Physical Chemistry

Hardcover | March 31, 2000

byR. Stephen Berry, Stuart A. Rice, John Ross

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

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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 th...

R. Stephen Berry and Stuart A. Rice are both at University of Chicago. John Ross is at Stanford University.

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Format:HardcoverPublished:March 31, 2000Publisher:Oxford University PressLanguage:English

The following ISBNs are associated with this title:

ISBN - 10:0195105893

ISBN - 13:9780195105896

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Table of Contents

PrefacePART I: THE STRUCTURE OF MATTER1. The Microscopic World: Atoms and Molecules1.1. Development of the Atomic Theory: Relative Atomic Weights1.2. Atomic Magnitudes1.3. The Charge-to-Mass Ratio of the Electron: Thomson's Method1.4. The Charge of the Electron: Millikan's Method1.5. Mass Spectrometry1.6. The Atomic Mass Scale and the Mole1.7. The Periodic Table2. Origins of the Quantum Theory of Matter2.1. The Franck-Hertz Experiment2.2. The Photoelectric Effect2.3. X-rays and Matter2.4. The Emission Spectra of Atoms2.5. The Nuclear Atom2.6. The Problem of Black-Body Radiation2.7. The Concept of Action2.8. The Harmonic Oscillator2.9. Action Quantized: The Heat Capacity of Solids2.10. Some Orders of Magnitude2.11. Bohr's Model of the AtomAppendix 2A: Rutherford Scattering: 3. Matter Waves in Simple Systems3.1. The de Broglie Hypothesis3.2. The Nature of Waves3.3. Dispersion Relations and Wave Equations: The Free Particle3.4. Operators3.5. Eigenfunctions and Eigenvalues3.6. The Particle in a One-Dimensional Box3.7. The Indeterminacy or Uncertainty Principle3.8. Expectation Values; Summary of Postulates3.9. Particles in Two- and Three-Dimensional Boxes3.10. Particles in Circular Boxes3.11. Particles in Spherical Boxes3.12. The Rigid RotorAppendix 3A: More on Circular Coordinates and the Circular Box: 4. Particles in Varying Potential Fields; Transitions4.1. Finite Potential Barriers4.2. The Quantum Mechanical Harmonic Oscillator4.3. The Hydrogen Atom4.4. The Shapes of Orbitals4.5. Transitions between Energy Levels5. The Structure of Atoms5.1. Electron Spin; Magnetic Phenomena5.2. The Pauli Exclusion Principle; the Aufbau Principle5.3. Electronic Configurations of Atoms5.4. Calculation of Atomic Structures5.5. Atomic Structure and Periodic Behavior5.6. Term Splitting and the Vector Model5.7. Fine Structure and Spin-Orbit InteractionsAppendix 5A: The Stern-Gerlach Experiment: 6. The Chemical Bond in the Simplest Molecules: H2+ and H26.1. Bonding Forces between Atoms6.2. The Simplest Molecule: The Hydrogen Molecule-Ion, H2+6.3. H2+: Molecular Orbitals and the LCAO Approximation6.4. H2+: Obtaining the Energy Curve6.5. H2+: Correlation of Orbitals; Excited States6.6. The H2 Molecule: Simple MO Description6.7. Symmetry Properties of Identical Particles6.8. H2: The Valence Bond Representation6.9. H2: Beyond the Simple MO and VB Approximations6.10. H2: Excited Electronic StatesAppendix 6A: Orthogonality: Appendix 6B: Hermitian Operators: 7. More About Diatomic Molecules7.1. Vibrations of Diatomic Molecules7.2. Rotations of Diatomic Molecules7.3. Spectra of Diatomic Molecules7.4. The Ionic Bond7.5. Homonuclear Diatomic Molecules: Molecular Orbitals and Orbital Correlation7.6. Homonuclear Diatomic Molecules: Aufbau Principle and Structure of First-Row Molecules7.7. Introduction to Heteronuclear Diatomic Molecules: Electronegativity7.8. Bonding in LiH: Crossing and Noncrossing Potential Curves7.9. Other First-Row Diatomic Hydrides7.10. Isoelectronic and Other SeriesAppendix 7A: Perturbation Theory: 8. Triatomic Molecules8.1. Electronic Structure and Geometry in the Simplest Cases: H3 and H3+8.2. Dihydrides: Introduction to the Water Molecule8.3. Hybrid Orbitals8.4. Delocalized Orbitals in H2O: The General MO Method8.5. Bonding in More Complex Triatomic Molecules8.6. Normal Coordinates and Modes of Vibration8.7. A Solvable Example: The Vibrational Modes of CO28.8. Transitions and Spectra of Polyatomic Molecules: Rotations and Vibrations8.9. Transitions and Spectra of Polyatomic Molecules: Magnetic Transitions8.10. Transitions and Spectra of Polyatomic Molecules: Electronic Transitions9. Larger Polyatomic Molecules9.1. Small Molecules9.2. Catenated Carbon Compounds; Transferability9.3. Other Extended Structures9.4. Some Steric Effects9.5. Complex Ions and Other Coordination Compounds: Simple Polyhedra9.6. Chirality and Optical Rotation9.7. Chiral and Other Complex Ions9.8. Magnetic Properties of Complexes9.9. Electronic Structure of ComplexesAppendix 9A: Schmidt Orthogonalization: 10. Intermolecular Forces10.1. Long-Range Forces: Interactions between Charge Distributions10.2. Empirical Intermolecular Potentials10.3. Weakly Associated Molecules11. The Structure of Solids11.1. Some General Properties of Solids11.2. Space Lattices and Crystal Symmetry11.3. X-ray Diffraction from Crystals: The Bragg Model11.4. The Laue Model11.5. Determination of Crystal Structures11.6. Techniques of Diffraction11.7. Molecular Crystals11.8. Structures of Ionic Crystals11.9. Binding Energy of Ionic Crystals11.10. Covalent Solids11.11. The Free-Electron Theory of Metals11.12. The Band Theory of Solids11.13. Conductors, Insulators, and Semiconductors11.14. Other Forms of Condensed MatterPART II: MATTER IN EQUILIBRIUM: STATISTICAL MECHANICS AND THERMODYNAMICS12. The Perfect Gas at Equilibrium and the Concept of Temperature12.1. The Perfect Gas: Definition and Elementary Model12.2. The Perfect Gas: A General Relation between Pressure and Energy12.3. Some Comments about Thermodynamics12.4. Temperature and the Zero-th Law of Thermodynamics12.5. Empirical Temperature: The Perfect Gas Temperature Scale12.6. Comparison of the Microscopic and Macroscopic Approaches13. The First Law of Thermodynamics13.1. Microscopic and Macroscopic Energy in a Perfect Gas13.2. Description of Thermodynamic States13.3. The Concept of Work in Thermodynamics13.4. Intensive and Extensive Variables13.5. Quasi-static and Reversible Processes13.6. The First Law: Internal Energy and Heat13.7. Some Historical Notes13.8. Microscopic Interpretation of Internal Energy and Heat13.9. Constraints, Work, and Equilibrium14. Thermochemistry and Its Applications14.1. Heat Capacity and Enthalpy14.2. Energy and Enthalpy Changes in Chemical Reactions14.3. Thermochemistry of Physical Processes14.4. Introduction to Phase Changes14.5. Standard States14.6. Thermochemistry of Solutions14.7. Molecular Interpretation of Physical Processes14.8. Bond Energies14.9. Some Energy Effects in Molecular Structures14.10. Lattice Energies of Ionic Crystals15. The Concept of Entropy: Relationship to the Energy-Level Spectrum of a System15.1. The Relationship between Average Properties and Molecular Motion in an N-Molecule System: Time Averages and Ensemble Averages15.2. Ensembles and Probability Distributions15.3. Some Properties of a System with Many Degrees of Freedom: Elements of the Statistical Theory of Matter at Equilibrium15.4. The Influence of Constraints on the Density of States15.5. The Entropy: A Potential Function for the Equilibrium StateAppendix 15A: Comments on Ensemble Theory: Appendix 15B: O(E) as a System Descriptor: Appendix 15C: The Master Equation: 16. The Second Law of Thermodynamics: The Macroscopic Concept of Entropy16.1. The Second Law of Thermodynamics16.2. The Existence of an Entropy Function for Reversible Processes16.3. Irreversible Processes: The Second-Law Interpretation16.4. The Clausius and Kelvin Statements Revisited16.5. The Second Law as an Inequality16.6. Some Relationships between the Microscopic and Macroscopic TheoriesAppendix 16A: Poincare Recurrence Times and Irreversibility: 17. Some Applications of the Second Law of Thermodynamics17.1. Choice of Independent Variables17.2. The Available Work Concept17.3. Entropy Changes in Reversible Processes17.4. Entropy Changes in Irreversible Processes17.5. Entropy Changes in Phase Transitions18. The Third Law of Thermodynamics18.1. The Magnitude of the Entropy at T=018.2. The Unattainability of Absolute Zero18.3. Experimental Verification of the Third Law19. The Nature of the Equilibrium State19.1. Properties of the Equilibrium State of a Pure Substance19.2. Alternative Descriptions of the Equilibrium State for Different External Constraints19.3. The Stability of the Equilibrium State of a One-Component System19.4. The Equilibrium State in a Multicomponent System19.5. Chemical Equilibrium19.6. Thermodynamic Weight: Further Connections between Thermodynamics and Microscopic Structure19.7. An Application of the Canonical Ensemble: The Distribution of Molecular Speeds in a Perfect Gas20. An Extension of Thermodynamics to the Description of Nonequilibrium Processes20.1. General Form of the Equation of Continuity20.2. Conservation of Mass and the Diffusion Equation20.3. Conservation of Momentum and the Navier-Stokes Equation20.4. Conservation of Energy and the Second Law of Thermodynamics20.5. Linear Transport Processes20.6. Negative Temperature20.7. Thermodynamics of Systems at Negative Absolute TemperatureAppendix 20A: Symmetry of the Momentum Flux Tensor: 21. The Properties of Pure Gases and Gas Mixtures21.1. Thermodynamic Description of a Pure Gas21.2. Thermodynamic Description of a Gas Mixture21.3. Thermodynamic Description of Gaseous Reactions21.4. An Example: The Haber Synthesis of NH321.5. Statistical Molecular Theory of Gases and Gas Reactions21.6. The Statistical Molecular Theory of the Equilibrium Constant21.7. The Statistical Molecular Theory of the Real GasAppendix 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 Solids22.1. Differences between Gases and Condensed Phases22.2. The Influence of Crystal Symmetry on Macroscopic Properties22.3. Microscopic Theory of the Thermal Properties of Crystalline Solids22.4. The Contribution of Anharmonicity to the Properties of a Crystal22.5. Some Properties of Complex Solids and of Imperfect Solids22.6. Electronic Heat Capacity of MetalsAppendix 22A: Evaluation of Fermi-Dirac Integrals: 23. Thermodynamic Properties of Liquids23.1. Bulk Properties of Liquids23.2. The Structure of Liquids23.3. Relationships between the Structure and the Thermodynamic Properties of a Simple Liquid23.4. The Molecular Theory of Monoatomic Liquids: General Remarks23.5. The Molecular Theory of Monoatomic Liquids: Approximate Analyses23.6. The Molecular Theory of Polyatomic LiquidsAppendix 23A: X-ray Scattering from Liquids: Determination of the Structure of a Liquid: Appendix 23B: Functional Differentiation: 24. Phase Equilibria in One-Component Systems24.1. General Survey of Phase Equilibria24.2. Thermodynamics of Phase Equilibria in One-Component Systems24.3. Phase Transitions Viewed as Responses to Thermodynamic Instabilities24.4. The Statistical Molecular Description of Phase TransitionsAppendix 24A: The Scaling Hypothesis for Thermodynamic Functions: Appendix 24B: Aspects of Density Functional Theory: 25. Solutions of Nonelectrolytes25.1. The Chemical Potential of a Component in an Ideal Solution25.2. The Chemical Potential of a Component in a Real Solution25.3. Partial Molar Quantities25.4. Liquid-Vapor Equilibrium25.5. Liquid-Solid Equilibrium25.6. The Colligative Properties of Solutions: Boiling-Point Elevation, Freezing-Point Depression, and Osmotic Pressure25.7. Chemical Reactions in Nonelectrolyte Solutions25.8. More about Phase Equilibrium in Mixtures25.9. Critical Phenomena in Mixtures25.10. The Molecular Theory of Solutions of Nonelectrolytes26. Equilibrium Properties of Solutions of Electrolytes26.1. The Chemical Potential26.2. Cells, Chemical Reactions, and Activity Coefficients26.3. Comments on the Structure of Water26.4. The Influence of Solutes on the Structure of Water26.5. The Statistical Mechanics of Electrolyte Solutions26.6. Molten Salts and Molten Salt Mixtures26.7. The Structure of an Electrolyte Solution Near an ElectrodePART III: PHYSICAL AND CHEMICAL KINETICS27. Molecular Motion and Collisions27.1. Kinematics27.2. Forces and Potentials27.3. Collision Dynamics27.4. Types of Collisions27.5. Scattering Cross Sections27.6. Elastic Scattering of Hard Spheres27.7. Elastic Scattering of Atoms27.8. Quantum Mechanical Scattering28. The Kinetic Theory of Gases28.1. Distribution Functions28.2. Collision Frequency in a Dilute Gas28.3. The Evolution of Velocity Distributions in Time28.4. The Maxwell-Boltzmann Distribution28.5. Collision Frequency for Hard-Sphere Molecules28.6. Molecular Fluxes of Density, Momentum Density, and Energy Density28.7. Effusion28.8. Transport Properties of Gases28.9. Energy Exchange Processes28.10. Sound Propagation and Absorption29. The Kinetic Theory of Dense Phases29.1. Transport Properties in Dense Fluids29.2. Some Basic Aspects of Brownian Motion29.3. Stochastic Approach to Transport29.4. Autocorrelation Functions and Transport Coefficients29.5. Transport in Solids29.6. Electrical Conductivity in Electrolyte Solutions30. Chemical Kinetics30.1. General Concepts of Kinetics30.2. Interactions between Reactive MoleculesVignette: Quantum Mechanical Computations of Potential Energy Hypersurfaces, by H.F. Schaefer: 30.3. Collisions between Reactive MoleculesVignette: Femtochemistry--Reaction Dynamics with Atomic Resolution, by A.H. Zewail: 30.4. Hard-Sphere Collision Theory: Reactive Cross Sections30.5. Hard-Sphere Collision Theory: The Rate Coefficient30.6. Activated-Complex Theory Vignette: Present Day View of Transition State Theory, by D.G. Truhlar: 30.7. Activated-Complex Theory: Thermodynamic Interpretation30.8. Theory of Reaction Kinetics in SolutionVignette: 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 Relationships30.10. Experimental Methods in Kinetics30.11. Analysis of Data for Complex Reactions30.12. Mechanisms of Chemical Reactions30.13. Bimolecular ReactionsVignette: Electron Transfer Reactions, by R.A. Marcus: 30.14. Unimolecular Reactions30.15. Termolecular Reactions31. Some Advanced Topics in Chemical Kinetics31.1. More about Unimolecular Reactions31.2. Kinetics of Photochemically Induced Reactions31.3. Chain Reactions31.4. Non-linear Phenomena31.5. Fluctuations in Chemical Kinetics31.6. Symmetry Rules for Chemical Reactions31.7. Introduction to Catalysis31.8. Enzyme Catalysis31.9. Acid-Base Catalysis31.10. Metal-Ion Complex and Other Types of Homogeneous Catalysis31.11. Heterogeneous Reactions: Adsorption of Gas on a Surface31.12. Heterogeneous Catalysis31.13. Kinetics of Electrode Reactions (a Vignette by C.E.D. Chidsey)Vignette: Applications of Physical Chemistry: A Biological Example, by B. Eisenberg: AppendicesII. Partial DerivativesIII. Glossary of SymbolsIV. Searching the Scientific LiteratureIndexSupporting Web Links

Editorial Reviews

"This is a well-written, logically-developed presentation of physical chemistry. It presents quantum chemistry first, as I believe should be done. It continues to be (in its new edition) the most demanding book in the field. Most of our undergraduates would find it too difficult, but itmight be appropriate for our graduate students."--Hal Harris, University of Missouri, St. Louis