Physical Chemistry

Preface ; PART ONE: THE STRUCTURE OF MATTER ; 1. THE MICROSCOPIC WORLD: ATOMS AND MOLECULES ; 1.1 Development of the Atomic Theory: Relative Atomic Weights ; 1.2 Atomic Magnitudes ; 1.3 The Charge-to-Mass Ratio of the Electron: Thomson's Method ; 1.4 The Charge of the Electron: Millikan's Method ; 1.5 Mass Spectrometry ; 1.6 The Atomic Mass Scale and the Mole ; 1.7 The Periodic Table ; 2. ORIGINS OF THE QUANTUM THEORY OF MATTER ; 2.1 The Franck-Hertz Experiment ; 2.2 The Photoelectric Effect ; 2.3 x Rays and Matter ; 2.4 The Emission Spectra of Atoms ; 2.5 The Nuclear Atom ; 2.6 The Problem of Black-Body Radiation ; 2.7 The Concept of Action ; 2.8 The Harmonic Oscillator ; 2.9 Action Quantized: The Heat Capacity of Solids ; 2.10 Some Orders of Magnitude ; 2.11 Bohr's Model of the Atom ; Appendix 2A: Rutherford Scattering ; 3. MATTER WAVES IN SIMPLE SYSTEMS ; 3.1 The de Broglie Hypothesis ; 3.2 The Nature of Waves ; 3.3 Dispersion Relations and Wave Equations: The Free Particle ; 3.4 Operators ; 3.5 Eigenfunctions and Eigenvalues ; 3.6 The Particle in a One-Dimensional Box ; 3.7 The Interdeterminacy or Uncertainty Principle ; 3.8 Expectation Values; Summary of Postulates ; 3.9 Particles in Two- and Three-Dimensional Boxes ; 3.10 Particles in Circular Boxes ; 3.11 Particles in Spherical Boxes ; 3.12 The Rigid Rotor ; Appendix 3A: More on Circular Cooridnates and the Circular Box ; 4. PARTICLES IN VARYING POTENTIAL FIELDS; TRANSITIONS ; 4.1 Finite Potential Barriers ; 4.2 The Quantum Mechanical Harmonic Oscillator ; 4.3 The Hydrogen Atom ; 4.4 The Shapes of Orbitals ; 4.5 Transitions Between Energy Levels ; 5. THE STRUCTURE OF ATOMS ; 5.1 Electron Spin; Magnetic Phenomena ; 5.2 The Pauli Exclusion Principle; the Aufbau Principle ; 5.3 Electronic Configuration of Atoms ; 5.4 Calculation of Atomic Structures ; 5.5 Atomic Structure and Periodic Behavior ; 5.6 Term Splitting and the Vector Model ; 5.7 Fine Structure and Spin-Orbit Interactions ; Appendix 5A: The Stern-Gerlach Experiment ; 6. THE CHEMICAL BOND IN THE SIMPLEST MOLECULES: H2+ AND H2 ; 6.1 Bonding Forces Between Atoms ; 6.2 The Simplest Molecule: The Hydrogen Molecule-Ion, H2+ ; 6.3 H2+: Molecular Orbitals and the LCAO Approximation ; 6.4 H2+: Obtaining the Energy Curve ; 6.5 H2+: Correlation of Orbitals; Excited States ; 6.6 The H2 Molecule: Simple MO Description ; 6.7 Symmetry Properties of Identical Particles ; 6.8 H2: The Valence BOnd Representation ; 6.9 H2: Beyond the Simple MO and VB Approximations ; 6.10 H2: Excited Electronic States ; Appendix 6A: Orthogonality ; Appendix 6B: Hermitian Operators ; 7. MORE ABOUT DIATOMIC MOLECULES ; 7.1 Vibrations of Diatomic Molecules ; 7.2 Rotations of Diatomic Molecules ; 7.3 Spectra of Diatomic Molecules ; 7.4 The Ionic Bond ; 7.5 Homonuclear Diatomic Molecules: Molecular Orbitals and Orbital Correlation ; 7.6 Homonuclear Diatomic Molecules: Aufbau Principle and the Structure of First-Row Molecules ; 7.7 Introduction to Heteronuclear Diatomic Molecules: Electronegativity ; 7.8 Bonding in LiH: Crossing and Noncrossing Potential Curves ; 7.9 Other First-Row Diatomic Hydrides ; 7.10 Isoelectronic and Other Series ; Appendix 7A: Perturbation Theory ; 8. TRIATOMIC MOLECULES ; 8.1 Electronic Structure and Geometry in the Simplest Cases: H3 and H3+ ; 8.2 Dihydrides: Introduction to the Water Molecule ; 8.3 Hybrid Orbitals ; 8.4 Delocalized Orbitals in H2O: The General MO Method ; 8.5 Bonding in More Complex Triatomic Molecules ; 8.6 Normal Coordinates and Modes of Vibration ; 8.7 A Solvable Example: The Vibrational Modes of CO2 ; 8.8 Transition and Spectra of Polyatomic Molecules ; 9. LARGER POLYATOMIC MOLECULES ; 9.1 Small Molecules ; 9.2 Catenated Carbon Compounds; Transferability ; 9.3 Other Extended Structures ; 9.4 Some Steric Effects ; 9.5 Complex Ions and Other Coordination Compounds: Simple Polyhedra ; 9.6 Chirality and Optical Rotation ; 9.7 Chiral and Other Complex Ions ; 9.8 Magnetic Properties of Complexes ; 9.9 Electronic Structure of Complexes ; Appendix 9A: Schmidt Orthogonalization ; 10. INTERMOLECULAR FORCES ; 10.1 Long-Range Forces: Interactions Between Charge Distributions ; 10.2 Empirical Intermolecular Potentials ; 10.3 Weakly Associated Molecules ; 11. THE STRUCTURE OF SOLIDS ; 11.1 Some General Properties of Solids ; 11.2 Space Lattices and Crystal Symmetry ; 11.3 x Ray Diffraction from Crystals: The Bragg Model ; 11.4 The Laue Model ; 11.5 Determination of Crystal Structures ; 11.6 Techniques of Diffraction ; 11.7 Molecular Crystals ; 11.8 Structures of Ionic Crystals ; 11.9 Binding Energy of Ionic Crystals ; 11.10 Covalent Solids ; 11.11 The Free-Electron Theory of Metals ; 11.12 The Band Theory of Solids ; 11.13 Conductors, Insulators, and Semicondutors ; 11.14 Other Forms of Condensed Matter ; PART TWO: MATTER IN EQUILIBRIUM: STATISTICAL MECHANICS AND THERMODYNAMICS ; 12. THE PERFECT GAS AT EQUILIBRIUM AND THE CONCEPT OF TEMPERATURE ; 12.1 The Perfect Gas: Definition and Elementary Model ; 12.2 The Perfect Gas: A General Relation Between Pressure and Energy ; 12.3 Some Comments About Thermodynamics ; 12.4 Temperature and the Zeroth Law of Thermodynamics ; 12.5 Empirical Temperature: The Perfect Gas Temperature Scale ; 12.6 Comparison of the Microscopic and Macroscopic Approaches ; 13. THE FIRST LAW OF THERMODYNAMICS ; 13.1 Microscopic and Macroscopic Energy in a Perfect Gas ; 13.2 Description of Thermodynamic States ; 13.3 The Concept of Work in Thermodynamics ; 13.4 Intensive and Extensive Variables ; 13.5 Quasi-static and Reversible Processes ; 13.6 The First Law: Energy and Heat ; 13.7 Some Historical Notes ; 13.8 Microscopic Interpretation of Internal Heat and Energy ; 13.9 Constraints, Work, and Equilibrium ; 14. THERMOCHEMISTRY AND ITS APPLICATIONS ; 14.1 Heat Capacity and Enthalpy ; 14.2 Energy and Enthalpy Changes in Chemical Reactions ; 14.3 Thermochemistry of Physical Processes ; 14.4 Introduction to Phase Changes ; 14.5 Standard States ; 14.6 Thermochemistry of Solutions ; 14.7 Molecular Interpretation of Physical Processes ; 14.8 Bond Energies ; 14.9 Some Energy Effects in Molecular Structures ; 14.10 Lattice Energies of Ionic Crystals ; 15. THE CONCEPT OF ENTROPY: RELATIONSHIP TO THE ENERGY LEVEL SPECTRUM OF A SYSTEM ; 15.1 The Relationship Between Average Propertis and Molecular Motion in an N-Molecule System: Time Averages and Ensemble Averages ; 15.2 Ensembles and Probability Distributions ; 15.3 Some Properties of a System with Many Degrees of Freedom: Elements of the Statistical Theory of Matter at Equilibrium ; 15.4 The Influences of Constraints on the Density of States ; 15.5 The Entropy: A Potential Function for the Equilibrium State ; Appendix 15A: Comments on Ensemble Theory ; Appendix 15B: (E) as a System Descriptor ; Appendix 15C: The Master Equation ; 16. THE SECOND LAW OF THERMODYNAMICS: THE MACROSCOPIC CONCEPT OF ENTROPY ; 16.1 The Second Law of Thermodynamics ; 16.2 The Existence of an Engropy Function for Reversible Processes ; 16.3 Irreversible Processes: The Second Law Interpretation ; 16.4 The Clausius and Kelvin Statements Revisited ; 16.5 The Second Law as an Inequality ; 16.6 Some Relationships Between the Microscopic and Macroscopic Theories ; Appendix 16A Poincaree Recurrence Times and Irreversibility ; 17. SOME APPLICATIONS OF THE SECOND LAW OF THERMODYNAMICS ; 17.1 Choice of Independent Variables ; 17.2 The Available Work Concept ; 17.3 Entropy Changes in Reversible Processes ; 17.4 Entropy Changes in Irreversible Processes ; 17.5 Entropy Changes in Phase Transitions ; 18. THE THIRD LAW OF THERMODYNAMICS ; 18.1 The Magnitude of the Entropy at T=0 ; 18,2 The Unattainability of Absolute Zero ; 18.3 Experimental Verification of the Third Law ; 19. THE NATURE OF THE EQUILIBRIUM STATE ; 19.1 Properties of the Equilibrium State of a Pure Substance ; 19.2 Alternative Descriptions of the Equilibrium State for Different External Constraints ; 19.3 The Stability of the Equilibrium State of a One-Component System ; 19,4 The Equilibrium State in a Multicomponent System ; 19.5 Chemical Equilibrium ; 19.6 Thermodynamic Weight: Further Connections Between Thermodynamics and Microscopic Structure ; 19.7 An Application of the Canonical Ensemble: The Distribution of Molecular Speeds in a Perfect Gas ; 20. AN EXTENSION OF THERMODYNAMICS TO THE DESCRIPTION OF NON-EQUILIBRIUM PROCESSES ; 20.1 General Form of the Equation of Continuity ; 20.2 Conservation of Mass and the Diffusion Equation ; 20.3 Conservation of Momentum and the Navier-Stokes Equation ; 20.4 Conservation of Energy and the Second Law of Thermodynamics ; 20.5 Linear Transport Processes ; 20.6 Negative Temperature ; 20.7 Thermodynamics of Systems at Negative Absolute Temperature ; Appendix 20A: Symmetry of the Momentum Flux Tensor ; 21. THE PROPERTIES OF PURE GASES AND GAS MIXTURES ; 21.1 Thermodynamic Description of a Pure Gas ; 21.2 Thermodynamic Description of a Gas Mixture ; 21.3 Thermodynamic Description of Gaseous Reactions ; 21.4 An Example: The Haber Synthesis of NH3 ; 21.5 Statistical Molecular Theory of Gases and Gas Reactions ; 21.6 The Statistical Molecular Theory of the Equilibrium Constant ; 21.7 The Statistical Molecular Theory of the Real Gas ; Appendix 21A: Influence of Symmetry of the Wave Function on the Distribution over States: Fermi-Dirac and Bose-Einstein Statistics ; Appendix 21B: Symmetry Properties of the Molecular Wave Function: Influence of Nuclear Spin on the Rotational Partition Function ; Appendix 21C: The Semiclassical Partition Function: The Equation of State of an Imperfect Gas ; 22. THERMODYNAMIC PROPERTIES OF SOLIDS ; 22.1 Differences Between Gases and Condensed Phases ; 22.2 The Influence of Crystal Symmetry on Macroscopic Properties ; 22.3 Microscopic Theory of the Thermal Properties of Crystalline Solids ; 22.4 The Contribution of Anharmonicity to the Properties of a Crystal ; 22.5 Some Properties of Complex Solids and of Imperfect Solids ; 22.6 Electronic Heat Capacity of Metals ; Appendix 22A: Evaluation of Fermi-Dirac Integrals ; 23. THERMODYNAMIC PROPERTIES OF LIQUIDS ; 23.1 Bulk Properties of Liquids ; 23.2 The Structure of Liquids ; 23.3 Relationships Between the Structure and the Thermodynamic Properties of a Simple Liquid ; 23.4 The Molecular Theory of Monoatomic Liquids: General Remarks ; 23.5 The Molecular Theory of Monoatomic Liquids: Approximate Analyses ; 23.6 The Molecular Theory of Polyatomic Liquids ; Appendix 23A: x Ray Scattering from Liquids: Determination of the Structure of a Liquid ; Appendix 23B: Functional Differentiation ; 24. PHASE EQUILIBRIA IN ONE-COMPONENT SYSTEMS ; 24.1 General Survey of Phase Equilibria ; 24.2 Thermodynamics of Phase Equilibria in One-Component Systems ; 24.3 Phase Transitions Viewed as Responses to Thermodynamic Instabilities ; 24.4 The Statistical Molecular Description of Phase Transitions ; Appendix 24A: The Scaling Hypothesis for Thermodynamic Functions ; Appendix 24B: Aspects of Density Functional Theory ; 25. SOLUTIONS OF NONELECTROLYTES ; 25.1 The Chemical Potential of a Component in an Ideal Solution ; 25.2 The Chemical Potential of a Component in a Real Solution ; 25.3 Partial Molar Quantities ; 25.4 Liquid-Vapor Equilibrium ; 25.5 Liquid-Solid Equilibrium ; 25.6 The Colligative Properties of Solutions: Boiling-Point Elevation, Freezing-Point Depression, and Osmotic Pressure ; 25.7 Chemical Reactions in Nonelectrolyte Solutions ; 25.8 More About Phas Equilibrium in Mixtures ; 25.9 Critical Phenomena in Mixtures ; 25.10 The Statistical Molecular Theory of Solutions of Nonelectrolytes ; 26. EQUILIBRIUM PROPERTIES OF SOLUTIONS OF ELECTROLYTES ; 26.1 The Chemical Potential ; 26.2 Cells, Chemical Reactions, and Activity Coefficients ; 26,3 Comments on the Structure of Water ; 26.4 The Influence of Solutes on the Structure of Water ; 26.5 The Statistical Molecular Theory of Electrolyte Solutions ; 26.6 Molten Salts and Molten Salt Mixtures ; 26.7 The Structure of an Electrolyte Solution Near an Electrode ; PART THREE: PHYSICAL AND CHEMICAL KINETICS ; 27. Molecular Motion and Collisions ; 27.1 Kinematics ; 27.2 Forces and Potentials ; 27.3 Collision Dynamics ; 27.4 Types of Collisions ; 27.5 Scattering Cross Sections ; 27.6 Elastic Scattering of Hard Spheres ; 27.7 Elastic Scattering of Atoms ; 27.8 Quantum Mechanical Scattering ; 28. THE KINETIC THEORY OF GASES ; 28.1 Distribution Functions ; 28.2 Collision Frequency in a Dilute Gas ; 28.3 The Evolution of Velocity Distributions in Time ; 28.4 The Maxwell-Boltzmann Distribution ; 28.5 Collision Frequency for Hard-Sphere Molecules ; 28.6 Molecular Fluxes of Density, Momentum Density, and Energy Density ; 28.7 Effusion ; 28.8 Transport Properties of Gases ; 28.9 Energy Exchange Processes ; 28.10 Sound Propagation and Absorption ; 29. THE KINETIC THEORY OF DENSE PHASES ; 29.1 Transport Properties in Dense Fluids ; 29.2 Some Basic Aspects of Brownian Motion ; 29.3 Stochastic Approach to Transport ; 29.4 Autocorrelation Functions and Transport Coefficients ; 29.5 Transport in Solids ; 29.6 Electrical Conductivity in Electrolyte Solutions ; 30. CHEMICAL KINETICS ; 30.1 General Concepts of Kinetics ; 30.2 Interactions Between Reactive Molecules ; 30.3 Collisions Between Reactive Molecules ; 30.4 Hard-Sphere Collision Theory: Reactive Cross Sections ; 30.5 Hard-Sphere Collision Theory: The Rate Coefficient ; 30.6 Activated-Complex Theory ; 30.7 Activated-Complex Theory: Thermodynamic Interpretation ; 30.8 Theory of Reaction Kinetics in Solution ; 30.9 Linear Free-Energy Relationships ; 30.10 Experimental Methods in Kinetics ; 30.11 Analysis of Data for Complex Reactions ; 30.12 Mechanisms of Chemical Reactions ; 30.13 Bimolecular Reactions ; 30.14 Unimolecular Reactions ; 30.15 Termolecular Reactions ; 31. SOME ADVANCED TOPICS IN CHEMICAL KINETICS ; 31.1 More About Unimolecular Reactions ; 31.2 Kinetics of Photochemically Induced Reactions ; 31.3 Chain Reactions ; 31.4 Non-linear Phenomena ; 31.5 Fluctuations in Chemical Kinetics ; 31.6 Symmetry Rules for Chemical Reactions ; 31.7 Introduction to Catalysis ; 31.8 Enzyme Catalysis ; 31.9 Acid-Base Catalysis ; 31.10 Metal-Ion, COmplex, and Other Types of Homogeneous Catalysis ; 31.11 Heterogeneous Reactions: Adsorption of Gas on a Surface ; 31.12 Heterogeneous Catalysis ; 31.13 Kinetics of Electrode Reactions (by C. Chidsey) ; APPENDICES ; I. Systems of Units ; II. Partial Derivatives ; III. Glossary of Symbols ; IV. Searching the Scientific Literature ; Index