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Preface and Acknowledgments | |
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Structure in Solids | |
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Limits on Homogeneity | |
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States of Matter | |
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Diffraction | |
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Producing Short Wavelength Radiation | |
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The Action of Crystals on the Radiation | |
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Bragg Reflection | |
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Standard Crystal Lattices | |
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Miller Indices | |
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Cubic Point Lattices | |
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Some Simple Crystal Types | |
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Stability Conditions | |
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Avogadro's Number | |
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Surface Structure | |
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The Quasicrystalline State | |
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Questions | |
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Problems | |
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References | |
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Structure in Molecules and Atoms | |
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Introduction | |
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Symmetric Coordination Structures | |
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Momentum and Energy Relationships | |
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Diffraction by Randomly Oriented Molecules | |
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Electron Diffraction Molecular Parameters | |
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Intensity in a Beam | |
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The Cross Section Concept | |
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The Nuclear Atom | |
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Composition of Atoms and Nuclei | |
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Questions | |
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Problems | |
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References | |
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Gases and Collective Properties | |
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Macroscopic Properties | |
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Elements of Ideal-Gas Theory | |
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Temperature | |
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Constants R and T[subscript 0] | |
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Gaseous Solutions | |
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Translational, Rotational, Vibrational Energies | |
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Quantum Restrictions | |
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Allowing for Molecular Interactions | |
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Gas-Liquid Isotherms | |
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Corresponding States | |
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Compressibility Factor for a Gas | |
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Virial Equation of State | |
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Distribution of Equivalent Particles in a Potential Field | |
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The Maxwell Distribution Law | |
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The Collision Rate Density | |
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Questions | |
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Problems | |
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References | |
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The First Law for Energy | |
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Independent Thermodynamic Variables | |
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Work | |
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Heat | |
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The First Law | |
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Compression (P-V) Work | |
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Isochoric and Isobaric Heats | |
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Energy Capacities | |
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Reversible Adiabatic Change in an Ideal Gas | |
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Conditions in a Planar Pressure Pulse | |
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Contributions to Energy Capacity C[subscript v] | |
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Relating Differentials and Partial Derivatives | |
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The Difference C[subscript p]-C[subscript v] | |
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Coefficients of Thermal Expansion and Isothermal Compressibility | |
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Exact Differentials | |
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Partial Molar Properties | |
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Questions | |
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Problems | |
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References | |
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Entropy and the Second Law | |
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Accessibility of States | |
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Integrability of the Reversible Heat | |
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Form for the Integrating Factor | |
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Entropy Changes of Systems | |
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The Second Law | |
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Entropy of Mixing | |
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Probability Change on Mixing | |
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Effectively Contributing Microstates | |
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Helmholtz Free Energy | |
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Gibbs Free Energy | |
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Key Thermodynamic Relations | |
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The Chemical Potential | |
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Concentration Gradients | |
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General Direction for a Process | |
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A Fourth Law | |
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Questions | |
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Problems | |
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References | |
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Relationships between Phases | |
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Intensive Variables | |
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The Gibbs Phase Rule | |
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Equilibrium States for Water | |
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Solutions | |
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Aspects of Multicomponent Phase Diagrams | |
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Singularities Separating Phases | |
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The Clapeyron and Ehrenfest Equations | |
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Variation of Vapor Pressure with Temperature | |
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Variation of Vapor Pressure with Total Pressure | |
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Variation of Vapor Pressure with Concentration | |
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The Mole-Fraction Activity | |
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Concentration Units | |
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Elevation of the Boiling Point | |
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Depression of the Freezing Point | |
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Permeability of Membranes | |
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Osmotic Pressure | |
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Equilibria among Phases | |
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Questions | |
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Problems | |
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References | |
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Relationships among Reactants | |
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Introduction | |
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Conventions | |
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Measuring Reaction Heats | |
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Relating the Isobaric and Isochoric Reaction Heats | |
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Variation in Heat of Reaction with Temperature | |
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Calorimetric Entropy | |
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Correcting the Calorimetric Entropy to the Ideal Gas State | |
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Correcting the Calorimetric Entropy for Frozen-in Disorder | |
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Key Thermodynamic Properties | |
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Partial Molar Gibbs Energy | |
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Gibbs Energy of Reaction | |
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Energetic Conditions on Equilibria | |
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Equilibria in Ideal Gaseous Phases | |
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Heterogeneous Gas Equilibria | |
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Variation of Equilibrium Constants with Temperature | |
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Variation of Equilibrium Constants with Pressure | |
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The Activity Coefficient Concept | |
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Helmholtz Energy of Reaction | |
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Questions | |
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Problems | |
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References | |
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Equilibria in Condensed Phases | |
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The Chemical Potential Revisited | |
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Useful Equilibrium Expressions | |
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Conditions Determining Equilibria | |
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Key Thermodynamic Considerations | |
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Average Electric Atmosphere about an Ion | |
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An Integral Form of Coulomb's Law | |
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Application of Gauss's Theorem to the Ionic Atmosphere | |
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Variation of Electric Potential in an Ionic Atmosphere | |
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Free Energy of the Ionic Atmosphere | |
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Debye-Huckel Equations | |
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Equilibria among Phases Revisited | |
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Determining Ionic Activities | |
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Limitations of the Debye-Huckel Treatment | |
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Questions | |
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Problems | |
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References | |
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Electrochemistry | |
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Definitions and Units | |
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Electrode Reactions | |
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Electrolyte Transference | |
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Moving Ion Clouds and Boundaries | |
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Ohm's Law | |
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Equivalent Conductance | |
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Determining Solubilities and Degrees of Ionization | |
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Variation of Ion Conductance with Viscosity | |
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Cell Conventions | |
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Measuring and Allocating Voltages | |
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Cell Energetics | |
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Cell with Transference | |
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Reference Cells and Electrodes | |
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Measuring the pH of Solutions | |
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Overpotential | |
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Electrode Potentials for Other Solvents | |
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Further Cell Thermodynamics | |
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Questions | |
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Problems | |
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References | |
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Basic Quantum Mechanics | |
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The Statistical Nature of the Path of a Mass Element or Particle | |
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Representing a Constituent State | |
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Introducing the Translational Symmetries | |
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Translational Motion in a General Direction | |
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Diffraction Experiments Revisited | |
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Rectangularly Symmetric Free Motion | |
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Translational Energy of the Molecules in an Ideal Gas | |
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Enumerating and Filling Translational States | |
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Normalization and Orthogonality Conditions | |
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Standing-Wave Translational Functions | |
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Confined Rectangularly Symmetric Motion | |
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Attenuated Motion | |
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Joining Different Constant-Potential Regions | |
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A Differential Equation for Multidirectional Propagation | |
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The Schrodinger Equations | |
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Suitable Solutions | |
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Expressing [down triangle, open superscript 2] in Orthogonal Generalized Coordinates | |
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Questions | |
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Problems | |
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References | |
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Free Rotational and Angular Motion | |
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Introduction | |
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Classical Rotational Kinetic Energy | |
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Quantized Angular Momentum States of a Linear Rotator | |
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Energy Levels for the Linear Rotator | |
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Rotational Spectrum of a Linear Molecule | |
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Broadening of Spectral Lines | |
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Quantization of Cylindrically Symmetric Rotators | |
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The Asymmetric Rotator | |
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Rotational Partition Functions and the Resulting Energies | |
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Independence of the Angular Factor Y([theta], [phi]) | |
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A Multiaxial Formula for Y([theta], [phi]) | |
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Directional Behavior of the Standard Rotational State Functions | |
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Normalization and Orthogonality Conditions Revisited | |
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Magnetic Energy Associated with Angular Momentum | |
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Observing Spatial Quantization in a Beam | |
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Spin States | |
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Questions | |
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Problems | |
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References | |
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Vibrational and Radial Motion | |
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Pertinent Potentials | |
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Schrodinger Equation for the Harmonic Oscillator | |
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Quantization of the Harmonic Oscillator | |
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Nodeless Solutions | |
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Acceptable Wavy Solutions | |
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Partition Function for a Vibrational Mode | |
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Selection Rules | |
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Vibration-Rotation Spectra | |
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Raman Spectra | |
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Bond Anharmonicity and its Effect | |
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Asymptotic Solutions for the Central Field | |
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Radial State Functions for a Hydrogenlike Atom | |
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Electronic Spectrum of a Hydrogenlike Atom | |
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Multiparticle Systems | |
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Multielectron Uninuclear Structures | |
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Combining Angular Momenta | |
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Questions | |
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Problems | |
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References | |
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Analyzing Organized Structures | |
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The General Behavior of Bases | |
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Representing Nondistortive Operations | |
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Symmetry Operations | |
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Pertinent Permutation Matrices | |
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Other Transformation Matrices | |
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Classifying Operations | |
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Character Vectors | |
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Symmetry Species | |
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Selection Rules | |
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The Orthogonality Condition | |
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Generating Primitive Symmetry Species | |
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Questions | |
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Problems | |
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References | |
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States of Molecular Electrons | |
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Introduction | |
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The Hydrogen Molecule Ion Model | |
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Correlations with Atomic Structures | |
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Bonding between Two Equivalent Atoms | |
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Symmetric Three-Center Bonds | |
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Symmetric Six-Center Bonds | |
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Conventional Resonance Energy and the True Delocalization Energy | |
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The Variation Theorem | |
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Linear Variation Functions | |
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Bonding between Two Nonequivalent Atoms | |
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Pi Bonding in Fulvene | |
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Questions | |
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Problems | |
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References | |
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Phenomenonological Chemical Kinetics | |
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The Rate of a Reaction | |
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Reaction Order and Molecularity | |
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Zero-Order Reactions | |
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First-Order Reactions | |
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Second-Order Reactions | |
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Third-Order Reactions | |
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Determining the Differential Rate Law | |
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Determining Order from an Integrated Form | |
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The Arrhenius Equation | |
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Reversible First-Order Reactions | |
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First-Order Reaction Opposed by a Second-Order Reaction | |
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Perturbation Experiments | |
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Reactions in High Pressure Gaseous and in Condensed Phases | |
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The Encounter Rate Constants | |
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Solution Reaction Rates | |
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Dependence of the Specific Reaction Rate on Activity Coefficients | |
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Questions | |
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Problems | |
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References | |
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Explanatory Mechanisms | |
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Types of Elementary Reactions | |
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Activation in Simple First-Order Reactions | |
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Decomposition of Nitrogen Pentoxide | |
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Hydrogen-Iodine Reactions | |
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Hydrogen-Bromine Reactions | |
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Hydrogen-Chlorine Reactions | |
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Thermal Explosions | |
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Hydrogen-Oxygen Reactions | |
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Decomposition of Ethane | |
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The Activity Coefficient Effect | |
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Conversion of Ammonium Cyanate to Urea | |
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Nitration of Aromatic Compounds | |
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Questions | |
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Problems | |
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References | |
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Statistical Thermodynamics | |
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Earlier Discussions | |
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Relating Thermodynamic Properties to the Partition Function | |
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Relating System Partition Functions to Molecular Ones | |
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Ideal Translational Entropy | |
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Energy and Entropy of a Vibrational Mode | |
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The Ideal Concentration Equilibrium Constant | |
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Basis for the Distribution Law | |
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Black-Body Radiation | |
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Allowance for Particle Transfer | |
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Fermi-Dirac Statistics | |
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Bose-Einstein Statistics | |
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Questions | |
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Problems | |
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References | |
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Reaction Rate Theory | |
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The Transition State | |
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The Eyring Equation | |
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The Kinetic Isotope Effect | |
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Static Nonideality | |
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Transition State Recrossings | |
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Thermodynamic Considerations | |
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Transition State Location | |
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Viscous Nonideality | |
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Variation of the Rate Coefficients with Temperature | |
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Further Relationships | |
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Questions | |
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Problems | |
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References | |
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Photochemistry | |
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Pertinent Wave Properties | |
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Pertinent Particle Properties | |
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Phenomenology of Absorption | |
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Absorption Intensities | |
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Electronic Transitions | |
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Reaction Possibilities | |
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The Hydrogen-Iodine Reaction | |
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The Hydrogen-Bromine Reaction | |
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The Hydrogen-Chlorine Reaction | |
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Photosensitization | |
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Chemiluminescence | |
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The Carbon Monoxide-Oxygen Reaction | |
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Questions | |
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Problems | |
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References | |
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Glossary | |
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Fundamental Units | |
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Derived Units | |
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Physical Constants | |
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Primitive Character Vectors and Basis Functions for Important Symmetry Groups | |
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Index | |