Some Problems of Chemical Kinetics and Reactivity

IntroductionPart I Radical Reactions (Propagation and Branching of Chain Reactions) 1. Uniradical Reactivities 1. Radical Reactions: Basic Types 2. Experimental Determination of Activation Energies 3. Bond Dissociation Energies 4. The Correlation of Activation Energies with Heats of Reaction 5. Radical and Molecular Activities 6. Empirical Formula for Computing Bond-Energies in Organic Molecules 7. Addition at Multiple Bonds 8. Radical Decomposition and the Energies of π-Bonds 9. Radical Isomerizations 10. Transfer Reactions 11. Polar Factors in Organic Reactions 12. Polar Factors in Polymerization 2. Alternative Univalent Free-Radical Reactions 1. The Occurrence of Alternative Radical Reactions 2. The Influence of Temperature and Pressure on Alternative Radical Reactions 3. Intermediary and Terminal Products in Chain Reactions 3. The Reactions of Biradicals 1. The Transition of Atoms to the Active-Valence State 2. Reactivity in the Molecules O2, S2 and Se2 3. Divalent Carbon 4. Complex Biradicals 5. Production and Reactivity of >Ch2 and —O— 6. The Role of Biradicals in Chain ReactionsPart II Initiation and Termination of Chain Reactions 4. Molecular Dissociation and Radical Combination 1. Homogeneous Initiation of Chains 2. Homogeneous Recombination of Radicals 3. Dependence of Overall Reaction Kinetics on Chain-Termination Mechanism 4. Special Aspects of Radical Generation and Recombination in Liquids 5. The Effects of Inhibitors on the Rates of Chain Reactions 5. Ions of Variable Valency as Chain Initiators 1. Formation of Radicals and Ionic Radicals by Electron Transfer 2. Thermodynamic and Kinetic Aspects of Free Radical Formation 3. Ions of Variable Valency as Chain Initiators 6. Wall Initiation and Retardation of Chain Reactions 1. Generation and Removal of Free Radicals at the Vessel Walls 2. The Method of Differential Calorimetry 3. Free Valencies in the Walls 4. Radical Production at Active Surfaces 5. Heterogeneous Production of Radicals When Gaseous Admixtures are Present 6. Heterogeneous Molecular Reactions Giving Free Radicals 7. Application of the above Concepts to Heterogeneous Catalysis 8. Heterogeneous Catalysis in BiologyPart III Kinetics of Chain Reactions 7. Chain Reactions Competing with Reactions between Saturated Molecules 1. Energy Dependence of Chain Reactions and Molecular Reactions 2. The Relative Rates of Direct Molecular and Chain Reactions 3. Alkyl Bromide Decompositions 4. Alkyl Chloride Decompositions 5. The Cracking of Hydrocarbons 6. Factors Influencing the Chain Length 7. The Elementary Act of Decomposition 8. Free-Radical Production by Reaction Molecules between Stable 9 Particular ExamplesAppendix I. The Activated ComplexAppendix II. The Quantum-Mechanical Calculation of Activation EnergiesName IndexSubject Index