The Oxidation of Cyclohexane

Preface

Chapter I. Theory of Slow Chain Oxidations (Degenerate Branching Chain Reactions)


1. Mechanism of Liquid Hydrocarbon Chain Oxidation


2. Applicability of the Stationary State Method to Liquid-Phase Oxidation Reactions


3. Kinetic Equations for Product Accumulation in Degenerate Branching Chain Reactions


4. Artificial Chain Initiation During the Initial Period of a Slowly Developing Chain Reaction


5. Kinetic Equilibrium of Intermediate Product Concentration During the Chain Reaction


6. Theory of the Effect of Inhibitors on Degenerate Branching Chain Reaction


7. Changes of Radical Composition During Reaction

References to Chapter I

Chapter II. The Products of Liquid-Phase Cyclohexane Oxidation


1. Cyclohexyl Hydroperoxide


2. Cyclohexanone


3. Cyclohexanol


4. Formation of Separate Phases During Cyclohexane Oxidation


5. Products of Extensive Cyclohexane Oxidation

Acids

Esters

δ-Formylvaleric Acid (Adipic Mono-Aldehyde)

ε-Hydroxycaproic Acid

Cyclohexane-1,2-Diol

Gaseous Products


6. Changes of the Volume of the Liquid Phase Due to Oxidation Product Formation

References to Chapter II

Chapter III. Experimental Apparatus for the Study of the Liquid-Phase Oxidation of Cyclohexane


1. General


2. Explosion Danger and Problems of Safety


3. Prevention of Cyclohexane Losses in the Waste Gases


4. Laboratory Apparatus for the Oxidation of Cyclohexane


5. Characteristics of Gas Sampling in Cyclohexane Oxidation Apparatus

References to Chapter III

Chapter IV. Kinetics of Uncatalysed Cyclohexane Oxidation


1. Kinetic and Diffusion Systems of Oxidation


2. Rate of Oxygen Absorption and Accumulation of Reaction Products


3. Characteristics of the Reaction Kinetics of Intermediate Products


4. Effect of Inhibitors on the Oxidation of Cyclohexane


5. Kinetics of Cyclohexane Oxidation in a Glass Reactor


6. Effect of Temperature on the Relative Yield of Cyclohexane Oxidation Products

References to Chapter IV

Chapter V. Kinetics of Cyclohexane Oxidation in Continuous Flow Systems


1. Principal Definitions


2. Ideal Displacement Reactor


3. Reactor with Ideal Mixing


4. Intermediate Type Reactor


5. Determination of Diffusion Factor p

References to Chapter V

Chapter VI. Sequence of Intermediate Product Conversion During Cyclohexane Oxidation


1. Likely Intermediate Reactions During Cyclohexane Oxidation


2. Isotope Tracer Method


3. Reaction of Cyclohexyl Hydroperoxide and Course of Cyclohexanol and Cyclohexanone Formation


4. Intermediate Reactions of Cyclohexanol


5. Intermediate Reactions of Cyclohexanone


6. Oxidation of Adipic Aldehyde and Adipic Acid


7. Reactions of Acids

References to Chapter VI

Chapter VII. Catalysed Oxidation of Cyclohexane


1. Chain Initiation by Salts as Catalysts


2. Chain Termination by Catalysts with Variable Valence Ions


3. Separate Stages of a Catalysed Oxidation of Hydrocarbons


4. Physico-Chemical Properties of Catalyst Salt Solutions in Hydrocarbons


5. Catalysts as Regulators of Product Composition


6. Gaseous Initiation of the Oxidation of Cyclohexane

References to Chapter VII

Chapter VIII. Fundamental Reaction Mechanism of the Cyclohexane Oxidation


1. Link Between Thermochemical and Kinetic Values


2. Heats of Product Formation and Bond Dissociation Energies in the Oxidation of Cyclohexane


3. Initiation of the Chain in Uncatalysed Reaction


4. Propagation of the Chain Reaction


5. Chain Branching Reaction


6. Chain Termination


7. Fundamental Reactions of Chain Propagation with Participation of Intermediate Products, and Changes of Free Radical Composition

References to Chapter VIII

Chapter IX. Gas-Phase Oxidation of Cyclohexane


1. Uncatalysed Oxidation of Cyclohexane


2. Oxidation of Cyclohexane in the Presence of Additives


3. Gas-Phase Oxidation of Cyclohexane Over Heterogeneous Catalysts


4. Comparison of Gas-Phase with Liquid-Phase Oxidation of Cyclohexane

References to Chapter IX

Chapter X. Cyclohexane Oxidation with Bound Oxygen


1. Oxidation with Nitric Acid


2. Oxidation with Nitrogen Dioxide


3. Reaction of Cyclohexane with Nitrogen Pentoxide


4. Oxidation with Chromium Trioxide and with Chromyl Chloride

References to Chapter X

Chapter XI. Some Technological Problems of Oxidizing Cyclohexane


1. Cyclohexane as Raw Material


2. Oxidation of Cyclohexane to Adipic Acid


3. Oxidation of Cyclohexane to Cyclohexanone and Cyclohexanol


4. Prospects of Development of Cyclohexane Oxidation Processes

References to Chapter XI

Author Index

Subject Index