Preface
Preface to the First Edition
1 Ideal and Nonideal Gases
1-1 Introduction
1-2 Equations of State
1-3 Development of the Concept of an Ideal Gas; The Absolute Temperature Scale
1-4 The Ideal Gas Law and Related Equations
1-5 Mixtures of Ideal Gases; Partial Pressures
1-6 Partial Volumes; Amagat's Law
1-7 The Barometric Equation
1-8 Deviations from Ideality—Critical Behavior
1-9 Semiempirical Equations of State. The van der Waals Equation
1-10 The van der Waals Equation, Critical Phenomena, and the Principle of Corresponding States
Commentary and Notes
Special Topics
General References
Cited References
Exercises and Problems
Exercises
Problems
Special Topics Problems
2 Kinetic Molecular Theory of Gases
2-1 Introduction
2-2 The Boltzmann Distribution Law
2-3 The Distribution of Molecular Velocities
2-4 Average Quantities from the Distribution Laws
2-5 Some Applications of Simple Kinetic Molecular Theory. Collision Frequency on a Plane Surface and Graham's Law
2-6 A Rederivation of the Ideal Gas Law
2-7 Bimolecular Collision Frequency and Mean Free Path
2-8 Transport Phenomena; Viscosity, Diffusion, and Thermal Conductivity
2-9 Summary of Kinetic Molecular Theory Quantities
Commentary and Notes
2-CN-1 Some Further Comments on the Various Distribution Laws
2-CN-2 Verification of the Distribution Laws
2-CN-3 Molecular Diameters; Avogadro's Number
2-CN-4 Transport Phenomena; Phenomenological Equations
2-CN-5 Verification of the Kinetic Molecular Theory
Special Topics
2-ST-1 Use of a Lennard-Jones Potential Function
2-ST-2 Collision Frequencies and Mean Free Paths for Mixtures
General References
Cited References
Exercises
Problems
Special Topics Problems
3 Some Additive Physical Properties of Matter
3-1 Introduction
3-2 Absorption of Light
3-3 Molar Refraction
3-4 Molar Polarization; Dipole Moments
3-5 Dipole Moments and Molecular Properties
Commentary and Notes
3-CN-1 Systems of Units
Special Topics
3-ST-1 The Charge Distribution of a Molecule
3-ST-2 Magnetic Properties of Matter
General References
Cited References
Exercises
Problems
Special Topics Problems
4 Chemical Thermodynamics. The First Law of Thermodynamics
4-1 Introduction
4-2 The Story of a Man
4-3 Energy and the First Law of Thermodynamics
4-4 Mathematical Properties of State Functions. Exact and Path-Dependent Differentials
4-5 Heat and Work for Various Processes
4-6 Enthalpy. An Alternative Form of the First Law
4-7 Applications of the First Law to Ideal Gases
4-8 Molecular Basis for Heat Capacities. The Equipartition Principle
4-9 Statistical Mechanical Treatment of First Law Quantities
4-10 Translational Partition Function for an Ideal Gas
4-11 The Rotational Partition Function
4-12 The Vibrational Partition Function
Commentary and Notes
4-CN-1 Internal Pressure
4-CN-2 Additional Aspects of Statistical Mechanical Treatments
Special Topics
4-ST-1 The Joule-Thomson Effect
4-ST-2 The Heat Capacity of a Solid
General References
Exercises
Problems
Special Topics Problems
5 Thermochemistry
5-1 Introduction
5-2 Measurement of Heats of Reaction: Relationship between ΔE and ΔH
5-3 Some Enthalpies of Combustion, Hydrogenation, and Solution
5-4 Combining ΔH or ΔΕ Quantities
5-5 Enthalpies of Formation
5-6 Dependence of ΔH and ΔE on Temperature
Commentary and Notes
5-CN-1 Explosions, Flames, and Rockets
5-CN-2 The Thermochemistry of Nutrition
Special Topics
5-ST-1 Chemical Bond Strengths
5-ST-2 Internal Energy and Enthalpy Functions
General References
Cited References
Exercises
Problems
Special Topics Problems
6 The Second and Third Laws of Thermodynamics
6-1 Introduction
6-2 The Carnot Cycle—Heat Machines
6-3 Generalization of the Carnot Cycle—The Entropy Function
6-4 Calculations of ΔS for Various Reversible Processes
6-5 Calculation of ΔS for Various Irreversible Processes
6-6 Free Energy. Criteria for Equilibrium
6-7 Second Law Relationships
6-8 The Third Law of Thermodynamics
6-9 Statistical Mechanical Treatment of Second Law Quantities
Commentary and Notes
6-CN-1 Summary of the Statements of the Laws of Thermodynamics
6-CN-2 Statistical Thermodynamics—Ensembles—and J. Willard Gibbs
6-CN-3 Additional Comments on the Third Law of Thermodynamics and on the Attainment of 0 Κ
Special Topics
6-ST-1 Thermodynamic Relationships
6-ST-2 Thermodynamic Treatment of a Nonideal Gas—Fugacity
6-ST-3 The Free Energy Function
General References
Cited References
Exercises
Problems
Special Topics Problems
7 Chemical Equilibrium
7-1 Introduction
7-2 The Thermodynamic Equilibrium Constant
7-3 The Determination of Experimental Equilibrium Constants
7-4 The Variation of KP with Temperature
7-5 Gas-Solid Equilibria
7-6 Le Châtelier's Principle
7-7 Free Energy and Entropy of Formation
Commentary and Notes
7-CN-1 Chemical Equilibrium and the Second Law of Thermodynamics
Special Topics
7-ST-1 Effect of Pressure on Chemical Equilibria Involving Gases
7-ST-2 Application of Statistical Thermodynamics to Chemical Equilibrium
General References
Cited References
Exercises
Problems
Special Topics Problems
8 Liquids and Their Simple Phase Equilibria
8-1 Introduction
8-2 The Vapor Pressure of Liquids (and Solids)
8-3 Enthalpy and Entropy of Vaporization; Trouton's Rule
8-4 Liquid-Solid and Solid-Solid Equilibria. Phase Maps
8-5 The Free Energy of a Liquid and Its Vapor
8-6 The Surface Tension of Liquids. Surface Tension as a Thermodynamic Quantity
8-7 Measurement of Surface Tension
8-8 Results of Surface Tension Measurements
8-9 The Kelvin Equation. Nucleation
8-10 Viscosity of Liquids
Commentary and Notes
8-CN-1 Additional Thermodynamic Properties of Liquids
8-CN-2 The Structure of Water
8-CN-3 Anomalous Water
Special Topics
8-ST-1 Intermodular Forces
8-ST-2 The Viscosity of Liquids
General References
Cited References
Exercises
Problems
Special Topics Problems
9 Solutions of Nonelectrolytes
9-1 Introduction
9-2 The Vapor Pressure of Solutions. Raoult's and Henry's Laws
9-3 The Thermodynamics of Multicomponent Systems
9-4 Ideal Gas Mixtures
9-5 Ideal and Nonideal Solutions. Activities and Activity Coefficients
9-6 The Temperature Dependence of Vapor Pressures
9-7 Boiling Point Diagrams
9-8 Partial Miscibility
Commentary and Notes
9-CN-1 Other Properties of Solutions
9-CN-2 Ideal, Regular, and Athermal Solutions
9-CN-3 Statistical Thermodynamics of Solutions
Special Topics
9-ST-1 Partial Molal Quantities
9-ST-2 The Surface Tension of Solutions. The Gibbs Equation
General References
Cited References
Exercises
Problems
Special Topics Problems
10 Dilute Solutions of Nonelectrolytes. Colligative Properties
10-1 Vapor Pressure Lowering
10-2 Boiling Point Elevation
10-3 Freezing Point Depression
10-4 Summary of the First Three Colligative Properties
10-5 Osmotic Equilibrium
10-6 Activities and Activity Coefficients for Dilute Solutions
10-7 Other Methods of Molecular Weight Determination
Commentary and Notes
10-CN-1 Colligative Properties and Deviations from Ideality
10-CN-2 Relationship between Freezing Point Depression and Solubility
10-CN-3 Osmotic Pressure
10-CN-4 Water Desalination
Special Topics
10-ST-1 Dilute Solution Conventions for Activities and Activity Coefficients
10-ST-2 Theoretical Treatment of Diffusion
General References
Cited References
Exercises
Problems
Special Topics Problems
11 Heterogeneous Equilibrium
11-1 The Gibbs Phase Rule
11-2 One-Component Systems
11-3 Two-Component Systems
11-4 Sodium Sulfate-Water and Other Systems
11-5 Three-Component Systems
11-6 Three-Component Solubility Diagrams
Commentary and Notes
11-CN-1 Definitions of the Terms Component and Phase
Special Topics
11-ST-1 Two-Component Freezing Point Diagrams. Partial Miscibility
11-ST-2 Partial Miscibility in Three-Component Systems
General References
Cited References
Exercises
Problems
Special Topics Problems
12 Solutions of Electrolytes
12-1 Introduction
12-2 Conductivity—Experimental Definitions and Procedures
12-3 Results of Conductance Measurements
12-4 Some Sample Calculations
12-5 Ionic Mobilities
12-6 Transference Numbers—Ionic Equivalent Conductivities
12-7 Activities and Activity Coefficients of Electrolytes
12-8 The Debye-Hückel Theory
12-9 Ionic Equilibria
Commentary and Notes
12-CN-1 Electrolytic Dissociation
12-CN-2 Activity Coefficients for Other than Dilute Aqueous Solutions
12-CN-3 Acids and Bases
Special Topics
12-ST-1 Ionic Diffusion Coefficients
12-ST-2 The Hittorf Method
12-ST-3 Treatment of Complex Ionic Equilibria
General References
Cited References
Exercises
Problems
Special Topics Problems
13 Electrochemical Cells
13-1 Definitions and Fundamental Relationships
13-2 Experimental Procedures
13-3 Determination of E0 Values and Activity Coefficients
13-4 Additivity Rules for Emf's. Standard Oxidation Potentials
13-5 Emf and Chemical Equilibria
13-6 Concentration Cells
13-7 Oxidation-Reduction Reactions
13-8 Determination of pH
13-9 Irreversible Electrode Processes
Commentary and Notes
13-CN-1 Standard Oxidation Potential E0 and Standard Electrode Potential V0
13-CN-2 Storage Batteries
13-CN-3 Thermodynamic Quantities for Aqueous Ions
13-CN-4 Electrocapillarity. Absolute Electrode Potentials
Special Topics
13-ST-1 Liquid Junctions
13-ST-2 Polarization at Electrodes. Polarography
General References
Cited References
Exercises
Problems
Special Topics Problems
14 Kinetics of Gas-Phase Reactions
14-1 Introduction
14-2 Rate Laws and Simple Mechanisms
14-3 Experimental Methods and Rate Law Calculations
14-4 Rate Laws and Reaction Mechanisms
14-5 Temperature Dependence of Rate Constants
14-6 Collision Theory of Gas Reactions
14-7 Unimolecular Reactions
14-8 Absolute Rate Theory. The Activated Complex
Commentary and Notes
14-CN-1 Termolecular Reactions
14-CN-2 Collision versus Transition-State Theory
14-CN-3 Radicals, Molecular Beams, and Reaction Trajectories
14-CN-4 Explosions
Special Topics
14-ST-1 Heterogeneous Catalysis. Chemisorption of Gases
14-ST-2 Statistical Thermodynamic Treatment of Transition-State Theory
General References
Cited References
Exercises
Problems
Special Topics Problems
15 Kinetics of Reactions in Solution
15-1 Additional Comments on Rate Laws. Reversible Reactions
15-2 Experimental Methods
15-3 Kinetic-Molecular Picture of Reactions in Solution
15-4 Diffusion-Controlled Reactions
15-5 Transition-State Theory
15-6 Linear Free Energy Relationships. Reactions Involving an Acid or a Base
15-7 Ionic Reactions. Role of Activity Coefficients
Commentary and Notes
15-CN-1 Comparison of Collision-Encounter and Transition-State Theories
15-CN-2 Relationship between the Equilibrium Constant for a Reaction and Its Rate Constants
15-CN-3 Entropy Production during a Chemical Reaction
Special Topics
15-ST-1 Enzyme Catalysis
15-ST-2 Integrated Forms for Some Additional Rate Laws
15-ST-3 Effect of Mechanical Pressure on Reaction Rates
General References
Cited References
Exercises
Problems
Special Topics Problems
16 Wave Mechanics
16-1 Introduction
16-2 Energy Units
16-3 Hydrogen and Hydrogen-Like Atoms
16-4 The Schrödinger Wave Equation
16-5 Some Simple Choices for the Potential Function V
16-6 The Harmonic Oscillator
16-7 Solutions of the Wave Equation for the Hydrogen Atom
16-8 The Graphical Appearance of Hydrogen-Like Orbitals
16-9 Graphical Appearance of the Electron Density around a Hydrogen-Like Atom
16-10 Hybrid Orbitals
16-11 The Variation Method. Polarizability of the Hydrogen Atom
Commentary and Notes
16-CN-1 Albert Einstein
16-CN-2 An Alternative Interpretation of the Uncertainty Principle
16-CN-3 Steps beyond Hydrogen-Like Wave Functions
Special Topics
16-ST-1 Atomic Energy States
16-ST-2 The Rigid Rotator
16-ST-3 First-Order Perturbation Theory
16-ST-4 Quantum Theory of Blackbody Radiation
General References
Cited References
Exercises
Problems
Special Topics Problems
17 Molecular Symmetry and Bonding
17-1 Introduction
17-2 Symmetry and Symmetry Operations
17-3 A Set of Symmetry Operations as Constituting a Group
17-4 Representations of Groups
17-5 Atomic Orbitals as Bases for Representations
17-6 Character Tables
17-7 Bonds as Bases for Reducible Representations
Commentary and Notes
17-CN-1 Crystal Field Theory
Special Topics
17-ST-1 The Direct Product
General References
Cited References
Exercises
Problems
Special Topics Problems
18 Wave Mechanics and Bonding
18-1 Introduction
18-2 The Valence Bond Method for the Hydrogen Molecule
18-3 Molecular Orbitals. The Hydrogen Molecule Ion, H2+
18-4 Variation Method for Obtaining Molecular Orbitals
18-5 Molecular Orbital Energy Levels for Diatomic Molecules
18-6 Triatomic Molecules. Walsh Diagrams
18-7 Polyatomic Molecules. The Hückel Method
Commentary and Notes
18-CN-1 Comparison of the Valence Bond and Molecular Orbital Methods
Special Topics
18-ST-1 Ligand Field Molecular Orbital Diagrams
General References
Cited References
Exercises
Problems
Special Topics Problems
19 Molecular Spectroscopy and Photochemistry
19-1 Introduction
19-2 Excited States of Diatomic Molecules
19-3 Electronic, Vibrational, and Rotational Transitions
19-4 Electronic Excited States of Polyatomic Molecules
19-5 Vibrational Spectra
Commentary and Notes
19-CN-1 Geometric and Electronic Nature of Ground-State Molecules
19-CN-2 Structure and Chemistry of Excited States
19-CN-3 Conversion of Light to Chemical Energy
Special Topics
19-ST-1 Emission and Absorption of Radiation. Transition Probability
19-ST-2 Optical Activity
19-ST-3 Vibrational-Rotational Spectra
19-ST-4 Glossary of Abbreviations
General References
Cited References
Exercises
Problems
Special Topics Problems
20 The Solid State
20-1 Space-Filling Lattices
20-2 Crystal Planes; Miller Indices
20-3 Some Simple Crystal Structures
20-4 Some Geometric Calculations
20-5 Diffraction by Crystals
Commentary and Notes
20-CN-1 Modern Crystal Structure Determination
20-CN-2 Some Structures of Biological Importance
20-CN-3 The Band Model for Solids. Semiconductors
20-CN-4 Crystal Defects
Special Topics
20-ST-1 Symmetry Notation for Crystals
20-ST-2 X-Ray Diffraction Intensities
20-ST-3 Lattice Energies
20-ST-4 Ionic Radii
General References
Cited References
Exercises
Problems
Special Topics Problems
21 Colloids and Macromolecules
21-1 Lyophobic Colloids
21-2 Association Colloids. Colloidal Electrolytes
21-3 Gels
21-4 Rheology
21-5 Liquid Crystals. Mesophases of Matter
21-6 Polymers
Special Topics
21-ST-1 Electrokinetic Effects
General References
Cited References
Exercises
Problems
Special Topics Problems
22 Nuclear Chemistry and Radiochemistry
22-1 Introduction
22-2 Nuclear Energetics and Existence Rules
22-3 Nuclear Reactions
22-4 Absorption of Radiation
22-5 Kinetics of Radioactive Decay
Commentary and Notes
22-CN-1 Theories of Radioactive Decay
22-CN-2 Nuclear Reactors and "Atomic" Bombs
22-CN-3 Nuclear Chemistry
22-CN-4 Quantum Statistics
22-CN-5 Experimental Detection Methods
22-CN-6 The Mossbauer Effect
Special Topics
22-ST-1 The Natural Decay Series. Age Dating
22-ST-2 Statistical Fluctuations in Radioactive Decay
General References
Cited References
Exercises
Problems
Special Topics Problems
Subject Index