《RADIOLYSIS OF HYDROCARBONS》

Chapter Ⅰ．Physicochemical Characteristics of Hydrocarbon Radiolysis1

1．Some Characteristics of Primary Events In Hydro-carbon Radiolysis1

2．Basic Experimental Data on Radiolysis of Hydro-carbons5

3．Some Characteristics of the Reactions Involved in Radiolysis of Hycrocarbons6

4．Effect of the Temperature and State of Aggregation on the Radiolysis of Hydrocarbons9

5．Reactions of Free Alkyl Radicals in Radiolysis10

6．Stabilized Hydrocarbon Radicals in Radiolysis12

7．Radiolysis of Hydrocarbons Adsorbed on Solid Surfaces14

8．Energy Transfer in Hydrocarbon Radiolysis15

References17

Chapter Ⅱ．Kinetics of Radiolysis of Hydrocarbons21

1．Statement of the Problem21

2．Material Balance Equations for Alkane Radiolysis22

3．Kinetic Equations of Nonchain,Unimolecular Radia-tion-Chemical Reactions27

4．Basic Macrocharacteristics of Alkane Radiolysis35

5．Ultraviolet Absorption Spectra of Various Irradiated Alkanes39

6．Radiolysis of n-Hexane in the Low-Dose Range(3·10 18-1·10 20 ev/ml)43

7．Radiolysis of Heptane in the High-Dose Range(0．25-28·10 21 ev/ml)50

8．Effect of Low Temperatures and of the State of Ag-gregation on the Radiolysis of Alkanes58

9．Discussion of the Possible Reaction Mechanism of Alkane Radiolysis62

References66

Chapter Ⅲ．Free Radicals in the Radiolysis of Hydrocarbons69

1．Formation and Stabilization of Alkyl Radicals in Radiolysis of Hydrocarbons at 77°K69

2．Some Regularities in the Electron Spin Resonance Spectra of Alkyl Radicals72

3．Effect of the Nature of the Hydrocarbon on the Struc-ture of Radicals Observed in the Low-Temperature γ Radiolysis of the Solid74

4．Formation of Saturated Heavy Products in the Solid-and Liquid-Phase Radiolysis of n-Hexane77

5．Recombination of Alkyl Radicals and Reactions of Hydrogen Atoms in the Liquid-Phase Radiolysis of n-Hexane83

6．Formation of Free Radicals in the Solid-Phase Radi-olysis of n-Hexane and Cyclohexane in the Presence of Small Amounts of Added Benzene and Dibenzyl Sulfide94

References101

Chapter Ⅳ．Radiolysis of Alkanes Adsorbed on Oxide Catalysts103

1．Introductory Remarks103

2．Electron Spin Resonance Spectra of Oxide Catalysts and Catalyst-Adsorbed Hydrocarbon Systems,With and Without Irradiation104

3．Kinetics of Radiolysis of n-Heptane,Adsorbed on Oxide Catalysts110

4．Kinetic Mechanism of Radiolysis of Various Catalyst-Adsorbed Alkanes115

5．Physical Model of the Energy Transfer from the Catalyst to the Adsorbed Alkane117

6．Calculation of the Proposed Mechanism of Energy Transfer120

References124

Chapter Ⅴ．Energy Transfer in the Radiolysis of Hydro-carbons126

1．Statement of the Problem126

2．Kinetics of n-Heptane in the Presence of Small Quan-tities of Dibenzyl and Dibenzyl Sulfide127

3．Composition of the Products of n-Heptane Radiolysis in the Presence of Small Amounts of Dibenzyl Sulfide130

4．Variation of the Yields of the Basic Products of n-Hexane Radiolysis as a Function of the Benzene Concentration133

5．Determination of the Form of the Function F(R)in Inhibited Radiolysis138

6．Molecular Iodine as an Excitation Acceptor in the Radiolysis of Alkanes143

7．Evaluation of the Linear Energy Transfer in Inhibited Radiolysis145

8．Discussion of a Possible Mechanism of Energy Trans-fer in Inhibited Radiolysis146

9．Calculation of the Proposed Mechanism of Energy Transfer in Inhibited Radiolysis148

10．Comparison of Theory With Experimental Data154

11．Conclusion158

References158

Chapter Ⅵ．Some Aspects of the Theory of Hydrocarbon Radiolysis161

A．Phenomenological Kinetics of Hydrocarbon Radiolysis161

1．Introduction161

2．Kinetics of Reactions Occurring in Tracks162

3．Kinetics of Radiolysis in the Presence of Hot Atoms and Molecular Fragments169

4．Conclusions174

B．Some Aspects of the Statistical Theory of Activated Processes Initiated by Ionizing Radiation in Condensed Substances174

1．Introduction174

2．Description of the Model;Basic Assumptions179

3．Evaluation of the Average Space-Time Ratios Defin-ing the Elementary Event of a Thermally Activated Process184

4．Calculation of the Rates of a Thermally Activated Process187

5．Calculation of the Rates of the Activated Processes Initiated by Ionizing Radiation192

6．Effect of the Electromagnetic Field,Produced by a Charged Particle,on the Rates of Activated Processes197

References200

Chapter Ⅶ．Radiation-Thermal Cracking of Hydrocarbons203

1．Statement of the Problem203

2．Static Radiation-Thermal Cracking of n-Heptane206

3．The Continuous Radiation-Thermal Cracking Unit and Experimental Procedure210

4．Continuous Radiation-Thermal Cracking of n-Heptane214

5．Radiation-Thermal Cracking of Light and Heavy Petroleum Stock218

References227

Subject Index228