The Gas-Phase Oxidation of Hydrocarbons

Foreword to the English Edition

Preface

I. Introduction. Three Stages in the Growth of Research on the Gaseous-phase Slow Oxidation of Hydrocarbons

References

II. Non-chain Schemes for the Oxidation of Hydrocarbons

1. Hydroxylation Scheme

2. Peroxidation Scheme

3. Aldehyde and Dehydrogenation Schemes

References

III. Basic Principles of the Theory of Chemical Chain Reactions. Kinetic Mechanism of and New Facts on the Phenomenon of Hydrocarbon Oxidation (Late Twenties—middle Thirties)

1. Basic Principles of the Theory of Chemical Chain Reactions

2. Kinetic Mechanism of the Gas-phase Oxidation of Hydrocarbons

3. New Facts on the Phenomenology of Hydrocarbon Oxidation (Cool Flames, Negative Temperature Coefficient of Reaction Rate, Three Limits of Spontaneous Ignition with Respect to Temperature and Pressure)

References

IV. Radical-chain Schemes of Oxidation of Paraffinic Hydrocarbons (1934-1937)

1. Di-radical Chain Schemes of Methane Oxidation

2. Mono-radical Chain Schemes for the Oxidation of the Higher Paraffinic Hydrocarbons

3. General Remarks on the Group of Schemes of 1934—1937

References

V. Experimental Investigations on the Oxidation of Paraffinic Hydrocarbons (1936-1947)

1. Chemical Nature of the Oxidation of Paraffinic Hydrocarbons and the Role of Organic Peroxides during the Course of this Reaction

2. Cool-flame Oxidation. Peroxide Concept of the Mechanism of Cool-flame Formation

3. Cool and Blue Flames in Unheated Mixture. Kinetic and Thermo-kinetic Schemes of Cool-flame Oxidation

References

VI. Fundamental Results of the Experimental Investigations on the Oxidation of the Higher Paraffinic Hydrocarbons from 1946-1959 and the Radical-chain Schemes Proposed on their Basis

1. Peroxidic Schemes and Experiments for the Investigation of the Kinetics and Phenomenology of Cool-flame Oxidation

2. The Mechanism of Propane Oxidation

3. The Oxidation Scheme of Higher Paraffinic Hydrocarbons by Means of Step-by-Step Degradation of Aldehydes

References

VII. The Oxidation of Methane

1. An Oxidation Scheme for Methane (1948) and Some New Experimental Data on the Effects of Formaldehyde on the Course of the Reaction

2. The Relationships between the Reaction Rate and the Concentration of the Branching Product, the Displacement of the Maximum Rate the Role of Formaldehyde and the Change in the Orders of Reaction during Methane Oxidation

3. The Role of Carbon Monoxide in Methane Oxidation

4. A Scheme for Methane Oxidation (1958) and its Quantitative Calculation

References

VII. The Effect of the Structure of a Paraffinic Hydrocarbon on its Reactivity in Oxidation. Contemporary Ideas on the Oxidation Mechanism of Paraffinic Hydrocarbons

1. Some Data on the Effect of the Structure of a Paraffinic Hydrocarbon on the Rate and Mode of Oxidation

2. Modern Ideas on the Mechanism of the Oxidation Reaction of n-Paraffin Hydrocarbons

a. The Strictly Oxidizing and Cracking Routes of the Overall Oxidation Reaction

b. The Kinetic Mechanism

c. The Chemical Nature of the Strictly Oxidizing Route of the Reaction

d. The Chemical Nature of the Cracking Route of the Reaction

e. The Negative Temperature-Coefficient of the Oxidation Reaction Rate and the Mechanism of the Degenerate-Branching Process

f. Cool-flame Oxidation and Two-stage Spontaneous Ignition

g. On the Two Temperature Regions of Spontaneous Ignition of Hydrocarbons

References

IX. The Oxidation of Olefinic Hydrocarbons

References

X. The Oxidation of Naphthenic and Aromatic Hydrocarbons

1. Oxidation of Naphthenic Hydrocarbons

2. Oxidation of Aromatic Hydrocarbons

References

XI. Problems of Controlling Hydrocarbon Oxidation Reactions

1. Increase in the Proportion of the Initial Hydrocarbon Undergoing Oxidation

2. Increase in the Yields of Valuable Oxygen-containing Products of the the Oxidation of Paraffins

3. Initiation of Hydrocarbon Oxidation at Low Temperatures by the Actions of Light and of Penetrating Radiation

4. Homogeneous Catalytic Additives

References

Index