Physical Chemistry
Second Edition
R. Stephen Berry, Stuart A. Rice, and John R. Ross
Table of Contents
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 Poincareé 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