Physical Chemistry

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