Oxidation of Organic Compounds

ContentsIntroduction 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 Processes1.5.1. 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 Complex3.2.3. 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 Kinetics3.3.4. Formation and Structure of -Rr-Complexes 3.3.5. p-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 Reactions4.1 Introduction 1874.2 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 branching4.3.1. 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 InitiatorsLiterature 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 Ketones5.3 Oxidation of Alkenes 5.