Physical Chemistry

by Robert G. Mortimer

• ISBN13: 9780805345605
• ISBN10: 0805345604
• Format: Hardcover
• Copyright: 1992-01-01
• Publisher: Benjamin-Cummings Publishing Company

Summary

Physical chemistry is a fascinating field of study. It can reasonably be claimed that many parts of physics and all parts of chemistry are included within physical chemistry and its applications. Furthermore, it is the course in which most chemistry students first have opportunity to synthesize what they have learned in mathematics, physics, and chemistry courses into a coherent pattern of knowledge.

Table of Contents

Periodic Table	p. xvii
Information Tables	p. xviii
Systems, States, and Processes	p. 1
Scientific Inquiry	p. 2
Systems and States	p. 3
Units of Measurements. SI Units	p. 6
State Functions	p. 8
The Relationship between Macrostates and Microstates	p. 11
Processes	p. 16
Problems	p. 19
The Equilibrium Macroscopic States of Gases and Liquids	p. 21
Mathematical Functions and the Equilibrium Macroscopic State of a Simple System	p. 22
Real Liquids and Solids	p. 25
Real Gases	p. 28
The Coexistence of Phases and the Critical Point	p. 32
Problems	p. 41
Work, Heat, and Energy: The First Law of Thermodynamics	p. 45
Work and the State of a System	p. 46
Heat	p. 53
Internal Energy. The First Law of Thermodynamics	p. 55
Calculation of Amounts of Heat and Energy Changes	p. 58
Enthalpy--A Convenience Variable	p. 68
Calculation of Enthalpy Changes for Non-Chemical Processes	p. 74
Calculation of Enthalpy Changes for a Class of Chemical Reactions	p. 77
Energy Changes of Chemical Reactions	p. 85
Problems	p. 90
The Second and Third Laws of Thermodynamics: Entropy	p. 95
The Second Law of Thermodynamics and the Carnot Heat Engine	p. 96
The Mathematical Statement of the Second Law. Entropy	p. 102
The Calculation of Entropy Changes	p. 107
Statistical Entropy	p. 116
The Third Law of Thermodynamics and Absolute Entropies	p. 119
Problems	p. 125
The Thermodynamics of Real Systems	p. 131
Criteria for Spontaneous Processes and for Equilibrium. The Gibbs and Helmholtz Energies	p. 132
Fundamental Relations for Closed Simple Systems	p. 137
Gibbs Energy Calculations	p. 142
The Description of Multicomponent and Open Systems	p. 146
Additional Useful Thermodynamic Identities	p. 152
Euler's Theorem and the Gibbs-Duhem Relation	p. 156
Problems	p. 162
Phase Equilibrium	p. 167
The Fundamental Fact of Phase Equilibrium	p. 168
The Gibbs Phase Rule	p. 170
Phase Equilibrium in a One-Component System	p. 174
The Gibbs Energy and Phase Transitions	p. 180
Surface Structure and Thermodynamics	p. 184
Surfaces in Multicomponent Systems	p. 191
Problems	p. 195
Multicomponent Systems	p. 199
Ideal Solutions	p. 200
Henry's Law and Dilute Nonelectrolyte Solutions	p. 209
The Activity and the Description of General Systems	p. 216
Activity Coefficients in Electrolyte Solutions	p. 228
Phase Diagrams for Nonideal Mixtures	p. 234
Colligative Properties	p. 244
Problems	p. 250
The Thermodynamics of Chemical Equilibrium	p. 255
Gibbs Energy Changes and Equilibria of Chemical Reactions. The Equilibrium Constant	p. 256
Reactions Involving Gases and Pure Substances	p. 261
Chemical Equilibrium in Solution	p. 264
Equilibria in Solutions of Strong Electrolytes	p. 266
Acid-Base Equilibrium Calculations	p. 270
Temperature Dependence of Equilibrium Constants. The Principle of Le Chatelier	p. 276
Chemical Reactions and Biological Systems	p. 280
Problems	p. 285
The Thermodynamics of Electrical Systems	p. 291
The Chemical Potential and the Electric Potential	p. 292
Electrochemical Cells at Equilibrium	p. 293
Half-Cell Potentials and Cell Potentials	p. 300
The Determination of Activity Coefficients of Electrolytes	p. 307
Thermodynamic Information from Electrochemistry	p. 312
Problems	p. 315
Gas Kinetic Theory. The Molecular Theory of Dilute Gases at Equilibrium	p. 319
The Model System for a Dilute Gas	p. 320
The Velocity Probability Distribution	p. 324
The Distribution of Molecular Speeds	p. 333
The Pressure of an Ideal Gas	p. 337
Wall Collisions and Effusion	p. 341
The Model System with Potential Energy	p. 343
The Hard-Sphere Gas	p. 347
The Molecular Structure of Liquids	p. 357
Problems	p. 359
Transport Processes	p. 365
The Macroscopic Description of Nonequilibrium States	p. 366
Transport Processes	p. 368
Transport Processes in the Hard-Sphere Gas	p. 380
The Structure of Liquids and Transport Processes in Liquids	p. 385
Transport in Electrolyte Solutions	p. 390
Problems	p. 397
The Rates of Chemical Reactions	p. 401
The Macroscopic Description of Chemically Reacting Systems	p. 402
Forward Reactions with one Reactant	p. 404
Forward Reactions with More Than One Reactant	p. 412
Inclusion of a Reverse Reaction. Chemical Equilibrium	p. 417
Consecutive Reactions and Competing Reactions	p. 420
The Experimental Study of Fast Reactions	p. 424
Problems	p. 430
Chemical Reaction Mechanisms	p. 435
Reaction Mechanisms and Elementary Processes in Gases	p. 436
Elementary Reactions in Liquid Solutions	p. 438
The Temperature Dependence of Rate Constants. The Collision Theory of Bimolecular Gaseous Reactions	p. 444
Reaction Mechanisms and Rate Laws	p. 450
Some Additional Mechanisms, Including Chain and Photochemical Mechanisms. Competing Mechanisms	p. 463
Catalysis	p. 469
Experimental Molecular Study of Chemical Reactions	p. 481
Problems	p. 487
The Principles of Quantum Mechanics. I. Classical Waves and the Schrodinger Equation	p. 493
Classical Mechanics	p. 494
Classical Waves	p. 497
The Old Quantum Theory	p. 507
De Broglie Waves and the Schrodinger Equation	p. 514
The Particle in a Box. The Free Particle	p. 522
The Harmonic Oscillator	p. 531
Problems	p. 534
The Principles of Quantum Mechanics. II. The Postulates of Quantum Mechanics	p. 539
The First Two Postulates of Quantum Mechanics	p. 540
Mathematical Operators	p. 541
Postulate 3. Mathematical Operators Corresponding to Mechanical Variables in Quantum Mechanics	p. 546
Postulate 4. Expectation Values	p. 549
Postulate 5. The Determination of the State of a System	p. 565
Problems	p. 569
The Electronic States of Atoms. I. The Hydrogen Atom and the Simple Orbital Approximation for Multielectron Atoms	p. 573
The Hydrogen Atom and the Central Force System. Angular Momentum	p. 574
The Wave Functions of the Hydrogen Atom	p. 582
The Helium Atom in the "Zero-Order" Orbital Approximation	p. 597
Atoms with More Than Two Electrons	p. 610
Problems	p. 616
The Electronic States of Atoms. II. Higher-Order Approximations for Multielectron Atoms	p. 619
The Variation Method and Its Application to the Helium Atom	p. 620
The Perturbation Method and Its Application to the Helium Atom	p. 625
The Self-Consistent Field Method	p. 627
Excited States of the Helium Atom	p. 629
Atoms with More than Two Electrons	p. 632
Problems	p. 642
The Electronic States of Molecules	p. 647
The Born-Oppenheimer Approximation. The Hydrogen Molecule Ion	p. 648
LCAO-MOs--Molecular Orbitals That Are Linear Combinations of Atomic Orbitals	p. 655
Homonuclear Diatomic Molecules	p. 660
Heteronuclear Diatomic Molecules	p. 672
Symmetry in Polyatomic Molecules. Groups of Symmetry Operators	p. 682
Electronic Structure of Polyatomic Molecules	p. 690
More Advanced Treatments of Molecular Electronic Structure	p. 709
Problems	p. 715
Translational, Rotational, and Vibrational States of Atoms and Molecules	p. 721
Translational Motions of Atoms	p. 722
The Nonelectronic States of Diatomic Molecules	p. 724
Rotation and Vibration in Polyatomic Molecules	p. 736
The Equilibrium Populations of Molecular States	p. 743
Problems	p. 746
Spectroscopy and Photochemistry	p. 751
Emmission/Absorption Spectroscopy and Energy Levels	p. 752
The Spectra of Atoms	p. 761
Rotational and Vibrational Spectra of Diatomic Molecules	p. 762
Electronic Spectra of Diatomic Molecules	p. 769
Spectra of Polyatomic Molecules	p. 771
Fluorescence, Phosphorescence, and Photochemistry	p. 775
Other Types of Spectroscopy	p. 781
Magnetic Resonance Spectroscopy	p. 792
Fourier Transform Spectroscopy	p. 806
Problems	p. 811
Equilibrium Statistical Mechanics	p. 817
The Quantum Statistical Mechanics of a Sample System of Four Harmonic Oscillators	p. 818
The Probability Distribution for a Dilute Gas	p. 823
The Probability Distribution and the Molecular Partition Function	p. 828
The Calculation of Molecular Partition Functions	p. 836
Calculations of Thermodynamic Functions of Dilute Gases	p. 845
Chemical Equilibrium in Dilute Gases	p. 858
The Activated Complex Theory of Bimolecular Chemical Reactions in Dilute Gases	p. 862
The Canonical Ensemble	p. 872
Classical Statistical Mechanics	p. 881
Problems	p. 892
The Structure of Solids and Liquids	p. 897
General Features of Solids	p. 898
Crystal Vibrations	p. 906
The Electronic Structure of Crystalline Solids	p. 913
The Structure of Liquids	p. 920
Polymer Formation and Conformation	p. 927
Rubber Elasticity	p. 936
Polymers in Solution	p. 940
Problems	p. 943
Some Additional Theories of Nonequilibrium Processes	p. 947
Theories of Unimolecular Chemical Reactions	p. 948
The Molecular Case History of a Chemical Reaction	p. 952
Theories of Transport Processes in Fluid Systems	p. 954
Nonequilibrium Electrochemistry	p. 958
Electrical Conductivity in Solids	p. 970
Problems	p. 975
Appendixes	p. 977
Tables of Numerical Data	p. 977
Some Useful Mathematics	p. 1001
A Short Table of Integrals	p. 1021
Classical Mechanics	p. 1025
Some Derivations of Thermodynamic Formulas and Methods	p. 1031
Some Mathematics in Quantum Mechanics	p. 1037
The Perturbation Method	p. 1045
The Huckel Method	p. 1047
Matrix Representations of Groups	p. 1051
Symbols Used in This Book	p. 1061
Answers to Selected Exercises and Problems	p. 1069
Additional Reading	p. 1097
Index	p. 1105
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