Principles of modern chemistry

6.941

Lithium

9.0122

Beryllium

22.9898

Sodium

24.3050

Magnesium

39.0983

Potassium

40.078

Calcium

44.9559

Scandium

47.867

Titanium

50.9415

Vanadium

51.9961

Chromium

54.9380

Manganese

55.845

Iron

4.0026

Helium

14.0067

Nitrogen

15.9994

Oxygen

30.9738

Phosphorus

32.065

Sulfur

63.546

Copper

65.409

Zinc

69.723

Gallium

72.64

Germanium

74.9216

Arsenic

78.96

Selenium

79.904

Bromine

83.798

Krypton

18.9984

Fluorine

20.1797

Neon

35.453

Chlorine

39.948

Argon

58.9332

Cobalt

58.6934

Nickel

10.811

Boron

12.0107

Carbon

26.9815

Aluminum

28.0855

Silicon

85.4678

Rubidium

87.62

Strontium

88.9058

Yttrium

91.224

Zirconium

92.9064

Niobium

95.94

Molybdenum

(98)

Technetium

101.07

Ruthenium

107.8682

Silver

112.411

Cadmium

114.818

Indium

118.710

Tin

121.760

Antimony

127.60

Tellurium

126.9045

Iodine

131.293

Xenon

102.9055

Rhodium

106.42

Palladium

132.9055

Cesium

137.327

Barium

178.49

Hafnium

180.9479

Tantalum

183.84

Tungsten

186.207

Rhenium

190.23

Osmium

196.9666

Gold

200.59

Mercury

204.3833

Thallium

207.2

Lead

208.9804

Bismuth

(209)

Polonium

(210)

Astatine

(222)

Radon

192.217

Iridium

195.084

Platinum

(223)

Francium

(226)

Radium

174.967

Lutetium

103

(262)

Lawrencium

I VIII

VI VII

104

(261)

Rutherfordium

105

(262)

Dubnium

106

(266)

Seaborgium

107

(264)

Bohrium

108

(277)

Hassium

109

(268)

Meitnerium

110

(281)

Darmstadtium

111

(272)

Roentgenium

112

(285)

Uub

Ununbium

114

(289)

Uuq

Ununquadium

113

(284)

Uut

Ununtrium

116

(293)

Uuh

Ununhexium

118

(294)

Uuo

Ununoctium

115

(288)

Uup

Ununpentium

1.0079

Hydrogen

II III IV V

Transition elements

Metals

Semimetals

Nonmetals

PERIODIC TABLE OF THE ELEMENTS

138.9053

Lanthanum

(227)

Actinium

140.116

Cerium

140.9076

Praseodymium

144.242

Neodymium

(145)

Promethium

157.25

Gadolinium

158.9254

Terbium

162.500

Dysprosium

164.9303

Holmium

167.259

Erbium

168.9342

Thulium

173.04

Ytterbium

150.36

Samarium

151.964

Europium

232.0381

Thorium

231.0359

Protactinium

238.0289

Uranium

(237)

Neptunium

(247)

Curium

(247)

Berkelium

(251)

Californium

(252)

Einsteinium

100

(257)

Fermium

101

(258)

Mendelevium

102

(259)

Nobelium

(244)

Plutonium

(243)

Americium

Lanthanide series

Actinide series

93661_32_ES_p2-4.qxd 2/22/07 8:01 AM Page 2

Physical Constants

Avogadro’s number NA 6.0221415 1023 mol1

Bohr radius a0 0.5291772108 Å 5.291772108 1011 m

Boltzmann’s constant kB 1.3806505 1023 J K1

Electron charge e 1.60217653 1019 C

Faraday constant 96,485.3383 C mol1

Masses of fundamental particles:

Electron me 9.1093826 1031 kg

Proton mp 1.67262171 1027 kg

Neutron mn 1.67492728 1027 kg

Permittivity of vacuum e0 8.854187817 1012 C2 J

1 m1

Planck’s constant h 6.62606893 1034 J s

Ratio of proton mass to electron mass mp/me 1836.15267261

Speed of light in a vacuum c 2.99792458 108 m s1 (exactly)

Standard acceleration of terrestrial gravity g 9.80665 m s2 (exactly)

Universal gas constant R 8.314472 J mol1 K1

0.0820574 L atm mol1 K1

Values are taken from the 2002 CODATA recommended values, as listed by the National Institute of Standards and Technology.

Conversion Factors

Ångström 1 Å 1010 m

Atomic mass unit 1 u 1.66053886 1027 kg

1 u 1.49241790 1010 J 931.494043 MeV (energy equivalent from E mc2

)

Calorie 1 cal 4.184 J (exactly)

Electron volt 1 eV 1.60217653 1019 J

96.485335 kJ mol1

Foot 1 ft 12 in 0.3048 m (exactly)

Gallon (U.S.) 1 gallon 4 quarts 3.78541 L (exactly)

Liter 1 L 103 m3 103 cm3 (exactly)

Liter-atmosphere 1 L atm 101.325 J (exactly)

Metric ton 1 t 1000 kg (exactly)

Pound 1 lb 16 oz 0.4539237 kg (exactly)

Rydberg 1 Ry 2.17987209 1018 J

1312.7136 kJ mol1

13.6056923 eV

Standard atmosphere 1 atm 1.01325 105 Pa

1.01325 105 kg m1 s

2 (exactly)

Torr 1 torr 133.3224 Pa

93661_32_ES_p2-4.qxd 2/22/07 8:01 AM Page 3

Principles of

Modern Chemistry

SIXTH EDITION

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Principles of

Modern Chemistry

DAVID W. OXTOBY

Pomona College

H . P. G I L L I S

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

K E L LY P. G A I T H E R

The University of Texas at Austin

SIXTH EDITION

Australia • Brazil • Canada • Mexico • Singapore • Spain

United Kingdom • United States

93661_00_FM-p000i-xxxi.qxd 2/21/07 3:49 PM Page iii

Principles of Modern Chemistry, Sixth Edition

David W. Oxtoby, H.P. Gillis, Alan Campion

Acquisitions Editor: Lisa Lockwood

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93661_00_FM-p000i-xxxi.qxd 2/21/07 3:49 PM Page iv

IN APPRECIATION OF

Harry B. Gray, Bruce H. Mahan†

, and George C. Pimentel†

for the legacy of their textbooks and lectures

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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UNIT I

Introduction to the Study of Modern Chemistry 1

1 The Atom in Modern Chemistry 2

2 Chemical Formulas, Chemical Equations, and Reaction Yields 29

UNIT II

Chemical Bonding and Molecular Structure 52

3 Chemical Bonding: The Classical Description 54

4 Introduction to Quantum Mechanics 114

5 Quantum Mechanics and Atomic Structure 169

6 Quantum Mechanics and Molecular Structure 211

7 Bonding in Organic Molecules 275

8 Bonding in Transition Metal Compounds and Coordination Complexes 313

UNIT III

Kinetic Molecular Description of the States of Matter 362

9 The Gaseous State 364

10 Solids, Liquids, and Phase Transitions 409

11 Solutions 441

UNIT IV

Equilibrium in Chemical Reactions 484

12 Thermodynamic Processes and Thermochemistry 486

13 Spontaneous Processes and Thermodynamic Equilibrium 529

14 Chemical Equilibrium 569

15 Acid–Base Equilibria 625

16 Solubility and Precipitation Equilibria 677

17 Electrochemistry 705

vii

Brief Contents

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UNIT V

Rates of Chemical and Physical Processes 748

18 Chemical Kinetics 750

19 Nuclear Chemistry 793

20 Interaction of Molecules with Light 825

UNIT VI

Materials 862

21 Structure and Bonding in Solids 864

22 Inorganic Materials 895

23 Polymeric Materials and Soft Condensed Matter 929

APPENDICES

A Scientific Notation and Experimental Error A.2

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

C Mathematics for General Chemistry A.21

D Standard Chemical Thermodynamic Properties A.37

E Standard Reaction Potentials at 25°C A.45

F Physical Properties of the Elements A.47

G Solutions to the Odd-Numbered Problems A.57

Index ■ Glossary I.1

viii Brief Contents

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When the first edition of Principles of Modern Chemistry appeared in 1986, the

standard sequence of topics in honors and high-level mainstream general chemistry courses began with macroscopic descriptions of chemical phenomena and

proceeded to interpret these in terms of molecular structure. This traditional

“macro-to-micro” approach has shifted in recent years, and today the central topics in these courses are chemical bonding and molecular structure. 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.

In preparing the sixth edition, we have revised the textbook extensively to meet

these present-day needs. In particular, we believe that the most logical sequence of

topics begins with the physical properties and structure of atoms; is followed by

structure, bonding, and properties of molecules; proceeds to describe macroscopic

collections of atoms and molecules; continues with a discussion of chemical properties and reactions under equilibrium conditions; and finishes with dynamics and

kinetics.

Significant Changes in This Edition

■ New Treatment and Placement of Structure and Bonding Chemical bonding

and molecular structure are now at the beginning of the book. We describe the

classical elements of bonding theory—ionic, covalent, and polar bonds; dipole

moments; Lewis electron diagrams; and Valence Shell Electron Pair Repulsion

(VSEPR) theory. We present 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 the development of computational quantum chemistry and molecular simulation programs that our students will encounter soon

in subsequent chemistry courses.

■ New Molecular Art 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. For this edition, the orbitals were plotted using stateof-the-art 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 three-dimensional objects with maximum clarity and to provide

chemical insight.

Preface

93661_00_FM-p000i-xxxi.qxd 2/21/07 3:49 PM Page ix

■ 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 user and reviewer comments, greater modularity and flexibility have been built into the text to make

it compatible with alternative sequences of topics. While moving the discussion of bonding and structure to 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 users and

reviewers, we provide a Chapter Summary, Chapter Review, and list of Key

Equations (with citations to the sections in which they appear) at the end of

each chapter. These are integrated with the Cumulative Exercises and Concepts

& Skills from previous editions to provide a comprehensive set of tools for

reviewing and studying the contents of each chapter.

■ New Problems Approximately 85 new problems have been added, mostly in

Unit II on bonding and structure. These follow the tradition established in previous editions that problems are based on real data for real chemical systems.

We intend the problems to guide our students to develop intuition for chemical

results and the magnitudes of chemical quantities, as well as facility in manipulating the equations in the problems.

■ OWL Online Homework System Homework management is now included in

the text’s instructional package. Approximately 15 problems from each chapter

are available for assignment in the OWL program. See the section on Supporting Materials for a description of OWL.

Major Changes in Content

and Organization

Chapter 1: The Atom in Modern Chemistry

This chapter has been reorganized to place greater emphasis on the physical structure of the atom, as determined from the classic experiments of Thomson, Millikan, and Rutherford. The chapter ends with direct scanning tunneling

microscopy images of individual atoms in chemical reactions. Section 1.6 in Principles of Modern Chemistry, fifth edition (mole, density, molecular volume), has

been moved to Chapter 2, which now gives a comprehensive treatment of formulas, stoichiometry, and chemical equations.

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 taste

whether to present the classical theory first and then gain deeper insight from the

x Preface

93661_00_FM-p000i-xxxi.qxd 2/21/07 3:49 PM Page x

quantum explanations, or to cover the quantum theory first and then see the classical theory as a limiting case. We have found 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. In our classroom experience, 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 3.2 is completely new. It illustrates the Coulomb potential with several

quantitative applications and introduces the screened potential in manyelectron atoms.

■ In Section 3.4 the description of electron affinity has been extended and clarified, and the Pauling and Mulliken descriptions of electronegativity are discussed together.

■ Section 3.5 describing forces and potential energy in molecules is completely

new. We identify the driving force for the formation of chemical bonds between

atoms as a reduction of the total energy of the system. We introduce the virial

theorem to analyze the separate contributions of potential and kinetic energy to

this total energy reduction in various bonding models.

■ The role of Coulomb stabilization in ionic bonding has been substantially simplified and clarified.

Chapter 4: Introduction to Quantum Mechanics

This chapter is the revision of Sections 15.1–15.5 in Principles of Modern Chemistry, fifth edition. It presents a significant introduction to the concepts and vocabulary of quantum mechanics through very careful choice of language, illustrations

with experimental data, interpretation with aid of simple models, and extensive

use of graphical presentations. We highlight five features of this new chapter:

■ We present quantitative, computer-generated plots of the solutions to the

particle-in-a-box models in two and three dimensions and use these examples

to introduce contour plots and three-dimensional isosurfaces as tools for

visual representation of wave functions. We show our students how to obtain

physical insight into quantum behavior from these plots without relying on

equations. In the succeeding chapters we expect them to use this skill repeatedly to interpret quantitative plots for more complex cases.

■ The discussion of Planck’s analysis of blackbody radiation has been greatly

simplified and clarified.

■ The description of the wavelike behavior of electrons has been extended and

clarified, based on a careful description of an electron diffraction experiment.

■ The explanation of uncertainty and indeterminacy has been extended and clarified.

■ Section 4.7 introduces the quantum harmonic oscillator and provides the

groundwork for subsequent discussions of vibrational spectroscopy. This section is completely new.

Preface xi

93661_00_FM-p000i-xxxi.qxd 2/21/07 3:49 PM Page xi

Chapter 5: Quantum Mechanics and Atomic Structure

This chapter is the revision of Sections 15.7–15.9 in Principles of Modern Chemistry, fifth edition. Three features are new:

■ The very long Section 15.8 has been broken into three parts (Sec. 5.2–5.4) for

greater ease of presentation.

■ Photoelectron spectroscopy has been moved into Section 5.4, where it fits logically with the discussion of the shell structure of the atom and the periodic

table.

■ All atomic orbitals have been re-calculated and rendered in modern style.

Chapter 6: Quantum Mechanics and Molecular Structure

This revision has the same logical structure as Chapter 16 of Principles of Modern

Chemistry, fifth edition. It achieves more uniform coverage and proper depth, and

it adds several important new features. The mathematical level is uniform throughout the chapter. Notable features of the present version include:

■ An expanded treatment of as the starting point for describing molecular quantum mechanics and for motivating the development of the linear combination of

atomic orbitals (LCAO) approximation. This expanded treatment includes:

■ A simplified and more thorough description of the Born–Oppenheimer

approximation.

■ New graphical representations of the exact molecular orbitals for that

make it easier to visualize these orbitals and interpret their meanings. These

images provide a foundation for developing MO theory for the first- and

second-period diatomic molecules.

■ Careful attention has been paid to the description and analysis of potential

energy curves, zero-point energy, and total energy.

■ “A Deeper Look” section shows how the molecular orbitals correlate

with sums and differences of hydrogen atomic orbitals at large internuclear

separations. This correlation provides a very clear motivation for developing the LCAO approximation to exact molecular orbitals.

■ Application of the virial theorem to reveal the interplay between kinetic and

potential energy in the mechanism of bond formation described by MO theory.

■ Application of the LCAO approximation to small polyatomic molecules to

demonstrate the generality of the method.

■ Molecular photoelectron spectroscopy to connect molecular orbital energy levels to experimental measurements.

■ Much more thorough treatment of the VB method than in the fifth edition; it is

now on equal footing with that for LCAO.

■ Detailed comparison between LCAO and VB methods, including ways to

improve both, showing how each is the starting point for high-level computational quantum chemistry.

Throughout this revision we have simplified notation to the maximum extent

possible without sacrificing clarity, and we have devoted considerable attention to

graphical explanations of the concepts.

Chapter 7: Bonding in Organic Molecules

This chapter represents a significant reorganization and extension of Chapter 20

and Section 16.4 in the fifth edition. We describe the bonding and nomenclature

xii Preface

93661_00_FM-p000i-xxxi.qxd 2/21/07 3:49 PM Page xii

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