 c 45 d
proton. [AIIMS 1994] 46 b 47 b 48 d 49 a 50 d
51 a 52 a 53 d 54 d 55 b
56 a 57 d 58 c 59 c 60 a
61 a 62 c 63 d 64 d 65 a
66 d 67 b 68 c 69 b 70 a
71 c 72 c 73 d 74 a 75 b
Nucleus (Stability and Reaction)
Rate of decay and Half-life
1 b 2 b 3 a 4 a 5 b
6 d 7 b 8 c 9 c 10 d 1 c 2 a 3 b 4 a 5 d

11 b 12 c 13 c 14 c 15 c 6 a 7 d 8 d 9 d 10 c

16 c 17 d 18 c 19 a 20 b 11 a 12 d 13 d 14 a 15 c

21 b 22 a 23 b 24 d 25 c 16 d 17 b 18 c 19 b 20 a

26 c 27 b 28 c 29 b 30 a 21 b 22 a 23 c 24 a 25 a

31 c 32 d 33 b 34 d 35 c 26 b 27 a 28 c 29 a 30 b

36 b 37 b 38 a 39 a 40 a 31 a 32 c 33 d 34 a 35 b

41 b 42 b 43 a 44 d 45 b 36 d 37 d 38 c 39 c 40 a

46 d 47 b 48 a 49 b 50 d 41 c 42 b 43 b 44 d 45 c

51 d 52 a 53 b 54 c 55 d 46 c 47 c 48 b 49 a 50 c

56 b 57 b 58 d 59 b 60 c 51 c 52 c 53 c 54 b 55 c

61 b 62 d 63 d 64 d 65 a 56 b 57 a 58 b 59 d 60 b

66 b 67 a 68 a 61 d 62 b 63 c 64 a 65 b
66 d 67 d 68 c 69 d 70 c
Radioactivity and ,  and - rays 71 d 72 a 73 c 74 a 75 a
76 c 77 b 78 b 79 a 80 a
1 c 2 d 3 a 4 b 5 c
81 a 82 a 83 b 84 c
6 b 7 c 8 c 9 b 10 b
11 a 12 a 13 a 14 b 15 c
Artificial transmutation
16 c 17 a 18 a 19 c 20 b
 288 Nuclear Chemistry

1 b 2 c 3 d 4 d 5 c 6 c 7 d 8 c 9 a 10 a

6 a 7 a 8 b 9 d 10 b 11 d 12 a 13 b 14 d 15 b
11 a 12 c 13 c 14 b 15 a 16 e 17 b 18 d
16 d 17 d 18 b 19 a 20 c
21 b 22 a 23 c 24 b 25 d
26 c 27 b 28 a 29 d 30 a
31 d 32 b 33 d 34 c 35 b
36 a 37 b 38 c 39 d 40 c
41 d 42 b 43 c 44 b 45 b
46 c 47 b 48 b 49 c 50 c Nucleus (Stability and Reaction)
51 d 52 c 53 a 54 d 55 d 1. (b) Protons + Neutrons = Nucleons
56 d 57 b,d 58 a 59 b 60 a 2. (b) A deutron (1 H 2 ) contains a neutron and a proton
61 d 62 a 63 a 64 d 65 d 3. (a) Low binding energy causes radioactivity.
66 d 67 d 68 b 69 b 70 d 4. (a) 7 N 14  2 He 4  8 O 17  1 H 1
71 a 72 b 73 a 74 a 75 a 5. (b) Follow Einstein mass-energy relation.

76 b 77 d 78 c 79 a 80 c
6. (d) Mass (weight) of positron and electron is 9.11  10 31 kg .

81 b

Isotopes-Isotones and Nuclear isomers

1 b 2 a 3 d 4 a 5 c
6 c 7 c 8 b 9 b 10 d
11 a 12 b 13 a 14 a 15 a
16 c 17 b 18 c 19 c 20 a
21 d 22 d 23 a 24 c 25 c
26 d 27 c 28 b 29 b 30 b
31 cd 32 d 33 a 34 c 35 c
36 b 37 a 38 a 39 a 40 b
41 c 42 a 43 a 44 d 45 b
46 a 47 d 48 d 49 a 50 a
51 b 52 d 53 b 54 c 55 ac
56 d 57 bd

Critical Thinking Questions

1 a 2 b 3 c 4 a 5 a
6 a 7 a 8 b 9 d 10 a
11 b 12 c 13 c 14 a 15 b
16 c 17 d 18 d 19 a 20 c
21 a 22 b 23 c 24 c 25 b
26 b 27 b 28 a 29 c 30 c
31 a 32 b

Assertion & Reason

1 c 2 a 3 d 4 a 5 b
 Nuclear Chemistry 291
49. (b) The atom which have lower value of packing fraction is stable.
7. (b) 3 Li 6  0 n 1  2 He 4  1 H 3
50. (d) Number of neutrons in 88 Ra 226  226  88  138 .
8. (c) 7 N 14 0 n1  6 C14  1 H 1
51. (d) Nuclear reactions involves exchange of nuclear energy.
9. (c) 17 Cl 37  1 H 2  18 Ar 38  0 n 1 52. (a) Na 23  1 H 1  12 Mg 23  0 n 1
11
10. (d) Because of its high unstability.
53. (b) 92 U 235 is radioactive because it is most unstable.
 
12. (c) 90 Th
234
 91 X 234   92 Y 234 

 90 Z 230 . 54. (c) Equate atomic no. and mass no.
13. (c) Isotopes of an element have similar chemical properties but
57. (b) 4 Be 9  2 He 4 6 C 12  o n 1
different physical properties.
14. (c) A nuclear reaction must be balanced in terms of mass and 58. (d) According to group displacement law.
energy. 59. (b) 9
Be  1 H 1  63 Li  4
4 2 He
15. (c) 52 Te 1 H 2  53 I131 0 n1
130 ( p) (  particle)
16. (c) The emission of positron takes place. 40
60. (c) 18 Ar having 40 – 18 = 22 neutrons
18. (c) An ion is electrically charged atom or a group of atoms.
While 40
21 Sc having 40 – 21 = 19 neutrons.
19. (a) Charge on positron and proton is about  1.602  10 19 C .
61. (b) Nuclear reactivity depends upon the number of protons and
20. (b) 12 Mg 24  2 He 4 o n1 14 Si 27 neutrons.
21. (b) The radioactive isotope 14
is produced in the atmosphere 63. (d) 29 Cu
64
 28 Ni64  1e 0
6C

by the action of cosmic ray neutrons on 7 N 14 65. 24

(a) 12 Mg  1 D 2  2 He 4 11
22
Na
66. (b) Equate atomic no. and mass no.
N 14 0 n1 6 C14 1 H 1
7
67. (a) X 227  Y  4  5 
96
23. (b) Tritium is the isotope.
45
On equating mass number
24. (d) 21 Sc (n, p) 20 Ca 45 according to Beath’s notation
227 = y + 4 × 4 + 0, y  211
25. (c) 7 N 14  1 H 1 8 O 15   On equating atomic number
96 = y + 2 × 4 – 5, y = 93.
26. (c) 93 Np 239 94 Pu 239  1 e o 68. (a) Meson was discovered by Yukawa
27. (b) Equate atomic no. and mass no.
28. (c) Magic no. are 2, 8, 20, 28, 50 and 82 protons in nucleus or 2, Radioactivity and ,  and - rays
8, 20, 28, 50, 82, 126 neutrons in nucleus. These numbers
imparts stability to nucleus. 1. (c)   rays does not contain material particles.
30. (a)
n
of 82 Pb 208 
126
 1 .53 2. (d)  -rays are neutral energy packet.
p 82 3. (a) The order of penetrating power is :  <  < -rays. It is due to
n 126 lower mass and high speed.
of 83 Bi 209
  1 .51
p 83 1 1
4. (b) -rays travel with a velocity which is th to th of that
31. (c) According to Beath’s notation 13 Al 27 (n, p) 12 Mg 27 . 10 20
of light.
32. (d) Azimuthal quantum no. is related to angular momentum.
5. (c) -rays have maximum penetrating power.
238  218 20 (b) -particles are 4 time heavier than neutrons.
33. (b) The value of n    5 1  4 6.
4 4
7. (c) 92 U
235
 0 n1  56 Ba145  36 Kr 88  3 10 n
34. (d) Mass number increases by one unit.
36. (b) Equal atomic number and mass number. 8. (c) Rutherford first of all used zinc sulphide (ZnS) as phosphor in
37. (b) 1 amu = 931.478 MeV. the detection of -particles.
38. (a) Positron is anti-particle of electron. 9. (b) -rays consist of a stream of He 2  .
39. (a) Isotopes are formed by the emission of one  - and two  - 10. (b) -rays are positively charged, -rays are negatively charged, -
particles respectively. rays carry no charge and thus not deflected in field.

40. (a) The

n
ratio of stable nucleoide is
n
 1. 11. (a) -particle is identical with 2 He 4 helium nucleus.
p p 12. (a) -rays have maximum penetrating power.
41. (b) Neutrino have no mass and no charge and thus known as ghost 13. (a) Henry Becquerel noticed the emission of penetrating
particles. rays from potassium uranyl sulphate and Madam Curie named it
42. (b) Equate mass number and atomic number on both sides. as radioactivity.
43. (a) Due to mass decay. 15. (c) Penetrating powers   rays    rays    rays
44. (d) Mesons () have 200-300 times mass of electron and + ve, 0
or – ve charges. 17. (a) -rays are positively charged, -rays are negatively charged, -
rays carry no charge.
45. (b) 1 e o is positron. 20. (b) Deflection in  -rays is large.
46. (d) Pb is the most stable atom.
21. (a) Penetrating power of  -rays are less than  ,  and X-rays.
47. (b) Anderson discovered positron in 1932.
48. (a) Even-Even are most stable 22. (c) Lead is a stable isotope.
Odd- Odd are most unstable 23. (d) Neutrons carry no charge.
 292 Nuclear Chemistry
24. (b) -rays has least penetrating power. No. of neutrons in C 14  14  6  8 .
25. (c)  -rays carry no charge. 
12. (c) 92 X 238 
90 Y 234
26. (d) Proton is not emitted by radioactive substances.
27. (d) Due to it’s nature. Number of neutrons = 234  90  144 .
n 13. (d) Z Am Z 1 Bm 1e 0
28. (c) 88 Ra 226 is radioactive because ratio for it is 1.56 which is
p 14. (b) r  . N
greater than 1.5.
15. (a) o n1  1 P1  1e 0 (  -particle comes out)
30. (a) Cf – 98 belongs to actinid series.
31. (d) Photons are not carry any charge. 16. (a) Element 57 to 71 are placed in III group.
2 
32. (c) N 14  2 He 4 (  particle) 8 O 17 1 H 1 17. (a) 5 X 14  7 N 14 than no. of neutrons in
7
33. (a) Definition of binding energy. 5 X 14
 14  5  9 .
34. (b)   particle is 2 He . 4 18. (a,b,c) An emission of -particle means that atomic number increases by
1 but mass number remains unaffected and neutron- proton ratio
35. (a) Gamma ray doesn’t deviate from electromagnetic field, the decreases.
main reason of it is that there is no charge on gamma rays.
36. (c) Energy liberated = loss of mass  931 19. (c) Suppose the no. of -particles emitted = x and the no. of -
particles emitted = y, then
 0.01864  931  17.36 MeV
38. (acd) Beta emission causes increase in atomic number by one unit. 92 U 82 Pb206  x  2 4  y 1  0
238

39. (a) Mass loss = mass of reactant – mass of product. Equating the mass number on both sides, we get
 (2.014  3.016)  (4.004  1.008) 32
238 = 206 + 4x + 0y or 4x = 32 or x  8
 5.030  5.012  0.018 amu 4
Hence 8 -particles will be emitted.
20. (c) Pb is the end product of each natural radioactive series.
Causes of Radioactivity and
Group Displacement Law n
21. (b) The ratio of 13 Al 29 places it above the belt of stability and
p
1. (b) In Am 241 the mass no. division by four gives a residue of 1. thus it emits  -particles.
95

In Th 234 the mass no. division by four gives a residue of 2. 22. (d) Y A X  Y 10 B X  32  m 2 He 4  n 1e 0
90
2. (d) On emission of  -particles daughter element shift 2 group to X  ( X )  32
Value of m = 8
the left. On emission of  -particles daughter element shift 1 4
group to the right. Value of n = Y – Y – 10 – 2 × 8 = 6.
3. (d) Protons + Neutrons = Nucleons 23. (d) During  -decay atomic mass is unaffected while atomic no.
4. (d) Radioactivity is characteristic property of unstable nucleus. increases by one unit.
5. (c) Chemical change is extra nuclear phenomenon. 24. (a) Equate atomic number and mass no.
8 
6. (c) U 
238
 X 206

25. (b) 2 
X 232   92 Y 232  82 Z 212  x 2 He 4
6 
92 82
90

Number of protons = 82; Number of neutrons = 124 232  212 20

No. of  -particles   5.
124 62 4 4
Neutron/proton ratio in the product nucleus  
82 41  
26. (d) 92 X 238   90 Y 234   91 Z 234
X 218  84 Y 214  x  2 y 1 
4 0
7. (c) 84 no. of neutrons = 234 – 91 = 143.
 
218  214 4 27. (b) Z A
M
 Z  2 B M 4 
  Z 4 C M 8 .
no. of -particle =  1 Gr.2 Gr. 18 Gr.16
4 4 28. (b) Equate atomic no. and mass no.
no. of -particle = 84  84  2  1  2 . 29. (b) The mass no. on division by four gives a residue of 2.
8. (a) When an -particle is emitted by any nucleus than atomic 30. (a)
weight decreases by four units and atomic number decreases Series Name of the series Parent End stable
by two units element element
 4n Thorium series Th-232 Pb–208
88 Ra 224 
 86 X 220
4n + 1 Neptunium series Pu-241 Bi–209
231  207
9. (b) Number of -particles = 6 4n + 2 Uranium series U-238 Pb–206
4 4n + 3 Actinium series U-235 Pb–207
Number of -particles  89  82  2  6  5 .
31. (a) 8O
16
 1 H 2  9 F 18
10. (a) 90 Th
228
83 Bi212
32. (a) 84 A 218  84 B 214  2 He 4  2 1e 0 .
228  212 16
No. of  -particles =  4 33. (c) It is also called Soddy and Fajan rule.
4 4
34. (b) Po 215  82 Pb 211  2 He 4
No. of  -particles = 90  83  2  4  1 .
84

35. (a) 92 U
238
 90 Th 234  2 He 4
11. (a) 6C
14
 7 N 14  1e 0
 Nuclear Chemistry 293

No 24 Hence 8  and 6  are emitted.

36. (b) N  and n  3
2n 8 0 .693 0 .693
59. (c) k   0.000693  6.93  10 4 s 1
40 40 t1 / 2 1000 s
N   5
23 8 60. (a) Bi is a stable end product of Neptunium series.
37. (c) 42
21 Sc 42 1e 0 62. (c) Pb – 208 is the stable end product of thorium series.
20 Ca
63. (d) Definition of disintegration series.

38. (b)  A 2 Y M 4
X M  
A
64. (d) 6 X 14  6 1 N
14
23
39. (c) 24
12 Mg   11 Na  11 H . in X 14 no. of neutrons 14 – 6 = 8.
6
40. (d) An element formed by losing one -particle occupies two
position left to parent element, Pb in IVA, thus Po should be in 65. (a) 18 Ar 40
VIA. Total no of protons = 18
41. (a) According to group displacement law. Total no of neutrons = 22
238  206 Mass defect  [m  p  m  n]  39.962384
42. (b) Number of -particles = 8
4
 [1.007825  18  1.008665  22]  39.962384
Number of -particles = 92  82  2  8  6 .
 [18.14085  22.19063]  39.962384  0.369
43. (c) X 41 Y 1e 0 (-emission)
40
Binding energy = mass defect  931
90 600  0.369  931  343.62 MeV
44. (c) n  3  N  3  75 atoms .
30 2
45. (d) Equate mass no. and atomic no. 66. (d) 90 Th
232
 82 Pb 208
46. (b) 92 U
236
 90 X 232  2 He 4 232  208
No. of  - particle  6
4
X 232 have 90 protons and 142 neutrons.
No. of  - particle  82  [90  6  2]  4
90

47. (b) -rays have high I.P. due to high kinetic energy.
48. (d) Going two positions back from 2 group gives zero group.
nd
67. (b) 92 M 238  y N x  2 2 He 4
49. (a) Ra belongs to (4 n  2) series. End product will also belong to
y N x  B LA  2  
the same series.
50. (d) Ra contaminated with uranium mineral shows appreciable y N x (92 22) N (238 42)  88 N 230
radioactivity.

2
51. (a) 92 U
238
 82 Pb206  x  2
4
y 1 
0
88 N 230  (88 2) L(230 )  86 L230
238  206 Total no of neutrons in L330
no. of -particles = 8 90
4 230  86  144
no. of -particles = 92  82  2  8  6
68. (c) 90 E 232  86 G 220
Total no. of particles = 8  6  14 .
52. (a) According to Group displacement law. 232  220
No. of  particle = 3
53. (d) Rate =  × number of atoms. 4

54. (d)  82 Pb208  x 2 He 4  y 1  0

232 No. of  particle  86  [90  2  3]  2
90 Th
Equating mass no. 0 .693 0 .693
69. (b) K 
232 = 208 + 4x + 0 y or 4x = 24 or x = 6 t1 / 2 1600
Equating atomic no.
 4.33  10 4 year 1
90 = 82 + 2x –y or 90 = 82 + 2 × 6 – y or y  4
Hence 6 and 4 particles will be emitted. 70. (a) 92 U
238
 90 Th 234  91 Pa234

(b) Z Am Z 1 Bm 1e 0 238  234 4

55. No. of  particle   1
56. (a) The mass no. division by four gives a residue of 1 4 4
 No. of  particle  91  90  1
57. (d) AX
m

 A 1 Y m
0 .693
58. (c) Suppose the no. of -particles emitted  x and 72. (c) K
t1 / 2
the no. of  -particles emitted =y. Then
0.693 0 .693
92 U
238
82 Pb206  x 4 2  y 1 
0
t1 / 2    1.2 hrs
K 0 .58
equating the mass number on both sides, we get
238 = 206 + 4x + 0 y or 4x = 32, x = 8 73. (d) A radioisotope first emits  or  particles, then it becomes
equating the atomic number on both sides, we get unstable and emits  -rays.
92 = 82 + 2x – y 2  
74. (a) 180
72 X 
 172
68 P  69 Q  69 X .
172 172

92 = 82 + 2× 8 –y
75. (b) Loss of beta particle is equivalent to decrease of one neutron
y=6 only.
 294 Nuclear Chemistry

n  p  e  v .  N 
No N
 o  10 .
10 N
Rate of decay and Half-life No 100
16. (d) Amount left    12.5 %
23 8
16 N 16.0 16.0
1. (c) n  2, N  no  2   4 .0 gm. No N
8 2 2 4 17. (b) N   6o n  6
2. (a) Mass of 6 neutrons = 6.05358 amu, Mass of 6 protons = 64 2
6.04884 amu, Mass of n + Mass of p =12.10242 amu Thus total time  2  6  12hr .
Mass defect = 12.10242 – 12.00710 = 0.09532
Binding energy = 0.09532  931 = 88.74292 MeV. 18. (c) -decay occurs by the nuclear change n  p  1e 0 .
Binding energy per neucleon = 88.74292/12
=7.39 MeV loge 2 1
19. (b) t1 / 2  , Average life 
80  
3. (b) T  t1 / 2  n,  n  4
20 No 60 1 1
1 1 1 20. (a) N  ,n   3; N o  1g, then N  3  .
Amount left  n  4 
n
. 2 20 2 8
2 2 16
21. (b) t1 / 2 of zero order reaction is independent of the
4. (a) X 232 89 Y 220  x 2 He 4  y 1 e o
92 concentration.
232  220 22. (a) Half-life is 1 hr and thus in each half-life, half of the sample
no. of  -particles = 3
4 decays.
no. of  -particles = 89 –[92 – 2 × 3] = 3. 2.303  t1 / 2 N
23. (c) t log o , N  0 .798 N o
5. (d) It is occurs by  -decay. 0.693 N
n n 24. (a) Half-life is independent of initial amount.
1  1
6. (a) N     N o = 125 mg =    1000 mg 25. (a) 80 years = 4 half lives
 
2 2 1
n Activity after n half lives  n  a .
1 125 1 2
   
2 1000 8 26. (b) t1 / 2 is independent of all external factors and is constant for
n 3 a given species.
1 1
     , n  3, so number, of t1 / 2  3 27. (a) In nucleus electrons formed by the following decay.
 
2 2
0n
1
1 P1 1e 0
24
Total time = 24 hours, Half-life time   8 hours . 28. (c) t1 / 2  2.95 days
3
= 2.95 × 24 × 60 × 60s = 254880

8. (d) 35 X 88 
 36 W 88  36 W 87  o n1 0 .693 0 .693
   2.7  10 6 s 1
9. (d) 75% of the substance disintegrates in two half lives. t1 / 2 254880
2 half lives = 30 min  t1 / 2  15 min . 29. (a) When a radioactive element emits an -particle, the atomic no.
of the resulting nuclide decreases by two units and atomic
10. (c)  -rays are electromagnetic waves. mass decreases by 4 units.
11. (a) Average life 0.693 0.693
30. (b) t1 / 2    0.3  10 4 yrs
( )  1.44 t1 / 2  1.44  69.3  99.7  100 minutes. k 2.31  10 4
n  3.0  10 3 yrs.
1 
12. (d) N     No n
2 1 40
31. (a) N  N0   . n  4
n 2 10
1 
1 .25     10 4
2 125 1 125
 N0   , N0   2  2  2  2  2g
n 3
1000 2 1000
1  1 .25 1  1 
 2   10  8   2  , n  3 127
 7 .94 MeV .
    32. (c) Binding energy per nucleon =
16
15 0 .693 0 .693
Half-life time =  5 days. 33. (d) k    0 .005min 1
3 t1 / 2 138.6 min
12 34. (a) Half-life period is independent of initial amount.
13. (d) n  4
3 35. (b) t = Feb 1 to July 1 = 28  31  30  31  30  150 days
 N o  N  2 n  3  2 4  48 g . 
2.303
log
8

2.303
log 2 5 
0 .693
day 1
150 0.25 150 30
14. (a) 6C
14
 7 N 14  1 e o , -active. 0.693
t1 / 2   30 days .
2 .303 0 .693 / 30
15. (c) 2.303   t1 / 2 log10
0.693
 Nuclear Chemistry 295

2 .303  t1 / 2No 1

n
36. (d) t log 56. (b) N  N0   
0 .693 N 2
480 N 4 4 n
37. (d) n   4 , N  no , N  4  = 0.25 gm. 1 1
120 2 2 16  1  ; n 1
2 2
28 N 1 1
38. (c) n   4 , N  no , N  4   0.0625 gm. t  n  t1 / 2  1  6000  6000 yrs.
7 2 2 16
2 .303 [ N ] 2.303 1 57. (a) For I order t1 / 2  0.693 K 1 .
st

39. (c)   log o  log

t [N ] 96 1/8 58. (b) 75% of the substance disintegrates in two half lives 2 half lives
= 60 min.  t1 / 2  30 min .
2 .303
  0.9  0 .0216
98 0 .693 2 .303 100
59. (d)   log
0.693 0.693 t1 / 2 180 12.5
 t1 / 2    32.0 min .
 0.0216 0.693  180
t1 / 2   60min  1 hr.
1 
n
1  25
n
1 1 
2 2.303  3  0.3010
40. (a) 25     100,      
2  2  100 4  2  60. (b) Tritium (1 H 3  2 He 3  1e 0 ) is a -emitter.
n = 2, No. of half lives = 2 61. (d) t1 / 2  ln 2 / 
so time required = 2  5760  11520 yr. 0 .693 0 .693
62. (b) t1 / 2    3.0  10  3 sec .
41. (c) t1 / 2  100 years.  231 sec 1
1 128
42. (b) Average life ( )  . 63. (c) The amount of 53 I left after 50 minutes will be

100 1
1 1 1 1 = 25 minutes   .
43. (b)  or 4  n or n  4 25 4
16 2 n 2 2 25
 Required time  4  t1 / 2  120min . 64. (a) N N o (at t  2 hr)
100
44. (d) The time required for complete decay (I order) is always 2 .303 N
infinite. Thus t   t1 / 2 log o
45. (c) After half-life time the half of the substance will be decayed. 0 .693 N
65. (b) Radioactive decay is a first order reaction.
15 N 20 20
46. (c) n   3, N  no  3   2 .5 gm. 66. (d) t1/2 is independent of all external factors.
5 2 2 8
3 
67. (d) Rate of decay of radioactive species is independent of all
47. (c) 6 X 14  9 Y 14 external factors.
25 100 N 100 100
48. (b) N N o (at t  32 minutes) 68. (c) n   4 , N  no  4   6.25 gm .
100 25 2 2 16
2 .303 N 69. (d) 92 U 235  0 n1  56 Ba145  36 Kr 88  310 n
Thus t   t1 / 2 log o
0 .693 N 70. (c) Half-life is independent of initial amount.
49. (a) Half-life period is a characteristic of radioactive isotope which 0.693 0.693
is independent of initial concentration. 71. (d) t1 / 2    0.1  10 6  10 5 yrs .
k 6.93  10  6
24 N 1 1
50. (c) n   3, N  no  3  mg . 72. (a) 1 milli curie = 3.7  10 7 dps
8 2 2 8
51. (c) Because t1 / 2  4.5  10 9 years, so after 4.5  10 9 years the 1.5 milli curie = 5.55  10 7 dps
238 5 .55  10 7
amount of 92 U will be half decayed.    1 .37  10 11
No
0 .693
52. (c) r  No T 75
t1 / 2 N  1  t1 / 2 N  1  25 N 1 1
3
73. (c)   ;   ;   
0 .693 6 .023  10 23 No  2  No  2  No  2  8
 
1600  365  24  60  60 226 T 24
6
N  1  t1 / 2 N 1 4 N 1
= 3.7  10 dps .
10
74. (a)   ;   ;  
No  2  200  2  200  2 
2.303  t1 / 2 N 1
53. (c) t log o ; N  200
0.693 N 16 N  3 .125 g
64
0 .693
54. (b) t1 / 2  75. (a) 2
X y 
 7 N 14
k or  x

3 N 1 X y 14  5 X 14
x 7  2
55. (c) n  3; N  3o  Total no. of neutrons =14 – 5 = 9
1 2 8
 296 Nuclear Chemistry

76. (c) K
0 .693
; K
0 .693
 0 .0693 yr 1 16. (d) Einstein’s law is E  mc 2 .
t1 / 2 10 17. (d)
T 192 192 18. (b) 11460 years = 2 half lives
4
N  1  t1 / 2  1   1  t1 / 2  1   1  t1 / 2 Activity left = 25% = 0.25.
77. (b)   ;    ;    
No  2   16   2  2 2 19. (a) The control rods used in nuclear reactor are made up of Cd –
113 or B -10. They can absorb neutrons.
t1 / 2  48 min
14
  
20. (c) The radioactive isotope 6C is produced in the atmosphere
78. (b) 92 U
235

 ( A) 
 (B) 
 (C)
by the action of cosmic ray neutrons on 7 N 14
(i) 92  2 A 235 4  90 A 231
22. (a) Heavy water (D2 O) is used as a moderator in a nuclear

(ii) 90 A 231 
 (90 1) B (231 )  91 B 231 reactor. It slows down the speed of neutrons. It also acts as a
 coolant.
(iii) 91 B
231

 (91 1)C 231  92 C 231
23. (c) Uranium or Plutonium are atomic fuel.
Isotopes are 92 U
235
and C 24. (b) atom bomb is based on the principal of nuclear fission.
25. (d) Hahn and Strassmann discovered the phenomenon of nuclear
0.693 0.693
80. (a) t1 / 2    0.296 sec fission in 1939.
K 2.34 26. (c) Rate of disintegration is not affected by environmental
0 .693 0 .693 conditions.
81. (a) K 
T1 / 2 5770 27. (b) It is believed that when an  or  -particle is emitted, the
nucleus becomes excited i.e. has higher energy and emits the
2.303 100 2.303  5770 100 excess energy in the from of radiation which form  -rays.
 t log  log
K 72 0.693 72
 19175.05  (log100  log72) 28. (a) Packing fraction  Isotopic mass  Mass number  10 4
Mass number
19175.05  0.143  2742.03 years.
30. (a) C is a natural radioactive isotope of C 12 .
14
82. (a) For 25% decay
31. (d) t1 / 2  10 yrs, t  20 yrs.
2.303 100 2.303
K log   0.1249  0.. 1438 t 20
20 75 20 n   2
For 75% decay, t1 / 2 10
2.303 100 No 1 1
t log  96.4 minute. N   N o   100% of N o  25 .
0.01438 25 22 4 4
1 N 1
n n 32. (b) Due to evolution of nuclear energy as a result of mass decay.
83. (b) N  N0     
 
2 N 2 33. (d) Heavy water (D2 O) is used as a moderator in nuclear reactor.
0
n 6 n 34. (c) It is a transformation of chlorine.
1 1 1 1
or       n6 35. (b) 48 gm of radioactive sodium will need 32 hours to become 3.0
64  2   
2 2 gm.
T  t1 / 2  n  2  6  12 hours. 36. (a) Mass decay occurs.
After 12 hours, sample became non-hazardous. 37. (b) In hydrogen bomb, the following reaction is occur,
84. (c) Half-life of same substance remains same. 2
 1 H 3  2 He 4 10 n  energy .
1H

38. (c) A reason for the C-14 dating technique.

Artificial transmutation
2.303 a 99
39. (d) t log , (a  x )   0.99 a
1. (b) C  14 dating method is used in estimate the age of most k 0.99 a 100
ancient geological formation. 0 .693 0 .693
2. (c) Joining up of two lighter nuclei is fusion. But k    0 .0653 year –1

t1 / 2 10.6
5. (c) Equate atomic no. and mass no.
2.303 1
6. (a) For studies on carbon dating, W. F. Libby was awarded a t log  70.4 yrs.
Nobel prize. 0.0653 0.99
7. (a) Spallation reactions are similar to fission reactions. They 41. (d) D2 O is heavy water.
brought about by high energy bombarding particles or
photons. 42. (b) D2 O is used as moderator in nuclear reactor.
9. (d) Uranium or Plutonium are atomic fuel.
45. (b) Liquid sodium use in nuclear reactors as heat exchanger or
11. (a) It is the required technique. coolant.
n 49 .2 / 12 .3 4
1 1 1 46. (c) Due to heavy mass -particles can not easily pass through solid
12. (c) N t  N o    32     32     2 .
 
2 2 2 matter so they are less effective for artificial transmutation.
14. (b) In hydrogen bomb, the following reaction is occur, 47. (b) Given N o  1, N t  0.70 and t1 / 2  5760 yrs.

1H
2
 1 H  2 He
3 4
10 n  energy . 0 .693 0 .693
k  .
15. (a) Heavy water is D2 O . t1 / 2 5760
 Nuclear Chemistry 297

We also know, k 
2 .303 N 0 .693
log 0 . 6. (c) Z Am z Bm  4  2 He 4  21 e 0
t N t 5760
7. (c) Co 60 is used in radiotherapy of cancer.
2.303  5760  0.155 8. (b) Atoms of different elements having different atomic no. but same
or t   2966yrs.
0.693 mass no. are called isobars.
48. (b) The splitting of a heavier atom like that of U-235 into a 9. (b) N 14  2 He 4 8 O17 1 H 1
7
number of fragments of much smaller mass by suitable
bombardment with sub-atomic particles with liberation of huge 10. (d) 1H
3
2 He 3  1e 0
amount of energy is called nuclear fission. 3 3
1H and 2 He are isobars (same mass no.)
49. (c) 13 Al
28
 2 He 4  15 P 31  0 n1
11. (a) The isotopes having an excessive n/p ratio exhibit e  -emission.
50. (c) Rate of radioactivity is independent of all external factors.
12. (b) 6 C 14 is an isotope of carbon (6 C 12 ) .
51. (d) I131 is used for goitre therapy, i.e. iodine deficiency.
14. (a) Isotopes differ in number of neutrons but have same number
52. (c) C-14 is found in nature abundantly and in definite ratio. of protons.
53. (a) Astatine (At) is resembles in properties with iodine.
15. (a) Z A m z B m  4  2 He 4  2 1 e o
56. (d) Equate mass number and atomic number.
16. (c) Atoms of different elements having different atomic no. but same
57. (b,d) D2 O is used as moderator in nuclear reactor. mass no. are called isobars.
58. (a) The rate of disintegration is expressed in terms of the number 17. (b) Isotopes differ in number of neutrons but have same number
of disintegrations per second. of protons.
14 18. (c) z A m Z B m  4  2 He 4  2 1 e o
59. (b) 6C is used in dating archeological findings.
n
40 19. (c) is minimum for this isotope.
60. (a) n 2 p
20
20. (a) In chlorine gas ratio of Cl 35 and Cl 37 is 3 : 1.
N 100
 Amount left n0  2  25 gm 21. (d) Isotones have the same number of neutrons but different
2 2
number of nucleons (n  p) . e.g., 18
39 40
Ar, 19 K.
61. (d) The definition of nuclear fission.
22. (d) Isobars have different no. of protons and neutrons.
62. (a) The huge amount of energy released during atomic fission is
due to loss of mass. 23. (a) Atoms of different elements having different atomic no. but same
mass no. are called isobars.
63. (a) Mass defect is the measure of binding energy of a nucleus. 24. (c) Isotopes differ in mass no. and hence in the number of
65. (d) Irene curie and Juliot studied the artificial radioactivity. neutrons.
No 560 1 1 25. (c) Isotones are the species which have same number of neutrons
66. (d) N n
and n   4; N  4  gm. and different number of nucleons (p + n).
2 140 2 16
67. (d) G.M counter is used to determine rate of decay. 26. (d) In 13 H their are 1 proton and 2 neutrons.
68. (b) Cd and boron rods are control rods used in reactors. 27. (c) Isotopes differ in mass number, and hence in the number of
69. (b) Graphite is used as moderator to slow down the speed of neutrons.
neutrons in atomic reactors. 28. (b) In isotones have same number of neutrons.
12 29. (b) Atoms of different elements having different atomic no. but same
70. (d) Isotope C is the modern basis of atomic weight. mass no. are called isobars.
14
71. (a) 6C is used to determine the mechanism of photosynthesis. 30. (b) Two isotopes of bromine are Br79 , 81
35 35 Br

74. (a) 28 Ni 60  0 n1 28 Ni 61 27 Co 60  1 p 1 No. of neutrons in 35 Br79 = 79  35  44

76. (b) 6C
14
used for dating process. No. of neutrons in 35 Br 81 = 81  35  46 .
T T 31. (c,d) Isotopes have same atomic number but different mass number
N  1  t1 / 2 13  1  5770 and same chemical properties.
79. (a)      33. (a) Isotopes have same atomic number but different mass number.
No  2  100  2 
 82 Pb207  x 2 He 4  y 1 
235 0
34. (c) 92 U
13 T
Taking log  log  log1 / 2  16989 yrs
100 5770 235  207 28
no. of -particles =   7
4 4
Isotopes-Isotones and Nuclear isomers no. of  -particles = 92  82  2  7  4  .
35. (c) z A m  2 o n1  Z A m  2 , an isotope of A.
1. (b) The definition of Isotopes.
36. (b) Atoms of different elements having different atomic no. but same
2. (a) Isotopes of hydrogen is 1 H 1 , 1 H 2 , 1 H 3 known as protium, mass no. are called isobars.

deuterium and tritium respectively. 37. (a) A X M   A  2 Y M  4
3. (d) 8O
18
isotope of oxygen have 10 neutrons and 8 protons. 38. (a) Isotopes have same atomic number but different mass number.
4. (a) Atoms of different elements having different atomic no. but same 39. (a) In isotope 32 X 65 , 32 is atomic number and 65 is atomic
mass no. are called isobars. weight.
5. (c) Isotopes have same atomic number but different mass number.
 298 Nuclear Chemistry
40. (b) Atoms of different elements having different atomic no. but same dx 1
mass no. are called isobars. 8. (b)  N 1 , 1  10 5  N 1
dt
41. (c) Atoms of different elements having different atomic no. but same
mass no. are called isobars. dx 2
 N 2 , 3.7  10 10  N 2
43. (a) Mass no. will remain same as proton is replaced by neutron. dt
44. (d) Isotopes differ in number of neutrons but have same number
N1 1  10 5 1  10 5
of protons.    0 .27  10  5 .
45. (b) Atoms of different elements having different atomic no. but same N 2 3 .7  10 10
3 .7
mass no. are called isobars.
9. (d) 92 U
235
 o n1 54 X e139  38 Sr 94  3 o n1
46. (a) 11 Na 24  12 Mg 24  1 e 0 (-particle comes out).
0 .693 0 .693
47. (d) Isotopes differ in number of neutrons but have same number 10. (a) k   0 .231 per hrs.
of protons. t1 / 2 3 hr.
48. (d) Atoms of different elements having different atomic no. but same 0 .693
mass no. are called isobars. 11. (b) t1 / 2 of C–14 = 5760 year,   ,
5760
49. (a) 1H
3
 2 He 3  1 e o
14
2 .303 C original
50. (a) Isotopes of same elements have the same number of protons Now t  log 14
but different number of neutrons.  C after time t
x  37  (100  x )35 3500  2 x 2.303  5760 100 2.303  5760  0 .9030
51. (b) 35.5 =  35.5   log 
100 100 0.693 12.5 0.693
2 x  50  x  25  Ratio 75 : 25 = 3 : 1 = 17281= 172.81 × 10 2 years.
52. (d) An ordinary oxygen contains a mixture of O-16 (99.8%), O-
17(0.037%), O-18(0.204%) isotopes. 12. (c) According to radioactive equilibrium  A N A  B N B
54. (c) They are isosters i.e, Number of atoms = same
0 .693  N A 0 .693  N B  0 .693 
Number of e  = same ;Physical properties = same or    
t1 / 2 ( A) t1 / 2 (B)  t1 / 2 
55. (ac) Isotopes have same atomic number but different mass number.
57. (bd) Both have 34 neutrons; Isotones have same number of Where t1 / 2 ( A) and t1 / 2 (B) are half periods of A and B
neutrons. respectively
NA NB N t ( A)
Critical Thinking Questions   or A  1 / 2
t1 / 2 ( A) t1 / 2 (B) NB t1 / 2 (B)
n  At equilibrium A and B are present in the ratio of their half
1. (a) 23
11 Na  ratio  12 / 11 1 1620
p lives 
2.8  10 6 Half life of uranium
n
24
11 Na  ratio  23 / 11  Half-life of uranium
p
n = 2.8  10 6  1620  4.53  10 9 years.
so decrease in ratio gives out  -particle
p 13. (c) Average life period = 1.44  t1 / 2

n  p  e (  ) . 1.44  1580  2275.2  2.275  10 3 yrs.

2. (b) Oxygen have 90% O 16 and 10% O 18 14. (a) N o  8 gms, N = 0.5g and t = 1 hr. = 60 min. find t1 / 2 by
 90 10  2 .303  t1 / 2 N
Atomic mass =   16   18  t log o .
 100 100  0 .693 N
1440  180 1620 0.693 2.303 a
=   16.2 . 15. (b) k   log
100 100 0.75 hr t a  0 .999a
3. (c) It is a neutron induced fission reaction.
2 .303
4. (a) Mass defect = mass of sulphur – mass of chlorine  log10 3  7.5 hrs .
t
 34.96903  34.96885  0.00018 g
1
Binding energy =mass defect  931 16. (c) T = 50 days, t1/ 2 = ?, N o  1, N  ,
32
 0.00018  931
n n
 0.1675 MeV 1 1 1
N  N o    or  1  ,
5. (a) The problem refers that rate is constant. 2 32 2
6. (a) 1C = Activity of 1 g of Ra226  3.7  1010 dps 1 1
5 n
or      or n = 5
Activity of 1g of Ra226  3.7  10 4 dps 2 2
So, the no. of  -particles are emitted per second by 1g of T  t1 / 2  2 , or t1 / 2 
50
 10 days.
Ra is 3.7  10 dps  3.62  10 / sec
4 4 5

7. (a) 2.92  10 4 -particles will be emitted per second.

 Nuclear Chemistry 299

2.303 a 2 .303 2
17. (d) K log  log 8 1
40 a  0.875a 40 28. (a) N t  N o   [  t1 / 2 = 22 years, T = 11 years, N o =2, N t =?]
2
 0.05199 min 1 t1 / 2 = 0.693/0.05199
11 1
= 13.33 min. = 13 min 20 sec. T  t1 / 2  n, 11= 2 × n or n  
22 2
18. (d) t1 / 2  10 days, N  125 1/2
1
2 .303  t1 / 2 N  N t  2 gm     1 .414 gm .
Calculate as, t  log o . 2
0 .693 125
2.303 15
19. (a) t1 / 2 
0.693

0 .693
 0.1098  10 4  1098 yrs . 29. (c) t  5000  log
k 6 .31  10 4 0.693 5

20. (c) T  t1 / 2  n,  3000  1500  n n = 2 2.303

  5000  log 3  7927  7.92  10 3 yrs.
0.693
1 1
 Amount left    0 .25 g .
22 4 6 .023  10 23
30. (c) 1g U-235  atoms
n 18 / 3 6 235
1 1 1
21. (a) N t  N o   , N t  256    256    4 .
2 2 2 6 .023  10 23
 energy released  3 .2  10 11  J  8.21  1010 J
15 235
22. (b) Quantity of radioactive element decayed 
16
 8.2  107 kJ .
15 1
Quantity left = 1   31. (a) Isotones have same number of neutrons.
16 16
85  3  87  1
1 1
n
1 1
4 n
32. (b) Average atomic weight of element   85.5
 1    or      3 1
16 2 2 2

one half-life =
40
 10 days.
Assertion & Reason
4
n 26 / 6 .5
1. (c) Atomic number defines identity of an atom because each atom
1 1 has a definite number of protons in its nucleus.
23. (c) N t  N o    48  10 19  
 
2 2 3. (d) The activity of 1 g of pure U  235 and that in U 3 O 8 is
4 same. Activity does not depend upon the state of combination.
1 5. (b) In some nuclides, the nucleus may capture an electron from the
 48  10 19    3  10 19 .
2 K -shell and the vacancy created is filled by electrons from
0.693 2.303 1 higher levels giving rise to characteristic X -rays. This process
24. (c)  log is known as K -electron capture or simply K -capture.
9 t 1  0.2
6. (c) Radioactivity of an element is independent of its physical state
0.693 2.303 16 its chemical environment or temperature, suggesting that it is a
25. (b)  log  560 days property of nucleus i.e., nuclear phenomenon.
140 t 16  15
5
7. (d) At onetime, it was believed that actinium series starts with
20 N 1 1 Ac  227 but now it is well known that it starts with
26. (b) n   5, t     ,  decayed
4 No  2  32 U  235 and Ac  227 is one of the main products.
 
 1  31 9. (a) 92 U
238
 0 n1  92 U 239 
 93 Np 239 
 94 Pu 239
 1 –   100   100  96.87 .
 32  32 In breeder reactors, the neutrons produced from fission of
U  235 are partly used to carry on the fission of U  235
27. (b) rnucleus  1.3  10 -13  ( A)1 / 3 , where A is mass number and partly used to produce some other fissionable material.
10. (a) The activation energies for fusion reactions are very high. They
rU 238  1.3  10 13  (238)1 / 3  8.06  10 13 cm.
require very high temperature ( 10 6 ) to over come
electrostatic repulsion between the nuclei.
rHe 4  1.3  10 13  (4 )1 / 3  2.06  10 13 cm.
12. (c) Loss of  or  -particle is to change N / P ratio so that it
Total distance in between uranium and  nuclei lies with in the stability belt. Loss of  -particle increases
= 8. 06× 10 13 + 2.06 × 10 13 = 10.12 × 10 13 cm N / P ratio while loss of  -particle decreases N / P ratio.
Now repulsion energy = 13. (b) It is correct that photochemical smog is produced by nitrogen
Q1 Q 2 92  4.8  10 10  2  4.8  10 10 oxide and it is also fact that vehicular pollution is a major
 erg source of nitrogen oxide but it is not correct explanation.
r 10.12  10 13
 418.9  10 7 erg = 418.9  10 7  6.242  1011 eV 14. (d) Binding energy per nucleon of 3 Li 7 (5.38 MeV) is lesser than
He 4 (7.08 MeV) as helium is found to be more stable than
= 26.147738  10 4 eV . 2
Li . As the atomic mass number increases, the binding energy
 300 Nuclear Chemistry
per nucleon decreases. As the atomic number and the atomic
mass number increase, the repulsive electrostatic forces with in
the nucleus increase due to the greater number of protons in
the heavy elements. To over come this increased repulsion, the
proportion of neutrons in the nucleus must increase to
maintain stability. This increase in the neutron to proton ratio
only partially compensates for the growing proton – proton
repulsive force in the heavier, naturally occurring elements.
Because the repulsive forces are increasing less energy must be
supplied, on the average, to remove a nucleon from the
nucleus. The BE/A has decreased. The BE/A of a nucleus is an
indication of its degree of stability. Generally, the more stable
nuclides have higher BE/A than the less stable ones. The
increase in BE/A as the atomic mass number decreases from
260 to 60 is the primary reason for the energy liberation in the
fission process. The increase in the BE/A as the atomic mass
number increases from 1 to 60 is the reason for the energy
liberation in the fusion process, which is the opposite reaction
of fission.
15. (b) It is correct that during nuclear fission energy is always
released and it is also true that nuclear fission is a chain
prouss.
16. (e) Neutrons are more effective than protons of equal energy in
causing artificial disintegration of atoms. neutrons are neutral
they penetrate the nucleus and do not exert any repulsive force
like positive charged protons.
17. (b) It is true that abeam of electrons deflects more than a beam of
 -particles in am electric field. It is also true that electrons
have –ve while  -particles have +ve charge. Here both are
true but reason is not a correct explanation.

Na 22  12 Mg 22  1 
0
18. (d) 11 .

Thus this change involves a  -particle emission and not a

positron. Also, proton emission convert proton into neutron as
: 1P 
1
 0 n 1  1  0
 Nuclear Chemistry 301

1. When 3 Li7 are bombarded with protons,  -rays are produced. (c) Nuclear charge higher by one unit
The nuclide formed is [CPMT 1987] (d) Nuclear charge lower by one unit
8 9. The end product of 4 n series is [MNR 1983]
(a) 3 Li (b) 4 Be 8
208 207
(a) 82 Pb (b) 82 Pb
9
(c) 3B (d) 4 Be 9
209
(c) 82 Pb (d) 83 Bi204
2. Nuclides [BVP 2003]
(a) Have specific atomic numbers 10. 92 U 235 belongs to group III B of periodic table. If it loses one  -
(b) Have same number of protons particle, the new element will belong to group
[MNR 1984; CPMT 2001]
(c) Have specific atomic number and mass numbers
(a) I B (b) I A
(d) Are isotopes
(c) III B (d) V B
3. In the following nuclear reactions
11. Radioactive disintegration differs from a chemical change in being
7 N 14  2 He 4 8 O 17  X 1 and 13 Al 27 1 D 2 14 Si 28  X 2 (a) An exothermic change
X 1 and X 2 are respectively [MP PMT 1999] (b) A spontaneous process
(c) A nuclear process
1 1 1
(a) 1H and 0n (b) 0n and 1 H 1
(d) A unimolecular first order reaction
(c) He 4 and 0 n 1 (d) 1
and He 4 12. Half-life is the time in which 50% of radioactive element
2 0n 2
disintegrates. Carbon-14 disintegrates 50% in 5770 years. Find the
4. Gamma rays are half-life of carbon-14 [DPMT 1996]
[NCERT 1978; MNR 1990; UPSEAT 1999, 2000] (a) 5770 years
(a) High energy electromagnetic waves (b) 11540 years
(b) High energy electrons
(c) 5770 years
(c) High energy protons
(d) None of the above
(d) Low energy electrons
14
13. The half-life of C is about [MP PET 1996]
5. Which particle can be used to change 13 Al 27 into 15 P
30

(a) 12.3 years

[MP PMT 2003]
(b) 5730 years
(a) Neutron (b) -particle
(c) 4.5  10 9 years
(c) Proton (d) Deuteron
6. Which of the following does not characterise X-rays (d) 2.52  10 5 years
[UPSEAT 2001] 14. Half-life for radioactive C 14 is 5760 years. In how many years
(a) The radiation can ionise gases
200 mg of C 14 sample will be reduced to 25 mg
(b) It causes ZnS to fluorescence
[CBSE PMT 1995]
(c) Deflected by electric and magnetic field
(d) Have wavelengths shorter than ultraviolet rays (a) 11520 years (b) 23040 years
(c) 5760 years (d) 17280 years
7. During emission of  -particle [Bihar MEE 1996]
(a) One electron increases 15. The decay constant of a radioactive element is 3  10 6 min 1 . Its
(b) One electron decreases half-life is
[MP PET 1993; Pb. CET 2002]
(c) One proton increases
(d) No change (a) 2.31  10 min 5

(e) None of these

(b) 2.31  10 6 min
8. Emission is caused by the transformation of one neutron into a
proton. This results in the formation of a new element having (c) 2.31  10 6 min
(a) Same nuclear charge
(d) 2.31  10 7 min
(b) Very lower nuclear charge
 302 Nuclear Chemistry
16. A radioactive sample decays to half of its initial concentration in (a) 4.8  10 3 days (b) 245 days
6.93 minutes.It further decays half in next 6.93 minutes. The rate
constant for the reaction is (c) 122.5 days (d) None of these
[RPET 2000] 23. If half-life of a substance is 5 yrs, then the total amount of substance
left after 15 years, when initial amount is 64 grams is [AIEEE 2002]
(a) 0.10 min –1
(b) 0.01 min –1

(a) 16 grams (b) 2 grams

(c) 1.0 min –1
(d) 0.001 min –1

(c) 32 grams (d) 8 grams

17. The half-life of an isotope is 10 hrs. How much will be left behind
24. An element has half-life 1600 years. The mass left after 6400 years
after 4 hrs in 1 gm sample [BHU 1997] will be [AFMC 2003]

(a) 45.6  10 23 atoms (a) 1/16 (b) 1/12

(c) 1/4 (d) 1/32
(b) 4.56  10 23 atoms
25. Wooden artitact and freshly cut tree are 7.6 and 15.2 min 1 g 1
(c) 4.56  10 21 atoms
of carbon ( t1 / 2  5760 years) respectively. The age of the artitact
(d) 45.6  10 21 atoms is [AIIMS 1980]
18. The half-life period t1 / 2 of a radioactive element is N years. The (a) 5760 years
period of its complete decay is [KCET 1998] 15.2
(b) 5760  years
2 7 .6
(a) N years (b) 2 N years
7 .6
1 2 (c) 5760  years
(c) N years (d) Infinity 15.2
2
(d) 5760  (15.2  7.6) years
19. A radioactive element has a half-life of 20 minutes. How much time
1 26. An element has two main isotopes of mass numbers 85 and 87. In
should elaspe before the element is reduced to th of the original nature they occur in the ratio of 75% and 25% respectively. The
8
atomic weight of the element will be approximately
mass [EAMCET 1990]
(a) 86.0 (b) 86.5
(a) 40 minutes
(c) 85.5 (d) 85.75
(b) 60 minutes 27. A sample of rock from moon contains equal number of atoms of
(c) 80 minutes uranium and lead ( t1 / 2 for U  4.5  10 9 years). The age of the
(d) 160 minutes rock would be [MNR 1988; UPSEAT 2000]
20. The half-life period of a radioactive material is 15 minutes. What % (a) 9.0  10 9 years
of radioactivity of that material will remain after 45 minutes [MP PMT 1991]
(b) 4.5  10 9 years
(a) 10 % (b) 12.5%
(c) 13.5  10 9 years
(c) 15% (d) 17.5%
226
(d) 2.25  10 9 years
21. Ra disintegrates at such a rate that after 3160 years only one-fourth
28. The value of one microcurie = ....... disintegrations / second
226
of its original amount remains. The half-life of Ra will be [MP PET 2002] [EAMCET 1982]
(a) 790 years (b) 3160 years (a) 3.7  10 5
(b) 3.7  10 7

(c) 1580 years (d) 6230 years (c) 3.7  10 4

(d) 3.7  1010
22. The ratio of the amount of two elements X and Y at radioactive 29. The sum of the number of neutrons and proton in the radio isotope
equilibrium is 1 : 2  10 6 . If the half-life period of element Y is of hydrogen is [IIT 1986]

4.9  10 4 days, then the half-life period of element X will be (a) 6 (b) 5
(c) 4 (d) 3

(SET -7)

1. (b) 7
 1 H 1  4 Be 8   3. (a) Equate atomic no. and mass no.
3 Li
4. (a) -rays are designated by hv.
2. (d) The isotopes of an element is represented by writing the symbol
of the element and representing the atomic number and mass 5. (b) Al 27  2 He 4  15 P 30  o n1
13
number as subscript and superscript respectively are called
nuclides.
 Nuclear Chemistry 291
6. (c) x-rays do not carry any charge and hence are not deflected by t 15
electric and magnetic fields. n   3
t1 / 2 5
7. (c) During  -particle emission one proton increases.
No N 1 1
8. (c) 1
 1 p 1  1e o (-particle comes out). Now N   3o  N o   64  8 grams.
on 2n 2 8 8
208
9. (a) The end product of 4n series is 82 Pb . 24. (a) T1 / 2  1600 yrs. , N o  1, N  ?, T  6400 yrs.
10. (c) Elements 89 to 103 are placed in III group.
6400
11. (c) Chemical reaction is not nuclear reaction, but radioactivity is T  t1 / 2  n, or n  4
1600
nuclear distingration.
n 4
12. (a) t1 / 2  5770 years. 1 1 1
N  No    , N  1    , N  .
2 2 16
13. (b) t1 / 2 of C 14 = 5730 years.
2 .303 ro
1 
n
1  25 1 1 
n 3 25. (a) ro  15.2 and r  7.6,  t  log .
14. (d) 25     200,        r
 
2  
2 200 8 2
26. (c) Isotopes have 75% and 25% respectively.
n = 3, Number of half lives = 3
so time required = 3 × 5760 = 17280 yrs.  75 25 
 Atomic mass =   85   87 
 100 100 
0 .693 0 .693
15. (a) t1 / 2    2.31  10 5 min.
 3  10  6 min1 6375  2175
=  85.5 .
0 .693 0 .693 100
16. (a) k   0.10 min 1
t1 / 2 6 .93 N0 2 .303  t1 / 2 N
27. (b) N n
, use t  log o
17. (b) 4.56 × 10 23 atoms will be left behind after 4 hrs in 1 2 0 .693 N
gm. sample.
28. (c) 1 Ci = 3.7  1010 dps or 3.7  10 10 Bq.
18. (d) The t1 / 2 of a radioactive element = N years
1mCi = 3.7  10 4 dps .
 The period of its complete decay is infinity.
1 29. (d) Tritium (1 H 3 ) consist of 1 proton and 2 neutrons.
19. (b) t1 / 2  20 minute, N  No
9
2 .303 N
Use, t   t1 / 2 log o .
0 .693 N
No 45
20. (b) N n
and n  3
2 15
100
Also use N o  100 than N   12.5 % .
23

***
21. (c) For an element to disintegrate
n
1
N  No   …..(i), t = n × t1/ 2 …..(ii)
2

N 1
For Ra 226  , from eq. (i)
No 4
n n 2 n
1 1 1 1 1
   or   or      , n  2 ; from eq. (ii)
4 2 2 2 2
t 3160
T1 / 2    1580 yrs.
n 2

NX t (X ) 4 .9  10 4
22. (b)  1/2 , t1 / 2 ( X )   245 days.
NY t1 / 2 (Y ) 2  10  6

23. (d) t1 / 2  5 yrs., t  15 yrs

 304 Chemical Equilibrium

Chapter

8
Chemical Equilibrium

Whenever we hear the word Equilibrium immediately a picture
arises in our mind an object under the influence of two opposing forces. For
chemical reactions also this is true. A reaction also can exist in a state of
equilibrium balancing forward and backward reactions.
Reversible and Irreversible reactions
A chemical reaction is said to have taken place when the
concentration of reactants decreases, and the concentration of the products
increases with time. The chemical reactions are classified on the basis of the
extent to which they proceed, into the following two classes;
(1) Reversible reactions : Reaction in which entire amount of the
reactants is not converted into products is termed as reversible reaction.
(i) Characteristics of reversible reactions
(a) These reactions can be started from either side,
(b) These reactions are never complete,
(c) These reactions have a tendency to attain a state of equilibrium,
in which Free energy change is zero (G = 0),
(d) This sign (⇌) represents the reversibility of the reaction,
(ii) Examples of reversible reactions
(a) Neutralisation between an acid and a base either of which or
both are weak e.g.,
CH 3 COOH  Na OH ⇌ CH 3 COONa  H 2 O
(b) Salt hydrolysis, e.g.,
Fe Cl 3  3 H 2 O ⇌ Fe OH 3  3 HCl
(c) Thermal decomposition, e.g.,
PCl5 (g ) ⇌ PCl3 (g)  Cl 2(g) Q
(d) Esterification, e.g.,
(2) Irreversible reactions : Reaction in which entire amount of the
reactants is converted into products is termed as irreversible reaction.
(i) Characteristics of irreversible reactions
(a) These reactions proceed only in one direction (forward
direction),
(b) These reactions can proceed to completion,
(c) In an irreversible reaction, G < 0,
(d) The arrow () is placed between reactants and products,
(ii) Examples of irreversible reactions
(a) Neutralisation between strong acid and strong base e.g.,
NaOH  HCl  NaCl  H 2 O 13.7 kcal
(b) Double decomposition reactions or precipitation reactions e.g.,
BaCl2(aq)  H 2 SO 4 (aq)  BaSO4 (s)  2 HCl(aq)
(c) Thermal decomposition, e.g.,
MnO 2 ,
2 KClO3 (s)   2 KCl (s)  3O 2 
(d) Redox reactions, e.g.,
SnCl 2(aq)  2 FeCl3 (aq)  SnCl 4 (aq)  2 FeCl2(aq)
Equilibrium and Its dynamic nature
“Equilibrium is the state at which the concentration of reactants
and products do not change with time. i.e. concentrations of reactants and
products become constant.”
Products

CH 3 COOH  C2 H 5 OH ⇌ CH 3 COOC 2 H 5  H 2 O
Concentration

(e) Evaporation of water in a closed vessel, e.g.,

Reactants
H 2 O(l) ⇌ H 2 O(g) Q
Time Equilibrium state
 Chemical Equilibrium 305
The important characteristics of equilibrium state are, K p  Kc (RT )n
(1) Equilibrium state can be recognised by the constancy of certain
measurable properties such as pressure, density, colour, concentration etc. K p  K x (P)n
by changing these conditions of the system, we can control the extent to n = number of moles of gaseous products – number of moles of
which a reaction proceeds. gaseous reactants in chemical equation.
(2) Equilibrium state can only be achieved in close vessel. As a general rule, the concentration of pure solids and pure liquids
(3) Equilibrium state is reversible in nature. are not included when writing an equilibrium equation.

(4) Equilibrium state is also dynamic in nature. Value of Relation between Kp Units of Kp Units of Kc
(5) At equilibrium state, n and Kc
0 Kp = Kc No unit No unit
Rate of forward reaction = Rate of backward reaction
>0 Kp > Kc (atm)n (mole l–1)n
(6) At equilibrium state, G = 0, so that H = TS. <0 Kp < Kc (atm)n (mole l–1)n

Characteristics of equilibrium constant

(1) The value of equilibrium constant is independent of the original
Rate of reaction

G= 0 concentration of reactants.

Equilibrium state
Time
Law of mass action and Equilibrium constant
On the basis of observations of many equilibrium reactions, two
Norwegian chemists Goldberg and Waage suggested (1864) a quantitative
relationship between the rates of reactions and the concentration of the
reacting substances. This relationship is known as law of mass action. It
states that
“The rate of a chemical reaction is directly proportional to the
product of the molar concentrations of the reactants at a constant
temperature at any given time.”
The molar concentration i.e. number of moles per litre is also called
active mass. It is expressed by enclosing the symbols of formulae of the
substance in square brackets. For example, molar concentration of A is expressed
as [A].
Consider a simple reversible reaction
aA  bB ⇌ cC  dD (At a certain temperature)
(2) The equilibrium constant has a definite value for every reaction
at a particular temperature. However, it varies with change in temperature.
(3) For a reversible reaction, the equilibrium constant for the
forward reaction is inverse of the equilibrium constant for the backward
reaction.
1
In general, K forward reaction 
K backward reaction
(4) The value of an equilibrium constant tells the extent to which a
reaction proceeds in the forward or reverse direction.
(5) The equilibrium constant is independent of the presence of
catalyst.
(6) The value of equilibrium constant changes with the change of
temperature. Thermodynamically, it can be shown that if K1 and K 2 be
the equilibrium constants of a reaction at absolute temperatures T1 and
T2 . If H is the heat of reaction at constant volume, then
 H  1 1
log K 2  log K1     (Van’t Hoff equation)
2 .303 R  T2 T1 

According to law of mass action The effect of temperature can be studied in the following three cases
(i) When H  0 i.e., neither heat is evolved nor absorbed
Rate of forward reaction  [ A]a [B]b  k f [ A]a [B]b
log K 2  log K1  0 or log K 2  log K1 or K 2  K1
Rate of backward reaction  [C]c [D]d  kb [C]c [D]d
Thus, equilibrium constant remains the same at all temperatures.
At equilibrium ,
(ii) When H = +ve i.e., heat is absorbed, the reaction is endothermic. The
Rate of forward reaction = Rate of backward reaction
temperature T2 is higher than T1 .
k f [ A] [B]  k b [C] [D]
a b c d

log K 2  log K1  ve or log K 2  log K1 or K 2  K1

kf [C]c [D]d
 Kc  The value of equilibrium constant is higher at higher temperature in
kb [ A]a [B]b
case of endothermic reactions.
Where, K c is called equilibrium constant.
(iii) When H = – ve, i.e., heat is evolved, the reaction is exothermic. The
In terms of partial pressures, equilibrium constant is denoted by
temperature T2 is higher than T1 .
K p and

PCc PDd log K 2  log K1  ve or log K1  log K 2 or K1  K 2

Kp 
PAa PBb The value of equilibrium constant is lower at higher temperature in
the case of exothermic reactions.
In terms of mole fraction, equilibrium constant is denoted by K x
(7) The value of the equilibrium constant depends upon the
and
stoichiometry of the chemical equation.
( X C )c ( X D )d
Kx  For the reaction
( X A )a ( X B )b
Relation between K , K and K 2SO 3 (g) ⇌ 2SO 2 (g)  O2 (g) and SO 3 (g) ⇌ SO 2 (g)  1 / 2O2 (g)
p c x
 306 Chemical Equilibrium

[SO 2 ]2 [O 2 ] [SO 2 ][O 2 ]1 / 2 (iii) If Q = K, the reaction mixture is already at equilibrium.

K and K  
[SO 3 ] 2
[SO 3 ] Thus, a reaction has a tendency to form products if Q < K and to
form reactants if Q > K.
K   K or (K)1 / 2
(i) Similarly, if a particular equation is multiplied by 2, the
equilibrium constant for the new reaction (K) will be the square of the
equilibrium constant (K) for the original reaction i.e., K   K 2
Q Kc Q Kc Q Kc
(ii) If the chemical equation for a particular reaction is written in
two steps having equilibrium constants K1 and K 2 , then the equilibrium
constants are related as K  K1  K 2
Reactants  Products Equilibrium Reactants  Products
Q<K Q=K Q>K
Applications of equilibrium constant
(Forward reaction) (At equilibrium) (Reverse reaction)
(1) Judging the extent of reaction
Fig. 8.1
(i) If K c  10 3 , products predominate over reactants. If K c is Types of equilibria
very large, the reaction proceeds almost all the way to completion. The equilibrium between different chemical species present in the
3
(ii) If K c  10 , reactants predominate over products. If K c is same or different phases is called chemical equilibrium. There are two types
of chemical equilibrium.
very small, the reaction proceeds hardly at all.
(1) Homogeneous equilibrium : The equilibrium reactions in which
(iii) If K c is in the range 10 3 to 10 3 , appreaciable all the reactants and the products are in the same phase are called
concentration of both reactants and products are present. homogeneous equilibrium reactions.
K
c

C 2 H 5 OH (l)  CH 3 COOH (l) ⇌ CH 3 COOC2 H5 (l)  H 2O(l)

Reaction proceeds Reaction proceeds to
hardly at all 10 –3
10
3

completion N 2 (g)  3 H 2 (g) ⇌ 2 NH 3 (g)

Both reactants and
products are present at 2SO 2 (g)  O 2 (g) ⇌ 2SO 3 (g)
equilibrium
(2) Predicting the direction of reaction : The concentration ratio, i.e.,
(2) Heterogeneous equilibrium : The equilibrium reactions in which
ratio of the product of concentrations of products to that of reactants is
the reactants and the products are present in different phases are called
also known as concentration quotient and is denoted by Q.
heterogeneous equilibrium reactions.
[ X ][Y ]
Concentration quotient, Q  . 2 NaHCO 3 (s) ⇌ Na 2 CO 3 (s)  CO 2 (g)  H 2 O (g)
[ A][B]
It may be noted that Q becomes equal to equilibrium constant (K) Ca(OH )2 (s)  H 2 O (l) ⇌ Ca 2 (aq)  2OH  (aq)
when the reaction is at the equilibrium state. At equilibrium,
Q  K  K c  K p . Thus, CaCO 3 (s) ⇌ CaO (s)  CO 2 (g)

(i) If Q > K, the reaction will proceed in the direction of reactants H 2 O (l) ⇌ H 2 O (g)
(reverse reaction).
(ii) If Q < K, the reaction will proceed in the direction of the
products (forward reaction).
Table : 8.1 Homogeneous equilibria and equations for equilibrium constant (Equilibrium pressure is P atm in a V L flask)
n  0 ; K p  Kc n  0 ; K p  Kc n  0; K p  Kc

H2 + I2 ⇌ 2 HI N 2  3 H 2 ⇌ 2 NH 3 2 SO 2  O2 ⇌ 2 SO 3 PCl 5 ⇌ PCl3  Cl 2
(g) (g) (g) (g) (g) (g) (g) (g) (g) (g) (g)
(g)

Initial mole 1 1 0 1 3 0 2 1 0 1 0 0
Mole at (1–x) (1– x) 2x (1–x) (3–3x) 2x (2–2x) (1–x) 2x (1–x) x x
Equilibrium
Total mole at 2 (4 – 2x) (3 – x) (1 + x)
equilibrium
Active masses
1  x  1  x  2x  1  x   1  x   2x   2  2x   1  x   2x  1  x  x x
      3               
 V   V  V  V   V   V   V   V   V   V  V V
Mole fraction 1 x 31 x 
1  x  1  x  2x
 
x  2  2x   1  x   2x  1 x   x   x 
               
 2   2  2 2 2  x  2  2  x  (2  x )  3x  3  x 3  x 1  x  1  x  1  x 
 Chemical Equilibrium 307
Partial pressure 1  x  1  x   2x   1  x   3(1  x )  Px  2  2x  1 x   2x  1 x   x   x 
p  p  p  P   P 
  P  P  P  P  P  P 
 2   2   2   2(2  x ) _   2(2  x )  (2  x )  3x  3 x 3  x 1 x  1 x  1 x 
Kc 4x2 4 x 2V 2 x 2V x2
1  x  2 27 1  x  4 1  x  3 1  x  V
Kp 4x2 16 x 2 2  x  2 x 2 3  x  Px 2
1  x  2 27 1  x  P 4 2
P 1  x  3

1  x2 
Table : 8.2 Heterogeneous equilibria and equation for equilibrium constant (Equilibrium pressure is P atm)

NH 4 HS (s) ⇌ NH 3 (g) + H 2 S (g) C(s)  CO 2 (g) ⇌ 2CO (g) NH 2CO 2 NH 4 (s) ⇌ 2 NH 3 (g)  CO 2 (g)

Initial mole 1 0 0 1 1 0 1 0 0
Mole at equilibrium (1–x) x x (1–x) (1–x) 2x (1–x) 2x x
Total moles at equilibrium 2x (1+x) 3x
(solid not included)
Mole fraction x

1 1 1  x  2 1
 
2x 2 2 1  x  3 3
 2x 
 
1  x 
Partial pressure P P 1  x  2P P
P 
2 2 1  x  3 3
 2x 
P 
1  x 
Kp P2 4P x2 4 P3
4 (1  x 2 ) 27

For components in solution: a  molar concentration.

Relationship between equilibrium constant and G°
G for a reaction under any condition is related with G° by the Le-Chatelier's principle
relation, G  G  2.303 RT log Q Le-Chatelier and Braun (1884), French chemists, made certain
Standard free energy change of a reaction and its equilibrium generalizations to explain the effect of changes in concentration,
constant are related to each other at temperature T by the relation, temperature or pressure on the state of system in equilibrium. When a
Go  2.303 RT log K system is subjected to a change in one of these factors, the equilibrium gets
disturbed and the system readjusts itself until it returns to equilibrium. The
For a general reaction aA  bB ⇌ cC  dD generalization is known as Le-Chatelier's principle. It may be stated as :
(aC )c (aD )d “Change in any of the factors that determine the equilibrium
K
(a A )a (aB )b conditions of a system will shift the equilibrium in such a manner to reduce
or to counteract the effect of the change.”
Where a represent the activity of the reactants and products. It is
unit less. The principle is very helpful in predicting qualitatively the effect of
For pure solids and liquids: a  1 . change in concentration, pressure or temperature on a system in
For gases: a  pressure of gas in atm. equilibrium.

Table : 8.3 The effect of varying conditions on the equilibrium a A + b B ⇌ c C + d D, n = (c + d) – (a + b)

Change imposed on the system in Equilibrium position moves Equilibrium constant Any other points
equilibrium
Conc. of A and/or B increased To right No change No change
Conc. of C and /or D increased To left No change No change
Pressure increased To right if (c  d )  (a  b) , i.e. n  ve No change Very little effect, if any, on reactions in
No change liquid solution.
To left if (c  d )  (a  b) , i.e. n  ve No change
No change if (c  d )  (a  b) , i.e. n  0
Temperature increased To left if H  ve (exothermic) Value decreased Equilibrium achieved faster
Value increased
To right if H  ve (endothermic)

Addition of catalyst No change No change Equilibrium achieved faster

 308 Chemical Equilibrium
(b) At higher pressure, less sulphur will melt as melting increases
Application of Le-Chatelier's principle volume.
The Le-Chateliers principle has a great significance for the chemical, (c) At higher pressure, melting point of sulphur is increased.
physical systems and in every day life in a state of equilibrium. (iii) Boiling of water (water- water vapour system) Water ⇌
(Low volume)
(1) Applications to the chemical equilibrium
(i) Synthesis of ammonia (Haber’s process) Water Vapours  x kcal
(Higher volume)
N 2  3 H 2 ⇌ 2 NH 3  23kcal (exothermic) (It is accompanied by absorption of heat and increase in volume.)
1 vol 3 vol 2 vol
(a) At high temperature more vapours are formed.
(a) High pressure (n  0) (b) At higher pressure, vapours will be converted to liquid as it
(b) Low temperature decreases volume.
(c) At higher pressure, boiling point of water is increased (principle
(c) Excess of N 2 and H 2
of pressure cooker).
(d) Removal of NH 3 favours forward reaction. (iv) Solubility of salts : If solubility of a salt is accompanied by
absorption of heat, its solubility increases with rise in temperature; e.g.,
(ii) Formation of sulphur trioxide
NH 4 Cl, K2 SO 4 , KNO 3 etc.
2 SO 2  O 2 ⇌ 2 SO 3  45 kcal (exothermic)
2 vol 1 vol 2 vol KNO 3(s)  (aq)  KNO 3(aq )  x kcal
(a) High pressure (n  0) On the other hand if it is accompanied by evolution of heat,
(b) Low temperature solubility decreases with increase in temperature; e.g., CaCl 2 ,
(c) Excess of SO 2 and O 2 , favours the reaction in forward Ca(OH )2 , NaOH, KOH etc.
direction. Ca(OH )2( s)  (aq)  Ca(OH )2 (aq)  x kcal
(iii) Synthesis of nitric oxide
N 2  O2 ⇌ 2 NO  43.2 kcal (endothermic ) Relation between vapour density and
1 vol 1 vol 2 vol
Degree of dissociation
(a) High temperature
In the following reversible chemical equation.
(b) Excess of N 2 and O 2 A ⇌ yB
(c) Since reaction takes place without change in volume i.e., Initial mol 1 0
n  0 , pressure has no effect on equilibrium. At equilibrium (1–x) yx x = degree of dissociation
(iv) Formation of nitrogen dioxide Number of moles of A and B at equilibrium
 1  x  yx  1  x (y  1)
2 NO  O 2 ⇌ 2 NO 2  27.8 Kcal
1 vol 2 vol
If initial volume of 1 mole of A is V, then volume of equilibrium
2 vol
mixture of A and B is,  [1  x (y  1)]V
(a) High pressure Molar density before dissociation,
(b) Low temperature molecular weight m
D 
(c) Excess of NO and O 2 favours the reaction in forward volume V
direction. Molar density after dissociation,
(v) Dissociation of phosphours pentachloride m D Dd
d ;  [1  x (y  1)] ; x 
PCl5 ⇌ PCl3  Cl 2  15 kcal [1  x (y  1)]V d d (y  1)
1 vol 1 vol 1 vol y is the number of moles of products from one mole of reactant.
(a) Low pressure or high volume of the container, n  0 (b) High D
is also called Van’t Hoff factor.
temperature (c) Excess of PCl5 . d
(2) Applications to the physical equilibrium M m
In terms of molecular mass, x 
(i) Melting of ice (Ice – water system) (y  1) m
Ice ⇌ Water  x kcal Where M  Initial molecular mass,
(Greater Volume) (Lesser Volume) m  molecular mass at equilibrium
(In this reaction volume is decreased from 1.09 c.c. to 1.01 c.c. per Thus for the equilibria
gm.) (I) PCl5(g) ⇌ PCl3(g)  Cl 2(g) , y  2
(a) At high temperature more water is formed as it absorbs heat. (II) N 2 O 4 (g) ⇌ 2 NO 2(g) , y  2
(b) At high pressure more water is formed as it is accompanied by
decrease in volume. 1
(III) 2NO 2 ⇌ N 2 O 4 , y 
(c) At higher pressure, melting point of ice is lowered, while boiling 2
point of water is increased. Dd 2(d  D)
 x (for I and II) and x  (for III)
(ii) Melting of sulphur : S (s) ⇌ S (l)  x kcal d d
(This reaction accompanies increase in volume.) Also D  2  Molecular weight (theoretical value)
(a) At high temperature, more liquid sulphur is formed. d  2  Molecular weight (abnormal value) of the mixture.
 Chemical Equilibrium 309
[MP PMT 1990]
(a) Is reversible
(b) Is reversible and endothermic
(c) Is exothermic
(d) Is reversible or irreversible and endothermic or exothermic
7. Amongst the following chemical reactions the irreversible reaction is
 Pure ice can be made to melt at a temperature slightly below 0°C (a) H 2  I 2 ⇌ HI
by increasing the pressure. As the water so obtained on melting is
below 0°C, it refreezes when pressure is reduced. It is called (b) AgNO3  NaCl ⇌ AgCl  NaNO 3
regelation of ice. (c) CaCO 3 ⇌ CaO  CO 2
 Increase in external pressure always increases the boiling point and vice- (d) O 2  2SO 2 ⇌ 2SO 3
versa.
 If the reaction is multipled by 2, the equilibrium constant is squared.
 When a bottle of coca or beer is opened, the pressure is decreased
and dissolved CO gas escapes out with a fizze.
2

 Increase in pressure favours melting of ice into water

 Flash evaporation is a technique generally used for concentrating certain
aqueous solutions which cannot be concentrated by normal boiling.
 Freeze drying is a technique where water is made to sublime off at a
temperature below 0°C.

Reversible and Irreversible reaction

1. A reversible reaction is one which
[MP PET 1986]
(a) Proceeds in one direction
(b) Proceeds in both directions
(c) Proceeds spontaneously
(d) All the statements are wrong
2. Which of the following is a characteristic of a reversible reaction [AFMC 1993]
(a) Number of moles of reactants and products are equal
(b) It can be influenced by a catalyst
(c) It can never proceed to completion
(d) None of the above
3. The reaction CaCO 3 ⇌ CaO  CO 2 (g) goes to completion in
lime kiln because
[MP PMT/PET 1988; CPMT 1990]
(a) Of the high temperature
(b) CaO is more stable than CaCO 3
(c) CaO is not dissociated
(d) CO 2 escapes continuously
4. In the given reaction N 2  O 2 ⇌ 2 NO , equilibrium means that [MADT Bihar 1984]
(a) Concentration of reactants is changing where as concentration
of products is constant
(b) Concentration of all substances is constant
(c) Concentration of reactants is constant where as concentration
of products is changing
(d) Concentration of all substances is changing
5. Which of the following reactions is reversible
[MADT Bihar 1980]
(a) H 2  I 2  2 HI
(b) H 2 SO 4  Ba(OH )2  BaSO 4  2 H 2 O
(c) NaCl  AgNO3  NaNO 3  AgCl
(d) Fe  S  FeS
6. All reactions which have chemical disintegration
 310 Chemical Equilibrium
(c) The concentration of reactants and products are constant but
Equilibrium state different
(d) Both forward and backward reactions occur at all times with
1. In any chemical reaction, equilibrium is supposed to be establish same speed
when 10. The number of gram molecules of a substance present in unit
[CPMT 1974, 80, 89; EAMCET 1975, 77, 79; volume is termed as [MP PMT 1993]
MP PMT 1990; NCERT 1980; MP PET 1995] (a) Activity (b) Normal solution
(a) Mutual opposite reactions undergo (c) Molar concentration (d) Active mass
(b) Concentration of reactants and resulting products are equal
(c) Velocity of mutual reactions become equal Law of mass action
(d) The temperature of mutual opposite reactions become equal
1. According to law of mass action rate of a chemical reaction is
2. Which of the following conditions represents an equilibrium proportional to [AFMC 2005]
(a) Freezing of ice in a open vessel, temperature of ice is constant (a) Concentration of reactants
(b) Few drops of water is present along with air in a balloon,
(b) Molar concentration of reactants
temperature of balloon is constant
(c) Concentration of products
(c) Water is boiling in an open vessel over stove, temperature of
water is constant (d) Molar concentration of products
(d) All the statements (a), (b) and (c) are correct for the 2. In a reaction the rate of reaction is proportional to its active mass,
equilibrium this statement is known as [IIT 1979]
3. When rate of forward reaction becomes equal to backward reaction, (a) Law of mass action
this state is termed as (b) Le-chatelier principle
[NCERT 1975, 80; CPMT 1973, 74, 77] (c) Faraday law of electrolysis
(a) Chemical equilibrium (b) Reversible state (d) Law of constant proportion
(c) Equilibrium (d) All of these 3. The active mass of 64 gm of HI in a two litre flask would be
[CPMT 1979]
4. In chemical reaction A ⇌ B , the system will be known in
equilibrium when [MP PMT 1990; NCERT 1977] (a) 2 (b) 1
(a) A completely changes to B (c) 5 (d) 0.25
(b) 50% of A changes to B 4. Under a given set of experimental conditions, with increase in the
concentration of the reactants, the rate of a chemical reaction
(c) The rate of change of A to B and B to A on both the sides are
same (a) Decreases
(d) Only 10% of A changes to B (b) Increases
5. A chemical reaction is at equilibrium when (c) Remains unaltered
[NCERT 1975; CPMT 1974; MP PMT 1996; (d) First decreases and then increases
KCET 1993; IIT 1978; Manipal MEE 1995; Pb. PMT 2002] 5. The law of mass action was enunciated by [MP PMT 1995]
(a) Reactants are completely transformed into products (a) Guldberg and Waage (b) Bodenstein
(b) The rates of forward and backward reactions are equal (c) Birthelot (d) Graham
(c) Formation of products is minimised 6. Theory of ‘active mass’ indicates that the rate of chemical reaction is
(d) Equal amounts of reactants and products are present directly proportional to the [MP PET 1990]
(a) Equilibrium constant
6. In the chemical reaction N 2  3H 2 ⇌ 2NH 3 at equilibrium (b) Properties of reactants
point, state whether [NCERT 1977] (c) Volume of apparatus
(a) Equal volumes of N 2 and H 2 are reacting (d) Concentration of reactants
(b) Equal masses of N 2 and H 2 are reacting 7. The rate at which substances react depends on their
[MP PMT 1997]
(c) The reaction has stopped (a) Atomic weight (b) Molecular weight
(d) The same amount of ammonia is formed as is decomposed into (c) Equivalent weight (d) Active mass
N 2 and H 2 8. Which is false [AMU 1999]
7. For the reaction PCl3 (g)  Cl2 (g) ⇌ PCl5 (g) the position of (a) The greater the concentration of the substances involved in a
reaction, the lower the speed of the reaction
equilibrium can be shifted to the right by [MP PMT 2004]
(b) The point of dynamic equilibrium is reached when the reaction
(a) Increasing the temperature
rate in one direction just balances the reaction rate in the
(b) Doubling the volume opposite direction
(c) Addition of Cl 2 at constant volume (c) The dissociation of weak electrolyte is a reversible reaction
(d) Addition of equimolar quantities of PCl3 and PCl5 (d) The presence of free ions facilitates chemical changes
9. Chemical equations convey quantitative information on the
8. If a system is at equilibrium the rate of forward to the reverse
[Orissa JEE 2002]
reaction is [UPSEAT 2004]
(a) Less (b) Equal (a) Type of atoms/molecules taking part in the reaction
(c) High (d) At equilibrium (b) Number of atoms/molecules of the reactants and products
involved in the reaction
9. Chemical equilibrium is dynamic in nature because
[IIT 1977]
(c) Relative number of moles of reactants and products involved in
the reaction
(a) Equilibrium is maintained rapidly
(d) Quantity of reactant consumed and quantity of product formed
(b) The concentration of reactants and products become same at
equilibrium
 Chemical Equilibrium 311
10. In the thermal decomposition of potassium chlorate given as (d) Concentration of H 2 is less than that of N 2
2 K ClO3  2 KCl  3O 2 , law of mass action
9. For the system A(g)  2 B(g) ⇌ C(g) , the equilibrium
[MADT Bihar 1983] concentrations are (A) 0.06 mole/litre (B) 0.12 mole/litre (C) 0.216
(a) Cannot be applied mole/litre. The K eq for the reaction is
(b) Can be applied
[CPMT 1983]
(c) Can be applied at low temperature
(a) 250 (b) 416
(d) Can be applied at high temp. and pressure
(c) 4  10 3 (d) 125
Law of equilibrium and Equilibrium constant 10. The equilibrium constant for the given reaction H 2  I 2 ⇌ 2 HI
is correctly given by expression
1. For the system 3 A  2 B ⇌ C , the expression for equilibrium [CPMT 1984]
constant is [H 2 ][I 2 ] [H 2 ][I 2 ]
[NCERT 1981; CPMT 1989; MP PMT 1990; (a) Kc  (b) Kc 
RPMT 1999; Pb. PMT 2002; Pb. CET 2002] [HI] [2 HI]
[3 A][2 B] [C ] [H 2 ][I 2 ] [HI]2
(a) (b) (c) Kc  2
(d) Kc 
C [3 A][2 B] [HI] [H 2 ][I 2 ]
3
[ A] [ B] 2
[C ] 11. Partial pressures of A, B, C and D on the basis of gaseous system
(c) (d)
[C] [ A] 3 [ B] 2 A  2 B ⇌ C  3 D are A = 0.20; B = 0.10; C = 0.30 and D = 0.50
atm. The numerical value of equilibrium constant is
2. In the reversible reaction A  B ⇌ C  D , the concentration of (a) 11.25 (b) 18.75
each C and D at equilibrium was 0.8 mole/litre, then the equilibrium
(c) 5 (d) 3.75
constant K c will be [MP PET 1986]
(a) 6.4 (b) 0.64 12. For the reaction A  2 B ⇌ C , the expression for equilibrium
constant is
(c) 1.6 (d) 16.0
[MNR 1987; MP PMT 1999; UPSEAT 2002]
3. 4 moles of A are mixed with 4 moles of B. At equilibrium for the
2
reaction A  B ⇌ C  D , 2 moles of C and D are formed. The (a)
[ A][B]
(b)
[ A][B]
equilibrium constant for the reaction will be [CPMT 1992] [C ] [C ]
1 1 [C ] [C ]
(a) (b) (c) (d)
4 2 [ A][B] 2 2[B][ A]
(c) 1 (d) 4
13. 2 moles of PCl5 were heated in a closed vessel of 2 litre capacity.
4. On a given condition, the equilibrium concentration of HI, H 2 and
At equilibrium, 40% of PCl5 is dissociated into PCl3 and Cl 2 .
I 2 are 0.80, 0.10 and 0.10 mole/litre. The equilibrium constant for
The value of equilibrium constant is
the reaction H 2  I 2 ⇌ 2 HI will be [MP PET 1986] [MP PMT 1989; RPMT 2000; UPSEAT 2004;
(a) 64 (b) 12 Kerala CET 2005]
(c) 8 (d) 0.8 (a) 0.266 (b) 0.53
5. In which of the following, the reaction proceeds towards completion [MNR 1990]
(c) 2.66 (d) 5.3
(a) K  10 3 (b) K  10 2 14. For which of the following reactions does the equilibrium constant
(c) K  10 (d) K  1 depend on the units of concentration
6. A reversible chemical reaction having two reactants in equilibrium. If [AIIMS 1983]
the concentrations of the reactants are doubled, then the 1 1
equilibrium constant will (a) NO (g) ⇌ N 2 ( g )  O 2( g )
[CPMT 1982, 90; MP PMT 1990,2004; MNR 1992;
2 2
UPSEAT 2002; KCET 1999; Pb. CET 2004] (b) Zn(s)  Cu (2aq ) ⇌ Cu (s)  Zn(2aq )
(a) Also be doubled (b) Be halved
(c) Become one-fourth (d) Remain the same (c) C 2 H 5 OH (l)  CH 3 COOH (l) ⇌ CH 3 COOC 2 H 5(l)  H 2 O(l)
7. The equilibrium constant in a reversible reaction at a given (Reaction carried in an inert solvent)
temperature [AIIMS 1982]
(d) COCl 2(g) ⇌ CO (g)  Cl 2 (g)
(a) Depends on the initial concentration of the reactants
(b) Depends on the concentration of the products at equilibrium 15. Unit of equilibrium constant for the reversible reaction H 2  I 2 ⇌
(c) Does not depend on the initial concentrations
2 HI is [DPMT 1984]
(d) It is not characteristic of the reaction
1 2
8. Pure ammonia is placed in a vessel at temperature where its (a) mol litre (b) mol litre
dissociation constant (  ) is appreciable. At equilibrium
[IIT 1984; Kurukshetra CEE 1998] (c) mol litre1 (d) None of these
(a) K p does not change significantly with pressure 16. The decomposition of N 2 O 4 to NO 2 is carried out at 280 K in
(b)  does not change with pressure chloroform. When equilibrium has been established, 0.2 mol of
(c) Concentration of NH 3 does not change with pressure
 312 Chemical Equilibrium

N 2 O 4 and 2  10 3 mol of NO 2 are present in 2 litre solution. (a) litre1 mole 1 (b) litremole 1
The equilibrium constant for reaction N 2 O 4 ⇌ 2NO 2 is (c) [AIIMS
mole litre2
2 1984]
(d) mole litre1
2 3
(a) 1  10 (b) 2  10 26. For the reaction 2SO 2  O 2 ⇌ 2SO 3 , the units of K c are
5
(c) 1  10 (d) 2  10 5 [CPMT 1990]
17. Concentration of a gas is expressed in the following terms in the (a) litremole 1
(b) mol litre 1
calculation of equilibrium constant [EAMCET 1982]
(a) No. of molecules per litre (c) (mol litre1 )2 (d) (litremole 1 )2
(b) No. of grams per litre
27. A quantity of PCl5 was heated in a 10 litre vessel at 250 o C ;
(c) No. of gram equivalent per litre
(d) No. of molecules equivalent per litre PCl5 (g) ⇌ PCl3 (g)  Cl 2 (g) . At equilibrium the vessel contains
0.1 mole of PCl5 0.20 mole of PCl3 and 0.2 mole of Cl 2 . The
18. The unit of equilibrium constant K for the reaction A  B ⇌ C
would be [CPMT 1987]
equilibrium constant of the reaction is
[KCET 1993, 2001; MP PMT 2003]
(a) mol litre1 (b) litremol 1 (a) 0.02 (b) 0.05
(c) mol litre (d) Dimensionless (c) 0.04 (d) 0.025
28. A mixture of 0.3 mole of H 2 and 0.3 mole of I 2 is allowed to
19. In a reaction A  B ⇌ C  D , the concentrations of A, B, C and
D (in moles/litre) are 0.5, 0.8, 0.4 and 1.0 respectively. The react in a 10 litre evacuated flask at 500 o C . The reaction is
equilibrium constant is [BHU 1981] H 2  I 2 ⇌ 2 HI , the K is found to be 64. The amount of
(a) 0.1 (b) 1.0 unreacted I 2 at equilibrium is [KCET 1990]
(c) 10 (d) 
(a) 0.15 mole (b) 0.06 mole
20. In a chemical equilibrium A  B ⇌ C  D , when one mole each (c) 0.03 mole (d) 0.2 mole
of the two reactants are mixed, 0.6 mole each of the products are
29. In a chemical equilibrium, the rate constant of the backward
formed. The equilibrium constant calculated is
[CBSE PMT 1989] reaction is 7.5  10 4 and the equilibrium constant is 1.5. So the
(a) 1 (b) 0.36 rate constant of the forward reaction is [KCET 1989]
(c) 2.25 (d) 4/9 (a) 5  10 4 (b) 2  10 3
21. For the reaction N 2(g)  3 H 2(g) ⇌ 2 NH 3(g) , the correct (c) 1.125  10 3
(d) 9.0  10 4
expression of equilibrium constant K is
30. 28 g of N 2 and 6 g of H 2 were kept at 400 o C in 1 litre
[CPMT 1984, 2000]
vessel, the equilibrium mixture contained 27.54 g of NH 3 . The
[ NH 3 ]2 [ N 2 ][H 2 ]3
(a) K (b) K approximate value of K c for the above reaction can be (in
[ N 2 ][H 2 ]3 [ NH 3 ]2 2 2
mole litre ) [CBSE PMT 1990]
2[ NH 3 ] [ N 2 ]  3[H 2 ]
(c) K (d) K (a) 75 (b) 50
[ N 2 ]  3[H 2 ] 2[ NH 3 ]
(c) 25 (d) 100
22. The suitable expression for the equilibrium constant of the reaction 31. The equilibrium concentration of X, Y and YX 2 are 4, 2 and 2
2 NO (g)  Cl 2(g) ⇌ 2 NOCl (g) is
moles respectively for the equilibrium 2 X  Y ⇌ YX 2 . The value
[CPMT 1983, 87]
of K c is [EAMCET 1990]
[2 NOCl ] [ NOCl ]2
(a) Kc  (b) Kc  (a) 0.625 (b) 0.0625
[2 NO ][Cl 2 ] [ NO ]2 [Cl 2 ] (c) 6.25 (d) 0.00625
[ NOCl ]2 [ NOCl ]2 32. An amount of solid NH 4 HS is placed in a flask already containing
(c) Kc  (d) Kc  ammonia gas at a certain temperature and 0.50 atm. pressure.
[ NO ][Cl 2 ]2 [ NO ]2 [Cl 2 ]2
Ammonium hydrogen sulphide decomposes to yield NH 3 and
23. A + B ⇌ C + D. If finally the concentration of A and B are both H 2 S gases in the flask. When the decomposition reaction reaches
equal but at equilibrium concentration of D will be twice of that of equilibrium, the total pressure in the flask rises to 0.84 atm. The
A then what will be the equilibrium constant of reaction. [BHU 2005]
equilibrium constant for NH 4 HS decomposition at this
(a) 4 / 9 (b) 9 / 4
temperature is
(c) 1 / 9 (d) 4 [AIEEE 2005]
24. If in the reaction N 2 O4  2 NO 2 , is that part of N 2 O 4 which (a) 0.30 (b) 0.18
dissociates, then the number of moles at equilibrium will be[MP PET 1990; MH CET (c)
2001; 0.17
KCET 2005] (d) 0.11
(a) 3 (b) 1 33. In the reaction A  2 B ⇌ 2C , if 2 moles of A, 3.0 moles of B
(c) (1   )2 (d) (1   ) and 2.0 moles of C are placed in a 2 .0 l flask and the equilibrium
25. In the gas phase reaction, C 2 H 4  H 2 ⇌ C 2 H 6 , the equilibrium concentration of C is 0.5 mole/ l . The equilibrium constant (K c )
constant can be expressed in units of for the reaction is [KCET 1996]
[CBSE PMT 1992; Pb. PMT 1999] (a) 0.073 (b) 0.147
 Chemical Equilibrium 313
(c) 0.05 (d) 0.026 43. Equilibrium concentration of HI, I2 and H 2 is 0.7, 0.1 and
34. In a 500ml capacity vessel CO and Cl 2 are mixed to form 0 .1 M respectively. The equilibrium constant for the reaction
COCl 2 . At equilibrium, it contains 0.2 moles of COCl 2 and 0.1 I2  H 2 ⇌ 2 HI is [JIPMER 2000]
mole of each of CO and CO 2 . The equilibrium constant K c for (a) 36 (b) 49
the reaction CO  Cl 2 ⇌ COCl 2 is (c) 0.49 (d) 0.36
[CBSE PMT 1998] 44. For the equilibrium N 2  3H 2 ⇌ 2 NH 3 , K c at 1000K is
(a) 5 (b) 10 3
2.37  10 . If at equilibrium [ N 2 ]  2 M,[H 2 ]  3 M , the
(c) 15 (d) 20
concentration of NH 3 is [JIPMER 2000]
35. A reaction is A  B  C  D . Initially we start with equal
concentration of A and B . At equilibrium we find the moles of (a) 0.00358 M (b) 0.0358 M
C is two times of A . What is the equilibrium constant of the (c) 0.358 M (d) 3.58 M
reaction [BHU 1998; KCET 2000] 45. In the reaction, A  B ⇌ 2C , at equilibrium, the concentration of
(a) 4 (b) 2
A and B is 0.20 mol l 1 each and that of C was found to be
(c) 1 / 4 (d) 1 / 2
36. 4.5 moles each of hydrogen and iodine heated in a sealed ten litre 0.60 mol l 1 . The equilibrium constant of the reaction is
vessel. At equilibrium, 3 moles of HI were found. The equilibrium (a) 2.4 (b) 18
constant for H 2 (g)  I 2 (g) ⇌ 2 HI(g) is (c) 4.8 (d) 9
[EAMCET 1998] 46. 15 moles of H 2 and 5.2 moles of I 2 are mixed and allowed to
(a) 1 (b) 10 attain equilibrium at 500 o C . At equilibrium, the concentration of
(c) 5 (d) 0.33 HI is found to be 10 moles. The equilbrium constant for the
37. An equilibrium mixture of the reaction formation of HI is
2 H 2 S (g) ⇌ 2 H 2 (g)  S 2 (g) had 0.5 mole H 2 S , 0.10 mole H 2 [KCET 2005]
and 0.4 mole S 2 in one litre vessel. The value of equilibrium (a) 50 (b) 15
(c) 100 (d) 25
constant (K ) in mole litre is
-1

47. In a chemical reaction equilibrium is established when

[AIIMS 1998; IIT 1992; AFMC 1999; UPSEAT 2001]
[MP PET 2001]
(a) 0.004 (b) 0.008
(c) 0.016 (d) 0.160 (a) Opposing reaction ceases
38. At 3000 K the equilibrium pressures of CO , CO and O are 0.6,0.4
2 2
(b) Concentration of reactants and products are equal
and 0.2 atmospheres respectively. K p for the reaction, (c) Velocity of opposing reaction is the same as that of forward
reaction
2CO 2 ⇌ 2CO  O 2 is [JIPMER 1999]
(d) Reaction ceases to generate heat
(a) 0.089 (b) 0.0533
48. For the reaction H 2  I2  2 HI ,the equilibrium concentration of
(c) 0.133 (d) 0.177
39. The rate constant for forward and backward reactions of hydrolysis H 2 , I2 and HI are 8.0, 3.0 and 28.0 mol per litre respectively, the
of ester are 1.1  10 2 and 1.5  10 3 per minute respectively. equilibrium constant of the reaction is
Equilibrium constant for the reaction is [BHU 2000; CBSE PMT 2001]
CH 3 COOC 2 H 5  H 2 O ⇌ CH 3 COOH C 2 H 5 OH (a) 30.66 (b) 32.66
[AIIMS 1999] (c) 34.66 (d) 36.66
(a) 4.33 (b) 5.33 49. Change in volume of the system does not alter the number of moles
(c) 6.33 (d) 7.33 in which of the following equilibrium
[AIEEE 2002]
40. At a certain temp. 2HI ⇌ H + I Only 50% HI is dissociated at
N 2(g)  O2(g) ⇌ 2 NO (g)
2 2

equilibrium. The equilibrium constant is (a)

[DCE 1999]
(a) 0.25 (b) 1.0 (b) PCl5(g) ⇌ PCl3(g)  Cl 2(g)
(c) 3.0 (d) 0.50
(c) N 2(g)  3 H 2 (g) ⇌ 2 NH 3(g)
41. When 3 mole of A and 1 mole of B are mixed in 1 litre vessel the
following reaction takes place A(g)  B(g) ⇌ 2C( g ) . 1.5 moles of C (d) SO 2 Cl 2(g) ⇌ SO 2(g)  Cl 2(g)
are formed. The equilibrium constant for the reaction is[MP PMT 2000] 50. The rate of forward reaction is two times that of reverse reaction at
(a) 0.12 (b) 0.25 a given temperature and identical concentration. K is [KCET 2002]
equilibrium

(c) 0.50 (d) 4.0 (a) 2.5 (b) 2.0

42. A 1 M solution of glucose reaches dissociation equilibrium according
(c) 0.5 (d) 1.5
to equation given below 6 HCHO ⇌ C6 H12 O6 What is the .
51. Write the equilibrium constant K for
concentration of HCHO at equilibrium if equilibrium constant is
CH 3 COOH  H 2 O  H 3 O   CH 3 COO 
6  10 22 [MP PMT 2000]
[Kerala (Med.) 2002]
(a) 1.6  10 8 M (b) 3.2  10 6 M

(c) 3.2  10 4 M (d) 1.6  10 4 M (a) K
[H 3 O ][H 2 O]
[CH 3 COO  ][CH 3 COOH ]
 314 Chemical Equilibrium

[H 3 O  ][CH 3 COO  ] dissociation at this temperature was found to be 22%. The number
(b) K of moles of hydrogen iodide present at equilibrium are [BHU 1982]
[H 2 O][CH 3 COOH ] (a) 2.496 (b) 1.87
[H 3 O  ][H 2 O] (c) 2 (d) 4
(c) K 60. 56 g of nitrogen and 8 g hydrogen gas are heated in a closed vessel.
[CH 3 COOH ][CH 3 COO  ] At equilibrium 34 g of ammonia are present. The equilibrium
number of moles of nitrogen, hydrogen and ammonia are
[H 2 O][CH 3 COO  ]
(d) K respectively [KCET 2004]
[H 2 O][CH 3 COOH ] (a) 1,2,2 (b) 2,2,1
52. The equilibrium constant (K )
c
for the reaction (c) 1,1,2 (d) 2,1,2
 
HA  B ⇌ BH  A is 100. If the rate constant for the forward 61. The reaction, 2SO 2(g)  O2(g) ⇌ 2 SO 3(g) is carried out in a
reaction is 10 then rate constant for the backward reaction is[CBSE PMT 2002]
5,

1 dm 3 vessel and 2 dm 3 vessel separately. The ratio of the reaction

(a) 10 7 (b) 10 3 velocities will be [KCET 2004]
(c) 10 3 (d) 10 5 (a) 1:8 (b) 1 : 4
53. 9.2 grams of N 2 O4 (g) is taken in a closed one litre vessel and (c) 4 : 1 (d) 8 : 1
heated till the following equilibrium is reached N 2 O4 (g) ⇌ 62. The compound A and B are mixed in equimolar proportion to form
the products, A  B ⇌ C  D . At equilibrium, one third of A
2 NO 2(g) . and B are consumed. The equilibrium constant for the reaction is [KCET 2004]
At equilibrium, 50% N 2 O4 (g) is dissociated. What is the (a) 0.5 (b) 4.0
equilibrium constant (in mol litre ) (Molecular weight of
–1
(c) 2.5 (d) 0.25
N 2 O 4  92) [MP PET 2003] 63. Calculate the partial pressure of carbon monoxide from the
(a) 0.1 (b) 0.4 following

(c) 0.2 (d) 2 CaCO 3(s)  CaO(s)  CO 2  ; K p  8  10 2
54. Two moles of NH 3 when put into a previously evacuated vessel
CO 2(g)  C(s)  2CO(g) ; K p  2 [Orissa JEE 2004]
(one litre), partially dissociate into N 2 and H 2 . If at equilibrium
one mole of NH is present, the equilibrium constant is
3
(a) 0.2[MP PET 2003] (b) 0.4
(a) 3/4 mol litre 2 2
(b) 27/64 mol litre 2 2 (c) 1.6 (d) 4
2 64. The equilibrium constant for the reaction N 2( g )  O2( g ) ⇌
(c) 27/32 mol litre 2
(d) 27/1 mol 2 litre2
55. In a reaction, reactant ‘A’ decomposes 10% in 1 hour, 20% on 2 hour 2 NO(g) at temperature T is 4  10 4 . The value of K c for the
and 30% in 3 hour. The unit of rate constant of this reaction is [MP PET 2003]
1 1
(a) sec 1
(b) mol litre sec 1 1 reaction NO(g) ⇌ N 2(g )  O2( g) at the same temperature is
2 2
(c) litre mol 1 sec 1 (d) litre2 mol 2 sec 1 (a) 4  10 4 (b) 50
56. In the reaction PCl5(g) ⇌ PCl3(g) Cl 2(g) . (c) 2.5  10 2
(d) 0.02
The equilibrium concentrations of PCl5 and PCl3 are 0.4 and 0.2 65. What is the equilibrium expression for the reaction
mole/litre respectively. If the value of K c is 0.5 what is the P4 (s)  5 O2(g) ⇌ P4 O10 (s) [AIEEE 2004]
concentration of Cl 2 in moles/litre [EAMCET 2003] (a) Kc  [O2 ]5 (b) K c  [P4 O10 ] / 5[P4 ][O2 ]
(a) 2.0 (b) 1.5
(c) 1.0 (d) 0.5 (c) Kc  [P4 O10 ] /[P4 ][O2 ]5
(d) Kc  1 /[O2 ]5
57. In Haber process 30 litres of dihydrogen and 30 litres of dinitrogen
were taken for reaction which yielded only 50% of the expected 66. In the reaction, H 2  I2 ⇌ 2 HI . In a 2 litre flask 0.4 moles of
product. What will be the composition of gaseous mixture under the each H 2 and I2 are taken. At equilibrium 0.5 moles of HI are
aforesaid condition in the end
[CBSE PMT 2003] formed. What will be the value of equilibrium constant, K c
(a) 20 litres ammonia, 25 litres nitrogen, 15 litres hydrogen (a) 20.2 (b) 25.4
(b) 20 litres ammonia, 20 litres nitrogen, 20 litres hydrogen
(c) 0.284 (d) 11.1
(c) 10 litres ammonia, 25 litres nitrogen, 15 litres hydrogen
(d) 20 litres ammonia, 10 litres nitrogen, 30 litres hydrogen 67. Ammonia carbonate when heated to 200°C gives a mixture of NH 3
58. For the reaction equilibrium N 2 O 4 ⇌ 2 NO 2(g) , the and CO 2 vapour with a density of 13.0. What is the degree of
concentrations of N 2 O4 and NO 2 at equilibrium are dissociation of ammonium carbonate
2 2 1
[Kerala PMT 2004]
4.8  10 and 1.2  10 mol litre respectively. The value of
(a) 3 / 2 (b) 1 / 2
K c for the reaction is [AIEEE 2003]
(c) 2 (d) 1
1 1
(a) 3.3  10 mol litre
2
(b) 3  10 mol litre1 (e) 5/2
3 1 1
(c) 3  10 mol litre (d) 3  10 mol litre 3
68. 2 mol of N 2 is mixed with 6 mol of H 2 in a closed vessel of one
59. 3.2 moles of hydrogen iodide were heated in a sealed bulb at litre capacity. If 50% of N 2 is converted into NH 3 at equilibrium,
444 o C till the equilibrium state was reached. Its degree of the value of K c for the reaction N 2(g)  3 H 2(g) ⇌ 2 NH 3(g) is
 Chemical Equilibrium 315

(a) 4 / 27 (b) 27 / 4 1. In which of the following reaction, the value of K p will be equal to
(c) 1 / 27 (d) 24 Kc [MP PMT 1995]
(e) 9
(a) H 2  I 2 ⇌ 2 HI (b) PCl5 ⇌ PCl3  Cl 2
69. For a reaction H 2  I2 ⇌ 2 HI at 721K, the value of equilibrium
(c) 2NH 3 ⇌ N 2  3H 2 (d) 2SO 2  O 2 ⇌ 2SO 3
constant is 50. If 0.5 mols each of H 2 and I 2 is added to the
system the value of equilibrium constant will be 2. Equilibrium constants K1 and K 2 for the following equilibria
[DCE 2004] 1 K
NO (g)  O2 1

NO 2 (g)
(a) 40 (b) 60 2
(c) 50 (d) 30 and 2 NO 2 (g) K 2 2 NO(g)  O2 (g) are related as
70. What is the effect of halving the pressure by doubling the volume [CBSE PMT 2005]
on the following system at 500°C 1
(a) K 2  (b) K2  K12
H 2(g)  I2(g) ⇌ 2 HI(g) [UPSEAT 2004] K1
K1 1
(a) Shift to product side (c) K2  (d) K2 
(b) Shift to product formation
2 K12

(c) Liquefaction of HI 3. For the reaction PCl3 (g)  Cl 2 (g) ⇌ PCl5 (g) at 250 o C ,
(d) No effect the value of K c is 26, then the value of K p on the same
71. When NaNO 3 is heated in a closed vessel, O 2 is liberated and temperature will be [MNR 1990; MP PET 2001]
NaNO 2 is left behind. At equilibrium (a) 0.61 (b) 0.57
[IIT 1986; Roorkee 1995] (c) 0.83 (d) 0.46
(a) Addition of NaNO 3 favours forward reaction 4. The relation between equilibrium constant K p and K c is
[IIT 1994; MP PMT 1994; CPMT 1997; AMU 2000;
(b) Addition of NaNO 2 favours reverse reaction
RPMT 2000, 02;MP PET 2002; Kerala PMT 2002]
(c) Increasing pressure favours reverse reaction
(a) K c  K p (RT )n (b) K p  K c (RT )n
(d) Increasing temperature favours forward reaction
n
72. For the reaction : H 2(g)  CO 2(g) ⇌ CO(g)  H 2O(g) , if the K 
(c) K p   c  (d) K p  K c  (RT )n
initial concentration of [H 2 ]  [CO 2 ] and x moles/litre of  RT 
hydrogen is consumed at equilibrium, the correct expression of K p 5. CH 3 COOH (l)  C 2 H 5 OH (l) ⇌ CH 3 COOC 2 H 5 (l)  H 2 O(l)
is [Orissa JEE 2005] In the above reaction, one mole of each of acetic acid and alcohol
are heated in the presence of little conc. H 2 SO 4 . On equilibrium
x2 (1  x )2
(a) (b) being attained
(1  x )2 (1  x )2
[CPMT 1985; MP PET 1992]
x2 x2 (a) 1 mole of ethyl acetate is formed
(c) (d)
(2  x )2 1  x2 (b) 2 mole of ethyl acetate are formed
73. 0.6 mole of NH in a reaction vessel of 2dm capacity was brought to
3
(c) 1/2 moles of ethyl acetate is formed
3

equilibrium. The vessel was then found to contain 0.15 mole of H 2

(d) 2/3 moles of ethyl acetate is formed
formed by the reaction
6. If the equilibrium constant of the reaction 2 HI ⇌ H 2  I 2 is
2 NH 3(g)  N 2(g)  3 H 2(g)
0.25, then the equilibrium constant of the reaction H 2  I 2 ⇌
Which of the following statements is true [KCET 1999] 2 HI would be [MP PMT 1989, 95]
(a) 0.15 mole of the original NH had dissociated at equilibrium
3
(a) 1.0 (b) 2.0
(b) 0.55 mole of ammonia is left in the vessel (c) 3.0 (d) 4.0

(c) At equilibrium the vessel contained 0.45 mole of N 2 7. For N 2  3H 2 ⇌ 2NH 3  heat
[CPMT 1990; MP PMT 1997; RPMT 1999;
(d) The concentration of NH at equilibrium is 0.25 mole per dm 3

3
MP PET 2000; KCET 2001]
74. 5 moles of SO and 5 moles of O are allowed to react to form SO in
2 2 3
(a) K p  K c (RT ) (b) K p  K c (RT )
a closed vessel. At the equilibrium stage 60% of SO is used up. The 2

total number of moles of SO , O and SO in the vessel now is[KCET 2001]

2 2 3

(c) K p  K c (RT )2 (d) K p  K c (RT )1

(a) 10.0 (b) 8.5
(c) 10.5 (d) 3.9 8. In the reaction N 2 (g)  3 H 2 ⇌ 2 NH 3 (g) , the value of the
equilibrium constant depends on
Kp & Kc Relationship and Characteristics of K [CPMT 1990; AIIMS 1991; MP PET 1996]
(a) Volume of the reaction vessel
 316 Chemical Equilibrium
(b) Total pressure of the system 14. For the reaction C(s)  CO 2 (g) ⇌ 2CO (g) , the partial pressure
(c) The initial concentration of nitrogen and hydrogen
of CO 2 and CO are 2.0 and 4.0 atm respectively at equilibrium.
(d) The temperature
The K p for the reaction is [Roorkee 1990]
9. For the chemical equilibrium, CaCO 3 (s) ⇌
(a) 0.5 (b) 4.0
CaO(s)  CO 2 (g), H r can be determined from which one of the (c) 8.0 (d) 32.0
following plots [AIIMS 2005]
15. K for the synthesis of HI is 50. K for dissociation of HI is[Roorkee 1990]
(a) 50 (b) 5
2/p°

2/p°
(c) 0.2 (d) 0.02
log pCO

(a) (b) log pCO

10

10
16. In which one of the following gaseous equilibria K p is less than
1/T T K c [EAMCET 1989; MP PET 1994; Pb. PMT 2000;
KCET 2001; CBSE PMT 2002]
(c) (d) (a) N 2 O 4 ⇌ 2NO 2 (b) 2 HI ⇌ H 2  I 2
2/p°
ln pCO

2/p°
pCO

(c) 2SO 2  O 2 ⇌ 2SO 3 (d) N 2  O 2 ⇌ 2 NO

10.
log T
In which of the following equilibria, the value of K p is less than
10
1\T 17. For which of the following reactions K p  K c
[KCET 1991; IIT 1991; EAMCET 1992;
Kc [MP PMT 1993]
AIIMS 1996; KCET 2000; AMU 2000]
(a) H 2  I2 ⇌ 2 HI (a) 2 NOCl (g) ⇌ 2 NO(g)  Cl 2 (g)

(b) N 2  3H 2 ⇌ 2NH 3 (b) N 2 (g)  3 H 2 (g) ⇌ 2 NH 3 (g)

(c) H 2 (g)  Cl 2 (g) ⇌ 2 HCl(g)
(c) N 2  O2 ⇌ 2 NO
(d) N 2 O 4 (g) ⇌ 2 NO 2 (g)
(d) CO  H 2 O ⇌ CO 2  H 2
18. For the reaction H 2 (g)  I 2 (g) ⇌ 2 HI(g) at 721K the value of
1
11. Two gaseous equilibria SO 2(g )  O 2( g ) ⇌ SO 3(g) and equilibrium constant (K c ) is 50. When the equilibrium
2
concentration of both is 0 .5 M , the value of K p under the same
2 SO 3(g) ⇌ 2SO 2(g)  O 2(g) have equilibrium constants K 1 and
conditions will be [CBSE PMT 1990]
K 2 respectively at 298 K . Which of the following relationships (a) 0.002 (b) 0.2
between K 1 and K 2 is correct (c) 50.0 (d) 50 / RT
[CPMT 1988; CBSE PMT 1989; MP PET 1993, 95; 19. In which of the following reaction K p  K c [AFMC 1995]

RPMT 1999; MP PMT 2001] (a) N 2  3H 2 ⇌ 2NH 3 (b) H 2  I 2 ⇌ 2 HI

(a) K1  K 2 (b) K2  K12 (c) PCl3  Cl 2 ⇌ PCl5 (d) 2SO 3 ⇌ O 2  2SO 2

1 1 20. For the reaction PCl5 (g) ⇌ PCl3 (g)  Cl 2 (g)

(c) K2  (d) K2  [MP PET 1996]
K 12 K1
1
(a) K p  Kc (b) K p  K c (RT )
12. H 2  I 2 ⇌ 2 HI
(c) K p  K c (RT ) (d) K p  K c (RT )2
In the above equilibrium system if the concentration of the reactants
21. The equilibrium constant of the reaction H 2 (g)  I 2 (g) ⇌
at 25 o C is increased, the value of K c will
2 HI(g) is 64. If the volume of the container is reduced to one
[BHU 1979; CPMT 1990; CBSE PMT 1990] fourth of its original volume, the value of the equilibrium constant
(a) Increase will be [MP PET 1996]
(a) 16 (b) 32
(b) Decrease
(c) 64 (d) 128
(c) Remains the same
22. For the following gaseous reaction H 2  I 2 ⇌ 2 HI , the
(d) Depends on the nature of the reactants equilibrium constant [MP PMT 1996; MP PET/PMT 1998]
13. At a given temperature, the equilibrium constant for reaction (a) K p  K c (b) K p  K c
PCl5 (g) ⇌ PCl3 (g)  Cl 2 (g) is 2.4  10 3 . At the same (c) K p  K c (d) K p  1 / Kc
temperature, the equilibrium constant for reaction 23. For the reaction
PCl3 (g)  Cl 2 (g) ⇌ PCl5 (g) is [KCET 1992] 2 NO 2(g) ⇌ 2 NO(g)  O2(g)
(a) 2.4  10 3 (b)  2.4  10 3 (Kc  1.8  10 6 at 184C)
(c) 4.2  10 2 (d) 4.8  10 2 (R  0.0831kJ / (mol. K))
 Chemical Equilibrium 317

When K p and K c are compared at 184°C it is found that (d) Changes with temperature
[AIEEE 2005] 32. The equilibrium constant for the reaction N 2  3H 2 ⇌ 2NH 3 is
(a) K p is greater than K c K, then the equilibrium constant for the equilibrium
(b) K p is less than K c 1 3
NH 3 ⇌ N 2  H 2 is
(c) K p  K e 2 2
[CBSE PMT 1996; UPSEAT 2001]
(d) Whether K p is greater than, less than or equal to K c
(a) 1/ K (b) 1 / K 2
depends upon the total gas pressure
1
24. In equilibrium CH 3 COOH  H 2 O ⇌ CH 3 COO  H 3 O (c) K (d)
K
The equilibrium constant may change when 33. Which of the following statements regarding a chemical equilibrium
(a) CH 3 COO  are added (b) CH 3 COOH is added is wrong [JIPMER 1999]
(c) Catalyst is added (d) Mixture is heated (a) An equilibrium can be shifted by altering the temperature or
pressure
25. For reaction 2NOCl(g) ⇌ 2 NO(g)  Cl 2 (g) , K C at 427°C is
(b) An equilibrium is dynamic
3  10 6 L mol 1 . The value of K P is nearly [AIIMS 2005] (c) The same state of equilibrium is reached whether one starts
5 5
with the reactants or the products
(a) 7.50  10 (b) 2.50  10 (d) The forward reaction is favoured by the addition of a catalyst
(c) 2.50  10 4
(d) 1.75  10 4 34. The reaction between N 2 and H 2 to form ammonia has
26. For which one of the following reactions K p  K c K c  6  10 2 at the temperature 500°C. The numerical value of
[MP PET 1997]
K p for this reaction is [UPSEAT 1999]
(a) N 2  3H 2 ⇌ 2NH 3 (b) N 2  O 2 ⇌ 2 NO
(a) 1.5  10 5 (b) 1.5  10 5
(c) PCl5 ⇌ PCl3  Cl 2 (d) 2SO 3 ⇌ 2SO 2  O 2
27. The equilibrium constant for the reversible reaction, N 2  3H 2 ⇌ (c) 1.5  10 6 (d) 1.5  10 6
35. For the gaseous phase reaction
1 3
2NH 3 is K and for the reaction N 2  H 2 ⇌ NH 3 the 2NO ⇌ N 2  O2 H    43.5 kcal mol 1
2 2
Which statement is correct [MH CET 1999]
equilibrium constant is K  . K and K  will be related as [MP PET 1997]
(a) K varies with addition of NO
(a) K  K (b) K  K (b) K decrease as temperature decreases
(c) K Increases as temperature decreases
(c) K  K (d) K  K  1 (d) K is independent of temperature
28. The equilibrium constant (K p ) for the reaction 36. For the reversible reaction,
PCl5 (g)  PCl3 (g)  Cl 2 (g) is 16. If the volume of the container N 2(g)  3 H 2(g) ⇌ 2 NH 3(g)
is reduced to one half its original volume, the value of K p for the at 500°C, the value of K P is 1.44  10 5 when partial pressure is
reaction at the same temperature will be measured in atmospheres. The corresponding value of K c with
[KCET 1996]
concentration in mole litre , is
-1

(a) 32 (b) 64 [IIT Screening 2000; Pb. CET 2004]

(c) 16 (d) 4
/ 0.082  500 
5 2
(a) 1.44  10
29. 2NO 2 ⇌ 2 NO  O 2 ; K  1.6  10 12
/ 8.314  773 
5 2
1 (b) 1.44  10
NO  O 2 ⇌ NO 2 K   ? [CPMT 1996]
1.44  10 5 / 0.082  773 
2
2 (c)
(d) 1.44  10 5 / 0.082  773 
1 1 2
(a) K  (b) K 
K2 K 37. A chemical reaction is catalyzed by a catalyst X. Hence X
1 [AIIMS 2000]
(c) K  (d) None of these (a) Reduces enthalpy of the reaction
K
(b) Decreases rate constant of the reaction
30. The value of Kp for the following reaction (c) Increases activation energy of the reaction
2 (d) Does not affect equilibrium constant of reaction
2 H 2 S (g) ⇌ 2 H 2 (g)  S 2 (g) is 1.2  10 o
at 106.5 C . The
38. At 490°C, the equilibrium constant for the synthesis of HI is 50, the
value of K c for this reaction is value of K for the dissociation of HI will be
[EAMCET 1997; AIIMS 1999; AFMC 2000; KCET 2001] [KCET 2000]
2
(a) 1.2  10 (b)  1.2  10 2 (a) 20.0 (b) 2.0
(c) 0.2 (d) 0.02
(c) 83 (d)  1.2  10 2
39. In which of the following case K is less than K
31. Which statement for equilibrium constant is true for the reaction p c

[AFMC 1997; Pb. PMT 2000]

AB ⇌C [CPMT 1997]
(a) H 2  Cl 2 ⇌ 2 HCl (b) 2SO 2  O 2 ⇌ 2SO 3
(a) Not changes with temperature
(b) Changes when catalyst is added (c) N 2  O 2 ⇌ 2 NO (d) PCl5 ⇌ PCl3  Cl 2
(c) Increases with temperature
 318 Chemical Equilibrium
40. CaCO 3(s) ⇌ CaO(s)  CO 2(g) which of the following expression 1
(b) C(g )  O 2( g )  CO (g)
is correct [MH CET 2000] 2
(a) K P  (PCaO  PCO 2 / PCaCO 3 ) (c) H 2( g ) + O 2( g )  H 2 O 2(g)
(d) None of these
(b) K P  PCO 2
49. A chemical reaction was carried out at 300 K and 280 K. The rate
(c) K P  (PCaO  PCO 2 ).PCaCO 3 constants were found to be K and K respectively. The energy of
1 2

activation is 1.157  10 4 cal mole1 and R  1.987 cal . Then

K p [CaO][CO 2 ]
(d) (a) K 2  0.25 K1 (b) K 2  0.5 K1
[CaCO 3 ]
(c) K 2  4 K1 (d) K 2  2K1
41. If K c is the equilibrium constant for the formation of NH 3 , the
50. n , the change in the number of moles for the reaction,
dissociation constant of ammonia under the same temperature will
be [DPMT 2001] C12 H 22 O11 (s) 12O 2(g) ⇌ 12CO 2(g) 11H 2 O(l)
(a) K c (b) Kc at 25°C is [Pb. PMT 2002]
(a) 0 (b) 2
(c) K c2 (d) 1 / K c (c) 4 (d) – 1
51. Value of K p in the reaction
42. 3.2 moles of hydrogen iodide were heated in a scaled bulb at 444°C
till the equilibrium was reached. The degree of dissociation of HI at MgCO3(s) ⇌ MgO(s)  CO 2(g) is
this temperature was found to be 22%. The number of moles of
hydrogen iodide present at equilibrium are [MH CET 2001] [CBSE PMT 2000; RPMT 2002]
(a) 1.87 (b) 2.496 (a) K P  PCO 2
(c) 4.00 (d) 2.00 Pco2  PMgO
(b) K P  Pco2 
43. The K c for H 2(g)  I2(g) ⇌ 2 HI(g ) is 64. If the volume of the PMgCO 3
container is reduced to one-half of its original volume, the value of the
Pco 2  PMgO
equilibrium constant will be [JIPMER 2001] (c) K P
(a) + 28 (b) 64 PMgCO 3
(c) 32 (d) 16 PMgCO 3
44. A reversible reaction H 2  Cl 2 ⇌ 2 HCl is carries out in one litre (d) KP 
PCO 2  PMgO
flask. If the same reaction is carried out in two litre flask, the
equilibrium constant will be [JIPMER 2001] 52. For N 2  3H 2 ⇌ 2NH 3 equilibrium constant is k then equilibrium
(a) Decreased (b) Doubled constant for 2N + 6H ⇌ 4NH is
(c) Halved (d) Same
2 2 3

[RPMT 2002]
45. For the reaction
2
2 NO 2(g) ⇌ 2 NO(g)  O2(g) Kc  1.8  10 6 at 185°C. At 185°C (a) k (b) k
,

1 (c) k/2 (d) k 1

the K for NO (g) +
c
O 2( g ) ⇌ NO 2( g) is
2 53. For the reaction, PCl3(g) + Cl 2(g) ⇌ PCl5(g) , the value of K c at
[JIPMER 2001]
250°C is 26. The value of K p at this temperature will be
(a) 1.95  10 3 (b) 1.95  10 3
[UPSEAT 1999, 2000, 02]
(c) 7.5  10 2 (d) 0.9  10 6
(a) 0.61 (b) 0.57
1
46. If for H 2 (g )  S 2(S ) ⇌ H 2 S (g ) and (c) 0.83 (d) 0.46
2 54. A tenfold increase in pressure on the reaction
H 2(g)  Br2(g) ⇌ 2 HBr(g) N 2( g ) 3 H 2(g) ⇌ 2 NH 3(g) at equilibrium, makes K p
The equilibrium constants are K and K respectively, the reaction
1 2
[MP PET 2003]
1
Br2 (g)  H 2 S (g) ⇌ 2 HBr(g)  S 2(S ) would have equilibrium (a) Unchanged (b) Two times
2 (c) Four times (d) Ten times
constant [MP PMT 2001]
55. If equilibrium constant for reaction
(a) K1  K 2 (b) K1 / K 2
2 AB ⇌ A2  B2 , is 49, then the equilibrium constant for reaction
(c) K 2 / K1 (d) K 22 / K1
1 1
47. Some solid NH 4 HS is placed in a flask containing 0.5 atm of AB ⇌ A 2  B 2 , will be
2 2
NH 3 , what would be pressures of NH 3 and H 2 S when [EAMCET 1998; MP PMT 2003]
equilibrium is reached (a) 7 (b) 20
NH 4 HS (g) ⇌ NH 3(g)  H 2 S (g) , K p  0.11 [UPSEAT 2001] (c) 49 (d) 21
(a) 6.65 atm (b) 0.665 atm 56. In the manufacture of ammonia by Haber's process,
(c) 0.0665 atm (d) 66.5 atm N 2(g)  3H 2 ⇌ 2 NH 3(g)  92.3kJ ,
48. In which of the following reactions, increase in the volume at
constant temperature don’t affect the number of moles at which of the following conditions is unfavourable
equilibrium. [AIEEE 2002] [KCET 2004]
(a) 2NH 3 ⇌ N 2  3H 2 (a) Increasing the temperature
 Chemical Equilibrium 319
(b) Increasing the pressure (d) None of these
(c) Reducing the temperature 65. If equilibrium constants of reaction, N 2  O2 ⇌ 2 NO is K1 and
(d) Removing ammonia as it is formed
1 1
57. The chemical equilibrium of a reversible reaction is not influenced N 2  O 2 ⇌ NO is K 2 , then [BHU 2004]
by [KCET 2004] 2 2
(a) Pressure (a) K1  K 2 (b) K 2  K1
(b) Catalyst
(c) Concentration of the reactants 1
(c) K1  2K 2 (d) K1  K2
(d) Temperature 2
58. Of the following which change will shift the reaction towards the 1
product 66. For the following reaction in gaseous phase CO  O 2  CO 2 ;
2
I2 (g) ⇌ 2 I(g), H r0 (298 K)  150 kJ [AIIMS 2004] K p / K c is [DCE 2002]
(a) Increase in concentration of l (a) (RT )1 / 2 (b) (RT )1 / 2
(b) Decrease in concentration of I 2
(c) (RT ) (d) (RT )1
(c) Increase in temperature
(d) Increase in total pressure 67. For the reaction N 2(g)  O2(g) ⇌ 2 NO (g) , the value of K c at
59. For the reaction, CO(g)  Cl 2(g) ⇌ COCl 2(g) the K p / K c is 800 o C is 0.1. When the equilibrium concentrations of both the
equal to [AIEEE 2004] reactants is 0.5 mol, what is the value of K p at the same
temperature [KCET 2005]
(a) RT (b) RT
(a) 0.5 (b) 0.1
(c) 1 / RT (d) 1 .0 (c) 0.01 (d) 0.025
60. Consider the following reversible reaction at equilibrium, 2 H 2 O(g) 68. A(g)  3 B(g) ⇌ 4 C(g ) . Starting concentration of A is equal to B,
⇌ 2 H 2(g)  O2(g) ; H  241.7 kJ equilibrium concentration of A and C are same. Kc 
Which one of the following changes in conditions will lead to [Kerala CET 2005]
maximum decomposition of H 2 O(g) [Kerala PMT 2004] (a) 0.08 (b) 0.8
(a) Increasing both temperature and pressure (c) 8 (d) 80
(b) Decreasing temperature and increasing pressure (e) 1/8
(c) Increasing temperature and decreasing pressure 69. NH 4 COONH 2(s) ⇌ 2 NH 3(g)  CO 2(g) if equilibrium pressure
(d) Increasing temperature at constant pressure is 3 atm for the above reaction K p for the reaction is [
61. For reaction, 2 A(g) ⇌ 3C(g)  D(s) , the value of K c will be (a) 4 (b) 27
equal to [Pb. CET 2003] (c) 4/27 (d) 1/27
(a) K p (RT ) (b) K p / RT
Activation energy, Standard free energy and
(c)  Kp (d) None of these
Degree of dissociation and Vapour density
62. In the reaction, A2 (g)  4 B2 (g) ⇌ 2 AB4 (g)
H  0 the formation of AB4 is will be favoured at 1. The vapour density of completely dissociated NH 4 Cl would be
[IIT Screening 1990; MP PET 2004]
(a) Slight less than half that of NH 4 Cl
(a) Low temperature, high pressure
(b) High temperature, low pressure (b) Half that of NH 4 Cl
(c) Low temperature, low pressure
(c) Double that of NH 4 Cl
(d) High temperature, high pressure
63. The formation of SO 3 takes place according to the following (d) Determined by the amount of solid NH 4 Cl in the
experiment
reaction, 2SO 2  O2 ⇌ 2SO 3 ; H  45.2 kcal
2. In an equilibrium reaction for which G 0  0 , the equilibrium
The formation of SO 3 is favoured by [UPSEAT 2004]
constant K  [BHU 1987]
(a) Increasing in temperature (a) 0 (b) 1
(b) Removal of oxygen
(c) 2 (d) 10
(c) Increase of volume
(d) Increasing of pressure 3. For a system in equilibrium G  0 under conditions of constant
64. What is the effect of increasing pressure on the dissociation of (a) Temperature and pressure
PCl5 according to the equation (b) Temperature and volume
(c) Energy and volume
PCl5(g) ⇌ PCl3(g)  Cl 2(g)  x cal [UPSEAT 2004]
(d) Pressure and volume
(a) Dissociation decreases 4. A reaction attains equilibrium when the free energy change
(b) Dissociation increases accompanying it is [KCET 1989]
(c) Dissociation does not change (a) Positive and large (b) Zero
 320 Chemical Equilibrium
(c) Negative and large (d) Negative and small (a) The speed of forward and backward reaction increases
5. G (HI, g)  1.7 kJ . What is the equilibrium constant
0
at (b) The speed of forward and backward reaction decreases

25 C for 2 HI(g)  H 2 (g)  I 2 (g)

o
[KCET 1992] (c) Only the speed of that reaction increases which nullifies the
factor causing increase of speed
(a) 24.0 (b) 3.9
(d) No difference
(c) 2.0 (d) 0.5
4. Which of the following reactions proceed at low pressure
6. The standard state gibbs free energy change for the given
[MP PET 1985; CPMT 1984; MP PMT 1995; RPMT 1997]
isomerization reaction cis-2-pentene ⇌ trans –2 -pentene is
3.67 kJ / mol at 400 K . If more trans-2-pentene is added to the (a) N 2  3H 2 ⇌ 2NH 3 (b) H 2  I 2 ⇌ 2 HI
reaction vessel, then
(c) PCl5 ⇌ PCl3  Cl 2 (d) N 2  O 2 ⇌ 2 NO
[CBSE PMT 1995; BHU 1999; AFMC 2000]
(a) More cis –2–pentene is formed 5. Le-chatelier principle is applicable
(b) Equilibrium is shifted in the forward direction (a) Both for physical and chemical equilibrium
(c) Equilibrium remains unaffected (b) Only for chemical equilibrium
(d) Additional trans–2–pentene is formed (c) Only for physical equilibrium
7. In a reversible reaction, the catalyst [KCET 2003] (d) Neither for (b) nor for (c)
(a) Increases the activation energy of the backward reaction 6. In the following reversible reaction
(b) Increases the activation energy of the forward reaction
2SO 2  O 2 ⇌ 2SO 3  Q Cal
(c) Decreases the activation energy of both, forward and backward
reaction Most suitable condition for the higher production of SO 3 is
(d) Decreases the activation energy of forward reaction [NCERT 1974; DPMT 1983, 89; IIT 1981; MP PET 1992;
8. For the reaction H 2 (g)  I 2 (g) ⇌ 2 HI(g) , the equilibrium MP PMT 1990, 91, 94, 99; CPMT 1973, 77, 84, 89, 94, 99]
constant changes with (a) High temperature and high pressure
[IIT 1981; MNR 1983, 85; NCERT 1984; MP PMT 1987, 97; (b) High temperature and low pressure
MP PET/PMT 1988; CPMT 1976, 90; UPSEAT 2000] (c) Low temperature and high pressure
(a) Total pressure (d) Low temperature and low pressure
(b) Catalyst
7. When the pressure is applied over system ice ⇌ water what will
(c) The amounts of H 2 and I 2 taken happen ?
(d) Temperature [MP PMT 1990; CPMT 1983; NCERT 1978; DPMT 2002]
(a) More water will form
9. Calculate G for conversion of oxygen to ozone
3 / 2 O2 (g)  O3 (g) at 298 K, if K p for this conversion is (b) More ice will form
(c) There will be no effect over equilibrium
2.47  10 29 [DPMT 2004]
(d) Water will decompose in H 2 and O 2
1
(a) 163 kJ mol (b) 2.4  10 kJ mol 1
2

8. The reaction A  B ⇌ C  D +heat has reached equilibrium. The

(c) 1.63 kJ mol 1 (d) 2.38  10 6 kJ mol 1 reaction may be made to proceed forward by
[IIT 1978]
Le-Chaterlier principle and It’s application (a) Adding more C
(b) Adding more D
1. When in any system at equilibrium state pressure, temperature and (c) Decreasing the temperature
concentration is changed then the equilibria shifted to such a
(d) Increasing the temperature
direction which neutralize the effect of change. This is known as
9. On the velocity in a reversible reaction, the correct explanation of
[MP PMT/PET 1988; DPMT 1985] the effect of catalyst is [MP PMT 1987]
(a) First law of thermodynamics (a) It provides a new reaction path of low activation energy
(b) Le-chatelier's principle (b) It increases the kinetic energy of reacting molecules
(c) Ostwald's rule (c) It displaces the equilibrium state on right side
(d) Hess's law of constant heat summation (d) It decreases the velocity of backward reaction
10. Select the correct statement from the following
2. N 2  O 2 ⇌ 2 NO  Q cals [MP PMT 1985]
In the above reaction which is the essential condition for the higher (a) Equilibrium constant changes with addition of catalyst
production of NO [CPMT 1971, 89; MP PMT 1985] (b) Catalyst increases the rate of forward reaction
(a) High temperature (b) High pressure (c) The ratio of mixture at equilibrium is not changed by catalyst
(d) Catalyst are active only in solution
(c) Low temperature (d) Low pressure
11. According to Le-chatelier principle, if heat is given to solid-liquid
3. A reversible reaction is in equilibrium. If a factor is changed which system, then [MNR 1990]
affect it, then (a) Quantity of solid will reduce
 Chemical Equilibrium 321
(b) Quantity of liquid will reduce 19. Consider the reaction HCN (aq ) ⇌ H (aq )  CN (aq ) . At
(c) Increase in temperature 
equilibrium, the addition of CN (aq would [NCERT 1979]
(d) Decrease in temperature )

(a) Reduce HCN (aq ) concentration

12. In the reaction A(g)  2 B(g) ⇌ C(g)  Q kJ , greater product

will be obtained or the forward reaction is favoured by (b) Decrease the H (aq ) ion concentration
[MNR 1988; MP PMT 1989, 97] (c) Increase the equilibrium constant
(a) At high temperature and high pressure (d) Decrease the equilibrium constant
(b) At high temperature and low pressure 20. In the gaseous equilibrium H 2 X 2  heat ⇌ 2 HX , the
(c) At low temperature and high pressure formation of HX will be favoured by [CPMT 1977]
(d) At low temperature and low pressure (a) High pressure and low temperature
13. Following gaseous reaction is undergoing in a vessel (b) High temperature and low pressure
C 2 H 4  H 2 ⇌ C 2 H 6 ; H  32.7 Kcal (c) Low temperature and low pressure
Which will increase the equilibrium concentration of C 2 H 6 (d) High temperature and high pressure
[IIT 1984; MP PET/PMT 1988; MADT Bihar 1995] 21. Raising the temperature of an equilibrium system
(a) Increase of temperature [MP PMT 1987]
(b) By reducing temperature (a) Favours the exothermic reaction only
(c) By removing some hydrogen (b) Favours the endothermic reaction only
(d) By adding some C 2 H 6 (c) Favours both the exothermic and endothermic reactions
14. The effect of increasing the pressure on the equilibrium (d) Favours neither the exothermic nor endothermic reactions
2 A  3 B ⇌ 3 A  2 B is [EAMCET 1980; MP PMT 1991] 22. Reaction in which yield of product will increase with increase in
pressure is [NCERT 1984]
(a) Forward reaction is favoured
(b) Backward reaction is favoured (a) H 2(g)  I 2(g) ⇌ 2 HI(g)
(c) No effect
(b) H 2 O(g)  CO (g) ⇌ CO 2(g)  H 2(g)
(d) None of the above
15. For the equilibrium 2 NO 2 (g) ⇌ N 2O4 (g) 14.6 kcal the (c) H 2 O(g)  C(s) ⇌ CO (g)  H 2(g)
increase in temperature would [CPMT 1974, 78]
(d) CO (g)  3 H 2(g) ⇌ CH 4 (g)  H 2 O(g)
(a) Favour the formation of N 2 O 4
(b) Favour the decomposition of N 2 O 4 23. In reaction N 2(g)  3 H 2(g) ⇌ 2 NH 3(g) ; H  93.6 kJ , the
yield of ammonia does not increase when [CPMT 1988]
(c) Not alter the equilibrium
(d) Stop the reaction (a) Pressure is increased
16. Which of the following factors will favour the reverse reaction in a (b) Temperature is lowered
chemical equilibrium [AIIMS 1982] (c) Pressure is lowered
(a) Increase in the concentration of one of the reactants (d) Volume of the reaction vessel is decreased
(b) Removal of at least one of the product at regular time intervals 24. The equilibrium which remains uneffected by change in pressure of
(c) Increase in the concentration of one or more products the reactants is
(d) None of these [CPMT 1987; KCET 1991; EAMCET 1992;
17. In the formation of SO 3 by contact process, the conditions used MP PET 1992, 95; MP PMT 1999]
are [CPMT 1984] (a) N 2(g)  O 2(g) ⇌ 2 NO (g)
(a) Catalyst, optimum temperature and higher concentration of
reactants (b) 2SO 2(g)  O 2(g) ⇌ 2 SO 3(g)
(b) Catalyst, optimum temperature and lower concentration of
reactants (c) 2 O 3 ( g ) ⇌ 3 O 2( g )
(c) Catalyst, high temperature and higher concentration of
reactants (d) 2 NO 2(g) ⇌ N 2 O 4 (g)
(d) Catalyst, low temperature and lower concentration of reactants 25. The endothermic reaction (M  N  P ) is allowed to attain an
18. Given reaction is 2 X (gas)  Y(gas) ⇌ 2 Z(gas)  80 kcal equilibrium at 25 o . Formation of P can be increased by[BHU 1981]
Which combination of pressure and temperature gives the highest (a) Raising temperature
yield of Z at equilibrium [NCERT 1979] (b) Lowering temperature
(a) 1000 atm and 500 o C (c) Keeping temperature constant
(d) Decreasing the concentration of M and N
(b) 500 atm and 500 o C
26. According to Le-chatelier's principle, an increase in the temperature
(c) 1000 atm and 100 o C of the following reaction will
(d) 500 atm and 100 o C N 2  O 2 ⇌ 2 NO  43,200 kcal [MP PMT 1985, 93]

(a) Increase the yield of NO

(b) Decrease the yield of NO
 322 Chemical Equilibrium
(c) Not effect the yield of NO (d) Concentration, pressure and temperature
(d) Not help the reaction to proceed in forward direction 36. If pressure increases then its effect on given equilibrium
27. In the manufacture of NH 3 by Haber's process, the condition C(s)  H 2 O(g) ⇌ CO(g)  H 2 (g) it is satisfied in
which would give maximum yield is [BCECE 2005]
N 2  3H 2 ⇌ 2 NH 3  Q kcal (a) Forward direction (b) Backward direction
[NCERT 1978; EAMCET 1980; MNR 1987; AFMC 1999; (c) No effect (d) None of these
CPMT 1983, 84, 86, 94; MP PMT 1999]
(a) High temperature, high pressure and high concentrations of 37. The exothermic formation of ClF3 is represented by the equation
the reactants
Cl 2(g)  3 F2(g) ⇌ 2ClF3(g) ; H  329 kJ
(b) High temperature, low pressure and low concentrations of the
reactants Which of the following will increase the quantity of ClF3 in an
(c) Low temperature and high pressure
equilibrium mixture of Cl 2 , F2 and ClF3 [AIEEE 2005]
(d) Low temperature, low pressure and low concentration of H 2
(a) Increasing the temperature
28. Suppose the reaction PCl5(s) ⇌ PCl3(s)  Cl 2(g) is in a closed
vessel at equilibrium stage. What is the effect on equilibrium (b) Removing Cl 2
concentration of Cl 2(g) by adding PCl5 at constant temperature[MP PMT 1992] (c) Increasing the volume of the container
(a) Decreases (d) Adding F2
(b) Increases
(c) Unaffected 38. What would happen to a reversible reaction at equilibrium when an
inert gas is added while the pressure remains unchanged
(d) Cannot be described without the value of K p
(a) More of the product will be formed
29. In which of the following equilibrium reactions, the equilibrium
would shift to the right, if total pressure is increased [KCET 1993]
(b) Less of the product will be formed
(c) More of the reactants will be formed
(a) N 2  3H 2 ⇌ 2NH 3 (b) H 2  I 2 ⇌ 2 HI
(d) It remains unaffected
(c) H 2  Cl 2 ⇌ 2 HCl (d) N 2 O 4 ⇌ 2 NO
39. Formation of SO 3 takes place according to the reaction
30. In which of the following gaseous equilibrium an increase in
pressure will increase the yield of the products 2SO 2  O 2  2SO 3 ; H  45.2 kcal
[EAMCET 1988] Which of the following factors favours the formation of SO 3
(a) 2 HI ⇌ H 2  I 2 (b) 2SO 2  O 2 ⇌ 2SO 3 [MP PET/PMT 1998]
(c) H 2  Br2 ⇌ 2 HBr (d) H 2 O  CO ⇌ H 2  CO 2 (a) Increase in temperature
31. In the reaction A(g)  B(g) ⇌ C(g) , the backward reaction is (b) Increase in pressure
favoured by [EAMCET 1986] (c) Removal of oxygen
(a) Decrease of pressure (b) Increase of pressure (d) Increase in volume
(c) Either of the two (d) None of the two 40. For the chemical reaction 3 X (g)  Y (g) ⇌ X 3 Y (g) , the amount of
32. The formation of NO 2 in the reaction 2 NO  O 2 ⇌ 2NO 2 + X 3 Y at equilibrium is affected by [IIT 1999]
heat is favoured by
[Rookee Qualifying 1998] (a) Temperature and pressure
(a) Low pressure (b) High pressure (b) Temperature only
(c) Low temperature (d) Reduction in the mass of (c) Pressure only
33. For the reaction PCl5 (g) ⇌ PCl3 (g)  Cl 2 (g) , the forward (d) Temperature, pressure and catalyst
reaction at constant temperature is favoured by 41. In N 2  3H 2 ⇌ 2NH 3 reversible reaction, increase in pressure
[IIT 1991; AMU 2001] will favour [DPMT 1996]
(a) Introducing an inert gas at constant volume (a) Reaction in forward direction
(b) Introducing chlorine gas at constant volume (b) Reaction in reverse direction
(c) Introducing an inert gas at constant pressure (c) Will not exert any effect
(d) Decreasing the volume of the container (d) In backward and forward direction equally
34. Which of the following conditions is favourable for the production 42. In the reaction N 2  3 H 2  2 NH 3 , the product increases on [
of ammonia by Haber's process [MP PET 1994]
(a) High concentration of reactants (a) Increasing temperature
(b) Increasing pressure
(b) Low temperature and high pressure
(c) Increasing temperature and pressure both
(c) Continuous removal of ammonia (d) Decreasing temperature and pressure both
(d) All of these (e) None of these
35. According to Le-chatelier's principle, which of the following factors 43. In which of the following system, doubling the volume of the
influence a chemical system [MP PMT 1996] container cause a shift to the right [AIIMS 1996]
(a) Concentration only (a) H 2 (g)  Cl 2 (g)  2 HCl(g)
(b) Pressure only (b) 2CO(g)  O 2 (g)  2CO 2 (g)
(c) Temperature only
 Chemical Equilibrium 323

(c) N 2 (g)  3 H 2 (g)  2 NH 3 (g) 52. In a vessel containing SO 3 , SO 2 and O 2 at equilibrium, some
helium gas is introduced so that the total pressure increases while
(d) PCl5 (g) ⇌ PCl3 (g)  Cl 2 (g) temperature and volume remain constant. According to Le–Chatelier
44. Which of the following information can be obtained on the basis of principle the dissociation of SO 3
Le-chatelier's principle
[UPSEAT 2000]
[AIIMS 1998; Pb. PMT 1999; BHU 2000; DPMT 2004]
(a) Entropy change in a reaction (a) Increases (b) Decreases
(b) Dissociation constant of a weak acid (c) Remains unaltered (d) Changes unpredictably
(c) Equilibrium constant of a chemical reaction 53. H 2(g)  I2(g) ⇌ 2 HI(g) H  q cal, then formation of HI:
(d) Shift in equilibrium position on changing value of a constant
[AMU 2000]
45. The equilibrium 2SO 2(g)  O2(g) ⇌ 2 SO 3(g) shifts forward, if
(a) Is favoured by lowering the temperature
[CPMT 1988]
(b) Is favoured by increasing the pressure
(a) A catalyst is used
(c) Is unaffected by change in pressure
(b) An adsorbent is used to remove SO 3 as soon as it is formed
(d) Is unaffected by change in temperature
(c) Low pressure
(d) Small amounts of reactants are used 54. In which of the following equilibrium systems is the rate of the
backward reaction favoured by increase of pressure
46. The equilibrium SO 2 Cl 2(g) ⇌ SO 2(g)  Cl 2(g) is attained at 25°C [KCET 2001]
in a closed container and an inert gas helium is introduced which of
the following statement is correct (a) PCl5 ⇌ PCl3  Cl 2 (b) 2SO 2  O2 ⇌ 2SO 3
[MP PMT 2000]
(c) N 2  3H 2 ⇌ 2NH 3 (d) N 2  O2 ⇌ 2 NO
(a) More chlorine is formed
(b) Concentration of SO 2 is reduced 55. Which of the following equilibrium is not shifted by increase in the
pressure [MP PMT 2001]
(c) More SO 2 Cl 2 is formed
(a) H 2(g)  I2(g) ⇌ 2 HI(g )
(d) Concentration of SO 2 Cl 2 , SO 2 and Cl 2 does not change
47. Which of the following equilibria will shift to right side on (b) N 2(g)  3 H 2(g) ⇌ 2 NH 3 (g)
increasing the temperature [MP PMT 2000]
(c) 2CO(g)  O2(g) ⇌ 2CO 2 (g)
(a) CO (g)  H 2 O(g) ⇌ CO 2 (g)  H 2 (g)
(d) 2C(S )  O2(g) ⇌ 2CO (g)
(b) 2SO 2 (g)  O 2 (g) ⇌ 2 SO 3 (g)
56. According to Le–Chatelier’s principal adding heat to a solid and
1
(c) H 2 O(g) ⇌ H 2 (g )  (O 2 )( g) liquid in equilibrium with endothermic nature will cause the [JIPMER 2000; MP P
2 (a) Temperature to rise
(d) 4 HCl(g)  O 2 (g) ⇌ 2 H 2 O(g)  2Cl 2 (g) (b) Temperature to fall
48. Sodium sulphate dissolves in water with evolution of heat. Consider (c) Amount of solid to decrease
a saturated solution of sodium sulphate. If the temperature is raised, (d) Amount of liquid to decrease
then according to Le-Chatelier principle 57. [MP PET
On addition of 2000]
an inert gas at constant volume to the reaction
(a) More solid will dissolve N 2  3H 2 ⇌ 2NH 3 at equilibrium
(b) Some solid will precipitate out from the solution
[Pb. PMT 2001]
(c) The solution will become supersaturated
(a) The reaction remains unaffected
(d) Solution concentration will remain unchanged
(b) Forward reaction is favoured
49. Consider the equilibrium
(c) The reaction halts
N 2 (g)  3 H 2 (g) ⇌ 2 NH 3 (g) ;  H = – 93.6 KJ. The maximum (d) Backward reaction is favoured
yield of ammonia is obtained by
58. Le-Chatelier principle is not applicable to [MH CET 2001]
[UPSEAT 1999; AMU 2000]
(a) Decrease of temp. and increase of pressure (a) H 2(g)  I2(g) ⇌ 2 HI(g )
(b) Increase of temp. and decrease of pressure (b) Fe(S )  S (S ) ⇌ FeS (S )
(c) Decrease of both the temp. and pressure
(d) Increase of both the temp. and pressure (c) N 2(g)  3 H 2(g) ⇌ 2 NH 3(g)

50. In the equilibrium AB ⇌ A  B ; if the equilibrium concentration (d) N 2(g)  O2(g) ⇌ 2 NO (g)
of A is doubled, the equilibrium concentration of B would become:[AMU 2000]
(a) Twice (b) Half 59. For the reaction: A + B + Q ⇌ C + D, if the temperature is
(c) 1/4 th
(d) 1/8 th increased, then concentration of the products will
51. Le-Chatelier’s principle is applicable only to a [AFMC 2001]
[MP PET/PMT 1988; KCET 1999; AFMC 2000; (a) Increase (b) Decrease
Pb. CET 2002] (c) Remain same (d) Become Zero
(a) System in equilibrium (b) Irreversible reaction 60. H 2( g ) + I2( g ) ⇌ 2 HI(g )
(c) Homogeneous reaction (d) Heterogeneous reaction
In this reaction when pressure increases, the reaction direction [RPMT 2002]
 324 Chemical Equilibrium
(a) Does not change (b) Forward (a) Low temperature and high pressure
(c) Backward (d) Decrease (b) High temperature and high pressure
61. The rate of reaction of which of the following is not affected by (c) High temperature and low pressure
pressure [MP PMT 2002] (d) Low temperature and low pressure
71. For a reaction if K p  K c , the forward reaction is favoured by[RPET 2003]
(a) PCl3  Cl 2 ⇌ PCl5 (b) N 2  3H 2 ⇌ 2NH 3
(a) Low pressure (b) High pressure
(c) N 2  O2 ⇌ 2NO (d) 2SO 2  O2 ⇌ 2SO 3 (c) High temperature (d) Low temperature

62. In the equilibrium N + 3H ⇌ 2NH + 22 kcal, the formation of 72. A2(g)  B2(g) ⇌ 2 AB( g) ; H  ve [BHU 2003]
2 2 3

ammonia is favoured by [MP PET 2000, 02] (a) Unaffected by pressure

(a) Increasing the pressure (b) It occurs at 1000 pressure
(b) Increasing the temperature (c) It occurs at high temperature
(d) It occurs at high pressure and high temperature
(c) Decreasing the pressure
73. Consider the reaction equilibrium, 2 SO 2(g) + O 2( g ) ⇌ 2 SO 3(g) ;
(d) Adding ammonia
H  = –198kJ. On the basis of Le-Chatelier’s principle, the condition
63. The reaction 2SO 2  O2 ⇌ 2SO 3 ; H = – ve is favoured by[CPMT 2002; Pb. PMT 2001] for the forward reaction is
favourable [
(a) Low temperature, low pressure (a) Lowering of temperature as well as pressure
(b) Increasing temperature as well as pressure
(b) Low temperature, high pressure (c) Lowering the temperature and increasing the pressure
(c) High temperature, high pressure (d) Any value of temperature and pressure
(d) High temperature, low pressure
64. Which of the following will favour the reverse reaction in a chemical
equilibrium [Kerala (Med.) 2002]
(a) Increasing the concentration of the reactants
(b) Removal of at least one of the products at regular intervals
(c) Increasing the concentration of one or more of the products
1. If dissociation for reaction, PCl5 ⇌ PCl3  Cl 2
(d) Increasing the pressure
(e) None of these Is 20% at 1 atm. pressure. Calculate K c
65. Under what conditions of temperature and pressure the formation [Kerala (Med.) 2003]
of atomic hydrogen from molecular hydrogen will be favoured most[UPSEAT 2000, 01, 02]
(a) High temperature and high pressure (a) 0.04 (b) 0.05
(b) Low temperature and low pressure (c) 0.07 (d) 0.06
(c) High temperature and low pressure 2. Ammonia under a pressure of 15 atm at 27°C is heated to 347°C in
(d) Low temperature and high pressure a closed vessel in the presence of a catalyst. Under the conditions,
66. The formation of nitric oxide by contact process N 2  O2 ⇌ 2NO. NH 3 is partially decomposed according to the equation,
 H = 43.200 kcal is favoured by [AMU 2002]
2NH 3 ⇌ N 2  3H 2 .The vessel is such that the volume remains
(a) Low temperature and low pressure
effectively constant where as pressure increases to 50 atm. Calculate
(b) Low temperature and high pressure
the percentage of NH 3 actually decomposed. [IIT 1981; MNR 1991; UPSEAT 2001]
(c) High temperature and high pressure
(d) High temperature and excess reactants concentration (a) 65% (b) 61.3%
67. The chemical reaction: BaO2(S ) ⇌ BaO(s) O 2(g )  H = + ve. In
’
(c) 62.5% (d) 64%
equilibrium condition, pressure of O depends upon
2
3. K for the following reaction at 700 K is 1.3  10 3 atm The K at
-1.

[CBSE PMT 2002] p c

(a) Increase mass of BaO same temperature for the reaction 2SO 2  O2  2SO 3 will be [AIIMS 2001]
(b) Increase mass of BaO 2
(a) 1.1  10 2 (b) 3.1  10 2
(c) Increase in temperature
(d) Increase mass of BaO and BaO both
2
(c) 5.2  10 2 (d) 7.4  10 2
68. The yield of product in the reaction
A2(g ) + 2 Bg  ⇌ C(g ) + Q.kJ. would be high at 4. For the reaction 2 NO 2 (g) ⇌ 2 NO(g)  O 2 (g)
[UPSEAT 2002]
(a) High temperature and high pressure K c  1.8  10 6 at 185°C. At 185°C, the value of K c for the
(b) High temperature and low pressure 1
reaction NO g   O 2 ⇌ NO 2 g  is [UPSEAT 2000]
(c) Low temperature and high pressure 2 g 
(d) Low temperature and low pressure
69. Which reaction is not effected by change in pressure (a) 0.9  10 6 (b) 7.5  10 2
[UPSEAT 2003]
(c) 1.95  10 3 (d) 1.95  10 3
(a) H 2  I2 ⇌ 2HI (b) 2C  O2 ⇌ 2CO
(c) N 2  3H 2 ⇌ 2NH 3 (d) PCl5 ⇌ PCl3  Cl 2

70. The gaseous reaction A + B ⇌ 2C + D; + Q is most favoured at [Karnataka CET 2003]

 Chemical Equilibrium 325

5. 2SO 3 ⇌ 2SO 2  O 2 . If K c  100,   1 , half of the reaction is (d) Increasing the amount CO (g)
completed, the concentration of SO 3 and SO 2 are equal, the 11. At constant temperature, the equilibrium constant (K ) for the p

concentration of O 2 is [CPMT 1996] decomposition reaction N 2 O4 ⇌ 2NO 2 is expressed by

(4 x 2 P)
(a) 0.001 M (b)
1
SO 2 KP  ,
2 (1  x 2 )

(c) 2 times of SO 2 (d) Data incomplete where P  pressure, x  extent of decomposition. Which one of
the following statements is true
6. At 700 K, the equilibrium constant K p for the reaction [IIT Screening 2001]
3
2 SO 3(g) ⇌ 2SO 2(g)  O2(g) is 1.80  10 and kP is 14, (R =
a
(a) K increases with increase of P
p

8.314 Jk mol ). The numerical value in moles per litre of K c for this
-1 –1
(b) K increases with increase of x
p

reaction at the same temperature will be (c) K increases with decrease of x

p

[AFMC 2001] (d) K remains constant with change in P and x

p

7 8
(a) 3.09  10 mol-litre (b) 5.07  10 mol-litre
(c) 8.18  10 9 mol-litre (d) 9.24  10 10 mol-litre
7. 0.1 mole of N 2 O4 (g) was sealed in a tube under one atmospheric
conditions at 25°C. Calculate the number of moles of NO 2( g)
present, if the equilibrium N 2 O4 (g) ⇌ 2 NO 2(g) (K p  0.14 ) is
Read the assertion and reason carefully to mark the correct option out of
reached after some time the options given below :
[UPSEAT 2001] (a) If both assertion and reason are true and the reason is the correct
explanation of the assertion.
(a) 1.8  10 2
(b) 2.8  10 2
(b) If both assertion and reason are true but reason is not the correct
explanation of the assertion.
(c) 0.034 (d) 2.8  10 2 (c) If assertion is true but reason is false.
(d) If the assertion and reason both are false.
8. The partial pressures of CH 3 OH, CO and H 2 in the equilibrium (e) If assertion is false but reason is true.
mixture for the reaction 1. Assertion : The equilibrium constant is fixed and is the
CO  2H 2 ⇌ CH 3 OH characteristic of any given chemical reaction at a
specified temperature.
at 427°C are 2.0, 1.0 and 0.1 atm respectively. The value of K P for Reason : The composition of the final equilibrium mixture
at a particular temperature depends upon the
the decomposition of CH 3 OH to CO and H 2 is starting amount of reactants. [AIIMS 2000]
[Roorkee 1999] 2. Assertion : K p  Kc for all reaction.
1
(a) 1  10 atm
2
(b) 2  10 atm
2 Reason : At constant temperature, the pressure of the gas
is proportional to its concentration.
(c) 50 atm2 (d) 5  10 3 atm2 3. Assertion : The equilibrium constant for the reaction
9. One mole of a compound AB reacts with one mole of a compound CaSO 4 .5 H 2 O(s) ⇌ CaSO 4 .3 H 2O(s)  2 H 2O(g)
CD according to the equation [CaSO 4 .3 H 2 O][H 2 O]2
is KC 
AB + CD ⇌ AD + CB. [CaSO 4 .5 H 2 O]
Reason : Equilibrium constant is the ratio of the product
3 of molar concentration of the substances
When equilibrium had been established it was found that mole
4 produced to the product of the molar
each of reactant AB and CD had been converted to AD and CB. concentrations of reactants with each
There is no change in volume. The equilibrium constant for the concentrations term raised to the power equal to
reaction is [Kerala (Med.) 2003] the respective stoichiometric constant.
4. Assertion : On cooling a freezing mixture, colour of the
9 1 mixture turns to pink from deep blue for a
(a) (b)
16 9 reaction. Co (H 2O)62 (aq )  4 Cl (aq ) ⇌
16 CoCl 42 (aq )  6 H 2O(l) .
(c) (d) 9
9
Reason : Reaction is endothermic so on cooling, the
10. For the reaction CO(g)  H 2 O(g) ⇌ CO 2 (g)  H 2 (g) at a given reaction moves to backward direction.
temperature, the equilibrium amount of CO 2 (g) can be increased 5. Assertion : If Qc (reaction quotient)  KC (equilibrium
by [IIT 1998] constant) reaction moves in direction of
reactants.
(a) Adding a suitable catalyst Reason : Reaction quotient is defined in the same way as
(b) Adding an inert gas equilibrium constant at any stage of he reaction.
(c) Decreasing the volume of the container 6. Assertion : NaCl solution can be purified by passage of
hydrogen chloride through brine.
 326 Chemical Equilibrium
Reason : This type of purification is based on Le-
Chaterlier's principle.
7. Assertion : According to Le-Chatelier's principle addition of heat
to an equilibrium solid ⇌ liquid results in decrease
in the amount of solid. Reversible and Irreversible reaction
Reason : Reaction is endothermic, so on heating forward
reaction is favoured. 1 b 2 c 3 d 4 b 5 a
8. Assertion : Equilibrium constant has meaning only when the
corresponding balanced chemical equation is 6 d 7 b
given.
Reason : Its value changes for the new equation obtained Equilibrium state
by multiplying or dividing the original equation
by a number.
1 c 2 b 3 a 4 c 5 b
9. Assertion : Equilibrium constant for the reverse reaction is
the inverse of the equilibrium constant for the 6 d 7 c 8 b 9 cd 10 cd
reaction in the forward direction.
Reason : Equilibrium constant depends upon the way in
which the reaction is written. Law of mass action
10. Assertion : The value of K gives us a relative idea about the
extent to which a reaction proceeds. 1 b 2 a 3 d 4 b 5 a
Reason : The value of K is independent of the
stochiometry of reactants and products at the 6 d 7 d 8 a 9 c 10 a
point of equilibrium.
11. Assertion : Catalyst affects the final state of the equilibrium. Law of equilibrium and Equilibrium constant
Reason : It enables the system to attain a new equilibrium
state by complexing with the reagents.
1 d 2 d 3 c 4 a 5 a
12. Assertion : For the reaction,
6 d 7 c 8 a 9 a 10 d
2 NH 3 (g) ⇌ N 2 (g) 3 H 2 (g) , the unit of
K p will be atm. 11 b 12 c 13 a 14 d 15 d
16 c 17 a 18 b 19 b 20 c
Reason : Unit of K p is (atm)n .
21 a 22 b 23 d 24 d 25 b
13. Assertion : Effect of temperature of Kc or K p depends on
26 a 27 c 28 b 29 c 30 a
enthalpy change.
Reason : Increase in temperature shifts the equilibrium in 31 b 32 d 33 c 34 b 35 a
exothermic direction and decrease in temperature 36 a 37 c 38 a 39 d 40 a
shifts the equilibrium position in endothermic
direction. 41 d 42 d 43 b 44 c 45 d
14. Assertion : For a gaseous reaction, 46 a 47 c 48 b 49 a 50 b
xA  yB ⇌ lC  mD, K p  KC . 51 b 52 b 53 c 54 d 55 b
Reason : Concentration of gaseous reactant is taken to be 56 c 57 c 58 c 59 a 60 c
unity.
61 d 62 d 63 b 64 b 65 d
15. Assertion : Ice ⇌water, if pressure is applied water will
evaporate. 66 d 67 d 68 a 69 c 70 d
Reason : Increase of pressure pushes the equilibrium 71 abcd 72 a 73 d 74 b
towards the side in which number of gaseous
mole decreases.
1
Kp & Kc Relationship and Characteristics of K
16. Assertion : SO 2 (g)  O2 (g) ⇌ SO 3 (g)  heat.
2
Forward reaction is favoured at high temperature 1 a 2 d 3 a 4 b 5 d
and low pressure. 6 d 7 c 8 d 9 a 10 b
Reason : Reaction is exothermic.
11 c 12 c 13 c 14 c 15 d
17. Assertion : For a reaction H 2 (g)  I2 (g) ⇌ 2 HI(g) if the
16 c 17 c 18 c 19 d 20 c
volume of vessel is reduced to half of its original
volume, equilibrium constant will be doubled. 21 c 22 c 23 a 24 d 25 d
Reason : According to Le-Chatelier principle, reaction 26 b 27 b 28 c 29 c 30 b
shifts in a direction that tends to undo the effect
of the stress. 31 d 32 d 33 d 34 a 35 b
36 d 37 d 38 d 39 b 40 b
41 d 42 b 43 b 44 d 45 c
 Chemical Equilibrium 327

46 c 47 b 48 d 49 a 50 a
51 a 52 b 53 a 54 a 55 a
56 a 57 b 58 c 59 c 60 c
61 b 62 a 63 d 64 a 65 b
66 b 67 b 68 c 69 b

Activation energy, Standard free energy and

Degree of dissociation and Vapour density

1 b 2 b 3 a 4 b 5 d
6 a 7 c 8 d 9 a

Le-Chaterlier principle and It’s application

1 b 2 a 3 c 4 c 5 a
6 c 7 a 8 c 9 a 10 c
11 a 12 c 13 b 14 c 15 b
16 c 17 a 18 c 19 b 20 b
21 b 22 d 23 c 24 a 25 a
26 a 27 c 28 b 29 a 30 b
31 a 32 b,c 33 c 34 d 35 d
36 b 37 d 38 d 39 b 40 a
41 a 42 b 43 d 44 d 45 b
46 d 47 c 48 b 49 a 50 b
51 a 52 b 53 c 54 a 55 a
56 c 57 a 58 b 59 a 60 a
61 c 62 a 63 b 64 c 65 c
66 d 67 a 68 c 69 a 70 d
71 a 72 a 73 c

Critical Thinking Questions

1 b 2 b 3 d 4 b 5 d
6 a 7 c 8 d 9 d 10 d
11 d

Assertion & Reason

1 c 2 e 3 e 4 a 5 e
6 c 7 b 8 a 9 a 10 c
11 d 12 e 13 c 14 d 15 e
16 e 17 e
 Chemical Equilibrium 329

[C] [D] 2  2
Equilibrium constant =  1
[ A] [B] 2  2
4. (a) H 2  I2 ⇌ 2HI; [HI] = 0.80, [H 2 ]  0.10 , [I2 ]  0.10

[HI] 2 0 .80  0 .80

Kc    64
[H 2 ] [I 2 ] 0 .10  0 .10
Reversible and Irreversible reaction 5. (a) Those reaction which have more value of K proceeds towards
completion.
1. (b) Reversible reaction always attains equilibrium which proceeds 6. (d) K c is a characteristic constant for the given reaction.
both sides and never go for completion.
2. (c) In a reversible reaction some amount of the reactants remains 7. (c) Equilibrium constant is independent of original concentration
unconverted into products. of reactant.
3. (d) In lime klin CO 2 escaping regularly so reaction proceeds in 8. (a) K p is constant and does not change with pressure.
forward direction.
7. (b) The reaction is not reversible. 9. (a) For reaction A + 2B ⇌ C
[C] 0 .216
K   250 .
Equilibrium state [ A] [B] 2
0.06  0.12  0 .12

1. (c) When rate of forward reaction is equal to the rate of backward 11. (b) A + 2B ⇌C + 3D
reaction then equilibrium is supposed to be established.
[ pC] [ pD]3 0 .30  0 .50  0 .50  0 .50
2. (b) Equilibrium can be achieved only in closed vessel. K   18.75
4. (c) When rate of forward reaction is equal to rate of backward [ pA] [ pB]2 0 .20  0 .10  0 .10
reaction the reaction is said to be in equilibrium.
13. (a) PCl5 ⇌ PCl3  Cl 2
6. (d) At equilibrium rate of forward reaction is equal to the rate of 2 0 0
backward reaction.
7. (c) According to Le-chatelier principle when concentration of 2  60 2  40 2  40
reactant increases, the equilibrium shift in favour of forward 100 100 100
reaction.
Volume of container = 2 litre.
8. (b) At equilibrium, the rate of forward & backward reaction
become equal. 2  40 2  40

Kc  100  2 100  2  0 .266 .
Law of mass action 2  60
100  2
1. (b) According to law of mass-action, “at a given temperature, the
rate of a reaction at a particular instant is proportional to the 14. (d) n = 1 for this change
product of the active masses of the reactants at that instant So the equilibrium constant depends on the unit of
raised to powers which are numerically equal to the numbers of concentration.
their respective molecules in the stoichiometric equation
describing the reaction”. 15. (d) Unit of K p  (atm)n

3. (d) [HI] 
64 gm
 0 .25 Unit of Kc  (mole / litre)n
128  2 litre
Active mass is the concentration in moles/litre.  [mole / litre]0  0
8. (a) As we increase the concentration of substance, then speed of  10 3 
2
the reaction increases. 2  
9. (c) Chemical reaction quantitatively depend on the reactant and [ NO 2 ] 2
 2  10  6
product molecule. 16. (c) K    10  5 .
[N 2 O4 ]  .2  10 1
2
 
Law of equilibrium and Equilibrium constant
19. (b) For A + B ⇌ C + D
1. (d) Equilibrium constant for the reaction , 3A + 2B ⇌ C is [C] [D] 0.4  1
K  1.
K 
[C ]
. [ A] [B] 0 .5  0 .8
[ A]3 [B]2
2. (d) Suppose 1 mole of A and B each taken then 0.8 mole/litre of C and 20. (c) A+ B ⇌C+ D
D each formed remaining concentration of A and B will be (1 – Initial 1 1 0 0
0.8) = 0.2 mole/litre each.
remaining at equilibrium 0.4 0.4 0.6 0.6
[C] [D] 0 .8  0 .8
Kc    16.0
[ A] [B] 0 .2  0 .2 [C] [D] 0.6  0 .6 36
K    2 .25 .
[ A] [B] 0 .4  0 .4 16
3. (c) AB ⇌ CD
Initial conc. 4, 4 0 0 [ NH 3 ]2
21. (a) K
After T time conc. (4-2) (4-2) 2 2 [ N 2 ] [H 2 ]3

23. (d) A + B ⇌ C + D
 330 Chemical Equilibrium
x x 0 0 2 .5 4 1
2x 2x Molar  1 .25 2  0 .5
2 2 2
[C][D] 2 x . 2 x [0 .5]2
Kc   4 K  0 .05
[ A][B] x.x [1 .25]  [2]2
24. (d) N 2 O 4 ⇌ 2 NO 2 34. (b) CO  Cl 2 ⇌ COCl 2
1 0
(1  ) 2 0 .1 0.1 0.2
[CO ]  , [Cl 2 ]  , [COCl 2 ] 
total mole at equilibrium  (1   )  2  1   0 .5 0 .5 0.5
0 .2
[C 2 H 6 ] [mole / litre]
25. (b) K  [COCl 2 ] 0 .5 2
[C 2 H 4 ] [H 2 ] [mole / litre] [mole / litre]  0   25  10
[CO ] [Cl 2 ] 0 . 1 0 . 1 5

= litre/mole. or litre mole . –1

0 .5 0 .5
0 .2 0 .2
 35. (a) A+ B ⇌ C+ D
[PCl3 ] [Cl 2 ] 10 10 at equilibrium a a 2a 2a
27. (c) Kc    0 .04 .
[PCl5 ] 0.1 10  2a  2a
K 4
aa
[HI]2 x2
28. (b) Kc  ; 64  36. (a) H 2  I2 ⇌ 2HI
[H 2 ] [I2 ] 0 .03  0 .03
Initial conc. 4.5 4.5 0
x 2  64  9  10 4 x x 2x
from question 2x = 3
x  8  3  10 2  0.24 3
x is the amount of HI at equilibrium amount of I 2 at x   1.5
2
equilibrium will be So conc. at eqm. 4.5  1.5 of H 2
0.30  0.24  0.06  4.5  1.5 of I 2 and 3 of HI
Kf
29. (c) Kc  [HI]2 33
Kb K  1.
[I 2 ] [H 2 ] 3  3
K f  Kc  Kb  1.5  7.5  10 4  1.125  10 3 [H 2 ]2 [S 2 ] [0 .10]2 [0 .4 ]
37. (c) K   0 .016
30. (a) N 2  3H 2 ⇌ 2NH 3 [ H 2 S ]2 [0 .5]2

Initial conc. 1 3 0 [PCO ]2 [PO2 ] [0 .4 ]2  [0 .2]

38. (a) Kp  2
  0 .0888 .
at equilibrium 1-0.81 3-2.43 1.62 [PCO 2 ] [0 .6]2
0.19 0.57
39. (d) K f  1.1  10 2 ; Kb  1.5  10 3
28
No. of moles of N 2   1 mole Kf 1 .1  10 2
28 Kc    7 .33 .
Kb 1 .5  10  3
6
No. of moles of H 2   3 mole 40. (a) 2HI ⇌ H 2  I2
2 100 0 0
50 25 25
27.54
No. of moles of NH 3   1 .62 mole [H 2 ] [I2 ] 25  25
17   0 .25 .
[HI]2 50  50
[ NH 3 ]2 [1 .62]2
Kc   =75 41. (d) A  B  2C
[ N 2 ] [H 2 ]3 [0 .19] [0 .57]3 (3  0.75 ) (1  0.75 ) 1 .5
2
[C] (1 .5)2 2 .25
31. (b) Kc 
[YX 2 ]

2

1
 0.0625 . K    4 .0 .
[ X ]2 [Y ] 4  4  2 16 [ A] [B] 2 .25  0 .25 2 .25  0 .25

32. (d) NH 4 HS ⇌ NH 3 ( g )  H 2 S ( g ) K
42. (d) 6 HCHO C6 H12 O6 forward reaction
2

a 0 .5 atm
a x 0 .5 x x K
C6 H12 O6 6 HCHO backward reaction
1

Total pressure  0.5  2 x  0.84

16
 1 
16
i.e., x  0.17  1 
K2    ; K2   22 
K p  PNH 3 .PH 2S  (0.67).(0.17) =0.1139  K1   6  10 
K 2  1.6  10 4 M
33. (c) A + 2B ⇌ 2C
Initial conc. 2 3 2 [HI] 2 [0 .7] 2
43. (b) Kc    49
at eqm. 2.5 4 1 [H 2 ] [I 2 ] [0 .1] [0 .1]
 Chemical Equilibrium 331

[ NH 3 ]2 According to eq. (i) 2 mole of ammonia are present & to

44. (c) Kc  produce 2 mole of NH 3 , we need 1 mole of N 2 and 3 mole
[ N 2 ] [H 2 ]3
of H 2 hence 2  1  1 mole of N 2 and 4  3  1 mole of
x2
2 .37  10  3   x 2  0 .12798 H 2 are present at equilibrium in vessel.
[2] [3]3
61. (d) 2SO 2 (g)  O 2 (g) ⇌ 2SO 3 (g)
x = 0.358 M.
For 1dm 3 R  k[SO 2 ]2 [O 2 ]
45. (d) A  B ⇌ 2C
2
 1  1 
[C]2 [0 .6]2 R  K     1
Kc   9  T  1 
[ A] [B] [0 .2] [0 .2]
2
46. (a) H 2 + I2 ⇌ 2 HI 1  1  1
For 2dm 3 R  K     
15 5.2 0 2 2 8
(15–5) (5.2–5) 10 So, the ratio is 8 : 1
[HI]2 10  10 1 1

KC    50 [C][D] 3 3 1
[H 2 ][I2 ] 10  0 .2 62. (d) K     0 .25
[ A][B] 2 2 4
47. (c) Rate of backward reaction = Rate of forward reaction 
3 3
[HI]2 (28)2
48. (b) Kc    32.66 So, K  0.25
[H 2 ] [I2 ] 8  3

63. (b) Given, CaCO 3 (s)  CaO(s)  CO 2 (g) 
49. (a) N 2(g)  O 2(g) ⇌ 2 NO (g) ; n  2  2  0
50. (b) The rate of forward reaction is two times that of reverse C(s)  CO 2 (g) ⇌ 2CO (g)
reaction at a given temperature and identical concentration
[ pCO ]2
Kequilibrium is 2 because the reaction is reversible. So Kp 2  ; pCO  [Kp 1  Kp 2 ]
[ pCO 2 ]
K1 2
K  2.
K2 1 pCO  [8  10 2  2]  16  10 2  4  10 1  0.4
Kf Kf 10 5 64. (b) N 2 (g)  O 2 (g) ⇌ 2 NO (g)
52. (b) Kc  Kb    10 3
Kb Kc 100 [ NO ]2
Kc   4  10 4
[ NO 2 ] 2
4  (0 .05) 2
[ N 2 ][O 2 ]
53. (c) Kc    4  0 .05  0 .2
[N 2 O4 ] 0 .05 1 1
NO 2 ⇌ N 2 (g )  O 2 (g )
3
[ N 2 ][H 2 ] 1 3
3 2 2
54. (d) 2 NH 3 ⇌ N 2  3H 2 ; K   27
initial 2 0 0 [ NH 3 ]2 1 [ N 2 ]1 / 2 [O2 ]1 / 2 1 1
at. equil . 1 1 3 Kc   
[PCl3 ] [Cl 2 ] 0 .2  x
[ NO ] Kc 4  10  4
56. (c) K c    0 .5 , x  1
[PCl5 ] 0 .4 1 100
   50
57. (c) N 2  3H 2 ⇌ 2NH 3 2  10 2 2
30 30 0 65. (d) P4 (s)  5 O 2 (g) ⇌ P4 O10 (s)
30-x 30-3x 2x [P4 O10 (s)]
10 Kc 
2x = 10 ; x = 5 [P4 (s)][O 2 (g)]5
2 We know that concentration of a solid component is always
N 2  30  5  25 litre 1
taken as unity K c 
H 2  30  3  5  15 litre [O 2 ]5
NH 3  2  5  10 litre 66. (d) H2  I2 ⇌ 2HI
2 2 0 . 50
[ NO 2 ] 2
[1 .2  10 ] 0 .4
0 .4 0 .25  0 .15
0 .4
58. (c) K    0.3  10 2  3  10 3 0 .4 0 .25  0 .15 / 2 0 .50 / 2
[ N 2 O4 ] [4 .8  10  2 ]
2
22  0 .5 
59. (a)  3 .2  0 .704 [HI]2  2  0.5  0 .5
100 Kc       11.11
 at equil. moles of HI =3.2–0.704 = 2.496 [H 2 ][I 2 ]  0 . 15   0 . 15  0 .15  0 .15
 2  2 
60. (c) N 2  3H 2 ⇌ 2NH 3 ….. (i)   
at t  0 56 gm 8 gm 0 gm 67. (d) NH 2 COONH 4 ⇌ 2 NH 3  CO 2
= 2mole 4 mole 0mole Dd
 where D is the density (initial)
at equilibrium 2  1 4  3 34 gm (n  1) d
= 1 mole = 1 mole = 2 mole
 332 Chemical Equilibrium
mol. wt 78 9. (a) For the reaction,
D   39
2 2 CaCO ⇌ CaO + CO
3(g) ( s) 2(g)

n  no. of product = 3 d  final density K = PCO 2 and K = [CO ]

p C 2

39  13
  1 , so   1 ( [CaCO ] = 1 and [CaO] = 1 for solids]
(3  1)13
3

According to Arrhenius equation we have

a b 0
68. (a) N 2  3 H 2 ⇌ 2 NH 3 K  Ae H r / RT
(a  x ) (b  3 x ) (2 x ) Taking logarithm, we have
50% Dissociation of N 2 take place so, H ro
log K p  log A 
2  50 RT (2 .303)
At equilibrium  1 ; value of x  1
100 This is an equation of straight line. When log K is plotted p

against 1 / T. we get a straight line.

[2]2 4 4
Kc  3
 so, K c 
[1][3] 27 27
( log K p  log pCO 2 )
69. (c) The equilibrium constant does not change when concentration log pCO 2
of reactant is changed as the concentration of product also get
changed accordingly.
70. (d) We know that PV  nRT
1 / Tline = log A, slope = –∆H° / 2.303 R
The intercept of this
1 r

P become P & V bcome 2 V so, Knowing the value of slope from the plot and universal gas
2
constant R, ∆H ° can be calculated.
r

1
P  2 V  PV  nRT (Equation of straight line : Y = mx + C. Here,
2
So there is no effect in equation. H ro  1 
log K p      log A
71. (abcd)All options are true for that equilibrium. 2 .303 R  T 
72. (a) H 2(g)  CO 2(g) ⇌ CO(g)  H 2O(l) Y m x C
n
Initial conc. 1 1 0 0 10. (b) K p  Kc (RT ) ; When n  2  (2  1)  1 , i.e. negative,
At equili (1– x) (1 – x) x x K p  Kc .
pCO . p H 2 O x.x x2
Kp    [SO 3 ] [SO 2 ]2 [O 2 ] 1
p H 2 . pCO 2 (1  x )(1  x ) (1  x )2 11. (c) K1  and K 2  ; K2  .
[SO 2 ] [O 2 ]12
[SO 3 ]2 K12
Kp & Kc Relationship and Characteristics of K 13. (c) Reaction is reversed. Hence
1
1. (a) n p  nr then K p  K c K  4 .2  10 2
(2 .4  10  3 )
where n p = no. of moles of product
[Pco ]2 44
14. (c) Kp   8.
nr = no. of moles of reactant. [PCO ] 2
2

[ NO 2 ] [ NO ] 2 [O 2 ] 15. (d) K c1 for H 2  I2 ⇌ 2HI is 50

2. (d) K1  ; K2 
[ NO ][O 2 ]1 / 2 [ NO 2 ] 2
K c2 for 2HI ⇌ H 2  I2
[ NO 2 ] 2
1 [ NO 2 ] 1
    1 1
2
[ NO ] [O 2 ] K 2 [ NO ] [O 2 ]1 / 2 K2 K c2    0 .02
K c1 50
1 1
 K1  ; K2  . 16. (c) K p  Kc (RT )n
K2 K 12
n  1 for reaction 2SO 2  O2 ⇌ 2SO 3
3. (a) K p  K c (RT )n  26 (0.0821  523)1  0.61 .
So for this reaction K p is less than K c .
n g  1  2  1
5. (d) In presence of little H 2 SO 4 (as catalyst) about 2/3 mole of 17. (c) K p  Kc (RT )n ; n  2  2  0
each of CH 3 COOH and C 2 H 5 OH react to form 2/3 mole 18. (c) For the reaction H 2  I2 ⇌ 2HI
of the product at equilibrium. n  0
6. (d) K1 for reaction 2HI ⇌ H 2  I2 is 0.25 K 2 for reaction So K p  K c 50.0
1 1
H 2  I2 ⇌ 2HI will be K 2   4 19. (d) For reaction 2SO 3 ⇌ O2  2SO 2
K1 0 .25
n is + ve so K p is more than K c .
Because II reaction is reverse of I .
nd st
 Chemical Equilibrium 333

By K p  Kc (RT )n K 2 H [T2  T1 ]

35. (b) 2.303 log 
K1 R T1  T2
20. (c) n =2-1=1
H  +ve for the reaction
K p  Kc (RT )
36. (d) N 2  3H 2 ⇌ 2 NH 3
21. (c) For this reaction there is no change in equilibrium constant by 4 2
change of volume.
n = 2 – 4 = – 2
22. (c) If n =0 then K p  K c
K p  K c [RT ]n ; K p  Kc [RT ]2
n
23. (a) k p  k c (RT )
Kp 1 .44  10 5
n  3  2  1 ; k p  k c . Kc  2

[RT ] [0 .082  773] 2
24. (d) Equilibrium constant depends upon temperature. 37. (d) Catalyst does not affect equilibrium constant.
25. (d) 2NOCl = 2NO + Cl
(g) (g) 2(g) 38. (d) K for dissociation of HI =?
K = K (RT)
H 2  I2 ⇌ 2HI
∆n

p C

K = 3  10 (0.0821  700) = 172.41  10

p
–6 –6

1
= 1.72  10 –4
K a  50 , K b   0 .02
50
1
27. (b) K   K n ; Hence n  39. (b) 2 SO 2  O 2 ⇌ 2SO 3 for this reaction
2 3 2

 K  K1 / 2  K n = –1 ;  K c  K p
29. (c) 2NO 2 ⇌ 2 NO  O 2 ……(i) 40. (b) CaCO 3(s) ⇌ CaO(s)  CO 2(g)
12
K  1.6  10 K p  PCO 2
1
NO  O 2 ⇌ NO 2 ……(ii) Solid molecule does not have partial pressure so in calculation
2 of K p only PCO 2 is applicable.
Reaction (ii) is half of reaction (i)
1 3
[ NO ]2 [O 2 ] 41. (d) NH 3 ⇌ N2  H2
K ……(i) 2 2
[ NO 2 ]2
[ N 2 ]1 2 [H 2 ]3 2 1 3
[ NO 2 ] Kc  and N 2  H 2 ⇌ NH 3
K  '
……(ii) NH 3 2 2
[ NO ] [O 2 ]1 2
[ NH 3 ]
On multiplying (i) and (ii) Kc 
[ N 2 ]1 2 [H 2 ]3 2
[ NO ]2 [O 2 ] [ NO 2 ] [ NO ] [O 2 ]1 2 1
KK  '
2
 12
  ' 1
[ NO 2 ] [ NO ] [O 2 ] [ NO 2 ] K So for dissociation 
Kc
1 1 1
K  K'  ; K ; K'  . 22
K' K '2 K 42. (b) Given x  and a  3.2
100
30. (b) K p  Kc (RT )n ; n  1
 22 
[HI ]at equilibrium  3 .2 1    2 .496
So K c will be less than K p .  100 
43. (b) K c does not depend upon initial concentration of reactants or
32. (d) K 1 for N 2  3H 2 ⇌ 2NH 3
product.
1 3
K 2 for NH 3 ⇌ N2  H2 44. (d) K p and K c are characteristic for a given reaction if
2 2
n  0 then there is no change.
[ NH 3 ]2 [ N ]1 2 [H 2 ]3 2
K1  K 2   2 [ NO ]2 [O 2 ] [ NO 2 ]
[ N 2 ] [H 2 ]3
[ NH 3 ] 45. (c) K c1   1 .8  10  6  K c2 
[ NO 2 ]2 [ NO ] [O 2 ]1 2
1 1
K1  K 2  ; K2  1 1
K2 K1 K c1  2
; 1 .8  10  6   K c2  7.5  10 2
K c2 K c2 2
34. (a) K p  Kc (RT )n ; n  2  4  2
[H 2 S ] [HBr]2
46. (c) K1  ; K2 
K p  6  10 2  (0.0812  773)2 [H 2 ] [S 2 ]12
[H 2 ] [Br2 ]

6  10 2 [HBr]2  [S 2 ]1 2 K 2
Kp   1 .5  10  5 . K3  ;  K3
(0 .0812  773)2 [Br2 ] [H 2 S ] K1
 334 Chemical Equilibrium

p2 p2 1 1
N 2  O 2 ⇌ NO
47. (b) Kp  ; 0 .11   p 2  0 .44 ……(ii)
4 4 2 2
For equation number (i)
or p  0.44  0.66444  0.665 atm
[ NO ]2
50. (a) C12 H 22 O11(s)  12O2(g)  12CO 2(g)  11H 2 O K1  ….. (iii)
[ N 2 ][O 2 ]
n  12  12  0 For equation number (ii)
51. (a) In this reaction gaseous molecule count [ NO ]
K2  …... (iv)
MgCO3  MgO(s)  CO 2(g) [ N 2 ]1 / 2 [O 2 ]1 / 2
K p  PCO 2 From equation (iii) & (iv) it is clear that

53. (a) K p  Kc [RT ]n ; n  1, Kc  26 K 2  (K1 )1 / 2  K1 ; Hence, K 2  K1

ng
R  0.0812, T  250  273  523 K 66. (b) K p  K c [RT ]
K p  26[0.0812  523]1  0.605  0.61 n g  1  1.5  0.5

55. (a) 2 AB ⇌ A2  B2 Kp
K p  K c [RT ]1 / 2   [RT ]1 / 2
[ A 2 ] [B 2 ] Kc
Kc 
[ AB]2 67. (b) N 2(g)  O 2(g) ⇌ 2 NO (g)
1 1
For reaction AB ⇌ A2  B2 K c  0.1, K p  K c (RT )n
2 2
n  0, K p  K c  0.1
[ A 2 ]1 2 [B 2 ]1 2
Kc '  ; K c  K c  49  7 .
'
[ AB] 68. (c)
A + 3B 4C
56. (a) For this reaction n is negative & H is positive so it take ⇌
forward by decrease in temperature. a b 0
57. (b) Chemical equilibrium of reversible reaction is not influenced by (a – x) (b – 3x) 4x
catalyst. It is affected by pressure, temperature & concentration
[C]4 4 x .4 x .4 x .4 x
of reactant. KC  
[ A][B]3 (a  x )(b  3 x )
58. (c) H is positive so it will shift toward the product by increase
in temperature. Given a  b, a  x  4 x  a  5 x  b
59. (c) CO(g)  Cl 2 (g) COCl 2 (g)
4 x .4 x .4 x .4 x 4 x .4 x .4 x .4 x
n  1  2  1 KC   8.
(5 x  x )(5 x  3 x ) 4 x .2 x .2 x .2 x
Kp 1 69. (b) Equilibrium pressure = 3atm
K p  K c [RT ]n ;   [RT ]1 
Kc RT
NH 4 COONH 2(s) ⇌ 2 NH 3(g)  CO 2(g)
60. (c) H is positive so reaction move forward by increase in
temperature & value of n  3  2  1 is positive so it K p  p NH
2
3
. p CO 2  3 2 .3  27
forward with decrease in pressure.
61. (b) 2 A(g) 3C(g)  D(s) Activation energy, Standard free energy and
For this reaction, n g  3  2  1 Degree of dissociation and Vapour density
Kp Kp Normal molecular weight
 K p  K c [RT ]1 or  RT or K c  1. (b) =1+
Kc RT experiment al molecular wt.
62. (a) According to Le-Chatelier principle exothermic reaction is
forwarded by low temperature, in forward direction number of NH 4 Cl ⇌ NH 3  HCl
moles is less, hence pressure is high.
nor.mol.wt .
63. (d) In this reaction H is negative so reaction move forward by   1 Experimental Molecular wt =
2
decrease in temperature while value of n  2  3  1 i.e.,
negative so the reaction move forward by increase in pressure. 2. (b) If G o  0
64. (a) PCl5 (g) ⇌ PCl3 (g)  Cl 2 (g) G o  2.303 RT log K p
For this reaction n  2  1  1 log K p  0 (log1  0)
Value of n is positive so the dissociation of PCl5 take
Kp  1 .
forward by decrease in pressure & by increase in pressure the
dissociation of PCl5 decrease. 5. (d) G o  2.303  8.314  10 3  298 log K p
65. (b) N 2  O2 ⇌ 2 NO …..(i)
 Chemical Equilibrium 335

1.7  2.303  8.314  10 3  298  log K p 20. (b) H 2 X 2  heat ⇌ 2HX.

Reaction is endothermic and volume increasing in forward
K p  0 .5
direction so according to Le chatelier’s principle for formation
6. (a) Equilibrium shifts backward by Le-chatelier’s principle. of HX, Temperature of the reaction should be high and
7. (c) Decreases the activation energy of both forward and backward pressure should be low.
reaction. 21. (b) According to Le chatelier’s principle.
8. (d) Equilibrium constant changes with temperature, pressure and 22. (d) In reaction CO  3H 2 ⇌ CH 4  H 2 O
the concentration of either reactant or product.
Volume is decreasing in forward direction so on increasing
9. (a) As we know that, G o  2.303 RT log K p pressure the yield of product will increase.
25. (a) In endothermic reaction rate of forward reaction can be
Therefore, G o  2.303  (8.314)  (298) increased by raising temperature.
26. (a) Being endothermic, the forward reaction is favoured by high
(log 2.47  10 29 ) temperature.
G o  16,3000 J mol 1  163 KJ mol 1 27. (c) According to Le chatelier’s principle.
28. (b) On adding more PCl5 , equilibrium shifts forward.
29. (a) According to Le chatelier’s principle.
Le-Chaterlier principle and It’s application
30. (b) Increase in pressure causes the equilibrium to shift in that
direction in which no. of moles (volume) is less.
2. (a) N 2  O 2 ⇌ 2NO; Q cal 32. (b,c) According to Le-chatelier’s principle.
The above reaction is endothermic so for higher production of 37. (d) By increasing the amount of F2 in the reaction the amount of
NO, and the temperature should be high. ClF3 increases.
4. (c) At low pressure, reaction proceeds where volume is increasing. 39. (b) According to Le chatelier’s principle when we increase pressure
This is the favourable condition for the reaction. reaction proceeds in that direction where volume is decreasing.
PCl5 ⇌ PCl3  Cl 2 . 40. (a) Factors affecting equilibrium are pressure, temperature and
concentration of product or reactant.
6. (c) Reaction is exothermic and volume is decreasing from left to
42. (b) According to Le chatelier’s principle.
right so for higher production of SO 3 there should be low
43. (d) Increase in volume, i.e., decrease in pressure shifts the
temperature and high pressure. equilibrium in the direction in which number of moles
7. (a) Ice ⇌ Water increases (n positive)
more volume less volume
46. (d) At constant volume. Three is no change in concentration
On increasing pressure, equilibrium shifts forward. (closed container).
8. (c) Exothermic reaction is favoured by low temperature to proceed 1
47. (c) H 2 O(g) ⇌ H 2(g )  O 2( g )
in forward direction. 2
9. (a) Effect of catalyst is that it attains equilibrium quickly by In this reaction volume is increasing in the forward reaction. So
providing a new reaction path of low activation energy. It does on increasing temperature reaction will proceed in forward
not alter the state of equilibrium. direction.
11. (a) On increasing temperature equilibrium will shift in forward 48. (b) When temperature increases precipitation of sodium sulphate
direction due to decrease in intermolecular forces of solid. takes place. Because reaction is exothermic so reverse reaction
will take place.
12. (c) Both n and H are negative. Hence, high pressure and low 49. (a) For high yield of ammonia low temperature, high pressure and
temperature will forward reaction. high concentration of the reactant molecule.
13. (b) Exothermic reaction, favoured by low temperature. 53. (c) Since n  0 .
14. (c) n  0 , No effect of pressure. 54. (a) The rate of backward reaction favoured by increase of pressure
15. (b) The reaction is endothermic in reverse direction and hence in the reaction as n is positive
increase in temperature will favour reverse reaction. PCl5 ⇌ PCl3  Cl 2
16. (c) A reaction is in equilibrium it will shift in reverse or backward
direction when we increase the concentration of one or more 55. (a) H 2(g)  I2(g ) ⇌ 2HI
2
product (from Le chatelier’s principle). 2

17. (a) According to Le chatelier’s principle. n  0 ;  K c  K p

18. (c) The reaction takes place with a reduction in number of moles
(volume) and is exothermic. So high pressure and low 56. (c) Solid + liquid ⇌ Solution H =+ve
temperature with favour the reaction in forward direction Increase in temperature favours forward reaction.
19. (b) At equilibrium, the addition of (CN ) would decrease the 57. (a) Addition of an inert gas of constant volume condition to an
equilibrium has no effect.
(H  ) ion concentration to produce more and more HCN to
58. (b) Le chatelier principle is not applicable to solid-solid
nullified the increase of CN  aq . equilibrium.
 336 Chemical Equilibrium
59. (a) ABQ ⇌ CD K  1 1.8  10 6  7.5  10 2
2 2

The reaction is endothermic so on increase temperature 5. (d) Conc. is not known so we can’t calculate.
concentration of product will increase.
6. (a) 2SO 3 ⇌ 2 SO 2  O 2
60. (a) In that type of reaction the state of equilibrium is not effected 2 3
by change in volume (hence pressure) of the reaction mixture.
61. (c) N 2  O2 ⇌ 2 NO ; n  0 n  3  2  1 ; K p  1.80  10 3

65. (c) High temperature and low pressure. [RT ]n  (8.314  700)1
66. (d) High temperature and excess concentration of the reactant
concentration. Kp 1 .8  10 3
Kc  
68. (c) Low temperature and high pressure. (RT )n (8 .314  700)1

69. (a) H 2  I2 ⇌ 2HI  n  2  2  0 .  3.09  10 7 mole-litre.

70. (d) Low temperature and low pressure. 7. (c) N 2 O 4 ⇌ 2 NO 2
73. (c) It is an exothermic reaction hence low temperature and 0 .1 0

increasing pressure will favour forward reaction (.1-) 2

Critical Thinking Questions ∵ P  0.1

If V and T are constant (P0.1+ )
 20   20  P  (0.1   ) / 0.1

[PCl 3 ][Cl 2 ]  100   100 
1. (b) Kc   [2 ]2  P  40 2
[PCl5 ]  80  Kp    or K p   0 .14
 100  [0 .1   ]  0 .1    [0 .1   ]
 
  0.017
0 .2  0.2 0.04
   0 .05
0 .8 0.8 NO 2  0.017  2  0.034 mole
2. (b) 2NH 3 ⇌ N 2  3H 2 8. (d) CH 3 OH  CO  2H 2
Initial mole a 0 0
[H 2 ]2 [CO ] 0 .1  0 .1  1 0 .01 10  10 3
Mole at equilibrium (a  2 x ) x 3x   
[CH 3 OH ] 2 2 2
Initial pressure of NH 3 of a mole = 15 atm at 27 o C
 5  10 3 .
The pressure of 'a' mole of NH 3  p atm at 347 C o
9. (d) AB + CD ⇌ AD + CD
15 p
  mole at t  0 1 1 0 0
300 620
 p  31 atm  3  3 3 3
Mole at equilibrium  1    1   ⇌    
 4  4 4 4
At constant volume and at 347 o C , mole  pressure
a  31 (before equilibrium) 0.25 0.25 ⇌ 0.75 0.75

 a  2 x  50 (after equilibrium) 0.75  0.75 0.5625

Kc   9
0.25  0.25 0.0625
a  2 x 50
  10. (d) According to Le-chatelier’s principle.
a 31
11. (d) K p (equilibrium constant) is independent of pressure and
19
 x a concentration.
62
2x Assertion & Reason
 % of NH 3 decomposed   100
a
2. (e) Assertion is false but reason is true.
2  19 a
  100  61.33% K p  K c for all reaction.
62  a
K p  K c (RT )n
3. (d) K p  K c (RT )n R = Gas constant
n  number of moles of products – number of moles of
Kp 1 .3  10 3 reactants in the balanced chemical equation.
Kc    7 .4  10  2
(RT )n (0 .0821  700)1 So, if for a reaction n  0 . Then K p  K c
4. (b) Reaction is reversed and halved. 3. (e) Assertion is false but reason is true.
 Chemical Equilibrium 337

K c  [H 2 O]2 , because concentration of solids is taken to be 9. (a) H 2(g)  I2(g) ⇌ 2 HI(g )

unity.
4. (a) Both assertion and reason are true and reason is the correct KC 
HI2
explanation of assertion. H 2 I2 
CO (H 2 O)62 (Pink) while CoCl 42  (blue). So, on For reverse reaction 2 HI(g ) ⇌ H 2(g)  I2(g)
Cooling because of Le-chatelier’s principle the reaction tries to
over come the effect of temperature.
KC 
H 2 I2   1 .
5. (e) Assertion is false but reason is true. HI2 KC
[C]c [D]d 10. (c) The value of K depends on the stoichiometry of reactants and
aA  bB ⇌ cC  dD , Qc 
[ A]a [B]b products at the point of equilibrium. For e.g., if the reaction is
multiplied by 2, the equilibrium constant is squared.
If Qc  K c , reaction will proceed in the direction of reactants.
11. (d) Catalyst does not affect the final state of the equilibrium. It
If Qc  K c , reaction will move in direction of products. enables the system to attain equilibrium state earlier by
If Qc  K c , the reaction mixture is already at equilibrium. providing an alternative path which involve lower energy of
activation.
6. (c) Assertion is true but reason is false. This is based on common
ion effect. p H3 2  p N 2 (atm)3 (atm)
12. (e) Kp    (atm)2
p NH 3 (atm)2
NaCl ⇌ Na   Cl  ; HCl ⇌ H   Cl 

Concentration of Cl  ions increases due to ionisation of or n  4  2  2 .

 
HCl which increases the ionic product [ Na ][Cl ] . This Unit of K p for given reaction  (atm)2 .
result in the precipitation of pure NaCl .
13. (c) According to Le-Chatelier's principle endothermic reaction
7. (b) Both assertion and reason are true and reason is not the favours increase in temperature. However exothermic reaction
correct explanation of assertion, solid+heat ⇌ liquid, so on favours decrease in temperature.
heating forward reactions is favoured and amount of solid will
14. (d) K p  Kc (RT )n ; where n  (l  m)  (x  y)
decrease.
Concentration of solids and liquids is taken to be unity.
8. (a) aA  bB ⇌ cC  dD
15. (e) Increase in pressure favours melting of ice into water because
KC 
C C Dd at higher pressure melting point of ice is lowered.
A a B b 16. (e) As assertion is exothermic, low temperature favours forward
reaction. High pressure favours forward reaction as it is
For 2aA  2bB ⇌ 2cC  2dD accompanied by decrease in the number of moles.

KC 
C 2c D2 d .
17. (e) There is no change in number of gas molecules. Therefore the
A 2a B 2b expression for K is independent of volume. Hence K will remain
same.
 338 Chemical Equilibrium

1. One mole of SO 3 was placed in a litre reaction vessel at a certain Where K c is the equilibrium constant
temperature. The following equilibrium was established 2SO 3 ⇌ 8. In the thermal dissociation of PCl5 the partial pressure in the
,

2SO 2  O 2 gaseous equilibrium mixture is 1.0 atmosphere when half of PCl5 is

At equilibrium 0.6 moles of SO 2 were formed. The equilibrium found to dissociate. The equilibrium constant of the reaction (K p )
constant of the reaction will be [MP PMT 1991] in atmosphere is [JIPMER 2002]
(a) 0.36 (b) 0.45 (a) 0.25 (b) 0.50
(c) 0.54 (d) 0.675 (c) 1.00 (d) 0.3
2. For the following homogeneous gas reaction 4 NH 3  5 O 2 ⇌ 9. HI was heated in a closed tube at 440 o C till equilibrium is
4 NO  6 H 2 O , the equilibrium constant K c has the dimension obtained. At this temperature 22% of HI was dissociated. The
of [CPMT 1990; MP PET/PMT 1998] equilibrium constant for this dissociation will be
[MP PET 1988, 92; MNR 1987; UPSEAT 2000]
(a) Conc 10 (b) Conc 1 (a) 0.282 (b) 0.0796
(c) Conc 1 (d) It is dimensionless (c) 0.0199 (d) 1.99
3. Consider the imaginary equilibrium 10. The following equilibrium exists in aqueous solution CH 3 COOH
4A + 5B ⇌ 4X + 6Y ⇌ CH 3 COO   H  . If dilute HCl is added without a change
The equilibrium constant K c has the unit [RPMT 2000] in temperature, then the [MNR 1987]
(a) Mole litre 2 -2
(b) Litre mole -1
(a) Concentration of CH 3 COO  will increase
(c) Mole litre -1
(d) Litre mole
2 -2

(b) Concentration of CH 3 COO  will decrease

4. For the reaction CO(g)  2 H 2 (g) ⇌ CH 3 OH(g) , true condition
(c) Equilibrium constant will increase
is
(d) Equilibrium constant will decrease
(a) K p  Kc (b) K p  Kc
11. Which of the following is not favourable for SO 3 formation
(c) K p  Kc (d) K c  0 but K p  0
2SO 2 (g)  O 2 (g) ⇌ 2SO 3 (g); H  45.0 kcal
1 Kp [IIT 1984; MP PET 1997]
5. For the reaction CO (g)  O 2 (g ) ⇌ CO 2 (g) ; is
2 Kc (a) High pressure
equivalent to [MP PET/PMT 1998; AIEEE 2002] (b) High temperature
(a) 1 (b) RT (c) Decreasing SO 3 concentration
1 (d) Increasing reactant concentration
(c) (d) (RT )1 / 2
RT 12. 120 gm of urea are present in 5 litre solution, the active mass of
6. 2 N 2 O5  4 NO 2  O 2 what is the ratio of the rate of urea is [MP PMT 1994]
(g) (g) (g) (a) 0.2 (b) 0.06
decomposition of N 2 O 5 to rate of formation of NO 2 (c) 0.4 (d) 0.08
[DCE 2003] 13. For the system 2 A(g)  B(g) ⇌ 3 C(g) , the expression for
(a) 1 : 2 (b) 2 : 1 equilibrium constant K is [NCERT 1973; DCE 1999]
(c) 1 : 4 (d) 4 : 1 [2 A]  [ B ] [ A] 2  [ B]
7. The reaction quotient (Q) for the reaction (a) (b)
[3 C ] [C ]3
N 2(g)  3 H 2(g) ⇌ 2 NH 3(g)
[3 C ] [C ]3
(c) (d)
[2 A]  [ B ]
2
is given by Q 
[ NH 3 ]
. The reaction will proceed from right [ A] 2  [ B]
[ N 2 ][H 2 ]3 14. If concentration of reactants is increased by ' x ' , then K becomes[AFMC 1997]
to left is [CBSE PMT 2003]
(a) ln ( K / x ) (b) K / x
(a) Q = 0 (b) Q = K c
(c) Kx (d) K
(c) Q < K c (d) Q > K c

(SET -8)
 Chemical Equilibrium 339

1. (d) 2 SO 3 ⇌ 2 SO 2  O 2 9. (c) 2HI ⇌ H 2  I2

(10 .6 ) (0 .6 ) (0 .3 )
Initial conc. 2 moles 0 0
[SO 2 ]2 [O 2 ] 0 .6  0 .6  0 .3
Kc    0 .675 . at equilibrium
22
 2 0.22 0.22
[SO 3 ] 0 .4  0 .4 100
2. (b) K has the units of (conc.)n , where n  10  9  1  2  0.44  1.56
3. (c) Unit of K c  (unit of concentration) [H 2 ] [I2 ] 0 .22  0 .22
K   0 .0199 .
n

[HI]2 [1 .56]2
= (mole litre ) –1 n

10. (b) When adding HCl in CH 3 COOH solution the concentration

n = 10 – 9 = 1
of H  is increased. So reaction is proceed in reverse direction
 K c  mol Litre . –1

and the concentration of CH 3 COO  is decreased.

4. (c) When nr  n p then K p  K c
11. (b) The reaction is exothermic so high temperature will favour
where nr = no. of moles of reactant backward reaction.
moles
n p = no. of moles of product. 12. (c) Active mass 
litre
1
5. (c) For CO  O 2 ⇌ CO 2 
wt.in gm/molecular wt. 120 60 2
   .4
2 V in litre 5 5
1 1
1 1  Kp 1
K p  K c (RT ) 2  K c (RT ) 2 ;  [C]3
Kc RT 13. (d) K .
[ A] 2 [ B ]
6. (b) 2 N 2 O5  HNO 2  O2 14. (d) There is no effect of change in concentration on equilibrium
Rate of decomposition of N 2 O5 constant.

1 K[ N 2 O 5 ]
 .
2 dt
1 d[ NO 2 ]
Rate of formation of NO 2  .
4 dt
 Ratio = 2 : 1
7. (d) If Q  K c reaction will proceed right to left to decrease
concentration of product.

***

8. (d) PCl5 ⇌ PCl3  Cl 2

Initial conc. 1 0 0
At equilibrium 0.5 0.5 0.5
Px 2 1  0 .5  0 .5 0 .5  0.5 1
Kp      0.3
(1  x )
2
[1  (0.5)2 ] 0.75 3
 340 Ionic Equilibrium

Chapter

9
Ionic Equilibrium

In chemical equilibrium we studied reaction involving (ii) Degree of ionization( )

molecules only but in ionic equilibrium we will study reversible
reactions involving formation of ions in water. When solute is polar
covalent compound then it reacts with water to form ions.
Electrical conductors
Substances, which allow electric current to pass through them, are
known as conductors or electrical conductors. Conductors can be divided
into two types,
(1) Conductors which conduct electricity without undergoing any
chemical change are known as metallic or electronic conductors.
(2) Conductors which undergo decomposition (a chemical change)
when an electric current is passed through them are known as electrolytic
conductors or electrolytes.
Number of dissociated molecules

Total number of molecules of electrolyte before dissociation
(iii) At moderate concentrations, there exists an equilibrium
between the ions and undissociated molecules, such as, NaOH ⇌ Na 
 OH  ; KCl ⇌ K   Cl 
This equilibrium state is called ionic equilibrium.
(iv) Each ion behaves osmotically as a molecule.
(2) Factors affecting degree of ionisation
(i) At normal dilution, value of  is nearly 1 for strong electrolytes,
while it is very less than 1 for weak electrolytes.

Electrolytes are further divided into two types on the basis of their (ii) Higher the dielectric constant of a solvent more is its ionising
strengths, power. Water is the most powerful ionising solvent as its dielectric constant
is highest.
(i) Substances which almost completely ionize into ions in their
aqueous solution are called strong electrolytes. Degree of ionization for this 1 1
(iii)   
type of electrolyte is one i.e.,   1 . Con. of solution wt. of solution

For example : HCl, H 2 SO 4 , NaCl, HNO3 , KOH , NaOH,  Dilution of solution  Amount of solvent
HNO3 , AgNO3 , CuSO 4 etc. means all strong acids, bases and all types (iv) Degree of ionisation of an electrolyte in solution increases with
rise in temperature.
of salts.
(v) Presence of common ion : The degree of ionisation of an
(ii) Substances which ionize to a small extent in their aqueous
electrolyte decreases in the presence of a strong electrolyte having a
solution are known as weak electrolytes. Degree of ionization for this types
common ion.
of electrolytes is   1 .
Ostwald's dilution law
For example : H 2O, CH 3COOH , NH 4 OH, HCN, Liq. SO 2 ,
The strength of an acid or a bas is experimentally measured by
HCOOH etc. means all weak acids and bases. determining its dissociation or ionisation constant.
When acetic acid (a weak electrolyte) is dissolved in water, it
Arrhenius theory of electrolytic dissociation
dissociates partially into H  or H 3 O  and CH 3 COO  ions and the
(1) Postulates of Arrhenius theory
following equilibrium is obtained,
(i) In aqueous solution, the molecules of an electrolyte undergo
CH 3 COOH  H 2O ⇌ CH 3 COO   H 3 O 
spontaneous dissociation to form positive and negative ions.
 Ionic Equilibrium 341
Applying law of chemical equilibrium, Dissociation Constant for polybasic acid : Polybasic acids ionise
  stepwise as, for example, orthophosphoric acid ionises in three steps and
[CH 3 COO ]  [H 3 O ]
K each step has its own ionisation constant.
[CH 3 COOH ]  [H 2 O]
H 3 PO4 ⇌ H   H 2 PO4 (I step)
In dilute solution, [H 2 O] is constant. The product of K and
H 2 PO4 ⇌ H   HPO42 (II step)
constant [H 2 O] is denoted as K a , the ionization constant or dissociation
constant of the acid is, HPO42 ⇌ H  
PO43 (III step)
 
[CH 3 COO ]  [H 3 O ] Let K1 , K 2 and K 3 be the ionization constants of first, second
Ka  …..(i)
[CH 3 COOH ] and third steps respectively. Thus,
The fraction of total number of molecules of an electrolyte which ionise [H  ][H 2 PO4 ] [H  ][HPO42 ] [H  ][PO43 ]
into ions is known as degree of dissociation/ionisation  . K1  ; K2  ; K 
[H 2 PO4 ] [HPO4 2 ]
3
[H 3 PO4 ]
If ' C ' represents the initial concentration of the acid in moles L1 In general, K1  K 2  K 3
and  the degree of dissociation, then equilibrium concentration of the
The overall dissociation constant (K ) is given by the relation,
ions (CH 3 COO  and H 3 O  ) is equal to C  and that of the
K  K1  K2  K3
undissociated acetic acid  C(1   ) i.e., we have
(2) Dissociation constant for weak base : The equilibrium of
CH 3 COOH  H 2O ⇌ CH 3 COO   H 3 O  NH 4 OH (a weak base) can be represented as,
Initial conc C 0 0
NH 4 OH ⇌ NH 4  OH 
Conc. at eqb. C(1   ) C C
[ NH 4 ][OH  ]
Substituting the values of the equilibrium concentrations in equation Applying the law of mass action, K b 
(i), we get [ NH 4 OH ]
C  .C  C 2 2 C 2 K b is constant at a definite temperature and does not change with
Ka    …..(ii)
C(1   ) C(1   ) 1   the change of concentration.
In case of weak electrolytes, the value of  is very small and can be Common ion effect
neglected in comparison to 1 i.e., 1    1 . The degree of dissociation of an electrolyte (weak) is suppressed by
Hence, we get the addition of another electrolyte (strong) containing a common ion, this is
termed as common ion effect. Acetic acid is a weak electrolyte and its
Ka
Ka  C 2 or   …..(iii) ionisation is suppressed in presence of a strong acid ( H  ion as common
C
ion) or a strong salt like sodium acetate (acetate ion is a common ion).
The degree of dissociation,  can therefore be calcualted at a given Similarly, the addition of NH 4 Cl or NaOH to NH 4 OH solution will
concentration, C if K a is known. Furher, if V is the volume of the
suppress the dissociation of NH 4 OH due to common ion either NH 4 or
solution in litres containing 1 mole of the electrolyte, C  1 / V . Hence we
have OH  .

  Ka V …..(iv) CH 3 COOH ⇌ CH 3 COO   H  NH 4 OH ⇌ NH 4  OH 

Similarly, for a weak base like NH 4 OH , we have CH 3 COONa  CH 3 COO   Na  NH 4 Cl  NH 4  Cl 

  Kb / C  Kb V …..(v) Common ion Common ion

The above equations lead to the following result
“For a weak electrolyte, the degree of ionisation is inversely
proportional to the square root of molar concentration or directly
proportional to the square root of volume containing one mole of the
solute.”
As a result of common ion effect, the concentration of the ion of
weak electrolyte which is not common in two electrolytes, is decreased. The
use of this phenomenon is made in qualitative analysis to adjust
concentration of S 2  ions in second group and OH  ion concentration
in third group.

This is called Ostwald’s dilution law. Isohydric solution

Dissociation constants of acids and Bases If the concentration of the common ions in the solution of two
(1) Dissociation constant for weak acid : Consider an acid HA electrolytes , for example H  ion concentration in HCl and HNO 3 or
which, when dissolved in water ionizes as, OH  ion concentration in Ca(OH )2 and Ba(OH )2 is same, then on
 
HA ⇌ H  A mixing them there is no change in the degree of dissociation of either of the
electrolytes. Such solutions are called isohydric solutions.
[H  ][ A  ]
Applying the law of mass action, K a  Consider two isohydric solutions of acids HA1 and HA2 . Let V1
[HA]
Where, K a is the dissociation constant of the acid, HA . It has and V2 be their dilutions and  1 and  2 be their degree of dissociation
constant value at definite temperature and does not change with the change at the respective dilution. Then,
of concentration.
 342 Ionic Equilibrium
1 2 K sp  [ Ag  ]2 [CrO42  ] ; Ksp  [2 x ]2 [x ] ; K sp  4 x 3

V1 V2
K sp
Above equation is useful for calculating the relative dilution of two x 3
acids at which they would be isohydric. 4

Solubility product (iv) Electrolyte of type A2 B3 (2 : 3 type salt)

In a saturated solution of sparingly soluble electrolyte two equilibria exist and e.g., As2 S 3 , Sb 2 S 3
 
can be represented as, AB ⇌ AB ⇌ A B As2 S 3 ⇌ 2 As 3   3 S 2 
Solid Unionised 2x 3x
(Dissolved ) ions
3 2 2 3
K sp  [ As ] [S ] ; K sp  [2 x ]2 [3 x ]3 ; K sp  4 x 2  27 x 3
[ A  ][B  ]
Applying the law of mass action, K
[ AB ] K sp
Since the solution is saturated, the concentration of unionised
Ksp  108 x 5 ; x  5
108
molecules of the electrolyte is constant at a particular temperature, i.e.,
(v) Electrolyte of type AB3 (1 : 3 type salt)
[ AB]  K   constant.
e.g., AlCl3 , Fe(OH )3
Hence, [ A  ][B  ]  K[ AB]  KK   K sp (constant)
AlCl3 ⇌ Al    3 Cl 
K sp is termed as the solubility product. It is defined as the product x 3x
3 
of the concentration of ions in a saturated solution of an electrolyte at a Ksp  [ Al ][3Cl ] ; Ksp  [x ] [3 x ]3
given temperature.
Consider, in general, the electrolyte of the type A x By which K sp
K sp  27x 4 ; x  4 .
27
dissociates as, A x By ⇌ xA y   yB x 
(3) Criteria of precipitation of an electrolyte : When Ionic product of
[ A y  ]x [B x  ]y an electrolyte is greater than its solubility product, precipitation occurs.
Applying law of mass action, K
[ A x By ] (4) Applications of solubility product
(i) In predicting the formation of a precipitate
When the solution is saturated, [ A x By ]  K  (constant) or
Case I : When Kip  Ksp , then solution is unsaturated in which
[ A y  ]x [B x  ]y  K[ A x By ]  KK   K sp (constant) more solute can be dissolved. i.e., no precipitation.
Thus, solubility product is defined as the product of concentrations Case II : When Kip  K sp , then solution is saturated in which no
of the ions raised to a power equal to the number of times the ions occur more solute can be dissolved but no ppt. is fomed.
in the equation representing the dissociation of the electrolyte at a given
temperature when the solution is saturated. Case III : When Kip  K sp , then solution is supersaturated and
(1) Difference between solubility product and ionic product : Both precipitation takes place.
ionic product and solubility product represent the product of the When the ionic product exceeds the solubility product, the
concentrations of the ions in the solution. The term ionic product has a equilibrium shifts towards left-hand side, i.e., increasing the concentration of
broad meaning since, it is applicable to all types of solutions, either undissociated molecules of the electrolyte. As the solvent can hold a fixed
unsaturated or saturated and varies accordingly. amount of electrolyte at a definite temperature, the excess of the electrolyte
On the other hand, the term solubility product is applied only to a is thrown out from the solutions as precipitate.
saturated solution in which there exists a dynamic equilibrium between the (ii) In predicting the solubility of sparingly soluble salts Knowing
undissolved salt and the ions present in solution. Thus the solubility the solubility product of a sparingly soluble salt at any given temperature,
product is in fact the ionic product for a saturated solution at a constant we can predict its solubility.
temperature.
(2) Different expression for solubility products (iii) Purification of common salt : HCl gas is circulated through
(i) Electrolyte of type AB (1 : 1 type salt) e.g., AgCl, BaSO 4 the saturated solution of common salt. HCl and NaCl dissociate into
their respective ions as,
AgCl ⇌ Ag   Cl 
x x NaCl ⇌ Na   Cl  ; HCl ⇌ H   Cl 
K sp  [ Ag  ][Cl  ] ; K sp  x 2 ; x  K sp The concentration of Cl  ions increases considerably in solution
(ii) Electrolytes of type AB2 (1:2 type salt) e.g., PbCl2 , CaF2 due to ionisation of HCl and due to common ion effect, dissociation of
NaCl is decreased. Hence, the ionic product [ Na  ][Cl  ] exceeds the
PbCl2 ⇌ Pb2   2Cl 
x 2x solubility product of NaCl and therefore pure NaCl precipitates out
from the solution.
K sp  [Pb2  ][Cl  ]2 ; Ksp  [x ] [2 x ]2 ; K sp  4 x 3
(iv) Salting out of soap : From the solution, soap is precipitated by
x  3 K sp / 4 the addition of concentrated solution of NaCl .

(iii) Electrolyte of type A B (2 : 1 type salt) e.g., Ag2CrO4 , H 2 S

2
RCOONa ⇌ RCOO   Na  ; NaCl ⇌ Na   Cl 
Soap

Ag2CrO4 ⇌ 2 Ag   CrO42  Hence, the ionic product [RCOO ] [Na ] exceeds the solubility
– +

2x x
product of soap and therefore, soap precipitates out from the solution.
 Ionic Equilibrium 343
(v) In qualitative analysis : The separation and identification of HCl
H2O
H   Cl  ; NaOH
H2O
Na   OH 
various basic radicals into different groups is based upon solubility product ( Acid) (aq .) (aq .) (Base ) (aq .) (aq )
principle and common ion effect. Some acids and bases ionise almost completely in solutions and are
(a) Precipitation of group first radicals (Pb , Ag , Hg ) The group
+2 + +2
called strong acids and bases. Others are dissociated to a limited extent in
 
reagent is dilute HCl. [ Ag ][Cl ]  Ksp for AgCl. solutions and are termed weak acids and bases.
HCl, HNO3 , H 2 SO 4 , HClO4 , etc., are examples of strong acids and
(b) Precipitation of group second radicals (Hg , Pb , Bi , Cu , Cd , As , +2 +2 +3 +2 +2 +3

Sb and Sn ) : The group reagent is H 2 S in presence of dilute HCl .

+3 +2 NaOH, KOH , (CH 3 )4 NOH are strong bases. Every hydrogen

[Pb2 ][S 2 ]  K sp for PbS . compound cannot be regarded as an acid, e.g., CH 4 is not an acid.
Similarly, CH 3 OH, C2 H 5 OH , etc., have OH groups but they are not
(c) Precipitation of group third radicals (Fe , Al and Cr ) The group
+3 +3 +3

bases.
reagent is NH 4 OH in presence of NH 4 Cl .
(i) Utility of Arrhenius concept : The Arrhenius concept of acids and
[Fe3 ][OH  ]3  K sp bases was able to explain a number of phenomenon like neutralization, salt
hydrolysis, strength of acids and bases etc.
(d) Precipitation of group fourth radicals (Co , Ni , Mn and Zn ) : +2 +2 +2 +2

(ii) Limitations of Arrhenius concept

The group reagent is H 2 S in presence of NH 4 OH .
[Co 2 ][S 2 ]  Ksp
(e) Precipitation of group fifth radicals (Ba , Sr , Ca ) The group +2
(a) For the acidic or basic properties, the presence of water is
absolutely necessary. Dry HCl shall not act as an acid. HCl is regarded
as an acid only when dissolved in water and not in any other solvent.
+2 +2

(b) The concept does not explain acidic and basic character of
reagent is ammonium carbonate in presence of NH 4 Cl and NH 4 OH . substances in non-aqueous solvents.
[Ba2 ] [CO 32 ]  Ksp (c) The neutralisation process is limited to those reactions which
can occur in aqueous solutions only, although reactions involving salt
(vi) Calculation of remaining concentration after precipitation :
formation do occur in absence of solvent.
Sometimes an ion remains after precipitation if it is in excess. Remaining
concentration can be determined, (d) It cannot explain the acidic character of certain salts such as
AlCl3 in aqueous solution.
K sp [ AB] K sp [Ca(OH ) 2 ]
Example : [ A  ]left  
; [Ca 2  ]left 
[B ] [OH  ] 2 (2) Bronsted–Lowry concept : According to this concept,
“An acid is defined as a substance which has the tendency to give a
K sp [ Am Bn ] proton (H ) and a base is defined as a substance which has a tendency to
[ A n  ]mleft
+

In general 
[B m n
] accept a proton. In other words, an acid is a proton donor whereas a base is
a proton acceptor.”
 Initialconc. - Remaining conc.  HCl  H 2 O ⇌ H 3 O   Cl  …..(i)
% precipitation of ion =    100
 Initialconc.  Acid Base

(vii) Calculation of simultaneous solubility : Solubility of two CH 3 COOH  H 2 O ⇌ H 3 O   CH 3 COO  …..(ii)

Acid Base
electrolytes having common ion; when they are dissolved in the same
(i) HCl and CH 3 COOH are acids because they donate a proton
solution, is called simultaneous solubility.
Calculation of simultaneous solubility is divided into two cases. to H 2 O .(ii) NH 3 and CO 32  are bases because they accept a proton
Case I : When the two electrolytes are almost equally strong (having from water.
In reaction (i), in the reverse process, H O can give a proton and +

close solubility product). hence is an acid while Cl can accept the proton and hence is a base. Thus
–
3

e.g., AgBr (K sp  5  10 13 ) ; AgSCN (K sp  10 12 ) there are two acid-base pairs in reaction (i). These are HCl – Cl and H O – –

3
+

H O. These acid-base pairs are called conjugate acid-base pairs.

2

Here, charge balancing concept is applied.

Conjugate acid ⇌ Conjugate base  H 
Charge of Ag  = Charge of Br  + Charge of SCN  Conjugate base of a strong acid is a weak base and vice a versa.
Weak acid has a strong conjugate base and vice a versa.
[ Ag  ] = [Br  ] + [SCN  ] Levelling effect and classification of solvents : In acid-base strength
series, all acids above H O in aqueous solution fall to the strength of H O .
+ +

(a  b)
3 3

= a b Similarly the basic strength of bases above OH fall to the strength of OH in

– –

Case II : When solubility products of two electrolytes are not close, aqueous solution. This is known as levelling effect. Levelling effect of water
is due to its high dielectric constant and strong proton accepting tendency.
i.e., they are not equally strong. On the basis of proton interaction, solvents are of four types,
e.g., CaF2 (K sp  3.4  10 11 ) ; SrF2 (K sp  2.9  10 9 ) (i) Protophilic solvents : Solvents which have greater tendency to
accept protons, i.e., water, alcohol, liquid ammonia, etc.
Most of fluoride ions come of stronger electrolyte. (ii) Protogenic solvents : Solvents which have the tendency to
produce protons, i.e., water, liquid hydrogen chloride, glacial acetic acid, etc.
Acid and Bases (iii) Amphiprotic solvents : Solvents which act both as protophilic or
(1) Arrhenius concept : According to Arrhenius concept all protogenic, e.g., water, ammonia, ethyl alcohol, etc.
substances which give H ions when dissolved in water are called acids while
+ (iv) Aprotic solvents : Solvents which neither donate nor accept
those which ionise in water to furnish OH ions are called bases.
–
protons, e.g., benzene, carbon tetrachloride, carbon disulphide, etc.
 344 Ionic Equilibrium
HCl acts as acid in H O, stronger acid in NH , weak acid in
2 3
(i) The protonic definition cannot be used to explain the reactions
CH COOH, neutral in C H and a weak base in HF.
3 6 6
occuring in non-protonic solvents such as COCl , SO , N O , etc.
2 2 2 4

HCl  HF  H 2 Cl   F  (ii) It cannot explain the reactions between acidic oxides like
Base Acid Acid Base CO 2 , SO 2 , SO 3 etc and the basic oxides like CaO, BaO, MgO etc
Utility of Bronsted – Lowry concept which take place even in the absence of the solvent e.g.,
(i) Bronsted – Lowry concept is not limited to molecules but CaO  SO 3  CaSO 4
includes even the ionic species to act as acids or bases.
There is no proton transfer in the above example.
(ii) It can explain the basic character of the substances like
(iii) Substances like BF , AlCl etc, do not have any hydrogen and hence
Na 2 CO 3 , NH 3 etc.
3 3

cannot give a proton but are known to behave as acids.

(iii) It can explain the acid-base reactions in the non-aqueous
medium or even in the absence of a solvent (e.g., between HCl
and NH ).
2

Limitations of Bronsted lowry concept

Table: 9.1 Conjugate acid-base pairs
Acid Conjugate base
HClO4 (Perchloric acid) ClO4 (Perchlorate ion)
H 2 SO 4 (Sulphuric acid) HSO 4 (Hydrogen sulphate ion)

HCl (Hydrogen chloride) Cl  (Chloride ion)

HNO 3 (Nitric acid) NO 3 (Nitrate ion)

H3O (Hydronium ion) H 2O (Water)

Increasing order of basic strength

HSO 4 (Hydrogen sulphate ion) SO 42  (Sulphate ion)
Increasing order of acidic strength

H 3 PO4 (Ortho phosphoric acid) H 2 PO4 (Dihydrogen phosphate ion)

CH 3 COOH (Acetic acid) CH 3 COO  (Acetate ion)
H 2 CO 3 (Carbonic acid) HCO 3 (Hydrogen carbonate ion)

H2S (Hydrogen sulphide) HS  (Hydrogen sulphide ion)

NH 4 (Ammonium ion) NH 3 (Ammonia)

HCN (Hydrogen cyanide) CN  (Cyanide ion)

C6 H 5 OH (Phenol) C6 H 5 O  (Phenoxide ion)

H 2O (Water) OH  (Hydroxide ion)

C 2 H 5 OH (Ethyl alcohol) C2 H 5 O  (Ethoxide ion)

NH 3 (Ammonia) NH 2 (Amide ion)

CH 4 (Methane) CH 3 (Methyl carbanion)

(3) Lewis concept : This concept was proposed by G.N. Lewis, in (d) Molecules having a multiple bond between atoms of dissimilar
1939. According to this concept, “a base is defined as a substance which can electronegativity e.g., CO 2 , SO 2 .
furnish a pair of electrons to form a coordinate bond whereas an acid is a
substance which can accept a pair of electrons.” The acid is also known as (ii) Types of Lewis bases : The following species can act as Lewis
electron pair acceptor or electrophile while the base is electron pair donor bases.
or nucleophile. (a) Neutral species having at least one lone pair of electrons
A simple example of an acid-base is the reaction of a proton with .. ..
hydroxyl ion, H   OH   HOH : NH 3 ,  N H 2 , R  O  H
Acid Base ..
Lewis concept is more general than the Bronsted Lowry concept. All (b) Negatively charged species or anions
Bronsted bases are also Lewis bases but all Bronsted acids are not Lewis
(iii) Hard and Soft principle of acids and bases : Lewis acids and
acids. [e.g., HCl, H 2 SO 4 as they are not capable of accepting a pair of bases are classified as hard and soft acids and bases. Hardness is defined as
electrons] the property of retaining valence electrons very strongly. Thus a hard acid is
(i) Types of Lewis acids : According to Lewis concept, the following that in which electron-accepting atom is small, has a high positive charge
species can act as Lewis acids. and has no electron which can be easily polarised or removed e.g.,
(a) Molecules in which the central atom has incomplete octet Li  , Na  , Be 2  , Mg 2 , Al 3 BF3 , SO 3 etc.. On the contrary, a soft
BF3 , BCl 3 , AlCl3 , BeCl 2 , etc. acid is that in which the acceptor atom is large, carries a low positive
charge or it has electrons in orbitals which are easily polarised or distorted
(b) All cations are expected to act as Lewis acids since they are
deficient in electrons. e.g., Pb2 , Cd 2 , Pt2 , Hg 2 , Ro  , Rs , I2 etc..
(c) Molecules in which the central atom has empty d- A Lewis base which holds its electrons strongly is called hard base,
orbitals. e.g., SiF4 , SnCl 4 , PF5 etc. e.g., OH  , F  , H 2O, NH 3 , CH 3 OCH 3 , etc. on the other hand, a Lewis

base in which the position of electrons is easily polarised or removed is
called a soft base e.g., I  , CO, CH 3 S  , (CH 3 )3 P , etc.
In general, hard acids prefer to bind to hard bases and soft acids
prefer to bind to soft bases. The bonding between hard acids and hard
bases is chiefly ionic and that between soft bases and soft acids is mainly
covalent.
(iv) Utility of Lewis concept : Lewis concept is the most general of
all the concepts and can explain the acidic and basic nature of all those
substances which could not be explained by the earlier concepts. Similarly, it
can explain even those acid-base reactions which could not be explained by
the other concepts.
(v) Limitations of lewis concept : It does not explain behaviour of
well known protonic acids, as HCl, H 2 SO 4 etc, as which do not form
coordinate bonds with bases.
It does not explain relative strengths of acids and bases. Many lewis
acids do not posses catalytic property.
Relative strength of acids and Bases
In practice K a is used to define the strength only of those acids
that are weaker than H 3 O  and Kb is used to define the strength of only
those bases that are weaker than OH  . For two weak acids HA1 and
HA 2 of ionisation constant K a1 and K a2 respectively at the same
concentration C , we have,
Acid strength of HA1 K a1

Acid strength of HA 2 K a2
Similarly, relative strengths of any two weak bases at the same
concentration are given by the ratio of the square-roots of their dissociation
constants. i.e.,
Basic strength of BOH 1 K b1

Basic strength of BOH 2 K b2
(1) Relative strength of Inorganic acids
(i) Hydrides
(a) The acidic strength increases with the increase in the
electronegativity of the element directly attached with the hydrogen.
H  F  H  OH  H  NH 2  H  CH 3
HCI  H 2 S  PH3  SiH 4
(b) The acidic strength increases with the increase in atomic size,
HF  HCl  HBr  HI ; H 2 O  H 2 S  H 2 Se  H 2 Te
(ii) Oxyacids
(a) Among oxyacids of the same type formed by different elements,
acidic nature increases with increasing electronegativity,
HOI  HOBr  HOCl ; HIO4  HBrO4  HClO4
(b) In oxyacids of the same element, acidic nature increases with its
oxidation number
HOCl  HClO2  HClO3  HClO4 ; H 2 SO 3  H 2 SO 4
1 3 5 7
HNO 2  HNO 3
(c) The strength of oxyacids increases from left to right across a
period
H 4 SiO4  H 3 PO4  H 2 SO 4  HClO4
(d) For the same oxidation state and configuration of the elements, acid
strength decreases with increase in size of the atom.
HNO3  HPO3 ; H 3 PO4  H 3 AsO4
HClO4  HBrO4  HIO4
(2) Relative strength of organic acids
(i) A compound is acidic in nature, if its conjugate base can stabilize
through resonance. Thus phenol is acidic while ethanol is neutral because the
Ionic Equilibrium 345
conjugate base of phenol (C 6 H 5 O  ) can be stabilized through resonance
while that of alcohol (C 2 H 5 O  ) can not.
(ii) Hydrogen atom attached to sp-hybridized carbon is more acidic
than that on sp 2 hybridized carbon which in turn is more acidic than that
on sp 3 hybridized carbon.
Thus, HC  CH  CH 2  CH 2  CH 3  CH 3
sp
sp 2 sp 3
(3) Relative strength of Inorganic bases
(i) The basicity of a compound decreases with increase in
electronegativity of the atom holding the electron pair,
. . . . . .
N H3  H2 O :  H F :
. .
(ii) The larger the size of the atom holding the unshared electrons,
the lesser is the availability of electrons.
F   Cl   Br   I  ; O 2  S 2
(iii) Presence of negative charge on the atom holding the electron
pair increases the basicity, while the presence of positive charge on the
atom holding the electron pair decreases the basicity.
OH   H 2 O  H 3 O 
(iv) Among alkali and alkaline earth hydroxides (oxides) the basic
nature increases with electropositivity
LiOH  NaOH  KOH  RbOH  CsOH ;
Be(OH)2  Mg(OH)2  Ca(OH)2  Sr(OH)2  Ba(OH)2
CsOH is the strongest known base
(v) On going down the group; basic nature decreases with size of
the central atom due to decrease in the ability to donate the lone pair.
NH 3  PH 3  AsH 3  SbH 3  BiH3
(4) Relative strength of Organic bases
(i) Higher the electron density on nitrogen, more is the basic
character of amine.
(ii) A compound is basic in nature, if its conjugate acid can be
NH 2
|
stabilized through resonance. Thus guanidine ( NH 3  C  NH ) is as
strong alkali as metal hydroxides because its conjugate acid
NH 2
|
(H 3 N   C  NH ) is very much stabilised through resonance.
The acid-base neutralisation and Salt
The reaction between an acid and a base to form salt and water is
termed neutralisation
HCl(aq.)  NaOH(aq.) ⇌ NaCl(aq .)  H 2 O(l)
Sodium Chloride
Salt
The process of neutralisation does not produce the resulting solution
always neutral; no doubt it involves the interaction of H  and OH  ions.
The nature of the resulting solution depends on the particular acid and the
particular base involved in the reaction.
Salts : Salts are regarded as compounds made up of positive and
negative ions. The positive part comes from a base while negative part from
an acid. Salts are ionic compounds.The salts can be classified into following
classes,
(1) Simple salts : The salt formed by the interaction between acid
and base, is termed as simple salt. These are of three types,
 346 Ionic Equilibrium
(i) Normal salts : the salts formed by the loss of all possible protons

(replaceable hydrogen atoms as H ) are called normal salts. Such a salt
“pH of a solution is the negative logarithm to the base 10 of the
concentration of H ions which it contains.”
+

does not contain either replacable hydrogen or a hydroxyl group. 1

pH   log[H  ] or pH  log
Examples : NaCl, NaNO 3 , K 2 SO 4 , Ca 3 (PO4 )2 , Na 3 BO 3 , [H  ]
Na 2 HPO3 (one H atom is not replaceable as H 3 PO2 is a dibasic Just as pH indicates the hydrogen ion concentration, the pOH
represents the hydroxyl ion concentration, i.e.,
acid) NaH 2 PO2 (both H atoms are not replaceable as H 3 PO2 is a
monobasic acid) etc. pOH   log[OH  ]
(ii) Acidic salts : Salts formed by incomplete neutralisation of poly- Considering the relationship, [H  ][OH  ]  Kw  1  10 14
basic acids are called acidic salts. Such salts still contain one or more
replaceable hydrogen atoms. These salts when neutralised by bases form Taking log on both sides, we have
normal salts. log[H  ]  log[OH  ]  log Kw  log(1  10 14 ) or
Examples : NaHCO 3 , NaHSO 4 , NaH 2 PO4 , Na 2 HPO4 , etc.
(iii) Basic salts : Salts formed by incomplete neutralisation of poly  log[H  ]  log[OH  ]   log Kw   log(1  10 14 )
acidic bases are called basic salts. Such salts still contain one or more or pH  pOH  pKw  14
hydroxyl groups. These salts when neutralised by acids form normal salts.
Examples: Zn(OH)Cl, Mg(OH)Cl, Fe(OH)2 Cl, Bi(OH)2 Cl [H+] [OH–] pH pOH
Acidic solution > 10–7 < 10–7 <7 >7
(2) Double salts : The addition compounds formed by the
Neutral solution 10–7 10–7 7 7
combination of two simple salts are termed double salts. Such salts are
Basic solution < 10–7 > 10–7 >7 <7
stable in solid state only.
Examples : Ferrous ammonium sulphate, Potash alum and other pH of some materials
alums. Material pH Material pH
(3) Complex salts : These are formed by combination of simple salts Gastric juice 1.4 Rain water 6.5
or molecular compounds. These are stable in solid state as well as in Lemon juice 2.1 Pure water 7.0
solutions. Vinegar 2.9 Human saliva 7.0
FeSO 4  6 KCN  K 4 [Fe(CN )6 ] K 2 SO 4 Soft drinks 3.0 Blood plasma 7.4
Simple salts Complex salt Beer 4.5 Tears 7.4
(4) Mixed salts : The salt which furnishes more than one cation or Black coffee 5.0 Egg 7.8
more than one anion when dissolved in water is called a mixed salt. Cow’s milk 6.5 Household ammonia 11.9
OCl Na Na
Examples : Ca /\ ; \ SO ; NH 4 PO4 Limitations of pH scale
/ 4
Cl K H (i) pH values of the solutions do not give us immediate idea of the
relative strengths of the solutions. A solution of pH =1 has a hydrogen ion
Ionic product of water concentration 100 times that of a solution pH = 3 (not three times). A
Water is a weak electrolyte and undergoes selfionistion to a small 4  10 5 N HCl is twice concentrated of a 2  10 5 N HCl solution,
extent.
but the pH values of these solutions are 4.40 and 4.70 (not double).
“The product of concentrations of H  and OH  ions in water at
a particular temperature is known as ionic product of water.” It is (ii) pH value zero is obtained in 1 N solution of strong acid. If the
designated as K w . concentration is 2 N , 3 N , 10 N , etc. the respective pH values will be
H 2 O ⇌ H   OH  ; H  57.3 kJM 1 negative.
[H  ][OH  ] (iii) A solution of an acid having very low concentration, say
K ; K[H 2 O]  [H  ][OH  ] ; K w  [H  ][OH  ]
[H 2 O] 10 8 N , can not have pH 8, as shown by pH formula but the actual pH
The value of K w increases with the increase of temperature, i.e., value will be less than 7.
the concentration H and OH ions increases with increase in temperature. pK value : p stands for negative logarithm. Just as H  and OH 
+ –

The value of K w at 25 o C is 1  10 14 mole/litre. Since pure
 
water is neutral in nature, H ion concentration must be equal to OH
ion concentration.
[H  ]  [OH  ]  x or [H  ][OH  ]  x 2  1  10 14 or
x  1  10 7 M or [H  ]  [OH  ]  1  10 7 mole litre1
This shows that at 25 o C , in 1 litre only 10 7 mole of water is in
ionic form out of a total of approximately 55.5 moles.
Thus when, [H  ]  [OH  ] ; the solution is neutral
[H  ]  [OH  ] ; the solution is acidic
[H  ]  [OH  ] ; the solution is basic
ion concentrations range over many negative powers of 10, it is convenient
to express them as pH or pOH, the dissociation constant (K) values also
range over many negative powers of 10 and it is convenient to write them as
pK. Thus, pK is the negative logarithm of dissociation constant.
pK a   log K a and pKb   log K b
Weak acids have higher pK a values. Similarly weak bases have
higher pK b values
For any conjugate acid-base pair in aqueous solution,
K a  K b  Kw
pKa  pKb  pKw  14 (at 298 K) o

Hydrogen ion concentration – pH scale

Calculation of the pH of 10 8 M HCl & 10 8 M NaOH
Sorensen, a Danish biochemist developed a scale to measure the
acidity in terms of concentrations of H  in a solution. As defined by him,
 Ionic Equilibrium 347

If we use the relation pH   log[H 3 O  ] we get pH equal to 8, (viii) The pH value of gastric juice is maintained between 1.6 and
1.7 due to buffer system.
but this is not correct because an acidic solution connot have pH greater
(4) Henderson - Hasselbalch equation : pH of an acidic or a basic
than 7. In this condition H  concentration of water cannot be neglected.
buffer can be calculated by Henderson- Hasselbalch equation.
Therefore, [H  ]total  H Acid
 
 H water [salt]
For acidic buffers, pH  pK a  log
Since HCl is strong acid and completely ionised, [acid]
[salt]
[H  ]HCl  1  10 8 , [H  ]H 2O  10 7 When  10 , then, pH  1  pK a and
[acid]
[H  ]total  [H  ]HCl  [H  ]H 2O  10 8  10 7  10 8 [1  10] [salt] 1
when  , then, pH  pK a  1
8
 10  11 [acid] 10
So weak acid may be used for preparing buffer solutions having
pH   log10 8  log11  6.958
pH values lying within the ranges pK a  1 and pK a  1 . The acetic
Similarly if NaOH concentration is 10 8 M acid has a pK a of about 4.8; it may, therefore, be used for making buffer
Then, [OH  ]total  [10 8 ] NaOH  [10 7 ]H 2O solutions with pH values lying roughly within the range 3.8 to 5.8.
[salt]
[OH  ]  10 8  11 ; pOH  6.96 pH  7.04 For basic Buffers, pOH  pK b  log
[base]
Buffer solutions
Knowing pOH , pH can be calculated by the application of
A solution whose pH is not altered to any great extent by the formula, pH  pOH  14
addition of small quantities of either sirong acid (H ions) or a sirong base
+

(OH ions) is called the buffer solution. It can also be defined as a solution
–
of reserve acidity or alkalinity which resists change of pH upon the
addition of small amount of acid or alkali.
(1) Types of buffer solutions : There are two types of buffer
solutions,
(i) Solutions of single substances : The solution of the salt of a weak
acid and a weak base.
Example : ammonium acetate (CH 3 COONH 4 ) , NH 4 CN act as
a buffer.
(ii) Solutions of Mixtures : These are further of two types,
(a) Acidic buffer : It is the solution of a mixture of a weak acid and
a salt of this weak acid with a strong base.
Example : CH 3 COOH  CH 3 COONa
(b) Basic buffer : It is the solution of a mixture of a weak base and a
salt of this weak base with a strong acid.
Example : NH 4 OH  NH 4 Cl
(2) Buffer action : Buffer action is the mechanism by which added H
pH of a buffer solution does not change with dilution but it varies
with temperature because value of Kw changes with temperature.
(5) Buffer capacity : The property of a buffer solution to resist
alteration in its pH value is known as buffer capacity. It has been found that
[salt] [salt]
if the ratio or is unity, the pH of a particular buffer does
[acid ] [base ]
not change at all. Buffer capacity is defined quantitatively as number of
moles of acid or base added in one litre of solution as to change the pH by
unity, i.e.,
Number of moles of acid or base added to 1 litre
Buffer capacity ( ) 
Change in pH
Thus greater the buffer capacity, the greater is its capacity to resist
change in pH value. Buffer capacity is greatest when the concentration of
salt and weak acid/base are equal, or when pH  pK a or pOH  pK b .
(6) Significance of buffer solutions
(i) Buffer solutions are used for comparing colorimetrically the
hydrogen ion concentration of unknown solutions.
(ii) Acetic acid-sodium acetate is used in the removal of phosphate
+

radical during the qualitative analysis of the mixture.

ions or OH ions are almost neutralised; so that pH practically remains
–

(iii) NH 4 Cl / NH 4 OH buffer is used for the precipitation of

constant. Reserved base of buffer neutralises the added H  ions while the hydroxides of third group of qualitative analysis.
reserved acid of buffer neutralises the added OH ions.–

(iv) In industries, buffer solutions are used in the alcoholic

(3) Examples of buffer solutions fermentation (pH 5 to 6.5), tanning of leather, electroplating, manufacture
of sugar, paper manufacturing etc.,
(i) Phthalic acid + potassium hydrogen phthalate
(v) In bacteriological research culture media are generally buffered
(ii) Citric acid + sodium citrate. to maintain the pH required for the growth of the bacteria being studied.
(iii) Boric acid + borax (sodium tetraborate). (vi) In biological systems buffer system of carbonic acid and sodium
bicarbonate is found in our blood. It maintains the pH of blood to a
(iv) Carbonic acid (H 2 CO 3 ) + sodium hydrogen carbonate constant value (about 7.4) inspite of various acid and base-producing
(NaHCO 3 ) . This system is found in blood and helps in maintaining pH reactions going on in our body.
of the blood close to 7.4 ( pH value of human blood lies between 7.36 – Salt hydrolysis
7.42; a change in pH by 0.2 units may cause death). It is the reaction of the cation or the anion or both the ions of the
(v) NaH 2 PO4  Na 3 PO4 salt with water to produce either acidic or basic solution. Hydrolysis is the
reverse of neutralization.
(vi) NaH 2 PO4  Na 2 HPO4 Neutral No hydrolysis
Salt 2 Aqueous solution
H O
(vii) Glycerine + HCl Acidic Cationic hydrolysis
Basic Anionic hydrolysis
 348 Ionic Equilibrium
the titrations. The change in pH in the vicinity of the equivalence point is
(1) Hydrolysis constant : The general equation for the hydrolysis of a most important for this purpose. The curve obtained by plotting pH as
ordinate against the volume of alkali added as abscissa is known as
salt (BA), BA  H 2 O ⇌ HA BOH
salt acid base neutralisation or titration curve. The suitable indicators for the following
Applying the law of chemical equilibrium, we get titrations are,
[HA][BOH ] (i) Strong acid Vs strong base : Phenolphthalein (pH range 8.3 to
 K , where K is the equilibrium constant. 10.5), methyl red (pH range 4.4 – 6.5) and methyl orange (pH range 3.2 to
[BA][H 2 O]
4.5).
Since water is present in very large excess in the aqueous solution,
(ii) Weak acid Vs strong base : Phenolphthalein.
its concentration [H 2 O] may be regarded as constant so,
(iii) Strong acid Vs weak base : Methyl red and methyl orange.
[HA][BOH ] (iv) Weak acid vs. weak base : No suitable indicator can be used for
 K[ H 2 O ]  K h
[BA] such a titration.
where K h is called the hydrolysis constant. Reason for use of different indicators for different systems :
Indicators are either weak acids or weak bases and when dissolved in water
(2) Degree of hydrolysis : It is defined as the fraction (or their dissociated form acquires a colour different from that of the
percentage) of the total salt which is hydrolysed at equilibrium. For undissociated form. Consider a weak acid indicator of the general formula
example, if 90% of a salt solution is hydrolysed, its degree of hydrolysis is HIn, where in represents indicator. The equilibrium established in aqueous
0.90 or as 90%. It is generally represented by ‘ h ’. solution will be
Number of moles of the salt hydrolysed HIn(aq.) ⇌ H  (aq.)  In (aq.)
h
Total number of moles of the salt taken Red Green

Types of salt Exp. for Kh Exp. for h Exp. for pH Let K In be the equilibrium constant
(i) Salt of weak Kh=Kw / Ka
acid and strong K  1
pH=– [log Kw+log Ka– [H  ][In ] [HIn] [H  ]
h  h  2 K In  or 
base  C  [HIn] [In ] K In
  log C]
(ii) Salt of strong Kh=Kw / Kb 1 The human eye can detect the change in colour if the ratio of the two
acid and weak K  pH=– [log Kw– log forms of indicator ranges between 0.1 to 10.
h  h  2
base  C 
  Kb+ log C] [HIn]
If,  1 .0 , the colour visible will be yellow
(iii) Salt of weak Kw h  (K h ) 1 [In ]
acid and weak Kh  pH=– [log Ka+ log
base Ka Kb 2 [HIn]
Kw– log Kb]  10 , the colour visible will be red.
[In ]
(iv) Salts of strong acids and strong bases do not undergo hydrolysis (they
undergo only ionization) hence the resulting aqueous solution is neutral. [HIn]
 0 .1 , the colour visible will be green.
[In ]
Indicators
An indicator is a substance, which is used to determine the end point in a In other words,
titration. In acid-base titrations, organic substance (weak acids or weak bases) The colour visible will be red, when pH  pK In  1
are generally used as indicators. They change their colour within a certain
pH range. The colour change and the pH range of some common The colour visible will be yellow, when pH  pK In
indicators are tabulated below The colour visible will be green, when pH  pK In  1
Table : 9.2 Colour changes of indicators with pH
Thus, our imaginary indicator will be red at any pH which just
Indicator pH range Colour
Acid solution Base solution falls below pK In  1 and green at any pH which just exceeds pK In  1 .
Cresol red 1.2 – 1.8 Red Yellow The indicator changes its colour in the narrow pH range pK In  1 to
Thymol blue 1.2 – 2.8 Red Yellow pK In  1 from red to (red-yellow, yellow, yellow-green) green. We can
Methyl yellow 2.9 – 4.0 Red Yellow therefore use this indicator to locate this narrow pH range. In other
Methyl orange 3.1 – 4.4 Pink Yellow words, in order to use the indicator effectively in this range, we should have
Methyl red 4.2 – 6.3 Red Yellow a solution for which pH is very near to pK In of the indicator. The colour
Litmus 5.0 – 8.0 Red Blue change of an indicator can, therefore, be summarised as,
Bromothymol blue 6.0 – 7.6 Yellow Blue
First change of Mid point of change Colour change
Phenol red 6.4 – 8.2 Yellow Red colour complete
Thymol blue (base) 8.1 – 9.6 Yellow Blue [H+] 10 KIn KIn 0.1 KIn
Phenolphthalein 8.3 – 10.0 Colourless Pink
pH PKIn – 1 PKIn PKIn + 1
Thymolphthalein 8.3 – 10.5 Colourless Blue It is for this reason that we use different indicators for different
Alizarin yellow R 10.1 – 12.0 Blue Yellow
systems.
Nitramine 10.8 – 13.0 Colourless Orange, Brown

Two theories have been proposed to explain the change of colour of

acid-base indicators with change in pH.
(i) Ostwald’s Theory (ii) Quinonoid theory
(1) Selection of suitable indicator or choice of indicator : In order to
choose a suitable indicator, it is necessary to understand the pH changes in
 pH of boiling water is 6.5625. It does not mean that boiling water
 Ionic Equilibrium 349
is not neutral. It is due to greater dissociation of H O into H and
2
+

OH .
–

 pH values of solutions do not give the exact idea of their relative

strengths e.g., (i) A solution with pH = 1 had [H ] 100 times than that
+

with pH = 3 and not 3 times. (ii) A 4 × 10 M HCl solution is twice

–5

concentrated as compared to 2 × 10 M HCl solution but pH values of

–5

these solutions are 4.4 and 4.7 respectively and not double.
 pH can be zero in 1M HCl or it can be negative for more concentrated
solutions like 2M, 3M, 10M etc.
 At the temperature of the human body which is nearly 37°C, pH of
neutral solution is 6.8.
 Buffer solutions have reserve acidity and reserve alkalinity.
 The greater the buffer capacity, the greater is its capacity to resist
change in pH value.
 Buffers cannot withstand the addition of large amounts of acids or
alkalies. The addition of 0.1mol per litre of [H ] or OH is about the
+ –

maximum that any buffer can be expected to withstand.

 350 Ionic Equilibrium
(c) Can best be determined from measurements on dilute solutions
of NaF, NaCl and HCl
(d) Is an undefined quantity
11. If  is the degree of ionization, C the concentration of a weak
electrolyte and K a the acid ionization constant, then the correct
relationship between  , C and K a is
Electrical conductors, Arrhenius theory and
[CET Pune 1998; Pb. PMT 1998; RPMT 2002]
Ostwald's dilution law
Ka C
(a)  2  (b)  2 
1. Which of the following is non-electrolyte [CPMT 2001] C Ka
(a) NaCl (b) CaCl 2 Ka C
(c)  (d)  
(c) C12 H 22 O11 (d) CH 3 COOH C Ka
2. Ammonium hydroxide is a [CPMT 1977] 12. Theory of ionization was given by
(a) Strong electrolyte [AMU 1983; DPMT 1985]
(b) Weak electrolyte (a) Rutherford (b) Graham
(c) Both under different conditions (c) Faraday (d) Arrhenius
(d) Non-electrolyte 13. An ionizing solvent has
3. Ammonium hydroxide is a weak base because (a) Low value of dielectric constant
[MP PET 2000] (b) High value of dielectric constant
(a) It has low vapour pressure (c) A dielectric constant equal to 1
(b) It is only slightly ionized (d) Has a high melting point
(c) It is not a hydroxide of any metal 14. The extent of ionization increases [MNR 1982]
(d) It has low density (a) With the increase in concentration of solute
4. Electrolytes when dissolved in water dissociate into their constituent (b) On addition of excess water to solution
ions. The degree of dissociation of an electrolyte increases with [CPMT 1974] (c) On decreasing the temperature of solution
(a) Increasing concentration of the electrolyte (d) On stirring the solution vigorously
(b) Decreasing concentration of the electrolyte 15. Which is generally true about ionic compounds
(c) Decreasing temperature [Pb. PMT 2002]
(d) Presence of a substance yielding a common ion (a) Have low boiling point
5. An electrolyte [MP PMT/PET 1988; CPMT 1974] (b) Have low melting point
(a) Gives complex ions in solution (c) Soluble in non polar solvents
(b) Dissolves in water to give ions (d) Conduct electricity in the fused state
16. At infinite dilution, the percentage ionisation for both strong and
(c) Is ionized in the solid state weak electrolytes is [CPMT 1999]
(d) Generates ions on passing electric current (a) 1% (b) 20%
6. A monoprotic acid in 1.00 M solution is 0.01% ionised. The (c) 50% (d) 100%
dissociation constant of this acid is [BVP 2003] 17. The degree of ionization of a compound depends on
8 4
[MNR 1980]
(a) 1  10 (b) 1  10 (a) Size of solute molecules
(c) 1  10 6 (d) 10 5 (b) Nature of solute molecules
7. Molten sodium chloride conducts electricity due to the presence of (c) Nature of vessel used
[BHU 2001]
(d) Quantity of electricity passed
(a) Free electrons
(b) Free ions 18. For a weak acid HA, Ostwald's dilution law is represented by the
(c) Free molecules equation
(d) Atoms of sodium and chlorine c  2c
(a) Ka  (b) Ka 
8. An example for a strong electrolyte is [KCET 2002] 1 2 1 
(a) Urea (b) Ammonium hydroxide
Kac  2c
(c) Sugar (d) Sodium acetate (c)  (d) K a 
9. Which one is strongest electrolyte in the following 1c 1 2
[CPMT 1990] 19. Acetic acid is a weak electrolyte because [CPMT 1974]
(a) NaCl (b) CH 3 COOH (a) Its molecular weight is high
(b) It is covalent compound
(c) NH 4 OH (d) C6 H12 O6
(c) It does not dissociate much or its ionization is very less
10. The equivalent conductance at infinite dilution of a weak acid such
(d) It is highly unstable
as HF [Pb. PMT 1998]
20. In which of the following dissociation of NH 4 OH will be
(a) Can be determined by measurement of very dilute HF
solution minimum [MP PET 2000]
(b) Can be determined by extrapolation of measurements on dilute (a) NaOH (b) H 2O
solutions of HCl, HBr and HI
(c) NH 4 Cl (d) NaCl
 Ionic Equilibrium 351

21. Vant hoff factor of BaCl2 of conc. 0.01M is 1.98. Percentage (c) 1.25  10 6 (d) 4.8  10 5
dissociation of BaCl2 on this conc. Will be 32. The best conductor of electricity is a 1.0 M solution of
[Kerala CET 2005] [NCERT 1973]
(a) 49 (b) 69 (a) Boric acid (b) Acetic acid
(c) 89 (d) 98 (c) Sulphuric acid (d) Phosphoric acid
(e) 100 33. The colour of an electrolyte solution depends on
22. In which of the following solutions, ions are present [DPMT 1985]
[NCERT 1981] (a) The nature of the anion
(b) The nature of the cation
(a) Sucrose in water (b) Sulphur in CS 2
(c) The nature of both the ions
(c) Caesium nitrate in water (d) Ethanol in water (d) The nature of the solvent
23. The following equilibrium exists inaqueous solution, 34. Ionisation depends upon [CPMT 2004]
CH 3 COOH ⇄ CH 3 COO   H  if dil HCl is added, without (a) Pressure (b) Volume
change in temperature, the [UPSEAT 2000, 02] (c) Dilution (d) None of these
(a) Concentration of CH 3 COO  will increase 35. The values of dissociation constants of some acids (at 25 o C ) are
as follows. Indicate which is the strongest acid in water
(b) Concentration of CH 3 COO  will decrease
(a) 1.4  10 2 (b) 1.6  10 4
(c) The equilibrium constant will increase
(d) The equilibrium constant will decrease (c) 4.4  10 10 (d) 4.3  10 7
24. Which will not affect the degree of ionisation 36. Concentration CN  in 0.1 M HCN is [Ka  4  10 10 ]
[MP PMT 1994]
[RPET 2000]
(a) Temperature (b) Concentration
(c) Type of solvent (d) Current (a) 2.5  10 6 M (b) 4.5  10 6 M
25. The addition of a polar solvent to a solid electrolyte results in [NCERT 1973] (c) 6.3  10 6 M (d) 9.2  10 6 M
(a) Polarization (b) Association
(c) Ionization (d) Electron transfer Acids and Bases
26. The degree of dissociation of 0.1 M HCN solution is 0.01%. Its
ionisation constant would be [RPMT 1999] 1. Which of the following is not a Lewis acid [MP PET 2002]
(a) CO (b) SiCl4
(a) 10 3 (b) 10 5
(c) 10 7 (d) 10 9 (c) SO 3 (d) Zn 2 
27. The hydrogen ion concentration in weak acid of dissociation 2. Review the equilibrium and choose the correct statement
constant K a and concentration c is nearly equal to HClO4  H 2 O ⇄ H 3 O   ClO4 [RPMT 2000]
[CBSE PMT 1989; RPMT 2000] (a) HClO4 is the conjugate acid of H 2 O
(a) Ka / c (b) c / Ka (b) H 3 O  is the conjugate base of H 2 O
(c) Kac (d) Kac (c) H 2 O is the conjugate acid of H 3 O 

28. Degree of dissociation of 0.1 N CH 3 COOH is (d) ClO4 is the conjugate base of HClO4

(Dissociation constant  1  10 5 ) [MP PET 1997] 3. A solution of FeCl3 in water acts as acidic due to
[BVP 2003]
(a) 10 5 (b) 10 4 3
(a) Hydrolysis of Fe (b) Acidic impurities
(c) 10 3 (d) 10 2 (c) Dissociation (d) Ionisation
29. Which of the following substance is an electrolyte 4. A white substance having alkaline nature in solution is
[MADT Bihar 1980] [BVP 2003]
(a) Chloroform (a) NaNO 3 (b) NH 4 Cl
(b) Benzene
(c) Toluene (c) Na 2 CO 3 (d) Fe2 O3
(d) Magnesium chloride 5. Which of the following can act both as Bronsted acid and Bronsted
base [MP PET 1995; MP PET/PMT 1998]
30. In weak electrolytic solution, degree of ionization
(a) Will be proportional to dilution (a) Cl  (b) HCO 3
(b) Will be proportional to concentration of electrolyte (c) H 3O  (d) OH 
(c) Will be proportional to the square root of dilution
6. Lewis acid [MP PMT 1987]
(d) Will be reciprocal to the dilution (a) Presence of H atom is necessary
31. 0.2 molar solution of formic acid is ionized 3.2%. Its ionization (b) Is a electron pair donor
constant is [MP PMT 1991]
(c) Always a proton donor
(a) 9.6  10 3 (b) 2.1  10 4 (d) Is a electron pair acceptor
 352 Ionic Equilibrium
7. For two acids A and B, pKa  1.2, pKb  2.8 respectively in CH 3 COOH  HF ⇄ CH 3 COOH 2  F 

[BHU 1987]
value, then which is true [Bihar MEE 1998]
(a) A and B both are equally acidic (a) F  is the conjugate acid of CH 3 COOH
(b) A is stronger than B
(b) F  is the conjugate base of HF
(c) B is stronger than A

(d) Neither A nor B is strong (c) CH 3 COOH is the conjugate acid of CH 3 COOH 2
(e) None of these
8. Aq. solution of sodium cyanide is [BHU 1981] (d) CH 3 COOH 2  is the conjugate base of CH 3 COOH
(a) Acidic (b) Amphoteric 21. The compound that is not a Lewis acid is [IIT 1985]
(c) Basic (d) Netural (a) BF3 (b) AlCl3
9. Which of the following is the strongest conjugate base
[MADT Bihar 1983; CBSE PMT 1999; KCET (Med.) 2001] (c) BeCl 2 (d) NH 3
(a) Cl 
(b) CH 3 COO  22. Which of the following dissolves in water to give a neutral solution [Bihar MADT
(a) (NH 4 )2 SO 4 (b) Ba(NO 3 )2
(c) SO 4   (d) NO 2 
(c) CrCl3 (d) CuSO 4
10. NaOH is a strong base because [AIIMS 2001]
23. Which of the following is the strongest acid [AMU 1982]
(a) It gives OH  ion (b) It can be oxidised
(a) H 3 PO4 (b) H 2 SO 4
(c) It can be easily ionised (d) Both (a) and (c)
11. Which one of the following can be classified as a Bronsted base (c) HNO
[KCET
2 2001] (d) CH 3 COOH
(a) NO 3 (b) H 3O  24. An example of a Lewis acid is
[MADT Bihar 1982; AMU 1982; MNR 1994;
(c) NH 4 (d)
CH 3 COOH RPMT 1997; KCET 2000; Orissa JEE 2005]
12. Which one of the following substance has the highest proton affinity (a) NaCl (b) MgCl2
[AIEEE 2003]
(a) H 2O (b) H 2S (c) AlCl3 (d) SnCl 4

(c) NH 3 (d) PH3 25. In the equilibrium HClO +H O ⇌ H O + ClO4

4 2 2
+

13. Which of the following is the strongest Lewis acid [BHU 1981, 86]
[EAMCET 1998] (a) HClO4 is the conjugate acid of H 2 O
(a) BI3 (b) BBr3
(b) H 2 O is the conjugate acid of H 3 O 
(c) BCl 3 (d BF3
(c) H 3 O  is the conjugate base of H 2 O
14. An aqueous solution of ammonia consists of
[MP PET 2001] (d) ClO4 is the conjugate base of HClO4
 
(a) H (b) OH 26. Which of the following would be expected to form ionic solution in
 water [CPMT 1976; Kurukshetra CEE 1998]
(c) NH 4 (d) NH 4 and OH
(a) CCl 4 (b) O 2
15. Which of the following is not a Lewis acid
[CBSE PMT 1996] (c) NaBr (d) CHBr3
(a) BF3 (b) FeCl3 27. A solution of sodium bicarbonate in water turns
[NCERT 1971]
(c) SiF4 (d) C2 H 4 (a) Phenolphthalein pink (b) Methyl orange yellow
16. The conjugate base of NH 2  is [EAMCET 1998]
(c) Methyl orange red (d) Blue litmus red
28. Accepting the definition that an acid is a proton donor, the acid in
2
(a) NH 3 (b) NH the following reaction NH 3  H 2 O  NH 4  OH  is [Kerala (Med.) 2003]
(c) NH 4 (d) N3 (a) NH 3 (b) H
17. The strength of an acid depends on its tendency to (c) NH 4 (d) H 2O
[MP PET 1996]
(a) Accept protons (b) Donate protons 29. With reference to protonic acids, which of the following statements
is correct [CPMT 1990]
(c) Accept electrons (d) Donate electrons
(a) PH 3 is more basic than NH 3
18. Which is not a electrophile [RPET 1999]
(a) AlCl3 (b) BF3 (b) PH 3 is less basic than NH 3
(c) PH 3 is equally basic as NH 3
(c) (CH 3 )3 C  (d) NH 3
(d) PH 3 is amphoteric while NH 3 is basic
19. Ammonia gas dissolves in water to give NH 4 OH . In this reaction
water acts as [CPMT 1990; MP PMT 1990] 30. NH 4 OH is weak base because [CPMT 1979]
(a) An acid (b) A base (a) It has low vapour pressure
(c) A salt (d) A conjugate base (b) It is only slightly ionized
20. In the equilibrium (c) It is not a hydroxide of metal
(d) It has low density
 Ionic Equilibrium 353

31. HNO 3 in liquid hydrogen fluoride behaves (c) Both A and B (d) Neither A nor B
(a) As an acid 45. The conjugate acid of NH 2 is [IIT 1985; Roorkee 1995;
(b) As a base EAMCET 1997;CBSE PMT PMT 2000; MP PET 1996,2000]
(c) Neither as a base nor as an acid (a) NH 3 (b) NH 4
(d) As a base and as an acid
(c) NH 2 OH (d) N 2 H 4
32. Aqueous solution of CuSO 4 .5 H 2 O changes blue litmus paper to
red due to [CPMT 1979; MP PMT 1989]
46. Correct statement is [CPMT 1985]
(a) NH 4 Cl gives alkaline solution in water
(a) Presence of Cu   ions
(b) CH 3 COONa gives acidic solution in water
(b) Presence of SO 4   ions
(c) CH 3 COOH is a weak acid
(c) Hydrolysis taking place
(d) Reduction taking place (d) NH 4 OH is a strong base
33. In the following reaction 47. pKa of a weak acid is defined as [JIPMER 1999]
   
HC2 O4  PO4 ⇄ HPO4  C 2 O4 1
(a) log 10 Ka (b)
Which are the two Bronsted bases [MP PMT 1991] log10 K a
(a) HC 2 O4  and PO4    (b) HPO4   and C 2 O4   (c) log
1
(d) –log
1
10 10
Ka Ka
(c) HC 2 O4  and HPO4   (d) PO4    and C 2 O4  
48. A salt ' X ' is dissolved in water (pH  7), the resulting solution
34. Which of the following is the weakest acid [CPMT 2001]
becomes alkaline in nature. The salt is made of
(a) HF (b) HCl [CPMT 1983]
(c) HBr (d) HI (a) A strong acid and strong base
35. The degree of dissociation in a weak electrolyte increases (b) A strong acid and weak base
[CBSE PMT 1989; MP PMT 1997] (c) A weak acid and weak base
(a) On increasing dilution (b) On increasing pressure (d) A weak acid and strong base
(c) On decreasing dilution (d) None of these 49. Which one is not an acid salt [MNR 1984]
36. H  is a [MADT Bihar 1983] (a) NaH 2 PO2 (b) NaH 2 PO3
(a) Lewis acid (b) Lewis base
(c) NaH 2 PO4 (d) None
(c) Bronsted-Lowry base (d) None of the above
37. Dissociation of H 3 PO4 takes place in following steps 50. A white substance was alkaline in solution. Which of the following
substances could it be [CPMT 1989]
[CPMT 1976; NCERT 1987]
(a) 1 (b) 2 (a) Fe2 O3 (b) Na 2 CO 3
(c) 3 (d) 4 (c) NH 4 Cl (d) NaNO 3
38. The aqueous solution of disodium hydrogen phosphate is
[MADT Bihar 1982] 51. An aqueous solution of ammonium carbonate is
(a) Acidic (b) Neutral [MP PMT 1989]
(c) Basic (d) None (a) Weakly acidic (b) Weakly basic
39. Which of the following is a conjugated acid-base pair (c) Strongly acidic (d) Neither acidic nor basic
[MADT Bihar 1984; DPMT 2001] 52. 100 ml of 0.2 M H 2 SO 4 is added to 100 ml of
(a) HCl, NaOH (b) NH 4 Cl, NH 4 OH 0.2 M NaOH. The resulting solution will be [BHU 1996]
(c) H 2 SO 4 , HSO 4  (d) KCN , HCN (a) Acidic (b) Basic
40. The solution of strong acid and weak base (FeCl3 ) is (c) Neutral (d) Slightly basic
[MADT Bihar 1981; CPMT 1979, 83, 84] 53. H 3 BO3 is [IIT Screening 2003]
(a) Acidic (b) Basic (a) Monobasic and weak Lewis acid
(c) Neutral (d) None of the above (b) Monobasic and weak Bronsted acid
41. The conjugate acid of HPO32  is [EAMCET 1989] (c) Monobasic and strong Lewis acid
(a) H 3 PO4 (b) H 3 PO3 (d) Tribasic and weak Bronsted acid
54. In the reaction SnCl 2  2Cl   SnCl 4 , Lewis acid is
(c) H 2 PO3 (d) PO43 
[EAMCET 1987]
42. What name is given to the reaction between hydrogen ion and

hydroxyl ion [MP PMT 1990] (a) SnCl 2 (b) Cl
(a) Hydrogenation (b) Hydroxylation
(c) Hydrolysis (d) Neutralization (c) SnCl 4 (d) None of these
43. Among the following, the weakest Lewis base is 55. Lewis base is [RPMT 1997]
[NCERT 1981] (a) CO 2 (b) SO 3
(a) H (b) OH 
(c) SO 2 (d) ROH
(c) Cl  (d) HCO 3
56. 10 ml of 1 M H 2 SO 4 will completely neutralise
44. The pKa for acid A is greater than pKa for acid B. The strong
acid is [DPMT 2000] (a) 10 ml of 1 M NaOH solution
(a) Acid B (b) Acid A
 354 Ionic Equilibrium
(b) 10 ml of 2 M NaOH solution (c) NaOH (d) NaCl
 
(c) 5 ml of 2 M KOH solution 70. In the reaction I2  I  I3 , the Lewis base is
(d) 5 ml of 1 M Na 2 CO 3 solution [CPMT 1997; RPMT 2002; BCECE 2005]

57. Which of the following compounds are diprotic (a) I2 (b) I

[Pb. PMT 2000]
(c) I3  (d) None of these
(a) H 2 PO5 (b) H 2S
71. The strength of an acid depends on its tendency to
(c) HClO3 (d) H 3 PO3 [UPSEAT 2001]
58. When 100 ml of 1M NaOH solution is mixed with 10 ml of 10 M (a) Accept protons (b) Donate protons
H 2 SO 4 , the resulting mixture will be [AMU 2002] (c) Accept electrons (d) Donate electrons
(a) Acidic (b) Alkaline 72. In Lewis acid-base theory, neutralization reaction may be considered
(c) Neutral (d) Strongly alkaline as [NCERT 1977]

59. The pH indicators are [KCET 1996]

(a) Formation of salt and water
(a) Salts of strong acids and strong bases (b) Competition for protons by acid and base
(b) Salts of weak acids and weak bases (c) Oxidation reduction
(c) Either weak acids or weak bases (d) Coordinate covalent bond formation
(d) Either strong acids or strong bases 73. The salt that forms neutral solution in water is
60. Which of the following is not Lewis acid [BHU 1997] [EAMCET 1981]
(a) BF3 (b) AlCl3 (a) NH 4 Cl (b) NaCl

(c) FeCl3 (d) PH 3 (c) Na 2 CO 3 (d) K 3 BO3

74. Which of the following cannot act as a Lewis or Bronsted acid
61. A solution of sodium acetate in water will [MNR 1979]
(a) Turn red litmus blue (b) Turn blue litmus red (a) BF3 (b) AlCl3
(c) Not effect litmus (d) Decolourises litmus (c) SnCl 4 (d) CCl 4
 75. Which one of the following salts gives an acidic solution in water
62. Cl is the conjugate base of
[NCERT 1979; CPMT 1976; MP PET/PMT 1988] (a) CH 3 COONa (b) NH 4 Cl
(a) HClO4 (b) HCl (c) NaCl (d) CH 3 COONH 4
(c) HOCl (d) HClO3 76. Which of the anhydrous salts when come in contact with water
turns blue [AMU 1981, 82]
63. Which of the following behaves as both Lewis and Bronsted base [MP PMT 2003]
(a) Ferrous sulphate (b) Copper sulphate
(a) BF3 (b) Cl  (c) Zinc sulphate (d) Cobalt sulphate
77. The species among the following, which can act as an acid and a
(c) CO (d) None of these base is [AIEEE 2002; KCET 2005]
64. The conjugate acid of a strong base is a [EAMCET 1979]
(a) HSO 4 (b) SO 42 
(a) Strong acid (b) Weak acid
(c) Strong base (d) Weak base (c) H 3 O  (d) Cl 
65. Which one is the weakest acid [DPMT 2002] 78. The strongest base from the following species is
(a) HNO 3 (b) HClO4 [KCET 1996]

(c) H 2 SO 4 (d) HBr (a) NH 2  (b) OH 

(c) O 2  (d) S 2
66. Conjugate base of HPO42  is [MP PMT 1995] 79. Which one is Lewis acid [CPMT 1997]
 
(a) PO43  (b) H 2 PO4 (a) Cl (b) Ag
(c) H 3 PO4 (d) H 4 PO3 (c) C 2 H 5 OH (d) S 2
67. Which of the following is not Lewis acid [RPET/PMT 2002] 80. The conjugate acid of H 2 PO4 is [MP PET 1990]
(a) FeCl3 (b) AlCl3
(a) H 3 PO4 (b) H 2 PO4
(c) BCl 3 (d) NH 3
(c) PO43  (d) H 3O 
68. (i) A strong acid has a weak conjugate base
(ii) An acid is an electron pair acceptor 81. The conjugate acid of S 2 O82  is [EAMCET 1984]
The above statements (i) and (ii) (a) H 2 S 2 O8 (b) H 2 SO 4
(a) Correct
(b) Wrong (c) HSO 4 (d) HS 2 O8
(c) (i) Correct and (ii) Wrong 82. In the reaction BCl 3  PH3  Cl 3 B  PH3 , Lewis base is
(d) (i) Wrong and (ii) Correct [EAMCET 1986]
69. The pH is less than 7, of the solution of (a) BCl 3 (b) PH 3
[Pb. PMT 2002; MP PMT 2003]
(c) Cl 3 B  PH3 (d) None of these
(a) FeCl3 (b) NaCN
83. Which of the following statement is true [MP PMT 1996]
 Ionic Equilibrium 355
(a) The conjugate base of a strong acid is a strong base 97. In the reaction HCl  H 2 O ⇌ H 3 O   Cl 
(b) The conjugate base of a weak acid is a strong base
[NCERT 1978; EAMCET 1982, 89]
(c) The conjugate base of a weak acid is a weak base
(d) The base and its conjugate acid react to form a neutral solution (a) H 2 O is the conjugate base of HCl acid

84. What is the conjugate base of OH  [AIEEE 2005] (b) Cl  is the conjugate base of HCl acid
(a) O 2 (b) H 2O (c) Cl  is the conjugate acid of H 2 O base

(c) O  (d) O 2  (d) H 3 O  is the conjugate base of HCl

85. Which of the following is a Lewis base [BHU 1995] 98. According to Lewis concept, an acid is a substance which
(a) CH 4 (b) C 2 H 5 OH [EAMCET 1981; NCERT 1981;
CPMT 1986; MP PMT 1987]
(c) Acetone (d) Secondary amine (a) Accepts protons
86. The correct order of acid strength is [CBSE PMT 2005] (b) Donates protons
(a) HClO  HClO2  HClO3  HClO4 (c) Accepts a lone pair of electrons
(d) Donates a lone pair of electrons
(b) HClO4  HClO  HClO2  HClO3
99. Water is a [KCET 2002]
(c) HClO2  HClO3  HClO4  HClO (a) Amphoteric acid (b) Aprotic solvent
(d) HClO4  HClO3  HClO2  HClO (c) Protophobic solvent (d) None of these
100. Conjugate base of NH 3 is [RPMT 2002]
87. The strongest acid is [DPMT 2000]
(a) H 3 AsO4 (b) H 3 AsO3 (a) NH 4 (b) NH 2
(c) H 3 PO3 (d) H 3 PO4 (c) NH 2 (d) N 2
88. Which of the following is the strongest base [Roorkee 2000] 101. Which of the following species is an acid and also a conjugate base
of another acid [NCERT 1981]
(a) C 2 H 5 (b) C2 H 5 COO 

(a) HSO 4 (b) H 2 SO 4

 
(c) C2 H 5 O (d) OH
(c) OH  (d) H 3O 
89. The aqueous solution of which one of the following is basic
[MP PMT 2001] 102. Which of the following is Lewis acid
[NCERT 1978; EAMCET 1987; MP PET 1994;
(a) HOCl (b) NaHSO 4 CPMT 1990; AFMC 1997; RPMT 1999]
(c) NH 4 NO 3 (d) NaOCl (a) BF3 (b) Cl 
90. Which of the following is the weakest base [IIT 1980] (c) H 2O (d) NH 3
(a) NaOH (b) Ca (OH )2 103. According to Bronsted-Lowry concept, base is a substance which is[NCERT 1982
(c) NH 4 OH (d) KOH (a) A proton donor
91. The suitable indicator for strong acid and weak base is (b) An electron pair acceptor
[RPMT 1997; UPSEAT 2002]
(c) A proton acceptor
(a) Methyl orange (b) Methyl red (d) An electron pair donor
104. Which of the following is known as hydronium ion
(c) Phenol red (d) Phenolphthalein
[NCERT 1976]
92. Among the following acids, the weakest one is
 
[NCERT 1984] (a) H (b) H 2O

(a) HF (b) HCl (c) H 3O (d) H 2 O 2
(c) HBr (d) HI 105. An aqueous solution of aluminium sulphate would show
93. The compound HCl behaves as …. in the reaction, [NCERT 1977]
HCl  HF  H 2 Cl  F  [JIPMER 2001] (a) An acidic reaction
(a) Weak base (b) Weak acid (b) A neutral reaction
(c) A basic reaction
(c) Strong base (d) Strong acid
(d) Both acidic and basic reaction
94. The conjugate base of a strong acid is a [EAMCET 1978]
106. The aqueous solution of aluminium chloride is acidic due to
(a) Strong base (b) Strong acid
[MNR 1986, 88]
(c) Weak acid (d) Weak base (a) Cation hydrolysis
95. Which among the following is strongest acid [BHU 2005] (b) Anion hydrolysis
(a) H(ClO)O 2
(b) H(ClO)O 3 (c) Hydrolysis of both anion and cation
(c) H(ClO)O (d) H(ClO) (d) Dissociation
96. In the reaction 2 H 2 O ⇄ H 3 O   OH  , water is 107. HSO 4 is the conjugate base of [NCERT 1977]
[MP PET 1989] 
(a) A weak base (a) H (b) H 2 SO 3
(b) A weak acid (c) SO 42  (d) H 2 SO 4
(c) Both a weak acid and a weak base
108. An acid is a compound which furnishes (Bronsted-Lowry concept)[EAMCET 1975
(d) Neither an acid nor a base
 356 Ionic Equilibrium
(a) An electron (b) A proton (d) None of these
(c) An electron and a proton (d) None of the above 122. Which shows weak ionisation in water [MH CET 2001]
109. The conjugate base of sulphuric acid is (a) H 2 SO 4 (b) NaCl
[EAMCET 1974]
(c) HNO 3 (d) NH 3
(a) Sodium hydroxide (b) Hydrochloric acid
(c) Bisulphate ion (d) Barium hydroxide 123. An organic dye, cosine used to detect end point of precipitation
titration by adsorption is called
110. Which is strongest Lewis base [CPMT 1994]
[MH CET 1999]
(a) SbH 3 (b) AsH3 (a) Absorption indicator (b) Adsorption indicator
(c) PH 3 (d) NH 3 (c) Chemical indicator (d) None of these
124. The indicator used in the titration of iodine against sodium
111. According to Bronsted principle, an aqueous solution of HNO 3 thiosulphate is [AFMC 2002]
will contain [MP PMT/PET 1988] (a) Starch (b) K 3 Fe(CN )6
(a) NO 2 (b) NO 3 (c) K 2 CrO4 (d) Potassium

(c) NO 2 (d) NO 125. Phenolphthalein does not act as an indicator for the titration
between [Pb. PMT 2002]
112. Aqueous solution of an acid is characterised by the presence of
(a) NaOH and CH 3 COOH
[NCERT 1977]
(a) 
H ions (b) H 2 ions (b) H 2 C2 O4 and KMnO4
(c) Ba(OH )2 and HCl
(c) H 3 O  ions (d) H 4 O  ions
(d) KOH and H 2 SO 4
113. Ammonium ion is [RPMT 1999; KCET 2002]
(a) Neither an acid nor base (b) Both an acid and a base 126. Which is not example of Bronsted Lowry theory
[AIEEE 2003]
(c) A conjugate acid (d) A conjugate base
(a) AlCl3 (b) H 2 SO 4
114. Aqueous solution of AlCl3 is [RPMT 2002]
(a) Acidic (b) Basic (c) SO 2 (d) HNO 3
(c) Amphoteric (d) None of these 127. An aqueous solution of sodium carbonate is alkaline because sodium
115. carbonate CET
The species which acts as a Lewis acid but not a Bronsted acid is [MP PMT 1999; Kurukshetra is a 2002]
salt of [MP PET 2002]
(a) Weak acid and weak base
(a) NH 2 (b) O 2  (b) Strong acid and weak base
(c) BF3 (d) OH  (c) Weak acid and strong base
(d) Strong acid and strong base
116. Among the following, the weakest base is [MP PMT 2002]
128. The acid that results when a base accepts a proton is called
(a) H  (b) CH 3 [Kerala (Med.) 2002]
(a) Conjugate base of the acid
(c) CH 3 O  (d) Cl  (b) Conjugate protonated base
117. Which of the following is not lewis base (c) Lewis base
[EAMCET 1975; RPMT 2002] (d) Conjugate acid of the base
(a) NH 3 (b) PH3 (e) None of these
(c) (CH 3 )3 N (d) HN 3 129. Ammonia gas dissolves in water to form NH 4 OH . In this reaction
118. pK a value of the strongest acid among the following is water acts as [KCET (Engg./Med.) 1999]
(a) A conjugate base (b) A non-polar solvent
[MP PMT 1990]
(c) An acid (d) A base
(a) 3.0 (b) 4.5
(c) 1.0 (d) 2.0 130. The conjugate base in the following reaction
119. The most acidic compound in water is [CBSE PMT 2001] H 2 SO 4  H 2 O ⇄ H 3 O   HSO 4 [DCE 1999]
(a) AlCl3 (b) BeCl 2 (a) H 2O (b) HSO 4
(c) FeCl3 (d) None of these
(c) H 3O  (d) SO 2
120. BF3 is used as a catalyst in several industrial processes due to its 131. [Kerala (Med.) 2002]
An aqueous solution of aluminium sulphate shows
(a) Strong reducing agent [DPMT 2001]
(b) Weak reducing agent (a) A basic nature
(b) An acidic nature
(c) Strong Lewis acid nature
(c) A neutral nature
(d) Weak Lewis acid character
(d) Both acidic and basic nature
121. The aqueous solution of AlCl3 is acidic due to the hydrolysis of 132. [UPSEAT of
Neutralization 2001,
an02]acid with a base invariably results in the
(a) Aluminium ion production of [CPMT 1983]
(b) Chloride ion (a) H 3O  (b) OH 
(c) Both aluminium and chloride ion
 Ionic Equilibrium 357

(c) H 2O (d) H  and OH  (a) CH 3  (b) F

133. The conjugate acid of HPO42  is (c) NH 2  (d) OH 
[MP PMT 1987, 90, 91; EAMCET 1993]
146. The aqueous solution of CuSO 4 is [CPMT 1985]
(a) H 2 PO4 (b) PO43  (a) Acidic (b) Basic
(c) H 3 PO4 (d) H 3 PO3 (c) Neutral (d) Amphoteric
134. Which of the following is not used as a Lewis acid 147. The acid having the highest pKa value among the following is
[MP PET 2000] (a) HCOOH (b) CH 3 COOH
(a) SnCl 4 (b) FeCl3
(c) ClCH 2 COOH (d) FCH 2 COOH
(c) KCl (d) BF3 148. The indicator used in the titration of sodium carbonate with
135. Orthoboric acid in aqueous medium is [AMU 2000] sulphuric acid is [DPMT 2001]
(a) Monobasic (b) Dibasic (a) Phenolphthalein
(c) Tribasic (d) All are correct (b) Methyl orange
136. According to Lewis concept which one of the following is not a base[MP PET/PMT 1988;
(c) Pb.
Potassium ferrocynide
CET 2003]
(a) OH 
(b) H 2 O (d) Potassium ferricynide
149. According to Bronsted law, water is a/an
(c) Ag  (d) NH 3 [MP PET/PMT 1988]
137. The aqueous solution of ammonium chloride is (a) Base (b) Acid
[CPMT 1987] (c) Acid and base both (d) Salt
(a) Neutral (b) Basic 150. Which of the following can give base OH 
(c) Acidic (d) Amphoteric [MP PET/PMT 1988]
138. In the process BCl3  PH3  BCl3 : PH3 The Lewis acid is
(a) H 2 O (b) H 3 O 
[RPMT 2000]
(a) PH3 (b) BCl 3 (c) H2 (d) HCl
(c) Both (d) None 151. Conjugate base of HBr is [MP PET/PMT 1988]
139. The conjugate acid of NH 3 is  
(a) H 2 Br (b) H
[BHU Varanasi 1999; Pb. PMT 2004]
(c) Br  (d) Br 
(a) NH 3 (b) NH 4
152. Molar heat of neutralization of NaOH with HCl in comparison
(c) N2H4 (d) NH 2 OH to that of KOH with HNO 3 is [MP PMT 1989]
140. Which halide of nitrogen is least basic [DPMT 2001] (a) Less (b) More
(a) NBr3 (b) NI 3 (c) Equal (d) Depends on pressure
(c) NCl 3 (d) NF3 153. Which of the following is not a Lewis acid [J & K 2005]
(a) BF3 (b) AlCl3
141. When FeCl3 gets soluble in water, then its solution represents
which of the characteristics [MP PET/PMT 1988] (c) HCl (d) LiAlH4
(a) Amphoteric (b) Acidic 154. The solvent which neither accepts proton nor donates proton is
(c) Basic (d) Neutral called [RPMT 2000]
142. Lewis acid are those substances [MP PMT 1987] (a) Amphoteric (b) Neutral
(a) Which accept electron pair (c) Aprotic (d) Amphiprotic
(b) Which provide H  ion in the solution
155. For the reaction in aqueous solution Zn 2   X  ⇄ ZnX  , the
(c) Which give electron pair
K eq is greatest when X is [Pb. PMT 1998]
(d) Which accept OH  ion
(a) F (b) NO 3
143. The conjugate base of HCO 3 is

(a) H 2 CO 3 (b) CO 32  (c) ClO4 (d) I

156. Why are strong acids generally used as standard solutions in acid-
(c) CO 2 (d) H 2O base titrations [Pb. PMT 1998]
144. In the reaction NH 3  BF3 ⇌ NH 3  BF3 , BF3 is (a) The pH at the equivalence point will always be 7
[MP PMT 1989; MHCET 2001] (b) They can be used to titrate both strong and weak bases
(a) Lewis acid (c) Strong acids form more stable solutions than weak acids
(b) Lewis base (d) The salts of strong acids do not hydrolysed
(c) Neither Lewis acid nor Lewis base 157. For an aqueous solution, the characteristic species of acid is
(d) Lewis acid and Lewis base both [RPMT 1999]
145. The strongest Lewis base in the following
 
[MP PET/PMT 1988] (a) H ion (b) H 3 O ion
 358 Ionic Equilibrium

(c) H 2  ion (d) H 4 O  ion (a) 2.0  10 6 M (b) 1.0  10 4 M

158. Which is a Lewis base [CPMT 1988; JEE Orissa 2004] (c) 1.6  10 4 M (d) 4.0  10 10 M
4. In a saturated solution of electrolyte, the ionic product of their
(a) B2 H 6 (b) LiAlH4 concentration are constant at constant temperature and this
(c) AlH3 (d) NH 3 constant for electrolyte is known as [CPMT 1983]
(a) Ionic product (b) Solubility product
159. For a weak acid, the incorrect statement is [Pb. PMT 2004] (c) Ionization constant (d) Dissociation constant
(a) Its dissociation constant is low 5. If the solubility product K sp of a sparingly soluble salt MX 2 at
(b) Its pKa is very low
25C is 1.0  10 11 , the solubility of the salt in mole litre at this –1

(c) It is partially dissociated temperature will be [RPMT 2000]

(d) Solution of its sodium salt is alkaline in water (a) 2.46  1014 (b) 1.36  10 4
160. Boron halides behave as Lewis acids, because of their (c) 2.60  10 7 (d) 1.20  10 10
[CBSE PMT 1996; BHU 2004]
6. The unit of ionic product of water Kw are
(a) Ionic nature (b) Acidic nature
[UPSEAT 2001, 02]
(c) Covalent nature (d) Electron deficient nature
(a) Mol1 L1 (b) Mol2 L2
161. Would gaseous HCl be considered as an Arrhenius acid
[UPSEAT 2004] (c) Mol2 L1 (d) Mol2 L2
3
(a) Yes 7. A solution which is 10 M each in Mn2  , Fe2  , Zn 2  and
(b) No Hg 2  is treated with 10 16 M sulphide ion. If K sp of
(c) Not known
(d) Gaseous HCl does not exist MnS, FeS , ZnS and HgS are 10 15 ,10 23 ,10 20 and 10 54
162. Which one of the following is called amphoteric solvent respectively, which one will precipitate first
[IIT Screening 2003]
[UPSEAT 2004]
(a) FeS (b) MgS
(a) Ammonium hydroxide (b) Chloroform
(c) Benzene (d) Water (c) HgS (d) ZnS
163. Strongest conjugate base is [DPMT 2004] 8. Let the solubility of an aqueous solution of Mg(OH )2 be x then its
(a) Cl  (b) Br  k sp is [AIEEE 2002]
  (a) 4x 3
(b) 108 x 5
(c) F (d) I
4
164. The conjugate base of H 2 PO4 is [AIEEE 2004] (c) 27 x (d) 9 x
9. The solubility product of BaSO4 at 25C is 1.0  10 9 . What
(a) H 3 PO4 (b) P2 O 5
would be the concentration of H 2 SO 4 necessary to precipitate
(c) PO43  (d) HPO42  BaSO4 from a solution of 0.01 M Ba2  ions
[RPMT 1999]
165. Conjugate base of HSO 4 is [MH CET 2004]
(a) 10 9 (b) 10 8
(a) SO 42  (b) H 2 SO 4 (c) 10 7
(d) 10 6
10. The solubility in water of a sparingly soluble salt AB2 is
(c) H 3 SO 4 (d) None of these
5 1
1.0  10 mol l . Its solubility product number will be
Common ion effect, Isohydric solutions, Solubility [AIEEE 2003]
product, Ionic product of water and Salt hydrolysis (a) 4  10 15
(b) 4  10 10

(c) 1  10 15 (d) 1  10 10

1. The expression for the solubility product of Al2 (SO 4 )3 is
11. The solubility of CaF2 is a moles/litre. Then its solubility product
(a) K sp  [ Al 3  ] (SO 42  ] (b) K sp  [ Al 3  ]2 (SO 42  ]3 is ….. [Orissa JEE 2002]
(c) K sp  [ Al 3  ]3 (SO 42  ]2 (d) K sp  [ Al 3  ]2 (SO 42  ]2 (a) s2 (b) 4 s3
2. On addition of ammonium chloride to a solution of ammonium (c) 3s 2 (d) s3
hydroxide [CPMT 1976, 80, 81, 99;
NCERT 1976, 77; MP PMT 1989, 99; DPMT 1983] 12. On passing a current of HCl gas in a saturated solution of NaCl,
(a) Dissociation of NH 4 OH increases the solubility of NaCl
[CPMT 1989; CBSE PMT 1989]
(b) Concentration of OH  increases (a) Increases (b) Decreases
(c) Concentration of OH  decreases (c) Remains unchanged (d) NaCl decomposes
(d) Concentration of NH 4 and OH  increases 13. Which is the correct representation of the solubility product
3. The solubility product of a salt having general formula MX 2 , in constant of Ag 2 CrO4 [NCERT 1974, 75]

water is : 4  10 12 . The concentration of M 2  ions in the (a) [ Ag  ]2 [CrO42 ] (b) [ Ag  ] [CrO42 ]
aqueous solution of the salt is [AIEEE 2005]
 Ionic Equilibrium 359

(c) [2 Ag  ] [CrO42 ] (d) [2 Ag  ]2 [CrO42 ] 24. Which is the correct alternate for hydrolysis constant of NH 4 CN [CBSE PMT 1

14. The solubility of CaF2 is 2  10 4 moles / litre. Its solubilily (a)

Kw
(b)
Kw
product (K sp ) is [NCERT 1981; BHU 1983, 86; Ka Ka  Kb
MP PET 1992; CBSE PMT 1999] Kb Ka
4 3
(c) (d)
(a) 2.0  10 (b) 4.0  10 c Kb
12
(c) 8.0  10 (d) 3.2  10 11 25. Which of the following salts undergoes hydrolysis
25
[CPMT 1972, 74, 78; DPMT 1985]
15. Solubility product of a sulphide MS is 3  10 and that of another (a) (b)
CH 3 COONa KNO 3
sulphide NS is 4  10 40 . In ammoniacal solution
[NCERT 1981]
(c) NaCl (d) K 2 SO 4
(a) Only NS gets precipitated 26. What will happen if CCl 4 is treated with AgNO3
(b) Only MS gets precipitated [DPMT 1983]
(c) No sulphide precipitates (a) A white ppt. of AgCl will form
(d) Both sulphides precipitate (b) NO 2 will be evolved
16. Which of the following salts when dissolved in water will get
hydrolysed (c) CCl 4 will dissolve in AgNO3
[MNR 1985; CPMT 1989; CBSE PMT 1989; MP PET 1999] (d) Nothing will happen
(a) NaCl (b) NH 4 Cl 27. The correct representation for solubility product of SnS 2 is
[CPMT 1977; MP PET 1999;RPMT 2000]
(c) KCl (d) Na 2 SO 4
4 2 2
(a) [Sn ] [S ] (b) [Sn 2  ] [S 2  ]2
17. The aqueous solution of FeCl3 is acidic due to
[CPMT 1972, 79, 83, 84; (c) [Sn 2  ] [2S 2  ] (d) [Sn 4  ] [2S 2  ]2
MP PET/PMT 1988; RPMT 2000] 28. A precipitate of calcium oxalate will not dissolve in
(a) Acidic impurities (b) Ionisation [CPMT 1971, 89; IIT 1986]
(c) Hydrolysis (d) Dissociation (a) HCl (b) HNO 3
18. A precipitate of AgCl is formed when equal volumes of the
(c) Aquaregia (d) CH 3 COOH
following are mixed. [K sp for AgCl  10 10 ] [KCET 2005]
29. Baking soda is [RPMT 2000]
(a) 10 4 M AgNO3 and 10 7 M HCl (a) Basic salt (b) Acidic salt
(c) Complex salt (d) Double salt
(b) 10 5 M AgNO3 and 10 6 M HCl 30. Which one of the following substances will be a mixed salt
[DPMT 1982; CPMT 1972]
(c) 10 5 M AgNO3 and 10 4 M HCl (a) NaHCO 3
(d) 10 6 M AgNO3 and 10 6 M HCl (b) Ca(OCl)Cl
19. The solubility of silver chromate in 0.01 M K 2 CrO4 is (c) K 2 SO 4 Al2 (SO 4 )3 .24 H 2 O
(d) Mg (OH )Br
2  10 8 mol dm 3 . The solubility product of silver chromate will
be [MH CET 2000] 31. Solubility product of BaCl2 is 4  10 9 . Its solubility in
24 24 moles/litre would be
(a) 8  10 (b) 16  10
18
[AFMC 1982; Roorkee 1990; BHU 2000]
(c) 1.6  10 (d) 16  10 18 3
(a) 1  10 (b) 1  10 9
20. Some salts although containing two different metallic elements give
27
test for only one of them in solution. Such salts are [MNR 1979] (c) 4  10 (d) 1  10 27
(a) Double salts (b) Normal salts 32. Which hydroxide will have lowest value of solubility product at
(c) Complex salts (d) Basic salts normal temperature (25 o C) [IIT 1990; RPMT 1997]
N (a) Mg (OH )2 (b) Ca (OH )2
21. What is the pH value of KOH solution
1000
(c) Ba (OH )2 (d) Be (OH )2
[CPMT 1975; MNR 1986, 91; Pb. CET 2004]
33. Which will not be hydrolysed [MP PMT 1989]
(a) 10 11 (b) 3 (a) Potassium nitrate
(c) 2 (d) 11 (b) Potassium cyanide
22. Mohr's salt is a [MNR 1986] (c) Potassium succinate
(a) Normal salt (b) Acid salt (d) Potassium carbonate
(c) Basic salt (d) Double salt 34. Which pair will show common ion effect
23. Aqueous solution of sodium acetate is [MP PMT 1990, 99; Pb. PMT 2001]
[MNR 1978; CPMT 1971, 80, 81; (a) BaCl2  Ba (NO 3 )2 (b) NaCl  HCl
MADT Bihar 1982; MP PMT 1985;]
(a) Neutral (b) Weakly acidic (c) NH 4 OH  NH 4 Cl (d) AgCN  KCN
(c) Strongly acidic (d) Alkaline 35. Which is least soluble in water [UPSEAT 1999]
 360 Ionic Equilibrium
(a) AgCl (b) AgF 47. The solubility of AgI in NaI solution is less than that in pure
(c) AgI (d) Ag2 S water because [UPSEAT 2001]
(a) AgI forms complex with NaI
36. A white salt is readily soluble in water and gives a colourless
(b) Of common ion effect
solution with a pH of about 9. The salt would be (c) Solubility product of AgI is less than that of NaI
[Pb. PMT 1998] (d) The temperature of the solution decreases
(a) NH 4 NO 3 (b) CH 3 COONa
48. The solubility product of BaSO 4 is 1.5  10 9. The precipitation
(c) CH 3 COONH 4 (d) CaCO 3
in a 0.01 M Ba 2  solution will start, on adding H 2 SO 4 of

37. If acetic acid mixed with sodium acetate, then H ion concentration concentration [CPMT 1988]
will be [Roorkee 1995]
(a) Increased (b) Decreased (a) 10 9 M (b) 10 8 M
7
(c) Remains unchanged (d) pH decreased (c) 10 M (d) 10 6 M
38. Solubility of AgCl will be minimum in 49. At 20 o C, the Ag  ion concentration in a saturated solution of
[CBSE PMT 1995] Ag 2 CrO4 is 1.5  10 4 mole / litre. At 20 o C, the solubility
(a) 0.001 M AgNO3 (b) Pure water product of Ag 2 CrO4 would be
(c) 0.01 M CaCl 2 (d) 0.01 M NaCl [MP PET 1997; MP PMT 1999]
39. In absence of formation of complex ions by the addition of a (a) 3.3750  10 12 (b) 1.6875  10 10
common ion, the solubility of a given salt is [BHU 1979]
(a) Increased (c) 1.6875  10 12 (d) 1.6875  10 11
(b) Decreased 50. The solubility of PbCl2 is [MP PMT 1995; DCE 1999]
(c) Unaffected 3
(a) K sp (b) K sp
(d) First increased and then decreased
6
40. At 298 K, the solubility product of PbCl2 is 1.0  10 . What 3 K sp
(c) (d) 8 K sp
will be the solubility of PbCl2 in moles/litre 4
[MP PMT 1990; CPMT 1985, 96] 51. The solubility product of AgCl is 1.44  10 4 at 100 o C . The
3 3
(a) 6.3  10 (b) 1.0  10 solubility of silver chloride in boiling water may be
3 [MP PMT 1994; Bihar MEE 1998]
(c) 3.0  10 (d) 4.6  10 14 4
41. Solubility product is [CET Pune 1998] (a) 0.72  10 M (b) 1.20  10 2 M
(a) The ionic product of an electrolyte in its saturated solution (c) 0.72  10 2 M (d) 1.20  10 4 M
(b) The product of the solubilities of the ions of the electrolyte
(c) The product of solubilities of the salts 52. If the solubility of a sparingly soluble salt of the type BA2 (giving
(d) The product of the concentration of the ions three ions on dissociation of a molecule) is x moles per litre, then
42. Ionic product of water increases, if its solubility product is given by [BHU 1987]
[AMU 1983; MP PET 1986; MP PET/PMT 1988; (a) x2 (b) 2x 3
JIPMER 2002]
(c) 4x2 (d) 4x3
(a) Pressure is reduced (b) H  is added
(c) OH  is added (d) Temperature increases 53. The solubility product of Ag 2 CrO4 is 32  10 12 . What is the
43. Which one is a mixed salt [DPMT 1985] concentration of CrO4 ions in that solution
(a) NaHSO 4 (b) NaKSO 4 [BHU 1997; DPMT 2004]
(c) K 4 Fe(CN )6 (d) Mg(OH )Cl (a) 2  10 4 m / s (b) 16  10 4 m / s
44. If K sp for HgSO4 is 6.4  10 5 , then solubility of the salt is (c) 8  10 4 m / s (d) 8  10 8 m / s
[AFMC 1997; KCET 2000; CPMT 2000; JIPMER 2001]
54. The addition of HCl will not suppress the ionization of
(a) 8  10 3 (b) 8  10 6 [MP PET 1993]
(c) 6.4  10 5 (d) 6.4  10 3 (a) Acetic acid (b) Benzoic acid
45. The solubility of BaSO 4 in water is 2.33  10 3 gm / litre. Its (c) H 2 S (d) Sulphuric acid
2
solubility product will be (molecular weight of BaSO4  233) [AIIMS 1998]
55. On the addition of a solution containing CrO4 ions to the
5 10 2 2 2
(a) 1  10 (b) 1  10 solution of Ba , Sr and Ca ions, the precipitate obtained
15 20 first will be of
(c) 1  10 (d) 1  10 [MP PMT 1993]
46. The solubility of AgCl in 0.2 M NaCl solution (K sp for (a) CaCrO4 (b) SrCrO4

AgCl  1.20  10 10

) is [MP PET 1996] (c) BaCrO4 (d) Mixture of (a), (b), (c)
10 56. The solubility product of a sparingly soluble salt AB at room
(a) 0.2 M (b) 1.2  10 M
temperature is 1.21  10 6 . Its molar solubility is
(c) 0.2  10 10 M (d) 6.0  10 10 M [CPMT 1987; MP PET 2001]
6
(a) 1.21  10 (b) 1.21  10 3
 Ionic Equilibrium 361

(c) 1.1  10 4 (d) 1.1  10 3 66. When NH 4 Cl is added to NH 4 OH solution, the dissociation of
57. The precipitation occurs if ionic concentration is ammonium hydroxide is reduced. It is due to
[AFMC 1995; J & K 2005] [MP PMT 1993]
(a) Less than solubility product (a) Common ion effect (b) Hydrolysis
(b) More than solubility product (c) Oxidation (d) Reduction
(c) Equal to solubility product 67. At 298 K, the solubility of PbCl2 is 2  10 2 mol/lit , then k sp 
(d) None of these
[RPMT 2002]
58. If S and K sp are respectively solubility and solubility product of a 7 7
(a) 1  10 (b) 3.2  10
sparingly soluble binary electrolyte, then
[CPMT 1988; MP PMT 1999] (c) 1  10 5 (d) 3.2  10 5
(a) S  K sp (b) S  K sp
2 68. The solubility product of silver sulphide is 3.2  10 11. Its solubility
at the experimental temperature is
(c) S  K sp (d) S 
1
K sp (a) 2  10 4 moles per litre
2 (b) 6  10 6 moles per litre
59. Any precipitate is formed when
[AIIMS 1982; DPMT 1985; KCET 1999; MP PMT 2004]
(c) 1.2  10 5 moles per litre
(a) Solution becomes saturated (d) 8  10 4 moles per litre
(b) The value of ionic product is less that than the value of 69. The solubility of CaCO 3 in water is 3.05  10 4 moles / litre. Its
solubility product solubility product will be [MP PMT 1997]
(c) The value of ionic product is equal than the value of solubility
product (a) 3.05  10 4 (b) 10
4
(d) The value of ionic product is greater than the value of (c) 6.1  10 (d) 9.3  10 8
solubility product 70. Solubility of BaF2 in a solution Ba(NO 3 )2 will be represents by
60. The solubility product of AgCl is 4.0  10 10 at 298 K. The the concentration term
solubility of AgCl in 0.04 m CaCl 2 will be [UPSEAT 2001, 02; CPMT 2002]

[KCET 1996] (a) [Ba ] (b) [F  ]
(a) 2.0  10 5 m (b) 1.0  10 4 m 1 
(c) [F ] (d) 2 [ NO 3 ]
9 4 2
(c) 5.0  10 m (d) 2.2  10 m
61. Hydrolysis of sodium acetate will give [MNR 1978] 71. The solubility of PbCl2 at 25 o C is 6.3  10 3 mole/litre. Its
(a) Acidic solution (b) Basic solution solubility product at that temperature is
(c) Neutral solution (d) Normal solution [NCERT 1979; CPMT 1985]
9 3 3
62. If the solubility product of BaSO 4 is 1.5  10 in water, its (a) (6.3  10 )  (6.3  10 )
solubility in moles per litre, is
(b) (6.3  10 3 )  (12.6  10 3 )
[BHU 1995; MP PET 1995; UPSEAT 204]
(a) 1.5  10 9 (b) 3.9  10 5 (c) (6.3  10 3 )  (12.6  10 3 )2
(c) 7.5  10 5 (d) 1.5  10 5 (d) (12.6  10 3 )  (12.6  10 3 )
63. On passing H 2 S gas through a highly acidic solution containing 72. Which of the following cannot be hydrolysed
2 [MP PMT 1996]
Cd ions, CdS is not precipitated because
(a) Of common ion effect (a) A salt of weak acid and strong base
(b) The solubility of CdS is low (b) A salt of strong acid and weak base
(c) A salt of weak acid and weak base
(c) Cd 2  ions do not form complex with H 2 S
(d) A salt of strong acid and strong base
(d) The solubility product of CdS is low 73. pH of water is 7. When a substance Y is dissolved in water, the
64. Which of the following will occur if a 0.1 M solution of a weak acid
pH becomes 13. The substance Y is a salt of
is diluted to 0.01 M at constant temperature
[MP PMT 1997]
[UPSEAT 2001, 02]
(a) Strong acid and strong base
(a) [H  ] will decrease to 0.01 M (b) Weak acid and weak base
(b) pH will decrease (c) Strong acid and weak base
(c) Percentage ionization will increase (d) Weak acid and strong base
(d) K a will increase 74. Which is a basic salt [MP PMT 1985]
(a) PbS (b) PbCO3
65. If solubility of calcium hydroxide is 3 , then its solubility product
will be [MH CET 2002] (c) PbSO4 (d) 2 PbCO3 .Pb(OH )2
(a) 27 (b) 3
75. The saturated solution of Ag 2 SO 4 is 2.5  10 2 M . Its solubility
(c) 9 (d) 12 3
product (K sp ) is [NCERT 1980]
 362 Ionic Equilibrium

(a) 62.5  10 6 (b) 6.25  10 4 (c) Ionic product of NaCl becomes greater than its K sp
6 6
(c) 15.625  10 (d) 3.125  10 (d) HCl is a weak acid
76. K sp for sodium chloride is 36 mol 2 / litre2 . The solubility of 85. The solubility product of BaSO 4 is 1.3  10 9 . The solubility of
sodium chloride is [BHU 1981]
this salt in pure water will be [MP PET 2002]

1 1 (a) 1.69  10 9 mol litre1 (b) 1.69  10 18 mol litre1

(a) (b)
36 6 (c) 3.6  10 18 mol litre1 (d) 3.6  10 5 mol litre1
(c) 6 (d) 3600 86. The solubility product of AgCl under standard conditions of
77. Sodium chloride is purified by passing hydrogen chloride gas in an temperature is given by [Kerala (Med.) 2003]
impure solution of sodium chloride. It is based on
[MP PMT 1996]
(a) 1.6  10 5 (b) 1.5  10 8
10
(a) Buffer action (b) Common ion effect (c) 3.2  10 (d) 1.5  10 10
(c) Association of salt (d) Hydrolysis of salt 87. An aqueous solution of CH 3 COONa will be
78. If the concentration of lead iodide in its saturated solution at [MP PET 2001]
(a) Acidic (b) Alkaline
25 o C be 2  10 3 moles per litre, then its solubility product is[CPMT 1984]
(c) Neutral (d) None of these
(a) 4  10 6 (b) 8  10 12 88. In which of the following salt hydrolysis takes place
9 9 [CPMT 1974, 78]
(c) 6  10 (d) 32  10
(a) KCl (b) NaNO 3
79. The precipitate of CaF2 (K sp  1.7  10 10 ) is obtained when
(c) CH 3 COOK (d) K 2 SO 4
equal volumes of the following are mixed
[IIT 1992; UPSEAT 2000] 89. At 90 C pure water has [H 3 O ]  10 6 M , the value of K w at
o 

(a) 10 4 M Ca 2   10 4 M F  this temperature will be

[IIT 1981; MNR 1990; CBSE PMT 1993; UPSEAT 1999]
(b) 10 2 M Ca 2   10 3 M F  (a) 10 6 (b) 10 12
14
(c) Both (c) 10 (d) 10 8
(d) None of these
90. Solubility of MX 2 type electrolyte is 0.5  10 4 mole/litre. The
80. In the reaction: H 2 S ⇄ 2 H   S   , when NH 4 OH is added, value of K sp of the electrolyte is [CBSE PMT 2002]
then [KCET (Med.) 1999; AFMC 2000]
(a) 5  10 13 (b) 25  10 10
(a) S   is precipitate 13
(b) No action takes places (c) 1.25  10 (d) 5  1012
(c) Concentration of S   decreases 91. According to the reaction PbCl2  Pb 2  2Cl  , the solubility
 coefficient of PbCl2 is [MP PET/PMT 1988]
(d) Concentration of S increases
2  2
81. What is the minimum concentration of SO 42  required to precipitate (a) [Pb ][Cl ] (b) [Pb ][Cl  ]
2

BaSO4 in a solution containing 1.0  10 4 mol Ba 2  ? ( K sp for (c) [Pb 2  ]2 [Cl  ] (d) None of these
BaSO4 is 4  10 10
) 92. K sp value of Al (OH )3 and Zn (OH )2 are 8.5  10 23 and
[MP PMT 2000] 1.8  10 14 respectively. If NH 4 OH is added in a solution of
10 7
(a) 4  10 M (b) 2  10 M
Al 3  and Zn 2  , which will precipitate earlier
(c) 4  10 6 M (d) 2  10 3 M [MP PMT 1989; CPMT 1989]
82. Solubility product for salt AB2 is 4  10 12 . Calculate solubility [RPET 2003] (a) Al (OH )3 (b) Zn (OH )2
3 (c) Both together (d) None
(a) 1  10 gm mol / litre
93. Why pure NaCl is precipitated when HCl gas is passed in a
(b) 1  10 5 gm mol / litre saturated solution of NaCl
[NCERT 1977; MP PMT 1987; CPMT 1974, 78, 81]
(c) 1  10 4 gm mol / litre (a) Impurities dissolves in HCl
(d) 1  10 2 gm mol / litre (b) The value of [ Na  ] and [Cl  ] becomes smaller than K sp of
83. Solubility product of a salt AB is 1  10 8 in a solution in which NaCl
concentration of A is 10 3 M . The salt will precipitate when the (c) The value of [ Na  ] and [Cl  ] becomes greater than K sp of
concentration of B becomes more than
NaCl
[MP PET 1990; KCET 2003]
(d) HCl dissolves in the water
(a) 10 4 M (b) 10 7 M 94. Pure NaCl is prepared by saturating a cold saturated solution of
6
(c) 10 M (d) 10 5 M common salt in water with HCl gas. The principle used is
84. At equilibrium, if to a saturated solution of NaCl, HCl is passed, (a) Le Chatelier principle (b) Displacement law
(c) Common ion effect (d) Fractional distillation
NaCl gets precipitated because [RPMT 1999]
95. What is the solubility of calcium fluoride in a saturated solution, if
(a) HCl is a strong acid
its solubility product is 3.2  10 11
(b) Solubility of NaCl decreases [CPMT 1997]
 Ionic Equilibrium 363

(a) 2.0  10 4 mole / litre (b) 12.0  10 3 mole / litre (a) OH  (b) NH 4
(c) 0.2  10 4 mole / litre (d) 2  10 3 mole / litre (c) H 3O  (d) O 2
96. The following equilibrium exists in an aqueous solution of hydrogen 107. The compound insoluble in acetic acid is [IIT 1986]
sulphide :
(a) Calcium oxide
H 2 S ⇄ H   HS  (b) Calcium carbonate
If dilute HCl is added to an aqueous solution of H 2 S without (c) Calcium oxalate
any change in temperature [NCERT 1989] (d) Calcium hydroxide
(a) The equilibrium constant will change 108. A saturated solution of Ag 2 SO 4 is 2.5  10 2 M; The value of its
(b) The concentration of HS  will increase solubility product is [Pb.CET 2004]
(c) The concentration of undissociated H 2 S will decrease
(a) 62.5  10 6 (b) 6.25  10 4
(d) The concentration of HS  will decrease
(c) 15.625  10 6 (d) 3.125  10 6
97. Solubility of a salt M 2 X 3 is y mol dm 3 . The solubility product
of the salt will be 109. Solubility product of AgCl is 1  10 6 at 298 K. Its solubility in
[IIT 1990, 97; AFMC 1991; RPMT 1999; mole litre1 would be [Pb.CET 2001]
MP PET 2001; MP PMT 2003; Orissa JEE 2005]
6
(a) 1  10 mol / litre
(a) 6y 4 (b) 64y 4
(c) 36y 5 (d) 108y 5 (b) 1  10 3 mol / litre
98. Which one of the following is most soluble (c) 1  10 12 mol / litre
[CBSE PMT 1994; RPMT 2000]
(d) None of these
(a) CuS (K sp  8  10 37 ) (b) MnS (K sp  7  10 16 ) 110. A litre of solution is saturated with AgCl. To this solution if
(c) Bi2 S 3 (K sp  1  10 70
) (d) Ag 2 S (K sp  6  10 51
) 1.0  10 4 mole of solid NaCl is added, what will be the [ Ag  ] ,
assuming no volume change [UPSEAT 2004]
99. The solubility product of PbCl2 at 20 o C is 1.5  10 4 . (a) More (b) Less
Calculate the solubility [Bihar CEE 1995; BHU 2002] (c) Equal (d) Zero
(a) 3.75  10 4 (b) 3.34  10 2 111. The concentration of KI and KCl in certain solution containing both
(c) 3.34  10 2 (d) None of these is 0.001M each. If 20 ml of this solution is added to 20 ml of a
saturated solution of AgI in water? What will happen [MP PMT 2004]
100. Which one of the following compounds is a Lewis acid
[EAMCET 1997] (a) AgCl will be precipitated
(a) PCl3 (b) BCl 3 (b) AgI will be precipitated
(c) Both AgCl and AgI will be precipitated
(c) NCl 3 (d) CHCl 3
(d) There will be no precipitated
101. Which one of the following salt is most acidic in water
112. The solubility product of a sparingly soluble salt AX 2 is
[IIT 1995]
11
(a) NiCl2 (b) BeCl 2 3.2  10 . Its solubility (in moles / litres) is
[CBSE PMT 2004]
(c) FeCl3 (d) AlCl3 4 4
(a) 2  10 (b) 4  10
102. Which of the following aqueous solution will have a pH less than
(c) 5.6  10 6 (d) 3.1  10 4
7.0 [MP PMT 1991, 92]
113. 0.5 M ammonium benzoate is hydrolysed to 0.25 percent, hence its
(a) KNO 3 (b) NaOH hydrolysis constant is [MH CET 2004]
(c) FeCl3 (d) NaCN (a) 2.5  10 5 (b) 1.5  10 4
103. Hydrolysis constant for a salt of weak acid and weak base would be (c) 3.[RPMT 10 6
125 1999] (d) 6.25  10 4
Kw Kw The solubility of Sb 2 S 3 in water is 1.0  10 5 mol / litre at 298 K.
(a) Kh  (b) Kh  114.
Ka Kb What will be its solubility product [CPMT 2004]

(c) Kh 
Kw
(d) None of these (a) 108  10 25 (b) 1.0  10 25
K a Kb (c) 144  10 25 (d) 126  10 24
104. Which salt will give basic solution on hydrolysis
115. The ionic product of water at 25 o C is 10 14 . The ionic product
[RPMT 1997]
at 90 o C will be [CBSE PMT 1996]
(a) KCN (b) KCl
(c) NH 4 Cl (d) CH 3 COONH 4 (a) 1  10 20 (b) 1  10 12
105. Which of the following sulphides has the lowest solubility product[KCET 1996] (c) 1  10 14 (d) 1  10 16
(a) FeS (b) MnS 116. In hydrolysis of a salt of weak acid and strong base, A   H 2 O ⇄
(c) PbS (d) ZnS HA  OH  , the hydrolysis constant (Kh ) is equal to.…
106. The concentration of which ion is to be decreased, when NH 3
solution is added [RPMT 1997]
 364 Ionic Equilibrium

(a)
Kw
(b)
Kw (c) 10 5 (d) 10 9
Ka Kb
11. The pH of a solution in which the [H  ]  0.01, is
Ka Kw [MADT Bihar 1980]
(c) (d) (a) 2 (b) 1
C K a  Kb
(c) 4 (d) 3
12. At 25°C, the dissociation constant of a base BOH is 1.0  10 12 .
Hydrogen ion concentration- pH scale and The concentration of Hydroxyl ions in 0.01 M aqueous solution of
the base would be [CBSE PMT 2005]
Buffer solution
(a) 2.0  10 6 mol L1 (b) 1.0  10 5 mol L1
1. The pH of blood does not appreciably change by a small addition (c) 1.0  10 6 mol L1 (d) 1.0  10 7 mol L1
of an acid or a base because blood
[CBSE PMT 1995] 13. Aqueous solution of HCl has the pH  4 . Its molarity would be
(a) Contains serum protein which acts as buffer (a) 4 M (b) 0.4 M
(b) Contains iron as a part of the molecule (c) 0.0001 M (d) 10 M
(c) Can be easily coagulated 14. Which is a buffer solution
(d) It is body fluid [CPMT 1985, 88; AIIMS 1980; MP PMT 1994; AFMC 2004]
2. The pH of a 0.001 M NaOH will be (a) CH 3 COOH  CH 3 COONa
[MP PMT 1995; UPSEAT 2001]
(b) CH 3 COOH  CH 3 COONH 4
(a) 3 (b) 2
(c) 11 (d) 12 (c) CH 3 COOH  NH 4 Cl
3. pH value of a solution, whose hydronium ion concentration is (d) NaOH  NaCl
6.2  10 9 mol/ l, is [AFMC 1999; AIIMS 2000] 15. The addition of solid sodium carbonate to pure water causes
(a) 6.21 (b) 7.21 [NCERT 1973]
(c) 7.75 (d) 8.21 (a) An increase in hydronium ion concentration
4. 0.1 mole of CH NH (K = 5  10 ) is mixed with 0.08 mole of HCl
3 2 b
4
(b) An increase in alkalinity
and diluted to one litre. What will be the H concentration in the
+

(c) No change in acidity

solution? [IIT 2005]
(d) A decrease in hydroxide ion concentration
(a) 8  10 M 2
(b) 8  10 M 11

16. The aqueous solution of which of the following salt has the lowest
(c) 1.6  10 M 11
(d) 8  10 M 5
pH [CBSE PMT 2002]
5. What will be the sum of pH and pOH in an aqueous solution ? (a) NaClO
[MP PET/PMT 1998] (b) NaClO2
(a) 7 (b) pk w (c) NaClO3 (d) NaClO4
(c) Zero (d) 1 10
17. The pH of a 10 M NaOH solution is nearest to
6. Hydrogen ion concentration in mol/L in a solution of pH  5.4
[UPSEAT 2001, 02]
will be [AIEEE 2005]
(a) 10 (b) 7
(a) 3.98  10 8 (b) 3.88  10 6
(c) 4 (d) 10
(c) 3.68  10 6 (d) 3.98  10 6 18. Which will have maximum pH [NCERT 1979]
7. When solid potassium cyanide is added in water then
(a) Distilled water
[CPMT 2002; BHU 2002]
(a) pH will increase (b) 1 M NH 3
(b) pH will decrease (c) 1 M NaOH
(c) pH will remain the same (d) Water saturated by chlorine
(d) Electrical conductivity will not change 19. pH of a solution is 9.5. The solution is [MH CET 2000]
8. pH of a 10 3 M solution of hydrochloric acid will be (a) Neutral (b) Acidic
[MP PET 2000] (c) Basic (d) Amphoteric
(a) 1.3 (b) 2.0
20. The pH of a 10 9 M solution of HCl in water is
(c) 3.0 (d) 4.5
[UPSEAT 2000, 02]
9. The pH of water at 25 o C is nearly (a) 8 (b) – 8
[CPMT 1986, 89, 90, 93; CBSE PMT 1989; (c) Between 7 and 8 (d) Between 6 and 7
MADT Bihar 1995] 21. pH  pOH equal to [NCERT 1975]
(a) 2 (b) 7
(a) Zero (b) Fourteen
(c) 10 (d) 12
(c) A negative number (d) Infinity
10. pH of a solution is 5. Its hydroxyl ion concentration is 22. Which of the following 0.1M solution will contain the largest
[JIPMER 1999] concentration of hydronium ions [NCERT 1971, 73]
(a) 5 (b) 10 (a) NaHCO 3 (b) NH 4 Cl
 Ionic Equilibrium 365

(c) HCl (d) NH 3 N

32. pH values of HCl and NaOH solutions each of strength
23. Which one has pH 12 [Roorkee 1995] 100
will be respectively [MP PMT 1999]
(a) 0.01 M KOH (b) 1 N KOH ml (a) 2 and 2 (b) 2 and 12
(c) 1 N NaOH ml (d) 1 N Ca(OH )2 ml (c) 12 and 2 (d) 2 and 10
33. When rain is accompained by a thunderstorm, the collected rain
24. What is the correct relationship between the pHs of isomolar water will have a pH value [AIEEE 2003]
solutions of sodium oxide ( pH1 ) , sodium sulphide ( pH 2 ), sodium (a) Slightly lower than that of rain water without thunderstorm
selenide ( pH 3 ) and sodium telluride ( pH 4 ) ? [CBSE PMT 2005] (b) Slightly higher than that when the thunderstorm is not there
(c) Uninfluenced by occurrence of thunderstorm
(a) pH1  pH 2  pH 3  pH 4
(d) Which depends on the amount of dust in air
(b) pH1  pH 2  pH 3  pH 4 34. Which of the following is the buffer solution of strong acidic nature
[MP PET 2002]
(c) pH1  pH 2  pH 3  pH 4
(a) HCOOH  HCOO 
(d) pH1  pH 2  pH 3  pH 4
(b) CH 3 COOH  CH 3 COO 
25. Given pH of a solution A is 3 and it is mixed with another solution
B having pH 2. If both mixed then resultant pH of the solution will (c) H 2 C2 O4  C2 O42 
be [BHU 2005]
(a) 3.2 (b) 1.9 (d) H 3 BO3  BO33 
(c) 3.4 (d) 3.5
26. On adding solid potassium cyanide to water 35. The dissociation constant of an acid HA is 1  10 5 . The pH of
[MP PMT 1989] 0.1 molar solution of the acid will be
(a) pH will increase [KCET (Engg./Med.) 1999]
(b) pH will decrease (a) Five (b) Four
(c) pH will not change (c) Three (d) One
(d) Electrical conductance will not change 36. The pH value of 1.0  10 8 M HCl solution is less than 8 because
27. A is an aqueous acid; B is an aqueous base. They are diluted
separately, then [KCET 2002]
(a) HCl is completely ionised at this concentration
(b) The ionization of water is negligible
(a) pH of A increases and pH of B decreases
(c) The ionization of water cannot be assumed to be negligible in
(b) pH of A increases and pH of B decreases till pH in each comparison with this low concentration of HCl
case is 7 (d) The pH cannot be calculated at such a low concentration of
(c) pH of A and B increase HCl
(d) pH of B and A decrease 37. What is the pH for a neutral solutions at the normal temperature of
the human body [JIPMER 2000]
28. The compound whose 0.1 M solution is basic is
[IIT 1986; MP PMT 1991]
(a) 7.2 (b) 14.0
(a) Ammonium acetate (c) 6.8 (d) 6.0
(b) Calcium carbonate 38. 1 M NaCl and 1 M HCl are present in an aqueous solution. The
(c) Ammonium sulphate solution is [AIEEE 2002]
(d) Sodium acetate (a) Not a buffer solution with pH < 7
29. The following reaction is known to occur in the body CO 2  H 2 O (b) Not a buffer solution with pH > 7
(c) A buffer solution with pH < 7
⇌ H 2 CO 3 ⇌ H   HCO 3 . If CO 2 escapes from the system[NCERT 1973; RPMT (d) 1997]
A buffer solution with pH > 7
(a) pH will decrease 39. A solution has pH  5 , it is diluted 100 times, then it will become[NCERT 1978
(b) Hydrogen ion concentration will decrease (a) Neutral (b) Basic
(c) H 2 CO 3 concentration will be unaltered (c) Unaffected (d) More acidic
(d) The forward reaction will be promoted 40. 0.02 M monobasic acid dissociates 2% hence, pH of the solution is
30. For preparing a buffer solution of pH 6 by mixing sodium acetate [MH CET 2000]
and acetic acid, the ratio of the concentration of salt and acid should (a) 0.3979 (b) 1.3979
5 (c) 1.699 (d) 3.3979
be (K a  10 ) [MP PET 1997]
41. Components of buffer solution are 0.1 M HCN and
(a) 1 : 10 (b) 10 : 1
0.2 M NaCN . What is the pH of the solution [RPET 2000]
(c) 100 : 1 (d) 1 : 100
(a) 9.61 (b) 6.15
31. Which is incorrect for buffer solution [CPMT 1985] (c) 2.0 (d) 4.2
(a) It contains weak acid and its conjugate base
42. pH of a solution of 10 ml . 1N sodium acetate and 50 ml 2N acetic
(b) It contains weak base and its conjugate acid
(c) In this there is very less change is pH value when very less acid (Ka  1.8  10 5 ), is approximately
amount of acid and base is mixed [MP PMT 2003]
(d) None of the above (a) 4 (b) 5
(c) 6 (d) 7
 366 Ionic Equilibrium
43. By adding 20 ml 0.1 N HCl to 20 ml 0.001 N KOH , the (c) 7 (d) 14.2
pH of the obtained solution will be [KCET 2000] 57. pH of completely dissociated 0.005 M H 2 SO 4 is
(a) 2 (b) 1.3 [RPET 2003]
(c) 0 (d) 7 (a) 3 (b) 4
44. The pH of the solution containing 10 ml of a 0.1 N NaOH and (c) 2 (d) 5
10 ml of 0.05 N H 2 SO 4 would be 58. The pKa of a weak acid is 4.8. What should be the ratio of
[Pb. PMT 2002, 04] [Acid]/[Salt] of a buffer if pH  5.8 is required
(a) 1 (b) 0 [MP PET 2003]
(c) 7 (d) > 7 (a) 10 (b) 0.1
45. The pH of 10 7 M NaOH is [MP PMT 2001] (c) 1 (d) 2
(a) 7.01 (b) Between 7 and 8 59. Which of the following salt is acidic
(c) Between 9 and 10 (d) Greater than 10 [CPMT 1979, 81; NCERT 1979, 81;
MP PET 1990; JIPMER 2002]
46. The hydrogen ion concentration of 0.1 N solution of
(a) Na 2 SO 4 (b) NaHSO 3
CH 3 COOH , which is 30% dissociated, is [JIPMER 2002]
(a) 0.03 (b) 3.0 (c) Na 2 SO 3 (d) Na 2 S
(c) 0.3 (d) 30.0 60. 20ml of 0.5 N HCl and 35 ml of 0.1 N NaOH are mixed.
47. What is the pH of 0.1 M NH 3 [RPET 2000] The resulting solution will [KCET 2005]
(a) 11.27 (b) 11.13 (a) Be neutral
(c) 12.0 (d) 9.13 (b) Be basic
48. By adding a strong acid to the buffer solution, the pH of the buffer (c) Turn phenolphthalein solution pink
solution [DPMT 1996] (d) Turn methyl orange red
(a) Remains constant (b) Increases
61. The pH of a 0.02 M solution of hydrochloric acid is
(c) Decreases (d) Becomes zero
[MP PMT 1993]
49. The pH of 0.1 M NaOH is [MP PET 2003]
(a) 2.0 (b) 1.7
(a) 11 (b) 12
(c) 0.3 (d) 2.2
(c) 13 (d) 14
62. A sample of Na 2 CO 3 .H 2 O weighing 0.62 g is added to
50. pH of human blood is 7.4. Then H  concentration will be
[RPMT 2002] 100 ml of 0.1 N (NH 4 )2 SO 4 solution. What will be the
8 8 resulting solution [BHU 1997]
(a) 4  10 (b) 2  10
4
(a) Acidic (b) Neutral
(c) 4  10 (d) 2  10 4 (c) Basic (d) None of these
51. Assuming complete ionisation, the pH of 0.1 M HCl, is 1. The 63. The pH of the solution is 4. The hydrogen ion concentration of the
molarity of H 2 SO 4 with the same pH is solution in mol/litre is [UPSEAT 2000]
[Pb. PMT 2002] (a) 9.5 (b) 10 4
(a) 0.1 (b) 0.2
(c)10 4 (d) 10 2
(c) 0.05 (d) 2.0
52. Highest pH 14 is given by [DCE 1999] 64. NaOH (aq ) , HCl(aq ) and NaCl(aq ) concentration of each is
(a) 0.1 M H 2 SO 4 (b) 0.1 M NaOH 10 3 M . Their pH will be respectively [BHU 2003]
(c) 1 N NaOH (d) 1 N HCl (a) 10, 6, 2 (b) 11, 3, 7
(c) 10, 2, 6 (d) 3, 4, 7
53. What will be the pH of a 10 8 M HCl solution 65. The pH of 10 5 M aqueous solution of NaOH is
[MP PET/PMT 1998; RPET 1999;MP PMT 2000] [MP PET 1996]
(a) 8.0 (b) 7.0 (a) 5 (b) 7
(c) 6.98 (d) 14.0 (c) 9 (d) 11
54. When 10 ml of 0.1 M acetic acid (pKa  5.0) is titrated against 10 66. The pH of 0.05 M solution of dibasic acid is
[MH CET 2002]
ml of 0.1M ammonia solution (pKb  5.0) , the equivalence point
occurs at pH [AIIMS 2005]
(a) 1 (b) 1
(a) 5.0 (b) 6.0 (c) 2 (d) 2
(c) 7.0 (d) 9.0 67. A buffer solution contains 0.1 M of acetic acid and 0.1 M of
55. Which on reaction with water will have pH less than 7 sodium acetate. What will be its pH , if pK a of acetic acid is 4.75
[MH CET 2001] (a) 4.00 (b) 4.75
(a) BaO (b) CaO (c) 5.00 (d) 5.25
68. To obtain a buffer which should be suitable for maintaining a
(c) Na 2 O (d) P2 O5
pH of about 4  5, we need to have in solution, a mixture of
56. A solution of MgCl2 in water has pH (a) A strong base + its salt with a weak acid
[MP PMT 2002] (b) A weak base + its salt with a strong acid
(a) < 7 (b) > 7 (c) A strong acid + its salt with a weak base
 Ionic Equilibrium 367
(d) A weak acid + its salt with a strong base 79. pH of a solution can be expressed as
69. The concentration of NaOH solution is 10 8 M . Find out the [CPMT 1999; UPSEAT 2001]

(OH  ) concentration [CPMT 1993] (a)  loge (H ) (b)  log10 (H  )

(a) 10 8 (c) loge (H  ) (d) log10 (H  )

(b) Greater than 10 6 80. The solution of sodium carbonate has pH [MP PET 2000]
(a) Greater than 7 (b) Less than 7
(c) 10 6 (c) Equal to 7 (d) Equal to zero
(d) Lies between 10 6 and 10 7 81. The pH of 10 7 N HCl is [RPMT 2000]
70. The pH of 0.0001 N solution of KOH will be
(a) 6.0 (b) 6.97
[BHU 1997; CET Pune 1998] (c) 8.0 (d) 10.0
(a) 4 (b) 6
82. If the pH of a solution is 2, its normality will be
(c) 10 (d) 12
[MADT Bihar 1982; MP PET 2000]
71. Given that the dissociation constant for H 2 O is Kw  1  10 14
(a) 2N (b) 1
2
N
2 2
mole litre , what is the pH of a (c) 0.01 N (d) None of these
0.001 molar KOH solution 83. The buffer solution of 100 ml having a pH value 4 when added
[MP PET 1995; MP PET/PMT 1998] to 1 ml dilute HCl , then the pH of buffer solution
(a) 10 11 (b) 3 [NCERT 1976, 77]
(c) 14 (d) 11 (a) Converts to 7 (b) Does not change
72. An acidic buffer solution can be prepared by mixing solution of [MNR 1983] (c) Converts to 2 (d) Changes to 10
(a) Ammonium acetate and acetic acid 84. In a solution of acetic acid, sodium acetate is added, then its pH
(b) Ammonium chloride and hydrochloric acid value [NCERT 1977; DPMT 1985; MP PMT 1994]
(c) Sulphuric acid and sodium sulphate (a) Decreases
(d) Acetic acid and sulphuric acid (b) Increases
(e) NaCl and NaOH (c) Remains unchanged
73. Which of the following mixtures forms an acid buffer (d) (a) and (b) both are correct
[MP PMT 1993; IIT 1981; CPMT 1989; CBSE PMT 1989]
85. If pOH of a solution is 6.0, then its pH will be
(a) NaOH  HCl [MP PMT 1987]
(b) CH 3 COOH  CH 3 COONa (a) 6 (b) 10
(c) NH 4 OH  NH 4 Cl (c) 8 (d) 14
(d) H 2 CO 3  (NH 4 )2 CO 3 86. In a solution of pH  5, more acid is added in order to reduce the
pH  2. The increase in hydrogen ion concentration is[MP PET 1989; CPMT 199
74. A buffer solution has equal volumes of 0.2 M NH 4 OH and
(a) 100 times (b) 1000 times
0.02 M NH 4 Cl . The pK b of the base is 5. The pH is
(c) 3 times (d) 5 times
[CBSE PMT 1989; KCET 2005]
(a) 10 (b) 9 87. Which solution contains maximum number of H  ion
(c) 4 (d) 7 (a) 0.1 M HCl (b) 0.1 M NH 4 Cl
75. The pH of a simple sodium acetate buffer is given by
(c) 0.1 M NaHCO 3 (d) 0.1 M
[Salt]
pH  pK a  log
[ Acid] 88. A certain buffer solution contains equal concentration of X  and
K a of acetic acid  1.8  10 5 HX . The K b for X  is 10 10 . The pH of the buffer is
[IIT 1984; RPMT 1997; CPMT 1996; DPMT 2004]
If [Salt] = [Acid] = 0.1 M, the pH of the solution would be about [BHU 1987]
(a) 4 (b) 7
(a) 7 (b) 4.7
(c) 5.3 (d) 1.4 (c) 10 (d) 14
76. Amongst the following solutions, the buffer solution is 89. The defination of pH is [EAMCET 1980; UPSEAT 2001]
[MP PMT 1999]
1
(a) NH 4 Cl  NH 4 OH solution (a) pH  log (b) pH  log[H  ]
[H  ]
(b) NH 4 Cl  NaOH solution
1 
(c) NH 4 OH  HCl solution (c) pH   log (d) pH   log[ H ]
[H  ]
(d) NaOH  HCl solution
90. Which of the following does not make any change in pH when
77. The pH of solution having [OH  ]  10 7 is [AIIMS 1996]
added to 10 ml dilute HCl [NCERT 1975]
(a) 7 (b) 14
(a) 5 ml pure water (b) 20 ml pure water
(c) Zero (d) 7
78. 50 ml water is added to a 50 ml solution of Ba(OH )2 of (c) 10 ml HCl (d) Same 20 ml dilute HCl
91. 1999]A compound whose aqueous solution will have the highest pH
strength 0.01 M . The pH value of the resulting solution will be[MP PMT
(a) 8 (b) 10 [CPMT 1974, 75, 78; MP PET 1996; DPMT 1982, 83]
(c) 12 (d) 6
 368 Ionic Equilibrium
(a) NaCl (b) Na 2 CO 3 (c) 2, 5  dihydroxy benzoic acid (pKa  2.97)
(c) NH 4 Cl (d) NaHCO 3 (d) Acetoacetic acid (pKa  3.58)

92. o 
At 80 C, distilled water has [H 3 O ] concentration equal to 103. In a mixture of a weak acid and its salt, the ratio of concentration of
acid to salt is increased ten-fold. The pH of the solution
1  10 6 mole / litre. The value of K w at this temperature will be[CBSE PMT 1994; RPMT 2000;
(a) Decreases by one (b) Increases by one-tenth
AFMC 2001; AIIMS 2002; BHU 2002] (c) Increases by one (d) Increases ten-fold
6 9
(a) 1  10 (b) 1  10 104. When an acid or alkali is mixed with buffer solution, then pH of
(c) 1  10 12 (d) 1  10 15 buffer solution [CPMT 1997]
(a) Not changes (b) Changes slightly
93. The pH value of 0.1 M NaOH solution is (when there is a
(c) Increases (d) Decreases
given reaction [H  ][OH  ]  10 15 ) [CPMT 1997] 105. How much sodium acetate should be added to a 0 .1 m solution of
(a) 13 (b) 12 CH 3 COOH to give a solution of pH  5.5 (pKa of
(c) 11 (d) 2
CH 3 COOH  4.5) [KCET 1996]
94. Which oxychloride has maximum pH [CPMT 1997]
(a) 0 .1 m (b) 0 .2 m
(a) NaClO (b) NaClO2
(c) 1 .0 m (d) 10.0 m
(c) NaClO3 (d) NaClO4
106. The pH of the aqueous solution containing 0.49 gm of H 2 SO 4
95. pH of HCl (10 12 M ) is [CPMT 1997; Pb. PET/PMT 1999] in one litre is [EAMCET 1997]
(a) 2 (b) 1
(a) 12 (b) 12
(c) 1.7 (d) 0.3
(c)  7 (d) 14 107. Which of the following solutions can act as buffer
96. Which one is buffer solution [CPMT 1997] [JIPMER 1997]
–  3– – (a) 0.1 molar aq. NaCl
(a) [PO4 ] [[HPO4 ] (b) [PO3 ] [[H 2 PO4 ]
(b) 0.1 molar aq. CH 3 COOH  0.1 molar NaOH
(c) [HPO4–  ] [[H 2 PO4–  ] (d) All of these
(c) 0.1 molar aq. ammonium acetate
97. When 100 ml of M / 10 NaOH solution and 50 ml of (d) None of the above
M / 5 HCl solution are mixed, the pH of resulting solution 108. The pH of a solution obtained by mixing 50 ml of
would be [RPMT 1997] 0.4 N HCl and 50 ml of 0.2 N NaOH is [KCET 1996]
(a) 0 (b) 7
(a)  log 2 (b)  log 0.2
(c) Less than 7 (d) More than 7
(c) 1.0 (d) 2.0
98. How many millilitres of 6.0 M hydrochloric acid should be used to 109. Which of the following is a buffer
prepare 150 ml of a solution which is 0.30 M in hydrogen ion [Pb. PMT 1998] [MP PMT 1991; BHU 1995]
(a) 3.0 (b) 7.5 (a) NaOH  CH 3 COONa
(c) 9.3 (d) 30 (b) NaOH  Na 2 SO 4
99. The pH of 0.1 M acetic acid is 3, the dissociation constant of acid
will be (c) K 2 SO 4  H 2 SO 4
(a) 1.0  10 4 (b) 1.0  10 5 (d) NH 4 OH  CH 3 COONH 4
(c) 1.0  10 3 (d) 1.0  10 8 110. If 4.0 gm NaOH is present in 1 litre solution, then its pH will be
[CPMT 1989]
100. The pH of a buffer solution containing 25 ml of
(a) 6 (b) 13
1 M CH 3 COONa and 25 ml of 1 M CH 3 COOH will be (c) 18 (d) 24
appreciably affected by 5 ml of [CPMT 1987] 111. The pOH of beer is 10.0. The hydrogen ion concentration will be
(a) 1 M CH 3 COOH (b) 5 M CH 3 COOH (a) 10 2 (b) 10 10
(c) 5 M HCl (d) 1 M NH 4 OH (c) 10 8 (d) 10 4
112. When a buffer solution of sodium acetate and acetic acid is diluted
101. The pH value of decinormal solution of NH 4 OH which is 20%
with water [CPMT 1985]
ionised, is [CBSE PMT 1998] (a) Acetate ion concentration increases
(a) 13.30 (b) 14.70
(b) H  ion concentration increases
(c) 12.30 (d) 12.95
102. A physician wishes to prepare a buffer solution at pH  3.58 that (c) OH  ion concentration increases
efficiently resists changes in pH yet contains only small (d) H  ion concentration remain unaltered
concentration of the buffering agents. Which of the following weak 113. What is the pH of Ba(OH )2 if normality is 10
acids together with its sodium salt would be best to use[CBSE PMT 1997] [CPMT 1996]
(a) m  chlorobenzoic acid (pKa  3.98) (a) 4 (b) 10
(c) 7 (d) 9
(b) p  chlorocinnamic acid (pKa  4.41)
 Ionic Equilibrium 369

114. What will be the pH of a solution formed by mixing 40 ml of (a) Basic (b) Acid
(c) Neutral (d) Both (a) and (b)
0.10 M HCl with 10 ml of 0.45 M NaOH
[Manipal MEE 1995] 128. The pH of a solution is increased from 3 to 6. Its H  ion
(a) 12 (b) 10 concentration will be [EAMCET 1998]
(c) 8 (d) 6 (a) Reduced to half
115. The pH of a solution having [H  ]  10  10 4 moles / litre will (b) Doubled
be [BHU 1981]
(c) Reduced by 1000 times
(a) 1 (b) 2 (d) Increased by 1000 times
(c) 3 (d) 4 129. Pure water is kept in a vessel and it remains exposed to atmospheric
CO 2 which is absorbed, then its pH will be
116. If 0.4 gm NaOH is present in 1 litre solution, then its pH will
be [CPMT 1985; BHU 1980] [MADT Bihar 1984; DPMT 2002]
(a) Greater than 7
(a) 2 (b) 10
(b) Less than 7
(c) 11 (d) 12
(c) 7
117. Which of the following is not a Bronsted acid [BHU 1997]
(d) Depends on ionic product of water
(a) CH 3 NH 4 (b) CH 3 COO 
130. The pH of a solution is 2. If its pH is to be raised to 4, then the
(c) H 2O (d) HSO 4 [H  ] of the original solution has to be [MP PET 1994]
118. pH of 0.005 M H 2 SO 4 solution will be [NCERT 1980] (a) Doubled
(a) 0.005 (b) 2 (b) Halved
(c) 1 (d) 0.01 (c) Increased hundred times
119. A buffer solution is a mixture of [MP PMT 1987] (d) Decreased hundred times
(a) Strong acid and strong base 131. Which of the following solutions cannot act as a buffer
(b) Weak acid and weak base [EAMCET 1998]
(c) Weak acid and conjugate acid (a) NaH 2 PO4  H 3 PO4
(d) Weak acid and conjugate base
(b) CH 3 COOH  CH 3 COONa
120. When pH of a solution decreases, its hydrogen ion concentration [MADT Bihar 1981]
(a) Decreases (b) Increases (c) HCl  NH 4 Cl
(c) Rapidly increases (d) Remains always constant (d) H 3 PO4  Na 2 HPO4
121. If the pH of a solution is 4.0 at 25 o C, its pOH would be 132. Assuming complete ionisation, the pH of 0.1 M HCl is 1. The
(Kw  10 14 ) [MP PMT 1989] molarity of H 2 SO 4 with the same pH is
(a) 4.0 (b) 6.0 [KCET 1998]
(c) 8.0 (d) 10.0 (a) 0.2 (b) 0.1
122. An aqueous solution whose pH  0 is (c) 2.0 (d) 0.05
[CPMT 1976; DPMT 1982] 133. The pH of blood is
(a) Alkaline (b) Acidic (a) 5.2 (b) 6.3
(c) Neutral (d) Amphoteric (c) 7.4 (d) 8.5
123. In a solution of acid H  concentration is 10 10 M . The pH of this 134. The pH of 10 8 molar aqueous solution of HCl is
solution will be [CPMT 1988; MNR 1983, 90; MP PMT 1987; IIT 1981;
(a) 8 (b) 6 BHU 1995; AFMC 1998; MP PET 1989, 99; BCECE 2005]
(c) Between 6 and 7 (d) Between 3 and 6
(a) 8
124. The concentration of hydronium (H 3 O  ) ion in water is (b) 8
[CET Pune 1998] (c) 6  7 (Between 6 and 7)
(a) Zero (b) 1  10 7 gm ion / litre (d) 7  8 (Between 7 and 8)
14 7
(c) 1  10 gm ion / litre (d) 1  10 gm ion / litre 135. As the temperature increases, the pH of a KOH solution
125. A solution whose pH value is less than 7 will be [UPSEAT 2001]
(a) Basic (b) Acidic (a) Will decreases
(c) Neutral (d) Buffer (b) Will increases
126. When the pH of a solution is 2, the hydrogen ion concentration in (c) Remains constant
moles per litre is (d) Depends upon concentration of KOH solution
[NCERT 1973; MNR 1979]
136. The hydrogen ion concentration in a given solution is 6  10 4 . Its
14 2
(a) 1  10 (b) 1  10 pH will be [EAMCET 1978]
(c) 1  10 7 (d) 1  10 12 (a) 6 (b) 4
127. A base is dissolved in water yields a solution with a hydroxide ion (c) 3.22 (d) 2
concentration of 0.05 mol litre1 . The solution is [AFMC 1997]
 370 Ionic Equilibrium
N 150. pH value of N / 10 NaOH solution is
137. The pH of HCl would be approximately
100 [CBSE PMT 1996;Pb. CET 2001; Pb. PMT 2002]
[CPMT 1971; DPMT 1982, 83; (a) 10 (b) 11
MP PMT 1991; Bihar MEE 1996] (c) 12 (d) 13
(a) 1 (b) 1.5 151. A solution of sodium borate has a pH of approximately
(c) 2 (d) 2.5 [JIPMER 2001]
138. A solution which is resistant to change of pH upon the addition of (a) < 7 (b) > 7
an acid or a base is known as [BHU 1979]
(c) = 7 (d) Between 4 to 5
(a) A colloid (b) A crystalloid 152. If pH of A, B, C and D are 9.5, 2.5, 3.5 and 5.5 respectively,
(c) A buffer (d) An indicator then strongest acid is [AFMC 1995]
139. 10 6 M HCl is diluted to 100 times. Its pH is (a) A (b) C
(c) D (d) B
[CPMT 1984]
(a) 6.0 (b) 8.0 153. At 25C the pH value of a solution is 6. The solution is
(c) 6.95 (d) 9.5 [AFMC 2001]
(a) Basic (b) Acidic
140. The pH of a 10 10 molar HCl solution is approximately
(c) Neutral (d) Both (b) and (c)
[NCERT 1977]
(a) 10 (b) 7 154. A certain buffer solution contains equal concentration of X  and
(c) 1 (d) 14 HX . The K a for HX is 10 8 . The pH of the buffer is
141. The H  ion concentration is 1.0  10 6 mole/litre in a solution. Its [UPSEAT 2001]
pH value will be (a) 3 (b) 8
[MP PMT 1985; AFMC 1982] (c) 11 (d) 14
(a) 12 (b) 6
(c) 18 (d) 24 155. The dissociation constant of HCN is 5  10 10 . The pH of the
142. The pH of a solution is the negative logarithm to the base 10 of its solution prepared by mixing 1.5 mole of HCN and 0.15 moles of KCN
hydrogen ion concentration in in water and making up the total volume to 0.5 dm 3 is
[Manipal MEE 1995] (a) 7.302 (b) 9.302
(a) Moles per litre (b) Millimoles per litre (c) 8.302 (d) 10.302
(c) Micromoles per litre (d) Nanomoles per litre
156. Which buffer solution out of the following will have pH  7
143. When 10 8 mole of HCl is dissolved in one litre of water, the [MP PET 2001]
pH of the solution will be
(a) CH 3 COOH  CH 3 COONa
[CPMT 1973, 94; DPMT 1982]
(a) 8 (b) 7 (b) HCOOH  HCOOK
(c) Above 8 (d) Below 7 (c) CH 3 COONH 4
144. The pH of the solution containing 10 ml of 0.1 N NaOH and 10
(d) NH 4 OH  NH 4 Cl
ml of 0.05 N H 2 SO 4 would be
[CPMT 1987; Pb. PMT 2002,04] 157. The pKa of equimolecular sodium acetate and acetic acid mixture
(a) 0 (b) 1 is 4.74. If pH is [DPMT 2001]
(c) > 7 (d) 7 (a) 7 (b) 9.2
145. The pH of 0.001 molar solution of HCl will be (c) 4.74 (d) 14
[MP PET 1986; MP PET/PMT 1988; CBSE PMT 1991]
158. pH of NaCl solution is [CET Pune 1998]
(a) 0.001 (b) 3
(c) 2 (d) 6 (a) 7 (b) Zero
146. Which salt can be classified as an acid salt [CPMT 1989] (c)  7 (d)  7
(a) Na 2 SO 4 (b) BiOCl 159. A solution of sodium chloride in contact with atmosphere has a
(c) Pb(OH )Cl (d) Na 2 HPO4 pH of about [NCERT 1972, 77]

147. Given a 0.1M solution of each of the following. Which solution has (a) 3.5 (b) 5
the lowest pH [MNR 1987] (c) 7 (d) 1.4
(a) NaHSO 4 (b) NH 4 Cl 160. Which would decrease the pH of 25 cm 3 of a 0.01 M solution
(c) HCl (d) NH 3 of hydrochloric acid [MH CET 2001]
148. Out of the following, which pair of solutions is not a buffer solution (a) The addition of 25 cm 3 0.005 M hydrochloric acid
(a) NH 4 Cl  NH 4 OH
(b) The addition of 25 cm 3 of 0.02 M hydrochloric acid
(b) NaCl  NaOH
(c) The addition of magnesium metal
(c) Na 2 HPO4  Na 3 PO4
(d) None of these
(d) CH 3 COOH  CH 3 COONa
161. The condition for minimum change in pH for a buffer solution is
149. If the dissociation constant of an acid HA is 1  10 5 , the pH of (a) Isoelectronic species are added
a 0.1 molar solution of the acid will be approximately [NCERT 1979] (b) Conjugate acid or base is added
(a) Three (b) Five
(c) One (d) Six
 Ionic Equilibrium 371

(c) pH  pKa (a) Increase by one (b) Remains unchanged

(c) Decrease by one (d) Increase by 10
(d) None of these
172. The gastric juice in our stomach contains enough HCl to make the
162. A buffer solution with pH 9 is to be prepared by mixing NH 4 Cl
hydrogen ion concentration about 0.01 mole / litre. The pH of
and NH 4 OH . Calculate the number of moles of NH 4 Cl that gastric juice is [NCERT 1974]
should be added to one litre of 1.0 M NH 4 OH. (a) 0.01 (b) 1
[Kb  1.8  10 ]5
[UPSEAT 2001] (c) 2 (d) 14
173. Addition of which chemical will decrease the hydrogen ion
(a) 3.4 (b) 2.6 concentration of an acetic acid solution [MP PMT 1990]
(c) 1.5 (d) 1.8 (a) NH 4 Cl (b) Al2 (SO 4 )3
163. The ionization constant of a certain weak acid is 10 4 . What
(c) AgNO3 (d) HCN
should be the [salt] to [acid] ratio if we have to prepare a buffer
with pH = 5 using this acid and one of the salts [CPMT 2000; KCET 2000; Pb. CET 2000]
174. The one which has the highest value of pH is
(a) 1 : 10 (b) 10 : 1 (a) Distilled water
(c) 5 : 4 (d) 4 : 5 (b) NH 3 solution in water
164. Which solution has the highest pH value [JIPMER 2000]
(c) NH 3
(a) 1 M KOH
(d) Water saturated with Cl 2
(b) 1 M H 2 SO 4
175. The solution of Na 2 CO 3 has pH [AMU 1988]
(c) Chlorine water
(a) Greater than 7 (b) Less than 7
(d) Water containing carbon dioxide
(c) Equal to 7 (d) Equal to zero
165. One weak acid (like CH 3 COOH ) and its strong base together 176. Which is not a buffer solution [CPMT 1990]
with salt (like CH 3 COONa ) is a buffer solution. In which pair (a) NH 4 Cl  NH 4 OH
this type of characteristic is found
(b) CH 3 COOH  CH 3 COONa
[AIIMS 1982; CPMT 1994; MP PET 1994]
(a) HCl and NaCl (b) NaOH and NaNO 3 (c) CH 3 COONH 4
(d) Borax + Boric acid
(c) KOH and KCl (d) NH 4 OH and NH 4 Cl
166. If the pH of a solution of an alkali metal hydroxide is 13.6, the 177. What will be hydrogen ion concentration in moles litre1 of a
concentration of hydroxide is [JIPMER 2000] solution, whose pH is 4.58 [UPSEAT 2001]
(a) Between 0.1 M and 1 M (a) 2.63  10 5 (b) 3.0  10 5
(b) More than 1 M (c) 4.68 (d) None of these
(c) Less than 0.001 M
178. Assuming complete dissociation, the pH of a 0.01 M
(d) Between 0.01 M and 1 M
NaOH solution is equal to
167. The pK a of acetylsalicylic acid (aspirin) is 3.5. The pH of gastric [NCERT 1975; CPMT 1977; DPMT 1982; BHU 1997]
juice in human stomach is about 2-3 and the pH in the small (a) 2.0 (b) 14.0
intestine is about 8. Aspirin will be (c) 12.0 (d) 0.01
[IIT 1988; KCET 2003] 179. 50 ml of 2 N acetic acid mixed with 10 ml of 1 N sodium
(a) Unionized in the small intestine and in the stomach acetate solution will have an approximate pH of
(b) Completely ionized in the small intestine and in the [MP PMT/PET 1988]
stomach (a) 4 (b) 5
(c) Ionized in the stomach and almost unionized in the small (c) 6 (d) 7
intestine 180. The hydrogen ion concentration of 0.001 M NaOH solution is
(d) Ionized in the small intestine and almost unionized in the (a) 1  10 2 mole / litre (b) 1  10 11 mole / litre
stomach
168. The concentration of hydrogen ion in water is (c) 1  10 14 mole / litre (d) 1  10 12 mole / litre
[MP PET 1990] 181. A weak monoprotic acid of 0.1 M, ionizes to 1% in solution. What
will be the pH of solution [MNR 1988]
7
(a) 8 (b) 1  10 (a) 1 (b) 2
(c) 7 (d) 1 / 7 (c) 3 (d) 11
169. pH of a 10 M solution of HCl is [CBSE PMT 1995] 182. pH of a solution is 4. The hydroxide ion concentration of the
solution would be
(a) Less than 0 (b) 2
[NCERT 1981; CBSE PMT 1991; MP PMT 1994]
(c) 0 (d) 1
(a) 10 4 (b) 10 10
170. The pH of 1 N H 2 O is [CPMT 1988]
(c) 10 2 (d) 10 12
(a) 7 (b) >7
(c) <7 (d) 0 183. The pH of an aqueous solution containing [H  ]  3  10 3 M is
[MP PET 2001,04]
171. If H  ion concentration of a solution is increased by 10 times its pH (a) 2.471 (b) 2.523
will be [DCE 2000] (c) 3.0 (d) – 3
 372 Ionic Equilibrium
184. pH of blood is maintained constant by mechanism of 197. Which of the following statement(s) is(are) correct
[MH CET 2002] [IIT 1998]
(a) Common ion effect (b) Buffer (a) The pH of 1.0  10 8 M solution of HCl is 8
(c) Solubility (d) All of these
185. The pH of normal KOH is [MP PET 1990] (b) The conjugate base of H 2 PO4 is HPO42 
(a) 1 (b) 0 (c) Autoprotolysis constant of water increases with temperature
(c) 14 (d) 7 (d) When a solution of a weak monoprotic acid is titrated against
186. The concentration of hydrogen ion [H  ] in 0.01 M HCl is a strong base, at half neutralization point pH  12 pKa
[EAMCET 1979]
198. An aqueous solution of sodium carbnate has a pH greater than 7
(a) 10 12 (b) 10 2 becaue [DCE 2003]
(c) 10 1 (d) 10 12 (a) It contains more carbonate ions than H 2 O molecules
187. A solution of weak acids is diluted by adding an equal volume of
(b) Contains more hydroxide ions than carbonate ions
water. Which of the following will not change
[JIPMER 1997] (c) Na  ions react with water
(a) Strength of the acid (d) Carbonate ions react with H 2 O
(b) The value of [H 3 O  ]
199. A pH of 7 signifies [CPMT 1974; DPMT 1982]
(c) pH of the solution (a) Pure water (b) Neutral solution
(d) The degree of dissociation of acid (c) Basic solution (d) Acidic solution
188. Ka of H 2 O2 is of the order of [DCE 2004] 200. Assuming complete dissociation, which of the following aqueous
12 14 solutions will have the same pH value
(a) 10 (b) 10
[Roorkee Qualifying 1998]
(c) 10 16 (d) 10 10
189. Equivalent weight of an acid [UPSEAT 2004] (a) 100 ml of 0.01 M HCl
(a) Depends on the reaction involved
(b) 100 ml of 0.01 M H 2 SO 4
(b) Depends upon the number of oxygen atoms present
(c) Is always same (c) 50 ml of 0.01 M HCl
(d) None of the above
(d) Mixture of 50 ml of 0.02 M H 2 SO 4 and 50 ml of
190. pH scale was introduced by [UPSEAT 2004]
(a) Arrhenius (b) Sorensen 0.02 M NaOH
(c) Lewis (d) Lowry 201. A buffer solution can be prepared from a mixture of
191. Buffer solution is prepared by mixing [MH CET 2003] [IIT 1999; KCET 1999; MP PMT 2002]
(a) Strong acid + its salt of strong base (a) Sodium acetate and acetic acid in water
(b) Weak acid + its salt of weak base (b) Sodium acetate and hydrochloric acid in water
(c) Strong acid + its salt of weak base (c) Ammonia and ammonium chloride in water
(d) Weak acid + its salt of strong base (d) Ammonia and sodium hydroxide in water
192. The pH of millimolar HCl is [MH CET 2004] 202. Which of the following will not function as a buffer solution
(a) 1 (b) 3 [Roorkee 2000]
(c) 2 (d) 4 (a) NaCl and NaOH
193. Which of the following is a Lewis base [CPMT 2004] (b) NaOH and NH 4 OH
(a) NaOH (b) NH 3 (c) CH 3 COONH 4 and HCl
(c) BCl 3 (d) All of these (d) Borax and boric acid
203. Which one of the following statements is not true
194. What will be the pH value of 0.05 M Ba(OH )2 solution [AIEEE 2003]
[CPMT 2004] (a) The conjugate base of H 2 PO4 is HPO42 
(a) 12 (b) 13
(b) pH  pOH  14 for all aqueous solutions
(c) 1 (d) 12.96
195. In a mixing of acetic acid and sodium acetate the ratio of (c) The pH of 1  10 8 M HCl is 8
concentration of the salts to the acid is increased ten times. Then (d) 96,500 coulombs of electricity when passed through a
the pH of the solution [KCET 2004]
CuSO 4 solution deposits 1 gram equivalent of copper at the
(a) Increase by one (b) Decreases by one
cathode
(c) Decrease ten fold (d) Increases ten fold
204. The pH value of 0.1 M HCl is approximately 1. What will be the
196. The rapid change of pH near the stoichiometric point of an acid-
base titration is the basis of indicator detection. pH of the solution is approximate pH value of 0.05 M H 2 SO 4
related to ratio of the concentrations of the conjugate acid (HIn) and [MP PMT 1991]
base (In ) forms of the indicator by the expression (a) 0.05
[CBSE PMT 2004] (b) 0.5
(c) 1 (d) 2
[HIn] [In ]
(a) log 
 pH  pK In (b) log  pH  pK In 205. The K sp of Mg(OH )2 is 1  10 12 , 0.01M Mg(OH )2 will
[In ] [HIn]
precipitate at the limiting pH [DPMT 2005]
[In ] [HIn] (a) 3 (b) 9
(c) log  pK In  pH (d) log  pK In  pH (c) 5 (d) 8
[HIn] [In ]
 Ionic Equilibrium 373

206. The pH of an aqueous solution having hydroxide ion concentration (a) Energy has to be spent for the total dissociation of weak acid
5 (b) Salt of weak acid and strong base is not stable
as 1  10 is [MP PMT 1991]
(a) 5 (b) 9 (c) Incomplete dissociation of weak acid
(c) 4.5 (d) 11 (d) Incomplete neutralisation of weak acid
10. pKa values of two acids A and B are 4 and 5. The strengths of
these two acids are related as [KCET 2001]
(a) Acid A is 10 times stronger than acids B
(b) Strength of acid A : strengtha of acid B  4 : 5
(c) The strengths of the two acids can not be compared
(d) Acid B is 10 times stronger than acid A
1. The K SP of AgI is 1.5  10 16 . On mixing equal volumes of the
11. The dissociation constant of two acids HA1 and HA2 are
following solutions, precipitation will occur only with
[AMU 2000] 3.14  10 4 and 1.96  10 5 respectively. The relative strength
of the acids will be approximately [RPMT 2000]
(a) 10 7 M Ag  and 10 19 M I  (a) 1 : 4 (b) 4 : 1
(b) 10 8 M Ag  and 10 8 M I  (c) 1 : 16 (d) 16 : 1
12. An aqueous solution of ammonium acetate is
(c) 10 16 M Ag  and 10 16 M I  [NCERT 1980, 81; RPMT 1999]
9  9  (a) Faintly acidic (b) Faintly basic
(d) 10 M Ag and 10 M I
2. The strongest Bronsted base in the following anion is (c) Fairly acidic (d) Almost neutral
[IIT 1981; MP PET 1992, 97; MP PMT 1994; RPMT 1999; 13. The dissociation constant of a weak acid is 1.0  10 5 , the
KCET 2000; AIIMS 2001; UPSEAT 2002; equilibrium constant for the reaction with strong base is
AFMC 2002; Pb. CET 2004] [MP PMT 1990]
(a) ClO  (b) ClO2 (a) 1.0  10 5
(b) 1.0  10 9

(c) ClO3 (d) ClO4 (c) 1.0  10 9

(d) 1.0  1014
3. Which one of the following compound is not a protonic acid 14. The pH of 0.1 M solution of the following salts increases in the
[CBSE PMT 2003] order [IIT 1999]
(a) SO 2 (OH )2 (b) B(OH )3 (a) NaCl  NH 4 Cl  NaCN  HCl
(c) PO(OH )3 (d) SO (OH )2 (b) HCl  NH 4 Cl  NaCl  NaCN
4. Calculate the hydrolysis constant of the salt containing NO 2 . Given (c) NaCN  NH 4 Cl  NaCl  HCl
10
the K a for HNO 2  4.5  10 (d) HCl  NaCl  NaCN  NH 4 Cl
[UPSEAT 2001] 15. Which of the following is the strongest acid
[AMU 1999; MH CET 1999, 2002]
(a) 2.22  10 5 (b) 2.02  10 5
(a) SO (OH )2 (b) SO 2 (OH )2
(c) 4.33  10 4 (d) 3.03  10 5
(c) ClO3 (OH ) (d) PO(OH )3
5. The molar solubility (mol L1 ) of a sparingly soluble salt MX 4 is
16. The strongest of the four acids listed below is
' s' . The corresponding solubility product is K sp . ' s' is given in [NCERT 1984]
terms of K sp by the relation [AIEEE 2004] (a) HCOOH (b) CH 3 COOH
(c) ClCH 2 COOH (d) FCH 2 COOH
(a) s  (256 K sp )1 / 5 (b) s  (128 K sp )1 / 4
17. Which equilibrium can be described as an acid-base reaction using
(c) s  (K sp / 128)1 / 4 (d) s  (K sp / 256)1 / 5 the Lewis acid-base definition but not using the Bronsted-Lowry
definition [AIIMS 1980]
6. Electrophiles are [RPET 2000]
(a) 2 NH 3  H 2 SO 4 ⇄ 2 NH 4  SO 42 
(a) Lewis acids (b) Lewis base
(c) Bronsted acid (d) Bronsted base (b) NH 3  CH 3 COOH ⇄ NH 4  CH 3 COO 
7. Total number of moles for the reaction 2 HI ⇄ H 2  I2 . if  is (c) H 2 O  CH 3 COOH ⇄ H 3 O   CH 3 COO 
degree of dissociation is [CBSE PMT 1996]
(a) 2 (b) 2  (d) [Cu(H 2 O)4 ]2   4 NH 3 ⇄ [Cu(NH 3 )4 ]2   4 H 2 O

(c) 1 (d) 1   18. The hydride ion H  is stronger base than its hydroxide ion OH  .
8. Which one is a Lewis acid [RPMT 1997] Which of the following reaction will occur if sodium hydride
(NaH ) is dissolved in water [CBSE PMT 1997]
(a) ClF3 (b) H 2O
(a) H  (aq)  H 2 O  H 2 O
(c) NH 3 (d) None of these
9. Heat of neutralisation of weak acid and strong base is less than the (b) H  (aq)  H 2 O (l)  OH   H 2
heat of neutralisation of strong acid and strong base due to [KCET 2002]
 374 Ionic Equilibrium

(c) H   H 2 O  No reaction 29. The solubility product of Mg (OH )2 is 1.2  10 11 . The solubility of
(d) None of these this compound in gram per 100 cm 3 of solution is
4
19. Dissociation constant of a weak acid is 1  10 . Equilibrium [Roorkee 2000]
constant of its reaction with strong base is [UPSEAT 2003]
(a) 1.4  10 4 (b) 8.16  10 4
(a) 1  10 4 (b) 1  1010 (c) 0.816 (d) 1.4
(c) 1  10 10 (d) 1  1014 30. What is [H  ] of a solution that is 0.01 M in HCN and
20. Arrange the acids (I) H 2 SO 3 (II) H PO and (III) HClO in the
3 3 3
0.02 M in NaCN
decreasing order of acidity [UPSEAT 2001]
(a) I > III > II (b) I > II > III (K a for HCN  6.2  10 10 ) [MP PMT 2000]
(c) II > III > I (d) III > I > II
(a) 3.1  1010 (b) 6.2  10 5
21. Self-ionisation of liquid ammonia occurs as,
10
(c) 6.2  10 (d) 3.1  10 10
2NH 3 ⇄ NH 4  NH 2 ; K  10 10 . In this solvent, an acid might
31. Which is neucleophile [DPMT 2001; RPMT 2002]
be [JIPMER 2001]
(a) BF3 (b) NH 3
(a) NH 4
(c) BeCl 2 (d) H 2O
(b) NH 3
4
32. The solubility of CuBr is 2  10 mol/l at 25C . The K sp
(c) Any species that will form NH 4
value for CuBr is [AIIMS 2002]
(d) All of these
8 2 2 11 2 1
(a) 4  10 mol l (b) 4  10 mol L
22. H f (H 2O)  X ; Heat of neutralisation of CH 3 COOH and
4 2 2
NaOH will be [BHU 2003] (c) 4  10 mol l (d) 4  10 mol 2l 2
15

(a) Less than 2X (b) Less than X 33. A 0.004 M solution of Na 2 SO 4 is isotonic with a 0.010 M solution
(c) X (d) Between X and 2X of glucose at same temperature. The apparent degree of disociation
of Na 2 SO 4 is
23. Which of the following oxides will not give OH  in aqueous
solution [NCERT 1980] [IIT JEE Screening 2004]
(a) 25% (b) 50%
(a) Fe2 O3 (b) MgO
(c) 75% (d) 85%
(c) Li2 O (d) K2O
34. K sp for Cr(OH )3 is 2.7  10 31 . What is its solubility in moles /
10
24. A precipitate of CaF2 (K sp  1.7  10 ) will be obtained when litre. [JEE Orissa 2004]
equal volume of the following are mixed (a) 1  10 8 (b) 8  10 8
[MP PMT 1990, 95; IIT 1982; MNR 1992]
(c) 1.1  10 8 (d) 0.18  10 8
(a) 10 4 M Ca 2  and 10 4 M F 
35. pK a of acetic acid is 4.74 . The concentration of CH 3 COONa
(b) 10 2 M Ca 2  and 10 3 M F  is 0.01 M. The pH of CH 3 OONa is
5 2 3  [Orissa JEE 2004]
(c) 10 M Ca and 10 M F
(a) 3.37 (b) 4.37
(d) 10 3 M Ca 2  and 10 5 M F  (c) 4.74 (d) 0.474
25. The degree of hydrolysis of a salt of weak acid and weak base in its 36. If the solubility product of AgBrO3 and Ag 2 SO 4 are
0.1 M solution is found to be 50%. If the molarity of the solution is 5 5
0.2 M, the percentage hydrolysis of the salt should be [AMU 1999] 5.5  10 and 2  10 respectively, the relationship between the
solubilities of these can be correctly represented as [EAMCET 1985]
(a) 50% (b) 35%
(a) S AgBrO3  S Ag2SO 4 (b) S AgBrO3  S Ag2SO 4
(c) 75% (d) 100%
26. The pH of 0.1 M solution of a weak monoprotic acid 1% ionized is (c) S AgBrO3  S Ag2SO 4 (d) S AgBrO3  S Ag2SO 4
[UPSEAT 2001; Pb. PMT 2001] 37. The ionisation constant of phenol is higher than that of ethanol
(a) 1 (b) 2 because [JIPMER 2002]
(c) 3 (d) 4 (a) Phenoxide ion is bulkier than ethanoxide
27. Which one is the strongest acid (b) Phenoxide ion is stronger base than ethanoxide
[MH CET 1999; AMU 1999,2000; (c) Phenoxide ion is stabilised through delocalisation
Pb.CET 2001,03; MP PET 2001] (d) Phenoxide ion is less stable than ethoxide
(a) HClO (b) HClO2 38. A weak acid HX has the dissociation constant 1  10 5 M . It forms
a salt NaX on reaction with alkali. The degree of hydrolysis of 0.1 M
(c) H 2 SO 4 (d) HClO4 solution of NaX is
28. Which of the following is Lewis acid [Pb. CET 2000] [IIT JEE Screening 2004]
(a) S (b) : CH 2 (a) 0.0001% (b) 0.01%
(c) 0.1% (d) 0.15%
(c) (CH 3 )3 B (d) All of these
 Ionic Equilibrium 375

39. In the equilibrium A   H 2 O ⇌ HA  OH  (Ka  1.0  10 5 ) . 47. The solubility product of a binary weak electrolyte is 4  10 10 at
The degree of hydrolysis of 0.001 M solution of the salt is [AMU 1999] 298 K . Its solubility in mol dm 3 at the same temperature is [KCET 2001]
(a) 10 3 (b) 10 4 (a) 4  10 5 (b) 2  10 5
5 6 10
(c) 10 (d) 10 (c) 8  10 (d) 16  10 20
40. The sulphide ion concentration [S 2  ] in saturated H 2 S solution is 48. Solubility of AgCl at 20 o C is 1.435  10 3 gm per litre. The
1  10 22 . Which of the following sulphides should be solubility product of AgCl is
quantitatively precipitated by H 2 S in the presence of dil. HCl [CPMT 1989; BHU 1997; AFMC 2000; CBSE PMT 2002]
5
Sulphide Solubility Product (a) 1  10 (b) 1  10 10
5
(I) 1.4  10 16 (c) 1.435  10 (d) 108  10 3
49. pK a value for acetic acid at the experimental temperature is 5. The
(II) 1.2  10 22
percentage hydrolysis of 0.1 M sodium acetate solution will be
(III) 8.2  10 46
(a) 1  10 4 (b) 1  10 2
(IV) 5.0  10 34 3
(c) 1  10 (d) 1  10 5
(a) I, II (b) III, IV
50. At 30 o C, the solubility of Ag 2 CO 3 (K sp  8  10 12 ) would
(c) II, III, IV (d) Only I
be greatest in one litre of [MP PMT 1990]
41. When equal volumes of the following solutions are mixed,
(a) 0.05 M Na 2 CO 3 (b) 0.05 M AgNO3
precipitation of AgCl (K sp  1.8  10 10 ) will occur only with
(c) Pure water (d) 0.05 M NH 3
[IIT 1988; CBSE PMT PMT 1992; DCE 2000]
51. The values of K sp for CuS , Ag2 S and HgS are 10 31 ,10 42
(a) 10 4 M Ag  and 10 4 M Cl 
and 10 54 respectively. The correct order of their solubility in
(b) 10 5 M Ag  and 10 5 M Cl  water is [MP PMT 2003]
(c) 10 6 M Ag  and 10 6 M Cl  (a) Ag2 S  HgS  CuS (b) HgS  CuS  Ag2 S
(c) HgS  Ag2 S  CuS (d) Ag2 S  CuS  HgS
(d) 10 10 M Ag  and 10 10 M Cl 
52. The pH of a soft drink is 3.82. Its hydrogen ion concentration will
42. K sp of an electrolyte AB is 1  10 10 . [ A  ]  10 5 M , which be [MP PET 1990]
(a) 1.96  10 2 mol / l (b) 1.96  10 3 mol / l
concentration of B  will not give precipitate of AB
[BHU 2003] (c) 1.5  10 4 mol / l (d) 1.96  10 1 mol / l
6 5
(a) 5  10 (b) 1  10 53. The pH of a solution at 25C containing 0.10 m sodium acetate
5
(c) 2  10 (d) 5  10 5 and 0.03 m acetic acid is ( pKa for CH 3 COOH  4.57) [AIIMS 2002; BHU
43. 7
One litre of water contains 10 mole hydrogen ions. The degree of (a) 4.09 (b) 5.09
ionization in water will be [CPMT 1985, 88, 93] (c) 6.10 (d) 7.09
54. A weak acid is 0.1% ionised in 0.1 M solution. Its pH is
(a) 1.8  10 7% (b) 0.8  10 9% [BVP 2004]
7 9 (a) 2 (b) 3
(c) 3.6  10 % (d) 3.6  10 % (c) 4 (d) 1
44. If the solubility products of AgCl and AgBr are 1.2  10 10 55. The solubility product of As 2 S 3 is 2.8  10 72 . What is the
13
and 3.5  10 respectively, then the relation between the solubility of As 2 S 3 [Pb. CET 2003]
solubilities (denoted by the symbol ' S ' ) of these 15
(a) 1.09  10 mole / litre
salts can correctly be represented as [MP PET 1994]
(a) S of AgBr is less than that of AgCl (b) 1.72  10 15 mole / litre
(b) S of AgBr is greater than that of AgCl (c) 2.3  10 16 mole / litre
(c) S of AgBr is equal to that of AgCl (d) 1.65  10 36 mole / litre
For a weak acid HA with dissociation constant 10 9 , pOH of
6
(d) S of AgBr is 10 times greater than that of AgCl 56.
8 its 0.1 M solution is
45. If the solubility product of lead iodide (Pbl2 ) is 3.2  10 , then [CBSE PMT 1989]
(a) 9 (b) 3
its solubility in moles/litre will be [MP PMT 1990]
(c) 11 (d) 10
(a) 2  10 3 (b) 4  10 4
57. The dissociation of water at 25 o C is 1.9  10 7% and the density
5 5
(c) 1.6  10 (d) 1.8  10 of water is 1.0 g / cm 3 . The ionisation constant of water is[IIT 1995]
46. Calculate the solubility of AgCl (s) in 0.1 M NaCl at 25C.
(a) 3.42  10 6 (b) 3.42  10 8
K sp ( AgCl)  2.8  10 10 [UPSEAT 2001] 14
(c) 1.00  10 (d) 2.00  10 16
(a) 3.0  10 8 ML1 (b) 2.5  10 7 ML1 58. What is the pH of 0.01 M glycine solution? For glycine,
9 1 1 Ka1  4.5  10 3 and Ka 2  1.7  10 10 at 298 K
(c) 2.8  10 ML (d) 2.5  10 ML 7
[AIIMS 2004]
 376 Ionic Equilibrium
(a) 3.0 (b) 10.0 68. The number of moles of hydroxide (OH  ) ion in 0.3 litre of 0.005
(c) 6.1 (d) 7.2
M solution of Ba(OH )2 is [JIPMER 2001]
59. The concentration of [H  ] and concentration of [OH  ] of a 0.1
aqueous solution of 2% ionised weak acid is (a) 0.0050 (b) 0.0030
(c) 0.0015 (d) 0.0075
[Ionic product of water  1  10 14 ]
69. The pH of pure water or neutral solution at 50C is ….
[DPMT 2004; CBSE PMT 1999]
(pKw  13.26  13.26 at 50C)
(a) 2  10 3 M and 5  10 12 M
[Pb. PMT 2002; DPMT 2002]
(b) 1  10 3 M and 3  10 11 M (a) 7.0 (b) 7.13
(c) 0.02  10 3 M and 5  10 11 M (c) 6.0 (d) 6.63
70. pH of 0.1 M solution of a weak acid (HA) is 4.50. It is neutralised
(d) 3  10 2 M and 4  10 13 M with NaOH solution to decrease the acid content to half pH of
the resulting solution [JIPMER 2002]
60. If solubility product of HgSO 4 is 6.4  10 5 , then its solubility is
(a) 4.50 (b) 8.00
[BHU 2004]
(c) 7.00 (d) 10.00
(a) 8  10 3 mole / litre (b) 6.4  10 5 mole / litre 71. If 50 ml of 0.2 M KOH is added to 40 ml of
(c) 6.4  10 3 mole / litre (d) 2.8  10 6 mole / litre 0.5 M HCOOH , the pH of the resulting solution is
61. At 298K a 0.1 M CH 3 COOH solution is 1.34% ionized. The 4
(Ka  1.8  10 ) [MH CET 2000]
ionization constant K a for acetic acid will be
(a) 3.4 (b) 7.5
[AMU 2002; AFMC 2005]
(c) 5.6 (d) 3.75
5
(a) 1.82  10 (b) 18.2  10 5 72. The Bronsted acids in the reversible reaction are
5
(c) 0.182  10 (d) None of these HCO 3 (aq.)  OH  (aq.) ⇄ CO 32  (aq.)  H 2 O [DPMT 2002]
62. Hydrogen ion concentration of an aqueous solution is 1  10 4 M . 
(a) OH and CO 32 
The solution is diluted with equal volume of water. Hydroxyl ion

concentration of the resultant solution in terms of mol dm 3 is [KCET 2001] (b) OH and H 2 O
8 6
(a) 1  10 (b) 1  10 (c) HCO 3 and H 2 O
(c) 2  10 10 (d) 0.5  10 10
63. Which one of the following is not a buffer solution (d) HCO 3 and CO 32 
[AIIMS 2003] 73. A 0.1N solution of an acid at room temperature has a degree of
(a) 0.8 M H 2 S  0.8 M KHS ionisation 0.1. The concentration of OH  would be [MH CET 1999]

(a) 10 12 M (b) 10 11 M
(b) 2 M C6 H 5 NH 2  2 M C6 H 5 N H 3 Br
9
(c) 10 M (d) 10 2 M
(c) 3 M H 2 CO 3  3 M KHCO 3
74. Increasing order of acidic character would be [RPMT 1999]
(d) 0.05 M KClO4  0.05 M HClO4 (a) CH 3 COOH  H 2 SO 4  H 2 CO 3
64. The hydrogen ion concentration of a 0.006 M benzoic acid (b) CH 3 COOH  H 2 CO 3  H 2 SO 4
solution is (K a  6  10 5 ) [MP PET 1994] (c) H 2 CO 3  CH 3 COOH  H 2 SO 4
4 4
(a) 0.6  10 (b) 6  10 (d) H 2 SO 4  H 2 CO 3  CH 3 COOH
(c) 6  10 5 (d) 3.6  10 4
75. The correct order of increasing [H 3 O  ] in the following aqueous
65. Calculate the amount of (NH 4 )2 SO 4 in grams which must be
solutions is [UPSEAT 2000]
added to 500 ml of 0.200 M NH 3 to yield a solution with (a) 0.01 M H S <0.01 M H SO < 0.01 M NaCl
2 2 4

5 < 0.01 M NaNO 2

pH  9.35 (Kb for NH 3  1.78  10 ) [UPSEAT 2001]
(a) 10.56 gm (b) 15 gm (b) 0.01 M NaCl <0.01 M NaNO < 0.01 M H S 2 2

(c) 12.74 gm (d) 16.25 gm < 0.01 M H SO 2 4

66. pH of a solution produced when an aqueous solution of pH 6 is (c) 0.01 M NaNO <0.01 M NaCl < 0.01 M H S
2 2

< 0.01 M H SO
mixed with an equal volume of an aqueous solution of pH 3 is (d) 0.01 M H S < 0.01 M NaNO < 0.01 M NaCl
2 4

about [KCET 2001]

2 2

< 0.01 M H SO
(a) 3.3 (b) 4.3 76. A base dissolved, in water, yields a solution with a hydroxyl ion
2 4

(c) 4.0 (d) 4.5

concentration of 0.05 mol litre1 . The solution is
67. Calculate the H  ion concentration in a 1.00 (M ) HCN litre [CBSE PMT 2000]
10 (a) Basic (b) Acid
solution (K a  4  10 ) [Bihar CEE 1995]
(c) Neutral (d) Either (b) or (c)
(a) 4  10 14 mole / litre 77. In the given reaction, the oxide of sodium is
(b) 2  10 5
mole / litre  4 Na  O2  2 Na 2 O 
….   [Orissa JEE 2002]
5
(c) 2.5  10 mole / litre  Na 2 O  H 2 O  2 NaOH 
(a) Acidic (b) Basic
(d) None of these
(c) Amphoteric (d) Neutral
 Ionic Equilibrium 377

78. What is the pH of a 1M CH 3 COOH a solution K a of acetic acid

 1.8  10 5.
K  10 14 mol 2litre2 [DPMT 2002]
(a) 9.4 (b) 4.8
(c) 3.6 (d) 2.4
 Ionic Equilibrium 379

1 c 2 b 3 b 4 b 5 b
6 a 7 b 8 d 9 a 10 a
11 c 12 d 13 b 14 b 15 d
16 d 17 b 18 b 19 c 20 c
21 a 22 c 23 b 24 d 25 c
Read the assertion and reason carefully to mark the correct option out of 26 d 27 a 28 d 29 d 30 c
the options given below :
31 b 32 c 33 c 34 c 35 a
(a) If both assertion and reason are true and the reason is the correct 36 c
explanation of the assertion.
(b) If both assertion and reason are true but reason is not the correct
explanation of the assertion. Acids and Bases
(c) If assertion is true but reason is false.
(d) If the assertion and reason both are false.
1 a 2 d 3 a 4 c 5 b
(e) If assertion is false but reason is true.
6 d 7 b 8 c 9 b 10 a
1. Assertion : pH of hydrochloric acid solution is less than that
11 a 12 c 13 a 14 d 15 d
of acetic acid solution of the same concentration.
Reason : In equimolar solutions, the number of titrable 16 b 17 b 18 d 19 a 20 b
protons present in hydrochloric acid is less than 21 d 22 b 23 b 24 c 25 d
that persent in acetic acid.
[NDA 1999] 26 c 27 c 28 d 29 b 30 b
2. Assertion : A ionic product is used fro any types of 31 b 32 c 33 d 34 a 35 a
electrolytes whereas solubility product is 36 a 37 c 38 c 39 c 40 a
applicable only to sparingly soluble salts.
Reason : Ionic product is defined at any stage of the 41 c 42 d 43 c 44 a 45 a
raction whereas solubility product is only 46 c 47 c 48 d 49 a 50 b
appicable to the saturation stage. 51 b 52 a 53 a 54 a 55 d
[AIIMS 2001]
3. Assertion : A solution of FeCl3 in water produce brown 56 b 57 ab 58 a 59 c 60 d
precipitate on standing. 61 a 62 b 63 b 64 b 65 a
Reason : Hydrolysis of FeCl3 takes place in water 66 a 67 d 68 a 69 a 70 b
4. Assertion : BaCO3 is more soluble in HNO 3 than in 71 b 72 d 73 b 74 d 75 b
plain water. 76 b 77 a 78 a 79 b 80 a
Reason : Carbonate is a weak base and reacts with the 81 d 82 b 83 b 84 d 85 bd
H  from the strong acid, casuing the barium 86 a 87 d 88 a 89 d 90 c
salt to dissociate.
91 a 92 a 93 a 94 d 95 b
5. Assertion : CHCl 3 is more acidic than CHF3 .
96 c 97 b 98 c 99 d 100 c
Reason : The conjugate base of CHCl 3 is more stable
101 a 102 a 103 c 104 c 105 a
than CHF3 . 106 a 107 d 108 b 109 c 110 d
6. Assertion : Addition of silver ions to a mixture of aqueous 111 b 112 c 113 c 114 a 115 c
sodium chloride and sodium bromide solution
will first precipitate AgBr rather than AgCl . 116 d 117 d 118 c 119 c 120 c
121 a 122 d 123 b 124 a 125 b
Reason : K sp of AgCl  K sp of AgBr . [AIIMS 2004]
126 c 127 c 128 d 129 c 130 b
7. Assertion : The pKa of acetic acid is lower than that of
131 b 132 c 133 a 134 c 135 a
phenol.
Reason : Phenoxide ion is more resonance stabilized.[AIIMS 2004] 136 c 137 c 138 b 139 b 140 b
8. Assertion : Sb (III) is not precipitated as sulphide when in 141 b 142 a 143 b 144 a 145 a
its alkaline solution H 2 S is passed. 146 a 147 b 148 b 149 c 150 a
Reason : The concentration of S 2  ion in alkaline 151 c 152 c 153 d 154 c 155 a
medium is inadequate for precipitation. 156 b 157 a 158 d 159 b 160 d
[AIIMS 2004]
9. Assertion : Ionic reactions are not instantaneous. 161 b 162 d 163 c 164 d 165 a
Reason : Oppositely charged ions exert strong forces.
Common ion effect, Isohydric solutions, Solubility
product, Ionic product of water and Salt hydrolysis

1 b 2 c 3 b 4 b 5 b
6 d 7 c 8 a 9 c 10 a
11 b 12 b 13 a 14 d 15 d
Electrical conductors, Arrenius theory and
16 b 17 c 18 c 19 d 20 c
Ostwald’s dilution law
21 d 22 d 23 d 24 b 25 a
 380 Ionic Equilibrium
26 d 27 a 28 d 29 b 30 b 131 c 132 d 133 c 134 c 135 a
31 a 32 d 33 a 34 c 35 d 136 c 137 c 138 c 139 c 140 b
36 b 37 b 38 c 39 b 40 a 141 b 142 a 143 d 144 b 145 b
41 a 42 d 43 b 44 a 45 b 146 d 147 c 148 b 149 a 150 d
46 d 47 b 48 c 49 c 50 c 151 b 152 d 153 b 154 b 155 c
51 b 52 d 53 a 54 d 55 c 156 d 157 c 158 a 159 c 160 d
56 d 57 b 58 c 59 d 60 c 161 c 162 d 163 b 164 a 165 d
61 b 62 b 63 a 64 bc 65 d 166 a 167 d 168 b 169 c 170 a
66 a 67 d 68 a 69 d 70 c 171 c 172 c 173 d 174 b 175 a
71 c 72 d 73 d 74 d 75 a 176 c 177 a 178 c 179 a 180 b
76 c 77 b 78 d 79 b 80 d 181 c 182 b 183 b 184 b 185 c
81 c 82 c 83 d 84 c 85 d 186 b 187 b 188 a 189 a 190 b
86 d 87 b 88 c 89 b 90 a 191 d 192 b 193 b 194 b 195 a
91 a 92 a 93 c 94 c 95 a 196 b 197 b 198 b 199 a 200 ad
96 d 97 d 98 b 99 b 100 ab 201 ac 202 a bc 203 c 204 c 205 b
101 d 102 c 103 c 104 a 105 c 206 b
106 c 107 c 108 a 109 b 110 b
111 b 112 a 113 a 114 a 115 b Critical Thinking Questions
116 a
1 b 2 a 3 b 4 a 5 d
Hydrogen ion concentration - pH scale and 6 a 7 c 8 a 9 a 10 a
Buffer solution 11 b 12 d 13 c 14 d 15 c
16 d 17 d 18 b 19 b 20 d
1 a 2 c 3 d 4 b 5 b
21 a 22 b 23 a 24 b 25 a
6 d 7 a 8 c 9 b 10 d
26 c 27 d 28 d 29 b 30 d
11 a 12 d 13 c 14 a 15 b
31 b 32 a 33 c 34 a 35 a
16 d 17 b 18 c 19 c 20 d
36 b 37 c 38 b 39 a 40 b
21 b 22 c 23 a 24 d 25 b
41 a 42 a 43 a 44 a 45 a
26 a 27 a 28 d 29 b 30 b
46 c 47 b 48 b 49 b 50 c
31 d 32 b 33 a 34 a 35 c
51 d 52 c 53 b 54 c 55 a
36 c 37 c 38 a 39 a 40 d
56 d 57 d 58 c 59 a 60 a
41 a 42 a 43 b 44 d 45 b
61 a 62 c 63 d 64 b 65 a
46 a 47 b 48 a 49 c 50 a
66 a 67 b 68 b 69 d 70 b
51 a 52 c 53 c 54 c 55 d
56 a 57 c 58 b 59 b 60 c 71 a 72 c 73 a 74 c 75 c

61 b 62 c 63 b 64 b 65 c 76 a 77 b 78 a

66 a 67 b 68 d 69 a 70 c
71 d 72 a 73 b 74 a 75 b Assertion & Reason
76 a 77 a 78 c 79 b 80 a
81 b 82 c 83 b 84 b 85 c 1 c 2 b 3 a 4 a 5 a
86 b 87 a 88 a 89 a 90 d 6 c 7 c 8 a 9 e
91 b 92 c 93 a 94 a 95 c
96 b 97 b 98 b 99 b 100 b
101 c 102 c 103 a 104 a 105 c
106 a 107 c 108 c 109 d 110 b
111 d 112 d 113 b 114 a 115 c
116 d 117 b 118 b 119 d 120 c
121 d 122 b 123 c 124 d 125 b Electrical conductors, Arrhenius theory and
126 b 127 a 128 c 129 b 130 d Ostwald's dilution law
 Ionic Equilibrium 381

1. (c) C12 H 22 O11 is a sugar and non-electrolyte. 2

2. (b) It is a weak electrolyte since it is slightly ionized. K ;   KV  1  10 5  10 ;   1  10 2
V
3. (b) It is a weak electrolyte since slightly ionized.
4. (b) Because the degree of dissociation is inversely proportional to 29. (d) MgCl2 ⇌ Mg   2Cl  in aqueous solution it is dissociated
the concentration of the electrolyte. into ions.
5. (b) Electrolytes are those substances which on dissolving in water
give ions. 30. (c) Ostwald’s dilution formula is  2  K(1   ) / C but for weak
 2C 0 .01  0 .01 
2
electrolyte  is very small. So that (1   ) is neglected for
6. (a) K ;   1  K   2C    1 weak electrolytes. So for weak electrolyte the dilution formula
1  100  100 
 1  10 8 . K
is   .
7. (b) As NaCl ionises completely to yield free ions. C
8. (d) CH 3 COONa ⇌ CH 3 COO   Na   32 
2
31. (b) Ka  C  2  0 .2     2 .048  10  4 .
H 2 O ⇌ H   OH   100 
CH 3 COOH  NaOH 32. (c) H 2 SO 4 ⇌ H   H SO 4 ⇌ H   SO 4 
9. (a) NaCl , being a salt, is a strong electrolyte. Because of it is completely ionised.
10. (a) We can determine by measurement of very dilute HF solutions.
33. (c) Colour of electrolyte depends on the nature of both ions.
K(1   )
11. (c) According to the Ostwald’s dilution formula  2  . e.g. CuSO 4 is blue because Cu 2  ions are blue.
C
But for weak electrolytes  is very small. So that (1   ) can 34. (c) Ionisation depends upon dilution, when dilution increases then
ionisation is also increased.
Ka
be neglected. So that   . 35. (a) More is K a , lesser is pKa (pKa   log Ka ) more is acidic
C strength.
12. (d) Arrhenius proposed the theory of ionisation.
13. (b) higher the dielectric constant of a solvent more of its ionising
power.
14. (b)   dilution of solution. Acids and Bases
15. (d) Generally ionic compound are conduct electricity in fused state.
16. (d) According to Ostwald’s dilution law because degree of 1. (a) CO doesn’t have a vacant d-orbital.
ionization is directly proportional to the dilution.
2. (d) HClO4  H 2O ⇌ H 3 O   ClO4
17. (b) The degree of ionisation of a solute depends upon its nature,
concentration, and temperature. Conjugate acid and base pair
18. (b) Mathematical form of Ostwald’s dilution law.
19. (c) It is a weak electrolyte because it’s ionization is very less. 3. (a) FeCl3  3 H 2O ⇌ Fe (OH )3  3 HCl . Strong acid and
20. (c) When we add NH 4 OH in NH 4 Cl solution ionization of weak base.
NH 4 OH is decreased due to common ion effect. 4. (c) Na2CO3  2 H 2O ⇌ 2 NaOH  H 2CO 3
2 
21. (a) BaCl 2 ⇌ Ba + 2Cl 5. (b) Those substance accept the proton are called Bronsted base
Initially 1 0 0 and which is donate the proton are called Bronsted acid.
After dissociation a    2 HCO3  H  ⇌ H 2CO 3 Bronsted base.
Total = 1      2  1  2
HCO 3 ⇌ H   CO 3  Bronsted acid.
1.98  1 0.98
   0 .49
  7. (b) The value of pK a for strong acid is less.
for a mole   0.49 8. (c) Because it is a salt of strong base and weak acid.
0 .49 9. (b) Because it is conjugate base of weak acid.
For 0.01 mole    49
0 .01 CH 3 COOH ⇌ CH 3 COO   H  .
22. (c) It is an ionic salt.
11. (a) Those compound which accept H  is called bronstad base
23. (b) Due to common ion effect of H  .
24. (d) Current does not affect the degree of ionization. NO 3 accept H  and form HNO 3 . So it is a base.
25. (c) Polar solvent facilitate ionisation of strong electrolytes due to 13. (a) Larger the size of halogen atom less is the back donation of
dipole-ion attraction. electrons into empty 2p orbital of B.

26. (d) HA ⇌ H   A  14. (d) H 2O  NH 3 ⇌ NH 4  OH 
K  Ca 2  0.1  (10 4 )2  10 9 16. (b) NH 2 ⇌ NH 2  H 
28. (d) Degree of dissociation  = ? Conjugate acid, base pair.
1 17. (b) Those substances which lose proton are called acid.
Normality of solution = 0.1 N  N
10 e.g. strong acid have a strong tendency to donate a proton.
Volume = 10 litre 18. (d) Electron donating species called nucleophile. NH 3 have a lone
Dissociation constant K  1  10 5 pair of electron.
 382 Ionic Equilibrium

19. (a) H 2 O acts as acid as it provides H  to NH 3 . 2  0.2 M

52. (a) M.eq. of 0.2M H 2 SO 4   100  0 .04 m/l
1000
20. (b) CH 3 COOH  HF ⇌ CH 3 COOH 2  F  . HF gives H 
0 .2
to the CH 3 COOH . So it is a conjugate base of HF. M.eq. of .2M NaOH   100  0 .02 m/l
1000
22. (b) Ba(NO 3 )2 does not undergo hydrolysis. left [H  ]  .04  .02  .02 .
23. (b) H 2 SO 4 is a mineral acid. .02
Total volume  200   .0001  10 4 M
24. (c) Because it is a electron pair acceptor it’s central atom have a 200
vacant d-orbital.
pH  4 .
25. (d) HClO4 is a acid and their conjugate base is ClO4 . 53. (a) H 3 BO 3 is a weak monobasic acid it does not act as a
26. (c) It is completely ionised because their ionization is very high. H  donor but behaves as a Lewis acid.
27. (c) NaHCO3 in water is alkaline in nature due to hydrolysis of 54. (a) Because SnCl 2 is a electron acceptor according to Lewis
HCO 3 ion. NaCO 3 ⇌ Na   HCO3 concept.
55. (d) ROH is a Lewis base because it has an lone pair of electron.
28. (d) In this reaction H 2 O acts as a acid.
56. (b) H 2 SO 4  2 H 2 O ⇌ 2 H 3 O   SO 4 
29. (b) The basic character of hydride decreases down the group.
30. (b) Its ionization is very less. NaOH ⇌ Na   OH 
2 
32. (c) Hydrolysis of Cu produces H ions in solution. 1 mole of H 2 SO 4 acid gives 2 moles of H 3 O  ions. So 2
2 
Cu  2 H 2O  Cu(OH )2  2 H moles of OH  are required for complete neutralization.
33. (d) Both possess the tendancy to accept proton. 57. (ab) Diprotic solvents give 2 H  ions or OH  ions.
34. (a) HF does not give proton easily.
58. (a) N NaOH  1  1  1 N
35. (a) In weak electrolyte the degree of dissociation is very small. So it
increases with increasing dilution. N H 2SO 4  2  10  20 N
36. (a) Because it is a electron pair acceptor. M.eq. of NaOH  1  100  100
I step

37. (c) H 3 PO4 H  H 2 PO4 M.eq. of H 2 SO 4  20  10  200
II step Thus M.eq. of acid are left and therefore pH< 7, so the
H 2 PO4 H   HPO4  resulting mixture will be acidic.
III step
HPO4  H   PO4   60. (d) PH 3 is a Lewis base.
61. (a) Because of CH 3 COONa is a salt of weak acid and strong
38. (c) Na 2 HPO4 on hydrolysis of HPO42  ion produces free
base.
OH  ion in solution.
62.  H
(b) Acid 

 conjugate base.
39. (c) H 2 SO 4 ⇌ H   HSO 4 .
 H
Base 

 conjugate acid.
40. (a) Fe3   3 H 2O  Fe(OH )3  3 H 
 63. (b) HCl  Cl 
41. (c) H 2 PO4 ⇌ H   HPO42 action. Acid Base
Conjugate acid
65. (a) HClO4  H 2 SO 4  HCl  HNO 3 .
42. (d) H   OH  ⇌ H 2 O, it is a neutralization reaction. Aciedic character decreases

43. (c) It is a conjugate base of the strong acid. 66. (a) Those substances which accept the H  are called conjugate
base.
44. (a) Because those acid have higher pKa value are weak acid.
67. (d) NH 3 is a Lewis base, which donate a lone pair of electron.
45. (a) Conjugate acid is obtained from the base by gain of H  .
69. (a) FeCl 3  3 H 2 O ⇌ Fe(OH )3  3 HCl . Strong acid have
46. (c) CH 3 COOH is weak acid shows dissociation equilibrium as
less than 7 pH.
CH 3 COOH ⇌ CH 3 COO   H  70. (b) It donates their e  pair.
1 71. (b) The strength of the acid will depend upon the proton donation.
47. (c) pKa  log10
Ka 73. (b) Because it is a salt of strong acid and strong base.
48. (d) A weak acid and strong base. H  (aq)  Cl  (aq)  Na  (aq)  OH  (aq) ⇌
49. (a) In NaH 2 PO2 both hydrogen are bonded with ‘P ,’ so it is
not replaceable. H 2 O(l)  Na  (aq)  Cl 
50. (b) Aqueous solution of Na2CO 3 is alkaline due to hydrolysis of 74. (d) CCl 4 is not a Lewis or bronsted acid. It does not contain
CO 3  . H.
51. (b) Because they give CO 3  in solution.
 Ionic Equilibrium 383

75. (b) NH 4 Cl  H 2 O ⇌ NH 4 OH  HCl . So it is acidic in 109. (c) Conjugate base of H 2 SO 4 is HSO 4 .

Weak base Strong acid

nature. 110. (d) Presence of lone pair.

76. (b) Cu(II) complexes are blue. The four water molecules are 111. (b) According to Bronsted principle HNO 3 is acid they give H  in
attached with secondary valencies of the metal atom e.g.
aqueous solution and form NO 3 .
[Cu(H 2 O)4 ] SO 4 . H 2 O .
77. (a) The species which can accept as well as donate H  can act 112. (c) H 2 O  H 2 O ⇌ H 3 O   OH  .
both as an acid and a base.
113. (c) NH 4 is a conjugate acid;
HSO 4  
H ⇌ H 2 SO 4
base NH 4 ⇌ NH 3  H 
HSO 4 ⇌ SO 42   H  114. (a) AlCl3  3 H 2 O ⇌ Al(OH ) 3  3 HCl
acid Stron acid

78. (a) NH 4 is the weakest acid. So its conjugate base is strongest. 116. (d) HCl is a strong acid its conjugate base means Cl  is a weak
base.
79. (b) Ag  is an electron deficient compound and hence is a Lewis
acid. 117. (d) Hydrazoic acid (HN 3 ) is a Lewis acid.
80. (a) H 3 PO4 ⇌ H   H 2 PO4 118. (c) Smaller the pK a value than. Stronger the acid.
Conjugate acid
120. (c) BF3 is acidic because due to Lewis concept it accept a lone
81. (d) HS 2 O 8 ⇌ H   S 2 O 8  pair of electron.
Conjugate acid Conjugate base
122. (d) Because it is a weak electrolyte.
82. (b) PH3 donates electron pair to BCl 3 . 126. (c) AlCl3 and SO 2 both are example of Lewis theory.
83. (b) The conjugate base of weak acid is a strong base.
127. (c) Na 2 CO 3  2 H 2 O ⇌ 2 NaOH  H 2 CO 3 . It is a strong
84. (d) OH   O 2  H 
Conjugate base of OH  base and weak acid so it is a basic.
85. (bd) Presence of lone pair of electron and they donate two electron 129. (c) H 2 O  NH 3 ⇌ NH 4  OH  .
pairs. Acid base
86. (a) On increasing oxidation number Acidic strength increases.
In this reaction H 2 O acts as acid because it donate a proton.
87. (d) H 3 PO4 is shows +5 maximum oxidation state.
88. (a) C 2 H 5 is a strongest base. 130. (b) H 2 SO 4  H 2 O ⇌ H 3 O   HSO 4
89. (d) NaOCl is a mixture of strong base and weak acid.
Conjugate acid and base pair
90. (c) NH 4 OH gives minimum OH  ion. So it is a weak base. 131. (b) Al2 (SO 4 )3 ⇌ 2 Al 3   3 SO 4
2

91. (a) Solution become acidic and methyl orange act on acidic pH. Al(OH )3  H 2 SO 4
92. (a) Larger is bond length, more is acidic nature (for halogen acids). Weak base Strong acid
HF bond length is small. Neutralization
132. (c) NaOH  HCl NaCl  H 2 O
93. (a) HCl is accepting proton in HF medium and acts as weak base. Reaction Salt

95. (b) For oxoacids of the same element, the acidic strength increases 133. (a) Conjugate acid is obtained from the base by gain of H  .
with increase in the oxidation number of that element. 134. (c) KCl is a ionic compound .
1 3 5 7
HClO  HClO2  HClO3  HClO4 135. (a) H 3 BO 3  H 2 O ⇌ [B(OH )4 ]  H 
96. (c) Because their conjugate base and conjugate acids are strong. H 3 BO 3 is a weak monobasic acid if does not act as a H 
97. (b) HCl is a strong acid and their conjugate base is a very weak donor but behaves as a Lewis acid.
base. 136. (c) Because it is not accept the proton.
100. (c) NH 3 ⇌ NH 2  H  137. (c) NH 4 Cl is a salt of weak base ( NH 4 OH )and strong acid
(HCl).
101. (a) H 2 SO 4 ⇌ H   HSO 4 ⇌ H   SO 4 
138. (b)Because it accept electron pair from the PH 3
HSO 4 is conjugate base. But it is also an acid because it lose 139. (b) NH 4 ⇌ NH 3  H 

H .
141. (b) Hydrolysis of Fe 3 
102. (a) BF3 is a Lewis acid because ‘B’ has incomplete octet.
Fe 3   3 H 2 O  Fe(OH )3  3 H 

104. (c) H 3 O , however it exists as H 9 O 4 . 142. (a) According to the Lewis concept.
105. (a) Al 2 (SO 4 )3 is a salt of weak base Al 2 (OH )3 and strong acid 143. (b) Conjugate base is obtained from the acid by loss of H  .
H 2 SO 4 . 144. (a) BF3 accept electron pair from NH 3 so it is Lewis acid.

106. (a) Al    of AlCl3 undergoes hydrolysis. 145. (a) CH 4 has almost no acidic nature and thus CH 3 is strongest
base.
107. (d) H 2 SO 4 ⇌ H   HSO 4
 384 Ionic Equilibrium
146. (a) CuSO 4 is a salt of weak base, (Cu (OH ) 2 ) and strong acid K sp 1  10 11
(H 2 SO 4 ) . S 3 3  1 .35  10  4
4 4
147. (b) Weak acid consists of highest pK a value and strongest acid 8. (a) Mg(OH )2 ⇌ Mg    2OH2 
(X ) (2 X )
consist of less pK a value.
149. (c) Because it gain and also lose the proton K sp  4 X 3

 
H 2 O  H 2 O ⇌ H 3 O  OH 9. (c) BaSO 4 ⇌ Ba    SO 4 
(S ) (S )
150. (a) H 2 O  H 2 O ⇌ H 3 O   OH  0 .01 5

151. (c) HBr  H 2 O ⇌ H 3 O   Br  Ksp  S 2  S  S  0.01  S

152. (c) Because both are strong acid and strong base. K sp 1  10 9
153. (d) LiAlH4 is a nucleophilic and capable of donating electron S (SO 2  )    10 7 mole/litre
4 S ( Ba  ) 0 .01
pair, thus acts as a Lewis base.
154. (c) The solvent which neither accept proton nor donates. 10. (a) AB2 ⇌ A   2B 
110 5 210 5
155. (a) Because of F  is a highly electronegative. So it is easily lose the
electron and reaction occur rapidly. K sp  [1  10 5 ] [2  10 5 ]2  4  10 15
156. (b) Strong acid can be used titrate both strong and weak base.
11. (b) CaF2 ⇌ Ca   2 F2 ; K sp  4S 3
159. (b) For a weak acid value of pKa will be vary high but in case of (S ) (2 S )

strong acid value of pKa will be vary low. 12. (b) Due to common ion effect.
160. (d) Boron halides behave as Lewis acid because of their electron 13. (a) Ag 2 CrO4 ⇌ [2 Ag  ]  [CrO4  ]
deficient nature eg., as
F Hence K sp  [ Ag  ]2 [CrO4  ]
(Deficiency of two electron for inert configuration)
B 14. (d) K sp for CaF2  4 s 3  4  [2  10 4 ]3  3.2  10 11 .
F F 15. (d) The concentration of S 2  ions in group II is lowered by
161. (b) Gaseous HCl does not give H  but liquid HCl gives H  in
aquous solution there for gaseous HCl is not a Arrhenius acid maintaining acidic medium in the presence of NH 4 Cl . The
due to covalent bonding in gaseous condition. ionization of H 2 S is supressed due to common ion effect. So
162. (d) H 2 O  H   OH  [Acid due to donation of proton] the ionic product is less than solubility product.
NH 4 Cl is hydrolysed and give [H  ]
Acid
16. (b)
H 2 O  H   H 3 O  [Basic due to gaining of proton]
Base NH 4 Cl  H . OH ⇌ NH 4 OH  HCl

163. (c) F strongest conjugate base due to it smallest size in a group NH 4   H . OH ⇌ NH 4 OH  H 
and gain proton due to most electronegative capacity.
H   F   HF 17. (c) FeCl 3 is a salt of weak base (Fe(OH )3 ) and strong acid
(HCl).
164. (d) H 2 PO4  H   HPO42  18. (c) For the precipitation of an electrolyte, it is necessary that the
Conjugate acid Conjugate base
ionic product must exceed its solubility product.
165. (a) HSO 4 H  SO 42  19. (d) K sp  [ Ag  ]2 [Cro 4  ]  [2S ]2 [0.01]
Conjugate acid Conjugate base

= 4 S 2 [0.01]  4[2  10 8 ]2  0.01  16  10 18 .

Common ion effect, Isohydric solutions, Solubility 20. (c) Complex salts contain two different metallic elements but give
product, Ionic product of water and Salt hydrolysis test for only one of them. e.g. K 4 Fe(CN )6 does not give test
for Fe 3  ions.
1. (b) Solubility of Al 2 (SO 4 )3
21. (d) 10 3 N KOH will give [OH  ]  10 2 M
Al 2 (SO 4 )3 ⇌ 2 Al     3 SO 4 
pOH  2
K sp  [ Al 3  ] 2 [SO 42  ]3
 pH  pOH  14 , pH  14  2  12
2. (c) Due to common ion effect.
22. (d) It is FeSO 4 (NH 4 )2 SO 4 . 10 H 2 O .
3. (b) MX 2 ⇌ M 2   2 X 
S 2S
23. (d) Salt of a strong base with a weak acid.
K sp  (2S )2 (S )  4 S 3 24. (b) NH 4 CN is a salt of weak acid and weak base and thus for it
K sp 4  10 12 25. (a) Because it is a salt of strong base with a weak acid.
 S 2 3 3  1 .0  10 4 M . 26. (d) Because CCl 4 is a organic solvent and AgNO 3 is insoluble in
4 4
  organic solvent.
5. (b) MX 2 ⇌ M  2 X 2 ; K sp  4S 3
(S ) (2 S ) 27. (a) SnS 2 ⇌ Sn 4   2S 2 
 Ionic Equilibrium 385

K sp  [Sn 4  ] [S 2  ] 2 1.20  10 10  0.2a

28. (d) It does not dissociate much or its ionization is very less. 1 .20  10 10
a  6  10 10 mole
29. (b) NaHCO 3 has one replaceable hydrogen. 0 .20
47. (b) Solubility is decreased due to common ion effect.
30. (b) CaOCl 2 has two anions Cl  and OCl  along with
AgI ⇌ Ag   I 
Ca 2 ions.
Common ion
4  10 9 NaI ⇌ Na   I 
31. (a) K sp  4 S , 3
S 
3
 10 9
4
48. (c) K sp of BaSO 4  1.5  10 9 ; Ba   0.01M
3
S  10 M.
1 .5  10 9
32. (d) Be(OH ) 2 has lowest solubility and hence lowest solubility SO 4    1 .5  10 7
0 .01
product.
33. (a) Because it is a salt of strong acid and strong base. 49. (c) AgCrO4 ⇌ 2 Ag   CrO 4
( 2 S )2 S

34. (c) NH 4 OH ⇌ NH 4  OH 
K sp  4S 3 given 2S  1.5  10 4
 
NH 4 Cl ⇌ NH 4  Cl
K sp  (2S ) 2  S
Common ion
35. (d) It is a less ionic, so that least soluble in water.  1 .5  10 4 
 (1 .5  10 4 )2     1.6875  10 12

36. (b) pH of 9 means the salt solution should be fairly basic.  2 
37. (b) CH 3 COOH ⇌ CH 3 COO   H  50. (c) PbCl 2 ⇌ Pb 2   2Cl 
S S
On adding CH 3 COONa , [H  ] decreases.
K sp of PbCl2  [Pb ]  [Cl  ] 2 ; K sp  S  (2S ) 2
2


38. (c) 0.01 M CaCl 2 gives maximum Cl ions to keep K sp of AgCl
K sp K sp
constant, decrease in [ Ag  ] will be maximum. K sp  S  4S 2  4S 3 ; S 3  ; S  3
4 4
39. (b) Due to the common ion effect.
 
51. (b) AgCl ⇌ [ Ag ] [Cl ] ; K sp  S  S ; K sp  S 2
40. (a) K sp  4 s 3
S  K sp  1.44  10 4  1.20  10 2 M.
K sp 1 .0  10 6
S 3 3  6.3  10 3 .
4 4 52. (d) By formula BA2  B   2 A 
42. (d) K w increases with increase in temperature. K sp  4 x 3
43. (b) It contains two cations and one anion.
53. (a) AgCrO4  2 Ag   CrO 4  
44. (a) HgSO 4 of K sp  S 2 S 2S S

K sp  (2S ) 2 S  4 S 3
S  K sp ; S  6.4  10 5 ; S  8  10 3 m/l.
1 1
45. (b) The solubility of BaSO 4 in g/litre is given 2.33  10 3  K sp  3  32  10 12  3
S       2  10 4 M.
  
W 2 .33  10 3  4   4 
 in mole/litre. n   1  10 5  54. (d) Common ion effect is noticed only for weak electrolyte
m . wt 233
dissociation. H 2 SO 4 is strong electrolyte.
Because BaSO 4 is a compound
55. (c) When we added barium ion in chromate ion solution we
K sp  S  [1  10 ]
2 5 2
 1  10 10 obtained yellow ppt of BaCrO4 .

BaCl 2  K 2 CrO4  BaCrO4   2 KCl

46. (d) AgCl ⇌ Ag   Cl  Yellow ppt.
a a a
56. (d) AB is a binary electrolyte.
NaCl ⇌ Na   Cl 
S  K sp  1.21  10 6  1.1  10 3 M
0 .02 0 .02 0 .02

10
K sp AgCl  1.20  10 57. (b) Precipitation occurs when ionic product > solubility.
  58. (c) For a binary electrolyte, so that
K sp AgCl  [ Ag ] [Cl ]  a  [a  0.2]  a  0.2a 2

K sp  S  S  S 2
a 2 is a very small so it is a neglected.
K sp AgCl  0.2a S  K sp .
 386 Ionic Equilibrium
61. (b) CH 3 COONa is a salt of weak acid and strong base. Hence its OH   H  ⇌ H 2 O . So that S 2  is increased.
aqueous solution is alkaline.
81. (c) BaSO 4 ⇌ Ba 2   SO 42 
62. (b) BaSO 4 ⇌ Ba 2   SO 4 
Solubility constant  S  S K sp  S 2  S  K sp ; K sp  [Ba 2  ]  [SO 42  ]

1.5  10 19  S 2 ; S  1.5  10 19 ; S  3.9  10 5 4  10 10  [1  10 4 ]  [SO 42  ]

 
65. (d) Ca(OH ) 2 ⇌ Ca  2OH2
(S ) 4  10 10
[SO 42  ]   4  10 6 .
(2 S )

K sp  4 S  4  3  3  3  12 3
3 1  10  4

66. (a) Due to common ion effect. 82. (c) AB 2 ⇌ A 2   2 B 2

(S ) (2 S )
67. (d) PbCl 2 ⇌ Pb 2   2Cl 2
(S ) (2 S ) K sp  4S 3

K sp  4 S 3  4  (2  10 2 )3  3.2  10 5 K sp 4  10 12
S 3 3  1  10 4 gm. mol / litre
  4 4
68. (a) Ag 2 S ⇌ 2 Ag  S
K sp AB 1  10 8
K sp  4S 3 83. (d) [B]    1  10 5 M
[ A] 10 3
K sp 3 .2  10 11 Where ionic product > K sp , ppt formed
S  3 3  2  10 6
4 4
 8 should be more then 10 5 M .
69. (d) CaCO 3 ⇌ Ca 
 CO 3  84. (c) NaCl (s) ⇌ Na (aq )  Cl (aq )
S S S

Solubility product of CaCO 3 HCl ⇌ H   Cl  . The increase in [Cl  ] brings in an

K sp  S 2 ; S  K sp increase in [ Na  ] [Cl  ] which will lead for backward reaction

because
It is a binary electrolyte.
K sp (NaCl)  [ Na  ] [Cl  ]
S 2  K sp ; (3.05  10 4 )2  K sp ; K sp  9.3  10 8
means Ionic product  K sp
71. (c) PbCl 2  Pb    2Cl 
S 2S 85. (d) BaSO 4 ⇌ Ba    SO 4 
(S )
K sp  S  (2S ) 2  [6.3  10 3 ]  [12.6  10 3 ]2 .
(S )

72. (d) A salt of strong acid and strong base cannot be hydrolysed. In K sp  S 2 ; S  K sp  1.3  10 9
this case the equilibrium cannot shifted towards the backward.
73. (d) If we mixed any substance into the solution. Then the value of  3.6  10 5 mol / litre
pH is increased these substance is a salt of weak acid and 87. (b) Alkaline,
strong base.
CH 3 COONa  H 2 O ⇌ CH 3 COOH  NaOH
74. (d) It is a salt of strong base and weak acid. Weak acid Strong base

75. (a) K sp  4 s 3  4  [2.5  10 2 ]3  62.5  10 6 . 88. (c) Because it is a strong base.

Na   Cl  89. (b) For pure water [H  ]  [OH  ] , K w  10 12 s

76. (c) NaCl ⇌
S S 90. (a) MX 2 ⇌ M 2   2 X2 ; 4 S 3  4  (0.5  10 4 )3
(S ) (2 S )
K sp  S 2 , S  K sp  36  6 . 13
 5  10
 
78. (d) PbI2 ⇌ Pb  2I 91. (a) Solubility coefficient  [Pb 2  ] [Cl  ]2
K sp S 2S
92. (a) Solubility of Al(OH )3 is lesser than Zn(OH )2 .
K sp  4 S 3  4  [2  10 3 ]3  32  10 9 .
93. (c) NaCl(s) ⇌ Na  (aq )  Cl (aq )
79. (b) When ionic product is greater than K sp then precipitation
occur HCl ⇌ H   Cl 
K sp  10 2 M Ca 2   10 3 M F  The increase in [Cl  ] brings in an increase in
 
[ Na ] [Cl ] which will lead for backward reaction because
80. (d) In IV group the S 2  concentration increase when added the
th

NH 4 OH because K sp NaCl  [ Na  ] [Cl  ] .

94. (c) Common ion effect.
NH 4 OH ⇌ NH 4  OH 
95. (a) CaF2 ⇌ Ca    2 F2
 2
H 2 S ⇌ 2H  S S S (2 S )

K sp  4S 3
 Ionic Equilibrium 387

K sp 3 .2  10 11  2C  .25 
S 3 3  2  10 4 m/l. K    
4 4 1   100 
96. (d) In aqueous solution following euilibrium is exist. K   2C  1    Very small 
H 2 S ⇌ H   HS 
.25 .25
K   .5 ; K  3.125  10 6
While adding the dilute HCl solution 100 100
(HCl ⇌ H   Cl  ) equilibrium is shift to the left side in 114. (a) Sb 2 S 3  2 Sb 2  3 S   ; K sp  (2 x )2 .(3 x )3
  2x 3x
H 2 S ⇌ H  HS
K sp  108 x 5 ; K sp  108  (1  10 5 )5  108  10 25 .
97. (d) M 2 X 3 ⇌ 2 M 2  + 3 X 3
K sp (2 y ) (3 y ) 115. (b) When increasing the temperature the value of ionic product
also increases.
d
Solubility product K sp  108 y 5 mol Kw
m3 116. (a) Hydrolysis constant h 
Ka
98. (b) Solubility is directly proportional to the K sp .

99. (b) PbCl2 ⇌ Pb   2Cl2

S S (2 S ) Hydrogen ion concentration - pH scale and
K sp  S  (2S )  4 S 2 3 Buffer solution
1. (a) pH of blood does not change because it is a buffer solution.
K sp 1 .5  10 4
S 3 3  3 .34  10 2 .
4 4 2. (c) 0.001 M of NaOH means [OH  ]  .001
101. (d) AlCl3 on hydrolysis gives weak base and strong acid among  10 3 M  pOH  3
all. pH  pOH  14  pH  14  3  11
102. (c)Fe 3  ions are hydrolysed to develop acidic nature.
3. (d) [H 3 O  ] means [H  ]  6.2  10 9 mol / l
Kw
103. (c) K h 
Ka  Kb pH   log(6.2  10 9 )  8.21
104. (a) KCN is salt of strong base and weak acid. 4. (b) CH NH + HCl  CH 3 NH 3 Cl 
3 2

105. (c) Sulphides of Group-II radicals have low solubility product.

0.1 0.08 0
106. (c) Because NH 3 acts as Lewis acid and they give electron pair to 0.02 0 0.08
H 3 O  ion. H 3 O  is a Lewis base. Which accept the electron (Basic buffer solution)
pair from NH 3 . 0 . 08
pOH = pK + log b

107. (c) Due to common ion effect. 0 . 02

= pK + 0.602
108. (a) For Ag 2 SO 4  2 Ag   SO 4 b

2x x = 3.30 + 0.602= 3.902

K sp  (2 x )2 . x ; K sp  4 x 3 ; K sp  4  (2.5  10 2 )3  pH = 10.09
[H ] = 7.99  10  8  10 M
+ 11 11

K sp  62.5  10 6 5. (b) pH  pOH  pKw

 
109. (b) For AgCl  Ag  Cl 6. (d) pH   log[H  ]
x x
5.4   log[H  ] ; [H  ]  3.98  10 6 .
K sp  x 2 ; x  K sp , 1  10 6  1  10 3 mole / litre.
7. (a) KCN  H 2 O ⇌ KOH  HCN . KOH is a strong base and
110. (b) AgCl  Ag   Cl  HCN is a weak acid.
x x
8. (c) [H  ]  10 3 M , pH   log[10 3 ], pH  3
After NaCl is added x x  1  10 4
That is why Ag  will be less. 9. (b) [H  ]  [OH  ]
111. (b) Because of ionic product of AgI  solubility product of its. Kw  [H  ] [OH  ]  1014
112. (a) AX 2  A  2 X [H  ]  10 7 , pH   log[H  ]  7 .
x 2x

3 .2  10 11 10. (d) pH  5 means [H  ]  10 5

K sp  4 x 3 ; x  3 ; x  2  10 4 mole/litre.
4 pOH  14  pH  14  5  9

113. (c) C6 H 5 COONH 4  C6 H 5 COO  NH 4 [OH  ]  10  pOH  10 9

0 .5 
.25 . 25 . 25 11. (a) pH   log [H  ] ; [H  ]  0.01 N
100 100 100
pH   log [10 2 ] ; pH  2
According to Ostwald dilution law.
 388 Ionic Equilibrium
12. (d) N
Initial
BOH
C 0
B +
+
0
OH –

32. (b)  0 .01 N HCl ; [H  ]  10 2 M ; pH  2

100
At eq. C – C C C
[OH ]  10 2 M for NaOH
C  2 2
pH  pOH  14 ; pH  14  2 ; pH  12
Kb   C  2 assuming   1 ; 1   ~– 1
C(1   ) 34. (a) It is a buffer solution of strong acid and its weak conjugate
base.
10 12  10 2   2 ;  2  10 10 ;   10 5
35. (c) HA ⇌ H   A 
[OH  ]  C  .01  10 5  10 7
[H  ]  0.1 M ; [H  ]2  Ka  C
13. (c) pH  4 means; [H  ]  10 4 mol
14. (a) Buffer solution is a mixture of weak acid and its conjugate [H  ]  Ka  C  1  10 5  0.1  10 6
base.
15. (b) Adding Na 2CO 3 to water makes the solution basic and hence [H  ]  10 3 M ; pH  3
a pH increases from 7. 36. (c) As the solution is acidic, pH  7 . This is because [H  ] from
16. (d) NaClO is a salt of strong acid HClO4 . So it is a strong acid
H 2 O cannot be neglected in comparison to 10 8 .
4

salt.
17. (b) NaOH is a base, so that its pH  7 37. (c) Human body contain buffer solution. Its pH= 6.8
38. (a) It is a neutral solution and its pH = 7
18. (c) It is a strong base.
39. (a) pH  5, means [H  ]  10 5 M .
1 M NaOH has maximum [OH  ] and minimum [H  ] and
maximum pH. After dilution [H  ]  10 5 / 100  10 7 M
19. (c) When pH = 7 means neutral, pH < 7 means acidic, pH > 7
means basic. [H  ] from H 2 O cannot be neglected.
20. (d) As the solution is acidic, pH  7 . This is because [H  ] from Total [H  ]  10 7  10 7  2  10 7
H 2 O [10 7 M ] cannot be neglected in comparison to 10 10 pH  7  0.3010  6.6990  7 (neutral).
M 2
22. (c) It is a strong acid and they lose proton in a solution. 40. (d) [H  ]   .C   .02 ; [H  ]  4  104 M
100
23. (a) [OH  ]  10 2 M ; pOH  2
pH   log [H  ]  4  log 4 ; pH  3.3979
pH  pOH  14 ; pH  14  pOH
 salt 
pH  14  2  12 41. (a) pH = p K a + log  
 acid 
24. (d) Order of acidic strength is H 2 Te  H 2 Se  H 2 S  H 2 O
Na 2 O is a salt of NaOH  H 2 O and H 2 O is least acidic  0 .2 
= 9.30 + log   = 9.30 + 0.3010 = 9.6.
m  0 .1 
among given acids hence pH in this case will be max .
[Salt]
25. (b) pH of the solution A = 3 42. (a) pH  pK a  log
[H ] = 10 M.
+

A
–3 [Acid]
pH of the solution B = 2 [10]
[H ] =10 M
+ –2 pH   log (1 .8  10 5 )  log
B
[100]
[H ] = 10 + 10 = 10 + 10  10 = 11  10 .
+ –3 –2 –3 –3 –3

pH = – log(11  10 ) = 3 – log 11 –3   log 1.8  5  log 10 1

= 3 – 1.04 = 1.95   0.2553  5  1  3.7447 or  4
26. (a) CN   H 2 O  HCN  OH 
0 .1
43. (b) 20 ml. of 0.1 NHCl =  20 g eq. = 2  10 3 g eq.
Because OH  concentration is increased. 1000
27. (a) On dilution the pH of acid A increases while pH of base B
decreases. 0 .001
20ml. of 0.001 KOH =  20 gm eq.
28. (d) CH 3 COONa is a salt of weak acid, ( CH 3 COOH ) and 1000
strong base (NaOH ) . = 2 × 10 5 g eq.
29. (b) The equilibrium will shift in the backward direction.
 HCl left unneutralised = 2(10 3  10 5 )
30. (b) K a  10 5 ; pH  6
 2  10 3 (1  0.01) = 2  0.99  10 3  1.98  10 3 g eq .
[Salt] 5 [Salt]
pH  logK a  log ; 6  log10  log
[Acid] [Acid] Volume of solution = 40 ml.
[Salt] [Salt] 1 .98  10 3
6  5 log10  log ; 6  5  log  [HCl] =  1000 M = 4.95  10 2
[Acid] [Acid] 40
[Salt] [Salt] 10  pH = 2  log 4.95 = 2 – 0.7 = 1.3.
log  6  5 1; 
[Acid] [Acid] 1 45. (b) 10 7 M NaOH means [OH  ]  10 7 ; pOH  7
31. (d) All are true – (a) is true for acid buffer, (b) for basic buffer,
(c) is called buffer solution. pH  14  7  7
 Ionic Equilibrium 389

30 35  0 .1
46. (a) [H  ]  c    0 . 1   0.03 M   0 .35  10  2
100 1000
48. (a) The pH of buffer solution never changed. Total = 20 + 35 = 55 ml.
10 14  (1.0–0.35)10 =0.65  10 mole HCl
[H  ]   10 13 mol / litre pH  13.
–2 –2

49. (c)
10 1 HCl = H +Cl+ –

50. (a) 
pH   log[H ] ; 7.4   log[H ] ; [H ]  4  10 M   8  [HCl] = [H ]+[Cl ] + –

51. (a) The pH of 0.1M HCl  1 Ionization of H 2 SO 4 takes place in 55 ml contains 0.65  10 mole of H ions
–2 +

two steps. 0 .65  10 2  10 3 6 .5

1000 ml  
H 2 SO 4 ⇌ H  
HSO 4 ; HSO 4 ⇌ H   SO4  55 55
52. (c) 1N NaOH solution have highest pH pH   log[H  ]   log(6.5 / 55)
[OH  ]  1; pOH  0 ; pH  pOH  14  log 55  log 6.5  0.92
pH  14  0  14 Due to acidic nature of solutions the colour of phenolphthalein
  becomes pink.
53. (c) H 2 O ⇌ [H ] [OH ]
61. (b) [H  ]  2  10 2 M
HCl ⇌ [H  ] [Cl  ]
 pH  log [2  10 2 ] ;
Total [H  ]  [H  ]H 2 O  [H  ]HCl  10 7  10 8
pH  1.7 i.e. in between 1 and 2.
 10 7 [1  10 1 ]
63. (b) pH  4, (H  )  10  pH  10 4 M
 7 11
[H ]  10 
10 65. (c) NaOH ⇌ Na   OH 
 11 
pH   log[H  ]   log10 7   ; pH  6.958 [OH  ]  10 5 M ; [H  ] [OH  ]  10 14
 10 
54. (c) pK = – log K , pK = – log K 10 14
a u b b
[H  ]  ; [H  ]  10 9 M ; pH  9 .
1 10  5
pH =  [log Ka  log Kw  log Kb ]
2 [Salt] 0.1
67. (b) pH  pK a  log ; pH  4 .75  log
1 [Acid] 0.1
  [5  log(1  10 14 )  (5)]
2 pH  4.75  log 1 ; pH  4.75
1 1
  [5  14  5]   (14 )  7 68. (d) A weak acid and its salt with a strong base maintain pH 4 – 5
2 2
55. (d) BaO, CaO and Na 2 O are shows more than 7 pH because of 69. (a) NaOH ⇌ Na   OH   [OH  ]  10 8 MMM.
their basic nature. 70. (c) [OH  ]  0.0001 N , pOH  4 , pH  pOH  14
56. (a) MgCl2  2 H 2O ⇌ Mg(OH )2  2 HCl
pH  14  pOH  14  4  10
57. (c) H 2 SO 4 ionized in two step.
71. (d) 0.001 M KOH solution
[Salt]
58. (b) pH  pKa  log [OH  ]  0.001 M  1  10 3 M
[Acid]
[Salt] [Salt] [H  ]  [OH  ]  1  10 14
5 .8  4 .8  log or log  1 .0
[Acid] [Acid]
1  10 14
[H  ] 
[Salt]
 antilog 1 .0  10 [OH  ]
[Acid]
1  10 14
[Acid] 1 [H  ]   1  10 14  10 3
   0.1 1  10  3
[Salt] 10
59. (b) It contains replacable H atom. [H  ]  10 11 M
60. (c) (i) 20 ml of 0.5 N HCl pH  11
0.5 N  1000 ml 0.5 mole HCl is present in 20 ml 72. (a) An acid buffer solution consists of solution of weak acid with
20  0.5 strong base of its salt.
  1 .0  10  2 73. (b) An acid buffer solution consists of a weak acid and its salt with
1000
strong base. i.e. CH 3 COOH  CH 3 COONa
(ii) 35 ml of 0.1 N NaOH
0.1 N  1000ml of 0.1 mole NaOH is 35 ml [salt]
74. (a) pOH  pK b  log
[base]
 390 Ionic Equilibrium

 5  log
0.02
 5  log
1
 5  (1)  4 10 2
Thus increase in [H  ]   1000 times
0.2 10 10  5
pH  14  pOH  14  4  10 87. (a) The HCl is a strong acid and they lose easily H  in solution.
75. (b) [Salt]= 0.1 M, [Acid]= 0.1 M
88. (a) X   H 2 O ⇌ OH   HX
[Salt]
K a  1.8  10 5 ; pH  logK a  log
[Acid] [OH  ] [HX ]
Kb 
0.1 [X  ]
 log1 .8  10  5  log  log 1.8  10 5
0.1 HX ⇌ H   X 
pH  4.7 .
[H  ] [ X  ]
76. (a) NH 4 Cl and NH 4 OH is a buffer solution (weak base and Ka 
[HX ]
salt of strong acid).
77. (a) pH  pOH  14 ; pH  14  pOH K a  K b  [H  ] [OH  ]  K w  10 14

Hence K a  10 4

Now as [ X  ]  [HX ], pH  pK a  4 .
90. (d) Buffer solution is formed. So the pH will not change.
91. (b) Na 2 CO 3 when react with water form strong base and weak
acid. So its aqueous solution is basic.
92. (c) Kw  [H 3 O  ] [OH  ]

Concentration of H 3 O  in distilled water  1  10 6 mol/l.

Now [H 3 O  ]  [OH  ]

Kw  [1  10 6 ]  [1  10 6 ]  1  10 12 .

93. (a) [OH  ]  10 1 M ; pOH  1

pH  pOH  14 ; pH  14  1  13 .
94. (a) Maximum pH HClO is a weak acid all of these. So that the salt
of weak acid is also weak.
[OH  ]  10 7 95. (c) As the solution is acidic pH  7 . This is because [H  ] from
pOH  7 H 2 O [10 7 ] cannot be neglected in comparison to 10 12 M.
pH  14  7  7 . 96. (b) [Normal salt + acidic salt] is a buffer solution.
78. (c) 0.01 M Ba(OH )2  0.02 N Ba(OH )2 M M
97. (b) 100 ml of NaOH = 50ml of NaOH. They exactly
N1 V1  N 2 V2 10 5
[0.02 N ]  [50 ml]  N 2  100 ml N
neutralise 50 ml HCl. Hence pH of resulting solution = 7.
5
0 .02  50
N2   10 2 N ; [OH  ]  10 2 N 98. (b) M1  6.0 M of HCl ; V1  ?
100
pOH  2 or pH  12 M 2 =0.30 M is H  concentration in solution.

79. (b) pH   log [H ] .
V2  150 ml of solution.
80. (a) Na 2 CO 3 is a mixture of weak acid and strong base, so it is a
base. M1 V1  M 2 V2 ; 6.0  V1  .30  150

81. (b) 10 7 N HCl means (H  )  10 7 M .30  150

V1   7 .5 ml.
6
pH   log(H  ), pH  7
82. (c) pH  2 ; pH   log [H  ] ; 2   log [H  ] 99. (b) pH  3 , [H  ]  10 3 M

[H  ]  10 2  0.01 N  [H  ]  K  c
83. (b) pH does not change on addition of some concentration of HCl. [10 6 ]
[10 3 ]2  K  c ;  K  10  5
84. (b) Solution of CH 3 COONa on addition to acid shows a 0.1
decrease in dissociation of acid due to common ion effect. To 100. (b)When ratio of concentration of acid to salt is increased pH decrease.
decrease in [H  ] or increase pH. 101. (c) For NH 4 OH .
85. (c) pH  pOH  14 ; pH  14  pOH ; pH  14  6  8 .
1
86. (b) [H  ]I  10 5 [H  ]II  10 2 [OH  ]  C . ; C  M ,   0.2
10
 Ionic Equilibrium 391

[OH  ] 
1
 0.2  2  10  2 M pOH   log[OH  ]   log(1  10 4 )  4
10
pH  pOH  14 ; pH  14  4  10 .
pOH   log [OH  ]  log [2  10 2 ] ; pOH  1.7
0.10
114. (a) M.eq. of 0.10 M HCl   40  0.004 M
pH  14  pOH  14  1.7  12.30 . 1000
[Salt] 0.45  10
102. (c) pH  pK a  log . For small concentration of buffering M.eq. of 0.45 M NaOH   0.0045 M
[Acid] 1000
[Salt]
agent and for maximum buffer capacity 1. Now left [OH  ]  0.0045  0.004  5  10 4 M
[Acid]
Total volume = 50 ml.
103. (a) [H  ] = increased ten fold means pH of solution decreased by
one. 5  10 4
[OH  ]   1000 ; [OH  ]  1  10 2
1 50
pH  log 
[H ] pOH = 2 ; pH = 14 – pOH = 12.
104. (a) Because the pH of buffer are not changed. 115. (c) 0.001 M HCl  10 3 M [H  ], pH  3 .
[Salt] [Salt]
105. (c) pH  pK a  log ; 5 .5  4 .5  log 0 .4
[Acid] [0.1] 116. (d) [ NaOH ]   0.01M ; [OH  ]  10  2 M
[Salt] 40
log  5 .5  4 .5  1
0 .1 [H  ]  10 12 , pH   log[H  ]  12
[Salt]
 antilog 1 = 10 ; [Salt]  1 117. (b) Those substance which give a proton is called Bronsted acid
0 .1
while CH 3 COO  doesn’t have proton so it is not a Bronsted
0.49
106. (a) Moles of H 2 SO 4   5  10  3 moles of H 2 SO 4 acid.
98
.005 120. (c) pH   log [H  ]
present per litre of solution (molarity)   .005 M.
1 121. (d) pH  pOH  14 , pH  4 .0
H 2 SO 4  2 H 2 O ⇌ 2 H 3 O   SO 4 
pOH  14  pH ; pOH  14  4 .0  10.0
one mole of H 2 SO 4 give 2 moles of H 3 O  ions.
122. (b) pH  0 means [H  ]  10 o  1M . Hence solution is strongly
H 3 O   2  (H 2 SO 4 )  2  0.005  0.01 M acidic.

[H  ]  10 2 M ; pH  2 123. (c) As the solution is acidic, pH < 7. This is because [H  ] from

107. (c) CH 3 COONH 4 is a simple buffer and called salt of weak acid. H 2 O (10 7 M ) cannot be neglected in comparison to

0.4 10 10 M HCl.

108. (c) N.eq. for HCl   50  0.02
1000 124. (d) H 3 O  ⇌ OH   H 2
0.2
N.eq. for NaOH   50  0 .1 pOH  pH  14 ; 7  7  14 ; [H  ]  [OH  ]  10 14
1000
Now [OH  ] left  0.1  0.02 10 7  10 7  10 14 ; [OH  ]  10 7 gm ion/l.

[OH  ]  .08  8  10 2 M 126. (b) When pH  2 , [H  ]  10 2 M

pOH   log 8  10 2 M ; pOH  1.0 127. (a) [OH  ] ion conc.  0 .05
mol
 5  10  2
mol
l l
109. (d) Buffer is mixture of weak base and its acid salt.
110. (b) [ NaOH]  0 .4 40 mole l.  0.1 M pOH   log [OH  ]   log [5  10 2 ]

[OH  ]  10 1 M , [H  ]  10 13 M , pH  13 pOH  1.30 ; pH  pOH  14

pH  14  pOH  14  1.30  12.7
111. (d) pH  pOH  14, pH  4 , H   10 4 mole/litre.
112. (d) Buffer solution have constant pH. When we add the water into 128. (c) When pH  3 , then [H  ]  10 3 M
this buffer solution. So no effect on it.
after that we increased the pH from 3 to 6 then
113. (b) Ba(OH )2 ⇌ Ba 2   2OH  [H  ]  10 6 M means reduced 1000 times.
One molecule on dissociation furnishes 2OH  ions. 129. (b) CO 2 is acidic oxide which on dissolution in water develops
 4 acidic nature.
So, [OH ]  2  10 N
130. (d) If pH of any solution is 2.
N 2  10 4
N  M2 ; M    10  4 Then [H  ]  10 2 M
2 2
 392 Ionic Equilibrium
If pH of any solution is just double then pH  4 and N
150. (d) In NaOH have [OH  ]  10 1 M means pOH  1 and
[H  ] will be 10 4 . 10
then pH  pOH  14
131. (c) A strong acid is not used to make a buffer.
pH  14  pOH  13 .
132. (d) pH  1 means [H  ]  10 1 M
151. (b) Borate ions are hydrolyzed to develop alkaline nature in
solution.
10 1 1
Hence [H 2 SO 4 ]    0 .05 M 152. (d) Less the pH, more acidic is the solution.
2 20 154. (b) The equal conc. of salt and acid.
133. (c) The pH of blood is 7.4 due to presence of bicarbonates ions [KCN ]
155. (c) pH   log K a  log
 [HCN ]
134. (c) As the solution is acidic, pH < 7. This is because [H ] from
H 2 O [10 7 ] cannot be neglected in comparison to 10 8  0 .15 
pH   log[5  10 10 ]  log   8 .302
 1.5 
135. (a) pH will decrease because [OH  ] increased due to this
[Salt]
pOH is decreased. 157. (c) pH  pK a  log equimolar means
[Acid]
136. (c) [H  ]  6  10 4 M [Salt]
 1 ; pH  4.74  0  4.74
 4 [Acid]
pH   log [H ]   log [6  10 ]  3.22 .
158. (a) Because of NaCl is a salt of strong acid and strong base. So
137. (c) 0.01 M HCl  10 2 M [H  ], pH  2 . that it is neutral.
159. (c) When strong acid and strong base are react neutral salt are
138. (c) Because buffer solution have a constant pH. formed. So that NaCl is a neutral salt.
139. (c) 10 6 M HCl  10 8 M [H  ] . Also from H 2 O [Salt]
162. (d) pH  log K b  log
[Acid]
[H  ]  10 7 M
[Salt]
pH  log[1.8  10 5 ]  log
Total [H  ]  10 7  10 8  10 7 [1  0.1]  10 7 [1.1] 1.0

Hence pH  7  0.0414  6.96 . [Salt] [Salt]

9  4 .7  log ; log  4 .7  9  4 .3
1 .0 1 .0
140. (b) 10 10 M HCl  10 10 M [H  ] . But pH  10 because [Salt] 1
 Antilog ; [S alt]  1.8
solution is acidic. This is because H  from 1.0 4 .3
H 2 O(10 7 M ) cannot be neglected. [salt]
163. (b) pH   log K b  log
[acid]
Total [H  ]  10 7  10 10
[salt]
7 3 7 5   log10 4  log
 10  (1  10 )  10 (1.001) [acid]
That is why pH  7 (slightly less than 7) log
[salt]
1
[acid]
141. (b) [H  ]  1.00  10 6 mole/litre
[salt]
 antilog1  10 : 1
6
pH   log [1.00  10 ] ; pH = 6. [acid]
164. (a) 1 M KOH show highest pH value because it is a strong base.
142. (a) [H  ] is in moles per litre. 165. (d) NH 4 OH is a weak acid and NH 4 Cl is a strong base salt.
143. (d) As the solution is acidic, pH  7 . This is because [H  ] from 166. (a) pH  13.6
7 8
H 2 O (10 M ) cannot be neglected in comparison to 10 . pOH  14  13.6  0.4

145. (b) pH of 0.001 M HCl  10 3 M[H  ] , pH = 3. [OH  ]  Antilog(0.4 )  0.3979 . So the value of

[OH ] between 0.1 M and 1 M
146. (d) Because it can furnish H  ions in solutions.
167. (d) Aspirin is a weak acid. Due to common ion effect it is
147. (c) Because it is a strong acid. unionised in acid medium but completely ionised in alkaline
H   10 1 medium.
168. (b) [H  ] [OH  ]  10 14 ; (10 7 )(10 7 )  10 14
pH   log [H  ]   log [10 1 ] ; pH  1 .
148. (b) Buffer solution is a combination of weak acid and conjugate 169. (c) HCl  10 o M has pH  0 . The value of pH decreases as
base. NaCl is a salt and NaOH is the base. concentration further increases.
170. (a) Because pure water has a 7 pH.
149. (a) [H  ]  Kc  10 5  0.1  10 3 , pH  3 .
171. (c) When concentration of [H  ] increased then the value of pH is
decreases.
 Ionic Equilibrium 393

1 1 1
pH  log pOH  log  log  1
[H  ] [OH ] .1
172. (c) The concentration of [H  ]  10 2 mole/litre pH  pOH  14 ; pH  1  14 ; pH  14  1  13
195. (a) If concentration of acid is increases ten times in a buffer then
pH  log[H  ]  log[10 -2 ] ; pH  2 pH of the solution is increase by one.
173. (d) Due to common ion effect.
198. (b) pH  7  Basic
174. (b) In water solution.
It means contain more hydroxide ions than carbonate ions.
NH 3  H 2 O ⇌ NH 4  OH 
199. (a) At 7pH the concentration of OH  and H  are equal.

concentration of OH is increased so that solution become .01  100
more basic and the pH is increased. 200. (a,d) M.eq. of 0.01 M HCl   1  10 3
1000
175. (a) Na 2 CO 3 is basic in nature. So its pH is greater than 7. pH  3
176. (c) It is not a mixture of weak acid or base and their strong salt.
.04  50
M.eq. of .02 M H 2 SO 4   2  10 3
177. (a) [H  ]  Antilog(4.58) ; 1000
[H  ]  2.63  10 5 moles / litre 0.02  50
M.eq. of .02 M NaOH   1  10 3
1000
178. (c) 10 2 M NaOH will give [OH  ]  10 2
Left [H  ]  2  10 3  1  10 3  1  10 3 ; pH  3
pOH  2 , Also pH  pOH  14 202. (a,b,c) Because buffer solution are mixture of weak acid or weak
pH  12 . base and their salt.
203. (c) Because pH  8 is basic nature but HCl is a strong acid.
[Salt] 10  1
179. (a) pH  pK a  log   log 2  10 5  log 4. 204. (c) H 2 SO 4  0.05  2
[Acid] 50 2
180. (b) 0.001 M NaOH means [OH  ]  10 3 ; pOH  3 [H  ]  0.1 and pH  1

pH  pOH  14; pH  14  3 205. (b) Mg(OH ) 2 ⇌ Mg 2   2OH 

pH  11 ; [H  ]  10 11 mole-litre –1
K sp  [Mg 2  ][OH  ] 2
181. (c) [H  ]  C .  1  10 12  0.01 [OH  ] 2

[H  ]  0 . 1 
1
 10 3 [OH  ] 2  1  10 10  [OH  ]  10 5
100
[H  ]  10 14 / 10 5  10 9
pH   log [H  ]   log10 3  3
pH   log[H  ]   log[10 9 ]  9
182. (b) pH  4
206. (b) [OH  ]  1  10 5
pH  pOH  14 ; pOH  14  pH
pOH   log[OH  ]  5
pOH  14  4  10 ; [OH  ]  10 10 M
pH  pOH  14  pH  14  5  9 .
1 1
183. (b) pH  log  log  2 .523
[H  ] [3  10 3 ] Critical Thinking Questions
185. (c) It is a strong base.
1. (b) K sp of AgI  1.5  10 16
186. (b) [H  ] Concentration in 0.01M HCl is 10 2 M because 0.01 M
HCl have only H  10 8 M Ag  and 10 8 M I 

HCl ⇌ H   Cl  . Ionic product  10 16

187. (b) The value of H 3 O  ions will not changed. K sp  Ionic product

CH 3 COOH  H 2 O ⇌ CH 3 COO   H 3 O  . 2. (a) HClO is the weakest acid. Its conjugate base ClO  is the
strongest base.
188. (a) H 2 O 2 (Hydrogen peroxide) is a corrosive volatile liquid. It is
3. (b) B(OH )3 not have H 
slightly acidic in nature. Its pKa value is approximately
10 12 . kw 1  10 14
4. (a) h   2 .22  10 5
k a 4 .5  10 10
1 1
192. (b) pH  log ; pH  log 3 ; pH  3 .
H 10 5. (d) MX 4  M  4 X ; K sp  (4 s)4 s ; K sp  256s 5
s 4s
193. (b) NH 3 is Lewis base because of one lone pair of electron.
1/5
Ba(OH ) 2  Ba 2  2OH   K sp 
194. (b) s   
 .
.05 M 20.5 M
 256 
6. (a) Lewis acid are electrophiles because they accept election pairs.
 394 Ionic Equilibrium
2
7. (c) 2 HI ⇌ H 2  I2  10 2  V   10 3  V 
Initial 2 24. (b) [Ca 2  ] [F  ]2   
9
  1.25  10 .
0 0
 2 V   2 V 
   
At equilibrium 2    2     2 . 25. (a) The degree of hydrolysis of a salt of weak acid and weak base is
2 2 2 2 independent of concentration of salt.
8. (a) Because they have vacant d-orbital in central atom.
26. (c) C  0.1M ;   1%; (H  )  C  
9. (a) Energy has to be spent for the total dissociation of weak acid.
1
10. (a) pK a of acid A  4 ; pK a of acid B  5  0 .1   10 3 ; (H  )  10 3 ; pH = 3.
100
We know that pK a   log K a
27. (d) HClO4 is a strong acid, because its oxidation no is + 7.
 Acid A K a  10 4 28. (d) Acceptor of electron pair is known as lewis acid. S, :
5 CH 2 , (CH 3 )3 B all can accept an electron pair so answer is
Acid B K a  10
(d).
Hence A is ten times stronger than that of B.
29. (b) Mg(OH )2 ⇌ Mg 2   2OH 
4
1
2
K a1 3 .14  10 (s ) ( 2 s)
11. (b)    4 :1
2 K a2 1 .6  10 5 K sp 1 .2  10 11
K sp  4 S 3  S  3 3
12. (d) It is a salt of weak acid and weak base. 4 4
 
13. (c) HA ⇌ H   A  ; K a 
[H ] [ A ]
……(i) S  8.16  10 4
[HA]
[H  ] [CN  ]
neutralization of the weak acid with strong base is 30. (d) Ka 
[HCN  ]
HA  OH  ⇌ A   H 2 O
[H  ] [0 .02]
[A  ] 6 .2  10 10 
K ……(ii) [0 .01]
[HA] [OH  ]
6 .2  10 10  0 .01
K [H  ]   3 .1  10 10
dividing (i) by (ii) a  [H  ] [OH  ]  K w  10 14 0 .02
K

K 10 5 31. (b) N H 3 presence of lone pair of electrons.
K  a  14  10 9 .
K w 10
32. (a) CuBr ⇌ Cu   Br 
14. (d) NH 4 Cl undergoes cationic hydrolysis hence pH is  7 K sp (S ) (S )

because the solution due to cationic hydrolysis in acids. mol 2

NaCN undergoes anionic hydrolysis hence pH is >7. K sp  S 2  (2  10  4 )2  4  10 8
l2
HCl is strong acid and NaCl is neutral solution.
Hence the pH of given solutions will increases. 33. (c) Na 2 SO 4 ⇌ 2 Na   SO 42 
(0 .004  x ) 2x x
HCl  NaCl  NaCN  NH 4 Cl
Since both the solution are isotonic 0.004  2 x  0.01
15. (c) It is a HClO4
 x  3  10 3
16. (d) Smaller the p K a value, strong the acid.
3  10 3
17. (d) It involves gain and loss of electron pair (Lewis concept).  Percent dissociation   100  75% .
0 .004
18. (b) H  (aq.)  H 2 O(l)  OH   H 2 .
34. (a) Cr(OH )3  Cr 3  3 OH 
4 x 3x
Ka 10 1
19. (b) KH     10 10 .
K w 10 14 10 10 K sp  x .(3 x )3  27 x 4
20. (d) Acidity is directly propotional to oxidation number. As the
K sp 2 .7  10 31
O.No. of S, P and Cl in H 2 SO 3 , H 3 PO3 & HClO3 is +4, +3 x 4 ; x 4
& +5 respectively so decreasing order of acidity will be III > I > 27 27
II.
x  1  10 8 mole/litre.
21. (a) A substance which can donate a proton is known as acid so
NH 4 will be a acid. 35. (a) H   c .  Ka . c

22.
23.
(b) Acetic acid is a weak acid.
(a) Because it is a acidic oxide.

pH   log K a . c 
1/2

1
2
[ log K a  log c]
 Ionic Equilibrium 395

1 1 So that S of AgBr is less than that of AgCl.

 [4 .74  log10  2 ]  [4 .74  2]  3 .37 .
2 2 45. (a) K sp  4S 3
36. (b) Ag2 SO 4 ⇌ 2 Ag   SO 4 
4S 2 S
4 S 3  3.2  10 8 ; S  2  10 3 M .
2 .8  10 10
Ksp  4 S 3 ; Ksp  2  10 5 46. (c)  2 .8  10 9 ML1 .
0.1
2  10 5 47. (b) AB ⇌ A   B  ; K sp  S 2
S 3  0 .017 m /l  1.7  10 2
4
S  Ksp  4  10 10  2  10 5
Ag BrO3 ⇌ Ag   BrO3
S S
1 .435  10 3
48. (b) S  1.435  10 3 g / l ,   10 5 M
Ksp  S 2 ; Ksp  5.5  10 5 143.5
K sp  S  S  10 10
S  5.5  10 5  7.4  10 3 m / l.
37. (c) 49. (b) pKa  5 , so Ka  1  10 5
OH Phenol are more acidic than ethanol
Ka 1  10 5
because of stabilization of phenoxide    1  10  2
as compare to ethoxide ion. C 0.1
50. (c) Presence of common ion decreases the solubility of salt.
38. (b) 
X  H 2 O ⇌ HX  OH  51. (d) Ag2 S  CuS  HgS .

10 14 10 9 Solubility of CuS  10 31  3.16  10 16 mol / lit.

Kh  5
so h   10 4
10 10 1 Solubility of Ag2 S
4 2
100  10  10 K sp 10 42
So, 0.01%. 3 3  6 .3  10  5 mole / litre
4 4
39. (a) Ka  1.0  10 5
Solubility of HgS  K sp  10 54  10 27 mol / litre.
K h  hydrolysisconstant
52. (c) pH  3.82   log[H  ]
K 10 14
Kh  w   10  9
Ka 10  5 [H  ]  1.5  10 4 mole/litre.
[salt] 0.10
Kh 53. (b) pH  pKa  log  4.57  log  5 .09
degree of hydrolysis (h ) = acid 0 .03
C
54. (c) For a monobasic acid
10 9 [H  ]  C 
 = 10 6 = 10 3 ; h  10 3
0 .001
1
40. (b) Basic radicals of group II & IV are precipitated by H 2 S in the   0 .001  10 4  pH = 4
10
form of their sulphides. IInd group in acidic medium & IV
group in alkaline medium. They precipitate when ionic product K sp
increases than solubility product. 55. (a) K sp  [ As 3  ][S 2 ] , S  5
108
41. (a) After mixing [ Ag  ] [Cl  ]  K sp
2 .8  10 72
10 11 5  1.09  10 15
42. (a) K sp  ionic product 1  10  5  10 108
43. (a) 1 litre of water contains 1000/18 mole. 56. (d) Dissociation constant of HA  10 9
10 7  18 HA ⇌ H   A 
So degree of ionization   1 .8  10 7 %.
1000
Ka 10 9
44. (a) AgCl K sp  1.2  10 10 [H  ]   ; [H  ]  10 4
C 0 .1

S  1.2  10 10 ; S  1.09  10 5 pH  4

pH  pOH  14
AgBr K sp  3.5  10 13
pOH  14  pH  14  4 ; pOH  10
S  3.5  10 13  5.91  10 6
 396 Ionic Equilibrium
1000 [Salt]
57. (d)   1.9  10 9 ; C  14  9.35   log(1.78  10 5 )  log
18 100
[H  ] [OH  ] w
K  C 2 [Salt]  79.9   1000  79.9  w  10.56
(H 2 O ) 132
1000 66. (a) pH  6 means [H  ]  10 6 M
 1.9  10  9  1.9  10  9   2.0  10 16 .
18
pH  3 means [H  ]  10 3 M
3
58. (c) K  Ka1  Ka2  4.5  10  1.7  10 10
After mixing,

H   Kc  4.5  10 3  1.7  10 10  .01 (10 6  10 3 ) 1 .001  10 3

Total [H  ]  
2 2
 .87  10 7
pH   log 0.87  10 7  7  0.93  6.07 .  5.005  10 4
59. (a) Given that pH  4  log 5.005 ; pH  3.301 .
Concentration of solution =.1
67. (b) [H  ]  K  C
2
Degree of ionisation  2 %   .02
100 [H  ]  4  10 10  1 ; [H  ]  2  10 5 mole/litre
Ionic product of water  1  10 14 68. (b) Moles of [OH  ]  M  V

Concentration of [H ] = Concentration of solution X degree of Number of NaOH  0.3  0.005  2  0.0030
ionisation  .1  .02  2  10 3 M
69. (d) [H  ][OH  ]  10 13 .26
Ionic product of water

Concentration of [OH ] 
[H  ]  [H  ]  [OH  ],  [H  ]2  10 13 .26

1  10 14 13 .26

  0.5  10 11  5  10 12 M . [H  ]  10 2
2  10  3
pH = 6.63.
60. (a) HgSO 4  Hg    SO 4 
x x [Salt]
70. (b) pH  pKa  log
[ Acid]
K sp  x 2 ; x  K sp ; x  6.4  10 5
pH  pKa
x  8  10 3 mole/litre.
2
Ka  0.1  (10 3.5 )2  0.1  10 7  10 8  pH  8
 1 .34 
61. (a) K  c 2  0 .1     1 .8  10 5 . [Salt]
 100  71. (a) pH  logKa  log
[Acid]
62. (c) [H  ]  1  10 4 M  [H  ] [OH  ]  1  10 14
0 .2  50 0.5  40
14
[Salt]   0 .01 ; [Acid]  0.02
1  10 1000 1000
 [OH  ]   2  10 10 M
0 .5  10  4 0 .01
pH  log (1.8  10  4 )  log
63. (d) Because HClO4 is a strong acid. While buffer is a mixture of 0 .02
weak acid and their salt. pH  4  log (1.8)  log 0.5
5
64. (b) Initial concentration = 0.006 M  Ka  6  10 pH  4  log (1.8)  0.301
equilibrium reaction.
pH  3.4
C6 H 5 COOH ⇌ C6 H 5 COO   H 
C O O initial 72. (c) HCO 3  and H 2 O
C (1  a) Ca Ca

Ka  C 2 (1    1) for weak electrolyte

73. (a) [H  ]  C    0.1  0.1  10 2 M
5
Ka 6  10
 ;   ;   10 1 pH = 2; pOH = 12 ; [OH  ]  10 12 M .
C 0 .006
74. (c) Decreasing order of acidic character is
[H  ]  C  0.006  10 1  6  10 4 M. H 2 SO 4  CH 3 COOH  H 2 CO 3

[Salt] 75. (c) The acidic nature increases in the order.

65. (a) pOH  pKb  log
[Base] NaNO2  NaCl  H 2 S  H 2 SO 4

76. (a) [OH  ]  0.05  5  10 2 M

 Ionic Equilibrium 397

pOH  2  log 5  1.3

pH  pOH  14
pH  14  1.3  12.7
77. (b) Na 2 O form NaOH. So that it is basic oxide.

78. (a) CH 3 COO   H 2 O ⇌ CH 3 COOH  OH 

Kw 10 14
 [OH  ]  c  h; h  c  1
Ka 1 .8  10 5

 2.35  10 5
 pOH  4.62 ; pH  9.38  9.4

Assertion & Reason

1. (c) HCl is a strong electrolyte since it will produce more H  ,

comparison than that of CH 3 COOH . Hence assertion is true
but reason false.
2. (b) For sparingly soluble salts, reason is not a correct explanation.
Hence both assertion and reason are true but reason is not a
correct explanation of assertion.
3. (a) Aq. solution of FeCl3 on standing produce brown ppt. Due
to hydrolysis it produce ppt. of Fe(OH )3 which is of brown
colour. Hence both are correct and reason is a correct
explanation.
4. (a) Barium carbonate is more soluble in HNO 3 than in water
become carbonate is a weak base and reacts with the H  ion of
HNO 3 causing the barium salt to dissociate.
BaCO3  HNO 3  Ba(NO 3 )2  CO 2  H 2 O
5. (a) The conjugate base of CHCl 3 is more stable than conjugate
base of CHF3 (CF3 ) . CCl 3 stabilized by –I effect of chlorine
atoms as well as by the electrons. But conjugate base of
CH 3 (CH 3 ) is stabilized only by –I effect of flourine atoms.
Here both assertion and reason are true and reason is correct
explanation of assertion.
6. (c) Ionic product of AgBr is greater than that of AgCl in
comparison with there solubility product AgBr will
precipitate. First rather than that of AgCl .
9. (e) It is fact that ionic reactions are instantaneous due to the fact
that oppositely charged ions exert strong forces and combine
immediately.
 398 Ionic Equilibrium

1. The most important buffer in the blood consists of (a) 2.26 (b) 3.40
[BHU 1981] (c) 3.75 (d) 2.76
(a) HCl and Cl  (b) H 2 CO 3 and HCO 3 [salt]
9. Henderson’s equation is pH  pKa + log . If the acid gets
[acid ]
(c) H 2 CO 3 and Cl  (d) HCl and HCO 3
half neutralized the value of pH will be : [ pKa  4.30]
2. The solubility product of AgI at 25C is 1.0  10 16 mol 2 L2 . [RPMT 2000]
The solubility if AgI in 10 4 N solution of KI at 25C is (a) 4.3 (b) 2.15
approximately (in mol l 1 ) (c) 8.60 (d) 7
[CBSE PMT 2003] 10. The pH of a 0.01 M solution of acetic acid having degree of
dissociation 12.5% is [JIPMER 2000]
(a) 1.0  10 8 (b) 1.0  10 16
(a) 5.623 (b) 2.903
(c) 1.0  10 12 (d) 1.0  10 10 (c) 3.723 (d) 4.509
M 11. Which of the following solutions will have pH close to 1.0
3. The pH of the solution: 5 mL of , HCl  10 mL of
5 [IIT 1992; MP PET 1993; AMU 1999]
M
NaOH is [MH CET 2004] M M
10 (a) 100 ml of HCl  100 ml of NaOH
10 10
(a) 5 (b) 3
M M
(c) 7 (d) 8 (b) 55 ml of HCl  45 ml of NaOH
10 10
4. Given that the dissociation constant for H 2O is
M M
14 (c) 10 ml of HCl  90 ml of NaOH
Kw  1  10 2 2
mole / litre . What is the pH of a 0.001 molar 10 10
KOH solution [UPSEAT 2000; MP PET 2001] M M
(d) 75 ml of HCl  25 ml of NaOH
11 3 5 5
(a) 10 (b) 10
(c) 3 (d) 11 12. In which of the following solvents will AgBr have the highest
5. The pH of 0.1 M solution of the following salts increases in the order solubility [CBSE PMT 1992]
[Pb. CET 2004]
(a) 10 3 M NaBr (b) 10 3 M NH 4 OH
(a) NaCl  NH 4 Cl  NaCN  HCl
(c) Pure water (d) 10 3 M HBr
(b) HCl  NH 4 Cl  NaCl  NaCN
13. How many grams of CaC 2 O4 will dissolve in distilled water to
(c) NaCN  NH 4 Cl  NaCl  HCl make one litre of saturated solution ? (Solubility product of
(d) HCl  NaCl  NaCN  NH 4 Cl CaC 2 O4 is 2.5  10 9 mole 2 litre2 and its molecular weight is
6. The degree of hydrolysis in hydrolytic equilibrum 128) [MP PET 1993; MP PMT 2000]
(a) 0.0064 gm (b) 0.0128 gm
A   H 2 O ⇌ HA  OH  at salt concentration of 0.001 M is (c) 0.0032 gm (d) 0.0640 gm
K a  1  10 5  [UPSEAT 2004] 14. The solubility product of CuS , Ag2 S , HgS are
31 44 54
10 , 10 , 10 respectively. The solubilities of these
(a) 1  10 3 (b) 1  10 4
sulphides are in the order [CBSE PMT 1997]
(c) 5  10 4 (d) 1  10 6
(a) Ag2 S  CuS  HgS (b) Ag2 S  HgS  Cus
7. If pK b for fluoride ion at 25 o C is 10.83, the ionisation constant of
hydrofluoric acid in water at this temperature is (c) HgS  Ag2 S  Cus (d) CuS  Ag2 S  HgS
[IIT 1997] 15. The solubility product constant K sp of Mg(OH )2 is 9.0  10 12 .
(a) 1.74  10 3 (b) 3.52  10 3
If a solution is 0.010 M with respect to Mg 2  ion, what is the
4 2
(c) 6.75  10 (d) 5.38  10 maximum hydroxide ion concentration which could be present
8. If the hydrogen ion concentration of a given solution is without causing the precipitation of Mg (OH )2
5.5  10 3 mol litre1 , the pH of the solution will be (a) 1.5  10 7 M (b) 3.0  10 7 M
[AMU 1985]
 Ionic Equilibrium 399
[JIPMER 2000]
(c) 1.5  10 5 M (d) 3.0  10 5 M
(a) One mole of HC2 H 3 O2 and 0.5 mole of NaOH
16. If the Kb value in the hydrolysis reaction
(b) One mole of NH 4 Cl and one mole of HCl
B   H 2 O ⇄ BOH  H  is 1.0  10 6 , then the hydrolysis
constant of the salt would be [Roorkee Qualifying 1998] (c) One mole of NH 4 OH and one mole of NaOH
6 7
(a) 1.0  10 (b) 1.0  10 (d) One mole of HC2 H 3 O2 and one mole of HCl
8 9
(c) 1.0  10 (d) 1.0  10 24. Which of the following base is weakest [DCE 2003]
17. For a sparingly soluble salt A p Bq , the relationship of its solubility (a) NH 4 OH : K b  1.6  10 6
product (LS ) with its solubility (S ) is
(b) C 6 H 5 NH 2 : K b  3.8  10 10
[IIT Screening 2001]
(c) C 2 H 5 NH 2 : K b  5.6  10 4
(a) Ls  S p  q . p p .q q (b) Ls  S p  q . p q .q p

(c) Ls  S pq . p p .q q (d) Ls  S pq .( p.q)p  q (d) C 6 H 7 N : K b  6.3  10 10

18. Arrange NH 4 , H 2 O, H 3 O  , HF and OH  in increasing order 25. HClO is a weak acid. The concentration of H  ions in 0 .1 M
of acidic nature [BVP 2003] solution of HClO (Ka  5  10 8 ) will be equal to
(a) H 3 O   NH 4  HF  OH   H 2 O [CPMT 1993]
5 9
(b) NH 4  HF  H 3 O   H 2 O  OH  (a) 7.07  10 m (b) 5  10 m

(c) OH   H 2 O  NH 4  HF  H 3 O  (c) 5  10 7 m (d) 7  10 4 m

26. Upto what pH must a solution containing a precipitate of
(d) H 3 O   HF  H 2 O  NH 4  OH 
Cr(OH )3 be adjusted so that all of precipitate dissolves
19. How many grams of CaC2 O4 (molecular weight = 128) on
(When Cr 3   0.1 mol/ l, K sp  6  10 31 ) [MP PET 2003]
dissolving in distilled water will give a saturated solution
[K sp (CaC2 O4 )  2.5  10 9 mol 2l 2 ] [KCET 2003] (a) Upto 4.4 (b) Upto 4.1
(c) Upto 4.2 (d) Upto 4.0
(a) 0.0064 g (b) 0.1280 g
(c) 0.0128 g (d) 1.2800 g 27. NH 4 Cl is acidic, because [JEE Orissa 2004]

20. If the concentration of CrO4 ions in a saturated solution of silver (a) On hydrolysis NH 4 Cl gives weak base NH 4 OH and strong
4 acid HCl
chromate is 2  10 . Solubility product of silver chromate will be [MP PET 1992; CPMT 1993]
(b) Nitrogen donates a pair of electron
(a) 4  10 8 (b) 8  10 12
(c) It is a salt of weak acid and strong base
(c) 12  10 12 (d) 32  10 12 (d) On hydrolysis NH 4 Cl gives strong base and weak acid
21. According to Bronsted-Lowry concept, the correct order of relative
strength of bases follows the order 28. A solution of weak acid HA containing 0.01 moles of acid per litre of
solutions has pH  4 . The percentage degree of ionisation of the
[Pb. PMT 2001]
acid and the ionisation constant of acid are respectively [UPSEAT 2001]
(a) CH 3 COO   Cl   OH 
(a) 1%, 10 6 (b) 0.01%, 10 4
  
(b) CH 3 COO  OH  Cl
(c) 1%, 10 4 (d) 0.01%, 10 6
  
(c) OH  CH 3 COO  Cl 29. The pH of a buffer solution containg 0.2 mole per litre
(d) OH   Cl   CH 3 COO  CH 3 COONa and 1.5 mole per litre CH 3 COOH is (Ka for acetic
acid is 1.8  10 5 ) [CPMT 2001]
22. H 2 SO 4  OH   SO 42   H 2 O Which is correct about
(a) 4.87 (b) 5.8
conjugate acid base pair [JEE Orissa 2004]
(c) 2.4 (d) 9.2
(a) HSO 42  is conjugate acid of base SO 42  30. 100 mL of 0.04 N HCl aqueous solution is mixsed with 100 mL of
0.02 N NaOH solution. The pH of the resulting solution is [UPSEAT 2004]
(b) HSO 4 is conjugate base of acid SO 42 
(a) 1.0 (b) 1.7
(c) SO 4 is conjugate acid of base HSO 4 (c) 2.0 (d) 2.3
(d) None of these 31. An alcoholic drink substance pH  4.7 then OH ion
14
23. Which may be added to one litre of water to act as a buffer concentration of this solution is (Kw  10 2
mol / l ) 2
 400 Ionic Equilibrium
[RPMT 2002] 36. A monoprotic acid in a 0.1 M solution ionizes to 0.001%. Its
10 10
(a) 3  10 (b) 5  10 ionisation constant is
10 8
(c) 1  10 (d) 5  10 [MP PET 1985,88,99; MP PMT1988; CPMT 2003]
32. In its 0.2 M solution, an acid ionises to an extent of 60%. Its 3
(a) 1.0  10 (b) 1.0  10 6
hydrogen ion concentration is
(a) 0.6 M (b) 0.2 M (c) 1.0  10 8 (d) 1.0  10 11
(c) 0.12 M (d) None of these
37. Select the pK a value of the strongest acid from the following
33. pH of 0.1 M NH 3 aqueous solution is
[KCET 2004]
(Kb  1.8  10 5 ) [UPSEAT 2004]
(a) 1.0 (b) 3.0
(a) 11.13 (b) 12.5
(c) 2.0 (d) 4.5
(c) 13.42 (d) 11.55
34. 40 mg of pure sodium hydroxide is dissolved in 10 litres of distilled 38. At 90°C, pure water has H3O ion concentration of
water. The pH of the solution is 6 1
[Kerala PMT 2004] 10 mol / L . The K w at 90°C is [DCE 2004]
(a) 9.0 (b) 10
(a) 10 6 (b) 10 14
(c) 11 (d) 12
(e) 8 (c) 10 12 (d) 10 8
35. Solubility of PbI2 is 0.005 M. Then, the solubility product of 39. By adding 20 ml 0.1 N HCl to 20 ml 0.1 N KOH , the pH
PbI2 is [BVP 2004] of the obtained solution will be [CPMT 1975, 86, 93]
(a) 0 (b) 7
(a) 6.8  10 6
(c) 2 (d) 9
(b) 6.8  10 6

(c) 2.2  10 9
(d) None of these

(SET -9)

1. (b) Blood consists of H 2 CO 3  HCO 3 buffer solution. 1 .0  10 16 mol 2

S 4
 1  10 12 2
10 l
2. (c) AgI ⇌ Ag   I  ; K sp  S 2  10 4  S
(s)
(s ) 1
3. (c) Milliequivalents of HCl  5  1
5
 Ionic Equilibrium 401

1 14. (a)
Milliequivalents of NaOH  10  1
10 15. (d) Mg(OH ) 2 ⇌ Mg    2OH 
K sp  S ( 2 S )2
M M
 5 ml HCl  10 ml HCl
5 5 K sp  S  4S 2
Hence the solution will be neutral i.e., pH  7 .
K sp 9  10 12
4. (d) pH  14  pOH  14  3  11 S2   2 .25  10 10
S 4 .010  4

5. (b) HCl is strong acid. In its .1M solution, [H ]  0.1M and
S  2.25  10 10  1.5  10 5 m/l
hence, pH  1
Kw 10 14
NH 4 Cl(aq ) hydrolyses in solution and give acidic solution 16. (c) For hydrolysis of B  ; K H    10 8 .
Kb 10 6
which is less acidic than .1M HCl . NaCl is not hydrolysed in
aqueous solutions. Its pH  7 NaCN undergoes hydrolysis in 17. (a) A p Bq ⇌ pA1  qB p 
solution to give alkaline solution. So that pH increases in the
order, HCl  NH 4 Cl  NaCl  NaCN Ls  [ Aq  ]p [B p  ]q  (p  S )p (q  S )q  S p q . p p .q q .

K 10 14 18. (c) H 3 O   HF  NH 4  H 2O  OH  .

6. (a) Kh  w   10 9
Ka 1  10 5 Acidic nature is decreasing order.

Kh 1  10 9 19. (a) Solubility of CaC2O4  Ksp  2.5  10 9

Kh   2C ;     1  10  3
C .001
 5  10 5 molL1
7. (c) Ka  Kb  Kw
 5  10 5  128  640  10 5  0.0064 g
14
Kw 10
K a    6.75  10 4 20. (d) K sp of Ag 2 CrO4  [ Ag  ] 2 [Cro 4  ]
Kb 1 .48  10 11
CrO4   2  10 4 then Ag   2  2  10 4
8. (a) [H  ]  5.5  10 3 mole/litre
K sp  (4  10 4 )2 (2  10 4 )  32  10 12
pH   log [H  ] ; pH   log [5.5  10 3 ] ; pH  2.26
21. (c) Relative strength of bases can be shown by their conjugated
[Salt] acids.
9. (a) pH  pKa  log
[Acid]
Conjugate acid of OH  is H 2 O which is a weak acid
1
conjugate acid of CH 3 COO  is CH 3 COOH which is
pH  4 .3  log 2  4 .3  log 1 ; pH  4.3  0  4.3
1 stronger than H 2 O . while conjugate acid of Cl  is HCl
2 which is strongest out of there. so the order of relative
1.25 strength of bases is OH   CH 3 COO   Cl  .
10. (b) [H  ]  C   0 .01 
100
22. (a) HSO 4  OH   SO 42   H 2 O
H   1.25  10 3 ; pH  between 2 or 3  2.90
Conjugate acid Conjugate base

23. (a) One mole oxalic acid & 0.5 mole of NaOH will make.
1
11. (d) M.eq. of HCl   75  15 24. (b) Smallest value of Kb indicates that aniline (C2 H 5 NH 2 ) is the
5
weakest base.
1
M.eq. of NaOH  25  5 25. (a) [H  ]2  C .   0.1  5  10 8
5
Total No. of eq.  15  5  10 H   5  10 9  7.07  10 5 M.
Total volume = 100
26. (d) K sp  [Cr 3  ][OH  ]3
10 1
Normality   , [H  ]  10 1 M
100 10 6  10 31
[OH ] 3  K sp / Cr 3    6  10  30
12. (b) AgBr are not dissolved in NaBr and HBr due to common ion 1  10 1
effect. And pure water is a neutral solvent. They do not have
ions. [OH ]  1.8  10 10
13. (a) CaC 2 O 4 is a binary electrolyte. Then solubility is pOH  (log1.8  log1010 )  10  0.25  1  11.25

S  K sp  2.5  10 9 pH  14  11.25  2.27

27. (a) NH 3 Cl  H 2 O ⇌ NH 4 OH  HCl
 5  10 5 mole/l.  0.0064 gm/l.
 402 Ionic Equilibrium
NH 4 Cl is a salt of weak base & strong acid so solution will HA ⇌ H   A 
be acidic.
Ionisation constant = ?
28. (a) H   C 0 .001
  0.001 %   10 5
H  10 4 100
   2  10  6
C 10 2 [10 5 ] 2
K   10 11 .
[Salt] V 10
29. (a) pH  log K a  log
[Acid] 37. (a) pKa  then strongest acid

  log [1.8  10 5 ]  log

0.2
 4.87 pKa  then weak acid
0.1
1
30. (c) N1V1  .04  100  4 pKa 
Acidicstrength
N 2 V2  .02  100  2
38. (c) H 3O   H 2O  H 
6
N 1 V1  N 2 V2  N 3 V3 10 6 10 6 10
K w  [H 2 O][H  ] = [10 6 ][10 6 ]  10 12
4  2  N 3  200 , N 3  10 2 M
39. (b) Neutralization reaction will takes place and form salt of strong
1 1 acid and strong base. Which does not hydrolysed and thus pH
pH  log10  log10  2.
H 10  2 7.
31. (b) pH  4.7
pH  pOH  14 ; pH  14  4.7 ; pOH  9.3

[OH  ]  Antilog [ pOH ]  Antilog [9.3]

[OH  ]  5  10 10

***
32. (c) [H  ]  C .  ,  0.2  0.60  0.12 M

33. (a) NH 4 OH ⇌ NH 4  OH 

1 .8  10 5
K b  C 2 ;   2 ;   1.34  10 3
.1
[OH  ]   . C  1.34  10 3  .1

1
pOH  log10 ; pOH  2.87
1 .34  10  4
pH  pOH  14 ; pH  2.87  14
pH  14  2.87 ; pH  11.13
Solute in 1 litresolution
34. (b) M 
Molecular weight of solute

40  10 3 1
   10  4 M
40 10
1 1
pOH  log10  log10 4
[OH  ] 10 4
pH  pOH  14 ; pH  4  14  pH  10 .
35. (d) PbI2  Pb I 2
x 2x
K sp  4 x 3  4(.005)3  4  .005  .005  .4  10 6 .

36. (d)  Monoprotic acid HA


`
Thermodynamics and Thermochemistry
Thermodynamics
Thermodynamics (Greek word thermo means heat and dynamics
means motion) is the branch of science which deals with the study of
different forms of energy and the quantitative relationships between them.
The complete study of thermodynamics is based upon three
generalizations called first, second and third law of thermodynamics. These
laws have been arrived purely on the basis of human experience and there is
no theoretical proof for any of these laws.
Basic concepts
(1) System, surroundings and Boundary : A specified part of the
universe which is under observation is called the system and the remaining
portion of the universe which is not a part of the system is called the
surroundings.
The system and the surroundings are separated by real or imaginary
boundaries. The boundary also defines the limits of the system. The system
and the surroundings can interact across the boundary.
(2) Types of systems
(i) Isolated system : This type of system has no interaction with its
surroundings. The boundary is sealed and insulated. Neither matter nor
energy can be exchanged with surrounding. A substance contained in an
ideal thermos flask is an example of an isolated system.
(ii) Closed system : This type of system can exchange energy in the
form of heat, work or radiations but not matter with its surroundings. The
boundary between system and surroundings is sealed but not insulated. For
example, liquid in contact with vapour in a sealed tube and pressure cooker.
(iii) Open system : This type of system can exchange matter as well as
energy with its surroundings. The boundary is neither sealed nor insulated.
Sodium reacting with water in an open beaker is an example of open system.
(iv) Homogeneous system : A system is said to be homogeneous
when it is completely uniform throughout. A homogeneous system is made
of one phase only. Examples: a pure single solid, liquid or gas, mixture of
gases and a true solution.
(v) Heterogeneous system : A system is said to be heterogeneous
when it is not uniform throughout, i.e., it consist of two or more phases.
Examples : ice in contact with water, two or more immiscible liquids,
insoluble solid in contact with a liquid, a liquid in contact with vapour, etc.
(vi) Macroscopic system : A macroscopic system is one in which
there are a large number of particles (may be molecules, atoms, ions etc. )
(3) Macroscopic properties of the system
Thermodynamics and Thermochemistry 403
Chapter
10
Thermodynamics deals with matter in terms of bulk (large number
of chemical species) behaviour. The properties of the system which arise
from the bulk behaviour of matter are called macroscopic properties. The
common examples of macroscopic properties are pressure, volume,
temperature, surface tension, viscosity, density, refractive index, etc.
The macroscopic properties can be subdivided into two types,
(i) Intensive properties : The properties which do not depend upon
the quantity of matter present in the system or size of the system are called
intensive properties. Its examples are pressure, temperature, density,
specific heat, surface tension, refractive index, viscosity, melting point,
boiling point, volume per mole, concentration etc.
(ii) Extensive properties : The properties whose magnitude depends
upon the quantity of matter present in the system are called extensive
properties. Its examples are total mass, volume, internal energy, enthalpy,
entropy etc. These properties are additive in nature.
Any extensive property if expressed as per mole or per gram
becomes an intensive property.
(4) State of a system and State Variables
Macroscopic properties which determine the state of a system are
referred to as state variables or state functions or thermodynamic
parameters. The change in the state properties depends only upon the initial
and final states of the system, but it is independent of the manner in which
the change has been brought about. In other words, the state properties do
not depend upon a path followed.
(5) Thermodynamic equilibrium : “A system is said to have attained
a state of thermodynamic equilibrium when it shows no further tendency to
change its property with time”.
The criterion for thermodynamic equilibrium requires that the
following three types of equilibrium exist simultaneously in a system,
(i) Chemical Equilibrium : A system in which the composition of the
system remains fixed and definite.
(ii) Mechanical Equilibrium : No chemical work is done between
different parts of the system or between the system and surrounding. It can
be achieved by keeping pressure constant.
(iii) Thermal Equilibrium : Temperature remains constant i.e. no
flow of heat between system and surrounding.
(6) Thermodynamic process : When the thermodynamic system
changes from one state to another, the operation is called a process. The
various types of the processes are
 404 Thermodynamics and Thermochemistry
(i) Isothermal process : In this process operation is done at constant Electrical work = potential difference  charge = V.q
temperature. dT = 0 thus E  0 . Gravitational work = mgh
(ii) Adiabatic process : In this a process there is no exchange of heat (i) Units of heat and work : The heat changes are measured in
takes place between the system and surroundings. The system is thermally calories (cal), Kilo calories (kcal), joules (J) or kilo joules (kJ). These are
isolated, i.e., dQ = 0 and its boundaries are insulated. related as, 1 cal = 4.184 J; 1kcal = 4.184kJ
(iii) Isobaric process : In this process the pressure remains constant
The S.I. unit of heat is joule (J) or kilojoule. The Joule (J) is equal to
throughout the change i.e., dP = 0.
Newton – metre (1 J= 1 Nm).
(iv) Isochoric process : In this process volume remains constant
throughout the change, i.e., dV = 0. Work is measured in terms of ergs or joules. The S.I. unit of work is
Joule.
(v) Cyclic process : When a system undergoes a number of different
processes and finally return to its initial state, it is termed cyclic process. 1 Joule = 10 7 ergs = 0.2390 cal.
For a cyclic process dE = 0 and dH = 0.
1 cal > 1 joule > 1 erg
(vi) Reversible process : A process which occurs infinitesimally
slowly, i.e. opposing force is infinitesimally smaller than driving force and (ii) Sign conventions for heat and work
when infinitesimal increase in the opposing force can reverse the process, it Heat absorbed by the system = q positive
is said to be reversible process.
Heat evolved by the system = q negative
(vii) Irreversible process : When the process occurs from initial to
final state in single step in finite time and cannot be reversed, it is termed Work done on the system = w positive
an irreversible process. Amount of entropy increases in irreversible process. Work done by the system = w negative.
Irreversible processes are spontaneous in nature. All natural processes
are irreversible in nature Zeroth law of thermodynamics
This law forms the basis of concept of temperature. This law can be
Internal energy, heat and Work stated as follows,
(1) Internal energy (E) : “Every system having some quantity of “If a system A is in thermal equilibrium with a system C and if B is
matter is associated with a definite amount of energy. This energy is known also in thermal equilibrium with system C, then A and B are in thermal
as internal energy.” equilibrium with each other whatever the composition of the system.”
E  Etranslational  Erotational  Evibrational  Ebonding  Eelectronic  ...... A ⇌ C B ⇌ C
(i) Characteristics of internal energy
(a) Internal energy of a system is an extensive property. A ⇌ B
(b) Internal energy is a state property.
First law of thermodynamics
(c) The change in the internal energy does not depend on the path
by which the final state is reached. Helmholtz and Robert Mayer proposed first law of thermodynamics.
This law is also known as law of conservation of energy. It states that,
(d) There is no change in internal energy in a cyclic process.
“Energy can neither be created nor destroyed although it can be
(e) The internal energy of an ideal gas is a function of temperature converted from one form into another.”
only.
E2  E1  E  q  w
(f) Internal energy of a system depends upon the quantity of
substance, its chemical nature, temperature, pressure and volume. i.e. (Change in internal energy) = (Heat added to the system) +(Work
(g) The unit of E is ergs in CGS or joules in SI done on the system)
If a system does work (w) on the surroundings, its internal energy
1 Joule = 10 7 ergs.
decreases. In this case, E  q  (w)  q  w
(ii) Change in internal energy ( E ) : It is neither possible nor
necessary to calculate the absolute value of internal energy of a system i.e.(Change in internal energy)=(Heat added to the system) – (work
done by the system)
then, E  E f  Ein ; E is positive if E f  Ein and negative if
The relationship between internal energy, work and heat is a
E f  Ein . mathematical statement of first law of thermodynamics.
(2) Heat (q) and work (w) : The energy of a system may increase or Enthalpy and Enthalpy change
decrease in several ways but two common ways are heat and work.
Heat content of a system at constant pressure is called enthalpy
Heat is a form of energy. It flows from one system to another denoted by ‘H’.
because of the difference in temperature between them. Heat flows from
higher temperature to lower temperature. Therefore, it is regarded as From first law of thermodynamics, q  E  PV ……….(i)
energy on the move.
Heat change at constant pressure can be given as
Work is said to be performed if the point of application of force is
displaced in the direction of the force. It is equal to the force multiplied by q  E  PV ……….(ii)
the displacement (distance through which the force acts). At constant pressure heat can be replaced at enthalpy.
There are three main types of work which we generally come across.
These are, Gravitational work, electrical work and mechanical work. H  E  PV ………(iii)

Mechanical work = Force  displacement = F.d

 Thermodynamics and Thermochemistry 405

H  Heat change or heat of reaction (in chemical process) at (1) Isothermal Expansion : For an isothermal expansion, T  0 ;
constant pressure E  0.
E  Heat change or heat of reaction at constant volume. According to first law of thermodynamics,
In case of solids and liquids participating in a reaction, E  q  w q  w

H  E (PV  0) This shows that in isothermal expansion, the work is done by the
system at the expense of heat absorbed.
Difference between H and E is significant when gases are Since for isothermal process, E and T are zero respectively,
involved in chemical reaction. hence, H  0
H  E  PV (i) Work done in reversible isothermal expansion : Consider an ideal
gas enclosed in a cylinder fitted with a weightless and frictionless piston.
H  E  nRT
The cylinder is not insulated. The external pressure, Pext is equal to
PV  nRT pressure of the gas, Pgas .
Here, n  n – n P R
Pext  Pgas  P
Specific and Molar heat capacity If the external pressure is decreased by an infinitesimal amount dP,
(1) Specific heat (or specific heat capacity) of a substance is the the gas will expand by an infinitesimal volume, dV. As a result of expansion,
quantity of heat (in calories, joules, kcal, or kilo joules) required to raise the the pressure of the gas within the cylinder falls to Pgas  dP , i.e., it
temperature of 1g of that substance through 1o C . It can be measured at becomes again equal to the external pressure and, thus, the piston comes to
constant pressure (c p ) and at constant volume (cv ) . rest. Such a process is repeated for a number of times, i.e., in each step the
gas expands by a volume dV.
(2) Molar heat capacity of a substance is the quantity of heat
required to raise the temperature of 1 mole of the substance by 1o C . Pext – dP
Pext
 Molar heat capacity = Specific heat capacity  Molecular weight,
i.e., Cv  cv  M and C p  c p  M .
(3) Since gases on heating show considerable tendency towards dV
expansion if heated under constant pressure conditions, an additional energy
has to be supplied for raising its temperature by 1o C relative to that Pgas
required under constant volume conditions, i.e., Since the systemPgas
is in thermal equilibrium with the surroundings,
C p  Cv or C p  Cv  Work done in expansion, PV( R) the infinitesimally small cooling produced due to expansion is balanced by
Fig. 10.1
the absorption of heat from the surroundings and the temperature remains
where, C p  molar heat capacity at constant pressure constant throughout the expansion.
The work done by the gas in each step of expansion can be given as,
Cv  molar heat capacity at constant volume.
dw  (Pext  dP)dV  Pext .dV  dP . dV
(4) Some useful relations of C and C
p v
dP.dV, the product of two infinitesimal quantities, is negligible.
(i) C p  Cv  R  2 calories 8.314 J The total amount of work done by the isothermal reversible
3 3 expansion of the ideal gas from volume V1 to volume V2 is, given as,
(ii) Cv  R (for monoatomic gas) and Cv   x (for di and
2 2 V2 V
w  nRT loge or w  2 .303nRT log10 2
polyatomic gas), where x varies from gas to gas. V1 V1
Cp At constant temperature, according to Boyle’s law,
(iii)   (Ratio of molar capacities) V P P
Cv P1 V1  P2 V2 or 2  1 So, w  2 .303nRT log10 1
V1 P2 P2
(iv) For monoatomic gas, Cv  3 calories whereas, Isothermal compression work of an ideal gas may be derived
C p  Cv  R  5 calories similarly and it has exactly the same value with positive sign.
V P
5 w compressio n  2 .303nRT log 1  2 .303nRT log 2
R
Cp V2 P1
(v) For monoatomic gas, ( )   2  1 .66 (ii) Work done in irreversible isothermal expansion : Two types of
Cv 3
R irreversible isothermal expansions are observed, i.e., (a) Free expansion and
2
(b) Intermediate expansion. In free expansion, the external pressure is zero,
7 i.e., work done is zero when gas expands in vacuum. In intermediate
Cp R
(vi) For diatomic gas ( )   2  1 .40 expansion, the external pressure is less than gas pressure. So, the work done
Cv 5 when volume changes from V1 to V2 is given by
R
2

V2
Cp 8R w   Pext  dV   Pext (V2  V1 )
(vii) For triatomic gas ( )    1 .33 V1
Cv 6R
Since Pext is less than the pressure of the gas, the work done
Expansion of an ideal gas during intermediate expansion is numerically less than the work done
 406 Thermodynamics and Thermochemistry
during reversible isothermal expansion in which Pext is almost equal to Examples of Spontaneous and Non-spontaneous processes
(1) The diffusion of the solute from a concentrated solution to a
Pgas .
dilute solution occurs when these are brought into contact is spontaneous
(2) Adiabatic Expansion : In adiabatic expansion, no heat is allowed process.
to enter or leave the system, hence, q  0 . (2) Mixing of different gases is spontaneous process.
According to first law of thermodynamics, (3) Heat flows from a hot reservoir to a cold reservoir is
spontaneous process.
E  q  w  E  w
(4) Electricity flows from high potential to low potential is
work is done by the gas during expansion at the expense of internal spontaneous process.
energy. In expansion, E decreases while in compression E increases. (5) Expansion of an ideal gas into vacuum through a pinhole is
The molar specific heat capacity at constant volume of an ideal gas spontaneous process.
is given by All the above spontaneous processes becomes non-spontaneous
when we reverse them by doing work.
 dE 
Cv    or dE  Cv .dT Spontaneous process and Enthalpy change : A spontaneous process
 dT v is accompanied by decrease in internal energy or enthalpy, i.e., work can be
and for finite change E  Cv T So, w  E  Cv T obtained by the spontaneous process. It indicates that only exothermic
reactions are spontaneous. But the melting of ice and evaporation of water
The value of T depends upon the process whether it is reversible are endothermic processes which also proceeds spontaneously. It means,
or irreversible. there is some other factor in addition to enthalpy change (H ) which
(i) Reversible adiabatic expansion : The following relationships are explains the spontaneous nature of the system. This factor is entropy.
followed by an ideal gas under reversible adiabatic expansion.
Second law of thermodynamics
PV  constant
where, P = External pressure, V = Volume All the limitations of the first law of thermodynamics can be remove
by the second law of thermodynamics. This law is generalisation of certain
Cp experiences about heat engines and refrigerators. It has been stated in a
 
Cv number of ways, but all the statements are logically equivalent to one
another.
where, C p  molar specific heat capacity at constant pressure, (1) Statements of the law
Cv  molar specific heat capacity at constant volume. (i) Kelvin statement : “It is impossible to derive a continuous supply
  1 1 
of work by cooling a body to a temperature lower than that of the coldest
 T1  P  P  of its surroundings.”
   1    2 
T  P   (ii) Clausius statement : “It is impossible for a self acting machine,
 2   2   P1 
unaided by any external agency, to transfer heat from one body to another
knowing  , P1 , P2 and initial temperature T1 , the final at a higher temperature or Heat cannot itself pass from a colder body to a
temperature T2 can be evaluated. hotter body, but tends invariably towards a lower thermal level.”
(iii) Ostwald statement : “It is impossible to construct a machine
(ii) Irreversible adiabatic expansion : In free expansion, the external
functioning in cycle which can convert heat completely into equivalent
pressure is zero, i.e, work done is zero. Accordingly, E which is equal to amount of work without producing changes elsewhere, i.e., perpetual
w is also zero. If E is zero, T should be zero. Thus, in free expansion motions are not allowed.”
(adiabatically), T  0 , E  0 , w  0 and H  0 . (iv) Carnot statement : “It is impossible to take heat from a hot
In intermediate expansion, the volume changes from V1 to V2 reservoir and convert it completely into work by a cyclic process without
transferring a part of it to a cold reservoir.”
against external pressure, Pext .
(2) Proof of the law : No rigorous proof is available for the second
 RT RT  law. The formulation of the second law is based upon the observations and
w  Pext (V2  V1 )   Pext  2  1 
 has yet to be disproved. No deviations of this law have so far been reported.
 P2 P1  However, the law is applicable to cyclic processes only.
 T P  T1 P2  The Carnot cycle
  Pext  2 1  R

 P1 P2  Carnot, a French engineer, in 1824 employed merely theoretical and
an imaginary reversible cycle known as carnot cycle to demonstrate the
 T P  T1 P2  maximum convertibility of heat into work.
or w  Cv (T2  T1 )   RPext  2 1 

 P1 P2  The system consists of one mole of an ideal gas enclosed in a
cylinder fitted with a piston, which is subjected to a series of four successive
Spontaneous and Non-spontaneous processes operations.
A process which can take place by itself under the given set of For cyclic process, the essential condition is that net work done is
conditions once it has been initiated if necessary, is said to be a equal to heat absorbed. This condition is satisfied in a carnot cycle.
spontaneous process. In other words, a spontaneous process is a process
w T  T1
that can occur without work being done on it. The spontaneous processes  2  Thermodynamic efficiency
are also called feasible or probable processes. q2 T2
On the other hand, the processes which are forbidden and are made Thus, the larger the temperature difference between high and low
to take place only by supplying energy continuously from outside the temperature reservoirs, the more the heat converted into work by the heat
system are called non-spontaneous processes. In other words, non engine.
spontaneous processes can be brought about by doing work.
 Thermodynamics and Thermochemistry 407

T2  T1 from the surroundings and therefore. The entropy of the surroundings

Since  1 , it follows that w  q 2 . This means that only a decreases.
T2
part of heat absorbed by the system at the higher temperature is In general, there will be an overall increase of the total entropy (or
transformed into work. The rest of the heat is given out to surroundings. disorder) whenever the disorder of the surroundings is greater than the
The efficiency of the heat engine is always less then 1. This has led to the decrease in disorder of the system. The process will be spontaneous only
following enunciation of the second law of thermodynamics. when the total entropy increases.
It is impossible to convert heat into work without compensation. (5) Entropy change during phase transition : The change of matter
from one state (solid, liquid or gas) to another is called phase transition.
Entropy and Entropy change Such changes occur at definite temperature such as melting point (solid to
(1) Definition : Entropy is a thermodynamic state quantity which is a liquid). boiling point (liquid to vapours) etc, and are accompanied by
measure of randomness or disorder of the molecules of the system. absorption or evolution of heat.
Entropy is represented by the symbol “S”. It is difficult to define the When a solid changes into a liquid at its fusion temperature, there is
actual entropy of a system. It is more convenient to define the change of absorption of heat (latent heat). Let H f be the molar heat of fusion. The
entropy during a change of state. entropy change will be
The entropy change of a system may be defined as the integral of all
the terms involving heat exchanged (q) divided by the absolute temperature H f
S f 
(T) during each infinitesimally small change of the process carried out Tf
reversibly at constant temperature.
Similarly, if the latent heat of vaporisation and sublimation are
q rev
S  S final  S initial  denoted by H vap and H sub , respectively, the entropy of vaporisation
T
and sublimation are given by
If heat is absorbed, then S  ve and if heat is evolved, then
H vap H sub
S  ve . S vap  and S sub 
(2) Units of entropy : Since entropy change is expressed by a heat Tb Ts
term divided by temperature, it is expressed in terms of calorie per degree,
Since H f , H vap and H Sub are all positive, these processes are
i.e.,cal deg . In SI units, the entropy is expressed in terms of joule per
-1

accompanied by increase of entropy and the reverse processes are

degree Kelvin, i.e., JK 1 .
accompanied by decrease in entropy.
(3) Characteristics of entropy : The important characteristics of
(6) Entropy change for an ideal gas : In going from initial to final
entropy are summed up below
state, the entropy change, S for an ideal gas is given by the following
(i) Entropy is an extensive property. Its value depends upon the
relations,
amount of the substance present in the system.
(i) When T and V are two variables,
(ii) Entropy of a system is a state function. It depends upon the
T2 V
state variables (T , p, V , n) . S  nCv ln  nR ln 2 . Assuming Cv is constant
(iii) The change in entropy in going from one state to another is T1 V1
independent of the path. (ii) When T and p are two variables,
(iv) The change in entropy for a cyclic process is always zero. T2 p
S  nC P ln  nR ln 2 . Assuming C p , is constant
(v) The total entropy change of an isolated system is equal to the T1 p1
entropy change of system and entropy change of the surroundings. The sum
is called entropy change of universe. (a) Thus, for an isothermal process (T constant),
V p
S universe  S sys  S Surr S  nR ln 2 or  nR ln 2
V1 p1
(a) In a reversible process, S universe  0 and, therefore T2
(b) For isobaric process (p constant), S  n C p ln
S sys  S Surr T1

(b) In an irreversible process, S universe  0 . This means that
there is increase in entropy of universe is spontaneous changes.
(vi) Entropy is a measure of unavailable energy for useful work.
Unavailable energy = Entropy × Temperature
(vii) Entropy, S is related to thermodynamic probability (W) by the
relation,
S  k loge W and S  2.303 k log10W
where, k is Boltzmann's constant
(4) Entropy changes in system & surroundings and total entropy
change for Exothermic and Endothermic reactions : Heat increases the
thermal motion of the atoms or molecules and increases their disorder and
hence their entropy. In case of an exothermic process, the heat escapes into
the surroundings and therefore, entropy of the surroundings increases on
the other hand in case of endothermic process, the heat enters the system
(c) For isochoric process (V constant), S  n Cv ln
T2
T1
(d) Entropy change during adiabatic expansion : In such process q=0
at all stages. Hence S  0 . Thus, reversible adiabatic processes are called
isoentropic process.
Free energy and Free energy change
Gibb's free energy (G) is a state function and is a measure of
maximum work done or useful work done from a reversible reaction at
constant temperature and pressure.
(1) Characteristics of free energy
(i) The free energy of a system is the enthalpy of the system minus
the product of absolute temperature and entropy i.e., G  H  TS
 408 Thermodynamics and Thermochemistry
(ii) Like other state functions E, H and S, it is also expressed as
G . Also G  H  TS system where S is entropy change for system
only. This is Gibb's Helmholtz equation.
(iii) At equilibrium G  0
(iv) For a spontaneous process decrease in free energy is noticed i.e.,
G  ve .
(v) At absolute zero, TS is zero. Therefore if G is – ve,
H should be – ve or only exothermic reactions proceed spontaneously at
absolute zero.
G o  2.303 RT log10 K, where K is equilibrium constant.
(a) Thus if K  1, then G o  ve thus reactions with
equilibrium constant K>1 are thermodynamically spontaneous.
(b) If K<1, then G o  ve and thus reactions with equilibrium
constant K<1 are thermodynamically spontaneous in reverse direction.
(2) Criteria for spontaneity of reaction : For a spontaneous change
G  ve and therefore use of G  H  TS , provides the following
conditions for a change to be spontaneous.

(vi) Gsystem  TS universe , where H  0

(vii) The standard free energy change,
Table :10.1 Criteria for spontaneity of reaction
ΔH ΔS ΔG Reaction characteristics Example
– + Always negative Reaction is spontaneous at all temperatures 2 O 3 ( g )  3 O 2( g )
+ – Always positive Reaction is non spontaneous at all temperatures 3O 2(g)  2O3(g)
– – Negative at low temperature but Reaction is spontaneous at low temperature but becomes CaO(s)  CO 2(g)  CaCO 3(s)
positive at high temperature non spontaneous at high temperature
+ + Positive at low temperature but Reaction is non spontaneous at low temperature but CaCO 3(s)  CaO(s)  CO 2(g)
negative at high temperature becomes spontaneous at high temperature

(at constant temperature and pressure)

Third law of thermodynamics
This law was first formulated by German chemist Walther Nernst in
1906. According to this law,
“The entropy of all perfectly crystalline solids is zero at the absolute
zero temperature. Since entropy is a measure of disorder, it can be
interpretated that at absolute zero, a perfectly crystalline solid has a perfect
order of its constituent particles.”
The most important application of the third law of thermodynamics
is that it helps in the calculation of absolute entropies of the substance at
any temperature T.
S  2.303C p logT
Where C is the heat capacity of the substance at constant pressure
P
or C(s)  O2 (g)  CO 2 (g); H  393.5kJ
1
(ii) H 2 (g)  O 2 (g)  H 2 O(l); H  285.8kJ
2
(iii) Fermentation is also an example of exothermic reaction.
(2) Endothermic reactions : The chemical reactions which proceed
with the absorption of heat energy are called endothermic reactions. Since the
heat is added to the reactants in these reactions, the heat absorbed is
indicated by either putting (–) or by writing the actual numerical value of
heat on the reactant side
A  B  C  D  q (heat energy)
The heat absorbed at constant temperature and constant pressure

and is supposed to remain constant in the range of 0 to T. measures enthalpy change. Because of the absorption of heat, the enthalpy
Limitations of the law of products will be more than the enthalpy of the reactants. Consequently,
(1) Glassy solids even at 0 K has entropy greater than zero.
o H will be positive (ve ) for the endothermic reactions.
(2) Solids having mixtures of isotopes do not have zero entropy at H  H p  H r ; H p  H r ; H  ve
0 K. For example, entropy of solid chlorine is not zero at 0 K.
o o

(3) Crystals of CO, N O, NO, H O, etc. do not have perfect order

2 2
Example : (i) N 2 (g)  O2 (g)  2 NO(g); H  180.5 kJ
even at 0 K thus their entropy is not equal to zero.
o

(ii) C(s)  2S (s)  CS 2 (l) H  92.0kJ

Thermochemistry
“Thermochemistry is a branch of physical chemistry which is
concerned with energy changes accompanying chemical transformation. It is
also termed as chemical energetics. It is based on the first law of
thermodynamics.”
Exothermic and Endothermic reactions
(1) Exothermic reactions : The chemical reactions which proceed
with the evolution of heat energy are called exothermic reactions. The heat
energy produced during the reactions is indicated by writing +q or more
precisely by giving the actual numerical value on the products side. In
general exothermic reactions may be represented as, A  B  C  D  q
(heat energy)
In the exothermic reactions the enthalpy of the products will be less
than the enthalpy of the reactants, so that the enthalpy change is negative
as shown below
H  H p  H r ; H p  H r ; H   ve
Examples : (i) C(s)  O2 (g)  CO 2 (g)  393.5kJ
(iii) Preparation of ozone by passing silent electric discharged
through oxygen is the example of endothermic reaction.
(iv) Evaporation of water is also the example of endothermic
reaction.
For exothermic reaction : H or E  ve
For endothermic reaction : H or E  ve
Heat of reaction or Enthalpy of reaction
Heat of reaction is defined as the amount of heat evolved or
absorbed when quantities of the substances indicated by the chemical
equation have completely reacted. The heat of reaction (or enthalpy of
reaction) is actually the difference between the enthalpies of the products
and the reactants when the quantities of the reactants indicated by the
chemical equation have completely reacted. Mathematically,
Enthalpy of reaction (heat of reaction)  H  H P  H R
(1) Factors which influence the heat of reaction : There are a
number of factors which affect the magnitude of heat of reaction.

(i) Physical state of reactants and products : Heat energy is involved
for changing the physical state of a chemical substance. For example in the
conversion of water into steam, heat is absorbed and heat is evolved when
steam is condensed. Considering the following two reactions
1 N 2 (g)  H 2 (g)  NH 3 (g); H (g)  11kcal
H 2 (g)  O 2 (g)  H 2 O(g); H   57.8 kcal
2
1 H 2 (g)  Cl 2 (g)  HCl ;
H 2 (g )  O 2 (g)  H 2 O(l); H   68.32 kcal
2
It is observed that there is difference in the value of H if water is
obtained in gaseous or liquid state. H value in second case is higher
because heat is evolved when steam condenses. Hence, physical sate always
affects the heat of reaction.
(ii) Allotropic forms of the element : Heat energy is also involved
when one allotropic form of an element is converted into another. Thus, the
value of H depends on the allotropic form used in the reaction. For
example, the value of H is different when carbon in the form of diamond
or in amorphous form is used.
C (diamond) O2 (g)  CO 2 (g); H   94.3 kcal
C (amorphous) O2 (g)  CO 2 (g); H   97.6 kcal
The difference between the two values is equal to the heat absorbed
when 12g of diamond is converted into 12g of amorphous carbon. This is
termed as heat of transition.
(iii) Temperature : Heat of reaction has been found to depend upon
the temperature at which reaction is occurring. The variation of the heat of
reaction with temperature can be ascertained by using Kirchhoff's equation.
H T2  H T1
 C P
T2  T1
Kirchhoff's equation at constant volume may be given as,
ET2  ET1
 C
T2  T1
(iv) Reaction carried out at constant pressure or constant volume :
When a chemical reaction occurs at constant volume, the heat change is
called the internal energy of reaction at constant volume. However, most of
the reactions are carried out at constant pressure; the enthalpy change is
then termed as the enthalpy of reaction at constant pressure. The difference
in the values is negligible when solids and liquids are involved in a chemical
change. But, in reactions which involve gases, the difference in two values is
considerable.
E  nRT  H or qv  nRT  q p
E = q v  heat change at constant volume;
E H = q p  heat change at constant pressure,
n  total number of moles of gaseous product
- total number of moles of gaseous reactants.
(2) Types of heat of reaction
(i) Heat of formation : It is the quantity of heat evolved or absorbed
(i.e. the change in enthalpy) when one mole of the substance is formed
from its constituent elements under given conditions of temperature and
pressure. It is represented by H f . When the temperature and pressure
are as 25°C and 1 atmospheric pressure. The heat of formation under these
conditions is called standard heat of formation. It is usually represented by
H 0f .
Thermodynamics and Thermochemistry 409
The standard heat of formation of 1 mole of NH 3 (g) and 1 mole
of HCl (g) .
1 3
2 2
1 1
H f  22 kcal
2 2
It may be calculated by
H 0  [H 0 (products) – H 0 (Reactants)]
(ii) Heat of combustion : It is the amount of heat evolved or
absorbed (i.e. change in enthalpy) when one mole of the substance is
completely burnt in air or oxygen. For example
CH 4 (g)  2O 2 (g)  CO 2 (g)  2 H 2 O(l); H   192 kcal
C2 H 6 (g)  3.5 O2 (g)  2CO 2 (g)  3 H 2 O(l); H   372.8 kcal
It may be calculated by
H 0  [H 0f (Products) - H 0f (Reactants)]
The enthalpy or heat of combustion have a number of applications.
Some of these are described below,
(a) Calorific value of foods and fuels : Energy is needed for the
working of all machines. Even human body is no exception. Coal, petroleum,
natural gas etc. serve as the principal sources of energy for man-made
machines, the food which we eat serves as a source of energy to our body.
The energy released by the combustion of foods or fuels is usually
compared in terms of their combustion energies per gram. It is known as
calorific value. The amount of heat produced in calories or Joules when one
gram of a substance (food or fuel) is completely burnt or oxidised.
When methane burns, 890.3 kJ mol of energy is released.
–1
CH 4 (g)  2O2 (g)  CO 2 (g)  2 H 2 O(l); H CH 4  890.3 kJ
1 mole (16g)
890.3
So, the calorific value of methane =   55.6 kJ / g
16
(b) Enthalpies of formation : Enthalpies of formation of various
compounds, which are not directly obtained, can be calculated from the
data of enthalpies of combustions easily by the application of Hess's law.
Heat of reaction   Heat of combustion of reactants
–  Heat of combustion of product s.
(iii) Heat of neutralisation : It is the amount of heat evolved (i.e.,
change in enthalpy) when one equivalent of an acid is neutralised by one
equivalent of a base in fairly dilute solution, e.g., Neutralisation reactions are
always exothermic reaction and the value of H is (ve ) .
HCl(aq.)  NaOH (aq.)  NaCl(aq.)  H 2 O
H   13.7 kcal
The heat of neutralisation of a strong acid against a strong base is
always constant (13.7 kcal or 57 kJ mole 1 ) . It is because in dilute
solutions all strong acids and bases ionise completely and thus the heat of
neutralisation in such cases is actually the heat of formation of water from
H  and OH  ions, i.e.,
H   OH   H 2 O; H   13.7 kcal
 410 Thermodynamics and Thermochemistry
In case of neutralisation of a weak acid or a weak base against a strong
base or acid respectively, since a part of the evolved heat is used up in ionising the
weak acid or base, it is always less than 13.7 kcal mole 1 (57 kJ mole 1 ) .
For example,
HCN (aq.)  NaOH (aq.)  NaCN(aq.)  H 2 O
H   2.9 kcal
HCN (aq.) ⇌ H + CN ; H = 10.8 Kcal
+ –
10.8 KCal of heat is absorbed for ionisation of HCN it is heat
of dissociation or ionisation
(iv) Heat of solution : It is the amount of heat evolved or absorbed
(i.e., change in enthalpy) when one mole of the solute is dissolved
completely in excess of the solvent (usually water). For example,
NH 4 Cl(s)  H 2 O(l)  NH 4 Cl(aq.); H   3.90 kcal
BaCl2 (s)  H 2 O(l)  BaCl2 (aq.); H   2.70 kcal
(v) Heat of hydration : It is the amount of heat evolved or absorbed
(i.e change in enthalpy) when 1 mole of an anhydrous or a partially
hydrated salt combines with the required number of moles of water to form
a specific hydrate. For example,
CuSO 4 (s)  5 H 2 O(l)  CuSO 4 . 5 H 2 O(s); H   18.69
(vi) Heat of vapourisation : When a liquid is allowed to evaporate, it
absorbs heat from the surroundings and evaporation is accompanied by
increase in enthalpy. For example: 10.5 k cals is the increase in enthalpy
when one mole of water is allowed to evaporate at 25 o C . When the
vapours are allowed to condense to liquid state, the heat is evolved and
condensation of vapour is accompanied by decrease in enthalpy.
The evaporation and condensation can be represented as,
H 2 O(l)  H 2 O(g); H   10.5 kcals (43.93 kJ )
H 2 O(g)  H 2 O(l); H   10.5 kcals (43.93 kJ )
Thus the change in enthalpy when a liquid changes into vapour state
or when vapour changes into liquid state is called heat of vapourisation.
(vii) Heat of fusion : When a solid is allowed to melt, it changes into
liquid state with the absorption of heat (increase in enthalpy) and when a
liquid is allowed to freeze, it changes into solid with the evolution of heat
(decrease in enthalpy). The change in enthalpy of such type of
transformations is called enthalpy of fusion. For example,
H 2 O(ice)  H 2 O(liquid); H   1.44 kcals ( 6.02 kJ )
H 2 O (liquid)  H 2 O (ice); H   1.44 kcals ( 6.02 kJ )
(viii) Heat of precipitation : It is defined as the amount of heat
liberated in the precipitation of one mole of a sparingly soluble substance
when solutions of suitable electrolytes are mixed, for example
Ba 2  SO 42 (aq)  BaSO 4 (s): H   4.66 kcal
(ix) Heat of sublimation : Sublimation is a process in which a solid
on heating changes directly into gaseous state below its melting point.
Heat of sublimation of a substance is the amount of heat absorbed
in the conversion of 1 mole of a solid directly into vapour phase at a given
temperature below its melting point.
I2 (s)  I2 (g) ; H   62.39 kJ
Most solids that sublime are molecular in nature e.g. iodine and
naphthalene etc.
H sub .  H fusion  H vaporisation
(3) Experimental determination of the heat of reaction : The heat
evolved or absorbed in a chemical reaction is measured by carrying out the
reaction in an apparatus called calorimeter. The principle of measurement is
that heat given out is equal to heat taken, i.e.,
Q  (W  m)  s  (T2  T1 ),
Where Q is the heat of the reaction (given out), W is the water
equivalent of the calorimeter and m is the mass of liquid in the calorimeter
and s its specific heat, T is the final temperature and T1 the initial
2
temperature of the system. Different types of calorimeters are used but two
of the common types are,
(i) Water calorimeter and (ii) Bomb calorimeter
Bomb calorimeter : This is commonly used to find the heat of
combustion of organic substances.
Since the reaction in a bomb calorimeter proceeds at constant volume,
the heat of combustion measured is E
(W  m )(t 2  t1 )  s
E   M kcal
w1
Where M is the molecular mass of the substance, w 1 is the weight
of substance taken, W is the water equivalent of calorimeter, m is the mass
of liquid in the calorimeter and s is the specific heat of liquid.
H can be calculated from the relation, H  E  nRT
Laws of thermochemistry
(1) Levoisier and Laplace law : According to this law enthalpy of
decomposition of a compound is numerically equal to the enthalpy of
formation of that compound with opposite sign, For example,
C(s)  O2  CO 2 (g); H  94.3 kcal
CO 2 (g)  C(s)  O2 (g); H  94.3kcal
(2) Hess's law (the law of constant heat summation) : This law was
presented by Hess in 1840. According to this law “If a chemical reaction can
be made to take place in a number of ways in one or in several steps, the
total enthalpy change (total heat change) is always the same, i.e. the total
enthalpy change is independent of intermediate steps involved in the
change.” The enthalpy change of a chemical reaction depends on the initial
and final stages only. Let a substance A be changed in three steps to D with
enthalpy change from A to B, H 1 calorie, from B to C, H 2 calorie and
from C to D, H 3 calorie. Total enthalpy change from A to D will be
equal to the sum of enthalpies involved in various steps, Total
enthalpy change H steps  H1  H 2  H 3
Now if D is directly converted into A, let the enthalpy change be
H direct. According to Hess's law H steps  H direct  0, i.e. H steps
must be equal to H direct numerically but with opposite sign. In case it is
not so, say H steps (which is negative) is more that H direct (which is
positive), then in one cycle, some energy will be created which is not
possible on the basis of first law of thermodynamics. Thus, H steps must
be equal to H direct numerically.
(i) Experimental verification of Hess's law
(a) Formation of carbon dioxide from carbon
 Thermodynamics and Thermochemistry 411
First method : carbon is directly converted into CO 2 (g). The bond dissociation energy of a diatomic molecule is also called
bond energy. However, the bond dissociation energy depends upon the
C(s)  O2 (g)  CO 2 (g); H  94.0 kcal nature of bond and also the molecule in which the bond is present. When a
molecule of a compound contains more than one bond of the same kind,
Second method : Carbon is first converted into CO (g) and then
the average value of the dissociation energies of a given bond is taken. This
CO (g) into CO 2 (g) , i.e. conversion has been carried in two steps, average bond dissociation energy required to break each bond in a
1
compound is called bond energy.
C(s)  O 2  CO (g) ; H  26.0 kcal
2 Bond energy is also called, the heat of formation of the bond from
gaseous atoms constituting the bond with reverse sign.
1
CO (g)  O 2  CO 2 (g); H   68.0 kcal
2 H (g)  Cl(g)  H  Cl (g); H   431 kJ mol 1
Total enthalpy change C(s) to CO 2 (g); H  94.0 kcal Bond energy of H  Cl   (enthalpy of formation)
(b) Formation of ammonium chloride from ammonia and 1
 (431)   431 kJ mol
hydrochloric acid:
Consider the dissociation of water molecule which consists of two
First method NH 3 (g)  HCl  NH 4 Cl(g); H   42.2 kcal
O  H bonds. The dissociation occurs in two stages.
NH Cl(g)+aq= NH Cl(aq); H = + 4.0 kcal
H 2 O(g)  H (g)  OH(g); H  497.89 kJ mol 1
4 4

NH 3 (g)  HCl(g)  aq  NH 4 Cl(aq); H  38.2 kcal

OH(g)  H(g)  O(g); H  428.5 kJ mol 1
Second method
The average of these two bond dissociation energies gives the value
NH 3 (g)  aq  NH 3 (aq); H  8.4 kcal
of bond energy of O  H .
HCl(g)  aq  HCl(aq); H  17.3 kcal
Bond energy of O  H bond
NH 3 (aq)  HCl(aq)  NH 4 Cl(aq); H  12.3 kcal
497.8  428.5
  463.15 kJ mol 1
NH 3 (g)  HCl(g)  aq  NH 4 Cl(aq); H  38.0 kcal 2

(ii) Applications of Hess's law
(a) For the determination of enthalpies of formation of those
compounds which cannot be prepared directly from the elements easily
using enthalpies of combustion of compounds.
(b) For the determination of enthalpies of extremely slow reactions.
(c) For the determination of enthalpies of transformation of one
allotropic form into another.
(d) For the determination of bond energies.
H reaction   Bond energies of reactants –  Bond energies of
products.
(e) For the determination of resonance energy.
(f) For the determination of lattice energy.
Bond energy or Bond enthalpies
When a bond is formed between atoms, energy is released.
Obviously same amount of energy will be required to break the bond. The
energy required to break the bond is termed bond dissociation energy. The
more precise definition is,
“The amount of energy required to break one mole of bond of a
particular type between the atoms in the gaseous state, i.e., to separate the
atoms in the gaseous state under 1 atmospheric pressure and the specified
temperature is called bond dissociation energy.”
Similarly, the bond energy of N  H bond in NH 3 is equal to
one – third of the energy of dissociation of NH 3 and those of C  H
bond in CH 4 is equal to one – fourth of the energy of dissociation of
CH 4 .
1664
Bond energy of C  H   416 kJ mol 1
4
[CH 4 (g)  C(g)  4 H (g); H  1664 kJ mol 1 ]
Applications of bond energy
(1) Heat of a reaction   Bond energy of reactants –  Bond
energy of products.
(2) Determination of resonance energy : When a compound shows
resonance, there is considerable difference between the heat of formation as
calculated from bond energies and that determined experimentally.
Resonance energy = Experimental or actual heat of formation –
Calculated heat of formation.

For example, H  H (g)  2 H (g); H   433 kJ mol 1

 T 
 Joule thomson coeffient    
Cl  Cl(g)  2Cl (g); H   242.5 kJ mol 1  p  H

H  Cl(g) H (g)  Cl(g); H   431 kJ mol 1 For cooling   ve

For Heating   ve
 412 Thermodynamics and Thermochemistry

Neither cooling nor heating   0 7. Which of the following units represents the largest amount of
energy [CPMT 1989; MP PET 2000]
 The temperature at which a real gas shows neither cooling nor heating (a) Electron volt (b) Erg
effect on adiabatic expansion (i.e.,   0 ) is called inversion
(c) Joule (d) Calorie
temperature.
8. Energy equivalent to one erg, one joule and one calorie is in the
 Hydrogen has highest calorific value. order [NCERT 1980; CPMT 1997]
 13.7 Kcal / mol  57 KJ / mol (be cause of 1 cal =4.2 Joule) (a) 1 erg 1 joule1 calorie (b) 1 erg 1 calorie1 joule
 Enthalpy of fusion of ice per mole is 6 KJ . (c) 1 calorie1 joule1 erg (d) 1 joule1 calorie1 erg
 Order of bond energy in halogen Cl 2  Br2  F2  I2 .
 Heat of vapourisation of water per mole is 10.5 KCal.
 The heat of reaction is independent of the time consumed in the
process.

Basic concepts
1. Internal energy of an ideal gas depends on
(a) Volume (b) Temperature
(c) Pressure (d) None of these
2. Any series of operations so carried out that at the end, the system is
back to its initial state is called
(a) Boyle's cycle (b) Reversible process
(c) Adiabatic process (d) Cyclic process
3. One calorie is equal to [CPMT 1988]
(a) 0.4184 Joule (b) 4.184 Joule
(c) 41.84 Joule (d) 418.4 Joule
4. The total internal energy change for a reversible isothermal cycles is
(a) Always 100 calories per degree
(b) Always negative
(c) 0
(d) Always positive
5. A well stoppered thermos flask contains some ice cubes. This is an
example of a [AIIMS 1992]
(a) Closed system
(b) Open system
(c) Isolated system
(d) Non-thermodynamic system
6. Identify the intensive quantity from the following
[IIT JEE 1993]
(a) Enthalpy and temperature
(b) Volume and temperature
(c) Enthalpy and volume
(d) Temperature and refractive index
 414 Thermodynamics and Thermochemistry
9. Heat produced in calories by the combustion of one gram of carbon 22. The intensive property among these quantities is
is called [KCET 2002]
(a) Heat of combustion of carbon (a) Enthalpy (b) Mass/volume
(c) Mass (d) Volume
(b) Heat of formation of carbon
23. In thermodynamics which one of the following is not an intensive
(c) Calorific value of carbon property [Kerala (Med.) 2002]
(d) Heat of production of carbon (a) Pressure (b) Density
10. Conditions of standard state used in thermochemistry is (c) Volume (d) Temperature
(a) 0 o C and 1 atm (b) 20 o C and 1 atm 24. If in a container neither mass and nor heat exchange occurs then it
constitutes a [MP PMT 1993; AFMC 2003]
(c) 25 o C and 1 atm (d) 0 K and 1 atm (a) Closed system (b) Open system
11. The temperature of the system decreases in an [KCET 2005] (c) Isolated system (d) Imaginary system
25. Which of the following is not a state function [DCE 2002]
(a) Adiabatic compression (b) Isothermal compression
(a) S (b) G
(c) Isothermal expansion (d) Adiabatic expansion
12. For the isothermal expansion of an ideal gas (c) H (d) Q
(a) E and H increases 26. Which of the following is true for an adiabatic process
[DCE 2002; MP PET 1995, 98, 2004;
(b) E increases but H decreases CPMT 1990; MP PMT 1998, 2002]
(c) H increases but E decreases (a) H  0 (b) W  0
(d) E and H are unaltered (c) Q  0 (d) V  0
13. If a refrigerator's door is opened, then we get 27. Which of the following is not a state function
[CPMT 1980] [MH CET 2004; AIIMS 2001]
(a) Room heated (a) Internal energy (b) Enthalpy
(b) Room cooled (c) Work (d) Entropy
(c) More amount of heat is passed out 28. Among them intensive property is [AFMC 2004]
(d) No effect on room (a) Mass (b) Volume
(c) Surface tension (d) Enthalpy
14. The cooling in refrigerator is due to [KCET 2005]
(a) Reaction of the refrigerator gas
First law of thermodynamics and Hess law
(b) Expansion of ice
(c) The expansion of the gas in the refrigerator 1. The first law of thermodynamics is only
(d) The work of the compressor (a) The law of conservation of energy
15. Point out the wrong statement in relation to enthalpy
(b) The law of conservation of mass
(a) It is a state function
(c) The law of conservation of momentum
(b) It is an intensive property
(c) It is independent of the path followed for the change (d) Both (a) and (b)
(d) Its value depends upon the amount of substance in the system 2. A mixture of two moles of carbon monoxide and one mole of
16. Which of the following is zero for an isochoric process oxygen, in a closed vessel is ignited to convert the carbon monoxide
to carbon dioxide. If H is the enthalpy change and E is the
(a) dP (b) dV
change in internal energy, then [KCET 2005]
(c) dT (d) dE
(a) H  E
17. Mark the correct statement [MP PET 1997]
(a) For a chemical reaction to be feasible, G should be zero (b) H  E
(b) Entropy is a measure of order in a system (c) H  E
(c) For a chemical reaction to be feasible, G should be positive (d) The relationship depends on the capacity of the vessel
(d) The total energy of an isolated system is constant 3. Which of the following is always negative for exothermic reaction? [BCECE 2005]
18. In an isochoric process the increase in internal energy is (a) H (b) S
[MP PMT 1997] (c) G (d) None of these
(a) Equal to the heat absorbed
4. The relation between E and H is
(b) Equal to the heat evolved
[MP PET 1992; MP PMT 1996; MP PET/PMT 1998]
(c) Equal to the work done
(d) Equal to the sum of the heat absorbed and work done (a) H  E  P V (b) H  E  P V
19. It is general principle that the less energy a system contains, it is [MH CET 1999] (c) E  V  H (d) E  H  P V
(a) Less stable (b) More stable
(c) Unstable (d) More unstable 5. At constant T and P, which one of the following statements is
20. Internal energy is an example of [Pb. PMT 2000] 1
(a) Path function (b) State function correct for the reaction, CO (g)  O2 (g)  CO 2 (g)
2
(c) Both (a) and (b) (d) None of these
[AIIMS 1982, 83; KCET 1988; BHU 1995; MP PET 1997, 99]
21. The process, in which no heat enters or leaves the system, is termed
as [Pb. PMT 1999; Kerala (Med.) 2002; J & K 2005] (a) H is independent of the physical state of the reactants of
(a) Isochoric (b) Isobaric that compound
(c) Isothermal (d) Adiabatic
 Thermodynamics and Thermochemistry 415
(b) H  E 14. Which of the following is the correct equation
[CBSE PMT 1996]
(c) H  E
(a) U  Q  W (b) W  U  Q
(d) H  E
(c) U  W  Q (d) None of these
6. For the reaction of one mole of zinc dust with one mole of sulphuric
acid in a bomb calorimeter, U and w correspond to [AIIMS 2005] 15. Hess law is applicable for the determination of heat of
[AIIMS 1998; Pb. PET/PMT 1999]
(a) U  0 , w  0 (b) U  0 , w  0
(a) Reaction (b) Formation
(c) U  0 , w  0 (d) U  0 , w  0
(c) Transition (d) All of these
7. Which is not the correct relation between enthalpy (H ) and 16. Enthalpy for the reaction C  O 2  CO 2 is
intrinsic energy  E) [EAMCET 1992]
[DPMT 1987, 91]
(a) H  E  P V (b) H  E  n RT (a) Positive (b) Negative
(c) H  E  P V (d) E  H  P V (c) Zero (d) None
17. During an isothermal expansion of an ideal gas its
8. The law of Lavoisier and Laplace illustrates
[CBSE PMT 1991]
[KCET 1989]
(a) Internal energy increases
(a) The principle of conservation of energy
(b) Enthalpy decreases
(b) Equivalence of mechanical and thermal energy
(c) Enthalpy remains unaffected
(c) The principle of conservation of matter
(d) Enthalpy reduces to zero
(d) Equivalence of mechanical and chemical energy
18. The work done in ergs for the reversible expansion of one mole of
9. For the reaction N 2  3H 2 ⇌ 2 NH 3 ; H  an ideal gas from a volume of 10 litres to 20 litres at 25 o C is[CMC Vellore 199
[Roorkee 2000; CBSE PMT 1991, 2002] (a) 2.303  298  0.082 log 2
(a) E  RT (b) E  2 RT
(b) 298  10 7  8.31  2.303 log 2
(c) E  RT (d) E  2 RT
(c) 2.303  298  0.082 log0.5
10. If H is the change in enthalpy and E the change in internal
energy accompanying a gaseous reaction (d) 8.31  10 7  298  2.303 log0.5
[KCET 1989; CBSE PMT 1990]
(e) 2.303  298  2 log 2
(a) H is always greater than E
19. The law of conservation of energy states that
(b) H  E only if the number of moles of the products is [NCERT 1984]
greater than the number of the reactants (a) The internal energy of a system is constant
(c) H is always less than E (b) The heat content of a system is constant
(c) Energy is neither created nor destroyed
(d) H  E only if the number of moles of the products is less
(d) There is an equivalence between energy and mass
than the number of moles of the reactants
20. The enthalpies of the elements in their standard states are assumed
11. “The resultant heat change in a reaction is the same whether it takes to be
place in one or several stages.” This statement is called[MP PMT/PET 1988; MP PMT 1989]
(a) Zero at 298 K
(a) Lavoisier and Laplace law (b) Unit at 298 K
(b) Hess's law (c) Zero at all temperatures
(c) Joule's law (d) Zero at 273 K
(d) Le–chatelier's principle 21. The heat Q for a reaction at constant volume is equal to
12. Hess's law of constant heat summation in based on (a) H  H (b) H  H
P R R P
[MP PET 2001]
(c) EP  ER (d) None of these
(a) E  mc 2 22. Which of the following expressions represents the first law of
(b) Conservation of mass thermodynamics
(c) First law of thermodynamics [MP PET 1996, 2000; AFMC 1997; BHU 1999; AMU 2000;
(d) None of the above KCET (Med.) 2000, 01; CBSE PMT 2000; MP PMT 2002]

13. Consider the reaction : N 2  3 H 2  2 NH 3 carried out at (a) E  q  W (b) E  q  W

constant temperature and pressure. If H and U are the (c) E  q  W (d) E  q  W

enthalpy and internal energy changes for the reaction, which of the 23. In a reversible isothermal process, the change in internal energy is
following expression is true [AIEEE 2005] (a) Zero (b) Positive
(a) H  0 (b) H  U (c) Negative (d) None of these
(c) H  U (d) H  U
 416 Thermodynamics and Thermochemistry
24. A schematic plot of lnK eq versus inverse of temperature for a 34. For the reaction
o
reaction is shown below CH 3 COOH (l)  2O 2 (g) ⇌ 2CO 2 (g)  2 H 2 O(l) at 25 C
6.0
and 1 atm. pressure, H  874 kJ . Then the change in internal
energy (E) is …. [Orissa JEE 2002]
ln Keq

(a) – 874 kJ (b) – 871.53 kJ

(c) – 876.47 kJ (d) + 874 kJ
2.0 35. In a closed insulated container, a liquid is stirred with a paddle to
1.5×10–3 1/T (K–1) 2.0×10–3 increase its temperature. In this process, which of the following is
The reaction must be [AIEEE 2005] true [CBSE PMT 2002]
(a) Exothermic (a) E  W  Q  0 (b) E  0, Q  W  0
(b) Endothermic
(c) One with negligible enthalpy change (c) E  W  0, Q  0 (d) E  Q  0, W  0
(d) Highly spontaneous at ordinary temperature 36. Hess law is based on [MH CET 2002]
25. Hess law of heat summation includes [AFMC 1992] (a) Law of conservation of mass
(a) Initial reactants only (b) Law of conservation of energy
(b) Initial reactants and final products (c) Enthalpy is a state function
(c) Final products only (d) None of these
(d) Intermediates only 37. For the reaction,
26. An ideal gas at constant temperature and pressure expands, then its[BHU 1998] C 3 H 8 (g)  5O 2 (g)  3CO 2 (g)  4 H 2 O(l)
(a) Internal energy remains same at constant temperature, H  E is [CBSE PMT 2003]
(b) Internal energy decreases (a) – RT (b) + RT
(c) Internal energy increases (c) – 3RT (d) + 3RT
(d) Entropy first increases and then decreases 38. According to Hess’s law, the heat of reaction depends upon
27. The internal energy of a substance [MP PMT 2003]
[KCET 1998; AFMC 2001; AIIMS 2001] (a) Initial condition of reactants
(a) Increases with increase in temperature
(b) Initial and final conditions of reactants
(b) Decreases with increase in temperature
(c) Intermediate path of the reaction
(c) Can be calculated by the relation E  mc 2 (d) End conditions of reactants
(d) Remains unaffected with change in temperature
39. The value of H  E for the following reaction at 27 o C will
28. The relation between change in internal energy (E) , change in
be 2 NH 3 (g)  N 2 (g)  3 H 2 (g) [Kerala (Med.) 2002]
enthalpy (H ) and work done (W) is represented as [AFMC 1999]
(a) H  E  W (b) W  E  H (a) 8.314  273  (2) (b) 8.314  300  (2)
(c) E  W  H (d) E  H  W (c) 8.314  27  (2) (d) 8.314  300  (2)
29. The enthalpy of neutralization of which of the following acids and 40. For which of the following E  H [MP PET 2003]
bases is nearly 13.6 Kcal [Roorkee 1999]
(a) N 2 O 4 (g) ⇌ 2 NO 2 (g)
(a) HCN and NaOH (b) HCl and KOH
(c) HCl and NaOH (d) HCl and NH OH 4
(b) 2SO 2 (g)  O 2 (g) ⇌ 2SO 3 (g)
30. Work done during isothermal expansion of one mole of an ideal gas
(c) H 2 (g)  Cl 2 (g) ⇌ 2 HCl(g)
from 10 atm to 1 atm at 300 K is (Gas constant = 2) [AIIMS 2000]
(a) 938.8 cal. (b) 1138.8 cal. 1
(c) 1381.8 cal. (d) 1581.8 cal. (d) H 2 (g )  O 2 (g) ⇌ H 2 O(l)
2
31. Joule-Thomson expansion is [JIPMER 2000]
41. One mole of an ideal gas is allowed to expand freely and
(a) Isobaric (b) Isoenthalpic adiabatically into vacuum until its volume has doubled. A statement
(c) Isothermal (d) None of these which is not true concerning this expression is
32. In which of the following E  H [MP PMT 2001] [Pb. PMT 1998]
(a) N 2 O 4 (g) ⇌ 2 NO 2 (g) (a) H  0 (b) S  0
(b) 2SO 2 (g)  O 2 (g) ⇌ 2SO 3 (g) (c) E  0 (d) W  0
o
(c) H 2 (g)  I 2 (g) ⇌ 2 HI(g) 42. At 27 C, one mole of an ideal gas is compressed isothermally and
reversibly from a pressure of 2 atm to 10 atm. The values of E
1
(d) H 2 (g )  O 2 (g) ⇌ H 2 O(l) and q are (R  2) [BHU 2001]
2
(a) 0, – 965.84 cal
33. In an adiabatic expansion of an ideal gas
[KCET (Med.) 2001; MH CET 2000] (b) – 965.84 cal, + 965.84 cal
(a) W  E (b) W  E (c) + 865.58 cal, – 865.58 cal
(d) – 865.58 cal, – 865.58 cal
(c) E  0 (d) W  0
 Thermodynamics and Thermochemistry 417
43. The work done by a system is 8 joule, when 40 joule heat is supplied (a) Heat of combustion of carbon is 110 kJ
to it. What is the increase in internal energy of system (b) Reaction is exothermic
[BHU 2001] (c) Reaction needs no initiation
(a) 25 J (b) 30 J
(d) All of these are correct
(c) 32 J (d) 28 J
44. A system absorb 600J of heat and work equivalent to 300J on its 54. An ideal gas expands in volume from 1  10 3 m 3 to 1  10 2 m 3
surroundings. The change in internal energy is at 300 K against a constant pressure of 1  10 5 Nm 2 . The work
[Pb. PMT 2004] done is [AIEEE 2004]
(a) 300 J (b) 400 J (a) 270 kJ (b) –900 kJ
(c) 500 J (d) 600 J (c) –900 J (d) 900 kJ
45. Work done during isothermal expansion of one mole of an ideal gas 55. Internal energy is [AFMC 2004]
from 10 atom. to 1 atm at 300K is [BHU 2004] (a) Partly potential and partly kinetic
(a) 4938.8 J (b) 4138.8 J (b) Totally kinetic
(c) 5744.1 J (d) 6257.2 J (c) Totally potential
46. If gas, at constant temperature and pressure expands then its (d) None of these
[MH CET 2003] 56. For which of the reaction H  E [MP PET 2004]
(a) Entropy increases and then decreases
(a) N 2  3H 2 ⇌ 2NH 3 (b) N 2  O2  2 NO
(b) Internal energy increases
(c) Internal energy remains the same (c) 2 Na  Cl2  2 NaCl (d) PCl5  PCl3  Cl2
(d) Internal energy decreases 57. The work done during the expansion of a gas from a volume of
47. For the reaction 4dm 3 to 6dm 3 against a constant external pressure of 3atm is
PCl5 (g)  PCl3 (g)  Cl2 (g) [MH CET 2004] ( 1L atm  101.32 J ) [CBSE PMT 2004]

(a) H  E (b) H  E (a) + 304 J (b) –304 J

(c) – 6 J (d) –608 J
(c) H  E (d) None of these
58. For the reaction, A(s)  2 B(g)  4 C(s)  D(l) . H and U are
48. Enthalpy (H ) is equal to [MH CET 2004]
related as ……… [Orissa JEE 2004]
(a) Internal energy (E)
(b) Product of pressure (P) and volume (V) of gas (a) H  U (b) H  U  3 RT
(c) Internal energy (E)+PV (c) H  U  RT (d) H  U  3 RT
(d) Work (W) done by a system
IInd & IIIrd Law of thermodynamics and Entropy
49. E o of combustion of isobutylene is  X kJ mol 1 . The value of
H o is [DCE 2004] 1. For a reversible spontaneous change S is
(a)  E o
(b)  E o E P V
(a) (b)
T T
(c)  0 (d)  E o
q
50. One mole of an ideal gas is allowed to expand reversibly and (c) (d) RT log K
T
adibatically from a temperature of 27 o C . If the work done during 2. When disorder of a system increases, the change is said to be
the process is 3 kJ , then final temperature of the gas is (a) Exothermic (b) Non-spontaneous
(CV  20 J / K) [Pb. CET 2002] (c) Endothermic (d) Spontaneous
3. The spontaneous flow of heat is always
(a) 100 K (b) 150 K (a) From low to high pressure
(c) 195 K (d) 255 K (b) From high to high pressure
51. Which of the following is correct regarding the internal energy of a (c) Unidirectional from lower temperature to higher temperature
substance [Pb. CET 2002] (d) Unidirectional from the higher to lower temperature
(a) It is a state function 4. Mixing of non-reacting gases is generally accompanied by
(b) It increases with increase in temperature (a) Decrease in entropy
(c) It can be calculated by experiment (b) Increase in entropy
(d) It remains unaffected with change in temperature (c) Change in enthalpy
(d) Change in free energy
52. For the gaseous reaction,
5. An irreversible process occuring isothermally in an isolated system
N 2O4  2NO 2 [Pb. CET 2003] leads to
(a) H  E (b) H  E (a) Zero entropy
(b) An increase in the total entropy of the system
(c) H  0 (d) H  E
(c) A decrease in the total entropy of the system
53. 2C  O2  2CO ; H  220 kJ (d) None of these
Which of the following statement is correct for this reaction 6. The entropy values (in JK mol ) of H = 130.6, Cl = 223.0 and HCl =
-1 -1

2(g) 2(g) (g)

[BVP 2004] 186.7 at 298 K and 1 atm pressure. Then entropy change for the
reaction
 418 Thermodynamics and Thermochemistry
H 2(g)  Cl 2(g)  2 HCl(g) is [BHU 2005] 1
(a) Ca(s)  O 2 (g)  CaO(s)
(a) + 540.3 (b) + 727.3 2
(c) – 166.9 (d) + 19.8 (b) CaCO 3 (s)  CaO(s)  CO 2 (g)
7. Which of the following is the least random state of water
(c) C(s)  O2 (g)  CO 2 (g)
(a) Ice
(b) Liquid water (d) N 2 (g)  O2 (g)  2 NO(g)
(c) Steam 17. The occurrence of a reaction is impossible if
(d) All present same random state [AIIMS 1982, 91; MP PET 1997;
8. Which one of the following process is non-spontaneous MP PMT 1999; DPMT 2002]
(a) Dissolution of CuSO 4 in water (a) H is +ve ; S is also + ve but H  TS
(b) Reaction between H 2 and O 2 to form water (b) H is – ve ; S is also – ve but H  TS
(c) Water flowing down hill (c) H is – ve ; S is + ve
(d) Flow of electric current from low potential to high potential (d) H is + ve ; S is – ve
9. Which of the following is zero during adiabatic expansion of the gas
18. If the enthalpy of vaporization for water is 186.5 kJ mol 1 , the
(a) T (b) S entropy of its vaporization will be
(c) E (d) None of these [CPMT 1988; DCE 2000]
10. The entropy of crystalline substances at absolute zero going by the 1 1
third law of thermodynamics should be taken as (a) 0.5 JK mol (b) 1.0 JK 1 mol 1
[J & K 2005]
(c) 1.5 JK 1 mol 1 (d) 2.0 JK 1 mol 1
(a) 100
(b) 50 19. Which of the following statement is true. The entropy of the
universe [MP PMT 1993; CET Pune 1998]
(c) Zero
(a) Increases and tends towards maximum value
(d) Different for different substances
(b) Decreases and tends to be zero
11. In which state, the matter have highest entropy
(a) Solid (b) Liquid (c) Remains constant
(c) Gas (d) Equal in all (d) Decreases and increases with a periodic rate
12. Which of the following pairs of a chemical reaction is certain to 20. When enthalpy and entropy change for a chemical reaction are
result in spontaneous reaction ? [CBSE PMT 2005]  2.5  10 3 cal and 7.4 cal deg 1 respectively. Predict the
(a) Exothermic and decreasing disorder reaction at 298 K is
(b) Endothermic and increasing disorder
[AFMC 1998; MH CET 1999; CBSE PMT 2000]
(c) Exothermic and increasing disorder
(a) Spontaneous (b) Reversible
(d) Endothermic and decreasing disorder
(c) Irreversible (d) Non-spontaneous
13. When one mole of monoatomic ideal gas at T K undergoes adiabatic
change under a constant external pressure of 1 atm changes volume 21. The total entropy change for a system and its surroundings
from 1 litre to 2 litre. increases, if the process is
The final temperature in Kelvin would be [IIT 2005] (a) Reversible (b) Irreversible
T 2 (c) Exothermic (d) Endothermic
(a) (b) T + 22. For chemical reactions, the calculation of change in entropy is
2 (2 / 3 )
3  0 .0821
normally done
2
(c) T (d) T  (a) At constant pressure
3  0 .0821 (b) At constant temperature
14. 9.0 gm of H 2 O is vaporised at 100 o C and 1 atm pressure. If the (c) At constant temperature and pressure both
latent heat of vaporisation of water is x J / gm , then S is given (d) At constant volume
by 23. When the value of entropy is greater, then the ability of work
x 18 x (a) Is maximum (b) Is minimum
(a) (b) (c) Is medium (d) None of these
373 100
24. Which of the following is true for the reaction H 2 O(l) ⇌ H 2 O(g)
18 x 1 18 x
(c) (d)  at 100 o C and 1 atmosphere
373 2 373
[KCET 1991; AIIMS 1996]
15. The S for the vaporisation of 1 mol of water is 88.3 J/mole K.
(a) E  0 (b) H  0
The value of S for the condensation of 1 mol of vapour will be
(c) H  E (d) H  TS
(a) 88.3 J/mol K (b) (88.3)2 J/mol K 25. The enthalpy change for the transition of liquid water to steam,
1 H vap  37.3 kJ mol 1 at 373 K . The entropy change for the
(c) – 88.3 J/mol K (d) J/mol K
88 . 3 process is [MP PET 1994]
16. For which reaction from the following, S will be maximum (a) 111.9 J mol 1 K 1 (b) 37.3 J mol 1 K 1
[AlIMS 1982, 83, 94; AMU 2000]
(c) 100 J mol 1 K 1 (d) 74.6 J mol 1 K 1
 Thermodynamics and Thermochemistry 419
26. When a solid is converted into liquid, entropy 37. In which of the following conditions a chemical reaction can not
[MP PET 1993, 95; MP PMT 1996] occur [AMU 1999]
(a) Becomes zero (b) Remains the same (a) H and S increase and TS  H
(c) Decreases (d) Increases (b) H and S decrease and H  TS
27. In a spontaneous process, the entropy of the system and its (c) H increases and S decreases
surroundings [MP PET 1996; NCERT 1975]
(d) H decreases and S increases
(a) Equals zero (b) Decreases
(c) Increases (d) Remains constant 38. An engine operating between 150 o C and 25 o C takes 500 J heat
from a higher temperature reservoir if there are no frictional losses,
28. The positive value of S indicates that [MP PMT 1997] then work done by engine is
(a) The system becomes less disordered [MH CET 1999]
(b) The system becomes more disordered (a) 147.7 J (b) 157.75 J
(c) The system is in equilibrium position (c) 165.85 J (d) 169.95 J
(d) The system tends to reach at equilibrium position 39. The entropy of a perfectly crystalline solid at absolute zero is
29. For reaction 2Cl(s)  Cl 2 (s) , the signs of H and S [AMU 2000]
respectively are [KCET 1996]
(a) Positive (b) Negative
(c) Zero (d) Not definite
(a) +, – (b) +, +
40. Which of the following conditions will always lead to a non-
(c) –, – (d) –, + spontaneous change [AMU 2000; KCET (Med.) 2000]
30. The enthalpy of water is 386 kJ . What is entropy of water (a) Positive H and positive S
[BHU 1997] (b) Negative H and negative S
(a) 0.5 kJ (b) 1.03 kJ (c) Positive H and negative S
(c) 1.5 kJ (d) 22.05 kJ
(d) Negative H and positive S
31. For which of the processes is S negative [Pb. PMT 1998] 41. Following data is known about melting of a compound AB.
(a) H 2 (g)  2 H (g) H  9.2 kJ mol 1 , S  0.008 kJ K 1 mol 1 . Its melting point
(b) N 2 (g)1atm  N 2 (g) 8 atm is [Pb. PMT 2000; AIIMS 2000]
(a) 736 K (b) 1050 K
(c) 2SO 3 (g)  2SO 2 (g)  O2 (g)
(c) 1150 K (d) 1150 o C
(d) C(diamond )  C(graphite)
42. The volume of a gas decreases from 500 cc to 300 cc when a
32. Identify the correct statement regarding entropy
sample of gas is compressed by an average pressure of 0.6 atm.
[CBSE PMT 1998; BHU 2001]
During this process 10 J of heat is liberated. The change in internal
o
(a) At 0 C , the entropy of a perfectly crystalline substance is energy is [Pb. PMT 2000]
taken to be zero (a) – 2.16 J (b) 12.156 J
(b) At absolute zero of temperature, the entropy of a perfectly (c) 2.16 J (d) 101.3 J
crystalline substance is ve
43. The standard entropies of CO 2 (g), C(s) and O 2 (g) are 213.5,
(c) At absolute zero of temperature, the entropy of all crystalline
substances is taken to be zero 5.690 and 205 JK 1 respectively. The standard entropy of formation
(d) At absolute zero of temperature, the entropy of a perfectly of CO 2 (g) is [CPMT 2001]
crystalline substance is taken to be zero
33. One mole of an ideal gas at 300 K is expanded isothermally from (a) 1.86 JK 1 (b) 1.96 JK 1
an initial volume of 1 litre to 10 litres. The change in energy for this
(c) 2.81 JK 1 (d) 2.86 JK 1
process is (R  2 cal mol 1 K 1 )
44. Which of the following endothermic processes are spontaneous[CBSE PMT 2001]
[CBSE PMT 1998]
(a) Melting of ice (b) Evaporation of water
(a) 163.7 cal (b) 850.2 cal
(c) Heat of combustion (d) Both (a) and (b)
(c) 1381.1 cal (d) Zero
34. If 900 J / g of heat is exchanged at boiling point of water, then 45. For the reaction H 2O(s) ⇌ H 2 O(l) at 0 o C and normal
what is increase in entropy [BHU 1998]
pressure [KCET 2001]
(a) 43.4 J/mole (b) 87.2 J/mole (a) H  TS (b) H  TS
(c) 900 J/mole (d) Zero (c) H  G (d) H  TS
35. A container has hydrogen and oxygen mixture in ratio of 4 : 1 by 46. One mole of an ideal gas is allowed to expand reversibly and
weight, then [BHU 1998] adiabatically from a temperature of 27 o C . If the work done during
(a) Internal energy of the mixture decreases the process is 3 kJ, the final temperature will be equal to
(b) Internal energy of the mixture increases (C v  20 JK 1 )
(c) Entropy of the mixture increases
[KCET 2000; AFMC 2000; AIIMS 2001]
(d) Entropy of the mixture decreases
(a) 150 K (b) 100 K
36. If 0.75 mole of an ideal gas expands isothermally at 27 o C from 15 o
litres to 25 litres, the maximum work obtained is (c) 26.85 C (d) 295 K
[AFMC 1999] 47. The entropy change, in the conversion of one mole of liquid water at
(a) 8.40 J (b) 9.34 J 373 K to vapour at the same temperature is (Latent heat of vaporization
(c) 10.86 J (d) 10.43 J of water, H vap  2.257 kJ / g)
[AFMC 2002; KCET 2002]
 420 Thermodynamics and Thermochemistry

(a) 105.9 Jk 1 (b) 107.9 Jk 1 58. H  (aq)  OH  (aq)  H 2O(l)

S o (298 K ) K 1mol 1 10 .7 70
(c) 108.9 Jk 1 (d) 109.9 Jk 1 Standard entropy change for the above reaction is
48. A heat engine absorbs heat Q 1 at temperature T1 and heat Q 2 [DPMT 2004]
1 1 1 1
at temperature T 2 . Work done by the engine is (Q1  Q 2 ) . This (a) 60.3 JK mol (b) 80.7 JK mol
data [AIEEE 2002]
(c)  70 JK 1mol 1 (d)  10.7 JK 1mol 1
(a) Violates I law of thermodynamics
st

(b) Violates I law of thermodynamics if Q 1 is –ve

st
59. One mole of water at 100 o C is converted into steam at 100 o C
at a constant pressure of 1 atm. The change in entropy is [heat of
(c) Violates I law of thermodynamics if Q 2 is –ve
st

vaporisation of water at 100o C  540 cal / gm ] [Pb. PMT 2004]

(d) Does not violate I law of thermodynamics
st

(a) 8.74 (b) 18.76

49. Equal volumes of monoatomic and diatomic gases at same initial
temperature and pressure are mixed. The ratio of specific heats of (c) 24.06 (d) 26.06
the mixture (C p / C v ) will be 60. For a carnot engine, the source is at 500 K and the sink at
300 K . What is efficiency of this engine [BHU 2004]
[AFMC 2002]
(a) 1 (b) 2 (a) 0.2 (b) 0.4
(c) 1.67 (d) 1.5 (c) 0.6 (d) 0.3
50. The law formulated by Dr. Nernst is [Kerala (Med.) 2002] 61. Heat require to raise the temperature of 1 mol of a substance by
(a) First law of thermodynamics 1o C is called [DCE 2002]
(b) Second law of thermodynamics (a) Specific heat (b) Molar heat capacity
(c) Third law of thermodynamics (c) Water equivalent (d) Specific gravity
(d) Both (a) and (b) 62. Maximum entropy will be in which of the following
51. The unit of entropy is [CBSE PMT 2002] [DCE 2004]
(a) Ice (b) Liquid water
(a) J mol 1 (b) JK mol 1
(c) Snow (d) Water vapours
(c) J mol 1 K 1 (d) J 1 K 1 mol 1 63. The standard entropies of CO 2 (g), C(s) and O2 (g) are 213.5,
52. The entropy changed involved in the conversion of 1 mole of liquid 5.740 and 205 JK 1 respectively. The standard entropy of
water at 373 K to vapour at the same temperature will be formation of CO 2 is [Pb. CET 2001]
[H vap  2.257kJ / gm] [MP PET 2002]
(a) 2.76 JK 1 (b) 2.12 JK 1
(a) 0.119 kJ (b) 0.109 kJ
(c) 0.129 kJ (d) 0.120 kJ (c) 1.12 JK 1 (d) 1.40 JK 1
53. When a liquid boils, there is [JIPMER 2002] 64. Which law of thermodyanamics help in calculating entropy at
(a) An increase in entropy different temperatures [Pb. CET 2003]
(b) A decrease in entropy (a) First law (b) Second law
(c) An increase in heat of vaporization (c) Third law (d) Zeroth law
(d) An increase in free energy 65. Entropy is maximum in case of [BVP 2004]

54. Which one of the following has S o

greater than zero (a) Steam (b) Water at 0 o C
[AIIMS 2003] (c) Water at 4 o C (d) Ice
(a) CaO  CO 2 (g) ⇌ CaCO 3 (s) 66. Considering entropy (S) as a thermodynamic parameter, the
criterion for the spontaneity of any process is
(b) NaCl (aq) ⇌ NaCl(s) [CBSE PMT 2004]
(c) 
NaNO 3 (s) ⇌ Na (aq)  NO 3 (aq) (a) S system  0 only
(d) N 2 (g)  3 H 2 (g) ⇌ 2 NH 3 (g) (b) S surroundin gs  0 only
55. The molar heat capacity of water at constant pressure is (c) S system  S surroundin gs  0
75 JK 1 mol 1 . When 1.0 kJ of heat is supplied to 100 g of water
(d) S system  S surroundin gs  0
which is free to expand the increase in temperature of water is[CBSE PMT 2003]
(a) 6.6 K (b) 1.2 K 67. A process is taking place at constant temperature and pressure.
Then [KCET 2004]
(c) 2.4 K (d) 4.8 K
56. The work done to contract a gas in a cylinder, is 462 joules. 128 (a) H  E (b) H  TS
joule energy is evolved in the process. What will be the internal (c) H  0 (d) S  0
energy change in the process [MP PMT 2003]
68. The enthalpy of vapourization of a liquid is 30 kJ mol 1 and
(a) + 590 joules (b) – 334 joules
(c) + 334 joules (d) – 590 joules entropy of vapourization is 75 J mol 1 K . The boiling point of the
57. Highest entropy is in [BVP 2003] liquid at 1 atm is [IIT JEE (Screening) 2004]
(a) Hydrogen (b) Water (a) 250K (b) 400K
(c) Graphite (d) Mercury (c) 450K (d) 600K
 Thermodynamics and Thermochemistry 421

Heat of reaction (a) 816.15 kJ (b) 1632.3 kJ

(c) 6528.2 kJ (d) 2448.45 kJ
10. Thermochemical reactions
1. If C  O2  CO 2  94.2 kcal 1
C(graphite)  O 2 (g)  CO (g); H  110.5 kJ
1 2
H2  O2  H 2 O  68.3 kcal
2 1
CO (g)  O 2 (g)  CO 2 (g); H  283.2 kJ
CH 4  2O2  CO 2  2 H 2O  210.8 kcal 2
From the above reaction, the heat of reaction for
then the possible heat of methane will be [MP PET 1990]
C(graphite)  O2 (g)  CO 2 (g) will be
(a) 47.3 kcal (b) 20.0 kcal
[CPMT 1988; MP PMT 1989]
(c) 45.9 kcal (d) – 47.3 kcal (a) – 393.7 kJ (b) + 393.7 kJ
2. Molar heat of vaporisation of a liquid is 6 kJ mol 1 . If the entropy (c) – 172.7 kJ (d) + 172.7 kJ
11. The following is (are) endothermic reaction [IIT JEE 1999]
change is 16 J mol 1 K 1 , the boiling point of the liquid is [KCET 2005] (a) Combustion of methane
(b) Decomposition of water
(a) 375 o C (b) 375 K
(c) Dehydrogenation of ethane to ethylene
(c) 273 K (d) 102o C (d) Conversion of graphite to diamond
3. The enthalpy of fusion of ice per mole 12. Evaporation of water is
[CPMT 1973; DPMT 1982; MP PMT 1989; MP PET 1999]
(a) 18 kJ (b) 8 kJ
(a) An endothermic change
(c) 80 kJ (d) 6 kJ (b) An exothermic change
4. In which of the following neutralisation reactions, the heat of (c) A process where no heat change occurs
neutralisation will be highest (d) A process accompanied by chemical reaction
[MP PMT 1989, 91; AIIMS 1999] 13. An exothermic reaction is one which
(a) NH 4 OH and CH 3 COOH [NCERT 1977; MP PMT 1990]
(a) Takes place only on heating
(b) NH 4 OH and HCl (b) Is accompanied by a flame
(c) Is accompanied by a absorption of heat
(c) NaOH and CH 3 COOH
(d) Is accompanied by evolution of heat
(d) NaOH and HCl 14. An endothermic reaction is one in which
[MNR 1980; NCERT 1976]
5. If S  O2  SO 2 ; (H  298.2)
(a) Heat is converted into electricity
1 (b) Heat is absorbed
SO 2  O2  SO 3 ; (H  98.2)
2 (c) Heat is evolved
(d) Heat is converted into mechanical work
SO 3  H 2O  H 2 SO 4 ; (H  130.2)
15. Which of the following statement is correct
1 [NCERT 1978]
H2  O2  H 2 O; (H  287.3)
2 (a) H is positive for exothermic reaction
then the enthalpy of formation of H 2 SO 4 at 298K will be (b) H is negative for endothermic reaction
[DPMT 1983; Orissa JEE 2005] (c) The heat of neutralization of strong acid and strong base is
always the same
(a) 433.7 kJ (b) 650.3 kJ (d) The enthalpy of fusion is negative
(c) 320.5 kJ (d) 813.9 kJ 16. The absolute enthalphy of neutralisation of the reaction
6. From Kirchhoff's equation which factor affects the heat of reaction[MP PMT 1990] MgO(s)  2 HCl(aq)  MgCl2 (aq)  H 2 O(l) will be
(a) Pressure (b) Temperature [CBSE PMT 2005]
(c) Volume (d) Molecularity (a) Less than  57.33 kJ mol 1
7. The molar neutralization heat for KOH and HNO 3 as compared
(b)  57.33 kJ mol 1
to molar neutralization heat of NaOH and HCl
[MP PMT 1989] (c) Greater than  57.33 kJ mol 1
(a) Less (b) More
(c) Equal (d) Depends on pressure (d) 57.33 kJ mol 1
8. An exothermic reaction is one in which the reacting substances [CPMT 1974,17.
79; BiharMEE
H f 1982;
(298 K) of methanol is given by the chemical equation[AIIMS 2005]
KCET 1992; JIPMER 2001]
(a) Have more energy than the products (a) CH 4 (g)  1 / 2O2 (g)  CH 3 OH(g)
(b) Have less energy than the products (b) C (graphite) 1 / 2O2 (g)  2 H 2 (g)  CH 3 OH(l)
(c) Are at a higher temperature than the product
(d) None of the above (c) C (diamond) 1 / 2O2 (g)  2 H 2 (g)  CH 3 OH(l)
9. The heat evolved in the combustion of benzene is given by (d) CO(g)  2 H 2 (g)  CH 3 OH(l)
1
C 6 H 6  7 O 2  6 CO 2 (g)  3 H 2 O(l); H  3264.6 kJ 18. If H of for H 2 O 2 and H 2 O are 188 kJ / mole and
2
Which of the following quantities of heat energy will be evolved 286 kJ / mole . What will be the enthalpy change of the reaction
when 39 g C 6 H 6 are burnt 2 H 2 O2 (l)  2 H 2 O(l)  O2 (g) [MP PMT 1992]
[NCERT 1978; MP PET 1990; JIPMER 2001]
 422 Thermodynamics and Thermochemistry
(a) 196 kJ / mole (b) 146 kJ / mole (c) More than 56.1 kcal (d) 13.7 kcal
(c) 494 kJ / mole (d) 98 kJ / mole 28. The heat of formations of CO (g) and CO 2 (g) are 26.4 kcal
and 94.0 kcal respectively. The heat of combustion of carbon
19. The heat of transition (H t ) of graphite into diamond would be, monoxide will be
where [MP PET/PMT 1988; EAMCET 1993]
C(graphite)  O2 (g)  CO 2 (g); H  x kJ (a) 26.4 kcal (b) 67.6 kcal
C(diamond )  C 2 (g)  CO 2 (g); H  y kJ [Pb. PET 1985] (c) 120.6 kcal (d) 52.8 kcal
1 1
(a) (x  y)kJ mol (b) (x  y)kJ mol 29. The enthalpy of combustion at 25°C of H , cyclohexane (C H ) and
2 6 12

cyclohexene (C H ) are –241, –3920 and –800 KJ / mole respectively.

1
(y  x )kJ mol
6 10

(c) (d) None of these The heat of hydrogenation of cyclohexene is [BHU 2005]
20. Correct relationship between heat of fusion (H fus ) , heat of (a) – 121 KJ / mole (b) + 121 KJ / mole
(c) – 242 KJ / mole (d) + 242 KJ / mole
vaporization (H vap ) and heat of sublimation (H sub ) is
30. Heat of neutralisation of NH 4 OH and HCl is
(a) H fus  H vap  H sub
[EAMCET 1980; Roorkee 1990; MP PMT 1994]
(b) H vap  H fus  H sub (a) 13.7 kcal (b)  13.7 kcal
(c) H sub  H vap  H fus (c)  13.7 kcal (d) None of the above
(d) H sub  H vap  H fus 31. Heat of combustion H of CH 4 , C 2 H 6 , C 2 H 4 and C 2 H 2
21. Which of the following is an example of endothermic reaction[MP PMT 1980] gases are – 212.8, – 373.0, – 337.0 and – 310.5 kcal respectively at
the same temperature. The best fuel among these gases is
(a) C 2 H 2  2 H 2  C 2 H 6 ; E  314.0 kJ
(a) CH 4 (b) C 2 H 6
(b) C  O2  CO 2 ; E  393.5 kJ
(c) C2 H 4 (d) C 2 H 2
(c) N 2  O2  2 NO; E  180.5 kJ
32. Heat of formation of CO 2 (g), H 2 O(l) and CH 4 (g) are –
(d) 2 H 2  O2  2 H 2 O; E  571.8 kJ 94.0, – 68.4 and – 17.9 kcal respectively. The heat of combustion of
methane is
22. If the enthalpy of B is greater than of A, the reaction A  B is [MP PMT 1997]
(a) – 212.9 kcal (b) – 136.8 kcal
(a) Endothermic (b) Exothermic (c) – 304.3 kcal (d) – 105.2 kcal
(c) Instantaneous (d) Spontaneous 33. The heat of reaction does not depend upon
23. Given that (a) Temperature of the reaction
2C(s)  2O2 (g)  2CO 2 (g); H  787 kJ (b) Physical state of reactants and products
(c) Whether the reaction is carried out at constant pressure or at
1
H 2 (g)  O 2 (g)  H 2 O(l); H  286 kJ constant volume
2 (d) The method by which the final products are obtained from the
1 reactants
C 2 H 2 (g)  2 O 2 (g)  2CO 2 (g)  H 2 O(l); H  1301 kJ 34. Heat of neutralisation of a strong acid by a strong base is a constant
2
value because [KCET 1984]
Heat of formation of acetylene is (a) Salt formed does not hydrolyse
[KCET 1989; Orissa JEE 2005]
(b) Only H  and OH  ions react in every case
(a)  1802 kJ (b)  1802 kJ
(c) The strong base and strong acid react completely
(c) 800 kJ (d) 228 kJ (d) The strong base and strong acid react in aqueous solution
1 1 35. Heat of neutralisation of an acid by a base is highest when
24. Enthalpy change for reaction, H 2  Cl 2  HCl , is called [KCET 1985]
2 2 (a) Both the acid and base are weak
(a) Enthalpy of combination (b) Enthalpy of reaction (b) Both the acid and base are strong
(c) Enthalpy of formation (d) Enthalpy of fusion (c) The acid is strong and the base is weak
25. The enthalpy of neutralization is about 57.3 kJ for the pair (d) The acid is weak and the base is strong
(a) HCl and NH 4 OH 36. The standard molar heat of formation of ethane, CO 2 and water
(b) NH 4 OH and HNO 3 (l) are respectively – 21.1, – 94.1 and – 68.3 kcal. The standard molar
heat of combustion of ethane will be
(c) HCl and NaOH [IIT JEE 1986; DPMT 2005]
(d) CH 3 COOH and NaOH (a) – 372 kcal (b) 162 kcal
26. Conversion of oxygen to ozone represented by the equation (c) –240 kcal (d) 183.5 kcal
3O 2  2O3 is an endothermic reaction. Enthalpy change H 37. Which of the following reaction is endothermic
accompanying the reaction [KCET 1988, 92] [AFMC 1988]
(a) Is negative (b) Is positive (a) CaCO 3  CaO  CO 2
(c) Is zero (d) Depends on temperature (b) Fe  S  FeS
27. The mutual heat of neutralisation of 40 gm of NaOH and 60 gm
(c) NaOH  HCl  NaCl  H 2 O
CH 3 COOH will be [MP PET/PMT 1988]
(a) 56.1 kcal (b) Less than 56.1 kcal (d) CH 4  2O2  CO 2  2 H 2 O
 Thermodynamics and Thermochemistry 423
38. In the reaction (e) Heat of dilution
CO 2 (g)  H 2 (g)  CO(g)  H 2 O(g); H  80 kJ 49. Which is the best definition of “heat of neutralization”
[CMC Vellore 1991]
H is known as
(a) The heat set free when one gram molecule of a base is
[CPMT 1987; KCET 1993; Bihar CEE 1995] neutralized by one gram molecule of an acid in dilute solution
(a) Heat of formation (b) Heat of combustion at a stated temperature
(c) Heat of neutralization (d) Heat of reaction (b) The heat absorbed when one gram molecule of an acid is
39. Heat of combustion of a substance neutralized by one gram molecule of a base in dilute solution
[CPMT 1987, 96; AFMC 1992] at a stated temperature
(a) Is always positive (c) The heat set free or absorbed when one gram atom of an acid
(b) Is always negative is neutralized by one gram atom of a base at a stated
(c) Is equal to heat of formation temperature
(d) Nothing can be said without reaction (d) The heat set free or absorbed when a normal solution
containing one gram equivalent of an acid is neutralized by a
1 normal solution containing one gram equivalent of a base at a
40. The heat change for the reaction H 2 O 2  H 2 O is called
2 stated temperature
(a) Heat of reaction (b) Heat of formation (e) The heat set free when one gram equivalent of an acid is
(c) Heat of vaporisation (d) None of the above neutralized by one gram equivalent of a base in dilute solution
at a stated temperature
41. The heat change H for the reaction
50. The compound with negative heat of formation are known as[DPMT 1981]
2CO  O2  2CO 2 ; H  135 kcal is called (a) Endothermic compound
(a) Heat of formation (b) Heat of reaction (b) Exothermic compound
(c) Heat of combustion (d) Heat of solution (c) Heat of formation compound
42. The heats of combustion of rhombic and monoclinic sulphur are (d) None of the above
respectively 70960 and 71030 calories. What will be the heat of
conversion of rhombic sulphur to monoclinic 51. If H   OH   H 2 O  13.7 kcal , then the heat of
[MP PMT/PET 1988] neutralization for complete neutralization of one mole of H 2 SO 4
(a) 70960 calories (b) 71030 calories by base will be [MP PMT 1990]
(c) – 70 calories (d) + 70 calories (a) 13.7 kcal (b) 27.4 kcal
43. The heat of formation of H 2 O(l) is – 68.0 kcal, the heat of (c) 6.85 kcal (d) 3.425 kcal
formation of H 2 O(g) is likely to be 52. The lowest value of heat of neutralization is obtained for
(a) – 68.0 kcal (b) – 67.4 kcal [KCET 1988; MP PMT 1990]
(c) 80.0 kcal (d) – 58.3 kcal (a) HCl  NaOH
44. Which of the following fuels will have the highest calorific value (b) CH 3 COOH  NH 4 OH
(kJ/kg) [MP PMT 1990]
(a) Charcoal (b) Kerosene (c) NH 4 OH  HCl
(c) Wood (d) Dung (d) NaOH  CH 3 COOH
45. The heat of combustion of carbon is –94 kcal at 1 atm pressure. The
53. Heat of neutralisation for the given reaction
intrinsic energy of CO 2 is
NaOH  HCl  NaCl  H 2 O is 57.1 kJ mol 1 . What will be
(a) 94 kcal (b)  94 kcal
the heat released when 0.25 mole of NaOH is titrated against
(c) 47 kcal (d) 47 kcal 0.25 mole of HCl [CPMT 1990]
46. The heat of neutralisation of a strong acid and a strong alkali is
(a) 22.5 kJ mol 1 (b) 57.1 kJ mol 1
57.0 kJ mol 1 . The heat released when 0.5 mole of HNO 3
solution is mixed with 0.2 mole of KOH is (c) 14.3 kJ mol 1 (d) 28.6 kJ mol 1
[KCET 1991; AIIMS 2002; AMU (Engg.) 2002] 54. Reaction, H 2 (g)  I2 (g)  2 HI(g) H  12.40 kcal .
(a) 57.0 kJ (b) 11.4 kJ According to this, the heat of formation of HI will be
(c) 28.5 kJ (d) 34.9 kJ [MP PET 1990]
(a) 12.4 kcal (b) – 12.4 kcal
47. A solution of 500ml of 0.2 M KOH and 500 ml of (c) – 6.20 kcal (d) 6.20 kcal
0.2 M HCl is mixed and stirred; the rise in temperature is T1 . 55. All reactions with chemical dissociation are [MP PMT 1990]
The experiment is repeated using 250 ml each of solution, the (a) Reversible
temperature raised is T2 . Which of the following is true[EAMCET 1987; MP PET 1994]
(b) Reversible and endothermic
(a) T1  T2 (b) T1  2T2 (c) Exothermic
(d) Reversible or irriversible and endothermic or exothermic
(c) T1  4T2 (d) T2  9T1
56. The heat of formation is the change in enthalpy accompanying the
48. Enthalpy of a compound is equal to its formation of a substance from its elements at 298 K and 1 atm
[CMC Vellore 1991] pressure. Since the enthalpies of elements are taken to be zero, the
(a) Heat of combustion (b) Heat of formation heat of formation (H ) of compounds [NCERT 1978; KCET 1993]
(c) Heat of reaction (d) Heat of solution
(a) Is always negative
 424 Thermodynamics and Thermochemistry
(b) Is always positive 65. The enthalpy of formation of ammonia is  46.0 kJ mol 1 . The
(c) May be negative or positive
enthalpy change for the reaction 2 NH 3 (g)  2 N 2 (g)  3 H 2 (g)
(d) Is zero
is
57. The heat of combustion of CH 4 (g) ,C(graphite) and H 2(g) are
(a) 46.0 kJ mol 1 (b) 92.0 kJ mol 1
20 kcal,  40 kcal and 10 kcal respectively. The heat of
(c) – 23.0 kJ mol 1 (d) – 92.0 kJ mol 1
formation of methane is [EAMCET 1998]
66. The heat of combustion of benzene determined in a bomb
(a) 4.0 kcal (b) 40 kcal
calorimeter is  870 kcal mol 1 at 25 o C . The value of E for
(c) 80 kcal (d) 80 kcal the reaction is
58. If a chemical reaction is accompanied by the evolution of heat, it is [BHU 1979] (a) 1740 kcal (b) 870 kcal
(a) Catalytic (b) Photochemical
(c) 872 kcal (d) 874 kcal
(c) Endothermic (d) Exothermic
59. A reaction that takes place with the absorption of energy is 67.
The formation of water from H 2 (g) and O 2 (g) is an exothermic
[EAMCET 1977] reaction because [MP PMT/PET 1988]
(a) Burning of a candle (b) Rusting of iron (a) The chemical energy of H 2 (g) and O 2 (g) is more than that
(c) Electrolysis of water (d) Digestion of food of water
60. Which of the following is an endothermic reaction (b) The chemical energy of H 2 (g) and O 2 (g) is less than that of
[EAMCET 1980; MP PMT 1980; water
IIT JEE 1989; JIPMER 2002] (c) Not dependent on energy
(a) 2 H 2  O 2  2 H 2 O (d) The temperature of H 2 (g) and O 2 (g) is more than that of
(b) N 2  O 2  2 NO water
68. In the reaction for the transition of carbon in the diamond form to
(c) 2 NaOH  H 2 SO 4  Na 2 SO 4  2 H 2 O carbon in the graphite form, H is 453.5 cal . This points out
(d) 3O2  C 2 H 5 OH  2CO 2  3 H 2 O that [BHU 1981; KCET 1986, 89]
(a) Graphite is chemically different from diamond
61. One of the phenomena which cannot be described as combustion is [EAMCET 1979]
(b) Graphite is as stable as diamond
(a) Oxidation of coal in air
(c) Graphite is more stable than diamond
(b) Burning of magnesium in nitrogen
(d) Diamond is more stable than graphite
(c) Reaction of antimony in chlorine
69. In the combustion of hydrocarbons, H is [BHU 1981]
(d) Lighting of an electric lamp
(a) Negative (b) Zero
62. Which of the following statements is correct about heat of
combustion [MADT Bihar 1982] (c) Positive (d) Undeterminate
(a) It may be exothermic in some cases and endothermic in other 70. The standard heats of formation in kcal mol 1 of NO 2 (g) and
cases N 2 O 4 (g) are 8.0 and 2.0 respectively. The heat of dimerization of
(b) It is applicable to gaseous substances only
NO 2 in kcal is
(c) It is always an exothermic reaction
(d) Its value does not change with temperature 2 NO 2 (g)  N 2 O4 (g) [NCERT 1983]

1 (a) 10.0 (b) – 6.0

63. H2  O 2  H 2 O; H  68.39 kcal (c) – 12.0 (d) – 14.0
2
71. The difference between heats of reaction at constant pressure and at
1 constant volume for the reaction
K  H 2 O  Water  KOH (aq)  H 2 ; H  48 kcal
2 2C6 H 6 (l)  15O2 (g)  12CO 2 (g)  6 H 2 O(l) at 25 C in kJ is
o

KOH  Water  KOH (aq); H  14 kcal [IIT JEE 1991; Kerala PMT 2004]
(a) –7.43 (b) + 3.72
The heat of formation of KOH is (in kcal) [CPMT 1988]
(c) –3.72 (d) + 7.43
(a) 68.39  48  14 (b) 68.39  48  14 72. C (diamond) C 2 (g)  CO 2 (g); H  395 kJ
(c) 68.39  48  14 (d) 68.39 + 48 + 14 C (graphite) O2 (g)  CO 2 (g); H  393.5 kJ
64. Which of the following reaction can be used to define the heat of
formation of CO 2 (g) From the data, the H when diamond is formed from graphite, is [CBSE PMT
[MP PMT 1989; MH CET 2001] (a) 1.5 kJ (b)  1.5 kJ
(a) C(graphite) O2 (g)  CO 2 (g) (c)  3.0 kJ (d) 3.0 kJ
(b) CH 4 (g)  2O2 (g)  CO 2 (g)  2 H 2 O(l) 73. Which of the following values of heat of formation indicates that the
product is least stable [MP PMT 1991]
1 (a) 94 kcal (b)  231.6 kcal
(c) CO (g)  O 2 (g)  CO 2 (g)
2
(c) 21.4 kcal (d)  64.8 kcal
1
(d) C 6 H 6 (l)  7 O 2 (g)  6 CO 2  3 H 2 O(l) 74. Which of the following equations correctly represents the standard
2
heat of formation (H of ) of methane
 Thermodynamics and Thermochemistry 425
[IIT JEE (Screening) 1992] (d) H is always positive
(a) C(diamond)  2 H 2 (g)  CH 4 (g) 81. The energy evolved is highest for which of the following reactions [MP PET 1994]
(b) C(graphite)  2 H 2 (g)  CH 4 (l) (a) F  e   F 1 (b) Cl  e   Cl 
(c) C(graphite)  2 H 2 (g)  CH 4 (g) (c) S  2e   S 2  (d) O  2e   O 2
(d) C(graphite)  4 H  CH 4 (g) 82. In the combustion of 2.0 gm of methane 25 kcal heat is
75. In which of the following reactions does the heat change represent liberated, heat of combustion of methane would be
the heat of formation of water [EAMCET 1991] [MP PMT 1994]
(a) 2 H 2 (g)  O2 (g)  2 H 2 O(l); H  116 kcal (a) 100 kcal (b) 200 kcal
1 (c) 300 kcal (d) 400 kcal
(b) H 2 (g)  O 2 (g)  H 2 O(l); H  58 kcal
2 83. Complete combustion of CH 4 gives [BHU 1995]
(c) H  (aq.)  OH  (aq.)  2 H 2 O(l); H  13.7 kcal (a) CO 2  H 2 O (b) CO 2  H 2
1
(d) C 2 H 2 (g)  2 O 2 (g)  2CO 2 (g)  H 2 O(l) ; (c) COCl 2 (d) CO  CO 2  H 2 O
2
84. If enthalpies of formation of C 2 H 4 (g), CO 2 (g) and H 2 O(l) at
H  310 kcal
25 o C and 1 atm pressure be 52, – 394 and  286 kJ mol 1
76. Values of heats of formation for SiO2 and MgO are 48.4 and
respectively, the enthalpy of combustion of C 2 H 4 (g) will be
34.7 kJ respectively. The heat of the reaction
[CBSE PMT 1995; AIIMS 1998; Pb. PMT 1999]
2 Mg  SiO2  2 MgO  Si is [KCET 1990]
1
(a)  1412 kJ mol (b)  1412 kJ mol 1
(a) 21.16 kJ (b) 21.10 kJ
(c) 13.62 kJ (d) 13.6 kJ (c)  141.2 kJ mol 1 (d)  141.2 kJ mol 1
85. Carbon and carbon monoxide burn in oxygen to form carbon
77. Based on the following thermochemical equations
dioxide according to the following reactions
H 2 O(g)  C(s)  CO(g)  H 2 (g); H  131 kJ
C  O 2  CO 2 ; H  394 kJ mol 1
1
CO (g)  O 2 (g)  CO 2 (g); H  282 kJ 2CO  O 2  2CO 2 ; H  569 kJ mol 1
2
1 The heat of formation of 1 mol of carbon monoxide is thus
H 2 (g)  O 2 (g)  H 2 O(g); H  242 kJ
2 [MP PET 1995]
1
C(s)  O2 (g)  CO 2 (g); H  X kJ (a)  219.0 kJ mol (b)  109.5 kJ mol 1
The value of X is [CBSE PMT 1992] (c)  175.0 kJ mol 1 (d)  87.5 kJ mol 1
(a) 393 kJ (b)  655 kJ 86. Heat of formation in the reaction
(c)  393 kJ (d) 655 kJ H 2  Cl 2  2 HCl  44 kcal is [MP PMT 1995]
78. Heat of transition is the heat evolved or absorbed when a substance (a) 44 kcal (b) 44000 kcal
is converted from [KCET 1984] (c) 22 kcal (d) 11 kcal
(a) Solid to liquid 87. When water is added to quick lime, the reaction is
(b) Solid to vapour [MP PMT 1995]
(c) Liquid to vapour (a) Exothermic (b) Endothermic
(d) One allotropic form to another allotropic form (c) Explosive (d) None of these
79. For the allotropic change represented by equation 88. In an exothermic reaction H is
C(diamond)  C(graphite) ; the enthalpy change is [MP PMT 1995; CPMT 1999]
H  1.89 kJ . If 6 g of diamond and 6 g of graphite are (a) Positive (b) Negative
separately burnt to yield carbon dioxide, the heat liberated in the (c) Zero (d) Both positive or negative
first case is [KCET 1988; DPMT 2000]
89. The heat change for the following reaction C(s)  2S (s)  CS 2 (l)
(a) Less than in the second case by 1.89 kJ
is known as [MP PMT 1996]
(b) More than in the second case by 1.89 kJ (a) Heat of vaporization (b) Heat of solution
(c) Less than in the second case by 11.34 kJ (c) Heat of fusion (d) Heat of formation
90. The enthalpy of combustion of benzene from the following data will
(d) More than in the second case by 0.945 kJ be
80. For an exothermic reaction (i) 6C(s)  3 H 2 (g)  C6 H 6 (l); H  45.9 kJ
[MP PET 1994; Manipal MEE 1995]
1
(a) H of the products is less than H of the reactants (ii) H 2 (g)  O 2 (g)  H 2 O(l); H  285.9 kJ
2
(b) H of the products is more than H of the reactants
(c) H of the products is equal to H of the reactants (iii) C(s)  O2 (g)  CO 2 (g); H  393.5 kJ
 426 Thermodynamics and Thermochemistry
(a) + 3172.8 kJ (b) – 1549.2 kJ 99. The values of heat of formation of SO 2 and SO 3 are 298.2 kJ
(c) – 3172.8 kJ (d) – 3264.6 kJ and 98.2 kJ . The heat of reaction of the following reaction will
91. Enthalpy of formation of HF and HCl are  161 kJ and be
 92 kJ respectively. Which of the following statements is incorrect[KCET 2003] 1
SO 2  O2  SO 3 [BHU 1997; CBSE PMT 2000]
(a) HCl is more stable than HF 2
(b) HF and HCl are exothermic compounds (a) 200 kJ (b) 356.2 kJ
(c) The affinity of fluorine to hydrogen is greater than the affinity (c) 200 kJ (d) 396.2 kJ
of chlorine to hydrogen
100. Calculate the standard heat of formation of carbon disulphide (l) ,
(d) HF is more stable than HCl
given that the standard heat of combustion of carbon (s) , sulphur
92. The heat of reaction at constant pressure is given by
(s) and carbon disulphide (l) are 393.3,  293.72 and
[MP PMT 1997]
(a) EP  ER (b) ER  EP  1108.76 kJ mol 1 respectively
[Roorkee 1989; BHU 1997]
(c) HP  HR (d) HR  HP 1
(a)  128.02 kJ mol (b)  12.802 kJ mol 1
93. In an endothermic reaction, the value of H is
[CBSE PMT 1999; AIIMS 1998; BHU 2000; MP PMT 2000] (c)  128.02 kJ mol 1 (d)  12.802 kJ mol 1
(a) Zero (b) Positive 101. Fermentation is a reaction called [RPMT 1997]
(c) Negative (d) Constant (a) Endothermic (b) Exothermic
(c) Isotemperature (d) Reversible
94. 2.2016 gm of acetaldehyde produced 13.95 kcal of heat on
102. 8 gm of CH 4 is completely burnt in air. The number of moles of
combustion in O 2 . Calculate the heat of combustion of
water produced are [Orissa JEE 1997]
CH 3 CHO [Bihar CEE 1995]
(a) 0.5 (b) 1
(a) 279 kcal (b) 972 kcal (c) 2 (d) 18
(c) 27.9 kcal (d) 2.79 kcal 103. For the reaction A(g)  2 B(g)  2C(g)  3 D(g) , the value of
1 E at 27 o C is 19.0 kcal. The value of H for the reaction
95. C O 2  CO ; H  42 kJ
2 would be (R  2.0 cal K 1mol 1 )
1 [Roorkee Qualifying 1998]
CO  O 2  CO 2 ; H  24 kJ
2 (a) 20.8 kcal (b) 19.8 kcal
(c) 18.8 kcal (d) 20.2 kcal
The heat of formation of CO 2 is [CPMT 1996]
104. The enthalpy of solution of BaCl2 (s) and BaCl2 .2 H 2 O(s) are
(a) – 16 kJ (b) + 66 kJ
(c) + 16 kJ (d) – 66 kJ 20.6 and 8.8 kJ mol 1 respectively. The enthalpy change for
96. Standard molar enthalpy of formation of CO 2 is equal to the reaction BaCl2 (s)  2 H 2O  is
[IIT JEE 1997; BHU 2001] [Roorkee Qualifying 1998]
(a) Zero (a) 29.4 kJ (b) – 11.8 kJ
(b) The standard molar enthalpy of combustion of gaseous carbon (c) – 20.6 kJ (d) – 29.4 kJ
(c) The sum of standard molar enthalpies of formation of CO 105. The enthalpy change of a reaction does not depend on
and O 2 [AIIMS 1997]
(a) The state of reactants and products
(d) The standard molar enthalpy of combustion of carbon
(graphite) (b) Nature of reactants and products
(c) Different intermediate reaction
97. In the complete combustion of butanol C4 H 9 OH(l) , if H is
(d) Initial and final enthalpy change of a reaction
enthalpy of combustion and E is the heat of combustion at
constant volume, then [EAMCET 1997] 3
106. S O2  SO 3  2 x kcal
(a) H  E 2
(b) H  E 1
SO 2  O 2  SO 3  y kcal
(c) H  E 2
(d) H , E relation cannot be predicted Find out the heat of formation of SO 2
98. C  O2  CO 2 ; H  X [AIIMS 1997; CBSE PMT 1999; KCET 1999]
(a) 2x  y (b) 2x  y
1
CO  O2  CO 2 ; H  Y
2 (c) x  y (d) 2 x / y
Then the heat of formation of CO is 107. The combustion enthalpies of carbon, hydrogen and methane are
[BHU 1997; DPMT 2002]  395.5 kJ mol 1 ,  285.8 kJ mol 1 and  890.4 kJ mol 1
(a) X Y (b) Y  2X respectively at 25 o C . The value of standard formation enthalpies
(c) X Y (d) 2X  Y of methane at that temperature is [Pb. PMT 1998]
 Thermodynamics and Thermochemistry 427

(a) 890.4 kJ mol 1 (b)  298.8 kJ mol 1 The molar enthalpy of vaporisation of water at 1 atm and 25 o C is
44 kJ. The standard enthalpy of formation of 1 mole of water vapour
(c)  74.7 kJ mol 1 (d)  107.7 kJ mol 1 at 25 o C is [KCET 1999]
108. Equal volumes of methanoic acid and sodium hydroxide are mixed. If (a) – 241.8 kJ (b) 241.8 kJ
x is the heat of formation of water, then heat evolved on (c) 329.8 kJ (d) –329.8 kJ
neutralisation is [BHU 1998] 117. When 4 g of iron is burnt to ferric oxide at constant pressure, 29.28
(a) More than x (b) Equal to x kJ of heat is evolved. What is the enthalpy of formation of ferric
(c) Twice of x (d) Less than x oxide (At. Wt. of Fe = 56)
109. The neutralisation of a strong acid by a strong base liberates an [AIIMS 1999]
(a) – 81.98 kJ (b) – 819.8 kJ
amount of energy per mole of H  that [BHU 1998]
(c) – 40.99 kJ (d) + 819.8 kJ
(a) Depends upon which acid and base are involved
118. When a strong acid, strong base or their salt are dissolved in water,
(b) Depends upon the temperature at which the reaction takes they are completely ionised. If a strong acid is added to a strong
place
base, H  ions from the former combine with OH  ions of the
(c) Depends upon which catalyst is used latter forming water. The formation of each water molecule liberates
(d) Is always the same a certain quantity of energy and the reaction is exothermic. The heat
110. When 0 .5 g of sulphur is burnt to SO 2 , 4.6 kJ of heat is liberated when one mole of water is formed by combining
hydrochloric acid and sodium hydroxide is 13.7 kcal. The heat
liberated. What is the enthalpy of formation of sulphur dioxide[KCET 1998; AFMC 2001]
liberated when one mole of water is formed by combining sulphuric
(a) + 147.2 kJ (b) – 147.2 kJ acid and sodium hydroxide is [AMU (Engg.) 1999]
(c) – 294.4 kJ (d) + 294.4 kJ (a) 25.5 kcal (b) 8.5 kcal
111. Ozone is prepared by passing silent electric discharge through (c) 13.7 kcal (d) 34 kcal
oxygen. In this reaction [AFMC 1998]
119. 2.1 g of Fe combines with S evolving 3.77 kJ. The heat of formation
(a) Energy is given out of FeS in kJ/mol is [AMU (Engg.) 1999]
(b) Energy is absorbed (a) – 1.79 (b) – 100.5
(c) Oxygen is loaded with energy (c) – 3.77 (d) None of these
(d) Oxygen is dissociated into atoms
120. In the reaction: H 2  Cl 2  2 HCl, H  194 kJ . Heat of
112. Combustion of glucose takes place according to the equation,
C 6 H 12 O6  6 O 2  6CO 2  6 H 2 O , H  72 kcal . How formation of HCl is [KCET 2000; AFMC 2000; CPMT 2000]

much energy will be required for the production of 1.6 g of glucose (a) + 97 kJ (b) + 194 kJ
(Molecular mass of glucose = 180 g) [AFMC 1999] (c) – 194 kJ (d) – 97 kJ
(a) 0.064 kcal (b) 0.64 kcal 121. Enthalpy of neutralisation of acetic acid by NaOH is
(c) 6.4 kcal (d) 64 kcal 50.6 kJ / mol. and the heat of neutralisation of a strong acid
113. Given that
with a strong base is – 55.9 kJ/mol. What is the value of H for
C(s)  O 2 (g)  CO 2 (g), H  394kJ the ionisation of CH COOH [AIIMS 2000]
3
2 H 2 (g)  O 2 (g)  2 H 2 O(l), H  568kJ (a) + 5.3 kJ/mol (b) + 6.2 kJ/mol
CH 4 (g)  2O 2 (g)  CO 2 (g)  2 H 2 O(l) H  892 kJ (c) + 8.2 kJ/mol (d) + 9.3 kJ/mol
Heat of formation of CH 4 is [DCE 1999] 122. Heat of neutralization of the acid-base reaction is 57.32 kJ for [JIPMER 2000]
(a) – 70 kJ (b) 71.8 kJ (a) HNO 3  LiOH (b) HCOOH  KOH
(c) – 244 kJ (d) + 782 kJ (c) HCl  NH 4 OH (d) CH 3 COOH  NaOH
114. Calculate the heat of formation of PCl5 (s) from the following data
123. The heat change for the following reaction at 298 o K and at
2 P(s)  3Cl 2 (g)  2 PCl3 (l); H  151.8 kcal
constant pressure is 7.3 kcal
PCl3 (l)  Cl 2 (g)  PCl5 (s); H  32.8 kcal
A 2 B(s)  2 A(s)  1 / 2 B 2 (g) , H  7.3 kcal
[JIPMER 1999]
(a) – 108.7 kcal (b) + 108.7 kcal The heat change at constant volume would be
(c) – 184.6 kcal (d) + 184.6 kcal [DCE 2000]
115. When 50 cm 3
of a strong acid is added to 50 cm 3
of an alkali, (a) 7.3 kcal (b) More than 7.3
o 3 (c) Zero (d) None of these
the temperature rises by 5 C . If 250 cm of each liquid are
124. The heat evolved in the combustion of benzene is given by the
mixed, the temperature rise would be equation
[KCET 1999]
1
(a) o
5 C (b) 10 C o
C6 H 6 (l)  7 O2 (g)  3 H 2 O(l)  6 CO 2 (g)
2
(c) 25 o C (d) 20 o C
1 H  781.0 kcal mol 1
116. H 2 (g)  O2 (g)  H 2O(l) ;
2 Which of the following quantities of heat energy will be evolved
when 39 g of benzene is burnt in an open container
H at 298 K = – 285.8 kJ
[MP PET 2000]
1
(a) 122.25 kcal mol (b) 390.5 kcal mol 1
 428 Thermodynamics and Thermochemistry

(c) 1562.0 kcal mol 1 (d) 586.75 kcal mol 1 134. If the heat of combustion of carbon monoxide at constant volume and at
17 o C is – 283.3 kJ, then its heat of combustion at constant
125. H 2 (g)  Cl 2 (g)  2 HCl(g). H  44 kcal
pressure (R  8.314 J degree -1 mol 1 ) [CPMT 2001]
2 Na(s)  2 HCl(g)  2 NaCl(s)  H 2 (g), H  152 kcal
(a) – 284.5 kJ (b) 284.5 kJ
1 (c) 384.5 kJ (d) – 384.5 kJ
For the reaction Na(s)  Cl 2 (g)  NaCl(s), H 
2 135. Heat of formation of H 2 O is 188 kJ / mole and H 2 O 2 is
[KCET 2000] 286 kJ / mole. The enthalpy change for the reaction
(a) – 108 kcal (b) – 196 kcal 2 H 2 O 2  2 H 2 O  O 2 is [BHU 2001]
(c) – 98 kcal (d) 54 kcal
(a) 196 kJ (b) – 196 kJ
126. The H of for CO 2 (g), CO(g) and H 2 O(g) are – 393.5, – (c) 984 kJ (d) – 984 kJ
110.5 and – 241.8kJmol respectively. The standard enthalpy change (in
–1

136. The values of H for the combustion of ethene and ethyne are –
kJ) for the reaction CO 2 (g)  H 2 (g)  CO(g)  H 2O(g) is[IIT JEE (Screening) 2000]
341.1 and – 310.0kcal respectively. Which of the following is a better
(a) 524.1 (b) 41.2 fuel [BHU 2001]
(c) – 262.5 (d) – 41.2 (a) C 2 H 2 (b) C 2 H 4

127. Which of the following compounds will absorb the maximum (c) Both of these (d) None of these
quantity of heat when dissolved in the same amount of water ? The 137. For exothermic reaction, the equilibrium constant
heats of solution of these compounds at 25 o C in kJ/mole of each [JIPMER 2001]
solute is given in brackets [AMU (Engg.) 2000] (a) Increases with increase of P
(a) HNO 3 (H  33) (b) KCl(H  17.64) (b) Decreases with increase of P
(c) Increases with increase of temperature
(c) NH 4 NO 3 (H  25.5) (d) HCl (H  74.1) (d) Decreases with increase of temperature
128. In the reaction C  2S  CS 2  H , H is the 138. In order to decompose 9 g water 142.5 kJ heat is required. Hence the
enthalpy of formation of water is [KCET 2001]
[AMU (Engg.) 2000]
(a) – 142.5 kJ (b) + 142.5 kJ
(a) Heat of combustion (b) Heat of neutralisation
(c) – 285 kJ (d) + 285 kJ
(c) Heat of solution (d) None of these
139. What is n for combustion of 1 mole of benzene, when both the
129. The heat of formation of methane C(s)  2 H 2 (g)  CH 4 (g) at
reactants and the products are gas at 298 K
constant pressure is 18500 cal at 25 o C . The heat of reaction at [Pb. PMT 2001]
constant volume would be [MH CET 2000] (a) 0 (b) 3/2
(a) 17904 cal (b) 18202 cal (c) – 3/2 (d) 1/2
(c) 18798 cal (d) 19096 cal 140. If C  O2  CO 2  94.2 kcal
130. The enthalpy of combustion of C 6 H 6(l) is – 3250 kJ. When
1
0.39 g of benzene is burnt excess of oxygen in an open vessel, the H2  O 2  H 2 O  68.3 kcal
amount of heat evolved is 2
[KCET 2000; AFMC 2000; DCE 2000] CH 4  2O 2  CO 2  2 H 2 O  210.8 kcal
(a) 16.25 J (b) 16.25 kJ Then the possible heat of methane will be [UPSEAT 2001]
(c) 32.5 J (d) 32.5 kJ (a) 47.3 kcal (b) 20.0 kcal
131. C(s)  O 2 (g)  CO 2 ; H  94 kcal (c) 45.9 kcal (d) – 47.3 kcal
1 141. Heat of neutralization of strong acid and weak base is
CO (g)  O 2 (g)  CO 2 ; H  135.2 kcal [UPSEAT 2001]
2
(a) 57.1 kJ mol 1
Then heat of formation of CO (g) is [DCE 2001]
(a) – 26.4 kcal (b) 41.2 kcal (b) 13.7 kJ mol 1
(c) 26.4 kcal (d) – 229.2 kcal (c) Less than 13.7 kcal mol 1
132. The heat of neutralization of HCl and NaOH is
[MP PET 2001] (d) More than 13.7 kcal mol 1
(a) Zero (b) – 57.3 kJ 142. A system is changed from state A to state B by one path and from B
(c) + 57.3 kJ (d) None of these to A another path. If E1 and E 2 are the corresponding changes in
133. The following thermochemical reactions are given internal energy, then
1 [Pb. PMT 2001]
M O 2  MO  351.4 kJ (a) E1  E 2  ve (b) E1  E 2  ve
2
1 (c) E1  E 2  0 (d) None of these
X O 2  XO  90.8 kJ
2 143. The heat evolved during the combination of 24 g C and 128 g S
It follows that the heat of reaction for the following process following the change is
M  XO ⇌ MO  X is given by [AMU 2001] C  S 2  CS 2 ; H  22.0 kcal [MH CET 2001]
(a) 422.2 kJ (b) 268.7 kJ (a) 11 kcal (b) 32 kcal
(c) – 442.2 kJ (d) 260.6 kJ (c) 44 kcal (d) 22 kcal
 Thermodynamics and Thermochemistry 429
144. When the aqueous solution of 0.5 mole HNO 3 is mixed with the 1
(d) CO (g)  O 2 (g)  CO 2 (g)
0.3 mole of OH  solution, then what will be the liberated heat 2
(Enthalpy of neutralization is = 57.1 kJ) 154. On combustion, carbon forms two oxides CO and CO 2 , Heat of
[Kerala CET 2005]
formation of CO 2 gas is 94.3 kcal and that of CO is 26.0 kcal.
(a) 28.5 kJ (b) 17.1 kJ
Heat of combustion of carbon is [JIPMER 2002]
(c) 45.7 kJ (d) 1.7 kJ
(a) 26.0 kcal (b) – 94.3 kcal
(e) 2.85 kJ
145. A cylinder of gas is assumed to contain 11.2 kg of butane (C 4 H 10 ) . If (c) 68.3 kcal (d) – 120.3 kcal
a normal family needs 20000 kJ of energy per day. The cylinder will 155. 1 mole of conc. HCl requires X moles of dilute NaOH for
last: (Given that H for combustion of butane is – 2658 kJ)[AMU (Engg.) 2002] neutralisation and 1 mole of concentrate H 2 SO 4 requires Y moles
(a) 20 days (b) 25 days of small dilute NaOH then which of the following reaction is true [MH CET 2
(c) 26 days (d) 24 days 1 1
146. Compounds with high heat of formation are less stable because [KCET 2002] (a) Y  X (b) X  Y
2 2
(a) High temperature is required to synthesise them
(b) Molecules of such compounds are distorted (c) X  2Y (d) None of these
(c) It is difficult to synthesis them
156. Which of the reaction defines H of
(d) Energy rich state leads to instability
147. The heat evolved in the combustion of methane is given by the [IIT -JEE (Screening) 2003]
following equations:
(a) C(diamond )  O 2 (g)  CO 2 (g)
CH 4 (g)  2O 2 (g)  CO 2 (g)  H 2 O(l); H  890.3 kJ
How many grams of methane would be required to produce 445.15 1 1
(b) H 2 (g)  F2 (g)  HF(g)
kJ of heat of combustion [AMU 2002] 2 2
(a) 4 g (b) 8 g
(c) N 2 (g)  3 H 2 (g)  2 NH 3 (g)
(c) 12 g (d) 16 g
148. Heats of combustion (H o ) for C(s), H 2 (g) and CH 4 (g) are (d) CO (g) 
1
O 2 (g)  CO 2 (g)
2
94,  68 and 213 kcal / mol. respectively. The value of H o

for the reaction, 157. One gram sample of NH 4 NO 3 is decomposed in a bomb

C(s)  2 H 2 (g)  CH 4 (g) is [CBSE PMT 2002] calorimeter. The temperature of the calorimeter increases by 6.12 K
the heat capacity of the system is 1.23 kJ/g/deg. What is the molar
(a) – 85 kcal (b) – 111 kcal
heat of decomposition for NH 4 NO 3
(c) – 17 kcal (d) – 170 kcal
149. If the value of H in a reaction is positive, then the reaction is [AIIMS 2003]
called [BHU 2002] (a) – 7.53 kJ/mol (b) – 398.1 kJ/mol
(a) Exothermic (b) Endothermic (c) – 16.1 kJ/mol (d) – 602 kJ/mol
(c) Polymorphic (d) Polytropic
158. For which one of the following equations is H react
o
equal to H of
150. Enthalpy of neutralisation of NH 4 OH and HCl , is numerically
for the product [CBSE PMT 2003]
[JIPMER 2002; Kurukshetra CEE 2002]
(a) 2CO(g)  O 2 (g)  2CO 2 (g)
(a) 57.1 kJ mol 1 (b)  57.1 kJ mol 1
(b) N 2 (g)  O 3 (g)  N 2 O 3 (g)
(c)  57.1 kJ mol 1 (d) Zero
151. The heat of neutralisation will be highest in [MP PMT 2002] (c) CH 4 (g)  2Cl 2 (g)  CH 2 Cl 2 (l)  2 HCl(g)
(a) NH 4 OH and CH 3 COOH (d) Xe(g)  2 F2 (g)  XeF4 (g)
(b) NH 4 OH and HCl 159. Enthalpy change for a reaction does not depend upon
(c) KOH and CH 3 COOH [AIEEE 2003]
(d) KOH and HCl (a) The physical states of reactants and products
152. If a mole of H 2 molecule is heated to high temperature the (b) Use of different reactants for the same product
following reaction takes place [Kerala (Med.) 2002] (c) The nature of intermediate reaction steps
(a) H 2 (g)  436 kJ  H(g)  H (g) (d) The differences in initial or final temperatures of involved
substances
(b) H 2 (g)  820 kJ  2 H 2 (g)
160. Cdia + O 2  CO 2 ; H  395.3 kJ / mole
(c) 2 H 2 (g)  436 J  2 H 2
(d) H 2  H 2  H   H  C gr  O 2  CO 2 ; H  393.4 kJ / mole
153. Which of the following reactions is not exothermic C gr  C dia ; H  [BHU 2003]
[MP PET 2002]
(a) C(s)  O 2 (g)  CO 2 (g) (a) – 3.8 (b) – 1.9
(c) + 3.8 (d) + 1.9
(b) C(s)  2S (s)  CS 2 (g)
161. What is the weight of oxygen that is required for the complete
(c) CH 4 (g)  2O 2 (g)  CO 2 (g)  2 H 2 O(l) combustion of 2.8 kg of ethylene? [BVP 2003]
 430 Thermodynamics and Thermochemistry
(a) 9.6 kg (b) 96.0 kg (c) – 35.5 kJ (d) – 20.0 kJ
(c) 6.4 kg (d) 2.8 kg 3
171. Given : 2 Fe  O2  Fe2O3 , H  193.4 kJ ;
162. For complete neutralization of HCl with NaOH , the heat of 2
neutralization is [MP PET 2003]
1
Mg  O2  MgO, H  140.2 kJ
(a)  13.70 kJ mol 1 (b)  13.70 kJ mol 1 2
(c)  57.32 kJ mol 1 (d)  57.32 kJ mol 1 What is the H of the reaction
Mg  Fe2O3  3 MgO  2 Fe [Orissa JEE 2005]
163. The heat of combustion of carbon to CO 2 is 393.5 kJ / mol .
(a) – 1802 kJ (b) +1802 kJ
The heat released upon formation of 35.2 g of CO 2 from carbon
and oxygen gas is [UPSEAT 2004]
(c) – 800 kJ (d) + 228 kJ

(a)  315 kJ (b)  31.5 kJ 172. The enthalpy change (H ) for the neutralisation of 1M HCl by
caustic potash in dilute solution at 298 K is
(c) 315 kJ (d) 31.5 kJ [DPMT 2005]
164. Which of the following equations correctly represents the standard (a) 68 kJ (b) 65 kJ
heat of formation (H of ) of methane (c) 57.3 kJ (d) 50 kJ
[UPSEAT 2004]
(a) C (diamond) 4 H(g)  CH 4 (g) Bond energy
(b) C (diamond) 2 H 2 (g)  CH 4 (g)
1. If the bond dissociation energies of XY , X 2 and Y 2 (all diatomic
(c) C (graphite) 2 H 2 (g)  CH 4 (g)
molecules) are in the ratio of 1 : 1 : 0.5 and  f H for the formation
(d) C (graphite) 4 H(g)  CH 4 (g) of XY is  200 kJ mole 1 . The bond dissociation energy of X 2
165. If the heat of formation of CO 2 is 393 kJ . The amount of heat will be [AIEEE 2005]
evolved in the formation of 0.156 kg of CO 2 is (a) 100 kJ mol 1 (b) 800 kJ mol 1
[MH CET 2004] (c) 300 kJ mol 1 (d) 400 kJ mol 1
(a) 1357.9 kJ (b) 1275.9 kJ 2. Energy required to dissociate 4 gm of gaseous hydrogen into free
(c) 1572.0 kJ (d) 1165.5 kJ gaseous atoms is 208 kcal at 25 o C . The bond energy of H  H
bond will be
166. Which of the following pairs has heat of neutralisation equal to 13.7
[CPMT 1989; MP PET 2000; J & K 2005]
Kcals [DCE 2003]
(a) 104 kcal (b) 10.4 kcal
(a) HCl, NH 4 OH (b) HNO3 , KOH (c) 1040 kcal (d) 104 cal
(c) NaOH, CH 3 COOH (d) H 2 SO 4 , NH 4 OH 3. The bond dissociation energy needed to form benzyl radical from
toluene is ..... than the formation of the methyl radical from methane[IIT 1994]
167. The enthalpies of combustion of carbon and carbon monodie are – (a) Less (b) Much
393.5 and –283 kJ mol respectivley. The enthalpy of formation of
–1

carbon monoxide per mole is (c) Equal (d) None of the above
[AIEEE 2004] 4. Which one of the following bonds has the highest average bond
energy (kcal/mol) [CPMT 1994]
(a) 676.5 kJ (b) 676.5 kJ
(a) S  O (b) C  C
(c) 110.5 kJ (d) 110.5 kJ (c) C  N (d) N  N
5. The bond dissociation energies of gaseous H 2 ,Cl 2 and HCl are
168. The enthalpy of combustion of methane at 25 o C is 890 kJ . The
104, 58 and 103 kcal respectively. The enthalpy of formation of
heat liberated when 3 .2 g of methane is burnt in air is [KCET 2004] HCl gas would be
(a) 445 kJ (b) 278 kJ [MP PET 1997; MP PMT 1999, 2001]
(a) – 44 kcal (b) 44 kcal
(c) 890 kJ (d) 178 kJ
(c) – 22 kcal (d) 22 kcal
169. If (i) C  O2  CO 2 , (ii) C  1 / 2O2  CO , (iii) 6. The first ionization energy for Li is 5.4 eV and electron affinity of Cl
CO  1 / 2O2  CO 2 , the heats of reaction are Q,  12,  10 is 3.61eV. The H (in kJ/mol) for the reaction
respectively. Then Q  [Orissa JEE 2004] Li(g)  Cl(g)  Li   Cl  is (if resulting ions do not combine with
(a) – 2 (b) 2 each other) (1 eV  1.6  10 19 J ) [MP PMT 2000, 03]
(c) – 22 (d) – 16 (a) 70 (b) 100
170. How much energy is released when 6 mole of octane is burnt in air (c) 170 (d) 270
? Given H of for CO 2 (g), H 2O(g) and C8 H18 (l) respectively 7. Given that C(g)  4 H(g)  CH 4 (g); H  166 kJ
are – 490,– 240 and + 160 kJ/mol The bond energy C  H will be [AMU 2002]
[AIIMS 2004]
(a) 208 kJ/mole
(a) – 6.2 kJ (b) – 37.4 kJ (b) – 41.6 kJ/mole
 Thermodynamics and Thermochemistry 431
(c) 832 kJ/mole (a) H for the reaction is zero
(d) None of these (b) G for the reaction is zero
8. The H  H bond energy is 430 kJ mol and Cl  Cl bond (c) G for the reaction is negative
energy is 240 kJ mol 1 . H for HCl is 90 kJ . The H  Cl
(d) [G]  [H ]
bond energy is about [BVP 2003]
8. At constant pressure and temperature, the direction to the result of
(a) 180 kJ mol 1 (b) 360 kJ mol 1 any chemical reaction is where, there is less amount of
(a) Entropy (b) Enthalpy
(c) 213 kJ mol 1 (d) 425 kJ mol 1
(c) Gibb's free energy (d) None of the above
9. If enthalpies of methane and ethane are respectively 320 and 360
9. The dependence of Gibbs free energy on pressure for an isothermal
calories then the bond energy of C  C bond is process of an ideal gas is given by
[UPSEAT 2003] [MP PET 1996]
(a) 80 calories (b) 40 calories
P V2
(c) 60 calories (d) 120 calories (a) GT  nRT ln 2 (b) GT  nRT ln
P1 V1
10. If the bond energies of H  H , Br  Br and HBr are 433, 192
and 364 kJ mol 1 respectively, the H o for the reaction, (c) GT  nRT log
P1
(d) GT  nRT log
V2
H 2 (g)  Br2 (g)  2 HBr(g) is [CBSE PMT 2004] P2 V1
(a) + 261 kJ (b) – 103 kJ 10. For the change H 2 O(l)  H 2 O(g); P  1 atm , T  373 K , the
(c) – 261 kJ (d) + 103 kJ free energy change G  0 . This indicates that
(a) H 2 O(l) is in equilibrium with H 2 O(g)
Free energy and Work function
(b) Water boils spontaneously at 373 K
1. The free energy change for a reversible reaction at equilibrium is
(c) Water does not boil spontaneously at 373 K
[NCERT 1984; Kurukshetra CEE 1998; AMU 1999]
(a) Large positive (b) Small negative (d) Condensation of water vapour occurs spontaneously at 373 K
(c) Small positive (d) 0
2. For a spontaneous change, free energy change G is 11. What is the free energy change G when 1.0 mole of water at
[MNR 1983; BHU 1981, 95; AMU 1999; 100 o C and 1 atm pressure is converted into steam at 100 o C
DCE 2000, 01; BHU 2000; MP PMT 2003]
(a) Positive and 1 atm pressure [MP PET/PMT 1998]
(b) Negative (a) 540 cal (b) 9800 cal
(c) Zero
(d) Can be positive or negative (c) 9800 cal (d) 0 cal
3. A minus sign of the free energy change denotes that
(a) The reaction tends to proceed spontaneously 12. G o for the reaction X  Y ⇌ Z is – 4.606 kcal . The value of
(b) The reaction is non-spontaneous equilibrium constant of the reaction at 227 o C is
(c) The system is in equilibrium (R  2.0 cal. mol 1 K 1 ) [Roorkee 1999]
(d) The reaction is very much unlikely
(a) 100 (b) 10
4. The relation between G and H is
[MP PMT 1994, 95, 97; AFMC 1997; (c) 2 (d) 0.01
Kurukshetra CEE 1998] 13. The standard enthalpy of the decomposition of N 2 O 4 to NO 2 is
(a) H  G  T S (b) G  H  T S 58.04 kJ and standard entropy of this reaction is 176.7 J/K. The
(c) T S  G  H (d) H  T G  S standard free energy change for this reaction at 25 o C is [AIIMS 1999]
(a) 539 kJ (b) – 539 kJ
5. At 300 K, the reactions which have following values of
thermodynamic parameters occur spontaneously (c) – 5.39 kJ (d) 5.39 kJ
[Roorkee 1999] 14. Spontaneity of a chemical reaction is decided by the negative change
in [MP PET 2001]
(a) G o  400 kJ mol 1 (a) Internal energy (b) Enthalpy
(c) Entropy (d) Free energy
(b) H o  200 kJ mol 1 , S o  4 JK 1 mol 1
15. For a reaction at 25 o C enthalpy change and entropy changes are
1 1 1
(c) H o
 200 kJ mol , S o
 4 JK mol  11.7  10 3 J mol 1 and  105 J mol 1 K 1 respectively. What
(d) H o 1
 200 J mol , S o
 40 JK 1 mol 1 is the Gibbs free energy [BHU 2001]
(a) 15.05 kJ (b) 19.59 kJ
6. The relation G  H  TS was given by (c) 2.55 kJ (d) 22.55 kJ
[MP PMT 2000; KCET 2002] 16. Born-Haber cycle is used to determine [UPSEAT 2001]
(a) Boltzmann (b) Faraday (a) Crystal energy (b) Electron affinity
(c) Gibbs–Helmholtz (d) Thomson (c) Lattice energy (d) All of these
17. Gibbs free energy G, enthalpy H and entropy S are interrelated as in
7. For precipitation reaction of Ag  ions with NaCl , which of the [MP PMT 2002]
following statements is correct [CPMT 1988]
(a) G  H  TS (b) G  H  TS
 432 Thermodynamics and Thermochemistry
(c) G  TS  H (d) G  S  H [CBSE PMT 2004]
1
18. The essential condition for the feasibility of a reaction is that (a) – 439.3 kJ mol (b) – 523.2 kJ mol 1
[JIPMER 2002]
(a) The reaction should be exothermic (c) – 221.1 kJ mol 1 (d) – 339.3 kJ mol 1
(b) The entropy of products must be larger than that of reactants 26. For spontaneity of a cell, which is correct
(c) The reaction is to be accompanied with free energy decrease [Orissa JEE 2004]
(d) The reaction has to possess high activation energy (a) G  0, E  0
19. The correct relationship between free energy change in a reaction
and the corresponding equilibrium constant K c is (b) G  ve , E  0

[AIEEE 2003] (c) G  ve , E  ve

(a) G  RT ln Kc (b) G  RT ln Kc (d) G  ve , E  ve
(c) G  RT ln Kc
o
(d)  G  RT ln Kc
o
27. The free energy for a reaction having H  31400 ca; .
1 1
20. In an irreversible process taking place at constant T and P and in S  32 cal K mol o
at 1000 C is [Orissa JEE 2005]
which only pressure-volume work is being done, the change in Gibbs
(a) – 9336 cal (b) – 7386 cal
free energy (dG) and change in entropy (dS ) , satisfy the criteria[AIEEE 2003]
(c) –1936 cal (d) + 9336 cal
(a) (dS )V , E  0, (dG)T , P  0 28. The H and S for a reaction at one atmospheric pressure are
(b) (dS )V , E  0, (dG)T , P  0 +30.558 kJ and 0.066 kJk 1 respectively. The temperature at
which the free energy change will be zero and below of this
(c) (dS )V , E  0, (dG)T , P  0 temperature the nature of reaction would be [Kerala CET 2005]
(d) (dS )V , E  0, (dG)T , P  0 (a) 483 K, spontaneous
(b) 443 K, non-spontaneous
21. The densities of graphite and diamond at 298 K are 2.25 and 3.31 g cm , –3

(c) 443 K, spontaneous

respectively. If the standard free energy difference (G ) is equal to
o
(d) 463 K, non-spontaneous
1895 J mol 1 , the pressure at which graphite will be transformed (e) 463 K, spontaneous
diamond at 298 K is
[CBSE PMT 2003]
(a) 9.92  10 Pa 5
(b) 9.92  10 Pa
8

(c) 9.92  10 Pa 7
(d) 9.92  10 6 Pa
22. The free energy change for the following reactions are given below,
5
O2 (g)  2CO 2 (g)  H 2O(l); G  1234 kJ
o
C 2 H 2 (g)  1. Adsorption of gases on solid surface is generally exothermic because[IIT JEE (Scr
2
(a) Enthalpy is positive (b) Entropy decreases
C(s)  O 2 (g)  CO 2 (g) G o  394 kJ (c) Entropy increases (d) Free energy increase
1 2. Two mole of an ideal gas is expanded isothermally and reversibly
H 2 (g)  O 2 (g)  H 2 O(l) G o  237kJ from 1 litre ot 10 litre at 300 K . The enthalpy change (in kJ ) for
2
the process is
What is the standard free energy change for the reaction
[IIT JEE (Screening) 2004]
H 2 ( g )  2 C (s )  C 2 H 2 ( g ) [Kerala (Med.) 2002]
(a) 11.4 kJ (b) –11.4 kJ
(a) – 209 kJ (b) – 2259 kJ (c) 0 kJ (d) 4.8 kJ
(c) + 2259 kJ (d) 209 kJ 3. Heat of neutralization of strong acid against strong base is constant
23. The equilibrium concentration of the species in the reaction and is equal to
A  B  C  D are 3, 5, 10 and 15 mole L1 respectively at [EAMCET 1980; AFMC 1989; DPMT 1991;
MP PET 1999; BHU 1999; MP PMT 1995]
300 K the G for the reaction is [Pb. PMT 2004]
(a) 13.7 kcal (b) 57 kJ
(a) 13.81 (b) – 1381.8
(c) – 138.18 (d) 1391.6 (c) 5.7  10 J4
(d) All of the above

24. Gibb’s free enrgy (G) is defined as [Pb. CET 2001] 4. The value of heat generated when 36.5 gm HCl and 40 gm of
NaOH reacts during neutralization
T
(a) G  H  TS (b) G  H  [NCERT 1984; CPMT 1993]
S (a) 76.5 kcal (b) 13.7 kcal
(c) H  G  TS (d) G  H  T .C p (c) More than 13.7 kcal (d) 108 kcal
25. Standard enthalpy and standard entropy changes for the oxidation of 5. When a gas undergoes adiabatic expansion, it gets cooled due to [DCE 2002]
(a) Loos of kinetic energy
ammonia at 298 K are  382.64 kJ mol 1 and
(b) Fall in temperature
 145.6 JK 1mol 1 , respectively. Standard Gibbs energy change (c) Decrease in velocity
for the same reaction at 298 K is (d) Energy used in doing work
 Thermodynamics and Thermochemistry 433
6. The heat content of a system is called
(a) Internal energy (b) Entropy (a) (b)
(c) Free energy (d) Enthalpy
7. To calculate the amount of work done in joules during reversible
isothermal expansion of an ideal gas, the volume must be expressed
in [KCET (Med.) 2001]
(c) (d)
(a) m 3 only (b) dm 3 only
(c) cm 3 only (d) Any one of them
8. In an isobaric process, the ratio of heat supplied to the system
(dQ) and work done by the system (dW ) for diatomic gas is [AFMC 2002]17. In endothermic reaction, the value of change in enthalpy (H ) is [Pb. CET 200
(a) 1 : 1 (b) 7 : 2 (a) Positive (b) Negative
(c) 7 : 5 (d) 5 : 7 (c) Zero (d) None of these
9. The enthalpy change for the reaction of 50.00 ml of ethylene with 18. Which of the following would be expected to have the largest
50.00 ml of H 2 at 1.5 atm pressure is H  0.31 kJ . The value antropy per mole [MP PMT 2004]

of E will be [DPMT 2004] (a) SO 2Cl 2 (s) (b) SO 2Cl 2 (g)

(a) –0.3024 kJ (b) 0.3024 kJ (c) SO 2Cl 2 (l) (d) SO 2 (g)
(c) 2.567 kJ (d) –0.0076 kJ
19. The enthalpies of formation of Al2 O 3 and Cr2 O 3 are
10. Enthalpy of solution of NaOH (solid) in water is
1596 kJ and 1134 kJ respectively. H for the reaction
 41.6 kJ mol 1 . When NaOH is dissolved in water, the
2 Al  Cr2 O3  2Cr  Al2 O3 is [KCET 2003]
temperature of water [UPSEAT 2004]
(a) Increase (b) Decreases (a) 2730 kJ (b) 462 kJ
(c) Does not change (d) Fluctuates indefinitely (c) 1365 kJ (d)  2730 kJ
11. In which of the following entropy decreases ?
20. Heat of reaction at constant volume is measured in the apparatus
[CPMT 1988, 94; MP PMT 2000]
(a) Bomb calorimeter (b) Calorimeter
(a) Crystallization of sucrose from solution
(c) Pyknometer (d) Pyrometer
(b) Rusting of iron
21. Which of the following gas has the highest heat of combustion
(c) Melting of ice
(a) Methane (b) Ethane
(d) Vaporization of camphor (c) Ethylene (d) Acetylene
12. For conversion C (graphite)  C (diamond) the S is 22. The amount of heat measured for a reaction in a bomb calorimeter
[MP PMT 2001; MP PET 2003] is [AIIMS 1991]
(a) Zero (b) Positive (a) G (b) H
(c) Negative (d) Unknown (c) E (d) PV
13. For a reaction H  9.08 kJ mol 1 and 23. For an endothermic reaction where H represents the enthalpy of
1 1
the reaction in kJ/mole, the minimum value for the energy of
S  35.7 JK mol activation will be
Which of the following statements is correct for the reaction [IIT JEE 1992; MP PET 1993]
[AMU (Engg.) 2000] (a) Less than H (b) Zero
(a) Reversible and Isothermal (c) More than H (d) Equal to H
(b) Reversible and Exothermic 24. The heat of neutralization of a strong acid by a strong base is nearly
(c) Spontaneous and Endothermic equal to [MP PET 1993; BCECE 2005]
(d) Spontaneous and Exothermic (a) + 57.32 J (b) – 57.32 kJ
14. For a reaction to occur spontaneously [CBSE PMT 1995] (c) + 13.7 J (d) – 13.7 kJ
25. A Beckmann thermometer is used to measure
(a) (H  TS ) must be negative
[Kurukshetra CEE 2002]
(b) (H  TS ) must be negative (a) High temperature (b) Low temperature
(c) H must be negative (c) Normal temperature (d) All temperature
(d) S must be negative 26. The heat required to raise the temperature of a body by 1 K is called
[AIEEE 2002]
15. The total amount of energy in the universe is fixed, but
(a) Specific heat (b) Thermal capacity
[AMU (Engg.) 1999]
(c) Water equivalent (d) None of these
(a) Disorder is increasing (b) Lightning is increasing
27. Mechanical work is specially important in system that contain [Kerala (Med.) 200
(c) Matter is increasing (d) Gravitation is decreasing
(a) Solid-liquid (b) Liquid-liquid
16. If for a given substance melting point is T B and freezing point is (c) Solid-solid (d) Amalgam
T A , then correct variation shown by graph between entropy change (e) Gases
and temperature is [DCE 2001] 28. “The quantity of heat which must be supplied to decompose a
TB compound into its element is equal to the heat evolved during the

S TB S

TA TA

T T

TB TA TB
 434 Thermodynamics and Thermochemistry
formation of that compound from the elements.” This statement is therefore [DPMT 2001]
known as
(a) C(graphite)  C(diamond) ; H 298
o
K  450 cal mol 1
(a) Hess's law
1
(b) Joule's law (b) C(diamond)  C(graphite) ; H 298
o
K  450 cal mol
(c) Le–chatelier's principle (c) Graphite is the stabler allotrope
(d) Lavoiser and Laplace law (d) Diamond is harder than graphite
29. Hess law deals with [BHU 1979] 38. Enthalpy of formation of two compounds x and y are – 84 kJ and –
(a) Changes in heat of reaction 156 kJ respectively. Which of the following statements is correct[CBSE PMT 2001
(b) Rate of reaction (a) x is more stable than y
(b) x is less stable than y
(c) Equilibrium constant
(c) Both x and y are unstable
(d) Influence of pressure on volume of a gas (d) x and y are endothermic compounds
30. For which one of the following reactions, H is not equal to E [IIT JEE 1995]
39. For the process dry ice  CO 2 (g) [KCET 2000]
(a) H 2(g)  I2(g) ⇌ 2 HI(g) (a) H is positive while  is negative
(b) C(s)  O 2(g) ⇌ CO 2(g) (b) Both H and  are negative
(c) Both H and  are positive
(c) N 2(g)  3 H 2(g) ⇌ 2 NH 3(g)
(d) H is negative while  is positive
(d) HCl(aq)  NaOH(aq) ⇌ NaCl(aq)  H 2 O
40. For melting of 3 moles of water at 0 o C the G o is
31. The heat liberated when 1.89 g of benzoic acid is burnt in a bomb [MP PMT 2001]
calorimeter at 25 o C increases the temperature of 18.94 kg of (a) Zero (b) + ve
water by 0.632 o C .If the specific heat of water at 25 o C is 0.998 (c) – ve (d) Unpredictable
cal/g-deg, the value of the heat combustion of benzoic acid is [CPMT 1999; BHU The equilibrium constant of a reaction at 298 K is 5  10 3 and
41. 2000]
(a) 771.1 kcal (b) 871.2 kcal
at 1000 K is 2  10 5 . What is the sign of H for the reaction[Pb. CET 199
(c) 881.1 kcal (d) 981.1 kcal
(a) H  0 (b) H is negative
32. For a hypothetic reaction A  B , the activation energies for forward
(c) H is positive (d) None of these
and backward reactions are 19 kJ/mole and 9 kJ/mole respectively. The
heat of reaction is 42. Which of the following has lowest fusion temperature
[MP PET 2003]
[CBSE PMT 2000]
(a) Naphthalene (b) Diamond
(a) 28 kJ (b) 19 kJ
(c) NaCl (d) Mn
(c) 10 kJ (d) 9 kJ 43. Consider the reactions
33. The enthalpy of neutralization of HCN by NaOH is C(s)  2 H 2 (g)  CH 4 (g), H   x kcal
 12.13 kJ mol 1 . The enthalpy of ionisation of HCN will be
C(g)  4 H (g)  CH 4 (g), H   x1 kcal
[BHU 1997]
CH 4 (g)  CH 3 (g)  H(g), H  y kcal
(a) 4.519 kJ (b) 45.10 kJ
(c) 451.9 kJ (d) 45.19 kJ The bond energy of C  H bond is [JIPMER 1997]
1
34. In thermodynamics, a process is called reversible when (a) y kcal mol (b) x 1 kcal mol 1
[AIIMS 2001]
(c) x / 4 kcal mol 1 (d) x1 / 4 kcal mol 1
(a) Surroundings and system change into each other
(b) There is no boundary between system and surroundings 44. Given the bond energies N  N , H  H and N  H bonds are
(c) The surroundings are always in equilibrium with the system 945, 436 and 391 kJ mole 1 respectively, the enthalpy of the
(d) The system changes into the surroundings spontaneously following reaction N 2 (g)  3 H 2 (g)  2 NH 3 (g) is
35. Which of the following unit represents largest amount of energy[AMU 2001] [EAMCET 1992; JIPMER 1997]
(a) Calorie (b) Joule (a) 93 kJ (b) 102 kJ
(c) Erg (d) Electron volt
(c) 90 kJ (d) 105 kJ
36. Which of the following will have the highest bond energy
[MP PMT 1990]
45. The relation between G and E for a cell is G  nFE ; the
cell reaction will be spontaneous if [MP PET 1995]
(a) F2 (b) Cl 2 (a) G is negative (b) G is positive
(c) Br2 (d) I2 (c) E is negative (d) E is positive
46. Which of the following is not a correct statement?
37. C(graphite)  O2 (g)  CO 2 (g) [AMU (Engg.) 2002]
(a) When G is negative, the process is spontaneous
H  94.05 kcal mol 1 (b) When G is zero, the process is in a state of equilibrium
(c) When G is positive, the process is non-spontaneous
C(diamond)  O 2 (g)  CO 2 (g); H  94.50 kcal mol 1 (d) None of these
 Thermodynamics and Thermochemistry 435

47. If at 298 K the bond energies of C  H , C  C, C  C and 1. Assertion : The enthalpy of formation of gaseous oxygen
H  H bonds are respectively 414, 347, 615 and 435 kJ mol 1 , molecules at 298 K and under pressure of
the value of enthalpy change for the reaction 1 atm is zero.
H 2 C  CH 2 (g)  H 2 (g)  H 3 C  CH 3 (g) at 298 K will be Reason : The entropy of formation of gaseous oxygen
[AIEEE 2003] molecules under the same condition is zero. [AIIMS 1996]
(a) + 250 kJ (b) – 250 kJ
(c) + 125 kJ (d) – 125 kJ 2. Assertion : We feel cold on touching the ice.
48. The equation Reason : Ice is a solid form of water. [AIIMS 1999]
1 1 3. Assertion : Entropy of ice is less than water.
H 2  Cl 2  HCl ( H 298  22060 kcal ) means
2 2 Reason : Ice have cage like structure. [AIIMS 2000]
[CMC Vellore 1991] 4. Assertion : The heat absored during the isothermal
(a) The heat absorbed when one gram molecule of HCl is expansion of an ideal gas against vacuum is zero.
formed from its elements at 25 o C is 22.060 kcal Reason : The volume occupied by the molecules of an
(b) The heat given out when one gram molecule of HCl is ideal gas is zero. [AIIMS 2002]
formed from its elements at 298 K is 22.060 kcal 5. Assertion : Absolute values of internal energy of substance
(c) The heat absorbed when one atom of hydrogen reacts with one can not be determined.
atom of chlorine to form one molecule of HCl at 25 o C Reason : It is impossible to determine exact values of
and one atmospheric pressure is 22.060 kcal constituent energies of the substances.
(d) The heat absorbed when one gram equivalent of HCl is [AIIMS 2002]
formed from its elements at 298 K is 22.060 kcal 6. Assertion : Mass and volume are extensive properties.
(e) The intrinsic heat of one molecule of HCl is 22.060 kcal Reason : Mass / volume is also an extensive parameter. [AIIMS 2002]
more than the intrinsic heats of one atom of hydrogen and one 7. Assertion : Molar entropy of vaporization of water is
atom of chlorine different from ethanol.
49. The H 2 O(g) molecule dissociates as Reason : Water is more polar than ethanol.
(i) H 2 O(g)  H(g)  OH(g); H  490 kJ 8. Assertion : The increase in internal energy (E) for the
(ii) OH(g)  H(g)  O(g); H  424 kJ vaporiation of one mole of water at 1 atm and
The average bond energy (in kJ) for water is 373K is zero.
(a) 490 (b) 424 Reason : For all isothermal processes E  0 .
(c) 914 (d) 914/2 [AIIMS 2003]
50. When 50cm 3 of 0.2 N H 2 SO 4 is mixed with 50cm 3 of 9. Assertion : H and E are almost the same for the
1 N KOH , the heat liberated is [KCET 2004] reaction. N 2 (g)  O 2 (g) ⇌ 2 NO (g) .
(a) 11.46 kJ (b) 57.3 kJ
Reason : All reactants and products are gases.
(c) 573 kJ (d) 573 J
51. Following reaction occurring in an automobile [AIIMS 2003]
2C8 H18 (g)  25O2 (g)  16CO 2 (g)  18 H 2 O(g). The sign of 10. Assertion : The enthalpies of neutralisation of strong acids
and strong bases are always same.
H , S and G would be [CBSE PMT 1994; KCET 1999]
Reason : Neutralisation is heat of formation of water.
(a) +, –, + (b) –, +, – [AIIMS 1996]
(c) –, +, + (d) +, +, –
52. For the reaction 11. Assertion : Zeroth law can also be termed as law of thermal
equilibirum.
1
H 2 (g)  O 2 (g)  H 2 O(l), H  285.8 kJ mol 1 Reason : Two objects in thermal equilibrium with the
2
third one, are in thermal equilibrium with each
1 1
S  0.163 kJ mol K . What is the value of free energy other.
change at 27 o C for the reaction [KCET 1999] 12. Assertion : There is no reaction known for which G is
1 1 positive, yet it is spontaneous.
(a)  236.9 kJ mol (b)  281.4 kJ mol
1 Reason : For photochemical reactions G is negative.
(c)  334.7 kJ mol (d)  334.7 kJ mol 1
13. Assertion : Heat of neutralisation of perchloric acid,
HClO4 with NaOH is same as is that of
HCl with NaOH .
Reason : Both HCl and HClO4 are strong acids.
14. Assertion : Heat absorbed in a reaction at constant
temperature and constant volume is G .
Read the assertion and reason carefully to mark the correct option out of
the options given below : Reason : G should be negative for the reaction to be
(a) If both assertion and reason are true and the reason is the correct spontaneous.
explanation of the assertion. 15. Assertion : T, P and V are state variables or state functions.
(b) If both assertion and reason are true but reason is not the correct Reason : Their values depends on the state of the system
explanation of the assertion. and how it is reached.
(c) If assertion is true but reason is false.
(d) If the assertion and reason both are false. 16. Assertion : Internal energy is an extensive property.
(e) If assertion is false but reason is true.
 436 Thermodynamics and Thermochemistry
Reason : Internal energy depends upon the amount of the 46 c 47 b 48 c 49 d 50 b
system.
51 a 52 d 53 b 54 c 55 a
17. Assertion : For the combustion reactions, the value of H
is always negative. 56 b 57 d 58 d
Reason : The combustions reactions are always
endothermic.
IInd & IIIrd Law of thermodynamics and Entropy
18. Assertion : For an isothermal reversible process Q  w
i.e. work done by the system equals the heat 1 c 2 d 3 d 4 b 5 b
absorbed by the system.
6 d 7 a 8 d 9 b 10 c
Reason : Enthalpy change (H ) is zero for isothermal
process. 11 c 12 c 13 d 14 d 15 c
19. Assertion : Enthalpy of formation of graphite is zero but of 16 b 17 d 18 a 19 a 20 a
diamond is not zero.
21 d 22 c 23 a 24 d 25 c
Reason : Enthalpy of formation of most stable allotrope is
taken as zero. 26 d 27 c 28 b 29 c 30 b
20. Assertion : If a refrigerator’s door is kept open room gets 31 b 32 d 33 d 34 a 35 c
cooled.
36 b 37 c 38 a 39 c 40 c
Reason : Material kept inside the refrigerator reamins cool.
21. Assertion : Enthalpy and entropy of any elementary 41 c 42 c 43 c 44 d 45 b
substance in the standard state are taken as zero. 46 a 47 c 48 d 49 d 50 c
Reason : At zero degree absolute, the constituent particles 51 c 52 b 53 a 54 c 55 c
become completely motionless.
22. Assertion : A process is called adiabatic if the system does 56 c 57 a 58 b 59 d 60 b
not exchange heat with the surroundings. 61 b 62 d 63 a 64 c 65 a
Reason : It does not involve increase or decreae in
66 c 67 b 68 b
temperature of the system.

Basic concepts

1 b 2 d 3 b 4 c 5 c
6 d 7 d 8 c 9 c 10 c
11 d 12 d 13 a 14 c 15 b
16 b 17 d 18 a 19 b 20 b
21 d 22 b 23 c 24 c 25 d
26 c 27 c 28 c

First law of thermodynamics and Hess law

1 d 2 b 3 a 4 b 5 c
6 a 7 c 8 a 9 b 10 d
11 b 12 c 13 c 14 c 15 b
16 b 17 c 18 b 19 c 20 a
21 c 22 c 23 a 24 a 25 b
26 a 27 a 28 a 29 bc 30 c
31 b 32 c 33 b 34 a 35 c
36 b 37 c 38 b 39 d 40 c
41 d 42 a 43 c 44 a 45 c
 Thermodynamics and Thermochemistry 439

Free energy and Work function

Heat of reaction
1 d 2 b 3 a 4 b 5 acd
1 b 2 b 3 d 4 d 5 d
6 c 7 c 8 c 9 a 10 a
6 b 7 c 8 a 9 b 10 a
11 d 12 a 13 d 14 d 15 b
11 bcd 12 a 13 d 14 b 15 c
16 d 17 b 18 c 19 d 20 b
16 a 17 b 18 a 19 b 20 c
21 b 22 d 23 b 24 a 25 d
21 c 22 a 23 d 24 c 25 c
26 d 27 a 28 d
26 b 27 b 28 b 29 a 30 c

31 a 32 a 33 d 34 b 35 b Critical Thinking Questions

36 a 37 a 38 d 39 b 40 b
1 b 2 c 3 d 4 b 5 b
41 c 42 c 43 b 44 b 45 b
6 d 7 d 8 b 9 a 10 a
46 b 47 a 48 c 49 e 50 b
11 a 12 c 13 c 14 a 15 a
51 a 52 b 53 c 54 c 55 b 16 a 17 a 18 d 19 b 20 a
56 c 57 c 58 d 59 c 60 b 21 b 22 c 23 c 24 b 25 b
61 d 62 c 63 b 64 a 65 b 26 b 27 e 28 d 29 a 30 c
66 b 67 a 68 c 69 a 70 d 31 a 32 c 33 d 34 ac 35 a
71 a 72 b 73 d 74 c 75 b 36 b 37 c 38 b 39 c 40 a

76 b 77 a 78 d 79 d 80 a 41 b 42 a 43 a 44 a 45 d

81 b 82 b 83 a 84 b 85 b 46 d 47 d 48 b 49 d 50 d

86 c 87 a 88 b 89 d 90 d 51 b 52 a

91 a 92 c 93 b 94 a 95 d
Assertion & Reason
96 d 97 c 98 a 99 c 100 c

101 b 102 c 103 d 104 d 105 c 1 b 2 b 3 b 4 c 5 a

106 a 107 c 108 d 109 d 110 c 6 b 7 b 8 a 9 b 10 a

11 a 12 d 13 a 14 e 15 c
111 a 112 b 113 a 114 a 115 a
16 a 17 c 18 b 19 a 20 e
116 a 117 b 118 c 119 b 120 a
21 c 22 c
121 a 122 a 123 d 124 b 125 b

126 b 127 c 128 d 129 d 130 b

131 d 132 b 133 d 134 a 135 a

136 a 137 d 138 c 139 d 140 b

141 c 142 d 143 c 144 b 145 c

146 d 147 b 148 c 149 b 150 b

151 d 152 a 153 b 154 b 155 b

Basic concepts
156 b 157 a 158 d 159 c 160 d 1. (b) Internal energy of an ideal gas is a function of temperature
only.
161 a 162 c 163 c 164 c 165 c
2. (d) In cyclic process, a system in a given state goes through a
166 b 167 d 168 d 169 c 170 b series of different processes, but in the end returns to its initial
171 a 172 c state.
4. (c) E  0 for isothermal reversible cycle.
Bond energy 5. (c) In isolated system neither exchange of matter nor exchange of
energy is possible with surroundings.

1 b 2 a 3 a 4 d 5 c
9. (c) It is the definition of calorific value.
11. (d) When a real gas is forced through a porous plug into a region
6 c 7 b 8 d 9 b 10 b of low pressure, it is found that due to expansion, the gas on
the side of low pressure gets cooled.
 440 Thermodynamics and Thermochemistry
The phenomenon of producing lowering of temperature when H  E  PV  E  nRT  0  0  0 .
a gas is made to expand adiabatically from a region of high
pressure into a region of low pressure is known as Joule- V2
18. (b) W  2 .303 nRT log
Thomson effect. V1
12. (d) In isothermal reversible process ideal gas has constant volume
20
and so E  0 and H  E  0 .  2.303  1  8.314  10 7  298 log
13. (a) The compressor has to run for longer time releasing more heat 10
to the surroundings.  298  10 7  8.314  2.303 log 2 .
14. (c) This is based on Joule-Thomson effect.
15. (b) Enthalpy is an extensive property. 20. (a) The enthalpies of all elements in their standard state at
16. (b) dV  0 for an isochoric process. 25 o C or 298K are zero.
17. (d) Total energy of an isolated system is constant. 21. (c) E  E P  E R .
v
18. (a) For isochoric process V  0 so q  E i.e. heat given to 22. (c) E  q  w .
v
a system under constant volume is used up in increasing E . 23. (a) E = 0 for reversible isothermal process.
19. (b) The less energy of a system and more is its stability. 25. (b) Hess law includes initial reactants and final products.
20. (b) The functions whose value depends only on the state of a
system are known as state functions. 26. (a) At constant T and P internal energy of ideal gas remains
unaffected.
21. (d) For adiabatic process q  0 .
27. (a) E increases with temperature.
22. (b) The intensive property is mass/volume.
28. (a) H  E  W or H  E  PV .
23. (c) Volume is not an intensive property.
24. (c) An isolated system neither shows exchange of heat nor matter 29. (bc) Heat of neutralisation of a strong acid and strong base is equal
with surroundings. to 13.7 kcal .
25. (d) Q is not a state function. p1
30. (c)  W   2.303 nRT log
26. (c) For adiabatic process Q  0 . p2
27. (c) Work is not a state function as during a process its value
depends on the path followed. The value of enthalpy, internal 10
W  2.303  1  2  300 log  1381.8 cal.
energy and entropy depends on the state and not on the path 1
followed to get that state, hence these are state functions. 31. (b) Joule-Thomson expansion is isoenthalpic.
28. (c) Surface tension is an intensive property which do not depend 32. (c) Here n  0 so, E  H .
upon the quantity of matter present in the system.
33. (b) q  E  W if q  0 for adiabatic process, than E  W .
First law of thermodynamics and Hess law 34. (a) For this reaction n  0 than E  H .
35. (c) As the system is closed and insulated no heat enter or leave the
1. (d) First low of thermodynamics is also known as Law of system, i.e. q  0 ;  E  Q  W  W .
conservation of mass and energy. 37. (c) H  E  nRT ; n  3
2. (b) Formation of CO 2 from CO is an exothermic reaction; heat so, H  E  3 RT .
is evolved from the system, i.e., energy is lowered. Thus, 38. (b) According to Hess’s law. The heat of reaction depends upon
exothermic reactions occur spontaneously on account of initial and final conditions of reactants.
decrease in enthapy of system. Thus, E  H .
39. (d) H  E  nRT
4. (b) H  E  PV .
also, 2 NH 3(g)  N 2(g)  3 H 2(g)
3 1
5. (c) n  1   , As n is negative, thus H  E . n  2 .
g 2 2 g
6. (a) Bomb calorimeter is commonly used to find the heat of 40. (c) n  0 for this reaction so, E  H .
combustion of organic substances which consists of a sealed 41. (d) W = 0 is not true.
combustion chamber, called a bomb. If a process is run in a P
sealed container then no expansion or compression is allowed, 42. (a) W  2 .303 nRT log 2
P1
so w = 0 and ∆U = q.
∆U < 0, w = 0 10
 2.303  1  2  300 log  965.84
9. (b) H  E  nRT 2
Since n  2 at constant temperature, E  0.
Than H  E  2 RT . E  q  w ; q  w  965.84 cal .
10. (d) If n  ve than H  E . 43. (c) q  40 J
12. (c) Hess’s law is an application of first law of thermodynamics . w  8 J (work done by the system)
13. (c) At constant P or T E  q  w  40  8  32 J .
H  U  nRT  n  n p  n R  2  4  2 44. (a) We know that E  Q  W  600  (300)  300 J
 H  U . W  300 , because the work done by the system.
45. (c) Given that
16. (b) It is a combustion reaction, H   ve .
P1  10 atm , P2  1 atm , T  300 K , n  1
17. (c) During isothermal expansion of ideal gas, T  0
 Thermodynamics and Thermochemistry 441

R  8.314 J / K / mol Thus, we can say that internal energy is partly potential and
partly kinetic.
Now, by using
P2 56. (b) N 2 (g)  O2 (g)  2 NO(g) ; ng  2  2  0
W  2 .303 nRT log10
P1 H  E  ng RT ; H  E  0 ; H  E
1 (d) W   pV ; W  3  (6  4 )
 2.303  1  8.314  300 log10 57.
10
W  6  101.32 ( 1 L atm  101.32 J )
W  5744.1 Joule
46. (c) We know that internal energy of a gas depends upon its W  608 J
pressure and temperature. Thus if a gas expands at constant
temperature and pressure, then its internal energy remains 58. (d) A(s)  3 B(g)  4 C(s)  D(l)
same. ng  0  3  3 ; H  E  ngRT [ E  U]
47. (b) PCl5 (g)  PCl3 (g)  Cl 2 (g)
 H  U  (3)(RT )
For this reaction ng  2  1  1
H  U  3 (RT ) ; H  U  3 RT
ng is positive, i.e., there is an increase in the number of
gaseous moles then H  E
48. (c) Enthalpy (H ) is defined as the sum of internal energy
IInd & IIIrd Law of thermodynamics and Entropy
E  PV , H  E  PV .
2. (d) When S  ve the change is spontaneous.
49. (d) (CH 3 )2 C  CH 2 (g)  6O2 (g)  4 CO 2 (g)  4 H 2 O(l)
3. (d) Heat is always flow from the higher to lower temperature.
ng  4  6  2 (i.e., negative) 4. (b) Mixing of non-reacting gases increases randomness and so
we know that H  E  ngRT increase entropy .
 E  (ng)RT ( ng  ve ) 5. (b) Entropy of the system increases as the process occur
irreversibly and isothermally in an isolated system.
 H  E
50. (b) Given number of moles =1 6. (d) S o  2S HCl
o
 (S Ho 2  S Cl
o
2
)
Initial temperature  27 o C  300 K  2  186.7  (130.6  223.0)  19.8 JK 1mol 1
Work done by the system  3 KJ  3000 K
9. (b) For adiabatic expansion q  0 than according to following
It will be () because work is done by the system.
q
Heat capacity at constant volume (Cv )  20 J / k relation S  , S  0 .
T
We know that work done 10. (c) It is the third law of thermodynamics.
W  nCV (T2  T1 ) ; 3000  1  20 (T2  300) 11. (c) Entropy of gases is highest.
3000  20T2  6000 12. (c) G  H  TS
3000 for spontaneous process G should be negative in option (3)
20T2  3000 ; T2   150 K H  ve and ΔS  ve than
20
51. (a) Internal energy of a system is a state function and extensive G  (ve )  T (ve )   ve
property and is independent of the path by which it is
obtained. 15. (c) For reverse reaction sign will be change.
52. (d) N 2 O4 (g)  2 NO 2 (g) 16. (b) Solid  Gas, S is maximum.
For this reaction ng  2  1  1 17. (d)  ve H and  ve S both oppose the reaction.
ng is positive i.e., there is an increase in the number of 18. (a) S  186.5 / 373  0.5 JK 1 mol 1 .
vap
gaseous moles then H  E
53. (b) 2C  O2  2CO ; H  220 KJ 20. (a) When H = –ve, S = +ve and G = –ve than reaction is
spontaneous .
This reaction does not represent complete combustion of 21. (d) For endothermic process S increases.
carbon, hence heat of combustion of carbon will not be equal 22. (c) Calculation of change in entropy is done at constant
to 110 kJ . The negative sign of H indicates that this temperature and pressure both.
reaction is exothermic. Also, despite being spontaneous 23. (a) When the value of entropy is greater, then ability of work is
reaction, it requires initiation. maximum.
54. (c) W  PV  1  10 5 (1  10 2  1  10 3 ) 24. (d) At equilibrium, G = 0
Hence 0 = H  TS or H  TS .
 1  10 5  9  10 3  900 J H
vap 37.3 KJ mol 1
55. (a) The exact value of internal energy is not known as it includes 25. (c) S vap  
all type of energies of molecules constituting the given mass of T 373 K
matter such as translational, vibrational, rotational. The kinetic
& potential energy of the nuclei & electron with in the  0.1 kJ mol 1 K 1  100 J mol 1 K 1 .
individual molecules and the manner in which the molecule are 26. (d) Solid  Liquid, S increases .
linked together etc.
27. (c) S  ve than process is spontaneous.
E  Etranslational  Erotational  Evibrational 28. (b) S  ve than the system is more disordered.
29. (c) Because solid  solid, S is same and H is –ve.
 442 Thermodynamics and Thermochemistry
H 3 5
vap 386 RT  RT
30. (b) S    1 .2 kJ . 2 2
vap T 298 Thus for mixture of 1 mole each, Cv  and
2
31. (b) Processes (a) and (c) take place with the increase of no. of
5 7
moles of gaseous species and hence the disorder or entropy RT  RT
increases. (b) on increasing pressure, disorder or randomness Cp  2 2
decreases and so also the entropy (d) is endothermic process 2
and S is positive. 3 RT
32. (d) This is the statement of third law of thermodynamics. Therefore, C p / Cv   1 .5 .
2 RT
33. (d) For isothermal expansion of ideal gas, E  0 .
q
(900  18) 51. (c) S  rev  unit of S is JK 1mol 1 .
34. (a) S   43.4 JK 1 mol 1 . T
vap 373
H vap
35. (c) Entropy of the mixture increases due to increase in impurity. 52. (b) H 2 O(l) ⇌ H 2 O(g) , S  ,
37. (c) If H   ve and S   ve than the reaction is non- T
spontaneous i.e. can not occur. H vap.  2.257 KJ / g
38. (a) T2  150  273  423 K or H vap  2.257  18 kJ / mol.  40.7 KJ / mol
T1  25  273  298 K
40.7
Q  500 K hence, S   0.109 kJ /mol/K.
373
W T2  T1  423  298  53. (a) Liquid  Vapour, entropy increases.
 ; W  500   147.7 J .
Q T2  423  54. (c) NaNO 3 is a solid, which is converted to liquid ions.
39. (c) According to III law of thermodynamics.
75
40. (c) When H  ve and S  ve reaction is non- 55. (c) Heat capacity of water per gram   4 .17 J
spontaneous. 18
H fusion 9.2 Q  mst ; 1000  100  4.17  t
41. (c) Tm    1150 K .
S fusion 0 .008 1000
t  2 .4 K .
42. (c) Here: Change in 100  4 .17
Volume (V )  500  300  200cc  0.2 litre, 56. (c) As the work is done on system, it will be positive
i.e. W  462 joule, E  128 joule (heat is evolving)
Pressure (P)  0.6 atm and heat liberated (q) = 10J
From the I law of thermodynamics
st

Work done (W )  PV  (0.2  0.6)  0.12 litre atm E  q  w  (128)  (462)  334 Joules.
But 1 litre atm  101.3 J . 57. (a) Gases show highest entropy.
hence W  0.12  101.3  12.156 J . We also know that 58. (b) H  (aq )  OH  (aq )  H 2 O(l)
S o (298 K )K mol 1 10 .7 70
heat is liberated, therefore it would be negative. Thus change in
E  q  W  10  12.16  2.16 J . S (298 K)  S P  S R  70  (10.7  0)
o

43. (c) Formation of CO 2 is, 80.7 JK 1 mol 1

C(s)  O 2(g)  CO 2(g) heat of vaporis ation
59. (d) The entropy change 
S  213.5  5.690  205  2.81 JK
o 1
. temperatur e
Here, heat of vaporisation  540 cal / gm
45. (b) H 2 O(g) ⇌ H 2 O(l)
 540  18 cal mol 1
we know G  H  TS
Temperature of water  100  273  373 K
at equilibrium G  0
540  18
Therefore H  TS .  entropy change   26.06 cal mol 1 K 1
373
46. (a) We know that work done, W  Cv (T1  T2 )
60. (b) Given that, T1  500 K, T2  300 K
3  1000  20 (300  T2 ) ;  3000  6000  20 T2 T1  T2 500  300 200
By using,      0 .4 .
3000 T1 500 500
 T2   150 K .
20 61. (b) It is molar heat capacity.
48. (d) It does not violates the first law of thermodynamics but violates 62. (d) Entropy is the measure of randomness in the molecules.
the II law of thermodynamics. Randomness is maximum in case of gases. Hence, entropy is
maximum for water vapours.
3 5
49. (d) Cv  RT ; C p  RT for monoatomic gas 63. (a) Standard entropy of formation of CO 2 (g) = standard entropy
2 2
of CO 2 (g)  [Standard entropy of C(s)  standard entropy of
5 7
Cv  RT; C p  RT for diatomic gas O 2 (g ) ]
2 2
 213.5  [5.740  205]  2.76 J / K .
 Thermodynamics and Thermochemistry 443
64. (c) Third law of thermodynamics help in calculating entropy of 15. (c) H  ve for exothermic reaction.
different temperatures.
65. (a) In case of gas randomness is maximum therefore entropy is H  ve for endothermic reaction
maximum in case of steam. Enthalpy of fusion is + ve.
66. (c) S system  S surroundin gs  O (for spontaneity) 16. (a) Heat of neutralisation will be less than
57.33 kJ / mole because some amount of this energy will
V2
Because of S  R ln be required for the dissociation of weak base (MgO)
V1
Here the volume of gas increase from V1 to V2 at constant 18. (a) H 2  O2  H 2 O2 H of  188 kJ / mole ….(i)
temperature T. 1
The total increase in entropy of the system and its surrounding H2  O 2  H 2 O H of  286 kJ / mole ….(ii)
2
during the spontaneous process of expansion considered above
eq. (i) – eq. (ii) × 2 gives the required result.
V 
is, thus R ln  2  since V2  V1 it is obvious that the 19. (b) Graphite  diamond H  (x  y) kJ mol 1 .
 V1  t
spontaneous (irreversible) isothermal expansion of a gas is 21. (c) Heats of combustions are always exothermic except oxidation of
accompanied by an increase in the entropy of the system and N as,
its surrounding considered together. 1
S system  S surroundin gs  0 . N2  O 2  N 2 O H   ve
2
67. (b) G  H  TS N 2  O2  2 NO H   ve
at constant temperature and pressure G  0
22. (a) For exothermic reactions H p  H R .
0  T  TS so H  TS
dQrev. 30  10 3 For endothermic reactions H p  H R .
68. (b) dS  ; T ; T  400 K
T 75 23. (d) Aim: 2C  H 2(g)  C 2 H 2(g) .

Heat of reaction eq. (ii) + eq. (iii)  eq. (iv) – eq. (i)
find the required result.
1. (b) C  O2  CO 2  94.2 Kcal. …..(i) 24. (c) Enthalpy of formation of HCl.
25. (c) Heat of neutralisation between strong acid and a strong base is
1
H2  O 2  H 2 O  68.3 Kcal. ….(ii) about 13.7 Kcal.
2
On multiplication of eq. (ii) by 2 and than adding in eq. (i) 26. (b) For endothermic reaction, H  ve .
27. (b) Heat of neutralisation is less than 56.1 Kcal when a strong base
C  2 H 2  2O2  CO 2  2 H 2 O  230.8 Kcal …(iii) and a weak acid reacts.
On subtracting eq. (iii) by following eq. 1
28. (b) Aim: CO  O 2  CO 2
CH 4  2O2  CO 2  2 H 2 O  210.8 Kcal. we get, 2
C  2 H 2  CH 4 H  20 Kcal.  1 
H  H 0f (CO 2 )  H 0f (CO )  H 0f (O 2 )
2. (b) S  16 J mole K 1 1  2 
  94.0  (26.4)  67.6 kcal.
H vapour 6  1000
Tb . p .    375 K 29. (a)
S vapour 16
1
4. (d) Heat of neutralisation between strong acid and a strong base is (i) H2  O2  H 2 O, H  241 kJ
2
about 13.7 Kcal.
17
6. (b) Effect of temperature in heat of reaction is given by Kirchoff’s (ii) C6 H10  O2  6 CO 2  5 H 2 O, H  3800 kJ
equation. 2
7. (c) Heat of neutralisation between strong acid and a strong base is (iii) C6 H12  9O2  6CO 2  6 H 2O, H  3920 kJ
about 13.7 Kcal. C6 H10  H 2  C6 H12
8. (a) For exothermic reactions H p  H R . Eq. (i) + Eq. (ii) – Eq. (iii)
For endothermic reactions H p  H R . H  241  3800  (3920)
9. (b) 78g of benzene on combustion produces  4041  3920  121 kJ
heat = – 3264.6 kJ 30. (c) NH 4 OH is a weak base. Heat of neutralisation < 13.7kcal.
3264.6
 39 g will produce   1632.3 kJ . 31. (a) CH 4 is the best fuel because its calorific value
2
212.8
10. (a) eq. (i ) + eq. (ii ) gives the required result.   13.3 kcal / g is higher among the other gases.
11. (bcd) (b,c,d) are endothermic reactions because they proceeds by 16
the absorption of heat. 32. (a) Find H for CH 4  2O2  CO 2  2 H 2 O .
(g)
12. (a) Change of liquid to vapour takes energy in the form of heat so
it is endothermic reaction. 34. (b) In neutralisation of a strong acid and base only H  and OH 
13. (d) In exothermic reactions heat is evolute. ions react.
 444 Thermodynamics and Thermochemistry
35. (b) When both acid and base are strong than heat of neutralisation 1 1
63. (b) Aim: K(S )  O2  H  KOH (S )
is 57.1 kJ mol 1 . 2 (g) 2 2(g)
eq. (ii) + eq. (i) – eq. (iii) gives
7
36. (a) C2 H 6  O 2  2CO 2  3 H 2 O substitute the values. H  48  (68.39)  (14)  68.39  48  14 .
2 64. (a) By definition of heat of formation.
37. (a) Decomposition is an endothermic process. 68. (c) C D  CG , H  453.5 cal.
38. (d) H for this reaction is Heat of reaction.
i.e. energy of C G is less and thus more stable.
40. (b) One mole of H 2 O is formed from its initial components.
69. (a) H combustion is always negative .
41. (c) One mole of a substance is completely oxidized in air.
70. (d) H reaction  H 0f (N 2 O4 )  2H 0f (NO 2 )
42. (c) S (rhombic)  O2  SO 2 , H  70960 cal. …(i)
 2  2 (8)  14 kcal.
S (monoclinic)  O2  SO 2 H  71030 cal …(ii)
71. (a) H  E  nRT  3  8.314  298
Aim: S (rhombic)  S (monoclinic)
 7432 J  7.43 kJ .
eq. (i) – eq. (ii) gives the required result.
43. (b) When H 2 O is convert to form H 2 O , heat is absorbed 72. (b) Aim: C  C(diamond) ; eq. (i) – (ii) gives the result.
(l) (g ) (graphite)
73. (d) In the formation of a compound, more the heat absorbed, less
hence H1  H 2 . stable is the compound.
44. (b) Out of given substances, kerosene oil has maximum calorific 74. (c) C(graphite)  2 H 2(g)  CH 4 (g) .
value.
75. (b) Heat of formation is the formation of one mole of the
45. (b) C(S )  O2(g)  CO 2 (g) , n  1  1  0 substance from its elements.
g
76. (b) H (reaction)  2H 0f (MgO)  H 0f (SiO2 )
 E  H  94 kcal
 2 ( 34.7)  ( 48.4 )  21 kJ .
E  ECO 2  (EC  EO2 )  ECO 2  (0  0)
77. (a) eq. (i) + eq. (ii) + eq. (iii) gives
or ECO 2  E  94 kcal. X  131  282  242   393 kJ .
46. (b) 0.2 mole will neutralize 0.2 mole of HNO 3 , heat evolved 78. (d) It is the definition of heat of transition.
 57  0.2  11.4 kJ . 79. (d) C(graphite)  C(diamond ), H  1.9 kJ
47. (a) Suppose heat evolved in I case is Q1 and that in the II case it
st nd
C(graphite)  O2  CO 2 , H  H1
1
is Q 2 . Then Q 2  Q1. C(diamond )  O2  CO 2 , H  H 2
2
(  H1 )  (  H 2 )  1.9 kJ or H 2  H1  1.9
But Q1  1000 T1 and Q2  500 T2
For combustion of 6 g, H 2  H1 by 1.9 / 2  0.95 kJ .
1
 500 T2   1000 T1 i.e. T2  T1 .
2 80. (a) H product  H reactant for exothermic reaction.
48. (c) Enthalpy of a compound = Heat of reaction of that compound. 81. (b) Due to high electron affinity of Cl the highest energy is
49. (e) It is the definition of heat of neutralization. evolved.
50. (b) H   ve for exothermic compound.
82. (b) CH 4  2O2  CO 2  2 H 2 O
51. (a) If acid or base or both are strong, heat of neutralization
 13.7 kcal. Molecular weight of CH 4  12  4  16
52. (b) Both NH 4 OH and CH 3 COOH are weak.  On the combustion of 2.0gm of methane = 25.0 kcal
53. (c) 57.1  0.25  14.3 kJ mol 1 .  On the combustion of 16.0 gm  25  16  200 kcal.
2
54. (c) Heat of formation is for 1 mole.
Hence H 0f (HI)  12.40 / 2  6.20 kcal. 83. (a) CH 4  2O2  CO 2  2 H 2 O .
55. (b) Chemical dissociations are reversible and endothermic. 84. (b) C2 H 4  3O2  2CO 2  2 H 2 O
57. (c) Given,
(i) CH 4  2O2  CO 2  2 H 2 O , H  20 kcal H reaction  [2  H of (CO 2 )  2  H of (H 2 O)]
(ii) C  O2  CO 2 , H  40 kcal.  [H of (C 2 H 4 )  3  H of (O2 )]
1
(iii) H 2  O 2  H 2 O , H  10 kcal.  [ 2 (  394)  2 (  286)]  [52  0]  1412 kJ .
2
Aim: C  2 H 2  CH 4 85. (b) C  O2  CO 2  394 kJ .
(ii) + 2 × (iii) – (i) gives. 2C  2O2  2CO 2  788 kJ ….(i)
H  40  2 (10)  ( 20)  80 kcal.
58. (d) For exothermic reaction heat is evolved. 2CO  O2  2CO 2  569 kJ ….(ii)

59. (c)
electrolysis
H 2 O  H 2(g)  O 2(g) .
1 2CO 2  2CO  O2  569 kJ …..(iii)
(l) 2 eq. (i) + eq. (iii) = –109.5 kJ mol .
–1

61. (d) All other are combustion phenomena.

H 44
62. (c) combusion = –ve, so exothermic process. 86. (c) H f  kcal  22 kcal .
2
 Thermodynamics and Thermochemistry 445

87. (a) CaO  H 2 O  Ca (OH )2 is exothermic.

(s) (l)
 32 gm of sulphur on burning produce 64 gm.. of SO 2

88. (b) H  ve in exothermic reaction.  H  (  4.6 kJ )  64   294.4 kJ .

89. (d) According to the definition of heat of formation. 111. (a) 3O 2 ⇌ 2O 3 – energy is given out.
90. (d) Multiplying eq. (ii) by (iii) and eq. (iii) by (vi), and then add 72  1.6
15
112. (b) H per 1.6 g   0.64 kcal .
6 C  3H 2  O 2  6 CO 2  6 H 2 O; H  3218.7 180
2 113. (a) C  O2  CO 2 , H  394 kJ …..(i)
Subtract eq. (i) from the above equation and find the required
result. 2 H 2  O2  2 H 2 O, H  568 kJ ….(ii)
91. (a) HF is more stable than HCl. CH 4  2O2  CO 2  2 H 2 O, H  892 kJ …..(iii)
92. (c) H ( H P  H R )  q p . (i) + (ii) – (iii) and find the required result.

93. (b) H  ve for endothermic reaction. 115. (a) No doubt heat evolved during neutralisation of 250 cm 3 of
each acid and base is five time the heat evolved during
13.95  44
94. (a) H   278.7 kcal . neutralisation of 50 cm 3 of each acid and base but the
2 .2016
quantity if solution taking heat is also five time thus same
95. (d) eq. (i) + eq. (ii) gives the required result.
temperature rise is noticed.
96. (d) Standard molar heat enthalpy (H o ) of a compound is equal to 1
its standard heat of formation from most stable states of initial 116. (a) H2  O 2  H 2 O(l) ; H  285.8 KJ
2
components.
97. (c) In the complete combustion of butanol H  E . H 2 O(l)  H 2 O(g) ; H  44 KJ
98. (a) X – Y and find the required result. 1
 H2  O 2  H 2 O(g) ; H o  241.8 KJ
99. (c) S  O2  SO 2 H  298.2 kJ ….(i) 2
1 117. (b) Given: Weight of iron burnt  4 g; Heat liberated
SO 2  O 2  SO 3 H  98.2 kJ ….(ii)
2  29.28 KJ and atomic weight of iron (Fe)  56 . We know
eq. (i) – (ii) and find the required result. that in ferric oxide (Fe2 O3 ), 2 moles of iron or
100. (c) C  2S  CS 2 H  ?
2  56  112 gram of iron are burnt. We also know that
C  O2  CO 2 H  393.3 kJ ….(i) when 4grams of iron are burnt, then heat liberated =
S  O2  SO 2 H  293.72 kJ …..(ii) 29.28 kJ, therefore when 112 grams of the iron are burnt,
CS 2  3O2  CO 2  2SO 2 H  1108.76 kJ …..(iii) 29.28  112
then heat liberated   819.8 kJ (Minus sign
eq. (ii) × 2 + eq. (i) – (iv) eq. (iii) – eq. (iv) and find required 4
result . due to liberation of heat).
101. (b) Fermentation is exothermic reaction.
118. (c) H   OH   H 2 O, H neutralization  13.7 kcal .
102. (c) CH 4  2O2  CO 2  2 H 2 O .
3.77  56
103. (d) Use H  E  n RT 119. (b) H / mole of FeS   100.5 .
2 .1
H  19  2  2  10 3  300  20.2 kcal ; n  2 . 194
120. (a) Heat of formation   97 kJ .
1 2
104. (d)  20.6  8.8 KJ mol  29.4 kJ .
106. (a) Subtract equation (ii) from (i). 121. (a) H  H ioniz  H neu =  50.6  H ioniz  (55.9)
107. (c) CH 4  2O2  CO 2  2 H 2 O, H   890.4 kJ ….(i) H ioniz   5.3 kJ / mol .
C  O2  CO 2 , H   395.5 kJ …..(ii) 122. (a) Strong acid (HNO 3 ) and strong base (LiOH) .
C  O2  CO 2 , H   395.5 kJ .….(ii) 123. (d) H  E  nRT or E  H  nRT
1 1
H 2  O 2  H 2 O, H   285.8 kJ …..(iii)  E  7.3   0.002  298  7.3  0.298 = 7 kcal.
2 2
from (i), (ii), (iii). 124. (b) Heat evolved during burning of 39 g
H (CH 4 )
comb . 781.0  39
 H f (CO 2 )  2H f (H 2 O)  H f (CH 4 )  2H f (O 2 ) C6 H 6   390.5 kcal mol 1
78
 890.4  395.5  2 (285.5)  H f (CH 4 )  2  0 1
125. (b) By (i) + (ii) ; Na  Cl 2  NaCl, H  196 kcal .
1 2
H f (CH 4 )  76.7 kJ mol .
108. (d) As methanoic acid is weak acid, heat of neutralization < x. 126. (b) C  O2  CO 2(g) , H of  393.5 kJ mol 1 ….(i)
109. (d) Neutralization of a strong acid by a strong base is always same. 1
C O 2  CO (g) , H of  110.5 kJ mol 1 ….(ii)
110. (c) S  O2  SO 2 , H f   4.6 kJ 2
 0.5 gm. of sulphur on burning produce 1gm of SO 2
 446 Thermodynamics and Thermochemistry
1 15 1
H2  O 2  H 2 O(g) , H of  241.8 kJmol 1 ...(iii) n  6  3  1   .
2 2 2
By (ii) + (iii) – (i) 140. (b) By 2 × (i) + (ii) – (iii)
CO 2(g)  H 2(g)  CO(g)  H 2 O(g) , H  41.2 . H of methane  20.0 kcal .
127. (c) More +ve is H s more is heat of solution. 141. (c) Heat of neutralization of strong acid and weak base is less than
128. (d) CS 2 is formed from its initial components carbon and sulphur 13.7 kcal mol 1 .
so, H is heat of formation of CS 2 . 142. (d) E  0 for a cyclic process.
129. (d) H  18500  E  nRT 143. (c) 22.0  2  44 kcal .
or 18500  E  (1)  2  298  19096 cal . 144. (b) 0.3 mole OH  , neutralize 0.3 mole of HNO 3
130. (b) Heat evolved during combustion of 0.39g
Evolved heat,  57.1  0.3  17.13kJ
3250  0.39
C6 H 6   16.25 kJ . 146. (d) Compounds with high heat of formation are less stable because
78 energy rich state leads to instability.
131. (d) By (i) – (ii) : C 
1
O 2  CO ; H  229.2. 445.15  16
2 147. (b) CH 4 required   8 gm .
890.3
132. (b) Strong acid (HCl) and strong base (NaOH ) shows 148. (c) C(s)  2 H 2 (g)  CH 4 (g) …..(i)
H neutralization = –57.3 kJ.
C(s)  O2(g)  CO 2(g) H  94 kcal mol 1 …..(ii)
133. (d) By (i) – (ii) and find required result.
1 1 1 1
134. (a) CO (g)  O 2  CO (g) , n  1  1    H 2( g )  O 2(g)  H 2 O(l) H  68 kcal mol 1 … (iii)
2 (g) 2 2 2
H  E  nRT CH 4  3 / O2  CO 2  2 H 2 O
2
1 8.314
H  283.3    290  284.5 kJ . H  213 kcal mol 1 … (iv)
2 1000
to obtain equation (i) operate-(ii) + 2 × (iii) – (iv).
1
135. (a) H2  O 2  H 2 O H  188 kJ /mole ..…..(i) 149. (b) H  ve for endothermic reactions.
2
150. (b) It pertains to neutralization of strong acid weak base.
H 2  O2  H 2 O2 ; H  286 kJ /mole ..….(ii)
151. (d) Strong base (KOH) and strong acid (HCl)
By 2 × (i) and (ii)
153. (b) This reaction absorbed heat, so it is endothermic reaction.
2 H 2  O2  2 H 2 O ; H  376 kJ /mole …..(iii)
154. (b) C  O2  CO 2 , H   94.3
2 H 2  2O2  2 H 2 O2 H  572 kJ /mole …..(iv)
This is also heat of formation of CO 2
By (iii) – (iv)
1
2 H 2 O2  2 H 2 O  O2 H  196 kJ . C O 2  CO , H  26.0 .
2
136. (a) H for C 2 H 6  341.1 K cal
1
155. (b) X Y .
341.1 2
its calorific value   11.37 kcal / g .
30 157. (a) Molecular weight of NH 4 NO 3  80
H for C 2 H 2  310.0 kcal
Heat evolved  1.23  6.12
310.0  Molar heat capacity  1.23  6.12  C .
its Calorific value   11.92,
26
158. (d) Both X e and F2 are gaseous elements at 25 o C and in their
hence C 2 H 2 is a better fuel.
standard states and form XeF4 (g) hence H (f )  H react

.
138. (c) For the decomposition of 9gm of water heat required
 142.5 kJ 159. (c) According to Hess low, enthalpy change for a reaction does not
depend on the nature of inter mediate reaction steps.
we know H 2 O  2  16  18
160. (d) By (ii) – (i), C gr  Cdia , H  1.9 .
Therefore heat required for decomposition of 18gm water
18 162. (c) Heat of neutralization of strong acid and strong base is equal
  142.5  285 KJ
9 to the  57.32 KJ mol 1
Than, enthalpy of formation of water is reverse of heat 163. (c) C  O2  CO 2 H  393.5 KJ / mol
required = – 285 kJ.
15  44 gm of CO 2 form by which heat released
139. (d) C6 H 6(g)  O 2(g)  6 CO 2(g)  3 H 2 O(g)
2  393. 5 kJ
 Thermodynamics and Thermochemistry 447

 1 gm of CO 2 form by which heat released  

393.5 H o  3920  2160  160  6240 KJ / mol
44
H o  for 6 moles of octane  6240  6
 35.2 gm (given) of CO 2 form by which heat released
 37440 KJ / mol  37.4 KJ
393.5
  35.2  315 kJ 3
44 171. (d) 2 Fe  O 2  Fe 2 O 3 ; H  193.4 kJ .....(i)
2
164. (c) C(graphite)  2 H 2 (g)  CH 4 (g)
1
165. (c) Heat of formation of a substance is the heat exchanged when Mg  O 2  MgO; H  140.2 kJ .....(ii)
one mole of that substance is formed by its constituent 2
elements. On multiplying eq. (ii) by 3
 Heat evolved when 1 mole (44 g) CO 2 is formed 3
3 Mg  O 2  3 MgO; H  420.6 kJ ......(iiii)
 393 kJ 2
 Heat evolved when 0.156 Kg (156 g) is formed Resulting equation can be obtained by subtracting eq. (i) from
(iii)
393  156
 3
44 3 Mg  O 2  3 MgO; H  420.6 kJ
2
 H for the process  1572 kJ  1572.0 kJ
3
2 Fe  O 2  Fe 2 O 3 ; H  193.4 kJ
166. (b) It is heat of neutralisation (13.7 Kcal) for strong acid and 2
strong base. Subtraction :
167. (d) C(s)  O2 (g)  CO 2 (g) 3 Mg  Fe2 O 3  2 Fe  3 MgO; H  227.2 kJ

H  393.5 KJ mol 1 …..(i) 172. (c) HCl and KOH both are strong

CO(g)  1 / 2O2 (g)  CO 2 (g)

Bond energy
1
H  283 KJ mol …..(ii)
1. (b) XY  X (g)  Y(g) ; H  a kJ / mole ……….(i)
On substracting equation (ii) from equation (i)
We get X 2  2 X ; H  a kJ / mole ………. (ii)
C(s)  O 2 (g)  CO(g) ; H  110.5 KJ mol 1 Y 2  2Y ; H  0.5 a kJ / mole ……….(iii)
The enthalpy of formation of carbon monooxide per mole
1 1
 110.5 KJ mol 1  (ii)  (iii)- (i), gives
2 2
168. (d) 1 mole (i.e.,) 16 gm of methane on combustion liberate 1 1
X 2  Y 2  XY ;
890 kJ 2 2
890  3 .2  a 0.5 
 3.2 gm will liberate   178 KJ H     a  a  kJ / mole
16  2 2 
169. (c) C  O 2  CO 2 ; H  q a 0 .5 a
   a  200
2 2
C  1 / 2O 2  CO ; H  12 …..(i)
a  800
CO  1 / 2O2  CO 2 ; H  10 …..(ii)
2. (a) 4 g H 2  2 moles. Bond energy for 1 mole of
adding equation (i) and (ii) we can get H 2  208 / 2  104 kcal.
H  12  (10)  22 4. (d) By definition of Hess’s law.
170. (b) C  O2  CO 2 ; H F  490 KJ / mol – (I) 1 1
5. (c) Aim: H 2  Cl 2  HCl
H 2  1 / 2O2  H 2 O; H F  240 KJ / mol – (II) 2 2
H   B. E.   B. E.
8 C  18 H  C8 H18 ; H F  160 KJ / mol – (III) (Products) (Reactants)
applying 1 1 
 B. E.( HCl )   B. E.( H 2 )  B. E.(Cl 2 )
(I) 8  (II) 9  (III) 2 2 

25 1 1 
C 8 H 18  O 2  8 CO 2  9 H 2 O  103   (  104 )  (  58)
2  2 2 
 103  (  52  29 )  22 kcal .
 448 Thermodynamics and Thermochemistry
6. (c) First ionization potential of Li  5.4 eV 14. (d) Spontaneous change shows G  ve .
Electron affinity of Cl  3.61eV 15. (b) G  H  TS , T  25  273  298 K
We have H  I.P.  E. A.  11.7  10 3  298  (105)  19590 J  19.59kJ
22
 5.4  3.61  1.80eV  1.80  1.6  10 kJ 18. (c) If G  ve reaction is spontaneous.
22
H  2.86  10 kJ , 20. (b) (dS )V , E  0, (dG)T , P  0 .
for 1mol Avogadro’s number  6.02  10 23
. 21. (b) Only high pressure favours the conversion.
22. (d) By 2× (ii) – (i) – (iii)
H  2.86  10 22  6.02  10 23  170 kJ / mole.
H 2(g)  2C(s)  C 2 H 2(g) , G   209 kJ .
166
7. (b)  41.5 kJ / mole .
4 23. (b) G  2.303 RT log K  , Here R  2 cal, T  300 K

1 1 10  15
8. (d) H 2  Cl 2  HCl, H  90 KJ K   10 ; G  2.303  2  300  log10 10
2 2 35
1 1  2.303  2  300  1  1381.8 cal
 H  E H  H  ECl Cl
2 2 24. (a) G  H  TS (Gibb’s free energy equation)
1 1 25. (d) G  H  TS
or  90   430   240  E HCl
2 2 G  382.64  (145.6)  10 3  298
 E H Cl  425 kJ mol 1 .  339.3 KJ mol 1
9. (b) CH 4  C  4 H , H  320 26. (d) G  H  TS ; G  E  PV  TS
For spontaneity (G  ve )
EC  H  90 cal
 G  ve , E  ve
C2 H 6  2C  6 H, H  360
27. (a) G  H  TS  31400  1273  32
 360  EC  C  6 EC  H  31400  40736  9336 cal
 EC  C  360  320  40 cal . 28. (d) G  H  TS
0  30.558  T  0.066
10. (b) H  H  Br  Br  2 H  Br
30.558
433  192 2  364 or T   463 K
0 .066
625 728
If (dG)T , P  0 sign ' ' mean. If is reversible process
Energy absorbed = Energy released
Net energy released  728  625  103 kJ
Critical Thinking Questions
i.e.,  H  103 KJ
1. (b) Due to randomness of particles is reduced since entropy
decreases.
Free energy and Work function
2. (c) H  nCp T
1. (d) G at equilibrium = 0. The process is isothermal therefore
2. (b) For spontaneous change G  ve . G  0 ;  H  0
3. (a) When G  ve than the reaction is spontaneous in nature.
3. (d) 13.7 kcal  57 kJ  5.7  10 4 J .
5. (acd)When H  ve and S  ve than the reaction is non-
spontaneous. 4. (b) When strong acid and strong base neutralize each other than the
value of heat generated is about 13.7 kcal.
7. (c) Because the reaction is spontaneous .
5. (b) Due to fall in temperature.
8. (c) G = –ve.
6. (d) q  H .
P p
9. (a) GT  nRT ln 2 .
P1 V2 V
7. (d) w  2 .303 RT log . As it involves the ratio 2 , volume
V1 V1
10. (a) G  0 for equilibrium.
can be used in any units. (R should be in joules).
11. (d) At equilibrium G  0 .
dQ dQ
12. (a) G o   2.303 RT log K 8. (b)   ; dE  dW  dQ ; dW  dQ  dE
dW dQ  dE
 4.606   2.303  0.002  500 log K nc p dT cp
 
log K  2, K  100 . nc p dT  ncv dT (c p  c v )
 Thermodynamics and Thermochemistry 449

7R 7R 26. (b) Heat required to rise the temperature of a body by 1 K called

 {for diatomic of gas c p  } thermal capacity of the body.
2R 2
9. (a) C 2 H 2 (g)  H 2 (g)  C 2 H 4 (g) 27. (e) Mechanical work is important only in gases as they undergo
appreciable change in volume.
ng  1  2  1 ; H  0.31 KJ mol 1 28. (d) It is Lavoisier and Laplace law. This is another law of
thermochemistry which was put forward before Hess's law.
P  1.5 atm , V  50 mL  0.050 L
29. (a) It is also known as "constant heat summation" law. It state that
H  E  PV the total amount of heat evolved or absorbed in a reaction is
same whether the reaction takes place in one step or in a
0.31  E  0.0076 ; E  0.3024 KJ number of steps.

10. (a) Since process is exothermic then heat is evolved due to this 30. (c) In this reaction n  2  4  2 so H  E .
temperature of water increases. 18.94  0.632  0 .998  122
31. (a) Q = 771.1 Kcal
11. (a) Because randomness is decreases. 1.89
12. (c) Conversion of graphite into diamond is an endothermic 32. (c) H  Ea for forward reaction  Ea for backward reaction
reaction. So, heat of diamond is higher than that of graphite.  19  9  10 kJ .
But S would be negative for the conversion of graphite into
diamond. 33. (d) Q  18.94  0.632  0.998  1000

13. (c) H and S both are ve for spontaneous change, and 57.4  x  12.13
H  ve for endothermic reaction. x  45.2
14. (a) G  H  TS is negative for spontaneity. 34. (c) Thermodynamics is a reversible process in which surroundings
are always equilibrium with system.
15. (a) Entropy (a measure of disorder) of universe is increasing
toward maximum. This is II law of thermodynamics. 4 .18
35. (a) 1 cal  4.18 J  4.18  10 7 erg   10 19 eV .
16. (a) For a pure substance TA and TB represent the same 1.602
temperature. Hence A is a correct choice. 36. (b) Order of bond energy : Cl 2  Br2  F2  I2 .
17. (a) For endothermic reaction enthalpy of products (H P ) > 37. (c) Heat energy is also involved when one allotropic form of an
element is converted in to another. graphite is the stabler
enthalpy of reactant (H R ) allotrope because the heat of transformation of
Hence, change in enthalpy, C(diamond )  C(graphite) .
H  H P  H R  Positive (i) C(dia)  O2(g)  CO 2(g)H  94.5kcal
18. (d) Suppose the no. of gm, 1gm for each case so the max. no of (ii) C(graphite)  O2(g)  CO 2(g)H  94.0 k cal
mole expected for SO 2 (g) which has to expected maximum
entropy. H transforma tion  94.5  (94.0)

3  0.5k cal .
19. (b) 2 Al  O 2  Al2 O3 , H  1596 kJ …..(i)
2 38. (b) The compound Y possess less energy than the X and thus Y is
3 more stable than X.
2Cr  O 2  Cr2 O3 , H  1134 kJ …..(ii)
2 39. (c) Both H and p are positive.
By (i) – (ii)
40. (a) For equilibrium G o  0 .
2 Al  Cr2 O3  2Cr  Al2 O3 , H  462 kJ . 41. (b) Equilibrium constant is decreases with temperature and H
20. (a) Bomb calorimeter is used to measure heat of reaction. is also decreases so it is –ve.
21. (b) Larger the number of C and H atoms, greater is the heat of 42. (a) The fusion temperature of napthalene is minimum, because it
combustion. is non-polar covalent compound and has less fusion
temperature.
22. (c) The bomb calorimeter is used to measure E .
43. (a) The bond energy of C  H bond is y kcal mol 1 .
H
|
E E > H N  N  3 H  H  2N  H
Enthalpy

23. (c)
a
44. (a)
H
a

945  3  436 |
H
Energy absorbed 2 (3  391 )  2346

Energy released

Energy Net. energy released = 2346 – 2253 = 93 kJ

24. (b) H Neutralization  57.1 kJ  13.7 kcal . i.e. ΔH = – 93 kJ .
25. (b) Backmann thermometer is used to measure low temperature.
 450 Thermodynamics and Thermochemistry
45. (d) If E  ve than the cell reaction will be spontaneous. angular and show some polarity which is higher than that of
ethanol so both assertion and reason are correct but reason is
46. (d) All are the correct statements. not explaination assertion.
47. (d) CH 2  CH 2(g)  H 2(g)  H 3 C  CH 3(g) 8. (a) The assertion that the increase in internal energy for the
vaporisation of one mole of water at 1 atm and 373 K is zero is
414  4  1656 414  6  2484 true and this is because that for all isothermal process internal
energy is zero.
615  1  615 347  1  347
9. (b) N 2 (g)  O 2 (g) ⇌ 2 NO (g)
435  1  435 2831
2706
We know that H  E  nRT
H  2706  2831  125 kJ n  2  2  0 hence, nRT  0
48. (b) It means that the heat absorbed when one gram molecule of Therefore, H  E
HCl is formed from its elements at 298 K is 10. (a) The enthalpies of neutralisation of strong acids and strong
 22.060 k cal . bases are same they are 13.7 Kcal. The reason is that it is heat
of formation of water from H and OH  ions.
49. (d) eq. (i) + eq. (ii) find the required result and divide by 2.  
H  OH  H 2 O, H  13.7 Kcal . Thus, both assertion
50. (d) For complete neutralization of strong acid and strong base and reason are true.
energy released is 57.32 KJ / mol 11. (a) Zeroth (law of temperature) can also be summarized as two
objects at different temperature in thermal contact with each
0.2  50
No. of mole of H 2 SO 4   10 2 other tend to move towards the same temperature.
1000
12. (d) Photo chemical reactions have ve G .
1
No. of mole of KOH   50  5  10 2
1000

So  57.32  10 2  0.5732 KJ  573.2 Joule .

51. (b) For Combustion reaction, H is negative,

n  (16  18)  (25  2)  7 , so S is ve , reaction is
spontaneous, hence G is –ve.

52. (a) G  H  TS , T  27  273  300 K

G  (285.8)  (300)(0.163)  236.9 kJ mol 1

Assertion & Reason

1. (b) Assertion and reason show, reaction at equilibrium state in
which G  0 , S  0 , H  0 .
2. (b) It is correct that on touching the ice we feel cold because ice
absorb heat from our hand.
3. (b) Entropy of ice is less than water because water molecules in
solid state lose kinetic energy and hence their tendency of
movement minimise. Hence entropy decrease in solid state. The
reason that ice have cage like structure is also correct but
reason is not or correct explanation for assertion.
4. (c) During isothermal expansion of an ideal gas against vacuum is 14. (e) Heat absorbed in a reaction at constant temperature and
zero because expansion is isothermal. The reason, that volume constant volume (Qv)  E .
occupied by the molecules of an ideal gas is zero, is false.
15. (c) Values of state functions depend only on the state of the
5. (a) it is fact that absolute values of internal energy of substances system and not on how it is reached.
can not be determined. It is also true that to determine exact
values of constituent energies of the substance is impossible. 16. (a) The properties whose magnitude depends upon the quantity of
matter present in the system are called extensive properties.
6. (b) Mass and volume are extensive properties. mass/volume is also an
extensive parameter. Here, both assertion and reason are true. 17. (c) Combustion reactions are always accompanied by the evolution
of heat therefore, for such reactions the value of H is always
7. (b) The molar entropy of vaporization of water it differ from negative.
ethanol due to hydrogen bonding according to VSEPR theory
water molecule having two lone pair of electron by which it
 Thermodynamics and Thermochemistry 451

18. (b) In an isothermal process change in internal energy (E) is

zero (as it is a fucntion of temperature).  According to first
law of thermodynamics
 q  w  E , hence Q  W (if E  0)

If a system undergoes a change in which internal energy of the

system remains constant (i.e., E  0 ), then W  Q .
This means that work done by the system equals the heat
absorbed by the system.
20. (e) If a refrigerator’s door is kept open room gets heated as heat
energy is released to the surroundings.
21. (c) Enthalpy is zero but entropy is not zero. Vibrational motion
exists even at absolute zero.
22. (c) It may involve increase or decrease in temperature of the
system. Systems in which such process occur, are thermally
insulated from the surroundings.
 452 Thermodynamics and Thermochemistry

1. The internal energy change when a system goes from state A (c) Entropy (d) Free energy
to B is 40 kJ/mole. If the system goes from A to B by a reversible
path and returns to state A by an irreversible path what would be 9. Which of the following statements is true [KCET 2002]
the net change in internal energy
(a) E is always greater than H
[CBSE PMT 2003]
(a) 40 kJ (b) > 0 kJ (b) E is always less than H
(c) < 40 kJ (d) Zero (c) E may be lesser or greater or equal to H
2. The correct relationship is [DPMT 2002]
(d) E is always proportional to H
(a) H  PV  V (b) H  nRT  E
10. Mass and energy are conserved is demonstrated by
(c) E  nRT  P (d) None of these
[MH CET 2002]
3. For CaCO 3 (s) ⇌ CaO(s)  CO 2 (g) at 977 o C ; H  176 kJ
(a) First law of thermodynamics
mol, then E is [BVP 2003]
(a) 180 kJ (b) 186.4 kJ (b) Law of conservation of energy
(c) 165.6 kJ (d) 160 kJ (c) Law of conservation of mass
4. Values of H and S for five different reactions are given below. (d) Modified form of I law of thermodynamics
st

Reaction H (kJ mol 1 ) S (JK 1 mol 1 ) 11. The enthalpy of the reaction,
I +98.0 +14.8 1
H 2 (g)  O 2 (g)  H 2 O(g) is H 1 and that of
II – 55.5 –84.6 2
III +28.3 –17.0
1
IV – 40.5 +24.6 H 2 (g )  O 2 (g)  H 2 O(l) is H 2 . Then [KCET 2004]
2
V + 34.7 0.0
On the basis of these values predict which one of these will be (a) H 1  H 2 (b) H 1  H 2  0
spontaneous at all tempeature
[Kerala PMT 2004; KCET 1988,90] (c) H 1  H 2 (d) H 1  H 2
(a) Reaction I (b) Reaction II
12. A reaction occurs spontaneously if
(c) Reaction III (d) Reaction IV
[MP PET 2002; CBSE PMT 2005]
(e) Reaction V
5. Molar heat capacity of water in equilibrium with ice at constant (a) TS  H and both H and S are +ve
pressure is [IIT JEE 1997]
(b) TS  H and both H and S are +ve
(a) Zero (b) Infinity ()
(c) TS  H and both H and S are +ve
(c) 40.45 kJ K 1mol 1 (d) 75.48 J K 1
(d) TS  H and H is +ve and S is –ve
6. Internal energy does not include
[AIIMS 1999; CPMT 2000] 13. Which expression is correct for the work done in adiabatic reversible
(a) Nuclear energy expansion of an ideal gas [AMU 2002]
(b) Rotational energy V2 T2
(c) Vibrational energy (a) W  nRT ln (b) W  n e ln
V1 T1
(d) Energy arising by gravitational pull


2
7. Two moles of an ideal gas expand spontaneously into a vacuum. The (c) W  PV (d) W   PdV
work done is [AMU 2000] 1

(a) 2 Joule (b) 4 Joule 14. If an endothermic reaction is non-spontaneous at freezing point of
(c) Zero (d) Infinite water and becomes feasible at its boiling point, then
8. Heat exchanged in a chemical reaction at constant temperature and [AIEEE 2002]
constant pressure is called as H is ve , S is +ve
(a)
[BHU 1998; Pb. PET 2000; MP PET 2002]
(b) H and S both are +ve
(a) Internal energy (b) Enthalpy
 Thermodynamics and Thermochemistry 453

(c) H and S both are –ve (a)  68.0 kJ mol 1 (b)  43.8 kJ mol 1
(d) H is +ve, S is –ve
(c) 68.0 kJ mol 1 (d) 43.8 kJ mol 1
1 1
JK mol
15. What is the entropy change (in ) when one mole of ice 21. Equilibrium constant of a reaction is related to
o
is converted into water at 0 C (The enthalpy change for the [AIIMS 1991]
1 o
conversion of ice to liquid water is 6.0 kJ mol at 0 C )[CBSE PMT 2003] (a) Standard free energy change G o
(a) 21.98 (b) 20.13
(b) Free energy change G
(c) 2.013 (d) 2.198
(c) Temperature T
30.5 kJ
16. One mole of NaCl (s) on melting absorbed of heat and (d) None
28.8 JK 1
its entropy is increased by . The melting point of 22. The standard Gibbs free energy change G o is related to
NaCl is [DPMT 2004] equilibrium constant K p as [MP PET/PMT 1998]
(a) 1059 K (b) 30.5 K
G o
(c) 28.8 K (d) 28800 K  e 
(a) K p   RT ln G o (b) Kp   
(H )  RT 
17. The enthalpy change for the process
1
N 2 H 4 (g)  2 N (g)  4 H (g) 1724 KJ mol G o 
G o
in . If the bond
(c) K p   (d) K p  e RT
1 RT
391 KJ mol
energy of N  H bond in ammonia is . What is the
23. The standard enthalpy or the decomposition of N 2 O 5 to NO 2 is
bond energy of N  N bond is 2 4
N H
58.04 kJ and standard entropy of this reaction is 176.7 J / K .
[MP PMT 2004]
The standard free energy change for this reaction at 25 o C is [DCE 2004]
(a) 160 KJ mol 1 (b) 391 KJ mol 1
(a) –5.38 kJ (b) 5.38 kJ
(c) 1173 KJ mol 1 (d) 320 KJ mol 1
(c) 5.38 kJ (d) –538 kJ
18. Liquid ammonia is used in refrigeration because of its
24. For the equilibrium H 2 O(l) ⇌ H 2 O(g) at 1 atm and 298 K
[DCE 2003]
(a) High dipole moment [AIIMS 2004]
(b) High heat of vaporisation (a) Standard free energy change is equal to zero (Go  0)
(c) High basicity
(b) Free energy change is less than zero (G  0)
(d) All of these
19. A cylinder of gas supplied by Bharat Petroleum is assumed to (c) Standard free energy change is less than zero (G o  0)
14 kg 20,000 kJ
contain of butane. It a normal family requires
(d) Standard free energy change is greater than zero (G o  0)
of energy per day for cooking, butane gas in the cylinder last for ….
Days [Kerala PMT 2004] 25. For reaction Ag 2 O(s)  2 Ag(s)  (1 / 2)O 2 (g) the value of
( H c of C4 H10  2658 KJ per mole )  H  30.56 kJ mol 1 and S  0.066 k JK 1 mol 1 .
(a) 15 days (b) 20 days Temperature at which free energy change for reaction will be zero,
is [MH CET 1999]
(c) 50 days (d) 40 days
(e) 32 days (a) 373 K (b) 413 K
(c) 463 K (d) 493 K
20. The heat of neutralization of HCl by NaOH under certain
condition is – 55.9 kJ and that of HCN by NaOH is –12.1 kJ. the
heat of ionization of HCN is [MP PET 2001]

(SET -10)

40
1. (d) A 
 B
40
A 
 B
 Thermodynamics and Thermochemistry 437
H  40  40  0 . means their energy  391  4  1564
2. (b) H  E  nRT . so the bond energy of N  N in N 2 H 4

3. (c) n  1  0  1  1724  1564  160 KJ / mol

18. (b) Ammonia has high heat of vaporisation hence is used in
E  H  nRT refrigeration.
8.314 19. (e) Calorific value of butane
E  176  1   1240  165.6 kJ .
1000 H c 2658
   45.8 KJ / gm
4. (d) A spontaneous process is accompanied by decrease in enthalpy mol. wt. 58
and increase in entropy means H is negative and S is Cylinder consist 14 Kg of butane means 14000 gm of
positive.
butane
 H   1gm gives 45.8 KJ
5. (b) C P    , At equilibrium T is constant i.e.  T  0,
 T  P
14000 gm gives 14000  45.8
thus C P   .
 641200 KJ
6. (d) E  Eele.  Enucl.  Echemical  Epotential
Family need 20,000 KJ / day
 Ekinetic(Et  Ev  Er ) .
641200
So gas full fill the requirement for  32.06 days
7. (c) An ideal gas under going expansion in vacuum shows, 20,000
E  0, W  0 and q  0 . 20. (d)
8. (b) H  q p . 21. (a) G o  2.303 log k .

E may be greater or lesser or equal to H .

o
9. (c) 22. (d) K p  e  G / RT
.
 H  E  PV  E  nRT. 23. (d)
10. (d) It is a modified form of Ist law of thermodynamics. It is a 24. (b) For reaction H 2 O(l) ⇌ H 2 O(g)
conservation law of mass and energy.
n  1 means positive
11. (a) for reaction (i) n1  0.5
so when n is positive then G  0 .
for reaction (ii) n 2  1.5 25. (c) G  H  TS
So, H 1  H 2 G  0 at equilibrium
 H  TS or 30.56  T  0.066
12. (b) For spontaneous reaction G should be negative
G  H  TS  (ve )  T (ve ) T  463 K .

If TS  H then G will be negative and reaction will be ***

spontaneous.
13. (b) W  PV .
14. (b) H and S both are +ve than reaction is spontaneous.
q rev 6000
15. (a) S    21.98 JK 1 mol 1
T 273

16. (a) NaCl(s) ⇌ NaCl(l)

Given that : H  30.5 KJ mol 1

S  28.8 JK 1  28.8  10 3 KJ K 1
H
By using S 
T
30.5
  1059 K
28.8  10 3
H H
| |
17. (a) H  N  N  H (So, 4 N  H bond present)
 Chemical Kinetics 455

Chapter

11
Chemical Kinetics

The branch of physical chemistry which deals with the rate at x dx  x 2  x 1 

or  
dt  t 2  t1 
which the chemical reactions occur, the mechanism by which the chemical
t
reactions take place and the influence of various factors such as
concentration, temperature, pressure, catalyst etc., on the reaction rates is where x or dx is the concentration change, i.e., (x 2  x 1 ) in the
called the chemical kinetics. time interval t or dt, i.e., (t 2  t1 ) .
Types of chemical reactions Concentration is generally expressed in active mass, i.e., mole L –1

 The rate measured over a long time interval is called average rate
On the basis of reaction rates, the chemical reactions have been
and the rate measured for an infinitesimally small time interval is called
classified into the following three types, instantaneous rate and
(1) Very fast or instantaneous reactions : These reactions occur at a Instantaneous rate  (Average rate)t 0
very fast rate generally these reactions involve ionic species and known as
 For the reaction aA  bB  cC  dD
ionic reactions. It is almost impossible to determine the rates of these
Rate of disappearance of a reactant is negative
reactions.
d [ A]
Examples   Rate of disappearance of A
dt
(i) AgNO 3  NaCl  AgCl  NaNO 3 (Precipitation reaction) d [ B]
(PPt.)   Rate of disappearance of B
dt
(ii) HCl  NaOH  NaCl  H 2 O (Neutralization reaction) Rate of formation of a product is positive
(acid) (base) (Salt)
d[C ]
(2) Moderate reaction : These reactions proceed with a measurable  Rate of formation of C
dt
rates at normal temperature and it is these reactions are studied in chemical
d[D]
kinetics. Mostly these reactions are molecular in nature.  Rate of formation of D
dt
Examples
 In terms of stoichiometric coefficient rate may be expressed as
(i) Decomposition of H 2 O 2 : 2 H 2 O2  2 H 2 O  O2 dx 1 d[ A] 1 d[B] 1 d[C] 1 d[D]
   
(ii) Decomposition of N 2 O5 : 2 N 2 O5  2 N 2 O4  O2 dt a dt b dt c dt d dt
 The rate of reaction is always positive.
(3) Very slow reactions : These reactions are extremely slow and  The rate of chemical reaction decreases as the reaction proceeds.
take months together to show any measurable change. Unit of conc.
 Unit of rate of a reaction = =mole L time –1 –1

Examples Unit of time

In term of gaseous reaction the unit is atm time and
(i) Rusting of iron : Fe2 O3  xH 2 O 
-1

Fe2 O3 . xH 2 O
1 1
Hydrated ferric oxide (Rust) Rate in atm time = Rate in mole L time  RT
-1

(ii) 2 H 2  O2    2 H 2 O
Room temperature Factors affecting rate of a reaction
The rate of a chemical reaction depends on the following things
Rate of a reaction (1) Nature of reactants
The rate (speed or velocity) of a reaction is the change in (i) Physical state of reactants : This has considerable effect over rate
concentration in per unit time. of reaction.
Conc. of product
Conc. (mole/lit.)

Conc. of reactant

Time (Sec)
 456 Chemical Kinetics
Gaseous satae  Liquidstate  Solid state Where k is called rate constant or velocity constant.
  dx
Decreasing rate of reaction When [ A]  [B]  1 mol / litre, then k
dt
(ii) Physical size of the reactants : Among the solids, rate increases
Thus, rate constant k is also called specific reaction rate.
with decrease in particle size of the solid.
 The value of rate constant depends on, nature of reactant,
(iii) Chemical nature of the reactants
temperature and catalyst. It is independent of concentration of the
(a) Reactions involving polar and ionic substances including the reactants.
proton transfer reactions are usually very fast. On the other hand, the n 1 1 n
reaction in which bonds is rearranged, or electrons transferred are slow.  litre  mol 
 Unit of rate constant     sec 1     sec 1
(b) Oxidation-reduction reactions, which involve transfer of  mol   litre
electrons, are also slow as compared to the ionic substance. Where n  order of reaction.
(c) Substitution reactions are relatively much slower. Rate law : Molecularity and Order of a reaction
(2) Effect of temperature : The rate of chemical reaction generally Molecularity is the sum of the number of molecules of reactants
increases on increasing the temperature. The rate of a reaction becomes involved in the balanced chemical equation. Molecularity of a complete
almost double or tripled for every 10 o C rise in temperature. reaction has no significance and overall kinetics of the reaction depends
Temperature coefficient of a reaction is defined as the ratio of rate upon the rate determining step. Slowest step is the rate-determining step.
constants at two temperatures differing by (generally 25°C and 35°C) 10°C. This was proposed by Van't Hoff.
Example : NH 4 NO 2  N 2  2 H 2 O (Unimolecular)
k at (t  10 o C) k 35 o C
  Temperatur e coefficien t   NO  O 3  NO 2  O 2 (Bimolecular)
k at t o C k 25 o C
(3) Concentration of reactants : The rate of a chemical reaction is 2 NO  O 2  2 NO 2 (Trimolecular)
directly proportional to the concentration of the reactants means rate of The total number of molecules or atoms whose concentration
reaction decreases with decrease in concentration. determine the rate of reaction is known as order of reaction.
(4) Presence of catalyst : The function of a catalyst is to lower down Order of reaction = Sum of exponents of the conc. terms in rate law
the activation energy. The greater the decrease in the activation energy
For the reaction xA  yB  Products
caused by the catalyst, higher will be the reaction rate.
Reaction path
Without catalyst The rate law is Rate  [A]x [B[y
E a
Then the overall order of reaction. n  x  y
E a
Reaction where x and y are the orders with respect to individual reactants.
path with
catalyst  If reaction is in the form of reaction mechanism then the order is
Potential Energy

determined by the slowest step of mechanism.

Reactants
Energy of Reaction 2 A  3 B  A2 B3
Products A  B  AB(fast )
A catalyst changes the reaction path AB  B2  AB3 (slow) (Rate determining step)
(5) Effect of sunlight : There are many chemical reactions whose
rate are influenced by radiations particularly by ultraviolet and visible light. AB3  A  A2 B3 (fast )
Such reactions are called photochemical reactions. For example, (Here, the overall order of reaction is equal to two.)
Photosynthesis, Photography, Blue printing, Photochemical synthesis of
compounds etc.  Molecularity of a reaction is derived from the mechanism of the given
The radiant energy initiates the chemical reaction by supplying the reaction. Molecularity can not be greater than three because more than three
necessary activation energy required for the reaction. molecules may not mutually collide with each other.
 Molecularity of a reaction can't be zero, negative or fractional.
Law of mass action and Rate constant order of a reaction may be zero, negative, positive or in fraction and greater
The rate at which a substance reacts is directly proportional to its than three. Infinite and imaginary values are not possible.
active mass and the rate at which a reaction proceeds is proportional to the  When one of the reactants is present in the large excess, the
product of the active masses of the reacting substances. second order reaction conforms to the first order and is known as pesudo
 For a reaction, aA  bB  product unimolecular reaction. (Table 11.1)
 dx   dx 
Rate     [ A]a [B]b ;    k [ A]a [B]b
 dt   dt 
Table : 11.1 Order and molecularity of some reaction
S. Chemical equation Molecularity Rate law Order w.r.t.
No. First Second reactant Overall
reactant
1. aA  bB  product a+b  dx  a b a+b
   k [ A]a [B]b
 dt 
2. aA  bB  product a+b  dx  2 zero, if B is in excess 2
   k [ A]2 [B]0
 dt 
3. Pt, 
2 H 2O2   2 H 2O  O2 2 (Bimolecular)  dx  1* ----- 1
   k [H 2 O2 ]
 dt 
 Chemical Kinetics 457
4.  2 (Bimolecular)  dx  1* Zero, if H O is in 1
CH 3 COOC 2 H 5  H 2O 
H
    k [CH 3 COOC 2 H 5 ] excess
2

CH 3 COOH  C2 H5 OH  dt 
5.  2 (Bimolecular)  dx  1* Zero, if H O is in 1
C12 H 22 O11  H 2 O 
H
    k [C12 H 22 O11 ] excess
2

Sucrose
 dt 
C6 H12 O6  C6 H12 O6
Glucose Fructose
6. (CH 3 )3 CCl  OH   2 (Bimolecular)  dx  1* Zero, if OH does not
–
1
   k [(CH 3 )3 CCl ] take part in slow
(CH 3 )3 COH  Cl   dt  step
7.  2 (Bimolecular)  dx  1 1 2
CH 3 Cl  OH  CH 3 OH  Cl     k [CH 3 Cl ][OH  ]
 dt 
8. 
C6 H 5 N 2Cl  C6 H 5 Cl  N 2 1 (Unimolecular)  dx  1 ---- 1
   k [C6 H 5 N 2 Cl ]
 dt 
9. 
CH 3 CHO  CH 4  CO 1 (Unimolecular)  dx  1.5 ---- 1.5
   k [CH 3 CHO ]3 / 2
 dt 
10. H 2O2  2 I   2 H   2 H 2O  I2 5  dx  1 1 2
   k [H 2 O2 ][I  ] (H is medium)
+

 dt 
11. 2O3  3O2 2 (Bimolecular)  dx  1 -1 with respect to O 1
   k [O 3 ] [O 2 ]
2
2

 dt 
*Pseudo-unimolecular reactions.
Table : 11.2 Rate constant and other parameters of different order reactions
Order Rate constant Unit of rate Effect on rate by changing conc. (Half-life period) T = 50

constant to m times
0 x conc. time –1
No change a
k0  (mol L s ) –1 –1

t 2k 0
1 2 .303  a  time (s ) –1 –1
m times 0 .693
k t
k1  log10   , C  C0 e 1
t ax  k1
2 .303 (a  x1 )
N  N 0 e  k 1 t , k1  log10
(t2  t1 ) (a  x 2 )
2 1  1 1 x conc time –1 –1
m times
2

1
k2      (for the case when (mol L ) s –1 –1

t  (a  x ) a  ta(a  x) L mol s –1 –1
k 2a
each reactant has equal concentration)
2 .303  b(a  x ) 
k2  log10   (for the case when both
t(a  b)  a(b  x ) 
reactants have different concentration)
3 1  1 1  conc time –2 –1
m times
3

3
k3     (mol L ) s –1 –2 –1

2 t  (a  x )2 a 2  2k 3 a 2
L mol s
2 –2 –1

n 1  1 1  conc time (1–n) –1

m times
n

2n 1  1
kn   n 1
 n 1  ; n  2 (mol L ) s –1 (1–n) –1

(n  1)t  (a  x ) (a)  L mol s

(n–1) (1–n) –1 (n  1)k n (a)n 1

Methods for determination of order of a reaction k

2 .303
log10
a
(For first order reactions)
(1) Integration method (Hit and Trial method) t (a  x )
(i) The method can be used with various sets of a, x and t with 1 1 1 
k  (For second order reactions)
integrated rate equations. t  a a  x 
(ii) The value of k is determined and checked for all sets of a, x
1  1 1 
and t .   2 k
(For third order reactions)
2 t  (a  x ) 2
a 
(iii) If the value of k is constant, the used equation gives the order
of reaction. (2) Half-life method : This method is employed only when the rate
law involved only one concentration term.
(iv) If all the reactants are at the same molar concentration, the
kinetic equations are : t1 / 2  a 1n ; t1 / 2  ka 1n ; log t1 / 2  logk  (1  n) loga
 458 Chemical Kinetics
A plotted graph of logt1 / 2 vs log a gives a straight line with slope Subtracting equation (ii) from (i),
(1  n) , determining the slope we can find the order n. If half-life at  dC1   dC2 
log10    log10  
different concentration is given then,
n  dt   dt  …..(iii)
n 1 log10 C1  log10 C 2
1 1 (t ) a 
(t1 / 2 )1  ; (t1 / 2 )2  n 1 ; 1 / 2 1   2 
a1n 1 a2 (t1 / 2 )2  a1  dC1 dC 2
and are determined from concentration Vs time
dt dt
log10 (t1 / 2 )1  log10 (t1 / 2 )2  (n  1) [log10 a2  log10 a1 ]
graphs and the value of 'n' can be determined.
log10 (t1 / 2 )1  log10 (t1 / 2 )2 (5) Ostwald's isolation method (Initial rate method)
n 1
(log10 a 2  log10 a1 ) This method can be used irrespective of the number of reactants
This relation can be used to determine order of reaction ‘n’ involved e.g., consider the reaction, n1 A  n2 B  n3 C  Products .
Plots of half-lives Vs concentrations (t  a ) 1/2
1–n
This method consists in finding the initial rate of the reaction taking
known concentrations of the different reactants (A, B, C).
Zero order 1st order 2nd order 3rd order
Suppose it is observed as follows,
t1/2 
t1/2 

t1/2 
t1/2 

(i) Keeping the concentrations of B and C constant, if concentration

of A is doubled, the rate of reaction becomes four times. This means that,
Rate  [A] 2 i.e., order with respect to A is 2
Conc. Conc. 1/a 1/a2
(3) Graphical method : A graphical method based on the respective (ii) Keeping the concentrations of A and C constant, if concentration
rate laws, can also be used. of B is doubled, the rate of reaction is also doubled. This means that, Rate
 [B] i.e., order with respect to B is 1
(i) If the plot of log(a  x ) Vs t is a straight line, the reaction
follows first order. (iii) Keeping the concentrations of A and B constant, if
concentration of C is doubled, the rate of reaction remains unaffected. This
1 means that rate is independent of the concentration of C i.e., order with
(ii) If the plot of Vs t is a straight line, the reaction
(a  x ) respect to C is zero. Hence the overall rate law expression will be, Rate =
follows second order. k[A] [B] [C]
2 0

(iii) If the plot of

1
Vs t is a straight line, the reaction  Overall order of reaction = 2 + 1 + 0 = 3.
(a  x )2 Theories of reaction rate
follows third order.
(1) Collision theory
1
(iv) In general, for a reaction of nth order, a graph of (i) The basic requirement for a reaction to occur is that the reacting
(a  x )n 1 species must collide with one another. This is the basis of collision theory
Vs t must be a straight line. for reactions.
Plots from integrated rate equations (ii) The number of collisions that takes place per second per unit
volume of the reaction mixture is known as collision frequency (Z). The
Zero order 1st order 2nd order 3rd order
Conc. [A] 

log. [A] 

value of collision frequency is very high of the order of 10 25 to 10 28 in

1 1
case of binary collisions.
[ A] [ A]2
(iii) Every collision does not bring a chemical change. The collisions
t t t t that actually produce the product are effective collisions. The effective
collisions, which bring chemical change, are few in comparison to the total
Plots of rate Vs concentrations [Rate = k(conc.) ] n

number of collisions. The collisions that do not form a product are

Zero order 1st order 2nd order 3rd order ineffective elastic collisions, i.e., molecules just collide and disperse in
Rate 
Rate 

different directions with different velocities.

Rate 
Rate 

Fraction of molecules
capable of bringing
effective collisions
Conc. Conc. (Conc.) 2

(Conc.)3
Fraction of
molecules

(4) Van't Haff differential method : The rate of reaction varies as

the n power of the concentration Where ' n' is the order of the reaction.
th

Thus for two different initial concentrations C1 and C 2 equation, can be

Energy E
written in the form, Distribution of energies at a definite
dC1 dC2 temperature
 kC 1n and  kC 2n (iv) For a collision to be effective, the following two barriers are to be
dt dt cleared,
Taking logarithms, (a) Energy barrier : “The minimum amount of energy which the
 dC1  colliding molecules must possess as to make the chemical reaction to occur,
log10    log10 k  n log10 C1 …..(i) is known as threshold energy”.
 dt   In the graph 'E' corresponds to minimum or threshold energy for
 dC 2  effective collision.
and log10    log10 k  n log10 C 2 …..(ii)
 dt 
 Chemical Kinetics 459
 There is an energy barrier for each reaction. The reacting species must Ea  E(Threshold energy)  E(Reactants)
be provided with sufficient energy to cross the energy barrier.
(b) Orientation barrier : The colliding molecules should also have Activation energy = Threshold energy – Average kinetic energy of
proper orientation so that the old bonds may break and new bonds are the reacting molecules.
formed. For example, NO 2 (g)  NO 2 (g)  N 2 O 4 (g). During this (a) Zero activation energy = Fraction of effective collision (f) will be
reaction, the products are formed only when the colliding molecules have very large = Very fast reaction (Instantaneous reaction).
proper orientation at the time of collisions. These are called effective
collisions. (b) Low activation energies = Fraction of effective collision (f) will
be large = Fast reactions.
Collisions not properly oriented
(c) High activation energies = Fraction of effective collision (f) will
O O be small = Slow reaction.
O O
N O N Molecules N O Molecules
The activation energy (Ea ) depends upon the nature of chemical
approach N Separate N N
O O O bonds undergoing rupture and is independent of enthalpies of reactants and
O O O products.
NO2 + NO2 Collision NO2 NO2
No product According to the concept of activation energy, the reactants do not
Properly oriented collisions form products change directly into the products. The reactant first absorb energy equal to
O O activation energy and form activated complex. At this state, the molecules
O O O O
Molecules
must have energy at least equal to the threshold energy. This means that the
N N N N Bond N N
approach
reaction involves some energy barrier which must be overcome before
Formation
O O O O O O products are formed. The energy barrier is known as activation energy barrier.
Threshold Activated
NO2 + NO2 Product energy (E ) complex
Collision N2O4 Et t

of collision
(v) Thus, the main pointsFig. 11.1 theory are as follows, Energy barrier
Ea (activation energy)
(a) For a reaction to occur, there must be collisions between the
reacting species.
(b) Only a certain fraction of the total number of collisions is Er Reactants
Energy of the
E reaction
effective in forming the products. (E )
Ep
r

Products (E )
(c) For effective collisions, the molecules should possess sufficient p

energy as well as orientation.

(vi) The fraction of effective collisions, under ordinary conditions
may vary from nearly zero to about one for ordinary reactions. Thus, the
rate of reaction is proportional to :
(a) The number of collisions per unit volume per second (Collision
frequency, Z) between the reacting species
(b) The fraction of effective collisions (Properly oriented and
possessing sufficient energy), f i.e., Rate 
dx
 fZ
dt
Where f is fraction of effective collision and Z is the collision
frequency.
(vii) The physical meaning of the activation energy is that it is the
minimum relative kinetic energy which the reactant molecules must possess
for changing into the products molecules during their collision. This means
that the fraction of successful collision is equal to e  Ea / RT called
Boltzmann factor.
(viii) It may be noted that besides the requirement of sufficient
energy, the molecules must be properly oriented in space also for a collision
to be successful. Thus, if Z AB is the collision frequency, P is the orientation
factor (Steric factor) then, k  PZ AB .e  Ea / RT . If we compare this
equation with Arrhenius equation. k  A e  Ea / RT
We know that pre-exponential form 'A' in Arrhenius equation is,
A  PZ AB .
Concept of activation energy
The excess energy (Over and above the average energy of the
reactants) which must be supplied to the reactants to undergo chemical
reactions is called activation energy (Ea ) ,
Progress of reaction
(2) Transition state theory
(i) According to transition state theory the activated complex is
supposed to be in equilibrium with the reactant molecules.
(ii) Once the transition state is formed it can either return to the
initial reactants or proceeds to form the products.
(iii) Assuming that once formed the transition state proceeds to products
we can say that rate is proportional to concentration of transition state.
Mathematically, Rate  Transition state
Rate= Constant × Transition state
(iv) The activation energy for the forward reaction, (Eaf ) and the
activation energy for the reverse reaction (Ear ) are related to the enthalpy
(H ) of the reaction by the equation H  Eaf  Ear .
(a) For endothermic reactions, H  0, so that Ear  Eaf
(b) For exothermic reaction, H  0, so that Ear  Eaf .
Arrhenius equation
Arrhenius proposed a quantitative relationship between rate
constant and temperature as,
k  A e  Ea / RT …..(i)
The equation is called Arrhenius equation.
In which constant A is known as frequency factor. This factor is related
to number of binary molecular collision per second per litre.
Ea is the activation energy.
T is the absolute temperature and
R is the gas constant
Both A and Ea are collectively known as Arrhenius parameters.
Taking logarithm equation (i) may be written as,
 460 Chemical Kinetics
Ea is consumed in the following two reactions, 2 NO 2 

k
log k  log A  …..(ii)
1
N 2 O4 ;
2 .303 RT
NO 2  SO 2 
 NO  SO 3
2 k
The value of activation energy (Ea ) increases, the value of k
decreases and therefore, the reaction rate decreases. The rate of disappearance of NO 2 will be sum of the rates of the
When log k plotted against 1 / T , we get a straight line. The d[ NO 2 ]
two reactions i.e.,   2k1 [ NO 2 ]2  k 2 [ NO 2 ][SO 2 ]
 Ea dt
intercept of this line is equal to log A and slope equal to .
2 .303 R Photochemical reaction
Therefore Ea  2.303 R  slope . Absorption of radiant energy by reactant molecules brings in
photophysical as well as photochemical changes. According to Einstein's law
of photochemical equivalence, the basic principle of photo processes, each
reactant molecule is capable of absorbing only one photon of radiant
log k

energy. The absorption of photon by a reactant molecule may lead to any of

the photo process. Reactant molecule
Slope   Ea
2 .303 R
Absorption of photon (As
per Einstein law)
1/T
Rate constants for the reaction at two different temperatures T1 Excitation of Knock out the electron from
and T2 , electronic level the reactant species

k2 Ea  1 1 
log     …..(iii) Excited molecule Photoelectric effect
k1 2 .303 R  T1 T2 
where k 1 and k 2 are rate constant at temperatures T1 and T2
respectively (T2  T1 ) . Photophysical process Photochemical process
(i) Oxidation
Mechanism of the reaction (i) Fluorescence (ii) Reduction
(ii) Phosphorescence (iii) Dissociation
(1) Reaction involving first order consecutive reactions (iv) Double decomposition
(i) In such reactions, the reactions form a stable intermediate (v) Isomeric transformation
compound before they are finally converted into the products. (vi) Photosensitization
(ii) For example, reactants (R) are first converted to intermediate (I)
which is then converted to product (P) as The chemical reactions, which are initiated as a result of absorption
of light, are known as photochemical reactions. In such cases, the absorbed
R  I  P
k1 k2
energy is sufficient to activate the reactant molecules to cross the energy
Therefore, the reaction takes place in two steps, both of which are barrier existing between the reactants and products or in other words,
first order i.e., energy associated with each photon supplies activation energy to reactant
molecule required for the change.
Step I : R  k1
I ; Step II : I  k2
P
(1) Characteristics of photochemical reactions
This means that I is produced by step I and consumed by step II. In these
(i) Each molecule taking part in a photo process absorbs only one
reactions, each stage will have its own rate and rate constant the reactant
concentration will always decrease and product concentration will always hc
photon of radiant energy thereby increasing its energy level by hv or
increase as shown in fig. 
P
(ii) Photochemical reactions do not occur in dark.
Concentration

(iii) Each photochemical reaction requires a definite amount of

I
energy which is characteristic of a particular wavelength of photon. For
example, reactions needing more energy are carried out in presence of UV
R
light (lower  , more E/Photon). A reaction-taking place in UV light may
Time
not occur on exposure to yellow light (lower  and lesser E/Photon)
Concentration profile of reactants (R), intermediate (I)
(iv) The rate of photochemical reactions depend upon the intensity
and products (P) as a function of time
of radiation’s absorbed.
(2) Reaction involving slow step : When a reaction occurs by a (v) The G values for light initiated reactions may or may not be
sequence of steps and one of the step is slow, then the rate determining negative.
step is the slow step. For example in the reaction (vi) The temperature does not have marked effect on the rate of
R  k1
I ; I  k2
 P , if k1  k 2 then I is converted into light initiated reactions.
products as soon as it is formed, we can say that (2) Mechanism of some photochemical reactions
d [ R ] d [ P ] (i) Photochemical combination of H and Cl : A mixture of H 2 and
  k1 [R]
2 2

dt dt Cl 2 on exposure to light give rise to the formation of HCl, showing a

(3) Parallel reactions : In such type of reactions the reactants are
more reactive, which may have different orders of the reactions taking place chain reaction and thereby producing 10 6 to 10 8 molecules of HCl per
simultaneously. For example, in a system containing NO 2 and SO 2 , NO 2 photon absorbed.
H 2  Cl2   2 HCl
sunlight
 Chemical Kinetics 461
The mechanism leading to very high yield of HCl as a result of
chemical change can be as follows. Chlorine molecules absorb radiant  Different reactions have different rates because their activation
energy to form an excited molecule which decomposes to chlorine free energies are different. Lesser the activation energy faster is the reaction.
radicals (Cl) to give chain initiation step. 1
 The reaction, NO  O2  NO 2 , exhibits a small negative
Light absorption step : Cl 2 

hv
Cl 2* ........(i) 2
  temperature coefficient and the rate of reaction decreases with increase of
Chain initiation step : Cl2  Cl  Cl
*
........(ii) temperature.
The chlorine free radical then combines with H 2 molecule to form  Fuels in contact with oxygen do not burn by themselves. This is because
HCl and H  free radical. The H  free radical so formed again combines they need activation energy (provided by the flame) to initiate the reaction.
Thus, fuels are thermodynamically unstable ( G is –ve) but kinetically
with another Cl 2 molecule to give HCl and Cl  free radical back resulting stable.
into chain propagation step.
 Quantum efficiency of the photochemical reaction,
Chain propagation step : Cl   H 2  HCl  H  ........(iii) H 2  Cl2 
hv
2 HCl is very high while that of
 
H  Cl 2  HCl  Cl H 2  Br2 
hv
2 HBr , is very low. This is because after the chain
The combination of two
terminating step.
Cl 
free radicals leads to chain 
initiating step X 2 
hv

2 X Cl  H 2  HCl  H is exothermic
whereas Br  H 2  HBr  H is endothermic.
Chain terminating step : Cl   Cl   Cl 2 ........(iv)
(ii) Photochemical combination of H and Br : The combination of
2 2
 Drapper’s effect : H 2  Cl2  2 HCl , Such reactions are
H 2 and Br2 to form HBr in presence of light is also an example of chain accompanied by the increase in the volume. This is called Drapper’s
effect. The reason is that the reaction is exothermic and heat released
reaction like photochemical combination of H 2 and Cl 2 . Here two Br2
raises the temperature and gas expands resulting in the increase in
molecules absorb photon, however, inspite of chain reaction only one volume.
molecule of HBr is formed for each 100 photon absorbed by 100 molecules
 Actinometer : A device which is used to measure the intensity of
of Br2 .
radiation is konwn as actimometer. e.g., Uranyl oxalate actinometer.
H 2  Br2  2 HBr
light
A0
 Amount of the substance left after ‘n’ half lives  .
Mechanism 2n
Light absorption step : Br2  hv  Br2* ........(i)  Free energy change (G) for thermochemical reactions is always
  negative but remember, G for photochemical reaction may not always
Chain initiation step : Br2  Br  Br
*
........(ii)
be negative. It may be +ve also because a part of the light energy
Chain propagation step : Br*  H 2  HBr  H  ........(iii) absorbed is converted into the free energy of the products.

H  Br2  HBr  Br ........(iv)
*  Negative catalysts or inhibitors are those substances which decrease
the rate of a reaction.
Chain termination step : Br  Br  Br2 ........(v)  Example of fourth order reaction, 4 KClO3 ⇌ 3 KClO4  KCl
The lower values of HBr formation per photon of light absorbed has
been attributed to the fact that step (III) is highly endothermic and thus  Grothus-Draper law : When light falls on a substance, a part of
before step (III) can take place most of the bromine free radicals recombine light is absorbed, a part is reflected and a part is transmitted. only that
part of light which is absorbed causes a particular reaction to occur.
as per step (V) to give Br2 molecule and thus providing less feasibility for
step (IV) i.e. steps regenerating free radicals. Also the decomposition of HBr  Stark’s Einstein law of photochemical equivalence According to this law,
increases with increase in temperature. every atom or molecule taking part in photochemical reaction absorbs only one
quantum of radiaton.
(3) Quantum yield (or quantum efficiency) : The quantum efficiency
or yield   of a photochemical reaction may be expressed as,  Kinetics of fast reactions can be studied by (i) Relaxation method
(ii) Flash photolysis technique etc.
No. of molecules reacted or product formed
  Enzyme catalysed reactions are faster than metal catalysed
No. of photon absorbed
reactions, the former has lower activation energy.
(4) Application of photochemistry : Photochemistry has significant
role in our daily life. Some of the photochemical reactions commonly known
as cited below,
(i) Photosynthesis in plants
(ii) Photography
(iii) The formation and destruction of ozone layer
(iv) Photoetching in electronic industry
(v) Many polymerization reactions. Rate of a reaction
(vi) Modern printing technology
(vii) Free radical combinations to obtain many compounds. 1. The rate of a chemical reaction
[MP PMT 1973; CPMT 1982]
(a) Increases as the reaction proceeds
(b) Decreases as the reaction proceeds
(c) May increase or decrease during the reaction
(d) Remains constant as the reaction proceeds
 462 Chemical Kinetics
2. The rate of a reaction that not involve gases is not dependent on [CPMT 1988; AFMC 1995]
(a) Pressure (b) Temperature
(c) Concentration (d) Catalyst
3. The rate at which a substance reacts depends on its
[MP PMT 1987; BHU 1999; KCET 2005]
(a) Atomic weight (b) Equivalent weight
(c) Molecular weight (d) Active mass
4. The rate law for the reaction
RCl  NaOH(aq)  ROH  NaCl is given by Rate
 K1 [RCl] . The rate of the reaction will be [IIT 1988]
(a) Doubled on doubling the concentration of sodium hydroxide
(b) Halved on reducing the concentration of alkyl halide to one half
(c) Decreased on increasing the temperature of the reaction
(d) Unaffected by increasing the temperature of the reaction
5. If doubling the concentration of a reactant `A' increases the rate 4
times and tripling the concentration of `A' increases the rate 9
times, the rate is proportional to [AIIMS 1991]
(a) Concentration of `A'
(b) Square of concentration of `A'
(c) Under root of the concentration of `A'
(d) Cube of concentration of `A'
6. The rate of chemical reaction at constant temperature is
proportional to
(a) The amount of products formed
(b) The product of masses of the reactants
(c) The product of the molar concentration of the reactants
(d) The mean free path of the reaction
7. The concentration of a reactant decreases from 0.2 M to 0.1 M in 10
minutes. The rate of the reaction is
(a) 0.01 M (b) 10 2
3 1
(c) 0.01 mol dm min (d) 1 mol dm 3 min 1
8. When a reaction is progressing
(a) The rate of the reaction goes on increasing
(b) The concentration of the products goes on decreasing
(c) The concentration of the reactants goes on decreasing
(d) The reaction rate always remains constant
 Chemical Kinetics 463

9. In a catalytic conversion of N 2 to NH 3 by Haber's process, the (a) Volume

rate of reaction was expressed as change in the concentration of (b) Force
(c) Pressure
ammonia per time is 40  10 3 mol litre1 s 1 . If there are no side (d) Concentration of reactant
reaction, the rate of the reaction as expressed in terms of hydrogen
20. For a given reaction 3 A  B  C  D the rate of reaction can be
is (in mol litre1 s 1 ) represented by [DCE 2000]
(a) 60  10 3 (b) 20  10 3 1 d[ A] d[B] d[C] d[D]
(a)    
(c) 1.200 (d) 10.3  10 3 3 dt dt dt dt
10. If the concentration of the reactants is increased, the rate of reaction 1 d[ A] d[C]
(b)    K[ A]m [B]n
[MP PMT 1989] 3 dt dt
(a) Remains unaffected (b) Increases 1 d[ A] d[C]
(c) Decreases (d) May increase or decrease (c)    K[ A]n [B]m
3 dt dt
11. Time required for completion of ionic reactions in comparison to (d) None of these
molecular reactions is
21. For the reaction N 2  3 H 2  2 NH 3
(a) Maximum (b) Minimum
(c) Equal (d) None [ NH 3 ] [H 2 ]
if  2  10  4 mol l 1 s 1 , the value of would be
12. For reaction 2 A  B  products, the active mass of B is kept t t
constant and that of A is doubled. The rate of reaction will then [MP PET 1993] [MP PMT 2000]
4 1 1
(a) Increase 2 times (b) Increase 4 times (a) 1  10 mol l s (b) 3  10 mol l 1 s 1
4

(c) Decrease 2 times (d) Decrease 4 times

(c) 4  10 4 mol l 1 s 1 (d) 6  10 4 mol l 1 s 1
13. In a reaction 2 A  B  A2 B , the reactant A will disappear at
[MP PET 1993] 22. A gaseous hypothetical chemical equation 2 A ⇌ 4 B  C is carried
out in a closed vessel. The concentration of B is found to increase by
(a) Half the rate that B will decrease
(b) The same rate that B will decrease 5  10 3 mol l 1 in 10 second. The rate of appearance of B is [AFMC 2001]
(c) Twice the rate that B will decrease (a) 5  10 4 mol l 1 sec 1 (b) 5  10 5 mol l 1 sec 1
(d) The same rate that A 2 B will form
(c) 6  10 5 mol l 1 sec 1 (d) 4  10 4 mol l 1 sec 1
14. The rate of a gaseous reaction is given by the expression K [ A][B] . 23. The rate of a chemical reaction depends upon
If the volume of the reaction vessel is suddenly reduced to 1/4th of [AFMC 2002]
the initial volume, the reaction rate relating to original rate will be[Roorkee 1992] (a) Time (b) Pressure
(a) 1/10 (b) 1/8 (c) Concentration (d) All of these
(c) 8 (d) 16 24. The rate of disappearance of SO 2 in the reaction 2SO 2  O2  2SO 3
15. A catalyst increases the rate of reaction because it
[EAMCET 1992] is 1.28  10 3 g / sec then the rate of formation of SO 3 is
(a) Increases the activation energy (a) 0.64  10 3 g / sec (b) 0.80  10 3 g / sec
(b) Decreases the energy barrier for reaction
(c) Decreases the collision diameter (c) 1.28  10 3 g / sec (d) 1.60  10 3 g / sec
(d) Increases the temperature coefficient 25. When the concentration of A in the reaction A  B ⇌ AB is
16. For the reaction N 2 (g)  3 H 2 (g)  2 NH 3 (g) under certain doubled, the rate of reaction will be [MP PMT 2002]
conditions of temperature and partial pressure of the reactants, the (a) Doubled (b) Decreased by half
(c) Unchanged (d) Increased by four times
rate of formation of NH 3 is 0.001 kg h 1 . The rate of conversion
26. The velocity of the chemical reaction doubles every 10 o C rise of
of H 2 under the same conditions is
temperature. If the temperature is raised by 50 o C , the velocity of
[IIT 1994] the reaction increases to about
4
(a) 1.82  10 kg / hr (b) 0.0015 kg / hr (a) 32 times (b) 16 times
(c) 20 times (d) 50 times
(c) 1.52  10 kg / hr
4
(d) 1.82  10 14 kg / hr
27. An increase in temperature by 10 o C , generally increases the rate
17. In the reaction 2 A  B  A2 B , if the concentration of A is of a reaction by
doubled and of B is halved, then the rate of the reaction will [MP(a) 2 times
PET 1994; CBSE PMT 2000] (b) 10 times
(a) Increase by four times (b) Decrease by two times (c) 9 times (d) 100 times
28. The temperature coefficient for reaction in which food deteriorates
(c) Increase by two times (d) Remain the same
is 2. Then food deteriorates ...... times as rapidly at 25 o C as it
 dc 
18. The term    in a rate equation refers to the does at 5 o C
 dt  (a) Two (b) Four
[MP PMT 1996] (c) Six (d) Twenty
(a) Concentration of the reactant
(b) Decrease in concentration of the reactant with time 29. The rate of a reaction is doubled for every 10 o rise in temperature.
The increase in reaction rate as a result of temperature rise from
(c) Increase in concentration of the reactant with time
(d) Velocity constant of the reaction 10 o to 100 o is
[KCET 1993; Kerala PET 2002; MP PET 2003]
19. The rate of a reaction depends upon the [Pb. PMT 1999]
 464 Chemical Kinetics
(a) 112 (b) 512 (c) May increase or decrease with increase in temperature
(c) 400 (d) 614 (d) Does not depend on temperature
30. A catalyst increases the rate of a chemical reaction by 41. For the reaction 2 N 2O5(g)  4 NO 2(g)  O2(g) , if concentration of
[MNR 1988; CPMT 1999; Pb. PMT 2000]
(a) Increasing the activation energy NO 2 in 100 seconds is increased by 5.2  10 3 m . Then rate of
(b) Decreasing the activation energy reaction will be
(c) Reacting with reactants [Kerala CET 2005]
(d) Reacting with products
(a) 1.3  10 5 ms 1 (b) 5  10 4 ms 1
31. Velocity constant of a reaction at 290 K was found to be
3.2  10 3 . At 310 K it will be about [KCET 1989, 91] (c) 7.6  10 4 ms 1 (d) 2  10 3 ms 1
(a) 1.28  10 2 (b) 9.6  10 3 (e) 2.5  10 5 ms 1
(c) 6.4  10 3 (d) 3.2  10 4 42. A first order reaction complete its 10% in 20 minutes then time
required to complete its 19% is [Kerala CET 2005]
32. The temperature coefficient of a reaction is
(a) 30 minutes (b) 40 minutes
(a) Specific reaction rate at 25 o C
(c) 50 minutes (d) 38 minutes
(b) Rate of the reaction at 100 o C (e) 45 minutes
(c) Ratio of the rate constants at temperatures 35 o C and
25 o C Rate law and Rate constant
(d) Ratio of the rate constants at two temperatures differing by
1. Which of these does not influence the rate of reaction
1o C [KCET 2005]
33. The main function of a catalyst in speeding up a reaction is (a) Nature of the reactants
(a) To increase the rate of the forward reaction
(b) Concentration of the reactants
(b) To change the reaction path so as to decrease the energy of
activation for the reaction (c) Temperature of the reaction
(c) To reduce the temperature at which the reaction can occur (d) Molecularity of the reaction
(d) To increase the energy of the molecules of the reactants 2. The rate law for reaction A  2 B  C  2 D will be
34. The rate of a reaction [CPMT 1973] (a) Rate  K[ A][B] (b) Rate  K[ A][2 B]
(a) Increases with increase in temperature
(b) Decreases with increase in temperature [C][D]2
(c) Rate  K[ A][B]2 (d) Rate  K
(c) Does not depend on temperature [ A][B]2
(d) Does not depend on concentration 3. In the reaction 2 N 2O5  4 NO 2  O2 , initial pressure is
35. Which of the following statements is false in relation to enzyme [MP PMT 2003]
(a) pH affects their functioning 500 atm and rate constant K is 3.38  10 5 sec 1 . After 10
(b) Temperature affects their functioning minutes the final pressure of N 2 O5 is [Orissa JEE 2005]
(c) They always increase activation energy
(a) 490 atm (b) 250 atm
(d) Their reactions are specific
(c) 480 atm (d) 420 atm
36. A reaction is catalysed by ‘X ’. Here ‘X ’ [MP PMT 2003]
(a) Decreases the rate constant of reaction 4. The rate law for the reaction

(b) Does not affect the equilibrium constant of reaction Sucrose + Water   Glucose + Fructose is given by
[H ]
(c) Decreases the enthalpy of reaction
(d) Decreases the activation energy (a) Rate  K [sucrose] [water]
37. Which reaction characteristics are changing by the addition of a (b) Rate  K [sucrose] [water] 0
catalyst to a reaction at constant temperature
(i) Activation energy (ii) Equilibrium constant (c) Rate  K [sucrose] 0 [water]
(iii) Reaction entropy (iv) Reaction enthalpy
(d) Rate  K [sucrose] 1 / 2 [water] 1 / 2
[DCE 2003]
d[ A]
(a) (i) Only (b) (iii) only 5. A  2B  C  D . If   5  10  4 mol l 1 s 1 1, then
(c) (i) and I(ii) only (d) All of these dt
38. The velocity constant of a reaction at 290 K was found to be d [ B]
 is [DPMT 2005]
3.2  10 3 . At 300 K it will be [MP PMT 2004] dt
(a) 1.28  10 2 (b) 6.4  10 3 (a) 2.5  10 4 mol l1 s 1 (b) 5.0  10 4 mol l 1 s 1
(c) 9.6  10 3 (d) 3.2  10 4 (c) 2.5  10  3mol l 1 s 1 (d) 1.0  10 3 mol l 1 s 1
39. In which of the following cases, does the reaction go farthest to
completion [UPSEAT 2001] 6. The data for the reaction A  B  C is [CBSE PMT 1994]
2
(a) K  10 3
(b) K  10 Exp. [A]0 [B]0 Initial rate
(c) K  10 (d) K  1 (1) 0.012 0.035 0.10
40. Rate of reaction [Pb. CET 2004]
(2) 0.024 0.070 0.80
(a) Decreases with increase in temperature
(3) 0.024 0.035 0.10
(b) Increases with increase in temperature
 Chemical Kinetics 465

(4) 0.012 0.070 0.80 (a) Temperature (b) Mass

(c) Weight (d) Time
The rate law corresponds to the above data is
14. In a first order reaction the concentration of reactant decreases from
(a) Rate  k [B]3 (b) Rate  k [B]4 800 mol / dm 3 to 50 mol / dm 3 is 2  10 2 sec . The rate
(c) Rate  k [ A][B]3 (d) Rate  k [ A]2 [B]2 constant of reaction in sec 1 is
[IIT-JEE (Screening) 2003]
7. The experimental data for the reaction 2 A  B2  2 AB is
(a) 2  10 4
(b) 3.45  10 5
[CBSE PMT 1997]
Exp. [A]0 [B]0 Rate (mole s 1 ) (c) 1.386  10 2 (d) 2  10 4

(1) 0.50 0.50 15. For a reaction A  B , the rate of reaction quadrupled when the
1.6  10 4 concentration of A is doubled. The rate expression of the reaction is
(2) 0.50 1.00 3.2  10 4 r  K( A)n . when the value of n is
(3) 1.00 1.00 3.2  10 4 (a) 1 (b) 0
(c) 3 (d) 2
The rate equation for the above data is
16. The velocity constant of a reaction is K. Which of the following
(a) Rate  k [B 2 ] (b) Rate  k [B 2 ]2 statements is not true regarding K
(a) K is a constant for a reaction at a given temperature
(c) Rate  k[ A]2 [B]2 (d) Rate  k [ A]2 [B] (b) The value of K changes when the temperature changes
8. The reaction 2 NO(g)  O2 (g) ⇌ 2 NO 2 (g) is of first order. If (c) K is the velocity of the reaction at unit concentrations of the
volume of reaction vessel is reduced to 1/3, the rate of reaction reactant
would be [MP PMT 2001] (d) K is a constant for all reactions
(a) 1/3 times (b) 2/3 times 17. For the following reaction scheme (homogeneous), the rate constant
(c) 3 times (d) 6 times has units : A  B  K
C [MP PET 1999]
9. For a reaction 2 A  B  Products, doubling the initial
(a) sec 1 mole (b) sec 1
concentration of both the reactants increases the rate by a factor of
8, and doubling the concentration of B alone doubles the rate. The
rate law for the reaction is (c) sec 1 litremole 1 (d) sec
[MP PET 2001] 18. Which of the following oxides of nitrogen will be the most stable
one [NCERT 1978]
(a)   k[ A][B]2
(b)   k[ A] [B]2

(a) 2 NO 2 (g) ⇌ N 2 (g)  2O 2 (g); K  6.7  10 16 mol l 1

(c)   k[ A][B] (d)   k[ A] [B]2 2

(b) 2 NO (g) ⇌ N 2 (g)  O 2 (g); K  2.2  10 30 mol l 1

10. For a reactions A  B  product, it was found that rate of reaction
increases four times if concentration of ‘A’ is doubled, but the rate (c) 2 N 2 O5 (g) ⇌ 2 N 2 (g)  5 O 2 (g); K  1.2  10 34 mol l 5
of reaction remains unaffected. If concentration of ‘B’ is doubled.
Hence, the rate law for the reaction is [MP PET/PMT 1998; MP PMT 2003] (d) 2 N 2 O(g) ⇌ 2 N 2 (g)  O 2 (g); K  3.5  10 33 mol litre1
(a) rate  k[ A][B] (b) rate  k[ A]2 19. The rate of reaction is determined by slow step reaction. The step is
called
(c) rate  k[ A]2 [B]1 (d) rate  k[ A]2 [B]2 (a) Reaction rate (b) Activation step
11. Velocity constant K of a reaction is affected by (c) Rate determining step (d) None of the above
20. The rate of the reaction
(a) Change in the concentration of the reactant
CCl 3 CHO  NO  CHCl 3  NO  CO is given by Rate
(b) Change of temperature
(c) Change in the concentration of the product  K [CCl 3 CHO][ NO ] . If concentration is expressed in moles/litre,
the units of K are [MP PET 1993]
(d) None of the above
12. Point out the wrong statement : (a) litre2 mole 2 sec 1 (b) mole litre1 sec 1
For a first order reaction (c) litremole 1 sec 1 (d) sec 1
(a) Time for half-change (t1 / 2 ) is independent of initial 21. Rate constant for a reaction H 2  I2  2 HI is 49, then rate
concentration
constant for reaction 2 HI  H 2  I2 is [Bihar MEE 1997]
(b) Change in the concentration unit does not change the rate
(a) 7 (b) 1/49
constant (K )
(c) 49 (d) 21
(c) Time for half-change  rate constant  0.693 (e) 63
(d) The unit of K is mole 1 min 1 22. The reaction
13. The rate constant of a reaction depends on 1
N 2 O5 (in CCl 4 solution)  2 NO 2 (solution)  O2 (g)
[CPMT 1989; DPMT 2001] 2
 466 Chemical Kinetics

is of first order in N 2 O 5 with rate constant 6.2  10 1 s 1 . (a) Concentration of the reactants
(b) Concentration of the products
What is the value of rate of reaction when
(c) Time of reaction
[ N 2 O5 ]  1.25 mole l 1 [AFMC 1998] (d) Temperature of reaction
(a) 7.75  10 1 mole l 1 s 1 (b) 6.35  10 3 mole l 1 s 1 32. If the concentration is expressed in moles per litre, the unit of the
rate constant for a first order reaction is
(c) 5.15  10 5 mole l 1 s 1 (d) 3.85  10 1 mole l 1 s 1 [MNR 1986; MP PET 1994, 2000, 01;Bihar MEE 1996;
CPMT 1997; MP PMT 1995, 96, 99;AFMC 2002]
23. A reaction that is of the first order with respect to reactant A has a rate 1
(a) mole litre sec 1 (b) mole litre 1
constant 6 min 1 . If we start with [ A]  0.5 mol l 1 , when would
(c) sec 1 (d) mole 1 litre 1 sec 1
[A] reach the value 0.05mol l 1 [KCET 2000]
33. The dimension of rate constant of a second order reaction involves
(a) 0.384 min (b) 0.15 min (a) Neither time nor concentration
(c) 3 min (d) 3.84 min (b) Only time
24. The rate constant for the reaction, 2 N 2 O5  4 NO 2 O 2 is (c) Time and concentration
5 1
(d) Time and square of concentration
3  10 sec . If the rate is 2.40  10 5 mol litre -1 sec 1 . 34. The unit of rate constant of second order reaction is usually
Then the concentration of N 2 O 5 (in mol litre ) is -1
expressed as
[NCERT 1983, 84; MNR 1983; MP PMT 1994, 99]
[IIT Screening 2000]
(a) mole litre sec 1 (b) mole 1 litre1 sec 1
(a) 1.4 (b) 1.2
(c) 0.04 (d) 0.8 (c) mole litre1 sec 1 (d) mole 1 litresec 1
25. For the reaction 2 N 2 O5  4 NO 2  O2 rate of reaction and rate 35. A zero order reaction is one whose rate is independent of
4 5 1
[NCERT 1981]
constant are 1.02  10 and 3.4  10 sec respectively. The (a) Temperature of the reaction
concentration of N 2 O5 at that time will be (b) The concentrations of the reactants
[BHU 2001] (c) The concentration of the products
(a) 1.732 (b) 3 (d) The material of the vessel in which the reaction is carried out
4 36. The unit of rate constant for a zero order reaction is
(c) 1.02  10 (d) 3.4  10 5
[NCERT 1981; MP PMT 2000; RPET 2000]
26. The rate law of the reaction 2 N 2 O5  4 NO 2  O2 is 1
(a) litre sec (b) litre mole 1 sec 1
[MP PET 2002]
(a) r  K[ N 2 O5 ] (b) r  K[ N 2 O5 ]2 (c) mole litre1 sec 1 (d) mole sec 1
37. Which of the following rate laws has an overall order of 0.5 for
(c) r  K[ N 2 O5 ]0 (d) r  K[ NO 2 ]4 [O2 ] reaction involving substances x , y and z
27. If R  K[ NO ]2 [O2 ], rate constant may be increased by [AIIMS 1983]
[BHU 2003] (a) Rate  K(C x )(C y )(C z )
(a) Increasing temperature
(b) Decreasing temperature (b) Rate  K(C x )0.5 (C y )0.5 (C z )0.5
(c) Increasing concentration of O 2
(c) Rate  K(C x )1.5 (C y )1 (C z )0
(d) Increasing concentration of NO
28. The value of rate constant A  B  products depends on (d) Rate  K(C x )(C z )n /(C y )2
[BHU 2003] 38. The rates of a certain reaction (dc/dt) at different times are as
(a) Concentration of A and B follows
(b) Pressure Time Rate (mole litre sec )–1 –1

(c) Temperature
(d) All of these 0 2.8  10 2
29. The rate constant of a reaction depends upon [BHU 2004] 10 2.78  10 2
(a) Extent of reaction
(b) Time of reaction 20 2.81  10 2
(c) Temperature of the system 30 2.79  10 2
(d) Concentration of the system The reaction is [NCERT 1978]
30. The rate equation for the reaction 2 A  B  C is found to be: (a) Zero order (b) First order
rate  k[ A][B] . The correct statement in relation to this reaction is (c) Second order (d) Third order
that the [AIEEE 2004] 39. For a chemical reaction A  B it is found that the rate of reaction
(a) Rate of formation of C is twice the rate of disappearance of A doubles, when the concentration of A is increased four times. The
(b) t1 / 2 is a constant order in A for this reaction is
[NCERT 1979; AIIMS 1997; J & K CET 2005]
(c) Unit of k must be s 1 (a) Two (b) One
(d) Value of k is independent of the initial concentrations of A and (c) Half (d) Zero
B
40. The following data are for the decomposition of ammonium nitrate
31. The specific rate constant of a first order reaction depends on the
in aqueous solution
[IIT 1981, 83; DPMT 1991; Bihar MEE 1995; KCET 1998]
 Chemical Kinetics 467

Volume of N 2 in cc Time (minutes) (a) Unimolecular

6.25 10 (b) Pseudo–unimolecular
9.50 15 (c) Bimolecular
11.42 20 (d) None of the above
13.65 25 50. A reaction involving two different reactants
35.05 Finally [KCET 1989; AIEEE 2005]
The order of the reaction is [NCERT 1980] (a) Can never be a second order reaction
(a) Zero (b) One (b) Can never be a unimolecular reaction
(c) Two (d) Three (c) Can never be a bimolecular reaction
41. The hydrolysis of ethyl acetate is a reaction of (d) Can never be a first order reaction
[MP PMT 1987] 51. By “the overall order of a reaction”, we mean
 (a) The number of concentration terms in the equation for the
CH 3 COOEt  H 2 O 
 CH 3 COOH  EtOH
H
reaction
(a) First order (b) Second order (b) The sum of powers to which the concentration terms are
(c) Third order (d) Zero order raised in the velocity equation
42. The rate of reaction between A and B increases by a factor of (c) The least number of molecules of the reactants needed for the
100, when the concentration of A is increased 10 folds. The order reaction
of reaction with respect to A is (d) The number of reactants which take part in the reaction
[CPMT 1985] 52. Catalyst decomposition of hydrogen peroxide is a ........ order reaction
(a) 10 (b) 1 (a) First (b) Second
(c) 4 (d) 2 (c) Third (d) Zero
43. Which of the following is a first order reaction 53. The half life of a first order reaction is
[MP PMT 1987]
(a) Independent of the initial concentration of the reactant
(a) NH 4 NO 2  N 2  2 H 2 O (b) Directly proportional to the initial concentration of the
(b) 2 HI  H 2  I2 reactants
(c) Inversely proportional to the initial concentration of the
(c) 2 NO 2  2 NO  O2 reactant
(d) 2 NO  O 2  2 NO 2 (d) Directly proportional to the square of the initial concentration
of the reactant
44. The inversion of cane sugar is represented by
54. The decomposition of N 2 O5 is a first order reaction represented
C12 H 22 O11  H 2 O  C6 H 12 O6  C6 H 12 O6
1
It is a reaction of by N 2 O 5  N 2 O 4  O 2 . After 15 minutes the volume of O 2
[AFMC 1982; MP PMT 1993; RPET 2000] 2
(a) Second order (b) Unimolecular produced is 9 ml and at the end of the reaction 35 ml . The rate
(c) Pseudo unimolecular (d) None of the three constant is equal to
45. Which one of the following formula represents a first order reaction [MP PMT 1999] [MP PET 1995]

x 1  1 1  1 35 1 44
K K  2 (a) ln (b) ln
(a) (b)  15 44 15 26
t 2 t  (a  x ) 2
a 
1 44 1 35
2 .303 a 1 x (c) ln (d) ln
(c) K log10 (d) K 15 35 15 26
t (a  x ) t a(a  x )
55. The unit of specific reaction rate constant for a first order (if the
46. The first order rate constant for the decomposition of N 2 O5 is concentration expressed in molarity) would be
6.2  10 4 sec 1 . The half life period for this decomposition in [MNR 1988; UPSEAT 2000, 01]
1 1
seconds is (a) mole litre s (b) mole litre1
[MNR 1991; MP PET 1997; UPSEAT 2000]
(a) 1117.7 (b) 111.7 (c) mole s 1 (d) s 1
(c) 223.4 (d) 160.9 56. A first order reaction requires 30 minutes for 50% completion. The
time required to complete the reaction by 75% will be
47. A first order reaction which is 30% complete in 30 minutes has a
half-life period of [AIIMS 1998] (a) 45 minutes (b) 15 minutes
(a) 24.2 min (b) 58.2 min (c) 60 minutes (d) None of these
(c) 102.2 min (d) 120.2 min 57. Inversion of canesugar in dilute acid (conversion into glucose and
48. The order of a reaction which has the rate expression fructose) is a
dc (a) Unimolecular reaction
 K[ E]3 / 2 [D]3 / 2 is
dt (b) Bimolecular reaction
(a) 3/2 (b) 3 (c) Trimolecular reaction
(c) 2 (d) 0 (d) Pseudo-unimolecular reaction
49. The reaction 2 N 2 O5 ⇌ 2 NO 2  O 2 follows first order kinetics. 58. The half life period of a first order reaction [AMU 2000]
Hence, the molecularity of the reaction is
 468 Chemical Kinetics
0 .693 0 .693 (c) Independent of
(a) (b)
t K (d) Equal to
69. Half life period of a first order reaction is 138.6 minutes. The
2 .303 0 .303 velocity constant of the reaction is
(c) (d)
t K1
(a) 0.05 min 1 (b) 0.00005 min 1
59. The order of a reaction is said to be 2 with respect to a reactant X,
when [DPMT 2000] (c) 0.005 min 1 (d) 200 min 1
(a) The rate of the reaction is proportional to [X]
70. An example of a pseudo –unimolecular reaction is
(b) The rate of the reaction is proportional [X ]2
(a) Dissociation of hydrogen iodide
(c) Two molecules of X are present in the stoichiometric equation
(b) Hydrolysis of methyl acetate in dilute solution
(d) The reaction occurs in two steps
(c) Dissociation of phosphorus pentachloride
60. Decay constant of a reaction is 1.1  10 9 / sec , then the half life (d) Decomposition of hydrogen peroxide
of the reaction is
71. About half life period of a first order reaction, which one of the
(a) 1.2  10 8 (b) 6.3  10 8 following statements is generally false
(c) 3.3  10 8 (d) 2.1  10 8 (a) It is independent of initial concentration
61. If the half life period of a reaction is inversely proportional to the (b) It is independent of temperature
initial concentration, the order of the reaction is (c) It decreases with the introduction of a catalyst
(a) Zero (b) One (d) It increases with increase of temperature
(c) Two (d) Three 72. Decomposition of nitrogen pentoxide is known to be a first order
62. Which one of the following statements is wrong reaction 75 percent of the oxide had decomposed in the first 24
(a) Molecularity of a reaction is always a whole number minutes. At the end of an hour, after the start of the reaction, the
(b) Order and molecularity of a reaction need not be same amount of oxide left will be
(c) Order of a reaction may be zero (a) Nil (b) About 1%
(d) Order of a reaction depends upon the mechanism of the (c) About 2% (d) About 3%
reaction 73. A reaction 2 A  products is found to follow zero oder kinetics,
63. The velocity constant of first order reaction is expressed in the units then
(a) Concentration per unit time dx dx
(b) Time per unit concentration (a)  k [A]2 (b)  k [A]0
dt dt
(c) Per unit time
dx dx
(d) Unit time per unit concentration (c)  k [A] (d)  k [ 2 A]
dt dt
64. For reation, A  B  products, it is found that the rate of the
reaction is proportional to the concentration of A, but it is 74. The alkaline hydrolysis of ethyl acetate is represented by the
independent of the concentration of B, then equation
(a) The order of the reaction 2 and molecularity 1 CH 3 COOC 2 H 5  NaOH  CH 3 COONa  C 2 H 5 OH
(b) Molecularity of the reaction is 2 but order is 1 Experimentally it is found that for this reaction
(c) Order is 2 and molecularity is 2
dx
(d) Order of the reaction is 2 but molecularity is 0  k[CH 3 COOC 2 H 5 ][ NaOH ]
65. For a zero order reaction dt
(a) The concentration of the reactant does not change during the Then the reaction is [JIPMER 1999]
reaction (a) Bimolecular and of first order
(b) The concentration change only when the temperature changes (b) Bimolecular and of second order
(c) The rate remains constant throughout (c) Pseudo–bimolecular
(d) The rate of the reaction is proportional to the concentration (d) Pseudo–unimolecular
66. If ‘a’ is the initial concentration and ‘n’ is the order of the reaction
and the half life period is ‘T’, then 75. For the reaction 2 HI ⇌ H 2  I2 , the rate of the reaction is
[MH CET 2000]
proportional to [HI]2 . This means that the reaction is
(a) T  an1 (b) T  a n
[AMU 1985; MP PET 2000]
1 1
(c) T  n (d) T  n 1 (a) Unimolecular (b) Bimolecular
a a
(c) Of first order (d) Of second order
67. In presence of HCl , sucrose gets hydrolysed into glucose and
fructose. The concentration of sucrose was found to reduce form 0.4 76. Inversion of sucrose is [AMU 1988; MP PET 2000]
M to 0.2 M in 1 hour and 0.1 M in 2 hours. The order of the reaction (a) Zero order reaction (b) First order reaction
is
(c) Second order reaction (d) Third order reaction
(a) Zero (b) One
(c) Two (d) None of these 77. The one which is unimolecular reaction is
68. The time of half change of a first order reaction in ....... initial [MP PMT 1999; UPSEAT 2001]
concentration
1
(a) Proportional to (a) 2 HI  H 2  I2 (b) N 2 O5  N 2 O4  O2
2
(b) Inversely proportional to
 Chemical Kinetics 469
(c) H 2  Cl 2  2 HCl (d) PCl3  Cl 2  PCl5 d [ A]
(d) K [ A] 1
78. Integrated velocity equation for first order reaction is dt
87. Which of the following statements regarding the molecularity of a
(a) [ A]o  [ A] e  Kt (b) K  [ A]o e  A / t reaction is wrong [CBSE PMT 1989]
(a) It is the number of molecules of the reactants taking part in a
[ A]o [ A]o
(c) Kt  2 .303 log (d) log  2 .303 Kt single step chemical reaction
[ A] [ A] (b) It is calculated from the reaction mechanism
79. If the surface area of the reactants increases, then order of the (c) It may be either a whole number or fractional
reaction (d) It depends on the rate determining step in the reaction
(a) Increases 88. Diazonium salt decomposes as
(b) Decreases C 6 H 5 N 2 Cl   C 6 H 5 Cl  N 2
(c) Remain constant
At 0 o C , the evolution of N 2 becomes two times faster when the
(d) Sometimes increases and sometimes dereases
initial concentration of the salt is doubled. Therefore, it is [MNR 1994; UPSEAT 2
80. Half life period t1 / 2 for first order reaction is (a) A first order reaction
1 .303 log 2 (b) A second order reaction
(a) K (b) (c) Independent of the initial concentration of the salt
K
(d) A zero order reaction
2 .303 log 2 9
(c) (d) 89. In the reaction A  B  Products, if B is taken in excess, then it
K K is an example of [EAMCET 1992]
81. Molecularity of reaction of inversion of sugar is (a) Second order reaction
(a) 3 (b) 2 (b) Zero order reaction
(c) 1 (d) 0 (c) Pseudounimolecular reaction
82. For any reaction, if we plot a graph between time ‘t’ and (d) First order reaction
log(a  x ) , a simple line is obtained. The order of reaction is 90. The half life of a first order reaction is 69.35 sec . The value of the
rate constant of the reaction is [CBSE PMT 1990]
(a) Zero (b) One
(c) Two (d) Three (a) 1 .0 s 1 (b) 0 .1 s 1
83. Value of velocity constant for first order reaction is (c) 0.01 s 1 (d) 0.001 s 1
3.46  10 3 min 1 , the time for half change is
1
(a) 100 minutes (b) 400 minutes 91. The half life for the reaction N 2 O5 ⇌ 2 NO 2  O 2 in 24 hrs
2
(c) 200 minutes (d) 346 minutes
at 30 o C . Starting with 10 g of N 2 O5 how many grams of
84. The unit of the velocity constant in case of zero order reaction is[CPMT 1994]
N 2 O5 will remain after a period of 96 hours
(a) Conc.  time1 (b) Conc. 1  time [KCET 1992]
1 1
(c) Conc.  time (d) Conc.  (time) 2
(a) 1.25 g (b) 0.63 g
85. For the reaction H 2 (g)  Br2 (g)  2 HBr(g) , the experimental (c) 1.77 g (d) 0 .5 g
data suggest, rate  K[H 2 ][Br2 ] 1/ 2
. The molecularity and order of 92. The half life of a first order reaction is 10 minutes. If initial amount
the reaction are respectively is 0.08 mol / litre and concentration at some instant is
[CPMT 1988; MP PET 1993] 0.01 mol / litre, then t  [Roorkee 1990]

3 3 3 (a) 10 minutes (b) 30 minutes

(a) 2, (b) ,
(c) 20 minutes (d) 40 minutes
2 2 2
93. Half life period of second order reaction is [MP PMT 1994]
1
(c) 1, 1 (d) 1, (a) Proportional to the initial concentration of reactants
2
(b) Independent of the initial concentration of reactants
86. The incorrect order indicated against the rate of reaction (c) Inversely proportional to initial concentration of reactants
A  B K
C is [BHU 1990] (d) Inversely proportional to square of initial concentration of
Rate Order reactants
d[C] 94. The reaction 2 H 2 O2  2 H 2 O  O2 is a
(a)  K [ A] 1
dt [Manipal MEE 1995]
d[C] (a) Zero order reaction (b) First order reaction
(b)  K[ A][B] 2 (c) Second order reaction (d) Third order reaction
dt
95. In a reaction involving hydrolysis of an organic chloride in presence
d [ A] of large excess of water
(c)  K [ A][B]0 2
dt RCl  H 2 O  ROH  HCl [MP PET 1995]
(a) Molecularity is 2, order of reaction is also 2
 470 Chemical Kinetics
(b) Molecularity is 2, order of reaction is 1 (a) Initial concentration
(c) Molecularity is 1, order of reaction is 2 (b) Cube root of initial concentration
(d) Molecularity is 1, order of reaction is also 1 (c) First power of final concentration
96. The thermal decomposition of a compound is of first order. If a (d) Square root of final concentration
sample of the compound decomposes 50% in 120 minutes, in what 106. Order of a reaction can have [DPMT 1996]
time will it undergo 90% decomposition
[MP PET 1996] (a) ve values (b) Whole number values
(a) Nearly 240 minutes (b) Nearly 480 minutes (c) Fractional values (d) All of the above
(c) Nearly 450 minutes (d) Nearly 400 minutes 107. The order of the reaction occurring by following mechanism should
be [JIPMER 1997]
97. The order of a reaction with rate equals kC A3 / 2 C B1 / 2 is
(i) A2  A  A (fast)
[MP PET 1996, 2001]
(a) 2 (b) 1 (ii) A  B 2  AB  B (slow)
1 3 (iii) A  B  (fast)
(c)  (d)
2 2 1 1
98. If the rate expression for a chemical reaction is given by Rate (a) 1 (b) 3
2 2
 k[ A]m [B]n [MP PMT 1996] (c) 2 (d) None of these
(a) The order of the reaction is m 108. For the reaction A  B , the rate law expression is : Rate  k [A]
(b) The order of the reaction is n
Which of the following statements is incorrect
(c) The order of the reaction is m  n
[Pb. PMT 1998]
(d) The order of the reaction is m  n
(a) The reaction is said to follow first order kinetics
99. The half-life period of a first order reaction is 100 sec. The rate
constant of the reaction is (b) The half life of the reaction will depend on the initial
concentration of the reactant
[MP PMT 1997; MP PET 2001]
3 1 (c) k is constant for the reaction at a constant temperature
(a) 6.93  10 sec (b) 6.93  10 4 sec 1
(d) The rate law provides a simple way of predicting the
(c) 0.693 sec 1 (d) 69.3 sec 1 concentration of reactants and products at any time after the
start of the reaction
100. For the first order reaction with rate constant k , which
109. If initial
expression gives the half-life period ? (Initial concentration  a )[MP PET/PMT 1998] concentration is reduced to its 1/4th in a zero order
reaction, the time taken for half of the reaction to complete
12 1 [BHU 1998]
(a) (b)
k ka (a) Remains same (b) Becomes 4 times
0 .693 3 (c) Becomes one-fourth (d) Doubles
(c) (d) 2 110. For a reaction whose rate expression is :
k 2ka
101. The rate constant of a first order reaction whose half-life is 480 Rate  k[ A]1 / 2 [B]3 / 2 , the order would be [Pune CET 1998]
seconds, is [MP PET 1999]
(a) 1.5 (b) 2
(a) 2.88  10 3 sec 1 (b) 1.44  10 3 sec 1
(c) 3 (d) 1
(c) 1.44 sec 1 (d) 0.72  10 3 sec 1
111. For the reaction A  B , the rate increases by a factor of 2.25
102. The conversion of A  B follows second order kinetics. Doubling when the concentration of A is increased by 1.5. What is the order
the concentration of A will increase the rate of formation of B by of the reaction [KCET 1998]
a factor (a) 3 (b) 0
[MP PET 1999; DCE 1999; KCET 2001; BCECE 2005] (c) 2 (d) 1
(a) 1/4 (b) 2
112. For the reaction H 2  Cl 2   2 HCl taking place on
Sunlight

(c) 1/ 2 (d) 4 water, the order of reaction is

103. The reaction 2 FeCl3  SnCl 2  2 FeCl 2  SnCl 4 is an [KCET 1998; AIIMS 2002; Pb. PMT 2002]
example of [CBSE PMT 1996; MP PET 1999] (a) 1 (b) 2
(a) First order reaction (c) 3 (d) 0
(b) Second order reaction
113. For a first order reaction, rate constant is 0.6932 hr 1 , then half-
(c) Third order reaction
life for the reaction is [Bihar MEE 1997]
(d) None of these
(a) 0.01 hr (b) 1 hr
104. If reaction between A and B to give C shows first order kinetics
in A and second order in B , the rate equation can be written as[MP PET 1999] (c) 2 hr (d) 10 hr
(a) Rate  k [ A][B] 1/ 2
(b) Rate  k[ A] 1/ 2
[B] (e) 0.1 hr

(c) Rate  k [ A][B]2 (d) Rate  k[ A]2 [B] 114. The rate constant of a reaction is 0.69  10 1 min 1 and the
105. For a first order reaction, the half-life period is independent of initial concentration is 0.2mol l 1 . The half-life period is
[CBSE PMT 1999] [AIIMS 1998]
 Chemical Kinetics 471
(a) 400 sec (b) 600 sec
(c) t1/2  CO 2 (d) t1 / 2  CO 0
(c) 800 sec (d) 1200 sec
115. The rate constant of a first order reaction is 3  10 6 per second. If 124. For a reaction 2 NO(g)  Cl 2 (g) ⇌ 2 NOCl (g) . When
the initial concentration is 0.10 m, the initial rate of reaction is concentration of Cl 2 is doubled, the rate of reaction becomes two
[AFMC 1999 Pb. PMT 1999, 2000; BHU 1999; times of the original. When the concentration of NO is doubled the
AIIMS 1999; KCET 2000; DCE 2004] rate becomes four times. What is the order of the reaction
(a) 3  10 5 ms 1 (b) 3  10 6 ms 1 (a) 1 (b) 2
(c) 3 (d) 4
(c) 3  10 8 ms 1 (d) 3  10 7 ms 1
116. Certain bimolecular reactions which follow the first order kinetics 125. The rate constant for a second order reaction is
are called [KCET (Med.) 1999] 8  10 5 M 1min 1 . How long will it take a 1M solution to be
(a) First order reactions reduced to 0.5 M [MH CET 2001]
(b) Unimolecular reactions (a) 8  10 5 min (b) 8.665  10 3 min
(c) Bimolecular reactions
(d) Pseudounimolecular reactions (c) 4  10 5 min (d) 1.25  10 4 min

117. The rate law of the reaction A  2 B  Product is given by 126. The rate for a first order reaction is 0.6932  10 2 mol l 1min 1
d[dB] and the initial concentration of the reactants is 1M, T1 / 2 is equal to
 k [B 2 ] . If A is taken in excess, the order of the reaction
dt [JIPMER (Med.) 2001]
will be [AMU (Engg.) 1999]
(a) 6.932 min (b) 100 min
(a) 1 (b) 2
(c) 3 (d) 0 (c) 0.6932  10 3 min (d) 0.6932  10 2 min
118. For a first order reaction A  product, the rate of reaction at 1
1 2 1 1
127. For a given reaction t1 / 2  . . The order of the reaction is
[ A]  0.2 mol l is 1.0  10 mol l min . The half life Ka
period for the reaction is [Roorkee 1999] [KCET 2001]
(a) 832 s (b) 440 s (a) 1 (b) 0
(c) 416 s (d) 13.86 s (c) 3 (d) 2
119. For the reaction A  B  products, doubling the concentration of 128. 75% of a first order reaction is completed in 30 minutes. What is
A the rate of the reaction is doubled, but on doubling the the time required for 93.75% of the reaction (in minutes)
concentration of B rate remains unaltered. The over all order of the (a) 45 (b) 120
reaction is [JIPMER 1999]
(c) 90 (d) 60
(a) 1 (b) 0
129. A First order reaction is half completed in 45 minutes. How long
(c) 2 (d) 3 does it need 99.9% of the reaction to be completed
120. Which among the following is a false statement [AIIMS 2001]
[KCET 1999] (a) 5 hours (b) 7.5 hours
(a) Half life of a third order reaction is inversely proportional to (c) 10 hours (d) 20 hours
the square of initial concentration of the reactant. 130. A substance ‘A’ decomposes by a first order reaction starting initially
(b) Molecularity of a reaction may be zero or fractional with [A] =2.00m and after 200 min [A] = 0.15m. For this reaction
what is the value of k [AIIMS 2001]
0 .693
(c) For a first order reaction t1 / 2  (a) 1.29  10 2 min 1 (b) 2.29  10 2 min 1
K
(d) Rate of zero order reaction is independent of initial (c) 3.29  10 2 min 1 (d) 4.40  10 2 min 1
concentration of reactant 131. Which of the following statements about zero order reaction is not
121. After how many seconds will the concentration of the reactants in a true [DCE 2001]
first order reaction be halved, if the decay constant is
(a) Its unit is sec 1
1.155  10 -3 sec 1 [CBSE PMT 2000]
(b) The graph between log (reactant) versus rate of reaction is a
(a) 100 sec (b) 200 sec straight line
(c) 400 sec (d) 600 sec (c) The rate of reaction increases with the decrease in
122. What is the order of a reaction which has a rate expression rate concentration of reactants
 K[ A]3 / 2 [B]1 [DCE 2000] (d) Rate of reaction is independent of concentration of reactants

(a) 3/2 (b) 1/2 132. The given reaction 2 NO  O2  2 NO 2 is an example of

(c) 0 (d) None of these [CBSE PMT 2001; JIPMER 2002]
123. Which of the following expression is correct for first order reaction? (a) First order reaction (b) Second order reaction
(CO ) refers to initial concentration of reactant (c) Third order reaction (d) None of these
[DCE 2000] 133. Order of a reaction is decided by [KCET 2002]
(a) Pressure
(a) t1 / 2  CO (b) t1 / 2  CO 1
(b) Temperature
 472 Chemical Kinetics
(c) Molecularity 145. The decomposition of N 2 O5 occurs as, 2 N 2 O5  4 NO 2  O2 ,
(d) Relative concentration of reactants and follows I order kinetics, hence
st

134. From the following which is a second order reaction [BVP 2003]
[AMU 2002] (a) The reaction is unimolecular
4 1
(b) The reaction is bimolecular
(a) K  5.47  10 sec
(c) T1 / 2  a 0
3 1
(b) K  3.9  10 mole lit sec (d) None of these
4 1 146. Which equation is correct for first order reactions
(c) K  3.94  10 lit mole -1
sec
[MP PMT 2003]
5
(d) K  3.98  10 lit mole -2
sec 1 1
(a) t1 / 2  C (b) t1 / 2  C
135. For the reaction A  2 B  C, rate is given by R  [ A][B]2 then
the order of the reaction is [AIEEE 2002] (c) t1 / 2  C 0 (d) t1 / 2  C 1 / 2
(a) 3 (b) 6 147. For the reaction system 2 NO(g)  O2 (g)  2 NO 2 (g) volume is
(c) 5 (d) 7 suddenly produced to half its value by increasing the pressure on it.
136. Units of rate constant of first and zero order reactions in terms of If the reaction is of first order with respect to O 2 and second
molarity M unit are respectively [AIEEE 2002]
order with respect to NO , the rate of reaction will [AIEEE 2003]
(a) sec 1 , M sec 1 (b) sec 1 , M (a) Diminish to one fourth of its initial value
(c) M sec 1 , sec 1 (d) M , sec 1 (b) Diminish to one eighth of its initial value
(c) Increase to eight times of its initial value
137. The reaction 2 N 2 O5 ⇌ 2 N 2 O4  O2 is [MP PMT 2002]
(d) Increase to four times of its initial value
(a) Bimolecular and second order
148. If the rate of the reaction is equal to the rate constant, the order of
(b) Unimolecular and first order the reaction is [CBSE PMT 2003]
(c) Bimolecular and first order
(a) 3 (b) 0
(d) Bimolecular and zero order
(c) 1 (d) 2
138. The half-life period for a first order reaction is 693 seconds. The
rate constants for this reaction would be 149. The reaction A  B follows first order kinetics. The time taken for
[MP PET 2002] 0.8 mole of A to produce 0.6 mole of B is 1 hour. What is the time
taken for conversion of 0.9 mole of A to produce 0.675 mole of B
(a) 0.1sec 1 (b) 0.01sec 1
(a) 2 hours (b) 1 hour
(c) 0.001sec 1 (d) 0.0001sec 1
(c) 0.5 hour (d) 0.25 hour
139. For an elementary reaction, 2A + B  C + D the molecularity is [Kurukshetra CEE 2002]
150. The unit of velocity constant in case of zero order reaction is
(a) Zero (b) One
[MP PMT 2004]
(c) Two (d) Three
1
140. If the order of the reaction x  y  hv
 x y is zero, it means that (a) Concentration  Time (b) Concentrat ion-1  Time -1
the rate of [Kurukshetra CEE 2002] (c) Concentrat ion  Time 2 (d) Concentrat ion-1  Time
(a) Reaction is independent of temperature 151. Which one of the following is wrongly matched
(b) Formation of activated complex is zero [KCET 2004]
(c) Reaction is independent of the concentration of reacting species
(a) Saponification of CH 3 COOC 2 H 5 – Second order reaction
(d) Decomposition of activated complex is zero
141. For a first order reaction velocity constant, K  10 3 s 1 . Two (b) Hydrolysis of CH 3 COOCH 3 – Pseudo uni-molecular
third life for it would be [MP PET 2001; UPSEAT 2003] reaction
(a) 1100 s (b) 2200 s
(c) Decomposition of H 2 O2 – First order reaction
(c) 3300 s (d) 4400 s
142. In a reaction, the concentration of reactant is increased two times (d) Combination of H 2 and Br2 to give HBr – Zero order
and three times then the increases in rate of reaction were four
times and nine times respectively, order of reaction is [UPSEAT 2003] reaction
(a) Zero (b) 1 152. Which of the following is an example of pseudo unimolecular
(c) 2 (d) 3 reaction [Pb. CET 2001]

143. For a chemical reaction....can never be a fraction (a) CH 3 COOCH 3  H 2 O 
H
 CH 3 COOH  CH 3 OH
[EAMCET 2003]

(a) Order (b) Half-life (b) CH 3 COOCH 3  H 2 O 
OH
 CH 3 COOH  CH 3 OH
(c) Molecularity (d) Rate constant
144. 75% of a first order reaction was completed in 32 minutes when (c) 2 FeCl3  SnCl 2  SnCl 4  2 FeCl2
was 50% of the reaction completed
[AMU 1999; Kerala (Med.) 2003] (d) NaOH  HCl  NaCl  H 2O
(a) 16 min. (b) 24 min. 153. Hydrolysis of DDT is a first order reaction, its half life is 10 years.
(c) 8 min. (d) 4 min. Time to hydrolyse 10 g DDT to half is [BVP 2004]
 Chemical Kinetics 473
(a) 100 years (b) 50 years (d) A plot of P versus 1 / V is linear at constant temperature
(c) 5 years (d) 10 years 165. For a first order reaction [IIT 1998]
154. In a first order reaction, the concentration of the reactant, decreases
from 0.8 M to 0.4 M in 15 minutes. The time taken for the (a) The degree of dissociation is equal to (1  e kt )
concentration to change from 0.1 M to 0.025 M is [AIEEE 2004] (b) A plot of reciprocal concentration of the reactant vs time gives
(a) 7.5 minutes (b) 15 minutes a straight line
(c) 30 minutes (d) 60 minutes (c) The time taken for the completion of 75% reaction is thrice the
155. In the first order reaction, the concentration of the reactant is t1 / 2 of the reaction
reduced to 25% in one hour. The half life period of the reaction is[DCE 2004] (d) The pre-exponential factor in the Arrhenius equation has the
(a) 2 hr (b) 4 hr dimension of time T 1
(c) 1/2 hr (d) 1/4 hr
166. For reaction a A  x P , when [ A]  2.2 mM , the rate was
156. For a reaction, X (g)  Y (g)  Z(g) the half life period is 10 min.
In What period of time would the concentration of X be reduced to found to be 2.4 mM s 1 . On reducing concentration of A to half,
10% of original concentration [DCE 2004]
the rate changes to 0.6 mM s 1 . The order of reaction with
(a) 20 min (b) 33 min
respect to A is [AIIMS 2005]
(c) 15 min (d) 25 min
(a) 1.5 (b) 2.0
157. A first order reaction with respect to the reactant A has a rate
(c) 2.5 (d) 3.0
constant of 6 sec 1 . If we start with [A] = 0.5 mol/litre, then in
167. Which one of the following statement for order of reaction is not
what time the concentration of A becomes 0.05 mol/litre correct [IIT 2005]
[DCE 2004] (a) Order can be determined experimentally.
(a) 0.384 sec (b) 0.214 sec (b) Order of reaction is equal to sum of the powers of
(c) 3.84 sec (d) 0.402 sec concentration terms in differential rate law.
158. Order of radioactive disintegration reaction is (c) It is not affected with the stoichiometric coefficient of the
[JEE Orissa 2004] reactants.
(a) Zero (b) First (d) Order cannot be fractional.
(c) Second (d) Third 168. t 1 can be taken as the time taken for the concentration of a
159. The rate of a first order reaction is 1.5  10 2 molL1 min 1 at 4

0.5 M concentration of the reactant. The half life of the reaction is[CBSE PMT 2004]reactant to drop to 3 of its initial value. If the rate constant for a
(a) 8.73 min (b) 7.53 min 4
(c) 0.383 min (d) 23.1 min first order reaction is K , the t 1 can be written as
160. A first order reaction was started with a decimolar solution of the 4
reactant, 8 minutes and 20 seconds later its concentration was [AIEEE 2005]
found to be M / 100 . So the rate of the reaction is [Kerala PMT 2004] (a) 0.10 / K (b) 0.29 / K
(a) 2.303  10 5 sec 1 (b) 2.303  10 4 sec 1 (c) 0.69 / K (d) 0.75 / K
3 1 5 1
(c) 4.606  10 sec (d) 2.606  10 sec 169. For a first order reaction A  B the reaction rate at reactant
(e) 2.603  10 4
sec 1 concentration of 0.01M is found to be 2.0  10 5 mol L1 s1 .
The half life period of the reaction is
161. Which is correct about zero order reaction
[CBSE PMT 2005]
[JEE Orissa 2004]
(a) Rate of reaction depends on decay constant (a) 220 s (b) 30 s
(b) Rate of reaction is independent of concentration (c) 300 s (d) 347 s
(c) Unit of rate constant is concentration –1 170. The rate of reaction between two reactants A and B decreases by a
factor of 4 if the concentration of reactant B is doubled. The order
(d) Unit of rate constant is concentration time –1 –1

of this reaction with respect to reactant B is

235
162. Decay of 92 U is .....order reaction [JEE Orissa 2004] (a) – 1 (b) – 2
(a) Zero (b) First (c) 1 (d) 2
(c) Second (d) Third 171. If a substance with half life 3 days is taken at other place in 12 days.
163. The half-life of 2 sample are 0.1 and 0.4 seconds. Their respective What amount of substance is left now [AFMC 2005]
concentration are 200 and 50 respectively. What is the order of the (a) 1/4 (b) 1/8
reaction [JEE Orissa 2004]
(c) 1/16 (d) 1/32
(a) 0 (b) 2
(c) 1 (d) 4 172. The half-life of a first order reaction having rate constant K = 1.7
164. The following statements(s) is(are) correct [IIT 1999]  10 s is
-5 -1
[BHU 2005]
(a) 12.1 h (b) 9.7 h
(a) A plot of log K p versus 1 / T is linear
(c) 11.3 h (d) 1.8 h
(b) A plot of log[ X ] versus time is linear for a first order
173. For the reaction A  B  C , it is found that doubling the
reaction X  P concentration of A increases the rate by 4 times, and doubling the
concentration of B doubles the reaction rate. What is the overal
(c) A plot of log P versus 1 / T is linear at constant volume order of the reaction. [KCET 2005]
 474 Chemical Kinetics
(a) 4 (b) 3/2 (a) E f  Er
(c) 3 (d) 1
174. Which of the following reactions end in finite time (b) E f  Er
[DPMT 2005] (c) E f  Er
(a) 0 order (b) 1st order
(c) 2nd order (d) 3rd order (d) No relation can be given between E f and E r as data are not
sufficient
Collision theory, Energy of activation 9. According to Arrhenius theory, the activation energy is
(a) The energy it should possess so that it can enter into an
and Arrhenius equation effective collision
(b) The energy which the molecule should possess in order to
1. A large increase in the rate of a reaction for a rise in temperature is undergo reaction
due to [EAMCET 1980; MP PET 1995]
(a) The decrease in the number of collisions (c) The energy it has to acquire further so that it can enter into a
effective collison
(b) The increase in the number of activated molecules
(d) The energy gained by the molecules on colliding with another
(c) The shortening of the mean free path molecule
(d) The lowering of the activation energy 10. The energy of activation is
2. Which of the following statements is not true according to collision (a) The energy associated with the activated molecules
theory of reaction rates
(b) Threshold energy – energy of normal molecules
(a) Collision of molecules is a precondition for any reaction to
occur (c) Threshold energy + energy of normal molecules
(b) All collisions result in the formation of the products (d) Energy of products – energy of reactants
(c) Only activated collisions result in the formation of the products 11. Which one of the following does not represent Arrhenius equation
(d) Molecules which have acquired the energy of activation can (a) k  Ae  E / RT
collide effectively
E
3. According to the collision theory of chemical reactions (b) loge k  loge A 
(a) A chemical reaction occurs with every molecular collision RT
(b) Rate is directly proportional to the number of collisions per E
(c) log10 k  log10 A 
second 2 .303 RT
(c) Reactions in the gas phase are always of zero order
(d) Reaction rates are of the order of molecular speeds (d) k  AE  RT
12. On increasing the temperature, the rate of the reaction increases
4. According to the collision theory of reaction rates, rate of reaction
because of [MP PMT 1997]
increases with temperature due to
(a) Decrease in the number of collisions
(a) Greater number of collisions
(b) Decrease in the energy of activation
(b) Greater velocity of the reacting molecules (c) Decrease in the number of activated molecules
(c) Greater number of molecules have activation energy (d) Increase in the number of effective collisions
(d) None of the above 13. Energy of activation of a reactant is reduced by
5. The reaction rate at a given temperature becomes slower, then (a) Increased temperature (b) Reduced temperature
(c) Reduced pressure (d) Increased pressure
[MP PMT 1993; DPMT 2000]
14. The minimum energy a molecule should possess in order to enter
(a) The free energy of activation is higher into a fruitful collision is known as
(b) The free energy of activation is lower [Kurukshetra CEE 2002]
(c) The entropy changes (a) Reaction energy (b) Collision energy
(c) Activation energy (d) Threshold energy
(d) The initial concentration of the reactants remains constant
15. Activation energy is
6. A rise in temperature increases the velocity of a reaction. It is (a) The amount of energy to be added to the actual energy of a
because it results in molecule so that the threshold energy is reached
(a) An increased number of molecular collisions (b) The amount of energy the molecule must contain so that it
(b) An increased momentum of colliding molecules reacts
(c) The energy which a molecule should have in order to enter into
(c) An increase in the activation energy an effective collision
(d) A decrease in the activation energy (d) The average kinetic energy of the molecule
7. The number of collisions depend upon 16. The reason for almost doubling the rate of reaction on increasing
(a) Pressure (b) Concentration the temperature of the reaction system by 10 oC is
[J & K 2005]
(c) Temperature (d) All the above
(a) The value of threshold energy increases
8. If E f and E r are the activation energies of forward and reverse (b) Collision frequency increases
reactions and the reaction is known to be exothermic, then
 Chemical Kinetics 475
(c) The fraction of the molecule having energy equal to threshold K1 Ea  T2  T1 
energy or more increases (b) log   
(d) Activation energy decreases K2 2 .303 R  T1 T2 
17. The activation energy for a simple chemical reaction A  B is E a K1 Ea  T1  T2 
(c) log   
in forward direction. The activation energy for reverse reaction [CBSE
K 2 PMT 2003]
2 .303 R  T1 T2 
(a) Is always double of E a (d) None of these
(b) Is negative of E a 26. A reaction having equal activation energies for forward and reverse
reaction has [MP PMT 2002]
(c) Is always less than E a (a) H  0 (b) S  0
(d) Can be less than or more than E a (c) Zero order (d) None of these
27. Collision theory is applicable to [MP PMT 2002]
18. Arrhenius equation is (a) First order reactions (b) Zero order reactions
d ln K d ln K (c) Bimolecular reactions (d) Intra molecular reactions
(a)  E * / RT (b)  E * / RT 2
dT dT 28. A graph plotted between log K vs 1/T for calculating activation
energy is shown by [MP PET 2002]
d ln K d ln K
(c)  E * / RT 2 (d)  E * / RT
dT dT
19. Activation energy of any reaction depends on log K log K
(a) Temperature (a) (b)
(b) Nature of reactants
1/T 1/T
(c) Number of collisions per unit time
(d) Concentration of reactants
20. Relation between rate constant and temperature by Arrhenius
equation is log K log K
(c) (d)
E E
(a) loge A  loge K  a (b) log K  A a
RT RT 29. 1/TK is 10 times less
1/T of a reaction at temperature 200
The rate constant
Ea than the rate constant at 400 K. What is the activation energy
(c) loge K  loge A  (d) log A  RT ln Ea  ln K
RT 2 (E a ) of the reaction (R = gas constant)
21. An endothermic reaction A  B has an activation energy [EAMCET 2003]
15 kcal / mole and energy of reaction 5 kcal / mole . The activation (a) 1842.4 R (b) 921.2 R
energy of the reaction B  A is [Pb. CET 1985] (c) 460.6 R (d) 230.3 R
(a) 20 kcal/mole (b) 15 kcal/mole
(c) 10 kcal/mole (d) None of these 30. In respect of the equation k  Ae  Ea / RT in chemical kinetics,
22. Which of the following plots is in accordance with the Arrhenius which one of the following statement is correct
equation [AIEEE 2003]
(a) k is equilibrium constant
(b) A is adsorption factor
log K K
(a) (b) (c) Ea is energy of activation
1/T 1/T (d) R is Rydberg’s constant
31. The rate constant is doubled when temperature increases from 27°C
to 37°C. Activation energy in kJ is
(c) log K (d) log K
[JEE Orissa 2004]
(a) 34 (b) 54
23. The Arrhenius Tequation expressing the effect oflogtemperature
T on the
(c) 100 (d) 50
rate constant of a reaction is [MP PET 1997]
32. The activation energy of a reaction is zero. The rate constant of this
(a) k  e  Ea / RT (b) k  Ea / RT reaction
Ea (a) Increases with increase of temperature
(c) k  loge (d) k  Ae  Ea / RT
RT (b) Decreases with an increase of temperature
24. For a reaction, activation energy (Ea )  0 and rate constant (c) Decreases with decrease of temperature
(K)  3.2  10 6 s 1 at 300 K. What is the value of the rate constant (d) Is independent of temperature
at 310 K [KCET (Med.) 1999]
33. The rate constant is given by the equation k  pze  E / RT . Which
(a) 3.2  10 12 s 1 (b) 3.2  10 6 s 1 factor should register a decrease for the reaction to proceed more
(c) 6.4  1012 s 1 (d) 6.4  10 6 s 1 rapidly [MP PET/PMT 1998]
25. Activation energy is given by the formula [DCE 1999] (a) T (b) Z
K Ea  T2  T1 
(a) log 2    (c) E (d) p
K1 2 .303 R  T1 T2 
34. An endothermic reaction with high activation energy for the forward
reaction is given by the diagram: [AIIMS 2005]
 476 Chemical Kinetics
[I2 ] [H 2 ] [HI]
Potential energy

Potential energy
(b)  
t t 2 t
R P
(a) (b) R
P [H 2 ] 1 [I2 ] [HI]
(c)  
Reaction coordinate Reaction coordinate t 2 t t
(d) None of these
Potential energy

Potential energy
P d (B )
(c) P (d) 2. If 3 A  2 B, then the rate of reaction of  is equal to
R
R dt
35. ConsiderReaction
an endothermic
coordinate reaction X  with the activation
Y coordinate
Reaction [CBSE PMT 2002]
energies Eb and E f for the backward and forward reactions, d ( A) 1 d ( A)
(a) 2 (b) 
respectively, in general [AIEEE 2005] dt 3 dt
(a) Eb  E f 2 d ( A) 3 d ( A)
(c)  (d) 
3 dt 2 dt
(b) Eb  E f
3. The differential rate law for the reaction
(c) Eb  E f H 2  I2  2 HI is [AIEEE 2002]
d[H 2 ] d[I2 ] 1 d[HI]
(d) There is no definite relation between Eb and E f (a)   
dt dt 2 dt
36. Temperature dependent equation can be written as d[H 2 ] d[HI] 1 d[HI]
(b)  
[Orrisa JEE 2005] dt dt 2 dt
(a) ln k  ln A  e Ea / RT lnk  ln A  e Ea / RT 1 d[H 2 ] 1 d[I 2 ] d[HI]
(b) (c)  
2 dt 2 dt dt
(c) lnk  ln A  e RT / Ea (d) All of these d[H 2 ] d[I 2 ] d[HI]
(d)  2  2 
dt dt dt
Photochemical reactions 4. The rate law for a reaction between the substances A and B is given
by, rate  k[ A]n [B]m . On doubling the concentration of A and
1. The formation of starch in plants results from halving the concentration of B, the ratio of the new rate to the
earlier rate of the reaction will be as [
(a) Photosynthesis (b) Photolysis
1
(c) Flash photolysis (d) None of the above (a) (b) (m  n)
2 (m  n)
2. The photolysis of water gives the substance (c) (n  m ) (d) 2(n  m )
(a) OH   H  (b) H 2  OH  5. If we plot a graph between log K and
1
by Arrhenius equation,
T
(c) H 2  O2 (d) H 2 O  H 2 O2 the slope is [UPSEAT 2001]
E E
3. The law of photochemical equivalence was given by (a)  a (b)  a
R R
(a) Drapper (b) Grauths Ea Ea
(c)  (d) 
(c) Einstein (d) Labbert 2 .303 R 2 .303 R
4. If ‘I’ is the intensity of absorbed light and C is the concentration of 6. For an endothermic reaction, where H represents the enthalpy of
AB for the photochemical process AB  hv  AB*, the rate of the reaction in kJ / mol , the minimum value for the energy of
formation of AB* is directly proportional to activation
[IITwill be 2001]
Screening [IIT 1992]
(a) Less than H (b) Zero
(a) C (b) I
(c) More than H (d) Equal to H
(c) I2 (d) C.I 7. The rate constant (K ) of one reaction is double of the rate
constant (K ) of another reaction. Then the relationship between
the corresponding activation energies of the two reactions ( E a 

and E a  ) will be
[MP PET 1994; UPSEAT 2001]
(a) Ea   Ea  (b) Ea   Ea 
1. For the reaction H 2 (g)  I2 (g) ⇌ 2 HI(g) , the rate of reaction is
(c) Ea   Ea  (d) Ea   4 Ea 
expressed as [CBSE PMT 1997; AIEEE 2002]
8. The rate constant, the activation energy and the arrhenius parameter
[I2 ] [H 2 ] 1 [HI] of a chemical reaction at 25 o C are 3.0  10 4 s 1 ,
(a)   
t t 2 t
 Chemical Kinetics 477

104.4 kJ mol 1 and 6.0  10 14 s 1 respectively. The value of the (b) Finding the amount of acetic acid formed at different intervals
(c) Using a voltmeter
rate constant as T   is
(d) Using a polarimeter
[IIT 1996]
1 1 16. Half life of a reaction is found to be inversely proportional to the
(a) 2.0  10 s 18
(b) 6.0  10 s
14
cube of its initial concentration. The order of reaction is
(c) Infinity (d) 3.6  10 30 s 1 [KCET 2002]
9. The H value of the reaction H 2  Cl 2 ⇌ 2 HCl (a) 2
is (b) 5
44.12 kcal . If E1 is the activation energy of the products, then (c) 3 (d) 4
for the above reaction [EAMCET 1997] 17. The integrated rate equation is Rt  log C 0  log C t . The
(a) E1  E 2 straight line graph is obtained by plotting [AIEEE 2002]

(b) E1  E 2 1
(a) time v/s logCt (b) v / s Ct
time
(c) E1  E 2
1 1
(d) H is not related to E1 and E 2 (c) time v / s C t (d) v/s
time Ct
(e) None is correct
18. For which order reaction a straight line is obtained along with x–axis
10. The temperature dependence of rate constant (k ) of a chemical
by plotting a graph between half life (t1 / 2 ) and initial concentration
reaction is written in terms of Arrhenius equation, K  A.e  E*/ RT . 'a' [RPET 2003]
Activation energy (E * ) of the reaction can be calculated by plotting[CBSE PMT 2003]
(a) 1 (b) 2
(c) 3 (d) 0
1
(a) logk vs (b) k vs T 19. The reaction, X  product follows first order kinetics. In 40
log T minutes the concentration of X changes from 0.1 M to 0.025 M Then
1 1 the rate of reaction when concentration of X is 0.01 M
(c) k vs (d) logk vs
log T T (a) 1.73  10 4 M min 1 (b) 3.47  10 5 M min 1
4
11. Activation energy of a chemical reaction can be determined by[CBSE PMT 1998; AFMC
(c) 1999;  10
BHU
3.47 2000] M min 1 (d) 1.73  10 5 M min 1
(a) Changing concentration of reactants
20. A Substance undergoes first order decomposition. The
(b) Evaluating rate constant at standard temperature decomposition follows two parallel first order reactions as
(c) Evaluating rate constants at two different temperatures
k1 B
(d) Evaluating velocities of reaction at two different temperatures
k1= 1.26  10–4 s–1--––––––
12. The activation energy for a reaction is 9.0 K cal/mol. The increase A dfsfsfsf
k1= 3.8  10–5 s–1--––––––
in the rate constant when its temperature is increased from 298K to k 2
C dfsfsfsf
308K is [JIPMER 2000] The percentage distribution of B and C are
(a) 63% (b) 50%
[Kerala PMT 2004]
(c) 100% (d) 10%
(a) 75% B and 25% C (b) 80% B and 20% C
13. Which of the following is the fastest reaction
[Pb. CET 2002] (c) 60% B and 40% C (d) 90% B and 10% C
1 250 C 1 500 C (e) 76.83% B and 23.17% C
(a) C O 2   CO (b) C O 2   CO
2 2
1 750 C 1 1000 C
(c) C O 2   CO (d) C O 2   CO
2 2
14. The rate constant k, for the reaction N 2 O 5 (g) 
1
2 NO 2 (g)  0 2 (g) is 2.3  10 2 s 1 . Which equation given Read the assertion and reason carefully to mark the correct option out of
2
below describes the change of [ N 2 O5 ] with time? [ N 2 O 5 ]0 and the options given below :
[ N 2 O 5 ]t correspond to concentration of N 2 O 5 initially and at (a) If both assertion and reason are true and the reason is the correct
explanation of the assertion.
time, t [AIIMS 2004]
(b) If both assertion and reason are true but reason is not the correct
(a) [ N 2O5 ]t  [ N 2O5 ]0  kt explanation of the assertion.
(b) [ N 2 O5 ]0  [ N 2 O5 ]t e kt (c) If assertion is true but reason is false.
(d) If the assertion and reason both are false.
(c) log10 [ N 2 O5 ]t  log10 [ N 2 O5 ]0  kt (e) If assertion is false but reason is true.
[N 2 O5 ]0
(d) In  kt 1. Assertion : Instantaneous rate of reaction is equal to
[N 2 O5 ]t
dx / dt .

15. For the reaction CH 3 COOCH 3  H 2 O 
H
 Reason : It is the rate of reaction at any particular instant
of time.
CH 3 COOH  CH 3 OH The progress of the process of reaction is 2. Assertion : Molecularity has no meaning for a complex
followed by reaction.
(a) Finding the amount of methanol formed at different intervals
 478 Chemical Kinetics
Reason : The overall molecularity of a complex reaction is
equal to the molecularity of the slowest step.
3. Assertion : If in a zero order reaction, the concentration of
the reactant is doubled, the half-life period is also
doubled.
Reason : For a zero order reaction, the rate of reaction is
independent of initial concentration.
4. Assertion : If the activation energy of a reaction is zero,
temperature will have no effect on the rate
constant.
Reason : Lower the activation energy, faster is the
reaction.
5. Assertion : According to steady state hypothesis, in a
multistep reaction, the change in concentration
with time for reactive intermediates is zero.
Reason : The intermediates are so reactive that after a
brief initial period their concentrations rise from
zero to a small value and remains constant for
most of the duration of the reaction.
6. Assertion : Half-life period of a reaction of first order is
independent of initial concentration.
Reason : Half-life period for a first order reaction
2 .303
t1 / 2  log 2 .
K
7. Assertion : The photochemical reactions
H 2  Cl 2  2 HCl and H 2  Br2  2 HBr
have equal quantum efficiencies.
Reason : Both the reactions proceed by similar
mechanism.
8. Assertion : Vision is not a photochemical reaction.
Reason : Halogenation of alkenes is a photochemical
reaction.
9. Assertion : Glow worm shows chemiluminescence.
Reason : Glow worm emits light due to oxidation of
protein, luciferin present in it.
10. Assertion : The rate of reaction is always negative.
Reason : Minus sign used in expressing the rate shows
that concentration of product is decreasing.
11. Assertion : The kinetic of the reaction
mA  nB  pC  m ' X  n' Y  p' Z obeys
dx
the rate expression as  k [ A]m [B]n .
dt
Reason : The rate of the reaction does not depend upon
the concentration of C.
 480 Chemical Kinetics

121 d 122 b 123 d 124 c 125 d

126 b 127 d 128 d 129 b 130 a

131 ac 132 c 133 d 134 c 135 a

136 a 137 c 138 c 139 d 140 c

Rate of a reaction 141 c 142 c 143 c 144 a 145 c

146 c 147 c 148 b 149 b 150 a

1 b 2 a 3 d 4 b 5 b
151 d 152 a 153 d 154 c 155 c
6 c 7 c 8 c 9 a 10 b
156 b 157 a 158 b 159 d 160 c
11 b 12 b 13 c 14 d 15 b
161 b 162 b 163 b 164 abd 165 ad
16 b 17 c 18 b 19 d 20 a
166 b 167 d 168 b 169 d 170 b
21 b 22 a 23 d 24 c 25 a
171 c 172 c 173 c 174 a
26 a 27 a 28 b 29 b 30 b

31 a 32 c 33 b 34 a 35 c

36 d 37 a 38 b 39 a 40 c Collision theory, Energy of activation

and Arrhenius equation
41 a 42 b

1 b 2 b 3 b 4 c 5 a
Rate law and Rate constant
6 d 7 d 8 b 9 c 10 b
11 d 12 d 13 a 14 d 15 a
1 d 2 c 3 a 4 b 5 a
16 b 17 d 18 b 19 b 20 a
6 a 7 a 8 c 9 b 10 b
21 c 22 a 23 d 24 b 25 a
11 b 12 d 13 a 14 c 15 d
26 ab 27 c 28 b 29 b 30 c
16 d 17 c 18 a 19 c 20 c
31 b 32 d 33 c 34 c 35 a
21 b 22 a 23 a 24 d 25 b
36 a
26 a 27 a 28 c 29 c 30 d
31 d 32 c 33 c 34 d 35 b
Photochemical reaction
36 c 37 c 38 a 39 c 40 b
41 a 42 d 43 a 44 c 45 c 1 a 2 a 3 c 4 b
46 a 47 b 48 b 49 c 50 b

51 b 52 a 53 a 54 d 55 d Critical Thinking Questions

56 c 57 d 58 b 59 b 60 b

61 c 62 d 63 c 64 b 65 c 1 a 2 c 3 a 4 d 5 c

66 d 67 b 68 c 69 c 70 b 6 c 7 c 8 b 9 a 10 d

71 d 72 d 73 b 74 b 75 d 11 c 12 a 13 d 14 d 15 b

76 b 77 b 78 c 79 c 80 c 16 d 17 a 18 b 19 c 20 e

81 b 82 b 83 c 84 a 85 a

86 c 87 c 88 a 89 c 90 c Assertion & Reason

91 b 92 b 93 c 94 b 95 b
96 d 97 b 98 c 99 a 100 c 1 b 2 b 3 b 4 b 5 a

101 b 102 d 103 c 104 c 105 a 6 a 7 d 8 e 9 a 10 d

106 d 107 a 108 b 109 c 110 b 11 a

111 c 112 d 113 b 114 b 115 d

116 d 117 b 118 d 119 a 120 b

 Chemical Kinetics 481

22. (a) Increase in concentration of B  5  10 3 mol l 1

Time  10 sec

Increase of conc. B
Rate of appearance of B 
Time taken
Rate of a reaction
5  10 3 mol l 1
  5  10 4 mol l 1 Sec 1
1. (b) Rate of reaction continuously decreases with time. 10 sec
2. (a) The rate of reaction depends upon conc. of reactant, surface
area of reactant, temperature, presence of light and catalyst. 24. (c) The rate of formation of SO 3 is 1.28  10 3 g / sec .
3. (d) According to law of mass action.
K t  10 rt  10
4. (b) R  K[RCl] , if [RCl] =1/2, then rate = R/2. 26. (a)   2 ; For an increase of temperature to
Kt rt
5. (b) 2 2  4, 3 2  9 50 o C , i.e. 5 times, the rate increases by 2 5 times, i.e. 32
times.
6. (c) The rate of chemical reaction  The product of the molar
conc. of the reactants (at constant T) K t  10 rt  10
28. (b)   2.
dx  0 .2  0 .1  0 .1 Kt rt
7. (c) Rate of reaction =  
dt  10  10 For an increase of temperature to 20C i.e. 2 times, the rate
increase by 2 2 times, i.e. 4 times.
 0.01 mol dm 3 min 1
k t  10 rt  10
8. (c) As reaction progressing the concentration of the reactants 29. (b)  2
decreases and the concentration of the product increases. Kt rt
 d(N 2 ) 1 d (H 2 ) 1 d ( NH 3 ) 3 For an increase of temperature to 90 o C i.e. 9 times, the rate
9. (a)   =  40  10  3
dt 3 dt 2 dt 2 increases by 2 9 times i.e. 512.
 60  10 3. 30. (b) Catalyst increases the rate by decreasing the activation energy.
10. (b) Greater are the concentrations of the reactants, faster is the 31. (a) For 10K rise in temperature, the rate of reaction nearly doubles.
reaction. Conversely, as the concentrations of the reactants
decreases, the rate of reaction also decreases. K 35 o C K 308 k
32. (c) Temperature coefficient   2 and 3 for most
11. (b) Ionic reactions are very fast reactions i.e. take place K 25 o C K 298 k
instantaneously. reactions.
12. (b) Rate = K( A)2 (B)1 on doubling the active mass of A the rate 33. (b) Catalyst decrease energy of activation.
of reaction increase 4 times. 34. (a) Thus both rate and rate constant K increase with temperature,
13. (c) ‘A’ will disappear at twice the rate at which ‘B’ will decrease. r  k (reactant) n and k  Ae  Ea / RT
1 35. (c) Enzymes does not always increase activation energy.
14. (d) When volume is reduced to , concentrations become four
4 36. (d) Catalyst reduce the activation energy for reaction and thus
times. increase the rate of reaction.
dN 2 1 dH 2 1 dNH 3 37. (a) Catalyst affect only activation energy. It brings down the
16. (b)  
dt 3 dt 2 dt activation energy of reaction.
38. (b) As we know that the velocity constant become double by
dH 2 3
  0.001  0.0015kg hr 1 . increasing the temperature by 10°C so if at 290 K, velocity
dt 2
constant  3.2  10 3 then at 300 K, velocity constant
18. (b) 
dc
refers as decrease in concentration of the reactant with  2(K 290 )  2  3.2  10 3  6.4  10 3 .
dt
time. 39. (a) Higher the value of rate constant so, faster the reaction rate.
40. (c) Rate of reaction may increase or decrease with increase in
19. (d) The rate of a reaction depends upon concentration of reactant.
temperature. If reaction is exothermic, rate decreases with
1 d[ A] d[B] d[C] d (D) increasing temperature while that of endothermic reactions
20. (a)     . increase with increasing temperature.
3 dt dt dt dt
41. (a) 2 N 2 O5(g)  4 NO 2(g)  O 2(g)
21. (b) N 2  3H 2 ⇌ 2NH 3
Rate of reaction with respect to NO 2
[ N 2 ] 1 [H 2 ] 1 [ NH 3 ]
  1 d[ NO 2 ] 1 5.2  10 3
t 3 t 2 t     1.3  10 5 ms 1
4 dt 4 100
[H 2 ] 3 [ NH 3 ] 3 2 .303 90
     2  10 4 42. (b) In first phase, K  log .....(i)
t 2 t 2 20 100
2 .303 81
 3  10 4 mol litre1 sec 1 In second phase K  log .....(ii)
t 100
 482 Chemical Kinetics
2.303 90 2.303 81 2.303 800 2.303
From eq. (i) log  log k log10  log10 16
20 100 t 100 2  10 2 50 2  10 2
20(log 81  log100) 2.303 2.303
t  log10 2 4   4  0.301
(log 90  log100) 2  10 2
2  10 4
20(1 .908  2) 20  (0 .092)  1.38  10 2 s 1
  = 40 minutes
(1 .954  2) (0 .046) 15. (d) Rate of reaction is quadrupled on doubling the concentration.
Thus r [A]2 .
Rate law and Rate constant
16. (d) K is not constant for all the reaction.
1. (d) Molecularity of the reaction does not influence the rate of 19. (c) Rate determining step is a slow step by which rate of reaction
reaction. can be determined.
20. (c) It is a second order reaction and the unit of k for second order
2. (c) The rate law for an reaction can be given by; rate = K( A)(B)2 ,
i.e. the powers are raised which are given as coefficient of reaction is litre mol 1 sec 1 .
reactant. 21. (b) For reversible reaction rate constant is also reverse.
3. (a) p 0  500 atm 22. (a) Rate  K(N 2 O 5 )  6.2  10 1  1.25
2 .303 p
K log10 0  7.75  10 1 mol l1 s 1
t pt
23. (a) We know that for first order kinetics
2 .303 500
3 .38  10  5  log 2 .303 a
10  60 pt k log
t ax
500 00
or 0 .00880  log   490 atm (a  x )  0.05 mol l 1 , 6 
2 .303
log
0 .5
pt 1 .02 t 0 .05
4. (b) It is a pseudo-unimolecular reaction. 2.303 0.5 2.303
5. (a) A  2 B  C  D or t  log   0.384 min
6 0.05 6
d[ A]
 5  10 4 24. (d) Rate = K(N 2O5 ) hence 2.4  10 5  3.0  10 5 (N 2O5 )
dt
1 d[B] 5  10 4 or (N 2 O5 )  0.8 mol l 1
   2 .5  10 4 mol 1 sec 1
2 dt 2 25. (b) R  K[A] , 1.02  10 4  3.4  10 5 , [ N 2 O 5 ]
8. (c) For following reaction, 2 NO (g)  O 2 (g)  2 NO 2 (g)
1 .02  10 4
or (N 2 O 5 )  ,K  3
When the volume of vessel change into
1
then concentration 3 .4  10 5
3 26. (a) Rate law for the reaction
of reactant become three times. 2 N 2O5  4 NO 2  O2
The rate of reaction for first order reaction  concentration.
So rate of reaction will increases three times. is r  k[ N 2 O5 ] first order reaction.
9. (b) 2 A  B  Products 28. (c) Rate constant depends on temperature only.
According to question : Rate of reaction of ‘A’  [B] as increase 29. (c) According to Arhenius concept
in rate is double when [B] is doubled.
Rate constant K  Ae Ea / RT , Hence rate constant depends only
Rate of reaction  [A] [B] as increase in rate is 8 times when
concentration of both reactant is doubled. It means that order upon temperature of the system.
of reaction is 3 and overall rate reaction should be 30. (d) For 2 A  B  C
r  K[ A]2 [B] Rate  K[ A][B]
10. (b) Let the rate of reaction depends on x power of [A]. Then
th

Value of rate constant K  Ae  Ea / RT here K is independent

r1  k[ A]x and r2  k[2 A]x of the initial concentration of A and B.
r1 [ A] x 1 1
2 31. (d) The specific rate constant of a first order reaction depends
     ( r2  4 r1 ) upon the temperature of reaction.
r2 [2 A] x
4 2
32. (c) Unit of K for first order reaction  sec 1
 x  2 . As the reaction rate does not depend upon the
concentration of B. Hence, the correct rate law will be 35. (b) The rate of zero order reaction is not depend on the
concentration of the reactants.
rate  K[ A]2 [B]o or  K[A]2
11. (b) Velocity constant ‘K’ is characteristic constant of a reaction and 36. (c) The unit of K for zero order reaction  mole litre1 sec 1 .
depends only on temperature and catalyst. 37. (c) Order of reaction is sum of the power raised on concentration
12. (d) Unit of K for I order reaction is Time
st
1
. terms to express rate expression.
38. (a) The concentration of reactant does not change with time for
13. (a) K  Ae  Ea / RT by this equation it is clear that rate constant zero order reaction (unit of K suggests zero order) since
of a reaction depends on temperature reactant is in excess.
2 .303 a 1 1
m
14. (c) k log10 ; t  2  10 2 , a  800, a  x  50 39. (c) r  K[ A]m also 2 r  K[4 A] m ,  
t ax 2 4
 Chemical Kinetics 483

1 65. (c) Rate of zero order reaction is independent of the concentration

m  of the reactant and remains constant throughout the reaction.
2
1
2 .303 V 66. (d) t1 / 2 
40. (b) K  log gives constant value of K. With the (a)n 1
t V  Vt
given date. Hence it is 1 order. 1
t1 / 2   reaction is of first order.
st

67. (b)
42. (d) r  K[ A] , 100r  K[10 A]
n n (Co )n 1
n 68. (c) For I order reaction half life is independent of concentration.
st

1  1 
Thus    or n = 2 0.693 0.693
100  10  69. (c) K ,K  0 .005 min 1
t1 / 2 138.6 min
43. (a) It is a standard example of first order because in that reaction
rate of reaction affected by only one concentration term. 
70. (b) CH 3 COOCH 3  H 2 O 
H
 CH 3 COOH CH 3 OH
44. (c) Inversion of cane sugar is a Pseudo unimolecular reaction.
45. (c) For 1 order reaction
st It is a pseudo-unimolecular reaction.
2 .303 a 1
K log10 71. (d) t1 / 2  and K  t
t (a  x ) K
0.693 0.693 dx
46. (a) t1 / 2    1117.7 sec. 73. (b) For zero order reactions  K( A)o
k 6.2  10  4 dt
2 .303 a 74. (b) It is an bimolecular and second order reaction.
47. (b) k  log
t ax dx
75. (d)  (HI)2 , then order of reaction = 2
0.693 2.303 100 dt
 log
T t 100  30 76. (b) Rate = K(Sucrose)(H 2O)o
 T  58.2 min.
77. (b) Because in this reaction one molecule of N 2 O5 is used.
3 3 33 6
48. (b) Order of reaction =    3 78. (c) Integrated velocity equation for first order reaction is:
2 2 2 2 2 .303 ( A)
49. (c) Two molecules are taking part in elementary step. k log o
t ( A)
50. (b) Because two molecules are taking part in elementary step.
51. (b) The overall order of a reaction is sum of powers T raised on 2.303 log 2 0.693
concentration terms in order to write rate expression. 80. (c) t1 / 2  
K K
52. (a) It is a first order reaction as is clear from rate law expression,
81. (b) Inversion of sugar is a pseudo-unimolecular reaction.
r  k (H 2O2 )
82. (b) For I order reaction
st

53. (a) For I order reaction half life is independent of concentration.

st

kt
log(a  x )  log a 
1  a  1  35  1  35  2 .303
54. (d) K log e   log e    log e  
t  a  x  15  35  9  15  26  y  c  mx
0 .693 2 .303  100  t1 / 2 
0.693

0.693
 200 min
56. (c) k  0 .0231 ; t  log  83. (c)
30 k  100  75  k 3.46  10  3
1 moles l 1
t
2 .303
log 4  60 minutes 84. (a)  (conc.)   moles l 1time1 for zero
0.0231 Time Time
order reaction.
57. (d) Rate  K(sugar)(H 2O)o 3
85. (a) The order of reaction is and molecularity is 2.
a 1 2
58. (b) Derive t1 / 2 from Kt  2 .303 log , putting t  and
ax 2 87. (c) Molecularity can never be fractional.
a 0 .693 88. (a) As doubling the initial conc. doubles the rate of reaction, order
x  . Therefore it is . = 1.
2 K
89. (c) When B is in excess, it becomes a pseudo-unimolecular
59. (b) r  [X ]2 or r  k[X ]2 reaction.
0.693 0.693
0.693 0.693 90. (c) k   9 .99  10  3  0.01 s 1
60. (b) t1 / 2  ,  6 .3  10 8 sec. t1 / 2 69.35
k 1.1  10 9
0 .693 1 2.303 10
61. (c) t1 / 2 
1
for II order reaction. 91. (b) k  hr  log
(a) 24 96 ax
10
62. (d) Order of reaction is an experimental value, while molecularity or log  1 .2036 or 1 – log (a – x) = 1.2036
is a theoretical value. ax
63. (c) K for 1 order reaction = per unit time i.e. Time 1 .
st or log(a  x )  0.2036  1.7964

64. (b) R  K[ A][B]0 so molecularity is two and order is two. or (a  x )  antilog 1 .7964  0.6258 gm
 484 Chemical Kinetics

92. (b) 0.08 mol l 1 to 0.01 mol l 1 involves 3 half-life. So the 121. (d) t
2 .303
log
a
t is 30 minutes k ax
93. (c) t1 / 2 of II order reaction is inversely proportional to initial 2.303 100
t 3
log  600 sec
concentration of reactants. 1.155  10 100  50
94. (b) As r  k (H 2O2 ) , it is a reaction of 1 order.
st

122. (b) Rate = K[ A]3 / 2 [B]1

97. (b) r  k (C A )3 / 2 (C B )1 / 2 3 1
 O.R.   (1) 
3  1 2 2 2
Order =      1
2  2 2 123. (d) t1 / 2  (CO )o i.e. half life for I order is independent of initial
st

concentration.
98. (c) If rate  K( A)m (B)n , then order of reaction  m  n .
124. (c) 2 NO(g)  Cl2(g)  2 NOCl(g)
0 .693 0.693
99. (a) k   6 .93  10  3 sec 1 Rate = K[ NO ]2 [Cl 2 ]1 ,  O.R.  2  1  3
t1 / 2 100 sec
1 1 1 1
t1 / 2 
0 .693 125. (d) 8  10  5   ; 8  10  5  [2  1]
t  0 .5 1 
100. (c)
k t
0.693 0.693 1
101. (b) t1 / 2  ,k  1.44  10  3 sec 1 . t  0.125  10 5  1 .25  10 4 min.
k 480 8  10 5
102. (d) r  k (A)2 , when concentration is doubled 0 .693  10 2
126. (b) r  k[reactant ]1 k  also
r  k (2 A)2  k 4( A)2 the rate becomes 4 times. 1
0.693 0.693
103 (c) r  K[FeCl3 ]2 [SnCl 2 ]1 . Order  2  1  3 t1 / 2    100 min .
k 0.693  10  2
105. (a) t1 / 2 for I order reaction independent of initial concentration. 1
127. (d) t1 / 2  for second order reactions.
107. (a) The rate will be given by slowest step. Thus Ka
[ A][ A]
r  K[ A][B2 ] . Kc  or [ A]  [Kc ]1 / 2 [ A2 ]1 / 2 2 .303  a  2 .303  100 
[ A2 ] 128. (d) k  log ; k  log 
t  a  x  30  100  75 
r  K  [Kc ]1 / 2 [ A2 ]1 / 2 [B2 ]  K[ A2 ]1 / 2 [B] . Thus order is 2 .303  100 
k log  Put the value of K from
0. 5  1  1 .5 t  100  93.75 
108. (b) For I order reaction half life is independent of concentration.
st

above equation we get the value of t therefore

110. (b) Rate = K[ A]1 / 2 [B]3 / 2  t  60 min .
1 3 4
 O.R.    2 129. (b) k 
0 .693
min 1 
2 .303
log
a
or
2 2 2 45 t99 .9% a  0 .999a
112. (d) The rate of this photochemical reaction is independent of the
concentration, therefore, it is zero order reaction. 2.303  45
t99 .9%  log10 3  448 min  7.5 hrs
0 .693 0 .693 0.693
113. (b) t1 / 2    1 hr . 130. (a) Given A(a) = 2.00 m, t = 200 min and a(a-x) = 0.15 m we know
k 0 .6932 hr 1
114. (b) The unit of rate constant shows that reaction is of first order. 2.303 a 2.303 2.00
k log  log
For first order reaction, half life is independent of initial conc. t ax 200 0 .15
of the reactant. Thus,
2.303
0.693 0.693  60   (0.301  0.824)  1.29  10  2 min 1
t1 / 2    600 sec 200
0.69  10 1 0.69  10 1
115. (d) Given : Rate constant of the first order reaction 131. (a,c) The unit for zero order reaction is mol litre 1time1
(K)  3  10 6 per sec and initial concentration 132. (c) It is a third order reaction because
[ A]  0.10 M . We know that initial rate constant Rate  K[NO]2 [O2 ] 1  O.R.  2  1  3
133. (d) Order of a reaction is decided by relative concentration of
K[ A]  3  10 6  0.10  3  10 7 ms 1 . reactants.
116. (d) It is the characteristic of pseudo-unimolecular reactions. 134. (c) Unit of rate constant for second order reaction is
117. (b) It is a second order reaction.
mol 1litre time1
118. (d) r  K [reactant]
1 .0  10 2 135. (a) R  K[ A]2 [B] order of reaction  2  1  3
K   0 .05
0.2 136. (a) Units of 1 rate constant order reaction are sec 1 and for zero
st

0.693 order reaction, these are mol litre1 sec 1 i.e. M sec 1 .
t1 / 2   13.86 s
0 .05 137. (c) This reaction is bimolecular and first order of reaction.
119. (a) For first order reactions rate is depend on the concentration of
0 .693
one reactant. 138. (c) t1 / 2  Given t1 / 2  693 sec
120. (b) Molecularity of a reaction never become zero or fraction. k
 Chemical Kinetics 485

0 .693 693  10 3 CH 3 COOCH 3  H 2 O 
 CH 3 COOH  CH 3 OH
H
693  , k ; k  10 3  0.001 sec 1 .
k 693 in this reaction molecularity is 2 but order of reaction is found
139. (d) 2A  B  C  B to be first order experimentally, so it is an example of pseudo
unimolecular reaction.
Rate = k[ A]2 [B]1 0 .693 0 .693
153. (d) K  
 O.R.  2  1  3 and molecularity is 3[2 A  B] . t1 / 2 10 years
140. (c) In photochemical reactions the rate of reaction is independent If initial concentration a  10 gm and final concentration
of the concentration of reacting species.
a
2 .303 a x  5 gm
141. (c) We know that k  log 2
t ax 2 .303 a 2 .303 10
2 .303 a 2 .303 then, t  log   10  log
10  3  log , 10  3  log 3 K ax .693 5
t 2a t
(a  ) 2 .303  10  log 2 2.303  10  0.301
3    10 years .
.693 0.693
2.303 2.303  0.4771
10  3   0.4771, t   3300 sec 154. (c) The concentration of the reactants decrease from 0.8 to 0.4 in 15
t 10  3 min i.e., T1 / 2  15 min, concentration from 0.1m to 0.025 will
R' fall in 2 half lives so total time taken
142. (c) R  K( A)2 , R '  K(2 A)2 ,  4  2  T1 / 2  2  15  30 min.
R
R' 2 .303 100 2 .303 100
R  K( A)2 , R '  K(3 A)2 , 9 155. (c) K log  log
R 1 hr 25 t 50
1
2 .303  a   log 4  log 2
144. (a) k log  t
t ax 
1 1
 2 log 2  log 2 ; t  hr .
2 .303  100  t 2
k log  .… (i)
32  100  75  156. (b) x (g)  y(g)  z(g)
The reaction is a first order reaction hence,
2 .303  100 
k log  ….(ii) 0 .693 2 .303 a 0 .693
t  100  50  K  log 
t1 / 2 t ax 10 min
from the two equation (i) and (ii), t  16 minutes.
2 .303 a 0.693 2 .303
146. (c) The relation between half – life period and initial concentration  log   log10
t a / 10 10 t
1
(c) for a n order reaction is given by t1 / 2  n 1 for first
th
2.303  10
C  t  33 min .
.693
1
order reaction (n  1) . t1 / 2  1 1 or t1 / 2  C 0 . 2 .303 a
C 157. (a) For the first order reaction t  log
K ax
147. (c) R  k[ NO ]2 [O2 ] , R'  k[2 NO ]2 [2O2 ] Given: a  0.5 mol / litre; a  x  0.05 , mol / litre

R'  k  4[ NO ]2 [O2 ]  k  8[ NO ]2 [O2 ] K  6 sec 1 .

2.303 0.5 2.303 2 .303
t log  log10   0 .384 sec .
R ' k  8[ NO ]2 [O2 ] 6 0.05 6 6
 8
R k [ NO ]2 [O2 ] 158. (b) The radioactive disintegration reactions are of first order
because in this rate of disintegration depends on the
148. (b) For zero order reaction r  k . concentration term of radioactive material only.
2.303 0.8 4  dx 
149. (b) k  log  2.303 log 159. (d) Rate    K . c ; 1.5  10 2  K  0.5
t 0 .6 3  dt 

t
2.303 0.9

2.303 4
log ; t  1 hour. 1.5  10 2
log For first order K   3  10  2 min ute1
k 0.675 k 3 0 .5
150. (a) For zero order reaction .693 .693
t1 / 2    23.1 min ute .
Velocity constant 
dx Concentrat ion
 K 3  10  2
dt Time 2 .303 a
160. (c) For first order reaction K  log
Unit  concentration  time -1 . t ax
151. (d) H 2  Br2 ⇌ 2 HBr is a 1.5 order reaction 1 1
Given: a   .1m ; a  x   .01m ; t = 500 sec
10 100
i.e., K  [H 2 ][Br2 ]1 / 2 .
2.303 .10 2.303
152. (a) When in any chemical reaction, one of the reactant is present  K log  log10
in large excess, then the second order reaction becomes first 500 .01 500
order reaction and is known as pseudo unimolecular reaction 2.303
e.g.,   0.004606  4.6  10  3 sec 1 .
500
 486 Chemical Kinetics
161. (b) For zero order reaction, rate of reaction is independent of Thus, overall order of reaction = 2 + 1= 3.
concentration R  K[Reactant]0 174. (a) In case of zero order reaction, the concentration of reactant
decreases linearly with time, as its rate is independent of the
162. (b) The radioactive disintegration reactions are of first order
concentration of the reactants.
because in this rate of disintegration depends on the
concentration term of radioactive material only.
1 n n 1 Collision theory, Energy of activation
0 .1 (200)1 n 1 4  1 
163. (b) t1 / 2  a1 n        and Arrhenius equation
0 .4 (50)1 n 4 1  4 
1 1 1. (b) The increase in collision frequency brings in an increase in
  n 1  n  1  1 ; n  2 .
4 1
4 effective collisions and thus rate of reaction increases.
d ln k H o 2. (b) All collisions are not effective and does not result in the
164. (abd) By Vant’s Hoff equation,  formation of the products
dt RT 2 3. (b) The increase in collision frequency brings in an increase in
H o effective collisions and thus rate of reaction increases.
or ln k p    I . Hence (a) is correct (b) is also correct 4. (c) The increase in collision frequency brings in an increase in
RT
as plot of log (X) vs time is linear. (c) is wrong because effective collisions and thus rate of reaction increases.
p  T at constant volume. (d) is correct by Boyle’s law. 5. (a) Slower reaction rate indicates higher energy of activation.
kt
6. (d) Energy of activation decreases, rate of reaction will increases.
165. (ad) (a) is correct because degree of dissociation  1  e at any 7. (d) Number of collision depend upon pressure, concentration and
time t. temperature.
(b) is wrong because plot of log [A] vs t is a straight line
9. (c) The definition of activation energy.
(c) is wrong because time taken for 75% 10. (b) Activation energy is the energy needed by reactant molecules to
reaction is two half life. gain threshold energy level.
(d) is correct because in k  Ae  Ea / RT , Ea / RT is 11. (d) All other are different forms of Arrhenius equation.
dimensionless hence A has the unit of K. 12. (d) Increase in the rate of reaction is determined by the increase in
166. (b) aA  xP the number of effective collisions.
Rate of reaction = [A] a 13. (a) Energy of activation reduced by increasing temperature.
Order of reaction = a 14. (d) The definition of threshold energy.
[A] = 2.2 mM, r = 2.4 m M s
1 1
...(i)
–1
15. (a) The definition of activation energy.
2 .4 16. (b) When the temperature is increased, heat energy is supplied
[A] = 2.2/2 mM, r = 0.6 m M s or,
2 1
–1
...(ii) which increases the kinetic energy of the reacting molecules.
4 this will increase the number of collisions and ultimately the
On reducing the concentration of A to half, the rate of reaction rate of reaction will be enhanced.
is decreased by four times. 17. (d) In exothermic and endothermic reactions will be more and less
Rate of reaction = [A] 2

than Ea respectively.
Order of reaction = 2.
167. (d) Order of a reaction can be fractional. 19. (b) The value of activation energy for a chemical reaction primarily
dependent on the nature of reacting species.
2 .303 1 0 .29
168. (b) t1 / 4  log  . E
K 1 K 20. (a) Arrhenius equation is logk  log A  a
1 RT
4
1
169. (d) R  K[A] 22. (a) A graph plotted between log k vs for calculating
T
5 2
2  10  K  10 activation energy.
K  2  10 3 sec 1 24. (b) When Ea  0 rate constant is independent of temperature.
.693 .693 693 25. (a) It is modified form of Arrhenius equation.
t1 / 2   3
  347 sec 1
K 2  10 2 28. (b) A graph plotted between log k Vs for calculating
n T
1 1
170. (b) R  k [B]n ; R  k [2 B]n ; 4    ; 4  2 n ; n  2 . activation energy is shown as
4 2 from Arrhenius equation
171. (c) T  t1 / 2  n i.e. 12  3  n  n  4 EA log k
log k  log A 
n 4 2 .303 RT 1/T
1 N 1 1
N  N0      
 
2 N 0  
2 16 30. (c) It is Arrhenius equation.

K  1.7  10 s 5 1 K2 Ea  1 1 
172. (c) 31. (b) log    
0.693 0.693 K1 2 .303 R  T1 T2 
t1 / 2    10 5  11.32h
K 1.7 K
If 2  2
173. (c) A  B  C K1
On doubling the concentration of A rate of reaction increases Ea  1 1 
log 2   300  310 
by four times. Rate  [A]2 2 .303  8 .314  
However on doubling the concentration of B , rate of reaction
increases two times. Rate  [B]
 Chemical Kinetics 487

 300  310  8. (b) T2  T (say), T  25 o C  298 K,

Ea  .3010  2 .303  8 .314  
 10  Ea  104.4 kJ mol 1  104.4  10 3 J mol 1
1
 53598.59 Jmol  54 kJ . K1  3  10 4 , K2  ,
32. (d) When Ea  0 , the rate of reaction becomes independent of K2 Ea 1 1
temperature. log    
K1 2 .303 R  1
T T2
(Ea = Energy of activation).
K2 104.4  10 3 J mol 1
log 4

pz 3  10 2 .303  (8 .314 J k 1 mol 1 )
33. (c) When k increases, rate of reaction also increases, k  E / RT
e  1 1 1
for k to increase p, z, T should increase and E should decrease.  298 K  T  As T  , T  0
( e  2.7 ).  

34. (c) Endothermic reactions are those which involve absorption of K2 104.4  10 3 J mol 1
 log 4

heat. High activation energy means potential energy of product 3  10 2 .303  8 .314  298
must be much greater than reactants.
K2 K2
log  18.297,  1.98  1018 or
35. (a) For endothermic reaction H = +ve 3  10 4
3  10  4
Then from equation H  EaF. R.  EaB. R. ; E B. R.  E F. R. K2  (1.98  1018 )  (3  10 4 )  6  1014 s 1
36. (a) Arrhenius suggested an equation which describes rate constant 9. (a) Because reaction is exothermic
(K) as a function of temperature. 0 1
10. (d) k  Ae  E / RT
log K  log A  E o / RT  log K Vs .
 Ea / RT mx T
K  Ae y c

K2 Ea  T2  T1 
ln K  ln A  e Ea / RT 11. (c) log   
K1 2 .303 R  T1T2 
Photochemical reactions K 2 Ea  T2  T1 
12. (a) 2 .303 log   
K1 R  T1T2 
2. (a) H 2O    OH   H 
Photolysis
K2 9 .0  10 3  308  298 
log 
3. (c) Stark - Einstein was given the law of photochemical K1 2 .303  2  308  298 
equivalence.
K2 1.63 K 1  K 1
4. (b) In photochemical reaction the rate of formation of product is  1.63 ; K 2  1.63 K 1 ;  100  63.0 %
directly proportional to the intensity of absorbed light. K1 K1
13. (d) Combustion is an exothermic process, which is expected to be
favoured by low temperature, but it is not true. Combustion
Critical Thinking Questions include burning of particles which takes place at higher
temperature. Thus at high temperature due to combustion of
1. (a) For the given reaction : more particles, the reaction proceeds at higher rate.
[I2 ] [H 2 ] 1 [HI] 14. (d) Rate constant  2.3  10 2 sec 1
   It means it is a first order reaction (because unit of rate
t t 2 t
constant is sec ) –1

1 d[ A] 1 d[B] d[B] 2 d[ A]
2. (c)     For first order reaction K  ln
1 a
3 dt 2 dt dt 3 dt t ax
3. (a) Concentration of reactants decreases while concentration of a [N O ]
product increases. Kt  ln  ln 2 5 0
ax [ N 2 O5 ]t
4. (d) R  K( A)n (B)m 15. (b) Because as reaction progresses the amount of acetic acid
m
increases.
B 16. (d) Half life of a reaction is found to be inversely proportional to
R '  K(2 A)n    K( A)n 2n (B)m 2m
2 the cube of initial concentration. The order of reaction is 4.
17. (a) It is similar to y  mx  c
n m R ' K( A)n (B)m 2n m
 K( A) (B) 2
n m
,   2n m 18. (b) r  K[ A]n , 100r  K[10 A]n
R K( A)n (B)m
n
1  1 
E Thus    or n = 2
5. (c) ln K  ln  a is Arrhenius equation. Thus plots of ln K vs 100  10 
RT
19. (c) Concentration will fall from 0.1 M concentration to 0.025 M
1/T will give slope   Ea / RT or  Ea / 2.303 R . concentration within 2 half lives.
6. (c) For a reaction E a for forward reaction  Ea for backward 2  T1 / 2  40 min
reaction + H .  T1 / 2  20 min

7. (c) As K '  K ", Ea'  Ea" (Greater the rate constant, less is the Rate of reaction = K . c 
0 .693
.c
activation energy). T1 / 2
 488 Chemical Kinetics
0 .693
  10  2 M / min  3.47  10 4 M / min 1 .
20
K1
20. (e) % distribution of B   100
K1  K 2

1 .26  10 4
  100
1 .26  10  4  3 .8  10  4
B%  76.83%
K2
%Distribution of C   100
K1  K 2
3 .8  10 4
  100
1 .26  10  4  3 .8  10  4
C%  23.17%

Assertion and Reason

1. (b) Instantaneous rate of a reaction is equal to small change in
concentration (dx ) during a small interval of time (dt) at that
particular instent of time divided by the time interval.
2. (b) Molecularity of a reaction can be defined only for an
elementary reaction because complex reaction does not take
place in one single step and it is almost impossible for all the
total molecules of the reactants to be in a state of encounter
simultaneously.
3. (b) For a zero order reaction, t1 / 2  [ A0 ] / 2 K .
4. (b) According to Arrhenius equation, K  Ae  Ea / RT when
Ea  0, K  A .
2 .303 a
6. (a) For a first order reaction, K  log , where a is
t ax
initial concentration, and x is the amount reacted in time t. For
half-life x  a / 2 , t  t1 / 2
2 .303 a
K log
K aa/2
2.303 0 .693
t1 / 2  log 2  .
K K
7. (d) H 2  Cl 2  2 HCl has much higher quantum efficiency
than H 2  Br2  2 HBr . The first step of secondary process
of H 2  Cl 2  2 HCl is exothermic while the same for
H 2  Br2  2 HBr is endothermic.
8. (e) Vision is a fast photochemical reaction in which the compound,
retinal, present in the eye undergoes isomerisation by
absorbing a photon of light.
9. (a) The emission of cold light during a chemical reaction is called
chemiluminescence.
10. (d) The rate reaction is never negative. Minus sign used in
expressing the rate only shows that the concentration of the
reactant is decreasing.
dx
11. (a) Rate expression  K[ A]m [B]n
dt
Shows that the total order of reactions is m  n  O
 m  n as the rate of reaction is independent of
concentration of C, i.e. the order with respect to C is zero. This
is the reason that C does not figure in the rate expression.
 Chemical Kinetics 489

1. The temperature coefficient of most of the reactions lies between [MP PET 1999]
6. The minimum energy necessary to permit a reaction is
(a) 1 and 3 (b) 2 and 3 [NCERT 1989]
(c) 1 and 4 (d) 2 and 4 (a) Internal energy
2. The influence of temperature on the rate of reaction can be found (b) Threshold energy
out by [AFMC 2001]
(c) Activation energy
(a) Clapeyron–Claussius equation
(d) Free energy
(b) Gibbs–Helmholtz equation
7. The formation of gas at the surface of tungsten due to adsorption is
(c) Arrhenius equation the reaction of order [AIEEE 2002]
(d) Vander Waal's equation (a) 0
3. The mechanism for the reaction is given below (b) 1
2P  Q  S  T (c) 2
P  Q  R  S (slow) (d) insufficient data
P  R  T (fast) 8. The time of completion of 90% of a first order reaction is
approximately [MP PET 2002]
The rate law expression for the reaction is
(a) 1.1 times that of half life
[Kurukshetra CEE 2002]
(b) 2.2 times that of half life
(a) r  k[P]2 [Q] (b) r  k[P][Q]
(c) 3.3 times that of half life
(c) r  k[ A][R] (d) r  k[P]2 (d) 4.4 times that of half life
4. Consider the following energy profile for the reaction. 9. In a photochemical reaction, the ratio of number of dissociate
X  Y  R  S . Which of the following deductions about the molecules and number of quanta of absorbed energy is called
reaction is not correct
(a) Einstein
100
80 (b) Quantum efficiency
60
(c) Quantum constant
40
20 x+y (d) Planck constant
0
(a) The energy of activation for the backward reaction is 80 kJ
Reaction Pathway 10. A reaction rate constant is given by

(b) The forward reaction is endothermic k  1.2  10 14 e (25000 / RT ) sec 1

(c) H for the forward reaction is 20 kJ It means [MP PET 1995]

(d) The energy of activation for the forward reaction is 60 kJ (a) logk versus log T will give a straight line with slope as –
5. The minimum energy required for molecules to enter into the 25000
reaction is called
(b) logk versus T will give a straight line with slope as –
[KCET 1986; EAMCET 1992; MP PMT 1993; MP PET 1994] 25000
(a) Potential energy
(c) logk versus log1 / T will give a straight line with slope as –
(b) Kinetic energy
25000
(c) Nuclear energy
(d) logk versus 1 / T will give a straight line
(d) Activation energy

(SET -11)
 Chemical Kinetics 487

K 35 o C
1. (b) Temperature coefficient = = between 2 and 3. 7. (a) The order of reaction for the formation of gas at the surface of
K 25 o C
tungsten due to adsorption is zero .
2. (c) Arrihenius equation is : K  Ae  Ea / RT 8. (c) For a first order reaction
2 .303 a
3. (b) The rate law expression for the reaction is r  k[P][Q] . K log
t (a  x )
4. (a) Ea of backward reaction  80  40  40kJ
2 .303 100 2 .303  t1 / 2 100
t log   log
Hence (a) statement is wrong. k (100  90) 0 .593 10
5. (d) The energy necessary for molecules to undergoes chemical  3.3  t1 / 2  log 10  3.3 t1 / 2
reaction is known as Activation energy.
9. (b) It is also known as Quantum yield and indicated by  .
6. (b) Molecules undergoing reaction should cross over the minimum
energy barrier or energy level known as threshold energy. 10. (d) According to the Arrihenius equation a straight line is to be
`obtained by plotting the logarithm of the rate constant of a
chemical reaction (log K) against 1/T.
***

Electrochemistry is the branch of physical chemistry which deals
with the relationship between electrical energy and chemical changes taking
place in redox reactions
Electrolytes and Electrolysis
(1) Definition : “The substances whose aqueous solution undergo
decomposition into ions when electric current is passed through them are
known as electrolytes and the whole process is known as electrolysis or
electrolytic decomposition.”
Solutions of acids, bases, salts in water and fused salts etc. are the
examples of electrolytes. Electrolytes may be weak or strong. Solutions of
cane sugar, glycerine, alcohol etc., are examples of non-electrolytes.
(2) Electrolytic cell or Voltameter : The device in which the process
of electrolysis or electrolytic decomposition is carried out is known as
electrolytic cell or voltameter.
(i) Voltameter convert electrical energy into chemical energy .
(ii) The electrode on which oxidation takes place is called anode (or
+ve pole) and the electrode on which reduction takes place is called cathode
(or –ve pole)
(iii) During electrolysis in voltameter cations are discharged on cathode
and anions on anode.
(iv) In voltameter, outside the electrolyte electrons flow from anode
to cathode and current flow from cathode to anode.
Flow of electrons
Anode Cathode
Flow of current
For voltameter, E cell  ve and ΔG  ve.
Table : 12.1 Products of electrolysis of some electrolytes
Electrolyte Electrode Product at cathode
Aqueous NaOH Pt or Graphite
2 H  2e  H 2
Fused NaOH Pt or Graphite Na   e   Na
Electrochemistry 491
Chapter
12
Electrochemistry
(v) The anions on reaching the anode give up their electrons and
converted into the neutral atoms.
At anode : A–  A  e  (Oxidation)
(vi) On the other hand cations on reaching the cathode take up
electrons supplied by battery and converted to the neutral atoms.
At cathode : B  e   B (Reduction)
This overall change is known as primary change and products
formed is known as primary products.
The primary products may be collected as such or they undergo
further change to form molecules or compounds. These are called secondary
products and the change is known as secondary change.
(3) Preferential discharge theory : According to this theory “If more
than one type of ion is attracted towards a particular electrode, then the ion
is discharged one which requires least energy or ions with lower discharge
potential or which occur low in the electrochemical series”.
The potential at which the ion is discharged or deposited on the
appropriate electrode is termed the discharge or deposition potential, (D.P.).
The values of discharge potential are different for different ions.
The decreasing order of discharge potential or the increasing order
of deposition of some of the ions is given below,
For cations : Li , K  , Na  , Ca 2  , Mg2  , Al3  , Zn 2  ,
Fe2 , Ni 2  , H  , Cu 2  , Hg 2  , Ag  , Au 3  .
For anions : SO 42  , NO 3 , OH  , Cl  , Br , I  .
Product at anode
 
1
2OH   O 2  H 2 O  2e 
2
1
2OH   O2  H 2 O  2 e 
2
 492 Electrochemistry
Aqueous NaCl Pt or Graphite 2 H   2e   H 2 2Cl   Cl 2  2e 
Fused NaCl Pt or Graphite Na   e   Na 2Cl   Cl 2  2e 
Aqueous CuSO Pt or Graphite Cu 2  2e   Cu 1
2OH   O2  H 2 O  2e 
4

2
Aqueous CuSO 4
Cu electrode Cu 2  2e   Cu Cu oxidised to Cu 2  ions
Dilute H SO Pt electrode 2 H   2e   H 2 1
2OH   O2  H 2 O  2e 
2 4

2
Conc. H SO
2 4
Pt electrode 2 H   2e   H 2 Peroxodisulphuric acid (H 2 S 2O8 )
Aqueous AgNO Pt electrode Ag   e   Ag 1
2OH   O2  H 2 O  2e 
3

2
Aqueous AgNO 3
Ag electrode Ag   e   Ag Ag oxidised to Ag  ions
(4) Application of electrolysis : Electrolysis has wide applications in Faraday's laws of electrolysis
industries. Some of the important applications are, as follows,
(i) Production of hydrogen by electrolysis of water. The laws, which govern the deposition of substances (In the form of
ions) on electrodes during the process of electrolysis, is called Faraday's laws
(ii) Manufacture of heavy water (D2O) . of electrolysis. These laws given by Michael Faraday in 1833.
(iii) The metals like Na, K, Mg, Al, etc., are obtained by electrolysis (1) Faraday's first law : It states that,
of fused electrolytes. “The mass of any substance deposited or liberated at any electrode
(iv) Non-metals like hydrogen, fluorine, chlorine are obtained by is directly proportional to the quantity of electricity passed.”i.e., W  Q
electrolysis. Where,
(v) In this method pure metal is deposited at cathode from a W = Mass of ions liberated in gm,
solution containing the metal ions Ag, Cu etc. Q  Quantity of electricity passed in Coulombs
(vi) Compounds like NaOH, KOH, Na 2CO 3 , KClO3 , white lead, = Current in Amperes (I) × Time in second (t)
KMnO4 etc. are synthesised by electrosynthesis method.
 W  I  t or W  Z  I  t
(vii) Electroplating : The process of coating an inferior metal with a In case current efficiency () is given, then
superior metal by electrolysis is known as electroplating. The aim of 
electroplating is, to prevent the inferior metal from corrosion and to make W  ZIt
100
it more attractive in appearance. The object to be plated is made the
where, Z  constant, known as electrochemical equivalent (ECE) of
cathode of an electrolytic cell that contains a solution of ions of the metal to
the ion deposited.
be deposited.
When a current of 1 Ampere is passed for 1 second (i.e., Q  1 ),
For electroplating Anode Cathode Electrolyte then, W  Z
With copper Cu Object Thus, electrochemical equivalent (ECE) may be defined as “the mass
CuSO 4  dilute H 2 SO 4
of the ion deposited by passing a current of one Ampere for one second
With silver Ag Object K[ Ag(CN )2 ] (i.e., by passing Coulomb of electricity)”. It's unit is gram per coulomb.
With nickel Ni Object Nickel ammonium Coulomb is the unit of electrical charge.
sulphate 96500 Coulombs  6.023  10 23 electrons = 1 mole electrons.
With gold Au Object K[ Au(CN )2 ] 6 .023  10 23
1 Coulomb   6 .28  1018 electrons,
With zinc Zn Iron objects ZnSO 4 96500
With tin Sn Iron objects SnSO or 1 electronic charge  1.6  10 19 Coulomb.
4
(2) Faraday's second law : It states that,
Thickness of coated layer : Let the dimensions of metal sheet to be
“When the same quantity of electricity is passed through different
coated be (a cm  b cm). electrolytes, the masses of different ions liberated at the electrodes are
Thickness of coated layer  c cm directly proportional to their chemical equivalents (Equivalent weights).” i.e.,
W1 E Z It E Z1 E
Volume of coated layer  (a  b  c) cm 3  1 or 1  1 or  1 ( W  ZIt)
W2 E2 Z 2 It E2 Z 2 E2
Mass of the deposited substance  Volume  density
Thus the electrochemical equivalent (Z) of an element is directly
 (a  b  c)  dg proportional to its equivalent weight (E), i.e.,
It E E  Z or E  FZ or E  96500  Z
 (a  b  c)  d 
96500
where, F  Faraday constant  96500 C mol 1
Using above relation we may calculate the thickness of coated layer.
So, 1 Faraday = 1F =Electrical charge carried out by one mole of
electrons.
1F = Charge on an electron × Avogadro's number.
 Electrochemistry 493

1F = e   N  (1.602  10 19 c)  (6.023  10 23 mol 1 ).
Number of electrons passed
Number of Faraday 
6.023  10 23
(3) Faraday's law for gaseous electrolytic product For
the gases, we use
It Ve
V
96500
where, V  Volume of gas evolved at S.T.P. at an electrode
Ve  Equivalent volume = Volume of gas evolved at an electrode at
S.T.P. by 1 Faraday charge
(4) Quantitative aspects of electrolysis : We know that,
one Faraday (1F) of electricity is equal to the charge carried by one mole
(6.023  10 23 ) of electrons. So, in any reaction, if one mole of electrons
are involved, then that reaction would consume or produce 1F of electricity.
Since 1F is equal to 96,500 Coulombs, hence 96,500 Coulombs of electricity
would cause a reaction involving one mole of electrons.
If in any reaction, n moles of electrons are involved, then the total
electricity (Q) involved in the reaction is given by,
Q  nF  n  96,500 C
Thus, the amount of electricity involved in any reaction is related to,
(i) The number of moles of electrons involved in the reaction,
(ii) The amount of any substance involved in the reaction.
Therefore, 1 Faraday or 96,500 C or 1 mole of electrons will reduce,
(a) 1 mole of monovalent cation,(b) 1/2mole of divalent cation,
(c) 1/3 mole of trivalent cation, (d) 1/n mole of n valent cations.
Metallic and Electrolytic conductors
All substances do not conduct electrical current. The substances,
which allow the passage of electric current, are called conductors. The best
metal conductors are such as copper, silver, tin, etc. On the other hand, the
substances, which do not allow the passage of electric current through
them, are called non-conductors or insulators. Some common examples of
insulators are rubber, wood, wax, etc.
The conductors are broadly classified into two types,
Metallic and electrolytic conductors.
Metallic conduction Electrolytic conduction
(i) It is due to the flow of electrons. (i) It is due to the flow of ions.
(ii) It is not accompanied by decomposition (ii) It is accompanied
of the substance.(Only physical changes decomposition of the substance.
occurs) (Physical as well as chemical change
occur)
(iii) It does not involve transfer of (iii) It involves transfer of matter in
matter. the form of ions.
(iv) Conductivity decreases with increase (iv) Conductivity increases with
in temperature. increases in temperature and degree of
hydration due to decreases in viscosity
of medium.
The electrolyte may, therefore, be defined as the substance whose
aqueous solution or fused state conduct electricity accompanied by chemical
decomposition. The conduction of current through electrolyte is due to the
movement of ions.
On the contrary, substances, which in the form of their solutions or
in their molten state do not conduct electricity, are called non-electrolytes.
Electrolytic conduction
When a voltage is applied to the electrodes dipped into an
electrolytic solution, ions of the electrolyte move and, therefore, electric
current flows through the electrolytic solution. The power of the electrolytes
to conduct electric current is termed conductance or conductivity.
(1) Ohm's law : This law states that the current flowing through a
conductor is directly proportional to the potential difference across it, i.e.,
IV
where I is the current strength (In Amperes) and V is the potential
difference applied across the conductor (In Volts)
V
or I  or V  IR
R
where R is the constant of proportionality and is known as
resistance of the conductor. It is expressed in Ohm's and is represented as
. The above equation is known as Ohm's law. Ohm's law may also be
stated as,
“the strength of current flowing through a conductor is directly
proportional to the potential difference applied across the conductor and
inversely proportional to the resistance of the conductor.”
(2) Resistance : It measures the obstruction to the flow of current .
The resistance of any conductor is directly proportional to the length (l)
and inversely proportional to the area of cross-section (a) so that
l l
R or R  ρ
a a
where  (rho) is the constant of proportionality and is called
specific resistance or resistivity. The resistance depends upon the nature of
the material.
Units : The unit of resistance is ohm (). In terms of SI, base unit
is equal to (kgm 2 ) / (s 3 A 2 ).
(3) Resistivity or specific resistance : We know that resistance R is
l
R ; Now, if l  1 cm, a  1 cm 2 then R  
a
Thus, resistivity is defined as the resistance of a conductor of 1 cm
length and having area of cross-section equal to 1 cm 2 .
a cm 2
Units : The units of resistivity are   R.  Ohm
l cm
 Ohm. cm
Its SI units are Ohm metre ( m ). But quite often Ohm centimetre
( cm) is also used.
(4) Conductance : It is a measure of the ease with which current
flows through a conductor. It is an additive property. It is expressed as G.
by It is reciprocal of the resistance, i.e.,
1
G
R
Units : The units of conductance are reciprocal Ohm (ohm 1 ) or
mho. Ohm is also abbreviated as  so that Ohm 1 may be written as
 1 .
According to SI system, the units of electrical conductance is
Siemens, S (i.e., 1S  1  1 ).
(5) Conductivity : The inverse of resistivity is called conductivity (or
specific conductance). It is represented by the symbol,  (Greek kappa).
The IUPAC has recommended the use of term conductivity over specific
conductance. It may be defined as, the conductance of a solution of 1 cm
length and having 1 sq. cm as the area of cross-section. In other words,
conductivity is the conductance of one centimetre cube of a solution of an
electrolyte.
1
Thus,  

Units : The units of conductivity are
 494 Electrochemistry
1 (8) Experimental measurement of conductance
  Ohm 1 cm or  1 cm 1
–1

(i) The conductance of a solution is reciprocal of the resistance,

Ohm. cm
therefore, the experimental determination of the conductance of a solution
In SI units, l is expressed in m area of cross-section in m 2 so that involves the measurement of its resistance.
the units of conductivity are S m 1 . (ii) Calculation of conductivity : We have seen that conductivity ()
(6) Molar conductivity or molar conductance : Molar conductivity is is reciprocal of resistivity ( ) , i.e.,
defined as the conducting power of all the ions produced by dissolving one
1 a
mole of an electrolyte in solution.   and   R
 l
It is denoted by  (lambda). Molar conductance is related to
specific conductance (  ) as, 1l l
     or   G 
 R a a

M where G is the conductance of the cell, l is the distance of
where, M is the molar concentration. separation of two electrodes having cross section area a cm 2 .

If M is in the units of molarity i.e., moles per litre (mol L1 ), the l
The quantity   is called cell constant and is expressed in
 may be expressed as, a
  1000 cm 1 . Knowing the value of cell constant and conductance of the solution,
 the specific conductance can be calculated as,
M
For the solution containing 1 gm mole of electrolyte placed between   G  Cell constant
two parallel electrodes of 1 sq. cm area of cross-section and one cm apart, i.e., Conductivity  Conductance  Cell constant
Conductance(G)  Conductivity  Molar conductivity()
Factors affecting the electrolytic conductance
But if solution contains 1 gm mole of the electrolyte therefore, the
measured conductance will be the molar conductivity. Thus, In general, conductance of an electrolyte depends upon the following
factors,
Molar conductivity()  100  Conductivity
(1) Nature of electrolyte : The conductance of an electrolyte depends
In other words, ()    V upon the number of ions present in the solution. Therefore, the greater the
number of ions in the solution the greater is the conductance. The number
where V is the volume of the solution in cm 3 containing one gram
of ions produced by an electrolyte depends upon its nature. The strong
mole of the electrolyte.
electrolytes dissociate almost completely into ions in solutions and,
If M is the concentration of the solution in mole per litre, then therefore, their solutions have high conductance. On the other hand, weak
M mole of electrolyte is present in 1000 cm 3 electrolytes, dissociate to only small extents and give lesser number of ions.
Therefore, the solutions of weak electrolytes have low conductance.
1000
1 mole of electrolyte is present in  cm 3 of solution (2) Concentration of the solution : The molar conductance of
M electrolytic solution varies with the concentration of the electrolyte. In
Thus,     Volume in cm 3 containing 1 mole of electrolyte. general, the molar conductance of an electrolyte increases with decrease in
concentration or increase in dilution.
  1000
or   The molar conductance of strong electrolyte ( HCl, KCl , KNO 3 ) as
M
Units of Molar Conductance : The units of molar conductance can well as weak electrolytes ( CH 3 COOH , NH 4 OH ) increase with decrease
be derived from the formula , in concentration or increase in dilution. The variation is however different
for strong and weak electrolytes.
  1000
 The variation of molar conductance with concentration can be
M
explained on the basis of conducting ability of ions for weak and strong
The units of  are S cm 1 and units of  are, electrolytes.
3
cm For weak electrolytes the variation of  with dilution can be
Λ  S cm 1   S cm 2 mol 1  S cm 2mol 1
mol explained on the bases of number of ions in solution. The number of ions
According to SI system, molar conductance is expressed as furnished by an electrolyte in solution depends upon the degree of
S m mol 1 , if concentration is expressed as mol m 3 .
2 dissociation with dilution. With the increase in dilution, the degree of
(7) Equivalent conductivity : It is defined as the conducting power of dissociation increases and as a result molar conductance increases. The
all the ions produced by dissolving one gram equivalent of an electrolyte in limiting value of molar conductance (0 ) corresponds to degree of
solution. dissociation equal to 1 i.e., the whole of the electrolyte dissociates.
It is expressed as  e and is related to specific conductance as
Thus, the degree of dissociation can be calculated at any
  1000 1000 concentration as,
e    (M is Molarity of the solution)
C M

c
where C is the concentration in gram equivalent per litre (or 
Normality). This term has earlier been quite frequently used. Now it is 0
replaced by molar conductance. The units of equivalent conductance are where  is the degree of dissociation,
Ohm 1 cm 2 (gm equiv)1 .
c is the molar conductance at concentration C and

0 is the molar conductance at infinite dilution.
For strong electrolytes, there is no increase in the number of ions
with dilution because strong electrolytes are completely ionised in solution
at all concentrations (By definition). However, in concentrated solutions of
strong electrolytes there are strong forces of attraction between the ions of
opposite charges called inter-ionic forces. Due to these inter-ionic forces the
conducting ability of the ions is less in concentrated solutions. With
dilution, the ions become far apart from one another and inter-ionic forces
decrease. As a result, molar conductivity increases with dilution. When the
concentration of the solution becomes very-very low, the inter-ionic
attractions become negligible and the molar conductance approaches the
limiting value called molar conductance at infinite dilution. This value is
characteristic of each electrolyte.
(3) Temperature : The conductivity of an electrolyte depends upon
the temperature. With increase in temperature, the conductivity of an
electrolyte increases.
Migration of ions
Electricity is carried out through the solution of an electrolyte by
migration of ions. Therefore,
(1) Ions move toward oppositely charged electrodes at different
speeds.
(2) During electrolysis, ions are discharged or liberated in equivalent
amounts at the two electrodes, no matter what their relative speed is.
(3) Concentration of the electrolyte changes around the electrode
due to difference in the speed of the ions.
(4) Loss of concentration around any electrode is proportional to
the speed of the ion that moves away from the electrode, so
Loss around anode Speed of cation

Loss around cathode Speed of anion
The relation is valid only when the discharged ions do not react with
atoms of the electrodes. But when the ions combine with the material of the
electrode, the concentration around the electrode shows an increase.
Transport number or Transference number
(1) Definition : “The fraction of the total current carried by an ion is
known as transport number, transference number or Hittorf number may
be denoted by sets symbols like t and t or t and t or n and n ”.
+ – c a c a
From this definition,
Current carried by an anion
ta 
Total current passed through the solution
tc 
Current carried by a cation
Total current passed through the solution
evidently, ta  tc  1.
(2) Determination of transport number : Transport number can be
determined by Hittorf's method, moving boundary method, emf method and
from ionic mobility.
(3) Factors affecting transport number
A rise in temperature tends to bring the transport number of
cation and anion more closer to 0.5
(4) Transport number and Ionic mobility : Ionic mobility or Ionic
conductance is the conductivity of a solution containing 1 g ion, at infinite
dilution, when two sufficiently large electrodes are placed 1 cm apart.
Ionic mobilities(a or c )  speeds of ions (uaor uc )
Unit of ionic mobility is Ohm cm or V S cm
–1 2 –1 -1 2
Ionic mobility and transport number are related as,
a orc  ta or tc  
Electrochemistry 495
Absolute ionic mobility is the mobility with which the ion moves
under unit potential gradient. It's unit is cm sec 1 .
Ionic mobility
Absoluteionic mobility 
96,500
Kohlrausch's law
(1) Kohlrausch law states that, “At time infinite dilution, the molar
conductivity of an electrolyte can be expressed as the sum of the
contributions from its individual ions” i.e., m         , where,
  and   are the number of cations and anions per formula unit of
electrolyte respectively and,  and  are the molar conductivities of the
cation and anion at infinite dilution respectively. The use of above equation
in expressing the molar conductivity of an electrolyte is illustrated as,
The molar conductivity of HCl at infinite dilution can be expressed
as,
HCl   H  H    Cl  Cl  ; For HCl,  H   1 and  Cl   1.
So, HCl  (1  H  )  (1  Cl  ) ; Hence, HCl  H   Cl 
(2) Applications of Kohlrausch's law : Some typical applications of the
Kohlrausch's law are described below,
(i) Determination of m for weak electrolytes : The molar
conductivity of a weak electrolyte at infinite dilution (m ) cannot be
determined by extrapolation method. However, m values for weak
electrolytes can be determined by using the Kohlrausch's equation.
CH 3 COOH  CH 3 COONa  HCl  NaCl
(ii) Determination of the degree of ionisation of a weak electrolyte :
The Kohlrausch's law can be used for determining the degree of ionisation
of a weak electrolyte at any concentration. If  cm is the molar conductivity
of a weak electrolyte at any concentration C and,  m is the molar
conductivity of a electrolyte at infinite dilution. Then, the degree of
cm cm
ionisation is given by,  c  
m (      )
 
Thus, knowing the value of cm , and m (From the Kohlrausch's
equation), the degree of ionisation at any concentration ( c ) can be
determined.
(iii) Determination of the ionisation constant of a weak electrolyte :
Weak electrolytes in aqueous solutions ionise to a very small extent. The
extent of ionisation is described in terms of the degree of ionisation ( ). In
solution, the ions are in dynamic equilibrium with the unionised molecules.
Such an equilibrium can be described by a constant called ionisation
constant. For example, for a weak electrolyte AB, the ionisation equilibrium
is, AB ⇌ A   B  ; If C is the initial concentration of the electrolyte AB
in solution, then the equilibrium concentrations of various species in the
solution are, [ AB]  C(1   ), [ A  ]  C and [B  ]  C
Then, the ionisation constant of AB is given by,
[ A  ][B  ] C  .C  C 2
K  
[ AB] C(1   ) (1   )
 496 Electrochemistry
We know, that at any concentration C, the degree of ionisation ( ) (vii) Like electrolytic cell, in electrochemical cell, from outside the
electrolytes electrons flow from anode to cathode and current flow from
is given by,   cm / m cathode to anode.
(viii) For electrochemical cell, Ecell  ve , G  ve .
C(cm / m )2 C(cm ) 2
Then, K  ; Thus, knowing (ix) In a electrochemical cell, cell reaction is exothermic.
[1  (cm / m )] m (m  cm ) (2) Salt bridge and its significance
m and cm at any concentration, the ionisation constant ( K) of the (i) Salt bridge is U – shaped glass tube filled with a gelly like
substance, agar – agar (plant gel) mixed with an electrolyte like KCl, KNO , 3

electrolyte can be determined. NH NO etc.

4 3

(iv) Determination of the solubility of a sparingly soluble salt : The
solubility of a sparingly soluble salt in a solvent is quite low. Even a
saturated solution of such a salt is so dilute that it can be assumed to be at
infinite dilution. Then, the molar conductivity of a sparingly soluble salt at
infinite dilution (m ) can be obtained from the relationship,
m      
The conductivity of the saturated solution of the sparingly soluble
salt is measured. From this, the conductivity of the salt ( salt ) can be
obtained by using the relationship,  salt   sol   wate r , where,  water is
the conductivity of the water used in the preparation of the saturated
solution of the salt.
1000  salt
salt 
Cm
From equation (i) and (ii) ;
1000  salt
Cm  , Cm is the molar concentration of the
(       )
sparingly soluble salt in its saturated solution. Thus, Cm is equal to the
solubility of the sparingly soluble salt in the mole per litre units. The
solubility of the salt in gram per litre units can be obtained by multiplying
Cm with the molar mass of the salt.
Electrochemical or Galvanic cell
“Electrochemical cell or Galvanic cell is a device in which a
spontaneous redox reaction is used to convert chemical energy into
electrical energy i.e. electricity can be obtained with the help of oxidation
and reduction reaction”.
(1) Characteristics of electrochemical cell : Following are the
important characteristics of electrochemical cell,
–
e e–
Voltmeter Salt bridge
Zn anode
Porous plug
ZnSO4 CuSO4
Fig. 12.1
(i) Electrochemical cell consists of two vessels, two electrodes, two
electrolytic solutions and a salt bridge.
(ii) The two electrodes taken are made of different materials and
usually set up in two separate vessels.
(iii) The electrolytes are taken in the two different vessels called as
half - cells.
(iv) The two vessels are connected by a salt bridge/porous pot.
(v) The electrode on which oxidation takes place is called the anode
(or – ve pole) and the electrode on which reduction takes place is called the
cathode (or + ve pole).
(vi) In electrochemical cell, ions are discharged only on the cathode.
(ii) The electrolytes of the two half-cells should be inert and should
not react chemically with each other.
(iii) The cation as well as anion of the electrolyte should have same
ionic mobility and almost same transport number, viz.
KCl , KNO 3 , NH 4 NO 3 etc.
(iv) The following are the functions of the salt bridge,
........(i) (a) It connects the solutions of two half - cells and completes the
cell circuit.
(b) It prevent transference or diffusion of the solutions from one
half cell to the other.
(c) It keeps the solution of two half - cells electrically neutral.
(d) It prevents liquid – liquid junction potential i.e. the potential
difference which arises between two solutions when they contact with each
other.
(3) Representation of an electrochemical cell
The cell may be written by arranging each of the pair left – right,
........(ii)
anode – cathode, oxidation – reduction, negative and positive in the
alphabetical order as,
Left Bridge Right
Anode Cathode
Reductio
Oxidation
n
Negative Positive
(4) Reversible and irreversible cells : A cell is said to be reversible if the
following two conditions are fulfilled
(i) The chemical reaction of the cell stops when an exactly equal
external emf is applied.
(ii) The chemical reaction of the cell is reversed and the current
flows in opposite direction when the external emf is slightly higher than
that of the cell. Any other cell, which does not obey the above two
conditions, is termed as irreversible. Daniell cell is reversible but
Zn| H 2 SO 4 | Ag cell is irreversible in nature
(5) Types of electrochemical cells : Two main types of
electrochemical cells have been reported, these are,
(i) Chemical cells : The cells in which electrical energy is produced
Cu cathode from the energy change accompanying a chemical reaction or a physical
process are known as chemical cells. Chemical cells are of two types,
(a) Chemical cells without transference : In this type of chemical
cells, the liquid junction potential is neglected or the transference number is
not taken into consideration. In these cells, one electrode is reversible to
cations while the other is reversible to the anions of the electrolyte.
(b) Chemical cells with transference : In this type of chemical cells,
the liquid-liquid junction potential or diffusion potential is developed across
the boundary between the two solutions. This potential develops due to the
difference in mobilities of  ve and  ve ions of the electrolytes.
(6) Concentration cells : “A cell in which electrical energy is
produced by the transference of a substance from a system of high
concentration to one at low concentration is known as concentration cells”.
Concentration cells are of two types.
(i) Electrode concentration cells : In these cells, the potential
difference is developed between two electrodes at different concentrations
dipped in the same solution of the electrolyte. For example, two hydrogen
electrodes at different gaseous pressures in the same solution of hydrogen
ions constitute a cell of this type.
 Electrochemistry 497

Pt, H 2 (pressure p1 )
| H |
H 2 (pressure p 2 ) Pt
;
Some Commercial cell (Batteries)
Anode Cathode One of the main use of galvanic cells is the generation of portable
0 .0591 (p ) electrical energy. These cells are also popularly known as batteries. The term
Ecell  log 1 at 25 o C If p1  p 2 , oxidation occurs at L. H. battery is generally used for two or more Galvanic cells connected in series.
2 (p2 )
Thus, a battery is an arrangement of electrochemical cells used as an energy
S. electrode and reduction occurs at R. H. S. electrode.
source. The basis of an electrochemical cell is an oxidation – reduction
In the amalgam cells, two amalgams of the same metal at two
reaction.
different concentrations are immersed in the same electrolytic solution.
Types of commercial cells : There are mainly two types of
M (Hg C1 ) | M n | Zn(Hg C 2 )
commercial cells,
The emf of the cell is given by the expression,
(1) Primary cells : In these cells, the electrode reactions cannot be
0 .0591 C
Ecell  log 1 at 25 o C reversed by an external electric energy source. In these cells, reactions occur
n C2 only once and after use they become dead. Therefore, they are not
(ii) Electrolyte concentration cells : In these cells, electrodes are chargeable. Some common example are, dry cell, mercury cell, Daniell cell
identical but these are immersed in solutions of the same electrolyte of and alkaline dry cell – +
Cu rod Zn rod
different concentrations. The source of electrical energy in the cell is the (i) Voltaic cell
tendency of the electrolyte to diffuse from a solution of higher
concentration to that of lower concentration. With the expiry of time, the
Dil. H2SO4
two concentrations tend to become equal. Thus, at the start the emf of the
cell is maximum and it gradually falls to zero. Such a cell is represented in
Local action
the following manner ( C 2 is greater then C 1 ). Cu
Polarisation
M | M n (C1 )| | M n  (C2 )| M Zn
Fig. 12.2
Zn | Zn 2  (C1 ) Zn 2  (C2 )| Zn Cathode : Cu rod Anode : Zn rod
or ||
Anode Cathode Electrolyte : dil. H 2 SO 4 Emf : 1.08 V
The emf of the cell is given by the following expression,
At cathode : Cu 2   2e   Cu
Ecell 
0 .0591 C
log 2(R. H .S ) e at 25 C
o At Anode : Zn  Zn 2   2e 
n C1( L. H .S .)
Over all reaction : Zn  Cu 2   Zn 2   Cu
Electrons flow
The concentration cells are used to determine the solubility of (ii) Daniel ecell
– e–
sparingly soluble salts, valency of the cation of the electrolyte and transition – Key +
Ammeter Current
point of the two allotropic forms of metal used as electrodes, etc.
Anode (Zn) Salt bridge Cathode (Cu)
(7) Heat of reaction in an electrochemical cell : Let n Faraday
charge flows out of a cell of emf E, then
G  nFE …….(i) Cotton Plugs

Gibbs – Helmholtz equation from thermodynamics may be given as

Zn2+ Cu2+
 G 
G  H  T   …….(ii)
 T  P 1M ZnSO (aq)
4
Fig. 12.3 1M CuSO4 (aq)
From equation (i) and (ii) we get, Cathode : Cu rod Anode : Zn rod (Depolariser)

Electrolyte : dil. H 2 SO 4 Emf : 1.1 V

 (nFE)   E 
 nFE  H  T    H  nFT T  At cathode : Cu 2   2e   Cu
 T P  P
At Anode : Zn  Zn 2   2e 
 E 
H  nFE  nFT  Over all reaction : Zn  Cu 2   Zn 2   Cu
 T  P (iii) Lechlanche cell (Dry cell)
+ Seal
 E  Graphite (cathode)
where   = Temperature coefficient of cell
 T  P MnO +C (Depolariser)
2

 E  Paste of NH Cl+ZnCl
Case I: When   = 0, then H  nFE
4 2

 T  P –
 E  Zinc anode
Case II: When   > 0, then nFE  H , i.e. process inside the Fig. 12.4
 T  Cathode : Graphite rod Anode : Zn pot
cell is endothermic. Electrolyte : Paste of NH 4 Cl  ZnCl2 in starch
Emf : 1.2 V to 1.5 V
 E 
Case III: When   < 0, then nFE  H , i.e., process inside the At cathode : NH 4  MnO2  2e   MnO(OH )  NH 3
 T 
cell is exothermic. At Anode : Zn  Zn 2   2e 
Over all reaction :
 498 Electrochemistry

Zn  NH 4  MnO2  Zn 2   MnO(OH )  NH 3 At cathode : HgO(s)  H 2 O(l)  2e   Hg(l)  2OH (aq)

(iv) Mercury cell
At Anode : Zn (s)  20 H (aq )  ZnO(s)  H 2 O(l)  2e 
(amalgam)

Over all reaction : Zn(s)  HgO(s)  ZnO(s)  Hg(l)

(2) Secondary cells : In the secondary cells, the reactions can be
reversed by an external electrical energy source. Therefore, these cells can
be recharged by passing electric current and used again and again. These
Cathode : Mercury (II) oxide Anode : Zn rod are also celled storage cells. Examples of secondary cells are, lead storage
battery and nickel – cadmium storage cell.
Electrolyte : Paste of KOH  ZnO Emf : 1.35 V

In charged Lead storage cell Alkali cell Ni(OH) 2

+ – + –
Glass vessel
Fe(OH)2

PbO 2
Perforated steel
grid
Pb
KOH 20%
dil. H SO2 4 + Li(OH), 1%
Positive electrode Perforated lead plates coated with PbO 2
Perforated steel plate coated with Ni(OH) 4

Negative electrode Perforated lead plates coated with pure lead Perforated steel plate coated with Fe
Electrolyte dil. H SO
2 4
20% solution of KOH + 1% LiOH
During charging Chemical reaction Chemical reaction
At anode : PbSO + 2H + 2e  Pb + H SO
4
+ –

2 4
At anode : Ni (OH) + 2OH – 2e  Ni(OH)
2
+ –

At cathode : PbSO + SO + 2H O – 2e  PbO

4
––

4 2
–

2
At cathode : Fe(OH) + 2K + 2e  Fe + 2KOH
2
+ –

+ 2H SO 2 4
Emf of cell : When cell is fully charged then E = 1.36
Specific gravity of H SO increases and when specific gravity
2 4
volt
becomes 1.25 the cell is fully charged.
Emf of cell: When cell is fully charged then E = 2.2 volt
During discharging Chemical reaction Chemical reaction
At anode : Pb + SO – 2e  PbSO
––

4
–

4
At anode : Fe + 2OH – 2e  Fe(OH)
– –

At cathode : PbO + 2H + 2e + H SO  PbSO +

2
+ –

2 4 4
At cathode : Ni(OH) + 2K + 2e  Ni(OH) +
4
+ –

2H O 2
2KOH
Specific gravity of H SO decreases and when specific gravity falls
2 4
Emf of cell : When emf of cell falls below 1.1 V it requires
below 1.18 the cell requires recharging. charging.
Emf of cell : When emf of cell falls below 1.9 volt the cell
requires recharging.
Efficiency 80% 60%

Fuel cells directly into electricity EMF of fuel cell is 1.23 V. This cell has been used for
electric power in the Apollo space programme. The important advantages of
These are Voltaic cells in which the reactants are continuously H2 O
fuel cells are
supplied to the electrodes. These are designed to convert the energy from Anode – + Cathode
the combustion of fuels such as H 2 , CO, CH 4 , etc. directly into electrical
energy. The common example is hydrogen-oxygen fuel cell as described Porous carbon electrode
below,
In this cell, hydrogen and oxygen are bubbled through a porous
carbon electrode into concentrated aqueous sodium hydroxide or potassium
hydroxide. Hydrogen (the fuel) is fed into the anode compartment where it
is oxidised. The oxygen is fed into cathode compartment where it is
reduced. The diffusion rates of the gases into the cell are carefully regulated OH–
to get maximum efficiency. The net reaction is the same as burning of H2 O2
hydrogen and oxygen to form water. The reactions are Electrolyte

At anode : 2[H 2 (g)  2OH  ](aq)  2 H 2O(l)  2e  (1) High efficiency : TheFig.fuel
12.6
cells convert the energy of a fuel
directly into electricity and therefore, they are more efficient than the
At cathode : O2 (g)  2 H 2O(l)  4 e   4 OH  (aq)
conventional methods of generating electricity on a large scale by burning
Overall reaction : 2 H 2 (g)  O2 (g)  2 H 2O(l) hydrogen, carbon fuels. Though we expect 100 % efficiency in fuel cells, so
Each electrode is made of porous compressed carbon containing a far 60 – 70% efficiency has been attained. The conventional methods of
production of electrical energy involve combustion of a fuel to liberate heat
small amount of catalyst (Pt, Ag or CoO ) . This cell runs continuously as
long as the reactants are fed. Fuel cells convert the energy of the fuel

which is then used to produce electricity. The efficiency of these methods is
only about 40%.
(2) Continuous source of energy : There is no electrode material to
be replaced as in ordinary battery. The fuel can be fed continuously to
produce power. For this reason, H 2  O 2 fuel cells have been used in space
crafts.
(3) Pollution free working : There are no objectionable byproducts
and, therefore, they do not cause pollution problems. Since fuel cells are
efficient and free from pollution, attempts are being made to get better
commercially practical fuel cells.
Electrode Potential
(1) When a metal (M) is placed in a solution of its ions (M ), either
of the following three possibilities can occurs, according to the electrode
potential solution pressure theory of Nernst.
(i) A metal ion M collides with the electrode, and undergoes no
n+
Electrochemistry 499
(3) Types of electrode potential : Depending on the nature of the
metal electrode to lose or gain electrons, the electrode potential may be of
two types,
(i) Oxidation potential : When electrode is negatively charged with
respect to solution, i.e., it acts as anode. Oxidation occurs.
M  M n   ne 
(ii) Reduction potential : When electrode is positively charged with
respect to solution, i.e. it acts as cathode. Reduction occurs.
M n   ne   M
(4) Standard electrode potential : “If in the half cell, the metal rod
(M) is suspended in a solution of one molar concentration, and the
++ temperature is kept at 298 K, the electrode potential is called standard
electrode potential, represented usually by E o ”. ‘or’
The standard electrode potential of a metal may be defined as “the

potential difference in volts developed in a cell consisting of two electrodes,

change. the pure metal in contact with a molar solution of one of its ions and the
(ii) A metal ion M collides with the electrode, gains n electrons and
n+
normal hydrogen electrode (NHE)”.
gets converted into a metal atom M, (i.e. the metal ion is reduced).
Standard oxidation potential for any half - cell  – (Standard reduction potential)
M n  (aq)  ne   M (s) Standard reduction potential for any half - cell  – (Standard reduction potential)

(iii) A metal atom on the electrode M may lose an electrons to the (5) Reference electrode or reference half - cells
n It is not possible to measure the absolute value of the single
electrode, and enter to the solution as M , (i.e. the metal atom is
electrode potential directly. Only the difference in potential between two
oxidised). M (s)  M n  (aq)  ne  .
electrodes can be measured experimentally. It is, therefore, necessary to
Thus, “the electrode potential is the tendency of an electrode to lose couple the electrode with another electrode whose potential is known. This
or gain electrons when it is in contact with solution of its own ions.” electrode is termed as reference electrode or reference half - cells. Various
(2) The magnitude of electrode potential depends on the following types of half – cells have been used to make complete cell with spontaneous
factors, reaction in forward direction. These half – cells have been summarised in
(i) Nature of the electrode, (ii) Concentration of the ions in solution, following table,
(iii) Temperature.
Table : 12.2 Various Types of Half – cells
Type Example Half – cell reaction Q= Reversible to Electrode Potential (oxidn), E
=
Gas ion half - cell Pt(H 2 ) | H  (aq) 1 [H  ] H 
E 0  0.0591 log[ H  ]
H 2 (g)  H  (aq)  e 
2
Pt(Cl 2 ) | Cl  (aq) 1 Cl  E 0  0.0591 log[Cl  ]
1
Cl  (aq)  Cl 2 (g)  e  [Cl  ]
2
Metal – metal ion Ag | Ag  (aq) Ag(s)  Ag  (aq)  e  [ Ag  ] Ag  E 0  0.0591 log[ Ag  ]
half – cell
Metal insoluble salt anion Ag, AgCl | Cl  (aq) Ag(s)  Cl  (aq)  AgCl (s)  e  1 Cl  E 0  0.0591 log[Cl  ]
half – cell [Cl  ]
Calomel electrode Hg, Hg 2 Cl 2 | Cl  (aq) 2 Hg(l)  2Cl  (aq)  1 Cl  E 0  0.0591 log[Cl  ]
[Cl  ]2
Hg 2 Cl 2 (s)  2e 
Metal – metal oxide Hg, HgO | OH  (aq) Hg(l)  2OH  (aq)  1 OH  E 0  0.0591 log[OH  ]
hydroxide half - cell [OH  ]2
HgO(s)  H 2 O(l)  2e 
Oxidation – reduction Pt | Fe 2  , Fe 3  Fe 2  (aq)  Fe 3  (aq)  e  [Fe 3  ] Fe 2  , Fe 3  [Fe 3  ]
half – dell (aq) (aq) E 0  0 .0591 log
[Fe 2  ] [Fe 2  ]

Cell potential or EMF of the cell (2) The emf of the cell or cell potential can be calculated from the
values of electrode potentials of two the half – cells constituting the cell.
(1) “The difference in potentials of the two half – cells of a cell known as
The following three methods are in use :
electromotive force (emf) of the cell or cell potential.”
(i) When oxidation potential of anode and reduction potential of
The difference in potentials of the two half – cells of a cell arises
cathode are taken into account
due to the flow of electrons from anode to cathode and flow of current
from cathode to anode. 0
E cell  Oxidation potential of anode + Reduction potential of
Flow of electrons cathode  Eox
0
(anode )  E red
0
(cathode)
Anode Cathode
Flow of current
 500 Electrochemistry
(ii) When reduction potentials of both electrodes are taken into [M (s)] = the concentration of the deposited metal,
account
[M n (aq)] = the molar concentration of the metal ion in the
0
Ecell  Reduction potential of cathode – Reduction potential of anode
solution,
 E Cathode
0
 E Anode
0
 Eright
o
 Eleft
o The concentration of pure metal M(s) is taken as unity. So, the

(iii) When oxidation potentials of both electrodes are taken into Nernst equation for the M n  / M electrode is written as,
account
2 .303 RT 1
EM n  / M  EM
0
n  log n 
o
Ecell  Oxidation potential of anode – Oxidation potential of /M nF [M (aq)]

cathode  Eox
0
(anode )  Eox
0
(cathode) At 298 K, the Nernst equation for the M n  / M electrode can be
written as,
(3) Difference between emf and potential difference
0.0591 1
Emf Potential difference EM n  / M  EM
0
n
/M
 log n 
n [M (aq)]
It is the potential difference It is the difference of the electrode
between two electrodes when no potentials of the two electrodes For an electrode (half - cell) corresponding to the electrode reaction,
current is flowing in the circuit. when the cell is under operation.
Oxidised form  ne   Reduced form
It is the maximum voltage that the It is always less then the maximum
cell can deliver. value of voltage which the cell can The Nernst equation for the electrode is written as,
deliver.
2 .303 RT [Reduced form ]
Ehalf  cell  Ehalf
0
 cell  log
It is responsible for the steady It is not responsible for the steady nF [Oxidised form]
flow of current in the cell. flow of current in the cell.
At 298 K, the Nernst equation can be written as,
(4) Cell EMF and the spontaneity of the reaction :
We know, G  nFEcell 0 .0591 [Reduced form ]
Ehalf  cell  Ehalf
0
 cell  log
n [Oxidised form]
Nature of reaction ΔG(or ΔG o ) Ecell (or Eocell )
(2) Nernst’s equation for cell EMF
Spontaneous – + For a cell in which the net cell reaction involving n electrons is,
Equilibrium 0 0 aA  bB  cC  dD
The Nernst equation is written as,
Non – spontaneous + –
RT [C]c [D]d
Nernst's equation Ecell  Ecell
0
 ln
nF [ A]a [B]b
(1) Nernst’s equation for electrode potential 0
Where, Ecell  Ecathode
0
 Eanode
0
.
The potential of the electrode at which the reaction,
o
The E cell is called the standard cell potential.
M n  (aq)  ne   M(s)
2 .303 RT [C]c [D]d
takes place is described by the equation, or Ecell  Ecell
o
 log a b
nF [ A] [B]
RT [M (s)]
EM n  / M  EM
0
n
/M
 ln n  At 298 K, above eq. can be written as,
nF [M (aq.)]
0 .0592 [C]c [D]d
2 .303 RT [M (s)] or Ecell  Ecell
o
 log a b
or EM n  / M  0
EM n
/M
 log n  n [ A] [B]
nF [M (aq)]
It may be noted here, that the concentrations of A, B, C and D
above eq. is called the Nernst equation. referred in the eqs. are the concentrations at the time the cell emf is
measured.
Where,
(3) Nernst’s equation for Daniells cell : Daniell’s cell consists of zinc
E M n  / M = the potential of the electrode at a given concentration, and copper electrodes. The electrode reactions in Daniell’s cell are,

0 At anode : Zn(s)  Zn 2  (aq)  2e 

EM n
/M
= the standard electrode potential
At cathode : Cu 2  (aq)  2e   Cu(s)
1 1
R = the universal gas constant, 8.31 J K mol
Net cell reaction : Zn(s)  Cu 2  (aq)  Cu(s)  Zn 2  (aq)
T= the temperature on the absolute scale, Therefore, the Nernst equation for the Daniell’s cell is,
n = the number of electrons involved in the electrode reaction,
2 .303 RT [Cu (s)][Zn 2  (aq)]
F = the Faraday constant : (96500 C), Ecdll  Ecell
0
 log
2F [ Zn(s)][Cu 2  (aq)]
 Electrochemistry 501
Since, the activities of pure copper and zinc metals are taken as volt, When zinc electrode is joined with SHE, it acts as anode (–ve
unity, hence the Nernst equation for the Daniell’s cell is, electrode) i.e., oxidation occurs on this electrode. Similarly, the +ve sign of
standard reduction potential indicates that the electrode when joined with
2 .303 RT [ Zn 2  (aq] SHE acts as cathode and reduction occurs on this electrode.
Ecdll  Ecell
0
 log
2F [Cu 2  (aq)] (ii) The substances, which are stronger reducing agents than
hydrogen are placed above hydrogen in the series and have negative values
The above eq. at 298 K is, of standard reduction potentials. All those substances which have positive
values of reduction potentials and placed below hydrogen in the series are
0 .0591 [ Zn 2  (aq] weaker reducing agents than hydrogen.
Ecdll  Ecell
o
 log V
2 [Cu 2  (aq)] (iii) The substances, which are stronger oxidising agents than
H  ion are placed below hydrogen in the series.
0
For Daniells cell, Ecell  1.1 V
(iv) The metals on the top (having high negative value of standard
(4) Nernst's equation and equilibrium constant reduction potentials) have the tendency to lose electrons readily. These are
For a cell, in which the net cell reaction involving n electrons is, active metals. The activity of metals decreases from top to bottom. The non-
metals on the bottom (having high positive values of standard reduction
aA  bB  cC  dD
potentials) have the tendency to accept electrons readily. These are active
The Nernst equation is non-metals. The activity of non-metals increases from top to bottom.
RT [C]c [D]d Table : 12.3 Standard reduction electrode potentials at 298K
ECell  Ecell
0
 ln .....(i) Element Electrode Reaction (Reduction) Standard Electrode
nF [ A]a [B]b
Reduction
At equilibrium, the cell cannot perform any useful work. So at potential E0, volt
equilibrium, E Cell is zero. Also at equilibrium, the ratio Li Li++ e– = Li –3.05
K K++ e– = K –2.925
Ba Ba+++ 2e = Ba –2.90
[C]c [D]d  [C]c [D]d 
   Kc Sr Sr+++ 2e = Sr –2.89
[ A]a [B]b  [ A]a [B]b  equilibrium Ca –2.87
Ca 2   2e   Ca
Na –2.714
Increasing tendency to accept electrons Increasing strength as

Relationship between potential, Gibbs energy Na   e   Na

Increasing strength as reducing agent Increasing tendency to

Mg –2.37
and equilibrium constant Mg 2   2e   Mg
Al –1.66
The electrical work (electrical energy) is equal to the product of the Al 3   3e   Al
EMF of the cell and electrical charge that flows through the external circuit Mn Mn+++ 2e = Mn –1.18
i.e., Zn Zn2+ +2e–=Zn –0.7628
oxidising agent

Wmax  nFEcell ......(i) Cr Cr3++3 e– = Cr –0.74

lose electrons
Fe Fe2++ 2e– = Fe –0.44
According to thermodynamics the free energy change (G) is Cd Cd2++2e– = Cd –0.403
equal to the maximum work. In the cell work is done on the surroundings Co Co+++ 2e = Co –0.27
by which electrical energy flows through the external circuit, So Ni Ni2++2e– = Ni –0.25
Wmax,  G ......(ii) Sn Sn2++2e– = Sn –0.14
Pb Pb+++ 2e = Pb –0.12
from eq. (i) and (ii) G  nFEcell H2 2H++2e– = H2 0.00
Cu Cu2++ 2e– = Cu +0.337
In standard conditions G 0   nFEcell
0
I2 I2+2e– = 2I– +0.535
Hg Hg2++2e– = Hg +0.885
Where G 0  standard free energy change Ag Ag++ e– = Ag +0.799
2 .303 Br2 Br2+2e– = 2Br– +1.08
0
But E cell  RT log K c
nF Pt Pt+++ 2e = Pt +1.20
Cl2 Cl2+2e– = 2Cl– +1.36
2.303
 G 0  nF  RT log K c Au Au 3++3e– = Au +1.50
nF F2 F2+2e–= 2F– +2.87
G 0   2.303 RT log Kc or G  G  2.303 RT log Q (3) Application of Electrochemical series
G  RT ln K c
0
(2.303 log X  ln X ) (i) Reactivity of metals: The activity of the metal depends on its

Electrochemical series
(1) The standard reduction potentials of a large number of electrodes
have been measured using standard hydrogen electrode as the reference
electrode. These various electrodes can be arranged in increasing or
decreasing order of their reduction potentials. The arrangement of elements
in order of increasing reduction potential values is called electrochemical
series.It is also called activity series, of some typical electrodes.
(2) Characteristics of Electrochemical series
(i) The negative sign of standard reduction potential indicates that
an electrode when joined with SHE acts as anode and oxidation occurs on
this electrode. For example, standard reduction potential of zinc is –0.76
tendency to lose electron or electrons, i.e., tendency to form cation (M n  ) .
This tendency depends on the magnitude of standard reduction potential.
The metal which has high negative value (or smaller positive value) of
standard reduction potential readily loses the electron or electrons and is
converted into cation. Such a metal is said to be chemically active. The
chemical reactivity of metals decreases from top to bottom in the series .
The metal higher in the series is more active than the metal lower in the
series. For example,
(a) Alkali metals and alkaline earth metals having high negative
values of standard reduction potentials are chemically active. These react
with cold water and evolve hydrogen. These readily dissolve in acids forming
 502 Electrochemistry
corresponding salts and combine with those substances which accept
electrons.
(b) Metals like Fe, Pb, Sn, Ni, Co, etc., which lie a little down in the
series do not react with cold water but react with steam to evolve hydrogen.
(c) Metals like Cu, Ag and Au which lie below hydrogen are less
reactive and do not evolve hydrogen from water.
(ii) Electropositive character of metals : The electropositive character
also depends on the tendency to lose electron or electrons. Like reactivity,
the electropositive character of metals decreases from top to bottom in the
electrochemical series. On the basis of standard reduction potential values,
metals are divided into three groups
(a) Strongly electropositive metals : Metals having standard reduction
potential near about – 2.0 volt or more negative like alkali metals, alkaline earth
metals are strongly electropositive in nature.
(b) Moderately electropositive metals : Metals having values of reduction
potentials between 0.0 and about – 2.0 volt are moderately electropositive Al, Zn,
Fe, Ni, Co, etc., belong to this group.
(c) Weakly electropositive : The metals which are below hydrogen and
possess positive values of reduction potentials are weakly electropositive metals.
Cu, Hg, Ag, etc., belong to this group.
(iii) Displacement reactions
(a) To predict whether a given metal will displace another, from its
salt solution: A metal higher in the series will displace the metal from its
solution which is lower in the series, i.e., The metal having low standard
reduction potential will displace the metal from its salt's solution which has
higher value of standard reduction potential. A metal higher in the series
has greater tendency to provide electrons to the cations of the metal to be
precipitated.
(b) Displacement of one nonmetal from its salt solution by another
(iv) Reducing power of metals : Reducing nature depends on the
tendency of losing electron or electrons. More the negative reduction
potential, more is the tendency to lose electron or electrons. Thus reducing
nature decreases from top to bottom in the electrochemical series. The
power of the reducing agent increases, as the standard reduction potential
becomes more and more negative. Sodium is a stronger reducing agent than
zinc and zinc is a stronger reducing agent than iron. (decreasing order of
reducing nature)
Element : Na  Zn  Fe
Reduction potential :  2.71  0.76  0.44
Alkali and alkaline earth metals are strong reducing agents.
(v) Oxidising nature of non-metals : Oxidising nature depends on
the tendency to accept electron or electrons. More the value of reduction
potential, higher is the tendency to accept electron or electrons. Thus,
oxidising nature increases from top to bottom in the electrochemical series.
The strength of an oxidising agent increases as the value of reduction
potential becomes more and more positive.
F2 (Fluorine) is a stronger oxidant than Cl 2 , Br2 and I 2 , Cl 2
(Chlorine) is a stronger oxidant than Br2 and I 2
I2 Br2 Cl 2 F2 <-Element :
 0.53  1.06  1.36  2.85 <-Reduction potential :

Oxidisingnature increases
Thus, in electrochemical series
(Strongest reducing agent)
Top
Highest negative reduction potential

Reducing
nature
nonmetal: A non-metal higher in the series (towards bottom side), i.e., or
Oxidising
nature

having high value of reduction potential will displace another non-metal

with lower reduction potential, i.e., occupying position above in the series.
The non-metal's which possess high positive reduction potentials have the
tendency to accept electrons readily. These electrons are provided by the
ions of the nonmetal having low value of reduction potential,. Thus, Cl 2
can displace bromine and iodine from bromides and iodides.
Cl2  2 KI  2 KCl  I2
2 I   I2  2e  .....(Oxidation)
Cl2  2e   2Cl  .....(Reduction)
[The activity or electronegative character or oxidising nature of the
nonmetal increases as the value of reduction potential increases.]
(c) Displacement of hydrogen from dilute acids by metals : The
metal which can provide electrons to H  ions present in dilute acids for
reduction, evolve hydrogen from dilute acids.
Mn  Mnn  ne  .....(Oxidation)
 
2 H  2e  H 2 .....(Reduction)
The metal having negative values of reduction potential possess the
property of losing electron or electrons.
Thus, the metals occupying top positions in the electrochemical
series readily liberate hydrogen from dilute acids and on descending in the
series tendency to liberate hydrogen gas from dilute acids decreases.
The metals which are below hydrogen in electrochemical series like
Cu, Hg, Au, Pt, etc., do not evolve hydrogen from dilute acids.
(d) Displacement of hydrogen from water : Iron and the metals
above iron are capable of liberating hydrogen from water. The tendency
decreases from top to bottom in electrochemical series. Alkali and alkaline
earth metals liberate hydrogen from cold water but Mg, Zn and Fe liberate
hydrogen from hot water or steam.
(Minimum reduction potential)
(Strongest oxidising agent)
Highest positive value of reduction potential
Bottom
(vi) Thermal stability of metallic oxides : The thermal stability of the
metal oxide depends on its electropositive nature. As the electropositivity
decreases from top to bottom, the thermal stability of the oxide also
decreases from top to bottom. The oxides of metals having high positive
reduction potentials are not stable towards heat. The metals which come
below copper form unstable oxides, i.e., these are decomposed on heating.
 1
Ag2 O  2 Ag  O2
2
BaO 

2 HgO  2 Hg  O2 ; Na 2 O  

No decomposit ion

Al2 O3 
(vii) Extraction of metals : A more electropositive metal can displace
a less electropositive metal from its salt's solution. This principle is applied
for the extraction of Ag and Au by cyanide process. silver from the solution
containing sodium argento cyanide, NaAg(CN )2 , can be obtained by the
addition of zinc as it is more electro-positive than Ag.
2 NaAg(CN )2  Zn  Na2 Zn(CN )4  2 Ag
Corrosion
(1) When metals are exposed to atmospheric conditions, they react
with air or water in the environment to form undesirable compounds
(usually oxides). This process is called corrosion. Almost all metals except
the least active metals such as gold, platinum and palladium are attacked by
environment i.e., undergo corrosion. For example, silver tarnishes, copper

develops a green coating, lead or stainless steel lose their lusture due to
corrosion. Corrosion causes enormous damage to building, bridges, ships
and many other articles made of iron.
Thus corrosion is a process of deterioration of a metal as a result of
its reaction with air or water (environment) surrounding it.
In case of iron, corrosion is called rusting. Chemically, rust is
hydrated form of ferric oxide, Fe 2 O 3 . xH 2 O . Rusting of iron is
generally caused by moisture, carbon dioxide and oxygen present in air. It
has been observed that rusting takes place only when iron is in contact with
moist air. Iron does not rust in dry air and in vacuum.
(2) Factors which affect corrosion : The main factors which affect
corrosion are
More the reactivity of metal, the more will be the possibility of the
metal getting corroded.
The impurities help in setting up voltaic cells, which increase the
speed of corrosion
Presence of electrolytes in water also increases the rate of corrosion
Presence of CO 2 in natural water increase rusting of iron.
(v) When the iron surface is coated with layers of metals more
active than iron, then the rate of corrosion is retarded.
A rise in temperature (with in a reasonable limit) increases the rate
of corrosion.
(3) Classification of corrosion process : Depending upon the nature
of corrosion, and the factors affecting it, the corrosion may be classified as
follows.
(i) Chemical corrosion : Such corrosion, generally takes place when
(a) Reactive gases come in contact with metals at high temperatures
e.g., corrosion in chemical industry.
(b) Slow dissolution of metal takes place when kept in contact with
non conducting media containing organic acids.
(ii) Bio-chemical corrosion or Bio-corrosion: This is caused by the
action of microorganisms. Soils of definite composition, stagnant water and
certain organic products greatly favour the bio-corrosion.
(iii) Electrochemical corrosion : It occurs in a gaseous atmosphere in
the presence of moisture, in soils and in solutions.
(4) Mechanism of rusting of iron : Electrochemical theory of rusting.
The overall rusting involves the following steps,
(i) Oxidation occurs at the anodes of each electrochemical cell.
Therefore, at each anode neutral iron atoms are oxidised to ferrous ions.
At anode : Fe(s)  Fe2  (aq)  2e  .
Thus, the metal atoms in the lattice pass into the solution as ions,
leaving electrons on the metal itself. These electrons move towards the
cathode region through the metal.
Drop of moisture
4H +O +4e 2H O
+ –
(Cathode)
2
Rust
Fe2+
Fe anode
+ formed.
2e –
Flow of
electrons
Iron
Schematic representation of mechanism of rusting of iron
Fig. 12.7
(ii) At the cathodes of each cell, the electrons are taken up by
hydrogen ions (reduction takes place). The H  ions are obtained either
from water or from acidic substances (e.g. CO 2 ) in water
H 2 O  H   OH  or CO 2  H 2O  H   HCO3
Electrochemistry 503
At cathode : H   e   H
The hydrogen atoms on the iron surface reduce dissolved oxygen.
4 H  O2  2 H 2O
Therefore, the overall reaction at cathode of different
electrochemical cells may be written as,
4 H   O2  4 e   2 H 2O
(iii) The overall redox reaction may be written by multiplying
reaction at anode by 2 and adding reaction at cathode to equalise number
of electrons lost and gained i.e.
Oxi. half reaction : Fe(s)  Fe2  (aq)  2e  ]  2 (E  0.44 V )
Red. half reaction : 4 H   O2  4 e   2 H 2O (E  1.23V )
 2
Overall cell reaction : 2 Fe(s)  4 H  O2  2 Fe (aq)  2 H 2O
(ECell  1.67 V )
The ferrous ions are oxidised further by atmospheric oxygen to form
rust.
4 Fe2  (aq)  O2 (g)  4 H 2O  2 Fe2O3  8 H  and
Fe2O3  xH 2O  Fe2O3 . xH 2O
Rust
It may be noted that salt water accelerates corrosion. This is mainly
due to the fact that salt water increases the electrical conduction of
electrolyte solution formed on the metal surface. Therefore, rusting becomes
more serious problem where salt water is present.
(5) Corrosion protection : Corrosion of metals can be prevented in
many ways. Some commonly used methods are
(i) By surface coating
(a) By applying, oil, grease, paint or varnish on the surface.
(b) By coating/depositing a thin layer of any other metal which does
not corrode. For example, iron surface can be protected from corrosion by
depositing a thin layer of zinc, nickel or chromium on it. Copper/brass can
be protected by coating it with a thin layer of tin. Tinning of brass utensils
is a very common practice in our country.
(c) By Galvanization : Prevention of corrosion of iron by Zn coating.
(ii) By connecting metal to a more electropositive metal : As long as
the more electropositive metal is there, the given metal does not get
corroded. For example, iron can be protected from corrosion by connecting
it to a block/plate of zinc or magnesium. This method of corrosion
protection is called cathodic protection.
(iii) By forming insoluble phosphate or chromate coating : Metal
surfaces are treated with phosphoric acid to form an insoluble phosphate.
Formation of a thin chromate layer also prevents the corrosion of metals.
(iv) Using anti – rust solutions : Solutions of alkaline phosphates
and alkaline chromates are generally used as anti – rust solutions. For
example, iron articles are dipped in boiling alkaline sodium phosphate
solutions, when a protective insoluble sticking film of iron phosphate is
 When two or more ions compete at the electrodes then the ion
with higher reduction potential gets liberated at the cathode while
the one with lower reduction potential at the anode.
 Cell constant is determined with the help of conductivity bridge,
 504 Electrochemistry
where a standard solution of KCl is used.
 If the external EMF is slightly more than the actual EMF, the
current will flow into the cell and reverse reaction takes place.
 Identification of cathode and anode is done by the use of
galvanometer.
 KCl / NaCl / NH Cl etc., can not be used in the salt bridge of a cell
4

containing silver salt as one of the electrodes as Cl ions form a ppt.

–

of AgCl with silver ion.

 Weston cell is a common example of standard cell. The emf of a
standard cell does not change with temperature.
 In Appolo moon flights, H2 – O2 fuel cell was the source of energy and
drinking water.
 Conductivity water is the highly purified water whose on
conductance is very small. It is prepared by the demineralisation of
ordinary water by passing through cation and anion exchange
resins.
 506 Electrochemistry
(a) Time consumed
(b) Electro chemical equivalent of electrolysis
(c) Quantity of electricity passed
(d) Mass of electrons
13. When the sample of copper with zinc impurity is to be purified by
electrolysis, the appropriate electrodes are
[AIEEE 2002]
Electrolytes and Electrolysis Cathode Anode
(a) Pure zinc Pure copper
1. Which of the following will not conduct electricity in aqueous (b) Impure sample Pure copper
solution [AMU 1982, 83]
(c) Impure zinc Impure sample
(a) Copper sulphate (b) Sugar
(d) Pure copper Impure sample
(c) Common salt (d) None of these
2. Strong electrolytes are those which [MNR 1983]
14. In the electrolytic cell, flow of electrons is from
[IIT Screening 2003]
(a) Dissolve readily in water
(b) Conduct electricity (a) Cathode to anode in solution
(c) Dissociate into ions at high dilution (b) Cathode to anode through external supply
(d) Completely dissociate into ions at all dilutions (c) Cathode to anode through internal supply
3. In aqueous solution, strong electrolytes [AMU 1983, 84] (d) Anode to cathode through internal supply
(a) Are partially ionized 15. An electric current is passed through an aqueous solution of the
(b) Do not ionise following. Which one shall decompose [NCERT 1972]
(c) Ionise almost completely (a) Urea (b) Glucose
(d) Form polymers (c) AgNO3 (d) Ethyl alcohol
4. An electrolyte [KCET 1984; MP PET/PMT 1988] 16. The electric conduction of a salt solution in water depends on the
(a) Forms complex ions in solution (a) Shape of its molecules
(b) Gives ions only when electricity is passed (b) Size of its molecules
(c) Possesses ions even in solid state (c) Size of solvent molecules
(d) Gives ions only when dissolved in water (d) Extent of its ionization
5. Electrolytes when dissolved in water dissociates into ions because[CPMT 1974, 78; MNR 1983]
17. A solution of sodium sulphate in water is electrolysed using inert
(a) They are unstable electrodes. The products at the cathode and anode are respectively[IIT 1987,96]
(b) The water dissolves it
(a) H 2 , O 2 (b) O 2 , H 2
(c) The force of repulsion increases
(d) The forces of electrostatic attraction are broken down by water (c) O 2 , Na (d) O2 , SO 2
6. Electrolyte can conduct electricity because
18. On electrolysing a solution of dilute H 2 SO 4 between platinum
(a) Their molecules contain unpaired electrons, which are mobile
electrodes, the gas evolved at the anode is
(b) Their molecules contain loosely held electrons which get free
under the influence of voltage [NCERT 1977, 79; MNR 1980; CBSE PMT 1992]
(c) The molecules break up into ions when a voltage is applied (a) SO 2 (b) SO 3
(d) The molecules are broken up into ions when the electrolyte is (c) O 2 (d) H 2
fused or is dissolved in the solvent
7. Which one of the following metals could not be obtained on 19. The addition of a polar solvent to a solid electrolyte results in [
electrolysis of aqueous solution of its salts [IIT 1990] (a) Polarization (b) Association
(a) Ag (b) Mg (c) Ionization (d) Non-liberation of heat
(c) Cu (d) Cr 20. During the electrolysis of fused NaCl, which reaction occurs at
8. Which of the following aqueous solution will conduct an electric anode [NCERT 1973; AFMC 1992; MP PMT 2002]
current quite well [MP PMT 1987] (a) Chloride ions are oxidized
(a) Glycerol (b) HCl (b) Chloride ions are reduced
(c) Sugar (d) Pure water (c) Sodium ions are oxidised
9. On the electrolysis of aqueous solution of sodium sulphate, on (d) Sodium ions are reduced
cathode we get [MP PMT 1992, 2002] 21. The amount of ion discharged during electrolysis is not directly
(a) Na (b) H 2 proportional to [NCERT 1973]
(c) SO 2 (d) SO 3 (a) Resistance
(b) Time
10. Electrolysis involves oxidation and reduction respectively at
(c) Current
[CPMT 1973; AMU 1983; NCERT 1983, 84; MH CET 2001]
(d) Chemical equivalent of the ion
(a) Anode and cathode (b) Cathode and anode
(c) At both the electrodes (d) None of the above 22. Electrolysis of aqueous HCl solution produces
11. Which of the following compounds will not undergo decomposition [CPMT 1987]
on passing electricity through aqueous solution (a) 2 gas
H[MP PETat2001]
the anode
(a) Sugar (b) Sodium Chloride (b) H 2 gas at the cathode
(c) Sodium Bromide (d) Sodium Acetate
12. During the electrolysis of an electrolyte, the number of ions produced, (c) Cl 2 gas at the cathode
is directly proportional to the [AFMC 2002]
 Electrochemistry 507

(d) Cl 2 and O 2 gases both at the anode (a) Hydrogen is liberated at the cathode
(b) Hydrogen is liberated at the anode
23. During electrolysis of NaCl solution, part of the reaction is
(c) There is no reaction
Na   e   Na. This is termed as [NCERT 1984]
(a) Oxidation (b) Reduction (d) H  ions produced migrate to the cathode
(c) Deposition (d) Cathode reaction 35. During electrolysis, the species discharged at cathode are
24. When a solution of an electrolyte is heated the conductance of the [AFMC 2000]
solution [KCET 1991] (a) Ions (b) Cation
(a) Increases because of the electrolyte conducts better (c) Anion (d) All of these
(b) Decreases because of the increased heat 36. Electrolysis of molten anhydrous calcium chloride produces
(c) Decreases because of the dissociation of the electrolyte is [AIIMS 2000]
suppressed (a) Calcium (b) Phosphorus
(d) Increases because the electrolyte is dissociated more (c) Sulphur (d) Sodium
25. The passage of current liberates H 2 at cathode and Cl 2 at anode. 37. Which of the following properties of pure metal makes it more
The solution is [EAMCET 1979,87] useful then the corresponding alloy [RPET 2000]
(a) Copper chloride in water (b) NaCl in water (a) It is harder than corresponding alloy
(c) H 2 SO 4 (d) Water (b) It has high density
(c) It can be extracted easily
26. Pure water does not conduct electricity because it
(d) It conducts heat and electricity easily
[Manipal MEE 1995]
38. Which of the following liberate hydrogen on reaction with dilute
(a) Has a low boiling point
(b) Is almost totally unionized H 2 SO 4 [Roorkee 2000]
(c) Is neutral (a) Fe (b) Cu
(d) Is readily decomposed (c) Al (d) Hg
27. Which is responsible for electrical conduction of molten sodium
39. Which one of the following material conducts electricity
chloride [MADT Bihar 1995]
[Kerala (Med.) 2003]
(a) Free electrons
(b) Free ions (a) Diamond
(c) Free molecules (b) Crystalline sodium chloride
(d) Atoms of sodium and chlorine (c) Barium sulphate
28. In electrolysis of aqueous copper sulphate, the gas at anode and (d) Fused potassium chloride
cathode is [AFMC 1995] (e) Molten sulphur
(a) O 2 and H 2 (b) SO 2 and H 2 40. Which of the following metals will give H 2 on reaction with NaOH
(c) H 2 and O 2 (d) SO 3 and O 2 (a) Mg (b) Ba
29. Use of electrolysis is [AFMC 1995] (c) Ca (d) Sr
(a) Electroplating (b) Electrorefining 41. Which of the following is not a non electrolyte [J & K 2005]
(c) (a) and (b) both (d) None of these (a) Acetic acid (b) Glucose
30. Sodium is made by the electrolysis of a molten mixture of about (c) Ethanol (d) Urea
40% NaCl and 60% CaCl 2 because
[CBSE PMT 1995] Faraday's law of electrolysis
(a) CaCl 2 helps in conduction of electricity
1. Amount of electricity that can deposit 108 gm of silver from AgNO 3

(b) This mixture has a lower melting point than NaCl solution is [AFMC 1993; MP PMT 2004]
(a) 1 ampere (b) 1 coulomb
(c) Ca   can displace Na from NaCl
(c) 1 faraday (d) None of the above
(d) Ca   can reduce NaCl to Na 2. When 9.65 coulombs of electricity is passed through a solution of
31. Electrolysis is a process in which the cations and anions of the silver nitrate (atomic weight of Ag  107.87 taking as 108) the
electrolyte are [MP PET 1995] amount of silver deposited is
(a) Hydrated (b) Hydrolysed [EAMCET 1992; KCET 2000]
(c) Charged (d) Discharged (a) 10.8 mg (b) 5.4 mg
32. Degree of ionisation of a solution depends upon (c) 16.2 mg (d) 21.2 mg
[BHU 1998] 3. Three faradays electricity was passed through an aqueous solution of
(a) Temperature (b) Nature of the electrolyte iron (II) bromide. The weight of iron metal (at. wt. = 56) deposited
(c) Nature of the solvent (d) None of these at the cathode (in gm) is
[EAMCET 1991]
33. Which of the following is non-electrolytes
(a) 56 (b) 84
[KCET (Med.) 1999]
(c) 112 (d) 168
(a) NaCl (b) CaCl 2 4. A silver cup is plated with silver by passing 965 coulombs of
(c) C12 H 22 O11 (d) CH 3 COOH electricity, the amount of silver deposited is
[EAMCET 1990; MP PET 1994, 97]
34. When a molten ionic hydride is electrolysed (a) 9.89 g (b) 107.87 g
[JIPMER 1999]
 508 Electrochemistry
(c) 1.0787 g (d) 1.002 g 96500 96500
(c) C (d) C
5. The atomic weight of Al is 27. When a current of 5 Faradays is 3 2
passed through a solution of Al    ions, the weight of Al 18. On passing one faraday of electricity through the electrolytic cells
deposited is [NCERT 1984] containing Ag  , Ni 2 and Cr 3 ions solution, the deposited
(a) 27 gm (b) 36 gm
Ag ( At. wt .  108), Ni ( At. wt .  59) and Cr ( At. wt .  52) is[AIIMS 1982]
(c) 45 gm (d) 39 gm
6. An apparatus used for the measurement of quantity of electricity is Ag Ni Cr
known as a [BHU 1979] (a) 108 gm 29.5 gm 17.3 gm
(a) Calorimeter (b) Cathetometer (b) 108 gm 59.0 gm 52.0 gm
(c) Coulometer (d) Colorimeter (c) 108.0 gm 108.0 gm 108.0 gm
7. The unit of electrochemical equivalent is [EAMCET 1980] (d) 108 gm 117.5 gm 166.0 gm
(a) Gram (b) Gram/ampere 19. One Faraday of electricity when passed through a solution of copper
(c) Gram/coulomb (d) Coulomb/gram sulphate deposits [CPMT 1978]
8. A certain current liberated 0.504 gm of hydrogen in 2 hours. How (a) 1 mole of Cu (b) 1 gm atom of Cu
many grams of copper can be liberated by the same current flowing
1 molecule of Cu
(c) 1998]
for the same time in a copper sulphate solution[NCERT 1973, 77; CPMT 1979, 89; AIIMS (d) 1 gm equivalent of Cu
(a) 12.7 gm (b) 15.9 gm 20. When 1 coulomb of charge is passed through electrolyte solution,
(c) 31.8 gm (d) 63.5 gm then the mass deposited is equal to
(a) Equivalent weight
9. What weight of copper will be deposited by passing 2 Faradays of
(b) 79]
electricity through a cupric salt (Atomic weight of Cu = 63.5)[NCERT 1975; CPMT 1977, Atomic weight
(a) 2.0 gm (b) 3.175 gm (c) Electrochemical equivalent
(d) Chemical equivalent
(c) 63.5 gm (d) 127.0 gm
21. The platinum electrodes were immersed in a solution of cupric
10. If the current is passed into the solution of an electrolyte sulphate and electric current passed through the solution. After
[AIIMS 1979] some time it was found that colour of copper sulphate disappeared
(a) Anions move towards anode, cations towards cathode with evolution of gas at the electrode. The colourless solution
(b) Anions and cations both move towards anode contains [NCERT 1984]
(c) Anions move towards cathode, cations towards anode (a) Platinum sulphate (b) Copper hydroxide
(d) No movement of ions takes place (c) Copper sulphate (d) Sulphuric acid
11. Unit of Faraday is 22. On passing C ampere of electricity through a electrolyte solution
(a) Ampere (b) Coulomb for t second, m gram metal deposits on cathode. The equivalent
1 1 weight E of the metal is [MP PMT 1990]
(c) Coulomb mole (d) Coulomb Sec
C  t C  m
12. On passing 0.1 Faraday of electricity through aluminium chloride, the (a) E  (b) E 
amount of aluminium metal deposited on cathode is ( Al  27) [MP PMT 1991] m  96500 t  96500
(a) 0.9 gm (b) 0.3 gm 96500  m C  t  96500
(c) E  (d) E 
(c) 0.27 gm (d) 2.7 gm C  t m
13. Which of the following represents the first law of Faraday 23. How many Faradays are required to generate one gram atom of
[MP PMT 1991] magnesium from MgCl2 [MADT Bihar 1982]

(a) E  mc 2 (b) E  hv (a) 1 (b) 2

(c) 3 (d) 4
(c) m  ect (d) PV  nRT
24. To deposit 0.6354 gm of copper by electrolysis of aqueous cupric
14. 5 amperes is passed through a solution of zinc sulphate for 40 sulphate solution, the amount of electricity required (in coulombs) is
minutes. Find the amount of zinc deposited at the cathode[CBSE PMT 1996]
(a) 9650 (b) 4825
(a) 40.65 gm (b) 4.065 gm
(c) 3860 (d) 1930
(c) 0.4065 gm (d) 65.04 gm
25. In electrolysis of a fused salt, the weight of the deposit on an
15. In an electroplating experiment m g of silver is deposited, when 4 electrode will not depend on [CPMT 1973]
amperes of current flows for 2 minutes. The amount (in gms ) of (a) Temperature of the bath
silver deposited by 6 amperes of current flowing for 40 seconds will (b) Current intensity
be [MNR 1991]
(c) Electrochemical equivalent of ions
(a) 4 m (b) m / 2 (d) Time for electrolysis
(c) m / 4 (d) 2m 26. Faraday's laws of electrolysis will fail when [NCERT 1971]
16. On passing 3 ampere of electricity for 50 minutes, 1.8 gram metal (a) Temperature is increased
deposits. The equivalent mass of metal is (b) Inert electrodes are used
[MP PMT 1992] (c) A mixture of electrolytes is used
(a) 20.5 (b) 25.8 (d) In none of these cases
(c) 19.3 (d) 30.7 27. According to the first law of Faraday, the weight of a substance
17. The desired amount of charge for obtaining one mole of Al from discharge at the electrode is
Al 3  (a) W  ZQ (b) W  eF
(a) 3  96500 C (b) 96500 C Z
(c) W It (d) W  ZI
F
 Electrochemistry 509
28. When 0.04 faraday of electricity is passed through a solution of (a) 9.65  10 4 Coulomb (b) 6.28  1018 Coulomb
CaSO 4 , then the weight of Ca 2  metal deposited at the cathode
is [BHU 1996] (c) 1.6  10 19 Coulomb (d) None of these
(a) 0.2 gm (b) 0.4 gm 40. When an electric current is passed through acidulated water 112 ml of
(c) 0.6 gm (d) 0.8 gm hydrogen gas at N.T.P. collect at the cathode in 965 seconds. The
29. A current 2.0 A is passed for 5 hours through a molten metal salt current passed, in amperes is
deposits 22 g of metal (At. wt. =177). The oxidation state of the [MNR 1991; UPSEAT 2001]
metal in the metal salt is [KCET 1996] (a) 1.0 (b) 0.5
(a) + 1 (b) + 2 (c) 0.1 (d) 2.0
(c) + 3 (d) + 4 41. How much chlorine will be liberated on passing one ampere current
30. How many atoms of calcium will be deposited from a solution of for 30 minutes through NaCl solution [BVP 2003]
CaCl 2 by a current of 25 milliamperes flowing for 60 seconds (a) 0.66 mole
[BHU 1999]
(b) 0.33 mole
(c) 0.66 gm (d) 0.33 gm
(a) 4.68  1018 (b) 4.68  1015 42. The number of electrons involved in redox reactions when a Faraday
of electricity is passed through an electrolyte in solution is[NCERT 1982; Pb. PMT
(c) 4.68  10 12
(d) 4.68  10 9

31. On passing 0.5 faraday of electricity through NaCl , the amount of (a) 6  10 23 (b) 6  10 23
Cl deposited on cathode is (c) 96500 (d) 8  1019
[BHU 1997; RPET 1999] 43. Coulomb is equal to [Orissa JEE 2002]
(a) 35.5 gm (b) 17.75 gm (a) ampere  second (b) ampere  minute
(c) 71 gm (d) 142 gm
(c) watt  second (d) volt  second
32. What is the amount of chlorine evolved when 2 amperes of current
44.
is passed for 30 minutes in an aqueous solution of NaCl [BHU 1998; AIIMS 1999] The energy required to release 1 electron from He  is…….
(a) 66 g (b) 1.32 g [Orissa JEE 2002]
(c) 33 g (d) 99 g (a) + 54.4 eV (b) – 13.6 eV
(c) + 27.2 eV (d) Cannot be predicted
33. On passing a current through KCl solution, 19.5 g of potassium
45. Faraday's laws of electrolysis are related to the [IIT 1983]
is deposited. If the same quantity of electricity is passed through a (a) Atomic number of cation
solution of aluminium chloride, the amount of aluminium deposited
is [EAMCET 1997] (b) Atomic number of anion
(a) 4.5 g (b) 9.0 g (c) Equivalent weight of the electrolyte
(c) 13.5 g (d) 27 g (d) Speed of the cation
(e) None is correct 46. The electric charge for electrode decomposition of one gram
equivalent of a substance is [IIT 1984; KCET 1992]
34. Electrolysis rules of Faraday’s states that mass deposited on
electrode is proportional to [CBSE PMT 2000] (a) One ampere per second
(b) 96500 coulombs per second
(a) m  I 2 (b) m  Q (c) One ampere for one hour
(c) m  Q 2
(d) None of these (d) Charge on one mole of electrons
47. The number of electrons passing per second through a cross-section
35. A current being passed for two hour through a solution of an acid
liberating 11.2 litre of oxygen at NTP at anode. What will be the of copper wire carrying 10 6 amperes of current per second is
amount of copper deposited at the cathode by the same current found to be [EAMCET 1985]
when passed through a solution of copper sulphate for the same 19 35
(a) 1.6  10 (b) 6  10
time [BVP 2003] 16
(a) 16 g (b) 63 g (c) 6  10 (d) 6  1012
(c) 31.5 g (d) 8 g 48. The electrolytic cells, one containing acidified ferrous chloride and
36. In a metal oxide, there is 20% oxygen by weight. Its equivalent another acidified ferric chloride are connected in series. The ratio of
weight is [Pb. PMT 2000]
iron deposited at cathodes in the two cells when electricity is passed
through the cells will be
(a) 40 (b) 64
[CPMT 1989]
(c) 72 (d) 32 (a) 3 : 1 (b) 2 : 1
37. On the basis of the information available from the reaction (c) 1 : 1 (d) 3 : 2
4 2
Al  O2  Al2O3 , G  827kJmol 1 of O2
,
the 49. When 96500 coulomb of electricity is passed through a copper
3 3 sulphate solution, the amount of copper deposited will be[MP PMT 1996]
minimum emf required to carry out an electrolysis of Al2 O3 is (F (a) 0.25 mol (b) 0.50 mol
= 96500C mol 1 ) [CBSE PMT 2003] (c) 1.00 mol (d) 2.00 mol
(a) 8.56 V (b) 2.14 V 50. During electrolysis of fused aluminium chloride 0.9 gm of
(c) 4.28 V (d) 6.42 V aluminium was deposited on the cathode. The volume of chlorine
38. Then during electrolysis of a solution of AgNO , 9650 coulombs of
3
liberated at the anode will be
charge pass through the electroplating bath, the mass of silver (a) 2.24 litres (b) 11.2 litres
deposited in the cathode will be
(c) 1.12 litres (d) 5.6 litres
[AIEEE 2003]
51. Faraday has the dimensions of [MP PET 1995]
(a) 1.08 g (b) 10.8 g
(a) Coulombs
(c) 21.6 g (d) 108 g
(b) Coulomb equivalent
39. Total charge on 1 mole of a monovalent metal ion is equal to
(c) Coulomb per equivalent
[DPMT 2001]
(d) Coulomb per degree Kelvin
 510 Electrochemistry
52. The required charge for one equivalent weight of silver deposite on [AMU 1983; AFMC 1989; MP PET 2001]
cathode is [Roorkee 1995] 1
(a) 95500 C mol (b) 96550 C mol 1
(a) 9.65  10 7 C (b) 9.65  10 4 C
(c) 96500 C mol 1 (d) 98500 C mol 1
(c) 9.65  10 3 C (d) 9.65  10 5 C
63. The quantity of electricity needed to liberate 0.5 gram equivalent of
53. 96500 coulombs of electric current liberates from CuSO 4 solution[MP PMT 1995]an element is [CPMT 1988; MP PMT 1997]
(a) 63.5 gm Cu (b) 31.75 gm Cu (a) 48250 Faradays (b) 48250 Coulombs
(c) 96500 gm Cu (d) 100 gm Cu (c) 193000 Faradays (d) 193000 Coulombs
64. The number of coulombs required for the deposition of 107.870 g of
54. A current of strength 2.5 amp was passed through CuSO 4 silver is [MP PET/PMT 1998]
solution for 6 minutes 26 seconds. The amount of copper deposited (a) 96,500 (b) 48,250
is
(c) 1,93,000 (d) 10,000
(Atomic weight of Cu  63.5 )
(1 faraday = 96500 coulombs) 65. When one of ampere current flows for 1 sec through a conductor,
[EAMCET 1989; MP PET 1994] this quantity of electricity is known as
(a) 0.3175 g (b) 3.175 g [MP PMT 1993]
(c) 0.635 g (d) 6.35 g (a) Faraday (b) Coulomb
55. A certain quantity of electricity is passed through an aqueous (c) E.M.F. (d) Ohm
solution of AgNO 3 and cupric salt solution connected in series. 66. The mass deposited at an electrode is directly proportional to
The amount of Ag deposited is 1.08 gm , the amount of copper [CPMT 1974; AFMC 1987; MP PET 2000]
deposited is (atomic weight of Cu = 63.5; Ag = 108) (a) Atomic weight
[EAMCET 1986] (b) Equivalent weight
(a) 0.6454 g (b) 6.354 g (c) Molecular weight (d) Atomic number
(c) 0.3177 g (d) 3.177 g 67. From the solution of which of the following one faraday of electricity
56. The number of electrons required to deposit 1gm atom of will liberate one gram atom of metal
aluminium (at. wt. = 27) from a solution of aluminium chloride will [MHCET 1999; MP PET 1993,2000; AFMC 2000]
be (where N is Avogadro's number)
[AIIMS 1992]
(a) NaCl (b) BaCl2
(a) 1 N (b) 2 N (c) CuSO 4 (d) AlCl3
(c) 3 N (d) 4 N
68. On electrolysis, 1 mole of aluminium will be deposited from its
57. Three faradays of electricity are passed through molten Al 2 O 3 , molten salt by [MH CET 2000]
aqueous solution of CuSO 4 and molten NaCl taken in different (a) 3 moles of electrons (b) 4 moles of electrons
electrolytic cells. The amount of Al, Cu and Na deposited at the (c) 2 moles of electrons (d) 1 mole of electrons
cathodes will be in the ratio of 69. The atomic weight of Fe is 56. The weight of Fe deposited from
[BHU 1990] FeCl3 solution by passing 0.6 Faraday of electricity is
(a) 1 mole : 2 mole : 3 mole
[MH CET 2000]
(b) 3 mole : 2 mole : 1mole
(c) 1 mole : 1.5 mole : 3 mole (a) 5.6 g (b) 11.2 g
(d) 1.5 mole : 2 mole : 3 mole (c) 22.4 g (d) 33.6 g
58. An electrolytic cell contains a solution of Ag 2 SO 4 and have 70. 2.5 F of electricity are passed through a CuSO 4 solution. The
platinum electrodes. A current is passed until 1.6 gm of O 2 has been number of gm equivalent of Cu deposited on anode is
[CPMT 1973; DPMT 1982; MP PMT 2001]
liberated at anode. The amount of silver deposited at cathode would
be [CPMT 1971] (a) Zero (b) 1.25
(a) 107.88 gm (b) 1.6 gm (c) 2.5 (d) 5.0
(c) 0.8 gm (d) 21.60 gm 71. The equivalent weight of a certain trivalent element is 20. Molecular
59. The aqueous solution of which of the following decomposes on weight of its oxide is [KCET 2003]
passing electric current [EAMCET 1973] (a) 152 (b) 56
(a) Canesugar (b) Urea (c) 168 (d) 68
(c) Methanol (d) Potassium iodide 72. Silver is removed electrically from 200 ml of a 0.1 N solution of
60. The number of Faradays needed to reduce 4 gram equivalents of AgNO3 by a current of 0.1 ampere. How long will it take to
Cu   to Cu metal will be [BHU 1981]
remove half of the silver from the solution [AMU 1999]
(a) 16 sec (b) 96.5 sec
(a) 1 (b) 2
(c) 100 sec (d) 10 sec
(c) 1/2 (d) 4
73. In order to separate oxygen from one mole of H 2 O the required
61. When electricity is passed through the solution of
quantity of coulomb would be [RPET 1999]
AlCl3 , 13.5 gm of Al are deposited. The number of Faraday
must be (a) 1.93  10 5 (b) 9.6  10 4
[NCERT 1974; MP PET 1992; MP PMT 1994] (c) 1.8 (d) 3.2
(a) 0.50 (b) 1.00 74. A current of 0.25A is passed through CuSO 4 solution placed in
(c) 1.50 (d) 2.00 voltameter for 45 minutes. The amount of Cu deposited on cathode
62. The value of one Faraday is is (At weight of Cu  63.6 )
[BHU 2001]
 Electrochemistry 511
(a) 0.20 g (b) 0.22 g [CPMT 1982;Pb.CET 2003]
(c) 0.25 g (d) 0.30 g (a) Kohlraush (b) Faraday
75. Faraday constant [KCET (Med.) 2001] (c) Nernst (d) Berthelot
(a) Is a numerical constant 88. How many atoms of calcium will be deposited from a solution of
(b) Depends on equivalent CaCl 2 by a current 0.25 mA following for 60 seconds
(c) Depends upon the current passed
(d) Depends on the number of electrons (a) 4.68  1018 (b) 4.68  1015
76. If 0.5 amp current is passed through acidified silver nitrate solution
for 10 minutes. The mass of silver deposited on cathode, is (eq. wt. (c) 4.68  1012 (d) 4.68  10 9
of silver nitrate = 108) [AFMC 2001] 89. The number of coulombs required to reduce 12.3 g of nitrobenzene
(a) 0.235 g (b) 0.336 g to aniline [UPSEAT 2003]
(c) 0.536 g (d) 0.636 g (a) 115800 C (b) 5790 C
77. The unit for the electric current is [KCET (Med.) 2001] (c) 28950 C (d) 57900 C
(a) Ohm (b) Volt 90. During the process of electrolytic refining of copper, some metals
(c) Ampere (d) Coulomb present as impurity settle as 'anode mud'. These are
78. The quantity of electricity required to liberate 112 cm 3 of [AIEEE 2005]
hydrogen at STP from acidified water is (a) Sn and Ag (b) Pb and Zn
[KCET (Med.) 2001] (c) Ag and Au (d) Fe and Ni
(a) 0.1 Faraday (b) 1 Faraday 91. A galvanic cell is set up from a zinc bar weighing 50g and 1.0litre, 1.0M,
(c) 965 Coulomb (d) 96500 Coulomb CuSO 4 solution. How long would the cell run, assuming it delivers a
79. Which solution will show highest resistance during the passage of steady current of 1.0 ampere
current [BHU 2001]
[Roorkee 2000]
(a) 0.05 N NaCl (b) 2 N NaCl (a) 48 hrs (b) 41 hrs
(c) 0.1 N NaCl (d) 1 N NaCl (c) 21 hrs (d) 1 hr
80. 4 g of copper was dissolved in concentrated nitric acid. The copper
nitrate solution on strong heating gave 5 g of its oxide. The 92. On passing electric current through molten aluminium chloride, 11.2
equivalent weight of copper is [KCET 2004] litre of Cl 2 is liberated at NTP at anode. The quantity of
(a) 23 (b) 32 aluminium deposited at cathode is (at. wt. of Al = 27)
(c) 12 (d) 20 (a) 9 g (b) 18 g
81. The amount of silver deposited by passing 241.25 coulomb of (c) 27 g (d) 36 g
current through silver nitrate solution is [MHCET 2003] 93. An electric current is passed through silver voltameter connected to
(a) 2.7 g (b) 2.7 mg a water voltameter. The cathode of the silver voltameter weighed
(c) 0.27 g (d) 0.54 g 0.108 g more at the end of the electrolysis. The volume of oxygen
82. When 1F of electricity is passed through acidulated water, evolved at STP is
[Kerala (Med.) 2003]
O 2 evolved is [MHCET 2004]
3 3
(a) 56 cm (b) 550 cm
(a) 11.2 dm 3 (b) 5.6 dm 3
3 3
(c) 5.6 cm (d) 11.2 cm
(c) 22.4 dm 3 (d) 1.0 dm 3
3
(e) 22.4 cm
83. Charge required to liberate 11.5 g sodium is
[AIIMS 1992; DCE 2002] 94. During electrolysis of aqueous NaOH, 4 g of O 2 gas is liberated
(a) 0.5 F (b) 0.1 F at NTP at anode, H 2 gas liberated at cathode is
(c) 1.5 F (d) 96500 coulombs [CBSE PMT 1998]
84. In the electrolysis of water, one Faraday of electrical energy would (a) 2.8 litres (b) 5.6 litres
evolve [DCE 2004] (c) 11.2 litres (d) 22.4 litres
(a) One mole of oxygen (b) One g atom of oxygen
(c) 8 g of oxygen (d) 22.4 litres of oxygen Conductor and conductance
85. In a galvanic cell, the electrons flow from [KCET 2004]
(a) Anode to cathode through the solution 1. Which one of the following statements is correct
(b) Cathode to anode through the solution [MP PET 1997]
(c) Anode to cathode through the external circuit (a) The oxidation number of oxygen in KO 2 is zero
(d) Cathode to anode through the external circuit
(b) The specific conductance of an electrolyte solution decreases
86. An electric current is passed through silver nitrate solution using with increase in dilution
silver electrodes. 10.79 g of silver was found to be deposited on the
cathode if the same amount of electricity is passed through copper (c) Sn 2  oxidises Fe 3 
sulphate solution using copper electrodes, the weight of copper
(d) Zn / ZnSO 4 is a reference electrode
deposited on the cathode is
[Kerala PMT 2004] 2. In infinite dilutions, the equivalent conductances of Ba 2  and Cl 
(a) 6.4 g (b) 2.3 g are 127 and 76 ohm 1cm 1 eqvt 1 . The equivalent conductivity
(c) 12.8 g (d) 1.6 g of BaCl2 at indefinite dilution is [CBSE 2000]
(e) 3.2 g
(a) 101.5 (b) 139.5
87. The law of electrolysis were proposed by
 512 Electrochemistry
(c) 203.5 (d) 279.5 (c) ohm cm 2 (gm equivalent)
3. The factor which is not affecting the conductivity of any solution is
(a) Dilution (b) Nature of electrolyte (d) S cm 2
(c) Temperature (d) None of these 14. It has been observed that gaseous hydrogen chloride is a very poor
4. Specific conductance of 0.1 m nitric acid is conductor of electricity but a solution of hydrogen chloride gas in
water is a good conductor of electricity. This is due to the fact that[NCERT 1976
6.3  10 2 ohm 1cm 1 . The molar conductance of solution is (a) Water is good conductor of electricity
[Kerala (Med.) 2003] (b) Hydrogen chloride gas in water solution ionizes
1 1
(a) 630 ohm cm mole 2
(b) 315 ohm cm 2mole 1
1 (c) A gas is non-conductor but a liquid conducts electricity
1 1 (d) Gas does not obey Ohm's law whereas solution does
(c) 100 ohm cm mole 2
(d) 6300 ohm 1cm 2mole 1
15. Electrolytic conduction differs from metallic conduction in that in
(e) 63.0 ohm 1cm 2mole 1 the case of electrolytic conduction
5. The conductivity of strong electrolyte is [CPMT 2003] [KCET 1987; Bihar CEE 1992]
(a) Increase on dilution slightly (a) The resistance increases with increasing temperature
(b) Decrease on dilution (b) The resistance decreases with increasing temperature
(c) The flow of current does not generate heat
(c) Does not change with dilution
(d) The resistance is independent of the length of the conductor
(d) Depend upon density of electrolytes itself
16. The electrolytic conductance is a direct measure of
6. If X is the specific resistance of the solution and M is the molarity of [KCET 1990; CPMT 2003]
the solution, the molar conductivity of the solution is given by[Kurukshetra CEE 2002]
(a) Resistance (b) Potential
1000 X 1000 (c) Concentration (d) Dissociation
(a) (b)
M MX 17. Conductivity of a strong electrolyte [KCET 1993]
1000 M MX (a) Increases on dilution
(c) (d) (b) Does not change considerably on dilution
X 1000
(c) Decreases on dilution
7. Conductivity (unit Siemen’s) is directly proportional to area of the
vessel and the concentration of the solution in it and is inversely (d) Depends on density
proportional to the length of the vessel then the unit of the constant 18. Which of the following statements is not applicable to electrolytic
of proportionality is [AIEEE 2002] conductors [AIIMS 1991]
(a) New products show up at the electrodes
(a) Sm mol 1 (b) Sm 2 mol 1
(b) Ions are responsible for carrying the current
(c) S 2 m 2 mol (d) S 2m 2 mol 2 (c) Show a positive temperature coefficient for conductance
8. If one end of a piece of a metal is heated, the other end becomes hot (d) A single stream of electrons flows from cathode to anode
after some time. This is due to 19. Which one is not a conductor of electricity [RPET 1999]
[CBSE PMT 1995] (a) NaCl (aqueous) (b) NaCl (solid)
(a) Energised electrons moving to the other part of the metal (c) NaCl (molten) (d) Ag metal
(b) Resistance of the metal 20. Solid sodium chloride is bad conductor of electricity because
(c) Mobility of atoms in the metal (a) It contains only molecules
(d) Minor perturbation in the energy of atoms (b) It does not possess ions
9. Conductivity of a solution is directly proportional to (c) The ions present in it are not free to move
[KCET 1984] (d) It does not contain free molecules
(a) Dilution (b) Number of ions 21. Which of the following is a poor conductor of electricity
(c) Current density (d) Volume of the solution [EAMCET 1992]
10. The increase in equivalent conductance of an electrolyte solution (a) CH 3 COONa (b) C 2 H 5 OH
with dilution is due to the increase in
[MP PMT 1996]
(c) NaCl (d) KOH
22. The molar conductivity is maximum for the solution of
(a) Ionic attraction
concentration [DCE 2002]
(b) Molecular attraction (a) 0.001 M (b) 0.005 M
(c) Degree of association of the electrolyte (c) 0.002 M (d) 0.004 M
(d) Degree of ionisation of the electrolyte 23. The unit of molar conductivity is [DCE 2002]
11. Which of the following conducts electricity [AFMC 1995] 1 2 1 2 1
(a)  cm mol (b)  cm mol
(a) Fused NaCl (b) CO 2
(c) 1cm 2mol 1 (d)  cm 2mol
(c) Br2 (d) Si
24. The highest electrical conductivity of the following aqueous solutions
12. Which of the following shows electrical conduction is of [AIEEE 2005]
[CBSE PMT 1999; AIIMS 1999] (a) 0.1 M acetic acid (b) 0.1 M chloroacetic acid
(a) Potassium (b) Graphite (c) 0.1 M fluoroacetic acid (d) 0.1 M difluoroacetic acid
(c) Diamond (d) Sodium 1
25. Given l / a  0.5 cm , R  50ohm, N  1.0 . The equivalent
13. The unit of equivalent conductivity is
[CPMT 1999; BCECE 2005] conductance of the electrolytic cell is [Orissa JEE 2005]
(a) ohm cm (a) 10 ohm 1 cm 2 gm eq 1 (b) 20 ohm 1 cm 2 gm eq 1
1 2 1
(b) ohm cm (gm equivalent) (c) 300 ohm 1 cm 2 gmeq 1 (d) 100ohm 1 cm 2 gmeq 1
 Electrochemistry 513

26. If equivalent conductance of 1 M benzoic acid is 12.8 ohm 1 cm 2 (d) 2 Fe(s)  O 2 (g)  4 H  (aq)  2 Fe 2  (aq)  2 H 2 O(l)
and if the conductance of benzoate ion and H  ion are 42 and 8. When lead storage battery is charged [MP PET 2003]
288.42 ohm 1 cm 2 respectively. its degree of dissociation is (a) PbO 2 is 2005]
[DPMT dissolved
(a) 39% (b) 3.9% (b) H 2 SO 4 is regenerated
(c) 0.35% (d) 0.039%
(c) PbSO4 is deposited on lead electrode
27. The unit ohm 1 is used for [J & K 2005]
(d) Lead is deposited on lead electrode
(a) Molar conductivity (b) Equivalent conductivity
9. When lead storage battery is charged
(c) Specific conductivity (d) Conductivity
[MP PET 1993; MP PMT 2000]
Cell constant and Electrochemical Cells (a) Lead dioxide dissolves
(b) Sulphuric acid is regenerated
1. When electric current is passed through a cell having an electrolyte, (c) The lead electrode becomes coated with lead sulphate
the positive ions move towards the cathode and the negative ions (d) The amount of sulphuric acid decreases
towards the anode. If the cathode is pulled out of the solution [AIIMS 1980]10. The electrolytic decomposition of dilute sulphonic acid with
(a) The positive and negative ions will move towards the anode platinum electrode in cathodic reaction is
(b) The positive ions will start moving towards the anode, the [MNR 1988; UPSEAT 1999, 2002]
negative ions will stop moving (a) Oxidation
(c) The negative ions will continue to move towards the anode and (b) Reduction
the positive ions will stop moving
(c) Oxidation and reduction both
(d) The positive and negative ions will start moving randomly
(d) Neutralisation
2. If the half cell reaction A  e   A  has a large negative
11. Which colourless gas evolves, when NH 4 Cl reacts with zinc in a
reduction potential, it follows that
dry cell battery [Orissa JEE 2003]
[MNR 1992; UPSEAT 2000, 02]
(a) A is readily reduced (b) A is readily oxidised (a) NH 4 (b) N 2
(c) A  is readily reduced (d) A  is readily oxidised (c) H2 (d) Cl 2
3. Mark the false statement [MP PET 1997]
12. Which of the substances Na, Hg, S , Pt and graphite can be used
(a) A salt bridge is used to eliminate liquid junction potential
as electrodes in electrolytic cells having aqueous solutions
(b) The Gibbs free energy change, G is related with
(a) Na, Pt and graphite (b) Na and Hg
electromotive force (E) , as G  nFE
(c) Nernst equation for single electrode potential is (c) Pt and graphite only (d) Na and S only
RT 13. In electrolysis of dilute H 2 SO 4 using platinum electrodes
E  Eo  ln a M n 
nF [DPMT 1983; IIT 1983; Kurukshetra CET 2002; AFMC 2005]
(d) The efficiency of a hydrogen oxygen fuel cell is 23% (a) H 2 is evolved at cathode
4. The specific conductance of a 0.1 N KCl solution at 23 o C is
(b) NH 3 is produced at anode
0.012 ohm 1 cm 1 . The resistance of cell containing the solution
at the same temperature was found to be 55 ohm. The cell constant (c) Cl 2 is obtained at cathode
will be (d) O 2 is produced
[CBSE PMT 1999, 2000; KCET 2001]
(a) 0.142 cm 1 (b) 0.66 cm 1 14. For cell reaction, Zn  Cu 2   Zn 2   Cu, cell representation is
(a) Zn | Zn | Cu |Cu
2+ 2+
(b) Cu | Cu | Zn | Zn 2+ 2+

(c) 0.918 cm 1 (d) 1.12 cm 1 (c) Cu | Zn | Zn | Cu

2+ 2+
(d) Cu | Zn | Zn | Cu
2+ 2+

5. Which of the following reactions occurs at the cathode of a common 15. Which one is not called a anode reaction from the following
dry cell [NCERT 1978]
1
(a) Mn  Mn 2   2e  (a) Cl   Cl 2  e  (b) Cu  Cu    2e 
2
(b) 2 MnO2  Zn 2   2e   ZnMn2 O4 (c) Hg   Hg    e  (d) Zn 2   2e   Zn
2 
(c) 2 ZnO2  Mn  2e  MnZn2 O4 16. A cell from the following which converts electrical energy into
chemical energy
(d) Zn  Zn 2   2e  (a) Dry cell (b) Electrochemical cell
6. In Cu  Zn cell [BHU 1981] (c) Electrolytic cell (d) None of these
(a) Reduction occurs at the copper cathode
17. In the cell Zn | Zn 2  || Cu 2  | Cu, the negative electrode is
(b) Oxidation occurs at the copper cathode
(c) Reduction occurs at the anode [MP PMT 1995]
(d) Chemical energy is converted to light energy 2
(a) Cu (b) Cu
7. Which of the following reaction is used to make a fuel cell
[AIIMS 2003] (c) Zn (d) Zn 2 
(a) Cd (s)  2 Ni(OH)3 (s)  CdO(s)  2 Ni(OH )  H 2 O(l) 18. Which of the following statements is correct ? Galvanic cell converts[KCET 1991;
(a) Chemical energy into electrical energy
(b) Pb(s)  PbO2 (s)  2 H 2 SO 4 (aq)  2 PbSO4 (s)  2 H 2 O(l)
(b) Electrical energy into chemical energy
(c) 2 H 2 (g)  O2 (g)  2 H 2 O(l) (c) Metal from its elemental state to the combined state
 514 Electrochemistry
(d) Electrolyte into individual ions 29. Which one of the following statement is true for a electrochemical
19. Hydrogen–oxygen fuel cells are used in space–craft to supply [MP PMT 1993; MP PET cell1999] [Pb. PMT 1999; KCET 1999]
(a) Power for heat and light (a) H 2 is cathode and Cu is anode
(b) Power for pressure (b) H 2 is anode and Cu is cathode
(c) Oxygen (c) Reduction occurs at H 2 electrode
(d) Water
(d) Oxidation occurs at Cu electrode
20. The standard cell potential of Zn | Zn 2 (aq ) || Cu 2 (aq ) | Cu cell is 30. In the reaction
1.10 V. The maximum work obtained by this cell will be [MP Cu )  2 Ag  (aq)  Cu 2 (aq)  2 Ag(s)
PET(s2002]
(a) 106.15 kJ (b) – 212.30 kJ The reduction half-cell reaction is [AIIMS 1997]
(c) – 318.45 kJ (d) – 424.60 kJ
(a) Cu  2e   Cu 2 (b) Cu  2e   Cu 2
21. The relationship between standard reduction potential of cell and
equilibrium constant is shown by [MP PET 2002] (c) Ag   e   Ag (d) Ag  e   Ag 
n 0 .059 31. Which of the following statements about galvanic cell is incorrect[JIPMER 1997]
(a) Ecell0
 log K c (b) Ecell0
 log K c (a) Anode is positive
0 .059 n
(b) Oxidation occurs at the electrode with lower reduction
log K c potential
(c) Ecell  0.059 n log Kc
0
(d) Ecell 
0
n (c) Cathode is positive
(d) Reduction occurs at cathode
22. Consider the Galvanic cell Zn  | ZnSO 4 || CuSO 4 | Cu  the
32. The molar conductances of NaCl, HCl and CH 3 COONa at
reaction at cathode is [AMU 2000]

infinite dilution are 126.45, 426.16 and 91 ohm 1 cm 2 mol 1
(a) Zn 2  2e   Zn
respectively. The molar conductance of CH 3 COOH at infinite
(b) Cu 2   2e   Cu dilution is [CBSE PMT 1997]

(c) Cu 2   Zn  Cu  Zn 2  (a) 201.28 ohm 1 cm 2 mol 1

(d) Zn 2   Cu  Zn  Cu 2  (b) 390.71 ohm 1 cm 2 mol 1

23. The cell reaction Cu  2 Ag   Cu 2  Ag is best represented (c) 698.28 ohm 1 cm 2 mol 1
by [AMU 2000]
(d) 540.48 ohm 1 cm 2 mol 1
2 
(a) Cu(s) | Cu (aq ) || Ag (aq ) | Ag(s) 33. The electrodes of a conductivity cell are 3 cm apart and have a
2 
(b) Pt| Cu || Ag (aq ) | Ag(s) cross-sectional area of 4 cm 2 . The cell constant of the cell (in

(c) Cu 2 | Cu || Pt | Ag cm 1 ) is
(a) 4  3 (b) 4 / 3
(d) None of the above representations
(c) 3 / 4 (d) 9 / 4
24. Zn(s) | Zn 2 (aq ) | | Cu 2 (aq ) | Cu (s) is [Kerala (Engg.) 2002] 34. The anode half-reaction occurring during the discharge of a lead
(anode) (cathode)
storage battery is
(a) Weston cell (b) Daniel cell (a) Pb(s)  SO 2  O 2  PbSO 4 (s)
(c) Calomel cell (d) Faraday cell
(e) Standard cell (b) Pb(s)  SO 42  (aq) ⇌ PbSO 4 (s)  2e 
25. The specific conductance of a solution is 0.2 ohm 1cm 1 and (c) PbO2 (s)  4 H  (aq)  2e   SO 42 (aq) ⇌
conductivity is 0.04 ohm 1 . The cell constant would be [RPET 1999] PbSO 4 (s)  2 H 2 O
1 1
(a) 1 cm (b) 0 cm
(d) Pb 2 (aq)  SO 42 (aq)  PbSO 4 (s)
1 1
(c) 5 cm (d) 0.2 cm 35. The unit of cell constant is [MP PET 1996]
26. If the conductance and specific conductance of a solution is one
1 1
then its cell constant would be [RPET 1999] (a) ohm cm (b) ohm cm
(a) 1 (b) Zero
(c) 0.5 (d) 4 (c) cm (d) cm 1
27. Saturated solution of KNO 3 is used to make ‘salt-bridge’ because 36. In dry cell
[IIT the reaction
Screening which takes place at the zinc anode is
2002]
[MP PET 1996]
(a) Velocity of K  is greater than that of NO 3 2 
(a) Zn  2e  Zn(s)
(b) Velocity of NO 3 is greater than that of K 
(b) Zn(s)  Zn 2   2e 
(c) Velocities of both K  and NO 3 are nearly the same
(c) Mn2   2e   Mn(s)
(d) KNO 3 is highly soluble in water
28. In balancing the half reaction S 2 O32   S (s) the number of (d) Mn(s)  Mn  e   1.5 V
electrons that must be added is [DPMT 2000] 37. The chemical reaction taking place at the anode of a cell is
(a) 4 on the left (b) 3 on the right [MP PET 1996]
(c) 2 on the left (d) 2 on the right (a) Ionisation (b) Reduction
 Electrochemistry 515
(c) Oxidation (d) Hydrolysis (b) Create potential difference between the two electrodes
38. Which of the following reactions occurs at the cathode during the (c) Generate heat
charging of a lead storage battery (d) Remove adsorbed oxygen from electrode surfaces
[Manipal MEE 1995; MP PET 2002] 49. ClCH 2COONa  224 ohm 1 cm 2 gmeq 1 ,
2 
(a) Pb  2e  Pb
 NaCl  38.2 ohm 1 cm 2 gmeq 1 ,
2
(b) Pb  SO 42   PbSO4
HCl  203 ohm 1 cm 2 gmeq 1 ,
2 
(c) Pb  Pb  2e What is the value of ClCH 2 COOH [JEE Orissa 2004]
(d) PbSO4  2 H 2 O  2 PbO2  4 SO 42   2e 
(a) 288.5 ohm 1 cm 2 gmeq 1
39. A depolarizer used in dry cell batteries is [NCERT 1981]
(b) 289.5 ohm 1 cm 2 gmeq 1
(a) Ammonium chloride (b) Manganese dioxide
(c) Potassium hydroxide (d) Sodium phosphate (c) 388.5 ohm 1 cm 2 gmeq 1
40. When a lead storage battery is discharged (d) 59.5 ohm 1 cm 2 gmeq 1
[IIT 1987; MP PMT 2004]
50. Which of the following statement is true for the electrochemical
(a) SO 2 is evolved Daniel cell [AIIMS 2004]
(b) Lead sulphate is consumed (a) Electrons flow from copper electrode to zinc electrode
(c) Lead is formed (b) Current flows from zinc electrode to copper electrode
(c) Cations move toward copper electrode which is cathode
(d) Sulphuric acid is consumed
(d) Cations move toward zinc electrode
41. In electroplating, the article to be electroplated serves as 51. Which of the following statement is true for an electrochemical cell
[AMU 1982, 83]
(a) H 2 is cathode and Cu is anode
(a) Cathode (b) Electrolyte
(c) Anode (d) Conductor (b) H 2 is anode and Cu is cathode
42. The position of some metals in the electrochemical series in (c) Reduction occurs at H 2 electrode
decreasing electropositive character is given as (d) Oxidation occurs at Cu electrode
Mg  Al  Zn  Cu  Ag. What will happen, if a copper spoon 52. Which of the following statements are true for an fuel cells
is used to stir a solution of aluminium nitrate [DPMT 2004]
[NCERT 1977]
(a) They run till the reactants are active
(a) The spoon will get coated with Al (b) They are free from pollution
(b) An alloy of Cu and Al is formed (c) They are more efficient
(c) The solution becomes blue (d) All of the above
(d) There is no reaction 53. For gold plating, the electrolyte used is [Pb.CET 2004]
43. In a electrochemical cell [AFMC 1989] (a) AuCl 3 (b) HAuCl4
(a) Potential energy changes into kinetic energy
(b) Kinetic energy changes into potential energy (c) k[ Au(CN )2 ] (d) None of these
(c) Chemical energy changes into electrical energy 54. The acid used in lead storage battery is [Pb.CET 2003]
(d) Electrical energy changes into chemical energy (a) H 2 SO 4 (b) H 3 PO4
44. In galvanic cell, the salt bridge is used to [MP PMT 2002]
(a) Complete the circuit (c) HCl (d) HNO 3
(b) Reduce the electric resistance in the cell
55. At 25°C specific conductivity of a normal solution of KCl is
(c) Separate cathode from anode
0.002765 mho. The resistance of cell is 400 ohms. The cell constant
(d) Carry salts for the chemical reaction is [Pb.PMT 2004]
45. If a strip of Cu metal is placed in a solution of ferrous sulphate[NCERT 1974; CPMT 1977; MP PET 2000]
(a) 0.815 (b) 1.016
(a) Copper will precipitate out
(b) Iron will precipitate out (c) 1.106 (d) 2.016
(c) Copper will dissolve 56. Which of the following is used widely in the manufacture of lead
(d) No reaction will take place storage battery [BHU 2004]
46. Which of the following is not used to construct salt bridge (a) Arsenic (b) Lithium
[MP PET 2003]
(c) Bismuth (d) Antimony
(a) CH 3 COOK (b) KCl
57. The chemical reaction, 2 AgCl(s)  H 2 (g) 
(c) NH 4 NO 3 (d) KNO 3
2 HCl(aq)  2 Ag(s) taking place in a galvanic cell is represented
47. The reference electrode is made by using [MP PMT 2002]
by the notation [AIIMS 2005]
(a) ZnCl 2 (b) CuSO 4
(a) Pt| H 2 (g),1bar | 1M KCl(aq)|AgCl(s)| Ag(s)
(c) HgCl2 (d) Hg2 Cl 2

48. In a hydrogen – oxygen fuel cell, combustion of hydrogen occurs to (b) Pt[AIEEE
(s)| H2004]
2 (g), 1bar | 1M HCl(aq)|| 1M Ag (aq)| Ag(s)
(a) Produce high purity water
 516 Electrochemistry
(c) Pt(s)| H 2 (g), 1bar | 1M HCl(aq)| AgCl(s)| Ag(s) [CPMT 1999]
(a) > copper (b) < copper
(d) Pt(s)| H 2 (g), 1bar | 1M HCl(aq)| Ag(s)| AgCl(s) (c) > sulphate (d) < sulphate
5. Which of the following metal does not react with the solution of
58. If the Zn 2 / Zn electrode is diluted to 100 times then the change copper sulphate [CPMT 1999]
in e.m.f. [DPMT 2005]
(a) Mg (b) Fe
(a) Increase of 59 mV
(c) Zn (d) Ag
(b) Decrease of 59 mV 6. A solution containing one mole per litre of each
Cu(NO 3 )2 , AgNO3 , Hg2 (NO 3 )2 and Mg(NO 3 )2 , is being
(c) Increase of 29.5 mV
electrolysed by using inert electrodes. The values of standard
(d) Decrease of 29.5 mV electrode potentials in volts (reduction potentials) are
Ag / Ag   0.80, 2 Hg / Hg 22  0.79, Cu / Cu 2  0.34,
59. If hydrogen electrode dipped in 2 solution of pH  3 and
Mg / Mg 2   2.37 with increasing voltage, the sequence of
pH  6 and salt bridge is connected the e.m.f. of resulting cell is [DPMT 2005]
deposition of metals on the cathode will be
(a) 0.177 V (b) 0.3 V [IIT 1984; AMU 1999; Kerala PMT 2004]
(c) 0.052 V (d) 0.104 V (a) Ag, Hg, Cu, Mg (b) Mg, Cu, Hg, Ag
60. The tendency of an electrode to lose electrons is known as (c) Ag, Hg, Cu (d) Cu, Hg, Ag
[J & K 2005] 7. The standard reduction electrode potentials of four elements are
(a) Electrode potential (b) Reduction potential A  0.250 V B  0.136 V
(c) Oxidation potential (d) e.m.f.
C  0.126 V D  0.402 V
61. When electric current is supplied through an ionic hydride of fused
state, then [Kerala CET 2005] The element that displaces A from its compounds is
(a) B (b) C
(a) Hydrogen is obtained at anode
(c) D (d) None of these
(b) Hydrogen is obtained at cathode
8. The standard oxidation potential of zinc and silver in water at
(c) No change 298 K are
(d) Hydride ion moves towards cathode
Zn (s)  Zn 2   2e  ; E  0.76 V
(e) hydride ion present in solution
Ag (s)  Ag 2   2e  ; E  0.80 V
Electrode potential, ECell, Nernt equation and ECS
Which of the following reactions actually take place
1. The hydrogen electrode is dipped in a solution of pH  3 at [NCERT 1983, 84; KCET 2003]
 
o
25 C . The potential of the cell would be (the value of (a) Zn(s)  2 Ag (aq)  Zn (aq)  2 Ag(s)
2.303 RT / F is 0.059 V) [KCET 1993,2005] (b) Zn   (aq)  2 Ag(s)  2 Ag  (aq)  Zn(s)
(a) 0.177 V (b) – 0.177 V
(c) 0.087 V (d) 0.059 V (c) Zn(s)  Ag(s)  Zn   (aq)  Ag  (aq)
2. The standard electrode potentials of Zn 2  / Zn and Ag  / Ag (d) Zn   (aq)  Ag  (aq)  Zn(s)  Ag(s)
are  0.763 V and  0.799 V respectively. The standard 9. Beryllium is placed above magnesium in the second group. Beryllium
potential of the cell is [KCET 1993] dust, therefore when added to MgCl2 solution will
(a) 1.56 V (b) 0.036 V
[CPMT 1977]
(c) – 1.562 V (d) 0.799 V
(a) Have no effect
3. The standard reduction potentials at 298 K for the following half
(b) Precipitate Mg metal
reactions are given against each
(c) Precipitate MgO
Zn 2  (aq.)  2e ⇌ Zn(s) ; – 0.762
(d) Lead to dissolution of Be metal
Cr 3  (aq)  3e ⇌ Cr(s) ; – 0.740
10. The name of equation showing relation between electrode potential
2 H  (aq)  2e ⇌ H 2 (g) ; 0.00 (E) standard electrode potential (E o ) and concentration of ions in
3 2 solution is
Fe (aq)  e ⇌ Fe (aq) ; 0.770
(a) Kohlrausch's equation (b) Nernst's equation
Which is the strongest reducing agent
[IIT 1981; MP PET/PMT 1988; MP PMT 1989; (c) Ohm's equation (d) Faraday's equation
MH CET 2001] 11. The correct representation of Nernst's equation is
(a) Zn(s) (b) Cr(s) 0.0591
(a) E M n / M  E o M n / M  log(M n  )
(c) H 2 (g ) (d) 2
Fe (aq) n
0.0591
4. When Zn piece is kept in CuSO 4 solution, the copper get (b) E M n / M  E o M n / M  log(M n  )
n
precipitated due to standard potential of zinc is
 Electrochemistry 517

(c) E M n / M  E o M n / M 
n
log(M n  ) 20. The reaction Zn 2   2e   Zn has a standard potential of
0.0591 0.76 V . This means [KCET 1992]
(d) None of the above (a) Zn can't replace hydrogen from acids
12. Standard electrode potential of NHE at 298 K is (b) Zn is a reducing agent
(a) 0.05 V (b) 0.1 V (c) Zn is a oxidising agent
(c) 0.00 V (d) 0.11 V (d) Zn 2  is a reducing agent
13. When a copper wire is placed in a solution of AgNO3 , the solution 21. 2 H  (aq)  2e   H 2 (g). The standard electrode potential for
acquires blue colour. This is due to the formation of the above reaction is (in volts) [CPMT 1988]
[Roorkee 1989] (a) 0 (b) + 1
2 (c) – 1 (d) None of these
(a) Cu ions
 22. K, Ca and Li metals may be arranged in the decreasing order of
(b) Cu ions
their standard electrode potentials as [CPMT 1990]
(c) Soluble complex of copper with AgNO3 (a) K, Ca, Li (b) Ca, K, Li
(d) Cu  ion by the reduction of Cu (c) Li, Ca, K (d) Ca, Li, K
14. Consider the reaction M (naq ) 
 ne  M (s) . The standard 23. The correct order of chemical reactivity with water according to
electrochemical series [MP PMT 1991]
reduction potential values of the elements M1 , M 2 and M 3 are (a) K  Mg  Zn  Cu (b) Mg  Zn  Cu  K
0.34 V,  3.05 V and 1.66 V respectively. The order of their (c) K  Zn  Mg  Cu (d) Cu  Zn  Mg  K
reducing power will be [NCERT 1990]
2
24. EMF of cell Ni | Ni (1.0 M ) || Au 3  (1.0 M ) | Au (Where
(a) M1  M 2  M 3 (b) M 3  M 2  M1
E o for Ni 2  | Ni is  0.25 V; E o for Au 3 | Au is
(c) M1  M 3  M 2 (d) M 2  M 3  M1
1.50 V ) is [MP PET 1993; MP PMT 2000]
RT
15. E 
0
In K eq . This is called (a) + 1.25 V (b)  1.75 V
nF
[CPMT 1988; MP PET 2000] (c) + 1.75 V (d) + 4.0 V
(a) Gibb's equation 25. Oxidation and reduction take place in a cell, then its electromotive
(b) Gibb's–Helmholtz equation force will be [RPET 1999]
(c) Nernst's equation (a) Positive (b) Negative
(d) Vander Waal's equation (c) Zero (d) Stable
16. Four alkali metals A, B, C and D are having respectively standard 26. For a spontaneous reaction the G, equilibrium constant (K) and
electrode potential as –3.05,–1.66,–0.40 and 0.80. Which one will be o
the most reactive E Cell will be respectively [AIEEE 2005]
[MP PMT/PET 1988 ; CPMT 1983; (a) ve ,  1,  ve (b) ve ,  1,  ve
MNR 1993; UPSEAT 2002]
(a) A (b) B (c) ve ,  1,  ve (d) ve ,  1,  ve
(c) C (d) D 27. The reference electrode is made from which of the following
17. Which one of the following metals cannot evolve H 2 from acids or [MP PET/PMT 1988]
H 2 O or from its compounds (a) ZnCl 2 (b) CuSO 4
[MP PET/PMT 1988; CPMT 1996; (c) Hg 2 Cl 2 (d) HgCl2
AFMC 1998, 99; Pb. PET 1999; BVP 2003]
28. The charge over anode in a galvanic cell is
(a) Hg (b) Al (a) Negative
(c) Pb (d) Fe (b) Positive
18. Which one of the following reaction is not possible (c) No charge
[MP PMT 1991] (d) Sometimes negative and sometimes positive
(a) Fe  H 2 SO 4  FeSO 4  H 2
29. The standard electrode potential for the two electrode A  / A and
(b) Cu  2 AgNO3  Cu (NO 3 )2  2 Ag
B  / B are respectively 0.5 V and 0.75 V . The emf of the given
(c) 2 KBr  I2  2 KI  Br2 cell A | A  (a  1) || B  (a  1) | B will be
(d) CuO  H 2  Cu  H 2 O (a) 1.25 V (b) – 1.25 V
19. When a rod of metal A is dipped in an aqueous solution of metal (c) – 0.25 V (d) 0.25 V
B (concentration of B 2  ion being 1M) at 25 o C , the standard 30. The standard reduction potential for Li  / Li ; Zn 2  / Zn ;
electrode potentials are A 2  / A =–0.76 volts, B 2  /B = + 0.34 volts[KCET 1992]
H  / H 2 and Ag  / Ag is 3.05,  0.762, 0.00 and
(a) A will gradually dissolve
0.80 V . Which of the following has highest reducing capacity
(b) B will deposit on A
(c) No reaction will occur (a) Ag (b) H2
(d) Water will decompose into H 2 and O 2 (c) Zn (d) Li
 518 Electrochemistry
31. If an iron rod is dipped in CuSO 4 solution Fe   2e   Fe ; E o  0.440 V
[MADT Bihar 1984]
Fe    3e   Fe ; E o  0.036 V
(a) Blue colour of the solution turns green
(b) Brown layer is deposited on iron rod The standard electrode potential (E o ) for
(c) No change occurs in the colour of the solution
Fe    e   Fe  is [AIIMS 1982]
(d) Blue colour of the solution vanishes
(a) – 0.476 V (b) – 0.404 V
(e) None of the above
(c) + 0.404 V (d) + 0.771 V
32. Eo values of Mg 2  / Mg is 2.37 V , of Zn 2  / Zn is 40. Reduction potential of four elements P, Q, R, S is
2
0.76 V and Fe / Fe is 0.44 V . Which of the following  2.90,  0.34,  1.20 and  0.76. Reactivity decreases in the
statements is correct [EAMCET 1989] order [MP PET 1989; UPSEAT 2001]
(a) Zn will reduce Fe 2  (a) P  Q  R  S (b) Q  P  R  S
(c) R  Q  S  P (d) P  S  Q  R
(b) Zn will reduce Mg 2 
41. Which of the following metal can deposit copper from copper
(c) Mg oxidises Fe sulphate solution [CPMT 1983; MP PMT 1989]
(a) Mercury (b) Iron
(d) Zn oxidises Fe
(c) Gold (d) Platinum
33. The standard reduction potential for Fe 2  / Fe and Sn 2 / Sn
42. Standard electrode potential of Ag  / Ag and Cu  / Cu is
electrodes are 0.44 and 0.14 volt respectively. For the given cell
0.80 V and 0.34 V respectively. these electrodes are joint
reaction Fe 2   Sn  Fe  Sn 2  , the standard EMF is[IIT Screening 1990; MP PMT 2003] by salt bridge if
together [AMU 2002]
(a) + 0.30 V (b) – 0.58 V
(a) Copper electrode is work like cathode, then E cell is 0.45 V
o
(c) + 0.58 V (d) – 0.30 V
34. Electrode potential of Zn 2  / Zn is 0.76 V and that of
o
(b) Silver electrode is work like anode then E cell is 0.34 V

Cu 2  / Cu is 0.34 V . The EMF of the cell constructed between

o
(c) Copper electrode is work like anode then E cell is 0.46 V
these two electrodes is
[EAMCET 1992; BHU 2001; CBSE PMT 2001; KCET 1990;
o
(d) Silver electrode is work like cathode then E cell is 0.34 V
MHCET 1999, 2003; Pb. CET 2002; (e) Silver electrode is work like anode then o
E cell will be
AFMC 2001; Pb. PMT 2004]
(a) 1.10 V (b) 0.42 V 1.14 V
(c) – 1.1V (d) – 0.42 V 43. The reaction is spontaneous if the cell potential is
35. EMF of a cell whose half cells are given below is [MP PET 1999]
Mg 2 
 2e  Mg(s); E  2.37 V (a) Positive (b) Negative
(c) Zero (d) Infinite
2
Cu  2e   Cu(s); E  0.33 V 44. Which substance eliminates bromine from KBr solution
[EAMCET 1987; MP PET 1994; Pb. PMT 2000] [IIT 1981]
(a) – 2.03 V (b) 1.36 V (a) I2 (b) Cl 2
(c) 2.7 V (d) 2.03 V
36. A cell constructed by coupling a standard copper electrode and a (c) HI (d) SO 2
standard magnesium electrode has emf of 2.7 volts. If the standard 45. A standard hydrogen electrode has zero electrode potential because[IIT 1997]
reduction potential of copper electrode is + 0.34 volt that of
magnesium electrode is [KCET 1989] (a) Hydrogen is easiest to oxidise
(a) + 3.04 volts (b) – 3.04 volts (b) The electrode potential is assumed to be zero
(c) + 2.36 volts (d) – 2.36 volts (c) Hydrogen atom has only one electron
37. When E oAg  / Ag  0.8 volt and E Zn
o
 0.76 volt, which of (d) Hydrogen is the lightest element
2
/ Zn 46. In the electrochemical cell
the following is correct [MP PMT 1994]
H 2 (g)1 atm| H  (1M )|| Cu 2 (1M )| Cu(s)
(a) Ag  can be reduced by H 2
Which one of the following statements is true
(b) Ag can oxidise H 2 into H  [EAMCET 1997]
2 (a) H 2 is cathode; Cu is anode
(c) Zn can be reduced by H 2
(b) Oxidation occurs at Cu electrode
(d) Ag can reduce Zn 2  ion
38. Adding powdered lead and iron to a solution that is 1.0 M in both (c) Reduction occurs at H 2 electrode
Pb 2  and Fe 2  ions, would result a reaction, in which (d) H 2 is anode; Cu is cathode
[CPMT 1987] 47. Expression representing the cell potential (E cell)
(a) More iron and Pb 2  ions are formed (a) E + E (b) E – E
(b) More lead and Fe 2  ions are formed
cathode anode anode cathode

(c) E – E
cathode anode
(d) E – E
left right

(c) Concentration of both Pb 2  and Fe 2  ions increases 48. Iron displaces copper from its salt solution, because
(d) There is no net change [MP PMT 1996]
39. Given standard electrode potentials (a) Atomic number of iron is less than that of copper
 Electrochemistry 519
(b) The standard reduction potential of iron is less than that of 56. The standard reduction potentials of 4 elements are given below.
copper Which of the following will be the most suitable reducing agent
(c) The standard reduction potential of iron is more than that of I = – 3.04 V, II = – 1.90 V, III = 0 V, IV = 1.90 V
copper [CPMT 1999]
(d) The iron salt is more soluble in water than the copper salt (a) I (b) II
49. (i) Copper metal dissolves in 1M silver nitrate solution and crystals (c) III (d) IV
of silver metal get deposited. 57. Electrode potential data are given below :
(ii) Silver metal does not react with 1 M zinc nitrate solution
Fe 3  (aq)  e   Fe 1 (aq); E o  0.77 V
(iii) Zinc metal dissolves in 1M copper sulphate solution and
copper metal gets deposited Al 3  (aq)  3e   Al(s); E o  1.66 V
Hence the order of decreasing strength of the three metals as
reducing agents will be Br2 (aq)  2e   2 Br  (aq); E o  1.08 V

(a) Cu  Ag  Zn (b) Ag  Cu  Zn Based on the data given above, reducing power of Fe 2 , Al and

(c) Zn  Cu  Ag (d) Cu  Zn  Ag Br  will increase in the order [Pb. PMT 1998]

50. Standard electrode potentials of Zn and Fe are known to be (i) (a) Br   Fe 2  Al (b) Fe 2  Al  Br 
0.76 V and (ii) 0.44 V respectively. How does it explain that (c) Al  Br   Fe 2 (d) Al  Fe 2  Br 
galvanization prevents rusting of iron while zinc slowly dissolves 58. The standard electrode potential (E o ) for OCl  / Cl  and
away
1
(a) Since (i) is less than (ii), zinc becomes the cathode and iron Cl  / Cl 2 respectively are 0.94 V and 1.36 V . The E o
the anode 2
(b) Since (i) is less than (ii), zinc becomes the anode and iron the 1
value for OCl  / Cl 2 will be [KCET 1996]
cathode 2
(c) Since (i) is more than (ii), zinc becomes the anode and iron the (a) 0.42 V (b)  2.20 V
cathode
(d) Since (i) is more than (ii), zinc becomes the cathode and iron (c) 0.52 V (d) 1.04 V
the anode 59. If the reduction potential is more, then [CPMT 1996]
51. Amongst the following electrodes the one with zero electrode (a) It is easily oxidised
potential is [MP PMT 1997] (b) It is easily reduced
(a) Calomel electrode (c) It acts as oxidising agent
(b) Standard hydrogen electrode (d) It has redox nature
(c) Glass electrode 60. One of the following is false for Hg [BHU 1998]
(d) Gas electrode (a) It can evolve hydrogen from H 2 S
52. Which of the following is correct expression for electrode potential (b) It is a metal
of a cell [MP PMT 1997]
(c) It has high specific heat
RT [product] (d) It is less reactive than hydrogen
(a) E  E o  ln
nF [reactant] 61. E o for the cell Zn | Zn 2 (aq)|| Cu 2 (aq)| Cu is 1.10 V at
RT [product] 25 o C , the equilibrium constant for the
(b) E  E o  ln reaction
F [reactant] Zn  Cu 2 (aq) ⇌ Cu  Zn 2 (aq) is of the order of
RT [reactant] [CBSE PMT 1997]
(c) E  E o  ln
nF [product] 28 37
(a) 10 (b) 10
18
RT [product] (c) 10 (d) 10 17
(d) E   ln
F [reactant] 62. Standard reduction potentials at 25 o C of
53. Calculate standard free energy change for the reaction  2 
Li | Li, Ba | Ba, Na | Na and Mg 2 | Mg are
1 1 1
Cu (s)  Cl 2 (g) ⇌ Cu 2   Cl  taking place at 25 o C in a 3.05,  2.90,  2.71 and 2.37 volt respectively. Which one of
2 2 2
the following is the strongest oxidising agent
cell whose standard e.m.f. is 1.02 volts [MP PMT 1997]
[CBSE PMT 1994; JIPMER 2002]
(a) – 98430 J (b) 98430 J
(a) Na  (b) Li 
(c) 96500 J (d) – 49215 J
54. In which cell the free energy of a chemical reaction is directly (c) Ba 2  (d) Mg 2 
converted into electricity ? [MP PET/PMT 1998] 63. Which of the following displaces Br2 from an aqueous solution
(a) Leclanche cell (b) Concentration cell containing bromide ions
(c) Fuel cell (d) Lead storage battery [CBSE PMT 1994; JIPMER (Med.) 2002]
55. Nernst equation is related with (a) Cl 2 (b) Cl 
(a) The electrode potential and concentration of ions in the (c) I2 (d) I 3
solution
(b) Equilibrium constant and concentration of ions 64. For the cell reaction
(c) Free energy change and E.M.F. of the cell Cu 2 (C1 aq)  Zn(s)  Zn 2 (C 2 aq)  Cu(s)
(d) None of these
 520 Electrochemistry
of an electrochemical cell, the change in free energy at a given (c) – 0.19 V (d) + 0.19 V
temperature is a function of [CBSE PMT 1998] 2 
74. Zn  2e  Zn(s); E   0.76 ,
o

(a) ln (C1 ) (b) ln (C 2 ) 3

Fe  e   Fe2  ; E o   0.77 ,
(c) ln (C1  C 2 ) (d) ln (C 2 / C1 )
Cr 3   3e   Cr ; E o   0.79 ,
65. The e.m.f. of the cell in which the following reaction
Zn(s)  Ni 2 (a  1.0) ⇌ Zn 2  (a  10)  Ni(s) occurs, is found H   2e   1 / 2 H 2 ; E o  0.00
to be 0.5105 V at 298K . The standard e.m.f. of the cell is Strongest reducing agent is [BHU 2003]
2
[Roorkee Qualifying 1998] (a) Fe (b) Zn
(a) 0.5400 (b) 0.4810 V (c) Cr (d) H 2
(c) 0.5696 V (d) – 0.5105 V 75. Standard reduction electrode potentials of three metals A, B and C are
66. For the redox reaction respectively + 0.5V, – 3.0V and – 1.2 V. The reducing powers of these
Zn(s)  Cu 2  (0.1M )  Zn 2  (1M )  Cu(s) taking place in a cell, metals are [IIT 1998; AIEEE 2003]
(a) B > C > A (b) A > B > C
 RT 
o
Ecell is 1.10 volt. Ecell for the cell will be  2 .303  0 .0591 (c) C > B > A (d) A > C > B
 F  76. For a cell reaction involving a two-electron change, the standard emf
[AIEEE 2003]
of the cell is found to be 0.295 V at 25 o C . The equilibrium
(a) 2.14 volt (b) 1.80 volt
(c) 1.07 volt (d) 0.82 volt constant of the reaction at 25 o C will be
[Roorkee 1999; AIEEE 2003; CBSE PMT 2004]
67. The emf of a Daniel cell at 298K is E1
10
(a) 1  10 (b) 29.5  10 2
Zn | ZnSO 4 || CuSO 4 | Cu when the concentration of ZnSO 4
(0.01 M ) (1.0 M ) (c) 10 (d) 1  1010
is 1.0 M and that of CuSO 4 is 0.01 M the emf changed to E 2 . What
,
77. For the electrochemical cell,
is the relationship between E1 and E 2 M | M  || X  | X , E o (M  / M ) = 0.44 V and E o (X / X  ) =
[CBSE PMT 2003] 0.33 V. From this data one can deduce that
(a) E2  0  E1 (b) E1  E2 [IIT-JEE (Screening) 2000]
 
(a) MX M  X is the spontaneous reaction
(c) E1  E2 (d) E1  E2
 
68. The oxidation potentials of following half-cell reactions are given (b) M  X  M  X is the spontaneous reaction
Zn  Zn 2   2e  ; E o  0.76 V , (c) Ecell = 0.77 V
Fe  Fe2   2e  ; E o  0.44 V what will be the emf of cell, (d) Ecell = – 0.77 V
2 2
whose cell-reaction is Fe (aq)  Zn  Zn (aq)  Fe 78. The standard potential at 25 o C for the following half reactions are
[MP PMT 2003] given against them
(a) – 1.20 V (b) + 0.32 V Zn 2   2e  Zn, E o  0.762V
(c) – 0.32 V (d) + 1.20 V Mg 2   2e  Mg, E o  2.37 V
69. The E o for half cells Fe / Fe2  and Cu / Cu 2  are – 0.44 V and When zinc dust is added to the solution of MgCl2
+ 0.32 V respectively. Then [MP PMT 2003]
[UPSEAT 2001]
(a) Cu 2  oxidises Fe (b) Cu 2  oxidises Fe 2  (a) ZnCl 2 is formed
(c) Cu oxidises Fe 2  (d) Cu reduces Fe 2  (b) Zinc dissolves in the solution
70. What is Eo
for electrode represented by (c) No reaction takes place
Pt, O 2 (1 atm) / 2 H  (Im) [JIPMER 1997] (d) Mg is precipitated
(a) Unpredictable (b) Zero 79. KMnO4 acts as an oxidising agent in the neutral medium and gets
(c) 0.018 V (d) 0.118 V reduced to MnO2 The equivalent weight of KMnO4 in neutral
.

71. The cell potential of a cell in operation is medium [AMU 2001]

(a) Zero (b) Positive (a) mol. wt/2 (b) mol.wt/3
(c) Negative (d) None of the above (c) mol. wt/4 (d) mol .wt/7
72. Which of the following is displaced by Fe [Roorkee 1995] 80. Which of the following condition will increase the voltage of the cell,
(a) Ag (b) Hg represented by the equation
(c) Zn (d) Na Cu (s)  2 Ag (aq )  Cu 2 (aq )  2 Ag(s) [CBSE PMT 2001]
73. The standard electrode potential of the half cells are given below
(a) Increase in the concentration of Ag  ion
Zn 2   2e   Zn; E  7.62 V,
(b) Increase in the concentration of Cu  ion
Fe 2   2e   Fe; E  7.81 V
(c) Increase in the dimension of silver electrode
The emf of the cell Fe 2   Zn  Zn 2   Fe is (d) Increase in the dimension of copper electrode
[CPMT 2003] 81. Which will increase the voltage of the cell
(a) 1.54 V (b) – 1.54 V
Sn(s)  2 Ag (aq)  Sn 2 (aq)  2 Ag(s) [DPMT 2001]
 Electrochemistry 521

(a) Increase in the concentration of Ag  ions 91. Which of the following has been universally accepted as a reference
electrode at all temperatures and has been assigned a value of zero
(b) Increase in the concentration of Sn 2  ions volt [AIIMS 1998]
(c) Increase in size of the silver rod (a) Graphite electrode
(d) None of these (b) Copper electrode
82. The mass of the proton is 1840 times that of electron, its potential (c) Platinum electrode
difference is V. The kinetic energy of proton is (d) Standard hydrogen electrode
[DCE 2001]
92. Aluminium is more reactive than Fe . But Al is less easily corroded
(a) 1840 KeV (b) 1 KeV
than iron because [DCE 1999]
1 (a) Al is noble metal
(c) KeV (d) 920 KeV
1840 (b) Iron forms both mono and divalent ions
83. What will be the emf for the given cell (c) Oxygen forms a protective oxide layer

Pt | H 2 (P1 )| H (aq ) || H 2 (P2 )| Pt [AIEEE 2002] (d) Fe undergoes reaction easily with H 2 O
RT P RT P 93. Zinc displaces copper from the solution of its salt because
(a) log 1 (b) log 1
f P2 2f P2 [MP PET 1995]
(a) Atomic number of zinc is more than that of copper
RT P
(c) log 2 (d) None of these (b) Zinc salt is more soluble in water than the copper salt
f P1
(c) Gibbs free energy of zinc is less than that of copper
84. What is the potential of a cell containing two hydrogen electrodes (d) Zinc is placed higher than copper in electro-chemical series
the negative one in contact with 10 8 M H  and positive one in 94. An electrochemical cell is set up as follows
contact with 0.025 M H  Pt(H 2 , 1 atm) / 0.1 M HCl
[MP PMT 2000]
(a) 0.18 V (b) 0.28 V | 0.1 M acetic acid /( H 2 , 1 atm ) Pt
(c) 0.38 V (d) 0.48 V E.M.F. of this cell will not be zero because
2 o [CBSE PMT 1995]
85. Will Fe(s) be oxidised to Fe by the reaction with 1 M HCl (E
(a) The pH of 0.1 M HCl and 0.1 M acetic acid is not the same
for Fe / Fe2  = + 0.44 V) [Pb. PMT 2000]
(b) Acids used in two compartments are different
(a) Yes (b) No
(c) E.M.F. of a cell depends on the molarities of acids used
(c) May be (d) Can’t say
(d) The temperature is constant
86. EMF of a cell in terms of reduction potential of its left and right
electrodes is [AIEEE 2002] 95. Cu  ion is not stable in aqueous solution because of
(a) E  Eleft  Eright (b) E  Eleft  Eright disproportionation reaction. E o value for disproportionation of
Cu  is
(c) E  Eright  Eleft (d) E  (Eright  Eleft)
o
(Given ECu 2
/ Cu 
 0.15 , ECu
o
2  0.34 V ) [IIT 1995]
87. Arrange the following in the order of their decreasing electrode / Cu
potential Mg, K, Ba, Ca [JIPMER 2002] (a) – 0.49 V (b) 0.49 V
(a) K, Ba, Ca, Mg (b) Ca, Mg, K, Ba (c) – 0.38 V (d) 0.38 V
(c) Ba, Ca, K, Mg (d) Mg, Ca, Ba, K 96. E o of a cell aA  bB  cC  dD is [CPMT 1997]
88. Which of the following has highest electrode potential RT c
[C] [D] d
[a] [b] B
A
(a)  log (b)  RT log
[Pb. PMT 2000] nF [ A]a [B]b [a]C [d ] D
(a) Li (b) Cu
RT [C]c [d ] D RT [C]c [d ] D
(c) Au (d) Al (c)  log a b (d)  log A b
nF [ A] [ B] nF [a] [B]
89. The cell reaction of a cell is
97. In the experiment set up for the measurement of EMF of a half cell
Mg(s)  Cu 2 (aq)  Cu (s)  Mg 2 (aq) using a reference electrode and a salt bridge, when the salt bridge is
removed, the voltage
If the standard reduction potentials of Mg and Cu are  2.37 [NCERT 1984; CPMT 1985]
(a) Does not change
and  0.34 V respectively. The emf of the cell is
(b) Decreases to half the value
[EAMCET 1995; JIPMER (Med.) 2001; (c) Increase to maximum
AFMC 2002; CBSE PMT 2002] (d) Drops to zero
(a) 2.03 V (b) – 2.03 V 98. Electrode potentials of five elements A, B, C, D and E are
(c) + 2.71 V (d) – 2.71 V respectively – 1.36 , – 0.32, 0, – 1.26 and –0.42. The reactivity order
90. The element which can displace three other halogens from their of these elements are in the order of
compound is [EAMCET 1998] [MP PMT 1995]
(a) A, D, E, B and C (b) C, B, E, D and A
(a) Cl (b) F
(c) B, D, E, A and C (d) C, A, E, D and B
(c) Br (d) I 99. What is wrongly stated about electrochemical series
 522 Electrochemistry
[DCE 1999] 109. The standard e.m.f. of a call, involving one electron change is found
(a) It is the representation of element in order of increasing or to be 0.591 V at 25°C. The equilibrium constant of the reaction is
decreasing standard electrode reductional potential
( F  96,500 C mol 1 ; R  8.314 JK 1mol 1 ) [AIEEE 2004]
(b) It does not compare the relative reactivity of metals
(c) It compares relative strengths of oxidising agents (a) 1.0  1010 (b) 1.0  10 5
(d) H 2 is centrally placed element
(c) 1.0  101 (d) 1.0  10 30
100. Which of the following statements is true for fuel cells
[KCET (Med.) 1999; AFMC 2000] 110. Standard electrode potential of cell H 2 | H  || Ag  | Ag is
(a) They are more efficient [AIEEE 2004]
(b) They are free from pollution (a) 0.8 V (b) – 0.8 V
(c) They run till reactants are active (c) – 1.2 V (d) 1.2 V
(d) All of these 111. A galvanic cell with electrode potential of ' A'  2.23 V and
101. What is the potential of a half-cell consisting of zinc electrode in 0.01m
' B'  1.43 V . The value of Ecell is [Pb.CET 2003]
ZnSO 4 solution at 258 o C (E o  0.763 V )
(a) 3.66 V (b) 0.80 V
[AIIMS 2000; BHU 2000]
(a) 0.8221 V (b) 8.221 V (c) – 0.80 V (d) – 3.66 V
(c) 0.5282 V (d) 9.232 V 112. The e.m.f. of a cell whose half cells are given below is
102. The emf of a galvanic cell, with electrode potentials of silver = +0.80V Mg 2   2e   Mg(s) E  2.37 V
and that of copper = + 0.34 V, is [AIIMS 1999]
Cu 2   2e   Cu(s) E  0.34 V [Pb.CET 2001]
(a) – 1.1 V (b) + 1.1 V
(c) + 0.46 V (d) + 0.76 V (a) + 1.36 V (b) + 2.71 V
103. Copper cannot replace….. from solution [DPMT 2002] (c) + 2.17 V (d) – 3.01 V
(a) Fe (b) Au 113. For the cell reaction, 2Ce 4   Co  2Ce 3   Co 2  Ecell is
(c) Hg (d) Ag 1.89 V. If ECe 4  / Ce 3  [Pb.CET 2000]
104. The strongest reducing agent of the alkali metal is
(a) – 1.64 V (b) + 1.64 V
[CBSE PMT 2000]
(c) – 2.08 V (d) + 2.17 V
(a) Li (b) Na
(c) K (d) Cs 114. If the G of a cell reaction AgCl  e   Ag  Cl  is
105. Which of the following is the most electropositive element 21.20 KJ ; the standard e.m.f., of cell is [MP PMT 2004]
[Pb. PMT 2000]
(a) 0.229 V (b) 0.220 V
(a) Carbon (b) Calcium
(c) – 0.220 V (d) – 0.110 V
(c) Chlorine (d) Potassium
106. The metal that forms a self protecting film of oxide to prevent 115. The e.m.f. of the cell Ag | Ag  (0.1M )|| Ag  (1M )| Ag at 298 K
corrosion, is [BHU 1999] is [DCE 2003]
(a) Cu (b) Al (a) 0.0059 V (b) 0.059 V
(c) Na (d) Au (c) 5.9 V (d) 0.59 V
107. In a cell that utilises the reaction Zn(s)  2 H  (aq)  116. The e.m.f. of the cell Zn | Zn 2  (0.01M )|| Fe2  (0.001M )| Fe at
Zn 2  (aq)  H 2(g) addition of H 2 SO 4 to cathode compartment, 298 K is 0.2905 then the value of equilibrium for the cell reaction is [IIT-JEE Scr
will [AIEEE 2004] 0 .32 0 .32
(a) (b)
(a) Increase the E and shift equilibrium to the right e 0.0295 10 0.0295
(b) Lower the E and shift equilibrium to the right 0 .26 0 .32
(c) Lower the E and shift equilibrium to the left (c) (d)
10 0.0295 10 0.0591
(d) Increase the E and shift equilibrium to the left 117. Aluminium displaces hydrogen from dilute HCl whereas silver does
108. For the electrochemical cell, M | M  || X  | X , not. The e.m.f. of a cell prepared by combining Al / Al3  and
E(M  | M )  0.44 V E(X | X  )  0.33 V From this data, one Ag / Ag  is 2.46 V. The reduction potential of silver electrode is
can deduce that [Pb.CET 2004] 0.80 V . The reduction potential of aluminium electrode is [KCET 2004]
(a) Ecell  0.77 V (a) 1.66 V (b) 3.26 V
 
(b) M  X  M  X is the spontaneous reaction (c) 3.26 V (d) 1.66 V
 
(c) M  X  M  X is the spontaneous reaction 118. Consider the following E 0 values :
(d) Ecell  .77 V
E 0 Fe 3  / Fe 2 = 0.77 V

E 0 Sn 2 / Sn  0.14 V
 Electrochemistry 523
Under standard conditions the potential for the reaction 127. Calculate the electrode potential at 298 o K for
Sn (s)  2 Fe3  (aq)  2 Fe2  (sq)  Sn 2  (aq) is [AIEEE 2004] 
Zn| Zn electrode in which the activity of zinc ions is 0.001 M and
(a) 0.91 V (b) 1.40 V E o Zn / Zn   is –0.74 volts [AMU 2002]
(c) 1.68 V (d) 0.63 V (a) 0. 38 volts (b) 0.83 volts
(c) 0.40 volts (d) 0.45 volts
119. Cr2 O72   I   I2  Cr 3  128. Which of the following expression is correct
[Orissa JEE 2005]
E 0
cell  0.79 V
(a) G o  nFEcell
o
(b) G o  nFEcell
o

0
ECr 2  1.33 V , E 0 I2 is [BVP 2004] (c) G o  2.303 RT nFEcell o
(d) G o  nF log K C
2 O7

129. For the feasibility of a redox reaction in a cell, the e.m.f. should be[J & K 2002]
(a) 0.10 V (b) 0.18 V (a) Positive (b) Fixed
(c) 0.54 V (d) 0.54 V (c) Zero (d) Negative

120. Zn(s)  Cl 2 (1 atm)  Zn 2   2Cl  . E 0 cell of the cell is 2.12 V. Corrosion

To increase E [BVP 2004]
1. Corrosion is basically a [Kerala (Med.) 2002]
(a) [ Zn 2 ] should be increased (a) Altered reaction in presence of H 2 O
(b) [ Zn 2 ] should be decreased (b) Electrochemical phenomenon
(c) Interaction
(c) [Cl  ] should be decreased (d) Union between light metal and heavy metal
2. Rusting of iron is catalysed by which of the following
(d) PCl 2 should be decreased [MNR 1990; UPSEAT 2001]
0 (a) Fe (b) O 2
121. The E M 3  / M 2 values for Cr, Mn, Fe and Co are
0.41,  1.57,  0.77 and 1.97 V respectively. For which one (c) Zn (d) H 
of these metals the change in oxidation state from 2 to 3 is 3. Which of the following is a highly corrosive salt
easiest [AIEEE 2004] [AFMC 2005]

(a) Fe (b) Mn (a) FeCl2 (b) PbCl2

(c) Cr (d) Co (c) Hg2 Cl 2 (d) HgCl2
122. The rusting of iron takes place as follows 4. Corrosion of iron is essentially an electrochemical phenomenon
where the cell reactions are [KCET 2005]
2H + +
2e
+ ½O  H O(l) ;
Fe is oxidised to Fe 2  and dissolved oxygen in water is
2 2

E° = +1.23 V (a)

Fe + 2e  Fe(s) ; E° = 0.44 V
2+

reduced to OH
Calculate G° for the net process [IIT 2005]
(b) Fe is oxidised to Fe 3  and H 2 O is reduced to O 22 
(a) 322 kJ mol (b) 161 kJ mol
1 1

(c) 152 kJ mol  (d) 76 kJ mol

1 1
(c) Fe is oxidised to Fe 2  and H 2 O is reduced to O 2
123. When an acid cell is charged, then [AFMC 2005]
(a) Voltage of cell increases (d) Fe is oxidised to Fe 2  and H 2 O is reduced to O 2
(b) Electrolyte of cell dilutes
(c) Resistance of cell increases
(d) None of these
124. The standard electrode potential is measured by
[KCET 2005]
(a) Electrometer (b) Voltmeter
(c) Pyrometer (d) Galvanometer
125. Aluminium displaces hydrogen from acids but copper does not. A 1. The limiting molar conductivities  0 for NaCl, KBr and KCl are 126,
galvanic cell prepared by combining Cu / Cu 2  and Al / Al 3  has 152 and 150 S cm 2 mol 1 respectively. The  0 for NaBr is
an e.m.f. of 2.0 V at 298 K. If the potential of copper electrode is +
0.34 V, that of aluminium is (a) 278 S cm 2 mol 1 (b) 176 S cm 2 mol 1
[CPMT 2001; KCET 2001]
(a) + 1.66 V (b) – 1.66 V (c) 128 S cm 2 mol 1 (d) 302 S cm 2 mol 1
(c) + 2.34 V (d) – 2.3 V 2. On the basis of the electrochemical theory of aqueous corrosion, the
reaction occurring at the cathode is
126. If the standard electrode potential of Cu 2 / Cu electrode is
0.34V, what is the electrode potential of 0.01M concentration of [MP PET 1994; UPSEAT 2001]

Cu 2  (T  298 K) [EAMCET 2003] (a) O2 (g)  4 H (aq ) 

 4 e  2 H 2 O(l)
(a) 0.399 V (b) 0.281 V (b) Fe(s)  Fe(2aq )  2e 
(c) 0.222 V (d) 0.176 V
(c) Fe(2aq )  Fe(3aq )  e 
 524 Electrochemistry

(d) H 2(g)  2OH(aq )  2 H 2 O(l)  2e  (a) 5.49  107 C of electricity

3. The reaction 1
H 2 (g)  AgCl(s)  H  (aq)  Cl  (aq)  Ag(s) (b) 1.83  10 7 C of electricity
2
occurs in the galvanic cell (c) 5.49  10 4 C of electricity
[IIT 1985; AMU 2002; KCET 2003] (d) 5.49  101 C of electricity
(a) Ag / AgCl(s) KCl (soln) || AgNO3 (soln) / Ag
11. Electrolyte : KCl KNO3 HCl NaOAc NaCl
(b) Pt / H 2 (g) HCl (soln) || AgNO3 (soln) / Ag  (Scm mol
 2 –1) : 149.9 145.0 426.2 91.0 126.5
(c) Pt / H 2 (g) HCl (soln) || AgCl (s) / Ag Calculate HOAc using appropriate molar conductances of the
(d) Pt / H 2 (g) KCl (soln) || AgCl (s) / Ag electrolytes listed above at infinite dilution in H 2 O at 25°C[AIEEE 2005]
o (a) 517.2 (b) 552.7
4. The standard reduction potential E for the half reactions are as
2  (c) 390.7 (d) 217.5
Zn  Zn  2e ; E  0.76 V
o
12. The mass of carbon anode consumed (giving only carbondioxide) in
Fe  Fe 2   2e  ; E o  0.41 V the production of 270kg of aluminium metal from bauxite by the
Hall process is [CBSE PMT 2005]
The EMF for cell reaction Fe 2   Zn  Zn 2   Fe is (a) 180kg (b) 270kg
[IIT 1988; CBSE PMT 1993, 96; BHU 1995, 2000; (c) 540kg (d) 90kg
CPMT 2000; KCET 2000; AIIMS 2001; Orissa JEE 2002] 13. 4.5g of aluminium (at mass 27amu) is deposited at cathode from
(a)  0.35 V (b)  0.35 V Al 3  solution by a certain quantity of electric charge. The volume
of hydrogen produced at STP from H  ions in solution by the
(c)  1.17 V (d)  1.17 V same quantity of electric charge will be
5. The number of electrons to balance the following equation [CBSE PMT 2005]
(a) 22.4 L (b) 44.8 L
NO 3  4 H   e   2 H 2 O  NO is [IIT Screening 1991] (c) 5.6 L (d) 11.2 L
(a) 5 (b) 4 14. What amount of Cl gas liberated at anode, if 1 amp. current is
2

passed for 30 min. from NaCl solution.

(c) 3 (d) 2 [BHU 2005]
6. The standard EMF for the given cell reaction (a) 0.66 moles (b) 0.33 moles
2 2 (c) 0.66 g (d) 0.33 g
Zn  Cu  Cu  Zn is 1.10 V at 25 o C . The EMF for
the cell reaction, when 0.1M Cu 2  and 0.1M Zn 2  solutions are
used, at 25 o C is
[MNR 1994; AMU 1999; UPSEAT 2002]
(a) 1.10 V (b) 0.110 V
(c) 1.10 V (d)  0.110 V Read the assertion and reason carefully to mark the correct option out of
the options given below :
7. A gas X at 1 atm is bubbled through a solution containing a
(a) If both assertion and reason are true and the reason is the correct
mixture of 1 M Y  and 1 M Z  at 25 o C . If the reduction explanation of the assertion.
potential of Z  Y  X , then [IIT 1999] (b) If both assertion and reason are true but reason is not the correct
explanation of the assertion.
(a) Y will oxidize X and not Z (c) If assertion is true but reason is false.
(b) Y will oxidize Z and not X (d) If the assertion and reason both are false.
(c) Y will oxidize both X and Z (e) If assertion is false but reason is true.
(d) Y will reduce both X and Z 1. Assertion : Sodium ions are discharged in preference to
8. The oxidation potential of a hydrogen electrode at pH = 10 and hydrogen ions at a mercury cathode.
pH 1  1 [JIPMER 2000] Reason : The nature of the cathode can effect the order of
discharge of ions.
(a) 0.059 V (b) 0.59 V 2. Assertion : In electrolysis, the quantity of electricity needed
(c) 0.00 V (d) 0.51 V for depositing 1 mole of silver is different from
that required for 1 mole of copper.
9. The decomposition of hydrogen peroxide is an example of Reason : The molecular weights of silver and copper are
[Roorkee 2000] different
(a) Exothermic reaction (b) Endothermic reaction 3. Assertion : Equivalent conductance of all electrolytes
(c) Negative catalysis (d) Auto-oxidation decreases with the increases in concentration.
Reason : Lesser number of ions are available per gram
10. Aluminium oxide may be electrolysed at 1000°C to furnish equivalent at higher concentration.
aluminium metal (At. Mass = 27 amu; 1 Faraday = 96,500 4. Assertion : Copper reacts with hydrochloric acid and
Coulombs). The cathode reaction is liberates hydrogen from the solution of dilute
Al3  3e   Al hydrochloric acid.
Reason : Hydrogen is below copper in the electrochemical
To prepare 5.12kg of aluminium metal by this method would series.
require [AIEEE 2005]
 Electrochemistry 525
5. Assertion : Copper liberates hydrogen from a solution of dil. Reason : The E 0 of zinc is 0.76 V and that of copper
HCl.
Reason : Hydrogen is below copper in the reactivity series. is 0.34 V .
6. Assertion : Zn metal is formed when a Cu plate in dipped in 22. Assertion : Identification of cathode and anode is done by
ZnSO 4 solution. the use of a thermometer.
Reason : Cu being placed above Zn in electrochemical Reason : Higher is the value of reduction potential, greater
series. would be its reducing power.
7. Assertion : Electrical conductivity of copper increases with 23. Assertion : An electrochemical cell can be set up only if the
increase in temperature. redox reaction is spontaneous.
Reason : The electrical conductivity of metals is due to the Reason : A reaction is spontaneous if free energy change is
motion of electrons. negative.
8. Assertion : A small amount of acid or alkali is added before 24. Assertion : Galvanised iron does not rust.
electrolysis of water. Reason : Zinc has a more negative electrode potential than
Reason : Pure water is weak electrolyte. iron. [AIIMS 2005]
9. Assertion : Copper reacts with HCl and liberates hydrogen. 25. Assertion : In an electrochemical cell anode and cathode are
Reason : Hydrogen is present above Cu in the reactivity respectively negative and positive electrodes.
series. Reason : At anode oxidation takes place and at cathode
10. Assertion : K and Cs are used in photoelectric cells. reduction takes place.
Reason : K and Cs emit electrons on exposure to light.
11. Assertion : A large dry cell has high e.m.f. 26. Assertion : Ni / Ni 2 (1.0 M )|| Au 3  (1.0 M )| Au , for this
Reason : The e.m.f. of a dry cell is proportional to its size.
12. Assertion : The resistivity for a substance is its resistance when cell emf is 1.75 V if E oAu 3  / Au  1.50 and
its is one meter long and its area of cross section is
one square meter.
o
E Ni 2
/ Ni
 0.25 V .
Reason : The SI uints of resistivity are ohm metre
Reason : Emf of the cell  Ecathode
o
 Eanode
o
.
( m ) and ohm centimeter ( cm) .
13. Assertion : When acidified zinc sulphate solution is 27. Assertion : Salts like KCl , KNO 3 i.e., inert electrolytes are
electrolysed between zinc electrodes, it is zinc used in salt bridge.
that is deposited at the cathode and hydrogen Reason : An inert electrolyte can easily be filled in the U-
evolution does not take place. tube.
Reason : The electrode potential of zinc is more negative 28. Assertion : Emf and potential difference are same for cell.
than hydrogen as the overvoltage for the Reason : Both gives the difference in electrode potential
hydrogen as the evolution on zinc is quite large. under any condition.
14. Assertion : If 0Na   0Cl  are molar limiting conductivity of
the sodium and chloride ions respectively, then
the limiting molar conducting for sodium
chloride is given by the equation:
 NaCl   Na   Cl  .
0 0 0

Reason : This is according to Kohlrausch law of

independent migration of ions.
15. Assertion : One coulomb of electric charge deposits weight
equal to the electrochemical equivalent of the Electrolytes and Electrolysis
substance.
Reason : One Faraday deposits one mole of the substance.
16. Assertion : Auric chloride ( AuCl3 ) solution cannot be 1 b 2 d 3 c 4 c 5 d
stored in a vessel made of copper, iron, nickel, 6 d 7 b 8 b 9 b 10 a
chromium, zinc or tin.
Reason : Gold is a very precious metal. 11 a 12 c 13 d 14 d 15 c
17. Assertion : For a cell reaction Zn(s)  Cu 2  (aq)  16 d 17 a 18 c 19 c 20 a
2
Zn (aq)  Cu (s) ; at the equilibrium, 21 a 22 b 23 b 24 d 25 b
voltmeter gives zero reading.
Reason : At the equilibrium, there is no change in the 26 b 27 b 28 a 29 c 30 b
concentration of Cu 2  and Zn 2  ions. 31 d 32 d 33 c 34 b 35 b
18. Assertion : A negative value of standard reduction potential
means that reduction take place on this electrode 36 a 37 d 38 c 39 d 40 a
with reference to standard hydrogen electrode.
Reason : The standard electrode potential of a half cell has 41 a
a fixed value.
19. Assertion : Weston is a standard cell.
Reason : Its e.m.f. does not change with temperature. Faraday’s law of electrolysis
20. Assertion : Galvanic cells containing hydrogen, methane,
methanol etc. as fuels are called fuel cells.
1 c 2 a 3 b 4 c 5 c
Reason : They are designed to convert the energy of
combustion of fuels directly into electrical 6 c 7 c 8 b 9 c 10 a
energy.
21. Assertion : Zinc displaces copper from copper sulphate 11 c 12 a 13 c 14 b 15 b
solution.
 526 Electrochemistry
16 c 17 a 18 a 19 d 20 c 16 a 17 a 18 c 19 b 20 b
21 d 22 c 23 b 24 d 25 a 21 a 22 b 23 a 24 c 25 a
26 d 27 a 28 d 29 c 30 a 26 a 27 c 28 a 29 d 30 d
31 b 32 b 33 a 34 b 35 b 31 b 32 a 33 d 34 a 35 c
36 b 37 b 38 b 39 a 40 a 36 d 37 a 38 b 39 d 40 d
41 c 42 a 43 a 44 b 45 c 41 b 42 c 43 a 44 b 45 b
46 b 47 d 48 d 49 b 50 a 46 d 47 c 48 b 49 c 50 b
51 c 52 b 53 b 54 a 55 c 51 b 52 a 53 a 54 c 55 a
56 c 57 c 58 d 59 d 60 d 56 a 57 a 58 a 59 c 60 a
61 c 62 c 63 b 64 a 65 b 61 b 62 d 63 a 64 d 65 b
66 b 67 a 68 a 69 b 70 c 66 c 67 b 68 b 69 a 70 b
71 c 72 b 73 a 74 b 75 c 71 b 72 ab 73 c 74 c 75 a
76 b 77 c 78 c 79 b 80 b 76 d 77 b 78 c 79 b 80 a
81 c 82 b 83 a 84 c 85 c 81 a 82 b 83 b 84 c 85 a
86 e 87 b 88 a 89 d 90 c 86 c 87 a 88 c 89 c 90 b
91 c 92 a 93 c 94 b 91 d 92 c 93 d 94 a 95 d
96 a 97 d 98 a 99 b 100 d
Conductor and Conductance 101 a 102 c 103 a 104 a 105 d

1 b 2 b 3 d 4 d 5 a 106 b 107 a 108 b 109 a 110 a

6 b 7 b 8 a 9 b 10 d 111 a 112 b 113 b 114 b 115 b

11 a 12 b 13 b 14 b 15 b 116 b 117 d 118 a 119 d 120 b

16 d 17 b 18 d 19 b 20 c 121 c 122 a 123 a 124 b 125 b

21 b 22 a 23 c 24 d 25 a 126 b 127 b 128 a 129 a
26 b 27 d
Corrosion
Cell constant and Electrochemical cells 1 b 2 d 3 d 4 a

1 d 2 d 3 d 4 b 5 b
Critical Thinking Questions
6 a 7 c 8 c 9 b 10 b
11 c 12 c 13 a 14 a 15 d 1 c 2 a 3 c 4 b 5 c

16 c 17 c 18 a 19 b 20 b 6 a 7 a 8 b 9 acd 10 a

21 b 22 b 23 a 24 b 25 c 11 c 12 d 13 c 14 c

26 a 27 c 28 a 29 b 30 c
Assertion & Reason
31 a 32 b 33 c 34 b 35 d
36 b 37 c 38 d 39 b 40 d 1 a 2 b 3 a 4 d 5 d
41 a 42 d 43 c 44 a 45 d 6 d 7 e 8 a 9 e 10 a
46 a 47 d 48 b 49 c 50 c 11 d 12 b 13 a 14 a 15 c
51 b 52 d 53 c 54 a 55 c 16 b 17 a 18 e 19 a 20 a

56 d 57 b 58 a 59 a 60 c 21 a 22 d 23 b 24 a 25 a

61 a 26 a 27 c 28 d

Electrode potential, ECell, Nernst equation and ECS

1 b 2 a 3 a 4 b 5 d
6 c 7 c 8 a 9 a 10 b
11 a 12 c 13 a 14 d 15 c
 Electrochemistry 529
32. (d) The degree of ionization depend upon the nature of the solute
the size of the solute molecules and the concentration of the
solution.
33. (c) C12 H 22 O11 is an non-electrolyte.
34. (b) On electrolysis molten ionic hydride liberate H 2 at the anode.
35. (b) During electrolysis cation discharged at cathode and anion
discharged at anode.
Electrolytes and Electrolysis 36. (a) Calcium is produces when molten anhydrous calcium chloride
is electrolysed.
37. (d) All metals conducts heat and electricity.
1. (b) Sugar solution does not form ion; hence does not conduct
electricity in solution. 38. (c) 2 Al  dil. H 2 SO 4  Al2 SO 4  H 2  .
3. (c) Strong electrolytes are almost completely ionised in polar 39. (d) Generally fussed potassium chloride flow the electric
solvent. conductivity.
7. (b) The reduction potential of Mg is less than that of water 41. (a) The substances whose aqueous solutions allow the passage of
electric current and are chemically decomposed, are termed
(E  0.83 V ) . Hence their ions in the aqueous solution
o
electrolytes. Electrolytic substances are classified as strong or
cannot be reduced instead water will be reduced weak according to how readily they dissociate into conducting
2 H 2O  2e   H 2  2OH  . ions. Acetic acid is a weak electrolyte. Glucose, ethanol and
urea are non-electrolytes.
8. (b) HCl is an electrolyte.
9. (b) Water is reduced at the cathode and oxidized at the anode
Faraday's law of electrolysis
instead of Na  and SO 42  .
Cathode: 2 H 2O  2e   H 2  2OH  1. (c) Ag   e   Ag; E Ag 
Atomic Mass
 108
1 1
Anode : H 2O  2 H   O2  2 e  . W Ag
2 108
Number of faraday   1.
10. (a) In electrolysis process oxidation occurs at anode and reduction E Ag 108
occurs at cathode.
11. (a) Because in it covalent bonding is present. E Ag  Q 108  9 .65
2. (a) WAg  
12. (c) According to Faraday’s law. 96500 96500
13. (d) Impure metal made anode while pure metal made cathode.
14. (d) In electrolytic cell, cathode acts as source of electrons.  1.08  10 2 gm  10.8 mg
15. (c) AgNO3 is an electrolyte. 56
3. (b) Fe 2   2e   Fe; E Fe   28

17. (a) At cathode: 2 H  2e  H 2 , 2
1 WFe  E Fe × Number of faraday  28  3  84 gm .
At anode : 2OH   H 2 O  O 2  2e
2 E Ag  Q 107.87  965
4. (c) W Ag    1 .0787 gm .
18. (c) In between dilute H 2 SO 4 and platinum electrode O 2 gas 96500 96500
evolve at anode. 5. (c) Al 3   3e   Al
19. (c) When polar solvent added in to solid electrolyte than it is
ionised. 27
E Al  9
20. (a) In fused NaCl chloride ions are oxidized at anode and it is 3
called oxidation. WAl  E Al  No. of faradays  9  5  45 gm .
21. (a) w  zit, Q  it .
6. (c) Cu voltameter or Cu or Ag coulometer are used to detect the
22. (b) 2 H   2e   H 2(g) at cathode. amount deposited on an electrode during passage of know
charge through solution.
23. (b) Na   e   Na , means oxidation number is decreased so Weight of Cu Eq. weight of Cu
1 0
8. (b) 
the reaction is reduction. Weight of H 2 Eq. weight. of H
24. (d) Degree of dissociation of weak electrolyte increases on
increasing temperature. Weight of Cu 63.6 / 2

25. (b) Since discharge potential of water is greater than that of 0 .50 1
sodium so water is reduced at cathode instead of Na  Weight of Cu  15.9 gm.
1
Cathode: H 2 O  e   H 2  OH  9. (c) Cu 2   2e   Cu
2
2 Faradays will deposit  1 g atom of Cu  63.5 g .
1
Anode: Cl  Cl 2  e  .

2 12. (a) At cathode; Al 3   3e   Al
26. (b) Because it does not have ions. 27
E Al  9
27. (b) NaCl ⇌ Na   Cl  . 3
W Al  E Al  No. of faradays  9  0.1  0.9 gm .
28. (a) Cathode: 2 H 2 O  2e   H 2  2OH 
32.69  5  60  40
1 14. (b) W  zit ; W   4.065 gm .
Anode : H 2 O  2 H   O 2  2e  . 96500
2
29. (c) Electrolysis use for electroplating and electrorefining. 15. (b) m  Z  4  120 ; M  Z  6  40
 530 Electrochemistry
M 6  40 1 ECl2  I  t 35.5  2  30  60
  ; M m/2. WCl2    1.32 gm .
m 4  120 2 96500 96500
E  I  t E  3  50  60 34. (b) It is Faraday’s law.
16. (c) Wmetal  
96500 96500 35. (b) Equivalent wt. of O 2 = Equivalent wt. of Cu
96500  w 96500  1 .8 36. (d) O 2 %  20%
E   19.3 .
3  50  60 3  50  60 80
Metal %  80%   8  32 g of metal .
17. (a) Al  Al 3   3e  . 20
The charged obtained is 3  96500 C . 827  10 3
37. (b) V  2 .14 V .
18. (a) Wt.of Ag deposited  Eq. wt of Ag  108 gm 4  96500
Wt.of Ni deposited  Eq. wt . of Ni  29.5 gm 38. (b) Ag   e
 Ag, 96500 C will liberate silver =108 gm.
Wt. of Cr deposited  Eq. wt . of Cr  17.3 gm . 9650C will liberate silver = 10.8 gm.
19. (d) One Faraday  1 gm of equivalent of Cu . 39. (a) One mole of monovalent metal ion means charge of
N electron i.e. 96500 C or 1 Faraday.
E 42. (a) 1 Faraday involves charge of 1 mole electrons.
20. (c) W  Zit ; Z  .
96500 43. (a) Coulomb = ampere (A) × second (S).
21. (d) During electrolysis of CuSO 4 . Cu 2  gets discharged at 44. (b)
13.6
E   2 for He  n  1
n
cathode and OH  at anode. Thus solution becomes acidic due
13.6
to excess of H  and SO 42  or H 2 SO 4 . E   2  13.6 eV .
1
23. (b) 1 mole of electrons  1 faraday 45. (c) w  E if i and t are constant.
 
Mg  2e  Mg ; 2 moles of electrons  2 faraday . 47. (d) Charge (Coulombs) pass per second  10 6
 number of electrons passed per second
24. (d) Cu  2e   Cu
10 6
63.54   6 .24  10 12 .
E Cu   31.77 1 .602  10 19
2
48. (d) At cathode;
Amount of electricity required to deposit .6354 gm of Cu
96500  0.6354 Fe 2  2e   Fe ; Fe 3   3e   Fe
  1930 Coulombs . Atomic.weight Atomic.weight
31.77 (E Fe )1  ; (E Fe )2 
25. (a) The amount deposited is directly proportional to current 2 3
intensity, electrochemical equivalent of ions and the time for Ratio of weight of Fe liberated
electrolysis and is independent of the temperature. Atomic weight Atomic weight
27. (a) W  ZQ ; W  Zit .  : 3 : 2 .
3 2
28. (d) Ca   2e   Ca 49. (b) 31.75 g copper gets deposited at cathode on passing 96500
coulomb charge. We know that 31.75 gm of Cu is equal to 0.5
40
E Ca   20 mole of Cu deposited at cathode on passing 1F of current.
2 52. (b) For deposition of one equivalent silver required charged is
WCa  ECa × No. of faradays  20  0.04  0.8 gm . 96500 C.
Weight of metal  96500 63.55
29. (c) E metal  53. (b) Cu   2e   Cu ; ECu   31.75 gm Cu .
Number of coulombs 2
54. (a) Q  2.5  386  96500 C
22.2  96500
  59.5 2 F(2  96500C) deposited Cu  63.5 g
2  5  60  60
177 Hence 965 C will deposited; Cu  0.3175 gm .
Oxidation number of the metal   3
59.5 Wt.of Cu Eq. wt.of Cu Wt. of Cu 63.5 / 2
25 55. (c)  ; 
30. (a) Quantity of electricity passed =  60  1 .5 Wt.of Ag Eq. wt.of Ag 1.08 108
1000
Wt. of Cu  0.3177 gm .
2 F  2  96500 C deposit Ca  1mole
56. (c) 1 g atom of Al = 3 equivalent of Al  3 faraday charge
1 3 mole electrons = 3 N electron.
 1.5 C will deposit Ca   1.5 mole
2  96500 57. (c) At cathode : Al 3   3e   Al
1 Atomic mass
  1.5  6.023  10 23 atom  4.68  10 18 . E Al 
2  96500 3
31. (b) Equivalent of Cl deposited At cathode : Cu 2  2e   Cu
= No. of Faraday passed = 0.5
Wt. of Cl  0.5  Eq. wt .  0.5  35.5  17.75 gm . Atomic mass
E Cu 
2
1
32. (b) At Andoe At Anode Cl   Cl 2  e  At cathode : Na   e   Na
2
Atomic mass
35.5  2 E Na 
ECl 2   35.5 1
2
For the passage of 3 faraday;
 Electrochemistry 531
mole atoms of Al deposited = 1 83. (a) Na   e   Na
1 3 Charge (in F) = moles of e used = moles of Na deposited
mole atoms of Cu deposited   1.5
–

2 11.5
mole atoms of Na deposited  1  3  3 .  gm  0 .5 Faraday.
23
58. (d) At cathode: Ag   e   Ag
84. (c) Hydrolysis of water : 2 H 2 O ⇌ 4 H   4 e   O 2
1
At Anode: 2OH   H 2 O  O 2  2e  4 F charge will produce = 1 mole O 2  32 gm O 2
2
1 32
 32 1 F charge will produce   8 gm O 2 .
108 4
E Ag   108; E O2  2 8
1 2 85. (c) In a galvanic cell, the electrons flow from anode to cathode
through the external circuit. At anode (–ve pole) oxidation and
W Ag WO2 1 .6  108
 ; W Ag   21.6 gm . at cathode (+ pole) reduction takes place.
E Ag E O2 8 86. (e) Number of equivalents of silver formed = Number of
59. (d) KI is an electrolyte. equivalents of copper formed.
60. (d) Number of gm equivalent = Number of faraday pass In AgNO3 , Ag is in +1 oxidation state.
4 gm = 4 faraday.
13.5 In CuSO 4 , Cu is in +2 oxidation state.
61. (c) Eq. of Al =  1.5 .
27/3 108
Equivalent weight of Ag =  108
Thus 1.5 Faraday is needed. 1
63. (b) Electricity required 63.6
= No. of gm equivalent  96500 coulombs Equivalent weight of Cu   31.8
2
= 0.5  96500 = 48250 C.
M1 E 10.79 108
64. (a) Equivalent weight of silver = 107.870 g.  1 ; 
1 Faraday = 96500 coulomb. M 2 E2 M Cu 31.8
67. (a) Equivalent weight and atomic weight of Na metal are the same, 10.79  31.8
so 1g atom of Na is deposited by one Faraday of current. M Cu   3.2 gm .
108
68. (a) Al  Al 3   3e  . 87. (b) Laws of electrolysis were proposed by Faraday.
70. (c)  1F obtained from 1 g equivalent 88. (a) Given, Current (i) = 25 mA = 0.025 A
 2.5 F obtained from 2.5 g equivalent. Time (t) = 60 sec
75. (c) Faraday constant depends upon the current passed. Q = i t  60  0.025  1.5 coulombs
80. (b) In 5 gm CuO, 4 gm Cu and 1 gm O be present.
1 .5  6 .023  10 23
No. of electrons 
Element Wt. At Wt. Wt. / At.Wt.  x Ratio 96500
Cu 4 gm 63.5 4/63.5=.0625 .0625
1
e   9.36  10 18
.0625 Ca  Ca 2  2e 
O 1 gm 16 1/16 =.0625 .0625
1 2e  are required to deposite one Ca atom
.0625
9 .36  1018
9.36  10 18 e  will be used to deposite 
Emperical formula = CuO of oxide 2
In this oxide, oxidation no. of Cu  2  4.68  10 18 .
Molecular weight 63.5 (d) C 6 H 5 NO 2  6 H   6 e   C 6 H 5 NH 2  2 H 2 O
Equivalent weight    31.75 89.
Oxidation no. 2 1 mole = 123 gm nitrogen requires 6 mole electron e
but Equivalent weight should be an integeral no. = 32
 6  96500 coulomb charge
81. (c) Given, Current = 241.25 columb
6  96500  12.3
1 coulomb current will deposite  1.118  10 3 gm Ag .  12.3 gm nitrobenzene will require 
123
 241.25 current will deposite = 1.118  10 3  241.25  6  9650  57900 C.
 0.27 gm silver. 90. (c) Au and Ag settle down below the anode as anode mud during
82. (b) Reaction for electrolysis of water is the process of electrolytic refining of copper.

2 H 2 O ⇌ 4 H   2O 2  Conductor and Conductance

2 
2O  O2  4 e
1  2
4 e  4 H   2H 2
 2. (b)   BaCl2   Ba    Cl 
2
 n  4 so 4 Faraday charge will liberate 127
  76  139.5 ohm 1 cm 1 eq 1 .
1 mole  22.4 dm oxygen
3
2
3. (d) Dilution, temperature and nature of electrolyte affect the
22.4
 1 Faraday charge will liberate  5 .6 dm 3 O 2 . conductivity of solution.
4 5. (a) Generally strong electrolyte on dilution shows conductivity
characters.
 532 Electrochemistry
1000 6. (a) Because the reduction potential of Cu is highest.
6. (b) Molar conductivity = .
MX 7. (c) Overall reaction - 2 H 2(g)  O 2(g)  2 H 2 O(l) .
K[ A] A C l Sm 9. (b) During charging of a lead storage battery, the reaction at the
7. (b) C  ,K   Sm 2 mol 1 . anode and cathode are
l [ A] A mol m 3 m 2
9. (b) Conductivity of a solution is directly proportional to the Anode: PbSO 4  2e   Pb  SO 42
number of ions. Cathode: PbSO 4  2 H 2 O  PbO2  4 H   SO 42  2e 
 
11. (a) NaCl ⇌ Na  Cl . So it conduct electricity. In both the reactions H 2 SO 4 is regenerated.
12. (b) Graphite is a good conductor of electricity.
15. (b) Electrolytic conduction resistance decreases with increasing 11. (c) 2 NH 4 Cl  Zn  2 NH 3  ZnCl 2  H 2  .
temperature. 13. (a) When platinum electrodes are dipped in dilute solution
16. (d) Because conductance is increase when the dissociation is more. H 2 SO 4 than H 2 is evolved at cathode.
17. (b) Strong electrolyte ionize completely at all dilutions and the 14. (a) Electrode on which oxidation occurs is written on L.H .S . and
number of ions does not increase on dilution. A small increase
the other on the R.H .S . as represented by
in  m volume with dilution is due to the weakening of
electrostatic attraction between the ions on dilution. Zn | Zn 2  || Cu 2  | Cu .
18. (d) In electrolytic conductors, a single stream of electrons flow Reduction
from cathode to anode.
15. (d) Zn 2  2e   Zn . It shows reduction reaction.
19. (b) In solid state NaCl does not dissociate into ions so it does not 16. (c) In the electrolytic cell electrical energy change into chemical
conduct electricity. energy.
20. (c) The ions are not free to move in solid state and held up in
lattice due to strong coulombic forces of attraction. 17. (c) In the cell Zn | Zn 2 || Cu 2 | Cu the negative electrode
21. (b) C 2 H 5 OH being non electrolyte so does not ionize. (anode) is Zn. In electrochemical cell representation anode is
always written on left side while cathode on right side.
1 18. (a) Galvanic cell converts the chemical energy into electrical
22. (a) Since molar conductance  . energy.
Molarity
19. (b) Fuel-cells are used to provide power and drinking water to
1 astronauts in space programme.
23. (c) Molar condcutivity 
M 2.303 RT 0.0591
21. o
(b) E cell  log K  log K c at 298 K .
So its unit will be  1 cm 2 mol 1 . nF n
25. (a) l / a  0.5 cm 1 , R  50 ohm 22. (b) Cu 2  2e   Cu
Ra 50 Reduction
p   100
l 0 .5 24. (b) The cell in which Cu and Zn roads are dipped in its solutions
called Daniel cell.
1000 1 1000 1 1000
k     K 0.2
N p N 100 1 25. (c) K  C  Cell constant    5 cm 1 .
C 0 .04
1 2 1
10 ohm cm gm eq K
26. (a)  Cell Constant .
26. (b) om (C6 H 5 COOH )  o(C   o(H  ) C
6 H 5 COO )

 42  288.42  330.42 27. (c) Velocities of both K  and NO 3 are nearly the same in
c 12.8 KNO 3 so it is used to make salt-bridge.
  om   3 .9% 28. (a) In this reaction 4 electrons are needed for the reaction volume.
m 330 .42
29. (b) In electrochemical cell H 2 release at anode and Cu is deposit
1 1
27. (d) Conductance    ohm 1 or mho at the cathode.
resistance ohm 31. (a) Anode has negative polarity.
32. (b)  mo (CH 3 COOH ) 
Cell constant and Electrochemical cells  o (CH 3 COONa )   o (HCl)   o (NaCl)
1. (d) In the absence of electric field the ions in the solution move  91  426.16  126.45  390.71 ohm 1 cm 2 mol 1 .
randomly due to thermal energy.
36. (b) At anode: Zn(s)  Zn 2  2e  .
2. (d) Since E oA / A  has large negative value, the tendency of A to be
38. (d) PbSO 4  2 H 2 O  2 PbO2  4 SO 4   2e  .
reduced to A  is very small. In other words tendency of
39. (b) MnO2 is used in dry batteries cell.
A  to be oxidized to A is very large.
3. (d) Practically only 60-70% efficiency has been attained. 40. (d) Pb  PbO2  2 H 2 SO 4 Discharge
2 PbSO 4  2 H 2 O .
Recharge
1 Sulphuric acid is consumed on discharging.
4. (b) K   Cell constant
R 42. (d) The metal placed below in electrochemical series does not react
1
with that metal salt solution which metal is placed above in
Cell constant  K  R ; 0.012  55  0.66 cm . series.
5. (b) In common dry cell. 43. (c) In the electrochemical cell chemical energy changes into
  electrical energy.
Anode : Zn  Zn  2e 44. (a) In galvanic cell, the salt bridge used to complete the circuit.
Cathode: 2 MnO2  Zn   2e   ZnMn2 O4 .
 Electrochemistry 533

45. (d) Cu  FeSO 4  No reaction Because Cu has E o  0.34 2 .303 RT 1

EH  log 
F [H ]
volt and Fe has E   0.44 volt.o

47. (d) Calomel electrode as reference electrode is made by using  0.059 pH  0.059  3  0.177 V .
Hg 2 Cl 2 . 2. o
(a) Ecell  Ecathode
o
 Eanode
o
= 0.799  (0.763)  1.562 V
48. (b) In hydrogen–oxygen fuel cell following reactions take place to 3. (a) More negative is the reduction potential, higher will be the
create potential difference between two electrodes. reducing property, i.e. the power to give up electrons.
2 H 2 (g)  4 OH  (aq )  4 H 2 O(l)  4 e  4. (b) Standard potential of Zinc < Copper.
6. (c) A cation having highest reduction potential will be reduced
O 2 (g)  2 H 2 O(l)  4 e   4 OH  (aq ) first and so on. However, Mg 2  in aqueous solution will not
Overall reaction = 2 H 2 (g)  O 2(g)  2 H 2 O(l)  0 
the net reaction is the same as burning (Combustion) of be reduced  E Mg 2 E  . Instead water
 / Mg H 2O / H 2 OH 
1 
hydrogen to form water.  2 
49. (c) Cl CH 2 COONa  HCl  ClCH 2 COOH  NaCl would be reduced in preference.
ClCH 2COONa   HCl  ClCH COOH  NaCl 7. (c) A is displace from D because D have a E o  0.402 V .
2

224  203  ClCH 2COOH  38.2 Reduction

o o
1 1
ClCH 2COOH  427  38.2  388.8 ohm cm gmeq . 2
8. (a) Zn(s)  2 Ag(aq )  Zn(2aq )  2 Ag(s)
50. (c) In daniel cell copper rod acts as cathode so there cations move
towards copper electrode and reduction take place on copper Oxidation
rod. In this reaction zinc act as a anode and Ag act as a cathode.
51. (b) Elements with lower reduction potential act as anode. His 9. (a) No doubt Be is placed above Mg in the second group of
placed above Cu in electrochemical series so it has lesser
periodic table but it is below Mg in electrochemical series.
reduction potential and thus act as anode and Cu act as
cathode. 10. (b) Nernst’s equation shows relation between E and E o .
52. (d) Fuel cells are more efficient as they are free from pollution and
RT 1 RT
hence they run till the reactants are active. They have longer 11. (a) E  Eo  ln ; E  Eo  ln[M n  ]
life than lead storage cells. nF [M n  ] nF
53. (c) For gold plating, the used electrolyte is KAu(CN )2  . 2.303 RT
E  Eo  log[M n  ]
54. (a) Dil. H 2 SO 4 is used in lead in lead storage battery as nF
electrolyte. Substituting the value of R, T (298K) and F we get
Specific conductivity 0.0591
55. (c) Cell constant  E  Eo  log(M n  ) .
Observed conductance n
0 .002765 12. (c) At 298 K standard electrode potential of NHE electrode is
 =0 .002765  400  1.106 . 0.00 V.
1/R
57. (b) 2AgCl + H  2HCl + 2Ag 13. (a) Since, Ag  ions are reduced to Ag and
( s) 2(g) (aq.) (s)

The activities of solids and liquids are takes as unity and at low E oAg  / Ag  ECu
o
 Cu is oxidized to Cu   .
concentrations, the activity of a solute is approximated to its / Cu

molarity. 14. (d) The reducing power decreases as the reduction potential
Th cell reaction will be increase (becomes less negative).
Pt | H , 1 bar | H 1 M | AgCl 1 M | Ag
( s) 2(g)
+

(aq) (aq) (s)

15. (c) Actually the equation is derived from Nerst equation assuming
0.059 1 0.059 1 equilibrium condition in a cell reaction, when E  0 .
58. (a) E cell  log   log 16. (a) More negative is the standard reduction potential, greater is
n C 2 100 the tendency to lose electrons and hence greater reactivity.
0.059
 (2)  0.059 V  59mV . (increase) 17. (a) Hg has greater reduction potential than that of H  and
2 hence cannot displace hydrogen from acid.
10 6 18. (c) Brown layer is deposited on iron rod because Cu has greater
59. (a) E cell  0.059 log  0.059 log10  3
10 3 reduction potential than that of Fe 2  .
 0.059  (3)  0.177V . 19. (b) Since E oA 2  / A  E Bo 2  / B . A has greater tendency to be
60. (c) The magnitude of the electrode potential of a metal is a oxidized.
measure of its relative tendency to lose or gain electrons. i.e., it
is a measure of the relative tendency to undergo oxidation (loss A  B 2  A 2  B .
of electrons) or reduction (gain of electrons). 20. o
(b) Since E Zn is negative, so Zn has greater tendency to be

M  M n   ne  (oxidation potential)
/ Zn
oxidized than hydrogen. Hence it can act as reducing agent.
M n   ne   M (reduction potential) 21. (a) Standard electrode potential of Hydrogen is zero.
61. (a) On electrolysis of fused ionic hydride (LiH) , hydrogen 22. (b) According to electrochemical series.
obtained at anode. 23. (a) The standard reduction potential of K  , Mg 2 , Zn 2 Cu 2
MH  H 2 O  MOH  H 2  increase in this order.
24. (c) Ecell  E oAu 3  / Au  E Ni
o
2
/ Ni
 1.50  (0.25)  1.75 V.
Electrode potential, Ecell, Nernst equation and ECS 25. (a) Electromotive force is +ve if oxidation and reduction both takes
place in a cell.
1. (b) Reduction potential of hydrogen electrode, 28. (a) In galvanic cell anode always made up of negative electrode.
 534 Electrochemistry
Anode Cathode
Where s.r.p. = Standard reduction potential
29. (d) A | A  (a  1)|| B  (a  1)| B
If EMF is positive then the reaction is spontaneous
EMF  Ecathode  Eanode  0.75  (0.5) ; EMF  0.25 V . For e.g. in Galvanic cell
(a) EMF = 1.1 volt
30. (d) E o  3.05 Li  / Li is most negative (minimum) and hence
(b) Cathode is made of copper
Li has maximum tendency to lose electrons or it is the (c) Anode is made of Zinc
strongest reducing agent. EMF = 0.34 –(– 0.76) = 1.1 volt.
31. (b) Brown layer is deposited on iron rod because Cu has greater 46. (d) H 2 is anode because oxidation takes place.
than reduction potential than that of Fe 2  . Cu is cathode because reduction is takes place.
32. (a) o
E Zn 
/ Zn
 E Fe
o

/ Fe
, so Zn will reduce Fe  . Zn cannot 47. o
(c) Ecell  Ecathode  Eanode .
reduce Mg 2 because E Zn
o

/ Zn
 E Mg
o

/ Mg
51. (b) Standard hydrogen electrode have zero electrode potential.
53. (a) G  nFEo
On similar reason Mg and Zn cannot oxidize Fe . G  1  96500  1.02 ; G  98430 .
33. (d) For the cell reaction, Fe acts as cathode and Sn as anode. 54. (c) Fuel cell converts the chemical energy into electrical energy.
Hence, 2 .303 RT [M ]
55. (a) E  E o  log n  .
o
Ecell  Ecathode
o
 Eanode
o
= – 0.44 – (– 0.14)= – 0.30V nF [M ]
56. (a) Less is the reduction potential stronger is the reducing agent.
The negative EMF suggests that the reaction goes
57. (a) Reducing power, i.e. the tendency to lose electrons increases as
spontaneously in reversed direction.
the reduction potential decreases.
34. (a) o
Ecell  Ecathode
o
 Eanode
o
 0.34  ( 0.76)  1.10 V . 58. (a) OCl   C  , E o  0.94 V
35. (c) o
Ecell  o
Ecathode  Eanode ; o
Ecell  0.34  ( 2.37) Cl  
1
Cl 2  e  E o  1.36 V
2
o
Ecell  2.71 V . adding the two equations, we get
(d) Mg lies above Cu in electrochemical series and hence Cu 1
36. OCl   Cl 2 , E o  0.94  1 .36  0 .42 V .
electrode acts as cathode 2
o
Ecell  ECu
o
 E Mg
o 60. (a) It cannot evolved H 2 from H 2 S
 
/ Cu / Mg
Hg  H 2 S  No reaction .
2.70 V  0.34  E Mg
o

o
; E Mg   2.36 V .
/ Mg / Mg 0 .059
61. (b) o
E cell  log K
37. (a) Because H 2 has greater reduction potential so it reduced the n
1.10  2
Ag  . log K   37.2881 or K  10 37 .
0.059
39. (d) G o  nE o F 62. (d) The oxidizing character i.e. acceptance of electrons increases
2  with the reduction potential.
Fe  2e  Fe …..(i) 63. (a) According to electrochemical series.
G  2  F  (0.440 V )  0.880 F
o
RT C 2
64. (d) Ecell  Ecell
o
 ln and G  nF Ecell
nF C1
Fe 3   3e   Fe …..(ii)
C 
G o  3  F  (0.036)  0.108 F hence G is the function of ln  2  .
On subtracting equation (i) from (ii)  C1 
Fe 3   e   Fe 2 0 .059 [ Zn   ] 0.059 1
66. (c) E  Eo  log 
 1 .10  log
G o  0.108 F  0.880 F  0.772F n [Cu ] 2 0 .1
 1.10  0.0295 log10  1.07 volt .
G o
Eo for the reaction  0.0591 0.01 0 .0591
nF 67. (b) E1  Eo  log  Eo  2
( 0.772 F) 2 1 2
   0 .772 V . 0.0591 100 0.0591
1 F E 2  Eo  log  Eo  4
40. (d) Reducing power i.e. the tendency to lose electrons increases as 2 0.01 2
the reduction potential decreases.  E1  E 2 .
41. (b) Cu   will be reduced and Fe will be oxidized. Oxidation
 
Cu  Fe  Cu  Fe . 68. (b) Fe 2
 Zn  Zn 2  Fe
42. (c) Cell reaction is
Reduction
Cu (s)  2 Ag   Cu 2   2 Ag EMF  Ecathode  Eanode  0.44  (0.76)  0.32 V .
Two half cell reaction is
69. (a) Fe is more electropositive than copper. Hence Cu 2  can
Cu  Cu 2   2e  Oxidation (anode) oxidise Fe.
Ag   e   Ag Reduction (cathode) 70. (b) E o  0 because hydrogen have zero potential.
ECell  Eox  ERe d  0.80  0.34  0.46 V 71. (b) Cell potential of the cell is positive.
72. (a,b) Because these comes after the Fe in electrochemical series.
43. (a) EMF = [s.r.p. of cathode–s.r.p of anode]
 Electrochemistry 535

Oxidation H  (0.025 M )  H  (10 8 M ) ; Ecell  0.38 V .

2 2
73. (c) Fe  Zn  Zn  Fe 85. (a) E o for Fe / Fe 2  0.44 V .
86. (c) (Reduction potential of cathode) – (reduction potential of
Reduction
anode).
EMF  Ecathode  Eanode  7.81  (7.62) 87. (a) The correct decreasing electrode potential order is :
EMF  0.19 V . K, Ba, Ca, Mg .

74. (c) Cr 3   Zn 2  H  Fe 3  . 89. (c) o

Ecell  Ecathode
o
 Eanode
o

Reducing nature decreasing order.  0.34  ( 2.37)   2.71 V .

75. (a) More is reduction potential, more is the power to get itself
reduced or lesser is reducing power or greater is oxidising 90. (b) Because flourine is most powerful reducing agent than other
power. halogens.
92. (c) Aluminium forms a protective oxide layer but iron does not.
76. (d) G  nFEo 93. (d) The reduction potential of Zn is very higher than Cu.
G  2.303 RT log K ; nFEo  2.303 RT log K 94. (a) The pH of 0.1 M HCl and 0.1 M acetic acid is not the same,
because HCl is a strong acid so its pH is less and
nFEo 2  96500  0.295
log K   CH 3 COOH is a weak acid, so its pH is more.
2 .303 RT 2.303  8.314  298
95. (d) The required reaction (Cu   Cu  2Cu  ) can be
log K  9.97  K  1  10 10 .
obtained by using the following reactions.
77. (b) For the given cell M | M  || X  | X , the cell reaction is Cu   e   Cu  ; ECu
o
 0.15 V …..(i)

/ Cu 
derived as follows:
 
RHS: reduction X  e   X  …..(i) Cu  2e  Cu ; o
ECu 
/ Cu
 0. 34 V …..(ii)
LHS: Oxidation M  M   e  …..(ii) Multiplying eq. (i) by 2 we get
Add (i) and (ii) M  X  M  X   2Cu   2e   2Cu  …..(iii)
The cell potential = 0.11 V G1  nFE  2  F  0.15

Since Ecell  – ve, the cell reaction derived above is not Cu   2e   Cu …..(iv)
spontaneous. In fact, the reverse reaction will occur G2  nFE  2  F  0.34
spontaneously. Subtract the eq. (iv) from (iii)
2 2
Cu   Cu  2Cu 
0
78. (c) Zn  MgCl2  ZnCl2  Mg No reaction
Oxidation G3   nFE  1  F  E o
Reduction Also G3  G1  G2
This type of reaction does not occur because
 1FEo  ( 2 F  0.15)  ( 2 F  0.34)
Mg 2 E o  2.37 V while Zn 2 E o  0.76 V .
E o   0.38
79. (b) In neutral medium Mn 7 oxidation state change into +4
This is the value for the reaction
M
oxidation state, hence equivalent weight of KMnO4  . Cu   Cu  2Cu 
3
But the given reaction is just reverse of it
80. (a) Increase in the concentration of Ag  ion increase the voltage  Ecell for given reaction = + 0.38V.
of the cell. 97. (d) It connect two solutions and complete the circuit.
0 .059 ( Ag  ) 98. (a) Greater the oxidation potential, greater is the reactivity.
81. (a) E cell   o
E cell log . 99. (b) Electrochemical series compare the relative reactivity of metals.
2 (Sn 2  ) 100. (d) Fuel cells are more efficient, free from pollution and they run
82. (b) The K.E. of proton is 1 KeV. till reactants are active.
83. (b) Anodic reaction : H 2 (P1 )  2 H  102. (c) E o  E oAg 2  / Ag  ECu
o
 0.34  0.80  0.46 V .
/ Cu 2 

Cathodic reaction : 2 H  H 2 (P2 ) 103. (a) Fe is placed above Cu in electrochemical series.
 2 104. (a) Lithium is the strongest reducing agent of the alkali metals.
RT P RT [H ] 105. (d) Potassium is more electropositive element, because it is the
Ecathode   ln 2 ; Eanode   ln
2 F [H  ]2 2F P1 only alkali metal among the given elements.
106. (b) Aluminium forms a self protecting film of oxide to prevent
Einf  Eanode  Ecathode corrosion.
RT (H  )2 RT P 107. (a) Zn(s)  2 H  (aq ) ⇌ Zn(2aq )  H 2(g)
 ln  ln 2 2
2F P1 2 F (H )
.059 [ Zn 2  ]
RT P2 RT P1 E Cell  E Cell
0
 log  2
 ln  ln . 2 [H ]
2 F P1 2 F P2
When H 2 SO 4 is added then [H  ] will increase therefore
1
84. (c) H 2  H  (10 8 M )  e  (oxidation) E Cell will also increases and equilibrium will shift towards
2
right.
1
H  (0.025 M )  e   H 2 (reduction) 108. (b) For M   X   M  X
2
Cell reaction is : 0
ECell  ECathode
0
 E 0Anode  0.44  0.33  0.11 V
 536 Electrochemistry
0
Since E Cell  () 0.11 V is positive hence this reaction 119. (d) I  get oxidised to I2 hence will form anode and Cr2 O72  get
should be spontaneous. reduced to Cr 3  hence will form cathode.
0.0591
109. (a) ECell  ECell
0
 log K c 0
ECell  ECathode
0
 E 0Anode ; ECell
0
E  E I02
n Cr2 O7 2

0.0591 0.79  1.33  E I02 ; E I02  1.33  0.79 ; E I02  0.54 V .

At 298 K ECell  0 O  0.591  log K c
n 120. (b) According to nernst's equation
0 .591  1 nRT c
log K c   10 ; K c  Antilog10  1  10 10 . E Cell  E Cell
0
 log 1
0 .0591 F c2
1
110. (a) H 2 | H  | | Ag  | Ag | For Zn(s)  Cl 2(1 atm)  Zn 2  2Cl 
2
c1  [Zn 2  ] and c 2  [Cl  ]
0
ECell  ECathode
0
 E 0Anode  E 0Ag  / Ag  E 0  1
H / H2
2 Hence to increase E, c1 should be decreased and c 2 should
(0.80)  (0.0)  0.80 V. be increased is [ Zn 2 ] should be decreased and Cl should be
111. (a) E A  2.23 V  E B  1.43 V increased.
So A will act as cathode in galvanic cell. Hence 121. (c)
Reduction
0
ECell  ECathode  E Anode  E A  E B Cell reaction E0 M 2  / M 3 
E0 M 3  / M 2  (Oxidation)
 (2.23)  (1.43)  3.66 V . – .41 V + . 41 V
Cr 2  Cr 3 
112. (b) 0
ECu  E Mg
0
hence Cu acts as cathode and Mg acts as anode. + 1.57 V
Mn 2
Mn 3 
– 1.57 V
+ 0.77 V 2 3 – 0.77 V
0
ECell  0
ECu  0
E Mg  (0.34)  (2.37)  2.71 V . Fe Fe
+ 1.97 V – 1.97 V
113. (b) In this cell Co is oxidised and it acts as anode and Ce acts as Co 2  Co 3 
cathode. As Cr has maximum oxidation potential value, therefore its
0
ECell  ECathode
0
 E 0Anode  1.89  ECell
0
 (0.28) oxidation should be easiest.
0
ECell  1.89  0.28  1.61 Volts. 122. (a) Fe(s) 
 Fe + 2e ; G1o 2+

114. (b) Given: G  21.20 kJ  21200 J 2H + 2e + ½O

+

2

 H O(l) ; G 2o
2

 G  nFE
Fe(s) + 2H + ½O
+

2

 Fe + H O ; G3o
2+

21200
E  0.2196 V  0 .22 V . Applying, G1o  G2o  G3o
1  96500
 
115. (b) Ag | Ag (.1m)|| Ag 1M | Ag | G 3o = (2F  0.44) + (2F  1.23)
2 .303 RT c 0 .059 1 G 3o = (2  96500  0.44+ 2  96500  1.23)
E Cell  log 1  log
nF c2 1 0.1 G 3o = 322310 J
 0.059 log10  0.059 Volt .
 G 3o = 322 kJ
116. (b) For this cell, reaction is: Zn  Fe 2  Zn 2  Fe
128. (a) G o  2.303 RT log K eq or G o  nFEcell
o
0 .0591 c 0 .0591 c
E  E0  log 1 ; E 0  E  log 1 129. (a) Any redox reaction would occur spontaneously if the free
n c2 n c2
energy change (G) is negative.
0.0591 10 2
 0.2905  log 3  0.32 V . G o  nFEo
2 10 Where n is the number of electrons involved, F is the value
0 .0591 0.32  2 0 .32 of Faraday and E o is the cell emf. G o can be negative if
E 
0
log K c ; log K c  
2 0.0591 0.0295 E o is positive.
0 .32
 Kc  .
10 0295 Corrosion
117. (d) Al displaces H from HCl but silver cannot it means Al is
situated above the Ag in ECS, hence Al will acts as anode and 2. (d) Rusting of iron is catalysed by [H  ] .
Ag will act as cathode. 3. (d) HgCl 2 has corrosive action. It is highly poisonous. It
0
ECell  ECathode
0
 E 0Anode  E 0Ag  / Ag  E 0Al3  / Al sublimes on heating. It is, therefore, known as corrosive
sublimate.
2.46  0.8  E 0Al3  / Al ; E 0Al  0.8  2.46  1.66 V . 4. (a) Fe  Fe 2  2e (anode reaction)
118. (a) For Sn (s)  2 Fe(3aq )  2 Fe(2aq )  Sn (2aq ) O 2  2 H 2 O  4 e  4 OH  (cathode reaction)
The overall reaction is
0
ECell  E Sn
0
/ Sn 2 
 E Fe
0
3
/ Fe 2 
 (0.14)  (0.77)
2 Fe  O 2  2 H 2 O  2 Fe(OH)2
E Cell  0.91 Volts.
 Electrochemistry 537

Fe(OH ) 2 may be dehydrated to iron oxide FeO , or further 1 2 1 270

12. (d)  ;  ; 1  90 kg .
oxidised to Fe(OH )3 and then dehydrated to iron rust, E1 E2 3 93
Fe 2 O 3 . 13. (c) Eq of Al = eq of H 2
4 .5 4 .5
Critical Thinking Questions  eq of H 2 ;  eq of H 2
27 9
3
1. (c) (126 scm 2 )  0NaCl   0Na    0Cl  .....(1)
2 H   2e   H 2
(152 scm 2
)  0KBr   0K    0Br  .....(2)
eq. of H 2 = Number of moles × n factor 0.5  n H 2  2
(150 scm 2
)  0KCl   0K    0Cl  .....(3) 0.5
VH 2   22.4 ; VH 2  5.6 L
By equation (1)+(2) – (3) 2
  NaBr  
0 0
  0Br  14. (c) The reaction taking place at anode is
Na 
2Cl  Cl + 2e
– –

 126  152  150  128 Scm 2 mol 1

2

1 mole 2  96500 coulomb

2. (a) At cathode : 2 H  (aq )  2e   2 H Q = i . t = 1  30  60 = 1800 coulomb.
The amount of chlorine liberated by passing 1800 coulomb of
1
2H  O2  H 2 O 1  1800  71
2 electric charge   0.66 g .
2  96500
1
2H   O 2  2e   H 2 O Assertion & Reason
2
3. (c) H 2 undergoes oxidation and AgCl ( Ag  ) undergoes 1. (a) The nature of the cathode can affect the order of discharge of
reduction. ions.
Oxidation 2. (b) 1 mole of silver = 1g equivalent of silver
2
2
0 0
1 mole of copper = 2g equivalent of copper
4. (b) In this reaction Fe  Zn  Zn  Fe
We know from Faraday's law of electrolysis that “The weight of
Reduction ion deposited on an electrode is directly proportional to the
EMF  Ecathode  Eanode  0.41  (0.76) quantity of electricity passed”.
4. (d) Copper is present below hydrogen therefore hydrogen from
EMF  0.35 V. HCl cannot be liberated by treating with copper. Hence
5. (c) NO 3  4 H   4 e   2 H 2 O  NO. In this equation all assertion is false while reason is true.
5. (d) Copper cannot liberate hydrogen from a dil. HCl solutions
the atoms are balanced. For balancing added 3 e  to L.H .S . because it is situated below hydrogen in the reactivity series.
we have, NO 3  4 H   3e   2 H 2 O  NO . Here both assertion and reason are false.
6. (d) The formation of Zn is not possible by placing Cu plate in
0 .059 (Zn  ) ZnSO 4 solution because Zn is placed above Cu in
6. (a) E cell  o
Ecell  log
2 (Cu  ) electrochemical series. Therefore, both assertion and reason are
false.
0.059 0.1
 1.10  log  1.10 V . 7. (e) Electrical conductivity of copper decreases with increase in
2 0.1 temperature because the metallic conductivity is due to the
7. (a) The tendency to gain electron is in the order motion of electrons. On increasing temperature the motion of
Z>Y>X electron increases which hinder in conductance of current.
Hence, here assertion is false but the reason is true.
Thus Y  e  Y  ; X  X   e .
8. (a) Dry air is heavier than wet air because the density of dry air is
0 .059 [H  ] more than water.
8. (b) E OP  o
EOP  log 9. (e) Copper is present below hydrogen therefore hydrogen from
1 PH 2 HCl cannot be liberated by treating with copper. Hence,
assertion is false while reason is true.
 [H  ]  10 10 ; PH 2  1 atm ; EOP  0.59 V .
10. (a) K and Cs emit electrons on exposure to light hence, both are
9. (a.c,d)Decomposition of H 2 O 2 is an example of exothermic used in photoelectric cells . Here, assertion and reason are true
reaction, negative catalysis and auto-oxidation. and reason is a correct explanation.
10. (a) 27 gm of Al is obtained by passing a current of 3 × 96500 C. l  l 
 1 gm of Al is obtained by passing a current of 12. (b) We know, R  or R     , where proportionality
A  A
96500
3 C. constant  is called resistivity. If l  1m and A  1m 2 , then
27
R   i.e. Resistance = Resistivity.
 5.12 × 10 gm of Al is obtained by passing a current of
3

96500 14. (a) According to Kohlrausch law, “Limiting molar conductivity of

3  5 .12  1000 an electrolyte can be represented as the sum of the individual
27 contributions of the anion and cation of the electrolyte”.
= 1.83 × 10 C × 3 = 5.49 × 10 C.
7 7

15. (c) One Faraday deposite one gram equivalent of the substance.
11. (c) HOAC  NaOAC  HCl  NaCl 16. (b) Gold has higher reduction potential than the given metals.
 91.0  426.2  126.5  390.7 Hence AuCl3 will react with these metals.
 538 Electrochemistry

17. (a) Zn(s)  Cu 2  (aq)  Zn 2  (aq)  Cu(s)

As the time passes, the concentration of Zn 2  keeps on
increasing while the concentration of Cu 2  keeps on
decreasing. At the same time voltage of the cell keeps on
decreasing. When there is no change in concentration of
Cu 2  and Zn 2  ions, voltmeter gives zero reading and this
state is known as equilibrium.
18. (e) A negative value of standard reduction potential means that
oxidation takes place on this electrode with reference to SHE.
19. (a) A standard cell is one whose e.m.f. almost does not change
with temperature.
22. (d) Identification of cathode and anode is done by the use of
ammeter/voltmeter. Higher is the value of reduction potentials
greater would be its oxidising power.
23. (b) If redox reaction is spontaneous, G is –ve and hence E 0 is
positive.  G 0  nFE0 cell
24. (a) Zinc metal which has a more negative electrode potential than
iron will provide electrons in preference of the iron, and
therefore corrode first. Only when all the zinc has been
oxidised does the iron start to rust.
25. (a) Both assertion and reason are true and reason is the correct
explanation of assertion.
Anode (oxidation) for eq. Zn  Zn 2   2e  , so
Excess of electrons and hence negatively charged while cathode
is positively charged.
26. (a) Both assertion and reason are true and reason is the correct
explanation of assertion.
E 0Au 3  / Au  ENi
0
/ Ni 2 
 1.50  (0.25)  1.75 V
27. (c) Assertion is true but reason is false. Ions of inert electrolytes
are not involved in any electrochemical change until they react
chemically with the electrolytes in the two half-cells.
28. (d) Both assertion and reason are false. Potential difference is the
difference between the electrode potential of the two electrodes
of the cell when cell is under operation while emf is the
potential difference generated by a cell when there is zero
electron flow.
 Electrochemistry 539

1. The mass of copper deposited from a solution of CuSO 4 by 7. Normal aluminium electrode coupled with normal hydrogen
passage of 5 A current for 965 second is (Mol. wt. of Copper = electrode gives an emf of 1.66 volts . So the standard electrode
63.5) [AIIMS 2001] potential of aluminium is [KCET 1987]
(a) 15.875 g (b) 1.5875 g (a) – 1.66 V (b) + 1.66 V
(c) 4825 g (d) 96500 g (c) – 0.83 V (d) + 0.83 V
2. The current in a given wire is 1.8 A. The number of coulombs that 8. Which one among the following is the strongest reducing agent
flow in 1.36 minutes will be [AIIMS 2001]
(a) 100 C (b) 147 C Fe 2   2e   Fe(0.44 V )

(c) 247 C (d) 347 C Ni 2   2e   Ni(0.25 V )

3. A solution of a salt of a metal was electrolysed for 150 minutes
with a current of 0.15 amperes . The weight of metal deposited Sn 2  2e   Sn (0.14 V )
was 0.783 gm. The equivalent weight of the metal is [AFMC 2001]
Fe 3   e   Fe 2 (0.77 V ) [BHU 1998]
(a) 55.97 gm (b) 65.97 gm
(c) 75.97 gm (d) 85.97 gm (a) Fe (b) Fe 2 
4. The resistance of 0.01N NaCl solution at 25 o C is 200 . Cell (c) Ni (d) Sn
constant of conductivity cell is 1 cm . The equivalent conductance is
–1
[CBSE PMT 1999]
9. The cell reaction of the galvanic cell
1 1 1 1 2 2
(a) 5  10  cm eq
2 2
(b) 6  10  cm eq
3 2
Cu (s) | Cu (aq ) || Hg (aq ) | Hg(l) is [EAMCET 2003]

(c) 7  10 4 1cm 2 eq 1 (d) 8  10 5 1cm 2 eq 1 (a) Hg  Cu 2   Hg 2   Cu

5. Which of the following reaction is possible at anode
(b) Hg  Cu 2   Cu   Hg 
[AIEEE 2002]
(c) Cu  Hg  CuHg
(a) 2Cr 3   7 H 2 O  Cr2 O7 2   14 H 

(b) F2  2 F  (d) Cu  Hg 2   Cu 2   Hg

1 10. The specific conductivity of N/10 KCl solution at 20 o C is

(c) O2  2 H   H 2 O
2 0.0212 ohm 1 cm 1 and the resistance of cell containing this
(d) None of these
solution at 20 o C is 55 ohm. The cell constant is
6. What is the standard cell potential for the cell
[AIIMS 1999]
Zn / Zn 2  (1M )|| Cu 2  (1M ) / Cu
(a) 1.166 cm 1
2 2
E for Zn / Zn (1M )  0.76 V & Cu
o
/ Cu  0.34 V
(b) 2.173 cm 1
[AIIMS 1980]
(a) 0.76  (0.34)  0.42 V (c) 3.324 cm 1

(b) 0.34  0.76  0.42 V (d) 4.616 cm 1

11. The oxide which is not reduced by hydrogen is
(c) 0.34  (0.76)  1.10 V
[JIPMER 1999]
(d) 0.76  (0.34)  1.10 V
(a) Ag 2 O (b) K2O

(c) Fe2 O3 (d) P4 O10

(SET -12)
 Electrochemistry 541

1. (b) Current (I) = 5A and time (t) = 965 sec.

6. (c) E o  Ecathode  Eanode
We know that equivalent weight of copper
Molecularweight 63.5 E o  0.34  (0.76) ; E o  1.10 volt .
  and quantity of electricity
Valancy 2
7. (a) o
Ecell  1.66  E Ho  / H  E oAl3  / Al
passed in coulomb = current × time = 5 × 965 = 4825C. Since 2

63 . 5
96500 coulombs will deposit g of copper therefore O E oAl3 / Al or E  1.66 V .
2 Al 3  / Al

4825 coulombs will deposit 8. (a) The reduction potential of Fe is very high, so it is a strongest
63.5  4825 reducing agent.
=  1 .5875 g .
96500  2 9. 
(b) Cu (s) | Cu (2Ag 2
) | | Hg( Ag) | Hg(l)
2. (b) Q  I  t ; 1.8  1.36  60  147C . anode oxidation cathode reduction

3. (a) Time (t) = 150 min = 9000 sec

Reduction
Current (I) = 0.15 A
2
Weight of metal (w) = 0.783 g. Cu  Hg  Cu 2   Hg .
We know Q  I  t = 0.15  9000  1350 C . Since 1350 C of Oxidation
electricity will deposited 0.783 g of metal, so, 96500 C of 1
10. (a) K  cell constant
0.783  96500 R
electricity will deposited  55.97 g .
1350
 K  R  0.0212  55  1.166 cm 1 .
1 l 1
4. (a)   k V   V   1  10,000
R a 200 11. (b) On the basis of electrochemical series K 2 O is not reduced by
1
 5  10  cm eq .
2 2 1 hydrogen.

5. (a) Oxidation always occurs at anode.

***
 Redox Reactions 541

Chapter

13
Redox Reactions

Chemical reactions involve transfer of electrons from one chemical (ii) Removal of hydrogen : H S+Cl  2HCl + S 2 2

substance to another. These electron – transfer reactions are termed as

oxidation-reduction or redox-reactions. (iii) Addition of Non-metal : Fe + S  FeS
Molecular and Ionic equations (iv) Removal of metal : 2KI+H O  2KOH+I 2 2 2

(1) Molecular equations : When the reactants and products involved

(v) Increase in +ve valency : Fe 2   Fe3   e 
in a chemical change are written in molecular forms in the chemical
equation, it is termed as molecular equation. (vi) Loss of electrons (also known as de-electronation)
Example : MnO2  4 HCl  MnCl2  2 H 2 O  Cl 2 4 3 2 1 0 1 2 3 4
M M M M M M M M M
In above example the reactants and products have been written in
molecular forms, thus the equation is termed as molecular equation. –e –e –e –e –e –e –e –e
– – – – – – – –

(2) Ionic equations : When the reactants and products involved in a Loss of electrons
chemical change are ionic compounds, these will be present in the form of
ions in the solution. The chemical change is written in ionic forms in (a) H 0  H   e  (Formation of proton)
chemical equation, it is termed as ionic equation. Example,
(b) MnO42   MnO4  e  (De-electronation of MnO42 )
MnO2  4 H   4 Cl   Mn2   2Cl   2 H 2 O  Cl 2
In above example the reactants and products have been written in (c) 2 Fe0  2 Fe 3   6 e  (De-electronation of iron)
ionic forms, thus the equation is termed as ionic equation.
(vii) Increase in oxidation number
(3) Spectator ions : In ionic equations, the ions which do not
undergo any change and equal in number in both reactants and products
(a) Mg 0  Mg 2 (From 0 to +2)
are termed as spectator ions and are not included in the final balanced
equations. Example,

(b) Fe 2 (CN )6 
4

 Fe 3 (CN )6 3
(From +2 to +3)

Zn  2 H  2Cl 
 Zn 2
 H 2  2Cl 
(Ionic equation)
(c) 2Cl   Cl 20 (From –1 to 0)
Zn  2 H   Zn 2  H 2 (Final ionic equation)
(2) Reduction : Reduction is just reverse of oxidation. Reduction is a
In above example, the Cl  ions are the spectator ions and hence process which involves; removal of oxygen, addition of hydrogen, removal of
are not included in the final ionic balanced equation. non-metal, addition of metal, decrease in +ve valency, gain of electrons and
decrease in oxidation number.
Oxidation-reduction and Redox reactions (i) Removal of oxygen : CuO  C  Cu  CO
(1) Oxidation : Oxidation is a process which involves; addition of (ii) Addition of hydrogen : Cl 2  H 2  2 HCl
oxygen, removal of hydrogen, addition of non-metal, removal of metal, (iii) Removal of non-metal
Increase in +ve valency, loss of electrons and increase in oxidation number. 2 HgCl2  SnCl 2  Hg 2 Cl 2  SnCl 4

(i) Addition of oxygen : 2Mg + O  2MgO (iv) Addition of metal : HgCl2  Hg  Hg2 Cl 2
2
 542 Redox Reactions
(v) Decrease in +ve valency Example : KMnO4 , K 2 Cr2 O7 , Na 2 Cr2 O7 , CrO3, H 2 SO 4 ,
3 2
(a) Fe  Fe (+ve valency decreases)
HNO3 , NaNO 3 , FeCl3 , HgCl2 , KClO4 , SO 3 , CO 2 , H 2 O2 etc.
3 4
(b) [Fe(CN )6 ]  [Fe(CN )6 ] (–ve valency increases)
(iii) Oxides of elements, MgO, CuO, CrO3 , CO 2 , P4 O10 , etc.
(vi) Gain of electrons (also known as electronation)
4 3 2 1 0 1 2 3 4 (iv) Fluorine is the strongest oxidising agent.
M M M M M M M M M (3) Important reducing agents
+e +e +e +e +e +e +e +e
– – – – – – – – (i) All metals e.g. Na, Zn, Fe, Al, etc.
Gain of electrons (ii) A few non-metals e.g. C, H , S etc.
2

2  2
(a) Zn (aq)  2e  Zn(S ) (Electronation of Zn ) (iii) Hydracids : HCl, HBr, HI, H S etc. 2

2  2 (iv) A few compounds containing anelement in the lower oxidation

(b) Pb  2e  Pb 0
(Electronation of Pb )
state (ous).
(c) [Fe(CN )6 ]3   e   [Fe(CN )6 ]4 
Example : FeCl2 , FeSO4 , SnCl 2 , Hg2 Cl 2 , Cu 2 O etc.
(Electronation of [Fe(CN )6 ]3  )
(v) Metallic hydrides e.g. NaH, LiH etc.
(vii) Decrease in oxidation number
(vi) Organic compounds like HCOOH and (COOH) and their salts,
(a) Mg 2  Mg 0
2

(From +2 to 0) aldehydes, alkanes etc.

(b) Fe(CN )6 3   Fe(CN )6 4  (From +3 to +2) (vii) Lithium is the strongest reducing agent in solution.
 (viii) Cesium is the strongest reducing agent in absence of water.
(c) Cl 20  2Cl (From 0 to –1)
Other reducing agents are Na 2 S 2 O3 and KI.
(3) Redox-reactions
(i) An overall reaction in which oxidation and reduction takes place (ix) Hypo prefix indicates that central atom of compound has the
simultaneously is called redox or oxidation-reduction reaction. These minimum oxidation state so it will act as a reducing agent.
reactions involve transfer of electrons from one atom to another. Thus every Example : H 3 PO2 (hypophosphorous acid).
redox reaction is made up of two half reactions; One half reaction
represents the oxidation and the other half reaction represents the (4) Substances which act as oxidising as well as reducing agents
reduction. Examples : H O ,SO ,H SO ,HNO ,NaNO ,Na SO ,O etc.
2 2 2 2 3 2 2 2 3 3

(ii) Types of redox reaction (5) Tips for the identification of oxidising and reducing agents
(a) Direct redox reaction : The reactions in which oxidation and
reduction takes place in the same vessel are called direct redox reactions. (i) If an element is in its highest possible oxidation state in a
compound, the compound can function as an oxidising agent.
(b) Indirect redox reaction : The reactions in which oxidation and
reduction takes place in different vessels are called indirect redox reactions. Example : KMnO4 , K2Cr2O7 , HNO3 , H 2 SO 4 , HClO4 etc.
Indirect redox reactions are the basis of electro-chemical cells.
(c) Intermolecular redox reactions : In which one substance is (ii) If an element is in its lowest possible oxidation state in a
oxidised while the other is reduced. compound, the compound can function only as a reducing agent.
For example, 2 Al  Fe2O3  Al2O3  2 Fe Example : H 2 S , H 2 C2 O4 , FeSO4 , Na 2 S 2 O3 , SnCl 2 etc.
Here, Al is oxidised to Al2 O3 while Fe2 O3 is reduced to Fe. (iii) If an element is in its intermediate oxidation state in a
compound, the compound can function both as an oxidising agent as well as
(d) Intramolecular redox reactions : In which one element of a
reducing agent.
compound is oxidised while the other is reduced.
 Example : H 2 O2 , H 2 SO 3 , HNO 2 , SO 2 etc.
For example, 2 KClO3  2 KCl  3 O2
(iv) If a highly electronegative element is in its highest oxidation
Here, Cl 5 in KClO3 is reduced to Cl 1 in KCl while O 2  in state in a compound, that compound can function as a powerful oxidising
agent.
KClO3 is oxidised to O 20 .
Example : KClO4 , KClO3 , KBrO3 , KIO3 etc.
Oxidising and Reducing agents (v) If an electronegative element is in its lowest possible oxidation
(1) Definition : The substance (atom, ion or molecule) that gains state in a compound or in free state, it can function as a powerful reducing
electrons and is thereby reduced to a low valency state is called an oxidising agent.
agent, while the substance that loses electrons and is thereby oxidised to a Example : I  , Br  , N 3  etc.
higher valency state is called a reducing agent.
(6) Equivalent weight of oxidising and reducing agents
Or
Equivalent weight of a substance (oxidant or reductant) is equal to
An oxidising agent is a substance, the oxidation number of whose molecular weight divided by number of electrons lost or gained by one
atom or atoms decreases while a reducing agent is a substance the oxidation molecule of the substance in a redox reaction.
number of whose atom increases.
Molecular weight
(2) Important oxidising agents Eq. wt. of O. A. =
No. of electrons gained by one molecule
(i) Molecules made up of electronegative elements.
Molecular weight
Example : O , O and X (halogens).
2 3 2
=
Change in O. N. per mole
(ii) Compounds containing an element which is in the highest
oxidation state.
 Redox Reactions 543

Molecular weight Molecular weight

Eq. wt. of R. A. = =
No. of electrons lostby one molecule Change in O. N. per mole
Table : 13.1 Equivalent weight of few oxidising/reducing agents
Change in Total
Agents O. N. Product O. N. O. N. per Change in Eq. wt.
atom O. N. per mole
Cr2 O7 2  +6 Cr 3  +3 3 3×2=6 Mol. wt./6

C 2 O4 2  +3 CO 2 +4 1 1×2=2 Mol. wt./2

S 2 O3 2  +2 S 4 O6 2  + 2.5 0.5 0.5 × 2 = 1 Mol. wt./1

H 2 O2 –1 H 2O –2 1 1×2=2 Mol. wt./2
H 2 O2 –1 O2 0 1 1×2=2 Mol. wt./2

MnO4 +7 Mn2  +2 5 5×1=5 Mol. wt./5

(Acidic medium)
MnO4 +7 MnO2 +4 3 3×1=3 Mol. wt./3
(Neutral medium)
MnO4 +7 MnO42  +6 1 1×1=1 Mol. wt./1
(Alkaline medium)

Oxidation number or Oxidation state V2O5 Vanadium (V) oxide CuO Copper (II) oxide

(1) Definition : Charge on an atom produced by donating or SnO2 Tin (IV) oxide FeCl3 Iron (III) chloride
accepting electrons is called oxidation number or oxidation state. It is the (4) Rules for the determination of oxidation number of an atom :
number of effective charges on an atom. The following rules are followed in ascertaining the oxidation number of an
(2) Valency and oxidation number : Valency and oxidation number atom,
concepts are different. In some cases (mainly in the case of electrovalent
(i) If there is a covalent bond between two same atoms then
compounds), valency and oxidation number are the same but in other cases
oxidation numbers of these two atoms will be zero. Bonded electrons are
they may have different values. Points of difference between the two have
symmetrically distributed between two atoms. Bonded atoms do not acquire
been tabulated below
any charge. So oxidation numbers of these two atoms are zero.
Oxidation number Valency
A : A or A – A  A + A * *

O.N. is the charge (real or imaginary) It is the combining capacity of the

present on the atom of the element element. No plus or minus sign is For example, Oxidation number of Cl in Cl , O in O and N in N is
2 2 2

when it is in combination. It may attached to it. zero.

have plus or minus sign.
O.N. of an element may have
different values. It depends on the
nature of compound in which it is
present.
O.N. of the element may be a whole
number or fractional.
O.N. of the element may be zero.
Valency of an element is usually fixed.
Valency is always a whole number.
Valency of the element is never zero
(ii) If covalent bond is between two different atoms then electrons
are counted towards more electronegative atom. Thus oxidation number of
more electronegative atom is negative and oxidation number of less
electronegative atom is positive. Total number of charges on any element
depends on number of bonds.
A – B  A + B : + –

except of noble gases.

(3) Oxidation number and Nomenclature A – B  A + : B :+2 –2

(i) When an element forms two monoatomic cations (representing The oxidation number of less electronegative element (A) is + 1 and
different oxidation states), the two ions are distinguished by using the + 2 respectively.
ending-ous and ic. The suffix – ous is used for the cation with lower
(iii) If there is a coordinate bond between two atoms then oxidation
oxidation state and the suffix – ic is used for the cation with higher number of donor atom will be + 2 and of acceptor atom will be – 2.
oxidation state.
For example : Cu (oxidation number +1) cuprous
+ A  B  A + :B : 2+ -2

Cu (oxidation number +2) cupric

2+
(iv) The oxidation number of all the atoms of different elements in
their respective elementary states is taken to be zero. For example, in
(ii) Albert Stock proposed a new system known as Stock system. In
this system, Roman numeral written in parentheses immediately after the N 2 , Cl2 , H 2 , P4 , S 8 , O2 , Br2 , Na, Fe, Ag etc. the oxidation number
name of the element indicates the oxidation states. For example, of each atom is zero.
(v) The oxidation number of a monoatomic ion is the same as the
Cu2O Copper (I) oxide SnO Tin (II) oxide
charge on it. For example, oxidation numbers of Na  , Mg 2  and
FeCl2 Iron (II) chloride Mn2O7 Manganess (VII) oxide
K2Cr2O7 Potassium dichromate Na2CrO4 Sodium chromate (VI) Al3  ions are + 1, + 2 and + 3 respectively while those of Cl  , S 2  and
(VI) N 3  ions are –1, –2 and –3 respectively.
 544 Redox Reactions
(vi) The oxidation number of hydrogen is + 1 when combined with IA ns1 +1
non-metals and is –1 when combined with active metals called metal
hydrides such as LiH, KH, MgH , CaH etc. II A ns2 +2
2 2

(vii) The oxidation number of oxygen is – 2 in most of its III A ns2np1 +3, +1
compounds, except in peroxides like H 2O2 , BaO2 etc. where it is –1. IV A ns np
2 2 +4,+3,+2,+1, –1, –2, –3, –4
Another interesting exception is found in the compound OF (oxygen 2 VA ns np
2 3 +5,+3,+1, –1, –3
difluoride) where the oxidation number of oxygen is + 2. This is due to the
fact that fluorine being the most electronegative element known has always VI A ns np
2 4
+6,+4,+2,–2
an oxidation number of –1. VII A ns2np5 +7,+5,+3, +1, –1
(viii) In compounds formed by union of metals with non-metals, the (xiii) Transition metals exhibit a large number of oxidation states
metal atoms will have positive oxidation numbers and the non-metals will due to involvement of ( n –1) d electron besides ns electron.
have negative oxidation numbers.
(xiv) Oxidation number of a metal in carbonyl complex is always zero.
Example : Ni has zero oxidation state in NiCO 4  .
For example,
(a) The oxidation number of alkali metals (Li, Na, K etc.) is always +1
(xv) Those compounds which have only C, H and O the oxidation
and those of alkaline earth metals (Be, Mg, Ca etc) is + 2.
number of carbon can be calculated by following formula,
(b) The oxidation number of halogens (F, Cl, Br, I) is always –1 in
(nO  2 - nH )
metal halides such as KF, AlCl , MgBr , CdI . etc.
3 2 2
Oxidation number of ' C ' 
nC
(ix) In compounds formed by the union of different elements, the
more electronegative atom will have negative oxidation number whereas the Where, nO is the number of oxygen atom, n H is the number of
less electronegative atom will have positive oxidation number. hydrogen atom, nC is the number of carbon atom.
For example, *
(a) N is given an oxidation number of –3 when it is bonded to less For example, (a) CH 3 OH ; nH  4, nC  1, nO  1
electronegative atom as in NH and NI , but is given an oxidation number of (1  2  4 )
 2
3 3

+ 3 when it is bonded to more electronegative atoms as in NCl . Oxidation number of ‘C’ =

3
1
(b) Since fluorine is the most electronegative element known so its *
oxidation number is always –1 in its compounds i.e. oxides, interhalogen (b) HCOOH ; nH  2, nO  2, nc  1
compounds etc.
(2  2  2)
(c) In interhalogen compounds of Cl, Br, and I; the more Oxidation number of carbon =  2
1
electronegative of the two halogens gets the oxidation number of –1. For
example, in BrCl , the oxidation number of Cl is –1 while that of Br is +3.
3
(5) Procedure for calculation of oxidation number : By applying the
above rules, we can calculate the oxidation numbers of elements in the
(x) For neutral molecule, the sum of the oxidation numbers of all
molecules/ions by the following steps.
the atoms is equal to zero. For example, in NH the sum of the oxidation 3

numbers of nitrogen atom and 3 hydrogen atoms is equal to zero. For a (i) Write down the formula of the given molecule/ion leaving some
complex ion, the sum of the oxidation numbers of all the atoms is equal to space between the atoms.
charge on the ion. For example, in SO 42  ion, the sum of the oxidation (ii) Write oxidation number on the top of each atom. In case of the
numbers of sulphur atom and 4 oxygen atoms must be equal to –2. atom whose oxidation number has to be calculated write x.
(xi) It may be noted that oxidation number is also frequently called (iii) Beneath the formula, write down the total oxidation numbers of
as oxidation state. For example, in H O, the oxidation state of hydrogen is +1
2
each element. For this purpose, multiply the oxidation numbers of each
and the oxidation state of oxygen is – 2. This means that oxidation number atom with the number of atoms of that kind in the molecule/ion. Write the
gives the oxidation state of an element in a compound. product in a bracket.
(xii) In the case of representative elements, the highest oxidation (iv) Equate the sum of the oxidation numbers to zero for neutral
number of an element is the same as its group number while highest molecule and equal to charge on the ion.
negative oxidation number is equal to (8 – Group number) with negative (v) Solve for the value of x.
sign with a few exceptions. The most common oxidation states of the
representative elements are shown in the following table,
Group Outer shell Common oxidation numbers (states)
configuration except zero in free state

Table : 13.2 Oxidation number of some elements in compounds, ions or chemical species
Element Oxidation Compounds, ions or chemical species
Number

Sulphur (S) –2 H S, ZnS, NaHS, (SnS ) , BaS, CS

2 3
2–

0 S, S , S , SCN 4 8
–

+1 S F , S Cl
2 2 2 2

+4 SO , H SO , (SO ) , SOCl , NaHSO , Ca[HSO ] , [HSO ] SF

2 2 3 3
2–

2 3 3 2 3
–

, 4
 Redox Reactions 545

+6 H SO , (SO ) , [HSO ] BaSO KHSO SO , SF , H S O , (S O )

2 4 4
2-

4
–

, 4, 4, 3 6 2 2 7 2 7
2–

Nitrogen (N) –3 NH , (NH ) , AlN, Mg N , (N) , Ca N , CN

3 4
+

3 2
3–

3 2
–

–2 N H , (N H )
2 4 2 5
+

–1 NH OH 2

–1/3 NaN , N H 3 3

0 N 2

+1 NO 2

+2 NO
+3 HNO , (NO ) , NaNO , N O , NF 2 2
–

2 2 3 3

+4 NO 2

+5 HNO , (NO ) , KNO , N O 3 3

–

3 2 5

Chlorine (Cl) –1 HCl, NaCl, CaCl , AlCl , ICl, ICl , SOCl , CrO Cl , KCl, K PtCl , HAuCl , CCl 2 3 5 2 2 2 2 6 4 4

0 Cl, Cl 2

+1 HOCl, NaOCl, (OCl) , Cl O –

+3 KClO , (ClO ) , HClO 2 2

–

+4 ClO 2

+5 (ClO ) , KClO , NaClO , HClO 3

–

3 3 3

+7 HClO , Cl O , KClO , (ClO ) 4 2 7 4 4

–

Hydrogen (H) –1 NaH, CaH , LiAlH , LiH 2 4

+1 NH , PH , HF 3 3

Phosphorus (P) –3 PH , (PH ) , Ca P 3 4

+

3 2

0 P 4

+1 H PO , KH PO , BaH P O
3 2 2 2 4 2 4

+3 PI , PBr , PCl , P O , H PO
3 3 3 2 3 3 3

+5 (PO ) , H PO , Ca (PO ) , H P O , P O , PCl , (P O ) , Mg P O , ATP

4
3–

3 4 3 4 2 4 2 7 4 10 5 2 7
4–

2 2 7

Oxygen (O) –2 H O, PbO , (CO ) , (PO ) , SO , (C O ) , HOCl, (OH) , (O)

2 2 3
2–

4
2–

2 2 4
2– – 2–

–1 Na O , BaO , H O , (O ) , Peroxides
2 2 2 2 2 2
2–

– 1/2 KO 2

0 O, O , O 2 3

+1 OF 2 2

+2 OF 2

Carbon (C) –4 CH 4

–3 CH 2 6

–2 CH Cl, C H 3 2 4

–1 CaC , C H 2 2 2

0 Diamond, Graphite, C H O , C H O , HCHO, CH Cl 6 12 6 2 4 2 2 2

+2 CO, CHCl , HCN 3

+3 H C O , (C O )
2 2 4 2 4
2–

+4 CO , H CO , (HCO ) , CCl , Na CO , Ca CO , CS , CF , (CO )

2 2 3 3
–

4 2 3 2 3 2 4 3
–2
 546 Redox Reactions

Chromium (Cr) +3 Cr (SO ) , CrCl , Cr O , [Cr(H O) Cl ]

2 4 3 3 2 3 2 4 3

+6 K CrO , (CrO ) , K Cr O , (Cr O ) , KCrO Cl, CrO Cl , Na Cr O , CrO

2 4 4
2–

2 2 7 2 7
2–

3 2 2 2 3 10 3

Manganese (Mn) +2 MnO, MnSO , MnCl , Mn(OH) 4 2 2

+ 8/3 Mn O 3 4

+3 Mn(OH) 3

+4 MnO , K MnO 2 2 3

+6 K MnO , (MnO )
2 4 4
2–

+7 KMnO , (MnO ) , HMnO 4 4

–

Silicon (Si) –4 SiH , Mg Si 4 2

+4 SiO , K SiO , SiCl

2 2 3 4

Iron (Fe) 8 Fe O

3 4

3
+2 FeSO . (NH ) SO (Ferrous ammonium sulphate), K Fe(CN) , FeCl
4 4 2 4 4 6 2

+3 K [Fe(CN) ], FeCl
3 6 3

Iodine (I) +7 H 4 IO 6 , KIO 4

Osmium (Os) +8 OsO 4

Xenon(Xe) +6 XeO , XeF 3 6

(6) Exceptional cases of evaluation of oxidation numbers : The rules Similarly Caro's acid, Marshall's acid also has a peroxide linkage so
described earlier are usually helpful in determination of the oxidation that in which S shows +6 oxidation state.
number of a specific atom in simple molecules but these rules fail in
Peroxide linkage
following cases. In these cases, the oxidation numbers are evaluated using
the concepts of chemical bonding involved. O O
Type I. In molecules containing peroxide linkage in addition to H O S O O S O H
element-oxygen bonds. For example, O O
(i) Oxidation number of S in H SO
Therefore the evaluation of oxidation state of sulphur should be
2 5

(Permonosulphuric acid or Caro's acid)

made as follow,
By usual method; H 2 SO 5
2 × (+1) + 2 × (x) + 6 × (–2) + 2 × (–1) = 0
2  1  x  5  (2)  0 or x  8 (for H) (for S) (for O) (for O–O)
But this cannot be true as maximum oxidation number for S cannot
or 2 + 2x – 12 – 2 = 0 or x = + 6.
exceed + 6. Since S has only 6 electrons in its valence shell. This exceptional
value is due to the fact that two oxygen atoms in H 2 SO 5 shows peroxide (iii) Oxidation number of Cr in CrO 5

linkage as shown below, (Blue perchromate)

O Peroxide linkage By usual method CrO5 ; x – 10 = 0 or x = + 10
H O S O O H
O This cannot be true as maximum O. N. of Cr cannot be more than +
6. Since Cr has only five electrons in 3d orbitals and one electron in 4s
Therefore the evaluation of o.n. of sulphur here should be made as orbital. This exceptional value is due to the fact that four oxygen atoms in
follows,
CrO are in peroxide linkage.
2 × (+1) + x + 3 × (–2) + 2 × (–1)
5

(for H) (for S) (for O) (for O–O) The chemical structure of CrO is 5

or 2 + x – 6 – 2 = 0 or x = + 6. O O
(ii) Oxidation number of S in H S O 2 2 8
Peroxide linkage Cr Peroxide linkage
(Peroxidisulphuric acid or Marshall's acid) O O
By usual method ; H 2 S 2O8 O
1 × 2 + 2x + 8 (–2) = 0 Therefore, the evaluation of o.n. of Cr should be made as follows
2x = + 16 – 2 = 14 or x=+7
x + 1 × (– 2) + 4 (–1) = 0
(for Cr) (for O) (for O–O)
 Redox Reactions 547
or x – 2 – 4 = 0 or x = + 6. Due to the presence of a co-ordinate bond between two sulphur
Type II. In molecules containing covalent and coordinate bonds, atoms, the acceptor sulphur atom has oxidation number of – 2 whereas the
following rules are used for evaluating the oxidation numbers of atoms. other S atom gets oxidation number of + 2.

(i) For each covalent bond between dissimilar atoms the less 2 × (+1) + 3 × (–2) + x × 1 + 1 × (– 2) = 0
electronegative element is assigned the oxidation number of + 1 while the (for Na) (for O) (for S) (for coordinated S)
atom of the more electronegative element is assigned the oxidation number
or + 2 – 6 + x – 2 = 0 or x = + 6
of –1.
Thus two sulphur atoms in Na S O have oxidation number of – 2
(ii) In case of a coordinate-covalent bond between similar or 2 2 3

and +6.
dissimilar atoms but the donor atom is less electronegative than the
acceptor atom, an oxidation number of +2 is assigned to the donor atom (ii) Oxidation number of chlorine in CaOCl 2

and an oxidation number of –2 is assigned to the acceptor atom. (bleaching powder)

Conversely, if the donor atom is more electronegative than the In bleaching powder, Ca ( OCl ) Cl , the two Cl atoms are in
acceptor atom, the contribution of the coordinate bond is neglected. different oxidation states i.e. , one Cl having oxidation number of –

Examples, –1 and the other as OCl having oxidation number of +1.

–


(iii) Oxidation number of N in NH NO
(a) Oxidation number of C in HC  N and HN  C 4 3

By usual method N H O ; 2x + 4 × (+1) + 3 × (–1) = 0

The evaluation of oxidation number of C cannot be made directly by 2 4 3

usual rules since no standard rule exists for oxidation numbers of N and C. 2x + 4 – 3 = 0 or 2x = + 1 (wrong)
In such cases, evaluation of oxidation number should be made using No doubt NH NO has two nitrogen atoms but one N has negative
4 3

indirect concept or by the original concepts of chemical bonding. oxidation number (attached to H) and the other has positive oxidation

number (attached to O). Hence the evaluation should be made separately
(b) Oxidation number of carbon in H – N  C for NH 4 and NO 3
The contribution of coordinate bond is neglected since the bond is
directed from a more electronegative N atom (donor) to a less NH 4 x + 4 × (+1) = +1 or x = – 3
electronegative carbon atom (acceptor).
NO 3 x + 3 (– 2) = –1 or x = + 5.

Therefore the oxidation number of N in HN  C remains – 3 as (iv) Oxidation number of Fe in Fe O 3 4

it has three covalent bonds.

In Fe O , Fe atoms are in two different oxidation states. Fe O can be
3 4 3 4

1 × (+ 1) + 1 × (– 3) +x = 0 considered as an equimolar mixture of FeO [iron (II) oxide] and Fe O [iron 2 3

(for H) (for N) (for C) (III) oxide]. Thus in one molecule of Fe O , two Fe atoms are in + 3 oxidation
3 4

state and one Fe atom is in + 2 oxidation state.

or 1 + x – 3 = 0 or x = + 2.
(v) Oxidation number of S in sodium tetrathionate (Na S O )
(c) Oxidation number of carbon in HC  N 2 4 6

Its structure can be represented as follows,

In HC  N , N is more electronegative than carbon, each bond
gives an oxidation number of –1 to N . There are three covalent bonds, O O

the oxidation number of N in HC  N is taken as – 3 Na O S S S S O Na 
Now HC  N  +1 + x – 3 = 0  x=+2 O O
Type III. In a molecule containing two or more atoms of same The two S-atoms which are linked to each other have oxidation
or different elements in different oxidation states. number zero. The oxidation number of other S-atoms can be calculated as
follows
(i) Oxidation number of S in Na S O
2 2 3

Let oxidation number of S = x.

By usual method Na 2 S 2 O3
 2×x + 2 × 0 + 6 × ( – 2) = – 2
 2 × (+1) + 2 × x + 3 (–2) = 0 or 2 + 2x – 6 = 0
(for S) (for S–S) (for O)
or x = 2. x = + 5.
But this is unacceptable as the two sulphur atoms in Na S O cannot
have the same oxidation number because on treatment with dil. H SO , one
2 2

2
3

sulphur atom is precipitated while the other is oxidised to SO .
Na 2 S 2 O3  H 2 SO 4  Na 2 SO 4  SO 2  S  H 2 O
4
Balancing of oxidation-reduction reactions
2
Though there are a number of methods for balancing oxidation –
reduction reactions, two methods are very important. These are,

In this case, the oxidation number of sulphur is evaluated from (1) Oxidation number method
concepts of chemical bonding. The chemical structure of Na S O is 2 2 3
(2) Ion – electron method
S (1) Oxidation number method : The method for balancing redox
Na  O S O Na  reactions by oxidation number change method was developed by Johnson. In
O a balanced redox reaction, total increase in oxidation number must be equal
to the total decrease in oxidation number. This equivalence provides the
basis for balancing redox reactions. This method is applicable to both
 548 Redox Reactions
molecular and ionic equations. The general procedure involves the following
steps,
(i) Write the skeleton equation (if not given, frame it) representing
the chemical change.
(ii) Assign oxidation numbers to the atoms in the equation and find
out which atoms are undergoing oxidation and reduction. Write separate
equations for the atoms undergoing oxidation and reduction.
(iii) Find the change in oxidation number in each equation. Make the
change equal in both the equations by multiplying with suitable integers.
Add both the equations.
(iv) Complete the balancing by inspection. First balance those
substances which have undergone change in oxidation number and then
other atoms except hydrogen and oxygen. Finally balance hydrogen and
oxygen by putting H O molecules wherever needed.
2
The final balanced equation should be checked to ensure that there
are as many atoms of each element on the right as there are on the left.
(v) In ionic equations the net charges on both sides of the equation
must be exactly the same. Use H ion/ions in acidic reactions and OH
+ –
ion/ions in basic reactions to balance the charge and number of hydrogen
and oxygen atoms.
The following example illustrate the above rules,
Step : I Cu  HNO3  Cu(NO 3 )2  NO 2  H 2O
(Skeleton equation)
Step: II Writing the oxidation number of all the atoms.
0 1 5  2 2 5 2 4 2 1 2
Cu  H N O 3  Cu ( N O 3 )2  N O 2  H 2 O
Step: III Change in oxidation number has occurred in copper and
nitrogen.
0 2
Cu  Cu (NO 3 )2 ......(i)
5 4
H N O3  N O 2 ......(ii)
Increase in oxidation number of copper = 2 units per molecule
Cu
Decrease in oxidation number of nitrogen = 1 unit per molecule
HNO 3
Step: IV To make increase and decrease equal, equation (ii) is
multiplied by 2.
Cu  2 HNO3  Cu (NO 3 )2  2 NO 2  H 2O
Step: V Balancing nitrate ions, hydrogen and oxygen, the
following equation is obtained.
Cu  4 HNO3  Cu (NO 3 )2  2 NO 2  2 H 2O
This is the balanced equation.
(2) Ion-electron method (half reaction method)
Jette and LaMev developed the method for balancing redox-reactions
by ion electron method in 1927. It involves the following steps
(i) Write down the redox reaction in ionic form.
(ii) Split the redox reaction into two half reactions, one for oxidation
and other for reduction.
(iii) Balance each half reaction for the number of atoms of each
element. For this purpose,
(a) Balance the atoms other than H and O for each half reaction
using simple multiples.
(b) Add water molecules to the side deficient in oxygen and H to +
the side deficient in hydrogen. This is done in acidic or neutral solutions.
(c) In alkaline solution, for each excess of oxygen, add one water
molecule to the same side and 2OH ions to the other side. If hydrogen is still
–
unbalanced, add one OH ion for each excess hydrogen on the same side and one
–
water molecule to the other side.
(iv) Add electrons to the side deficient in electrons as to equalise the
charge on both sides.
(v) Multiply one or both the half reactions by a suitable number so
that number of electrons become equal in both the equations.
(vi) Add the two balanced half reactions and cancel any term
common to both sides.
The following example illustrate the above rules
Step: I I2  OH   IO3  I   H 2O (Ionic equation)
Step: II Splitting into two half reactions,
I2  OH   IO3  H 2 O ; I2  I 
(Oxidation half reaction) (Reduction half reaction)
Step: III Adding OH  ions, I2  12OH   2 IO3  6 H 2O
Step: IV Adding electrons to the sides deficient in electrons, (Si)
I2  12OH   2 IO3  6 H 2 O  10e  ; I2  2e   2 I 
Step: V Balancing electrons in both the half reactions.
I2  12OH   2 IO3  6 H 2 O  10e  ; 5 [I2  2e   2 I  ]
Step: VI Adding both the half reactions.
6 I2  12OH   2 IO3  6 H 2 O  10 I  ;
Dividing by 2, 3 I2  6 OH   IO3  5 I   3 H 2 O
Autoxidation
(1) Turpentine and numerous other olefinic compounds, phosphorus
and certain metals like Zn and Pb can absorb oxygen from the air in
presence of water. The water is oxidised to hydrogen peroxide. This
phenomenon of formation of H O by the oxidation of H O is known as
2 2 2
autoxidation. The substance such as turpentine or phosphorus or lead which
can activate the oxygen is called activator. The activator is supposed to first
combine with oxygen to form an addition compound, which acts as an
autoxidator and reacts with water or some other acceptor so as to oxidise
the latter. For example;
Pb  O2  PbO2 ; PbO2  H 2 O  PbO  H 2 O2
(activator)
(autoxidator) (acceptor)
(2) The turpentine or other unsaturated compounds which act as
activators are supposed to take up oxygen molecule at the double bond
position to form unstable peroxide called moloxide, which then gives up the
oxygen to water molecule or any other acceptor.
RCH  CHR  O2  RHC CHR
O O
RHC CHR  2 H 2 O  RCH  CHR  2 H 2 O2
O O
2 KI  H 2O2  2 KOH  I2
The evolution of iodine from KI solution in presence of turpentine
can be confirmed with starch solution which turns blue.
(3) The concept of autoxidation help to explain the phenomenon of
induced oxidation. Na 2 SO 3 solution is oxidised by air but Na 3 AsO3
 Redox Reactions 549
solution is not oxidised by air. If a mixture of both is taken, it is observed can act as both oxidising & reducing agent. For example, H2O2,
both are oxidised. This is induced oxidation.
H2SO3, HNO3, SO2 etc.
Na 2 SO 3  O2  Na 2 SO 5
Moloxide
Na 2 SO 5  Na 3 AsO3  Na 3 AsO4  Na 2 SO 4
Na 2 SO 3  Na 3 AsO3  O2  Na 2 SO 4  Na 3 AsO4

Disproportionation
One and the same substance may act simultaneously as an oxidising Oxidation, Reduction
agent and as a reducing agent with the result that a part of it gets oxidised
to a higher state and rest of it is reduced to lower state of oxidation. Such a 
1. H 2 O2 reduces MnO4 ion to [KCET (Med.) 2000]
reaction, in which a substance undergoes simultaneous oxidation and
reduction is called disproportionation and the substance is said to (a) Mn (b) Mn 2 
disproportionate.
(c) Mn3  (d) Mn
Following are the some examples of disproportionation,
2. When a sulphur atom becomes a sulphide ion
[AMU 1999]
increase
(a) There is no change in the composition of atom
1 0 (b) It gains two electrons
(1) H 2 O2  H 2 O 2  H 2 O  O 2
(c) The mass number changes
–1 –2 (d) None of these
3. The ultimate products of oxidation of most of hydrogen and carbon
decrease in food stuffs are [DCE 2001]
decrease
(a) H 2 O alone (b) CO 2 alone
5 7 1
(2) 4 K Cl O3  3 K Cl O4  KCl (c) H 2 O and CO 2 (d) None of these
4. When P reacts with caustic soda, the products are PH 3 and
increase
NaH 2 PO2 . This reaction is an example of
decrease
[IIT 1980; Kurukshetra CEE 1993; CPMT 1997]
0 1 3 (a) Oxidation
(3) 4 P  3 NaOH  3 H 2 O  3 NaH 2 PO2  PH3 (b) Reduction
(c) Oxidation and reduction (Redox)
increase
(d) Neutralization
decrease 5. Which one of the following does not get oxidised by bromine water [MP PET/PM
0 1 5
(a) Fe 2 to Fe 3 (b) Cu  to Cu 2
(4) 3 Cl 2  6 NaOH  5 Na Cl  Na ClO3  3 H 2 O
hot
(conc .)
(c) Mn 2 to MnO4 (d) Sn 2 to Sn 4
increase 6. In the reaction H 2 S  NO 2  H 2 O  NO  S . H 2 S is
(a) Oxidised (b) Reduced
(c) Precipitated (d) None of these
7. The conversion of PbO2 to Pb(NO 3 )2 is
(a) Oxidation
(b) Reduction
(c) Neither oxidation nor reduction
 If an element is in its highest possible oxidation state in a
compound, it can act as an oxidising agent. for example, KMnO , (d) Both oxidation and reduction
4

K Cr O , HNO , H SO , HClO etc. 8. In the course of a chemical reaction an oxidant

2 2 7 3 2 4 4

[MP PMT 1986]

 If an element is in its lowest oxidation state in a compound, it can act (a) Loses electrons
as a reducing agent. For example, H S, H C O , FeSO , Na S O , SO , SnCl ,
2 2 2 4 4 2 2 3 2 2
(b) Gains electrons
many metals etc.
(c) Both loses and gains electron
 The strength of oxyacids of chlorine decrease in the order. HClO4 > (d) Electron change takes place
HClO3> HClO2 >HClO
9. 2CuI  Cu  CuI 2 , the reaction is [RPMT 1997]
 If highly electronegative element is in its highest oxidation state in (a) Redox (b) Neutralisation
a compound that compound can act as powerful oxidant. For
(c) Oxidation (d) Reduction
example, KClO4, KClO , KBrO3, KIO3 etc. 3

 If an element is in intermediate oxidation state in a compound, it

 Redox Reactions 551

10. H 2 S reacts with halogens, the halogens [JIPMER 2000] 21. When Sn 2  changes to Sn 4  in a reaction [CPMT 1981]
(a) Form sulphur halides (b) Are oxidised (a) It loses two electrons (b) It gains two electrons
(c) Are reduced (d) None of these (c) It loses two protons (d) It gains two protons
11. H 2 O 2 reduces K 4 Fe(CN )6 [MP PMT 1985] 22. Oxidation of thiosulphate (S 2 O32  ) ion by iodine gives
(a) In neutral solution (b) In acidic solution [NCERT 1976]
(c) In non-polar solvent (d) In alkaline solution (a) SO 32  (b) SO 42 
12. Max. number of moles of electrons taken up by one mole of NO 3
(c) S 4 O62  (d) S 2 O62 
when it is reduced to [DPMT 2002]
(a) NH 3 (b) NH 2 OH 23. Zn 2  (aq)  2e  Zn(s). This is [CPMT 1985]

(c) NO (d) NO 2 (a) Oxidation (b) Reduction

(c) Redox reaction (d) None of these
13. In the reaction 3 Mg  N 2  Mg3 N 2 [MP PMT 1999] 24. One gas bleaches the colour of flowers by reduction while the other
(a) Magnesium is reduced (b) Magnesium is oxidized by oxidation [EAMCET 1980]
(c) Nitrogen is oxidized (d) None of these (a) CO and Cl 2 (b) SO 2 and Cl 2
14. When sodium metal is dissolved in liquid ammonia, blue colour
solution is formed. The blue colour is due to (c) H 2 S and Br2 (d) NH 3 and SO 2
[NCERT 1981] 25. Reduction involves NCERT 1972]
(a) Solvated Na  ions (b) Solvated electrons (a) Loss of electrons
(b) Gain of electrons
(c) Solvated NH 2 ions (d) Solvated protons
(c) Increase in the valency of positive part
15. Following reaction describes the rusting of iron (d) Decrease in the valency of negative part
4 Fe  3O2  4 Fe3   6 O 2  26. In a reaction between zinc and iodine, in which zinc iodide is
Which one of the following statement is incorrect formed, what is being oxidised [NCERT 1975]
[NCERT 1981; MNR 1991; AIIMS 1998] (a) Zinc ions (b) Iodide ions
(a) This is an example of a redox reaction (c) Zinc atom (d) Iodine
27. Which one of the following reactions does not involve either
(b) Metallic iron is reduced to Fe 3  oxidation or reduction [EAMCET 1982]
(c) Fe 3  is an oxidising agent
(a) VO2  V2 O3 (b) Na  Na 
(d) Metallic iron is a reducing agent
16. SnCl 2 gives a precipitate with a solution of HgCl2 . In this process (c) CrO42   Cr2 O72  (d) Zn 2   Zn
HgCl2 is [CPMT 1983] 28. In the following reaction,
(a) Reduced 3 Br2  6 CO 32   3 H 2 O  5 Br   BrO3  6 HCO 3
(b) Oxidised [MP PMT 1994, 95]
(c) Converted into a complex compound containing both Sn and (a) Bromine is oxidised and carbonate is reduced
Hg (b) Bromine is reduced and water is oxidised
(d) Converted into a chloro complex of Hg (c) Bromine is neither reduced nor oxidised
17. Oxidation involves [NCERT 1971, 81; CPMT 1980, 82, 83; (d) Bromine is both reduced and oxidised
MP PMT 1983] 29. In the following reaction,
(a) Loss of electrons 4 P  3 KOH  3 H 2 O  3 KH 2 PO2  PH3 [Pb. PMT 2002]
(b) Gain of electrons (a) P is oxidized as well as reduced
(c) Increase in the valency of negative part (b) P is reduced only
(d) Decrease in the valency of positive part (c) P is oxidised only
18. Incorrect statement regarding rusting is [MP PET 2000]
(d) None of these
3
(a) Metallic iron is oxidised to Fe ions 30. In the following reaction
2
(b) Metallic iron is reduced to Fe ions Cr2 O7  14 H   6 I   2Cr 3   3 H 2 O  3 I2
(c) Oxygen gas is reduced to oxide ion
(d) Yellowish – brown product is formed Which element is reduced [CPMT 1976]
19. When copper turnings are added to silver nitrate solution, a blue (a) Cr (b) H
coloured solution is formed after some time. It is because, copper [CPMT 1974, 79; DPMT
(c) O 2000] (d) I
(a) Displaces silver from the solution
31. The conversion of sugar C12 H 22 O11  CO 2 is
(b) Forms a blue coloured complex with AgNO3
(a) Oxidation
(c) Is oxidised to Cu 2  (b) Reduction
(d) Is reduced to Cu 2  (c) Neither oxidation nor reduction
20. Solution of sodium metal in liquid ammonia is strongly reducing due (d) Both oxidation and reduction
to the presence of the following in the solution
32. Which halide is not oxidised by MnO2
[NCERT 1977; KCET (Med.) 2000]
(a) Sodium atoms (b) Solvated electrons [MNR 1985; JIPMER 2000]
(c) Sodium hydride (d) Sodium amide (a) F (b) Cl
 552 Redox Reactions
(c) Br (d) I (c) HClO2 (d) HOCl
2 3
33. When Fe changes to Fe in a reaction 6. Identify the correct statement about H 2 O 2 [AIIMS 1996]
(a) It loses an electron (b) It gains an electron (a) It acts as reducing agent only
(c) It loses a proton (d) It gains a proton (b) It acts as both oxidising and reducing agent
34. In acid solution, the reaction MnO4  Mn 2  involves (c) It is neither an oxidiser nor reducer
(d) It acts as oxidising agent only
[MP PMT 1989]
7. Several blocks of magnesium are fixed to the bottom of a ship to [AIEEE 2003]
(a) Oxidation by 3 electrons
(a) Keep away the sharks
(b) Reduction by 3 electrons
(b) Make the ship lighter
(c) Oxidation by 5 electrons
(c) Prevent action of water and salt
(d) Reduction by 5 electrons
(d) Prevent puncturing by under-sea rocks
35. When iron or zinc is added to CuSO 4 solution, copper is 8. Which of the following behaves as both oxidising and reducing
precipitated. It is due to [CPMT 1974, 79] agents [AFMC 1995]
(a) Oxidation of Cu 2 (b) Reduction of Cu 2 (a) H 2 SO 4 (b) SO 2
(c) Hydrolysis of CuSO 4 (d) Ionization of CuSO 4 (c) H 2S (d) HNO 3

36. In the reaction, 4 Fe  3O2  4 Fe3   6 O 2  which of the 9. The reaction H 2 S  H 2 O2  2 H 2 O  S shows
following statement is incorrect [UPSEAT 2001, 02] [JIPMER 2001]
(a) A Redox reaction (a) Oxidizing action of H 2 O2
(b) Metallic iron is a reducing agent (b) Reducing action of H 2 O2
(c) Fe3  is an oxidising agent (c) Alkaline nature of H 2 O2
(d) Metallic iron is reduced to Fe3  (d) Acidic nature of H 2 O2
37. Which of the following is redox reaction [CBSE PMT 1997]
10. Which of the following is not a reducing agent
(a) H 2 SO 4 with NaOH [EAMCET 1987]
(b) In atmosphere, O 3 from O 2 by lightning (a) NaNO 2 (b) NaNO 3
(c) Evaporation of H 2 O (c) HI (d) SnCl 2
(d) Nitrogen oxides form nitrogen and oxygen by lightning 11. Which of the following cannot work as oxidising agent
[CPMT 1996]
Oxidizing and Reducing agent (a) O2 (b) KMnO4
(c) I2 (d) None of these
1. Equation H 2 S  H 2 O2  S  2 H 2 O represents
12. H 2 O 2 is used as [CPMT 1994]
[UPSEAT 2001]
(a) Acidic nature of H 2 O2 (a) An oxidant only
(b) A reductant only
(b) Basic nature of H 2 O2 (c) An acid only
(c) Oxidising nature of H 2 O2 (d) An oxidant, a reductant and an acid
(d) Reducing nature of H 2 O2 13. In C  H 2 O  CO  H 2 , H 2 O acts as [AFMC 1988]

2. In the reaction (a) Oxidising agent (b) Reducing agent

C 2 O 42   MnO4 
 H  Mn 2
 CO 2  H 2 O (c) (a) and (b) both (d) None of these
14. Strongest reducing agent is [CPMT 1977;
the reductant is [EAMCET 1991]
BHU 1984, 96; MP PET 1990; AMU 1999]
(a) C 2 O 42  (b) MnO4 (a) F (b) Cl 
(c) Mn 2  (d) H  (c) Br  (d) I 
3. A reducing agent is a substance which can 15. A solution of sulphur dioxide in water reacts with H 2S
[CPMT 1971, 74, 76, 78, 80; NCERT 1976]
precipitating sulphur. Here sulphur dioxide acts as
(a) Accept electron (b) Donate electrons [NCERT 1980]
(c) Accept protons (d) Donate protons (a) As oxidising agent (b) A reducing agent
4. Which of the following is the most powerful oxidizing agent (c) An acid (d) A catalyst
[MNR 1990; CPMT 2003]
16. Which of these substances is a good reducing agent
(a) F2 (b) Cl 2 [NCERT 1979; CPMT 1988]
(c) Br2 (d) I2 (a) NaOCl (b) HI
5. Of the four oxyacids of chlorine the strongest oxidising agent in (c) FeCl3 (d) KBr
dilute aqueous solution is [MP PET 2000] 17. The strongest reducing agent is [MNR 1982]
(a) HClO4 (b) HClO3 (a) HNO 2 (b) H 2S
 Redox Reactions 553

(c) H 2 SO 3 (d) SnCl 2 [JEE Orissa 2004]

18. Which one is an oxidising agent [DPMT 1996] (a) HCl (b) HClO2
(a) FeSO 4 (c) HOCl (d) None of these
(b) HNO 3 29. In the reaction
Ag 2 O  H 2 O 2  2 Ag  H 2 O  O 2 , the H 2 O 2 acts as
(c) FeSO 4 .( NH 4 )2 SO 4 .6 H 2 O
[BHU 2004]
(d) H 2 SO 4
(a) Reducing agent (b) Oxidising agent
19. In which of the following reactions H 2 O 2 is a reducing agent (c) Bleaching agent (d) None of the above
[CPMT 1981; NCERT 1981; BHU 1999] 30. In the reaction
(a) 2 FeCl2  2 HCl  H 2 O2  2 FeCl3  2 H 2 O HAsO2  Sn 2   As  Sn 4   H 2 O oxidising agent is
(b) Cl 2  H 2 O2  2 HCl  O2 [BVP 2004]
(c) 2 HI  H 2 O2  2 H 2 O  I2 (a) Sn 2
(b) Sn 4

(d) H 2 SO 3  H 2 O2  H 2 SO 4  H 2 O (c) As (d) HAsO2

20. When NaCl is dissolved in water the sodium ion becomes 31. Which of the following substances acts as an oxidising as well as a
[NCERT 1976] reducing agent [UPSEAT 2004; DCE 2004]
(a) Oxidised (b) Reduced (a) Na 2 O (b) SnCl 2
(c) Hydrolysed (d) Hydrated
21. Strongest reducing agent is [MNR 1984, 89]
(c) Na 2 O 2 (d) NaNO 2
(a) K (b) Mg 32. In the reaction
(c) Al (d) Br P  NaOH  PH 3  NaH 2 PO2 [MP PET 2004]
(e) Na (a) P is oxidised only
22. Which substance is serving as a reducing agent in the following (b) P is reduced only
reaction (c) P is oxidized as well as reduced
14 H   Cr2 O72  3 Ni  2Cr 3   7 H 2 O  3 Ni 2 (d) Na is reduced
[CBSE PMT 1994; AFMC 2000; DPMT 2001]
(a) H 2O (b) Ni Oxidation number and Oxidation state
(c) H (d) Cr2 O72  1. The oxidation number of C in CO 2 is [MP PET 2001]
23. Which of the following acid possesses oxidising, reducing and (a) – 2 (b) + 2
complex forming properties [MNR 1985] (c) – 4 (d) + 4
(a) HNO 3 (b) H 2 SO 4 2. The oxidation number of As is [RPMT 1997]
(c) HCl (d) HNO 2 (a) + 2 and + 3 (b) + 3 and + 5
(c) + 3 and + 4 (d) None of these
24. Which one is oxidising substance [CPMT 1997]
3. The oxidation number of Ba in barium peroxide is
(a) C2 H 2 O2 (b) CO [Pb. PMT 2002]
(a) + 6 (b) + 2
(c) H2S (d) CO 2 (c) 1 (d) + 4
25. The compound that can work both as oxidising and reducing agent 4. HNO 2 acts both as reductant and oxidant, while HNO 3 acts only
is [CPMT 1986; MP PET 2000]
as oxidant. It is due to their [AIIMS 2000]
(a) KMnO4 (b) H 2 O2 (a) Solubility ability
(c) BaO2 (d) K 2 Cr2 O7 (b) Maximum oxidation number
(c) Minimum oxidation number
26. Which one is oxidising agent in the reaction below (d) Minimum number of valence electrons
2CrO42  2 H   Cr2 O72  H 2 O [CPMT 1997] 5. Chlorine is in +1 oxidation state in
[MP PMT 1981; NCERT 1974; CPMT 1971, 78]
(a) H (b) Cr2 O 4 (a) HCl (b) HClO4
 (c) ICl (d) Cl 2 O
(c) Cr (d) None of these
27. Which is the best description of the behaviour of bromine in the 6. The valency of Cr in the complex [Cr(H 2 O)4 Cl 2 ]
reaction given below
[MP PMT 2000]
H 2 O  Br2  HOBr  HBr [CBSE PMT 2004] (a) 1 (b) 3
(a) Oxidised only (c) 5 (d) 6
(b) Reduced only 7. In the conversion Br2  BrO3 , the oxidation state of bromine
(c) Proton acceptor only changes from
(d) Both oxidised and reduced [EAMCET 1990; AMU 1999; RPMT 2002]
28. What is the oxidising agent in chlorine water (a) – 1 to – 1 (b) 0 to – 1
(c) 0 to + 5 (d) 0 to – 5
 554 Redox Reactions
8. In the chemical reaction Cl 2  H 2 S  2 HCl  S , the oxidation (a) + 1 (b) 0
number of sulphur changes from [MP PMT 1999] (c) + 2 (d) – 2
(a) 0 to 2 (b) 2 to 0 23. Maximum oxidation state of Cr is [RPMT 2002]
(c) – 2 to 0 (d) – 2 to – 1 (a) 3 (b) 4
9. Oxidation number of cobalt in K[Co (CO )4 ] is (c) 6 (d) 7
24. In which of the following compound transition metal has zero
[KCET 1996] oxidation state [CBSE PMT 1999; BHU 2000]
(a) + 1 (b) + 3
(a) CrO5 (b) NH 2 .NH 2
(c) – 1 (d) – 3
10. When K 2 Cr2 O7 is converted to K 2 CrO4 , the change in the (c) NOClO4 (d) [Fe(CO )5 ]
oxidation state of chromium is [NCERT 1981] 25. Carbon is in the lowest oxidation state in
(a) 0 (b) 6 [NCERT 1979; MH CET 1999]
(c) 4 (d) 3 (a) CH 4 (b) CCl 4
11. The oxidation number of chlorine in HOCl (c) CF4 (d) CO 2
(a) – 1 (b) 0
(c) + 1 (d) + 2 26. Oxidation number of carbon in H 2 C 2 O4 is
[CPMT 1982]
12. Oxidation number of S in S 2  is [CPMT 1979]
(a) + 4 (b) + 3
(a) – 2 (b) 0
(c) + 2 (d) – 2
(c) – 6 (d) + 2
13. Oxidation number of N in (NH 4 )2 SO 4 is [CPMT 1996] 27. The oxidation number of Pt in [Pt(C 2 H 4 ) Cl 3 ] is
(a) – 1 / 3 (b) – 1 [MNR 1993]
(c) + 1 (d) – 3 (a) + 1 (b) + 2
14. In which compound, oxidation state of nitrogen is 1 (c) + 3 (d) + 4
[MP PMT 1989] 28. The oxidation number of carbon in CH 2 Cl 2 is
(a) NO (b) N 2O [CPMT 1976; Pb. PET 1999; AFMC 2004]
(c) NH 2 OH (d) N2H4 (a) 0 (b) + 2
(c) 2 (d) + 4
15. Oxidation number of nickel in Ni(CO )4 29. The oxidation states of phosphorus vary from
[AIIMS 1984; MNR 1985; CPMT 1997; [CPMT 1976]
MP PET/PMT 1998; AMU 2000; 01] (a) – 3 to +5 (b) – 1 to +1
(a) 0 (b) + 4 (c) – 3 to +3 (d) – 5 to +1
(c) – 4 (d) + 2 30. The process in which oxidation number increases is known as
16. The oxidation number of sulphur in H 2 SO 4 is [CPMT 1976]
(a) Oxidation (b) Reduction
[CPMT 1979Pb. CET 2002]
(c) Auto-oxidation (d) None of the above
(a) – 2 (b) + 2
(c) + 4 (d) + 6 31. The oxidation number of S in H 2 S 2 O8 is [MP PET 2002]
17. Oxidation state of chlorine in perchloric acid is (a) + 2 (b) + 4
[EAMCET 1989] (c) + 6 (d) + 7
(a) – 1 (b) 0 32. The oxidation state of nitrogen in N 3 H is
(c) – 7 (d) + 7 [NCERT 1977, 81]
18. Oxidation number of N in HNO 3 is 1
(a)  (b) + 3
[BHU 1997] 3
(a) – 3.5 (b) + 3.5 1
(c) – 3, +5 (d) + 5 (c) 1 (d) 
3
19. The oxidation number of Mn in MnO41 is 33. Which of the following statements is correct [AFMC 1997]
(a) + 7 (b) – 5 (a) Hydrogen has oxidation number 1 and  1
(c) + 6 (d) + 5 (b) Hydrogen has same electronegativity as halogens
20. 
Sn loses two electrons in a reaction. What will be the oxidation (c) Hydrogen will not be liberated at anode
number of tin after the reaction (d) Hydrogen has same ionization potential as alkali metals
(a) + 2 (b) Zero 34. The oxidation state of Cr in [Cr(NH 3 )4 Cl 2 ] is
(c) + 4 (d) – 2 [AIEEE 2005]
21. The oxidation state of Mn in K 2 MnO4 (a) +3 (b) +2
[CPMT 1982, 83, 84; DPMT 1982; (c) +1 (d) 0
NCERT 1973; AMU 2000] 35. Sulphur has highest oxidation state in
(a) + 2 (b) + 7 [EAMCET 1991]
(c) – 2 (d) + 6 (a) SO 2 (b) H 2 SO 4
22. Oxidation number of oxygen in O 2 molecule is (c) Na 2 S 2 O3 (d) Na 2 S 4 O6
[CPMT 1984] 36. The oxidation number of Fe and S in iron pyrites are
 Redox Reactions 555
[RPMT 1997] (d) Fe2 O
(a) 4, – 2 (b) 2, – 1
(c) 3, – 1.5 (d) 3, – 1 (e) K 2 FeO4

37. The oxidation number of nitrogen in NO 3 is 52. The oxidation number of hydrogen in MH 2 is
[CPMT 1982] [CPMT 1976]
(a) – 1 (b) + 2 (a) + 1 (b) – 1
(c) + 3 (d) + 5 (c) + 2 (d) – 2
38. Oxidation state of elemental carbon is [MNR 1983]
53. Oxidation number of iodine varies from [CPMT 1982]
(a) 0 (b) 1 (a) – 1 to +1 (b) – 1 to +7
(c) 2 (d) 3 (c) +3 to +5 (d) – 1 to +5
39. The sum of the oxidation numbers of all the carbons in 54. When SO 2 is passed through acidic solution of potassium
C6 H 5 CHO is [EAMCET 1986] dichromate, then chromium sulphate is formed. Change in valency
of chromium is [CPMT 1979]
(a) + 2 (b) 0
(a) +4 to +2 (b) +5 to +3
(c) + 4 (d) –4
40. Which one of the following has the highest oxidation number of (c) +6 to +3 (d) +7 to +2
iodine [CPMT 1982] 55. The oxidation states of the most electronegative element in the
products of the reaction of BaO2 with dilute H 2 SO 4 are
(a) KI 3 (b) KI
[IIT 1991; CBSE PMT 1992; BHU 2000]
(c) IF5 (d) KIO4 (a) 0 and – 1 (b) – 1 and – 2
41. The oxidation number of N in N 2 H 5 [Pb. PMT 2001]
(c) – 2 and 0 (d) – 2 and + 1
56. The highest oxidation state of Mn is shown by
(a) – 3 (b) (– 2) [MNR 1983; RPMT 1999]
(c) – 1 (d) + 2 (a) (b)
K 2 MnO4 KMnO4
42. In which of the following compounds the oxidation number of
carbon is maximum (c) MnO2 (d) Mn2 O 2
(a) HCHO (b) CHCl 3 (e) MnO
(c) CH 3 OH (d) C12 H 22 O11 57. The oxidation number of carbon in CH 2 O is
43. The oxidation state of chlorine in KClO4 is [CPMT 1985] [IIT 1982; EAMCET 1985; MNR 1990; UPSEAT 2001
CPMT 1997, 2004]
(a) – 1 (b) + 1
(a) – 2 (b) + 2
(c) + 7 (d) – 7
(c) 0 (d) + 4
44. The oxidation state of I in H 4 IO6 is [CBSE PMT 1994] 58. Oxidation state of oxygen in hydrogen peroxide is
(a) + 7 (b) + 5 [DPMT 1984; 91; CPMT 1988; MNR 1994;
(c) + 1 (d) – 1 UPSEAT 2001; RPMT 2002; JEE Orissa 2004]
45. An element which never has a positive oxidation number in any of (a) – 1 (b) + 1
its compounds [AIIMS 1981] (c) 0 (d) – 2
(a) Boron (b) Oxygen 59. The oxidation number of Cr in K 2 Cr2 O7 is
(c) Chlorine (d) Fluorine
[CPMT 1981, 85, 90, 93, 99; KCET 1992;
46. In an oxidation process, oxidation number [CPMT 1976]
BHU 1988, 98; AFMC 1991, 99; EAMCET 1986;
(a) Decreases
MP PMT 1996, 99, 2002; MP PET/PMT 1998;
(b) Increases Bihar CEE 1995; RPET 2000]
(c) Does not change (a) +6 (b) – 7
(d) First increases then decreases
(c) +2 (d) – 2
47. If HNO 3 changes into N 2 O , the oxidation number is changed by[BHU 1997;60. AFMC 2001] of the following compounds transition metal is in oxidation
In which
(a) + 2 (b) – 1 state zero [NCERT 1982]
(c) 0 (d) + 4 (a) [Co (NH 3 )6 ]Cl 2 (b) [Fe(H 2 O)6 SO 4 ]
48. The characteristic oxidation number of atoms in free metals is [NCERT 1975]
(a) Minus one (b) Any number (c) [ Ni(CO )4 ] (d) [Fe(H 2 O)3 ](OH )2
(c) One (d) Zero 61. Oxidation number of osmium (Os) in OsO4 is
49. In which one of the following changes there are transfer of five
[AIIMS 1999]
electrons [NCERT 1982]
(a) + 4 (b) + 6
 2 3
(a) MnO4  Mn (b) CrO4  Cr
2
(c) + 7 (d) + 8
2
(c) MnO4  MnO2 2
(d) Cr2 O7  2Cr 3 62. The atomic number of an element which shows the oxidation state
of + 3 is [CPMT 1989, 94]
50. Oxidation number of C in C6 H12 O6 is [KCET 1992] (a) 13 (b) 32
(a) + 6 (b) – 6 (c) 33 (d) 17
(c) 0 (d) + 4 63. The oxidation number of iron in the compound K 4 [Fe(CN )6 ] is
51. In which of the following compounds iron has lowest oxidation state[MNR 1984] [NCERT 1976; MNR 1986; AIIMS 2000]
(a) FeSO 4 .( NH 4 )2 SO 4 .6 H 2 O (a) + 6 (b) + 4
(b) K 4 Fe(CN )6 (c) + 3 (d) + 2
(c) Fe(CO )5
 556 Redox Reactions
64. The brown ring complex compound is formulated as (a) + 4; 1s 2 2 s 2 2 p 6 3 s 2
[Fe(H 2 O)5 NO ] SO 4 . The oxidation state of iron is
[EAMCET 1987; IIT 1987; MP PMT 1994; (b) + 2; 1s 2 2 s 2 2 p 6 3 s 2 3 p 2
AIIMS 1997; DCE 2000]
(c) + 3; 1s 2 2 s 2 2 p 6 3 s 2 3 p1
(a) 1 (b) 2
(c) 3 (d) 0 (d) + 6; 1s 2 2 s 2 2 p 6
65. Oxidation state of oxygen in F2 O is 78. The oxidation number of Mn in KMnO4 is
[BHU 1982; UPSEAT 2001; MH CET 2002] [CPMT 1982, 83; EAMCET 1992, 93; RPET 1999]
(a) + 1 (b) + 2 (a) + 7 (b) – 7
(c) 1 (d) 2 (c) + 1 (d) – 1
66. Phosphorus has the oxidation state of +3 in 79. Oxidation number of As atoms in H 3 AsO4 is
[NCERT 1982; RPMT 1999]
[DPMT 2001]
(a) Orthophosphoric acid (b) Phosphorus acid
(c) Metaphosphoric acid (d) Pyrophosphoric acid (a) – 3 (b) + 4
(c) + 6 (d) + 5
67. Oxidation number of P in Mg2 P2 O7 is
80. In XeO 3 and XeF6 the oxidation state of Xe is
[CPMT 1989; MP PMT 1995]
(a) + 3 (b) + 2 [MP PET 2003]
(c) + 5 (d) – 3 (a) + 4 (b) + 6
68. The oxidation state of nitrogen is highest in (c) + 1 (d) + 3
[MP PMT 2001; BHU 2002] 81. Oxidation number of carbon in CH 3  Cl is
(a) N3H (b) NH 2 OH [MP PET 2000]
(c) N2H4 (d) NH 3 (a) – 3 (b) – 2
(c) – 1 (d) 0
69. Oxidation number of P in KH 2 PO2 is
[CPMT 1987; MH CET 1999] 82. The oxidation state of Cr in Cr2 O72  is
(a) + 1 (b) + 3 [BHU 2000; CPMT 2000]
(c) + 5 (d) – 4 (a) 4 (b) – 6
70. The most common oxidation state of an element is –2. The number (c) 6 (d) – 2
of electrons present in its outermost shell is 83. Oxidation state of ‘S’ in H 2 SO 3 [RPET 2003]
[BHU 1983; NCERT 1974; CPMT 1977]
(a) 4 (b) 2 (a) + 3 (b) + 6
(c) 6 (d) 8 (c) + 4 (d) + 2
71. Sulphur has lowest oxidation number in 84. Oxidation numbers of two Cl atoms in bleaching powder,
[EAMCET 1993] CaOCl 2 are
(a) H 2 SO 3 (b) SO 2 (a) – 1, – 1 (b) + 1, – 1
(c) H 2 SO 4 (d) H 2 S (c) + 1, + 1 (d) 0, – 1
72. The oxidation number and covalency of sulphur in the sulphur 85. Select the compound in which chlorine is assigned the oxidation
number +5 [NCERT 1984, 94]
molecule (S 8 ) are respectively [NCERT 1977]
(a) HClO4 (b) HClO2
(a) 0 and 2 (b) 6 and 8
(c) 0 and 8 (d) 6 and 2 (c) HClO3 (d) HCl
73. In ferrous ammonium sulphate oxidation number of Fe is 86. When KMnO4 is reduced with oxalic acid in acidic solution, the
[CPMT 1988]
(a) + 3 (b) + 2 oxidation number of Mn changes from
(c) + 1 (d) – 2 [MNR 1987; MP PET 2000; CBSE PMT 2000;
UPSEAT 2000, 02; BHU 2003; AMU 2002]
74. The oxidation number of nitrogen in NH 2 OH is
(a) 7 to 4 (b) 6 to 4
[NCERT 1981] (c) 7 to 2 (d) 4 to 2
(a) + 1 (b) – 1 87. Oxygen has oxidation states of +2 in the
(c) – 3 (d) – 2 [NCERT 1973; DPMT 1983; MP PET 2000]
75. The oxidation number of phosphorus in Ba(H 2 PO2 )2 is (a) H 2 O2 (b) CO 2
[Kurukshetra CEE 1998; DCE 2004]
(c) H 2O (d) OF2
(a) – 1 (b) + 1
(c) + 2 (d) + 3 88. The element exhibiting most stable  2 oxidation state among the
76. A compound is in its low oxidation state. Then its will be following is [IIT 1995]
[DCE 2001] (a) Ag (b) Fe
(a) Highly acidic
(c) Sn (d) Pb
(b) Highly basic
89. Oxidation number of sulphur in is S 2 O 32  [CPMT 1979]
(c) Highest oxidising property
(d) Half acidic, half basic (a) – 2 (b) + 2
77. The oxidation number and the electronic configuration of sulphur in (c) + 6 (d) 0
90. Carbon has zero oxidation number in
H 2 SO 4 is [KCET 2002]
[Kurukshetra CEE 2002]
 Redox Reactions 557

(a) CO (b) CH 4 (a) – 1 (b) + 1

(c) + 2 (d) – 2
(c) CH 2 Cl 2 (d) CH 3 Cl
104. Oxidation number of Fe in K 3 [Fe(CN )6 ] is
91. Oxidation state of oxygen atom in potassium superoxide is
[AMU 1988]
[MNR 1988; NCERT 1980]
(a) + 2 (b) + 3
(a) 0 (b) – 1
(c) + 1 (d) + 4
(c)  12 (d) – 2
105. Oxidation number of N in NH 3 is
92. Oxidation number of S in S 2 Cl 2 is [CPMT 1979; Pb CET 2004]
(a) + 1 (b) – 1 (a) – 3 (b) + 3
(c) + 6 (d) 0 (c) 0 (d) + 5
93. What is the oxidation number of sulphur in Na 2 S 4 O6 106. What is the net charge on ferrous ion [AFMC 2004]
(a) + 2 (b) + 3
[AIIMS 1998; DCE 1999]
(c) + 4 (d) + 5
2 3 107. Which of the following elements never show positive oxidation
(a) (b)
3 2 number [CPMT 2004]
3 5 (a) O (b) Fe
(c) (d)
5 2 (c) Ga (d) F
108. The oxidation state shown by silicon when it combines with strongly
94. When CuSO 4 reacts with KI , the oxidation number of Cu
electropositive metals is [MH CET 2004]
changes by [BHU 1997] (a) – 2 (b) – 4
(a) 0 (b) – 1 (c) + 4 (d) – 2
(c) 1 (d) 2
109. The oxidation number of sulphur in H 2 S is
95. The oxidation number of N in NH 4 Cl is
[Pb. CET 2002]
(a) + 5 (b) + 3 (a) – 2 (b) + 3
(c) – 5 (d) – 3 (c) + 2 (d) – 3
96. In which reaction there is a change in valency 110. Oxidation number of nitrogen in NaNO 2 is
[NCERT 1971; CPMT 1971]
[Pb. CET 2000]
(a) 2 NO 2  N 2 O4 (a) + 2 (b) + 3
(b) 2 NO 2  H 2 O  HNO 2  HNO 3 (c) + 4 (d) – 3
(c) NH 4 OH  NH 4  OH  111. Oxidation number of S in SO 42  [BCECE 2005]
(a) + 6 (b) + 3
(d) CaCO 3  CaO  CO 2 (c) + 2 (d) – 2
97. Oxidation state of Fe in Fe3 O 4 is 112. The oxidation state of chromium in the final product formed by the
[CBSE PMT 1999; AIIMS 2002]
reaction between KI and acidified potassium dichromate solution is [AIEEE 2005
(a) +4 (b) +6
3 4 (c) +2 (d) +3
(a) (b)
2 5 113. The oxidation state of I in IPO4 is [Orissa JEE 2005]
5 8 (a) +1 (b) +3
(c) (d)
4 3 (c) +5 (d) +7
98. Nitrogen show different oxidation states in the range
[Kerala (Med.) 2003] Redox reaction and Method for balancing
(a) 0 to +5 (b) – 3 to + 5 Redox reaction
(c) – 5 to + 3 (d) – 3 to + 3
99. Oxidation number of Mn in K 2 MnO4 and MnSO 4 are
1. The value of x in the partial redox equation MnO4  8 H   xe
respectively [CPMT 1997]
(a) + 7, + 2 (b) + 6, + 2 ⇌ Mn 2   4 H 2 O is
(c) + 5, + 2 (d) + 2, + 6 (a) 5 (b) 3
100. Identify the element which can have highest oxidation numbers[AIIMS 1996] (c) 1 (d) 0
(a) N (b) O 2. C2 H 6 (g)  nO2  CO 2 (g)  H 2 O (l)
(c) Cl (d) C In this equation, the ratio of the coefficients of CO 2 and H 2 O is[KCET 1992]
101. What is the oxidation number of Co in [Co (NH 3 )4 ClNO 2 ] (a) 1 : 1 (b) 2 : 3
(c) 3 : 2 (d) 1 : 3
[BHU 1999]
(a) + 2 (b) + 3 3. The number of electrons involved in the reduction of Cr2 O72  in
(c) + 4 (d) + 5 acidic solution to Cr 3  is [EAMCET 1983]
102. The oxidation number of nickel in K 4 [ Ni(CN )4 ] is (a) 0 (b) 2
[JIPMER 1999] (c) 3 (d) 5
(a) – 2 (b) – 1 4. When KMnO4 acts as an oxidising agent and ultimately forms
(c) + 2 (d) 0 [ MnO4 ]2 , MnO2 , Mn2 O3 , Mn2 then the number of electrons
103. The oxidation number of fluorine in F2 O is transferred in each case respectively is
[CPMT 1982; BHU 1982; EAMCET 1986] [AIEEE 2002]
 558 Redox Reactions
(a) 4, 3, 1, 5 (b) 1, 5, 3, 7 (c) MnO4 / Mn2  , E o  1.52
(c) 1, 3, 4, 5 (d) 3, 5, 7, 1
5. Starch paper is used to test for the presence of (d) Cr2 O72  / Cr 3  , E o  1.33
[NCERT 1979]
14. In the balanced chemical reaction,
(a) Iodine (b) Oxidising agent
(c) Iodide ion (d) Reducing agent IO3  a I   b H   c H 2 O  d I2
6. How many moles of K 2 Cr2 O7 can be reduced by 1 mole of Sn 2  [MP PMT 2003]a, b, c and d respectively correspond to [AIIMS 2005]
(a) 1/3 (b) 1/6 (a) 5, 6, 3, 3 (b) 5, 3, 6, 3
(c) 2/3 (d) 1 (c) 3, 5, 3, 6 (d) 5, 6, 5, 5
7. 2 MnO4  5 H 2 O2  6 H   2 Z  5 O2  8 H 2 O . In this 15. The number of moles of KMnO4 reduced by one mole of
reaction Z is [RPMT 2002]
KI in alkaline medium is: [CBSE PMT 2005]
(a) Mn2 (b) Mn4
(a) One fifth (b) five
(c) MnO2 (d) Mn (c) One (d) Two
8. What is ‘ A’ in the following reaction
2 Fe3 (aq)  Sn 2 (aq)  2 Fe2 (aq )  A [MP PET 2003] Auto oxidation and Disproportionation
3 4
(a) Sn (b) Sn
(aq ) (aq )
1. In the equation H 2 S  2 HNO 3  2 H 2 O  2 NO 2  S
2
(c) Sn (aq ) (d) Sn The equivalent weight of hydrogen sulphide is [BVP 2003]
9. For the redox reaction (a) 16 (b) 68
MnO4  C 2 O42  H   Mn 2   CO 2  H 2 O (c) 34 (d) 17
the correct coefficients of the reactants for the balanced reaction are[IIT 1988,
2. 92; BHU
If 1.21995;
g ofCPMT
metal1997;
displace 1.12 litre hydrogen at normal temperature
RPMT 1999; DCE 2000; MP PET 2003] and pressure ,equivalent weight of metal would be [DPMT 2001]
MnO4 C 2 O 42  H (a) 24 (b) 12
(a) 2 5 16 (c) 1.2 11.2 (d) 1.2  11.2
(b) 16 5 2 3. Which one of the following nitrates will leave behind a metal on
(c) 5 16 2 strong heating [AIEEE 2003]
(d) 2 16 5 (a) Ferric nitrate (b) Copper nitrate
10. Which of the following is a redox reaction (c) Manganese nitrate (d) Silver nitrate
[AIEEE 2002]
4. To prevent rancidification of food material, which of the following is
(a) NaCl  KNO 3  NaNO 3  KCl added [CPMT 1996]
(b) CaC2 O4  2 HCl  CaCl 2  H 2C2 O4 (a) Reducing agent (b) Anti-oxidant
(c) Mg(OH)2  2 NH 4 Cl  MgCl2  2 NH 4 OH (c) Oxidising agent (d) None of these
(d) Zn  2 AgCN  2 Ag  Zn(CN )2 5. Prevention of corrosion of iron by zinc coating is called
[MP PMT 1993; CPMT 2002]
11. Which of the following reaction is a redox reaction
(a) Galvanization (b) Cathodic protection
[MP PMT 2003]
(c) Electrolysis (d) Photo–electrolysis
(a) P2 O5  2 H 2 O  H 4 P2 O7
6. The metal used in galvanizing of iron is
(b) 2 AgNO3  BaCl2  2 AgCl  Ba(NO 3 )2 [MP PET 1985, 96]
(c) BaCl2  H 2 SO 4  BaSO4  2 HCl (a) Pb (b) Zn
(c) Al (d) Sn
(d) Cu  2 AgNO3  2 Ag  Cu(NO 3 )2
7. In which of the following reactions there is no change in valency[NCERT 1974; C
12. Which of the following reactions involves oxidation-reduction
(a) 4 KClO3  3 KClO4  KCl
[NCERT 1972; AFMC 2000; Pb. CET 2004; CPMT 2004]
(b) SO 2  2 H 2 S  2 H 2 O  3 S
(a) NaBr  HCl  NaCl  HBr
(c) BaO2  H 2 SO 4  BaSO4  H 2 O2
(b) HBr  AgNO3  AgBr  HNO 3
(d) 2 BaO  O2  2 BaO2
(c) H 2  Br2  2 HBr
8. The equivalent weight of phosphoric acid (H 3 PO4 ) in the reaction
(d) 2 NaOH  H 2 SO 4  Na 2 SO 4  2 H 2 O NaOH  H 3 PO4  NaH 2 PO4  H 2O is
13. Which of the following is the strongest oxidising agent [AIIMS 1999]
[Pb. CET 2000] (a) 25 (b) 49
(a) BrO3 / Br 2  , E o  1.50 (c) 59 (d) 98
9. What is the equivalent mass of IO 4 when it is converted into I 2
(b) Fe3  / Fe2  , E o  0.76 in acid medium [Kerala PMT 2004]
 Redox Reactions 559
(a) M/6 (b) M/7 4. Of all the three common mineral acids, only sulphuric acid is found
(c) M/5 (d) M/4 to be suitable for making the solution acidic because
[Kurukshetra CEE 2002]
(e) None of these
(a) It does not react with KMnO4 or the reducing agent
10. For decolourization of 1 mole of KMnO 4 , the moles of H 2 O 2
required is [AIIMS 2004] (b) Hydrochloric acid reacts with KMnO4
(a) 1/2 (b) 3/2 (c) Nitric acid is an oxidising agent which reacts with reducing
(c) 5/2 (d) 7/2 agent
(d) All of the above are correct
11. In the reaction I2  2S 2 O3   2 I   S 4 O6  equivalent weight
5. For H 3 PO3 and H 3 PO4 the correct choice is
of iodine will be equal to [MP PET 2004]
[IIT Screening 2003]
(a) 1/2 of molecular weight
(a) H 3 PO3 is dibasic and reducing
(b) Molecular weight
(c) 1/4 of molecular weight (b) H 3 PO3 is dibasic and non-reducing
(d) None (c) H 3 PO4 is tribasic and reducing
12. The equivalent weight of KIO3 in the reaction (d) H 3 PO3 is tribasic and non-reducing
2Cr(OH )3  4 OH  KIO3  2CrO42  5 H 2 O  KI is 6. Match List I with List II and select the correct answer using the
[MP PMT 2004] codes given below the lists
List I (Compound) List II (Oxidation state of N)
Mol.wt.
(a) Mole wt. (b) (A) NO 2 (1) + 5
6
Mol.wt. Mol.wt. (B) HNO (2) – 3
(c) (d) (C) NH 3 (3) + 4
2 3
13. The product of oxidation of I  with MnO4 in alkaline medium is (D) N 2 O 5 (4) + 1
[IIT-JEE Screening 2004] Codes :
(a) A B C D
(a) IO3 (b) I2
2 3 4 1
(c) IO  (d) IO4 (b) A B C D
3 1 2 4
14. In alkaline medium ClO2 oxidize H 2 O2 in O 2 and reduced itself (c) A B C D
in Cl  then how many mole of H 2 O2 will oxidize by one mole of 3 4 2 1
ClO2 [Kerala CET 2005]
(d) A B C D
2 3 1 4
(a) 1.0 (b) 1.5
7. M 3 ion loses 3 e  . Its oxidation number will be
(c) 2.5 (d) 3.5
[CPMT 2002]
(e) 5.0 (a) 0 (b) + 3
(c) + 6 (d) – 3
8. In the reaction Zn  2 H   2Cl   Zn 2   2Cl   H 2 , the
spectator ion is [AIIMS 2001]
(a) Cl  (b) Zn 2 
1. In which of the following acid, which acid has oxidation reduction (c) H (d) All of these
and complex formation properties
[UPSEAT 2001] 9. The oxidation number of sulphur in H 2 S 2 O7 and iron in
(a) HNO 3 (b) H 2 SO 4 K4 Fe(CN )6 is respectively [AIIMS 2000]

(c) HCl (d) HNO 2 (a) + 6 and + 2 (b) + 2 and + 2

2. The compound which could not act both as oxidising as well as (c) + 8 and + 2 (d) + 6 and + 4
reducing agent is [IIT Screening 1991] 10. Oxidation number of oxygen in potassium super oxide (KO 2 ) is[UPSEAT 1999,
(a) SO 2 (b) MnO2
(a) – 2 (b) – 1
(c) Al2 O3 (d) CrO (c) – 1/2 (d) – 1/4
3. H 2 S acts only as a reducing agent while SO 2 can act both as a 11. One mole of N 2 H 4 loses 10 mol of electrons to form a new
reducing and oxidizing agent because [AMU 1999] compound Y. Assuming that all nitrogen appear in the new
(a) S in H 2 S has – 2 oxidation state compound, what is the oxidation state of N 2 in Y ? (There is no
change in the oxidation state of hydrogen)
(b) S in SO 2 has oxidation state + 4
[IIT 1981; Pb. PMT 1998]
(c) Hydrogen in H 2 S more +ve than oxygen (a) + 3 (b) – 3
(d) Oxygen is more – ve in SO 2 (c) – 1 (d) + 5
 560 Redox Reactions
12. Amongst the following identify the species with an atom in + 6 21. MnO42  (1 mole) in neutral aqueous medium is disproportionate to
oxidation state [IIT Screening 2000]
[AIIMS 2003]
(a) MnO4 (b) Cr(CN )63 
(a) 2/3 mole of MnO4 and 1/3 mole of MnO2
(c) NiF62  (d) CrO2 Cl 2
(b) 1/3 mole of MnO4 and 2/3 mole of MnO2
13. In which of the following compounds, is the oxidation number of
iodine is fractional [BVP 2003]
(c) 1/3 mole of Mn2 O7 and 1/3 mole of MnO2
(a) IF3 (b) IF2
(d) 2/3 mole of Mn2 O7 and 1/3 mole of MnO2
(c) I3 (d) IF7
22. The conductivity of a saturated solution of BaSO 4 is
14. The compound YBa 2 Cu 3 O7 which shows superconductivity has
6 1 1
copper in oxidation state ........ Assume that the rare earth element 3.06  10 ohm cm and its equivalent conductance is
Yttrium is in its usual  3 oxidation state 1.53 ohm 1
cm 1
equivalent1 . The K sp of the BaSO 4 will
[IIT 1994] be [KCET 1996]
(a) 3/7 (b) 7/3
(c) 3 (d) 7 (a) 4  10 12 (b) 2.5  10 9

15. The oxidation number of sulphur in S 8 , S 2 F2 , H 2 S respectively, (c) 2.5  10 13 (d) 4  10 6
are [IIT 1999]
23. When MnO2 is fused with KOH, a coloured compound is formed,
(a) 0, +1 and – 2 (b) + 2, +1 and – 2
the product and its colour is [IIT Screening 2003]
(c) 0, + 1 and + 2 (d) – 2, + 1 and – 2
16. Which one of the following reactions is not an example of redox (a) K 2 MnO4 , purple green
reaction [Kurukshetra CEE 1998]
(b) KMnO4 , purple
(a) Cl 2  2 H 2 O  SO 2  4 H   SO 4   2Cl 
(c) Mn2 O3 , brown
(b) Cu   Zn  Zn   Cu
(c) 2H 2  O2  2H 2 O (d) Mn3 O4 black

(d) HCl  H 2 O  H 3 O   Cl 
17. For the reactions, C  O2  CO 2 ; H  393 J

2 Zn  O2  2 ZnO; H  412 J [AIEEE 2002]

(a) Carbon can oxidise Zn

Read the assertion and reason carefully to mark the correct option out of
(b) Oxidation of carbon is not feasible the options given below :
(c) Oxidation of Zn is not feasible (a) If both assertion and reason are true and the reason is the correct
explanation of the assertion.
(d) Zn can oxidise carbon (b) If both assertion and reason are true but reason is not the correct
18. In the reaction B2 H 6  2 KOH  2 X  2Y  6 H 2 , X and Y are explanation of the assertion.
(c) If assertion is true but reason is false.
respectively [EAMCET 2003] (d) If the assertion and reason both are false.
(a) H 2 , H 3 BO3 (b) HCl , KBO3 (e) If assertion is false but reason is true.

(c) H 2 O, KBO3 (d) H 2 O , KBO 2 1. Assertion : SO 2 and Cl 2 both are bleaching agents.
Reason : Both are reducing agents. [AIIMS 1995]
19. In a balanced equation H 2 SO 4  x HI  H 2 S  y I2  z H 2 O , 2. Assertion : Fluorine exists only in –1 oxidation state.
the values of x, y, z are [EAMCET 2003] Reason : Fluorine has 2 s 2 2 p 5 configuration.
(a) x = 3, y = 5, z = 2 [AIIMS 2001]
3. Assertion : Stannous chloride is a powerful oxidising agent
(b) x = 4, y = 8, z = 5 which oxidises mercuric chloride to mercury.
(c) x = 8, y = 4, z = 4 Reason : Stannous chloride gives grey precipitate with
mercuric chloride, but stannic chloride does not
(d) x = 5, y = 3, z = 4 do so. [AIIMS 2002]
20. Which of the following can act as an acid and as a base 4. Assertion : HClO4 is a stronger acid than HClO3 .
[AMU 1999] Reason : Oxidation state of Cl in HClO4 is +VII and in
HClO3 +V. [AIIMS 2004]
(a) HClO3 (b) H 2 PO4
5. Assertion : In a reaction Zn(s)  CuSO 4 (aq) 
(c) HS  (d) All of these ZnSO 4 (aq)  Cu(s) , Zn is a reductant but
itself get oxidized.
 Redox Reactions 561
Reason : In a redox reaction, oxidant is reduced by 26 b 27 b 28 a 29 a 30 a
accepting electrons and reductant is oxidized by
losing electrons. 31 c 32 d 33 a 34 a 35 b
6. Assertion : Oxidation number of carbon in CH 2 O is zero. 36 a 37 d 38 a 39 d 40 d
Reason : CH 2 O formaldehyde, is a covalent compound. 41 b 42 b 43 c 44 a 45 d
7. Assertion : The oxidation numbers are artificial, they are 46 b 47 d 48 d 49 a 50 c
useful as a ‘book-keeping’ device of electrons in
reactions. 51 c 52 b 53 b 54 c 55 b
Reason : The oxidation numbers do not usually represent
56 b 57 c 58 a 59 a 60 c
real charges on atoms, they are simply
conventions that indicate what the maximum 61 d 62 a 63 d 64 b 65 b
charge could possibly be on an atom in a
molecule. 66 b 67 c 68 a 69 a 70 c
8. Assertion : H 2 SO 4 cannot act as reducing agent. 71 d 72 a 73 b 74 b 75 b
Reason : Sulphur cannot increase its oxidation number 76 c 77 d 78 a 79 d 80 b
beyond + 6.
81 b 82 c 83 c 84 b 85 c
9. Assertion : Equivalent weight of NH 3 in the reaction
N 2  NH 3 is 17/3 while that of N 2 is 28/6. 86 c 87 d 88 d 89 b 90 c
Reason : Equivalent weight 91 c 92 a 93 d 94 c 95 d
Molecular weight 96 b 97 d 98 b 99 b 100 c
= .
number of e – lost or gained
101 a 102 d 103 a 104 b 105 a
106 a 107 d 108 b 109 a 110 b
111 a 112 d 113 b

Redox reaction and Method for balancing

Redox reaction
Oxidation, Reduction
1 a 2 b 3 c 4 c 5 a
1 b 2 b 3 c 4 c 5 c
6 a 7 a 8 b 9 a 10 d
6 a 7 b 8 b 9 a 10 c
11 d 12 c 13 c 14 a 15 d
11 b 12 a 13 b 14 b 15 b
16 a 17 a 18 b 19 c 20 b Auto oxidation and Disproportionation
21 a 22 c 23 b 24 b 25 b
26 c 27 c 28 d 29 a 30 a 1 d 2 a 3 d 4 b 5 a

31 a 32 a 33 a 34 d 35 b 6 b 7 c 8 d 9 b 10 c

36 d 37 d 11 a 12 d 13 a 14 c

Oxidizing and Reducing agent Critical Thinking Questions

1 c 2 a 3 b 4 a 5 d 1 d 2 c 3 a,b 4 d 5 a
6 b 7 c 8 b 9 a 10 b 6 c 7 c 8 a 9 a 10 c
11 c 12 d 13 a 14 d 15 a 11 a 12 d 13 c 14 b 15 a
16 b 17 b 18 bd 19 b 20 d 16 d 17 d 18 d 19 c 20 d
21 a 22 b 23 d 24 d 25 b 21 a 22 d 23 a
26 d 27 d 28 c 29 a 30 d
31 d 32 c Assertion & Reason

Oxidation number and Oxidation state 1 c 2 b 3 e 4 b 5 a

6 b 7 a 8 a 9 a
1 d 2 b 3 b 4 b 5 d
6 b 7 c 8 c 9 c 10 a
11 c 12 a 13 d 14 b 15 a
16 d 17 d 18 d 19 a 20 c
21 d 22 b 23 c 24 d 25 a
 562 Redox Reactions

Oxidation, Reduction

1. (b) 2 MnO4  5 H 2 O2  6 H   Mn2   5 O2  8 H 2 O .

2. (b) S  2e   S 2 
0 3
4. (c) P4  3 NaOH  3 H 2 O  3 NaH 2 PO2  PH3 .
Sodium
hypophosph ite

It shows oxidation and reduction (Redox) properties.

6. (a) In this reaction H 2 S is oxidised because the oxidation state of
‘S’ change from – 2 to 0.
4 2
7. (b) PbO2  Pb(NO 3 )2 . In this reaction reduction occurs.
8. (b) Any substance which is capable of oxidising other substances
and is capable of accepting/gaining electron during oxidation is
called oxidising agent or oxidant.
 Redox Reactions 563

1 2 12
x  6
O
9. (a) 2CuI  Cu  CuI 2 . Oxidation and Reduction both occur so 2
the reaction is redox. In this reaction oxidation and reduction are not involved
10. (c) H 2 S  X 2 (Cl, Br, I  X )  2 HX  S . Here the halogen are because there is no change in oxidation number.
1 5
reduced. 0
28. (d) 3 Br2  6 CO 32   3 H 2 O  5 Br   BrO3  6 HCO 3 . In this
11. (b) When H 2O2 reduces with K 4 [Fe(CN )6 ] . It is present in reaction bromine is oxidised as well as reduced.
acidic solution. 29. (a) P is oxidized as well as reduced (as in option a).
2 K 4 [Fe(CN )6  H 2 SO 4  H 2 O 2  Reduction
6
2 K 3 [Fe(CN ) 6 ]  K 2 SO 4  2 H 2 O 30. (a) Cr2 O72   14 H   6 I   2Cr 3   3 H 2 O  3 I2
13. (b) In the given reaction oxidation state of Mg is changing from 0 31. (a) In this reaction oxidation occur.
to +2 while in nitrogen it is changing from 0 to –3. So
oxidation of Mg and reduction of nitrogen takes place. 32. (a) Fluorine has highest E o – value and more reactive than
MnO2 .
14. (b) When sodium metal is dissolved in liquid ammonia to form
coloured solution. Dilute solutions are bright blue in colour due to 33. (a) Fe2   Fe3   e  oxidation.
the presence of solvated electrons.
34. (d) MnO4  Mn2  . In this reaction 5 e  are needed for the
Na  (x  y)NH 3  [ Na( NH 3 ) x ]  [e( NH 3 )y ]
Blue Colour
reduction of Mn2  as:
MnO4  5 e   Mn2  .
15. (b) The metallic iron is oxidised to Fe 3 .
Oxidation
Oxidation 0 2 0
2 1 4 35. (b) Zn  CuSO 4  ZnSO 4  Cu
16. (a) SnCl 2  2 HgCl2  SnCl 4  Hg 2 Cl 2 (s)
Reduction
Reduction
In this reaction Cu 2  change in Cu o , hence it is called as
reduction reaction.
In this reaction HgCl2 is reduced in Hg .
0 3
17. (a) It is the process in which electrons are lost (de-electronation). 36. (d) 4 Fe 3O2  4 Fe 6 O 2  , in this reaction metallic iron is
oxidised to Fe3  .
18. (b) 4 Fe  3O 2  4 Fe 3   6 O 2 
0 2 2
19. (c) Cu is above of Ag in electrochemical series and thus 0
37. (d) 2 N 2  O2  2 N O
 2
Cu  2 Ag  Cu  2 Ag reaction occurs.
Here O.N. of N increases from O in N 2 to +2 in NO, 2– and
21. (a) Sn 2   Sn 4   2e  . In this reaction Sn 2  change in that of decreased from O in O 2 to –2 in O, therefore, it is a
Sn 4  it is called an oxidation reaction. redox reaction.

22. (c) 2S 2 O32   I2  S 4 O62   2 I  .

Oxidizing and Reducing agent
2 0
23. (b) Zn(aq )  2e   Zn(s) reduction. 2 0
1. (c) H 2 S  H 2 O2  S  2 H 2 O
24. (b) SO 2 bleaches by reduction while chlorine bleaches colour of Oxidation
flowers by oxidation. The oxidation of S shows oxidising nature of H 2 O 2 .
25. (b) It is the process in which electrons are gained (electronation).
2. (a) C2 O42   MnO4  H   Mn2   CO 2  H 2 O .
Oxidation
In this reaction C 2 O42  act as a reducing agent.
o o 2 1
26. (c) Zn  I2  ZnI2 3. (b) A substance which is capable of reducing other substances and
is capable of donating electrons during reduction is called a
Reduction reducing agent or reductant.
In this reaction Zn atom oxidised to Zn 2  ion and iodine 4. (a) Fluorine is a most powerful oxidizing agent because it consist
reduced to I  . of E o  2.5 volt .
 
5. (d) HClO is the strongest oxidising agent. The correct order of
27. (c) CrO42  Cr2 O72  1 3 5 7
oxidising power is HClO  H ClO2  H ClO3  H ClO4 .
x  [(2)  4 ]  2 2 x  (2)  7  2
6. (b) It acts both oxidizing and reducing agent.
x  8  2  6 2 x  14  2  12 ,
7. (c) Prevent action of water and salt.
 564 Redox Reactions
9. (a) In this reaction H 2 O2 acts as a oxidizing agent. 2 NO  2 H 2 O  I2
10. (b) NaNO 2 , SnCl 2 and HI have reducing and oxidizing Reducing property
properties but NaNO 3 have only oxidizing property. H 2 O2  NaNO 2  NaNO 3  H 2 O .
Reduction
11. (c) Because I2 is a reducing agent.
0 3 1
13. (a) In this reaction H 2 O acts as oxidising agent. 32. (c) P  NaOH  PH3  NaH 2 PO2
Oxidation
14. (d) I  act as a more reducing agent than other ions.
15. (a) When sulphur dioxide is react with H 2 S here SO 2 act as an Oxidation number and Oxidation state
oxidising agent and H 2 S act as reducing agent.


16. (b) HI (Hydrogen Iodide) is a good reducing agent than other 1. (d) CO 2
compound. x  2 (2)  0 ; x  4  0 ; x  4 .
17. (b) Hydrogen sulphide (H 2 S ) acts as strong reducing agent as it 3. (b) +2 it is a second group element.
decomposes by evolving hydrogen. 

o 1
4. (b) In HNO 2 oxidation number of N = + 3
19. (b) Cl2  H 2 O2  2 HCl  O2 . In this reaction chlorine reduced 
from zero to – 1 oxidation state. In HNO 3 oxidation number of N = + 5.
20. (d) NaCl  H 2O  NaOH  HCl 5. (d) In case of Cl 2 O chlorine shows + 1 oxidation state.

Sodium ion hydrated in water.
6. (b) [Cr (H 2 O)4 Cl 2 ]
21. (a) Potassium has higher negative value of reduction potential
hence it shows more reducing properties. x  0  2 (1)   1 ; x  2   1
22. (b) The oxidation number of Ni changes from 0 to 1 x   3 for Cr in complex.
23. (d) HNO 2 (Nitrous acid) acid acts as a oxidising, reducing agent 0 5

and has complex formation properties. 7. (c) Br2  BrO3 , in this reaction oxidation state change from 0
to + 5.
24. (d) CO 2 is an oxidizing agent.
8. (c) Oxidation state of sulphur in H 2 S is –2, while it is zero in ‘S’
25. (b) Hydrogen peroxide (H 2 O2 ) act as a both oxidising and i.e. in this reaction oxidation of sulphur and reduction of
reducing agent. chlorine is takes place.

27. (d) H 2 O  Br2  HOBr HBr 9. (c) K[Co(CO )4 ]
0 1 1
1  x  0  0; x  1 .
In the above reaction the oxidation number of Br2 increases
6 6
from zero (in Br2 ) to +1 (in HOBr ) and decrease from zero 10. (a) K 2 Cr2 O7  K 2 CrO4 .In this reaction no change in oxidation
( Br2 ) to – 1 (in HBr ). Thus Br2 is oxidised as well as state of chromium.
reduced & hence it is a redox reaction. 11. (c) In hypochlorous acid chlorine atom has + 1 oxidation number.

28. (c) Cl 2  H 2 O  HCl  HOCl 12. (a) S  S 2  O.N. of S = –2.

13. (d) (NH 4 )2 SO 4 ⇌ 2 NH 4   SO 4  

HOCl  HCl  [O]

HOCl can furnish, nascent oxygen. NH 4
Reduction (oxidisingagent)
x  4  1; x  1  4  3 .
29. (a) Ag2 O  H 2 O2  2 Ag  H 2 O  O2 14. (b) In N 2 O nitrogen have +1 oxidation state.
Oxidation (reducing agent) 15. (a) If any central metal atom combined with corbonyl group than
central metal atom shows always zero oxidation state.
30. (d) Oxidizing agent itself, undergoes reduction during a redox

reaction 16. (d) H 2 SO 4
3 2 0 2
HAsO2  Sn  As Sn  H 2 O 2  x  2  4  0 , x  8  2  6 .

Hence, here HAsO2 is acting as oxidizing agent. 17. (d) HClO4
31. (d) NaNO 2 (Sodium nitrite) act both as oxidising as well as 1  x  2  4  0; 1  x  8  0
reducing agent because in it N atom is in +3 oxidation state x  8  1  7 oxidation state.
(intermediate oxidation state)

Oxidising property 18. (d) H N O3 ; 1  x  6  0 ; x  5 .
2 NaNO 2  2 KI  2 H 2 SO 4  Na 2 SO 4  K 2 SO 4 19. (a) Mn shows + 7 oxidation state in MnO41
 Redox Reactions 565
 x 4 0 4  2x  0
MnO41 x  4 2 x  4
x  (2  4 )  1 4
x  2 .
x  8  1 2
x  1  8  7 . 

20. (c) Sn 2   Sn 4   2e  37. (d) NO 3

 x  2  3  1 ; x  6  1  5 .
21. (d) K 2 MnO4
38. (a) Every element always shows zero oxidation state.
2  x  24  0 39. (d) In benzaldehyde all carbon atoms show – 4 oxidation state.
x  8  2  6 . 
22. (b) Each molecule always show zero oxidation state. 40. (d) KIO4
23. (c) Maximum oxi. state for Cr is + 6.
1  x  2  4  0 ; x  8  1  7 .
24. (d) In [Fe(CO )5 ] , transition metal Fe has zero oxidation state.

25. (a) In (b, c, d) carbon show + 4 oxidation state while in (a) carbon 41. (b) N 2 H 5
show – 4 oxidation state.
 2 x  5  1 ; 2 x  1  5
26. (b) H 2 C 2 O4
2 x  4 ; x  2 .
2  2x  2  4  0 ; 2x  8  2  6 42. (b) Oxidation number of C in
6 HCHO  0
x   3 .
2 CHCl 3  2
27. (b) In complex [Pt(C2 H 4 )Cl3 ] Pt have + 2 oxidation state.
CH 3 OH  2

28. (a) CH 2 Cl 2 C12 H 22 O11  0
x 220; x 0 . 
29. (a) Phosphorus shows – 3 to + 5 oxidation state. 43. (c) KClO4
31. (c) The chemical structure of H 2 S 2O8 is as follows:- 2  2x  2  7  0
O O 2 x  14  2  0 .
|| ||

H O  SO O  SO H
|| || 44. (a) H 4 IO6
O O
4  x  12  1 ; x  1  8   7 .
So the oxidation number of S should be :
45. (d) Fluorine always shows – 1 oxidation state.
2  (1) 2  X  6  (2) 2  (1)  0 or X  6 .
(for H ) (for S ) (for O ) (for O O ) 46. (b) In oxidation process oxidation state always increases.
1 
32. (d) In hydrazoic acid ( N 3 H ) nitrogen shows  oxidation 47. (d) HNO 3 ⇌ N 2 O
3
state. 1  x  6  0 2x  2  0
 x  5 2x  2
N3H
2
1 x  1 .
3 x  1  0 , 3 x  1 , x   . 2
3 48. (d) All free metals always shows zero oxidation state.
33. (a) Hydrogen have oxidation no. + 1 and – 1.
49. (a) MnO4  Mn2   5 e  .
34. (a) Cr(NH 3 )4 Cl 2  
50. (c) C has oxidation number = 0.
x  4  (0)  2  1  x  0  2  1 51. (c) Iron has zero oxidation state in carbonyl complexes.
 x = 1 + 2 = + 3. 52. (b) In all alkali and alkaline earth metal hydride hydrogen always
shows – 1 oxidation state.

35. (b) SO 2  4 53. (b) Iodine shows – 1 to + 7 oxidation state.
 Reduction
H 2 SO 4  6 6
54. (c) K 2 Cr2 O7  3 SO 2  H 2 SO 4 

Na 2 S 2 O3  2 3


K 2 SO 4  Cr2 (SO 4 )3  H 2 O
5
Na 2 S 4 O6   . In this reaction chromium change from + 6 to +3 oxidation
2 state.
 
36. (a) FeS 2 FeS 2 55. (b) In H 2 O2 oxygen shows = – 1 (peroxide) oxidation state and in
BaSO4 oxygen shows = – 2 oxidation state.
 566 Redox Reactions
7  
56. (b) Mn shows highest oxidation state in KMnO4 . 71. (d) H 2 SO 3  4 ; SO 2  4
  
57. (c) CH 2 O H 2 SO 4  6 ; H 2 S  2 .
x 220 72. (a) The oxidation number of sulphur in the sulphur molecule (S 8 )
x 0. is 0 and 2.
58. (a) In all peroxide oxygen shows – 1 oxidation state. 73. (b) In ferrous ammonium sulphate Fe shows +2 oxidation state.
 
59. (a) K 2 Cr2 O7 74. (b) NH 2 OH
2  2 x  2  7  0 ; 2 x  14  2  0 x  2 (1)  2  1  0
12 x  2  2  1  0 ; x  1 .
2 x  12 ; x   6 .
2  
60. (c) Nickle shows zero oxidation state in carbonyl complex. 75. (b) Ba(H 2 PO2 )2 ; BaH4 P2 O4

2  4  2x  8  0 ; 2x  2
61. (d) Os O 4
2
x  4(2)  0 x  1 .
2
x 8 0 
x  8 . 77. (d) H 2 SO 4
62. (a) Al shows + 3 oxidation state. 2  (1)  x  4  (2)  0

63. (d) K 4 [Fe(CN )6 ] 2  x  8  0 ; x  8  2  6
1  4  x  (1  6)  0, 4  x  6  0 Electronic configuration of sulphur in H 2 SO 4 is
x  2 . 1s 2 , 2 s 2 , 2 p 6 .
In this complex compound Iron show + 2 oxidation state. 
64. (b) In this complex iron is a central metal atom showing + 2 78. (a) KMnO4
oxidation state.
65. (b) Oxygen shows + 2 oxidation state in F2 O . As F most 1  x  2  4  0 ; x  8  1  7 .
electronegative element, it always has an O. No. =–1 79. (d) H 3 AsO4

66. (b) H 3 PO3 3  x  2  4  0 ; x  8  3  5 .

3  x  2  3  0 ; x  6  3  3 . 80. (b) The oxidation state of Xe in both XeO 3 and XeF6 is + 6

  
67. (c) Mg2 P2 O7 XeO 3 XeF6
4  2 x  2  7  0 ; 2 x  14  4  10 x  23  0 x 6 0

2 x  10 ; x 
10
 5 . x  6 x  6 .
2 
81. (b) CH 3  Cl
68. (a) 3  x  1 (1)  0
x  3(1)  (1)  1  0
3x  1  0 x  3 1  0 ; x  2  0
3 x  1,  x  
1
in N 3 H x  2 .
3 

x  2 (1)  1 (2)  1(1)  0 82. (c) Cr2 O72 

2 x  2  7  2 ; 2 x  14  2  12
x  1 in NH 2 OH
12
4 x  6 .
x  2  4 (1)  0 x    2 in N 2 H 4 2
2 
83. (c) H 2 SO 3
x  3 (1)  0 x  3 in NH 3
2  x  2  3  0 ; x  6  2  4 .
Hence, highest in N 3 H . 84. (b) Two Cl atom shows +1 and –1 oxidation state.
 
69. (a) In KH 2 PO2 85. (c) HClO3
1  2  x  (2  2)  0 1  x  2  3  0 ; x  6  1  5 .
COOH 7
3  x  4  0 ; x  1 . 86. (c) 5 |  2 KMnO4  3 H 2 SO 4 
70. (c) Oxygen has 6 electrons in the outer most shell and shows COOH
common oxidation state – 2. 2
K 2 SO 4  2 MnSO 4  10 CO 2  8 H 2 O
 Redox Reactions 567
In this reaction oxidation state of Mn change from + 7 to + 2. 
105. (a) NH 3
87. (d) Oxygen have + 2 oxidation state in OF2 .
 x  3(1)  0 , x  3 .
89. (b) S 2 O32 
106. (a) Fe [ Ar] 3d 6 4 S 2
2 x  3(2)  2 ; x  2 . 26

90. (c) x  2  (1)  2(1)  0 Fe  [ Ar] 3d 6 4 S 0

x  2  2  0 ; x  0 in CH 2Cl 2 .
Fe   [ Ar] 3d 5 4 S 0
1
91. (c) In potassium superoxide (KO 2 ) oxygen shows,  oxidation
2 In +2 state Fe is called Ferrous & in +3 state as ferric.
state. 107. (d) Fluorine is the most electronegative element in the periodic
 table so it never shows positive oxidation state.
92. (a) S 2 Cl 2
108. (b) Silicon forms silicides with strongly electropositive metals (like
2 x  2(1)  0 ; 2 x  2  0 Na, Mg, K etc.) In these compounds. It has oxidation number
x  1 .
 4 .

93. (d) Na 2 S 4 O6 109. (a) H 2 S [O.N. of H  1 ]
2  4 x  12  0
(1)  2  x  0
10 5
4 x  10 x  x .
4 2 2  x  0 ; x  2
2
94. (c) CuSO 4  2 KI ⇌ K2 SO 4  CuI 2 110. (b) Let the oxidation number of N in NaNO 2 be x
1 1  x  (2)  2  0
2 CuI 2 
 Cu 2 I2  I2
 1  x  4  0 ; x  3
95. (d) NH 4 Cl ⇌ NH 4  Cl 

111. (a) x  8  2  6

NH 4 112. (d) K 2 Cr2 O7  6 KI  7 H 2 SO 4  4 K 2 SO 4  Cr2 (SO 4 )3
x  4  1 ; x  1  4  3 . 7 H 2 O  3 I2
4 5
96. (b) 2 NO 2  H 2 O  HNO 2  HNO 3 . In this reaction oxidation * 3
C r2 (SO 4 )3  2 Cr  3 SO 42 
state changes.
 113. (b) Let the oxidation number of I in IPO4  x
97. (d) Fe 3 O4
3 x  (8)  0 ; 3 x  8  0 Oxidation number of PO4  3
8 x  (3)  0  x  3
3x  8 ; x  .
3
  Redox reaction and Method for balancing
99. (b) K 2 MnO4 MnSO 4 Redox reaction
2 x 8 0 x 6 8 0
x  6 x  2 . 1. (a) MnO4  8 H   5 e  ⇌ Mn   4 H 2 O .
100. (c) Chlorine have oxidation state – 1 to + 7. 2. (b) The balanced equation is 2C2 H 6  7 O2  4 CO 2  6 H 2 O .
 Ratio of the coefficients of CO 2 and H 2 O is 4 : 6 or 2 : 3.
101. (a) [Co (NH 3 )4 ClNO2 ]
x  4(0)  1(1)  1(1)  0 3. (c) Cr2 O7 2   3e   Cr 3  .

x  0 1 1  0 Reduction
x  2  0 ; x  2 . In this reaction three electrons are required for the reduction

of Cr2 O72  into Cr 3  .
102. (d) K 4 [ Ni(CN )4 ]
4  (1)  x  4  (1)  0 4. (c) Number of e  transferred in each case is 1, 3, 4, 5.
5. (a) Starch paper are used for iodine test
4  x  4  0  x  0 .
103. (a) Fluorine always shows – 1 oxidation state in oxides. as: I   oxidant  I2

104. (b) K 3 [Fe(CN )6 ] I2  starch  blue colour

1  3  x  (1  6)  0 6. (a) Cr2O72   14 H   6 e   2Cr 3   7 H 2O

3  x  6  0 ; x  3 .
 568 Redox Reactions

(Sn 2   Sn 4   2e  )  3 2 KMnO4  KI  H 2 O  2 MnO2  2 KOH  KIO3 .

Cr2O72   14 H   3 Sn 2   3 Sn 4   2Cr 3   7 H 2O Auto oxidation and Disproportionation

It is clear from this equation that 3 moles of Sn 2  reduce one 0
1 1. (d) H 2 S  S  2e
mole of Cr2 O72  , hence 1 mol. of Sn 2  will reduce moles
3
Mol.wt. 34
of Cr2 O72  . Equivalent wt. = = =17.
2 2
7. (a) 2 MnO4  5 H 2 O2  6 H   2 Mn2   5 O2  8 H 2 O . 2. (a) 1.12 ltrH 2  1.2 g; 22.4 ltrH 2  24 g .
Reduction

3. (d) 2 AgNO3  2 Ag  2 NO 2  O2 .
8. (b) 2 Fe 3   Sn 2  2 Fe 2  Sn 4 
4. (b) To prevent rancidification of food material we add anti-oxidant
Oxidation which are called oxidation inhibitor.

9. (a) MnO4  8 H   5 e   Mn2   4 H 2 O  2 6. (b) Zn 2  / Zn. E o  0.76 V

C2 O42   2CO 2  2e   5 Al3  / Al E o  1.662

2 MnO4  5 C2 O42   16 H   2 Mn2   10 CO 2  8 H 2 O Sn 2  / Sn E o  0.136

Thus the coefficient of MnO4 , C 2 O42  and H  in the above
Pb2  / Pb E o  0.126
balanced equation respectively are 2, 5, 16.
0 1 0 2 In galvanizing action Zn is coated over iron.
10. (d). Zn  2 AgCN  2 Ag  Zn(CN )2 .
Reduction 8. (d) Molecular weight of H 3 PO4 is 98 and change in
Oxidation its valency = 1 equivalent wt. of H 3 PO4
Oxidation Reduction Molecularweight 98
   98 .
o 1 2 o Change in valency 1
11. (d) Cu  2 AgNO3  Cu (NO 3 )2  2 Ag . This is a redox
reaction. 9. (b) Equivalent mass

Oxidation Molecular weight


Change in oxidation number per mole
0 0  
12. (c) H 2  Br2  2H  Br Suppose molecular weight is M
Reduction Oxidation number of I2 in IO4 in
13. (c) Higher is the reduction potential stronger is the oxidising
Acidic medium i.e., I  (8)  1e   7
agent. Hence in the given options. MnO4 is strongest
oxidising agent. So eq. wt.  M / 7 .
14. (a) IO + aI + bH  cH O + dI
3
– – +

2 2
10. (c) 2 KMnO4  3 H 2 SO 4  K 2 SO 4  2 MnSO4
Step 1 : I  I (oxidation)
3 H 2 O  5 O
–1

IO  I (reduction)
–

5 H 2 O 2  5 O  5 H 2 O  5 O 2
3 2

Step 2 : 2IO + 12H  I + 6H O –

3
+

2 2

2 KMnO4  3 H 2 SO 4  5 H 2 O2  K 2 SO 4  2 MnSO 4

Step 3 : 2IO + 12H + 10e  I + 6H O 3
– +

2 2

2I  I + 2e
– 8 H 2 O  5 O2
2

Step 4 : 2IO + 12H + 10e  I + 6H O – + –

Molecular weight
3 2 2
11. (a) = Equivalent weight of Iodine.
2
[2I  I + 2e]5
–

Molecular weight
Step 5 : 2IO + 10I + 12H  6I + 6H O 3
– – +

2 2
12. (d) Because in KIO3 effective oxidation
3
IO + 5I + 6H  3I + 3H O
3
– – +

2 2
number is 3.
On comparing, a = 5, b = 6, c = 3, d = 3 13. (a) 6 MnO4  I   6 OH   6 MnO42   IO3  3 H 2 O
15. (d) In alkaline medium
 Redox Reactions 569

14. (c) ClO2  Cl  x  6  4  2 for Fe .

 1
ClO2  2 H 2 O  5 e  Cl   4 OH  10. (c) KO 2 ,  1  2 x  0, x   .
2
H 2 O2  O2
11. (a) N 22   2 N a   10e 

H 2 O 2  2OH  O 2  2 H 2 O  2e  2a  [2  (2)]  10
ClO2  2 H 2 O  5 e  Cl   4 OH  ]  2  a  3 .

H 2 O 2  2OH   O 2  2 H 2 O  2e ]  2 12. (d) CrO2 Cl 2 , x  4  2  0, x  6 .

2ClO2  5 H 2 O 2  2OH   2Cl   5 O 2  5 H 2 O 13. (c) 3 x  1, x  1 / 3 .


2ClO2  5 H 2 O 2 14. (b) Ba2 Cu 3 O7
 ClO2  2.5 H 2 O 2 3  2  2  3 x  (2  7)  0
3  4  3 x  14  0
Critical Thinking Questions
3x  7
1. (d) HNO 2 shows both oxidation and reduction properties. 7
x .
2. (c) Al2 O3 could not act as a oxidising and reducing agent. 3

3. (a, b) In H 2 S sulphur shows –2 oxidation state and in SO 2 15. (a) S8  0
shows +4 oxidation state. Hence SO 2 shows both oxidising 
and reducing properties. S 2 F2  1
4. (d) All the given statements are true. 

H H 2 S  2 .
|
5. (a) H  O  P  OH , hence it is dibasic. It acts as reducing 16. (d) In reaction HCl  H 2 O  H 3 O   Cl  , only reduction

O has taken place not oxidation.
agent also. 17. (d) Zn can oxidise carbon because heat of combusion of Zn  C .

6. (c) (a) N O 2 ; x  4  0 ; x   4 18. (d) B2 H 6  2 KOH  2 H 2 O  2 KBO2  6 H 2 .
 19. (c) The values of x , y, z are 8, 4, 4 respectively hence the
(b) H N O ; 1  x  2  0 ; x  1 reaction is
 H 2 SO 4  8 HI  H 2 S  4 I 2  4 H 2 O
(c) NH 3 ; x  3  0 ; x  3
20. (d) Acid Base
 10
(d) N 2 O5 ; 2 x  10  0 ; 2 x  10 ; x  ; x = 5. HClO3 ClO32 
2

7. (c) 2 × No. of e  losses = Oxi. no. HS  S 2

2  3e   6 . H 2 PO4 HPO42 
8. (a) The ion which is not affected during the course of reaction is 2
known as spectator ion. 21. (a) MnO42  in neutral aqueous medium is disproportionate to
3

1
9. (a) H 2 S 2 O7 mole of MnO4 and mole of MnO2 .
3
2  (1)  2  x  7  (2)  0
1000 K 1000  3.06  10 6
2  2 x  14  0 22. (d) m    1 .53
S S
2 x  14  2  12
mol
12 S  2  10  3
x  6 for S litre
2

Ksp (BaSO 4 )  S 2  (2  10 3 )2  4  10 6 .
K 4 Fe(CN )6

23. (a) 2 MnO2  4 KOH  O2  2 K 2 MnO4  2 H 2 O .
4  (1) x  6  (1)  0 purple green

4  x 6 0
Assertion & Reason
 570 Redox Reactions
9. (a) Both assertion and reason are true and reason is the correct
1. (c) It is true that SO 2 and Cl 2 both are bleaching agents. But explanation of assertion.
0
Cl 2 is an oxidising agent while SO 2 is a reducing agent. N 2  6 e   2 N 3 
Therefore, in this questions assertion is true while reason is
false.  equivalent weight of
14  3 17
2. (b) It is correct that fluorine exists only in –1 oxidation state NH 3   (M. wt. of NH 3 )
2 5 3 3
because it has 1s 2 p electronic configuration and thus
shows only –1 oxidation state in order to complete its octet. 14  2 28
while for N 2  
Hence, both assertion and reason are true and reason is not a 6 6
correct explanation of assertion.
3. (e) Here, assertion is false, because stannous chloiride is a strong
reducing agent not strong oxidising agent. Stannous chlorides
gives Grey precipitate with mercuric chloride. Hence, reason is
true.

4. (b) Both assertion and reason are true but reason is not the
correct explanation of assertion. Greater the number of
negative atoms present in the oxy-acid make the acid stronger.
In general, the strengths of acids that have general formula
(HO)m ZOn can be related to the value of n . As the value of
n increases, acidic character also increases. The negative atoms
draw electrons away from the Z-atom and make it more
positive. The Z-atom, therefore, becomes more effective in with
drawing electron density away from the oxygen atom that
bonded to hydrogen. in turn, the electrons of H  O bond are
drawn more strongly away from the H -atom. The net effect
makes it easier from the proton release and increases the acid
strength.
5. (a) Both assertion and reason are true and reason is the correct
explanation of assertion.
Oxidation loss of 2e

Zn(s)  Cu 2 (aq)  Zn 2 (aq)  Cu(s)

Reduction gain of 2e
6. (b) Both assertion and reason are true but reason is not the
correct explanation of assertion.
Oxidation number can be calculated using some rules. H is
assigned +1 oxidation state and 0 has oxidation number –2
 O. No. of C in CH 2 O :
O. no. of C  2(1)  (2)  0
 O. No. of C  0
7. (a) Both assertion and reason are true and reason is the correct
explanation of assertion.
8. (a) Both assertion and reason are true and reason is the correct
explanation of assertion.
Maximum oxidation state of S is +6, it cannot exceed it.
Therefore it can’t be further oxidised as S 2 can’t be reduced
further.
 Redox Reactions 571

1. When a piece of wire of copper is dipped in AgNO3 solution, the 10. A metal ion M 3  after loss of three electrons in a reaction will have
colour of the solution turns blue due to an oxidation number equal to
[MP PMT 1992; JIPMER 2002] [CPMT 1980, 83, 84, 94, 99]
(a) Formation of soluble complex (a) Zero (b) + 2
(b) Oxidation of copper (c) + 3 (d) + 6
(c) Oxidation of silver 11. Oxidation number of oxygen in ozone (O 3 ) is
(d) Reduction of copper [MP PET 2000; MP PMT 2001]
2. HBr and HI can reduce H 2 SO 4 , HCl can reduce KMnO4 (a) + 3 (b) – 3
and HF can reduce [IIT 1981] (c) – 2 (d) 0
(a) H 2 SO 4 (b) KMnO4 12. The oxidation states of sulphur in the anions SO 32  , S 2 O42  and
(c) K 2 Cr2 O7 (d) None of the above S 2 O62  follow the order [CBSE PMT 2003]
3. Consider the following statements : (a) S 2 O62   S 2 O42  SO 32  (b) S 2 O42   SO 32   S 2 O62 
In the chemical reaction
MnO2  4 HCl  MnCl 2  2 H 2 O  Cl 2 (c) SO 32   S 2 O42   S 2 O62  (d) S 2 O42  S 2 O62   SO 32 
(1) Manganese ion is oxidised 13. The oxidation number of hydrogen in LiH is
(2) Manganese ion is reduced (a) + 1 (b) – 1
(3) Chloride ion is oxidised (c) 2 (d) 0
(4) Chloride ion is reduced 14. Which of the following is not a redox reaction
Which of these statements are correct [NDA 1999] [RPMT 1999]
(a) 1 and 3 (b) 1 and 4 (a) 2 Rb  2 H 2 O  2 RbOH  H 2
(c) 2 and 3 (d) 2 and 4
4. The oxide which cannot act as a reducing agent is
(b) 2CuI 2  2CuI  I2
[CBSE PMT 1995; AIIMS 2000; JIPMER 2002; (c) 2 H 2 O2  2 H 2 O  O 2
Kurukshetra CEE 2002]
(d) 4 KCN  Fe(CN )2  K4 Fe(CN )6
(a) SO 2 (b) NO 2
15. Which of the following equations is a balanced one
(c) CO 2 (d) ClO2 [EAMCET 1980]
5. In the reaction between ozone and hydrogen peroxide, H 2 O2 acts (a) 5 BiO3  22 H   Mn 2   5 Bi3   7 H 2 O  MnO4
as [RPET 2000]
(a) Oxidising agent (b) 5 BiO3  14 H   2 Mn 2   5 Bi3   7 H 2 O  2 MnO4
(b) Reducing agent (c) 2 BiO3  4 H   Mn 2   2 Bi3   2 H 2 O  MnO4
(c) Bleaching agent
(d) Both oxidising and bleaching agent (d) 6 BiO3  12 H   3 Mn 2   6 Bi3   6 H 2 O  3 MnO4
6. The oxidation state of each oxygen atom in Na 2 O 2 is 16. In the equation
[NCERT 1971] 4 M  8 CN   2 H 2 O  O 2  4[M(CN )2 ]  4 OH 
(a) – 2 each (b) – 2 and zero
Identify the metal M [AFMC 1998]
(c) – 1 each (d) None of the above
(a) Copper (b) Iron
7. The oxidation state of sulphur in SO 42  is (c) Gold (d) Zinc
[Bihar MEE 1996] 17. In alkaline condition KMnO4 reacts as
(a) 4 (b) 2
2 KMnO4  2 KOH  2 K2 MnO4  H 2 O  O . The equivalent
(c) 6 (d) – 6
weight of KMnO4 would be (Atomic mass of K = 39, Mn = 55, O
8. The charge on cobalt in [Co (CN )6 ]3  is [CPMT 1985, 93]
= 16) [MP PMT 2002]
(a) – 6 (b) – 3 (a) 158.0 (b) 79.0
(c) + 3 (d) + 6 (c) 52.7 (d) 31.6
9. Oxidation number of S in Na 2 SO 4 is [CPMT 1989] 18. In acidic medium, equivalent weight of K 2 Cr2 O7 (mol. wt .  M )
(a) – 2 (b) + 2 is [AFMC 1988]
(c) – 6 (d) + 6 (a) M / 3 (b) M / 4
(c) M / 6 (d) M / 2

(SET -13)
 572 Redox Reactions

1 1
1. (b) 2 Ag   Cu  Cu    2 Ag  ; E oAg  / Ag  ECu
o

/ Cu
. 13. (b) Li H .

2. (d) F  can be oxidised to F2 only by electrolysis. 14. (d) In the reaction 4 KCN  Fe(CN )2  K 4 Fe(CN )6 , change
in oxidation state is not taking place.
3. (c) Because the oxidation state of chlorine is – 4 to 0 while
Manganese ion is reduced because its oxidation state + 4 to + 2. 15. (b) 5 BiO3  14 H   2 Mn 2   5 Bi 3   7 H 2 O  2 MnO4
4. (c) CO 2 is a acidic oxide. is the balanced reaction.

5. (b) H 2 O2 acts as a reducing agent in the reaction between O3 16. (c) 4 Au  8 CN   2 H 2 O  O2  4[ Au(CN )2 ]  4 OH  .

and H 2 O2 . M
17. (a) e   Mn7   Mn 6   E  .
1
6. (c) In Na 2 O2 oxygen show – 1 oxidation state.

18. (c) Cr2O72   14 H   6 e  2Cr 3   7 H 2O
7. (c) SO 42  Equivalent weight of K2Cr2O7
x  2  4  2
Molecular Mass 294.2 M
   .
x  8  2  6 . 6 6 6
8. (c) In [Co (CN )6 ]3  complex Co shows + 3 oxidation state.

9. (d) Na 2 SO 4

2  x  24  0
x  6 .

10. (d) M 3   M 6   3e  . Thus the oxidation number of metal = +

6.

***

11. (d) Molecule and free atoms show zero oxidation state O3 is a
molecule shows zero oxidation state.

12. (b) S 2O42   SO 32   S 2 O62 

Oxi. state of sulphur in S 2 O42   3

Oxi. state of sulphur in SO 32   4

Oxi state of sulphur in S 2 O62   5 .

 Surface Chemistry 573

Chapter

14
Surface Chemistry

“The branch of physical chemistry, which deals the nature of

surfaces and also with the chemical and physical processes which takes (3) Difference between adsorption and absorption
place on the surfaces, is called surface chemistry”. Adsorption Absorption
In surface chemistry, we study the phenomenon of adsorption, It is a surface phenomenon. It concerns with the whole mass of the
catalysis and colloidal properties. absorbent.
In it, the substance is only retained on It implies that a substance is uniformly
Adsorption the surface and does not go into the distributed, through the body of the
(1) Definition : The phenomenon of attracting and retaining the bulk or interior of the solid or liquid. solid or liquid.
molecules of a substance on the surface of a liquid or solid resulting in to In it the concentration of the adsorbed In it the concentration is low.
higher concentration of the molecules on the surface is called adsorption. molecules is always greater at the free
phase.
(2) Causes of adsorption : Unbalanced forces of attraction or free
It is rapid in the beginning and slows It occurs at the uniform rate.
valencies which is present at the solid or liquid surface, have the property to down near the equilibrium.
attract and retain the molecules of a gas or a dissolved substance on to Examples : (i) Water vapours adsorbed Examples : (i) Water vapours absorbed
their surfaces with which they come in contact. by silica gel. by anhydrous CaCl2
Example : Ammonia gas placed in contact with charcoal gets (ii) NH3 is adsorbed by charcoal. (ii) NH3 is absorbed in water forming
adsorbed on the charcoal whereas ammonia gas placed in contact with NH4OH
water gets absorbed into water,
(4) Surface forces : Only the surface atoms of an adsorbent play an
Table : 14.1 Some basic terms used in adsorption
active role in adsorption. These atoms posses unbalanced forces of various
Interface : Any surface is a plane which Adsorbate and Adsorbent : The types such as, Vander Waal’s forces and chemical bond forces.
separates any two phases in contact substance which gets adsorbed on any
with each other. The plane which surface is called adsorbate for example, Thus, the residual force-field on a free surface which is responsible
separates any two phase is generally if a gas gets adsorbed on to the surface for adsorption is produced. For example, when a solid substance is broken
called an interface between the two of a solid, then the gas is termed as into two pieces, two new surfaces are formed and therefore, the number of
phases. the adsorbate. unbalanced forces becomes more. As a result the tendency for adsorption
The substance on the surface of which become large.
adsorption takes place is called (5) Reversible and Irreversible adsorption : The adsorption is
adsorbent.
reversible, if the adsorbate can be easily removed from the surface of the
adsorbent by physical methods.If the adsorbate can not be easily removed
Desorption : The removal of the Absorption : When the molecules of a from the surface of the adsorbent is called irreversible adsorption.
adsorbed substance from a surface is substance are uniformly distributed
called desorption. throughout the body of a solid or Example for reversible adsorption: A gas adsorbed on a solid surface can
liquid. This phenomenon is called be completely removed in vacuum.
absorption.
Example for irreversible adsorption: Adsorption of O on tungusten
Sorption : The phenomenon in which Occlusion : When adsorption of gases 2

adsorption and absorption occur
simultaneously is called sorption.
Mc. Bain introduced a general term
sorption describeing both
processes, however adsorption is
instantaneous i.e. a fast process while
absorption is a slow process.
adsorbent.
occur on the surface of metals this is
called occlusion. (6) Characteristics of adsorption
(i) Adsorption refers to the existence of a higher concentration of
the
any particular component at the surface of a liquid or a solid phase.
(ii) Adsorption is accompanied by decrease in the G (free energy
change) of the system when G  0 , adsorption equilibrium is said to be
established.
 574 Surface Chemistry
(iii) Adsorption is invariably accompanied by evolution of heat, i.e. it (i) In general, easily liquefiable gases e.g., CO , NH , Cl and SO etc.
2 3 2 2

is an exothermic process. In other words, H of adsorption is always are adsorbed to a greater extent than the elemental gases e.g. H , O , N , He 2 2 2

negative. etc. (while chemisorption is specific in nature.)

(iv) When a gas is adsorbed, the freedom of movement of its
molecules becomes restricted. On account of it decrease in the entropy of
the gas after adsorption, i.e. S is negative.
(v) For a process to be spontaneous, the thermodynamic
requirement is that G must be negative, i.e. there is decrease in free
energy. On the basis of Gibb’s Helmholtz equation, G  H  TS ,
G can be negative if H has sufficiently high negative value and TS
has positive value.
Classification of adsorption
Adsorption can be classified into two categories as described below,
(1) Depending upon the concentration : In adsorption the
(ii) Porous and finely powdered solid e.g. charcoal, fullers earth,
adsorb more as compared to the hard non-porous materials. Due to this
property powdered charcoal is used in gas masks.
(2) Surface area of the solid adsorbent
(i) The extent of adsorption depends directly upon the surface area
of the adsorbent, i.e. larger the surface area of the adsorbent, greater is the
extent of adsorption.
(ii) Surface area of a powdered solid adsorbent depends upon its
particle size. Smaller the particle size, greater is its surface area.
(3) Effect of pressure on the adsorbate gas
(i) An increase in the pressure of the adsorbate gas increases the
extent of adsorption. Adsorption tends to
(ii) At low temperature, the reach limiting value

Extent of adsorption
concentration of one substance is different at the surface of the other extent of adsorption increases rapidly
substance as compared to adjoining bulk or interior phase. with pressure.
(iii) Small range of pressure, the
(i) Positive adsorption : If the concentration of adsorbate is more on extent of adsorption is found to be
the surface as compared to its concentration in the bulk phase then it is directly proportional to the pressure. Adsorption increases
called positive adsorption. rapidly at the beginning
(iv) At high pressure (closer Pressure
Example : When a concentrated solution of KCl is shaken with blood to the saturation vapour pressure of
charcoal, it shows positive adsorption. the gas), the adsorption tends to achieve a limiting value.
(ii) Negative adsorption : If the concentration of the adsorbate is less (4) Effect of temperature
than its concentration in the bulk then it is called negative adsorption.
(i) As adsorption is accompanied by evolution of heat, so according
Example : When a dilute solution of KCl is shaken with blood to the Le-Chatelier’s principle, the magnitude of adsorption should decrease
charcoal, it shows negative adsorption. with rise in temperature.
(2) Depending upon the nature of force existing between adsorbate
molecule and adsorbent P - Constant
P - Constant
(i) Physical adsorption : If the forces of attraction existing between
adsorbate and adsorbent are Vander Waal’s forces, the adsorption is called x/m x/m
physical adsorption. This type of adsorption is also known as physisorption
or Vander Waal’s adsorption. It can be easily reversed by heating or
decreasing the pressure. Temperature Temperature
(ii) Chemical adsorption : If the forces of attraction existing between Physical adsorption Chemical adsorption
adsorbate particles and adsorbent are almost of the same strength as (ii) The relationship between the extent of adsorption and
chemical bonds, the adsorption is called chemical adsorption. This type of temperature at any constant pressure is called adsorption isobar.
adsorption is also called as chemisorption or Langmuir adsorption. This type (iii) A physical adsorption isobar shows a decrease in x/m (where ‘m’
of adsorption cannot be easily reversed. is the mass of the adsorbent and ‘x’ that of adsorbate) as the temperature
Comparison between physisorption and chemisorption rises.
Physisorption Chemisorption (iv) The isobar of chemisorption show an increase in the beginning
(Vander Waal's adsorption) (Langmuir adsorption) and then decrease as the temperature rises.
Low heat of adsorption usually in High heat of adsorption in the range of Adsorption isotherms
range of 20-40 kJ/mol 50-400 kJ/mol
Force of attraction are Vander Waal's Forces of attraction are chemical bond A mathematical equation, which describes the relationship between
forces. forces. pressure (p) of the gaseous adsorbate and the extent of adsorption at any
It is reversible It is irreversible fixed temperature, is called adsorption isotherms.
It is usually takes place at low It takes place at high temperature. The extent of adsorption is expressed as mass of the adsorbate
temperature and decreases with adsorbed on one unit mass of the adsorbent.
increasing temperature.
Thus, if x g of an adsorbate is adsorbed on m g of the adsorbent,
It is related to the case of liquefication It is not related.
of the gas. then
It forms multimolecular layers. It forms monomolecular layers. x
Extent of adsorption 
It does not require any activation It requires high activation energy. m
energy.
Various adsorption isotherms are commonly employed in describing
High pressure is favourable. Decrease High pressure is favourable. Decrease
the adsorption data.
of pressure causes desorption of pressure does not cause desorption.
It is not very specific. It is highly specific. (1) Freundlich adsorption isotherm
(i) Freundlich adsorption isotherm is obeyed by the adsorptions
Factors which affect the extent of adsorption : The following are the where the adsorbate forms a monomolecular layer on the surface of the
factors which affect the adsorption, adsorbent.
(1) Nature of the adsorbate (gas) and adsorbent (solid)
 Surface Chemistry 575
1 Limitation of Langmuir theory
x
 kp n (Freundlich adsorption isotherm) or (a) Langmuir’s theory of unimolecular adsorption is valid only at low
m
pressures and high temperatures.
x 1
log  log k  log p (b) When the pressure is increased or temperature is lowered,
m n additional layers are formed. This has led to the modern concept of
where x is the weight of the gas adsorbed by m gm of the multilayer adsorption.
adsorbent at a pressure p, thus x/m represents the amount of gas adsorbed
by the adsorbents per gm (unit mass), k and n are constant at a particular Adsorption from solutions
temperature and for a particular adsorbent and adsorbate (gas), n is always (1) The process of adsorption can take place from solutions also.
greater than one, indicating that the amount of the gas adsorbed does not (2) In any solution, there are two (or more) components ; solute and
increase as rapidly as the pressure. solvent. The solute may be present in the molecular or ionic form.
(ii) At low pressure, the extent of adsorption varies linearly with (3) The extent of adsorption from solution depends upon the
x concentration of the solute in the solution, and can be expressed by the
pressure.  p'
m Freundlich isotherm.
x (4) The Freundlich adsorption isotherm for the adsorption from
(iii) At high pressure, it becomes independent of pressure.  p0 1
m x
solution is,  kc n where, x is the mass of the solute adsorbed, m is the
x m
(iv) At moderate pressure depends upon pressure raised to
m mass of the solid adsorbent, c is the equilibrium concentration of the solute
1 in the solution, n is a constant having value greater than one,
x k is the proportionality constant, (The value of k depends upon the
powers  pn
m nature of solid, its particle size, temperature, and the nature of solute and
x
 p1
x
 p0
solvent etc.)
m m (5) The plot of x/m against c is similar to that Freundlich
adsorption isotherm. The above equations may be written in the following
log (x/m)

1 x
x/m slope 
n m
x
 p1 / n intercept = log k
m
x/m log p
p
Freundlich adsorption isotherm: plot Plot of log x/m against log p for the
of x/m against p adsorption of a gas on a solid
(2) The Langmuir - adsorption isotherms
(i) One of the drawbacks of Freundlich adsorption isotherm is that
it fails at high pressure of the gas. Irving Langmuir in 1916 derived a simple
adsorption isotherm, on theoretical considerations based on kinetic theory
of gases. This is named as Langmuir adsorption isotherm.
(a) Adsorption takes place on the surface of the solid only till the
whole of the surface is completely covered with a unimolecular layer of the
adsorbed gas.
(b) Adsorption consists of two opposing processes, namely
Condensation of the gas molecules on the solid surface and Evaporation
(desorption) of the gas molecules from the surface back into the gaseous
phase.
(c) The rate of condensation depends upon the uncovered (bare)
surface of the adsorbent available for condensation. Naturally, at start when
whole of the surface is uncovered the rate of condensation is very high and
as the surface is covered more and more, the rate of condensation
progressively decreases. On the contrary, the rate of evaporation depends
upon the covered surface and hence increases as more and more of the
surface is covered ultimately an equilibrium will be set up at a stage when
the rate of condensation becomes equal to the rate of evaporation
(adsorption equilibrium).
(d) The rate of condensation also depends upon the pressure of the
1
form, log  log k  log c where c, is the equilibrium concentration
n
of the solute in the solution.
Application of adsorption
The phenomenon of adsorption finds a number of applications.
Important applications are given as follows.
(1) Production of high vacuum
(2) In Gas masks : This apparatus is used to adsorb poisonous gases
(e.g. Cl 2 , CO , oxide of sulphur etc.) and thus purify the air for breathing.
(3) For desiccation or dehumidification : These substances can be
used to reduce/remove water vapours or moisture present in the air. Silica
gel and alumina are used for dehumidification in electronic equipment.
(4) Removel of colouring matter from solution : (i) Animal charcoal
removes colours of solutions by adsorbing coloured impurities. (ii) Animal
charcoal is used as decolouriser in the manufacture of cane sugar.
(5) Heterogeneous catalysis : Mostly heterogeneous catalytic
reactions proceed through the adsorption of gaseous reactants on solid
catalyst. For example,
(i) Finely powdered nickel is used for the hydrogenation of oils.
(ii) Finely divided vanadium pentaoxide (V2 O 5 ) is used in the
contact process for the manufacture of sulphuric acid.
(6) Separation of inert gases : Due to the difference in degree of
adsorption of gases by charcoal, a mixture of inert gases can be separated
by adsorption on coconut charcoal at different low temperatures.
(7) Softening of hard water
(i) The hard water is made to pass through a column packed with
zeolite (sodium aluminium silicate)
(ii) Ca , Mg ions which are responsible for hardness, get adsorbed
++ ++

gas since according the kinetic theory of gases, the number of molecules on zeolite, exchanging sodium ions.
striking per unit area is proportional to the pressure. Na 2 Al2 Si2O8  CaCl2  CaAl2 Si2O8  2 NaCl
x ap (iii) The exhausted zeolite is regenerated with 10% of sodium
Mathematically,  , where a and b are constants and chloride solution.
m 1  bp
their value depends upon the nature of gas (adsorbate), nature of the solid CaAl2 Si2O8  2 NaCl  Na 2 Al2 Si2O8  CaCl2
adsorbent and the temperature. Their values can be determined from the (8) De-ionisation of water
experimental data.
 576 Surface Chemistry
(i) Water can be de-ionised by removing all dissolved salts with the
help of cation and anion-exchanger resin.
(ii) Cation-exchanger is an organic synthetic resin such as
polystyrene-containing a macroanion (R  SO 3 etc.) which has adsorbed
H ions.
+
(iii) A resin containing a basic group (R 3 N  etc.) which has
adsorbed OH  ions acts as anion exchanger.
(9) In curing diseases : A number of drugs are adsorbed on the
germs and kill them or these are adsorbed on the tissues and heat them.
(10) Cleaning agents : Soap and detergents get adsorbed on the
interface and thus reduce the surface tension between dirt and cloth,
subsequently the dirt is removed from the cloth.
(11) Froth floatation process
A low grade sulphide ore is concentrated by separating it from
silica and other earthy matter by this method.
(12) In adsorption indicators
Surface of certain precipitates such as silver halide, have the
property of adsorbing some dyes like eosin, fluorescein etc.
(13) Chromatographic analysis
The phenomenon of adsorption has given an excellent technique of
analysis known as chromatographic analysis.
(14) In dyeing : Many dyes get adsorbed on the cloth either directly
or by the use of mordants.
Catalysis
“Catalyst is a substance which speeds up and speeds down a
chemical reaction without itself being used up.”
Berzelius (1836) introduced the term catalysis and catalyst.
Ostwald (1895) redefined a catalyst as, “A substance which changes
the reaction rate without affecting the overall energetics of the reaction is
termed as a catalyst and the phenomenon is known as catalysis.”
Types of catalysis
Catalytic reactions can be broadly divided into the following types,
(1) Homogeneous catalysis : When the reactants and the catalyst are
in the same phase (i.e. solid, liquid or gas). The catalysis is said to be
homogeneous. The following are some of the examples of homogeneous
catalysis.
(i) In the lead chamber process
2SO 2 (g)  O 2 (g)   2SO 3 (g)
NO ( g )
(ii) In the hydrolysis of ester
CH 3 COOCH 3 (l)  H 2 O(l)  
HCl (l)
CH 3 COOH (l)  CH 3 OH(l)
(iii) In the hydrolysis of sugar
C12 H 22 O11 (l) H 2 O(l) 

H 2 SO 4 (l)
(Sucrose solution)
C6 H 12 O6 (l)  C6 H 12 O6 (l)
(Glucose solution) (Fructose solution)
(2) Heterogeneous catalysis : The catalytic process in which the
reactants and the catalyst are in different phases is known as heterogeneous
catalysis. Some of the examples of heterogeneous catalysis are given below.
(i) In contact process for H 2 SO 4
2SO 2 (g)  O2 (g)   2SO 3 (g)
Pt(s )
BrV2 O5
(ii) In Haber’s process for NH 3
N 2 (g)  3 H 2 (g)   2 NH 3 (g)
Fe(s)
(iii) In Ostwald’s process for HNO 3
4 NH 3 (g)  5 O2 (g)   4 NO(g)  6 H 2O(g)
Pt(s)
(3) Positive catalysis : When the rate of the reaction is accelerated
by the foreign substance, it is said to be a positive catalyst and phenomenon
as positive catalysis. Some examples of positive catalysis are given below.
(i) Decomposition of KClO3
2 KClO3 (s)   2 KCl (s)  3O2 (g)
MnO 2 (s)
270 o C
(ii) Oxidation of SO 2
2SO 2 (g)  O2 (g)   2SO 3 (g)
V2 O5 (s)
or Pt(s)
(iii) Decon’s process
4 HCl(g)  O2 (g)   2Cl 2 (g)  2 H 2 O(g)
CuCl 2 (s)
450 o C
(4) Negative catalysis : There are certain, substance which, when
added to the reaction mixture, retard the reaction rate instead of increasing
it. These are called negative catalyst or inhibitors and the phenomenon is
known as negative catalysis. Some examples are as follows.
(i) Oxidation of sodium sulphite
2 Na 2 SO 3 (s)  O2 (g)    2 Na 2 SO 4 (s)
Alcohol(l)
(ii) Oxidation of benzaldehyde
2C6 H 5 CHO(l)  O2 (g)   2C6 H 5 COOH (l)
Diphenyl
amine (l)
(iii) Tetra ethyl lead (TEL) is added to petrol to retard the ignition
of petrol vapours on compression in an internal combustion engine and
thus minimise the knocking effect.
(5) Auto-catalysis : In certain reactions, one of the product acts as a
catalyst. In the initial stages the reaction is slow but as soon as the products
come into existences the reaction rate increases. This type of phenomenon
is known as auto-catalysis. Some examples are as follows,
(i) The rate of oxidation of oxalic acid by acidified potassium
permanganate increases as the reaction progresses. This acceleration is due
to the presence of Mn 2  ions which are formed during reaction. Thus
Mn 2  ions act as auto-catalyst.
5 H 2C2O4  2 KMnO4  3 H 2SO 4  2 MnSO4  K2 SO 4
10CO 2  8 H 2O
(ii) When nitric acid is poured on copper, the reaction is very slow
in the beginning, gradually the reaction becomes faster due to the formation
of nitrous acid during the reaction which acts as an auto-catalyst.
(6) Induced catalysis : When one reaction influences the rate of
other reaction, which does not occur under ordinary conditions, the
phenomenon is known as induced catalysis. Some examples are as follows,
(i) Sodium arsenite solution is not oxidised by air. If, however, air is
passed through a mixture of the solution of sodium arsenite and sodium
sulphite, both of them undergo simultaneous oxidation. The oxidation of
sodium sulphite, thus, induces the oxidation of sodium arsenite.
(ii) The reduction of mercuric chloride (HgCl2 ) with oxalic acid is
very slow, but potassium permanganate is reduced readily with oxalic acid.
If, however, oxalic acid is added to a mixture of potassium permanganate
and HgCl2 both are reduced simultaneously. The reduction of potassium
permanganate, thus, induces the reduction of mercuric chloride.
(7) Acid-base catalysis : According to the Arrhenius and Ostwald H +
or H ion act as a catalyst.
–
 Surface Chemistry 577
(i) For example, Hydrolysis of an ester, (i) For example, the presence of traces of arsenious oxide ( As2O3 )

CH 3 COOC 2 H 5 (l)  H 2O(l)  
 CH 3 COOH (l)  C2 H 5 OH (l)
H or in the reacting gases reduces the activity of platinized asbestos which is
OH  used as catalyst in contact process for the manufacture of sulphuric acid.
(ii) Inversion of cane sugar, (ii) The activity of iron catalyst is destroyed by the presence of
 H 2 S or CO in the synthesis of ammonia by Haber’s process.
C12 H 22 O11 (l)  H 2 O 
H
 C6 H12 O6 (l) C6 H12 O6 (l)
Sugar Fructose Glucose (iii) The platinum catalyst used in the oxidation of hydrogen is
(iii) Conversion of acetone into diacetone alcohol, poisoned by CO .
 (8) Change of temperature alters the rate of catalytic reaction as it
CH 3 COCH 3 (l)  CH 3 COCH 3 (l) 
OH
 does for the same reaction in absence of catalyst : By increasing the
temperature, there is an increase in the catalytic power of a catalyst but
CH 3 COCH 2 .C(CH 3 )2 OH(l) after a certain temperature its power begins to decrease. A catalyst has
thus, a particular temperature at which its catalytic activity is maximum.
Characteristics of catalysis This temperature is termed as optimum temperature.
The following are the characteristics which are common to must of (9) A positive catalyst lowers the activation energy
catalytic reactions. (i) According to the collision theory, a reaction occurs on account of
(1) A catalyst remains unchanged in mass and chemical composition effective collisions between the reacting molecules.
at the end of the reaction. (ii) For effective collision, it is necessary that the molecules must
(2) A small quantity of the catalyst is generally sufficient to catalyses possess a minimum amount of energy known as activation energy (E ). a

almost unlimited reactions (iii) After the collision molecules form an activated complex which
(i) For example, in the decomposition of hydrogen peroxide, one dissociate to yield the product molecules.
gram of colloidal platinum can catalyses 10 8 litres of hydrogen peroxide. (iv) The catalyst provides a new pathway involving lower amount of
(ii) In Friedel craft’s reaction, anhydrous aluminium chloride is activation energy. Thus,
required in relatively large amount to the extent of 30% of the mass of E E
benzene, E a a

Decreases
a

 RT  – RT 
C6 H 6  C2 H 5 Cl   C6 H 5 C2 H 5  HCl
AlCl3
Decreases –Increases
(3) The catalyst can not initiate the reaction: The function of the
catalyst is to alter the speed of the reaction rather than to start it.
e
–Ea/RT k
(4) The catalyst is generally specific in nature: A substance, which  Reaction speeds up
acts as a catalyst for a particular reaction , fails to catalyse the other Increases
Increases 
reaction , different catalysts for the same reactant may for different
products. larger number of effective collisions occur in the presence of
Examples : Al2 O3
C 2 H 4 (g)  H 2 O(g) a catalyst in comparison to effective collisions at the same
(Dehydrati on) temperature in absence of a catalyst. Hence the presence of a
catalyst makes the reaction to go faster.
C 2 H 5 OH (l)
(v) Figure shows that activation energy E a , in absence of a
Cu
Cu CH 3 CHO (g)  H 2 (g) catalyst is higher than the activation energy E , in presence of a a

(Dehydroge nation ) catalyst.

Cu (vi) E R and E p represent the average energies of
CO 2 (g)  H 2 (g)
(Dehydroge nation) reactants and products. The difference gives the value of G , i.e.,
HCOOH (l) G  ER  EP Uncatalysed
complex
Al2 O3
CO (g)  H 2 O(g)
(Dehydrati on) Energy
Chemical potential energy

(5) The catalyst can not change the position of equilibrium : The barrier
catalyst catalyse both forward and backward reactions to the same extent in Catalysed
a reversible reaction and thus have no effect on the equilibrium constant. complex
Ea
(6) Catalytic promoters : Substances which themselves are not
catalysts, but when mixed in small quantities with the catalysts increase
their efficiency are called as promoters or activators. Ea
(i) For example, in Haber’s process for the synthesis of ammonia,
traces of molybdenum increases the activity of finely divided iron which acts ER
Reactants G° of
as a catalyst. Initial
(A+B) reaction
state
(ii) In the manufacture of methyl alcohol from water gas EP
(CO  H 2 ) , chromic oxide (Cr2 O3 ) is used as a promoter with the Final state Products (C + D)
catalyst zinc oxide (ZnO) . Reaction sequence
(7) Catalytic poisons : Substances which destroy the activity of the Theories of catalysis
catalyst by their presence are known as catalytic poisons.
There are two theories of catalysis which is described as follows.
 578 Surface Chemistry
(1) Intermediate compound theory
(i) This theory was proposed by Clement and Desormes in 1806.
According to this theory, the desired reaction is brought about by a path
involving the formation of an unstable intermediate compound, followed by
its decomposition into the desired end products with the regeneration of
the catalyst.
(ii) The intermediate compund may be formed in either of two ways
(a) When the intermediate compound is reactive and reacts with the
other reactants.
AB  X  BX  A
intermediate
BX  C  CB  X .....(i)
(b) When the intermediate is unstable and decomposes to give the
final product.
A  B  X  ABX  AB  X .....(ii)
intermediate
Where, A, B and C are the reactant molecules and X is the molecule
of the catalyst. The first type of reaction sums up to, AB  C  CB  A
While the second to, A  B  AB in many cases, the intermediate
compounds postulated to be formed are known compounds and often their
presence is detected.
(2) Adsorption theory
(i) This theory is applicable to reactions between gases in the
presence of a solid catalyst. Some typical examples are as follows.
(ii) The contact process for the oxidation of SO 2 to SO 3 with
atmospheric oxygen in the presence of platinum as the catalyst.
(iii) The Haber’s process for the synthesis of ammonia with iron as
the catalyst.
(iv) Adsorption results in the loosening of the chemical bonds in the
reactant molecules, so that their rupture becomes easier. This is confirmed
by the observed lower activation energies for heterogeneous catalytic
reactions in the presence of the catalysts as compared to that for the same
reaction in the absence of the catalyst.
Enzyme catalysis
(1) Enzymes are complex nitrogenous substances these are actually
protein molecules of higher molecular mass.
(2) Enzymes catalyse numerous reactions, especially those connected
with natural processes.
(3) Numerous reactions occur in the bodies of animals and plants to
maintain the life process. These reactions are catalysed by enzymes. The
enzymes are thus, termed as bio-chemical catalysts and the phenomenon is
known as bio-chemical catalysis.
(4) Nitrogenase an enzyme present in bacteria on the root nodules
of leguminous plants such as peas and beans, catalyses the conversion of
atmospheric N 2 to NH 3 .
(5) In the human body, the enzyme carbonic anhydrase catalyses the
reaction of CO 2 with H 2 O ,
CO 2 (aq)  H 2O(l)  H  (aq.)  HCO3 (aq.)
The forward reaction occurs when the blood takes up CO 2 in the
tissues, and the reverse reaction occurs when the blood releases CO 2 in
lungs.
(6) In manufacturing of ethyl alcohol
(i) C12 H 22 O11 (l)  H 2O(l)   C6 H12 O6 (l) C6 H12 O6 (l)
Invertase
Glucose Fructose
C6 H12 O6 (l)   2C2 H 5 OH(l)  2CO 2 (l)
Zymase
(ii) Starch (l)   Maltose(l)
Diastase
Maltose    Glucose 
Maltase
 Alcohol
Zyamase
Activity and Selectivity
(1) Activity : Activity is the ability of catalysts to accelerate chemical
reaction, the degree of acceleration can be as high as 10 10 times in certain
reactions. For example reaction between H 2 and O 2 to form H 2 O in
presence of platinum as catalyst takes place with explosive violence.
In absence of catalyst, H 2 and O 2 can be stored indefinitely
without any reaction.
(2) Selectivity : Is the ability of catalysts to direct reaction to yield
particular products (excluding other).
Example :
CH 3
(i) n  heptane  Pt
Toluene O
||
(ii) CH 3 CH  CH 2  CH 2  CHCH
BiMoO4
Acrolein
Zeolite (Shape selective catalysis)
(1) Zeolite are alumino–silicates of the general formula,
M x / n [ AlO2 ]x .(SiO2 )y .mH 2 O , where, M may be simple cation like Na  ,
K  or Ca 2  , n is the charge on the simple cation, m is the number of molecules
of water of crystallization.
(2) Some well known zeolites are as follows,
Erionite  Na2 K2CaMg( AlO2 )2 (SiO2 )2 .6 H 2O
Gemelinite  Na 2Ca( AlO2 )2 (SiO2 )4 .6 H 2O
Faujasite (natural)  Na56 ( AlO2 )56 (SiO2 )136 .250 H 2O
ZSM-5  H x [( AlO2 )x (SiO2 )96  x ].16 H 2O
Linde-A (synthetic)  [ Na12 ( AlO2 )12 (SiO2 )12 .27 H 2O]8
(3) The characteristic feature of zeolites is the openness of the structure,
which permits cavities of different sizes.
(4) The open structure is provided by silica in which aluminium occupies
x/(x+y) fraction of the telrahedral sites.
(5) The negative charge of the aluminosilicate framework is
neutralized by the replaceable cations.
(6) The void space forms more than 50% of the total volume, which
is occupied by water molecules.
(7) The reaction- selectivity of zeolites depends upon the size of
cavities (cages), pores (apertures) and the distribution of pores in the
structure. The pore size in zeolites generally varies from 260 pm to 740
pm.
(8) Zeolite have high porosity due to the presence of one, two, or
three dimensional networks of interconnected channels and cavities of
molecular dimensions.
(9) There is a new class of highly siliceous zeolites with an optimal
pore diameter of 550pm. ZSM-5 is one such zeolite having the formula.
[H x ( AlO2 ) x .(SiO2 )96  x ].16 H 2 O
(10) The zeolite catalyst ZSM-5 converts alcohols to gasoline (petrol)
by dehydrating the alcohol and producing a mixture of wide variety of
hydrocarbons.
 Surface Chemistry 579

Colloidal state (i) Classification based on the physical state of the dispersed phase
and dispersion medium : Depending upon the physical state of dispersed
(1) The foundation of colloidal chemistry was laid down by an phase and dispersion medium whether these are solids, liquids or gases,
English scientist, Thomas Graham, in 1861. The credit for the various eight types of colloidal systems are possible.
advances in this field goes to eminent scientists like Tyndall, Hardy,
Zsigmondy, N.R. Dhar, S.S. Bhatnagar and others. Table : 14.3 Different types of colloidal systems
Dispersed Dispersion Colloidal Examples
(2) Thomas Graham classified the soluble substances into two
phase Medium System
categories depending upon the rate of diffusion through animal and
Liquid Gas Aerosol of Fogs, clouds, mists, fine
vegetable membranes or parchment paper.
liquids insecticide sprays
(i) Crystalloids : They have higher rate of diffusion and diffused Solid Gas Aerosol of Smoke, volcanic dust, haze
from parchment paper. solids
Examples : All organic acids, bases and salts and organic compounds Gas Liquid Foam or froth Soap lather. Lemonade
such as sugar, urea etc. froth, foam, whipped cream,
soda water
(ii) Colloids (Greek word, kolla, meaning glue-like) : They have Liquid Liquid Emulsions Milk, emulsified oils,
slower rate of diffusion and can not diffused from parchment paper. medicines
Examples : Starch, gelatin, gums, silicic acid and hdemoglobin etc. Solid Liquid Sols Most paints, starch in
water, proteins, gold sol,
(3) The above classification was discarded i.e., the terms colloid does arsenic sulphide sol, ink
not apply to a particular class of substances but is a state of matter like Gas Solid Solid foam Pumice stone, styrene
solid, liquid and gas. Any substance can be brought into colloidal state. rubber, foam rubber
(4) The colloidal state depends on the particle size. If is regarded as Liquid Solid Gels Cheese, butter, boot polish,
intermediate state between true solution and suspension. jelly, curd
Table : 14.2 Features of the three types of solutions Solid Solid Solid sols Ruby glass, some gem
(coloured glass) stones and alloys
Property Suspension Colloid solution True solution
(ii) Classification based on Nature of interaction between dispersed
Nature Heterogeneous Heterogeneous Homogeneous phase and dispersion medium: Depending upon the nature of interactions
Particle size > 100 nm 1 nm – 100 nm < 1 nm between dispersed phase and the dispersion medium, the colloidal solutions
Separation by can be classified into two types as (a) Lyophilic and (b) Lyophobic sols.
(i) Ordinary filtration Possible Not possible Not possible (a) Lyophilic colloids (water loving) : “The colloidal solutions in
(ii) Ultra- filtration Possible Possible Not possible which the particles of the dispersed phase have a great affinity for the
Settling of particles Settle under Settle only on Do not settle dispersion medium, are called lyophilic collodis.”
gravity centrifugation
Appearance Opaque Generally Transparent (b) Lyophobic colloids (water hateing) : “The colloidal solutions in
transparent which there is no affinity between particles of the dispersed phase and the
Tyndall effect Shows Shows Does not show dispersion medium are called lyophobic colloids.”
Diffusion of particles Does not diffuse Diffuses slowly Diffuses Distinction between lyophilic and lyophobic sols
rapidly
Property Lyophilic sols (suspensoid) Lyophobic sols (Emulsoid)
Brownian movement May show Shows Negligible Surface Lower than that of the Same as that of the medium
tension medium
Viscosity Much higher than that of Same as that of the medium
the medium
Reversibility Reversible Irreversible
Stability More stable Less stable
Visibility Particles can’t be detected Particles can be detected under
even under ultramicroscope ultramicroscope.
Suspension Colloidal solution True solution
Migration Particles may migrate in Particles migrate either towards
Size > 100 nm Size between Size < 1 nm either direction or do not cathode or anode in an electric
1-100 nm migrate in an electric field field because they carry charge.
Fig. 14.1 Three types solutions because do not carry any
Phases of colloids and Their classification charge.
Action of Addition of smaller quantity Coagulation takes place
(1) Phases of colloids : We know that a colloidal solution is of electrolyte of electrolyte has little effect
heterogeneous nature. It consists of two phases which are as follows Hydration Extensive hydration takes No hydration
place
(i) Internal phase or Dispersed phase (Discontinuous phase) : It is Examples Gum, gelatin, starch, Metals like Ag and Au,
the component present in small proportion and is just like a solute in a proteins, rubber etc. hydroxides like Al(OH )3 ,
solution. For example in the colloidal solution of silver in water (silver acts
Fe(OH )3 metal sulphides like
as a dispersed phase)
AS 2 S 3 etc.
(ii) External phase or Dispersion medium (continuous phase) : It is
generally component present in excess and is just like a solvent in a (iii) Classification based on types of particle of dispersed phase :
solution. For example, in the colloidal solution of silver in water. Water act Depending upon the type of the particles of the dispersed phase, the
as a dispersion medium. colloids are classified as follows.
(a) Multimolecular colloids
(2) Classification of colloids : The colloids are classified on the basis
of the following criteria
 580 Surface Chemistry
 When on dissolution, atoms or smaller molecules of substances
(having diameter less than 1nm) aggregate together to form particles of
colloidal dimensions, the particles thus formed are called multimolecular
colloids.
 In these sols the dispersed phase consists of aggregates of atoms
or molecules with molecular size less than 1 nm.
 For example, sols of gold atoms and sulphur (S 8 ) molecules. In
these colloids, the particles are held together by Vander Waal's forces. They
have usually lyophilic character.
(b) Macromolecular colloids
 These are the substances having big size molecules (called
macromolecules) which on dissolution form size in the colloidal range.
Such substances are called macromolecular colloids.
 These macromolecules forming the dispersed phase are generally
polymers having very high molecular masses.
 Naturally occurring macromolecules are starch, cellulose, proteins,
enzymes, gelatin etc. Artificial macromolecules are synthetic polymers such as
nylon, polythene, plastics, polystyrene etc.
 They have usually lyophobic character.
(c) Associated colloids
 These are the substances which on dissolved in a medium behave
as normal electrolytes at low concentration but behave, as colloidal particles
at higher concentration due to the formation of aggregated particles. The
aggregates particles thus formed are called micelles.
 Their molecules contain both lyophilic and lyophobic groups.
Micelles
 Micelles are the cluster or aggregated particles formed by
association of colloid in solution.
 The common examples of micelles are soaps and detergents.
 The formation of micelles takes place above a particular
temperature called Kraft temperature (Tk ) and above a particular
concentration called critical micellization concentration (CMC).
 They are capable of forming ions.
 Micelles may contain as many as 100 molecules or more.
 For example sodium stearate (C17 H 35 COONa) is a typical
example of such type of molecules.
 When sodium stearate is dissolved in water, it gives Na  and

C17 H 35 COO ions.
C17 H 35 COONa  C17 H 35 COO   Na 
Sodium stearate Stearate ion
The stearate ions associate to form ionic micelles of colloidal size.
 It has long hydrocarbon part of C17 H 35 radical. Which is
lyophobic and COO  part which is lyophilic.
 In the figure, the chain corresponds to stearate ion,
(C17 H 35 COO  ) . When the concentration of the solution is below from its
3 1
CMC (10 mol L ) , it behaves as normal electrolyte. But above this
concentration it is aggregated to behave as micelles.
Na+
– (d) By double decomposition : A sol of arsenic sulphide is obtained
+ – Na+ –
Na
Na+
Na+ – – As 2 O 3  3 H 2 S  As 2 S 3  3 H 2 O
Na+
– –
Na+
– Na+
Fig. 14.2 Aggregation of several ions to form ionic micelle
 The main function of a soap is to reduce oily and greasy dirt to
colloidal particles (an emulsion). Soap therefore, are known as emulsifying
agents.
 Some other examples of micelles are sodium palmitate
(C15 H 31 COONa ) , Sodium lauryl sulphate [CH 3 (CH 2 )11 SO 3 O  Na  ] ,
Cetyl trimethyl ammonium bromide CH 3 (CH 2 )15 (CH 2 )3 N  Br etc.
General methods of preparation of colloids
Lyophilic and lyophobic colloidal solutions (or sols) are generally
prepared by different types of methods. Some of the common methods are
as follows.
(1) Preparation of Lyophilic colloids
(i) The lyophilic colloids have strong affinity between particles of
dispersed phase and dispersion medium.
(ii) Simply mixing the dispersed phase and dispersion medium under
ordinary conditions readily forms these colloidal solutions.
(iii) For example, the substance like gelatin, gum, starch, egg,
albumin etc. pass readily into water to give colloidal solution.
(iv) They are reversible in nature become these can be precipitated
and directly converted into colloidal state.
(2) Preparation of Lyophobic colloids : Lyophobic colloids can be
prepared by mainly two types of methods.
(i) Condensation method : In these method, smaller particles of
dispersed phase are condensed suitably to be of colloidal size. This is done
by the following methods.
(a) By oxidation : A colloidal solution of sulphur can be obtained by
bubbling oxygen (or any other oxidising agent like HNO 3 , Br2 etc.)
through a solution of hydrogen sulphide in water.
2 H 2 S  O2 (or any other oxidisingagent)  2 H 2O  2S
(b) By reduction : A number of metals such as silver, gold and
platinum, have been obtained in colloidal state by treating the aqueous
solution of their salts, with a suitable reducing agent such as formaldehyde,
phenyl hydrazine, hydrogen peroxide, stannous chloride etc.
2 AuCl 3  3 SnCl 2  3 SnCl 4  2 Au
Gold sol
2 AuCl3  3 HCHO  3 H 2 O  2 Au  3 HCOOH  6 HCl
Gold sol
The gold sol, thus prepared, has a purple colour and is called
purple of cassius.
(c) By hydrolysis : Many salt solutions are rapidly hydrolysed by
boiling dilute solutions of their salts. For example, ferric hydroxide and
aluminium hydroxide sols are obtained by boiling solutions of the
corresponding chlorides.
FeCl 3  3 H 2 O  Fe(OH )3  3 HCl
Colloidalsol
Similarly silicic acid sol is obtained by the hydrolysis of sodium
silicate.
by passing hydrogen sulphide through a cold solution of arsenious oxide in
water.
(e) By excessive cooling : A colloidal solution of ice in an organic
solvent like ether or chloroform can be prepared by freezing a solution of
 Surface Chemistry 581
water in the solvent. The molecules of water which can no longer be held in  Freshly prepared ferric hydroxide can be converted into colloidal
solution, separately combine to form particles of colloidal size.
state by shaking it with water containing Fe3  or OH  ions, viz.
(f) By exchange of solvent : Colloidal solution of certain substances FeCl 3 or NH 4 OH respectively.
such as sulphur, phosphorus, which are soluble in alcohol but insoluble in
water can be prepared by pouring their alcoholic solution in excess of Fe(OH )3  FeCl3  [Fe(OH )3 Fe]3   3 Cl 
water. For example, alcoholic solution of sulphur on pouring into water Precipitate electrolyte Colloidal sol
gives milky colloidal solution of sulphur. + + +
+ + + + + +
(g) By change of physical state : Sols of substances like mercury and
sulphur are prepared by passing their vapour’s through a cold water Fe(OH)3 + Fe3+ + + + + + +

containing a suitable stabilizer such as ammonium salt or citrate. + + + + + +

From + + +
(ii) Dispersion methods : In these methods, larger particles of a Precipitate electrolyte FeCl3 Colloidal particles
substance (suspensions) are broken into smaller particles. The following of Fe(OH)3 of Fe(OH)3
methods are employed.
Fig. 14.5 Preparation of colloidal sol by peptisation
(a) Mechanical dispersion  A stable sol of stannic oxide is obtained by adding a small
 In this method, the Suspension amount of dilute HCl to stannic oxide precipitates.
substance is first ground to Driving Belt  Similarly, a colloidal solution of Al(OH )3 and AgCl are
coarse particles.
obtained by treating the corresponding freshly prepared precipitate with
 It is then mixed with Discharge Discharge very dilute solution of HCl and AgNO3 or KCl respectively.
the dispersion medium to get a
suspension. Purification of colloidal solution
 The suspension is Metal disc
The following methods are commonly used for the purification of
then grinded in colloidal mill. Fig. 14.3 Colloidal mill colloidal solutions.
 It consists of two (1) Dialysis
metallic discs nearly touching each other and rotating in opposite directions
at a very high speed about 7000 revolution per minute. (i) The process of separating the particles of colloid from those of
crystalloid, by means of diffusion through a suitable membrane is called
 The space between the discs of the mill is so adjusted that coarse dialysis.
suspension is subjected to great shearing force giving rise to particles of
colloidal size. (ii) It’s principle is based upon the fact that colloidal particles can
not pass through a parchment or cellophane membrane while the ions of
 Colloidal solutions of black ink, paints, varnishes, dyes etc. are the electrolyte can pass through it.
obtained by this method.
(iii) The impurities slowly diffused out of the bag leaving behind
(b) By electrical dispersion or Bredig’s arc method pure colloidal solution
 This method is used to Metal (iv) The distilled water is changed frequently to avoid accumulation
prepare sols of platinum, silver, electrodes
of the crystalloids otherwise they may start diffusing back into the bag.
copper or gold.
 The metal whose sol is Arc (v) Dialysis can be used for removing HCl from the ferric
to be prepared is made as two hydroxide sol.
electrodes which immerged in Water
ice (2) Electrodialysis
dispersion medium such as water
(i) The ordinary process of dialysis is slow.
etc.
(ii) To increase the process of purification, the dialysis is carried out
 The dispersion medium Fig. 14.4 Bredig's arc method
by applying electric field. This process is called electrodialysis.
is kept cooled by ice.
 An electric arc is struck between the electrodes. (iii) The important application of electrodialysis process in the
artificial kidney machine used for the purification of blood of the patients
 The tremendous heat generate by this method and give colloidal whose kidneys have failed to work. The artificial kidney machine works on
solution. the principle of dialysis.
 The colloidal solution prepared is stabilised by adding a small
(3) Ultra – filtration
amount of KOH to it.
(c) By peptisation (i) Sol particles directly pass through ordinary filter paper because
 The process of converting a freshly prepared precipitate into their pores are larger (more than 1  or 1000m  ) than the size of sol
colloidal form by the addition of suitable electrolyte is called peptisation. particles (less than 200m  ).
 The electrolyte is used for this purpose is called peptizing agent
(ii) If the pores of the ordinary filter paper are made smaller by
or stabilizing agent.
soaking the filter paper in a solution of gelatin of colloidion and
 Cause of peptisation is the adsorption of the ions of the subsequently hardened by soaking in formaldehyde, the treated filter paper
electrolyte by the particles of the precipitate. may retain colloidal particles and allow the true solution particles to escape.
 Important peptizing agents are sugar, gum, gelatin and Such filter paper is known as ultra - filter and the process of separating
electrolytes. colloids by using ultra – filters is known as ultra – filtration.
(4) Ultra – centrifugation
(i) The sol particles are prevented from setting out under the action
of gravity by kinetic impacts of the molecules of the medium.
 582 Surface Chemistry
(ii) The setting force can be enhanced by using high speed
centrifugal machines having 15,000 or more revolutions per minute. Such
machines are known as ultra–centrifuges.
Properties of colloidal solutions
The main characteristic properties of colloidal solutions are as
follows.
(1) Physical properties
(i) Heterogeneous nature : Colloidal sols are heterogeneous in
nature. They consists of two phases; the dispersed phase and the dispersion
medium.
(ii) Stable nature : The colloidal solutions are quite stable. Their
particles are in a state of motion and do not settle down at the bottom of
the container.
(iii) Filterability : Colloidal particles are readily passed
through the ordinary filter papers. However they can be retained by
special filters known as ultrafilters (parchment paper).
(2) Colligative properties
(i) Due to formation of associated molecules, observed values of
colligative properties like relative decrease in vapour pressure, elevation in
boiling point, depression in freezing point, osmotic pressure are smaller
than expected.
(ii) For a given colloidal sol the number of particles will be very
small as compared to the true solution.
(3) Mechanical properties
(i) Brownian movement
(a) Robert Brown, a botanist discovered in 1827 that the pollen
grains suspended in water do not remain at rest but move about
continuously and randomly in all directions.
(b) Later on, it was observed that the colloidal particles are moving
at random in a zig – zag motion. This type of motion is called Brownian
movement.
(c) The molecules of the dispersion medium are constantly
colloiding with the particles of the dispersed phase. It was stated by Wiener
in 1863 that the impacts of the dispersion medium particles are unequal, thus
causing a zig-zag motion of the dispersed phase particles.
(d) The Brownian movement explains the force of gravity acting on
colloidal particles. This helps in providing stability to colloidal sols by not
allowing them to settle down.
(ii) Diffusion : The sol particles diffuse from higher concentration to
lower concentration region. However, due to bigger size, they diffuse at a
lesser speed.
(iii) Sedimentation : The colloidal particles settle down under the
influence of gravity at a very slow rate. This phenomenon is used for
determining the molecular mass of the macromolecules.
(4) Optical properties : Tyandall effect
(i) When light passes through a sol, its path becomes visible because of
scattering of light by particles. It is called Tyndall effect. This phenomenon was
studied for the first time by Tyndall. The illuminated path of the beam is called
Tyndall cone.
(ii) The intensity of the scattered light depends on the difference
between the refractive indices of the dispersed phase and the dispersion
medium.
(iii) In lyophobic colloids, the difference is appreciable and,
therefore, the Tyndall effect is well - defined. But in lyophilic sols, the
difference is very small and the Tyndall effect is very weak.
(iv) The Tyndall effect confirms the heterogeneous nature of the
colloidal solution.
(v) The Tyndall effect has also been observed by an instrument
called ultra – microscope.
Some example of Tyndall effect are as follows
(a) Tail of comets is seen as a Tyndall cone due to the scattering of light
by the tiny solid particles left by the comet in its path.
(b) Due to scattering the sky looks blue.
(c) The blue colour of water in the sea is due to scattering of blue
light by water molecules.
(d) Visibility of projector path and circus light.
(e) Visibility of sharp ray of sunlight passing through a slit in dark
room.
(5) Electrical properties
(i) Electrophoresis
(a) The phenomenon of movement of colloidal particles under an
applied electric field is called electrophoresis.
(b) If the particles accumulate near the negative electrode, the
charge on the particles is positive.
(c) On the other hand, if the sol particles accumulate near the
positive electrode, the charge on the particles is negative.
(d) The apparatus consists of a U-tube with two Pt-electrodes in
each limb.
(e) When electrophoresis of a sol is carried out with out stirring, the
bottom layer gradually becomes more concentrated while the top layer
which contain pure and concentrated colloidal solution may be decanted.
This is called electro decanation and is used for the purification as well as
for concentrating the sol.
(f) The reverse of electrophoresis is called Sedimentation potential
or Dorn effect. The sedimentation potential is setup when a particle is
forced to move in a resting liquid. This phenomenon was discovered by
Dorn and is also called Dorn effect.
(ii) Electrical double layer theory
(a) The electrical properties of colloids can also be explained by
electrical double layer theory. According to this theory a double layer of
ions appear at the surface of solid.
(b) The ion preferentially adsorbed is held in fixed part and imparts
charge to colloidal particles.
(c) The second part consists of a diffuse mobile layer of ions. This
second layer consists of both the type of charges. The net charge on the second
layer is exactly equal to that on the fixed part.
(d) The existence of opposite sign on fixed and diffuse parts of
double layer leads to appearance of a difference of potential, known as zeta
potential or electrokinetic potential. Now when electric field is employed the
particles move (electrophoresis)
(iii) Electro-osmosis
(a) In it the movement of the dispersed particles are prevented from
moving by semipermeable membrane.
(b) Electro-osmosis is a phenomenon in which dispersion medium is
allowed to move under the influence of an electrical field, whereas colloidal
particles are not allowed to move.
(c) The existence of electro-osmosis has suggested that when liquid
forced through a porous material or a capillary tube, a potential difference
is setup between the two sides called as streaming potential. So the reverse
of electro-osmosis is called streaming potential.
Origin of the charge on colloidal particles
The origin of the charge on the sol particles in most cases is due to
the preferential adsorption of either positive or negative ions on their
surface. The sol particles acquire electrical charge in any one or more of the
following ways.
 Surface Chemistry 583
(1) Due to the dissociation of the surface molecules : Some colloidal Stability of sols
particles develope electrical charge due to the dissociation / ionisation of the
surface molecules. The charge on the colloidal particles is balanced by the Sols are thermodynamically unstable and the dispersed phase
oppositely charged ions in the sol. For example, an aqueous solution of (colloidal particles) tend to separate out on long standing due to the Vander
soap (sodium palmitate) which dissociates into ions as, Waal's attractive forces. However sols tend to exhibit some stability due to
(1) Stronger repulsive forces between the similarly charged particles
C15 H 31 COONa  C15 H 31 COO   Na  (2) Particle-solvent interactions : Due to strong particle-solvent
Sodium palmitate
(dispersion medium) interactions, the colloidal particles get strongly
The cations (Na ) pass into the solution while the anions
+

solvated.

(C15 H 31 COO ) have a tendency to form aggregates due to weak attractive
Coagulation or Flocculation or Precipitation
forces present in the hydrocarbon chains.
(2) Due to frictional electrification “The phenomenon of the precipitation of a colloidal solution by the
addition of the excess of an electrolyte is called coagulation or flocculation.”
(i) It is believed that the frictional electrification due to the rubbing
of the dispersed phase particles with that of dispersion medium results in
some charge on the colloidal particles. The coagulation of the lyophobic sols can be carried out by
following methods.
(ii) The dispersion medium must also get some charge, because of
the friction. Since it does not carry any charge, the theory does not seem to (1) By electrophoresis : In electrophoresis the colloidal particles move
be correct. towards oppositely charged electrode. When these come in contact with the
electrode for long these are discharged and precipitated.
(3) Due to selective adsorption of ions
(2) By mixing two oppositely charged sols : When oppositely
(i) The particles constituting the dispersed phase adsorb only those
charged sols are mixed in almost equal proportions, their charges are
ions preferentially which are common with their own lattice ions.
neutralised. Both sols may be partially or completely precipitated as the
(ii) For example, when a small quantity of silver nitrate
mixing of ferric hydroxide (+ve sol) and arsenious sulphide (–ve sol) bring
( AgNO3 ) solution is added to a large quantity of potassium iodide them in precipitated form. This type of coagulation is called mutual
(KI) solution, the colloidal particles of silver iodide adsorb I  from the coagulation or meteral coagulation.
(3) By boiling : When a sol is boiled, the adsorbed layer is disturbed
solution to become negatively charged, (at this stage KI is in excess, and
due to increased collisions with the molecules of dispersion medium. This
I  being common to AgI ) reduces the charge on the particles and ultimately they settle down to form
a precipitate.
AgI  I  ( AgI)I 
(Colloidal (in excess (Colloidal particle (4) By persistent dialysis : On prolonged dialysis, the traces of the
particle) in the becomes positively
medium) charged) electrolyte present in the sol are removed almost completely and the
colloids become unstable.
But, when a small quantity of potassium iodide (KI) solution is
(5) By addition of electrolytes : The particles of the dispersed phase
added to a large quantity of silver nitrate solution ( AgNO 3 ) ; the colloidal i.e., colloids bear some charge. When an electrolyte is added to sol, the
colloidal particles take up ions carrying opposite charge from the electrolyte.
silver iodide particles adsorb Ag  from the solution to become positively As a result, their charge gets neutralised and this causes the uncharged,
charged, (at this stage AgNO 3 is in excess and Ag  is common to AgI ), particles to come closer and to get coagulated or precipitated. For example,
if BaCl 2 solution is added to As 2 S 3 sol the Ba 2  ions are attracted by
AgI  Ag   ( AgI) Ag 
(Colloidal (in excess in (Colloidal particle the negatively charged sol particles and their charge gets neutralised. This
particle) the medium) becomes positively
Ag + charged) lead to coagulation.
I– (6) Hardy schulze rule : The coagulation capacity of different
Ag + – – – Ag +

I– +
+
+
I– electrolytes is different. It depends upon the valency of the active ion are
– AgI – + AgI + called flocculating ion, which is the ion carrying charge opposite to the
– – + + charge on the colloidal particles. “According to Hardy Schulze rule, greater
Ag+ – – Ag+ I– + + I–
the valency of the active ion or flocculating ion, greater will be its
Ag+ I– coagulating power” thus, Hardy Schulze law state:
Ag ions remain in dispersed
+
I ions remain in dispersion
–

medium (Agl, I Sol) –

medium (Agl, Ag Sol) + (i) The ions carrying the charge opposite to that of sol particles are
effective in causing coagulation of the sol.
Fig. 14.6
(iii) Depending upon the nature of charge on the particles of the (ii) Coagulating power of an electrolyte is directly proportional to
dispersed phase, the colloidal solutions are classified into positively charged the valency of the active ions (ions causing coagulation).
and negatively charged colloids. Some typical examples are as follows For example to coagulate negative sol of As 2 S 3 , the coagulation
(a) Negatively charged (b) Positively charged power of different cations has been found to decrease in the order as,
colloids colloids
Al3   Mg2   Na 
 Metal sulphides :  Metal hydroxides :
As 2 S 3 , CdS Al(OH )3 , Fe(OH )3 Similarly, to coagulate a positive sol such as Fe(OH )3 , the
coagulating power of different anions has been found to decrease in the
 Metal dispersions : Ag, Au, Pt  Metal oxide : TiO 2
order : [Fe(CN )6 ]4   PO43   SO 42   Cl 
 Acid dyes : Eosin, congo red  Basic dyes : Methylene blue
(7) Coagulation or flocculation value
 Sols of starch, gums, gold,  Haemoglobin
“The minimum concentration of an electrolyte which is required to
gelatin etc.  Sulphur sol cause the coagulation or flocculation of a sol is known as flocculation value.”
or
 584 Surface Chemistry
“The number of millimoles of an electrolyte required to bring about
the coagulation of one litre of a colloidal solution is called its flocculation
value.”
1 electrolytes in small amounts does not cause any flocculation of hydrophilic
Coagulation value or flocculating value 
Coagulating power
(8) Coagulation of lyophilic sols
(i) There are two factors which are responsible for the stability of
lyophilic sols.
(ii) These factors are the charge and solvation of the colloidal
particles.
(iii) When these two factors are removed, a lyophilic sol can be
coagulated.
(iv) This is done (i) by adding electrolyte (ii) and by adding suitable
solvent.
(v) When solvent such as alcohol and acetone are added to
hydrophilic sols the dehydration of dispersed phase occurs. Under this
(ii) Solvation effects contribute much towards the stability of
lyophilic systems. For example, gelatin has a sufficiently strong affinity for
water. It is only because of the solvation effects that even the addition of
sols. However at higher concentration, precipitation occurs. This
phenomenon is called salting out.
(iii) The salting out efficiency of an electrolyte depends upon the tendency
of its constituents ions to get hydrated i.e, the tendency to squeeze out water
initially fied up with the colloidal particle.
(iv) The cations and the anions can be arranged in the decreasing
order of the salting out power, such an arrangement is called lyotropic
series.
Cations : Mg 2   Ca 2   Sr 2   Ba 2   Li   Na   K 
 NH 4   Rb   Cs 
Anions : Citrate 3   SO 4 2   Cl   NH 3   I   CNS 

condition a small quantity of electrolyte can bring about coagulation. Ammonium sulphate, due to its very high solubility in water, is
Protection of colloids and Gold number oftenly used for precipitating proteins from aqueous solutions.
(v) The precipitation of lyophilic colloids can also be affected by the
 Lyophilic sols are more stable than lyophobic sols.
addition of organic solvents of non-electrolytes. For example, the addition of
 Lyophobic sols can be easily coagulated by the addition of acetone or alcohol to aqueous gelatin solution causes precipitation of
small quantity of an electrolyte. gelatin. Addition of petroleum ether to a solution of rubber in benzene
 When a lyophilic sol is added to any lyophobic sol, it becomes causes the precipitation of rubber.
less sensitive towards electrolytes. Thus, lyophilic colloids can prevent the Emulsion
coagulation of any lyophobic sol.
“The phenomenon of preventing the coagulation of a lyophobic sol “The colloidal systems in which fine droplets of one liquid are
due to the addition of some lyophilic colloid is called sol protection or dispersed in another liquid are called emulsions the two liquids otherwise
protection of colloids.” being mutually immiscible.” or
 The protecting power of different protective (lyophilic) colloids is “Emulsion are the colloidal solutions in which both the dispersed
different. The efficiency of any protective colloid is expressed in terms of phase and the dispersion medium are liquids.”
gold number. A good example of an emulsion is milk in which fat globules are
Gold number : Zsigmondy introduced a term called gold number to dispersed in water. The size of the emulsified globules is generally of the
describe the protective power of different colloids. This is defined as, order of 10 6 m. Emulsion resemble lyophobic sols in some properties.
“weight of the dried protective agent in milligrams, which when added to 10 (1) Types of Emulsion : Depending upon the nature of the dispersed
ml of a standard gold sol (0.0053 to 0.0058%) is just sufficient to prevent a phase, the emulsions are classified as;
colour change from red to blue on the addition of 1 ml of 10 % sodium
chloride solution, is equal to the gold number of that protective colloid.” (i) Oil-in-water emulsions (O/W) : The emulsion in which oil is
present as the dispersed phase and water as the dispersion medium
Thus, smaller is the gold number, higher is the protective action of
(continuous phase) is called an oil-in-water emulsion. Milk is an example of
the protective agent.
the oil-in-water type of emulsion. In milk liquid fat globules are dispersed in
1 water. Other examples are, vanishing cream etc.
Protectivepower 
Gold number (ii) Water-in-oil emulsion (W/O) : The emulsion in which water
Table : 14.4 Gold numbers of some hydrophilic substances forms the dispersed phase, and the oil acts as the dispersion medium is
Hydrophilic Gold number Hydrophilic substance Gold number called a water-in-oil emulsion. These emulsion are also termed oil emulsions.
substance Butter and cold cream are typical examples of this types of emulsions. Other
Gelatin 0.005 - 0.01 Sodium oleate 0.4 – 1.0 examples are cod liver oil etc.
Sodium 0.01 Gum tragacanth 2 (2) Properties of emulsion
caseinate (i) Emulsions show all the characteristic properties of colloidal
Hamoglobin 0.03 – 0.07 Potato starch 25 solution such as Brownian movement, Tyndall effect, electrophoresis etc.
Gum arabic 0.15 – 0.25 (ii) These are coagulated by the addition of electrolytes containing
polyvalent metal ions indicating the negative charge on the globules.
Congo rubin number : Ostwald introduced congo rubin number to
(iii) The size of the dispersed particles in emulsions in larger than
account for protective nature of colloids. It is defined as “the amount of
those in the sols. It ranges from 1000 Å to 10,000 Å. However, the size is
protective colloid in milligrams which prevents colour change in 100 ml of
smaller than the particles in suspensioins.
0.01 % congo rubin dye to which 0.16 g equivalent of KCl is added.”
(iv) Emulsions can be converted into two separate liquids by
Mechanism of sol protection
heating, centrifuging, freezing etc. This process is also known as
(i) The actual mechanism of sol protection is very complex. However demulsification.
it may be due to the adsorption of Lyophilic (3) Applications of emulsions
the protective colloid on the protecting (i) Concentration of ores in metallurgy
lyophobic sol particles, followed by Lyophobic particles
(ii) In medicine (Emulsion water-in-oil type)
its solvation. Thus it stabilises the particles (iii) Cleansing action of soaps.
sol via solvation effects.

Fig. 14.7 Protection of colloids

 Surface Chemistry 585
(iv) Milk, which is an important constituent of our diet an emulsion (8) Coating of Photographic plates : These are thin glass plates
of fat in water. coated with gelatin containing a fine suspension of silver bromide. The
(v) Digestion of fats in intestine is through emulsification. particles of silver bromide are colloidal in nature.
Gels
(1) “A gel is a colloidal system in which a liquid is dispersed in a
solid.”
(2) The lyophilic sols may be coagulated to give a semisolid jelly like
mass, which encloses all the liquid present in the sol. The process of gel
formation is called gelation and the colloidal system formed called gel.
(3) Some gels are known to liquify on shaking and reset on being  Chemisorption and physisorption both are exothermic.
allowed to stand. This reversible sol-gel transformation is called thixotropy.  Charcoal adsorbs many gases. It even adsorbs polluting gases present in
(4) The common examples of gel are gum arabic, gelatin, processed air in small concentration.
cheese, silicic acid, ferric hydroxide etc.
(5) Gels may shrink by loosing some liquid help them. This is known  The langmuir adsorption isotherm is restricted to the formation of
as synereises or weeping. unimolecular layer of gas molecules on the surface of solids.
(6) Gels may be classified into two types However, it was suggested that there is possibility of
(i) Elastic gels : These are the gels which possess the property of multimolecular layer of gas molecules on the surface of the solids
elasticity. They readily change their shape on applying force and return to rather than single layer on this basis Brunauer, Emmett and Teller
original shape when the applied force is removed. Common examples are proposed a new theory known as B.E.T. theory.
gelatin, agar-agar, starch etc.
(ii) Non-elastic gels : These are the gels which are rigid and do not  All Bronsted acids and bases act as acid base catalysts.
have the property of elasticity. For example, silica gel.  The principle of electrophoresis is employed for the separation of
Application of colloids proteins from nucleic acids removing sludge from sewage waste etc.
(1) Purification of water by alum (coagulation) : Alum which yield  Hydrophilic sols show greater stability than hydrophobic sols.
Al 3  ions, is added to water to coagulate the negatively charged clay
particles.
 Colloidal solution of graphite is called aquadug.
(2) In rubber and tanning industry (coagulation and mutual coagulation)  The phase in which the emulsifier is more soluble becomes outer
: Several industrial processes such as rubber plating, chrome tanning, dyeing, phase of the emulsion that is called Ben croft rule.
lubrication etc are of colloidal nature
(i) In rubber platting, the negatively charged particles of rubber
(latex) are made to deposit on the wires or handle of various tools by means
of electrophoresis. The article on which rubber is to be deposited is made
anode.
(ii) In tanning the positively charged colloidal particles of hides and
leather are coagulated by impregnating, them in negatively charged tanning
materials (present in the barks of trees). Among the tanning agent
chromium salts are most commonly used for the coagulation of the hide
material and the process is called chrome tanning.
(3) Artificial rains : It is possible to cause artificial rain by throwing
the electrified sand or silver iodide from an aeroplane and thus coagulating
the mist hanging in air.
(4) Smoke precipitation (Coagulation) : Smoke is a negative sol
consisting of carbon particles dispersed in air. Thus, these particles are
removed by passing through a chamber provided with highly positively
charged metallic knob.
(5) Formation of deltas (coagulation) : River water consists of
negatively charged clay particles of colloidal dimension. When the river falls
into the sea, the clay particles are coagulated by the positive
Na  , K  , Mg 2  ions etc. present in sea water and new lands called deltas
are formed.
(6) Clot formation : Blood consists of negatively charged colloidal
particles (albuminoid substance). The colloidal nature of blood explains why
bleeding stops by applying a ferric chloride solution to the wound. Actually
ferric chloride solution causes coagulation of blood to form a clot which
stops further bleeding.
(7) Colloidal medicine : Argyrol and protargyrol are colloidal
solution of silver and are used as eye lotions colloidal sulphur is used as
disinfectant colloidal gold, calcium and iron are used as tonics.
 588 Surface Chemistry
(a) Decreases
(b) Increases
(c) Remains unaffected
(d) Decreases first then increases
10. In physical adsorption, the gas molecules are held on solid surface
by [MP PET 1996; AIIMS 1998]
(a) Chemical forces (b) Electrostatic forces
Adsorption and Adsorption isotherm (c) Gravitational forces (d) Vander Waal's forces
11. Adsorption is multilayer in the case of [MP PET 1999]
1. Chemisorption
(a) Physical adsorption (b) Chemisorption
(a) Involves the weak attractive interactions between adsorbent (c) Both (d) None of both
and adsorbate
12. Physical adsorption
(b) Is irreversible in nature
(a) Involves the weak attractive interaction between the adsorbent
(c) Decreases with increase of temperature and adsorbate
(d) Involves multilayer formation of adsorbent on adsorbate (b) Involves the chemical interactions between the adsorbent and
2. Chemisorption adsorbate
(a) Increases with temperature (c) Is irreversible in nature
(b) Decreases with temperature (d) Increases with increase of temperature
(c) Remains unaffected by change of temperature 13. The charge on As2 S 3 sol is due to the adsorbed
(d) Either increases or decreases with temperature [MP PMT 1985]
3. Which among the following statement is false (a) H (b) OH 
[KCET (Med.) 2002] (c) O 2  (d) S 2 
(a) The adsorption may be monolayered or multilayered 14. In the adsorption of acetic acid on activated charcoal, the acetic acid
(b) Particle size of adsorbent will not affect the amount of is an [MP PET 1994; MP PMT 2002]
adsorption (a) Adsorber (b) Absorber
(c) Increase of pressure increases amount of adsorption (c) Adsorbent (d) Adsorbate
(d) Increase of temperature may decrease the amount of 15. Sticking of one substance at the surface of another is called
adsorption (a) Absorption (b) Chemisorption
4. Wood charcoal is used to decolourise sugar because it (c) Adsorption (d) Desorption
[CPMT 2002] 16. The charge on colloidal particles is due to
(a) Adsorbs coloured material (a) Presence of electrolyte
(b) Absorbs decolorised material (b) Very small size of particles
(c) Reduces coloured material (c) Adsorption of ions from the solution
(d) None of these (d) None of these
5. If the absorbate is held on a surface by weak Vander Waal's forces, 17. Which one of the following statement is not correct
the absorption process is called (a) The extent of adsorption depends on the nature of the
[Kerala (Med.) 2002] adsorbent and adsorbate
(a) Physical adsorption (b) Chemical adsorption (b) The extent of adsorption depends on the pressure of the gas
(c) Heat of adsorption (d) Enthalpy of adsorption (c) The extent of adsorption depends on the temperature
6. When the temperature is raised, the viscosity of liquid decreases, (d) The extent of adsorption has no upper limit
this is because [Kerala (Med.) 2002] 18. For the adsorption of a gas on a solid, the plot of log (x/m) versus
(a) Decreased volume of the solution log P is linear with slope equal to [CBSE PMT 1994]
(b) Increase in temperature increases the average kinetic energy of (a) k (b) log k
molecules, which overcome the attractive force between them (c) n (d) 1/n
(c) Decreased covalent and hydrogen bond forces 19. According to Langmuir adsorption isotherm, the amount of gas
adsorbed at very high pressures [MP PMT 1993]
(d) Increased attraction between molecules
(a) Reaches a constant limiting value
7. A solid acts as an adsorbent because it has
(b) Goes on increasing with pressure
(a) A definite shape
(c) Goes on decreasing with pressure
(b) Small pores in it
(d) Increases first and decreases later with pressure
(c) Unsaturated valencies
20. Which of the following statement is not correct
(d) A high lattice energy [MP PET 1993]
8. Point out the wrong statement : (a) Physical adsorption is due to Vander Wall's forces
Physical adsorption is characterised by (b) Chemical adsorption decreases at high temperature and low
(a) Attraction due to weak Vander Waal's forces pressure
(b) Irreversible nature of adsorption (c) Physical adsorption is reversible
(c) Multimolecular adsorption layers (d) Adsorption energy for a chemical adsorption is generally
(d) Decrease in adsorption with increase in temperature greater than that of physical adsorption
9. When the temperature is lowered and pressure is raised, the 21. In adsorption of oxalic acid on activated charcoal, the activated
adsorption of a gas on a solid [MP PMT 1997] charcoal is known as
 Surface Chemistry 589
(a) Adsorbent (b) Absorbate (a) H is of the order of 400 kJ
(c) Adsorber (d) Absorber (b) Adsorption is irreversible
22. Adsorption is phenomenon is which a substance (c) Adsorption may be multimolecular layer
(a) Goes into the body of the other substance (d) Adsorption is specific
(b) Remains close the other substance 35. The viscosity of the solvent depends on
(c) Accumulates on the surface of the other substance [Kerala (Med.) 2002]
(d) None of these (a) Isothermic nature
23. Physical adsorption is essentially quite appreciable (b) Solute - solute interaction
(a) At room temperature (b) At higher temperature (c) Solute - solvent interaction
(c) At lower temperature (d) None of these (d) Density of the liquid
24. Adsorption increase when 36. Which of the following kinds of catalysis can be explained by the
adsorption theory ? [MP PET/PMT 1998]
(a) Temperature increases
(a) Homogeneous catalysis (b) Acid base catalysis
(b) Temperature decreases (c) Heterogeneous catalysis (d) Enzyme catalysis
(c) Temperature remains constant 37. Adsorption due to strong chemical forces is called
(d) None of these [KCET (Med.) 2001]
25. In chemical adsorption, how many layers are adsorbed (a) Chemisorption (b) Physiosorption
[MP PMT 1996] (c) Reversible adsorption (d) Both (b) and (c)
(a) One (b) Two 38. In neutralisation of KI by AgNO3 positive charge is due to
(c) Multi (d) Zero
absorption of [AMU 2000]
26. The adsorption of a gas on a solid surface varies with pressure of
the gas in which of the following manner (a) Ag  ions (b) Ag
[CPMT 1999] (c) I ions (d) Both (b) and (c)
(a) Fast  slow  independent of the pressure 39. Physical adsorption is inversely proportional to the
(b) Slow  fast  independent of the pressure [AFMC 2000]
(a) Volume (b) Concentration
(c) Independent of the pressure  fast  slow
(c) Temperature (d) All of these
(d) Independent of the pressure  slow  fast
40. 50 ml of 1 M oxalic acid is shaken with 0.5 gm of wood charcoal.
27. Which of the following statements is not applicable to chemisorption The final concentration of the solution after adsorption is 0.5 M.
[KCET (Med.) 1999; BHU 2000]
Amount of oxalic acid absorbed per gm of charcoal is
(a) It is slow
(a) 3.45 gm (b) 3.15 gm
(b) It is irreversible
(c) 6.30 gm (d) None
(c) It is highly specific
41. Noble gases are adsorbed by [DCE 2004]
(d) It is independent of temperature
(a) Anhydrous calcium chloride
28. Adsorption is always [DPMT 2000]
(b) Ferric hydroxide
(a) Endothermic (b) Exothermic
(c) Conc. H 2 SO 4
(c) Either (a) or (b) (d) None of these
(d) Activated coconut charcol
29. The colloidal system consisting of a liquid adsorbent in a solid
adsorbate is termed as 42. Animal charcoal is used in decolourising colour of liquids because it
is a good [MHCET 2004]
(a) Aerosol (b) Sol (a) Adsorbate (b) Adsorbent
(c) Foam (d) Gel (c) Oxidising agent (d) Reducing agent
30. Which one of the following substances adsorb hydrogen gas most 43. What will be the effect of increase in temperature on physical
strongly adsorption [Pb. CET 2000]
(a) Activated carbon (b) Silica gel (a) It will decrease
(c) Platinum black (d) Iron powder (b) It will increase
31. According to the adsorption theory of catalysis, the speed of the (c) First increase then decrease
reaction increases because [CBSE PMT 2003] (d) None of these
(a) Adsorption lowers the activation energy of the reaction 44. 0.2 gm of fine animal charcoal is mixed with half litre of acetic acid
(b) The concentration of reactant molecules at the active centres of solution and shaken for 30 minutes
the catalyst becomes high due to adsorption [DPMT 2004]
(c) In the process of adsorption, the activation energy of the (a) Concentration remains same
molecules becomes large (b) Concentration increases
(d) Adsorption produces heat which increases the speed of the (c) Concentration of the solution decrease
reaction (d) None of these
32. In Freundlich adsorption, isotherm adsorption is proportional to 45. The equation for Freundlich adsorption isotherm is
pressure P as [AMU 2002] [MHCET 2004]
(a) P0 (b) P x
(a)  kp 1 / n (b) x  mkp 1/n
(c) P n (d) P1 / n m
33. Which one of the following characteristics is not correct for (c) x / m  kp n (d) All of these
physical adsorption [AIEEE 2003]
(a) Adsorption on solids is reversible 46. The extent of adsorption of a gas on a solid depends on
[KCET 2005]
(b) Adsorption increases with increase in temperature
(c) Adsorption is spontaneous (a) Nature of the gas (b) Pressure of the gas
(d) Both enthalpy and entropy of adsorption are negative (c) Temperature of the gas (d) All are correct
34. Which of the following is not a characteristic of chemisorption [KCET 2003]
 590 Surface Chemistry
47. Activated charcoal is used to remove colouring matter from pure
substances. It works by [KCET 2005]
(a) Oxidation (b) Reduction [AMU (Engg.) 1999]
(c) Bleaching (d) Adsorption (a) Al2O3 (b) Cr2O3
(c) Cr2O3 and Al2O3 (d) Zn dust
Catalyst and Catalysis
11. Enzymes with two sites are called [AIIMS 2002]
1. Mark the correct statement in a reversible reaction (a) Apoenzyme (b) Holoenzyme
[CPMT 1974; EAMCET 1978, 79; MP PMT 1993]
(c) Allosteric enzyme (d) Conjugate enzyme
(a) The catalyst catalyses the forward reaction 12. Which of the following types of metals make the most efficient
catalysts [DPMT 1985]
(b) The catalyst catalyses the backward reaction
(a) Alkali metals (b) Transition metals
(c) The catalyst influences the direct and the reverse reaction to (c) Alkaline–earth metals (d) Radioactive metals
the same extent
13. An example of autocatalytic reaction is [NCERT 1983]
(d) The catalyst increases the rate of forward reaction and
decreases the rate of backward reaction (a) The decomposition of nitroglycerine
2. A catalyst is used [CPMT 1989] (b) Thermal decomposition of KClO3 and MnO2 mixture
(a) Only for increasing the velocity of the reaction
(c) Break down of 6 C 14
(b) For altering the velocity of the reaction
(c) Only for decreasing the velocity of the reaction (d) Hydrogenation of vegetable oil using nickel catalysts
(d) All (a), (b) and (c) are correct 14. In the case of auto catalysis [KCET (Med.) 2002]
(a) Solvent catalyses
3. A catalyst is a substance which [NCERT 1981; CPMT 1996]
(b) Product catalyses
(a) Alters the equilibrium in a reaction
(c) Reactant catalyses
(b) Is always in the same phase as the reactants (d) Heat produced in the reaction catalyses
(c) Participates in the reaction and provides easier pathway for the 15. In a reversible reaction, a catalyst will affect the rate of
same [KCET (Med.) 2002]
(d) Does not participate in the reaction but speeds it up (a) Forward reaction
4. In Haber's process for the manufacture of ammonia (b) Reverse reaction
[AMU 1984; CPMT 1974, 90] (c) Forward and reverse reaction
(a) Finely divided iron is used as catalyst (d) Neither (a) nor (b)
(b) Finely divided molybdenum is used as catalyst 16. The role of a catalyst in a reversible reaction is to
(c) Finely divided nickel is used as catalyst [KCET (Med.) 2001]
(d) No catalyst is necessary (a) Increase the rate of forward reaction
(b) Decrease the rate of backward reaction
5. When KClO3 is heated, it decomposes into KCl  O2 . If some (c) Alter the equilibrium constant of the reaction
MnO2 is added, the reaction goes much faster because (d) Allow the equilibrium to be achieved quickly
[CPMT 1971,76,80,94] 17. The catalyst used in the contact process for manufacturing of
sulphuric acid is [MP PMT 1987]
(a) MnO2 decomposes to give O 2 (a) Copper (b) Iron/aluminium oxide
(b) MnO2 provides heat by reacting (c) Vanadium pentoxide (d) Platinized asbestos
18. For the functioning of enzymes which of the following statements is
(c) Better contact is provided by MnO2 not correct [MP PMT 2000]
(d) MnO2 acts as a catalyst (a) An optimum temperature is needed
(b) An optimum pH is needed
6. In the reaction 2 SO 2  O2 

Pt
2 SO 3 , As2 O3 acts as a (c) They are substrate specific
As 2 O 3 (d) They always increase activation energy
[MP PET 1995] 19. When a catalyst is added to a system the [JIPMER 2000]
(a) Autocatalyst (b) Poison (a) Value of equilibrium constant is decreased
(c) Promotor (d) Positive catalyst (b) The rate of forward reaction is increased and that of backward
7. Reactions in Zeolite catalysts depend on [BHU 2000] reaction is decreased
(a) Pores (b) Apertures (c) Equilibrium concentrations are unchanged
(c) Size of cavities (d) All of these (d) Equilibrium concentrations are increased
20. A catalyst can affect reversible reaction by [CPMT 2002]
8. What is the role of a catalyst in a catalysed reaction
(a) Changing equilibrium
[MP PMT 1996; Pb. PMT 2000;UPSEAT 2001,02]
(b) Slowing forward reaction
(a) Lowers the activation energy (c) Attaining equilibrium in both direction
(b) Increases the activation energy (d) None of these
(c) Affects the free energy change
C12 H 22 O11  H 2O 2   C6 H12 O6 (aq) C6 H12 O6 (aq)
dil. H SO
21. 4
(d) Affects the enthalpy change Sucrose Fructose Glucose
9. The catalyst used in the lead chamber process of sulphuric acid
manufacture is In this reaction, dilute H 2 SO 4 is called [AFMC 1997]
[CPMT 1977] (a) Homogeneous catalysis (b) Homogeneous catalyst
(a) Platinum (b) Oxide of nitrogen (c) Heterogeneous catalysis (d) Heterogeneous catalyst
(c) Nickel (d) Vanadium compounds 22. Which one of the following statement is wrong in case of enzyme
catalysis [MP PMT 1985, 2001]
10. In the following reaction the catalyst used is
(a) Enzymes work best at an optimum temperature
CH – CH
2 2
HC = HC (b) Enzymes work at an optimum pH
(c) Enzymes are highly specific for substances
HC2
CH 2 HC CH+3H 2

CH – CH2 2 HC – HC
 Surface Chemistry 591
(d) An enzyme raises activation energy (b) The catalyst actually forms a compound with the reactant
23. Which of the following catalyses the conversion of glucose into (c) The surface of the catalyst plays a very important role
ethanol (d) There is no change in the energy of activation
[CPMT 1983, 84; CBSE PMT 1989; KCET 1993]
35. Regarding criteria of catalysis which one of the following statements
(a) Zymase (b) Invertase is not true [CPMT 1990]
(c) Maltase (d) Diastase (a) The catalyst is unchanged chemically at the end of the reaction
24. Which of the following is used as a catalyst in the manufacture of
(b) A small quantity of catalyst is often sufficient to bring about a
toluene from benzene with CH 3 Cl considerable amount of reaction
[CPMT 1985] (c) In a reversible reaction the catalyst alters the equilibrium
(a) Ni (b) Anhydrous AlCl3 position
(d) The catalyst accelerates the reaction
(c) Pd (d) Pt
36. Which of the following reaction is catalysed by enzyme maltase
25. Hydrolysis of ethyl acetate is catalysed by aqueous
[MP PMT 2002] (a) Starch  maltose
(a) Na 2 SO 4 (b) K 2 SO 4 (b) Maltose  glucose
(c) H 2 SO 4 (d) BaSO4 (c) Lactose  maltose
26. Which of the following statements about a catalyst is true (d) Maltose  glucose + fructose
[AIIMS 1996] 37. The efficiency of an enzyme in catalysing a reaction is due to its
(a) It lowers the energy of activation capacity [NCERT 1982]
(b) The catalyst altered during the reaction is regenerated (a) To form a strong enzyme-substrate complex
(c) It does not alter the equilibrium (b) To decrease the bond energies of substrate molecule
(d) All of these (c) To change the shape of the substrate molecule
27. Which of the following statements is true for a catalyst (d) To lower the activation energy of the reaction
(a) It increases the energy of the reactants 38. A catalyst in a chemical reaction [BHU 1998]
(b) It decreases the energy of the products (a) Does not initiate a reaction
(c) It decreases the energy of the reactants (b) Increases the activation energy of the reaction
(d) It does not change the enthalpy of the reactants (c) Changes the equilibrium constant of a reaction
28. Which is not a characteristic of a catalyst [AFMC 1992] (d) Does not change the rate of the reaction
(a) It changes the equilibrium constant 39. Platinized asbestos is used as a catalyst in the manufacture of
(b) It alters the reaction path H 2 SO 4 . It is an example of [CPMT 1975]
(c) It increases the rate of reaction
(a) Heterogeneous catalyst (b) Autocatalyst
(d) It increases the average K.E. of the molecules
29. Which one of the following statements is correct in reversible (c) Homogenous catalyst (d) Induced catalyst
reaction. A catalyst [MP PET 1994; EAMCET 1987] 40. Catalyst used in hydrogenation of oils is
(a) Increases the rate of forward reaction [CPMT 1975; MNR 1986; DPMT 1982, 85;BHU 1973, 87;
(b) Decreases the rate of forward reaction EAMCET 1987; AFMC 1993; CET Pune 1998]
(c) Increases the rate of backward and forward reactions (a) Pt (b) Mo
(d) Alters the equilibrium constant of the reaction (c) Fe (d) Ni
30. A catalyst [MNR 1987; UPSEAT 2002] 41. Addition of catalyst in a system [MP PMT 1992]
(a) Increases the free energy change in the reaction (a) Increases equilibrium concentrations
(b) Decreases the free energy change in the reaction (b) No effect on equilibrium concentrations
(c) Does not increase or decrease the free energy change in the (c) Decreases equilibrium concentrations
reaction (d) Increases rate of forward reaction and decreases rate of
(d) Can either increase or decrease the free energy change backward reaction
depending on what catalyst we use
42. In which of the following processes, platinum is used as a catalyst[NCERT 1978,
31. Which one of the following changes when catalyst is used in a
reaction (a) Oxidation of ammonia to form nitric acid
(a) Heat of reaction (b) Product of reaction (b) Hardening of oils
(c) Equilibrium constant (d) Activation energy (c) Production of synthetic rubber
32. In the reversible reaction a catalyst is the substance which (d) Synthesis of methanol
[CBSE PMT 1992] 43. Enzymes are [CPMT 1974, 81]
(a) Increases the rate of the forward reaction (a) Micro-organisms (b) Proteins
(b) Decreases the value of enthalpy change in the reaction (c) Inorganic compounds (d) Moulds
(c) Reduces the time required for reaching the equilibrium state in 44. Protons accelerate the hydrolysis of esters. This is an example of [MP PMT 1987]
the reaction (a) A heterogeneous catalysis
(d) Decreases the rate of the reverse reaction (b) An acid-base catalysis
33. In the titration between oxalic acid and acidified potassium (c) A promoter
permanganate, the manganous salt formed catalyses the reaction. (d) A negative catalyst
The manganous salt is 45. Which of the following processes does not involve a catalyst
[KCET 1992] [KCET 1991; AIIMS 1996]
(a) A promoter (b) A positive catalyst (a) Haber's process (b) Thermite process
(c) An autocatalyst (d) None of these (c) Ostwald process (d) Contact process
34. Which one of the following statements is incorrect in the case of 46. Which of the statement is wrong among the following
heterogeneous catalysis [CPMT 1990] [AFMC 1993]
(a) The catalyst lowers the energy of activation (a) Haber's process of NH 3 requires iron as catalyst
 592 Surface Chemistry
(b) Friedel–Craft's reaction uses anhydrous AlCl3 57. Which one is false in the following statement
[MP PET 1997]
(c) Hydrogenation of oils uses iron as catalyst (a) A catalyst is specific in its action
(d) Oxidation of SO 2 to SO 3 requires V2 O 5 (b) A very small amount of the catalyst alters the rate of a reaction
47. A catalyst is a substance which (c) The number of free valencies on the surface of the catalyst
(a) Increases the rate of a reaction increases on subdivision
(b) Increases the amount of the products formed in a reaction (d) Ni is used as catalyst in the manufacture of ammonia
(c) Decreases the temperature required for the reaction 58. In the redox reaction
(d) Alters the speed of the reaction remaining unchanged 2 MnO4  5 C2O42   16 H  ⇌ 2 Mn2   10CO 2  8 H 2O
chemically at the end of the reaction
The ion acting as autocatalyst is [MP PMT 1986,94]
48. In the Ostwald's process for the manufacture of HNO 3 , the
(a) MnO4 (b) C2O42 
catalyst used is [AMU 1982, 83; MP PET 1999]
(a) Mo (b) Fe (c) H  (d) Mn2 
(c) Ni (d) Pt 59. In a homogeneous catalysis
49. A biological catalyst is essentially (a) The catalyst and the reactants should be gases
[NCERT 1978; AFMC 1998] (b) The catalyst and the reactants should form a single phase
(a) An amino acid (b) A carbohydrate (c) Catalyst and the reactants are all solids
(c) The nitrogen molecule (d) An enzyme (d) The catalyst and the reactions are all liquids
60. Which of the following statements is incorrect
50. A catalyst added to a reaction mixture
[CPMT 1985]
(a) Increases the equilibrium constant (a) Enzymes are in colloidal state
(b) Decreases the equilibrium constant (b) Enzymes are catalysts
(c) Does not change the equilibrium constant (c) Enzymes can catalyse any reaction
(d) None of these (d) Urease is an enzyme
51. The components of Zigler Natta catalyst, used in the polymerisation 61. Enzymes are [BHU 1982]
of propylene, are [MP PMT 2003] (a) Substances made by chemists to activate washing powder
(a) TiCl3  Al(C2 H5 )3 (b) TiCl4  Al(C2 H5 )3 (b) Very active vegetable catalysts
(c) Ti(C2 H 5 )3  AlCl3 (d) Ti(C2 H5 )4  AlCl3 (c) Catalysts found in organism
(d) Synthetic catalysts
52. Which of the following statements regarding catalyst is not true
[CPMT 1983, 84; MNR 1993; KCET 1999] 62. Catalyst used in the oxidation of SO 2  SO 3
(a) A catalyst remains unchanged in composition and quantity at [AIIMS 1996]
the end of the reaction (a) Nickel (b) ZnO.Cr2O3
(b) A catalyst can initiate a reaction
(c) V2 O 5 (d) Iron
(c) A catalyst does not alter the equilibrium in a reversible reaction
(d) Catalyst are sometimes very specific in respect of reaction 63. Which requires catalyst [AFMC 1987; MP PET 1999]
53. The enzyme ptylin used for the digestion of food is present in (a) S  O2  SO 2 (b) 2SO 2  O2  2SO 3
[CPMT 1981]
(a) Saliva (b) Blood (c) C  O2  CO 2 (d) All
(c) Intestine (d) Adrenal glands 64. The process which is catalysed by one of the products is called[MP PET 1999; AII
54. Amongst the following chemical reactions, the one representing (a) Acid-base catalysis (b) Autocatalysis
homogeneous catalysis is [MP PMT 1999]
(c) Negative catalysis (d) None of these
(a) N 2 (g)  3 H 2 (g) 
 2 NH 3 (g)
Fe
65. Adam's catalyst is [Pb.CET 2001]
(b) 2SO 2 (g)  O2 (g)  2SO 3 (g)  2 NO(g)
2 NO (a) Platinum (b) Iron
(c) Molybdenum (d) Nickel
(c) CO(g)  3 H 2 (g) 

Ni
CH 4 (g)  H 2O 66. A catalyst remains unchanged at the end of the reaction regarding[MP PET 1995
(d) 2SO 2 (g)  O2 (g)  2SO 3 (g)
V2 O5 (a) Mass
(b) Physical state
55. Platinised asbestos helps in the formation of SO 3 form SO 2 and
(c) Physical state and chemical composition
O 2 . But, if even a small amount of As2 O3 is present the
(d) Mass and chemical composition
platinised asbestos does not help in the formation of SO 3 . As2 O3 67. Wilhem Ostwald redefined the action of
acts here as [MP PMT 1997] [Kerala (Med.) 2002]
(a) A positive catalyst (b) A negative catalyst
(a) Anamers
(c) An autocatalyst (d) A poison
56. Which of the following statements is wrong (b) Isomers
(a) Catalysts can aid a rapid reaching of the equilibrium position, (c) Catalyst
but do not change the position of the equilibrium (d) Geometry of monomers
(b) Homogeneous catalysis generally involves an equilibrium 68. In a reversible reaction, a catalyst used
reaction between at least one of the reactants and the catalyst
(c) Heterogeneous catalysis involves chemisorption on the surface (a) Increases the speed of the forward reaction
of the catalyst (b) Decreases the speed of the backward reaction
(d) Positive catalysts raise the energy of activation of the reaction (c) Does not alter the final state of equilibrium
they catalyse
(d) Increases the amount of the products formed
 Surface Chemistry 593
69. Enzyme activity is maximum at [KCET 1989] (c) Lyophilic sol (d) Associated colloid
(a) 300 K (b) 310 K 6. Which of the following is most effective in coagulating a ferric
(c) 320 K (d) 330 K hydroxide sol [MP PET 1993, 97; MP PMT 2000]

70. A catalyst is used to [Pb.CET 2000] (a) KCl (b) KNO 3

(a) Increase the product (c) K 2 SO 4 (d) K3 [Fe(CN )6 ]
(b) Increase or decrease the rate of reaction 7. Sky looks blue due to [MNR 1986; MP PET 1992]
(c) Increase or decrease the products (a) Dispersion effect (b) Reflection
(d) Decrease the products (c) Transmission (d) Scattering
71. The transition metal used as a catalyst is [Pb. PMT 2004] 8. Which one is an example of gel
(a) Nickel (b) Platinum (a) Soap (b) Cheese
(c) Milk (d) Fog
(c) Cobalt (d) All of these
9. The random or zig-zag motion of the colloidal particles in the
72. Which of the following is true about catalyst [Pb.CET 2000] dispersion medium is referred to as
(a) It initiates reaction [CPMT 1985; JIPMER 1997; MP PET 2000]
(b) It changes equilibrium point (a) Electro-osmosis
(c) It increase average kinetic energy (b) Electrophoresis
(d) It accelerates the rate of reaction (c) Brownian movement
73. Which of the following types of metals form the most efficient (d) Tyndall effect
catalysts [KCET 2005]
10. Which of the following electrolytes is least effective in causing
(a) Alkali metals flocculation of ferric hydroxide sol
(b) Alkaline earth metals [MNR 1991; UPSEAT 1999]
(c) Transition metals (a) K4 [Fe(CN )6 ] (b) K2CrO4
(d) All of these (c) KBr (d) K 2 SO 4
74. Formation of ammonia from H 2 and N 2 by Haber's process using 11. If the dispersed phase is a liquid and the dispersion medium is a
Fe is an example of [J & K 2005] solid, the colloid is known as
[NCERT 1981; CBSE PMT 1989; KCET 1998]
(a) Heterogeneous catalysis (b) Homogeneous catalysis
(a) A sol (b) An emulsion
(c) Enzyme catalysis (d) Non-catalytic process (c) A gel (d) A foam
12. Zig-zag motion (eratic motion) of particles in colloid was observed
Colloids, Emulsion, Gel and Their properties by [CPMT 1985]
with application (a) Tyndall (b) Zsigmondy
(c) Robert brown (d) Thomas Graham
1. Gold number is [MP PET/PMT 1988] 13. On addition of one ml solution of 10% NaCl to 10 ml gold sol in
(a) The number of mg of lyophilic colloid which should be added the presence of 0.25 gm of starch, the coagulation is just prevented.
to 10 ml of ferric hydroxide sol so as to prevent its coagulation Starch has the following gold number
by the addition of 1 ml of 10% sodium chloride solution [MP PET/PMT 1988]
(b) The number of mg of lyophilic colloid which should be added (a) 0.025 (b) 0.25
to 10 ml of standard gold sol so as to prevent its coagulation by (c) 0.5 (d) 250
the addition of 1 ml of 10% NaCl 14. Tyndall effect would be observed in a
(c) The mg of gold salt to be added to a lyophilic colloid to [CPMT 1973, 79, 90, 91, 94; MP PET 1999;
coagulate it MP PMT 1973, 89; DPMT 1982, 83; AFMC 1999]
(d) The mg of an electrolyte required to coagulate a colloid (a) Solution (b) Colloidal solution
2. Which of the following statement is wrong for lyophobic sol (c) Precipitate (d) Solvent
(a) Dispersed phase is generally in organic material 15. Ferric hydroxide sol is positively charged colloid. The coagulating
(b) Can be easily coagulated by small addition of electrolyte power of NO 3 , SO 42  and PO43  ions would be in the order
(c) Dispersed phase particles are poorly hydrated and colloid is
stabilised due to charge on the colloidal particles (a) NO 3  SO 42   PO43  (b) SO 42   NO 3  PO43 
(d) Reversible in nature that is after coagulation can be easily set (c) PO43   SO 42   NO 3 (d) NO 3  SO 42   PO43 
into colloidal form
3. Which of the following statements is not true for a lyophobic sol 16. A colloidal solution can be purified by
[MP PET 1993; CPMT 1990; MP PMT 2001]
(a) It can be easily solvated
(a) Filtration (b) Peptization
(b) It carries charge
(c) Coagulation (d) Dialysis
(c) The coagulation of this sol is irreversible in nature 17. Gold number is associated with
(d) It is less stable in a solvent (a) Only lyophobic colloids
4. As2 S 3 sol has a negative charge. Capacity to precipitate it is (b) Only lyophilic colloids
highest in (c) Both lyophobic and lyophilic colloids
[CPMT 1982, 89, 93; DPMT 1983;MP PET 1999] (d) None of these
(a) AlCl3 (b) Na3 PO4 18. Which of the following forms a colloidal solution in water
[MP PET 1990; CPMT 1988]
(c) CaCl2 (d) K 2 SO 4
(a) NaCl (b) Glucose
5. Starch dispersed in hot water is an example of (c) Starch (d) Barium nitrate
(a) Emulsion (b) Hydrophobic sol
 594 Surface Chemistry
19. A negatively charged suspension of clay in water will need for (b) Both gases
precipitation the minimum amount of [CPMT 1973] (c) Both liquids
(a) Aluminium chloride (b) Potassium sulphate (d) One is solid and other is liquid
(c) Sodium hydroxide (d) Hydrochloric acid 34. Lyophilic sols are more stable than lyophobic sols because
20. Difference between colloids and crystalloids is of [NCERT 1982, 83]
[CPMT 1979] (a) The colloidal particles have positive charge
(a) Particle composition (b) Particle size (b) The colloidal particles have no charge
(c) Concentration (d) Ionic character (c) The colloidal particles are solvated
21. The purification of the colloidal particles from crystalloid dimensions (d) There are strong electrostatic repulsions between the negatively
through semipermeable membrane is known as charged colloidal particles
[BHU 1979; MP PMT 1999; CBSE 1996; Pb. CET 2002] 35. Which is the correct statement in case of milk
(a) Coagulation (b) Dialysis [CPMT 1977; MNR 1988; UPSEAT 2000, 01, 02]
(c) Ultrafiltration (d) Peptisation (a) Milk is an emulsion of protein in water
22. The stability of lyophilic colloids is due to (b) Milk is an emulsion of fat in water
[CPMT 1971, 81, 83, 93, 96; AFMC 1998; (c) Milk is stabilised by protein
MP PMT 1990, 95; MP PET 1992] (d) Milk is stabilised by fat
(a) Charge on their particles 36. Which of the following electrolytes have maximum coagulating
(b) A layer of dispersion medium on their particles power
(c) The smaller size of their particles (a) CCl 4 (b) ZnCl2
(d) The large size of their particles (c) KCl (d) NaCl
23. Milk is a colloid in which 37. Which one of the following is not a colloidal solution
[MP PMT 1985, 2002; MP PET 2001; [MADT Bihar 1983]
JIPMER (Med.) 2002]
(a) Smoke (b) Ink
(a) A liquid is dispersed in liquid (c) Air (d) Blood
(b) A solid is dispersed in liquid 38. Detergent action of soap is due to
(c) A gas is dispersed in liquid (a) Emulsification properties (b) Hydrolysis
(d) Some suger is dispersed in water (c) Ionization (d) High molecular weight
24. Smoke is an example of [CPMT 1984; BIT 1992]
39. When dispersion medium is water, the colloidal system is called
(a) Gas dispersed in liquid (b) Gas dispersed in solid (a) Sol (b) Aerosol
(c) Solid dispersed in gas (d) Solid dispersed in solid (c) Organosol (d) Aquasol
25. Gold number is minimum in case of [MP PMT 1985] 40. When a freshly precipitated substance is converted into a colloidal
(a) Gelatin (b) Egg albumin solution with the help of a third substance, the process is known as
(c) Gum arabic (d) Starch (a) Coagulation (b) Peptization
26. Movement of colloidal particles under the influence of electrostatic (c) Electrodispersion (d) Dialysis
field is 41. Which of the following will have highest coagulating power for
[AMU 1985, 88,02; MP PMT 1987, 89; CPMT 1988,94;
Roorkee 1995; MP PET 1992; AIIMS 2001; UPSEAT 2004] As2 S 3 colloid
(a) Electrophoresis (b) Electrolysis [CPMT 1988; DPMT 1984; Pb. PMT 2001; Pb. CET 2004]
(c) Dialysis (d) Ionisation (a) PO43 (b) SO 42
27. Which of the following substances gives a positively charged sol [CPMT 1983, 84; MP PMT 1990; MP PET 1992]
(a) Gold (b) A metal sulphite (c) Na  (d) Al3 
(c) Ferric hydroxide (d) An acidic dye 42. Which one of the following is a hydrophobic sol
28. Light scattering in colloidal particles is [MP PET 1991]
(a) Visible to naked eye (a) Starch solution
(b) Not visible by any means (b) Gum solution
(c) Visible under ordinary microscope (c) Protein solution
(d) Visible under ultra-microscope (d) Arsenic sulphide solution
29. Flocculation value is expressed in terms of [MP PMT 1986] 43. Purification of colloids is done by the process of
(a) millimole per litre (b) mole per litre [CPMT 1988]
(c) gram per litre (d) mole per millilitre (a) Electrophoresis (b) Electrodispersion
30. Which of the following is an emulsifier (c) Peptization (d) Ultra-filteration
(a) Soap (b) Water 44. Which of the following terms is not related with colloids
(c) Oil (d) NaCl [CPMT 1985, 87, 88]
31. Suspensions are [CPMT 1984] (a) Dialysis (b) Ultrafiltration
(a) Visible to naked eye (c) Wavelength (d) Brownian movement
(b) Invisible through microscope
45. When dispersed phase is liquid and dispersion medium is gas, then
(c) Not visible by any means the colloidal system is called [CPMT 1984]
(d) Invisible under electron microscope
(a) Smoke (b) Clouds
32. Gelatin is mostly used in making ice cream in order to
[NCERT 1979; MP PET/PMT 1988] (c) Emulsion (d) Jellies
(a) Prevent making of colloid 46. Tyndall phenomenon is exhibited by [CPMT 1985]
(b) To stabilise the colloid and prevent crystallisation (a) NaCl solution (b) Starch solution
(c) To stabilise mixture
(c) Urea solution (d) FeCl3 solution
(d) To enrich the aroma
33. In emulsions, the dispersion medium and dispersed phase are 47. The colloidal solution of gelatin is known [CPMT 1984]
(a) Both solids (a) Solvent loving sol (b) Reversible sol
 Surface Chemistry 595
(c) Hydrophilic colloids (d) All of these 61. The blue colour of water in the sea is due to [NCERT 1983]
48. The zig-zag motion of colloidal particles is due to (a) Refraction of blue light by the impurities in sea water
(a) Small size of colloidal particles (b) Reflection of blue sky by sea water
(c) Scattering of blue light by water moleules
(b) Large size of colloidal particles
(d) Absorption of other colours except the blue colour by water
(c) The conversion of potential energy into kinetic energy molecules
(d) Bombardment on colloidal particles by molecules of dispersion 62. Butter is a colloid. It is formed when
medium [MNR 1982; MP PET 1991;
49. Which is a natural colloidal [DPMT 1985] MP PMT 1994; CPMT 2002]
(a) Sodium chloride (b) Urea (a) Fat is dispersed in solid casein
(c) Canesugar (d) Blood (b) Fat globules are dispersed in water
(c) Water is dispersed in fat
50. Sodium stearate forms in water
(d) Casein is suspended in H 2 O
(a) True solution (b) A suspension
(c) An emulsion (d) A colloidal solution 63. Colloidal solution cannot be obtained from two such substances
which are
51. Blood contains (a) Insoluble in each other (b) In same physical state
(a) Positively charged particles (c) In different physical state (d) None of these
(b) Negatively charged particles 64. Which of the following reactions leads to the formation of a
(c) Neutral particles substance in the colloidal state
(d) Negatively as well as positively charged particles [MP PMT 1984; MP PET/PMT 1988]
52. Brownian motion is due to (a) Cu  HgCl2  CuCl 2  Hg
[MNR 1987; CPMT 1987; UPSEAT 2001, 02] (b) 2 HNO3  3 H 2 S  3 S  4 H 2O  2 NO
(a) Temperature fluctuation within the liquid phase (c) 2 Mg  CO 2  2 MgO  C
(b) Attraction and repulsion between charge on the colloidal
(d) Cu  CuCl 2  Cu 2Cl2
(c) Impact of molecules of the dispersion medium on the colloidal
particles (in presence of excess of HCl )
(d) Convective currents 65. Lyophobic colloids are [MP PMT 1986; DPMT 1996]
53. Milk can be preserved by adding a few drops of (a) Reversible colloids (b) Irreversible colloids
[MADT Bihar 1981] (c) Protective colloids (d) Gum proteins
66. Substances whose solutions can readily diffuse through parchment
(a) Formic acid solution
membranes are [CPMT 1984]
(b) Formaldehyde solution (a) Colloids (b) Crystalloids
(c) Acetic acid solution (c) Electrolytes (d) Non-electrolytes
(d) Acetaldehyde solution 67. Size of colloidal particles varies from
54. When a colloidal solution is observed under a microscope we can see [CPMT 1985] [CPMT 1982, 90, 93, 97; CBSE PMT 1996;
MP PMT 1995; AIIMS 2002; KCET 2004]
(a) Light scattered by colloidal particles
(b) Size of colloidal particles (a) 10 7 to 10 9 m (b) 10 9 to 10 17 m
(c) Shape of colloidal particles (c) 10 5 to 10 7 m (d) 10 4 to 10 10 m
(d) Relative size of the colloidal particles 68. Which of the following pairs of ions would be expected to form
55. Property of the colloidal solution is due to precipitate when their dilute solution are mixed
(a) Nature of dispersed phase [CPMT 1976]
(b) Nature of dispersion medium 
(a) Na , SO 32  (b) NH 4 , CO 32 
(c) Physical state of dispersed phase
 2
(d) Temperature of the system (c) Na , S (d) Fe3 , PO43
56. Which of the following has minimum value of flocculating power 69. Jelly is a[MP PETof1989, 90]
form
(a) Pb2 (b) Pb4 (a) Suspension (b) Colloidal solution
2  (c) Supersaturated solution (d) True solution
(c) Sr (d) Na
57. According to Graham, colloids are those substances which are 70. Bleeding is stopped by the application of ferric chloride. This is
(a) Insoluble in water because
(b) In solution do not pass through filter paper (a) Ferric chloride seal the blood cells.
(c) Of definite size of particles (b) Blood starts flowing in the other direction
(d) Separated from crystalloids by parchment paper (c) Blood is coagulated and blood vessel is sealed
58. (d) PMT
The reason for exhibiting Tyndall effect by the colloidal particle is[CPMT 1980, 86; MP None of these
1989]
(a) Reflection of light (b) Refraction of light 71. The colloidal particles can pass through
(c) Polarisation of light (d) Scattering of light (a) Filter paper as well as animal membrane
59. Which of the following shows the maximum hydrophobic behaviour (b) Animal[NCERT 1982]
membrane but not through filter paper
(a) Glycerine (b) Stearic acid (c) Filter paper but not through animal membrane
(c) Glucose (d) Adenine (d) Semipermeable membrane
60. A liquid aerosol is a colloidal system of [MP PMT 1987] 72. The emulsifying agent in milk is
(a) A liquid dispersed in a solid (a) Lactic acid (b) Casein
(b) A liquid dispersed in a gas (c) Lactose (d) Fat
(c) A gas dispersed in a liquid 73. Butter is [MP PMT 1990]
(d) A solid dispersed in a gas
(a) A gel (b) An emulsion
 596 Surface Chemistry
(c) A sol (d) Not a colloid (d) Is insoluble in water
74. An emulsion is a colloidal dispersion of [BCECE 2005] 87. Surface water contains [AFMC 2003]
(a) A liquid in a gas (b) A liquid in a liquid (a) Salt
(c) A solid in a liquid (d) A gas in a solid (b) Salt and organic compound
75. The colloidal solution of mercury in water can be easily obtained by (c) Organic compounds
(a) Mechanical precipitation (b) Bredig's arc method (d) Suspended impurities
(c) Repeated washing (d) Ultrasonic dispersion 88. Gelatin is mixed in ice-cream
76. The rate of dialysis depends upon (a) As a coagulant (b) For taste
(a) Nature of colloidal substance (c) For colour (d) As a protective colloid
(b) Temperature of the solution
89. Which of the following is an example of `water in oil' type emulsion
(c) Both of these
(a) Butter (b) Milk
(d) None of these
(c) Cream (d) Face cream
77. An emulsifier [MP PET 1995]
90. In which of the following Tyndall effect is not observed
(a) Accelerates the dispersion
[MP PET/PMT 1998]
(b) Homogenises the emulsion
(a) Suspensions (b) Emulsions
(c) Stabilizes the emulsion
(c) Sugar solution (d) Gold sol
(d) Aids the flocculation of emulsion
91. Which of the following is a lyophilic colloid
78. The difference between a lyophilic and lyophobic colloid is in their [MP PET/PMT 1998]
(a) Particle size (a) Milk (b) Gum
(b) Behaviour towards dispersion medium (c) Fog (d) Blood
(c) Filtrability 92. Which characteristic is true in respect of colloidal particle
(d) None of these [CPMT 1993; UPSEAT 2000]
79. When a substance comes in colloidal state the surface area of the (a) They always have two phases
particles (b) They are only in liquid state
(a) Increases (c) They can't be electrolysed
(b) Decreases (d) They are only hydrophilic
(c) Remains unchanged 93. Gold number is a measure of the
(d) First increases then decreases [MP PMT 1989; MP PET 1989,90;
80. Which of the impurity can be separated from a solution by DCE 1999; BHU 1999; CBSE PMT 1989]
electrodialysis (a) Protective action by a lyophilic colloid on a lyophobic colloid
(a) Alcohol (b) Alum (b) Protective action by a lyophobic colloid on a lyophilic colloid
(c) Sugar (d) Parchment paper (c) Number of mg of gold in a standard red gold sol
81. The reason for the stability of a lyophobic sol is (d) Stability of gold sol
(a) Brownian movement 94. Sulphur sol contains [UPSEAT 2002]
(b) Tyndall effect (a) Discrete sulphur atoms
(c) Electric charge (b) Discrete sulphur molecules
(d) Brownian movement and electric charge (c) Large agreegates of sulphur molecules
82. For coagulating As2 S 3 colloidal sol, which of the following will (d) Water dispersed in solid sulphur
have the lowest coagulation value 95. Pick out the statement which is not relevant in the discussion of
colloids [KCET 2003]
[MP PMT 1996; DCE 2000]
(a) Sodium aluminium silicate is used in the softening of hard
(a) NaCl (b) KCl water
(c) BaCl2 (d) AlCl3 (b) Potash alum is used in shaving rounds and as antiseptic in
83. Some substances behave as electrolytes in dilute solutions and as medicine
colloids in their concentrated solutions. Their colloidal forms are (c) Artificial rain is caused by throwing electrified sand on the
said to form [AMU 2002] clouds from an aeroplane
(a) Emulsions (b) Gels (d) Deltas are formed at a place where the river pours its water
(c) Micelles (d) Sols into the sea
96. Surface tension of lyophilic sols is [MP PMT 1992]
84. Which one can act as semipermeable membrane
[Pb. PMT 2002] (a) Lower than H 2 O (b) More than H 2 O
(a) Phenol layer (b) Ca3 (PO4 )2 (c) Equal to H 2 O (d) None of these
(c) Cu 2 Fe(CN )6 (d) All of these 97. When excess of electrolyte is added to a colloid it
[CBSE PMT 1989]
85. In which particles can pass through semipermeable membrane [Pb. PMT 2002]
(a) Coagulates (b) Precipitates
(a) Molecules of solvent (b) Complex ions
(c) Gets diluted (d) Does not change
(c) Simple ions (d) Molecules of solute
98. The shape of colloidal particles is
86. Silver iodide is used for producing artificial rain because AgI
(a) Sphere like (b) Rod like
[NCERT 1984]
(c) Disc like (d) Thread like
(a) Is easy to spray at high altitudes
(e) All of these
(b) Is easy to synthesize
99. Colloidal solution of arsenious sulphide is coagulated by
(c) Has crystal structure similar to ice
[MP PMT 1992]
 Surface Chemistry 597
(a) Addition of electrolyte 112. The size of particles in suspension, true solution and colloidal
(b) Addition of non-electrolyte solution varies in the order [BHU 1997]
(a) Suspension > Colloidal > True solution
(c) Addition of solid As2 S 3
(b) Suspension > (Colloidal + True solution)
(d) None of these (c) True solution > Suspension > Colloidal
100. Different colloidal particles of gold having different colours, obtained (d) None of these
from different methods due to 113. Which of the following represents surfactant molecule
[MP PET 1989; UPSEAT 2001, 02; EAMCET 2003] [JIPMER 1997]
(a) Variable valency of gold (a) C17 H 36 (b) C17 H 25 COO Na 

(b) Different concentration of gold particles
(c) Different types of impurities (c) H 2 O (d) None of these
(d) Different radius of colloidal particles 114. In lyophilic sols the attraction of sol particles towards the medium is
101. Which one of the following is lyophilic colloid due to
[MP PET 1989] (a) Covalent bond (b) Vander Waal's force
(a) Gelatin (b) Sulphur (c) Hydrogen bond (d) None of these
(c) Gold (d) Carbon 115. If some gelatin is mixed in colloidal solution of gold, then it does
102. Which one of the following properties of colloids is related with (a) Coagulation of gold
scattering of light [MP PMT 1989] (b) Peptization of gold
(a) Diffusion (b) Peptization (c) Protection of gold sol
(c) Tyndall effect (d) Brownian movement (d) Protection of gelatin
103. Which one of the following is a hydrophilic colloidal sol 116. Emulsifiers are generally
(a) Barium hydroxide sol (b) Arsenic sulphide sol (a) Soap (b) Synthetic detergents
(c) Starch solution (d) Silver chloride sol (c) Lyophilic sols (d) All of these
104. The coagulation power of an electrolyte for arsenious sulphide 117. In shaving cream, the dispersion medium is
decreases in the order [JIPMER 1997] (a) Liquid (b) Gas
(a) Na  , Al3 , Ba2 (b) PO43 , SO 42 , Cl  (c) Solid (d) None of these
118. The minimum quantity of sodium chloride which is necessary to
(c) Al3 , Ba2 , Na  (d) Cl  , SO 42 , PO43 precipitate 10 litres of sol in two hours is 0.585 gm. The flocculation
105. Size of colloidal particle is [BCECE 2005] value of sodium chloride is
(a) 1 nm (b) 1 – 100 nm (a) 0.585 (b) 0.0585
(c) > 100 nm (d) > 1000 nm (c) 0.1 (d) One
106. The concentration of electrolyte required to coagulate a given 119. Which one is an example of miceller system
amount of As2 S 3 sol is minimum in the case of (a) Soap + water (b) Protein + water
[KCET 2003] (c) Rubber + benzene (d) As2O3  Fe(OH )3
(a) Magnesium nitrate 120. “Delta” at the rivers are formed due to
(b) Potassium nitrate (a) Peptization (b) Coagulation
(c) Potassium sulphate (c) Hydrolysis (d) Precipitation
(d) Aluminium nitrate 121. Tyndall effect is more pronounced in
107. When a strong beam of light is passed through a colloidal solution, (a) Hydrophilic sols (b) Hydrophobic sols
the light will [BHU 1996; JIPMER 1997] (c) Starch solution (d) Both (b) and (c)
(a) Give a rainbow 122. Emulsifier is mixed to
(b) Be scattered (a) Increase the stability of emulsion
(c) Be reflected (b) Decrease the stability of emulsion
(d) Absorbed completely (c) Change oil into water like emulsion
108. A cleared solution which is again converted into colloidal solution, (d) None of these
the process is called [DPMT 1996]
123. White of an egg is partly coagulated by heating which can be again
(a) Peptisation (b) Electrolytic addition
obtained back by some pepsin and little HCl . This process is
(c) Electrophoresis (d) None of these
called
109. In dialysis, colloidal particles are separated from
(a) Peptization (b) Coagulation
[DPMT 1996]
(a) Solvent (c) Precipitation (d) None of these
(b) Dispersed phase 124. When sugar is added to a colloidal solution it brings about
(c) Ions of electrolytes (a) Ionization (b) Coagulation
(d) Particles of dispersion medium (c) Peptization (d) None of these
110. Colour of colloidal solution is due to [CPMT 1996] 125. Colloidal solutions of metals like gold, silver and platinum are
(a) Different size of colloidal particles generally prepared by using [DPMT 1984]
(b) Due to formation of complex (a) Peptization (b) Bredig's arc method
(c) Due to formation of hydrated crystal (c) Exchange of solvent (d) Oxidation method
(d) None of these 126. Liquid–liquid sols are known as [CPMT 1999]
111. Which of the following is property of colloid [CPMT 1996] (a) Aerosols (b) Emulsions
(a) Scattering of light (b) They show attraction (c) Foam (d) Gel
(c) Dialysis (d) Emulsion 127. Tyndall effect depends upon the
(a) Charge on the colloidal particles
 598 Surface Chemistry
(b) Osmotic pressure of colloidal solution 142. Size of colloidal particle is
(c) Difference between the refractive indices of dispersed phase [CPMT 1988; MP PMT 1991; RPET 2000]
and dispersion medium (a) 1 to 10 Å (b) 20 to 50 Å
(d) Size of colloidal particles (c) 10 to 1000 Å (d) 1 to 280 Å
128. Which one of the sols acts as protective colloid 143. Which one is Freundlich's equation
[MP PMT 1990; MP PET 1990, 92; RPET 2003] x 1 x
(a) As2 S 3 (b) Gelatin (a)  log K  log P (b)  exp ( KP )
m n m
(c) Au (d) Fe(OH )3 x x 1
(c)  KP 2 (d) log  log K  log C
129. The example of heteropolar sol is m m n
(a) Starch sol in water (b) Rubber sol in water 144. Ferric chloride is applied to stop bleeding cut because
(c) Protein sol in water (d) Sulphur sol
(a) Fe3  ion coagulates blood, which is a negatively charged sol
130. In Bredig's arc method some alkali is added because
(a) It increases electrical conductance (b) Fe3  ion coagulates blood, which is a positively charged sol
(b) To obtain molecular colloid (c) Cl  coagulates blood, which is a positively charged sol
(c) To obtain colloidal particles of same size
(d) Cl  ion coagulates blood, which is a negatively charged sol
(d) To stabilise the sol
145. At the critical micelle concentration, the surfactant molecules
131. Which one of the following is not a colloid [BIT 1992]
[CBSE PMT 1998]
(a) Milk (b) Blood (a) Decompose
(c) Solution of urea (d) Ice cream
(b) Dissociate
132. Milk is an example of [BIT 1992; CPMT 1994;
(c) Associate
MP PET 1996; BHU 1996]
(d) Become completely soluble
(a) Pure solution (b) Emulsion
(c) Gel (d) Suspension 146. The decomposition of H 2 O2 can be slowed down by the addition
133. Dialysis is the process of separation of of small amount of phosphoric acid which act as
(a) Suspended particles from colloids [JIPMER 2000]
(b) Suspended particles from crystalloids (a) Promoter (b) Inhibitor
(c) Colloidal particles from crystalloids (c) Detainer (d) Stopper
(d) Colloidal particles from gel 147. Which of the following molecules is most suitable to disperse
134. Minimum concentration of electrolyte which can precipitate any sol benzene in water [AIIMS 2005]
is [BIT 1992] (a) O
(a) Peptization value (b) Gold number O- Na+
(c) Avogadro's number (d) Flocculation value O
(b) Na + O-
135. Whipped cream is an example of [MNR 1978] O- Na+
Dispersion medium Dispersed phase O
(a) Gas Liquid
(b) Liquid Gas (c)
(c) Liquid Liquid
CH3
(d) Liquid Solid (d)
136. Milk is
[MP PMT 1995;CPMT 1988; MP PET 1991; MNR 1982] Cl
(a) Dispersed fats in oil (b) Dispersed fats in water 148. Luminosity observed as a result of scattering of light by particles is
(c) Dispersed water in fats (d) Dispersed water in oil observed in [RPET 2000]
137. A coagulating agent frequently added to water to remove the
(a) Suspension (b) Colloidal solution
suspended and colloidal impurities is
(a) Mohr salt (b) Alum (c) True solution (d) None of these
(c) Bleaching powder (d) Copper sulphate 149. Which of the following makes the lyophilic solution unstable
[MP PMT 1994]
138. Fe(OH )3 when treated with FeCl3 solution a reddish-brown
(a) Dialysis
solution is formed. The process involved is (b) Addition of electrolyte
[AFMC 1982]
(c) Addition of alcohol
(a) Dispersion (b) Exchange of solvent
(d) Addition of alcohol and electrolyte both
(c) Peptization (d) None of these
150. A detergent is a [CPMT 1993]
139. Alum purifies muddy water by
(a) Dialysis (b) Absorption (a) Cleaning agent (b) Drug
(c) Coagulation (d) Forming a true solution (c) Catalyst (d) Vitamin
140. Which of the following statements is not true for a lyophilic sol 151. Gold number is related with [MP PET 2000]
(a) It can be easily solvated (a) Colloids (b) Radioactivity
(b) It carries no charge (c) Gas equation (d) Kinetic energy
(c) Coagulation of this sol is reversible in nature 152. Small liquid droplets dispersed in another liquid is called
[Pb. PMT 2000]
(d) It is not very stable in a solvent
(a) Gel (b) Emulsion
141. High concentration of gelatin in water on heating gives colloidal
solution, which is called (c) Suspension (d) True solution
(a) Foam (b) Gel 153. Which of the following is used for the destruction of colloids
[CBSE PMT 2000]
(c) Gas (d) Air
(a) Dialysis (b) Condensation
 Surface Chemistry 599
(c) By ultrafiltration (d) By adding electrolyte (b) Sulphate part which combines with the dirt and removes it
154. An example of an associated colloid is (c) Aluminium which coagulates the mud particles
[CBSE PMT 2000; MP PET 2000] (d) Making mud water soluble
(a) Milk (b) Soap solution 169. Maximum coagulation power is in [MP PET 1989, 90]
(c) Rubber latex (d) Vegetable oil (a) Na  (b) Ba  
155. The movement of colloidal particles towards the oppositely charged 
electrodes on passing electricity is known as (c) Al (d) Sn    
[AFMC 2000]
170. Which of the following is not an emulsion [MP PET 2003]
(a) Butter (b) Ice cream
(a) Cataphoresis (b) Tyndall effect
(c) Milk (d) Cloud
(c) Brownian movement (d) None of these
171. Colloidal solution of gold cannot be prepared by
156. Tyndall effect is shown by [Pb. PMT 1999]
(a) Bredig's arc method (b) Mechanical dispersion
(a) Sol (b) Solution
(c) Reduction of gold chloride (d) Exchange of solvents
(c) Plasma (d) Precipitation 172. Which of the following ions can cause coagulation of proteins
157. Colloidal solutions of gold prepared by different methods have
different colours owing to [JIPMER 1999] (a) Ag  (b) Na 
(a) The difference in the size of the colloidal particles (c) Mg  (d) Ca  
(b) The fact that gold exhibits a variable valency of + 1 and + 3 173. Light scattering takes place in
(c) Different concentrations of gold [MP PMT 1991; BHU 2000; AFMC 2001; Kerala PET 2002]
(d) Presence of different types of foreign particles depending upon (a) Solutions of electrolyte (b) Colloidal solutions
the method of preparation of the colloid (c) Electrodialysis (d) Electroplating
158. Which of the following colloids are formed when hydrogen sulphide 174. Which of the following can stabilize gold sol from coagulation by
gas is passed through a cold solution of arsenious oxide NaCl [CPMT 2000]
solution
(a) As2 S 3 (b) As2 O3 (a) Fe(OH )3 (b) Gelatin
(c) As2 S (d) As2 H 2 (c) As2 S 3 (d) None of these
159. The simplest way to check whether a system is colloidal, is 175. At isoelectric point
[KCET (Med.) 2002] (a) Colloidal sol becomes highly stable
(a) Tyndall effect (b) Electro dialysis (b) Precipitation of a colloidal sol takes place
(c) Brownian movement (d) Finding out particle size (c) Colloidal particles becomes uncharged
160. Fog is an example of colloidal system (d) Peptization can be carried out
[MNR 1985; NCERT 1985; CPMT 1988; MP PMT 1991; 176. Which one is an example of multimolecular colloid system
MP PET 1996; UPSEAT 1999, 2000] (a) Soap dispersed in water (b) Protein dispersed in water
(a) Liquid dispersed in gas (b) Gas dispersed in gas (c) Gold dispersed in water (d) Gum dispersed in water
(c) Solid dispersed in gas (d) Gas dispersed in liquid 177. Metals like Pt and Pd can adsorb large volume of hydrogen under
161. In the measurement of gold number, the useful electrolyte is specific conditions. Such adsorbed hydrogen by the metal is known
(a) AuCl3 (b) NaCl as
(a) Occluded hydrogen (b) Absorbed hydrogen
(c) AlCl3 (d) FeCl3 (c) Reactive hydrogen (d) Atomic hydrogen
162. Blood may be purified by [MP PMT 2000] 178. A colloidal system in which gas bubbles are dispersed in a liquid is
(a) Dialysis (b) Electro-osmosis known as [MP PMT 1993]
(c) Coagulation (d) Filtration (a) Foam (b) Sol
163. The stability of lyophilic colloidal sol is due to (c) Aerosol (d) Emulsion
(a) Both charge and solvation 179. On adding few drops of dilute HCl or FeCl3 to freshly
(b) Only solvation precipitated ferric hydroxide a red coloured colloidal solution is
(c) Only charge obtained. The phenomenon is known as
(d) None of these [NCERT 1981; AFMC 1982; MP PMT 1989, 97]
164. The impurities present in rain water possess ..... charge (a) Peptisation (b) Dialysis
(a) Positive (b) Negative (c) Protective action (d) Dissolution
(c) Zero (d) Positive and negative 180. Surface tension of lyophilic sols is [MP PMT 2002]
165. Sodium lauryl sulphate is [RPET 2003] (a) Lower than that of H 2 O (b) More than that of H 2 O
(a) Cationic sol (b) Anionic sol
(c) Equal to that of H 2 O (d) None of these
(c) Neutral sol (d) None of these
166. Which of the following statement is false 181. Which of the following is not true of a detergent molecule
[JIPMER 2002]
(a) Every solid substance can be brought into colloidal state
(a) It has a non-polar organic part and a polar group
(b) Colloidal particles carry electrical charges
(b) It is not easily biodegraded
(c) Every solid substance can be made to behave like a lyophilic (c) It is a sodium salt of fatty acid
colliod
(d) It is a surface active agent
(d) Addition of electrolytes causes flocculation of colloidal particles
182. Which of the following can act as protective colloids
167. Which is a colloid [CPMT 1984]
(a) Hydrophobic sols (b) Hydrophilic sol
(a) Sugar solution (b) Urea solution (c) Gold sol (d) None of these
(c) Silicic acid (d) NaCl solution 183. Which of the following substances is not used for preparing lyophilic
168. Alum helps in purifying water by [AIEEE 2002] sols [MP PET 2002]
(a) Forming Si complex with clay particles (a) Starch (b) Gum
 600 Surface Chemistry
(c) Gelatin (d) Metal sulphide (a) Dispersion of a solid or liquid in a gas
184. Hydrophilic sols are (b) Dispersion of a solid in a liquid
(a) Reversible (b) Irreversible (c) Dispersion of a liquid in a liquid
(c) Unstable (d) None of these (d) Solid solution
185. Soap essentially forms a colloidal solution in water and removes the 199. Lyophilic sols are [IIT 2005]
greasy matter by (a) Irreversible sols
(a) Absorption (b) Emulsification (b) They are prepared from inorganic compound
(c) Coagulation (d) None of these (c) Coagulated by adding electrolytes
186. Toilet soap is a mixture of [UPSEAT 2001]
(d) Selfstabilizing
(a) Calcium and sodium salts of fatty acids
(b) Fatty acids and glycerol 200. The volume of a colloidal particle, VC as compared to the volume
(c) Sodium salts of fatty acids of a solute particle in a true solution VS , could be
(d) Potassium salt of fatty acids [AIEEE 2005]
187. Gold sol is an electronegative sol. The amount of electrolyte required VC ~ VC ~
to coagulate a certain amount of gold sol is minimum in the case of (a) –1 (b) – 10 23
[KCET (Med.) 2001] VS VS
(a) CaCl2 (b) NaCl VC ~ VC ~
(c) – 10  3 (d) – 10 3
(c) AlCl3 (d) Na 2 SO 4 VS VS
188. In the case of small cuts, bleeding is stopped by applying potash 201. The disperse phase in colloidal iron (III) hydroxide and colloidal gold
alum. Here alum acts as [KCET (Med.) 2001] is positively and negatively charged, respectivley. Which of the
following statements is NOT correct [AIEEE 2005]
(a) Fungicide (b) Disinfectant
(a) Magnesium chloride solution coagulates, the gold sol more
(c) Germicide (d) Coagulating agent readily than the iron (III) hydroxide sol
189. If gold number of A,B,C and D are 0.005, 0.05, 0.5 and 5 (b) Sodium sulphate solution causes coagulation in both sols
respectively, then which of the following will have the highest (c) Mixing the sols has no effect
protective power [Pb. CET 2001; CPMT 2000]
(d) Coagulation in both sols can be brought about by
(a) A (b) B electrophoresis
(c) C (d) D 202. The surface tension of which of the following liquid is maximum ?[CBSE PMT 20
190. Bredig arc method can not be used to prepare colloidal solution of (a) H 2 O (b) C6 H 6
which of the following [AFMC 2004]
(a) Pt (b) Fe (c) CH 3 OH (d) C2 H 5 OH
(c) Ag (d) Au 203. Which one of the following forms micelles in aqueous solution above
191. Gold number is maximum for the lyophilic sol is certain concentration ? [CBSE PMT 2005]
[BVP 2004] (a) Urea
(a) Gelatin (b) Haemoglobin (b) Dodecyl trimethyl ammonium chloride
(c) Sodium oleate (d) Potato starch (c) Pyridinium chloride
192. Which of the following is the best protective colloid (d) Glucose
[UPSEAT 2004] 204. Alum is a water purifier because it [KCET 2005]
(a) Gelatin (Gold No. = 0.005) (a) Coagulates the impurities
(b) Gum arabic (Gold No. = 0.15) (b) Softens hard water
(c) Egg albumin (Gold No. = 0.08) (c) Gives taste
(d) None of these (d) Destroys the pathogenic bacteria
193. The gold number of A, B C and D are 0.04, 0.002, 10 and 25 205. An emulsifier is a substance which [KCET 2005]
respectively. Protective power of A, B, C and D are in order [DCE 2003] (a) Stabilises the emulsion
(b) Homogenises the emulsion
(a) A  B  C  D (b) B  A  C  D
(c) Coagulates the emulsion
(c) D  C  B  A (d) C  A  B  D (d) Accelerates the dispersion of liquid in liquid
194. A catalyst is a substance which [Pb. CET 2004] 206. Muddy water can be purified through coagulation using
(a) Is always in the same phase as in the reactions [J & K 2005]
(b) Alters the equilibrium in a reaction (a) Common salt (b) Alums
(c) Does not participate in the reaction but alters the rate of (c) Sand (d) Lime
reaction 207. Fog is a colloidal solution of [J & K 2005]
(d) Participates in the reaction and provide an easier pathway for (a) Solid in gas (b) Liquid in gas
the same (c) Gas in liquid (d) Gas in solid
195. Cod liver oil is [MHCET 2004] 208. Lyophilic sols are more stable than lyophobic sols because their
(a) An emulsion (b) Solution particles are [Karala CET 2005]
(a) Positively charged (b) Negatively charged
(c) Colloidal solution (d) Suspension
(c) All soluble (d) Attract each other
196. Paste is [MHCET 2004] (e) Are heavier
(a) Suspension of solid in a liquid 209. Oils and fats are obtained by saponification of potassium stearate.
(b) Mechanical dispersion of a solid in liquid
Its formula is CH 3  (CH 2 )16  COO  K  . Lyophobic end of
(c) Colloidal solution of a solid in solid
(d) None of these atom is (CH 3 ) and lyophilic end is COO  K  . potassium stearate
197. A precipitate is changed to colloidal solution by the following is example of
process [UPSEAT 2004] [Kerala CET 2005]
(a) Dialysis (b) Ultrafiltration (a) Lyophobic colloids (b) Lyophilic colloids
(c) Peptization (d) Electrophoresis (c) Poly molecular colloids (d) Macromolecular colloids
198. An aerosol is a [UPSEAT 2004]
 Surface Chemistry 601
(e) Combined colloids or Miscells (a) Change the nature of reaction products
(b) Increase the reaction yield
(c) Decrease the need for reactants
(d) Decrease the time required for the reaction
12. Which one of the following is not represented by sols
[MP PMT 1992]
(a) Absorption (b) Tyndall effect
(c) Flocculation (d) Paramagnetism
1. Which of the following is contributed towards the extra stability of 13. Example of intrinsic colloid is
lyophilic colloids [CPMT 1983] (a) Glue (b) Sulphur
(a) Hydration (b) Charge (c) Fe (d) As2 S 3
(c) Colour (d) Tyndall effect
14. Colloidal solution of arsenious sulphide can be prepared by
2. Which of the following methods is used for sol destruction [AMU 1985]
[CPMT 1988] (a) Electrodispersion method
(a) Condensation (b) Peptization
(b) Dialysis (c) Double decomposition
(c) Diffusion through animal membrane (d) Hydrolysis]
(d) Addition of an electrolyte 15. The capacity to bring about coagulation increases with
3. A catalyst is a substance which [IIT 1983] (a) Ionic radii (b) Atomic radii
(a) Increases the equilibrium concentration of the product (c) Valency of an ion (d) Size of an ion
(b) Changes the equilibrium constant of the reaction 16. Gold number gives
[NCERT 1987; MNR 1987; UPSEAT 2002;
(c) Shortens the time to reach equilibrium Kurukshetra CET 2002; MP PMT 2004]
(d) Supplies energy to the reaction (a) The amount of gold present in the colloid
4. The decomposition of hydrogen peroxide can be slowed by the (b) The amount of gold required to break the colloid
addition of a small amount of acetamide. The latter acts as a (c) The amount of [MNRgold1978]
required to protect the colloid
(a) Detainer (b) Stopper (d) None of these
(c) Promoter (d) Inhibitor 17. Point out the false statement [MP PET 1997]
5. The ability of an ion to bring about coagulation of a given colloid (a) Brownian movement and Tyndall effect is shown by colloidal
depends upon [CPMT 1980; MP PET/PMT 1988; systems
CBSE PMT 1997; MP PMT 1989; MP PET 1994] (b) Gold number is a measure of the protective power of a
(a) Its size lyophilic colloid
(b) The magnitude of its charge only (c) The colloidal solution of a liquid in liquid is called is gel
(c) The sign of its charge (d) Hardy–Schulze rule is related with coagulation
18. Which of the following does not contain a hydrophobic structure[NCERT 1983]
(d) Both the magnitude and the sign of its charge
(a) Linseed oil (b) Lanolin
6. Which one of the following is an incorrect statement for (c) Glycogen (d) Rubber
physisorption [MP PET 2002]
19. The function of gum-arabic in the preparation of indian ink is
(a) It is a reversible process (a) Coagulation (b) Peptization
(b) It requires less heat of adsorption (c) Protective action (d) Absorption
(c) It requires activation energy 20. Identify the gas which is readily adsorbed by activated charcol
(d) It takes place at low temperature [KCET 2004]
7. Which is not colloidal [CPMT 1984; MP PET 1989, 91] (a) N2 (b) SO 2
(a) Chlorophyll (b) Egg (c) H2 (d) O 2
(c) Ruby glass (d) Milk
8. Which one of the following is not a surfactant [AIIMS 2003] 21. The density of gold is 19 g / cm 3 . If 1.9  10 4 g of gold is
CH dispersed in one litre of water to give a sol having spherical gold
3 particles of radius 10 nm, then the number of gold particles per
|
(a) CH 3  (CH 2 )15  N   CH 3 Br  mm 3 of the sol will be [Pb.CET 2004]
|
CH (a) 1.9  1012 (b) 6.3  1014
3
(c) 6.3  1010 (d) 2.4  10 6
(b) CH 3  (CH 2 )14  CH 2  NH 2
22. Which of the following forms cationic miscelles above certain
(c) CH 3  (CH 2 )16  CH 2OSO 2 Na  concentration [CBSE PMT 2004]
(a) Urea
(d) OHC  (CH 2 )14  CH 2  COO  Na  (b) Cetyltrimethylammonium bromide
(c) Sodium dodecyl sulphate
9. Size of colloidal particles is (d) Sodium acetate
[CPMT 1984; MP PMT 1990, 92]
(a) 0.1 m  to 0.001 m  (b) 10  to 20 
(c) 0.05 m  to 0.1 m  (d) 25  to 30 
10. Which of the following electrolytes is most effective in the
coagulation of gold solution [KCET 1996]
(a) NaNO 3 (b) K4 [Fe(CN )6 ]
(c) Na3 PO4 (d) MgCl2 Read the assertion and reason carefully to mark the correct option out of
the options given below :
11. A catalyst is used in a reaction to
[CPMT 1972, 75, 97; DPMT 1982]
 602 Surface Chemistry
(a) If both assertion and reason are true and the reason is the correct 14. Assertion : NH 3 absorb more readily over activated
explanation of the assertion.
(b) If both assertion and reason are true but reason is not the correct charcoal than CO 2 .
explanation of the assertion. Reason : NH 3 is non-polar. [AIIMS 2000]
(c) If assertion is true but reason is false.
(d) If the assertion and reason both are false. 15. Assertion : Sky appears blue colour.
(e) If assertion is false but reason is true. Reason : Colloidal particles of dust scatter blue light.
1. Assertion : When a finely divided active carbon or clay is [AIIMS 2000]
stirred into a dilute solution of a dye, the 16. Assertion : Physical absorption of molecules takes place on
intensity of colour in the solution is decreased. surface only.
Reason : The dye is adsorbed on the solid surface. Reason : In this process, the bonds of the absorbed
2. Assertion : The enthalpy of physisorption is greater than molecules are broken. [AIIMS 2002]
chemisorption. 17. Assertion : The micelle formed by sodium stearate in water
Reason : Molecules of adsorbate and adsorbent are held by has  COO  groups at the surface.
van der Waals forces in physisorption and by Reason : Surface tension of water is reduced by the
chemical bonds in chemisorption. addition of stearate. [AIIMS 2003]
3. Assertion : Silica gel is used for drying air. 18. Assertion : Aqueous gold colloidal solution is red in colour.
Reason : Silica gel adsorbs moisture from air. Reason : The colour arises due to scattering of light by
colloidal gold particles. [AIIMS 2004]
x
4. Assertion : According to Freundlich: k .P1 / n . 19. Assertion : Increase in surface area, increase in rate of
m
evaporation.
Reason : The isotherm shows variation of the amount of
Reason : Stronger the intermolecular attractive forces, fast
gas adsorbed by the adsorbent with temperature. is the rate of evaporation at a given temperature.
5. Assertion : A reaction cannot become fast by itself unless a
catalyst is added.
Reason : A catalyst always increases the speed of a
reaction.
6. Assertion : ZSM – 5 is used as a catalyst in petrochemical
industries.
Reason : Zeolites are three dimensional network silicates
in which some silicon atoms are replaced by Adsorption and Adsorption isotherm
aluminium atoms.
7. Assertion : Lyophilic colloids are called as reversible sols. 1 b 2 a 3 b 4 a 5 a

Reason : Lyophilic sols are liquid loving. 6 b 7 c 8 b 9 b 10 d

8. Assertion : Colloidal sols scatter light while true solutions do 11 a 12 a 13 d 14 d 15 c
not. 16 c 17 d 18 d 19 a 20 b
Reason : The particles in the colloidal sol more much
21 a 22 c 23 c 24 b 25 a
slower than that of the true solution.
26 a 27 d 28 b 29 b 30 c
9. Assertion : Colloidal particles show Brownian movement.
Reason : Brownian movement arises because of the impact 31 a 32 d 33 b 34 c 35 d
of the molecules of the dispersion medium with 36 c 37 a 38 a 39 c 40 c
the colloidal particles.
41 d 42 a 43 a 44 c 45 d
10. Assertion : For the coagulation of sols carrying positive
46 d 47 d
charge, PO43  ions are more efficient than
SO 42  or Cl  ions. Catalyst and Catalysis
Reason : This follows Hardy – Schulze rule.
11. Assertion : An emulsion becomes stable if soap is added to it 1 c 2 d 3 d 4 a 5 d
. 6 b 7 d 8 a 9 d 10 c
Reason : Soap contains hydrophilic and hydrophobic parts. 11 c 12 b 13 a 14 b 15 c
12. Assertion : Deep electric shock causes death of an animal.
16 d 17 c 18 d 19 c 20 c
Reason : Electric shock coagulate the blood.
21 b 22 d 23 a 24 b 25 c
[AIIMS 1995]
26 d 27 d 28 a 29 c 30 c
13. Assertion : A catalyst is more effective in finely divided form.
Reason : Finely divided form has more surface area. 31 d 32 c 33 c 34 d 35 c

[AIIMS 1998] 36 b 37 d 38 a 39 a 40 d
 Surface Chemistry 603

41 b 42 a 43 b 44 b 45 b 181 c 182 b 183 d 184 a 185 b

46 c 47 d 48 d 49 d 50 c 186 d 187 c 188 d 189 a 190 b
51 b 52 b 53 a 54 b 55 d 191 d 192 a 193 b 194 c 195 a

56 d 57 d 58 d 59 b 60 c 196 a 197 c 198 a 199 d 200 d

61 c 62 c 63 b 64 b 65 a 201 c 202 a 203 b 204 a 205 a

66 d 67 c 68 c 69 b 70 b 206 b 207 b 208 c 209 e

71 d 72 d 73 c 74 a
Critical Thinking Questions

Colloids, Emulsion, Gel and Their properties 1 a 2 d 3 c 4 d 5 d

with application 6 c 7 a 8 b 9 a 10 b
11 d 12 d 13 a 14 c 15 c
1 b 2 d 3 a 4 a 5 c
16 d 17 c 18 d 19 c 20 b
6 d 7 d 8 b 9 c 10 c
21 d 22 d
11 c 12 c 13 d 14 b 15 c
16 d 17 b 18 c 19 a 20 b Assertion & Reason
21 b 22 b 23 a 24 c 25 a
1 a 2 e 3 a 4 c 5 d
26 a 27 c 28 d 29 a 30 a
6 b 7 b 8 b 9 a 10 a
31 a 32 b 33 c 34 c 35 b
11 a 12 a 13 a 14 c 15 a
36 b 37 c 38 a 39 d 40 b
16 d 17 b 18 a 19 c
41 d 42 d 43 d 44 c 45 b
46 b 47 d 48 d 49 d 50 d
51 b 52 c 53 b 54 a 55 c
56 d 57 d 58 d 59 d 60 b
61 c 62 c 63 d 64 b 65 b
66 b 67 a 68 d 69 b 70 c
71 c 72 b 73 a 74 b 75 d
76 b 77 c 78 b 79 a 80 b
81 d 82 d 83 c 84 c 85 a
86 c 87 d 88 d 89 a 90 c
91 b 92 a 93 a 94 c 95 a
96 a 97 a 98 e 99 a 100 d
101 a 102 c 103 c 104 c 105 b
106 d 107 b 108 d 109 c 110 a
111 a 112 a 113 b 114 c 115 c
116 d 117 a 118 d 119 a 120 b
121 b 122 a 123 a 124 d 125 b
126 b 127 c 128 b 129 c 130 d
131 c 132 b 133 c 134 d 135 b
136 b 137 b 138 c 139 c 140 d
141 b 142 c 143 d 144 a 145 c
146 b 147 c 148 b 149 d 150 a
151 a 152 b 153 d 154 b 155 a
156 a 157 a 158 a 159 a 160 a
161 b 162 a 163 a 164 b 165 a
166 c 167 c 168 c 169 d 170 d
171 d 172 a 173 b 174 b 175 c
176 c 177 a 178 a 179 a 180 a
 606 Surface Chemistry
All of these equation represent freundlich adsorption isotherm.
47. (d) It has been observed that the surface of a solid (or liquid) has
the tendency to attract and retain the molecules of other
immiscible phase with which it is brought into contact. These
molecules remian only at the surface and do not go deeper into
the bulk. This tendency of accumulation of molecular species at
the surface than in the bulk of a solid (or liquid) it termed
adsorption.
Adsorption and Adsorption isotherm
1. (b) Chemical adsorption is irreversible due to formation of new
Catalyst and Catalysis
bonds and compounds.
3. (d) A catalyst does not take part in the reaction but can speed it
2. (a) Chemical adsorption increases with temperature. up. It can be recovered after the reaction.
6. (b) When the temperature is raised, the viscosity of liquid
4. (a) N 2  3 H 2    2 NH 3
Fe Catalyst
decreases, this is because increase in temperature increases the (g) (g) Mo promoter (g)
average kinetic energy of molecules which overcome the
attractive force between them. 5. (d) 2 KClO3 
 2 KCl  3O2
MnO 2

13. (d) Charge on As 2 S 3 sol is due to the adsorbed sulphide ion.

6. (b) 2SO 2  O 2   2 SO 3
Pt(Catalyst)

19. (a) According to langmuir Adsorption isotherm the amount of gas As2 O3 ( poison )
adsorbed at very high pressures reaches a constant limiting 7. (d) It is a shape-selective catalyst.
volume. 8. (a) All substance have average energy and before the reaction
21. (a) According to definition of adsorbent. occurs energy of the reactant should be higher than the
24. (b) Adsorption increase when temperature decreases (Adsorption average energy. We also know that catalyst lower the activation
 1/Temperature) energy. Therefore, rate of reaction is increased.
25. (a) In chemical adsorption, one layers are adsorbed. 9. (b) 2SO 2  O 2  2SO 3
NO

26. (a) Adsorption of a gas on solid independent of the pressure start fast
12. (b) Transition metals are most efficient catalysts due to half filled
and after some time becomes slow.
d-orbitals.
27. (d) Chemisorption first increases and then decreases with
16. (d) An increase in rate of reaction in forward direction by a
temperature.
catalyst for a reaction in equilibrium brings in an increase in
28. (b) Adsorption is an exothermic process. concentration of products and thus rate of backward reaction
1 also increase to same magnitude and so allow the equilibrium
32. (d) log x / m  log k  log p ; this is Freundlich isotherm. to be achieved quickly.
n
1 17. (c) 2 SO 2  O 2   2 SO 3
V2 O5
Thus p  . (g) (g) (g)
n
19. (c) Catalyst never change the equilibrium constant.
36. (c) Heterogeneous catalysis can be explained by the adsorption
theory. 21. (b) Because reactant and catalyst are present in same physical
state.
37. (a) Adsorption due to strong chemical bond is called chemical
adsorption or chemisorption or Langmuir adsorption. 23. (a) C 6 H 12 O 6   2C 2 H 5 OH  2CO 2
Zymase
Enzyme
39. (c) Physical adsorption decreases with increase of temperature. Glucose Ethanol

126  1  50 24. (b) C6 H 6  CH 3 Cl  C6 H 5 CH 3  HCl

Anhydrous
40. (c) W  6.3 AlCl3
1000
(Molecular weight of oxalic acid 163) 25. (c) CH 3 COOC 2 H 5  HOH   
Conc . H 2 SO 4
Catalyst
6.3
0 .5 gm  CH 3 COOH  C 2 H 5 OH
2
27. (d) Catalyst does not depend on the enthalpy of the reactants.
6 .3 30. (c) Catalyst does not depend on the free energy change in the
1 gm   1  6.3 gm.
2  0.5 reaction.
41. (d) Noble gases are adsorbed by coconut charcoal. The adsorption 31. (d) Activation energy changes when catalyst is used in a reaction.
of different noble gases occur at different temperatures, hence 32. (c) In the reversible reaction a catalyst is the substance which
charcoal is used to separate these gases. Helium is not reduces the time required for reaching the equilibrium state in
adsorbed by charcoal (as it is very difficulty liquifiable gas). the reaction.
42. (a) Animal charcoal is a good adsorbate. The impurities adsorbs on 36. (b) Maltose   Glucose
Maltase
enzyme
its surface and thus it decolourises colour of liquids.
37. (d) Efficiency of catalysing property is inversely proportional of
43. (a) Since adsorption is an exothermic process (taking place with activation energy.
the evolution of heat) therefore in accordance with Lechatelier's
principle, the magnitude of physical adsorption will decrease 39. (a) 2 SO 2  O 2    2 SO 3 ; Example of heterogeneous
Platinized

(g ) (g ) Asbestose
with the increase in temperature. In case of chemisorption the (s)
adsorption first increase and then decreases with increase in catalyst.
temperature.
44. (c) Concentration of the solution decreases because acetic acid gets 40. (d) Oil  H 2  Ni
Ghee .
adsorbed on charcoal. 41. (b) Catalyst is not effect on equilibrium concentrations.
x 42. (a) 4 NH 3  5 O 2   4 NO 
Pt guage
 4 NO 2
O2
45. (d)  kp 1 / n or x  m . kp 1 / n or x / m  kp n 1100 K
m
 Surface Chemistry 607

11. (c) Liquid  Solid  Gel (e.g. Butter)

2 H 2 O O2 (Dispersio n (Colloid)
  4 HNO3
(Dispersed
phase) medium

48. (d) 4 NH 3  5 O2  4 NO 

  4 NO 2
Pt guage
2 O 13. (d) By definition gold number of starch is the amount of starch in
1100 K mg added to 10 ml standard gold sol which prevents the
coagulation of gold on adding 1 ml of 10% NaCl solution. So
2 H 2O  O2 the amount of starch is 0.25g = 250 mg. Hence gold number is
   4 HNO 3 250.
(CH 3 CH 2 )3 Al  TiCl4
51. (b) nCH 3  CH  CH 2    15. (c) According to Hardy schulze rule the ions having opposite
Propylene charge to sol particle cause coagulation and greater the valency
of oppositely charged ion more is the coagulating power
 CH 3  (PO43   SO 42   NO 3 ).
 |  17. (b) Gold number is associated with only lyophilic colloids due to
 CH 2  CH  protective nature.
 
 n 19. (a) Negatively charged sols require minimum amount of electrolyte
Polypropyl ene having higher valence of cation.
53. (a) Ptyline (enzyme) is present in saliva. 22. (b) Lyophilic possesses solvent loving nature and thus a thin layer
54. (b) 2 SO 2  O 2   2 SO 3 2 NO (g) ,
2 NO ( g )
reactants and of dispersed phase is formed round sol particles.
(g) (g) (g) 23. (a) Milk is a colloid of liquid ( H 2 O ) dispersed in liquid (fat).
catalyst present in same phase. 24. (c) Smoke is an example of solid dispersed in gas.
55. (d) 2SO 2  O2   2SO 3
Platinised asbestos(c atalyst)
26. (a) Movement of (charged) colloidal particles under the influence
As 2 S 3 (Poison ) of electrostatic field is called electrophoresis due to opposite
 charge.
58. (d) Mn is a product in reaction so it is auto catalyst (according
to definition). 27. (c) Fe(OH )3 gives a positively charged sol as it adsorbs Fe 3 
62. (c) 2 SO 2  O2  2SO 3
V2O5
ions from FeCl 3 solution.
(Catalyst)
29. (a) Flocculation value is expressed in terms of millimole per litre.
2 SO 2  O2 
 2 SO 3 (g)
Pt Catalyst
63. (b) 32. (b) Gelatin is a protective colloid.
(g) ( g ) Asbestos(p romoter)
65. (a) Generally transition elements acts as catalysts. Adam's catalyst 36. (b) ZnCl 2 has maximum coagulation power due to more charge
is another name of platinum. on the Zn
69. (b) Enzyme activity is maximum at 310K. 37. (c) Air is not a colloidal solution because it is a homogeneous
70. (b) Catalyst is a substance which changes the rate of reaction mixture.
without affecting the overall energetics of the reaction.
43. (d) In Purification separation of colloids from crystalloids is done
71. (d) Ni, Pt and Co all three transition metals are used as a by the process of ultra-filtration.
catalysts. 45. (b) dispersed phase  dispersion medium
72. (d) Catalyst is a substance which changes the rate of reaction (liquid) (gas)
without affecting the overall energetics of the reaction.
 colloidal system
73. (c) Many of the d -block (transition) elements and their (clouds)
compounds act as catalyst. Catalytic property is probably due
46. (b) Tyndall phenomenon is exhibited by starch solution because
to the utilisation of (n  1)d orbitals or formation of
starch solution is a colloidal solution.
interstitial compounds.
53. (b) Milk can be preserved by adding a few drops of HCHO
74. (a)The catalytic process in which the reactants and the catalyst are solution. HCHO is an emulsifier.
in different phases is known as heterogenous catalysis.
55. (c) Properties of the colloidal solution depend upon physical state
N 2(g)  3 H 2(g)   2 NH 3(g)
Fe(s)
of dispersed phase and mol. wt.
The reactants are in gaseous state while the catalyst is in solid 57. (d) According to Graham, colloids are separated from crystalloids
state. by parchment paper.
60. (b) Liquid aerosol involves liquid dispersed in gas, e.g. cloud, fog,
mist etc.
Colloids, Emulsion, Gel and Their properties
64. (b) 2 HNO3  3 H 2 S  3 S  4 H 2O  2 NO
with application (Sol )

65. (b) Lyophobic colloids are irreversible colloids.

4. (a) Negatively charged As 2 S 3 sol coagulated most effectively
66. (b) Crystalloids are diffuse through parchment membranes.
by AlCl3 . This is because oppositely charged Al    ions have
67. (a) Colloidal particles range between 10 7 to 10 9 m or 10 5 to
maximum charge.
10 7 cm.
As 3   Ca 2   Na 
70. (c) Fe 3  ion coagulates –ve sol particles of blood and seals the
6. (d) K 3 [Fe(CN )6 ] is most effective in coagulating a ferric cut.
hydroxide sol. 79. (a) When a substance comes in colloidal state the surface area of the
7. (d) Sky looks blue due to scattering of light by dust particles particles increases due to small size than substance.
present in the atmosphere. 80. (b) Alum can be separated from a solution by electrodialysis due to
10. (c) KBr is least effective in causing flocculation of ferric hydroxide
alum give Al 3  ion in solution.
sol due to minimum charge at (KBr) Br 
82. (d) The amount of electrolyte required to coagulate a fixed amount
of a solution depends upon the valency of the flocculation ion.
 608 Surface Chemistry
The flocculating power of the various ions follows the following 175. (c) Colloidal particles becomes uncharged at isoelectric point.
order, larger the valency lesser will be coagulating value. 176. (c) Example of multimolecular colloid system is a gold dispersed in
Al 3   Mg 2   Na  , hence lowest coagulation value is of water.
AlCl3 179. (a) The phenomenon of converting of fresh mass into colloidal
state by the action of solute or solvent is known as peptization.
.

88. (d) Gelatin is a protective colloid in ice-cream. 180. (a) Surface tension of lyophilic sol is lower than that of the
90. (c) Tyndall effect is not observed in sugar solution due to dispersion medium (i.e. H 2 O in this case.)
homogeneous nature.
182. (b) Hydrophilic sol can act as protective colloids for hydrophobic
92. (a) Dispersion medium and dispersed phase are phase of colloid.
solution.
99. (a) As 2 S 3 is coagulated by addition of electrolyte due to 183. (d) Metal sulphide is not used for preparing lyophilic sol.
opposite charge. 185. (b) According to definition emulsification.
104. (c) According to Hardy-Schulze rule. 186. (d) Toilet soap is a mixture of potassium salt of higher fatty acids.
111. (a) Scattering of light is a property of colloid. 187. (c) Coagulation is governed by Hardy Schulze rule.
115. (c) Some gelatin is mixed in colloidal solution of gold to form ppt 1
of gold (peptization of gold). Because formation of layer on 189. (a) Protective power 
colloidal particle. Gold number
120. (b) “Delta” at the rivers are formed due to coagulation between sea Gold number of A is least, therefore, it has the highest
water (+ve charged particles) and river water (–ve charged protective power.
particles) 190. (b) Bredig's arc method is suitable for the preparation of colloidal
121. (b) Tyndall effect expressed by hydrophobic sols. solution of metal like gold silver, platinum etc. An arc is struck
129. (c) Protein sol in water is a example of heteropolar sol. between the metal electrode under the surface of water
containing some stabilizing agent such as a trace of KOH.
130. (d) For stabilise the sol. However, Fe does not react with alkalies that is why it is not
131. (c) Solution of urea is not a colloid. obtained by Bredig's arc method.
135. (b) Liquid  Gas  Whipped cream 191. (d) Gold number shows the protective power of a lyophilic
(Dispersion (Dispersed Colloidal solution solution. Lesser the gold number, greater will be the protecting
medium) phase) power of that colloid. Gelatin is one of the best protective
137. (b) Alum is a coagulating agent, frequently added to water to colloid. Among the given colloids, potato starch has maximum
remove impurities from water because impurities contain gold number.
negative charge and alum give positive charge particle for 1
coagulation. 192. (a) Protective power 
139. (c) Alum is purifies muddy water by coagulation due to opposite Gold number
charge. Thus gelatin is the best protective colloid.
142. (c) The particle size is in the order 10 Å  1000 Å . 1
193. (b) Protective power 
144. (a) FeCl 3 is a electrolyte give Fe 3  and blood contain negatively Gold number
colloid so stop bleeding due to coagulation. Hence, the correct order of protective power is
145. (c) AT (CMC) critical micellization concen-tration, the surfactant B AC D.
molecules associate to form miscelles. For soap CMC is 10 3
194. (c) A catalyst does not participate in the reaction but alters the
mol/litre rate of reaction.
146. (b) Inhibitors are also known as negative catalyst.
147. (c) Benzene is non polar in nature. As we know that non-polar 195. (a) A colloid of liquid in liquid is called emulsion cod liver oil is
disperses more to non-polar substances. Therefore, meta-metyl such an emulsion.
nonylbenzene being nonpolar from both sides will disperse 196. (a) Suspension of solid in a liquid.
more to benzene. All other substances (a, b and d) have either
one side polar or both sides polar. 197. (c) By the peptization, precipitate is changed to colloidal solution.
198. (a) An aerosol is a dispersion of a solid or liquid in a gas.
199. (d) Lyophilic sols are self stabilizing because these sols are
reversible and are highly hydrated in the solution.
 H19 C9  C6 H 4  CH 3 CH 3
Vc 10 5
non-polar end (metamethyl nonylbenzene) non-polar end 200. (d)   10 3
151. (a) The protective action of different colloids is expressed in terms Vs 10 7
of Gold number.
204. (a) Alum contains many cations and water has many anionic
156. (a) Tyndall effect may be defined as the scattering of light by the
impurities. On adding alum coagulates the suspended
colloidal particles present in a colloidal sol.
impurities and make water fit for drinking purposes.
158. (a) It is due to adsorption of S 2  ions on the surface of the 205. (a) For the stabilisation of an emulsion a third component called
colloidal particles and H  ions in the diffused layer. emulsifying agent is usually added. The emulsifier forms an
interfacial film between suspended particles and the medium.
168. (c) Alum helps in purifying water by Al 3  ions which coagulate
the negative mud particles. 206. (b) Alum is added to muddy water so as to destroy the bacteria as
well as to coagulate the suspended impurities.
169. (d) Sn 4 contain maximum coagulation power (coagulation
207. (b) Fog is an example of aerosol where the dispersed phase is
power  number of charge on ion)
liquid and dispersionmedium is gas.
170. (d) It is liquid in gas colloidal solution.
 Surface Chemistry 609
208. (c) Lyophilic sols, are more stable than Lyophobic sols because Mass
after vaporization its remaining residue, convert into colloidal 21. (d) Volume of the gold dispersed in one litre water 
state after the addition of solvent. Density
209. (e) The substance, whose molecules associate with given solvent to 1 .9  10 4 gm
  1  10 5 cm 3
form colloidal particle known as association colloidal. The 19 gm cm  3
molecule of soap & detergent are generally smaller than
colloidal particle. These molecules associate in concentration Radius of gold sol particle  10 nm  10  10 9 m
solution to form colloidal size particle. These association of
soap & detergent known as miscelle.  10  10 7 cm  10 6 cm

Critical Thinking Questions 4 3

Volume of the gold sol particle  r
3
1. (a) Lyophillic means liquid loving hence hydration is contributed 4 22
toward the extra stability of lyophillic colloids.    (10 6 )3  4.19  10 18 cm 3
2. (d) Traces of electrolytes are essential for stabilising the sales 3 7
hence for sales destruction addition of electrolytes are required. 1  10 5
3. (c) A catalyst is a substance which alters the rate of reaction and No. of gold sol particle in 1  10 5 cm 3 
shortens the time to reach equilibrium. 4 .19  10 18
4. (d) Inhibitors are also catalysts but they slow down the rate of  2.38  10 12
reaction.
5. (d) The ability of an ion to bring about coagulation of a given No. of gold sol particle in one mm 3
calloid depend upon both the magnitude and sign of its charge. 2 .38  10 12
6. (c) Physiorption is a process in which the particles of adsorbate  6
 2 .38  10 6
10
are held to the surface of adsorbent by physical forces hence
does not requires activation energy. 22. (d) Sodium acetate forms cationic micelles in the molecule of soap
7. (a) Egg is a calloid of solid and liquid; Ruby glass is a colloid of and detergent the negative ions aggregate to form a micelle of
solid and solid. Milk is a colloid of liquid and liquid but colloidal size. The negative ion has a long hydrocarbon chain
chlorophyll is a complex of magnesium. and a polar group (COO  ) at one end.
8. (b) Surfactant are those which have charge on their tail e.g.,
cetyltrimethyl ammonium bromide. Assertion & Reason
CH 3
|
1. (a) Both assertion and reason are true and reason is the correct
CH 3  (CH 2 )15  N   CH 3  Br  explanation of assertion.
|
CH 3 The surface of a solid (or liquid) tends to attract and retain
other molecules when it is brought in contact with a gas or a
Surfactants are those, which dissociate in water to yield solution.
positively charged ion.
2. (e) Assertions is false but reason is true.
9. (a) The size of colloidal particles is of the order 0.1m  to
The enthalpy of chemisorption is of the order of
0.001m  .
200 kJmol 1 while for physical adsorption it is of the order
10. (b) K 4 [Fe(CN )6 ] is most effective in the coagulation of gold-
of 20 kJmol 1 .
solution.
11. (d) A catalyst is used to decrease the time required for the reaction 3. (a) Both assertion and reason are true and reason is the correct
hence it can decease or increase the rate of reaction. explanation of assertion .
12. (d) Absorption, Tyndall effect and flocculation all are related to sol 4. (c) Assertion is true but reason is false.
but paramagnetism is not represented by sol. Freundlich adsorption isotherm gives an empirical relation ship
13. (a) On shaking with the dispersion medium, colloids directly form between the quantity of gas adsorbed by unit mass of solid
the colloidal sol. Hence they are called intrinsic colloids. i.e., adsorbent and pressure at a particular temperature.
glue. 5. (d) Both assertion and reason are false.
14. (c) Arsenious sulphide can be prepared by double decomposition There are reactions in which one of the products acts as
As 2 O3  3 H 2 S  As 2 S 3  3 H 2 O catalyst (autocatalysis) and no catalyst is added.
15. (c) The amount of electrolyte required to coagulate a fixed amount 6. (b) Both assertion and reason are true but reason is not the
of a sol depends upon the valency of flocculating ion. correct explanation of assertion.
16. (d) Gold no. is a measure of protective power of a lyophillic colloid. ZSM – 5 converts alcohols directly into gasoline (petrol) by
17. (c) The colloidal solution of liquid in liquid is called emulsion not dehydrating them so that a mixture of hydrocarbons is formed.
gel. 7. (b) Both assertion and reason are true but reason is not the
correct explanation of assertion.
18. (d) Linseed oil, lanolin and Glycogen attract water hence contain a
If the dispersion medium is separated from the dispersed
hydrophobic structure but rubber does not attract water and
does not contain a hydrophobic structure. phase, the lyophilic sol can be reconstituted by simply remixing
with the dispersion medium. That is why these sols are also
19. (c) Gum-arabic has protective power hence the function of it ion called reversible sols.
in preparation of indian ink is protective action. 8. (b) Both assertion and reason are true but reason is not the
20. (b) Easily liquefiable gases like SO 2 , NH 3 , CO 2 are adsorbed to a correct explanation of assertion.
The size of colloidal particles is large enough to scatter light
greater extent than the elemental gases like N 2 , O2 , H 2 . while particles of a true solution are too small to scatter light.
9. (a) Both assertion and reason are true and reason is the correct
explanation of assertion.
 610 Surface Chemistry
The impact of the molecules of the dispersion medium on the
colloidal particle are unequal leading to zig-zag motion i.e.,
Brownian movement.
10. (a) Both assertion and reason are true and reason is the correct
explanation of assertion.
According to Hardy – Schulze rule : Coagulating power of an
electrolyte is directly proportional to the fourth power of the
valency of the ions causing coagulation.
11. (a) Both assertion and reason are true and reason is the correct
explanation of assertion.
Soap coats the drops of an emulsion and checks them from
coming together and the emulsion is thus stabilised.
12. (a) It is fact that deep electric shock causes death of an animal and
the reason for this is that blood is coagulated by electric shock.
Therefore, here both assertion and reason are true.
13. (a) A catalyst is more effective in finely divided form because finely
divided form has more surface area. Therefore there is an
increase in active centres on the surface.
14. (c) NH 3 absorbs more readily over activated charcoal than
CO 2 it is correct. The reason is the polar nature of NH 3
due to which it readily absorb. Hence assertion is true but
reason is false.
15. (a) The sky appears blue because the colloidal particles of dust,
dirt in air scatter blue light to the maximum extent. Here both
assertion and reason are correct and reason is the correct
explanation of assertion.
16. (d) The assertion that physical absorption of molecules takes place
on surface only is false. Actually absorption takes place on the
whole body. In physical absorption the bonds of absorption
molecules are not broken. Hence, both assertion and reason are
false.
17. (b) Here both assertion and reason are correct but reason is not a
correct explanation of assertion. Micelle is formed if molecules
with polar and nonpolar ends assemble in bulk to give
nonpolar interior and polar exterior.
18. (a) Both assertion and reason are true and reason is the correct
explanation of assertion. Scattering of light is the main
phenomenon of colloidal particles. In which colloidal particles
scatter a particular wavelengths light.
19. (c) It is true that if we increase the surface area the rate of
evaporation also increase as evaporation is always takes place
from the surface. But if the intermolecular attraction is
stronger than the rate of evaporation is slower.
 Surface Chemistry 611

1. In which of the following commercial processes a catalyst is not used (c) [CPMT 1989]
RSNa
(a) Haber's process
(d) ROSO 2 Na
(b) Deacon's process
9. In which of the following processes shape-selective catalysis is
(c) Solvay process
occurring [MP PET 1994]
(d) Lead chamber process
(a) Conversion of alcohol to gasoline
2. A catalyst [IIT 1984; AFMC 1995; CBSE PMT 1995]
(b) Synthesis of methanol from CO and H 2
(a) Increases the average kinetic energy of reacting molecules
(b) Increases the activation energy (c) Polymerisation of ethylene
(c) Alters the reaction mechanism (d) Synthesis of ammonia
(d) Increases the frequency of collisions of reacting species 10. Which one of the following is used for reviving the exhausted
3. The coagulation of 100 ml of a colloidal sol of gold is completely permutite [EAMCET 2003]
prevented by addition of 0.25 g of a substance `X' to it before (a) HCl solution
adding 10 ml of 1% NaCl solution. The gold number of `X' is
(b) 10% CaCl 2 solution
(a) 0.25 (b) 25
(c) 250 (d) 2.5 (c) 10% MgCl2 solution
4. Which one of the following is not a property of hydrophilic sols (d) 10% NaCl solution
[AIIMS 1983, 84]
(a) High concentrations of dispersed phase can be easily attained 11. The ability of a catalyst to accelerate the chemical reaction is known
(b) Coagulation is reversible as [CPMT 2000; KCET 2000]
(c) Viscosity and surface tension are about the same as for water (a) Selectivelty
(d) The charge of the particle depends on the pH values of the (b) Activity
medium; it may be positive, negative or even zero (c) Negative catalyst
5. Peptising agent is (d) None of these
(a) Always an electrolyte 12. AlCl3 , in reactions, acts as [MADT Bihar 1983]
(b) Always a non-electrolyte
(a) Oxidizing agent
(c) Electrolyte or non-electrolyte
(b) Reducing agent
(d) A lyophilic colloid
6. The catalyst used in the manufacture of methanol from water gas is (c) Acid catalyst
[MP PET 2002]
(d) None of these
(a) V2 O5 (b) Ni + Mo
13. On addition of one ml of 10% NaCl solution to 10 ml gold sol in the
(c) ZnO + Cr2 O3 (d) Pt + W presence of 0.25 gm of starch. The coagulation is just prevented,
starch has gold number [MP PET 2004]
7. Organic catalysts differ from inorganic catalysts
[AFMC 1989]
(a) 0.025 (b) 0.25
(a) By acting at very high temperature (c) 2.5 (d) None
(b) By acting at low temperature 14. Milk is an example of
(c) Being used up [MP PET 2001; JIPMER 2002; MP PMT 2002,04]
(d) Being proteinous in nature (a) Pure solution
8. Commercial detergents mainly contain [CPMT 1993] (b) Gel
(a) RCOONa (c) Emulsion
(b) RONa (d) Suspension

(SET -14)

1. (c) In Haber's process we use iron as a catalyst, In Deacon's process use N 2 O5 as a catalyst but in solvay process no catalyst is
we use Cu 2 Cl 2 as a catalyst and in lead chamber process we used.
 612 Surface Chemistry
2. (d) A catalyst can increase the rate or reaction and hence increases 14. (c) Milk is the example of emulsion of fat globules in water.
the frequency of collision of reacting species.
3. (b) 250 mg of X is present in 100 ml of colloidal sol of gold. By
definition, gold no. of X is that amount of it in mg which is
present in 10 ml of colloidal gold solution. Hence in 10 ml, the
amount of X present is 25 mg which is the gold number of X.
4. (c) Viscosity and surface tension are not same for water in
hydrophillic sols.
5. (a) Process of converting precipitate into colloidal particles by
adding suitable electrolyte called peptisation and stabilizing
agent (electrolytes) as peptizing agent.
ZnO  Cr2 O3
6. (c) [CO  H 2 ]  H 2   CH 3 OH

***

7. (d) Organic catalyst are proteinous in nature and obtain from

living cell.
8. (a) Commercial detergents mainly contain salts of higher fatty
acids.
9. (a,c) Shape selective catalyst are zeolites and zeolites are
alminosilicates of general formula
M x / n [( AlO2 )x .(SiO2 )y ].mH 2 O . Zeolites are used in
conversion of alcohol to gasoline and in polymerisation of
ethylene.
10. (d) 10% NaCl solution is used for reviving the exhaust permutite.
11. (b) The ability of a catalyst to accelerate the chemical reaction is
known as its activity. Degree of acceleration can be as high as
10 10 times in certain reactions.
12. (c) AlCl3 may be written as Al 3 Cl  and all the tri-positive ions
are Lewis acid hence it can be acts as acid catalyst.
13. (d) 0.25  1000  250

Periodic table is an arrangement of elements with similar properties
placed together. The periodic table evolved largely as a result of
experimental observations.
Earlier attempt to classify elements
(1) Dobereiner’s law of triads (1829) : It was the classification of
elements into groups of three elements each with similar properties such
that the atomic weight of the middle element was the arithmetic mean of
the other two e.g. Ca, Sr, Ba, Cl, Br, I etc.
(2) Telluric screw or Helix (1862): It was proposed by Chancourtois.
(3) Newlands law of octaves (1864) : It was an arrangement of
elements in order of increasing atomic weights in which it was observed
that every eighth element had properties similar to those of the first just
like the eighth node of an octave of music.
(4) Mendeleef’s period law (1869) : The first significant classification
was given by Mendeleeff in the form of periodic table, commonly known as
Mendeleeff's periodic table. His periodic table was based on periodic law,
''The physical and chemical properties of elements are periodic functions of
their atomic weights.''
In Mendeleef’s periodic table elements are arranged in order of their
increasing atomic weights in such a way that elements with similar
properties are placed in the same group. It consists of seven horizontal rows
called periods. These are numbered from 1 to 7.
Mendeleef’s original table consists of 8 vertical columns called
groups. These are numbered as I, II III….. VIII. However, 9 vertical column
th
called Zero group was added with the discovery of inert gases. Except for
group VIII and zero, each group is further divided into two sub-groups
designated as A and B. Group VIII consists of 9 elements arranged in three
sets each containing three elements.
(5) Modern Periodic Law : The recent work has established that the
fundamental property of an atom is atomic number and not atomic weight.
Therefore, atomic number is taken as the basis of the classification of the
elements. The modern periodic law was given by Moseley, it may be stated as :
''The properties of elements are periodic functions of their atomic number".
When atomic number is taken as the basis for classification of elements,
many anomalies of Mendeleef's table disappear, such as the,
Chemical Periodicity 613
Chapter
15
Chemical Periodicity
(i) Position of hydrogen : Dual behaviour of hydrogen is explained on the
fact that it has one electron in its outermost orbit. When it loses its electron it
gives H and behaves like alkali metals and when it gains an electron it gives H
+ –
and behaves like halogens. Thus, it resembles with both the alkali metals and the
halogens.
(ii) Dissimilar elements placed together : The lengths of periods are
determined by the arrangement of electrons in different orbits. The period
ends on the completion of last orbits (last members always being the inert
gas). Different periods contain 2, 8, 18 or 32 elements. Now out of the two
elements which every long period adds to the group, one resembles the
typical elements while the other does not. This gives rise to formation of
subgroups. This explains the inclusion of dissimilar elements in the same
group but different subgroups.
(iii) Position of rare earth elements : The electronic arrangement of
rare earths can be written as 2, 8, 18, (18 + x), 9, 2 where x varies from 0 to
13, i.e., from Lanthanum to Lutecium. The number of electrons in valency
shell, in case of all the elements remain the same although the atomic
number increases. Since they possess the same number of valency electrons,
the chemical behaviour is also similar. This justifies their positions in the
same group and in the same place of the periodic table.
(iv) Anomalous pairs of elements : Now the basis of classification is
atomic number, therefore, this anomaly disappears as the elements occupy their
normal position in the new periodic table.
(v) Position of isotopes : Since the isotopes of same element possess
same atomic number they should occupy one and the same position in the
periodic table.
(vi) Position of VIII group elements : In long periods 18 elements are
to be distributed among 8 groups; 1 to 7 groups get 2 elements each and
zero group accommodates inert elements, the rest three elements are placed
at one place in a new group, known as VIII group. This lack of space
justifies the induction of VIII group in the periodic table.
(vii) Transuranic elements : These elements form a series known as
actinide series, it begins from actinium and ends at lawrencium (89–103).
This series has been placed outside the periodic table. The electronic
configuration of these elements can be written as 2, 8, 18, 32, (18 + x), 9, 2,
where x varies from zero (for actinium) to 14 (for lawrencium). The number
of valency electrons remains the same for all these elements although
 614 Chemical Periodicity
atomic number increases. Therefore, their chemical behaviour is similar.
This justifies their position outside the periodic table at one place.
Classification of element on the basis of
electronic configuration
According to Bohr the element have been grouped into four types
(1) Inert gases : These atom have been full fill outer most s and p
subshell and having the configuration ns 2np 6 (Exception helium having
1s 2 ) due to stable configuration these element do not show chemical
activity under normal condition and thus termed as inert gases. Under
special conditions, the higher members do form some compounds with
other elements and hence, the name has been changed to Noble gases. Six
element He, Ne , Ar, Kr, Xe and Rn belongs to this group.
(2) Representative or normal elements : Element in which atom have
all shells complete except outermost shell which is incomplete. The number
of electrons in the outermost shell varies from 1 to 7 i.e. the configuration of
the outermost shell varies from ns 1 to ns 2np 5 . These consist of some
metals, all non metals and metalloid. These are the elements which are
found in nature in abundance and active in nature. On account of this,
these elements are called representative elements. All the three types of
valencies are observed in the case of these elements. These elements have
one of the following configuration in their outermost shell.
ns1 ns 2 ns 2 np 1 ns 2 np 2 ns 2np 3 ns 2 np 4 ns 2 np 5
1 2 2 4 5 6 7
The number of electrons present in the outermost shell signify the
group to which these element belong.
(3) Transition elements : In the atoms of these elements the
outermost shell and the penultimate shell (Next to the outermost) are
incomplete. These elements have the general configuration
(n  1) d 19 ns 0 or 1 or 2 either in the ground state or in excited state. These
elements are present in IV th , V th , VIth and VIIth period of periodic table
and called transition elements. There are four transition series every series
consists 9 elements each.
(4) Inner transition elements : Atoms of these elements have three
outermost shell incomplete. The general configuration is
(n  2) f 114 (n  1) d 0 or 1ns 2 . There are two series of elements.
(i) Lanthanides or rare earths from Ce (58) to Lu (71) .
Discovery of element 104, 105 and 112 has recently been reported
(4f1–145d0–106s2)
(5f1–146d0–107s2)
(ii) Actinides from Th(90) to Lr(103)
Each series consists of 14 elements i.e. in the lanthanides, 4 f is
gradually filled up while in actinides, 5 f is gradually filled up.
The properties of these elements are similar to transition elements.
The members of actinide series are radioactive and majority of them are not
found in nature. The elements from atomic number of 93 onwards are
called transuranic elements and have been discovered artificial means.
In this classification the element, Zn, Cd and Hg have not been
included in any of the four groups of elements. The elements Lu and Lr of
the inner transition group have (n  2) f shell complete consisting 14
electron hence their inclusion in this group is not justified.
Extended or long form of periodic table
Modern periodic table is also called long form of the periodic table
or Bohr’s table. In this table, the elements are arranged in order of their
increasing atomic number. It consists of 4 blocks (s, p, d and f), 18 groups
numbered from 1 to 18 and 7 periods numbered from 1 to 7.
Blocks : The periodic table is divided into four main blocks (s, p, d
and f) depending upon the subshell to which the valence electron enters
into.
(1) Elements of group 1 and 2 constitute s-Block.
(2) Elements of group 13, 14, 15, 16, 17, 18 constitute p-Block
(3) Elements of group 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 constitute d-Block
(4) The f-Block elements comprise two horizontal rows placed at the
bottom of the periodic table to avoid its unnecessary expansion.
Elements of s- and p-blocks are called normal or representative
elements, those of d-block are called transition elements while the f-block
elements are called inner transition elements.
Groups : The 18 vertical columns are called groups. The elements
belonging to a particular group is known as a family and is usually named
after the first number. Apart from this some of the groups are given typical
names as examplified beneath,
(1) Elements of group 1 are called Alkali-Metals.
(2) Elements of group 2 are called Alkaline Earths.
(3) Elements of group 3 are called Pnicogens.
(4) Elements of group 16 are called Chalcogens.
(5) Elements of group 17 are called Halogens.
(6) Elements of group 18 are called Noble Gases or Aerogens.
[(n–2)f1–14(n–1)d0–10ns2]

All the other groups are named after the first member of each
group.
Periods : The horizontal rows are called periods. There are seven periods
in the long form of the periodic table,
(1) Ist period  2 He) contains 2 elements. It is the shortest
1H
period.
(2) 2nd period (3 Li 10 Ne ) and 3rd period (11 Na 18 Ar)
contains 8 elements each. These are short periods.
(3) 4th period (19 K 36 Kr) and 5th period (37 Rb 54 Xe)
contains 18 elements each. These are long periods.
(4) 6th period (55 Cs 86 Ra) consists of 32 elements and is the
longest period.
(5) 7th period starting with 87 Fr is incomplete and consists of 19
elements.
Periodicity in properties
''The repetition of similar electronic configuration after a definite period is
the cause of periodicity of the properties of elements.''
It can be explained with the help of electronic arrangement of
elements. According to the modern views, the valency of an element is
indicated by the number of electrons present in the outermost orbit. The
chemical properties of elements are dependent on valency electrons.
Variation in electronic arrangement leads to the variation in properties.
After a definite interval, recurrence of similar electronic arrangement takes
place when the number of valency electrons is the same. Thus, there is a
regular gradation and repetition in the properties of elements.
Periodic properties are directly or indirectly related to their
electronic configuration and show a regular gradation on moving from left
to right in a period or from top to bottom in a group. Some period or from
top to bottom in a group. Some important periodic properties are :
oxidation number, shielding effect, atomic radii, ionization energy, electron
affinity, electro-negativity, valency, density, m.pt. and b.pt.
The screening effect or shielding effect
A valence-electron in a multi-electron atom is attracted by the nucleus,
and repelled by the electrons of inner-shells. The combined effect of this
attractive and repulsive force acting on the valence-electron experiences less
attraction from the nucleus. This is called shielding or screening effect. The
magnitude of the screening effect depends upon the number of inner
electrons, i.e., higher the number of inner electrons, greater shall be the
value of screening effect. The screening effect constant is represented by the
symbol '  ' is determined by the Slater's rules.
The magnitude of screening constant in the case of s- and p- block
elements increases in a period as well as in a group as the atomic number
increases.
Effective nuclear charge
Chemical Periodicity 615
Due to screening effect the valency electron experiences less
attraction towards nucleus. This brings decrease in the nuclear charge (Z)
actually present on the nucleus. The reduced nuclear charge is termed
effective nuclear charge and is represented by Z * . It is related to actual
nuclear charge (Z) by the following formula,
Z *  (Z   ) where  is screening constant.
It is observed that magnitude of effective nuclear charge increases in
a period when we move from left to right.
In a subgroup of normal elements the magnitude of effective nuclear
charge remains almost the same.
Covalent, Ionic and Vander waal's radii
The radius of an atom is the distance between the centre of its
nucleus and electrons in the last orbit. However, according to quantum
mechanics, there is no certainty about the exact position of electrons at
any time. Theoretically, an electron, at one time, may be very close to
the nucleus while at other time it may be far away from the nucleus. In
spite of these limitations we need to have some operational definition of
the term atomic radius. There are three operational concepts of atomic
radius.
(1) If the bonding is covalent, the radius is called a covalent radius.
(2) If the bonding is ionic, the radius is called ionic radius.
(3) If the two atoms are not bonded by a chemical bond (as in noble
gases) the radius is called vander Waal's radius.
(1) Covalent radius : It is half of the distance between the nuclei of
two like atoms bonded together by a single bond. Thus covalent radius of
carbon in a compound having C – C single bond can be determined by
dividing the bond length by 2, i.e.,
C C
rc   C  C  2rc or rc  rc
2
where, rc is the single bond covalent radii (SBCR) of carbon.
However, if atoms forming the covalent bond are different i.e., one is more
electronegative than the other then the atomic radius is determined by the
relation
A  B  rA  rB  0.009 ( A   B )
where  A and  B are electronegativities of the atoms A and B
respectively. This relation was given by Stevenson in 1941.
In a given period, atomic radius generally decreases from left to
right and thus in any period, alkali metal is the largest and halogen is the
smallest atom. For example, in second period elements the covalent radii
decrease from Li to F.
Li Be B C N O F Ne
3 4 5 6 7 8 9 10
 616 Chemical Periodicity
1.23 0.89 0.80 0.77 0.74 0.74
The decrease in size along a period is due to the effect of successive
increasing nuclear charge without addition of a new shell, i.e., in each
element of a given period a new electron is added in the same principal
quantum number. For example, in the second period the nuclear charge
increases from + 3 in Li to + 9 in F. The increased nuclear charge attracts
the electrons more strongly to the nucleus and thus decreases the size of
the atom. In case of noble gases, the atomic radii are only the vander Waal's
radii which are naturally higher than the covalent radii of other elements.
In a given group, Atomic radius generally increases as one moves from top
to bottom, e.g., in group 1 atomic size increases steadily from lithium to cesium,
i.e. rCs  rRb  rK  rNa  rLi
The increase in size on descending a group is due to addition of
extra shell which outweighs the effect of increased nuclear charge.
Remember that He and Fr are smallest and largest atom respectively.
(2) Ionic radius : It is the effective distance from the nucleus of an
ion upto which it has its influence on its electron cloud.
A cation is always much smaller than the corresponding atom.
Further, more the number of electrons removed smaller will be the size of
the resulting positive ion. For example, rFe  r 2   r 3  . This is
Fe
1 .26 0 .76
due to following two factors
(i) A cation formed by the loss of electrons may result in the
complete disappearance of the outer shell and since the remaining inner
shells do not extend so far in space, the cation is much smaller than the
metal atom. For example,
Sodium atom (Na)  Sodium ion (Na ) +
0.72 1.6 The covalent radius is always smaller than the corresponding
vander Waal's radius. This is because of the fact that in the formation of a
chemical bond, the two atoms have to come closer to each other. This also
explains why covalent bonds are much stronger than the vander Waal's
forces. It is important to note that since the noble gases ordinarily do not
form any covalent bond, in crystals of noble gases, no chemical forces are
operating between the atoms. Hence the vander Waal's forces are the only
attractive forces in these cases. In other words, the vander Waal's radii
constitute the atomic radii of noble gases and since vander Waal's radii are
larger than covalent radii, atomic radii of noble gases are largest in their
respective periods (anomaly).
Ionisation potential or ionisation energy
The electrons in an atom are attracted by the nucleus. When an
electron is to be removed then work is done against this nuclear attraction.
In other words energy is required to remove an electron from an atom. To
understand the details of chemical behaviour of an element we must have
an indication of the energy with which an atom binds its electrons. This is
obtained by the measurement of ionisation potential or ionisation energy. It
may be defined as the energy required to remove an electron from the
outermost orbit of an isolated gaseous atom in its ground state. It is
expressed in electron volts (eV) or kilo calories per gram atom. In an atom,
the energy required to remove first electron from a gaseous atom is called
Fe
first ionisation energy. The energy required to remove one electron from a
0 .64
unipositive ion to form a bipositive ion is called second ionisation energy.
Second ionisation energy is higher than the first. The reason is that in
unipositive ion left after the removal of one electron from the atom, the
electrons are more firmly bound to the nucleus than in the atom. Hence
more energy is needed to remove the second electron.
A  A   e 1 (First I. E.)

A   A 2  e 1 (Second I. E.)
(2, 8, 1) (2, 8)
(ii) Whenever a cation is formed, the ratio of nuclear charge to the A 2  A 3  e 1 (Third I. E.)
number of electrons (Z/e ratio) is increased with the result the effective
nuclear charge is increased and the electrons are pulled towards the nucleus. Similarly, third ionisation energy is even more than second ionisation
Consequently, the cation becomes smaller. An anion is always larger than the energy.
corresponding atom. For example, Atomic radius of I = 1.23 ; Ionic radii of I –

= 2.16 (1) Variation of ionisation energy in periodic table

(i) Ionisation energy decreases in a group as the atomic number
This is again due to following two factors : (a) Since in the increases. It is based on the fact that as we move down a group, the size of
formation of an anion, one or more electrons are added, the electron cloud atom increases, and the outer electrons become farther away from the
expands and the ionic size increases. (b) In the formation of anion, the nucleus thus reducing the force of attraction and hence ionisation energy
effective nuclear charge decreases with the result the electrons get away decreases.
from the nucleus and thus the anion becomes larger than the corresponding
atom. Li Na K Rb Cs

In any particular group, the ions of elements increase in size on 5.4 eV 1. eV 4.3 eV 4.2 eV 3.9 eV
moving from top to bottom. (ii) Ionisation energy increases along a period with increase in
In case of isoelectronic ions (ions having same number of electrons atomic number. This is due to the size of atom since it decreases along a
but different nuclear charge); the greater the nuclear charge, the greater is period and outer electrons are most strongly attracted by the nucleus and
the attraction for electrons and smaller is ionic radius. Hence size of such hence more energy is required to remove the electron.
ions decreases. Which is as follows Li Be B C N O F Ne
4 3 2 1  2 3 4 5 6 7
C N O F  Ne  Na  Mg  Al  Si P S  Cl 5.4eV 9.3eV 8.3eV 11.3eV 14.6 eV 13.6eV 17.0eV 21.6eV

(iii) The ionisation energies of inert gases are greater than that of their
Size of ions (in decreasing order) immediate neighbour. It is due to their complete octet ns p configuration
2 6

(3) Vander Waal's radius : It is one–half of the distance between which is highly stable. Therefore, it is very difficult to remove an electron from
the outermost orbit of an inert gas.
the nuclei of two adjacent atoms belonging to two neighbouring molecules
of an element in the solid state. (2) Factors affecting the value of ionisation energy

(i) Size of atom : With an increase in atomic size, the ionisation
potential is reduced, since the distance of the outermost electron from the
nucleus increases and hence the force of attraction decreases.
(ii) The charge on the nucleus : With an increase in the nuclear
charge, there is an increase in force of attraction of nucleus for electrons
making the removal of the electrons more difficult. Thus an increase in
nuclear charge increases the ionisation potential.
(iii) The shielding or screening effect of inner shells : The valence
electrons in a multi–electron atom are pulled by the nucleus but are
repelled by the electrons of the inner shells. The valence electrons, therefore,
do not experience the total pull of the nucleus. Instead the total pull of the
nucleus is reduced by the electrons in inner shells. This effect of reducing
the force of attraction of nucleus by the inner shells is called screening
effect. This effect is exhibited maximum by s p (the most stable) shell.
2 6
Therefore, the ionisation energy of K is much less than Cu, however, both
have one electron in their fourth shell.
K19  1s 2 , 2 s 2 p 6 , 3 s 2 p 6 , 4 s1
Cu 29  1s 2 , 2 s 2 p 6 , 3 s 2 p 6 d 10 , 4 s 1
The ionisation energy of K is 4.33 eV while that of Cu is 7.72 eV.
This is due to a large screening effect of s 2 p 6 , penultimate orbit in K while
s 2 p 6 d 10 , penultimate orbit in Cu which exhibit little screening effect.
(iv) Type of electrons involved : Ionisation energy also depends upon
the type, i.e., s, p, d or f, electrons which are to be removed, s –electrons
are closer to the nucleus and are more tightly held as compared to p, d or f
electrons. Hence, ionisation energy decreases in the order of s > p > d > f
orbitals.
(v) Completely filled or half filled sub-shells : According to Hund's
rule, completely filled or half filled orbitals are more stable. Therefore, it is
comparatively difficult to remove the electrons from these shells. The
ionisation energy of Be (9.3 eV) is more than B (8.3 eV) because Be has 2s 2
configuration of the outermost orbit which is fully filled. Similarly, nitrogen
(14.6 eV) has more ionisation energy than oxygen (13.6 eV) because
nitrogen has outermost shell configuration as 2s p in which p shell is half
2 3
filled and is more stable. Similarly, ionisation energy of Mg is more than Al
and that of P is more than S.
(3) Relative ionisation energies
 IE and IE of the 2 period elements
nd
1 2
IE : Li < B < Be < C < O < N < F < Ne
1
IE : Be < C < B < N < F < O < Ne < Li
2 group as the atomic number increases. Its value increases as we move along
 IE and IE of the 3 period elements
rd
1 2
IE : Na < Al < Mg < Si < S < P < Cl < Ar
1
IE : Mg < Si < Al < P < S < Cl < Ar < Na
2
 IE of elements with very high values
1
Cl < H < O < Kr < N < Ar < F < Ne < He
(4) Importance of ionisation energy
(i) Lower is the ionisation potential of an element, more would be
its reducing power and also reactivity.
(ii) It gives rough estimate about the basic character of the
elements.
Chemical Periodicity 617
(iii) The relative values of ionisation potential and electron affinity of
two elements are related to the nature of bond formed during their
combination.
(iv) The ionisation potentials provide an indication about the
number of valence electron (s) in an atom; the abnormally high value
indicates that the electron removed is other than the valence electron.
For example, IE , IE and IE values are 5.39, 75.62 and 122.42 eV.
1 2 3
Since the values shows sudden jump, it indicates that the number of valence
electron in its atom is one. Similarly, values of IE , IE and IE as 9.32, 18.21
1 2 3
and 153.85 eV indicate that the number of valence electrons in its atom is
two.
Electron affinity
Those atoms whose nuclear forces are not completely screened by
electronic shells, offer attraction for electrons. Such atoms capture electrons
if these are available with in their effective fields to neutralise the
electrostatic forces of the nucleus. Energy is always liberated whenever there
is a force of attraction offered by an atom or ion, and this energy is called
electron affinity. This may be defined as, ''the energy released when an extra
electron is added to a neutral gaseous atom''.
When first electron is added in a neutral atom then some energy is
released that is called first electron affinity but in case of second electron
affinity energy will be absorbed due to electronic repulsion. Example as
(a) O(g)  e   O(g)  E1 (H  ve , Exoenergic)
(b) O(g)  e   O 2  E2 (H  ve , Endoenergic)
Thus, higher the energy released in the process of taking up an extra
electron, the higher will be the electron affinity. Higher the value of electron
affinity of an atom, the more is its tendency to change into anion. It is very
difficult to determine the electron affinity experimentally. The values have
been calculated on the basis of thermodynamic concepts. It is expressed in
electron volts. The values of inert gases are assumed to be zero because
they have stable ns p configuration and unable to accept any electron. The
2 6
values for alkali metals are between zero and one.
The electron affinities of Be, Mg and zero since they have complete
ns configuration which can not accommodate extra electron. Similarly, the
2
values for N and P are very low because they also have completely half–
filled p orbitals (ns p ) and are more stable.
2 3
(1) Factors affecting the value of electron affinity
(i) Atomic size : The value of electron affinity decreases with the
increase in the size of atom since the nuclear attraction decreases down a
a period since the size of atoms decreases along a period. The lower value
of F than Cl is due to the very small size of F in which negative charge is
highly concentrated and repels the incoming electron thereby reducing the
force of attraction of the nucleus towards the adding electron and hence
decreasing the electron affinity. Thus, chlorine has a highest value of
electron affinity.
(ii) Nuclear charge : The value of electron affinity increases with
increasing nuclear charge. Thus, its value increases with increase in nuclear
charge along a period.
(iii) Screening or shielding effect : The value of electron affinity
increases with the decrease in shielding effect of inner electrons. Besides,
the value of electron affinity also depends to some extent upon the type of
orbital in which electron is added. The value is greater when electron enters
's' orbital and decreases successively for p, d and f orbitals.
 618 Chemical Periodicity
(2) Importance of electron affinity : Certain properties of the
elements are predicted on the basis of values of electron affinity.
(i) The elements having high value high values of electron affinity
are capable of accepting electron easily. They form anions and electrovalent
compounds. These elements are electronegative in nature. (1) Factors affecting the value of electronegativity
(ii) The elements having high values of electron affinity act as strong (i) The size of the atom.
oxidising agents, for example, F, Cl, Br, O, S , etc. (ii) Electronic configuration. Small atoms attract electrons more than
the larger one and are therefore more electronegative. Secondly, atoms with
On the basis of the general trend of ionisation potential and electron
nearly filled shell of electrons, will tend to have higher electronegativity than
affinity, the following properties can be predicted,
those sparsely occupied ones.
(a) Metallic nature decreases in a period while nonmetallic nature
(2) Variation of electronegativity in the periodic table
increases. Metallic nature increases in a group while non-metallic nature
decreases. The arrow () represents a group and () represents a period. (i) In a period, electronegativity increases from left to right. This is
due to decrease in size and increase in nuclear charge. Thus the alkali
Metallic Non-Metallic metals possess the lowest value, while the halogens have the highest. Inert
gases have zero electronegativity.
Metallic Decreases Non-Metallic Increases
(Electro +Ve) (Electro –Ve)
(ii) In a group, electronegativity decreases from top to bottom. This
is due to increase in atomic size.
Increases Decreases
If an element exhibits various oxidation state, the atom in the higher
(b) Reducing nature decreases in a period while oxidising nature
oxidation state will be more negative due to greater attraction for the
increases. The reducing nature increases in a group while oxidising nature electron, e.g., Sn II (1.30) and Sn IV (1.90).
decreases.
(3) Electronegativity may be expressed on the following three scales
Reducing nature Oxidising nature
(i) Mulliken's scale : Mulliken regarded electronegativity as the
average value of ionization potential and electron affinity of an atom.
Reducing Decreases Oxidising Increases
nature nature Ionizationpotential  Electronaffinity
Electronegativity
Increases Decreases 2
(c) Stability of metal increases while activity of the metal decreases (ii) Allred-Rochow scale : Allred and Rochow defined electronegativity
in a period and in a group stability decreases while activity increases. as the electrostatic force exerted by the nucleus on the valence electrons. Thus
Stability of the metal 0 .359 Z
  0 .744 where Z is the effective nuclear charge and r is the
r2
Stability of Increases covalent radius of the atom in Å.
the metal
(iii) Pauling scale : Pauling scale of electronegativity is the most
Decreases widely used. It is based on excess bond energies. He determined
This trend is observed especially in IA, IIA and IIIA elements. electronegativity difference between the two atoms and then by assigning
(d) The basic nature of the oxides decreases in a period while arbitrary values to few elements (e.g. 4.00 to fluorine, 2.5 to carbon and 2.1
acidic nature increases. In a group, basic nature increases while acidic to hydrogen), he calculated the electronegativity of the other elements.
nature decrases.
 A   B  0.208 E where  A and  B are electronegativities of
the atoms A and B respectively, the factor 0.208 arises from the conversion
Basic nature of oxides Acidic nature of oxides of kcal to electron volt (1 eV = 23.0 kcal/mole),

Basic nature Decreases Acidic nature while E  Actual bond energy  (E A  A  E B  B )

Increases
of oxides of oxides
Pauling and Mulliken values of electronegativities are related as
Increase Decreases
below  (Pauling) = 0.34  (Mulliken) – 0.2
(4) Importance of electronegativity : The following predictions can
Electronegativity be made from value of electronegativity,
The tendency of an atom in a compound to attract a pair of bonded (i) Nature of the bond between two atoms can be predicted from the
electrons towards itself is known as electronegativity of the atom. It is eelctronegativity difference of the two atoms.
important to note that electron affinity and electronegativity both measure
(a) The difference X A  X B  0, i.e., X A  X B the bond is
the electrons attracting power but the former refers to an isolated gaseous
atom while the latter to an atom in a compound. Thus electron affinity is purely covalent.
attraction for a single electron while electronegativity is for a pair of bonded
(b) The difference X A  X B is small, i.e., X A  X B , the bond is
electrons. Further electron affinity is energy while electronegativity is a
tendency. polar covalent.
Activity of the metal

Activity of Decreases
the metal

Increases
 Chemical Periodicity 619

(c) The difference X A  X B is 1.7, the bond is 50% covalent and (3) Melting and boiling points : The melting points of the elements
50% ionic. exhibit some periodicity with rise of atomic number. It is observed that
elements with low values of atomic volumes have high melting points while
(d) The difference X A  X B is very high, the bond is more ionic and elements with high values of atomic volumes have low melting points. In
general, melting points of elements in any periodic at first increase and
less covalent. The molecule will be represented in such case as BA (B  A  ) .
become maximum somewhere in the centre and thereafter begins to
Percentage ionic character may be calculated as, decreases.
Percentage of ionic character  16(X A  X B )  3.5(X A  X B )2 Tungsten has the maximum melting point (3410°C) amongst metals
and carbon has the maximum melting point (3727°C) amongst non-metals.
where X A and X B represents electronegativity of bonded atoms A Helium has the minimum melting point (–270°C). The metals, Cs, Ga and
and B. Hg are known in liquid state at 30°C.
This relation was given by A.L. Allerd (1961). The boiling points of the elements also show similar trends,
(ii) Greater the value of difference (X A  X B ) more stable will be however, the regularities are not so striking as noted in the case of melting
points.
the bond.
(4) Oxidation state (Oxidation number, O.N.) : Oxidation number of an
HF H  Cl H  Br H I element in a compound is the total number of electrons it appears to have
(X A  X B ) 1.9 0.9 0.7 0.4 gained or lost (negative and positive oxidation states respectively) during
the formation of that particular compound.
Stability decreases
Note : For detail see chapter redox reaction.
Stability of compounds in which X A  X B is very small are
unstable in nature, SiH 4 (0.3), NCl 3 (0.0) , PH3 (0), AsH3 (0.1) are
unstable.
(iii) (X O  X A ) difference predicts the nature of the oxides formed
by the element A. X O is the electronegativity of oxygen.

X O  X A is large, the oxide shows basic nature, (e.g., Na 2O ).

X O  X A is small, the oxide shows acidic nature, (e.g., SO 2 ).

(iv) Ionic compounds having percentage ionic character less than
20% were found coloured, e.g.,
AgCl AgBr AgI Ag2 S
22% 18% 11% 8%
White Light yellow Dark yellow Black
Lesser the percentage ionic character, darker will be the colour.
Some other periodic properties
(1) Atomic volume : It is defined as the volume occupied by one
gram atom of an element. Mathematically,
Gram atomic weight
Atomic volume 
Densityin solidstate
Units of atomic volume are c.c./mole. Atomic volume signifies the
volume occupied by one mole (Avogadro number) of atoms of the given
element in solid state. Lower atomic volume generally leads to higher
density, increased hardness and brittleness, higher melting and boiling
points, less malleability and ductility.
(i) While descending a group, the atomic volume generally increases
which is due to increase in the number of shells though the valence
electrons in a given group remains constant.
(ii) While going left to right across a period the atomic volume first
decreases to a minimum and then increases. Francium has the highest atomic
volume and boron has lowest atomic volume.
(2) Density : The density of the elements in solid state varies
periodically with their atomic numbers. At first, the density increases
gradually in a period and becomes maximum somewhere for the central
members and then starts decreasing afterwards gradually.
 620 Chemical Periodicity
(5) Magnetic properties : Magnetic properties of matter depend on (ii) Covalent nature of hydrides increases across a period and
the properties of the individual atoms. A substance (atom, ion or decreases down the group.
compound) capable of being attracted into a magnetic field is known as (iii) Ionic hydride are better reducing agents than covalent hydride
paramagnetic. The paramagnetic substances have a net magnetic moment and reducing nature of hydride decreases across a period and increases
which in turn is due to the presence of unpaired electron(s) in atoms, ions down the group.
or molecules. Since most of the transition metal ions have unpaired d–
electrons, they show paramagnetic behaviour. The exceptions are
(A) (B) (C) LiH NaH MgH2 AlH3 SiH3
Sc 3  , Ti 4  , Zn 2  , Cu  , etc. which do not contain any unpaired electron
covalent
and hence are diamagnetic. NaH (A)
On the other hand, a substance which is repelled by a magnetic field ionic
is known as diamagnetic. Such substances do not have any net magnetic KH (B)
moment because they do not have any unpaired electron. Electrons reducing nature
RbH (C)
determine the magnetic properties of matter in two ways,
 Each electron can be treated as a small sphere of negative charge (Minimum Maximum)
CsH
spinning on its axis. The spinning of charge produces magnetic moment.
 An electron travelling in closed path around a nucleus will also (iv) Covalent and ionic hydrides are classified as follows,
produce magnetic moment just as does electric current travelling in a loop
of wire. Diagonal relationship
The observed magnetic moment is therefore the sum of the two Certain elements of 2 period show similarity with their diagonal
nd

moments: the spin moment and the orbital moment. It is expressed in units elements in the 3 period as shown below :
rd

called Bohr Magnetons (BM). In terms of n (number of unpaired electron),

Group 1 Group 2 Group 13 Group 14
magnetic moment is given by the formula,   n (n  2) 2 perio
nd
Li Be B C
Greater the number of unpaired electrons in a substance, the greater
is the magnetic moment of the substance. The value of magnetic moment 3 period
rd
Na Mg Al Si
has been used to calculate the number of unpaired electrons in an ion. In
some cases, even the structure of the molecule or complex is indicated by Thus, Li resembles Mg, Be resembles Al and B resembles Si. This is
its magnetic moment. called diagonal relationship and is due to the reason that these pairs of
Paramagnetism is generally measured by a simple device known as element have almost identical ionic radii and polarizing power (i.e.
Guoy's balance which involves weighing the species in presence of a charge/size ratio). Element of second period are known as bridge elements.
magnetic field. Anomalous behaviour of the first elements of a group: The first
Ferromagnetism is a special property observed in some substances element of a group differs considerably from its congeners (i.e. the rest of
in the solid state. Such substances are strongly attracted to magnetic field the element of its group). This is due to (i) small size (ii) high
and may retain the magnetic properties for some time even after the electronegativity and (iii) non availability of d-orbitals for bonding.
removal of the field. The most common example is of Fe followed by Co and Anomalous behaviour is observed among the second row elements (i.e. Li to
Ni. F).
(6) Hydration and hydration energy
(i) Hydration energy is the enthalpy change that accompanies the
dissolving of 1 mol of gaseous ions in water.
(ii) Size of ions and its charge determines extent of hydration.
Greater the charge smaller the size of the ion, greater the attraction for the
lone pair of O of H 2 O , hence greater the extent of hydration energy.
(a) Size of the hydration ion increases.
(b) Ionic mobility decreases i.e. heavier (hydrated) ions moves
slower.
(7) Acid-base-character of oxides
(i) On moving across a period, the basic character of the oxides
gradually changes first into amphoteric and finally into acidic character.
(ii) On moving down a group, reverse behaviour is observed i.e.,
from more acidic to more basic.
(iii) Stability of oxides decreases across a period.
(8) Hydrides
(i) Hydrogen combines with a number of other elements including
metals and non-metals to form compounds called hydrides.
 622 Chemical Periodicity
 The electron affinity of exactly half-filled configuration is
approximately zero and exactly zero for fully filled configuration.
 The electron affinities of gaseous anions are always negative.
 Some of the polar crystals when heated produce electric current.
This phenomena is termed as piezoelectric effect.
 The IUPAC nomenclature of elements > 100  All the elements of f- block (4f series – Lanthanides and 5f series –
In IUPAC system, the names are derived by using roots for the three Actinides) are placed in 3rd group (IIIB) and form a separate block
digits in the atomic number of the element and adding the ending : ium. at the bottom of the periodic table.
The roots for the numbers are
Number 0 1 2 3 4 5 6 7 8 9
Root nil un bi tri quad pent hex hept oct enn
Atomic
Number Name Symbol
101 un-nil-unium Unu
102 un-nil-bium Unb Extended or long form of periodic table
103 un-nil-trium Unt
104 un-nil-quadium Unq 1. Which of the following statement is not correct for the element
105 un-nil-pentium Unp having electronic configuration 1s 2 ,2 s 2 p 6 , 3 s1
106 un-nil-hexium Unh (a) It is a monovalent electropositive
(b) It forms basic oxide
107 un-nil-septium Uns
(c) It is a non-metal
108 un-nil-octium Uno (d) It has low electron affinity
109 un-nil-ennium Une 2. Which of these dose not reflect the periodicity of the elements [UPSEAT 2001; BI
110 un-un-nilium Uun (a) Bonding behaviour (b) Electronegativity
(c) Ionization energy (d) Neutron/proton ratio
111 un-un-unium Uuu 3. If an atom has electronic configuration
112 un-un-bium Uub 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 3 4 s 2 , it will be placed in
113 un-un-trium Uut [CBSE PMT 2002]
114 un-un-quadium Uuq (a) Second group (b) Third group
(c) Fifth group (d) Sixth group
115 un-un-pentium Uup
4. All the s–block elements of the periodic table are placed in the
116 un-un-hexium Uuh groups … [Orissa JEE 2002]
117 un-un-septium Uus (a) IA and IIA (b) IIIA and IVA
(c) B sub groups (d) VA to VIIA
118 un-un-octium Uuo
5. The electronic configuration of halogen is
119 un-un-ennium Uue [MP PET/PMT 1998; Pb. PMT 2001]
 Elements of second period are known as Bridge elements. Their (a) ns 2 np 6 (b) ns 2 np 3
properties resemble with the properties of diagonal elements of third
period. (c) ns 2 np 5 (d) ns 2

 For isoelectronic ions the size depends on the nuclear charge. 6. Hydrogen by donating one electron forms H  . In this property, it
Greater is the nuclear charge smaller is the size. resembles with
(a) Transitional metals (b) Alkaline earth metals
 The incease in magnitude of radii is more in the beginning of a (c) Alkali metals (d) Halogens
group because the difference in energy between energy shells is
more. 7. The tenth elements in the periodic table resembles with the
[CPMT 1988]
 The ionisation potentials provide an indication about the number of (a) First period (b) Second period
valence electrons (s) in an atom e.g., Na has IE >>> IE (because it
2 1 (c) Fourth group (d) Ninth group
has one valence electron) while Mg has IE >>> IE > IE because it
3 2 1
8. The element with quantum numbers n  2, l  1, m  1, s  1 / 2
has two valence electrons and attains noble gas configuration after has the following position in the periodic table
losing 2 electrons. (a) Group VII-A, period II (b) Group 0, period II
 The highest I.E. in a period is shown by noble gas. (c) Group VII-A, period III (d) Group 0, period III
9. Who developed the long form of periodic table
 The electronegativity of a series of transition metals is almost [MP PET 1997]
similar. The electronegativity of all lanthanide’s are identical (1.1). (a) Lothar Meyer (b) Niels Bohr
(c) Mendeleef (d) Moseley
 The most electronegative elements is Fluorine (value is 4.0 on the 10. The electronic configuration of an element is
Pauling scale). The least electronegative elements is Cs and Fr with
1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 3 . What is the atomic number of the
a value of 0.700.
element which is just below the above element in the periodic table[CBSE PMT
 Chemical Periodicity 623
(a) 33 (b) 34 25. Which of the following elements is a lanthanide (Rare–earth
(c) 31 (d) 49 element) [Manipal MEE 1995]
11. In the periodic table, the element with atomic number 16 will be (a) Cadmium (b) Californium
placed in the group [MP PET/PMT 1998] (c) Cerium (d) Cesium
(a) Third (b) Fourth 26. Mendeleef's periodic law is based on
(c) Fifth (d) Sixth (a) Atomic weight (b) Atomic number
12. The first element of rare–earth metals is [AFMC 1992] (c) Number of neutrons (d) None of the above
(a) Cerium (b) Actinium 27. The heaviest atom amongst the following is
(c) Uranium (d) Lanthanum [CPMT 1976; NCERT 1976]
13. The d -block elements consists mostly of [MP PMT 1994] (a) U (b) Ra
(a) Monovalent metals (c) Pb (d) Hg
(b) All non-metals 28. Which of the following pairs has both members from the same
group of the periodic table
(c) Elements which generally form stoichiometric metal oxide [CPMT 1985; MP PET/PMT 1998]
(d) Many metals with catalytic properties
(a) Mg  Ba (b) Mg  Na
14. “The 6 properties of the elements are periodic function of their
atomic numbers.” The statement was given by (c) Mg  Cu (d) Mg  K
[MNR 1995] 29. Which of the following pairs has both members from the same
(a) N. Bohr (b) J.W. Dobereiner period of the periodic table
(c) D.I. Mendeleef (d) H.G.J. Moseley [CPMT 1985; UPSEAT 2001; BHU 2003]
15. The long form of periodic table has (a) Na  Ca (b) Na  Cl
[CPMT 1986; KCET 1998] (c) Ca  Cl (d) Cl  Br
(a) Eight horizontal rows and seven vertical columns 30. Diagonal relationship is shown by [DPMT 1984]
(b) Seven horizontal rows and eighteen vertical columns (a) Elements of first period
(c) Seven horizontal rows and seven vertical columns (b) Elements of second period
(d) Eight horizontal rows and eight vertical columns (c) Elements of third period
16. The telluric helix was given by [AFMC 1990] (d) (b) and (c) both
(a) De Chan Courtois (b) Newlands 31. The elements having the electronic configuration, [ Kr ]
(c) L. Meyer (d) Mendeleef 4 d 10 f 14 , 5 s 2 p 6 d 2 , 6 s 2 belongs to [CPMT 1982]
17. Which one of the following belongs to representative group of (a) s-block (b) p-block
elements in the periodic table [Kurukshetra CEE 1991]
(c) d-block (d) f-block
(a) Lanthanum (b) Argon
32. Chemical property of Li and Mg similar because
(c) Chromium (d) Aluminium
[RPMT 2002]
18. An element of atomic number 29 belongs to
(a) These belong to same group
[CPMT 1991; Kurukshetra CEE 1991; MP PET 2001]
(b) Both ionisation potential is same
(a) s -block (b) p -block
(c) Shows diagonal relationship
(c) d -block (d) f -block (d) Both electron affinity is same
19. The element californium belongs to the family 33. According to the periodic law of elements, the variation in
[MNR 1987] properties of elements is related to their [AIEEE 2003]
(a) Actinide series (b) Alkali metal family (a) Atomic masses
(c) Alkaline earth family (d) Lanthanide series (b) Nuclear masses
20. On moving from left to right across a period in the table the (c) Atomic numbers
metallic character [CPMT 1986] (d) Nuclear neutron-proton number
(a) Increases 34. The element with atomic number 36 belongs to …… block in the
(b) Decreases periodic table [KCET 2003]
(c) Remains constant (a) p (b) s
(d) First increases and then decreases (c) f (d) d
21. An element with atomic number 20 will be placed in which period 35. Which group of the periodic table contains only metals
of the periodic table [MNR 1986; UPSEAT 1999]
[UPSEAT 2003]
(a) 4 (b) 3
(a) IIA (b) IB
(c) 2 (d) 1
(c) IA (d) None of these
22. The electronic structure (n  1) d 110 ns 0  2 is characteristic of 36. The elements in which s and p-orbitals are present
[CET Pune 1998] (a) Common elements
(a) Transition elements (b) Lanthanides (b) Inert gases
(c) Actinides (d) Rare gases (c) Halogens
23. The elements with atomic number 10, 18, 36, 54 and 86 are all[CPMT 1976] (d) Transitional elements
(a) Light metals (b) Inert gases 37. Aluminium is diagonally related to (in periodic table)
(c) Halogens (d) Rare–earths [MP PET 1993]
24. Elements of atomic number 6 is placed in [CPMT 1978]
(a) Li (b) C
(a) IV group (b) IV period
(c) B (d) Be
(c) VI group (d) III group
 624 Chemical Periodicity

38. An element has the electronic configuration 1s 2 , 2 s 2 2 p 6 , (c) As , Bi (d) Pb , Sb

50. Dobereiner traids is [RPMT 1997]
3 s 2 3 p 6 3d 5 , 4 s 1 . It is a
(a) Na , K , Rb (b) Mg, S , As
(a) s-block element (b) p-block element
(c) Cl , Br, I (d) P, S , As
(c) d-block element (d) Inert gas
51. As per the modern periodic law, the physical and chemical
39. Which of the following show diagonal relationship
properties of elements are periodic functions of their
[KCET 2003; MP PMT 2003] [RPMT 1997; EAMCET 1998]
(a) B and Si (b) B and Al (a) Atomic volume
(c) B and Ga (d) B and C (b) Electronic configuration
40. Which of the following dinegative anion is quite common (c) Atomic weight
[CPMT 2000] (d) Atomic size
(a) S 2
(b) Se 2 52. Elements after atomic number 103 have been discovered till now. If
an element with atomic number 106 were ever discovered which of
(c) Te 2  (d) O 2 the following electronic configuration will it possess [AIIMS 1982]
41. An element has electronic configuration 1s 2 2 s 2 2 p 6 3 s 2 3 p 4 . (a) [Rn] 5 f 14 6 d 4 7 s 2 (b) [Rn] 5 f 14 6 d 5 7 s1
Predict their period, group and block
[CPMT 2000]
(c) [Rn] 5 f 14 6 d 6 7 s 0 (d) [Rn] 5 f 14 6 d 1 7 s 2 7 p 3
(a) Period = 3 , block = p, group = 16
rd 53. The element X, Y, Z and T have the indicated electronic
configurations. Starting with the innermost shell, which is the most
(b) Period = 5 , block = s, group = 1
th

metallic element [CPMT 1979, 93]

(c) Period = 3 , block = p, group = 10
rd

(a) X  2, 8, 4 (b) Y  2, 8, 8
(d) Period = 4 , block = d, group = 12
th

42. If the atomic number of an element is 33, it will be placed in the (c) Z  2, 8, 8, 1 (d) T  2, 8, 8, 7
periodic table in the [RPET 1999; UPSEAT 2001, 02] 54. Which pair of atomic numbers represents s -block elements
(a) First gp (b) Third gp [EAMCET 1990; RPMT 1997; MP PET 2003]
(c) Fifth gp (d) Seventh gp (a) 7, 15 (b) 6, 12
43. Which of the following is the atomic number of a metal (c) 9, 17 (d) 3, 12
[AIIMS 2000] 55. Which pair of elements has same chemical properties
(a) 32 (b) 34 [EAMCET 1987]
(c) 36 (d) 38 (a) 13, 22 (b) 3, 11
44. Which of the following statement is not correct regarding hydrogen (c) 4, 24 (d) 2, 4
atom [AIIMS 2000] 56. Mosley's name is most closely associated with the discovery of
(a) It resembles halogens in some properties (a) Positron (b) Deutrons
(b) It resembles alkali metals in some properties (c) Atomic number (d) Atomic weight
(c) It can be placed in 7 group of periodic table
th
57. In the periodic table going down in fluorine group
(d) It can not be placed in first group of periodic table [CPMT 1981]
45. Lithium shows similarities to magnesium in its chemical behaviour (a) Reactivity will increase
because [AFMC 2000] (b) Electronegativity will increase
(a) Similar size, same electronegativity and lower polarizing power (c) Ionic radius will increase
(b) Similar size, greater electronegativity and similar polarizing (d) Ionization potential will increase
power 58. Beryllium resembles much with [CPMT 1988]
(c) Similar size, same electronegativity and similar high polarizing (a) Zn (b) Al
power
(c) Li (d) Ra
(d) None of these
59. The last member in each period of the periodic table is
46. On going left to right in a period, in transition metals, their atomic
volumes [MP PMT 2003] [DPMT 2001]
(a) Decrease (b) Increase (a) An inert gas element (b) A transition element
(c) Remain same (d) None of these of correct (c) A halogen (d) An alkali metal
47. Electronic configuration of chalcons in their outermost orbit is 60. Which one of the following combination represents a metallic
element [EAMCET 1979]
(a) s2 p3 (b) s2 p4 (a) 2, 8, 7 (b) 2, 8, 8
(c) s 2 p 5 (d) s 2 p 6 (c) 2, 8, 4 (d) 2, 8, 2
48. Which configuration represents a noble gas [DPMT 2000] 61. The electronic configuration of an atom A is 1s 2 , 2s 2 p 6 ,
(a) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 10 4 s 2 3 s 2 p 6 d 10 , 4 s 2 p 3 . The chemistry of A is therefore likely to be
similar to that of [MP PMT 1995]
(b) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 (a) Chlorine (b) Nitrogen
(c) 1s 2 2 s 2 2 p 6 3 p 6 (c) Oxygen (d) Boron
(d) 1s 2 2 s 2 2 p 6 3 s 2 62. The element having the electronic configuration 1s 2 ,
49. Which of the following pair has elements containing same number 2 s 2 2 p 6 , 3 s 2 3 p 1 is
of electrons in the outermost orbit (a) A transition element
[Kurukshetra CEE 1998; AFMC 2000]
(b) A representative element
(a) N, O (b) Na , Ca (c) An inert gas
 Chemical Periodicity 625
(d) An inner–transition element 75. Chemical behaviour of an atom is determined by
63. 2 2 6 2
The element with configuration 1s , 2 s p , 3 s would be (a) Atomic number (b) Mass number
(c) Binding energy (d) Number of isotopes
[CPMT 1986; MP PMT 1993]
76. Which of the following is a inert element
(a) A metal (b) A non-metal
(a) Na (b) Fe
(c) An inert gas (d) A metalloid
64. The long form of periodic table is based on [CPMT 1997]
(c) Li (d) He
77. The lightest metal is
(a) Shape of the atom
[CPMT 1976; NCERT 1976; AFMC 1988]
(b) Mass of the atom
(c) Atomic number of the atom (a) Li (b) Mg
(d) Electronegativity (c) Ca (d) Na
65. Chloride of an element A gives neutral solution in water. In the 78. Choose the typical element
periodic table, the element A belongs to (a) K (b) Na
[AIIMS 1992; UPSEAT 2001] (c) Sc (d) He
(a) First group (b) Third group 79. Of the following pairs, the one containing example of metalloid
(c) Fifth group (d) First transition series elements in the periodic table is
66. The fundamental basis of the present-day Periodic Table is that (a) Sodium and potassium
elements are [JIPMER 1999] (b) Fluorine and chlorine
(a) Arranged in the order of increasing atomic weights (c) Calcium and magnesium
(b) Grouped according to chemical properties (d) Boron and silicon
(c) Arranged in the order of increasing number of neutrons in the 80. The number of elements in each of the long periods in the periodic
atomic nucleus table is
(d) Arranged in the order of increasing number of protons in the (a) 2 (b) 8
nucleus (c) 18 (d) 32
67. 81.MP PET
All the elements in a group in the periodic table have the same [NCERT 1974; In the
1996;long form 1996]
MP PMT of the periodic table, all the non- metals are placed
(a) Atomic number under [EAMCET 1988]
(b) Electronic configuration (a) s-block (b) p-block
(c) Atomic weight (c) d-block (d) f-block
(d) Number of electrons in the outermost shell or number of 82. Elements with outer electronic configuration ns 2 np 6 are
electrons for bonding
[MP PET/PMT 1998]
68. The most predominantly ionic compounds will be obtained from the (a) Alkaline earth metals (b) Transition elements
combination of elements belonging to
(c) Chalcogenes (d) Noble gases
(a) 1 and 7 groups (b) 2 and 6 groups
83. Highest density is of ………. [RPET 2000]
(c) 3 and 5 groups (d) 0 and 7 groups
69. An atom with atomic number 21 belongs to the category of (a) Ir (b) Os
[Kurukshetra CEE 1991] (c) Pb (d) Hg
(a) s -block elements (b) p -block elements 84. Lithium shows diagonal relationship with
(c) d -block elements (d) f -block elements [MP PET 1995, 96; EAMCET 1990]
(a) Al (b) Mg
70. Which metal has 2 electrons in the outermost orbit
(c) Be (d) B
(a) Na (b) Cu
(c) Au (d) Be 85. 1s 2 2 s 2 2 p 6 3 s 2 is the electronic configuration of the metal
71. In the modern periodic table, elements are arranged in [RPET 2000]
[MP PMT 1990; MP PET 1995; CPMT 1971, 73, 78, 80] (a) Na (b) Mg
(a) Increasing mass
(c) Fe (d) Al
(b) Increasing volume
86. Element having atomic number 17 is placed in
(c) Increasing atomic number
[MP PET 1995]
(d) Alphabetically
(a) I-group (b) V-group
72. Alkali metals in each period have [MP PMT 1995]
(c) VIII-group (d) VII-group
(a) Smallest size
87. The most importasnt active step in the development of periodic
(b) Lowest ionization potential table was taken by [CPMT 1976]
(c) Highest ionization potential (a) Mendeleef (b) Dalton
(d) Highest electronegativity (c) Avogadro (d) Cavendish
73. The elements on the right side of the periodic table are 88. Who is called the father of chemistry [CPMT 1972]
[CPMT 1976] (a) Faraday (b) Priestley
(a) Metals (b) Metalloids (c) Rutherford (d) Lavosier
(c) Non-metals (d) Transition elements 89. The total number of rare–earth elements is [CPMT 1993]
74. The screening effect of d-electons is [RPMT 2000] (a) 8 (b) 32
(a) Equal to that of p-electrons (c) 14 (d) 10
(b) More than that of p-electrons 90. Which is metalloid [Bihar MEE 1997]
(c) Same as f-electrons
(a) Pb (b) Sb
(d) Less than p-electrons
 626 Chemical Periodicity
(c) Bi (d) Zn 104. To which block is related an element having electronic configuration
(e) Mg 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 10 4 s 1 in the periodic table [MP PMT 1995]
91. The element or elements whose position is anomalous in the (a) s - block (b) p - block
periodic table is (c) d - block (d) f – block
(a) Halogens (b) Fe, Co and Ni 105. Ce  58 is a member of
(c) Inert gases (d) Hydrogen (a) s-block elements (b) p-block elements
92. An element M has an atomic mass 19 and atomic number 9. Its ion (c) d-block elements (d) f-block elements
is represented by 106. Atomic number of elements represent
(a) M (b) M (a) Number of protons in the nucleus
(c) M 2  (d) M 2  (b) Number of neutrons in the nucleus
93. The number of elements in the 5th period of the periodic table are (c) Number of protons and neutrons in nucleus
(a) 8 (b) 10 (d) The valency of an element
(c) 18 (d) 32 107. As we go from left to right in period two of the periodic table, gram
atomic volume of the elements
94. The element with atomic number 55 belongs to
[MP PMT 1995] (a) Will change indefinitely
(a) s-block (b) p-block (b) Increases at a constant rate
(c) d-block (d) f-block (c) First increases then decrease
95. Coloured salts are formed by [Bihar MEE 1996] (d) Decreases
(a) Alkali metals (b) Lanthanides 108. The electronic configuration of the element which is just above the
(c) Actinides (d) Transition metals element with atomic number 43 in the same periodic group is[MNR 1992; UPSEA
(e) None of these (a) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3 d 5 4 s 2
96. Which one of the following is an s - block element
[MP PMT 1999] (b) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 10 4 s 2 4 p 5
(a) Aluminium (b) Chromium (c) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3 d 6 4 s 1
(c) Niobium (d) Potassium
97. In the modern periodic table, the place of the element with atomic (d) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 10 4 s 1 4 p 6
number 31 is in [MP PMT 1999]
109. The elements indicating following atomic numbers belong to same
(a) s - block (b) d- block group [RPMT 1997]
(c) p -block (d) f – block (a) 11 and 37 (b) 19 and 15
98. Last element of group-IV is found to be [DPMT 1996] (c) 39 and 88 (d) None of these
(a) Strong metallic
110. Elements in which 4 f orbitals are progressively filled are called as[MP PET 199
(b) Weak metallic
(a) Transition elements (b) Lanthanides
(c) Strong non-metallic
(c) Actinides (d) Inert gases
(d) Weak non-metallic
111. Hydrogen can be put in halogen group because
99. Elements of d group are called [DPMT 1996]
[RPMT 2000]
(a) Transition elements (b) Transuranic elements
(a) It has deuterium and tritium as isotopes
(c) Metals (d) Metalloids
(b) It forms hydrides like chlorides
100. Which of the following is a normal element
(c) It contains one electron only
(a) Ce (b) He
(d) It is light
(c) Li (d) Ar
112. In the main group elements (i) as we proceed down the same group
101. Which of the following is metalloid [BHU 1996; AMU 2000] in the periodic table and (ii) as we proceed from left to right in the
(a) Pb (b) Zn same period, the atomic radius
(c) As (d) None of these (a) (i) Increase continuously; (ii) Decreases continuously
102. Under normal condition which of the following electronic (b) (i) Decreases continuously; (ii) Increases continuously
configuration is able to form dipositive ion [RPET 2000] (c) (i) Increases continuously; (ii) Decreases upto the group IV and
(a) [ Ar] 4 s1 (b) [ Ne ] 2 s 2 3 p 6 then increases upto the end of the period.
(d) (i) Decreases continuously; (ii) Decreases upto the group IV
(c) [ Ne ] 3 s 2 (d) None of these and then increases upto the end of the period.
103. The statement that is true for the long form of the periodic table is[IIT 1988]
113. Cause of diagonal relationship is
(a) It reflects the sequence of filling the electrons in the order of (a) Similar electronic configuration of the elements
sub-energy levels s, p, d and f
(b) Similar e / r ratio of the elements
(b) It helps to predict the stable valency states of the elements
(c) It reflects trends in physical and chemical properties of the (c) Same number of valency electrons in the elements
elements (d) Same atomic weights of the elements
(d) It helps to predict the relative ionicity of the bonds between
any two elements 114. From which of the following the hydration energy of Mg 2  is
larger [MP PET 2000]
 Chemical Periodicity 627

(a) Na  (b) Al 3  (b) Number of protons

(c) Number of neutrons
(c) Be 2 (d) Cr 3 
(d) Number of isotopes
115. Group comprising of all metals is [RPET 2000]
(e) Number of nucleons
(a) IIIA (b) IVA 127. Beryllium shows diagonal relationship with [Pb.CET 2003]
(c) VIIA (d) IIA (a) Mg (b) Na
116. Whose name is not associated with the development of Periodic (c) B (d) Al
Table [DCE 1999]
128. Which of the properties remains unchanged on descending a group
(a) Prout’s (b) Newlands in the periodic table
(c) Rutherford (d) Loother Meyer [MP PMT 1997; RPMT 2002]
117. Element of atomic number 23 is placed in the periodic table in [MP PMT 1996] (a) Atomic size (b) Density
(a) s - block (b) p – block (c) Valence electrons (d) Metallic character
(c) d - block (d) f - block 129. Which of the following element does not occur in liquid form
[RPMT 2002]
118. In which of the following groups all the three members are of the
alkaline earth metals family (a) Hg (b) Li
(c) Ga (d) Br
(a) Al, Sr , Ti (b) Li, Na, K
130. The cause of periodicity of properties is
(c) Mg, Ba, Ca (d) Rb, Cs, Fr (a) Increasing atomic radius
119. Astatine is a [RPET 2000] (b) Increasing atomic weights
(c) Number of electrons in the valency orbit
(a) Halogen
(d) The re-occurrence of similar outer electronic configuration
(b) Rare earth element
131. The chemistry of lithium is very similar to that of magnesium even
(c) Alkaline earth metal though they are placed in different groups
(d) None of these [NCERT 1982]
120. The nitride ion in lithium nitride is composed of (a) Both are found together in nature
[CBSE PMT 2001] (b) Both have nearly the same size
(c) Both have similar electronic configuration
(a) 7 P  7e (b) 10 P  7 e
(d) The ratio of their charge to size is nearly the same
(c) 7 P  10e (d) 10 P  10e
121. Which set has the same number of unpaired electrons in their Atomic and Ionic radii
ground state [JIPMER 2000]

(a) Cl  , Fe3  , Cr 3  (b) Na  , Mg 2  , Al 1. The ratio between radii of He  ion and H atom is
[MP PET 1996]
(c) Na, P, Cl (d) N , P, V 1
(a) (b) 1
122. Which of the following doesn’t decompose on heating 2
[AMU 2002] 3
(c) (d) 2
(a) MgCO3 (b) Na 2 CO 3 2
2. The smallest among the following ions is [JIPMER 1999]
(c) Li2 CO 3 (d) Ca (HCO 3 )2  2
(a) Na (b) Mg
123. Which of the following has smallest bond angle 2
(c) Ba (d) Al 3 
[AMU 2002] 3. Which is smallest in size [RPMT 1997]
(a) H 2O (b) NH 3 2 4
(a) O (b) C
(c) CH 4 (d) CO 2 (c) F  (d) N 3 
4. Which of the following has largest size
124. The metal-having highest melting point is [MP PMT 1995, 2003; JIPMER (Med.) 2002]
[AMU 2002]
(a) Al (b) Al 
(a) Chromium (b) Tungston 2
(c) Al (d) Al 3
(c) Diamond (d) Silver 5. Of the following, the one with largest size is
125. The elements with atomic numbers 9, 17, 35, 53, 85 are all [EAMCET 1997; BHU 1999]
[KCET 2004] 
(a) Cl (b) Ar
(a) Noble gases (b) Halogens (c) K  (d) Ca 2 
(c) Heavy metals (d) Light metals 6. Which cation has smallest radius [RPET 2000]
126. The atomic number of an element is derived from (a) K (b) Na 
[Kerala PMT 2004]
(c) Li  (d) Be 2 
(a) Number of electrons  2
7. The radii of F, F , O and O are in the order of
 628 Chemical Periodicity
[AIIMS 1999; CPMT 1999]
(a) Mg 2   Na   F   Al
(a) O 2  F   O  F (b) O 2  F   F  O
(b) F   Al  Na   Mg 2 
(c) F   O 2  F  O (d) O 2  O  F   F
8. Which of the following has the smallest size (c) Al  Mg  F   Na 
[CBSE PMT 1996]
(d) Na   Al  F   Mg 2 
(a) Na  (b) Mg 2
21. In K  F  ionic radius of F  is more while atomic radius of K 
(c) Cl  (d) F is [CPMT 1997]
9. Which of the following is largest [CBSE PMT 1996]
(a) Less than F  (b) More than F 
(a) Cl  (b) S 2
(c) Equal of F  (d) None of these
(c) Na  (d) F  22. Which one of the following species possesses maximum size
10. Which of the following property displays progressive increase down [EAMCET 1993; MP PET 2001]
a group in the Bohr's periodic table 
(a) Electronegativity (b) Electron affinity (a) Na (b) F
(c) Ionization potential (d) Size of the atom (c) Ne (d) O 2 
11. Atomic radii of fluorine and neon in angstrom units are respectively 23. The ionic radii of N 3  , O 2  , F  and Na  follow the order[MP PET/PMT 19
given by [IIT 1987]
(a) 0.762, 1.60 (b) 1.60, 1.60 (a) N 3   O 2   F   Na 
(c) 0.72, 0.72 (d) None of these values (b) N 3   Na   O 2   F 
12. Which ion has greatest radius in the following
(c) Na   O 2  N 3   F 
[CPMT 1976; NCERT 1977]
(d) O 2   F   Na   N 3 
(a) H (b) F
24. On moving down a group of regular elements, both atomic and ionic
(c) Br  (d) I  radii increases with increasing [BMEE 1995]
13. Which has the maximum atomic radius (a) Atomic number (b) Atomic weight
[CPMT 1975; AIIMS 1982; DPMT 1982]
(c) Atomic mass (d) None of these
(a) Al (b) Si 25. Which one of the following indicates the correct order of atomic size[EAMCET 1
(c) P (d) Mg (a) Be > F > C > Ne (b) Be < C < F < Ne
14. Which one of the following ions has the highest value of ionic radius (c) Be > C > F > Ne (d) F < Ne < Be < C
[AIEEE 2004] 26. Which has the smallest size [MP PET 1999]
2 3
(a) O (b) B (a) Na  (b) Mg 2 
 
(c) Li (d) F
(c) Al 3  (d) P 5 
15. On going down a main sub-group in the periodic table (example Li
27. A sodium cation has a different number of electrons from
to Cs in IA or Be to Ra in IIA), the expected trend of changes
in atomic radius is a (a) O 2 (b) F
[CPMT 1981; NCERT 1979]
(c) Li  (d) Al 3 
(a) Continuous increase
28. Which of the following statement concerning lanthanides elements is
(b) Continuous decrease
false [CBSE PMT 1994]
(c) Periodic one, an increase followed by a decrease
(a) Lanthanides are separated from one another by ion exchange
(d) A decrease followed by increase method
16. Which one of the following is the smallest in size
(b) Ionic radii of trivalent lanthanides steadily increases with
[IIT 1989]
increase in the atomic number
(a) N 3 (b) O 2 (c) All lanthanides are highly dense metals
(c) F  (d) Na  (d) More characteristic oxidation state of lanthanide elements is
17. Which one is the correct order of the size of the iodine species +3
[Pb. CET 1986; CBSE PMT 1997; Kurukshetra CEE 1998; 29. The lanthanide contraction is responsible for the fact that
RPMT 1999; DCE 1999; MP PET 2000; [CBSE PMT 1997]
MP PMT 2001; BCECE 2005] (a) Zr and Y have about the same radius
(a) I  I  I (b) I  I  I (b) Zr and Nb have similar oxidation state
 
(c) I  I  I (d) I  I  I (c) Zr and Hf have about the same radius
18. Which one has larger radius [CPMT 1997; KCET 2005] (d) Zr and Zn have the same oxidation state
(a) Na  (b) F 30. Elements of which group form anions most readily
[CBSE PMT 1992]
(c) F  (d) Na (a) Oxygen family (b) Nitrogen group
19. In third row of periodic table the atomic radii from Na to Cl (c) Halogens (d) Alkali metals
[MP PMT 1986]
31. The unit representing atomic radii and ionic radii is
(a) Continuosly decreases
(b) Continuosly increases (a) nm (b) cm
(c) Remains constant (c) Å (d) m
(d) Increases but not continuously 32. The atomic radii in periodic table among elements from right to left[MP PET 199
20. The size of the following species increases in the order (a) Decreases
[IIT-JEE 1990; AFMC 1995]
 Chemical Periodicity 629
(b) Increases 44. Which is helpful in the formation of ionic bond
(c) Remain constant (a) Only small cation
(d) First decreases and then increases (b) Only small anion
33. Of the following the ion with the smallest ionic radius is (c) Small cation and small anion both
[MP PET 1996] (d) Low positive charge, large cation and small anion
 2 45. Which of the following has largest ionic radius
(a) K (b) Ca
[AFMC 1999; BHU 2003]
(c) Ti 3  (d) Ti 4   
34. Which of the following does not represent the correct order of the (a) Cs (b) Li
property indicated [CBSE PMT 1997] (c) Na  (d) K 
(a) Sc 3   Cr 3   Fe 3   Mn 3  ionic radii 46. Point out the wrong statement :
(b) Sc  Ti  Cr  Mn Density On moving horizontally from left to right across a period in the
periodic table
(c) Mn 2   Ni 2   Co 2  Fe 2 ionic radii (a) Metallic character decreases
(d) FeO  CaO  MnO  CuO Basic nature (b) Electronegativity increases
35. The order of magnitude of ionic radii of ions Na  , Mg 2 , Al 3  (c) Gram atomic volume first decreases and then increases
(d) Size of the atoms increases for normal elements
and Si 4  is [MP PMT 1996]
47. Which of the following statements is correct
 2 3 4
(a) Na  Mg  Al  Si [MP PET 1997]
2  3 4 
(b) Mg  Na  Al  Si (a) X ion is larger in size than X atom
3  4 2 
(c) Al  Na  Si  Mg (b) X ion is larger in size than X atom

(d) Na   Mg 2   Al 3   Si 4  (c) X ion is larger in size than X  ion
(d) X and X  ions are equal in size

36. The order of the magnitude of ionic radii of ions N 3  , O 2  and
48. The atomic radius of elements of which of the following series
F  is [MP PMT 1996] would be nearly the same [MP PET 1997]
(a) N 3   O 2  F  (b) N 3   O 2  F  (a) Na K Rb Cs (b) Li Be B C
(c) N 3   O 2   F  (d) N 3   O 2  F  (c) Fe Co Ni Cu (d) F Cl Br I
37. Which statement is correct 49. The decreasing order of size of isoelectronic series K  , Ca 2  , Cl 
(a) For potassium, the atomic radius < ionic radius; but for
bromine, the atomic radius > ionic radius and S 2  is [Roorkee 1995]
(b) For potassium and bromine both, the atomic radii > ionic radii  2 2 
(a) K  Ca S  Cl
(c) For potassium and bromine both, the atomic radii < ionic radii  2
(d) For potassium, the atomic radius > ionic radius but for (b) K  Ca  Cl  S 2 


2
bromine, the atomic radius < ionic radius (c) Ca  K  Cl   S 2 


38. Which of the following ion is the smallest ion

(d) S 2   Cl   K   Ca 2 
[AIIMS 2001]
50. Which of the following sets of elements have the strongest tendency
(a) O 2 (b) O 2 to form anions [MP PET 1993]
(c) O 2 (d) O 22 (a) N, O, F (b) P, S, Cl
(c) As, Se, Br (d) Sb, Te, I
39. The correct order of radii is [IIT-JEE (Screening) 2000]
51. Radius of the isoelectronic species [MP PET 1994]
(a) N  Be  B (b) F   O 2  N 3  (a) Increases with the increase of nuclear charge
(c) Na  Li  K (d) Fe3  Fe 2  Fe4  (b) Decreases with the increase of nuclear charge
40. Which one of the following should be most stable (c) Is the same for all
[MP PET 2000] (d) First increases and then decreases
(a) H 2 (b) H  52. In which of the following pairs the difference between the covalent
radii of the two metals is maximum
(c) H (d) H  [MP PET 1994]
41. Which of the following is the correct order of ionic radii (a) K, Ca (b) Mn , Fe
[BHU 2002] (c) Co , Ni (d) Cr , Mn
(a) F  Li  Na  K (b) F  K  Na  Li 53. An atom of an element has electronic configuration 2, 8, 1. Which of
the following statement is correct [MP PMT 1994]
(c) Na  K  F  Li (d) Li  Na  K  F
(a) The element's valency is 7
42. Smallest among these species is [KCET 2002]
(b) The element exists as a diatomic molecule
(a) Lithium ion (b) Hydrogen
(c) The element is of non-metallic nature
(c) Lithium (d) Helium
(d) The element forms a basic oxide
43. Which of the following ionic radius would be maximum
54. Which of the following ions has the smallest radius
[MP PET 1997]
[KCET 1992]
(a) C 4 (b) N 3 2 
(a) Be (b) Li
(c) O 2 (d) Mg 2 
(c) O 2 (d) F
 630 Chemical Periodicity
55. Point out the wrong statement : 67. The trivalent ion having largest size in lanthanide series is
In a given period of the periodic table the s - block element has, in [Pb.PMT 2004]
general, a lower value of [MP PMT 1997] (a) Ti (b) Zr
(a) Ionisation energy (b) Electronegativity
(c) Hf (d) La
(c) Atomic radius (d) Electron affinity
68. Which of the following alkali metal ions has lowest ionic mobility in
56. Arrange the following in increasing order of their atomic radius : aqueous solutions [DPMT 2004]
Na, K, Mg, Rb [AFMC 1995, 97; CPMT 1999]
(a) Mg < K < Na < Rb (b) Mg < Na < K < Rb (a) Rb  (b) Cs 
(c) Mg < Na < Rb < K (d) Na < K < Rb < Mg (c) Li  (d) Na 
3 2
57. In the isoelectronic species the ionic radii (Å) of N , O and 69. Ionic radii are [CBSE PMT 2003, 04]
F  are respectively given by [Pb. CET 1989] (a) Directly proportional to effective nuclear charge
(a) 1.36, 1.40, 1.71 (b) 1.36, 1.71, 1.40 (b) Directly proportional to square of effective nuclear charge
(c) 1.71, 1.40, 1.36 (d) 1.71, 1.36, 1.40 (c) Inversely proportional to effective nuclear charge
58. Al 3  has a lower ionic radius than Mg 2  because (d) Inversely proportional to square of effective nuclear charge.
[EAMCET 1992] 70. The correct sequence of increasing covalent character is represented
(a) Mg atom has less number of neutrons than Al by [CBSE PMT 2005]

(b) Al 3  has a higher nuclear charge than Mg 2  (a) LiCl  NaCl  BeCl 2 (b) BeCl 2  NaCl  LiCl
(c) Their electronegativities are different (c) NaCl  LiCl  BeCl (d) BeCl 2  LiCl  NaCl
(d) Al has a lower ionisation potential than Mg atom
71. Correct energy value order is [Orissa JEE 2004]
59. When a neutral atom is converted into cation, there is
[EAMCET 1986] (a) ns np nd(n  1) f (b) ns np(n  1)d (n  2) f
(a) Decrease in the atomic number
(c) ns np(n  1)d (n  1) f (d) ns(n  1)d n(n  1) f
(b) An increase in the atomic number
(c) A decrease in size 72. The ionic conductance of following cation in a given concentration
(d) An increase in size are in the order [Orissa JEE 2004]
60. A trend common to both groups I and VII elements in the periodic (a) Li   Na   K   Rb 
table as atomic number increases is
[NCERT 1981; EAMCET 1980] (b) Li   Na   K   Rb 
(a) Oxidising power increases
(b) Atomic radius increases (c) Li   Na   K   Rb 
(c) Maximum valency increases (d) Li   Na   K   Rb 
(d) Reactivity with water increases
61. Increasing order of atomic radii is [RPET 2003]
(a) Mg 2  Na   Ne  F   O 2
Ionisation energy
(b) Na   Mg   Ne  F   O 2
1. The incorrect statement among the following is
(c) O 2  F   Ne  Na   Mg 2 [IIT-JEE 1997]
2   2 (a) The first ionisation potential of Al is less than the first
(d) Ne  O  F  Na  Mg
62. Chloride ion and potassium ion are isoelectronic. Then ionisation potential of Mg
[KCET 2002] (b) The second ionisation potential of Mg is greater than the
(a) Potassium ion is relatively bigger
second ionisation potential of Na
(b) Depends on the other cation and anion
(c) Their size are same (c) The first ionisation potential of Na is less than the first
(d) Chloride ion is bigger than potassium ion ionisation potential of Mg
63. Which of the following has the largest ionic radius (d) The third ionisation potential of Mg is greater than the third
[Pb. PMT 2002; BHU 2003]
ionisation potential of Al
(a) Na  (b) Ni  2. The second ionisation potential of an element M is the energy
(c) Cs  (d) Mg 2 required to [JIPMER 1997]
64.    (a)
The ionic radii of Li , Na , K are in which of the following order [MP PMT 2002] Remove one mole of electron from one mole of gaseous anion
(b) Remove one mole of electron from one mole of gaseous cation
(a) K   Na   Li  (b) K   Na   Li  of the element
  
(c) K  Na  Li (d) Li   Na   K  (c) Remove one mole of electron from one mole of monovalent
65. Which of the following has smallest size gaseous cation of the element
[JIPMER (Med.) 2002] (d) Remove 2 moles of electrons from one mole of gaseous atoms
(a) Mg 2 (b) Na  3. The ionization energy of an element is
(a) The same as the electron affinity of the element
(c) Al 3  (d) Si 4 
(b) Equal in magnitude but of opposite sign to the electron affinity
66. Which one of the following is expected to have largest size of the element
[UPSEAT 2004]
(c) The energy released when an electron is added to an atom of
(a) F  (b) O 2 the element
(c) Al 3 (d) N 3
 Chemical Periodicity 631
(d) The energy required to remove the outermost electron of an (c) Boron has only one electron in p-sub-shell
atom of the element (d) Atomic size of boron is less than that of beryllium
4. The first ionisation energies of alkaline earth metals are higher than
those of the alkali metals. This is because 13. A  A   e, E1 and A   A 2   e, E 2 . The energy required
[MP PET 1996] to pull out the two electrons are E1 and E 2 respectively. The
(a) There is increase in the nuclear charge of the alkaline earth correct relationship between two energy would be
metals (a) E1  E 2 (b) E1  E 2
(b) There is a decrease in the nuclear charge of the alkaline earth
metals (c) E1  E 2 (d) E1  E 2
(c) There is no change in the nuclear charge 14. Which of the following element has maximum, first ionisation
(d) None of the above potential [AIIMS 2001]
5. The statement that is not correct for the periodic classification of (a) V (b) Ti
elements is [IIT-JEE 1992] (c) Cr (d) Mn
(a) The properties of elements are the periodic functions of their 15. Highest energy will be absorbed to eject out the electron in the
atomic numbers configuration [RPMT 2000]
(b) Non-metallic elements are lesser in number than metallic (a) 1s 2 2 s 2 2 p 1 (b) 1s 2 2 s 2 2 p 3
elements
(c) The first ionisation energies along a period do not vary in a (c) 1s 2 2 s 2 2 p 2 (d) 1s 2 2 s 2 2 p 4
regular manner with increase in atomic number 16. In which of the following process highest energy is absorbed
(d) For transition elements the d -sub-shells are filled with [RPET 2000]
electrons monotonically with increase in atomic number (a) Cu  Cu  (b) Br  Br 
6. Choose the correct statement
(c) I  I  (d) Li  Li 
(a) Ionization energy and electron affinity increases across a period
17. The first ionization potential of Na, Mg, Al and Si are in the order[IIT 1988; MP
(b) Ionization energy increases but electron affinity decreases along
a period (a) Na < Mg > Al < Si (b) Na > Mg > Al > Si
(c) Na < Mg < Al > Si (d) Na > Mg > Al < Si
(c) Ionization energy decreases but electron affinity increases
18. How many ionisation energies can carbon have
(d) Both decreases along a period
(a) 1 (b) 2
7. In halogens, with the increase of atomic number which habit is (c) 4 (d) 6
found
19. Which of the following gaseous atoms has highest value of IE
(a) Habit to loose electrons decreases
[JIPMER 1997; CPMT 1997; AIIMS 2000]
(b) Ionic radii decreases
(a) P (b) Si
(c) Ionization potential decreases
(c) Mg (d) Al
(d) In MX 2 (M  metal and X  halogen), covalent properties
20. Hydrogen has high ionization energy than alkali metals, due to its [AIIMS 1999]
decreases
(a) Large size (b) Small size
8. Ionization potential is lowest for (c) Ionic bond (d) Covalent bond
The first ionization potentials eV  of Be and B respectively are[CBSE PMT
[CPMT 1989; MP PET 2001]
21.
(a) Halogens (b) Inert gases
(c) Alkaline earth metals (d) Alkali metals (a) 8.29eV , 9.32eV (b) 9.32eV , 9.32eV
9. Which of the following explanation is best for not placing hydrogen (c) 8.29eV , 8.29eV (d) 9.32eV , 8.29eV
in either the group of alkali metals or halogens 22. Which ionisation potential IP  in the following equations involves
[NCERT 1978] the greatest amount of energy [Pune CET 1998]
(a) The ionization energy of hydrogen is to high for group of alkali (a) Na  Na   e  (b) K   K 2  e 
metals, but too low of halogen group
(b) Hydrogen can form compounds with all other elements (c) C 2   C 3   e  (d) Ca   Ca 2   e 
23. Which of the following has maximum ionization potential
(c) Hydrogen is much lighter element than the alkali metals or the
[MH CET 1999]
halogens
(a) K (b) Na
(d) None of the above (c) Al (d) Mg
10. The ionization energy of nitrogen is more than that of oxygen 24. The first four ionization energy values of an element are 191, 578,
because [MP PET 1993] 872 and 5962 kcal. The number of valence electrons in the element
(a) Nitrogen has half filled p-orbitals is
(b) Nitrogen is left to the oxygen in the same period of the (a) 1 (b) 2
periodic table (c) 3 (d) 4
(c) Nitrogen contains less number of electrons 25. Which of the following has least ionization potential
(d) Nitrogen is less electronegative [CPMT 1982, 93]
11. The energy required to remove an electron of a gaseous atom from (a) Li (b) Cs
its ground state is called [CPMT 1989, 94] (c) Cl (d) I
(a) Potential energy (b) Ionization energy 26. Which of the following element has the lowest ionization potential [CPMT 1976;
(c) Electrode potential (d) Activation energy (a) Fe (b) H
12. The first ionization energy of boron is less than that of beryllium (c) Li (d) He
because 27. As one moves along a given row in the periodic table, ionization
(a) Boron has higher nuclear charge energy
(b) Atomic size of boron is more than that of beryllium [CPMT 1976, 89; NCERT 1978; EAMCET 1985]
(a) Remains same
 632 Chemical Periodicity
(b) Increases from left to right (a) B (b) Li
(c) First increases, then decreases (c) Ne (d) F
(d) Decreases from left to right 42. The set representing the correct order of first ionisation potential is [IIT-JEE (S
28. Ionization energy is highest for [AFMC 2001; BVP 2003]
(a) K  Na  Li (b) Be  Mg  Ca
(a) Noble gases
(b) Platinum metals (c) B  C  N (d) Ge  Si  C
(c) Transition elements 43. Among the following options, the sequence of increasing first
(d) Inner–transition elements ionisation potential will be
29. Which one of the following elements has the highest ionisation [AIIMS 2000; MP PMT 2002]
energy [IIT-JEE 1990] (a) B  C  N (b) B  C  N
(a) [ Ne ] 3 s 2 3 p 1 (b) [ Ne ] 3 s 2 3 p 2 (c) C  B  N (d) N  C  B
(c) [ Ne ] 3 s 2 3 p 3 (d) [ Ar] 3d 10 4 s 2 4 p 2 44. The decreasing order of the ionisation potential in the following
elements is [MP PMT 2001]
30. Which of the following elements has the lowest ionistion potential [EAMCET 1993]
(a) Ne  Cl  P  S  Al  Mg
(a) N (b) O
(c) F (d) Ne (b) Ne  Cl  P  S  Mg  Al
31. Which of the following has lowest first ionisation potential (c) Ne  Cl  S  P  Mg  Al
[CPMT 1993]
(a) B (b) C (d) Ne  Cl  S  P  Al  Mg
(c) N (d) O 45. Which is the correct order of the first ionization potential of N, O
32. If first orbit energy of He  is – 54.4 eV, then the second orbit and C [AMU 2000]
energy will be [Roorkee 1995] (a) C  N  O (b) C  N  O
(a) – 54.4 eV (b) – 13.6 eV (c) O  N  O (d) C  N ~ O
(c) – 27.2 eV (d) + 27.2 eV
46. Which of the following order is wrong [CBSE 2002]
33. The screening effect of inner electrons of the nucleus causes
[MP PMT 1994] (a) NH 3  PH 3  AsH 3 -acidic nature
(a) A decrease in the ionisation potential (b) Li   Na   K   Cs  -ionic radius
(b) An increase in the ionisation potential
(c) Al2 O3  MgO  Na 2 O  K 2 O -basic
(c) No effect on the ionisation potential
(d) An increase in the attraction of the nucleus to the electrons (d) Li  Be  B  C -1 ionisation potential
st

34. Which of the following has highest first ionization energy 47. Which of the following has the least ionization potential
[MP PET 1994] [MP PET 2002]
(a) Sulphur (b) Oxygen (a) Lithium (Li) (b) Helium (He)
(c) Nitrogen (d) Phosphorus (c) Nitrogen (N) (d) Zinc (Zn)
35. The second ionization potential is 48. The first ionisation energy of lithium will be
[Bihar CEE 1995; CET Pune 1998] [EAMCET 1990]
(a) Less than the first ionization potential
(a) Greater than Be (b) Less than Be
(b) Equal to the first ionization potential
(c) Greater than the first ionization potential (c) Equal to that of Na (d) Equal to that of F
2
(d) None of these 49. Spectrum of Li is similar to that of [AIIMS 2002]
36. When the first ionization energies are plotted against atomic (a) H (b) He
number the peaks are occupied [CET Pune 1998] (c) Be (d) Ne
(a) Alkali metals (b) Halogens 50. Highest ionisation energy stands for [DPMT 2000]
(c) Rare gases (d) Transition elements (a) He (b) C
37. Among the following which has the highest first ionization energy
(c) N (d) H
(a) K (b) Na 51. Which of the following electrons should have the highest value of
(c) B (d) Kr ionisation energy (for the same value of the principal quantum
38. The first ionisation potential will be maximum for number)
[CPMT 2000] (a) s (b) p
(a) Lithium (b) Hydrogen (c) d (d) f
(c) Uranium (d) Iron 52. The correct sequence of elements in decreasing order of first
39. Arrange S, P, As in order of increasing ionisation energy ionisation energy is [MP PET 1997]
[JIPMER (Med.) 2002] (a) Na  Mg  Al (b) Mg  Na  Al
(a) S  P  As (b) P  S  As Al  Mg  Na Mg  Al  Na
(c) (d)
(c) As  S  P (d) As  P  S
53. Correct order of polarising power is
40. With reference to concept of ionisation potential, which one of the
following sets are correct [Kurukshetra CEE 1991] [MP PMT 2003; BHU 2003]
  2 3
(a) U  K  Cs (b) B  U  K (a) Cs  K  Mg  Al
(c) Cs  U  B (d) Cs  U  K (b)  
K  Cs  Mg 2
 Al 3 
41. Which among the following species has the highest ionisation
potential [KCET 2001] (c) Cs   K   Al 3  Mg 2
 Chemical Periodicity 633

(d) K   Cs   Al 3  Mg 2 (a) 13.6 eV (b)  13.6 eV

54. Correct increasing order of first ionistion potential is (c)  13.6 eV (d) 1.5 eV
[UPSEAT 2003] 68. Which of the following elements will have the lowest first ionisation
energy [KCET 1992]
(a) Na  Mg  Al  Si (b) Na  Mg  Al  Si
(a) Mg (b) Rb
(c) Na  Mg  Al  Si (d) Na  Mg  Al  Si (c) Li (d) Ca
55. The ionisation potential of hydrogen from ground state to the first 69. In the long form of periodic table, the element having lowest
excited state is [DCE 2001] ionisation potentials are present in [EAMCET 1992]
(a) 13.6 eV (b) 13.6 eV (a) I group (b) IV group
(c) VII group (d) Zero group
(c) 3.4 eV (d) 3.4 eV 70. The process requiring the absorption of energy is
56. In view of their low ionisation energies the alkali metals are [Roorkee 1990]
 
[MP PMT 2002] (a) FF (b) Cl  Cl
(a) Weak oxidising agents (c) O  O 2  (d) H  H 
(b) Strong reducing agents 71. In a period from Li to F , ionization potential
(c) Strong oxidising agents