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CHEMICAL BONDING
CHEMICAL BONDING
Ionic Bond or Electrovalent Bond
An ion is an atom or group of atoms which has acquired charge due to the loss or gain of one or more
electrons. When an atom gains an electron to form a negative ion (anion), it will increase in size. On the
other hand, when an atom loses an electron to give positive ion (cation), it will contract. The electron
lost or gained is always from the outermost shell.
When two atoms, one of which can lose one or more electrons to attain a noble gas configuration and
the other can receive these electrons and thereby acquire a noble gas configuration, they are said to be
bonded by an ionic bond. Since the loss and gain of electrons by atoms results in the formation of ions,
ionic bond is formed when two ions interact with each other and are thus held together by electrostatic
attraction. The formation of potassium chloride (KCl), is illustrated below.
K (1s 2 2s 2 2p 6 3s 2 3p 6 )
1 electron
gains
Cl (1s 2 2s2 2p6 3s 2 3p5 )
Cl (1s 2 2s 2 2p 6 3s 2 3p6 )
1 electron
(i)
(ii)
(Ar configuration)
From the above illustrations, it is clear that the formation of an ionic compound is obviously related to
the ease of formation of the cations and anions from the neutral atoms which depends on two main
factors:
Ionization energy: Lower the value of ionization energy of an atom, greater will be the ease of formation
of the cation from it.
Electron affinity: Higher the electron affinity of an atom, greater the ease of formation of the anion
from it.
Lattice Energy
When one mole of an ionic solid is formed from its constituent gaseous ions, the energy released is
called the lattice energy.
Energetics of Formation of Ionic Substances: The energy included in the formation of an ionic compound
from its constituent elements may be considered as shown by the Born-Haber Cycle for the formation
of one mole of sodium chloride from sodium and chlorine.
Na (s ) Sublimatio
n Na ( g )
Na (g ) e
S
1
on
of e Cl 2 (g ) Dissociati
Cl ( g ) Addition
Cl (g )
1
/
2
D
*
E
A
2
Na (g ) Cl (g ) Crystal
formation
NaCl (S)
U
Where
S
=
heat of sublimation of sodium metal
I
=
ionization energy of sodium
D
=
heat of dissociation of molecular chlorine
Ea
=
electron affinity of chlorine, and
U
=
lattice energy of sodium chloride
The amount of heat liberated in the overall reaction is the heat of formation of sodium chloride. From
1
D Ea U
2
The most important of these energy terms are I, Ea and U, since these are considerably greater than the
remaining terms S and D.
the above H = S + I +
42
CHEMICAL BONDING
More the negative value of the heat of formation, greater would be the stability of the ionic compound
produced. Thus on the basis of the above equation, formation of an ionic compound is favoured by
a)
low ionization energy (I) of the metal.
b)
high electron affinity (EA) of the other element.
c)
higher lattice energy (U) of the resulting compound.
Formation of Ions with Higher Charges: Formation of a cation with unit positive charge is easy if the first
ionization energy is low as in the case of alkali metals. Alkaline earth metals ionizes in two successive
steps.
+
Mg
Mg + e
2+
Mg+
Mg + e
But energy needed to ionize alkaline earth metals are higher than alkali metals.
However, bipositive ions like Mg2+, Ca2+, Sr2+ and Ba2+ are quite common. Formation of a tripositive
ion like Al3+ requires much more energy (= 5138 kJ) which is not available ordinarily. Successive
ionization energies of aluminium are:
E1
E1=577kJ
Al
Al e
E2
Al
Al2 e
E2=1816kJ
E3=2745kJ
It is on this account that most of aluminium compounds are covalent. In solution, however, aluminiumis
known to give hydrated ions [Al.6H2O]3+. This is possible because of the high heat of hydration of Al3+.
The energy liberated during hydration of ions is sufficient for ionization.
Similarly, anions with unit negative charge (e.g. Cl1, Br, I) are very common. This is because the
electron affinity of these atoms is positive and quite high. Formation of anions carrying two units of
negative charge (e.g. S2, O2) is not so easy as their electron affinities are negative i.e., energy is
needed to add second electron. Formation of anions carrying three units of negative charge (e.g. N3,
P3) is almost rare.
E3
Al2
Al3 e
43
CHEMICAL BONDING
Cl Cl
Hydrogen molecule
Chlorine molecule
F
d
In the case of hydrogen fluoride the bond is polar as the electron pair is unequally shared. Fluorine has
a greater attraction for electrons or has higher electronegativity than hydrogen and the shared pair of
electrons is nearer to the fluorine atom than hydrogen atom. The hydrogen end of the molecule, therefore,
appears positive with respect to fluorine.
Bond polarities affect both physical and chemical properties of compounds containing polar bond. The
polarity of a bond determines the kind of reaction that can take place at that bond and even affects the
reactivity at nearby bonds. The polarity of bonds can lead to polarity of molecules and affect melting
point, boiling point and solubility.
Dipole Moment: It is vector quantity and is defined as the product of the magnitude of charge on any of the
atom and the distance between the atoms. It is represented by .
Magnitude of dipole moment | | ( chargeqin esu) ( Dis tanrce in )
The unit = 1018 (esu) cm (D) is used in practice. In SI units charge q is measured in coulombs (C) and
the distance, r in metre, m
1C = 2.998 109 esu and 1 m = 102 cm
2.998 1011
2.998 10 29 D
1 Cm =
18
10
1
3.336 10 30 Cm
29
2,998 10
Dipole moment is a vector quantity and is often indicated by an arrow parallel to the line joining the
point of charge and pointing towards the negative end e.g., H F .
or
1D
% Ionic character of a covalent bond = Theoretical dipole moment assuming 100% ionic character 100
44
CHEMICAL BONDING
Illustration 1: The dipole moment of KCl is 3.336 1029 Cm. The interatomic distance K+andCl
ion in KCl is 260 pm. Calculate the dipole moments of KCl, if there were opposite
charges of the fundamental unit located at each nucleus. Calculate the percentage ionic
character of KCl.
Solution:
3.336 10 29
100 = 80.1%
% of ionic bond =
4.165 10 29
The bond is 80.1% ionic.
i)
ii)
In general a polar bond is established between two atoms of different radii and different electronegativities
while positive centres (nuclei) of different magnitudes combine to share an electron pair. Greater the
values of the dipole moment, greater is the polarity of the bond.
The following points may be borne in mind regarding dipole moments:
In case a molecule contains two or more polar bonds, its dipole moment is obtained by the vectorial
addition of the dipole moments of the constituent bonds.
A symmetrical molecule is non-polar even though it contains polar bonds.
For example, carbon dioxide, methane and carbon tetrachloride, being symmetrical molecules, have
zero dipole moments.
Dipole moment of methyl chloride is a vectorial addition of dipole moments of three C H bonds and
one C Cl bond.
1.75d
Cl
Cl
H
H
0D
Hydrogen
fluoride
Methane
Cl
Cl
Cl
H
H
0D
1.86D
Carbon
tetrachloride
Methyl
chloride
Dipole moment gives valuable information about the structure of molecules. For example, carbon dioxide
is assigned a linear structure since its dipole moment is zero.
We have seen that in a polar covalent bond between two atoms (say A and B), there is a partial
separation of charge. This bond is, therefore, said to have a partial ionic character. Greater the difference
of electronegativity between A and B, greater is the degree of ionic character (or polarity measured by
dipole moment of AB) of the bond. Pauling gave a fairly accurate rule by which the nature of the bond
can be predicted. According to this rule, If the difference on the electronegativity scale between
the two atoms is 1.9, the bond is 50% ionic in character. When the difference is greater than 1.9,
the bond is correspondingly more ionic. For example, when the electro negativity difference is 0.8,
1.2, 2.2 and 2.6, the corresponding partial ionic character is 12%, 25%, 61% and 74% respectively.
45
CHEMICAL BONDING
(ionic compound)
Conductivity: Covalent substances (whether of the molecular lattice or giant molecule type) do not conduct
electricity in the fused state since there are no free electrons or ions to carry the current. However,
substances like graphite which consists of separate layers conduct electricity because the electrons
have a passage in between the two flat layers.
Solubility: The characteristic solubility of covalent compounds in non-polar solvents such as benzene and
carbon tetrachloride can be described to the similar covalent nature of the molecules of solute and
solvent (i.e., like dissolves like). Covalent compounds in solution react more slowly as compared with
the ionic compounds which react instantaneously in solution. The solubility of covalent compounds is,
however, very much dependent upon the size of the molecule. Thus covalent substances having
giant molecules are insoluble in virtually all solvents due to the big size of the molecule unit.
Fajans Rules
i)
When two oppositely charged ions approach each other closely, the positively charged cation attracts
the outermost electrons of the anion and repel its positively charged nucleus. This results in the distortion
or polarization of the anion followed by some sharing of electrons between the two ions, i.e., the bond
becomes partly covalent in character.
Charge on Either of the ions: As the charge on the cation increases, its tendency to polarize the anion
increases. This brings more and more covalent nature in the electrovalent compound. Whereas with the
increasing charge of anion, its ability to get polarized, by the cation, also increases.
For example, in the case of NaCl, MgCl2 and AlCl3 the polarization increases, thereby covalent character
becomes more and more as the charge on the cation increases.
Similarly, lead forms two chlorides PbCl2 and PbCl4 having charges +2 and +4 respectively. PbCl4
shows covalent nature. Similarly among NaCl, Na2S, Na3P, the charge of the anions are increasing,
therefore the increasing order of covalent character.
NaCl < Na2S < Na3P
ii)
Size of the cation: Polarisation of the anion increases as the size of the cation decreases i.e., the
electrovalent compounds having smaller cations show more of the covalent nature. For example, in the
case of halides of alkaline earth metals, the covalent character decreases as we move down the group.
Hence melting point increases in the order of
BeCl2 < MgCl2 < CaCl2 < SrCl2 < BaCl2
iii)
Size of anion: The larger the size of the anion, more easily it will be polarized by the cation i.e., as the
size of the anion increases for a given cation, the covalent character increases. For example, in the case
of halides of calcium, the covalent character increases from F anion to I anion i.e.
CaF CaCl CaBr CaI
increasing covalent character
2
2
2
Similarly, in case of trihalides of aluminium, the covalent character increases with increase in size of
halide anion i.e.
AlF3
AlCl3
AlBr3
AlI3
46
CHEMICAL BONDING
Nature of the cation: Cations with 18 electrons (s2p6d10) in outermost shell polarize an anion more
strongly than cations of 8 electrons (s2p6) type. The d electrons of the 18 electron shell screen the
nuclear charge of the cation less effectively than the s and p electrons of the 18-electron shell. Hence
the 18-electron cations behave as if they had a greater charge. Copper (I) and Silver (I) halides are
more covalent in nature compared with the corresponding sodium and potassium halides although
charge on the ions is the same and the sizes of the corresponding ions are similar. This illustrates the
effect of 18-electron configuration of Cu+ (3s2, p6, d10) and Ag+ (4s2, p6, d10) ions.
Illustration 4: The decomposition temperature of Li2CO3 is less than that of Na2CO3. Explain.
Solution:
As Li+ ion is smaller than Na+ ion, thus small cation (Li+) will favour more covalent character in
Li2CO3 and hence it has lower decomposition temperature than that of Na2CO3.
iv)
BRAIN TEASER 1:
Hydrogen Bonding
In 1920, Latimer and Rodebush introduced the idea of hydrogen bond to explain the nature of
association in liquid state of substance like water, hydrogen fluoride, ammonia, formic acid etc. In a
hydrogen compound, when hydrogen is bonded to highly electronegative atom (such as F, O, N) by a
covalent bond, the electron pair is attracted towards electronegative atom so strongly that a dipole
results i.e., one end carries a positive charge (H-end) and other end carries a negative charge (X-end).
X H
or
Electro-negative atom
If a number of such molecules are brought nearer to each other, the positive end of one molecule and
negative end of the other molecule will attract each other and weak electrostatic force will develop.
Thus, these molecules will associate together to form a cluster of molecules.
X H X H X H X H X H
The attractive force that binds hydrogen atom of one molecule with electronegative atom of the other
molecule of the same or different substance is known as hydrogen bond.
i)
Ammonia
N H
N H
N H
N H
O H
ii)
Water
iii)
Acetic acid
O H
H3C
CH3
O
O H
47
CHEMICAL BONDING
This type of hydrogen bonding increases the boiling point of the compound and also its solubility in
water. The increase in boiling point is due to association of several molecules of the compound.
b)
Intramolecular hydrogen bonding: This type of bonding results between hydrogen and an
electronegative element both present in the same molecule. This type of bonding is generally present in
organic compounds. Examples are o-nitro-phenol, o-hydroxy benzoic acid, etc.
O
N
O
o-Nitrophenol
O
o-Hydroxy benzoic acid
This type of bonding decreases the boiling point of the compound. The solubility of the compound also
decreases. Hence compound becomes more volatile.
Properties Explained by Hydrogen Bonding
a)
Strength of certain acids and bases can be explained on the basis of hydrogen bonding.
b)
Solubility: An organic substance is said to be insoluble in water if it does not form hydrogen bonding
with water. The organic compound like alkanes, alkenes, ethers, etc., are insoluble in water as they do
not form hydrogen bonding with water, while alcohols and acids are soluble because they readily form
hydrogen bonds with water.
i)
Melting and boiling points of hydrides of N, O and F. If the melting points and boiling points of the
hydrides of the elements of IVA, VA, VIA and VIIA groups are plotted against the molecular weights
of these hydrides, we shall get the plots as shown in figure (a) and (b).
From these plots it may be seen that although in case of SbH3, AsH3, PH3 (VA group elements hydrides),
H2Te, H2Se, H2S (VI A group elements hydrides) and HI, HBr, HCl (VIII group elements hydrides)
there is a progressive decrease in their mps and b.ps with the decrease in their molecular weights, the
mps and b.ps of NH3, H2O and HF hydrides suddenly increase with a further decrease of their
molecular weights. The sudden increase in mps and bps in these hydrides is due to the inter-molecular
H-bonding in between H and F in case of HF, in between H and O in case of H2O and in between H
and N in case of NH3 respectively. The existence of H-bonding in these molecules gives polymerized
molecules (NH3)n. Thus mps and bps of these molecules are suddenly raised.
Having no power to form H-bonds, the simple carbon family hydrides (SnH4, GeH4, SiH4 and CH4)
show a decrease in their bps and mps with the decrease in their molecular weights.
100
100
H2O
H2O
0
H 2Se
NH 3
H 2 Se
H2S
HBr
-100
HI
VIA
VIIIA
VA
SbH 3
HCl
HF
AsH 3
PH3
SnH4
HF
H 2Se
NH3
H2S
SbH3
HI
HBr
-100
GeH 4
PH3
VA
VIIIA
SnH4
IVA
SnH4
IVA
CH 4
SnH 4
-200
H 2 Se
HCl
GeH 4
CH 4
VIA
-200
48
ii)
CHEMICAL BONDING
Ice has less density than water. The explanation of this fact is as follows: In the crystal structure of ice,
the O-atom is surrounded by four H-atoms. Two H-atoms are linked to O-atom by covalent bonds as
shown (by normal covalent bond) and the remaining two H-atoms are linked to O-atom by two Hbonds shown by dotted lines. Thus in ice every water molecule is associated with four other water
molecules by H-bonding in a tetrahedral fashion. Ice has an open cage like structure with a large empty
space due to the existence of H-bonds. As ice melts at 0C, a number of H-bonds are broken down
and the space between water molecules decreases so that water molecules move closer together. The
density of water increases, from 0 to 4C, and at 4C it is maximum. Above 4C the increase in
kinetic energy of the molecules is sufficient to cause the molecules to begin to disperse and the result is
that the density decrease with increasing temperature.
2.76
1.80
-
0.96
0.96
water molecule
H
H
H
H
H
BRAIN TEASER 2:
Although HF forms stronger hydrogen bond than H2O, Hv of H2O is greater than that of HF why?
Coordinate Bond
It is a special type of covalent bond in which both the shared electrons are contributed by one atom
only. It may be defined as a covalent bond in which both electrons of the shared pair are
contributed by one of the two atoms. Such a bond is also called as dative bond. A coordinate or a
dative bond is established between two such atoms, one of which has a complete octet and possesses
a pair of valence electrons while the other is short of a pair of electrons.
xx
+ B xx
xx
xx
Bx
xx x
or
49
CHEMICAL BONDING
i)
Formation of ammonium ion: Hydrogen ion (H+) has no electrons and thus accepts a lone pair
donated by nitrogen.
H
H
H
+ H
ii)
Formation of CO: Carbon has four valency electrons and oxygen has six. They combine to form two
double bond and a coordinate bond as to achieve their octet completed.
C
xx
+ xxOxx
Oxx
Acceptor Donor
1.
2.
3.
4.
In 1957 Gillespie and Nyhom gave this theory to predict and explain molecular shapes and bond angles
more exactly. The theory was developed extensively by Gillespie as the Valence Shell Electron Pair
Repulsion (VSEPR) theory. This may be summarized as:
The shape of the molecule is determined by repulsions between all of the electron pairs present in the
valence shell.
A lone pair of electrons takes up more space round the central atom than a bond pair, since the lone
pair is attracted to one nucleus whilst the bond pair is shared by two nuclei. It follows that repulsion
between two lone pairs is greater than repulsion between a lone pair and a bond pair, which in turn is
greater than the repulsion between two bond pairs. Thus the presence of lone pairs on the central atom
causes slight distortion of the bond angles from the ideal shape. If the angle between a lone pair, the
central atom and a bond pair is increased, it follows that the actual bond angles between the atoms must
be decreased. The order of repulsion between lone pairs and bond pairs of electrons follows the order
as:
Lone pair - lone pair repulsion > lone pair bond pair repulsion > bond pair bond pair repulsion.
The magnitude of repulsions between bonding pairs of electrons depends on the electronegativity
difference between the central atom and the other atoms.
Double bonds cause more repulsion than single bonds, and triple bonds cause more repulsion than a
double bond.
Effect of Lone Pairs: Molecules with four electron pairs in their outer shell are based on a tetrahedron. In
CH4 there are four bonding pairs of electrons in the outer shell of the C atom, and the structure is a
regular tetrahedron with bond angle H C H of 10928. In NH3 and N atom has four electron pairs
in the outer shell, made up of three bond pairs and one lone pair. Because of the lone pair, the bond
angle H N H is reduced from the theoretical tetrahedral angle of 10928 to 10728. In H2O the
O atom has four electron pairs in the outer shell. The shape of the H2O molecule is based on a tetrahedron
with two corners occupied by bond pairs and the other two corners occupied by lone pairs. The
presence of two lone pairs reduces the bond angle further to 10427.
NARAYANA II T ACAD EMY- C P 3 ,
50
CHEMICAL BONDING
In a similar way, SF6 has six bond pairs in the outer shell and is a regular octahedron with bond angles
of exactly 90. In BrF5, the Br also has six outer pairs of electrons, made up of five bond pairs and one
lone pair. The lone pair reduces the bond angles to 8430. Whilst it might be expected that two lone
pairs would distort the bond angles in an octahedral as in XeF4 but it is not so. Actual bond angle is 90,
reason being that the lone pairs are trans to each other in the octahedron, and hence the atoms have a
regular square planar arrangement.
Molecules with five pairs of electrons are all based on a trigonal bipyramid. Lone pairs distort the
structures as before. The lone pairs always occupy the equatorial positions (in an triangle), rather than
the axial positions (up and down).Thus in I 3 ion, the central I atom has five electron pairs in the outer
shell, made of two bond pairs and three lone pairs. The lone pairs occupy all three equatorial positions
and the three atoms occupy the top, middle, and bottom positions in the trigonal bipyramid, thus giving
a linear arrangement with a bond angle of exactly 180.
Effect of Electronegativity: NF3 and NH3 both have structures based on a tetrahedron with one
corner occupied by a lone pair. The high electronegativity of F push the bonding electrons further away
from N than in NH3. Hence the lone pair in NF3 causes a greater distortion from tetrahedral and gives
a F N F bond angle of 10230, compared with 10748 in NH3. The same effect is found in H2O
(bond angle 10427) and F2O (bond angle 102).
The effects of bonding and lone pairs on bond angles
Orbitals on
BeCl2
BF3
CH4
NH3
NF3
H 2O
F2O
PCl5
SF4
ClF3
XeF2
SF6
BrF5
XeF4
Shape
2
3
4
4
4
4
4
5
5
5
5
6
6
6
Number of
bond pairs
Linear
2
Plane triangle
3
Tetrahedral
4
Pyramidal
3
Pyramidal
3
Bent (V-shape)
2
Bent (V-shape)
2
Trigonal bipyramid
5
Trigonal bipyramid
4
T-shape
3
Linear
2
Octahedral
6
Square pyramidal
5
Square planar
4
Number of
lone pairs
0
0
0
1
1
2
2
0
1
2
3
0
1
2
central atom
Bond angle
180
120
10928
10748
10230
10427
102
120 & 90
10136 & 8633
8740
180
90
8430
90
51
CHEMICAL BONDING
Note: Thus PCl5 is highly reactive, and in the solid state it splits into [PCl4]+ and [PCl6] ions, which have
tetrahedral and octahedral structures respectively.
Cl
Cl
Cl
P
Cl
Cl
Structure of PCl5 molecule
Chlorine trifluoride ClF3: The chlorine atom is at the centre of the molecule and determines its shape.
The electronic configuration of Cl is 1s22s22p63s23p5. Three electrons form bonds to F, and four electrons
do not take part in bonding. Thus in ClF3, the Cl atom has five electron pairs in the outer shell, hence the
structure is a trigonal bipyramid. There are three bond pairs and two lone pairs.
It was noted previously that a trigonal bipyramid is not a regular shape since the bond angles are not all
the same. It therefore follows that all the corners are not equivalent. Lone pair occupy two of the
corners, and F atoms occupy the other three corners. Three different arrangements are theoretically
possible, as shown in figure below.
The most stable structure will be the one of lowest energy, that is the one with the minimum repulsion
between the five orbitals. The great repulsion occurs between two lone pairs. Lone pair bond pair
repulsions are next strongest, and bond pair-bond pair repulsions are weakest. Groups at 90 repel
each other strongly, whilst groups 120 apart repel each other much less.
F
Cl
F
Cl
Cl
F
F
II
III
Structure I is the most symmetrical, but has six 90 repulsions between lone pairs and atoms. Structure
II has one 90 repulsion between two lone pairs, plus three 90 repulsions between lone pairs and
atoms. These factors indicate that structure III is the most probable. The observed bond angles are
8040, which is close to the theoretical 90. This confirms that the correct structure is III, and the slight
distortion from 90 is caused by the presence of the two lone pairs.
As a general rule, if lone pairs occur in a trigonal bipyramid they will be located in the equatorial position
(round the middle) rather than the axial positions (top and bottom), since this arrangement minimizes
repulsive forces.
52
CHEMICAL BONDING
Sulphur hexafluoride SF6: The electronic structure of S is 1s22s22p63s23p6. All six of the outer electrons
are used to form bonds with the F atoms. Thus in SF6, the S has six electron pairs in the outer shell:
hence the structure is octahedral. There are no lone pairs, so the structure is completely regular with
bond angles of 90.
F
F
F
S
F
F
1.
2.
3.
4.
This theory was proposed by Linus Pauling, who was awarded the Noble Prize for
Chemistry 1954.
Atoms with unpaired electrons tend to combine with other atoms which also have unpaired electrons.
In this way the unpaired electrons are paired up, and the atoms involved, all attain a stable electronic
arrangement. This is usually a full shell of electrons(i.e. a noble gas configuration). Two electrons shared
between two atoms constitute a bond. The number of bonds formed by an atom is usually the same as
the number of unpaired electrons in the ground state, i.e. the lowest energy state. However, in some
cases the atom may form more bonds than this. This occurs by excitation of the atom (i.e. providing it
with energy) when electrons which were paired in the ground state are unpaired and promoted into
suitable empty orbitals. This increases the number of unpaired electrons, and hence it increases number
of bond which can be formed.
A covalent bond results from the pairing of electrons (one from each atom). The spins of the two
electrons must be opposite (antiparallel) because of the Pauli exclusion principle that no two electrons
in one atom can have all four quantum numbers the same.
In HF, H has a singly occupied s-orbital that overlaps with a singly filled 2p orbital on F.
In H2O, the O atom has two singly filled 2p orbitals, each of which overlaps with a single occupied sorbital from two H atoms.
In NH3, there are three singly occupied p orbitals on N which overlap with s orbitals from three H
atoms.
In CH4, the C atom in its ground state has the electronic configuration 1s2, 2s2, 2p1x , 2p1y and only has
two unpaired electrons, and so can form only two bonds. If the C atom is excited, then the 2s electrons
may be unpaired, giving 1s2, 2s1, 2p1x , 2p1y , 2p1x . There are now four unpaired electrons which overlap
with singly occupied s orbitals on four H atoms.
2p
2s
2px
2py 2p z
Electronic structure of
carbon atom - groun state
1s
Carbon atom - excited
state
Carbon atom having
gained four electrons
from H atoms in CH4
molecule.
2s
2p
sp 3 hybridisation
53
CHEMICAL BONDING
CH4 molecule uses its three p-orbitals px, py and pz, which are mutually at right angles to each other, and
the s orbital is spherically symmetrical. Hence they form tetrahedral structure.
CH4 H C H = 10928
A covalent bond is formed by the overlapping of atomic orbitals. Covalent bonds formed are of two
types depending upon the way the orbitals overlap each other.
Sigma bond ( bond): The bond formed by the overlapping of two half filled atomic orbitals along
their axis is known as sigma bond. bond is a strong bond because overlapping in it takes place to
large extent. The hybrid orbitals always from bond.
a)
s s overlapping
Molecular axis
b)
s p overlapping
c)
p p overlapping
pz
2.
head on
overlap
pz
p-p overlap
M.O.
Pi bond ( bond): The bond formed by the lateral overlapping of half filled atomic orbitals is known as
pi bond. The sidewise overlapping takes place to less extent. Therefore, bond formed is a weak
bond. bond overlapping takes place only at the sides of two lobes. A bond is formed when a
bond already exists between the combining atoms.
p-p overlapping
M.O.
Example:
In A B molecule the bond formed is bond.
In A
Thus, all the single bonds are bonds. Double bond has one and one bond. Triple bond has one
and two bonds.
Hybridisation
It is the mathematically fabricated concept that is introduced to explain the geometry/shapes of the
covalent molecules of polyatomic ions containing covalent bonds.
It is a process of intermixing of atomic orbitals with small difference in energy and belonging to the same
atom, at the time of bonding so as to give another set of orbitals with equivalent shapes and energies.
NARAYANA II T ACAD EMY- C P 3 ,
54
CHEMICAL BONDING
sp3 Hybridisation: In ground state, the electronic configuration of carbon is 1s2, 2s2, 2p2. It is proposed that
from 2s orbital, being quite near in energy to 2p orbitals, one electron may be promoted to the vacant
2pz orbital thus obtaining the excited atom. At this stage the carbon atom undoubtedly has four halffilled orbitals and can form four bonds. In the excited atom, all the four valence shell orbitals may mix up
to give four identical sp3 hybrid orbitals. Each of these four sp3 orbital possesses one electron and
overlaps with 1s orbitals of four H atoms thus forming four equivalent bonds in methane molecule. Due
to the tetrahedral disposition of sp3 hybrid orbitals, the orbital are inclined at an angle of 109 28. Thus
all the H C H angles are equal to 109 28
Energy
2p
2p
Promotion
sp3
of an electron
Hybridisation
2s
2s
Ground State
Hybridised State
Excited State
H
H
109.5
C
H
H
sp2 Hybridisation: When three out of the four valence obritals of carbon atom in excited state hybridize, we
have three sp2 hybrid orbitals lying in a plane and inclined at an angle of 120. If 2s and 2p, orbitals of
the excited carbon atom are hybridized, the new orbitals lie in the xy plane while the fourth pure 2pz
orbitals lies at right angles to the hybridized orbitals with its two lobes disposed above and below the
plane of hybrid orbitals. Two such carbon atoms are involved in the formation of alkenes (compounds
having double bonds). In the formation of ethene two carbon atoms (in sp2 hybridization state) form
one sigma bond by head-on overlap of two sp2 orbitals contributed one each by the two atoms. The
remaining two sp2 orbitals of each carbon form bonds with H atoms. The unhybridized 2p, orbitals of
the two carbon atoms undergo a side-wise overlap forming a bond. Thus the carbon to carbon
double bond in ethene is made of one bond and one bond. Since the energy of a bond is less than
that of a bond, the two bonds constituting the ethene molecule are not identical in strength. The
molecule is a planar one.
Pure p-orbital
Energy
2p
Promotion
2p
of an electron
2s
Ground State
sp2
Hybridisation
sp2 hybrid
orbitals
2s
Excited State
55
CHEMICAL BONDING
pz
pz
sp 2
sp 2
H
C
C
sp 2
sp 2
sp 2 2
sp
Different types of hybridization depend upon the type of atomic orbitals which are used for intermixing.
Types of hybridization and spatial orientation of hybrid orbitals: The geometry and shapes of various
species on the basis of VSEPR theory along with hybrid state of central atom is given below in tabular
form.
Types of atomic orbitals used
1.
Hybridisation Orientation of
Examples
hybrid orbitals
sp
Linear
BeF2 , BeCl 2 , C 2 H 2 , HgCl 2
2.
sp 2
3.
sp 3
Tetrahedral
CH 4 , CCl 4 , SiF4 , NH 4 , SO 24 , ClO 4
4.
one s + three p + d
sp 3 d
Trigonal bipyramidal
PF5 , PCl 5
5.
sp 3 d 2
Octahedral
6.
sp 3 d 3
Pentagonal Bipyramidal
7.
dsp 2
Square planar
IF7
Orbitals participating in hybridization must have only small difference in their energies.
Both half-filled and completely filled orbitals can get involved in hybridization.
The number of hybrid orbitals is equal to the number of orbitals participating in hybridization.
Hybrid orbital form more stronger bonds than pure atomic orbitals.
Same atom can assume different hybrid states under different situations.
Hybrid orbitals form sigma bonds.
Method of predicting the Hybrid state of the central atom in covalent molecules of polyatomic ions:
The hybrid state of the central atom in similar covalent molecule or polyatomic ion can be predicted by
using the generalized formula as described below :
Simple Molecule
Polyatomic Anion
Polyatomic Cation
1
X [V G]
2
1
X [V G a ]
2
1
X [ V G c]
2
56
CHEMICAL BONDING
Calculate the value of X and decide the hybrid state of central atom as follows :
X
2
3
4
5
6
7
Hybrid state
PF5
sp 2
sp
sp 3 d
sp 3 d 2 sp 3 d 3
ClO 4
COCl 2 NH 4
X 12 [5 5]
X 12 [2 4]
=5
=4
=3
sp 3
X 12 [4 5 1] X 12 [0 7 1]
=4
Hybrid state of P is sp 3 d
Hybrid state of C is sp 2
Hybrid state of N is sp 3
Hybrid state of Cl is sp 3
NO 3
IF5
CO 2
XeF4
X 12 [0 5 1] X 12 [5 7]
=3
=6
sp 2
sp 3 d 2 sp
PCl 6 PH3
=2
SF3
X 12 [0 4]
X 12 [ 4 8]
=6
sp 3 d 2
SF4
X 12 [6 5 1] X 12 [3 5]
X 12 [3 6 1] X 12 [4 6]
=6
=4
Hybrid state
=4
=5
Hybrid state
Hybrid state
Hybrid state
sp 3 d 2
sp 3
sp 3
sp 3 d
57
CHEMICAL BONDING
Bond order: It may be defined as the half the difference between the number of electrons present in the
bonding orbitals and the anti-bonding orbitals i.e.
No. of electrons in BMO - No. of electrons in ABMO
2
A positive bonding order suggest a stable molecule while a negative bond order or zero bond order
suggest an unstable molecule.
Magnetic Behaviour: If all the molecular orbitals in species are spin paired, the substance is diamagnetic.
However, if one or more molecular orbitals are singly occupied it is paramagnetic.
Illustration 2 Arrange the species O2, O2, O22 and O2+ in the decreasing order of bond order and
stability and also indicate their magnetic properties.
Solution:
The molecular orbital configuration of O2, O2, O22 and O22+areasfollows:
O2 = 1s2, *1s2, 2s2, *2s2, 2px2, 2py2, 2pz2, *2py1 = *2pz1
10 - 6
2 , No. of unpaired electrons = 2
2
paramagnetic
O2 = 1s2, *1s2, 2s2, *2s2, 2px2, 2py2, 2pz2, *2py2 = *2pz1
Bond order =
10 - 5
2.5 , No. of unpaired electrons = 1
2
paramagnetic
Bond order =
O22 = 1s2, *1s2, 2s2, *2s2, 2px2, 2py2, 2pz2, *2py2 = *2pz2
Bond order =
10 - 8
1 , No. of unpaired electrons = 0
2
diamagnetic
O2+ = 1s2, *1s2, 2s2, *2s2, 2px2, 2py2, 2pz2, *2py1 = *2pz0
10 - 5
2.5 , No. of unpaired electrons = 1
2
paramagnetic
Now as the bond order decreases in the order O2+ O2 O2 O22
So, same will be the stability order of the above species because stability is directionally proportional to
bond order.
Note: Bond length is inversely proportional to bond order.
Bond order =
58
CHEMICAL BONDING
PRAYAS - I
Q.1
Q.2
(D) SO2
(D) H Se H
Q.3
Q.4
Ionic compound is
(A) H2O
(C) Csl
Q.5
Q.6
(B) HCl
(D) NH3
(C) 420
(D) + 360
Q.7
Q.8
Q.9
If the formula of a compound is X2 Y5, then what will be the numbers of electrons present in the valance
shells of X and Y, respectively ?
(A) 5 and 6
(B) 6 and 3
(C) 2 and 3
(D) 5 and 2
Q.10 The compound with two lone pairs and two bond electrons is
(A) SCl2
(B) PH3
(C) NH3
Q.11
(C) CaO
(D) HF
(D) Cl2
(D) MgO
Q.13 A molecule MX3 has zero dipole moment. The orbitals used by M in the formation of bond will be(A) pure p
(B) sp2
(C) sp
(D) sp3d
Q.14 Which of the following ions has an atom in a state of sp2 hybridisation ?
(A) BeF3
(B) NF3
(C) OF2
(D) H3O+
59
CHEMICAL BONDING
(C) NH3
(D) H2O
(D) BCl3
(C) Cl2
Q.20 XPO4 is a compound of a metal X, then the formula of the chloride of X will be
(A) XCl3
(B) XCl
(C) X2Cl3
(D) X2Cl2
Q.21 Which of the following has pyramidal geometry ?
(A) PCl3
(B) SO3
(C) CO32
(D) NO3
(C) F
(D) Br
Q.30 Increasing order of dipole moment in H2O, NH3, NF3 and CCl4 is
(A) CCl4 < NF3 < NH3 < H2O
(B) CCl4 > NF3 > NH3 > H2O
(C) NF3 > H2O > CCl4 > H2O
(D) all the four have equal dipole moments
NARAYANA II T ACAD EMY- C P 3 ,
60
CHEMICAL BONDING
(D) BaClO4
(D) BF3
(D) 6
(C) 5
(D) BaCl2
sp3
2.
NH4+
sp2
3.
XeF2
sp3d2
4.
SF4
sp3d
(A) 4
(B) 3
(C) 2
(D) 1
Q.44 Formula of the phosphate of a metal is MHPO4. What will be the formula of its chloride
(A) MCl
(B) MCl2
(C) MCl3
(D) M2Cl2
Q.45 The central atom of which of the following compounds has four bond pairs and two lone pairs
(A) SF4
(B) XeF4
(C) NH+4
(D) SF6
61
CHEMICAL BONDING
Q.46 Three soluble salts of three metals A (Atomic weight 7), B (atomic weight 27) and C (atomic weigh 64)
on electrolysis liberate 2.1, 2.7 and 9.6 grams of metals, respectively at the electrode. The valencies of
the metals are, respectively ,
(A) 1, 3 and 2
(B) 3, 1 and 2
(C) 3, 1 and 3
(D) 2, 2 and 3
Q.47 Incorrect information about Cl2O is
(A) angular structure (B) 110 bond angle
Q.50 What will be the energy of the system on bringing x and y atoms closer upto bond distance ?
(A) infinity
(B) minimum
(C) maximum
(D) zero
Q.51 Bond angle of HCN is similar to all of the following except
(A) BeF2
(B) C2H2
(C) OF2
Q.52 When a molecule breaks, then
(A) it absorbs energy
(C) it neither transmit nor absorbs energy
(D) CO2
62
CHEMICAL BONDING
Q.60 In a compound, 50% X (valency 1) and 50% Y (valency 1) are present, then the formula of the
compound will be
(A) X2Y
(B) XY
(C) XY2
(D) X2Y3
Q.61 Electronic configuration of an atom is ns2 np2 , which forms 2 and 2 bonds in a hydrocarbon, then
hybridisation state and bond angle of the atom will be
(A) sp, 180
(B) sp2, 120
(C) sp3, 109 28
(D) dsp2, 90
Q.62 Which of the following compound is not known ?
(A) OF2
(B) SF4
(C) SF6
(D) OF6
Q.63 Which of the following bonds should have higher polarity than the remaining three
(A) C F
(B) C O
(C) C B
(D) C H
Q.64 Which of the following has maximum melting point ?
(A) ionic crystal
(B) covalent crystal
(C) metallic crystal
Q.65 Inorganic graphite is
(A) boron nitrate
(C) boron carbonate
(B) a base
(C) a salt
(D) KCN
(D) MnO
(D) C = C
(D) N H
(C) N2
(D) H2
(C) 2pz 2s
(C) H2Se
(D) H2Te
(D) CO32
Q.76 Which of the followin molecules has hybridisdation on central atom different from that on the remaining
three ?
(A) SiH4
(B) CH4
(C) BF4
(D) [Ni(CN4)2]
Q.77 Which of following has square planar geometry ?
(A) XeF4
(B) SiCl4
(C) NH4+
NARAYANA II T ACAD EMY- C P 3 ,
(D) BF41
63
CHEMICAL BONDING
(C) BF3
(D) ClO21
Q.79 Hybridisation state of carbon changes as follows. sp3 sp2 sp, then the angels of hybrid orbitals
will
(A) remain unchanged (B) go on increasing (C) go on decreasing (D) first inct
Q.80 CCl4 is a covalent compound, whereas LiCl is less covalent, because
(A) C Cl bond is nonpolar
(B) charge on CCl4 is more
(C) Li Cl bond is polar
(D) moment of Li Cl is not definite
Q.81 Shape of xenon hexafluoride is
(A) tetrahderal
(C) square planar
(C) ZnI2
(D) OH2
(C) sp3d3
Q.85 Relative stabilities of O2, O2 and O2+, O22 are in the order
(A) O2 > O2+ > O2 > O22
(B) O2+ > O2 > O2 > O22
(C) O2+ > O22 > O2 > O2
(D) O22 > O2 > O2+ > O2
Q.86 Which of the following is not paramagnetic
(A) S2
(B) NO
(C) O2
(D) N2
Q.87 The dipole moment of a molecule of the type AX4 having a square planar geometry is
(A) O
(B) 4D
(C) 2D
(D) none of the above
Q.88 The nodle plane in the bond of ethene is located in
(A)
the molecular plane
(B)
a plane parallel to the molecular plane
(C)
a plane perpendicular to the molecular plane which bisect the carbon-carbon bond at right
angle
(D)
a plane perpendicular to the molecular plane which contains the carbon-carbons bonds
Q.89 The type of bonds present in CuSO4.5H2O are .............. only
(A) electrovalent and covalent
(B) electrovalent and co-ordinate
(C) electrovalent, covalent and co-ordinate
(D) covalent and co-ordinate
Q.90 The structure of XeF4 is
(A) planer
(B) tetrahedral
(D) pyramidal
(C) Si2+
(D) Sn2+
64
CHEMICAL BONDING
(B) -bond
(D) neither sigma and -bonds
(C) CO32
(D) NO3
Q.96 NF3 is
(A) non-polar compound
(B) electrovalent compound
(C) having low value of dipole moment than NH3 (D) having more dipole moment than NH3
Q.97 The maximum possible number of hydrogen bonds in which a water (H2O) molecule can participate
(A) 4
(B) 3
(C) 2
(D) 6
Q.98 Variable valency is characteristic of
(A) noble gases
(B) alkali metals
Q.100 The type of bond formed between H+ and NH3 in NH4+ ion is
(A) ionic
(B) covalent
(C) dative
(D) hydrogen
PRAYAS - II
Q.1
Q.2
Q.3
Q.4
Q.5
Q.6
Q.7
Weakest bond is
(A) ionic bond
(D) s
(D) SnCl2
(D) PH3
(D) ClO2
65
CHEMICAL BONDING
Q.8
Electronic configuration of two elements X and Y are 2, 5 and 2, 7, respectively. If these elements form
a covalent compound with each other, then the formula of the compound will be
(A) XY3
(B) X2Y3
(C) XY2
(D) XY
Q.9
(D) 2
1
5
(B)
1
4
(C)
1
2
(D)
3
4
(D) Fe
(D) BCl3
(C) BaCl2
(D) LiCl
(D) CCl4
Q.19 Element X is strongly electropositive and Y is strongly electronegative. X and Y are monovalent, then
the compound formed from them will be
(A) X+ Y
(B) X - Y+
(C) X - Y
(D) X Y
Q.20 Which of the following statements is correct ?
(A)
all the covalent compounds are solids at room temperature
(B)
all the compounds of hydrogen are solids
(C)
all the halogen compounds are ionic
(D)
all the salts are generally ionic in nature
Q.21 The valency of B in BCl3 is 3. This is justified on the basis of
(A) resonance
(B) hybridisation
(C) electronic configuration
(D) shielding effect
66
CHEMICAL BONDING
(D) CCl4
Q.27 Which of the following molecules does not have co-ordinate bond
(A) SO2
(B) O3
(C) CH3NC
(D) CO2
(B) N N
(C) N = Y
(D) NX3
(C) resonance
(D) hybridisation
67
CHEMICAL BONDING
Q.37 Dimethyl ether is a gas and the boiling point of ethanol is 78, whereas molecular formula and molecular
weight of both the compounds are same. What is the region ?
(A) H-bonding in ethanol
(B) presence of covalent bond in ethanol
(C) ionic character of ethanol
(D) basic nature of dimethyl ether
Q.38 BeCl2 has which of the following types of orbital overlap ?
(A) sp2 p
(B) sp p
(C) sp3 p
(D) s p
Q.40 In which of the following, the hybridisation has not taken place ?
(A) C2H2
(B) SO2
(C) KCl
(D) NH4+
(D) XeF4
(D) OF2
Q.43 Atomic numbers of two atoms X and Y are 1 and 8, respectively, then what will be the formula of the
compound formed from them ?
(A) XY
(B) X2Y & X2Y2
(C) XY3
(D) X2Y
Q.44 Which of the following has minimum melting point ?
(A) Cu2Cl2
(B) CuCl2
(C) CaCl2
(D) KCl
Q.46 Iodine shows sp3d3 hybridisation in which of the following excited states ?
(A) III
(B) II
(C) I
(D) normal state
Q.47 According to Sudgen, the compound having a one electron bond is
(A) NCl3
(B) PCl5
(C) B2H6
(D) AlCl3
(C) AsH3
(D) SbH3
(C) As2O3
(D) Sb2O3
(D) NO
Q.53 Supposing that, an atom can be stabilised by 6 electrons and not by an octet, then the most stable
structure of N will be
(A) N+
(B) N
(C) N2
(D) N+2
Q.54 Correct order of boiling points of H2, Cl2 and Br2 is
(A) H2 < Cl2 < Br2
(B) Cl2 > Br2 > H2
(C) H2 > Cl2 < Br2
NARAYANA II T ACAD EMY- C P 3 ,
68
CHEMICAL BONDING
Q.55 The cation having ns2, np6, ndx configuration in which 2 + 6 + x = 9 to 18, are generally formed by
(A) alkali metals
(B) alkaline earth metals
(C) transition elements
(D) inner transition elements
Q.56 Total number of lone pairs in N2H4 should be
(A) 3
(B) 2
(C) 1
(D) 5
(D) SO3
(C) BeF2
Q.58 A covalent compound is good conductor of electricity. Which of the following is true for this
compound ?
(A) single macromolecule
(B) molecule formed by separate layers
(C) ionic molecule
(D) all of the above
Q.59 Which of the following starred atoms does not have a lone pair of electrons ?
(A)
(B)
(C)
(D)
Q.60 Which of the following cations is capable of maximum polarising the chloride ion ?
(A) Ca+2
(B) Zn+2
(C) Sr+2
(D) K+
Q.61 Most stable carbonate is
(A) CaCO3
(B) BaCO3
(C) SrCO3
(D) MgCO3
(D) C F
(C) N2O
(D) 4
(D) Na2S
(C) both
(D) none
(C) AlCl3
(D) SO2
Q.71 In which of the following the angle between the two covalent bonds is greatest ?
(A) H2O
(B) NH3
(C) CO2
(D) CH4
69
CHEMICAL BONDING
Q.72 AsF5 molecule is trigonal by pyramidal. The orbitals of As atom involved in hybridization are
(A) d x 2 y 2 , d z 2 , s, px, py
(B) dxy, s, px, py, pz
(D) d x 2 y 2 , s, p x , p y , p z
(D) N2+
Q.74 The compound which does not obey the octet rule is
(A) OF2
(B) SO2
(C) PCl3
(D) SnCl4
(D) O22
Q.76 Which of the following statements is not correct for sigma and pi bonds formed between two carbon
atoms?
(A)
Sigma-bond determines the direction between carbon atoms but a pi-bond has no primary
effect in this regard.
(B)
Sigma-bond is stronger than a pi-bond
(C)
Bond energies of sigma-and pi-bonds are of the order of 264 kJ/mol and 347 kJ/mol,
respectively
(D)
Free rotation of atoms about a sigma-bond is allowed but not in case of a pi-bond
Q.77 Which contains both polar and non-polar covalent bonds
(A) NH4Cl
(B) HCN
(C) H2O2
(D) CH4
Q.80 The lowest bond energy exist in the following bonds for
(A) C C
(B) N N
(C) H H
(D) O O
(D) 14
(C) metallic
(D) co-ordinate
Q.84 Among LiCl, BeCl2, BCl3 and CCl4, the covalent bond character follows the order
(A) LiCl > BeCl2 > BCl3 > CCl4
(B) LiCl < BeCl2 < BCl3 < CCl4
(C) LiCl > BeCl2 > CCl4 > BCl3
(D) LiCl < BeCl2 < BCl3 > CCl4
Q.85 The example of the p-p orbital overlapping is the formation of
(A) H2 molecule
(B) Cl2 molecule
(C) Hydrogen chloride
(D) hydrogen bromide molecule
Q.86 Which statement is not correct
(A) double bond is shorter than a single bond (B) sigma bond is weaker than pi-bond
(C) double bond is stronger than a sigma bond (D) covalent bond is stronger than hydrogen bond
70
CHEMICAL BONDING
(D) f
(C) AlBr3
(D) AlF3
(D) PCl5
(C) H2O
(D) O
Q.95 A molecule in which sp2-hybrid orbitals are used by the central atom in forming covalent bond is
(A) He2
(B) SO2
(C) PCl5
(D) N2
Q.96 Iron is tougher than sodium because
(A) iron atom is smaller
(C) metallic bonds are stronger in iron
(C) 4
(D) 8
Q.98 How many bonded electron pairs are present in IF7 molecule
(A) 6
(B) 7
(C) 5
(D) 8
(D) BF3
(C) CaF2
71
CHEMICAL BONDING
CHEMICAL BONDING
ANSWER KEY
PRAYAS-I
Q ue .
Ans
Q ue .
Ans
Q ue .
Ans
Q ue .
Ans
Q ue .
Ans
Q ue .
Ans
Q ue .
Ans
Q ue .
Ans
Q ue .
Ans
Q ue .
Ans
1
C
11
A
21
A
31
A
41
D
51
C
61
A
71
B
81
B
91
A
2
A
12
B
22
B
32
A
42
A
52
A
62
D
72
D
82
C
92
A
3
D
13
B
23
A
33
D
43
A
53
D
63
B
73
D
83
A
93
C
4
D
14
A
24
C
34
D
44
B
54
B
64
B
74
A
84
B
94
A
5
C
15
D
25
C
35
B
45
B
55
B
65
B
75
B
85
B
95
C
6
B
16
A
26
A
36
A
46
A
56
B
66
A
76
C
86
A
96
C
7
C
17
C
27
D
37
A
47
C
57
C
67
D
77
A
87
A
97
A
8
B
18
B
28
A
38
C
48
B
58
A
68
D
78
C
88
A
98
C
9
A
19
B
29
A, B
39
D
49
D
59
C
69
C
79
C
89
C
99
A
10
A
20
A
30
A
40
D
50
B
60
B
70
C
80
A
90
C
10 0
C
7
D
17
D
27
D
37
A
47
B
57
D
67
D
77
C
87
A
97
C
8
A
18
B
28
A
38
B
48
A, D
58
B
68
A
78
A
88
C
98
B
9
A
19
A
29
B
39
B
49
A
59
C
69
B
79
C
89
C
99
D
10
A
20
D
30
A
40
C
50
A
60
B
70
B
80
D
90
A
100
B
PRAYAS-II
Q ue .
Ans
Q ue .
Ans
Q ue .
Ans
Q ue .
Ans
Q ue .
Ans
Q ue .
Ans
Q ue .
Ans
Q ue .
Ans
Q ue .
Ans
Q ue .
Ans
1
D
11
C
21
B
31
A
41
A
51
D
61
B
71
C
81
A
91
B
2
B
12
A
22
A
32
A
42
C
52
D
62
D
72
C
82
C
92
B
3
D
13
A
23
A
33
A
43
B
53
B
63
B
73
A
83
B
93
D
4
D
14
A
24
D
34
B
44
B
54
A
64
C
74
B
84
B
94
B
5
A
15
D
25
B
35
D
45
D
55
C
65
B
75
C
85
B
95
B
6
A
16
B
26
B
36
B
46
A
56
B
66
B
76
C
86
B
96
C
72
CHEMICAL BONDING
PARIKRAMA - I
Q.1
Why the atoms of noble gases do not react with other atom to form compounds ?
Q.2
Why ? The ionic bond is called a non directional but covalent bond is called a direction bond.
Q.3
Q.4
Q.5
Why ionic compound do not conduct electricity when they are in the solid state ?
or
Q.6
Why the ionic solid conduct electricity when they are in water solution or in molten state ?
or
Q.7
Why the ionic solids are soluble in polar solvent like H2O. ?
or
Q.8
Q.9
Q.10 Explain why ionic solids are not soluble in non polar solvents ?
Q.11
73
CHEMICAL BONDING
PARIKRAMA -II
Q.1
Q.2
Why Co+3 ion is form with great difficulty but Fe+3 is not ?
Q.3
Q.4
Q.5
Explain why Cu+ cation polarises the anions more strongly than Na+ cation even both have +1 charge?
Q.6
Why Ag+ (cation) 4s2p6d10 has greater polarising power than K+ (cation) 3s2p6 ?
Q.7
Why Li+ compounds are soluble in non polar solvent but not in polar solvents ?
Q.8
74
Q.9
CHEMICAL BONDING
Why metals have intermediate melting and boiling point as compared to those of covalent and ionic
compounds ?
Q.12 Explain why melting point of o-nitrophenol is lesser than m and p-isomers ?
or
o-nitrophenol is volatile in steam and less soluble in water than the other two isomers ?
Q.13 Boiling point of hydrides of VA, VIA & VIIA decrease from top to bottom but NH3, H2O & HF show a
sudden increase why ?
Q.14 Explain why glycerol (CH2(OH) CH(OH) CH2(OH)) have more viscosity, high heat of vaporisation
and high dielectric constant ?
Q.15 The density of ice is less then that of water or ice floats over water. Explain ?
Q.16 Methanoic acid, HCOOH, has one carbon-oxygen bond of length 123 pm, and another of 136 pm.
Which bond has which length ?
Q.17 Both carbon-oxygen bonds in the methanoate ion, HCOO, have the same length (127 pm). What
does this tell about bonding ?
Q.18 Water can react with hydrogen ion to make the oxonium ion, H3O+. What is present in water molecule
that allows it to react with a hydrogen ion ? Describe the bonding in the oxonium ion. Draw a dot and
cross diagram for the molecule ?
Q.19 Why MgCl2 is linear but SnCl2 is angular ?
Q.20 Why NCl5 does not exist while PCl5 does ?
Q.21 Why Lead prefers to form divalent compounds ?
Q.22 Why CH4, NH3 and H2O contain same number of electron but their shapes are different ?
Q.23 Why Calcium fluoride is more ionic than CaI2 ?
Q.24 Why Ammonium salts are much more soluble in water than the corresponding sodium salts ?
Q.25 Why Carbon has two electrons unpaired in the outer most, but it forms tetravalent in organic compounds ?
Q.26 The electronegativities of nitrogen and chlorine are same but NH3 exists as liquid whereas HCl as gas.
Why ?
Q.27
Although CO2 has no dipole moment, SO2 and H2O have considerable dipole moments. Why?
Q.28 Nitrogen trifluoride (NF3) and ammonia (NH3) have identical shape and a lone pair of electrons on
nitrogen and further the electronegativity difference between the elements is nearly the same but the
dipole moment of NH3 is very high in comparison to NF3. Why ?
Q.29 Why Three carbon-oxygen bonds are equal in carbonate ion ?
Q.30 Why NF3 is weaker base than NH3, NCl3, NBr3 and NI3 ?
Q.31 Why BaSO4 is insoluble in water ?
Q.32 Why compounds of normal elements are diamagnetic ?
Q.33 Why IF7 is exist but ClF7 is not.
NARAYANA II T ACAD EMY- C P 3 ,
75
CHEMICAL BONDING
Q.34 Which among the following has highest boiling point and why ?
H2, He, Ne, Xe, CH4
Q.35 At room temperature, NO2 gas is paramagnetic in nature. When it is cooled below 0C acquires
diamagnetic behaviour. Explain this observation on the basis of structure ?
Q.36 Explain why the super oxides KO2, RbO2 and CsO2 are paramagnetic ?
Q.37 NH4+ has bond angle identical to CH4 but NH3 has different bond angle; explain with proper reasoning ?
Q.38 Explain why ClF2 is linear but ClF2+ is bent molecular ion ?
Q.39 Ether
and water
Q.42 Which among the following will have the highest melting point ?
PH3, NH3, (CH3)3N
Q.43 Discuss the hybridization and shape of the molecule
76
CHEMICAL BONDING
SOLUTIONS (Parikrama I)
Ans.1 Because the outer most electron configuration of the atoms of noble gas is a stable configuration of 8
electron which is also called octet.
Ans.2 Because in ionic bond, an ion can attract other opposite charged ions from any direction and extends
equally in all directions so the nature of ionic bond is non-directional, but on the other band a covalent
bond is formed by the proper overlapping of orbitals so it have directional character.
Ans.3 A/c to the force of attraction between constituent ions.
q1q 2
qq
1 2 2
2
d
(rA rB )
The electric charge on doubly charged Mg+2 and doubly charged O2 ion in Mg+2O2 ionic crystal is 4
times greater than between monovalent Na+ and Cl ions in Na+ Cl
Ans.5 Because Na+ is smaller than Cs+ ion so the force of attraction between Na+Cl ion in NaCl is higher than
attraction between Cs+Cl in CsCl. So NaCl have high lattice energy then CsCl and have greater
stability.
Ans.6 Due to the following two reasons (i) Unstable configuration of the core (Kernal)
(ii) Inert electron pair effect.
Ans.7 Because in the crystal lattice the cation and anions are tightly held together with each other so the ions
therefore ; can not move freely to any large extent when an electric current is passed through the ionic
solids.
Ans.8 Because when the ionic compound goes in to the molten state. The kinetic energy of ions becomes so
high that the attractive forces acting between the ions are over come so the arrangement of ions in
crystal is destroyed and the ions become free to move in liquid medium.
Ans.9 The electrostatic force between cation and anions is reduced by the high dielectric constant value of
polar solvent. Ions are move freely and interact with solvent molecule to form the solvated ions.
Ans.10 The water molecule is a dipole and hence the positive end of water dipole interact with the negative ion
of the ionic solids and the negative ion of the ionic solids and the negative end of the dipole interacts with
the positive ion of the same ionic crystals.
Ans.11 For an ionic solid to dissolve in a polar solvent the solvation energy of the solvent must be greater than
the lattice energy of the ionic solid so that the solvation energy may overcome the lattice energy.
Ans.12 Because the force of attraction between adjacent covalent molecules is weak.
Ans.13 Because these compounds having the layer lattices (graphite) and they have a free electrons which are
good conductors of electricity. In such solids electrons can pass from one layer to the other and thus
current can be carried.
Ans.14 Due to the similarity in covalent nature of the molecule of the solute and solvent their solubility is based
on the principle like dissolves like.
Ans.15 This is due to the fact because due to their big size, are not able to interact with the solvent molecule.
Ans.16 Because there are weak forces holding the molecules in solid crystal. A molecular layer in the crystal
easily slips relative to other adjacent layer and there are no forces of repulsion between the other layers
like those in ionic compound.
NARAYANA II T ACAD EMY- C P 3 ,
77
CHEMICAL BONDING
Ans.17 Because there are no strong electrical force is present to speed up the reaction between molecules.
Ans.18 Because ionic bonds are not rigid and non-directional but covalent bond are region and directional.
Ans.19 Because if an alloying metal is added to a metal. The structural homogeneity of the principal metal is
disturbed and hence the resulting allow is hard and brittle.
Ans.20 It is due to the great attraction between the positive metal ion and the mobile electron.
Ans.21 Due to the presence of the delocalised, electron (mobile electron) the attraction force between valence
electron and the nuclei is weak but on the other hand is covalent bond due to the presence of localised
electron there is more attraction between valence electron and nuclei is develop and thus covalent bond
is stronger than metallic bond.
Ans.22 It is due to their high electronegativity and small atomic size.
Ans.23 It is due to the presence of vacant d-orbitals in PH3 and H2S. In H2O due to more electronegativity of
O than N. Electron losing capacity of H2O will be less than NH3.
Ans.24 This is due to fact that the metal bond keeps the metal atoms closely packed in the metallic crystal.
Ans.25 Because the strength of metallic bond increases with increase of valence electrons and we know that
alkaline earth metals have two and alkali metals have one valence electron.
Ans.26 Because the size of Li+, Na+ and K+ ion is in the order.
Li+ < Na+ < K+
Ans.27 Due to the high electronegativity of O-atom than S, Se and Te. H2O molecule associate to form a
polymerised molecule while H2S, H2Se and H2Te cannot do so.
Ans.28 With increase of vander wall forces the boiling point or melting point of a substance also increase.
Ans.29 Because the overlapping of orbital involves a release of energy. This show that the formation of covalent bond is always accompanied by evolution of energy and thus stablilises the molecules.
Ans.30 Because -bond is formed by the side to side overlapping between two p-orbital which much less
effective than -bond which formed by the head to head overlapping between p-orbitals.
Ans.31 When the atoms combined together to form molecule there is always release of energy. Thus potential
energy of molecule is less than that of uncombined atoms and therefore, the molecule is more stable.
Ans.32 Because solid sodium chloride has crystalline structure in which the ions are not free to move the ion
become mobile when it is in molten state and thus the electricity can be conduct.
Ans.33 Because oxygen has high electronegativity than sulphur. As a result, H2S forms hydrogen bonding so
molecule of water come nearer to each other through hydrogen bonding. This results in higher boiling
point of water and hence it is a liquid.
Ans.34 Both are triangular and symmetrical molecules their dipole moment are zero.
Ans.35 The stability is explained by symmetrical linear structure of BeF2 and triangular planer structure of BF3.
BeF2 is more stable because of its greater bond angle (180).
Ans.36 The non-bonded orbitals relatively occupy space compared to the bonded orbitals and thus repulsion
are greater.
Ans.37 Because there are no d-orbitals in oxygen and hence it can not extend it/s covalency but vacant dorbitals are present in S are paired orbitals can be unpaired by shifting electrons to d-orbital so either
making four orbitals singly occupied or six orbitals singly occupied showing valency 4 or 5 besides ?
NARAYANA II T ACAD EMY- C P 3 ,
78
CHEMICAL BONDING
Ans.38 HCl is a covalent compound and in gaseous state it does not conduct current. In water however it react
to form ions, HCl + H2O
H3+O + Cl and thus conduct current.
Ans.39 Because diamond is a giant molecule-three dimensional figure as every carbon is sp3 hybridised so one
carbon atom is linked to four other carbon atoms tetrahedrally. Due to continuous covalent bonding all
the atoms are held very closely are strongly as a result diamond is a very hard solid with a very high MP.
It is non conductor as free electrons are not available.
Ans.40 Due to large size of Cl ion than F ions there is greater degree of distortion in AlCl3.
Ans.41 Ge Ge < Si Si < C C
Bigger is the atomic size lower is the bond strength.
Ans.42 Intermolecular distance is high in gaseous state, low in solid state and inter mediate in liquid state. When
molecular weight increases, vander waal's forces also increases. So F2 and Cl2 are gases due to the
weak vander waals forces and I2 is solid.
Ans.43 CO2 has only weak vander waals forces but in SiO2, one silicon atom is surrounded by four oxygen
atoms tetrahedrally forming macromolecular string So SiO2 is solid.
Ans.44 Because H-bonding present in NH3, while PH3 is non polar due to same value of electronegativity of P
and H.
Ans.45 HI < HBr <HCl < HF.
It is because that the electronegativity difference is maximum in H and halogen atom.
Ans.46 H2Se < H2S < H2O. This is because the increasing electronegative difference between H atom and
O, S and Se atom.
Ans.47 PCl3 > NCl3, Because electronegativity difference of P and Cl is greater than N and Cl.
Ans.48 NH3 is more polar than NCl3 SO bond energy of N F will be higher.
Ans.49 String of PCl5 is unsymmetrical because the value of bond angles are different.
79
CHEMICAL BONDING
+B
A + B
IInd step In this the two electrons one each with A+ & B are shared by both the ion in this step is
similar to the formation of covalent bond.
A + B
Thus we say that a co-ordinate bond is equivalent to a combination of an electrovalent bond (polar
bond) and a covalent bond (non polar bond) so it is called semi polar bond.
Ans.10 Because H-atom has small size with only one electron in its Ist energy level, when this electron is taken
away, the proton (H+) left behind which can easily manage between two electronegative atoms bringing
them closer together by creating electrostatic force.
Ans.11 This is due to the reason that the attractive forces (metallic bond) in metallic crystal are intermediate
between those in covalent and ionic compound.
Ans.12 Because in o-nitrophenol a six membered ring (chelation) is formed by intramoleculer H-bond so it
have different properties from those of other isomers. Because this type of bonding is not possible in m
& p-isomer because of the size of the ring that would result.
Ans.13 The abnormal high boiling point of NH3, H2O and HF are due to the fact that the molecule are capable
of forming the associated molecule as (NH3)x, (H2O)x, and (HF)x by H-bonding between them.
Ans.14 This is because of this fact that glycerol with three OH group in its molecule can for any H-bond per
molecule. This result in greater attraction among the molecule of glycerol. Thus it is more viscous, have
high heat of vapourisation and high dielectric constant.
Ans.15 In ice, water molecule is associated with four other water molecule through hydrogen bonding in a
tetrahedral manner and form open-cage like structure. When ice melts the molecule come closer to
each other so the density of water in liquid state is more than in solid state thus ice floats on water.
80
CHEMICAL BONDING
.
O H
The double bonded carbon oxygen bond is shorter than the other. A double bond between two atoms
is always stronger and shorter than a single bond between the same atoms and HCOO have same
bond length.
Each bond has part of the character of single bond and part of character of a double bond. The electron
are delocalised over the three atoms.
Ans.18 There are two lone pairs, but only one of them make a co-ordinate bond with an empty orbital on
hydrogen atom.
There are three bond in the H3O+ ion all the three are identical but two of them are covalent and one coordinate is the dot and cross diagram is
H O
81
CHEMICAL BONDING
Ans.22 Because the central atom in each of the three molecules CH4, NH3 and H2O undergoes sp3 hybridisation.
In CH4 no lone pair is present the. In NH3 one lone pair is present, while in water molecule two lone
pair are present. The lone pair and bond pair electrons repulsion changed the molecules shapes
Ans.23 Because the size of the I ion is bigger than F ion. In CaI2 therefor more polarisation is present thus
CaF2 is more ionic than CaI2.
Ans.24 Na+ ion is solvated by ion-dipole interaction while NH4+ ion is solvated by Hbonding which is a
stronger attraction force.
Ans.25 Since all the four valencies of carbon are identical, 2s electron is shifted to one of the vacant p-orbital
with the result four unpaired orbitals are present, these undergo hybridisation and form four hybrid
orbitals.
Ans.26 Because the size of nitrogen is less then the size of chlorine, therefore, electron density in nitrogen is
more than that of chlorine, so nitrogen forms H-bonding leading to association of molecules. Hence
NH3 is a liquid. H-bonding is not possible with chlorine.
Ans.27 CO2 has linear structure while SO2 and H2S have V-shaped string.
= 1.84
N
F
F
F
So according the structure the net dipole moment of NH3 is nearly zero by vector rule.
Ans.29 The carbonate ion exhibits resonance and all the three C O bonds are equal.
Ans.30 It is due to larger electronegativity of F atoms of NF3. The lone pair is most difficult to be donated.
Ans.31 In BaSO4, lattice energy is more than it hydration energy.
Ans.32 Because normal element acquire inert gas configuration in compounds so all the orbitals are double
occupied and thus compound are diamagnetic.
Ans.33 IF7 is exist because electro negative difference & size of iodine is big which is help to expansion of
iodine orbital is possible but not in Cl.
Ans.34 Xe, it has highest vander waal's force because of having more electron.
82
CHEMICAL BONDING
Chlorine atom lies in sp3 hybrid state. Two lone pairs are oriented along two corners of tetrahedra.
[ClF2+]
Ans.39 In H2O, bond angle is less than 10928 due to lone pair and bond pair repulsion but in ether due to
strong mutual between two alkyl groups bond angle become greater than 10928.
Ans.40 In N(CH3)3; there is sp3 hybridisation at nitrogen but due to lone pair bond pair repulsion shape becomes pyramidal.
In tri silyl ammonia, there is vacant d-orbital at silicon hence, formation p d back bonding take
place and geometry becomes planar.
83
CHEMICAL BONDING
Ans.41 This molecule has bridged carbon with three centred bonding. Thus, covalency of carbon is maintained.
Ans.42 NH3, due to the presence of H bonding.
Ans.43
All fluorine atom do not lie in plane molecule is not symmetrical thus it will be polar.
Ans.44 Because H2O2 decomposes readily to H2O at room temperature
2H2O2
2H2O + O2
Ans.45 OF2 > ClO2
Because electronegativity difference in F O is greater is greater than in O Cl.
Ans.46 Because both the bonds, are physical bonds.
Ans.47 I is largest, so polarisation of I by Ag+ is maximum and the shared electrons are easily transferred to
higher energy level in visible light. So AgI is deep yellow, but in chloride; electrons are not transferrer
easily so AgCl is colourless.
Ans.48 In CCl4
(i) Octet of C is complete
(ii) there is no electron pair on C
(iii) there is no vacant d-orbital.
so CCl4 neither donates nor accepts electron and thus does not react with water.
In SiCl4 due to presence of vacant d-orbital in Si. It accept electrons and thus reacts with OH of water
and forms Si(OH)4 (unstable) which gets converted to more stable SiO2 by loss of two water molecule.
Ans.49 Because oxygen is a second period element, so due to absence of 3d orbitals the valency of oxygen will
not be six. But in sulphur due to presence of 3d orbitals the valency of sulphur may be six
84
CHEMICAL BONDING
(D) 14.6,14.6
(D) none
(D) P, Si, N, C
Q 4.
The bond between carbon atom (1) & carbon atom (2) in compound
N C-CH = CH2 involves the hybrids as:
1 2
(A) sp2 & sp2
(B) sp3 & sp
(C) sp & sp2
(D) sp & sp
Q 5.
(D) NI3
(D) Triethylamine
Q 6.
Q 7.
Q 8.
Silver chloride is sparingly soluble in water because its lattice energy is greater than _______ energy.
Q 9.
Q 10. In benzene carbon uses all the three p-orbitals for hybridisation.
Q 11. sp2 hybrid orbitals have equal S & P character.
Q 12. In group I A of alkali metals, the ionisation potential decreases down the group. Therefore lithium is a
poor reducing agent.
Q 13. Explain the molecule of magnesium chloride is linear whereas that of stannous chloride is angular.
1988
Q 14. Give reason carbon oxygen bond lengths in formic acid are 1.23 A0 & 1.36 A0 and both the carbon
oxygen bonds in sodium formate have the same value i.e. 1.27 A0.
Q 15. Give reason that valency of oxygen is generally two whereas sulphur shows of 2, 4 & 6.
Q 16. The first Ionization potential of Na, Mg, Al & Si are in the order
(A) Na < Mg > Al < Si
(B) Na > Mg > Al > Si
(C) Na < Mg <Al > Si
(D) Na > Mg > Al < Si
Q 17. The species which the central atom uses sp2 hybrid orbitals in its bonding is
(A) PH3
(B) NH3
(C) CH3+
(D) SbH3
Q 18. The molecule that has linear structure is
(A) CO2
(B) NO2
(C) SO2
(D) SiO2
85
CHEMICAL BONDING
Q 19. The statements that are true for the long form of the P.T.are
(a)
It reflects the sequence of filling the electrons in the order of sub-energy levels s, p, d & f
(b)
It helps to predict the stable valency states of the elements
(c)
It reflects trends in physical & chemical properties of elements
(d)
It helps to predict the relative ionicity of the bond between any two elements.
Q 20. Arrange N2, O2, F2, Cl2 in increasing order of bond dissociation energy.
Q 21. Arrange CO2, N2O5, SiO2, SO3 is the increasing order of acidic character.
Q 22. Arrange HOCl, HOClO2, HOClO3, HOClO in increasing order of thermal stability.
1989
Q 23. Explain the first I.E. of carbon atom is greater than that of boron atom whereas the reverse is true for
the second I.E.
Q 24. The compound which has zero dipole moment is
(A) CH2Cl2
(B) BF3
(C) NF3
(D) ClO2
(C) CO
(D) NO+
(C) CO32-
(D) NO3-
Q 27. The compound in which *C uses its sp3 hybrid orbitals for bond formation is :
(A) H*COOH
(B) (H2N)*CO
(C) (CH3)3*COH
(D) CH3*CHO
Q 28. The C - H bond distance is the longest in
(A) C2H2
(B) C2H4
(C) C2H6
(D) C2H2Br2
(D) Na+
(D) 6 sigma 4 pi
Q 31. Sodium sulphate is soluble in water whereas Barium sulphate is sparingly soluble because
(A)
the hydration energy of sodium sulphate is more than its lattice energy
(B)
the lattice energy of barium sulphate is more than its hydration energy
(C)
the lattice energy has no role to play in solubility
(D)
the hydration energy of sodium sulphate is less than its lattice energy
Q 32. All the Al - Cl bond in Al2Cl6 are equivalent
Q 33. Both potassium ferrocyanide & potassium ferricyanide are diamagnetic
1990
Q 34. Amongst the following the one having highest I.E. is
(A) [Ne] 3 s2 3 p1
(B) [Ne] 3 s2 3 p3
(C) [Ne] 3 s2 3 p2
(D) [Ar] 3 d0 4 s2 4 p3
86
CHEMICAL BONDING
1991
Q 38. The hybridisation of C atoms in C-C single bond of HC C - CH = CH2 is
(A) sp3 - sp3
(B) sp2 - sp3
(C) sp- sp2
(D) sp3 - sp
Q 39. The linear structure is assumed by :
(A) SnCl2
(B) NCO-
(D) NO2+
(C) CS2
(E) SO2
Q 40. Nitric oxide, though an odd electron molecule , is diamagnetic is liquid state
Q 41. Arrange the following as stated.
(i) Increasing order of ionic size :
N3- , Na + , F- , O2- , Mg2+
(ii) Increasing order of basic character : MgO, SrO, K2O, NiO, Cs2O
(iii) Increasing strength of H - bonding . (X...H - X) O, S, F, Cl, N
(iv) Increasing order of extent of hydrolysis CCl4, MgCl2, AlCl3, PCl5, SiCl4
Q 42. Write two resonance structures of ozone which satisfy the octet rule.
1992
Q 43. The statement that is not correct for the periodic classification of element is :
(A)
The properties of elements are periodic functions of their atomic number
(B)
Non metallic elements are lesser in number than metallic
(C)
The IE1 of elements along a period do not vary in a regular manner with increase in atomic
number
(D)
For transition elements the d-subshells are filled with electrons monotonically with increase
in atomic numbers
Q 44. The type of hybrid orbitals used by the chlorine atom in ClO2- is
(A) sp3
(B) sp2
(C) sp
(D) none
Q 45. The CN- & N2 are isoelectronic. But in contrast to CN- , N2 is chemically inert because of
(A)
Low bond energy
(B)
Absence of bond polarity
(C)
Unsymmetrical electron distribution
(D)
Presence of more number of electron in bonding orbitals
Q 46. The maximum possible number of hydrogen bonds a water molecule can form is
(A) 2
(B) 4
(C) 3
(D) 1
Q 47. The species that do not contains peroxide ions are
(A) PbO2
(B) H2O2
(C) SrO2
(D) BaO2
(D) CN+
Amongst the three isomers of nitrophenol, the one that is least soluble in water is _______ .
87
CHEMICAL BONDING
1993
Q51.
Q52.
Q53.
The basic nature of hydroxides of group 13 (IIIB) decreases progressively down the group.
Q54.
Q55.
Q56.
Q57.
The D.M. of KCl is 3.336 10-29 Coulomb-metre which indicates that it is highly polar molecule. The
interatomic distance between K+ and Cl in this molecule is 2.6 10-10m. Calculate the dipole moment
of KCl molecule if there were opposite charges of one fundamental unit located at each nucleus. Calculate
the % ionic character of KCl.
1994
Q58.
Q59.
The two types of bonds present in B2H6 are covalent and _________.
Q60.
Q61.
Using VSEPR theory, identify the type of hybridisation and draw the structure of OF2. What are
oxidation states of O and F.
1995
Q62.
Q63.
The experimentally determined N-F bond length in NF3 is greater than the sum of single bond covalent
redii of N and F. Explain.
1996
Q64.
Explain why the dipole moment of NH3 is more than that of NF3.
Q65.
The order of increasing thermal stabilities of K2CO3, MgCO3, CaCO3, BaCO3 is _____
Q66.
Q67.
(i)
The number and type of bonds between two C-atom in CaC2 are
(A) 1 sigma 1 pi
(B) 1 sigma 2 pi
(C) 1 sigma 1 and half pi (D) 1 sigma
(ii)
Which is correct for CsBr3.
(A) it is a covalent compound
(C) it contains Cs+ and Br3- ions
Q68.
Q69.
When N2 goes to N2+, the N-N distance ________ and when O2 goes to O2+, the O-O bond distance
__________.
Q70.
88
CHEMICAL BONDING
Q71.
Compare qualitatively the Ist and IInd IP of Cu and Zn. Explain the observation.
Q72.
Q73.
Q74.
(C) ZnO
(D) PbI4
(D) SiO2
1997
Q75.
Q76.
Q77.
Property of the alkaline earth metals that increases with their atomic number is
(A) IE
(B) solubility of their hydroxides
(C) solubility of their sulphates
(D) electronegativity
Q78.
Among N2O, SO2, I3+ and I3-, the linear species are ________ and _________.
Q79.
Among PCl3, CH3+, NH2- and NF3, __________ is least relative towards water.
Q80.
Q81.
Among the following compounds the one that is polar and has the central atom with sp2 hybridisation is
(A) H2CO3
(B) SiF4
(C) BF3
(D) HClO2
Q82.
(D) CH4
Q83.
The critical temp. of water is higher than that of O2, because the H2O molecule has:
(A) Fewer electron than O2
(B) 2 covalent bonds
(C) V shape
(D) dipole moment
Q84.
(C) N2O
(D) CO
Q85.
Compounds that formally contain Pb4+ are easily reduced to Pb2+. The stability of lower oxidation state
is due to ______________.
Q86.
Q87.
Q88.
Anhydrous AlCl3 is covalent. From the data given below predict whether it would remain covalent or
become ionic in aqueous solution. [IE for Al = 5137 kJ/mol]
H hydration for Al3+ = 4665 kJ/mol; Hhydra for Cl- = -381kJ/mol.
89
CHEMICAL BONDING
1998
Q89.
The geometry and the type of hybrid orbitals present about the central atom in BF3 is
(A) linear, sp
(B) trigonal planar, sp2
(C) tetrahedra sp3
(D) pyramidal, sp3
Q90.
Q91.
Interpret the non-linear shape of H2S molecule and non planar shape of PCl3 using VSEPR theory.
Q92.
1999
Q93.
(i)
(ii)
The correct order of increasing C-O bond length of, CO, CO32-, CO2 is
(A) CO32- < CO2 < CO
(B) CO2 < CO32- < CO
2(C) CO < CO3 < CO2
(D) CO < CO2 < CO32In the dichromate anion
(A) 4 Cr - O bonds are equivalent
(C) all Cr - O bonds are equivalent
(iii)
(iv)
In compounds type E Cl3, where E = B, P, As or Bi, the angles Cl-E-Cl for different E are in the order
(A) B >P = As = Bi
(B) B > P >As > Bi
(C) B < P = As = Bi
(D) B < P < As <Bi
(v)
(vi)
Ionic redii of
(A) Ti4+ < Mn7+
(vii)
(viii)
Discuss the hybridisation of C - atoms in allene (C3H4) and show the - orbital overlaps.
(xi)
2000
Q94.
(i)
(ii)
90
CHEMICAL BONDING
(iii)
The hybridisation of atomic orbitals of N in NO2+, NO3 and NH4+ are respectively.
(A) sp, sp3, sp2
(B) sp, sp2, sp3
(C) sp2, sp, sp3
(D) sp2, sp3, sp
(iv)
(v)
Q95.
Q96.
Amongst H2O, H2Se and H2Te the one with the highest boiling point is
(A) H2O of H-bonding
(B) H2Te of higher molecular weight
(C) H2S of H-bonding
(D) H2Se of lower molecular weight
Q97.
Write the M.O. electron distribution of O2. Specify its bond order and magnetic property.
Q98.
Draw the molecular structures of XeF2, XeF4 and XeO2F2, indicating the location of l.p. of electrons.
Q99.
Give reason why elemental nitrogen exists as a diatomic molecules where as elemental phosphorus is a
tetratomic molecule.
(C) 1
(D) zero
Q102. The common features of the species CN, CO, NO+ are
(A) bond order three and isoelectric
(B) B.O. = 3 and weak field ligand
(C) B.O. 2 and acceptor
(D) isoelectric and weak field ligands.
Q103. Between SiCl4 and CCl4 only SiCl4 reacts with H2O.
Q104. SiCl4 is ionic and CCl4 is covalent.
Q105. The complex ion which has no. d e- in the central atom is
(A) [MnO4]
(B) [Co(NH3)6]3+
(C) [Fe(CN)6]3
(D) [Cr(H2O)6]3+
(D) Fe>Si>C
(C) B>C>N
Q107. The correct order of hybridisation of the central atom in the following species NH3, [PtCl4]2-, PCl5 and
BCl3 is
(A) dsp2, dsp3, sp2, sp3
(B) sp3, dsp2, dsp3, sp2
2
2
3
3
(C) dsp , sp , sp , dsp
(D) dsp2, sp3, sp2, dsp3
Q108. The correct order of radii is
(A) N<Be<B
(B) F<O2<N3
(C) Na<Li<K
(D) Fe3+<Fe2+<Fe4+
(D) four
Q 110. The hybridisation of atomic orbitals of Nitrogen in NO2+, NO3- and NH4+ are
(A) sp, sp3, sp2
(B) sp, sp2, sp3
(C) sp2, sp, sp3
(D) sp2, sp3, sp
Q 111. The correct order of acid strength is
(A) Cl2O7 > SO2 > P4O10
(C) Na2O > MgO > Al2O3
NARAYANA II T ACAD EMY- C P 3 ,
91
CHEMICAL BONDING
2001
Q 119. Draw the structure of Diborane.
Q 120. State hybridisation of Cr in [Cr(NH3)4Cl2]Br and [Cr(NH3)4ClBr] Cl. Calculate their magnetic moments
(spin-only).
Q 121. Specify the coordination geometry around and hybridisation of N and B atoms in a 1 : 1 complex of
BF3 & NH3.
(A) N : tetrahedral sp3, B: tetrahedral sp3
(B) N : pyramidal sp3, B: pyarmidal sp3
(C) N : planar sp3, B: planar sp3
(D) N : pyramidal sp3, B: tetrahedral sp3
Q 122. Identify the correct order to solubility of Na2S, CuS and ZnS in aq. medium
(A) CuS > ZnS > Na2S
(B) ZnS > Na2S > CuS
(C) Na2S > CuS > ZnS
(D) Na2S > ZnS > CuS
Q 123. Identify the correct order of boiling point of
CH3 CH2 CH2 CH2 OH;
CH3 CH2 CH2 CHO;
(A) 1> 2> 3
(B) 3> 1> 2
(C) 1> 3 > 2
Q 124. Identify the correct order of acidic acid strengths , CO2 CuO, CaO, H2O
(A) CaO > CuO > H2O > CO2
(B) H2O < CuO < CaO < CO2
(C) CaO < H2O < CuO < CO2
(D) H2O < CO2 < CaO <CuO
Q 125. Identify the least stable ion amongst the following
(A) Li(B) Be(C) B-
(D) C-
(D) O22-
92
CHEMICAL BONDING
2002
Q128. Specify the coordination geometry around and hybridization of N and B atoms in a 1 : 1 complex of
BF3 and NH3
(A)
N : tetrahedral, sp3 ; B : tetrahedral, sp3
(B)
N : pyramidal, sp3; B : pyramidal, sp3
(C)
N : pyramidal, sp3; B : planar, sp2
(D)
N : pyramidal, sp3; B : tetrahedral, sp3
Q129. Which of the following molecular species has unpaired electrons(s)?
(A) N2
(B) F2
(C) O2
(D) O22
2003
Q130. Among the following the molecule with the highest dipole moment is :
(A) CH3Cl
(B) CH2Cl2
(C) CHCl3
(D) CCl4
Q131. Which of the following represent the given mode of hybridisation sp2-sp2-sp-sp from left to right?
(A) H 2C CH C N
(B) HC C C CH
(C) H 2C C C CH 2
(D)
Q132. Using VSEPR theory, draw the shape of PCl5 and BrF5.
2004
Q133. The number of lone pair(s) of electrons in XeOF4 is
(A) 3
(B) 2
(C) 1
(D) 4
(D) H2S2O6
(C) H2S4O6
2005
Q.136 The number of radial nodes in 3s and 2p are respectively
(A) 2 and 0
(B) 2 and 1
(C) 1 and 2
(D) 0 and 2
Q.137 When three oxygen atoms of [SiO4]4 tetrahedral is shared then the nature of the silicate is
(A) Sheet silicate
(B) Pyrosilicate
(C) Three dimensional silicate
(D) linear chain silicate
Q.138 Thermodynamically most stable allotrope of phosphorus is
(A) Red
(B) White
(C) Black
(D) Yellow
Q.139 In which of the following the maximum number of lone pairs is present on the central atom?
(A) [ClO3]
(B) XeF4
(C) SF4
(D) I3
93
CHEMICAL BONDING
2.
3.
4.
Select any one set from the below for the correct option:
Molecule
Hybridisation
Shape
3
2
(A) OSF4
(i) sp d
(a) Bent-T shaped
(B) ClF3
(ii) sp3d
(b) see-saw
(C) BrF4
(iii) sp3d
(D) XeO2F2
(iv) sp3d2
Set-I
A-iv-b-1
B-i-D-2
C-iii-a-3
D-ii-c-4
Set-II
A-ii-c-1
C-iii-a-2
B-i-d-3
D-iv-b-4
Set-III
A-i-b-3
B-iii-a-4
C-iv-c-2
D-ii-d-1
Select any one set from the below for the correct option
Species
Bond order
Magnetic moment
(A) O2
(i) 0
(a) paramagnetic
(B) He2
(ii) 1.5
(b) diamagnetic
(C) O22
(iii) 2.5
(c) diamagnetic
+
(D) O2
(iv) 1
(d) paramagnetic
+
(E) H2
(v) 0.5
(e) paramagnetic
Set-A
Set-B
Set-C
A-iii-b-4
A-ii-a-2
A-v-e-3
B-i-c-2
B-i-b-1
B-iv-b-4
C-iv-a-3
C-iv-c-3
C-ii-a-2
D-ii-d-1
D-iii-d-5
D-iii-c-5
E-v-e-5
E-v-e-4
E-i-d-1
Compound
(A) SF4
(B) I3
(C) XeF6
(D) B2H6
Explanation
(1) Distorted due to
presence of S=O
(2) In sp3d hybridize molecule
follow bent rule
(3) One lone pair of e are
in axial position
(4) Two lone pair of e are in
axial position
Set-III
A-ii-b-2
B-i-c-4
C-iii-d-1
D-iv-a-3
No. of unpaired es
(1) no unpaired es
(2) one unpaired es
(3) no unpaired es
(4) one unpaired es
(4) one unpaired es
Set-D
A-iv-d-5
B-v-e-3
C-i-a-2
D-iii-b-1
E-ii-c-4
Structure
Hybridisaton
(i) Linear
(a) sp3d2
(ii) see-saw
(b) sp3d
(iii) tetrahedral
(c) sp3d3
(iv) distorted octahedral
(d) sp3
Set A
A-iii-c
B-i-d
C-ii-a
D-iv-b-1
Set B
A-i-a
B-ii-c
C-iii-d
D-iv-b
(I) NF3
(II) PH4
(A) 1023
(B) 109 s1
(C) (SiH3)3N
(D) N3
(C) 120
(iv) 18
Set C
A-ii-b
B-i-b
C-iv-c
D-i-d
Set D
A-iv-d
B-iii-a
C-i-b
D-ii-c
(a) Less than 109 due to l.p. b.p repulsion
(b) Tetrahedral sp3 hybridization absece of
lone pair
(c) Due to presence of p-d back bonding
(d) Linear shape due to sp hybridization
94
CHEMICAL BONDING
SU BJEC TIV E
1.
Name the principal ore of aluminium and describe how aluminium metal is extracted from this ore.
2.
Explain why aluminium, though an electropositive metal, finds extensive use as a structural material.
3.
4.
How is lighium aluminium hydride (LiAlH4) prepared ? What is its important use ?
5.
6.
Name the principal ores of tin and lead and described how these metals are extracted from their
respective ores.
7.
8.
9.
10.
How far do your agree with the concept of inert pair effect ? Justify your answer ?
11.
State the difference in teh properties and structures of white and red phosphorus.
12.
P4O10 + H2O
P4 + KOH + H2O
13.
14.
(e) POF3
15.
Calculate the volume of 0.1 M NaOH soltuion required to neutralised the solution produced by dissolving
1.1 g of P4O6 in water.
16.
17.
Using VSEPR theory, predict the probable structures of SO32-, IF6-, XeF2, ClO4- ICl4- and IBr2-
18.
19.
20.
21.
(e) H2SO3
95
CHEMICAL BONDING
22.
(b)
(d)
HF from CaF2
I2 from NaIO3
23.
Calculate the weight of HI obtained by the reaction of 62g of red phsophorus with iodine in th epresence
of water.
24.
25.
26.
How are xenon fluorides XeF2, XeF4 and XeF6 prepared ? Deduce their structures applyign VSEPR
theory.
27.
How are XeO3 and XeOF4 prepared ? Describe their molecule shapes
28.
29.
(c) HI and
30.
Arrange the following in the order of property indicated for each set
(a)
F2, Cl2, Br2, I2 - increasing bond energy
(b)
HF, HCl, HBr, HI
- increasing acid strength
(c)
M - F, M - Cl, M - Br, M - I - decreasing ionic character
(d)
As2O3, ClO2, GeO2, Ga2O3 - increasing acidity
(e)
NH3, PH3, AsH3, SbH3, BiH3 - increasing base strength
(f)
H2O, H2S, H2Se, H2Te - increasing acid strength
(g)
HOCl, HOClO, HOClO2, HOClO3 - increasing
(h)
HOCl, HOBr, HOI - increasing acid strength
31.
32.
33.
(b) SiF62-
(d) HClO4
(d) IF3
(d) NaClO4
(c) PF5
96
CHEMICAL BONDING
SO LU T IO N S
1.
The principal ore of aluminium is bauxite. It can extracted from bauxite in two stages. In first stage, pure
alumina is obtained from bauxite and in the second stage, electrolysis of Al2O3 in molten crystolite
(Na3AlF6) is carried out to obtained aluminium metal.
2.
Due to its highly electropositive nature it readily reacts with oxygen to form a hard protectie layer of
Al2O3 which renders it passive. So for this reason it is used as a structural material.
3.
As s2p1 grouping is present in the outermost shell of the group IIIa, the expected oxidising state Ar +3
and +1 . So +3 is more stable oxidising state for Al, Ga and In. But in higher p block element Tl
shows +1 stable oxidising due to inert pair effect.
4.
5.
(a)
(b)
(c)
(d)
6.
The principal ores of tin and lead are cassiterite (SnO2) and galena (PbS)
7.
9.
10.
In higher P-block element the lower oxidising is more stable due to inert pair effect.
11.
White
(i)
(ii)
(iii)
(iv)
12.
13.
Ca3(PO4)2
14.
P4
It is soft wary solid
soluble in Cs2
chemically active
unstable
Red P4
It is brittle powder
insoluble in Cs2
less active
stable
97
CHEMICAL BONDING
17.
18.
19.
(a)
SF6
x-6=0
x = +6
(c)
H2SO3
2+x-6=0
x = +4
21.
(a)
(b)
(c)
(d)
22.
(a) Chlorine gas is prepared in the laboratory by heating a mixture of mangnese oxide and concentration
HCl.
(b)
Na 2S2O 3
2 + 2x - 6 = 0
2x = 4
x = +2
CaSO4 + NF (g)
(c) I2 from sodium iodate
NaIO3(aq) + 3NaHSO3(aq) NaI (aq)
NaIO3 (aq) + NaI + H2SO4 I2 + H2O + Na2SO4
(d) HBr from NaBr
NaBr + H3PO4 heat
Na3PO4 + HBr
23.
Red phosphorus reacts with I2 to form PI3 which dissolves in water to from H3PO3 and HI
(i)
P4 + 6I2 4PI3
PI3 + 3H2O H3PO3 + 3HI ] 4
P4 + 6I2 + 12H2O 4H3PO3 + 12HI
1 mole
12 moles
1 mole of P4 = (= 4 31 g) gives 12 moles of HI = 12 128 g
98
CHEMICAL BONDING
1 gm of P gives =
12 128
g of HI
4 31
62 gm of P gives =
12 128
62 = 768 g of HI
4 31
24.
25.
26.
Preparation of xenon fluorides : Xenon forms three fluorides XeF2, XeF4, XeF6. These can be obtained
by the direct inter-action between xenon and fluorine under appropriate experimental conditions.
(i)
Xe + F2 XeF2
2 :1
(ii)
Xe + 2F2
XeF4
1 : 5
(iii)
Xe + 3F2 XeF6
1 : 20
99
CHEMICAL BONDING
Structure of XeF2 :
Total electron pairs
No. of lone pairs
Type of hybridization
Shape
XeF4
Total no. of electron pair
No. of lone pairs of electrons
Type of hybridization
Shape :
XeF6
total no. of electron pairs
No. of lone pairs of electrons
Type of hybridization
Shape
=5
=3
= sp3d
= Linear
=6
=2
= sp3d2
square plan
=7
=1
=1
= Distorted octahedral.
27.
28.
AsH3 [Arsine] can be prepared by the reaciton of hydrochloric acid on Zn3As2 [Zinc arsenide]
Zn3As2 + HCl(aq) 2AsH3 + 3ZnCl2(aq)
(b) Preparation of H3PO3
(i)
PCl3 + 3H2O H3PO3 + 3HCl
(ii)
P4O6 + 6H2O 4H3PO3
(c) Preparation of HI
2I2(s) + N2H4(aq) 4HI(aq) + N2(g)
(d) preparation of HClO4 :
Anhydrous NaClO4 is treat with conc HCl .
NaClO4 + HCl NaCl + HClO4
It can also be prepared by the reaction fo Barium perchlorae Ba(ClO4)2 with conc. HCl. The free acid
HClO4 explodes above 365 K, but it can be distilled at low temperatures under reduced pressure.
29.
(a) Molecular shape of SbF3 : Sb undergoes sp3 hybridization. Three of the 4 sp3 hybrid orbitals
from three s bonds (S-F) with 3 halogen atoms, while the 4th sp3 hybrid orbital contains the lone pair of
electrons. The shape of Sb3F3 is pyramidal.
(b) Molecular shape of SF4 : Sulphur undergoes sp3 hybridization. It has a trigonal bipyramidal
structure with one equatorial position occupied by lone pair of electrons which repls the axial bondspair
thereby decreasing the bond angles from 180C to 173.
(c) Molecular shape of BrF5 : Br shows sp3d2 hybridization octahedral geometry with are position
occupied by a line pair of electrons.
(d) Molecular shape of IF3 : Here I shows sp3d hybridization and shows trigonal bipyramidal
geometries in which two equatorial positions are occupied by line pairs electrons. Thus the actual shape
is a T-shaped molecule.
30.
(a)
(c)
(e)
(g)
(b)
(d)
(f)
(h)
100
31.
CHEMICAL BONDING
(a) Cl2O
2x- 2 = 0
Oxiation state of Cl in Cl2O = + 1
(b) ClO2
x + 2 (-2) = 0
Oxiation state of Cl in ClO2 = + 4
(c) KBrO3
+1 + x + 3 (-2) = 0
x-5=0
Oxiation state of Br in KBrO3 = + 1
(d) NaClO4
+1 + x + 4 (-2) = 0
x-7=0
Oxiation state of Cl in NaClO4 = + 7
x=+1
x = +4
x = +5
x = +7
32.
Catenation : The peroperty of forming chains of identical atoms is called catenation. The property of
catenation depends upon the strength of atom atom bodn. the greater the strength of atom-atom bond,
greater is the extent of catenation. In the elements of the 16th group, s shows strongest tendency of
catenation because of s-s bond strength. Polysulphide showsing catenation are
HS S H
H S S S H
(polysulphides or
H S S S S H
polysulphanes)
Besides these polysulphanes (H Sn H) polysulphuric acids HO3S Sn SO3H and various
allotropic forms of the elements containing different sized Sn rings and chains are also known. The s-s
bond is also found in number of compounds of biological importance such as cysteine, proteins, enzymes
etc.
33.
101
CHEMICAL BONDING
2.
3.
For each of the following pair of hydrogen orbitals, indicated which is higher in energy ;
(a) 1s, 2s ;
(b) 2p, 3p
(c) 3dxy, 3dyz,
(d) 3s, 3d
(e) 4f, 5s
4.
Which orbital in each of the following pairs is lower in energy in amny-electron atom ?
(a) 2s, 2p
(b) 3p, 3d
(c) 3s, 4s
(d) 4d, 5f
5.
6.
The ground state electron configurations listed here are incorrect. Explain what mixtakes have been
made in each and write the correct electron configuration.
Al : 1s22s22p43s23p3
B : 1s22s22p5
C : 1s22s22p6
7.
Draw orbital diagrams for atoms with the following electronic configuraiton :
(a) 1s22s22p5
(b) 1s22s22p6
(c) 1s22s22p63s23p64s23d7
8.
Two p orbitals from one atom and two p orbitals from another atom are combined to form molecuar
orbitals. How many MOs will result from this combination ? Explain.
9.
Show the shapes of bonding and antibonding MOs formed by combination of (a) two s orbital (b) two
p orbitals (side to side)
10.
How do the bonding and antibonding MOs formed from a given pari to AOs compare to each other
with respect to (a) energy
(b) presence of nodes (c) internuclear electron density ?
11.
Arrange the following species in order of increasieng stability : Li2, Li2+, Li2Justify your choice with a molecular orbitla energy level diagram.
12.
Use molecular orbitla thoery to explain why the Be2 molecule cues not exist.
13.
Explain why the bond order of N2 is greater than N2+, but the bodn order of O2 is less than that of O2+.
14.
Compare the relative stability fo the followign species and indicating their magnetic properties (diamagnetic
or paramagnetic) ; O2, O2+, O2- (superoxide), O22- (peroxide ion)
15.
Explain the significance of bond order. Can bond order be used for quantiative compoarisons of the
strengths of chemcial bonds ?
16.
What is the energy gap in band theory ? compare its size in conductors, semiconductors and insulators.
17.
Which of the following substances exhibit H-bonding ? Draw the H bonds between two molecules of
the substnace where appropriate :
(A) CH3CH2OH
O
||
(B) CH 3 C OH
O
||
(C) CH 3 C CH 3
O
||
(D) CH 3 C NH 2
18.
How can one nonpolar molecule inducea dipole in a nearby nonpolar molecule ?
19.
What type(s) of intermolecualr forces exist between the following pairs ? (a) HBr and H2S (b) Cl2 and
CBr4, (c) I2 and NO3- and (d) NH3 and C6H6 ?
102
CHEMICAL BONDING
(Hint : To identify intermolecular forces, it is useful to classify the species being considered as (1)
nonpolar molecules, (2) polar molecules, and (3) ions. Keep in mind that dispersion forces exist
between all species.)
SOLUTIONS
1.
(a) 2py
(b) 3dz2
(c) 3dx2y2
2.
3.
(a) 2s
(b) 3p
(c) 3dxy & 3dz have equal energy.
(d) for hydrogen 3s and 3d orbital have identical energy.
(e) 5s has higher energy than 4f orbital for hydrogen.
4.
CHEMICAL BONDING
103
According to this
(i) in neutral atoms, a subshell with lower value of (n + 1), has lower energy
(ii) If two subshell have equal value of (n + 1), the subshell with lower value of n has lower energy
(a) out of 2s and 2p, 2s is filled first ; its n + 1 is lower or 2s has lower energy than 2p.
(b) Energy of 3p is lower than 3d
3p
3d
n=3
n=3
=1
=2
n+1=4
n+1=5
(c) 3s is lower in energy than 4s
3s
4s
n=3
n=4
=0
=0
n+1=3
n+1=4
(d) 4d is lower in energy than 5f
4d
5f
n=4
n=5
=2
=3
n+1=6
n+1=8
5.
4d6
Principal energy level = 4
Number of electrons = 6
Subshell = d
4 indicates the principal energy level. 4d indicates the d-subshell of the 4th valence shell. 6 indicated
the number of electrons present in 4d subshell.
6.
7.
(a) F = 9 = 2, 7
(b) P = 15 = 2, 8, 5
104
8.
CHEMICAL BONDING
For example if we take oxygen molecule both the oxygen atoms contains two porbitals.
If we take one porbital from one oxygen atom and another porbital from another oxygen atom then
If we take another set of p-orbitals each from each oxygen atom then
So we get 4 molecular orbitals from the combination of two p-orbitals from two atoms.
9.
In combine state
(A + B)2 = A2 + B2 + 2AB
NARAYANA II T ACAD EMY- C P 3 ,
105
CHEMICAL BONDING
Uncombined state
(A B)2 = A2 + B2 2AB
Nuclear nuclear repulsion will be more energy in more stability is less.
(a) Energy - Energy of the antibonding orbital is raised above the energy of the parent atomic orbitals
that have combined and the energy of the bonding orbital has lowered than the parent orbitals. The total
energy of two molecular orbitals however remains the same as that of the two original atomic orbitals.
(b) presence of node & (c) internuclear electron density - bonding molecular orbital most of the electron
density is located between the nuclei of the bonded atoms and hence the repulsion between the nuclei
is very low while in an antibonding molecular orbital, most of the electron density is located away from
the space between the nuclei, as a matter of fact there is a nodal plane (i.e., plane in which the electron
density is zero.)
11.
The electronic configuration of Li is 1s22s1. The M. O. energy level diagram of Li2 is as follows
For Li2
Bond order
1
(Nb Na)
2
1
2
(4 2) = = 1
2
2
106
CHEMICAL BONDING
For Li2+ one electron should be removed from the bonding molecular orbital so bond order will be
=
1
(Nb Na)
2
1
1
(3 2) = = 0.5
2
2
for Li2 one electron should be added to the antibonding molecular orbital so bond order will be
1
1
(4 3) = = 0.5
2
2
The greater the bond order of a diatomic molecule the more stable it will be
So in between Li2, Li2+, Li2 Li2 is more stable than both Li2+, Li2 stability order is Li2, Li2+, Li2
In Li2+, the positive charge is more that is the nucleus will attract the electrons so size will be less than
Li2 & stability is more.
12.
1
(Nb Na)
2
1
(4 4) = 0
2
If the bond order is zero i.e., the molecule doesnt exist.
107
CHEMICAL BONDING
13.
(z2pz)2
1
6
(10 4) = = 3
2
2
1
5
(9 4) = = 2.5
2
2
(one electron is removed from bonding molecular orbital)
So the bond order of N2+ is less than N2.
The electronic configuration of O2 molecule is
(1s)2 (1s*)2 (2s)2 (2s*)2 (2px)2 (py2py)2
(pz2pz)2
Bond order of O2 is =
(*y2py)1
(*z2pz1)
1
4
(10 6) = = 2
2
2
1
5
(10 5) = = 2.5
2
2
(i.e., One electron is removed from antibonding orbital i.e., p*)
so bond order of O2+ is greater than O2
14.
1
4
(10 6) = = 2
2
2
For O2+
1
5
(10 5) = = 2.5
2
2
For O2 :
(2px1 = *2py1)
1
3
(10 7) = = 1.5
2
2
1
2
(10 8) = = 1
2
2
As the bond order increases stability increase so the stability order is
O2+ > O2 > O2 > O22
Magnetic Properties
for O2 there are two unpaired electron so it is paramagnetic in nature. For O2+ it also contain one
unpaired electron so it is also paramagnetic in nature. For O2 it also has one unpaired electron so it is
also paramagnetic in nature. but O22 is diamagnetic due to absence of unpaired electron.
For O22 :
1
(Nb Na)
2
A positive bond order means a stable molecule while a negative (or) zero bond order means an unstable
molecule. Bond length decreases bond order increases.
Yes bond order can be used for quantitative comparison of the strength of the chemical bonds.
15.
Bond order =
16.
The highest occupied energy bond is valence bond while the lowest unoccupied energy bond is conduction
band. The energy gap between the top of the valence bond and the bottom of the conduction band is
called the energy gap (Eg). In case of insulators the energy gap is very large and in case of semiconductor
the energy gap is very small and in case of conductors the energy gap is zero.
108
CHEMICAL BONDING
17.
(A)
(C)
(D)
18.
If in an atom the electrons are moving at some distance from the nucleus. At any instant it is likely that
the atom has a dipole moment created by the specific position of electrons. It is instantaneous dipole
which lasts for just a fleeting moment and in the next instant the electron are in different positions and the
atom has a new instantaneous dipole and so on.
19.
(a)
(b)
(c)
(d)