Physical Chemistry

Preface
Contents
1 Physicochemical Systems
1. What Is Science?
2. Physical Chemistry
3. Mechanics: Force
4. Mechanical Work
5. Mechanical Energy
6. Equilibrium
7. The Thermal Properties of Matter
8. Temperature as a Mechanical Property
9. The Spring of the Air and Boyle’s Law
10. The Law of Gay-Lussac
11. Definition of the Mole
12. Equation of State of an Ideal Gas
13. The Equation of State and PVT Relationships
14. PVT Behavior of Real Gases
15. Law of Corresponding States
16. Equations of State for Gases
17. The Critical Region
18. The van der Waals Equation and Liquefaction of Gases
19. Other Equations of State
20. Mixtures of Ideal Gases
21. Mixtures of Nonideal Gases
22. The Concepts of Heat and Heat Capacity
23. Work in Changes of Volume
24. General Concept of Work
25. Reversible Processes
Problems
2 Energetics
1. History of the First Law of Thermodynamics
2. The Work of Joule
3. Formulation of the First Law
4. The Nature of Internal Energy
5. A Mechanical Definition of Heat
6. Properties of Exact Differentials
7. Adiabatic and Isothermal Processes
8. Enthalpy
9. Heat Capacities
10. The Joule Experiment
11. The Joule-Thomson Experiment
12. Application of the First Law to Ideal Gases
13. Examples of Ideal-Gas Calculations
14. ThermoÂ
15. Enthalpies of Formation
16. Experimental Thermochemistry
17. Heat Conduction Calorimeters
18. Heats of Solution
19. Temperature Dependence of Enthalpy of Reaction
20. Bond Enthalpies
21. Chemical Affinity
Problems
3 Entropy and Free Energy
1. The Carnot Cycle
2. The Second Law of Thermodynamics
3. The Thermodynamic Temperature Scale
4. Relation of Thermodynamic and Ideal-Gas Temperature Scales
5. Entropy
6. First and Second Laws Combined
7. The Inequality of Clausius
8. Entropy Changes in an Ideal Gas
9. Change of Entropy in Changes of State of Aggregation
10. Entropy Changes in Isolated Systems
11. Entropy and Equilibrium
12. Thermodynamics and Life
13. Equilibrium Conditions for Closed Systems
14. The Gibbs Function—Equilibrium at Constant T and P
15. Isothermal Changes in A and G
16. Thermodynamic Potentials
17. Legendre Transformations
18. Maxwell’s Relations
19. Pressure and Temperature Dependence of Gibbs Function
20. Pressure and Temperature Variation of Entropy
21. Applications of Thermodynamic Equations of State
22. The Approach to Absolute Zero
23. The Third Law of Thermodynamics
24. An Illustration of the Third Law
25. Third-Law Entropies
Problems
4 Kinetic Theory
1. Atomic Theory
2. Molecules
3. The Kinetic Theory of Heat
4. The Pressure of Gas
5. Gas Mixtures and Partial Pressures
6. Kinetic Energy and Temperature
7. Molecular Speeds
8. Molecular Effusion
9. Imperfect Gases—The van der Waals Equation
10. Intermolecular Forces and the Equation of State
11. Molecular Velocities—Directions
12. Collisions of Molecules with a Wall
13. Distribution of Molecular Velocities
14. Velocity in One Dimension
15. Velocity in Two Dimensions
16. Velocity in Three Dimensions
17. Experimental Velocity Analysis
18. The Equipartition of Energy
19. Rotation and Vibration of Diatomic Molecules
20. Motions of Polyatomic Molecules
21. The Equipartition Principle and Heat Capacities
22. Collisions Between Molecules
23. Derivation of Collision Frequency
24. The Viscosity of a Gas
25. Kinetic Theory of Gas Viscosity
26. Molecular Diameters and Intermolecular Force Constants
27. Thermal Conductivity
28. Diffusion
29. Solutions of Diffusion Equation
Problems
5 Statistical Mechanics
1. The Statistical Method
2. Entropy and Disorder
3. Entropy and Information
4. Stirling Formula for Nl
5. Boltzmann
6. How the State of a System Is Defined
7. Ensembles
8. Lagrange Method for Constrained Maximum
9. Boltzmann Distribution Law
10. Statistical Thermodynamics
11. Entropy in Statistical Mechanics
12. The Third Law in Statistical Thermodynamics
13. Evaluation of Z for Noninteracting Particles
14. Translational Partition Function
15. Partition Functions for Internal Molecular Motions
16. Classical Partition Function
Problems
6 Changes of State
1. Phases
2. Components
3. Degrees of Freedom
4. General Equilibrium Theory: The Chemical Potential
5. Conditions for Equilibrium Between Phases
6. The Phase Rule
7. Phase Diagram for One Component
8. Thermodynamic Analysis of PT Diagram
9. The Helium System
10. Vapor Pressure and External Pressure
11. Statistical Theory of Phase Changes
12. Solid-Solid Transformations—The Sulfur System
13. Measurements at High Pressures
Problems
7 Solutions
1. Measures of Composition
2. Partial Molar Quantities: Partial Molar Volume
3. Activities and Activity Coefficients
4. Determination of Partial Molar Quantities
5. The Ideal Solution—Raoult’s Law
6.Thermodynamics of Ideal Solutions
7. Solubility of Gases in Liquids—Henry’s Law
8. Mechanism of Anesthesia
9. Two-Component Systems
10. Pressure-Composition Diagrams
11. Temperature-Composition Diagrams
12. Fractional Distillation
13. Solutions of Solids in Liquids
14. Osmotic Pressure
15. Osmotic Pressure and Vapor Pressure
16. Deviations from Ideality
17. Boiling Point Diagrams
18. Solubility of Liquids in Liquids
19. Thermodynamic Condition for Phase Separation
20. Thermodynamics of Nonideal Solutions
21. Solid-Liquid Equilibria: Simple Eutectic Diagrams
22. Formation of Compounds
23. Solid Solutions
24. The Iron-Carbon Diagram
25. Statistical Mechanics of Solutions
26. The Bragg-Williams Model
Problems
8 Chemical Affinity
1. Dynamic Equilibrium
2. Free Enthalpy and Chemical Affinity
3. Condition for Chemical Equilibrium
4. Standard Free Enthalpies
5. Free Enthalpy and Equilibrium in Reactions of Ideal Gases
6. Equilibrium Constant in Concentrations
7. Measurement of Homogeneous Gas Equilibria
8. Principle of Le Chatelier and Braun
9. Pressure Dependence of Equilibrium Constant
10. Temperature Dependence of Equilibrium Constant
11. Equilibrium Constants from Heat Capacities and the Third Law
12. Statistical Thermodynamics of Equilibrium Constants
13. Example of a Statistical Calculation of KP
14. Equilibria in Nonideal Systems—Fugacity and Activity
15. Nonideal Gases—Fugacity and Standard State
16. Use of Fugacity in Equilibrium Calculations
17. Standard States for Components in Solution
18. Activities of Solvent and Nonvolatile Solute from Vapor Pressure of Solution
19. Equilibrium Constants in Solution
20. Thermodynamics of Biochemical Reactions
21. AG^ of Biochemicals in Aqueous Solution
22. Pressure Effects on Equilibrium Constants
23. Effect of Pressure on Activity
24. Chemical Equilibria Involving Condensed Phases
Problems
9 Chemical Reaction Rates
1. The Rate of Chemical Change
2. Experimental Methods in Kinetics
3. Order of Reaction
4. Molecularity of a Reaction
5. Reaction Mechanisms
6. First-Order Rate Equations
7. Second-Order Rate Equations
8. Third-Order Rate Equations
9. Determination of the Reaction Order
10. Opposing Reactions
11. Principle of Detailed Balancing
12. Rate Constants and Equilibrium Constants
13. Consecutive Reactions
14. Parallel Reactions
15. Chemical Relaxation
16. Reactions in Flow Systems
17. Steady States and Dissipative Processes
18. Nonequilibrium Thermodynamics
19. The Onsager Method
20. Entropy Production
21. Stationary States
22. Effect of Temperature on Reaction Rate
23. Collision Theory of Gas Reactions
24. Reaction Rates and Cross Sections
25. Calculation of Rate Constants from Collision Theory
26. Tests of Simple Hard-Sphere Collision Theory
27. Reactions of Hydrogen Atoms and Molecules
28. Potential Energy Surface for H + H2
29. Activated-Complex Theory
30. Transition-State Theory in Thermodynamic Terms
31. Chemical Dynamics—Monte Carlo Methods
32. Reactions in Molecular Beams
33. Theory of Unimolecular Reactions
34. Chain Reactions: Formation of Hydrogen Bromide
35. Free-Radical Chains
36. Branching Chains—Explosive Reactions
37. Trimolecular Reactions
38. Reactions in Solution
39. Catalysis
40. Homogeneous Catalysis
41. Enzyme Reactions
42. Kinetics of Enzyme Reactions
43. Enzyme Inhibition
44. An Exemplary Enzyme, Acetylcholinesterase
Problems
10 Electrochemistry: Ionics
1. Electricity
2. Faraday’s Laws and Electrochemical Equivalents
3. Coulometers
4. Conductivity Measurements
5. Molar Conductances
6. The Arrhenius Ionization Theory
7. Solvation of Ions
8. Transport Numbers and Mobilities
9. Measurement of Transport Numbers—Hittorf Method
10. Transport Numbers—Moving Boundary Method
11. Results of Transference Experiments
12. Mobilities of Hydrogen and Hydroxyl Ions
13. Diffusion and Ionic Mobility
14. Defects of the Arrhenius Theory
15. Activities and Standard States
16. Ion Activities
17. Activity Coefficients from Freezing Points
18. The Ionic Strength
19. Results of Activity Coefficient Measurements
20. A Review of Electrostatics
21. The Debye-Huckel Theory
22. The Poisson-Boltzmann Equation
23. The Debye-Huckel Limiting Law
24. Theory of Conductivity
25. Ionic Association
26. Effects of High Fields
27. Kinetics of Ionic Reactions
28. Salt Effects on Kinetics of Ionic Reactions
29. Acid-Base Catalysis
30. General Acid-Base Catalysis
Problems
11 Interfaces
1. Surface Tension
2. Equation of Young and LaPlace
3. Mechanical Work on Capillary System
4. Capillarity
5. Enhanced Vapor Pressure of Small Droplets—Kelvin Equation
6. Surface Tensions of Solutions
7. Gibbs Formulation of Surface Thermodynamics
8. Relative Adsorptions
9. Insoluble Surface Films
10. Structure of Surface Films
11. Dynamic Properties of Surfaces
12. Adsorption of Gases on Solids
13. The Langmuir Adsorption Isotherm
14. Adsorption on Nonuniform Sites
15. Surface Catalysis
16. Activated Adsorption
17. Statistical Mechanics of Adsorption
18. Electrocapillarity
19. Structure of the Double Layer
20. Colloidal Sols
21. Electrokinetic Effects
Problems
12 Electrochemistry—Electrodics
1. Definitions of Potentials
2. Electric Potential Difference for a Galvanic Cell
3. Electromotive Force (EMF) of a Cell
4. The Polarity of an Electrode
5. Reversible Cells
6. Free Energy and Reversible EMF
7. Entropy and Enthalpy of Cell Reactions
8. Types of Half-Cells (Electrodes)
9. Classification of Cells
10. The Standard EMF of Cells
11. Standard Electrode Potentials
12. Calculation of the EMF of a Cell
13. Calculation of Solubility Products
14. Standard Free Energies and Entropies of Aqueous Ions
15. Electrode-Concentration Cells
16. Electrolyte-Concentration Cells
17. Nonosmotic Membrane Equilibrium
18. Osmotic Membrane Equilibrium
19. Steady State Membrane Potentials
20. Nerve Conduction
21. Electrode Kinetics
22. Polarization
23. Diffusion Overpotential
24. Diffusion in Absence of a Steady State—Polarography
25. Activation Overpotential
26. Kinetics of Discharge of Hydrogen Ions
Problems
13 Particles and Waves
1. Simple Harmonic Motion
2. Wave Motion
3. Standing Waves
4. Interference and Diffraction
5. Black-Body Radiation
6. The Quantum of Energy
7. The Planck Distribution Law
8. Photoelectric Effect
9. Spectroscopy
10. The Interpretation of Spectra
11. The Work of Bohr on Atomic Spectra
12. Bohr Orbits and Ionization Potentials
13. Particles and Waves
14. Electron Diffraction
15. Waves and the Uncertainty Principle
16. Zero-Point Energy
17. Wave Mechanics—The Schrodinger Equation
18. Interpretation of the Functions
19. Solution of the Schrodinger Equation—The Free Particle
20. Solution of Wave Equation —Particle in Box
21. Penetration of a Potential Barrier
Problems
14 Quantum Mechanics and Atomic Structure
1. Postulates of Quantum Mechanics
2. Discussion of Operators
3. Generalization to Three Dimensions
4. Harmonic Oscillator
5. Harmonic Oscillator Wave Functions
6. Partition Function and Thermodynamics of Harmonic Oscillator
7. Rigid Diatomic Rotor
8. Partition Function and Thermodynamics of Diatomic Rigid Rotor
9. The Hydrogen Atom
10. Angular Momentum
11. Angular Momentum and Magnetic Moment
12. The Quantum Numbers
13. The Radial Wave Function
14. Angular Dependence of Hydrogen Orbitals
15. The Spinning Electron
16. Spin Postulates
17. The Pauli Exclusion Principle
18. Spin-Orbit Interaction
19. Spectrum of Helium
20. Vector Model of the Atom
21. Atomic Orbitals and Energies—The Variation Method
22. The Helium Atom
23. Heavier Atoms—The Self-Consistent Field
24. Atomic Energy Levels— Periodic Table
25. Perturbation Method
26. Perturbation of a Degenerate State
Problems
15 The Chemical Bond
1. Valence Theory
2. The Ionic Bond
3. The Hydrogen Molecule Ion
4. Simple Variation Theory of H2+
5. The Covalent Bond
6. The Valence-Bond Method
7. The Effect of Electron Spins
8. Results of the Heitler-London Method
9. Comparison of M.O. and V.B. Methods
10. Chemistry and Mechanics
11. Molecular Orbitals for Homonuclear Diatomic Molecules
12. Correlation Diagram
13. Heteronuclear Diatomic Molecules
14. Electronegativity
15. Dipole Moments
16. Polarization of Dielectrics
17. Induced Polarization
18. Determination of the Dipole Moment
19. Dipole Moments and Molecular Structure
20. Polyatomic Molecules
21. Bond Distances, Bond Angles, Electron Densities
22. Electron Diffraction of Gases
23. Interpretation of Electron Diffraction Pictures
24. Nonlocalized Molecular Orbitals—Benzene
25. Ligand Field Theory
26. Other Symmetries
27. Electron-Excess Compounds
28. Hydrogen Bonds
Problems
16 Symmetry and Group Theory
1. Symmetry Operations
2. Definition of a Group
3. Further Symmetry Operations
4. Molecular Point Groups
5. Transformations of Vectors by Symmetry Operations
6. Irreducible Representations
Problems
17 Spectroscopy and Photochemistry
1. Molecular Spectra
2. Light Absorption
3. Quantum Mechanics of Light Absorption
4. The Einstein Coefficients
5. Rotational Levels— Far-Infrared Spectra
6. Intemuclear Distances from Rotation Spectra
7. Rotational Spectra of Polyatomic Molecules
8. Microwave Spectroscopy
9. Internal Rotations
10. Vibrational Energy Levels and Spectra
11. Vibration-Rotation Spectra of Diatomic Molecules
12. Infrared Spectra of Carbon Dioxide
13. Lasers
14. Normal Modes of Vibration
15. Symmetry and Normal Vibrations
16. Raman Spectra
17. Selection Rules for Raman Spectra
18. Molecular Data from Spectroscopy
19. Electronic Band Spectra
20. Reaction Paths of Electronically Excited Molecules
21. Some Photochemical Principles
22. Bipartition of Molecular Excitation
23. Secondary Photochemical Processes: Fluorescence
24. Secondary Photochemical Processes: Chain Reactions
25. Flash Photolysis
26. Photolysis in Liquids
27. Energy Transfer in Condensed Systems
28. Photosynthesis in Plants
29. Magnetic Properties of Molecules
30. Paramagnetism
31. Nuclear Properties and Molecular Structure
32. Nuclear Paramagnetism
33. Nuclear Magnetic Resonance
34. Chemical Shifts and Spin-Spin Splitting
35. Chemical Exchange in NMR
36. Electron Paramagnetic Resonance
Problems
18 The Solid State
1. The Growth and Form of Crystals
2. Crystal Planes and Directions
3. Crystal Systems
4. Lattices and Crystal Structures
5. Symmetry Properties
6. Space Groups
7. X-Ray Crystallography
8. The Bragg Treatment
9. Proof of Bragg Reflection
10. Fourier Transforms and Reciprocal Lattices
11. Structures of Sodium and Potassium Chlorides
12. The Powder Method
13. Rotating Crystal Method
14. Crystal-Structure Determinations
15. Fourier Synthesis of a Crystal Structure
16. Neutron Diffraction
17. Closest Packing of Spheres
18. Binding in Crystals
19. The Bond Model
20. Electron-Gas Theory of Metals
21. Quantum Statistics
22. Cohesive Energy of Metals
23. Wave Functions for Electrons in Solids
24. Semiconductors
25. Doping of Semiconductors
26. Nonstoichiometric Compounds
27. Point Defects
28. Linear Defects: Dislocations
29. Effects Due to Dislocations
30. Ionic Crystals
31. Cohesive Energy of Ionic Crystals
32. The Born-Haber Cycle
33. Statistical Thermodynamics of Crystals: Einstein Model
34. The Debye Model
Problems
19 Intermolecular Forces and the Liquid State
1. Disorder in the Liquid State
2. X-Ray Diffraction of Liquid Structures
3. Liquid Crystals
4. Glasses
5. Melting
6. Cohesion of Liquids — The Internal Pressure
7. Intermolecular Forces
8. Equation of State and Intermolecular Forces
9. Theory of Liquids
10. Flow Properties of Liquids
11. Viscosity
Problems
20 Macromolecules
1. Types of Polyreactions
2. Distribution of Molar Masses
3. Osmotic Pressure
4. Light Scattering—The Rayleigh Law
5. Light Scattering by Macromolecules
6. Sedimentation Methods: The Ultracentrifuge
7. Viscosity
8. Stereo-chemistry of Polymers
9. Elasticity of Rubber
10. Crystallinity of Polymers
Problems
Appendix A
Appendix B
Name Index
Subject Index