《Some Problems of Chemical Kinetics and Reactivity Volume 1-2》

PART ⅠRADICAL REACTIONS (PROPAGATION AND BRANCHING OF CHAIN REACTIONS)1

1．UNIRADICAL REACTIVITIES1

1．Radical reactions:basic types1

2．Experimental determination of activation energies4

3．Bond dissociation energies10

4．The correlation of activation energies with heats of reaction26

5．Radical and molecular activities30

6．Empirical formulae for computing bond-energies in organic molecules46

7．Addition at multiple bonds52

8．Radical decomposition and the energies of π-bonds59

9．Radical isomerizations61

10．Transfer reactions67

11．Polar factors in organic reactions69

12．Polar factors in polymerization77

2．ALTERNATIVE UNIVALENT FREE-RADICAL REACTIONS85

1．The occurrence of alternative radical reactions85

2．The influence of temperature and pressure on alternative radical reactions88

3．Intermediary and terminal products in chain reactions95

3．THE REACTIONS OF BIRADICALS128

1．The transition of atoms to the active-valence state128

2．Reactivity in the molecules O2,S2 and Se2129

3．Divalent carbon130

4．Complex biradicals131

5．Production and reactivity of ＞CH2 and －O－135

6．The role of biradicals in chain reactions139

PART ⅡINITIATION AND TERMINATION OF CHAIN REACTIONS144

4．MOLECULAR DISSOCIATION AND RADICAL COMBINATION146

1．Homogeneous initiation of chains146

2．Homogeneous recombination of radicals152

3．Dependence of overall reaction kinetics on chain-termination mechanism157

4．Special aspects of radical generation and recombination in liquids159

5．The effects of inhibitors on the rates of chain reactions160

5．IONS OF VARIABLE VALENCY AS CHAIN INITIATORS172

1．Formation of radicals and ionic radicals by electron transfer172

2．Thermodynamic and kinetic aspects of free radical formation175

3．Ions of variable valency as chain initiators177

6．WALL INITIATION AND RETARDATION OF CHAIN REACTIONS183

1．Generation and removal of free radicals at the vessel walls183

2．The method of differential calorimetry187

3．Free valencies in the walls190

4．Radical production at active surfaces194

5．Heterogeneous production of radicals when gaseous admixtures are present195

6．Heterogeneous molecular reactions giving free radicals197

7．Application of the above concepts to heterogeneous catalysis198

8．Heterogeneous catalysis in biology205

PART ⅢKINETICS OF CHAIN REACTIONS209

7．CHAIN REACTIONS COMPETING WITH REACTIONS BETWEEN SATURATED MOLECULES209

1．Energy dependence of chain reactions and molecular reactions209

2．The relative rates of direct molecular and chain reactions213

3．Alkyl bromide decompositions228

4．Alkyl chloride decompositions239

5．The cracking of hydrocarbons243

6．Factors influencing the chain length250

7．The elementary act of decomposition251

8．Free-radical production by reaction between stable molecules260

9．Particular examples261

Appendix Ⅰ．THE ACTIVATED COMPLEX274

Appendix Ⅱ．THE QUANTUM-MECHANICAL CALCULATION OF ACTIVATION ENERGIES285

NAME INDEX297

SUBJECT INDEX302

PART ⅣBRANCHED CHAIN REACTIONS AND THERMAL IGNITIONS317

1.THERMAL IGNITION317

2.CHAIN SELF-IGNITION335

1.General considerations on chain self-ignition335

2.The oxidations of phosphorus，sulphur and certaincompounds342

3.CHAIN IGNITION IN HYDROGEN-OXYGEN MIX-TURES363

1.Kinetic approximation365

2.Pure diffusion381

4.INTERACTION OF CHAINS397

1.Negative chain interaction397

2.Positive chain interaction399

5.DEGENERATELY BRANCHED CHAIN REACTIONS410

1.Introduction410

2.The oxidation of methane419

3.The oxidation kinetics of H2S433

4.Liquid-phase hydrocarbon oxidation kinetics439

5.Some new phenomena in hydrocarbon and aldehyde oxidations452

NAME INDEX461

SUBJECT INDEX464

ERRATA AND ADDENDA TO VOLUME 1467