Physical

Chemistry
THIRD EDITION

Thomas Engel
University of Washington

Philip Reid
University of Washington

Chapter 26, “Computational Chemistry,”

was contributed by

Warren Hehre
CEO, Wavefunction, Inc.
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Library of Congress Cataloging-in-Publication Data

Engel, Thomas
Physical chemistry / Thomas Engel, Philip Reid, Warren Hehre. — 3rd ed.
p. cm.
Includes index.
ISBN 978-0-321-81200-1 (casebound)
1. Chemistry, Physical and theoretical—Textbooks. I. Reid, Philip (Philip J.) II. Engel, Thomas.
III. Hehre, Warren. IV. Title.
QD453.3.E54 2012
541–dc23
2011046907

1 2 3 4 5 6 7 8 9 10— CRK—15 14 13 12 11

ISBN-10: 0-321-81200-X; ISBN-13: 978-0-321-81200-1

www.pearsonhighered.com
To Walter and Juliane,
my first teachers,
and to Gloria,
Alex,
and Gabrielle.
Thomas Engel

To my family.
Philip Reid
 Brief Contents
1 Fundamental Concepts of Thermodynamics 1 21 Many-Electron Atoms 483
2 Heat, Work, Internal Energy, Enthalpy, and the 22 Quantum States for Many-Electron Atoms and
First Law of Thermodynamics 17 Atomic Spectroscopy 507
3 The Importance of State Functions: Internal 23 The Chemical Bond in Diatomic
Energy and Enthalpy 45 Molecules 537
4 Thermochemistry 67 24 Molecular Structure and Energy Levels for
Polyatomic Molecules 567
5 Entropy and the Second and Third Laws of
Thermodynamics 85 25 Electronic Spectroscopy 601
6 Chemical Equilibrium 125 26 Computational Chemistry 631
7 The Properties of Real Gases 165 27 Molecular Symmetry 687
8 Phase Diagrams and the Relative Stability of 28 Nuclear Magnetic Resonance
Solids, Liquids, and Gases 181 Spectroscopy 715
9 Ideal and Real Solutions 209 29 Probability 747
10 Electrolyte Solutions 243 30 The Boltzmann Distribution 771
11 Electrochemical Cells, Batteries, and Fuel 31 Ensemble and Molecular Partition
Cells 259 Functions 793
12 From Classical to Quantum Mechanics 293 32 Statistical Thermodynamics 825
13 The Schrödinger Equation 309 33 Kinetic Theory of Gases 857
14 The Quantum Mechanical Postulates 331 34 Transport Phenomena 877
15 Using Quantum Mechanics on Simple 35 Elementary Chemical Kinetics 909
Systems 343
36 Complex Reaction Mechanisms 955
16 The Particle in the Box and the Real
World 361 APPENDIX A Math Supplement 1007
17 Commuting and Noncommuting Operators APPENDIX B Data Tables 1029
and the Surprising Consequences of
APPENDIX C Point Group Character
Entanglement 383
Tables 1047
18 A Quantum Mechanical Model for the
Vibration and Rotation of Molecules 405
APPENDIX D Answers to Selected End-of-Chapter
Problems 1055
19 The Vibrational and Rotational Spectroscopy
of Diatomic Molecules 431 CREDITS 1071

20 The Hydrogen Atom 465 INDEX 1073

iv
 Contents
PREFACE xiii 3.4 The Variation of Enthalpy with Temperature at
Constant Pressure 55
3.5 How Are CP and CV Related? 57
1 Fundamental Concepts 3.6 The Variation of Enthalpy with Pressure at
of Thermodynamics 1 Constant Temperature 58
1.1 What Is Thermodynamics and Why Is 3.7 The Joule-Thomson Experiment 60
It Useful? 1 3.8 Liquefying Gases Using an Isenthalpic
1.2 The Macroscopic Variables Volume, Pressure, Expansion 63
and Temperature 2
1.3 Basic Definitions Needed to Describe
Thermodynamic Systems 6
4 Thermochemistry 67

1.4 Equations of State and the Ideal Gas Law 7 4.1 Energy Stored in Chemical Bonds Is Released or
Taken Up in Chemical Reactions 67
1.5 A Brief Introduction to Real Gases 10
4.2 Internal Energy and Enthalpy Changes
Associated with Chemical Reactions 68
2 Heat, Work, Internal Energy, 4.3 Hess’s Law Is Based on Enthalpy Being a State
Function 71
Enthalpy, and the First Law of 4.4 The Temperature Dependence of Reaction
Thermodynamics 17 Enthalpies 73
2.1 The Internal Energy and the First Law of 4.5 The Experimental Determination of ¢ U and ¢ H
Thermodynamics 17 for Chemical Reactions 75
2.2 Work 18 4.6 (Supplemental) Differential Scanning
2.3 Heat 21 Calorimetry 77
2.4 Doing Work on the System and Changing the
System Energy from a Molecular Level 5 Entropy and the Second and Third
Perspective 23
Laws of Thermodynamics 85
2.5 Heat Capacity 25
5.1 The Universe Has a Natural Direction
2.6 State Functions and Path Functions 28 of Change 85
2.7 Equilibrium, Change, and Reversibility 30 5.2 Heat Engines and the Second Law of
2.8 Comparing Work for Reversible and Irreversible Thermodynamics 86
Processes 31 5.3 Introducing Entropy 90
2.9 Determining ¢ U and Introducing Enthalpy, a 5.4 Calculating Changes in Entropy 91
New State Function 34
5.5 Using Entropy to Calculate the Natural Direction
2.10 Calculating q, w, ¢ U, and ¢ H for Processes of a Process in an Isolated System 96
Involving Ideal Gases 35
5.6 The Clausius Inequality 97
2.11 The Reversible Adiabatic Expansion
and Compression of an Ideal Gas 39 5.7 The Change of Entropy in the Surroundings and
¢Stotal = ¢S + ¢Ssurroundings 98
5.8 Absolute Entropies and the Third Law of
3 The Importance of State Thermodynamics 101
5.9 Standard States in Entropy Calculations 104
Functions: Internal Energy
5.10 Entropy Changes in Chemical Reactions 105
and Enthalpy 45
5.11 (Supplemental) Energy Efficiency: Heat Pumps,
3.1 The Mathematical Properties of State Refrigerators, and Real Engines 106
Functions 45
5.12 (Supplemental) Using the Fact that S Is a State
3.2 The Dependence of U on V and T 50 Function to Determine the Dependence of S on V
3.3 Does the Internal Energy Depend More Strongly and T 115
on V or T? 52

v
vi CONTENTS

5.13 (Supplemental) The Dependence of S on 8.2 The Pressure–Temperature Phase Diagram 184
T and P 117 8.3 The Phase Rule 190
5.14 (Supplemental) The Thermodynamic 8.4 The Pressure–Volume and Pressure–Volume–
Temperature Scale 118 Temperature Phase Diagrams 191
8.5 Providing a Theoretical Basis for the P–T Phase
6 Chemical Equilibrium 125 Diagram 193
6.1 The Gibbs Energy and the Helmholtz Energy 125 8.6 Using the Clausius–Clapeyron Equation to
6.2 The Differential Forms of U, H, A, and G 130 Calculate Vapor Pressure as a Function of T 194
6.3 The Dependence of the Gibbs and Helmholtz 8.7 The Vapor Pressure of a Pure Substance Depends
Energies on P, V, and T 132 on the Applied Pressure 196
6.4 The Gibbs Energy of a Reaction Mixture 134 8.8 Surface Tension 197
6.5 The Gibbs Energy of a Gas in a Mixture 135 8.9 (Supplemental) Chemistry in Supercritical Fluids 201
6.6 Calculating the Gibbs Energy of Mixing for Ideal 8.10 (Supplemental) Liquid Crystal Displays 202
Gases 136
6.7 Calculating ¢G°R for a Chemical Reaction 138
6.8 Introducing the Equilibrium Constant for a
9 Ideal and Real Solutions 209

Mixture of Ideal Gases 139 9.1 Defining the Ideal Solution 209
6.9 Calculating the Equilibrium Partial Pressures in a 9.2 The Chemical Potential of a Component in the
Mixture of Ideal Gases 141 Gas and Solution Phases 211
6.10 The Variation of KP with Temperature 142 9.3 Applying the Ideal Solution Model to Binary
Solutions 212
6.11 Equilibria Involving Ideal Gases and Solid or
Liquid Phases 145 9.4 The Temperature–Composition Diagram and
Fractional Distillation 216
6.12 Expressing the Equilibrium Constant in Terms of
Mole Fraction or Molarity 146 9.5 The Gibbs–Duhem Equation 218
6.13 The Dependence of the Extent of Reaction on T 9.6 Colligative Properties 219
and P 147 9.7 The Freezing Point Depression and Boiling Point
6.14 (Supplemental) A Case Study: The Synthesis of Elevation 220
Ammonia 148 9.8 The Osmotic Pressure 222
6.15 (Supplemental) Expressing U and H and Heat 9.9 Real Solutions Exhibit Deviations from
Capacities Solely in Terms of Measurable Raoult’s Law 224
Quantities 153 9.10 The Ideal Dilute Solution 227
6.16 (Supplemental) Measuring ¢G for the Unfolding 9.11 Activities Are Defined with Respect to Standard
of Single RNA Molecules 157 States 229
6.17 (Supplemental) The Role of Mixing in Determining 9.12 Henry’s Law and the Solubility of Gases in
Equilibrium in a Chemical Reaction 158 a Solvent 232
9.13 Chemical Equilibrium in Solutions 233
7 The Properties of Real Gases 165 9.14 Solutions Formed from Partially Miscible
7.1 Real Gases and Ideal Gases 165 Liquids 237
7.2 Equations of State for Real Gases and Their 9.15 The Solid-Solution Equilibrium 238
Range of Applicability 166
7.3 The Compression Factor 170
7.4 The Law of Corresponding States 173
10 Electrolyte Solutions 243
7.5 Fugacity and the Equilibrium Constant for 10.1 The Enthalpy, Entropy, and Gibbs Energy of Ion
Real Gases 175 Formation in Solutions 243
10.2 Understanding the Thermodynamics of Ion
8 Phase Diagrams and the Relative Formation and Solvation 246
10.3 Activities and Activity Coefficients for
Stability of Solids, Liquids, and Electrolyte Solutions 248
Gases 181 10.4 Calculating g ; Using the Debye–Hückel Theory 250
8.1 What Determines the Relative Stability of the 10.5 Chemical Equilibrium in Electrolyte
Solid, Liquid, and Gas Phases? 181 Solutions 254
 CONTENTS vii

13.3 Waves Are Conveniently Represented as

11 Electrochemical Cells, Batteries, Complex Functions 317
and Fuel Cells 259 13.4 Quantum Mechanical Waves and the Schrödinger
11.1 The Effect of an Electrical Potential on the Equation 318
Chemical Potential of Charged Species 259 13.5 Solving the Schrödinger Equation: Operators,
11.2 Conventions and Standard States in Observables, Eigenfunctions, and Eigenvalues 320
Electrochemistry 261 13.6 The Eigenfunctions of a Quantum Mechanical
11.3 Measurement of the Reversible Cell Operator Are Orthogonal 322
Potential 264 13.7 The Eigenfunctions of a Quantum Mechanical
11.4 Chemical Reactions in Electrochemical Cells Operator Form a Complete Set 324
and the Nernst Equation 264 13.8 Summing Up the New Concepts 326
11.5 Combining Standard Electrode Potentials to
Determine the Cell Potential 266
11.6 Obtaining Reaction Gibbs Energies and
14 The Quantum Mechanical
Reaction Entropies from Cell Potentials 267 Postulates 331
11.7 The Relationship between the Cell EMF and the 14.1 The Physical Meaning Associated with the Wave
Equilibrium Constant 268 Function Is Probability 332
11.8 Determination of Eº and Activity Coefficients 14.2 Every Observable Has a Corresponding
Using an Electrochemical Cell 270 Operator 333
11.9 Cell Nomenclature and Types of 14.3 The Result of an Individual Measurement 334
Electrochemical Cells 270 14.4 The Expectation Value 334
11.10 The Electrochemical Series 272 14.5 The Evolution in Time of a Quantum
11.11 Thermodynamics of Batteries and Fuel Cells 272 Mechanical System 338
11.12 The Electrochemistry of Commonly Used 14.6 Do Superposition Wave Functions Really Exist? 338
Batteries 273
11.13 Fuel Cells 277
11.14 (Supplemental) Electrochemistry at the Atomic
15 Using Quantum Mechanics on
Scale 280 Simple Systems 343
11.15 (Supplemental) Using Electrochemistry for 15.1 The Free Particle 343
Nanoscale Machining 286 15.2 The Particle in a One-Dimensional Box 345
11.16 (Supplemental) Absolute Half-Cell Potentials 287 15.3 Two- and Three-Dimensional Boxes 349
15.4 Using the Postulates to Understand the Particle in
12 From Classical to Quantum the Box and Vice Versa 350

Mechanics 293
12.1 Why Study Quantum Mechanics? 293
16 The Particle in the Box and the
Real World 361
12.2 Quantum Mechanics Arose out of the Interplay
of Experiments and Theory 294 16.1 The Particle in the Finite Depth Box 361
12.3 Blackbody Radiation 295 16.2 Differences in Overlap between Core and Valence
Electrons 362
12.4 The Photoelectric Effect 296
16.3 Pi Electrons in Conjugated Molecules Can Be
12.5 Particles Exhibit Wave-Like Behavior 298
Treated as Moving Freely in a Box 363
12.6 Diffraction by a Double Slit 300
16.4 Why Does Sodium Conduct Electricity and Why
12.7 Atomic Spectra and the Bohr Model of the Is Diamond an Insulator? 364
Hydrogen Atom 303
16.5 Traveling Waves and Potential Energy Barriers 365
16.6 Tunneling through a Barrier 367
13 The Schrödinger Equation 309 16.7 The Scanning Tunneling Microscope and the
13.1 What Determines If a System Needs to Be Atomic Force Microscope 369
Described Using Quantum Mechanics? 309 16.8 Tunneling in Chemical Reactions 374
13.2 Classical Waves and the Nondispersive Wave 16.9 (Supplemental) Quantum Wells and
Equation 313 Quantum Dots 375
viii CONTENTS

17 Commuting and Noncommuting 20 The Hydrogen Atom 465

Operators and the Surprising 20.1 Formulating the Schrödinger Equation 465
Consequences of Entanglement 383 20.2 Solving the Schrödinger Equation for the
Hydrogen Atom 466
17.1 Commutation Relations 383
20.3 Eigenvalues and Eigenfunctions for the
17.2 The Stern–Gerlach Experiment 385
Total Energy 467
17.3 The Heisenberg Uncertainty Principle 388
20.4 The Hydrogen Atom Orbitals 473
17.4 (Supplemental) The Heisenberg Uncertainty
20.5 The Radial Probability Distribution
Principle Expressed in Terms of Standard
Function 475
Deviations 392
20.6 The Validity of the Shell Model of
17.5 (Supplemental) A Thought Experiment Using a
an Atom 479
Particle in a Three-Dimensional Box 394
17.6 (Supplemental) Entangled States, Teleportation,
and Quantum Computers 396 21 Many-Electron Atoms 483
21.1 Helium: The Smallest Many-Electron Atom 483
18 A Quantum Mechanical Model for 21.2 Introducing Electron Spin 485
the Vibration and Rotation of 21.3 Wave Functions Must Reflect the
Indistinguishability of Electrons 486
Molecules 405
21.4 Using the Variational Method to Solve the
18.1 The Classical Harmonic Oscillator 405
Schrödinger Equation 490
18.2 Angular Motion and the Classical Rigid Rotor 409
21.5 The Hartree–Fock Self-Consistent Field
18.3 The Quantum Mechanical Harmonic Method 491
Oscillator 411
21.6 Understanding Trends in the Periodic Table
18.4 Quantum Mechanical Rotation in Two from Hartree–Fock Calculations 499
Dimensions 416
18.5 Quantum Mechanical Rotation in Three
Dimensions 419 22 Quantum States for
18.6 The Quantization of Angular Momentum 421 Many-Electron Atoms and
18.7 The Spherical Harmonic Functions 423 Atomic Spectroscopy 507
18.8 Spatial Quantization 425
22.1 Good Quantum Numbers, Terms, Levels, and
States 507
19 The Vibrational and Rotational 22.2 The Energy of a Configuration Depends on Both
Orbital and Spin Angular Momentum 509
Spectroscopy of Diatomic
22.3 Spin-Orbit Coupling Breaks Up a Term into
Molecules 431 Levels 516
19.1 An Introduction to Spectroscopy 431 22.4 The Essentials of Atomic Spectroscopy 517
19.2 Absorption, Spontaneous Emission, and 22.5 Analytical Techniques Based on Atomic
Stimulated Emission 433 Spectroscopy 519
19.3 An Introduction to Vibrational Spectroscopy 435 22.6 The Doppler Effect 522
19.4 The Origin of Selection Rules 438 22.7 The Helium-Neon Laser 523
19.5 Infrared Absorption Spectroscopy 440 22.8 Laser Isotope Separation 526
19.6 Rotational Spectroscopy 443 22.9 Auger Electron and X-Ray Photoelectron
19.7 (Supplemental) Fourier Transform Infrared Spectroscopies 527
Spectroscopy 449 22.10 Selective Chemistry of Excited States:
19.8 (Supplemental) Raman Spectroscopy 451 O(3P) and O(1D) 530
19.9 (Supplemental) How Does the Transition Rate 22.11 (Supplemental) Configurations with Paired and
between States Depend on Frequency? 453 Unpaired Electron Spins Differ in Energy 531

23 The Chemical Bond in Diatomic
Molecules 537
23.1 Generating Molecular Orbitals from Atomic
Orbitals 537
23.2 The Simplest One-Electron Molecule:
H2+ 541
23.3 The Energy Corresponding to the H2+
Molecular Wave Functions cg and cu 543
23.4 A Closer Look at the H2+ Molecular Wave
Functions cg and cu 546
23.5 Homonuclear Diatomic Molecules 548
23.6 The Electronic Structure of Many-Electron
Molecules 552
23.7 Bond Order, Bond Energy, and Bond
Length 555
23.8 Heteronuclear Diatomic Molecules 557
23.9 The Molecular Electrostatic Potential 560
24 Molecular Structure and Energy
Levels for Polyatomic Molecules 567
24.1 Lewis Structures and the VSEPR Model 567
24.2 Describing Localized Bonds Using Hybridization
for Methane, Ethene, and Ethyne 570
24.3 Constructing Hybrid Orbitals for Nonequivalent
Ligands 573
24.4 Using Hybridization to Describe Chemical
Bonding 576
24.5 Predicting Molecular Structure Using
Qualitative Molecular Orbital Theory 578
24.6 How Different Are Localized and Delocalized
Bonding Models? 581
24.7 Molecular Structure and Energy Levels from
Computational Chemistry 584
24.8 Qualitative Molecular Orbital Theory for
Conjugated and Aromatic Molecules: The
Hückel Mode 586
24.9 From Molecules to Solids 592
24.10 Making Semiconductors Conductive at Room
Temperature 593
25 Electronic Spectroscopy 601
25.1 The Energy of Electronic Transitions 601
25.2 Molecular Term Symbols 602
25.3 Transitions between Electronic States of
Diatomic Molecules 605
CONTENTS ix
25.4 The Vibrational Fine Structure of Electronic
Transitions in Diatomic Molecules 606
25.5 UV-Visible Light Absorption in Polyatomic
Molecules 608
25.6 Transitions among the Ground and Excited
States 610
25.7 Singlet–Singlet Transitions: Absorption and
Fluorescence 611
25.8 Intersystem Crossing and Phosphorescence 613
25.9 Fluorescence Spectroscopy and Analytical
Chemistry 614
25.10 Ultraviolet Photoelectron Spectroscopy 615
25.11 Single Molecule Spectroscopy 617
25.12 Fluorescent Resonance Energy
Transfer (FRET) 619
25.13 Linear and Circular Dichroism 623
25.14 Assigning + and - to © Terms of Diatomic
Molecules 625
26 Computational Chemistry 631
26.1 The Promise of Computational Chemistry 631
26.2 Potential Energy Surfaces 632
26.3 Hartree–Fock Molecular Orbital Theory: A Direct
Descendant of the Schrödinger Equation 636
26.4 Properties of Limiting Hartree–Fock Models 638
26.5 Theoretical Models and Theoretical Model
Chemistry 643
26.6 Moving Beyond Hartree–Fock Theory 644
26.7 Gaussian Basis Sets 649
26.8 Selection of a Theoretical Model 652
26.9 Graphical Models 666
26.10 Conclusion 674
27 Molecular Symmetry 687
27.1 Symmetry Elements, Symmetry Operations, and
Point Groups 687
27.2 Assigning Molecules to Point Groups 689
27.3 The H2O Molecule and the C2v Point Group 691
27.4 Representations of Symmetry Operators, Bases
for Representations, and the Character Table 696
27.5 The Dimension of a Representation 698
27.6 Using the C2v Representations to Construct
Molecular Orbitals for H2O 702
27.7 The Symmetries of the Normal Modes of
Vibration of Molecules 704
x CONTENTS

27.8 Selection Rules and Infrared versus Raman 30.4 Physical Meaning of the Boltzmann
Activity 708 Distribution Law 784
27.9 (Supplemental) Using the Projection Operator 30.5 The Definition of b 785
Method to Generate MOs That Are Bases for
Irreducible Representations 709
31 Ensemble and Molecular Partition
Functions 793
28 Nuclear Magnetic Resonance 31.1 The Canonical Ensemble 793
Spectroscopy 715
31.2 Relating Q to q for an Ideal Gas 795
28.1 Intrinsic Nuclear Angular Momentum and 31.3 Molecular Energy Levels 797
Magnetic Moment 715
31.4 Translational Partition Function 797
28.2 The Energy of Nuclei of Nonzero Nuclear Spin
31.5 Rotational Partition Function: Diatomics 800
in a Magnetic Field 717
31.6 Rotational Partition Function: Polyatomics 807
28.3 The Chemical Shift for an Isolated Atom 719
31.7 Vibrational Partition Function 809
28.4 The Chemical Shift for an Atom Embedded in a
Molecule 720 31.8 The Equipartition Theorem 814
28.5 Electronegativity of Neighboring Groups and 31.9 Electronic Partition Function 815
Chemical Shifts 721 31.10 Review 819
28.6 Magnetic Fields of Neighboring Groups and
Chemical Shifts 722
28.7 Multiplet Splitting of NMR Peaks Arises
32 Statistical Thermodynamics 825
through Spin–Spin Coupling 723 32.1 Energy 825
28.8 Multiplet Splitting When More Than Two Spins 32.2 Energy and Molecular Energetic Degrees of
Interact 728 Freedom 829
28.9 Peak Widths in NMR Spectroscopy 730 32.3 Heat Capacity 833
28.10 Solid-State NMR 732 32.4 Entropy 837
28.11 NMR Imaging 732 32.5 Residual Entropy 842
28.12 (Supplemental)The NMR Experiment in the 32.6 Other Thermodynamic Functions 843
Laboratory and Rotating Frames 734 32.7 Chemical Equilibrium 847
28.13 (Supplemental) Fourier Transform NMR
Spectroscopy 736
28.14 (Supplemental) Two-Dimensional NMR 740
33 Kinetic Theory of Gases 857
33.1 Kinetic Theory of Gas Motion and Pressure 857
33.2 Velocity Distribution in One Dimension 858
29 Probability 747 33.3 The Maxwell Distribution of Molecular
29.1 Why Probability? 747 Speeds 862
29.2 Basic Probability Theory 748 33.4 Comparative Values for Speed Distributions:
nave, nmp, and nrms 864
29.3 Stirling’s Approximation 750
33.5 Gas Effusion 866
29.4 Probability Distribution Functions 757
33.6 Molecular Collisions 868
29.5 Probability Distributions Involving Discrete and
Continuous Variables 759 33.7 The Mean Free Path 872
29.6 Characterizing Distribution Functions 762
34 Transport Phenomena 877
30 The Boltzmann Distribution 771 34.1 What Is Transport? 877
30.1 Microstates and Configurations 771 34.2 Mass Transport: Diffusion 879
30.2 Derivation of the Boltzmann Distribution 777 34.3 The Time Evolution of a Concentration
Gradient 882
30.3 Dominance of the Boltzmann Distribution 782
34.4 (Supplemental) Statistical View of Diffusion 884

34.5 Thermal Conduction 886
34.6 Viscosity of Gases 890
34.7 Measuring Viscosity 892
34.8 Diffusion in Liquids and Viscosity of Liquids 894
34.9 (Supplemental) Sedimentation and
Centrifugation 896
34.10 Ionic Conduction 899
35 Elementary Chemical Kinetics 909
35.1 Introduction to Kinetics 909
35.2 Reaction Rates 910
35.3 Rate Laws 912
35.4 Reaction Mechanisms 917
35.5 Integrated Rate Law Expressions 918
35.6 Numerical Approaches 923
35.7 Sequential First-Order Reactions 924
35.8 Parallel Reactions 929
35.9 Temperature Dependence of Rate Constants 931
35.10 Reversible Reactions and Equilibrium 933
35.11 (Supplemental) Perturbation-Relaxation
Methods 936
35.12 (Supplemental) The Autoionization of Water:
A Temperature-Jump Example 938
35.13 Potential Energy Surfaces 940
CONTENTS xi
35.14 Activated Complex Theory 942
35.15 Diffusion Controlled Reactions 946
36 Complex Reaction Mechanisms 955
36.1 Reaction Mechanisms and Rate Laws 955
36.2 The Preequilibrium Approximation 957
36.3 The Lindemann Mechanism 959
36.4 Catalysis 961
36.5 Radical-Chain Reactions 972
36.6 Radical-Chain Polymerization 975
36.7 Explosions 976
36.8 Feedback, Nonlinearity, and Oscillating
Reactions 978
36.9 Photochemistry 981
36.10 Electron Transfer 993
APPENDIX A Math Supplement 1007
APPENDIX B Data Tables 1029
APPENDIX C Point Group Character Tables 1047
APPENDIX D Answers to Selected End-of-Chapter
Problems 1055
CREDITS 1071
INDEX 1073
 About the Authors
Thomas Engel has taught chemistry at the University of Washington for more than
20 years, where he is currently professor emeritus of chemistry. Professor Engel
received his bachelor’s and master’s degrees in chemistry from the Johns Hopkins
University, and his Ph.D. in chemistry from the University of Chicago. He then spent
11 years as a researcher in Germany and Switzerland, in which time he received the
Dr. rer. nat. habil. degree from the Ludwig Maximilians University in Munich. In
1980, he left the IBM research laboratory in Zurich to become a faculty member at the
University of Washington.
Professor Engel’s research interests are in the area of surface chemistry, and he has
published more than 80 articles and book chapters in this field. He has received the Sur-
face Chemistry or Colloids Award from the American Chemical Society and a Senior
Humboldt Research Award from the Alexander von Humboldt Foundation.

Philip Reid has taught chemistry at the University of Washington since 1995. Professor Reid
received his bachelor’s degree from the University of Puget Sound in 1986, and his Ph.D.
from the University of California, Berkeley in 1992. He performed postdoctoral research at
the University of Minnesota, Twin Cities before moving to Washington.
Professor Reid’s research interests are in the areas of atmospheric chemistry, ultra-
fast condensed-phase reaction dynamics, and organic electronics. He has published
more than 100 articles in these fields. Professor Reid is the recipient of a CAREER
Award from the National Science Foundation, is a Cottrell Scholar of the Research
Corporation, and is a Sloan Fellow. He received the University of Washington
Distinguished Teaching Award in 2005.

xii
 Preface
The third edition of this book builds on user and reviewer comments on the previous
editions. Our goal remains to provide students with an accessible overview of the
whole field of physical chemistry while focusing on basic principles that unite
the subdisciplines of the field. We continue to present new research developments in
the field to emphasize the vibrancy of physical chemistry. Many chapters have been
extensively revised as described below. We include additional end-of-chapter concept
problems and most of the numerical problems have been revised. The target audience
remains undergraduate students majoring in chemistry, biochemistry, and chemical
engineering, as well as many students majoring in the atmospheric sciences and the
biological sciences. The following objectives, illustrated with brief examples, outline
our approach to teaching physical chemistry.
• Focus on teaching core concepts. The central principles of physical chemistry
are explored by focusing on core ideas, and then extending these ideas to a variety
of problems. The goal is to build a solid foundation of student understanding rather
than cover a wide variety of topics in modest detail.
• Illustrate the relevance of physical chemistry to the world around us. Many
students struggle to connect physical chemistry concepts to the world around them.
To address this issue, example problems and specific topics are tied together to help
the student develop this connection. Fuel cells, refrigerators, heat pumps, and real
engines are discussed in connection with the second law of thermodynamics. The
particle in the box model is used to explain why metals conduct electricity and why
valence electrons rather than core electrons are important in chemical bond forma-
tion. Examples are used to show the applications of chemical spectroscopies. Every
attempt is made to connect fundamental ideas to applications that are familiar to the

U.S. 2002 Carbon Dioxide Emissions from Energy

Consumption – 5,682* Million Metric Tons of CO2**

Renewables 3***
Electricity
power sector
1,875
2,249
Natural Gas
1,203 1,503
Residential/
437 commercial
2,206

433
Coal
2,070 10 35 3
179 643
Industrial
Coal cake imports 6 72
157 1,674

413
Petroleum
2,453

1,811 Transportation
1,850

Source: Energy Information Administration. Emissions of

Greenhouse Gases in the United States 2002. Tables 4–10.
*Includes adjustments of 42.9 million metric tons of carbon dioxide
from U.S. territories, less 90.2 MtCO2 from international and military bunker fuels.
**Previous versions of this chart showed emissions in metric tons of carbon, not of CO2.
***Municipal solid waste and geothermal energy.
Note: Numbers may not equal sum of components because of independent rounding.
xiii
xiv PREFACE

student. Art is used to convey complex information in an accessible manner as in the

images here of U.S. carbon dioxide emissions.
• Present exciting new science in the field of physical chemistry. Physical chem-
istry lies at the forefront of many emerging areas of modern chemical research.
Recent applications of quantum behavior include band-gap engineering, quantum
dots, quantum wells, teleportation, and quantum computing. Single-molecule spec-
troscopy has led to a deeper understanding of chemical kinetics, and heterogeneous
catalysis has benefited greatly from mechanistic studies carried out using the
techniques of modern surface science. Atomic scale electrochemistry has become
possible through scanning tunneling microscopy. The role of physical chemistry in
these and other emerging areas is highlighted throughout the text. The following
figure shows direct imaging of the arrangement of the atoms in pentacene as well as
imaging of a delocalized molecular orbital using scanning tunneling and atomic
force miscroscopies.

• Web-based simulations illustrate the concepts being explored and avoid math
overload. Mathematics is central to physical chemistry; however, the mathemat-
ics can distract the student from “seeing” the underlying concepts. To circumvent
this problem, web-based simulations have been incorporated as end-of-chapter
problems throughout the book so that the student can focus on the science and avoid
a math overload. These web-based simulations can also be used by instructors dur-
ing lecture. An important feature of the simulations is that each problem has been
designed as an assignable exercise with a printable answer sheet that the student can
submit to the instructor. The Study Area in MasteringChemistry® also includes a
graphing routine with a curve-fitting capability, which allows students to print and
submit graphical data. The 50 web-based simulations listed in the end-of-chapter
 PREFACE xv

problems are available in the Study Area of MasteringChemistry® for Physical

Chemistry. MasteringChemistry® also includes a broad selection of end-of-chapter
problems with answer-specific feedback.
• Show that learning problem-solving skills is an essential part of physical
chemistry. Many example problems are worked through in each chapter. They
introduce the student to a useful method to solve physical chemistry problems.

• The End-of-Chapter Problems cover a range of difficulties suitable for students

at all levels.

• Conceptual questions at the end of each chapter ensure that students learn to
express their ideas in the language of science.
 xvi PREFACE

• Integrate computational chemistry into the standard curriculum. The teaching of

quantum mechanics has not taken advantage of the widespread availability of Ab Initio
Software. Many chapters include computational problems for which detailed instruc-
tions for the student are available in the Study Area in MasteringChemistry®. It is our
experience that students welcome this material, (see L. Johnson and T. Engel, Journal of
Chemical Education 2011, 88 [569-573]) which transforms the teaching of chemical
bonding and molecular structure from being qualitative to quantitative. For example, an
electrostatic potential map of acetonitrile built in Spartan Student is shown here.
• Key equations. Physical chemistry is a chemistry subdiscipline that is mathemat-
ics intensive in nature. Key equations that summarize fundamental relationships
between variables are colored in red for emphasis.
• Green boxes. Fundamental principles such as the laws of thermodynamics and
the quantum mechanical postulates are displayed in green boxes.
• Updated graph design. Color is used in graphs to clearly display different rela-
50 tionships in a single figure as shown in the heat capacity for oxygen as a function of
Solid I temperature and important transitions in the electron spectroscopy of molecules.

40 Solid II
Cp,m /(JK1 mol1)

S1
Solid III
30
Liquid

20
Gas

10
Energy

0 20 40 60 80 100 120 T1
Temperature/K

Key
ISC

S0 IC

VR

Absorption

Fluorescence

Phosphorescence

This text contains more material than can be covered in an academic year, and this is
entirely intentional. Effective use of the text does not require a class to proceed sequen-
tially through the chapters, or to include all sections. Some topics are discussed in sup-
plemental sections that can be omitted if they are not viewed as essential to the course.
Also, many sections are self contained so that they can be readily omitted if they do not
serve the needs of the instructor. This text is constructed to be flexible to your needs, not
the other way around. We welcome the comments of both students and instructors how
the material was used and how the presentation can be improved.
Thomas Engel
University of Washington
Philip Reid
University of Washington
 PREFACE xvii

New to This Edition

The third edition of Physical Chemistry includes changes at several levels. The most far-
reaching change is the introduction of MasteringChemistry® for Physical Chemistry. Over
460 tutorials will augment the example problems in the book and enhance active learning
and problem solving. Selected end of chapter problems are now assignable within
MasteringChemistry® and numerical, equation and symbolic answer types are automati-
cally graded.
The art program has been updated and expanded, and several levels of accuracy
checking have been incorporated to increase accuracy throughout the text. Many new
conceptual problems have been added to the book and most of the numerical problems
have been revised. Significant content updates include moving part of the kinetic gas
theory to Chapter 1 to allow a molecular level discussion of P and T. The heat capac-
ity discussion previously in sections 2.5 and 3.2 have been consolidated in Chapter 2,
and a new section on doing work and changing the system energy from a molecular
level perspective has been added. The discussion of differential scanning calorimetry
in Chapter 4 has been expanded and a molecular level discussion of entropy has been
added to Chapter 5. The discussion of batteries and fuel cells in Chapter 11 has been
revised and updated. Problems have been added to the end of Chapter 14 and a new
section entitled on superposition wave functions has been added. A new section on
traveling waves and potential energy barriers has been added to Chapter 16. The dis-
cussion of the classical harmonic oscillator and rigid rotor has been better integrated
by placing these sections before the corresponding quantum models in Chapter 18.
Chapter 23 has been revised to better introduce molecular orbital theory. A new sec-
tion on computational results and a set of new problems working with molecular
orbitals has been added to Chapter 24. The number and breadth of the numerical prob-
lems has been increased substantially in Chapter 25. The content on transition state
theory in Chapter 32 has been updated. A discussion of oscillating reactions has been
added to Chapter 36 and the material on electron transfer has been expanded.

Acknowledgments
Many individuals have helped us to bring the text into its current form. Students have
provided us with feedback directly and through the questions they have asked, which has
helped us to understand how they learn. Many of our colleagues including Peter
Armentrout, Doug Doren, Gary Drobny, Graeme Henkelman, Lewis Johnson, Tom
Pratum, Bill Reinhardt, Peter Rosky, George Schatz, Michael Schick, Gabrielle Varani,
and especially Wes Borden and Bruce Robinson have been invaluable in advising us. Paul
Siders generously provided problems for Chapter 24. We are also fortunate to have access
to some end-of-chapter problems that were originally presented in Physical Chemistry,
3rd edition, by Joseph H. Noggle and in Physical Chemistry, 3rd edition, by Gilbert
W. Castellan. The reviewers, who are listed separately, have made many suggestions for
improvement, for which we are very grateful. All those involved in the production process
have helped to make this book a reality through their efforts. Special thanks are due to Jim
Smith, who helped initiate this project, to our editors Jeanne Zalesky and Jessica
Neumann, and to the staff at Pearson, who have guided the production process.
xviii PREFACE

3RD EDITION
MANUSCRIPT REVIEWERS
Nathan Hammer, Herve Marand,
The University of Mississippi Virginia Polytechnic Institute and
Geoffrey Hutchinson, State University
University of Pittsburgh Paul Siders,
George Kaminski, University of Minnesota–Duluth
Central Michigan University

ACCURACY REVIEWERS
Alexander Angerhofer, Jennifer Mihalik,
University of Florida University of Wisconsin–Oshkosh
Clayton Baum, David Zax,
Florida Institute of Technology Cornell University

PRESCRIPTIVE REVIEWERS
Geoffrey Hutchinson, Thomas Mason,
University of Pittsburgh University of California–Los Angeles
William Lester, Paul Siders,
University of California–Berkeley University of Minnesota–Duluth
Herve Marand,
Virginia Polytechnic Institute and
State University

2ND EDITION
PRESCRIPTIVE REVIEWERS
David L. Cedeño, Enrique Peacock-López,
Illinois State University Williams College
Rosemarie Chinni, Anthony K. Rappe,
Alvernia College Colorado State University
Allen Clabo, Markku Räsänen,
Francis Marion University University of Helsinki
Lorrie Comeford, Richard W. Schwenz,
Salem State College University of Northern Colorado
John M. Jean, Jie Song,
Regis University University of Michigan–Flint
Martina Kaledin, Michael E. Starzak,
Kennesaw State University Binghamton University
Daniel Lawson, Liliya Vugmeyster,
University of Michigan–Dearborn University of Alaska–Anchorage
Dmitrii E. Makarov, James E. Whitten,
University of Texas at Austin University of Massachusetts–Lowell
 PREFACE xix

ART REVIEWER
Lorrie Comeford,
Salem State College

MATH REVIEWER
Leon Gerber,
St. John’s University

MANUSCRIPT REVIEWERS
Alexander Angerhofer, Herve Marand,
University of Florida Virginia Polytechnic Institute and
Martha Bruch, State University
State University of New York at Thomas Pentecost,
Oswego University of Colorado
Stephen Cooke, Rajeev Prabhakar,
University of North Texas University of Miami
Douglas English, Sanford Safron,
University of Maryland–College Park Florida State University
Sophya Garashchuk, Ali Sezer,
University of South Carolina California University of Pennsylvania
Cynthia Hartzell, Andrew Teplyakov,
Northern Arizona University University of Delaware
George Kaminski, Daniel Zeroka,
Central Michigan University Lehigh University
www.masteringchemistry.com
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and feedback

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to see intermediate steps involved in
calculations of the final numerical result
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