Oxidation of Organic Compounds

Contents

Introduction

Chapter 1 Mechanism of the Liquid Phase Oxidation of OrganiC Compounds

1.1 Introduction

1.2 Chain Mechanism of Oxidation Reactions

1.3 Initially-Formed Intermediate Oxidation Processes

1.4 Kinetic Laws and The Overall Oxidation Reaction Scheme

1.5 Elementary Reactions Involved in the Oxidation Processes

1.5.1. Chain-Formation

1.5.2. Degenerate Chain-Branching

1.5.3. Chain-Propagation

1.5.4. Chain-Propagation in The Oxidation of Alkenes Mechanism of Alkene Epoxidation

1.5.5. Chain-Termination

Literature References

Chapter 2 Some Methods for Studying the Mechanism of Oxidation Reactions

2.1 Introduction

2.2 Methods For Measuring The Oxidation Rate

2.3 Determination of the Rate Constants of Elementary Chain propagation and Chain-Termination Reactions

2.3.1. Introduction

2.3.2. The Method of Discontinuous Illumination

2.3.3. The Electron Paramagnetic Resonance Method

2.3.4. Chemiluminescence Method For Determining the Rate Constant of the Quadratic Chain-Termination Reaction

2.4 Determination of the Rate Constant of the Elementary Reactions Involved in Free Radical Initiation

2.4.1. Introduction

2.4.2. Calculation of the Initiation Rate From The Oxidation Rate

2.4.3. Inhibitor Method

2.4.4. Chemiluminescence Method

2.5 Chemiluminescence Methods For Determining The Rate Constants of Chain-Termination Reactions Brought About by Inhibitors

Literature References

Chapter 3 The Role of Solvation in Chemical Reaction Kinetics

3.1 Introduction

3.2 Non-Specific Solvation

3.2.1. Definition

3.2.2. The Role of the Medium in Chemical Kinetics from the Point of View of the Theory of the Activated Complex

3.2.3. Non-Polar (Disperse) Solvents

3.2.4. Electrostatic (Coulombic) Solvation

3.2.5. Cage Effect

3.2.6. Dependence of the Entropy of Activation and of the Energy of Activation of the Reaction on the Polarity of the Medium

3.2.7. The Role of Solvation in Connection with the Change in the Potential Energy of A System of Reacting Particles

3.2.8. Correlations

3.3. Specific Solvation

3.3.1. Definition

3.3.2. The Nature of the Hydrogen Bond

3.3.3. The Role of the Hydrogen Bond in Chemical Kinetics

3.3.4. Formation and Structure of -Rr-Complexes

3.3.5. π-Complexes and Their Role in the Kinetics of Chemical Reactions

3.4 Effect of Complex Formation on the Kinetics and Mechanism of Reaction

3.4.1. Introduction

3.4.2. Methodology of Study

3.5 Some Specific Phenomena Relating Reactivities to the Physical State of Substances

3.5.1. Introduction

3.5.2. The Effect of A Filled Volume in The Liquid Phase

3.5.3. The Effect of Rigidity of the "Cage" Walls in the Condensed Phase

Literature References

Chapter 4 The Role of the Medium in Chain-Initiation Reactions

4.1 Introduction 187

4.2 The Role of the Medium in Processes of Chain-Initiation. The Influence of the Phase Composition of the Oxidant on the Mechanism of Chain-Initiation

4.3 The R61e of the Medium in Processes of Degenerate Chain branching

4.3.1. Differences in Mechanisms of Chain-Branching in the Vapor and Liquid Phases

4.3.2. Participation of Solvent Molecules in Reaction Steps Which Initiate Chain-Branching

4.3.3. Ketones As Solvents in Reactions of Radical Decomposition of Hydroperoxides

4.3.4. The Influence of Hydrogen Bonds on the Rate of the Radical Decomposition of Hydroperoxides

4.3.5. Influence of Solvents on the Mechanism of the Decomposition of Peroxidic Compounds

4.3.6. Role of Ionic Reactions in The Radical Decomposition of Hydroperoxide

4.4 Influence of Solvents on the Rate of Formation of Radicals Following the Thermal Decomposition of Initiators

Literature References

Chapter 5 Role of Non-Specific Solvation in Chain-Propagation and Chain Termination Reactions

5.1 Influence of the Polarity of the Medium on the Reactivity of Organic Compounds

5.2 Oxidation of Ketones

5.3 Oxidation of Alkenes

5.4 Oxidation of Non-Polar Hydrocarbons

Literature References

Chapter 6 The Role of Specific Solvation in Chain-Propagation and Chain Termination Reactions

6.1 Introduction

6.2 The Influence of Hydrogen Bonds on the Oxidation of Ketones

6.2.1. General

6.2.2. Hydration of Peroxyl Radicals Derived From Cyclohexanone

6.2.3. Hydration of Peroxyl Radicals Derived From Butan-2-One

6.2.4. Specific Solvation of Peroxyl Radicals Derived From Butan-2-One in Alcoholic Solutions

6.3 The Role of Hydrogen Bonds in The Oxidation of Alkenes

6.4 The Role of Hydrogen Bonds in The Oxidation of Saturated Hydrocarbons

6.5 The Influence of Hydrogen Bonds on the Rate of Reaction of Phenoxyl and Alkyl Radicals

6.5.1. The Influence of Hydrogen Bonds on the Kinetics and Mechanism of the Reaction of Nitrophenols with the Tri-Tert-Butylphenoxyl Radical

6.5.2. Hydrogen Bonds in Reactions of Radicals with Alcohols

6.6 The Influence of the Formation of Ir-Complexes on the Reactivity of Nitroxyl and Methyl Radicals

6.6.1. Influence of the Formation of Ir-Complexes on the Activity of Nitroxyl Radicals

6.6.2. The Influence of Ir-Complex Formation on the Activity of Methyl Radicals

Literature References

Chapter 7 The Role of Solvation in Chain-Termination Reactions in Inhibitors

7.1 Introduction

7.2 Effectiveness of Inhibitors in The Oxidation of Organic Compounds of Different Classes

7.3 Influence of Non-Specific Solvation on the Efficiency of Inhibitor Activity

7.3.1. Introduction

7.3.2. Oxidation of Hydrocarbons

7.3.3. Oxidation of Ketones

7.4 Influence of Specific Solvation on the Effectiveness of Inhibitors

7.4.1. Introduction

7.4.2. Oxidation of Hydrocarbons

7.4.3. Oxidation of Ketones

Literature References

Chapter 8 The Causes of the Difference Between the Composition of Products Formed in the Oxidation of Organic Substances in the Vapour and Liquid Phases

8.1 Introduction

8.2 Differences Between Liquid-Phase and Vapour-Phase Oxidation Reactions

8.3 Oxidation of Alkanic Hydrocarbons

8.3.1. Introduction

8.3.2. Oxidation of Butane

8.3.3. Oxidation of 2-Methylpropane

8.4 Oxidation of Butan-2-One

8.4.1. Liquid Phase Oxidation of Butan-2-One

8.4.2. Oxidation of Butan-2-One in The Vapour Phase

8.4.3. Comparison of the Oxidation of Butan-2-One in the Vapour and Liquid Phases

8.5 Oxidation of Ethyl Alcohol

8.5.1. Introduction

8.5.2. Liquid-Phase Oxidation of Ethyl Alcohol

8.5.3. Vapour-Phase Oxidation of Ethyl Alcohol

8.5.4. Comparison of the Oxidation of Ethyl Alcohol in the Vapour and Liquid Phases

8.6 Region of Chain-Oxidation by The Peroxide Mechanism

Literature References

Chapter 9 Influence of Solvents on the Rate and Direction of Oxidation Processes

9.1 Introduction

9.2 The Influence of Solvents on the Rates and Direction of the Oxidation of Butan-2-One and of Ethyl Alcohol

9.3 Influence of Non-Specific Solvation on the Rate and Direction of Oxidation

9.4 Influence of the Medium on the Selectivity of Oxidation

9.5 Influence of Water on the Rate Constant and Selectivity of Liquid-Phase Oxidation of Butane

9.6 Conclusions

Literature References

Chapter 10 Some Special Features of the Kinetic Laws and the Mechanism of Oxidation of Solid Polymers

10.1 Introduction

10.2 The Influence of the Rate of Structural Rearrangements on the Reaction Rate

10.3 The Influence of the Intensity of Molecular Motions on the Specificity of Reactions in A Solid Polymer

10.4 The Influence of the Addition of Plasticisers on the Relationships Governing Radical Reactions in the Solid Phase

10.5 Anti-Radical Activity of Antioxidants in A Solid Polymer

10.6 The Role of Surface Phenomena in The Degradation of Solid Polymers

10.7 Special Features of the Chain-Propagation and Chain Termination Reactions During the Oxidation of A Solid Polymer

10.8 The Role Played by Compounds of Low Molecular Weight in the Oxidation of Solid Polymers

10.9 The Influence of Inhomogeneities on the Rate of Oxidation of Polymers

10.10 Some Effective Methods For The Investigation of Processes Taking Place Within A Polymer Matrix

10.11 The Relationship Between The Kinetic Laws Governing Degradation Processes and The Internal Stresses in Polymer Molecules

10.12 Additional Data on the Characteristic Features of Chemical Conversions in A Polymer Matrix

Literature References

Appendix

Subject Index