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Physical Chemistry

Second Edition

R. Stephen Berry, Stuart A. Rice, and John Ross

Publication Date - 30 March 2000

ISBN: 9780195105896

1080 pages
8-1/2 x 11 inches


Every chemist should own a copy of this uniquely thorough yet incisive treatment of the basic principles of physical chemistry. Written by three eminent physical chemists, the second edition of this exceptional work is the most lucid and comprehensive physical chemistry reference available. The authors present the fundamentals of the three major areas of physical chemistry--the microscopic structure of matter, the equilibrium properties of systems, and the physical and chemical kinetics of transformations of systems--in a logical sequence, from the simple to the complex. Beginning with atomic and molecular structure, they progress to properties of condensed matter, to statistical and thermodynamic properties of systems in equilibrium, and then to transport phenomena and chemical reaction processes. The book's mathematical level begins with elementary calculus and rises to the use of simple properties of partial differential equations and the special functions that enter into their solutions. The conceptual structure of physical chemistry is emphasized throughout and appendices develop the details of the mathematical tools as they are needed.

This new edition features:
· In-depth and illuminating presentation of conceptual arguments
· No shortcuts--derives whole formulas
· 100 new problems
· New material on nuclear magnetic resonance
· Expanded treatment of linear and nonlinear irreversible processes and thermodynamics
· A completely revised treatment of electrode kinetics
· Many updates throughout
· Several vignettes--written by leaders in the field--that cover topics at the cutting edge of physical chemistry research

Previous Publication Date(s)

January 1984

Table of Contents

    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 Indeterminacy 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 Coordinates 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 Configurations 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 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. Transitions and Spectra of Polyatomic Molecules: Rotations and Vibrations
    8.9. Transitions and Spectra of Polyatomic Molecules: Magnetic Transitions
    8.10. Transitions and Spectra of Polyatomic Molecules: Electronic Transitions
    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 Semiconductors
    11.14. Other Forms of Condensed Matter
    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 Zero-th 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: Internal Energy and Heat
    13.7. Some Historical Notes
    13.8. Microscopic Interpretation of Internal Energy and Heat
    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 Properties 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 Influence 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: Ω(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 Entropy 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: Poincaré 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 Nonequilibrium 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 Phase Equilibrium in Mixtures
    25.9. Critical Phenomena in Mixtures
    25.10. The 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 Mechanics of Electrolyte Solutions
    26.6. Molten Salts and Molten Salt Mixtures
    26.7. The Structure of an Electrolyte Solution Near an Electrode
    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
    Vignette: Quantum Mechanical Computations of Potential Energy Hypersurfaces, by H.F. Schaefer
    30.3. Collisions between Reactive Molecules
    Vignette: Femtochemistry--Reaction Dynamics with Atomic Resolution, by A.H. Zewail
    30.4. Hard-Sphere Collision Theory: Reactive Cross Sections
    30.5. Hard-Sphere Collision Theory: The Rate Coefficient
    30.6. Activated-Complex Theory
    Vignette: Present Day View of Transition State Theory, by D.G. Truhlar
    30.7. Activated-Complex Theory: Thermodynamic Interpretation
    30.8. Theory of Reaction Kinetics in Solution
    Vignette: Kramers' Theory of Reactions in Solutions, by M.O. Vlad and J. Ross
    Vignette: Chemical Reactions in Condensed Phases, by P.G. Wolynes
    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
    Vignette: Electron Transfer Reactions, by R.A. Marcus
    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 (a Vignette by C.E.D. Chidsey)
    Vignette: Applications of Physical Chemistry: A Biological Example, by B. Eisenberg
    II. Partial Derivatives
    III. Glossary of Symbols
    IV. Searching the Scientific Literature
    Supporting Web Links

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