Some Problems of Chemical Kinetics and Reactivity Volume 1-2PDF电子书下载

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

1．UNIRADICAL REACTIVITIES 1

1．Radical reactions:basic types 1

2．Experimental determination of activation energies 4

3．Bond dissociation energies 10

4．The correlation of activation energies with heats of reaction 26

5．Radical and molecular activities 30

6．Empirical formulae for computing bond-energies in organic molecules 46

7．Addition at multiple bonds 52

8．Radical decomposition and the energies of π-bonds 59

9．Radical isomerizations 61

10．Transfer reactions 67

11．Polar factors in organic reactions 69

12．Polar factors in polymerization 77

2．ALTERNATIVE UNIVALENT FREE-RADICAL REACTIONS 85

1．The occurrence of alternative radical reactions 85

2．The influence of temperature and pressure on alternative radical reactions 88

3．Intermediary and terminal products in chain reactions 95

3．THE REACTIONS OF BIRADICALS 128

1．The transition of atoms to the active-valence state 128

2．Reactivity in the molecules O2,S2 and Se2 129

3．Divalent carbon 130

4．Complex biradicals 131

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

6．The role of biradicals in chain reactions 139

PART Ⅱ INITIATION AND TERMINATION OF CHAIN REACTIONS 144

4．MOLECULAR DISSOCIATION AND RADICAL COMBINATION 146

1．Homogeneous initiation of chains 146

2．Homogeneous recombination of radicals 152

3．Dependence of overall reaction kinetics on chain-termination mechanism 157

4．Special aspects of radical generation and recombination in liquids 159

5．The effects of inhibitors on the rates of chain reactions 160

5．IONS OF VARIABLE VALENCY AS CHAIN INITIATORS 172

1．Formation of radicals and ionic radicals by electron transfer 172

2．Thermodynamic and kinetic aspects of free radical formation 175

3．Ions of variable valency as chain initiators 177

6．WALL INITIATION AND RETARDATION OF CHAIN REACTIONS 183

1．Generation and removal of free radicals at the vessel walls 183

2．The method of differential calorimetry 187

3．Free valencies in the walls 190

4．Radical production at active surfaces 194

5．Heterogeneous production of radicals when gaseous admixtures are present 195

6．Heterogeneous molecular reactions giving free radicals 197

7．Application of the above concepts to heterogeneous catalysis 198

8．Heterogeneous catalysis in biology 205

PART Ⅲ KINETICS OF CHAIN REACTIONS 209

7．CHAIN REACTIONS COMPETING WITH REACTIONS BETWEEN SATURATED MOLECULES 209

1．Energy dependence of chain reactions and molecular reactions 209

2．The relative rates of direct molecular and chain reactions 213

3．Alkyl bromide decompositions 228

4．Alkyl chloride decompositions 239

5．The cracking of hydrocarbons 243

6．Factors influencing the chain length 250

7．The elementary act of decomposition 251

8．Free-radical production by reaction between stable molecules 260

9．Particular examples 261

Appendix Ⅰ．THE ACTIVATED COMPLEX 274

Appendix Ⅱ．THE QUANTUM-MECHANICAL CALCULATION OF ACTIVATION ENERGIES 285

NAME INDEX 297

SUBJECT INDEX 302

PART Ⅳ BRANCHED CHAIN REACTIONS AND THERMAL IGNITIONS 317

1.THERMAL IGNITION 317

2.CHAIN SELF-IGNITION 335

1.General considerations on chain self-ignition 335

2.The oxidations of phosphorus，sulphur and certaincompounds 342

3.CHAIN IGNITION IN HYDROGEN-OXYGEN MIX-TURES 363

1.Kinetic approximation 365

2.Pure diffusion 381

4.INTERACTION OF CHAINS 397

1.Negative chain interaction 397

2.Positive chain interaction 399

5.DEGENERATELY BRANCHED CHAIN REACTIONS 410

1.Introduction 410

2.The oxidation of methane 419

3.The oxidation kinetics of H2S 433

4.Liquid-phase hydrocarbon oxidation kinetics 439

5.Some new phenomena in hydrocarbon and aldehyde oxidations 452

NAME INDEX 461

SUBJECT INDEX 464

ERRATA AND ADDENDA TO VOLUME 1 467