The Theory of Kinetics

Preface

Chapter 1 Kinetic Characterization of Complex Reaction Systems

Introduction


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

Acknowledgment

References

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

References

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

Bibliograhy

References

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

References

Chapter 5 The Theory of Solid Phase Kinetics

Introduction


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

References

Index