Mortimer Physical Chemistry

3. Auflage 2008
ISBN: 978-0-08-087859-1
Verlag: Elsevier Science & Techn.
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, 1416 Seiten, Web PDF

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

Robert Mortimer has been a professor of chemistry at Rhodes College since 1981. He is the recipient of a Woodrow Wilson National Fellowship as well as a National Science Foundation Predoctoral Fellowship.

Autoren/Hrsg.

Mortimer, Robert G.

Inhaltsverzeichnis

1;Front Cover;1
2;Physical Chemistry;4
3;Copyright Page;5
4;Table of Contents;8
5;Preface;16
6;Acknowledgments;18
7;Part 1: Thermodynamics and the Macroscopic Description of Physical Systems;20
7.1;Chapter 1. The Behavior of Gases and Liquids;22
7.1.1;1.1 Introduction;23
7.1.2;1.2 Systems and States in Physical Chemistry;31
7.1.3;1.3 Real Gases;40
7.1.4;1.4 The Coexistence of Phases and the Critical Point;46
7.2;Chapter 2. Work, Heat, and Energy: The First Law of Thermodynamics;58
7.2.1;2.1 Work and the State of a System;59
7.2.2;2.2 Heat;70
7.2.3;2.3 Internal Energy: The First Law of Thermodynamics;74
7.2.4;2.4 Calculation of Amounts of Heat and Energy Changes;79
7.2.5;2.5 Enthalpy;93
7.2.6;2.6 Calculation of Enthalpy Changes of Processes without Chemical Reactions;100
7.2.7;2.7 Calculation of Enthalpy Changes of a Class of Chemical Reactions;105
7.2.8;2.8 Calculation of Energy Changes of Chemical Reactions;113
7.3;Chapter 3. The Second and Third Laws of Thermodynamics: Entropy;124
7.3.1;3.1 The Second Law of Thermodynamics and the Carnot Heat Engine;125
7.3.2;3.2 The Mathematical Statement of the Second Law: Entropy;133
7.3.3;3.3 The Calculation of Entropy Changes;140
7.3.4;3.4 Statistical Entropy;152
7.3.5;3.5 The Third Law of Thermodynamics and Absolute Entropies;158
7.4;Chapter 4. The Thermodynamics of Real Systems;170
7.4.1;4.1 Criteria for Spontaneous Processes and for Equilibrium: The Gibbs and Helmholtz Energies;171
7.4.2;4.2 Fundamental Relations for Closed Simple Systems;177
7.4.3;4.3 Additional Useful Thermodynamic Identities;186
7.4.4;4.4 Gibbs Energy Calculations;194
7.4.5;4.5 Multicomponent Systems;201
7.4.6;4.6 Euler’s Theorem and the Gibbs–Duhem Relation;207
7.5;Chapter 5. Phase Equilibrium;218
7.5.1;5.1 The Fundamental Fact of Phase Equilibrium;219
7.5.2;5.2 The Gibbs Phase Rule;221
7.5.3;5.3 Phase Equilibria in One-Component Systems;224
7.5.4;5.4 The Gibbs Energy and Phase Transitions;234
7.5.5;5.5 Surfaces in One-Component Systems;241
7.5.6;5.6 Surfaces in Multicomponent Systems;249
7.6;Chapter 6. The Thermodynamics of Solutions;256
7.6.1;6.1 Ideal Solutions;257
7.6.2;6.2 Henry’s Law and Dilute Nonelectrolyte Solutions;267
7.6.3;6.3 Activity and Activity Coefficients;277
7.6.4;6.4 The Activities of Nonvolatile Solutes;286
7.6.5;6.5 Thermodynamic Functions of Nonideal Solutions;294
7.6.6;6.6 Phase Diagrams of Nonideal Mixtures;301
7.6.7;6.7 Colligative Properties;311
7.7;Chapter 7. Chemical Equilibrium;322
7.7.1;7.1 Gibbs Energy Changes and the Equilibrium Constant;323
7.7.2;7.2 Reactions Involving Gases and Pure Solids or Liquids;329
7.7.3;7.3 Chemical Equilibrium in Solutions;334
7.7.4;7.4 Equilibria in Solutions of Strong Electrolytes;347
7.7.5;7.5 Buffer Solutions;350
7.7.6;7.6 The Temperature Dependence of Chemical Equilibrium. The Principle of Le Châtelier;354
7.7.7;7.7 Chemical Equilibrium and Biological Systems;362
7.8;Chapter 8. The Thermodynamics of Electrochemical Systems;370
7.8.1;8.1 The Chemical Potential and the Electric Potential;371
7.8.2;8.2 Electrochemical Cells;373
7.8.3;8.3 Half-Cell Potentials and Cell Potentials;380
7.8.4;8.4 The Determination of Activities and Activity Coefficients of Electrolytes;390
7.8.5;8.5 Thermodynamic Information from Electrochemistry;393
8;Part 2: Dynamics;400
8.1;Chapter 9. Gas Kinetic Theory: The Molecular Theory of Dilute Gases at Equilibrium;402
8.1.1;9.1 Macroscopic and Microscopic States of Macroscopic Systems;403
8.1.2;9.2 A Model System to Represent a Dilute Gas;405
8.1.3;9.3 The Velocity Probability Distribution;413
8.1.4;9.4 The Distribution of Molecular Speeds;424
8.1.5;9.5 The Pressure of a Dilute Gas;430
8.1.6;9.6 Effusion and Wall Collisions;435
8.1.7;9.7 The Model System with Potential Energy;437
8.1.8;9.8 The Hard-Sphere Gas;441
8.1.9;9.9 The Molecular Structure of Liquids;453
8.2;Chapter 10. Transport Processes;460
8.2.1;10.1 The Macroscopic Description of Nonequilibrium States;461
8.2.2;10.2 Transport Processes;463
8.2.3;10.3 The Gas Kinetic Theory of Transport Processes in Hard-Sphere Gases;479
8.2.4;10.4 Transport Processes in Liquids;486
8.2.5;10.5 Electrical Conduction in Electrolyte Solutions;494
8.3;Chapter 11. The Rates of Chemical Reactions;504
8.3.1;11.1 The Macroscopic Description of Chemical Reaction Rates;505
8.3.2;11.2 Forward Reactions with One Reactant;507
8.3.3;11.3 Forward Reactions with More Than One Reactant;518
8.3.4;11.4 Inclusion of a Reverse Reaction. Chemical Equilibrium;526
8.3.5;11.5 A Simple Reaction Mechanism: Two Consecutive Steps;529
8.3.6;11.6 Competing Reactions;532
8.3.7;11.7 The Experimental Study of Fast Reactions;534
8.4;Chapter 12. Chemical Reaction Mechanisms I: Rate Laws and Mechanisms;542
8.4.1;12.1 Reaction Mechanisms and Elementary Processes in Gases;543
8.4.2;12.2 Elementary Processes in Liquid Solutions;546
8.4.3;12.3 The Temperature Dependence of Rate Constants;552
8.4.4;12.4 Reaction Mechanisms and Rate Laws;559
8.4.5;12.5 Chain Reactions;575
8.5;Chapter 13. Chemical Reaction Mechanisms II: Catalysis and Miscellaneous Topics;584
8.5.1;13.1 Catalysis;585
8.5.2;13.2 Competing Mechanisms and the Principle of Detailed Balance;602
8.5.3;13.3 Autocatalysis and Oscillatory Chemical Reactions;604
8.5.4;13.4 The Reaction Kinetics of Polymer Formation;608
8.5.5;13.5 Nonequilibrium Electrochemistry;614
8.5.6;13.6 Experimental Molecular Study of Chemical Reaction Mechanisms;627
9;Part 3: The Molecular Nature of Matter;636
9.1;Chapter 14. Classical Mechanics and the Old Quantum Theory;638
9.1.1;14.1 Introduction;639
9.1.2;14.2 Classical Mechanics;640
9.1.3;14.3 Classical Waves;648
9.1.4;14.4 The Old Quantum Theory;659
9.2;Chapter 15. The Principles of Quantum Mechanics. I. De Broglie Waves and the Schrödinger Equation;672
9.2.1;15.1 De Broglie Waves;673
9.2.2;15.2 The Schrödinger Equation;676
9.2.3;15.3 The Particle in a Box and the Free Particle;682
9.2.4;15.4 The Quantum Harmonic Oscillator;693
9.3;Chapter 16. The Principles of Quantum Mechanics. II. The Postulates of Quantum Mechanics;702
9.3.1;16.1 The First Two Postulates of Quantum Mechanics;703
9.3.2;16.2 The Third Postulate. Mathematical Operators and Mechanical Variables;703
9.3.3;16.3 The Operator Corresponding to a Given Variable;707
9.3.4;16.4 Postulate 4 and Expectation Values;715
9.3.5;16.5 The Uncertainty Principle of Heisenberg;730
9.3.6;16.6 Postulate 5. Measurements and the Determination of the State of a System;736
9.4;Chapter 17. The Electronic States of Atoms. I. The Hydrogen Atom;744
9.4.1;17.1 The Hydrogen Atom and the Central Force System;745
9.4.2;17.2 The Relative Schrödinger Equation. Angular Momentum;748
9.4.3;17.3 The Radial Factor in the Hydrogen Atom Wave Function. The Energy Levels of the Hydrogen Atom;755
9.4.4;17.4 The Orbitals of the Hydrogen-Like Atom;760
9.4.5;17.5 Expectation Values in the Hydrogen Atom;768
9.4.6;17.6 The Time-Dependent Wave Functions of the Hydrogen Atom;772
9.4.7;17.7 The Intrinsic Angular Momentum of the Electron. “Spin”;774
9.5;Chapter 18. The Electronic States of Atoms. II. The Zero-Order Approximation for Multielectron Atoms;782
9.5.1;18.1 The Helium-Like Atom;783
9.5.2;18.2 The Indistinguishability of Electrons and the Pauli Exclusion Principle;785
9.5.3;18.3 The Ground State of the Helium Atom in Zero Order;787
9.5.4;18.4 Excited States of the Helium Atom;791
9.5.5;18.5 Angular Momentum in the Helium Atom;793
9.5.6;18.6 The Lithium Atom;800
9.5.7;18.7 Atoms with More Than Three Electrons;803
9.6;Chapter 19. The Electronic States of Atoms. III. Higher-Order Approximations;808
9.6.1;19.1 The Variation Method and Its Application to the Helium Atom;809
9.6.2;19.2 The Self-Consistent Field Method;815
9.6.3;19.3 The Perturbation Method and Its Application to the Ground State of the Helium Atom;818
9.6.4;19.4 Excited States of the Helium Atom. Degenerate Perturbation Theory;822
9.6.5;19.5 The Density Functional Method;824
9.6.6;19.6 Atoms with More Than Two Electrons;825
9.7;Chapter 20. The Electronic States of Diatomic Molecules;842
9.7.1;20.1 The Born–Oppenheimer Approximation and the Hydrogen Molecule Ion;843
9.7.2;20.2 LCAOMOs. Approximate Molecular Orbitals That Are Linear Combinations of Atomic Orbitals;852
9.7.3;20.3 Homonuclear Diatomic Molecules;857
9.7.4;20.4 Heteronuclear Diatomic Molecules;870
9.8;Chapter 21. The Electronic Structure of Polyatomic Molecules;886
9.8.1;21.1 The BeH2 Molecule and the sp Hybrid Orbitals;887
9.8.2;21.2 The BH3 Molecule and the sp2 Hybrid Orbitals;890
9.8.3;21.3 The CH4, NH3, and H2O Molecules and the sp3 Hybrid Orbitals;892
9.8.4;21.4 Molecules with Multiple Bonds;897
9.8.5;21.5 The Valence-Bond Description of Polyatomic Molecules;900
9.8.6;21.6 Delocalized Bonding;904
9.8.7;21.7 The Free-Electron Molecular Orbital Method;911
9.8.8;21.8 Applications of Symmetry to Molecular Orbitals;913
9.8.9;21.9 Groups of Symmetry Operators;915
9.8.10;21.10 More Advanced Treatments of Molecular Electronic Structure. Computational Chemistry;923
9.9;Chapter 22. Translational, Rotational, and Vibrational States of Atoms and Molecules;934
9.9.1;22.1 The Translational States of Atoms;935
9.9.2;22.2 The Nonelectronic States of Diatomic Molecules;938
9.9.3;22.3 Nuclear Spins and Wave Function Symmetry;949
9.9.4;22.4 The Rotation and Vibration of Polyatomic Molecules;952
9.9.5;22.5 The Equilibrium Populations of Molecular States;961
9.10;Chapter 23. Optical Spectroscopy and Photochemistry;968
9.10.1;23.1 Emission/Absorption Spectroscopy and Energy Levels;969
9.10.2;23.2 The Spectra of Atoms;978
9.10.3;23.3 Rotational and Vibrational Spectra of Diatomic Molecules;980
9.10.4;23.4 Electronic Spectra of Diatomic Molecules;991
9.10.5;23.5 Spectra of Polyatomic Molecules;994
9.10.6;23.6 Fluorescence, Phosphorescence, and Photochemistry;998
9.10.7;23.7 Raman Spectroscopy;1004
9.10.8;23.8 Other Types of Spectroscopy;1010
9.11;Chapter 24. Magnetic Resonance Spectroscopy;1020
9.11.1;24.1 Magnetic Fields and Magnetic Dipoles;1021
9.11.2;24.2 Electronic and Nuclear Magnetic Dipoles;1025
9.11.3;24.3 Electron Spin Resonance Spectroscopy;1029
9.11.4;24.4 Nuclear Magnetic Resonance Spectroscopy;1033
9.11.5;24.5 Fourier Transform NMR Spectroscopy;1043
10;Part 4: The Reconciliation of the Macroscopic and Molecular Theories of Matter;1056
10.1;Chapter 25. Equilibrium Statistical Mechanics. I. The Probability Distribution for Molecular States;1058
10.1.1;25.1 The Quantum Statistical Mechanics of a Simple Model System;1059
10.1.2;25.2 The Probability Distribution for a Dilute Gas;1066
10.1.3;25.3 The Probability Distribution and the Molecular Partition Function;1074
10.1.4;25.4 The Calculation of Molecular Partition Functions;1083
10.2;Chapter 26. Equilibrium Statistical Mechanics. II. Statistical Thermodynamics;1100
10.2.1;26.1 The Statistical Thermodynamics of a Dilute Gas;1101
10.2.2;26.2 Working Equations for the Thermodynamic Functions of a Dilute Gas;1108
10.2.3;26.3 Chemical Equilibrium in Dilute Gases;1120
10.2.4;26.4 The Activated Complex Theory of Bimolecular Chemical Reaction Rates in Dilute Gases;1125
10.2.5;26.5 Miscellaneous Topics in Statistical Thermodynamics;1135
10.3;Chapter 27. Equilibrium Statistical Mechanics. III. Ensembles;1140
10.3.1;27.1 The Canonical Ensemble;1141
10.3.2;27.2 Thermodynamic Functions in the Canonical Ensemble;1147
10.3.3;27.3 The Dilute Gas in the Canonical Ensemble;1149
10.3.4;27.4 Classical Statistical Mechanics;1152
10.3.5;27.5 Thermodynamic Functions in the Classical Canonical Ensemble;1160
10.3.6;27.6 The Classical Statistical Mechanics of Dense Gases and Liquids;1166
10.4;Chapter 28. The Structure of Solids, Liquids, and Polymers;1172
10.4.1;28.1 The Structure of Solids;1173
10.4.2;28.2 Crystal Vibrations;1181
10.4.3;28.3 The Electronic Structure of Crystalline Solids;1190
10.4.4;28.4 Electrical Resistance in Solids;1198
10.4.5;28.5 The Structure of Liquids;1203
10.4.6;28.6 Approximate Theories of Transport Processes in Liquids;1207
10.4.7;28.7 Polymer Conformation;1213
10.4.8;28.8 Polymers in Solution;1217
10.4.9;28.9 Rubber Elasticity;1219
10.4.10;28.10 Nanomaterials;1224
11;Appendix A. Tables of Numerical Data;1228
12;Appendix B. Some Useful Mathematics;1254
12.1;B.1 Differential Calculus with Several Variables;1254
12.2;B.2 Integral Calculus with Several Variables;1257
12.3;B.3 Vectors;1260
12.4;B.4 Solution of a Differential Equation from the Two-Step Mechanism of Chapter 11;1264
12.5;B.5 Complex and Imaginary Quantities;1265
12.6;B.6 Some Properties of Hermitian Operators;1266
12.7;B.7 Matrices and Determinants;1268
12.8;B.8 Fourier Series;1272
12.9;B.9 Fourier Integrals (Fourier Transforms);1274
13;Appendix C. A Short Table of Integrals;1276
13.1;C.1 Indefinite Integrals;1276
13.2;C.2 Definite Integrals;1277
13.3;C.3 The Error Function;1278
14;Appendix D. Some Derivations of Formulas and Methods;1280
14.1;D.1 Caratheodory’s Theorem;1280
14.2;D.2 Proof That the Liquid and Vapor Curves Are Tangent at an Azeotrope;1281
14.3;D.3 Euler’s Theorem5;1282
14.4;D.4 The Method of Intercepts;1283
14.5;D.5 An Integration for the Collision Theory of Bimolecular Reactions;1284
15;Appendix E. Classical Mechanics;1286
15.1;E.1 Newton’s Laws of Motion;1286
15.2;E.2 Derivation of the Wave Equation for a Flexible String;1287
15.3;E.3 Lagrangian Mechanics;1289
15.4;E.4 Hamiltonian Mechanics;1290
15.5;E.5 The Two-Body Problem;1291
16;Appendix F. Some Mathematics Used in Quantum Mechanics;1294
16.1;F.1 The Classical Wave Equations for Electromagnetic Radiation;1294
16.2;F.2 The Particle in a Three-Dimensional Box;1295
16.3;F.3 The Time-Independent Schrödinger Equation for the Harmonic Oscillator (the Hermite Equation);1297
16.4;F.4 The Hydrogen Atom Energy Eigenfunctions;1299
17;Appendix G. The Perturbation Method;1302
17.1;G.1 The Nondegenerate Case;1302
17.2;G.2 The Degenerate Case;1304
18;Appendix H. The Hückel Method;1308
19;Appendix I. Matrix Representations of Groups;1312
19.1;I.1 Representations of the C2v Group;1312
19.2;I.2 Classes in a Group;1314
19.3;I.3 Character Tables;1315
19.4;I.4 Bases for Representations;1316
19.5;I.5 Applications of Group Theory to Molecular Orbitals;1318
20;Appendix J. Symbols Used in This Book;1322
21;Appendix K. Answers to Numerical Exercises and Odd-Numbered Numerical Problems;1328
22;Additional Reading;1370
23;Index;1380