Periodic Table (Inside front cover)
List of Numerical Tables in Appendix A (Inside front cover)
Information Tables (Inside back cover)
Preface ........................................................ xv
Acknowledgments .............................................. xvii
Part 1 Thermodynamics and the Macroscopic Description of
Physical Systems ......................................... 1
Chapter 1 The Behavior of Gases and Liquids .................... 3
1.1. Introduction ............................................... 4
1.2. Systems and States in Physical Chemistry .................. 12
1.3. Real Gases ................................................ 21
1.4. The Coexistence of Phases and the Critical Point .......... 27
Chapter 2 Work, Heat, and Energy: The First Law of
Thermodynamics ...................................... 39
2.1. Work and the State of a System ............................ 40
2.2. Heat ...................................................... 51
2.3. Internal Energy: The First Law of Thermodynamics .......... 55
2.4. Calculation of Amounts of Heat and Energy Changes ......... 60
2.5. Enthalpy .................................................. 74
2.6. Calculation of Enthalpy Changes of Processes without
Chemical Reactions ........................................ 81
2.7. Calculation of Enthalpy Changes of a Class of Chemical
Reactions ................................................. 86
2.8. Calculation of Energy Changes of Chemical Reactions ....... 94
Chapter 3 The Second and Third Laws of Thermodynamics:
Entropy ............................................ 105
3.1. The Second Law of Thermodynamics and the Carnot Heat
Engine ................................................... 106
3.2. The Mathematical Statement of the Second Law: Entropy .... 114
3.3. The Calculation of Entropy Changes ....................... 121
3.4. Statistical Entropy ...................................... 133
3.5. The Third Law of Thermodynamics and Absolute Entropies ... 139
Chapter 4 The Thermodynamics of Real Systems ................. 151
4.1. Criteria for Spontaneous Processes and for
Equilibrium: The Gibbs and Helmholtz Energies ............ 152
4.2. Fundamental Relations for Closed Simple Systems .......... 158
4.3. Additional Useful Thermodynamic Identities ............... 167
4.4. Gibbs Energy Calculations ................................ 175
4.5. Multicomponent Systems ................................... 182
4.6. Euler's Theorem and the Gibbs-Duhem Relation ............. 188
Chapter 5 Phase Equilibrium .................................. 199
5.1. The Fundamental Fact of Phase Equilibrium ................ 200
5.2. The Gibbs Phase Rule ..................................... 202
5.3. Phase Equilibria in One-Component Systems ................ 205
5.4. The Gibbs Energy and Phase Transitions ................... 215
5.5. Surfaces in One-Component Systems ........................ 222
5.6. Surfaces in Multicomponent Systems ....................... 230
Chapter 6 The Thermodynamics of Solutions .................... 237
6.1. Ideal Solutions .......................................... 238
6.2. Henry's Law and Dilute Nonelectrolyte Solutions .......... 248
6.3. Activity and Activity Coefficients ....................... 258
6.4. The Activities of Nonvolatile Solutes .................... 267
6.5. Thermodynamic Functions of Nonideal Solutions ............ 275
6.6. Phase Diagrams of Nonideal Mixtures ...................... 282
6.7. Colligative Properties ................................... 292
Chapter 7 Chemical Equilibrium ............................... 303
7.1. Gibbs Energy Changes and the Equilibrium Constant ........ 304
7.2. Reactions Involving Gases and Pure Solids or Liquids ..... 310
7.3. Chemical Equilibrium in Solutions ........................ 315
7.4. Equilibria in Solutions of Strong Electrolytes ........... 328
7.5. Buffer Solutions ......................................... 331
7.6. The Temperature Dependence of Chemical Equilibrium.
The Principle of Le Chatelier ............................ 335
7.7. Chemical Equilibrium and Biological Systems .............. 343
Chapter 8 The Thermodynamics of Electrochemical Systems ....... 351
8.1. The Chemical Potential and the Electric Potential ........ 352
8.2. Electrochemical Cells .................................... 354
8.3. Half-Cell Potentials and Cell Potentials ................. 361
8.4. The Determination of Activities and Activity
Coefficients of Electrolytes ............................. 371
8.5. Thermodynamic Information from Electrochemistry .......... 374
Part 2 Dynamics ............................................... 381
Chapter 9 Gas Kinetic Theory: The Molecular Theory of
Dilute Gases at Equilibrium ........................ 383
9.1. Macroscopic and Microscopic States of Macroscopic
Systems .................................................. 384
9.2. A Model System to Represent a Dilute Gas ................. 386
9.3. The Velocity Probability Distribution .................... 394
9.4. The Distribution of Molecular Speeds ..................... 405
9.5. The Pressure of a Dilute Gas ............................. 411
9.6. Effusion and Wall Collisions ............................. 416
9.7. The Model System with Potential Energy ................... 418
9.8. The Hard-Sphere Gas ...................................... 422
9.9. The Molecular Structure of Liquids ....................... 434
Chapter 10 Transport Processes ................................ 441
10.1.The Macroscopic Description of Nonequilibrium States ..... 442
10.2.Transport Processes ...................................... 444
10.3.The Gas Kinetic Theory of Transport Processes in
Hard-Sphere Gases ........................................ 460
10.4.Transport Processes in Liquids ........................... 467
10.5.Electrical Conduction in Electrolyte Solutions ........... 475
Chapter 11 The Rates of Chemical Reactions .................... 485
11.1.The Macroscopic Description of Chemical Reaction
Rates .................................................... 486
11.2.Forward Reactions with One Reactant ...................... 488
11.3.Forward Reactions with More Than One Reactant ............ 499
11.4.Inclusion of a Reverse Reaction. Chemical Equilibrium .... 507
11.5.A Simple Reaction Mechanism: Two Consecutive Steps ....... 510
11.6.Competing Reactions ...................................... 513
11.7.The Experimental Study of Fast Reactions ................. 515
Chapter 12 Chemical Reaction Mechanisms I: Rate Laws and
Mechanisms ......................................... 523
12.1.Reaction Mechanisms and Elementary Processes in Gases .... 524
12.2.Elementary Processes in Liquid Solutions ................. 527
12.3.The Temperature Dependence of Rate Constants ............. 533
12.4.Reaction Mechanisms and Rate Laws ........................ 540
12.5.Chain Reactions .......................................... 556
Chapter 13 Chemical Reaction Mechanisms II: Catalysis
and Miscellaneous Topics ........................... 565
13.1.Catalysis ................................................ 566
13.2.Competing Mechanisms and the Principle of Detailed
Balance .................................................. 583
13.3.Autocatalysis and Oscillatory Chemical Reactions ......... 585
13.4.The Reaction Kinetics of Polymer Formation ............... 589
13.5.Nonequilibrium Electrochemistry .......................... 595
13.6.Experimental Molecular Study of Chemical Reaction
Mechanisms ............................................... 608
Part 3 The Molecular Nature of Matter ......................... 617
Chapter 14 Classical Mechanics and the Old Quantum Theory ..... 619
14.1.Introduction ............................................. 620
14.2.Classical Mechanics ...................................... 621
14.3.Classical Waves .......................................... 629
14.4.The Old Quantum Theory ................................... 640
Chapter 15 The Principles of Quantum Mechanics. I. De Broglie
Waves and the Schrodinger Equation ................. 653
15.1.De Broglie Waves ......................................... 654
15.2.The Schrodinger Equation ................................. 657
15.3.The Particle in a Box and the Free Particle .............. 663
15.4.The Quantum Harmonic Oscillator .......................... 674
Chapter 16 The Principles of Quantum Mechanics. II.
The Postulates of Quantum Mechanics ................ 683
16.1.The First Two Postulates of Quantum Mechanics ............ 684
16.2.The Third Postulate. Mathematical Operators and
Mechanical Variables ..................................... 684
16.3.The Operator Corresponding to a Given Variable ........... 688
16.4.Postulate 4 and Expectation Values ....................... 696
16.5.The Uncertainty Principle of Heisenberg .................. 711
16.6.Postulate 5.Measurements and the Determination of the
State of a System ........................................ 717
Chapter 17 The Electronic States of Atoms.I.The Hydrogen
Atom ............................................... 725
17.1.The Hydrogen Atom and the Central Force System ........... 726
17.2.The Relative Schrodinger Equation. Angular Momentum ...... 729
17.3.The Radial Factor in the Hydrogen Atom Wave Function.
The Energy Levels of the Hydrogen Atom ................... 736
17.4.The Orbitals of the Hydrogen-Like Atom ................... 741
17.5.Expectation Values in the Hydrogen Atom .................. 749
17.6.The Time-Dependent Wave Functions of the Hydrogen Atom ... 753
17.7.The Intrinsic Angular Momentum of the Electron. "Spin" ... 755
Chapter 18 The Electronic States of Atoms. II. The Zero-
Order Approximation for Multielectron Atoms ........ 763
18.1.The Helium-Like Atom ..................................... 764
18.2.The Indistinguishability of Electrons and the Pauli
Exclusion Principle ...................................... 766
18.3.The Ground State of the Helium Atom in Zero Order ........ 768
18.4.Excited States of the Helium Atom ........................ 772
18.5.Angular Momentum in the Helium Atom ...................... 774
18.6.The Lithium Atom ......................................... 781
18.7.Atoms with More Than Three Electrons ..................... 784
Chapter 19 The Electronic States of Atoms. III. Higher-
Order Approximations ............................... 789
19.1.The Variation Method and Its Application to the
Helium Atom .............................................. 790
19.2.The Self-Consistent Field Method ......................... 796
19.3.The Perturbation Method and Its Application to the
Ground State of the Helium Atom .......................... 799
19.4.Excited States of the Helium Atom. Degenerate
Perturbation Theory ...................................... 803
19.5.The Density Functional Method ............................ 805
19.6.Atoms with More Than Two Electrons ....................... 806
Chapter 20 The Electronic States of Diatomic Molecules ........ 823
20.1.The Born-Oppenheimer Approximation and the Hydrogen
Molecule Ion ............................................. 824
20.2.LCAOMOs.Approximate Molecular Orbitals That Are
Linear Combinations of Atomic Orbitals ................... 833
20.3.Homonuclear Diatomic Molecules ........................... 838
20.4.Heteronuclear Diatomic Molecules ......................... 851
Chapter 21 The Electronic Structure of Polyatomic
Molecules .......................................... 867
21.1.The BeH2 Molecule and the sp Hybrid Orbitals ............. 868
21.2.The BH3 Molecule and the sp2 Hybrid Orbitals ............. 871
21.3.The CH4, NH3, and H20 Molecules and the sp3 Hybrid
Orbitals ................................................. 873
21.4.Molecules with Multiple Bonds ............................ 878
21.5.The Valence-Bond Description of Polyatomic Molecules ..... 881
21.6.Delocalized Bonding ...................................... 885
21.7.The Free-Electron Molecular Orbital Method ............... 892
21.8.Applications of Symmetry to Molecular Orbitals ........... 894
21.9.Groups of Symmetry Operators ............................. 896
21.10.More Advanced Treatments of Molecular Electronic
Structure.Computational Chemistry ........................ 904
Chapter 22 Translational, Rotational, and Vibrational
States of Atoms and Molecules ...................... 915
22.1.The Translational States of Atoms ........................ 916
22.2.The Nonelectronic States of Diatomic Molecules ........... 919
22.3.Nuclear Spins and Wave Function Symmetry ................. 930
22.4.The Rotation and Vibration of Polyatomic Molecules ....... 933
22.5.The Equilibrium Populations of Molecular States .......... 942
Chapter 23 Optical Spectroscopy and Photochemistry ............ 949
23.1.Emission/Absorption Spectroscopy and Energy Levels ....... 950
23.2.The Spectra of Atoms ..................................... 959
23.3.Rotational and Vibrational Spectra of Diatomic
Molecules ................................................ 961
23.4.Electronic Spectra of Diatomic Molecules ................. 972
23.5.Spectra of Polyatomic Molecules .......................... 975
23.6.Fluorescence, Phosphorescence, and Photochemistry ........ 979
23.7.Raman Spectroscopy ....................................... 985
23.8.Other Types of Spectroscopy .............................. 991
Chapter 24 Magnetic Resonance Spectroscopy ................... 1001
24.1.Magnetic Fields and Magnetic Dipoles .................... 1002
24.2.Electronic and Nuclear Magnetic Dipoles ................. 1006
24.3.Electron Spin Resonance Spectroscopy .................... 1010
24.4.Nuclear Magnetic Resonance Spectroscopy.1014
24.5.Fourier Transform NMR Spectroscopy.1024
Part 4 The Reconciliation of the Macroscopic and Molecular
Theories of Matter .................................... 1037
Chapter 25 Equilibrium Statistical Mechanics I.The
Probability Distribution for Molecular States ..... 1039
25.1.The Quantum Statistical Mechanics of a Simple Model
System .................................................. 1040
25.2.The Probability Distribution for a Dilute Gas ........... 1047
25.3.The Probability Distribution and the Molecular
Partition Function ...................................... 1055
25.4.The Calculation of Molecular Partition Functions ........ 1064
Chapter 26 Equilibrium Statistical Mechanics. II.
Statistical Thermodynamics ........................ 1081
26.1.The Statistical Thermodynamics of a Dilute Gas .......... 1082
26.2.Working Equations for the Thermodynamic Functions of
a Dilute Gas ............................................ 1089
26.3.Chemical Equilibrium in Dilute Gases .................... 1101
26.4.The Activated Complex Theory of Bimolecular Chemical
Reaction Rates in Dilute Gases .......................... 1106
26.5.Miscellaneous Topics in Statistical Thermodynamics ...... 1116
Chapter 27 Equilibrium Statistical Mechanics, III.
Ensembles ......................................... 1121
27.1.The Canonical Ensemble .................................. 1122
27.2.Thermodynamic Functions in the Canonical Ensemble ....... 1128
27.3.The Dilute Gas in the Canonical Ensemble ................ 1130
27.4.Classical Statistical Mechanics ......................... 1133
27.5.Thermodynamic Functions in the Classical Canonical
Ensemble ................................................ 1141
27.6.The Classical Statistical Mechanics of Dense Gases
and Liquids ............................................. 1147
Chapter 28 The Structure of Solids, Liquids, and
Polymers .......................................... 1153
28.1.The Structure of Solids ................................. 1154
28.2.Crystal Vibrations ...................................... 1162
28.3.The Electronic Structure of Crystalline Solids .......... 1171
28.4.Electrical Resistance in Solids ......................... 1179
28.1.The Structure of Liquids ................................ 1184
28.6.Approximate Theories of Transport Processes in
Liquids ................................................. 1188
28.7.Polymer Conformation .................................... 1194
28.8.Polymers in Solution .................................... 1198
28.9.Rubber Elasticity ....................................... 1200
28.10.Nanomaterials .......................................... 1205
Appendices ................................................... 1209
A. Tables of Numerical Data .................................. 1209
B. Some Useful Mathematics ................................... 1235
С. A Short Table of Integrals ................................ 1257
D. Some Derivations of Formulas and Methods .................. 1261
E. Classical Mechanics ....................................... 1267
F. Some Mathematics Used in Quantum Mechanics ................ 1275
G. The Perturbation Method ................................... 1283
H. The Huckel Method ......................................... 1289
I. Matrix Representations of Groups .......................... 1293
J. Symbols Used in This Book ................................. 1303
K. Answers to Numerical Exercises and Odd-Numbered
Numerical Problems ........................................ 1309
Additional Reading ........................................... 1351
Index ........................................................ 1361
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