Physical Chemistry

"The authors have taken great care to present the material in a clear and concise way and have made links, where appropriate, between chapters. Throughout the book, diagrams and illustrations are clear and informative ... There is much to commend in this book and I would suggest that all chemistry libraries stock at least one copy ... The range and depth of topics covered will serve undergraduates on any physical chemistry or chemical physics course well, even to an advanced level, making this book good value for money." Dudley Shallcross in Education in Chemistry, May 2001

• 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