The Theory of Kinetics - 1st Edition - ISBN: 9780444406743, 9780444600707

The Theory of Kinetics, Volume 2

1st Edition

Editors: R.G. Compton C.H. Bamford C.F.H. Tipper†
eBook ISBN: 9780444600707
Imprint: Elsevier Science
Published Date: 1st January 1980
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Table of Contents


Chapter 1 Kinetic Characterization of Complex Reaction Systems


1. First Order Reactions

1.I Reversible Reactions

1.II Parallel Reactions

1.III Parallel Reactions with Reversible Reaction Step

1.IV Consecutive Reactions

1.V Consecutive Reactions with Reversible Reaction Step

1.VI Competitive-Consecutive Reactions

1.VII Competitive-Consecutive Reactions with Reversible Reaction Step

2. Second and Mixed First-Second Order Reactions

2.I Reversible Reactions

2.II Parallel Reactions

2.III Parallel Reactions with Reversible Reaction Step

2.IV Consecutive Reactions

2.V Consecutive Reactions with Reversible Reaction Step

2.VI Competitive-Consecutive Reactions

2.VII Competitive-Consecutive Reactions with Reversible Reaction Step

3. Third Order Reactions

3.I Reversible Reactions

4. nTH Order Reactions

4.I Parallel Reactions

4.II Consecutive Reactions



Chapter 2 Chain Reactions

1. Introduction

2. Formal Kinetics of Chain Reactions

2.1 Unbranched Chain Reactions

2.2 Branched Chain Reactions

2.3 Effect of the Wall on Chain Reactions

3. Radical Chain Reactions

3.1 Reactions of Halogens with Hydrogen

3.2 Reaction of Hydrogen with Oxygen

3.3 Oxidation of Hydrocarbons

4. The Energy Factor in Chain Reactions

4.1 Energy Exchange in the Chemical Interaction of Molecules

4.2 Radical-Energy Chains


Chapter 3 The Theory of the Kinetics of Elementary Gas Phase Reactions

1. Introduction

2. The Arrhenius Equation

3. Collision Theory

3.1 Principles

3.2 Rate of Bimolecular Collisions

3.3 Collisions Between Like Species

3.4 Comparison with Experiment: The 'P' Factor

3.5 Calculation of Activation Energies

3.6 Temperature Dependence of A and E

3.7 Sophisticated Collision Theories

4. Transition State Theory

4.1 Introduction

4.2 Thermodynamic Formulations

4.3 Statistical Thermodynamic Formulation

4.4 More General Treatments of the Transition State Theory

4.5 Potential Energy Surfaces

5. Unimolecular Reactions

5.1 Introduction

5.2 The Lindemann-Hinshelwood Theory

5.3 Application of the Transition State Theory to Unimolecular Reactions

5.4 Free Flow Theories

5.5 Marcus' Quantum Mechanical Transition State Formulation

5.6 Slater's Theory

5.7 Experimental Tests of Theories of Unimolecular Reaction

5.8 Conclusion

6. Termolecular and Third-Order Process



Chapter 4 The theory of Elementary Reactions in Solution

1. General Characteristics of Solution Reactions

1.1 Collisions in Solution

1.2 Diffusion Effects in Solution Reactions

1.3 Comparison of Reaction Rates in Solution and the Gas Phase

1.4 Effect of Solvent on Non-Ionic Reactions

1.5 The Effect of Pressure on Reaction Rate

2. Reactions of Ions and Dipoles

2.1 Energetic Considerations of Ions in Solution

2.2 Free Energy of Activation in Ionic Reactions

2.3 Energy and Entropy of Activation in Ionic Reactions

2.4 Reactions Involving Dipoles

2.5 Electron Transfer Reactions

3. Proton Transfer Reactions

3.1 Acids and Bases

3.2 Elementary Proton Transfer Processes

3.3 Acid-Base Catalysis

3.4 Isotope Effects on Proton Transfer Processes

4. Linear Free Energy Relations

4.1 General Considerations

4.2 Some Common Linear Free Energy Relations

4.3 Conclusion

General Bibliography


Chapter 5 The Theory of Solid Phase Kinetics


1. Reactions at a Moving Interface

1.1 Dependence of Rate Law on Shape of Interface

1.2 Nucleation and Development of Reaction Interface

1.3 Mutual Interference of Nuclei

1.4 The Rate of Advance kl of the Reaction Interface

2. Diffusion-Controlled Reactions

2.1 The Differential Equations of Diffusion

2.2 Some Solutions of the Diffusion Equation for Self-Diffusion

2.3 Grain Boundary Diffusion

2.4 Interdiffusion and Diffusion Accompanied by Reaction

3. Point Defects in Reaction Mechanisms

3.1 Types of Defect Involved in Reaction Mechanisms

3.2 Rates of Migration of Defects




The Theory of Kinetics covers the practice and theory of kinetics and the kinetics of inorganic and organic reactions in gaseous and condensed phases and at interfaces.

This text is composed of five chapters and starts with a review of the kinetic characterization of complex reaction systems. The succeeding chapter describes the formal and radical kinetics, as well as the energy factor in chain reactions. These topics are followed by a survey of the theory of the kinetics of elementary gas phase reactions and the unimolecular reaction of activated chemical species. The discussion then shifts to the general properties, reactions, and the theory of elementary reactions in solution. The last chapter examines the theory of kinetics of solid-state reactions.

This book is of great value to physical, inorganic, and organic chemists.


© Elsevier Science 1969
Elsevier Science
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About the Editors

R.G. Compton Editor

Affiliations and Expertise

University of Oxford, Oxford, UK

C.H. Bamford Editor

C.F.H. Tipper† Editor