# A Textbook of Physical Chemistry

## 2nd Edition

**Authors:**Arthur Adamson

**eBook ISBN:**9780323140706

**Imprint:**Academic Press

**Published Date:**1st January 1973

**Page Count:**1103

## Description

A Textbook of Physical Chemistry, Second Edition serves as an introductory text to physical chemistry. Topics covered range from wave mechanics and chemical bonding to molecular spectroscopy and photochemistry; ideal and nonideal gases; the three laws of thermodynamics; thermochemistry; and solutions of nonelectrolytes. The kinetics of gas-phase reactions; colloids and macromolecules; and nuclear chemistry and radiochemistry are also discussed. This edition is comprised of 22 chapters; the first of which introduces the reader to the behavior of ideal and nonideal gases, with particular emphasis on the van der Waals equation. The discussion then turns to the kinetic molecular theory of gases and the application of the Boltzmann principle to the treatment of molar polarization; dipole and magnetic moments; the phenomenology of light absorption; and classical and statistical thermodynamics. The chapters that follow focus on the traditional sequence of chemical and phase equilibria, electrochemistry, and chemical kinetics in gas phase and solution phase. This book also considers wave mechanics and its applications; molecular spectroscopy and photochemistry; and the excited state, and then concludes with an analysis of crystal structure, colloid and polymer chemistry, and radio and nuclear chemistry. This reference material is intended primarily as an introductory text for students of physical chemistry.

## Table of Contents

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

Special Topics

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

Special Topics

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

Special Topics

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 ΔE Quantities

5-5 Enthalpies of Formation

5-6 Dependence of ΔH and ΔE on Temperature

Commentary and Notes

Special Topics

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

Special Topics

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

Special Topics

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

Special Topics

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

Special Topics

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

Special Topics

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

Special Topics

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-Huckel Theory

12-9 Ionic Equilibria

Commentary and Notes

Special Topics

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 ɛ0

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

Special Topics

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

Special Topics

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

Special Topics

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

Special Topics

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

Special Topics

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

Special Topics

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

Special Topics

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

Special Topics

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

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

Special Topics

General References

Cited References

Exercises

Problems

Special Topics Problems

Subject Index

## Details

- No. of pages:
- 1103

- Language:
- English

- Copyright:
- © Academic Press 1973

- Published:
- 1st January 1973

- Imprint:
- Academic Press

- eBook ISBN:
- 9780323140706