Elsevier S & T

Physical Chemistry

Mortimer, Robert G.

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Table of contents

Contentsvii
Prefacexv
Acknowledgmentsxvii
Part 1. Thermodynamics and the Macroscopic Description of Physical Systems1
Chapter 1. The Behavior of Gases and Liquids3
1.1 Introduction4
1.2 Systems and States in Physical Chemistry12
1.3 Real Gases21
1.4 The Coexistence of Phases and the Critical Point27
Chapter 2. Work, Heat, and Energy: The First Law of Thermodynamics39
2.1 Work and the State of a System40
2.2 Heat51
2.3 Internal Energy: The First Law of Thermodynamics55
2.4 Calculation of Amounts of Heat and Energy Changes60
2.5 Enthalpy74
2.6 Calculation of Enthalpy Changes of Processes without Chemical Reactions81
2.7 Calculation of Enthalpy Changes of a Class of Chemical Reactions86
2.8 Calculation of Energy Changes of Chemical Reactions94
Chapter 3. The Second and Third Laws of Thermodynamics: Entropy105
3.1 The Second Law of Thermodynamics and the Carnot Heat Engine106
3.2 The Mathematical Statement of the Second Law: Entropy114
3.3 The Calculation of Entropy Changes121
3.4 Statistical Entropy133
3.5 The Third Law of Thermodynamics and Absolute Entropies139
Chapter 4. The Thermodynamics of Real Systems151
4.1 Criteria for Spontaneous Processes and for Equilibrium: The Gibbs and Helmholtz Energies152
4.2 Fundamental Relations for Closed Simple Systems158
4.3 Additional Useful Thermodynamic Identities167
4.4 Gibbs Energy Calculations175
4.5 Multicomponent Systems182
4.6 Euler’s Theorem and the Gibbs–Duhem Relation188
Chapter 5. Phase Equilibrium199
5.1 The Fundamental Fact of Phase Equilibrium200
5.2 The Gibbs Phase Rule202
5.3 Phase Equilibria in One-Component Systems205
5.4 The Gibbs Energy and Phase Transitions215
5.5 Surfaces in One-Component Systems222
5.6 Surfaces in Multicomponent Systems230
Chapter 6. The Thermodynamics of Solutions237
6.1 Ideal Solutions238
6.2 Henry’s Law and Dilute Nonelectrolyte Solutions248
6.3 Activity and Activity Coefficients258
6.4 The Activities of Nonvolatile Solutes267
6.5 Thermodynamic Functions of Nonideal Solutions275
6.6 Phase Diagrams of Nonideal Mixtures282
6.7 Colligative Properties292
Chapter 7. Chemical Equilibrium303
7.1 Gibbs Energy Changes and the Equilibrium Constant304
7.2 Reactions Involving Gases and Pure Solids or Liquids310
7.3 Chemical Equilibrium in Solutions315
7.4 Equilibria in Solutions of Strong Electrolytes328
7.5 Buffer Solutions331
7.6 The Temperature Dependence of Chemical Equilibrium. The Principle of Le Châtelier335
7.7 Chemical Equilibrium and Biological Systems343
Chapter 8. The Thermodynamics of Electrochemical Systems351
8.1 The Chemical Potential and the Electric Potential352
8.2 Electrochemical Cells354
8.3 Half-Cell Potentials and Cell Potentials361
8.4 The Determination of Activities and Activity Coefficients of Electrolytes371
8.5 Thermodynamic Information from Electrochemistry374
Part 2. Dynamics381
Chapter 9. Gas Kinetic Theory: The Molecular Theory of Dilute Gases at Equilibrium383
9.1 Macroscopic and Microscopic States of Macroscopic Systems384
9.2 A Model System to Represent a Dilute Gas386
9.3 The Velocity Probability Distribution394
9.4 The Distribution of Molecular Speeds405
9.5 The Pressure of a Dilute Gas411
9.6 Effusion and Wall Collisions416
9.7 The Model System with Potential Energy418
9.8 The Hard-Sphere Gas422
9.9 The Molecular Structure of Liquids434
Chapter 10. Transport Processes441
10.1 The Macroscopic Description of Nonequilibrium States442
10.2 Transport Processes444
10.3 The Gas Kinetic Theory of Transport Processes in Hard-Sphere Gases460
10.4 Transport Processes in Liquids467
10.5 Electrical Conduction in Electrolyte Solutions475
Chapter 11. The Rates of Chemical Reactions485
11.1 The Macroscopic Description of Chemical Reaction Rates486
11.2 Forward Reactions with One Reactant488
11.3 Forward Reactions with More Than One Reactant499
11.4 Inclusion of a Reverse Reaction. Chemical Equilibrium507
11.5 A Simple Reaction Mechanism: Two Consecutive Steps510
11.6 Competing Reactions513
11.7 The Experimental Study of Fast Reactions515
Chapter 12. Chemical Reaction Mechanisms I: Rate Laws and Mechanisms523
12.1 Reaction Mechanisms and Elementary Processes in Gases524
12.2 Elementary Processes in Liquid Solutions527
12.3 The Temperature Dependence of Rate Constants533
12.4 Reaction Mechanisms and Rate Laws540
12.5 Chain Reactions556
Chapter 13. Chemical Reaction Mechanisms II: Catalysis and Miscellaneous Topics565
13.1 Catalysis566
13.2 Competing Mechanisms and the Principle of Detailed Balance583
13.3 Autocatalysis and Oscillatory Chemical Reactions585
13.4 The Reaction Kinetics of Polymer Formation589
13.5 Nonequilibrium Electrochemistry595
13.6 Experimental Molecular Study of Chemical Reaction Mechanisms608
Part 3. The Molecular Nature of Matter617
Chapter 14. Classical Mechanics and the Old Quantum Theory619
14.1 Introduction620
14.2 Classical Mechanics621
14.3 Classical Waves629
14.4 The Old Quantum Theory640
Chapter 15. The Principles of Quantum Mechanics. I. De Broglie Waves and the Schrödinger Equation653
15.1 De Broglie Waves654
15.2 The Schrödinger Equation657
15.3 The Particle in a Box and the Free Particle663
15.4 The Quantum Harmonic Oscillator674
Chapter 16. The Principles of Quantum Mechanics. II. The Postulates of Quantum Mechanics683
16.1 The First Two Postulates of Quantum Mechanics684
16.2 The Third Postulate. Mathematical Operators and Mechanical Variables684
16.3 The Operator Corresponding to a Given Variable688
16.4 Postulate 4 and Expectation Values696
16.5 The Uncertainty Principle of Heisenberg711
16.6 Postulate 5. Measurements and the Determination of the State of a System717
Chapter 17. The Electronic States of Atoms. I. The Hydrogen Atom725
17.1 The Hydrogen Atom and the Central Force System726
17.2 The Relative Schrödinger Equation. Angular Momentum729
17.3 The Radial Factor in the Hydrogen Atom Wave Function. The Energy Levels of the Hydrogen Atom736
17.4 The Orbitals of the Hydrogen-Like Atom741
17.5 Expectation Values in the Hydrogen Atom749
17.6 The Time-Dependent Wave Functions of the Hydrogen Atom753
17.7 The Intrinsic Angular Momentum of the Electron. SpinŽ755
Chapter 18. The Electronic States of Atoms. II. The Zero-Order Approximation for Multielectron Atoms763
18.1 The Helium-Like Atom764
18.2 The Indistinguishability of Electrons and the Pauli Exclusion Principle766
18.3 The Ground State of the Helium Atom in Zero Order768
18.4 Excited States of the Helium Atom772
18.5 Angular Momentum in the Helium Atom774
18.6 The Lithium Atom781
18.7 Atoms with More Than Three Electrons784
Chapter 19. The Electronic States of Atoms. III. Higher-Order Approximations789
19.1 The Variation Method and Its Application to the Helium Atom790
19.2 The Self-Consistent Field Method796
19.3 The Perturbation Method and Its Application to the Ground State of the Helium Atom799
19.4 Excited States of the Helium Atom. Degenerate Perturbation Theory803
19.5 The Density Functional Method805
19.6 Atoms with More Than Two Electrons806
Chapter 20. The Electronic States of Diatomic Molecules823
20.1 The Born–Oppenheimer Approximation and the Hydrogen Molecule Ion824
20.2 LCAOMOs. Approximate Molecular Orbitals That Are Linear Combinations of Atomic Orbitals833
20.3 Homonuclear Diatomic Molecules838
20.4 Heteronuclear Diatomic Molecules851
Chapter 21. The Electronic Structure of Polyatomic Molecules867
21.1 The BeH2 Molecule and the sp Hybrid Orbitals868
21.2 The BH3 Molecule and the sp2 Hybrid Orbitals871
21.3 The CH4, NH3, and H2O Molecules and the sp3 Hybrid Orbitals873
21.4 Molecules with Multiple Bonds878
21.5 The Valence-Bond Description of Polyatomic Molecules881
21.6 Delocalized Bonding885
21.7 The Free-Electron Molecular Orbital Method892
21.8 Applications of Symmetry to Molecular Orbitals894
21.9 Groups of Symmetry Operators896
21.10 More Advanced Treatments of Molecular Electronic Structure. Computational Chemistry904
Chapter 22. Translational, Rotational, and Vibrational States of Atoms and Molecules915
22.1 The Translational States of Atoms916
22.2 The Nonelectronic States of Diatomic Molecules919
22.3 Nuclear Spins and Wave Function Symmetry930
22.4 The Rotation and Vibration of Polyatomic Molecules933
22.5 The Equilibrium Populations of Molecular States942
Chapter 23. Optical Spectroscopy and Photochemistry949
23.1 Emission/Absorption Spectroscopy and Energy Levels950
23.2 The Spectra of Atoms959
23.3 Rotational and Vibrational Spectra of Diatomic Molecules961
23.4 Electronic Spectra of Diatomic Molecules972
23.5 Spectra of Polyatomic Molecules975
23.6 Fluorescence, Phosphorescence, and Photochemistry979
23.7 Raman Spectroscopy985
23.8 Other Types of Spectroscopy991
Chapter 24. Magnetic Resonance Spectroscopy1001
24.1 Magnetic Fields and Magnetic Dipoles1002
24.2 Electronic and Nuclear Magnetic Dipoles1006
24.3 Electron Spin Resonance Spectroscopy1010
24.4 Nuclear Magnetic Resonance Spectroscopy1014
24.5 Fourier Transform NMR Spectroscopy1024
Part 4. The Reconciliation of the Macroscopic and Molecular Theories of Matter1037
Chapter 25. Equilibrium Statistical Mechanics. I. The Probability Distribution for Molecular States1039
25.1 The Quantum Statistical Mechanics of a Simple Model System1040
25.2 The Probability Distribution for a Dilute Gas1047
25.3 The Probability Distribution and the Molecular Partition Function1055
25.4 The Calculation of Molecular Partition Functions1064
Chapter 26. Equilibrium Statistical Mechanics. II. Statistical Thermodynamics1081
26.1 The Statistical Thermodynamics of a Dilute Gas1082
26.2 Working Equations for the Thermodynamic Functions of a Dilute Gas1089
26.3 Chemical Equilibrium in Dilute Gases1101
26.4 The Activated Complex Theory of Bimolecular Chemical Reaction Rates in Dilute Gases1106
26.5 Miscellaneous Topics in Statistical Thermodynamics1116
Chapter 27. Equilibrium Statistical Mechanics. III. Ensembles1121
27.1 The Canonical Ensemble1122
27.2 Thermodynamic Functions in the Canonical Ensemble1128
27.3 The Dilute Gas in the Canonical Ensemble1130
27.4 Classical Statistical Mechanics1133
27.5 Thermodynamic Functions in the Classical Canonical Ensemble1141
27.6 The Classical Statistical Mechanics of Dense Gases and Liquids1147
Chapter 28. The Structure of Solids, Liquids, and Polymers1153
28.1 The Structure of Solids1154
28.2 Crystal Vibrations1162
28.3 The Electronic Structure of Crystalline Solids1171
28.4 Electrical Resistance in Solids1179
28.5 The Structure of Liquids1184
28.6 Approximate Theories of Transport Processes in Liquids1188
28.7 Polymer Conformation1194
28.8 Polymers in Solution1198
28.9 Rubber Elasticity1200
28.10 Nanomaterials1205
Appendices1209
Appendix A. Tables of Numerical Data1209
Appendix B. Some Useful Mathematics1235
B.1 Differential Calculus with Several Variables1235
B.2 Integral Calculus with Several Variables1238
B.3 Vectors1241
B.4 Solution of a Differential Equation from the Two-Step Mechanism of Chapter 111245
B.5 Complex and Imaginary Quantities1246
B.6 Some Properties of Hermitian Operators1247
B.7 Matrices and Determinants1249
B.8 Fourier Series1253
B.9 Fourier Integrals (Fourier Transforms)1255
Appendix C. A Short Table of Integrals1257
C.1 Indefinite Integrals1257
C.2 Definite Integrals1258
C.3 The Error Function1259
Appendix D. Some Derivations of Formulas and Methods1261
D.1 Caratheodory’s Theorem1261
D.2 Proof That the Liquid and Vapor Curves Are Tangent at an Azeotrope1262
D.3 Euler’s Theorem51263
D.4 The Method of Intercepts1264
D.5 An Integration for the Collision Theory of Bimolecular Reactions1265
Appendix E. Classical Mechanics1267
E.1 Newton’s Laws of Motion1267
E.2 Derivation of the Wave Equation for a Flexible String1268
E.3 Lagrangian Mechanics1270
E.4 Hamiltonian Mechanics1271
E.5 The Two-Body Problem1272
Appendix F. Some Mathematics Used in Quantum Mechanics1275
F.1 The Classical Wave Equations for Electromagnetic Radiation1275
F.2 The Particle in a Three-Dimensional Box1276
F.3 The Time-Independent Schrödinger Equation for the Harmonic Oscillator (the Hermite Equation)1278
F.4 The Hydrogen Atom Energy Eigenfunctions1280
Appendix G. The Perturbation Method1283
G.1 The Nondegenerate Case1283
G.2 The Degenerate Case1285
Appendix H. The Hückel Method1289
Appendix I. Matrix Representations of Groups1293
I.1 Representations of the C2v Group1293
I.2 Classes in a Group1295
I.3 Character Tables1296
I.4 Bases for Representations1297
I.5 Applications of Group Theory to Molecular Orbitals1299
Appendix J. Symbols Used in This Book1303
Appendix K. Answers to Numerical Exercises and Odd-Numbered Numerical Problems1309
Additional Reading1351
Index1361

Book details

Vendor Elsevier S & T
SKU 9780123706171
ISBN-13 9780080878591
Author Mortimer, Robert G.
Edition 3rd
Category Science
Subject Industrial & Technical

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In this third edition, core applications have been added along with more recent developments in the theories of chemical reaction kinetics and molecular quantum mechanics, as well as in the experimental study of extremely rapid chemical reactions.

* Fully revised concise edition covering recent developments in the field
* Supports student learning with step by step explanation of fundamental principles, an appropriate level of math rigor, and pedagogical tools to aid comprehension
* Encourages readers to apply theory in practical situations

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