Principles of modern chemistry david w oxtoby, h pat gillis, alan campion

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PERIODIC TABLE OF THE ELEMENTS
KEY
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79

Au

Gold
196.9665

1

Period
number

1

H

Hydrogen
1.0079

Group number,
U.S. system

1A
(1)

Group number,
IUPAC system

3

2

Li

Lithium
6.941
11

3

Na

Sodium
22.9898
19

4

K

Potassium

39.0983
37

5

Rb

Rubidium
85.4678
55

6

Cs

Cesium
132.9055
87

7

Fr

Francium
(223)

Main group metals

Atomic number
Symbol

Name
Atomic weight

Transition metals
Metalloids

An element

8A
(18)

Nonmetals, noble gases

2

2A
(2)

3A
(13)

4

5

Be

B

Beryllium

9.0122

Boron
10.811
13

12

Mg

Magnesium
24.3050
20

Ca

3B
(3)
21

Sc

Calcium
40.078

Scandium
44.9559

38

39

Strontium
87.62

Yttrium
88.9058

Sr
56

Ba

Barium
137.327
88

Ra

Radium
(226)

4B
(4)

5B
(5)

22

23

Titanium
47.867

Vanadium
50.9415

Ti
40

Y

Zr

Zirconium
91.224

57

72

La

Hf

Lanthanum
138.9055

Hafnium

178.49

89

104

Actinium
(227)

Rutherfordium
(267)

Ac

Rf

V

41

Nb

Niobium
92.9064
73

Ta

Tantalum
180.9479

105

Db

Dubnium
(268)

6B
(6)
24

Cr

Chromium
51.9961
42

Mo

7B
(7)
25

Mn

Manganese
54.9380
43

Tc

Molybdenum Technetium
95.96
(98)
74

W

Tungsten
183.84
106

Sg

Seaborgium
(271)

75

Re

Rhenium
186.207
107

Bh

Bohrium
(272)

8B
(8)

8B
(9)

26

27

Fe

Co

Iron
55.845

Cobalt
58.9332

44

45

Ru

Ruthenium
101.07
76

Rh

Rhodium
102.9055
77

Os

Ir

Osmium
190.23

Iridium
192.217

108

109

Hs

Mt

8B
(10)
28

Ni

Nickel
58.6934
46

Pd

Palladium
106.42
78

Pt

Platinum
195.084
110

Ds

1B
(11)
29

Cu

Copper
63.546
47

Ag

Silver
107.8682
79

Au

Gold
196.9666
111

Rg

Meitnerium Darmstadtium Roentgenium
(281)
(280)
(276)

Hassium
(277)

2B
(12)
30

Zn

Zinc
65.38
48

Cd

Cadmium
112.411
80

Hg

Mercury
200.59
112

—

—
(285)

Al

Aluminum
26.9815
31

Ga

Gallium
69.723
49

In

Indium
114.818
81

Tl

Thallium
204.3833
113

—

—
(284)

4A
(14)
6

C

5A
(15)
7

N

6A
(16)

8

O

Carbon
12.0107

Nitrogen
14.0067

Oxygen
15.9994

14

15

16

Silicon
28.0855

Phosphorus
30.9738

Sulfur
32.065

Si
32

Ge

Germanium
72.64
50

Sn

Tin
118.710
82

Pb

Lead
207.2
114

—

—
(287)

P

33

As

Arsenic
74.9216
51

Sb

Antimony
121.760
83

Bi

Bismuth
208.9804
115

—

—
(288)

S

34

Se

7A
(17)
9

F

Fluorine
18.9984
17

Cl

Chlorine
35.453
35

Br

Selenium
78.96

Bromine
79.904

52

53

Tellurium
127.60

Iodine
126.9045

Te
84

Po

Polonium
(209)

I

85

At

Astatine
(210)

116

He

Helium
4.0026

1

10

Ne

Neon
20.1797

2

18

Ar

Argon
39.948

3

36

Kr

Krypton
83.798

4

54

Xe

Xenon
131.293

5

86

Rn

Radon
(222)

6

118

—

—

—
(293)

—
(294)

7

Numbers in parentheses are mass
numbers of radioactive isotopes.
58

Lanthanides 6

Ce

Cerium
140.116
90

Actinides 7

H
Li Be
Na Mg
K Ca Sc
Rb Sr Y
Cs Ba La
Fr Ra Ac

Ti
Zr
Hf
Rf

He
B C N O F Ne
Al Si P S Cl Ar
V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Db Sg Bh Hs Mt Ds Rg — — — — —

—
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Th Pa U Np Pu AmCm Bk Cf Es Fm Md No Lr

Th

Thorium
232.0381

59

Pr

60

Nd

61

62

Pm

Praseodymium Neodymium Promethium
140.9076
144.242
(145)
91

Pa

Protactinium
231.0359

92

U

Uranium
238.0289

This icon appears throughout the
book to help locate elements of
interest in the periodic table. The
halogen group is shown here.

93

Np

Sm

Samarium
150.36
94

Neptunium
(237)

Pu

Plutonium
(244)

63

Eu

Europium
151.964
95

Am

Americium
(243)

64

Gd

Gadolinium
157.25
96

Cm

Curium
(247)

65

Tb

Terbium
158.9254
97

Bk

Berkelium
(247)

66

Dy

Dysprosium
162.500
98

Cf

Californium
(251)

67

Ho

Holmium
164.9303
99

Es

Einsteinium
(252)

68

Er

Erbium
167.259
100

Fm

Fermium
(257)

69

Tm

Thulium
168.9342
101

Md

Mendelevium
(258)

70

Yb

71

Lu

Ytterbium
173.054

Lutetium
174.9668

102

103

Nobelium
(259)

Lawrencium
(262)

No

Elements for which the International Union of Pure and Applied Chemistry (IUPAC) has officially
sanctioned the discovery and approved a name are indicated by their chemical symbols in this
table. Elements that have been reported in the literature but not yet officially sanctioned and
named are indicated by atomic number. The name copernicium was proposed for element 112
in July 2009, but at that time this name had not been officially accepted by IUPAC.

Lr

6

7


Standard Atomic Weights 
of the Elements 2009, IUPAC

Name
Symbol

Atomic
Number

Based on Relative Atomic Mass of 12C 5 12, where 12C is a neutral atom
in its nuclear and electronic ground state.1

Atomic
Weight
Name
Symbol

Actinium2
Ac
89 (227)
Aluminum
Al
13
26.981 5386(8)
Americium2
Am
95 (243)
Antimony
Sb
51
121.760(1)
Argon
Ar
18
39.948(1)
Arsenic
As
33
74.921 60(2)
Astatine2
At
85 (210)
Barium
Ba
56
137.327(7)

Berkelium2
Bk
97 (247)
Beryllium
Be
4
9.012 182(3)
Bismuth
Bi
83
208.980 40(1)
Bohrium2
Bh
107 (272)
Boron
B
5
10.811(7)
Bromine
Br
35
79.904(1)
Cadmium
Cd
48
112.411(8)
Calcium
Ca
20
40.078(4)

Californium2
Cf
98 (251)
Carbon
C
6
12.0107(8)
Cerium
Ce
58
140.116(1)
Cesium
Cs
55
132.905 4519(2)
Chlorine
Cl
17
35.453(2)
Chromium
Cr
24
51.9961(6)
Cobalt
Co
27
58.933 195(5)
Copper
Cu
29

63.546(3)
Curium2
Cm
96 (247)
Darmstadtium2
Ds
110 (281)
Dubnium2
Db
105 (268)
Dysprosium
Dy
66
162.500(1)
Einsteinium2
Es
99 (252)
Erbium
Er
68
167.259(3)
Europium
Eu
63
151.964(1)
Fermium2
Fm
100 (257)
Fluorine
F

9
18.998 4032(5)
Francium2
Fr
87 (223)
Gadolinium
Gd
64
157.25(3)
Gallium
Ga
31
69.723(1)
Germanium
Ge
32
72.64(1)
Gold
Au
79
196.966 569(4)
Hafnium
Hf
72
178.49(2)
Hassium2
Hs
108 (277)
Helium
He

2
4.002 602(2)
Holmium
Ho
67
164.930 32(2)
Hydrogen
H
1
1.00794(7)
Indium
In
49
114.818(3)
Iodine
I
53
126.904 47(3)
Iridium
Ir
77
192.217(3)
Iron
Fe
26
55.845(2)
Krypton
Kr
36
83.798(2)

Lanthanum
La
57
138.905 47(7)
Lawrencium2
Lr
103 (262)
Lead
Pb
82
207.2(1)
Lithium
Li
3
[6.941(2)]†
Lutetium
Lu
71
174.9668(1)
Magnesium
Mg
12
24.3050(6)
Manganese
Mn
25
54.938 045(5)
Meitnerium2
Mt
109 (276)

Mendelevium2
Md
101 (258)
Mercury
Hg
80
200.59(2)


Molybdenum
Mo
Neodymium
Nd
Neon
Ne
Neptunium2
Np
Nickel
Ni
Niobium
Nb
Nitrogen
N
Nobelium2
No
Osmium
Os
Oxygen
O
Palladium

Pd
Phosphorus
P
Platinum
Pt
Plutonium2
Pu
Polonium2
Po
Potassium
K
Praseodymium
Pr
Promethium2
Pm
Protactinium2
Pa
Radium2
Ra
Radon2
Rn
Rhenium
Re
Rhodium
Rh
Roentgenium2
Rg
Rubidium
Rb
Ruthenium

Ru
Rutherfordium2
Rf
Samarium
Sm
Scandium
Sc
Seaborgium2
Sg
Selenium
Se
Silicon
Si
Silver
Ag
Sodium
Na
Strontium
Sr
Sulfur
S
Tantalum
Ta
Technetium2
Tc
Tellurium
Te
Terbium
Tb
Thallium

Tl
Thorium2
Th
Thulium
Tm
Tin
Sn
Titanium
Ti
Tungsten
W
Uranium2
U
Vanadium
V
Xenon
Xe
Ytterbium
Yb
Yttrium
Y
Zinc
Zn
Zirconium
Zr
—2,3,4
—2,3
—2,3
—2,3
—2,3

—2,3

Atomic
Number

Atomic
Weight

42
95.96(2)
60
144.242(3)
10
20.1797(6)
93(237)
28
58.6934(4)
41
92.906 38(2)
7
14.0067(2)
102(259)
76
190.23(3)
8
15.9994(3)
46
106.42(1)
15
30.973 762(2)

78
195.084(9)
94(244)
84(209)
19
39.0983(1)
59
140.907 65(2)
61(145)
91
231.035 88(2)
88(226)
86(222)
75
186.207(1)
45
102.905 50(2)
111(280)
37
85.4678(3)
44
101.07(2)
104(267)
62
150.36(2)
21
44.955 912(6)
106(271)
34
78.96(3)

14
28.0855(3)
47
107.8682(2)
11
22.989 769 28(2)
38
87.62(1)
16
32.065(5)
73
180.947 88(2)
43 (98)
52
127.60(3)
65
158.925 35(2)
81
204.3833(2)
90
232.038 06(2)
69
168.934 21(2)
50
118.710(7)
22
47.867(1)
74
183.84(1)
92

238.028 91(3)
23
50.9415(1)
54
131.293(6)
70
173.054(5)
39
88.905 85(2)
30
65.38(2)
40
91.224(2)
112(285)
113(284)
114(287)
115(288)
116(293)
118
(294)

1. The atomic weights of many elements vary depending on the origin and treatment of the sample. This is particularly true for Li; commercially available lithium-containing 
materials have Li atomic weights in the range of 6.939 and 6.996. Uncertainties are given in parentheses following the last significant figure to which they are attributed.
2. Elements with no stable nuclide; the value given in parentheses is the atomic mass number of the isotope of longest known half-life. However, three such elements (Th, 
Pa, and U) have a characteristic terrestrial isotopic composition, and the atomic weight is tabulated for these.
3.. Not yet named.
4. The name copernicium was proposed for element 112 in July 2009, but at that time this name had not been officially accepted by IUPAC.
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PRINCIPLES OF
MODERN CHEMISTRY
sEVENTH EDITION

DAVID W. OXTOBY
Pomona College

H.P. GILLIs
University of California—Los Angeles

ALAN CAMPION
The University of Texas at Austin
Images of orbitals in Chapters 4, 5, 6, and 8 contributed by

HATEM H. HELAL
California Institute of Technology and Cambridge University, UK

KELLY P. GAITHER
The University of Texas at Austin

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Principles of Modern Chemistry,
Seventh Edition
David W. Oxtoby, H.P. Gillis, Alan Campion
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IN APPRECIATION OF

Mostafa A. El-Sayed
Karl F. Freed
William M. Gelbart
our PhD advisers
for their distinguished careers in scientific research and education

The search for truth is in one way hard and in another easy, for it is evident that no one can
master it fully or miss it completely.
But each adds a little to our knowledge of nature, and from all the facts assembled there
arises a certain grandeur.
(Greek inscription, taken from Aristotle, on the facade of the National Academy of Sciences
building in Washington, D.C.)

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B rief

content s

UNIT

I

Introduction to the Study of Modern Chemistry  1
1 The Atom in Modern Chemistry  3
2 Chemical Formulas, Equations, and Reaction Yields  35
UNIT

II

Chemical Bonding and Molecular Structure  60
3
4
5
6
7
8
UNIT

Chemical Bonding: The Classical Description  63
Introduction to Quantum Mechanics  139
Quantum Mechanics and Atomic Structure  193
Quantum Mechanics and Molecular Structure  235
Bonding in Organic Molecules  307

Bonding in Transition Metal Compounds and Coordination Complexes  347

III

Kinetic Molecular Description of the States of Matter  392
9 The Gaseous State  395
10 Solids, Liquids, and Phase Transitions  443
11 Solutions  473
UNIT

IV

Equilibrium in Chemical Reactions  516
2
1
13
14
15
16
17

Thermodynamic Processes and Thermochemistry  519
Spontaneous Processes and Thermodynamic Equilibrium  571
Chemical Equilibrium  613
Acid–Base Equilibria  669
Solubility and Precipitation Equilibria  733
Electrochemistry  763

v
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vi

BRIEF CONTENTS
UNIT

V

Rates of Chemical and Physical Processes  832
8 Chemical Kinetics  835
1
19 Nuclear Chemistry  891
20 Molecular Spectroscopy and Photochemistry  941
UNIT

VI

Materials  1032
1 Structure and Bonding in Solids  1035
2
22 Inorganic Materials  1069
23 Polymeric Materials and Soft Condensed Matter  1105
APPENDICES

A
B
C
D

E
F
G

Scientific Notation and Experimental Error  A.2
SI Units, Unit Conversions, and Physics for General Chemistry  A.9
Mathematics for General Chemistry  A.21
Standard Chemical Thermodynamic Properties  A.35
Standard Reaction Potentials at 25°C  A.43
Physical Properties of the Elements  A.45
Solutions to the Odd-Numbered Problems  A.55

Index/Glossary  I.1

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C O N T E N TS

U N I T

1

Introduction to the Study of Modern Chemistry  1
CHAPTER

1

The Atom in Modern Chemistry  3

1.1 The Nature of Modern Chemistry  3
1.2 Macroscopic Methods for Classifying Matter  6
1.3 Indirect Evidence for the Existence of Atoms: Laws of Chemical

Combination  9
1.4 The Physical Structure of Atoms  16
CHAPTER

2

Chemical Formulas, Equations,
and Reaction Yields  35
2.1 The Mole: Weighing and Counting Molecules  36
2.2 Empirical and Molecular Formulas  40
2.3 Chemical Formula and Percentage Composition  41
2.4 Writing Balanced Chemical Equations  43
2.5 Mass Relationships in Chemical Reactions  47
2.6 Limiting Reactant and Percentage Yield  49

vii
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viii
U N I T

CONTENTS

2

Chemical Bonding and Molecular Structure  60
CHAPTER

3

Chemical Bonding: The Classical Description  63
3.1 Representations of Molecules  65
3.2 The Periodic Table  70
3.3 Forces and Potential Energy in Atoms  73
3.4 Ionization Energies, the Shell Model of the Atom, and Shielding  79
3.5 Electron Affinity  85
3.6 Electronegativity: The Tendency of Atoms to Attract Electrons in

Molecules  88
3.7 Forces and Potential Energy in Molecules: Formation of Chemical Bonds  91
3.8 Ionic Bonding  94
3.9 Covalent and Polar Covalent Bonding  98
3.10 Electron Pair Bonds and Lewis Diagrams for Molecules  107
3.11 The Shapes of Molecules: Valence Shell Electron-Pair Repulsion Theory  115
3.12 Oxidation Numbers  120
3.13 Inorganic Nomenclature  122
CHAPTER

4

Introduction to Quantum Mechanics  139
4.1 Preliminaries: Wave Motion and Light  141
4.2 Evidence for Energy Quantization in Atoms  145
4.3 The Bohr Model: Predicting Discrete Energy Levels in Atoms  153

4.4 Evidence for Wave–Particle Duality  157
4.5 The Schrödinger Equation  167
4.6 Quantum Mechanics of Particle-in-a-Box Models  172
4.7 A DEEPER LOOK Wave Functions for Particles in Two- and Three-

Dimensional Boxes  178
CHAPTER

5

Quantum Mechanics and Atomic Structure  193
5.1 The Hydrogen Atom  195
5.2 Shell Model for Many-Electron Atoms  210
5.3 Aufbau Principle and Electron Configurations  215
5.4 Shells and the Periodic Table: Photoelectron Spectroscopy  220
5.5 Periodic Properties and Electronic Structure  224

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CONTENTS
CHAPTER

6

Quantum Mechanics and Molecular Structure  235
6.1 Quantum Picture of the Chemical Bond  237

6.2 Exact Molecular Orbitals for the Simplest Molecule: H1
2  241
6.3 Molecular Orbital Theory and the Linear Combination of Atomic Orbitals

Approximation for H12  247

6.4 Homonuclear Diatomic Molecules: First-Period Atoms  251
6.5 Homonuclear Diatomic Molecules: Second-Period Atoms  253
6.6 Heteronuclear Diatomic Molecules  262
6.7 Summary Comments for the LCAO Method and Diatomic Molecules  265
6.8 Valence Bond Theory and the Electron Pair Bond  268
6.9 Orbital Hybridization for Polyatomic Molecules  273
6.10 Predicting Molecular Structures and Shapes  281
6.11 Using the LCAO and Valence Bond Methods Together  286
6.12 Summary and Comparison of the LCAO and Valence Bond Methods  289
6.13 A DEEPER LOOK Properties of the Exact Molecular Orbitals for H1
2  294
CHAPTER

7

Bonding in Organic Molecules  307
7.1 Petroleum Refining and the Hydrocarbons  308
7.2 The Alkanes  309
7.3 The Alkenes and Alkynes  314
7.4 Aromatic Hydrocarbons  319
7.5 Fullerenes  322
7.6 Functional Groups and Organic Reactions  324
7.7 Pesticides and Pharmaceuticals  334
CHAPTER

8

Bonding in Transition Metal Compounds
and Coordination Complexes  347
8.1 Chemistry of the Transition Metals  348
8.2 Introduction to Coordination Chemistry  355
8.3 Structures of Coordination Complexes  361
8.4 Crystal Field Theory: Optical and Magnetic Properties  367
8.5 Optical Properties and the Spectrochemical Series  374
8.6 Bonding in Coordination Complexes  376

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ix


x
U N I T

CONTENTS

3

Kinetic Molecular Description of the States of Matter  392
CHAPTER

9

The Gaseous State  395
9.1 The Chemistry of Gases  396
9.2 Pressure and Temperature of Gases  398
9.3 The Ideal Gas Law  405
9.4 Mixtures of Gases  408
9.5 The Kinetic Theory of Gases  410
9.6 Real Gases: Intermolecular Forces  417
9.7 A DEEPER LOOK Molecular Collisions and Rate Processes  422
CHAPTER

10

Solids, Liquids, and Phase Transitions  443
10.1 Bulk Properties of Gases, Liquids, and Solids: Molecular Interpretation  444
10.2 Intermolecular Forces: Origins in Molecular Structure  449
10.3 Intermolecular Forces in Liquids  455
10.4 Phase Equilibrium  459
10.5 Phase Transitions  460
10.6 Phase Diagrams  462
CHAPTER

11

Solutions  473
11.1 Composition of Solutions  474
11.2 Nature of Dissolved Species  478
11.3 Reaction Stoichiometry in Solutions: Acid–Base Titrations  481
11.4 Reaction Stoichiometry in Solutions: Oxidation–Reduction Titrations  485
11.5 Phase Equilibrium in Solutions: Nonvolatile Solutes  491
11.6 Phase Equilibrium in Solutions: Volatile Solutes  499

11.7 Colloidal Suspensions  504

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CONTENTS

U N I T

xi

4

Equilibrium in Chemical Reactions  516
CHAPTER

12

Thermodynamic Processes and Thermochemistry  519
12.1 Systems, States, and Processes  521
12.2 The First Law of Thermodynamics: Internal Energy, Work, and Heat  524
12.3 Heat Capacity, Calorimetry, and Enthalpy  530
12.4 The First Law and Ideal Gas Processes  533
12.5 Molecular Contributions to Internal Energy and Heat Capacity  537
12.6 Thermochemistry  542
12.7 Reversible Processes in Ideal Gases  551
12.8 A DEEPER LOOK Distribution of Energy among Molecules  556

CHAPTER

13

Spontaneous Processes and Thermodynamic
Equilibrium  571
13.1 The Nature of Spontaneous Processes  572
13.2 Entropy and Spontaneity: A Molecular Statistical Interpretation  575
13.3 Entropy and Heat: Macroscopic Basis of the Second Law of

Thermodynamics  580
13.4 Entropy Changes in Reversible Processes  582
13.5 Entropy Changes and Spontaneity  586
13.6 The Third Law of Thermodynamics  590
13.7 The Gibbs Free Energy  592
13.8 A DEEPER LOOK Carnot Cycles, Efficiency, and Entropy  597
CHAPTER

14

Chemical Equilibrium  613
14.1 The Nature of Chemical Equilibrium  614
14.2 The Empirical Law of Mass Action  618
14.3 Thermodynamic Description of the Equilibrium State  623
14.4 The Law of Mass Action for Related and Simultaneous Equilibria  630
14.5 Equilibrium Calculations for Gas-Phase and Heterogeneous Reactions  632
14.6 The Direction of Change in Chemical Reactions: Empirical Description  639
14.7 The Direction of Change in Chemical Reactions: Thermodynamic

Explanation  646

14.8 Distribution of a Single Species between Immiscible Phases: Extraction and

Separation Processes  650

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xii

CONTENTS
CHAPTER

15

Acid–Base Equilibria  669
15.1 Classifications of Acids and Bases  670
15.2 Properties of Acids and Bases in Aqueous Solutions: The Brønsted–Lowry

Scheme  677
15.3 Acid and Base Strength  681
15.4 Equilibria Involving Weak Acids and Bases  689
15.5 Buffer Solutions  694
15.6 Acid–Base Titration Curves  699
15.7 Polyprotic Acids  704
15.8 Organic Acids and Bases: Structure and Reactivity  710
15.9 A DEEPER LOOK Exact Treatment of Acid–Base Equilibria  714
CHAPTER

16

Solubility and Precipitation Equilibria  733
16.1 The Nature of Solubility Equilibria  734
16.2 Ionic Equilibria between Solids and Solutions  737
16.3 Precipitation and the Solubility Product  740
16.4 The Effects of pH on Solubility  744
16.5 Complex Ions and Solubility  746
16.6 A DEEPER LOOK Selective Precipitation of Ions  751
CHAPTER

17

Electrochemistry  763
17.1 Electrochemical Cells  764
17.2 Cell Potentials and the Gibbs Free Energy  770
17.3 Molecular Interpretation of Electrochemical Processes  780
17.4 Concentration Effects and the Nernst Equation  781
17.5 Molecular Electrochemistry  787
17.6 Batteries and Fuel Cells  800
17.7 Corrosion and Corrosion Prevention  808
17.8 Electrometallurgy  810
17.9 A DEEPER LOOK Electrolysis of Water and Aqueous Solutions  816

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CONTENTS

U N I T

5

Rates of Chemical and Physical Processes  832
CHAPTER

18

Chemical Kinetics  835
18.1 Rates of Chemical Reactions  836
18.2 Rate Laws  839
18.3 Reaction Mechanisms  846
18.4 Reaction Mechanisms and Rate  850
18.5 Effect of Temperature on Reaction Rates  856
18.6 Molecular Theories of Elementary Reactions  859
18.7 Reactions in Solution  868
18.8 Catalysis  869
CHAPTER

19

Nuclear Chemistry  891
19.1 Radioactivity  892
19.2 Nuclear Structure and Nuclear Decay Processes  894
19.3 Mass–Energy Relationships  903
19.4 Kinetics of Radioactive Decay  908
19.5 Radiation in Biology and Medicine  913
19.6 Nuclear Fission  917

19.7 Nuclear Fusion and Nucleosynthesis  922
19.8 A DEEPER LOOK The Shell Model of the Nucleus  925
CHAPTER

20

Molecular Spectroscopy and Photochemistry  941
20.1 Introduction to Molecular Spectroscopy  942
20.2 Experimental Methods in Molecular Spectroscopy  947
20.3 Rotational and Vibrational Spectroscopy  948
20.4 Nuclear Magnetic Resonance Spectroscopy  966
20.5 Electronic Spectroscopy and Excited State Relaxation Processes  973
20.6 Introduction to Atmospheric Chemistry  992
20.7 Photosynthesis  1009
20.8 A DEEPER LOOK The Einstein Radiation Relations and Lasers  1015

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xiii


xiv
U N I T

CONTENTS

6

Materials  1032

CHAPTER

21

Structure and Bonding in Solids  1035
21.1 Crystal Symmetry and the Unit Cell  1036
21.2 Crystal Structure  1042
21.3 Cohesion in Solids  1047
21.4 Defects and Amorphous Solids  1053
21.5 A DEEPER LOOK Lattice Energies of Crystals  1057
CHAPTER

22

Inorganic Materials  1069
22.1 Minerals: Naturally Occurring Inorganic Materials  1070
22.2 Properties of Ceramics  1075
22.3 Silicate Ceramics  1077
22.4 Nonsilicate Ceramics  1082
22.5 Electrical Conduction in Materials  1086
22.6 Band Theory of Conduction  1090
22.7 Semiconductors  1093
22.8 Pigments and Phosphors: Optical Displays  1096
CHAPTER

23

Polymeric Materials and Soft Condensed Matter  1105
23.1 Polymerization Reactions for Synthetic Polymers  1106
23.2 Applications for Synthetic Polymers  1110

23.3 Liquid Crystals  1117
23.4 Natural Polymers  1119

Appendices A.1
A

Scientific Notation and Experimental Error  A.2

B

SI Units, Unit Conversions, and Physics for General Chemistry  A.9

C

Mathematics for General Chemistry  A.21

D

Standard Chemical Thermodynamic Properties  A.35

E

Standard Reduction Potentials at 25°C  A.43

F

Physical Properties of the Elements  A.45

G

Answers to Odd-Numbered Problems  A.55

Index/Glossary  I.1

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AP P L I C A T I O NS

Connection to Nanotechnology: Imaging Atoms, Molecules, and Chemical
Reactions by Scanning Tunnelling Microscopy  26
Connection to Chemical Engineering: Sulfuric Acid Manufacturing  46
Cumulative Exercise: Titanium in Industry  53
Connection to Instrumental Analysis: Mass Spectrometry  68
Connection to Instrumental Analysis: Molecular Spectroscopy  102
Cumulative Exercise: Structure and Bonding in Metal Oxides and Peroxides  130
Cumulative Exercise: Conjugated Molecules in Dyestuffs and Biological
Materials  187
Cumulative Exercise: Atoms in Interstellar Space  230
Connection to Instrumental Analysis: Photoelectron Spectroscopy  266
Cumulative Exercise: Iodine in the Human Diet  303
Connection to Biology: Functional Groups in Proteins  332
Connection to Biology: Coordination Complexes in Heme Proteins  364
Cumulative Exercise: Platinum  387
Connection to Chemical Engineering: Uranium Enrichment for Nuclear Reactor
Fuel  428
Cumulative Exercise: Ammonium Perchlorate as a Rocket Fuel  434
Cumulative Exercise: Alloys of Bismuth and their Applications  468
Cumulative Exercise: Manufacturing of Maple Syrup  508

Cumulative Exercise: Methanol as a Gasoline Substitute  562
Cumulative Exercise: Purifying Nickel from Its Ores  606
Connection to Biology: Hemoglobin and Oxygen Transport  640
Cumulative Exercise: Production of Sulfuric Acid  657
Connection to Biology: Buffered Blood Plasma  708
Cumulative Exercise: Acid Rain  724
Cumulative Exercise: Carbonate Minerals in Fresh Water and Seawater  756
Connection to Energy: Solar Energy Conversion  798

xv
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xvi

APPLICATIONS

Cumulative Exercise: Manganese—A Versatile Reagent and Essential Mineral  822
Cumulative Exercise: Sulfite and Sulfate Kinetics in Atmospheric Chemistry  880
Connection to Medicine: Isotopes and Nuclear Medicine  914
Cumulative Exercise: Radon in the Environment  935
Cumulative Exercise: Bromine  1023
Cumulative Exercise: The Many States of Phosphorus  1064

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P R E F A C E

The seventh edition of Principles of Modern Chemistry is written for students in
honors and upper-mainstream general chemistry courses who seek to understand
and interpret chemical events at the molecular level. The relation of molecular
structure to function and properties requires the introduction of molecular structure early in the course and the use of structural arguments in presenting the remaining topics. Moreover, these students will soon be introduced to the great predictive power of chemical computations and simulations, for which a solid
background in the description of molecular structure is essential.
The seventh edition presents the material from a unified, molecular point of
view that continues to emphasize the central role of structure, but now with greater
focus on the electronic structure of molecules as a unifying theme. Chapters 17 and
20, for example, have been completely rewritten to provide additional insight into
the nature of electrochemical, spectroscopic, and photochemical processes by discussing the role of electronic excitations, energy transfer, and charge transfer in
these processes using the qualitative quantum mechanical concepts (energy levels
and their occupancy) developed earlier in the book.
The organization of the seventh edition is fundamentally the same as that of the
sixth edition, which was an extensive revision of the traditional “macro-to-micro”
approach employed in the first five editions. A number of changes and additions have
been made to improve the text. The quantum description of the chemical bond in
Chapter 6 has been simplified to make it more accessible to our students. A comprehensive introduction to molecular spectroscopy has been provided in Chapter 20;
those methods that are used to determine molecular structure are also introduced
earlier in the book with references to the relevant sections of Chapter 20. We have
provided these brief introductions at “point of use” for the convenience of instructors
who may wish to illustrate features of structure and bonding with spectroscopic examples or to provide background for laboratory classes being taken concurrently.
Greater reliance is placed on molecular structure in developing subsequent topics (for
example, acid–base equilibria, chemical kinetics, electrochemistry, organic chemistry,
and the chemistry of transition metal complexes) than in the sixth edition. A number
of new essays provide “Connections to. . .” other branches of science, engineering,
and medicine. Coupled with the interdisciplinary Cumulative Exercises that have long
been a hallmark of Principles of Modern Chemistry, these “Connections” introduce
our students to a wide range of applications of the principles of chemistry.

SIGNIFICANT CHANGES IN THIS EDITION
■

New Treatment of Structure and Bonding—Chemical bonding and molecular
structure remain at the beginning of the book. We describe the classical elements
of bonding theory—ionic, covalent, and polar bonds; dipole moments; Lewis
xvii

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xviii

PREFACE

electron dot diagrams; and Valence Shell Electron Pair Repulsion (VSEPR) theory. We have simplified the discussion of forces and potential energy in atoms
and molecules to place greater emphasis on graphical representations and simple
physical interpretations, to support the chemical concepts in classical bonding
theory, and to illustrate the magnitudes of energy and length scales at the atomic
and molecular level. We have reorganized the quantum description of chemical
bonding to make it more accessible to our students, to group more advanced
material at the end of the chapter, to provide a coherent treatment of the various
applications of the LCAO model, and to present a new discussion of the combined use of the LCAO and VB models as occurs in practice. The result is a unified and thorough treatment of quantum bonding theory, presenting the
molecular orbital (MO) and valence bond (VB) models on equal footing and at
the same intellectual and conceptual level. We provide detailed comparisons of
these two models and show how either one can be the starting point for applications of computational chemistry and molecular simulation programs that our
students will encounter soon in subsequent chemistry courses.

■

■

■

■

■

■

New Molecular Art—The sixth edition introduced an art program in which
molecular shapes are rendered with quantitative accuracy and in modern
graphical style. All illustrations of atomic and molecular orbitals, charge density, and electrostatic potential energy maps were generated from accurate
quantum chemistry calculations carried out at the California Institute of Technology. All orbitals were plotted using state-of-the-art visualization software at
the Texas Advanced Computing Center at the University of Texas at Austin.
The colors, lighting effects, and viewing angles were chosen to display threedimensional objects with maximum clarity and to provide chemical insight.
Revised Writing Style without Loss of Rigor—The language is more modern
and less formal. We have introduced a more conversational writing style,
designed to engage our students as active participants in developing the presentation. We have examined every sentence in the book to simplify and lighten
the language without compromising intellectual integrity.
Greater Flexibility in Topic Coverage—In response to comments by students,
faculty, and reviewers, greater modularity and flexibility have been built into the
text to make it compatible with alternative sequences of topics. While keeping the
discussion of bonding and structure at the beginning of the book, we have been
careful to maintain the option to follow the “macro-to-micro” approach used in
previous editions. Selecting alternative approaches is facilitated by the unit structure of the book; we offer several suggestions in the Teaching Options section.
New End-of-Chapter Student Aids—In response to suggestions by students,
faculty, and reviewers, we have consolidated the Chapter Review and list of

Key Equations with the Concepts and Skills sections to provide better organization of the review materials. The result is a focused review of the key topics
in each section, connected with specific in-text examples and end-of-chapter
problems that illustrate each topic. These are integrated with the Chapter Summary and Cumulative Exercises from previous editions to provide a comprehensive set of tools for reviewing and studying the contents of each chapter.
New Problems—We’ve added approximately 45 new problems throughout the
book. These follow the unique tradition established in previous editions that all
problems are based on actual experimental data measured on real chemical
systems. We intend the problems to guide our students in developing intuition
for chemical results and the magnitudes of chemical quantities, as well as facility in numerical calculations.
Instructors can choose to offer OWL Online Web Learning with the text. We
have added new end-of-chapter problems from each chapter that can be
assigned in OWL, for a total of approximately 25 problems in OWL per chapter. See the section later on Supporting Materials for a description of OWL.

Copyright 2011 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s).
Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.






PREFACE

xix

MAJOR CHANGES IN CONTENT
AND ORGANIZATION
Chapter 1: The Atom in Modern Chemistry
This chapter describes the physical structure of the atom, as determined from the
classic experiments of Thomson, Millikan, and Rutherford. New material has been
added describing the discovery that atoms can form positive ions of varying masses

and charges, which provides the basis for chemical analysis by mass spectrometry.
The chapter ends with direct scanning tunneling microscopy images of individual
atoms in chemical reactions, and a Connection to Nanotechnology that illustrates
how atoms can be manipulated into positions in nanostructures.

Chapter 3: Chemical Bonding: The Classical Description
This chapter provides a substantial introduction to molecular structure by coupling
experimental observation with interpretation through simple classical models. Today, the tools of classical bonding theory—covalent bonds, ionic bonds, polar covalent bonds, electronegativity, Lewis electron dot diagrams, and VSEPR theory—
have all been explained by quantum mechanics. It is a matter of preference whether
to present the classical theory first and then gain deeper insight from the quantum
explanations, or to cover the quantum theory first and then see the classical theory
as a limiting case. Our experience has been that presenting the classical description
first enables our students to bring considerably greater sophistication to their first
encounter with quantum mechanics and therefore to develop a deeper appreciation
for that subject. We have seen that this approach offers definitive pedagogical advantages by enabling students to
■

■

■

learn the language and vocabulary of the chemical bond starting from familiar
physical concepts.
become familiar with the properties of a broad array of real molecules before
attempting to explain these results using quantum mechanics.
develop experience in using physical concepts and equations to describe the
behavior of atoms and molecules.

We have revised this chapter to more effectively meet these goals. Changes include
the following:

■

■

■

■

Section 3.1, which is completely new, introduces the various pictorial representations of molecules. These images put a visual tone on the chapter from the
beginning and keep the reader focused on the issues that are being explained by
bonding concepts.
Section 3.3 illustrates the Coulomb potential with several quantitative applications in a more pictorial and physical manner than in the sixth edition. The
goal is to develop intuition for the magnitudes of energy and length scales that
appear in atomic structure.
Section 3.4 develops the shell model of the atom by examination of experimental values for successive ionization potentials and introduces the concepts of
screening and effective nuclear charge in many electron atoms to account for
the shell structure. This elementary physical description of effective nuclear
charge provides an easy-to-understand explanation for the physical origin of
the periodic trends observed in atomic properties. This explanation is refined
later by the quantum theory of atomic structure.
In Sections 3.5 and 3.6 the description of electron affinity has been extended
and clarified, the Pauling and Mulliken descriptions of electronegativity are
discussed together, and the relationship between the two scales is explained.

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Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.