-1.

1-

CHAPTER 1. FUNDAMENTAL CONCEPTS OF CHEMISTRY

A. Introduction Chemistry is the area of science concerned with the properties of atoms and aggregates of atoms called molecules. The goals of chemical investigation are to develop a fundamental understanding of phenomena relating to the formation, properties, interactions and transformations of molecules, and to utilize this knowledge for the good of humankind. In general, scientific investigation follows a logical sequence of steps called the scientific method. The scientific

Facts 6 (experimental Observations)

Laws 6 (summary statements of facts - prediction of what will happen)

Theories (simplified understanding of nature - tells how & why)

method consists of (a) characterizing the phenomenon of interest by making definitive experimental observations, (b) deducing laws which summarize a body of experimental facts and enable the prediction of what will happen when variables are changed, and (c) formulating theories which relate the observed behavior to the fundamental nature of matter. In this introductory course in chemistry, our main objectives will be to develop a language appropriate for the quantitative and qualitative study of the properties of atoms and molecules, and to cultivate an ability to formulate and solve problems utilizing the language and methods of chemistry. As an illustration of the magnitude of the task at hand, consider a familiar chemical process - the combustion of a piece of paper. Suppose we wish to arrive at a detailed understanding of this process. How should we proceed? As a start, we could make qualitative observations to establish the general characteristics of the phenomenon: light is produced, heat is evolved, gases are generated. We must next perform quantitative measurements (how much light, what are the wavelengths, how much heat, what kinds of gases, how much of each gas, etc.) and then utilize what is known about the origin of light (quantum theory and spectroscopy), the generation of heat (thermodynamics), the conversion of one substance into another (chemical reactions, stoichiometry

-1.2and kinetics) to achieve our objective of understanding what is happening when a piece of paper burns. All scientific languages require precise definitions of the properties to be investigated and quantitative scales and units by which they can be measured. Therefore, as the first topics of discussion, we shall embark on a brief review of common units of measurement and conversion factors. B. Units of Measurement Experimental observation requires measurement. To make a measurement one needs: 1. A precise definition of the property to be measured (i.e., length = straight-line distance between two points). 2. A measurement standard (e.g., Pt-Ir bar at the National Bureau of Standards). 3. A measurement device or instrument (a ruler or meter stick that has been calibrated against the standard). A wide variety of units are in common usage throughout the world. In the USA, we commonly use the English system of units for the various basic quantities listed in the table below.

Quantity Mass Length Time Temperature

Definition Quantity of matter Distance between two points Interval between two events Heat intensity (kinetic energy)

Common Units kg, g, oz, lb, ton km, m, cm, in, yd, ft, mi s, min, hr, yr
0

K, 0C, 0F, 0R

In scientific endeavors, however, it is customary to use the metric system of units. Two sets of metric units are in common usage; the cgs (centimeter, gram, second) system and the mks (meter, kilogram, second) system. In an effort to standardize units, a system of international units (Systeme Internationale or SI) has been agreed upon. The mks units were chosen as the SI units for distance, mass and time. Nevertheless, other units are still commonly used in special instances because of the convenience they offer. For example, when dealing with atomic dimensions, it is generally more convenient to express lengths in terms of Angstroms than meters.

-1.3-

Once a set of units has been chosen for the fundamental quantities discussed above, units for other quantities may be derived from their functional dependence on the fundamental quantities. Examples of common derived units are given in the following table.

Derived Units Volume Force (Length)3 dv F = ma = m d 2x dt =m dt 2 E = mv2 dx = m dt P = F/A

2

m3, cm3, L (1 L=1000 cm3) kg m/s2 = N (Newton) g cm/s2 = dyne kg (m/s)2 = J (Joule) g (cm/s)2 = erg N/m2 = Pa (Pascal) (1 atm = 101.3 k Pa = 14.7 psi; 1 bar = 100 k Pa)

Energy

Pressure

C. Conversion Factors Because we will be employing a variety of units in this course, it will be necessary for you to be able to easily convert from one to another. This can be accomplished by using conversion factors. A conversion factor is an equality in the sense that it relates two equal quantities. Examples of common conversion factors with which you should already be familiar are

l ft = l2 in l lb = l6 oz

l yd = 3 ft l ton = 2000 lb

1 mi = 5280 ft 1 hr = 3600 s.

Three very important conversion factors relating length, mass, and volume between the metric and English systems of units are

1 in = 2.54 cm

1 lb = 454 g

1 qt = 0.946 L

Since both quantities that make up a conversion factor (including units) are equal, their ratio must

-1.4be unity; 12 in ' 1 1 ft 12 1) . 1

(but

The units are treated as algebraic quantities, the same as x and y in the equation

12 x = y 12 x ' 1. y Since a conversion factor (such as the ratio 12 in/1 ft) is unity, multiplication by another quantity does not change the absolute magnitude of that quantity - only its units. 12 in ' 36 in . 1 ft

3 ft x

Both 3 ft and 36 in are expressions of the same length, only in different units! The procedure for unit conversion is simple: 1. Start with the quantity you want to convert. 2. Multiply it by an appropriate conversion factor arranged such that the old unit cancels algebraically and the new unit remains.

Examples: a). Convert 36x1015 in. to miles. 36x10 15 in. x 1 ft 1 mile (36x10 15) x ' mile ' 5.7x10 12 mile . 12 in. 5280 ft (12)(5280)

b). Convert 1 kilometer to miles.

-1.51000 m 100 cm 1 in. 1 ft 1 mi x x x x 1 km 1 m 2.54 cm 12 in. 5280 ft (1000)(100) mi ' 0.62mi. (2.54)(12)(5280)

1 km x '

c). Density ( = mass/volume) may be regarded as a conversion factor that relates the mass of a substance to its volume. What volume in liters is occupied by 2 lb of iron if its density is 7.86 g/cm3?

2 lb iron x

454 g iron 1 cm 3 iron 1 L iron x x 1 lb iron 7.86 g iron 1000 cm 3 iron

' 0.116 L iron. Exercises: a). Calculate the kinetic energy of a baseball having a mass of 4.0 oz and a speed of 60 mi/hr in SI units. (ANS = 41 J) E = mv2 = 0.5[(4.0 oz)(1 lb/16 oz)(454 g/1 lb)(1 kg/1000 g)][(60 mi/1 hr) (5280 ft/1 mi)(12 in./1 ft)(2.54 cm/1 in.)(1 m/100 cm)(1 hr/3600 s)]2 = 41 J. b). The density of silicon is 2.33 g/mL and the mass of a silicon atom is 4.65x10!23 g. Calculate the number of silicon atoms in a 1 in. cube of silicon. (ANS = 8.21x1023) 1 in.3 Si(2.543 cm3/1 in.3)(1 mL/1 cm3)(2.33 g Si/1 mL Si)(1 Si atom/4.65x10!23 g) = 8.21x1023. c). The density of ethanol is 0.794 g/mL at 25 oC. What volume of ethanol should be measured out to obtain a sample weighing 0.33 lb? (ANS = l.9x102 mL) 0.33 lb ethanol(454 g/1 lb)(1 mL ethanol/0.794 g ethanol) = 1.9x102 mL ethanol.

-1.6D. Temperature Conversion The English system temperature scale is the Fahrenheit scale while the metric system temperature scale is the Celsius scale. Temperatures that are measured on two different scales cannot be converted by simply multiplying by a conversion factor. Therefore, it is necessary to understand how the scales are defined:
Fahrenheit scale 212 oF water boils Celcius scale 100 o C

180

100

T F - 32 32 o F water freezes

TC 0 oC

Figure 1.1. Diagram illustrating the Fahrenheit and Celsius temperature scales.

With this in mind, conversion from one scale to the other is easily accomplished by setting up the following proportions; TF ! 32 180 so hence and TC 100

'

100(TF ! 32) = 180 TC TC = (100/180)(TF ! 32) TF = (180/100)TC + 32.

(Note: there is absolutely no need to memorize the above formulas since it is far easier to remember the scale definitions and set up the proportionality from which they are derived).

-1.7E. Significant Figures The result of a measurement should be expressed by numbers in which only the last digit is in doubt. The number 234.5, for example, implies that the measurement is accurate to 0.1 units. This number is said to have 4 significant figures. Rules of significant figures: 1. The digit 0 is only significant if it is preceded by another number (other than 0). 1060 has 4 significant figures 0.0016 has 2 significant figures 2. Addition and subtraction: round off at the digit closest to the decimal point; 63.43 ! 1.245 + 0.4652 = 62.65 (not 62.6502) 3. Multiplication and division: keep only the number of digits held by the number having the fewest significant figures; 0.156 x 84.25 x 1.7854 ' 15 (not 14.6659). 1.6 4. Terminal zeros should be expressed in exponential notation unless they are significant. 93,000,000 expressed to 3 significant figures is 9.30x107

Exercises: Carry out the following conversions observing the rules of significant figures. a). 12 oz to mg. (3.4x105 mg) b). 5 nickels to Swiss Francs where 1 SF = 0.36 $. (0.69 SF) c). 3x1010cm/sec to mi/hr. (7x108) d). The density of Hg (13.6 g/cm3 ) to lb/in3. (0.491 lb/in3)

F. Basic Constituents of Matter Atoms are the basic building blocks of matter. They are, however, not the most fundamental particles of nature (which are quarks and leptons). Atoms are composed of the following particles:

a). Electrons -

extremely small and light negatively-charged particles.

-1.8b). Protons particles having exactly the opposite charge of an electron, but possessing 1836 times more mass. c). Neutrons particles with slightly more mass than protons, but without charge.

The electrons of an atom are diffusely distributed about a very tiny nucleus in which the protons (in number equal to the number of electrons) and neutrons are tightly packed.

Anatomy of a carbon atom

Diffuse cloud containing six electrons circulating around a nucleus Diameter approx. 0.0000000002 m = 2x10 -10 m = 0.2 nm nucleus Diameter approx. 0.000000000000006 m = 6x10 -15 m = 6 fm

Figure 1.2. Schematic illustration of the nominal sizes of the atom and its nucleus.

If an atom were the size of the earth, its nucleus would only be 200 ft in diameter. The mass and charge properties of neutrons, protons and electrons are summarized in the table on the next page. Important properties of atoms: C In a normal atom, the number of electrons = the number of protons. Hence, the charge of an atom is zero. However, atoms having more or less electrons than protons (called ions) commonly occur in solids and solutions. Ions are atoms with nonzero charges.

-1.9-

Particle

Charge

Mass

Rest mass energy (m0c2)

Proton Neutron Electron

*

+e* 0 !e

1.673x10!27 kg 1.675x10!27 kg 9.109x10!31 kg

938.2 MeV 939.5 MeV 0.511 MeV

e = 1.602x10!19 Coulomb

C C C

The number of protons in an atom is called the atomic number and is designated by the letter Z. The number of nucleons (i.e., protons and neutrons) in an atom is called the atomic mass number and is designated by the letter A. The number of neutrons in the nucleus of an atom may be computed from the relationship

N = A ! Z.

An element is composed of atoms of a particular Z (presently 116 elements are known). Each element is given a special name and chemical symbol. For example, the chemical symbols for aluminum, sodium, and tin are Al, Na, and Sn, respectively. The chemical symbols of all the elements are displayed in the periodic table shown in Fig. 1.3. In this table, the elements are ordered according to their atomic numbers and arranged in a manner that places elements having similar chemical properties in columns (called groups). Two series of elements (called the inner transition elements) have such similar chemical properties that they are removed from the main body of the table and displayed at the bottom. They are known as the lanthanide (or rare earth) and actinide elements. Notable groups among the representative elements are the alkali metals (grp 1A), the alkaline earth metals (grp 2A), the halogens (grp 7A), and the noble gases (grp 8A). Both stable and unstable atoms of most elements exist or may be produced via nuclear reactions. Those atoms which are unstable transmute to stable atoms by means of radioactive

-1.10-

7A 1 H 1A 3 Li
6.939

8A 2 He

2A 4 Be
9.0122

3A 5 B

4A 6 C

5A 7 N

6A 8 O

1.0080 4.0026

9 F

10 Ne

10.811 12.011 14.007 15.999 18.998 20.183

11 Na

12 Mg 3B 21 Sc
44.956

13 Al 4B 22 Ti
47.90

14 Si

15 P

16 S

17 Cl

18 Ar

22.990 24.312

5B 23 V

6B 24 Cr

7B 25 Mn

7
26 Fe

8B 27 Co

6
28 Ni
58.71

1B 29 Cu
63.54

2B 30 Zn
65.37

26.982 28.086 30.974 32.064 35.453 39.948

19 K
39.102

20 Ca
40.08

31 Ga
69.72

32 Ge
72.59

33 As
74.922

34 Se
78.96

35 Br
79.909

36 Kr
83.80

50.942 51.996 54.938 55.847 58.933

37 Rb
85.47

38 Sr
87.62

39 Y
88.905

40 Zr
91.22

41 Nb
92.906

42 Mo
95.94

43 Tc
(98)

44 Ru

45 Rh

46 Pd
106.4

47 Ag

48 Cd

49 In

50 Sn

51 Sb

52 Te

53 I

54 Xe

101.07 102.91

107.87 112.40 114.82 118.69 121.75 127.60 126.90 131.30

55 Cs

56 Ba

71 * Lu

72 Hf

73 Ta

74 W

75 Re
186.2

76 Os
190.2

77 Ir
192.2

78 Pt

79 Au

80 Hg

81 Tl

82 Pb

83 Bi

84 Po
(210)

85 At
(210)

86 Rn
(222)

132.91 137.34 174.97 178.49 180.95 183.85

195.09 196.97 200.59 204.37 207.19 208.98

87 Fr
(223)

88 Ra
(226)

103 Lr
(262)

104 Rf
(261)

105 Db
(262)

106 Sg
(263)

107 Bh
(262)

108 Hs
(265)

109 Mt
(266)

110 Ds
(271)

111 Rg
(272)

112

113

114

115

116

118

(277)

(284)

(288)

(288)

(292)

(294)

* Lanthanide Series

57 La

58 Ce

59 Pr

60 Nd

61 Pm
(147)

62 Sm

63 Eu

64 Gd

65 Tb

66 Dy

67 Ho

68 Er

69 Tm

70 Yb

138.91 140.12 140.91 144.24

150.35 151.96 157.25 158.92 162.50 164.93 167.26 168.93 173.04

Actinide Series

89 Ac
(227)

90 Th
232.04

91 Pa
(231)

92 U
238.03

93 Np
(237)

94 Pu
(242)

95 Am
(243)

96 Cm
(247)

97 Bk
(247)

98 Cf
(251)

99 Es
(254)

100 Fm
(257)

101 Md
(258)

102 No
(259)

Figure 1.3. The periodic table of the elements.

decay processes. The stability of an atom is primarily determined by the relative numbers of protons and neutrons it has. There are no stable atoms of Tc, Pm, and elements above Bi. Consider the element aluminum. Fifteen different kinds of Al atoms are known. In order

-1.11to be Al atoms, they must all have 13 protons. However, they contain different numbers of neutrons. The only stable kind of Al atom contains 14 neutrons.

Stable Al:

Z = 13,

N = 14,

A = 27

Atoms of the same element having different numbers of neutrons are called isotopes. The isotope of aluminum having 14 neutrons may be completely specified using the following notation:
27 13Al .

Sometimes the number of neutrons is included as a subscript on the right hand side;
27 13Al14 ,

but this is really not necessary since the number of neutrons can always be determined from the mass number (A) and the atomic number (Z). The 15 kinds of Al atoms are shown in the diagram below.

22 13Al

23 13Al

24 13Al

25 13Al

26 13Al

27 13Al

28 13Al

29 13Al

30 13Al

31 13Al

32 13Al

33 13Al

34 13Al

35 13Al

36 13Al

proton excess

Stable

neutron excess

The stable isotopes of low-Z elements, such as aluminum, have very nearly the same number of protons and neutrons. For example, the stable isotope of aluminum (27Al) has 13 protons and 14 neutrons. The isotopes to the left of 27Al in the above diagram have a proton to neutron ratio greater than one (i.e., they have an excess of protons over neutrons) while the isotopes to the right have a proton to neutron ratio less than one. All of these isotopes are unstable and undergo a type of radioactive decay called beta decay. The particular types of beta decay processes by which proton

excess isotopes decay (known as

and electron capture decay) convert a proton to a neutron;

p+ 6 n + e+ (+ neutrino) where e+ is an antielectron (positron) Beta decay of proton excess isotopes: p+ + e! 6 n (+ neutrino) where e! is an electron.

The beta decay process by which neutron excess isotopes decay (known as neutron to a proton;

decay) converts a

-1.12Beta decay of neutron excess isotopes: n 6 p+ + e! (+ antineutrino).

The end result of a beta decay process is to transmute the original isotope into an isotope of
!

the adjacent element having atomic number Z!1 in the case of + 1 in the case of

and electron capture decay or Z

decay. For all of the beta decay processes, the product isotope (or daughter) has

the same atomic mass number as the parent since one kind of nucleon has simply been replaced by the other. It is important to note that the daughter isotope has a proton to neutron ratio that is closer to the proton to neutron ratio of the corresponding stable isotope than that of the parent. Ultimately, all unstable isotopes decay step by step to form stable isotopes.

Example:

Predict the type of beta decay the unstable isotope 14C undergoes and give the end product of the decay.

The atomic number of carbon is 6 (see periodic table) and so 14C has 8 neutrons. Therefore
14

C is a neutron excess isotope and will undergo

decay producing the isotope 14N.

Exercise: Predict the type of decay and product isotope for the radioactive isotope 36Ca. The atomic number of Ca is 20. Since Ca is a low-Z element, the stable isotopes of Ca should have nearly the same number of neutrons as protons (20). Therefore 36Ca is on the

proton excess side of stability and will decay by

/electron capture to give 36K.

G. Atomic Mass In order to deal quantitatively with atoms, one must have a means of counting them. The most straightforward way to count atoms is to determine their masses. From a knowledge of the mass of a single atom and the mass of a sample, the number of atoms in the sample may be determined. Just as a convenient mass scale has been devised for dealing with macroscopic quantities, so also has a convenient mass scale been defined for dealing with atomic (microscopic) quantities. The isotope of carbon having 6 neutrons, 12C, has been chosen as the mass standard for the atomic mass scale. Its mass is arbitrarily taken to be exactly 12 atomic mass units (amu). The masses of all other elements may then be compared with the mass of a 12C atom to determine their relative masses on this scale. One method for doing this is by mass spectrometry. Most elements have more than one stable isotope. The element magnesium, for example,

-1.13has three stable isotopes; 24Mg, 25 Mg, and 26 Mg. Any sample of magnesium atoms will contain fixed proportions of all three of these isotopes. In order to determine the average weight of a magnesium atom, which defines its atomic weight, it is necessary to know these fixed proportions or natural abundances as they are called. The natural abundances of the elements have been determined experimentally and for most elements they are amazingly constant from one sample to another. It is the variability of the natural abundances that limits the accuracy of most atomic weights. Lets determine the atomic weight of magnesium from the data given in the table below. Isotope
24 25 26

Atomic Mass (amu) 23.985042 24.985837 25.982594

Relative Abundance (%) 78.99 10.00 11.01

Mg Mg Mg

In any mineral containing Mg atoms, 78.99% of them will be 24Mg, 10.00% will be 25Mg and 11.01% will be 26Mg. Hence the average atomic mass (atomic weight) of Mg is

Atomic weight = (0.7899)(23.99) amu + (0.1000)(24.99) amu + (0.1101)(25.98) amu = 24.31 amu. This is the value that appears for magnesium in periodic tables. (Note that the sum of the natural abundances equals 1 and that the accuracy of the atomic weight is limited by the number of significant figures in the natural abundances). In order to convert the weights of atoms from the atomic mass scale to the metric scale, you must know the conversion factor:

1 g = 6.0221367x1023 amu

The number 6.022x1023 is called Avogadros number. Example: What is the average mass in g of 1 atom of Fe?

-1.14From the periodic table, we find the atomic weight of Fe to be 55.847 amu. 55.847 amu iron 1 g Fe x ' 9.274x10 !23 g Fe. 23 1 atom Fe 6.0221x10 amu Fe

1 atom Fe x

A very special unit has been defined for use in atom counting. This unit is called the mole (mol). 1 mole of atoms = 6.0221367x1023 Example: What is the mass of 1 mole of Fe atoms? 1 mole Fe atoms x 6.0221x10 23 Fe atoms 55.847 amu iron 1 g Fe x x 1 mole Fe atoms 1 Fe atom 6.0221x10 23 amu Fe

' 55.847 g Fe. This example shows explicitly that the definition of the mole has been chosen such that Atomic weight = mass of 1 mole of atoms Exercise: The radius of a nucleus is approximately given by the simple formula R = 1.4x10!13A1/3 cm. Calculate the density (in tons/cm3) of a nucleus of 27A1. The volume of a sphere is given by V = (4/3) R3 and so the volume of an Al nucleus is V = (4/3) [(1.4x10!13)3(27)] = 3.1x10!37 cm3. Density = (27 amu/3.1x10!37 cm3)(1 g/ 6.022x1023 amu)(1 lb/454 g)(1 ton)/2000 lb) = 1.6x108 ton/cm3. H. Molecules Modern chemistry is founded upon the following principles which were first delineated by Dalton: a). Atoms are the fundamental particles of which matter is composed. b). Atoms of any particular element are identical in all their chemical properties. c). Atoms of one element are different in mass and other properties from all other atoms (i.e. they are distinguishable). d). Chemical change is the result of the union or separation of atoms. The unit formed by the combination of two or more atoms is called a molecule. The idea

-1.15that molecules must be composed of integer combinations of atoms was supported by the law of definite proportions. This law states that the masses of the different elements making up a particular compound (a substance consisting of two or more elements combined as molecules) are in definite and unchanging proportions. Take the water molecule, H2O, for example. Since we now know that each molecule of water contains two atoms of hydrogen and one atom of oxygen, it is obvious that all water molecules, no matter what their origin, should exhibit the same mass ratio; (mass H)/(mass oxygen) = (2 amu)/(16 amu) =1/8. Another test of the hypothesis that molecules are composed of integer numbers of different atoms is provided by the law of multiple proportions: if two elements form more than one compound, the different weights of one which combine with the same weight of the other are in the ratio of small whole numbers. As an example of the application of the law of multiple proportions, consider two compounds formed from iron and oxygen atoms, FeO and Fe2O3; FeO: mass Fe 55.8 ' mass O 16.0 mass Fe (2)(55.8) ' mass O (3)(16.0) (2)(55.8) 2 (3)(16.0) ' . 3 55.8 16.0

Fe2O3: therefore mass Fe mass O mass Fe mass O I. Molecular Formulas

Fe2O3

'

FeO

Molecular formulas reveal the composition of a compound. They specify the exact number of atoms of each element that make up a single molecule. For example, the molecular formula of sulfuric acid is H2SO4. From this formula, one may deduce the following numerical relationships: One H2SO4 molecule contains:

2 atoms of H [mass = 2(1) amu] 1 atom of S [mass = 32 amu]

4 atoms of O [mass = 4(16) amu].

-1.16Therefore, the mass of 1 sulfuric acid molecule = 98 amu. Also One mole of H2SO4 molecules contains: 2 moles of H [mass = 2(1) g] 1 mole of S [mass = 32 g]

4 moles of O [mass = 4(16) g]. Therefore, the mass of 1 mole of sulfuric acid = 98 g. The mass of one molecule of a compound is its molecular weight. Hence, in the above example, the molecular weight of sulfuric acid is 98 amu.

Exercise: How many oxygen atoms are in 5.00 g of potassium dichromate (K2Cr2O7)? The molecular weight of PD is 2(39.1) + 2(52.0) + 7(16.0) = 294.2 amu. (5.00 g PD)(1 mol PD/294.2 g PD)(7 mol O/ 1 mol PD)(6.022x1023 atoms O/1 mol O) = 7.16x1022 atoms of O.

The empirical formula of a compound only indicates the relative numbers of atoms of each element that makes up a molecule. An empirical formula differs from a molecular formula by an integer: Molecular Formula = n x (Empirical Formula) where n is an integer.

Exercise:

What is the empirical formula of a compound containing 92.3% carbon and 7.69% hydrogen by weight?

In 100 g of compound there are 92.3 g C and 7.69 g H. (92.3 g C)x(1 mol C/12.0 g C) = 7.69 mol C (7.69 g H)(1 mol H/1.00 g H) = 7.69 mol H moles H/moles C = 1, therefore the empirical formula is CH. Exercise: If the molecular weight of the compound in the preceding exercise is 78 amu, what is its molecular formula? The empirical formula weight is 12.0 + 1.0 = 13.0 amu. Therefore, the number of CH units

-1.17per molecule is 78/13 = 6 and hence the molecular formula is C6H6.

J. Chemical Reactions Chemical reactions are processes whereby one substance is transformed into another as a result of the combination or disassociation of atoms. A chemical equation can be written to describe the transformation both qualitatively and quantitatively. For example, the transformation of silver ions by reaction with molecules of hydrogen sulfide in aqueous solution into solid silver sulfide and aqueous hydrogen ions may be concisely expressed as

In a chemical reaction, the following must be conserved: a). Atoms - neither created nor destroyed b). Charge c). Energy + mass - the sum of the energy plus the energy-equivalent of the mass (mc2) remains constant in a chemical reaction. Consider the reaction Na+ + OH! 6 NaOH + energy.

It is easy to see that the first two conservation principles are obeyed, but what about the third? In the above example, where did the energy come from? Since energy and mass are related by the Einstein equation, E = mc2, the energy + mass conservation principle means that mass of Na+ + mass of OH! = mass of NaOH + energy/c2.

-1.18In most chemical reactions, the energy involved is so small compared to the masses of the atoms that the conversion of mass into energy may be neglected and for most practical purposes, it may be assumed that mass alone is conserved. This is not a good assumption in nuclear reactions, however. Consider forming an 27Al atom by combining H atoms and neutrons. The mass + energy balance for this process is 13 1H + 14 n 6 27Al + energy 13(1.007825) amu + 14(1.008665) amu = 26.981535 amu + energy/c2 energy = mc2 = (13.1017 + 14.1213 - 26.9815)amu x (931.5 MeV/amu) = 225.0 MeV. This energy is the binding energy that holds the 27Al nucleus together. The mass change per mole is 0.242 g. A complete chemical equation must be balanced; both the numbers of atoms of each element and the total charge must be the same on both sides of the equation. For most reactions, this may be done by trial and error. For example, the steps involved in balancing the reaction NH3 + O2 6 NO + H2O are: C C C 1. Balance the hydrogens: 2 2. Balance the oxygens: 5/2 2 3

3. Clear all fractions: (multiply by 2) _____________________ 4 NH3 + 5 O2 6 4 NO + 6 H2O.

K. Chemical stoichiometry The quantitative information contained in balanced chemical equations, in conjunction with a knowledge of atomic masses, allows one to determine the amounts of reactants that are used and the amounts of products that are formed in chemical reactions. This procedure is referred to as stoichiometry. The following examples illustrate typical stoichiometric calculations.

Example: What weight of CO2 can be obtained from the complete combustion of 12.0 g of CO? Step 1: write a balanced chemical reaction.

-1.192 CO + O2 6 2 CO2. Step 2: use the relationships given by the chemical reaction to set up conversion factors for converting 12.0 g of CO to the equivalent mass of CO2. 2 mol CO2 44.0 g CO2 1 mol CO x x ' 18.9 g CO2. 28.0 g CO 2 mol CO 1 mol CO2

12.0 g CO x

What mass of oxygen was consumed? 1 mol O2 32.0 g O2 1 mol CO x x ' 6.85 g O2. 28.0 g CO 2 mol CO 1 mol O2

12.0 g CO x

Example:

How many grams of the compound C9H11NO4 can be formed from 20.0 g C, 10.0 g H2 , 3.00 g N2, and 5.00 g O2?

In this type of problem, you must first identify the limiting reagent. It is likely that the quantities of the various substances listed above are not in the same relative proportions as required by the reaction stoichiometry. Therefore, one of these substances will be totally consumed before the others causing the reaction to end. This substance is called the limiting reagent. The easiest way to find the limiting reagent is to convert each of the starting substances to the equivalent number of moles of product. Then the substance that yields the least amount of product is the limiting reagent and the amount of product it yields is all that can be produced under the given conditions. 1 mol C 1 mol cmpd x ' 0.185 mol cmpd 12.0 g C 9 mol C 1 mol H2 2.00 g H2 1 mol N2 28.0 g N2 1 mol O2 32.0 g O2 x 1 mol cmpd ' 0.909 mol cmpd 11/2 mol H2 1 mol cmpd ' 0.214 mol cmpd 1/2 mol N2 1 mol cmpd ' 0.0781 mol cmpd . 2 mol O2

20.0 g C x

10.0 g H2 x 3.00 g N2 x 5.00 g O2 x

-1.20Since the available oxygen gives the smallest yield of the compound, it is the limiting reagent. Therefore the maximum amount of compound that could be produced is 197 g cmpd ' 15.4 g cmpd . 1 mol cmpd

0.0781 mol cmpd x

How many grams of H2 are left after the reaction? (Ans. = 9.14 g)

Exercises: a). How many molecules of CH4 will be produced when 0.20 g of Al(OH)3 are prepared by the reaction

A14C3 + H2O 6 Al(OH)3 + CH4 ? (Ans. = l.2x1021) The balanced reaction is 0.20 g Al(OH)3 x A14C3 + 12 H2O 6 4 Al(OH)3 + 3 CH4. Therefore, 1 mol Al(OH)3 78.0 g Al(OH)3 x 3 mol CH4 4 mol Al(OH)3 x

6.022x10 23 molecules CH4 1 mol CH4

' 1.2x10 21 molecules CH4

b). How much Fe can be produced from the reaction of 1.00 ton C and 5.00 ton Fe2O3 using the reactions: C + O2 6 CO CO + Fe2O3 6 Fe + CO2? 2 C + O2 6 2 CO (Ans. = 3.10 ton Fe)

The balanced reactions are

3 CO + Fe2O3 6 2 Fe + 3 CO2. 1.00 ton C x (1 ton-mol C/12 ton C) x (2 ton-mol CO/2 ton-mol C) x (2 ton-mol Fe/3 ton-mol CO) x (55.8 ton Fe/1 ton-mol Fe) = 3.10 ton Fe. 5.00 ton Fe2O3 x (1 ton-mol Fe2O3/159.6 ton Fe2O3) x (2 ton-mol Fe/1 ton-mol Fe2O3) x (55.8 ton Fe/1 ton-mole Fe) = 3.50 ton Fe (hence C is the limiting reagent).

-1.21c). A quantity of FeCO3 was converted to Fe2O3 and CO2. The CO2 escaped as a gas and the ratio of the weight of the remaining solid sample to the weight of the original FeCO3 was 0.754. What fraction was converted into Fe2O3 and CO2? FeCO3 + O2 6 Fe2O3 + CO2. 4 FeCO3 + O2 6 2 Fe2O3 + 4 CO2. (Ans. = 0.791)

The balanced reaction is

Let X g = original weight of FeCO3 and Y g = weight of FeCO3 that reacted. Then the weight of Fe2O3 formed was Y g FeCO3 x (1 mol FeCO3/115.8 g FeCO3) x

(2 mol Fe2O3/4 mol FeCO3) x (159.6 g Fe2O3/1 mol Fe2O3) = 0.689Y g Fe2O3. The weight ratio is (X ! Y + 0.689Y)/X = 0.754, and so 1 ! Y/X + 0.689 Y/X = 0.754. Therefore, the fraction converted = Y/X = 0.246/0.311 = 0.791.

L. Solutions A solution consists of a mixture of at least two substances in the liquid phase -the solute (dissolved substance) and the solvent (substance in which the solute is dissolved). In order to work quantitatively with solutions, the amount of the solute and the amount of either the solvent or the solution must be specified. This is done by defining various concentration units. Common concentration units:

-1.22Exercises: a). Calculate the molarity of 32.6 mL of a solution containing 5.00g of NaCl. (Ans. = 2.62 M)

(5.00 g NaCl/32.6 mL soln) x (1 mol NaCl/58.5 g NaCl) x (1000 mL/1 L) = 2.62 mol NaCl/L soln. b). Calculate the molarity and molality of 100 g of solution containing 10.0 g NaCl and having a density of 1.071 g/mL. (Ans: M = 1.83, m = 1.90) (10.0 g NaCl/100 g soln) x (1 mol NaCl/58.5 g NaCl) x (1.071 g soln/1 mL soln) x (1000 mL/1 L) = 1.83 mol NaCl/L soln. [(10.0 g NaCl) x (1 mol NaCl/58.5 g NaCl)]/[(100 g soln - 10.0 g NaCl) x (1 kg/1000 g)] = 1.90 mol NaCl/kg solvent. c). Calculate the molarity and molality of a solution of ethanol (C2H5OH) in water if the mole fraction of ethanol is 0.050 and the density of the solution is 0.997 g/mL. (Ans: M = 2.57, m = 2.93) Let X = mols eth and Y = mols water. Then X/(X+Y) = 0.050 so X/Y = (0.05)/(1 ! 0.05) = 0.0526. In 1 L of solution there are 997 g of solution, so (Y mol water) x (18 g water/1 mol water) + (X mol eth) x (46.0 g eth/1mol eth) = 997, (18Y) + (46.0)(0.0526Y) = 996; Y = 48.8 mol water, X = 2.57 mol eth. Therefore M = 2.57 mol eth /L soln. Molality = (2.57 mol eth)/[(48.8 mol water) x (18 g water/1 mol water) x (1 kg /1000 g) = 2.93 mol eth/kg water.

Dilution problems: In the laboratory, it is frequently necessary to make a specified volume of solution having a particular concentration from a more concentrated stock solution. The following examples illustrate how this task may be accomplished.

Example:

Describe how to make 1.00 L of 1.00 M HCl from a solution of 12.0 M HCl.

The number of moles of HCl in 1.00 L of 1.00 M HCl = (1.00 L) x (1.00 mol/1 L) = 1.00 mol. The number of L of 12.0 M HCl that contains 1.00 mol = (1.00 mol) x ( 1 L/12.0 mol) = 0.0833

-1.23L. Therefore, 1.00 L of 1.00 M HCl may be obtained by measuring out 0.0833 L of 12.0 M HCl and diluting it with water to a total volume of 1.00 L.

Notice that the volume of 12.0 M HCl required in the above example is given by the simple dilution rule:

where

M1 = concentration of soln. 1, M2 = concentration of soln. 2,

V1 = volume of soln. 1, V2 = volume of soln. 2.

Neutralization reactions: Neutralization involves the reaction of an acid with a base. The most common acids and bases are defined by the following properties (first elaborated by Arrhenius):

An acid is a substance that increases the H+ concentration in solution; A base is a substance that increases the OH! concentration in solution.

In simple neutralization reactions, the net reaction that occurs when an acid and a base are mixed is H+ + OH! 6 H2O.

For example, when the strong acid HCl is mixed with the strong base NaOH, the reaction is H+ + Cl! + Na+ + OH! 6 H2O + Na+ + Cl!,

but since strong acids and bases completely dissociate into ions in solution, there is no need to include the Na+ and Cl! ions in the net reaction. As indicated by the stoichiometry of this reaction,

-1.241 mole H+ neutralizes 1 mole OH!.

The above relationship provides the key to solving neutralization problems.

Example:

How many moles of HCl does it take to neutralize 1 mole of Mg(OH)2?

1 mole of Mg(OH)2 provides 2 moles of OH! in aqueous solution, and so 2 moles of HCl would be required.

Sometimes it is more convenient to work neutralization problems in terms of equivalents rather than moles. An acid/base equivalent is defined as follows:

1 equivalent of acid = the quantity which gives 1 mole H+, 1 equivalent of base = the quantity which gives 1 mole OH!. Therefore, 1 eq HCl = 1 mole HCl 1 eq H2SO4 = 1/2 mole H2SO4 1 eq NaOH = 1 mole NaOH 1 eq Mg(OH)2 = 1/2 mole Mg(OH)2.

Example:

What is the equivalent weight of H2SO4?

1 eq H2SO4 x (1 mol H2SO4/2 eq H2SO4) x (98 g H2SO4/1 mol H2SO4) = 49 g H2SO4.

The reason that equivalents are convenient to use is that regardless of the reaction stoichiometry,

1 eq acid neuralizes 1 eq base.

Another commonly employed concentration unit is normality (N), defined as equivalents of acid or base . liters of solution

N '

-1.25The use of both moles and equivalents in neutralization reaction problems is illustrated in the following example.

Example:

How many grams of HNO3 are needed to neutralize 100 mL of 0.50 M Ba(OH)2? 0.50 mol Ba(OH)2 1000 mL Ba(OH)2 1 mol HNO3 1 mol H % x x 2 mol OH ! 1 mol H % x 1 mol Ba(OH)2 1 mol OH ! ' 6.30 g HNO3

Method 1: using moles 100 mL Ba(OH)2 x

63.0 g HNO3 1 mol HNO3

Method 2: using equivalents 100 mL Ba(OH)2 x 0.50 mol Ba(OH)2 1000 mL Ba(OH)2 1 mol HNO3 1 eq H % x x 2 eq OH ! 1 eq H % x 1 mol Ba(OH)2 1 eq OH ! ' 6.30 g HNO3.

63.0 g HNO3 1 mol HNO3

Titration is a method for determining the concentration of an acid or a base. The concentration of an acid, for example, may be accurately determined by the stepwise addition of a base having a known concentration. The equivalence point is reached when the number of equivalents of base added exactly equals the initial number of equivalents of acid. Experimentally, this point may be determined by using an indicator - a substance that causes the solution to change color at the equivalence point.

Example:

In a titration, 35.80 mL of 0.1000 M NaOH is needed to reach the equivalence point when added to 20.00 mL of an H2SO4 solution of unknown concentration. Calculate the molarity and normality of the original H2SO4 solution.

Solution using moles - Since the volume and concentration of the base are known, the number of moles of acid that were neutralized can be calculated using the stoichiometric coefficients of the balanced chemical reaction: 2 NaOH + H2SO4 6 2 H2O + Na2SO4.

-1.261 mol H2SO4 0.1000 mol NaOH 35.80 mL NaOH x x ' 1.790x10 !3 mol H2SO4. 1000 mL NaOH 2 mol NaOH Therefore, 1.790x10 !3 mol H2SO4 M ' ' 0.08950 mol H2SO4/L . 0.02000 L soln N ' 0.08950 mol H2SO4 1 L soln x 2 eq H2SO4 1 mol H2SO4 ' 0.1790 eq H2SO4/L .

Solution using equivalents - If equivalents are used, there is no need for a balanced reaction, but one has to take into account the fact that there are 2 equivalents of H2SO4 per mole; 35.80 mL NaOH x 0.1000 mol NaOH 1 eq NaOH x 1000 mL NaOH 1 mol NaOH 1 eq H2SO4 1 eq NaOH ' 3.580x10 !3 eq H2SO4.

Therefore, 3.580x10 !3 eq H2SO4 N ' ' 0.1790 eq H2SO4/L. 0.02000 L soln M ' 0.1790 eq H2SO4 1 L soln x 1 mol H2SO4 2 eq H2SO4 ' 0.08950 mol H2SO4/L.

Exercise:

The concentration of an oxalic acid (H2C2O4) solution is to be determined by titrating 25.00 mL of it with 0.100 M NaOH. It is found that the equivalence point is reached when 38.00 mL of the NaOH have been added. (Ans. = 0.0760 M)

38.00 mL NaOH x (0.100 mol NaOH/1000 mL NaOH) x (1 eq OH!/1mol NaOH) x (1 eq H+/1 eq OH!) x (1 mol oxalic acid/2 eq H+) = 1.90x10!3 mol oxalic acid. Therefore, M = (1.90x10!3 mol oxalic acid)/(0.0250 mL) = 0.0760 M. Another way: 38.0 mL OH! x (0.100 mol OH!/1000 mL OH!) x (1 mol H2C2O4/2 mol OH!) = 1.90x10!3 mol H2C2O4 M = 1.90x10!3 mol/0.0250 L = 0.0760 mol/L.

-1.27Exercise: A student mixes 25.00 mL of 0.1500 M HCl with 40.00 mL of 0.0500 M Ca(OH)2. What is the final concentration of each ion in this solution? HCl ! H+ + Cl! Ca(OH)2 ! Ca2+ + 2 OH! H+ + OH! ! H2O The numbers of moles initially are: H+ = 25.00 mL x (0.1500 mol/1000 mL) = 0.003750 mol Cl! = same = 0.003750 mol Ca2+ = 40.00 mL x (0.0500 mol/1000 mL) = 0.00200 mol OH! = 2 x Ca2+ = 0.00400 mol After mixing, all of the H+ has reacted and 0.00400-0.00375 = 0.00025 mol OH! remains. Therefore [H+] = 0, [Cl!] = 0.003750/0.06500 = 0.05769 M, [Ca2+] = 0.00200/0.06500 = 0.0308 M, and [OH!] = 0.00025/0.06500 = 0.0038 M.

-1.28Review questions 1. The potential energy of a spring is given by the equation Epot = kx2, where k is the force constant and x is distance. What are the SI units for the force constant? 2. An American traveling in Europe stops at a gasoline station to fill the tank of his American car. He knows the tank has a capacity of 20 gallons. How many liters should he expect the tank to hold? 3. The American in problem 2 now wishes to check the pressure of his tires, which should be inflated to 30 psi. What reading should he expect on a pressure gauge that reads in millibar? (Note: psi is not really a pressure unit, but rather the ratio m/A with m in lbs. Also, 1 bar = 1x105 Pa and a = 9.80 m/s2 where a is the acceleration of gravity). 4. An Eskimo walks out of his igloo to read the temperature on an outdoor thermometer and finds that the reading is the same on both the Celsius and Fahrenheit scales. Should he put on his coat? (What is the temperature?) 5. How many neutrons does a nucleus of the isotope 241Am contain? What is the daughter isotope that is formed when 241Am undergoes alpha decay? (In alpha decay, the nucleus emits a particle consisting of a 4He nucleus). 6. Stable isotopes of heavy elements contain many more neutrons than protons. For example, the most stable isotope of lead, 208Pb, contains 82 protons and 126 neutrons. Propose a reason for this excess of neutrons over protons. 7. Given the information below concerning the stable isotopes of chromium, determine its atomic weight. Isotope
50 52 53 54

Mass (amu) 49.946047 51.940511 52.940652 53.938884

Natural abundance (%) 4.345 83.79 9.50 2.365

Cr

Cr Cr Cr

-1.298. The composition of calcium pyrophosphate is 25.3% Ca, 39.2% P, and 35.5% oxygen by weight. What is the empirical formula of calcium pyrophosphate? 9. How many atoms of carbon would it take to make 15.0 g of 2-chlorobutane (CH3CHClCH2CH3)? How many grams of hydrogen would this sample contain? 10. A solution is formed by mixing 2.50 g of Ba(OH)2 in 600 mL of water. Calculate the molarity, molality, and normality of this solution. (Note: you may neglect the volume of the Ba(OH)2. Also, the density of water is 1.00 g/mL). 11. What is the total volume of a solution originally having a volume of 35.0 mL and containing 40.0 mg of AgNO3 per mL after it has been diluted to a concentration of 16.0 mg/mL? 12. What was the mass of thorium contained in a sample that required 35.0 mL of 0.0200 M H2C2O4 to completely precipitate the thorium as Th(C2O4)2? 13. A 0.250 g sample of a solid acid was dissolved in water and exactly neutralized by 40.0 mL of 0.125 N base. What is the equivalent weight of the acid? 14. What volume of 5.00 N H2SO4 is required to neutralize a solution containing 2.50 g NaOH? 15. What are the concentrations of ions remaining in solution when 10.0 mL of 0.205 M HNO3 is added to 15.0 mL of 0.235 M NaOH? Answers 1. Kg/s2 = N/m 2. 76 L 3. 2069 mbar 4. !40 5. 146, 237Np 7. 52.00 amu 8. Ca2P4O7 9. 3.91x1023 C atoms, 1.46 g H 10. M = 0.0243, m = 0.0243, N = 0.0487 11. 87.5 mL 12. 0.0842 g 13. 50.0 g 14. 12.5 mL 15. [OH!] = 0.0588 M, [Na+] = 0.141 M, [NO3!] = 0.0820 M

-1.30THINGS YOU SHOULD KNOW

Conversion factors:

English units of length, mass, time, and volume. English to metric conversion factors: 1 in. = 2.54 cm, 1 lb = 454 g, 1 qt = 0.946 L 1 g = 6.0221x1023 amu 1 mole = 6.022x1023 Mass of 1 mole = atomic weight expressed in grams

Definitions:

Density = mass/volume; Pressure = force/area Atomic number Atomic mass number Isotope Ion Beta decay Celcius and Fahrenheit temperature scales Molecular formula Empirical formula Limiting reagent Neutralization reaction Equivalent Concentration units (M, m, N, wt %, mole fraction) Arrhenius acid and base Equivalence point

Relationships:

Significant figures M1V1 = M2V2 1 mole H+ neutralizes 1 mole OH! 1 eq acid neutralizes 1 eq base