《CATALYSIS AND INHIBITION OF CHEMICAL REACTIONS》

PART ⅠINTRODUCTION1

1.CATALYSTS AND CATALYSED REACTIONS3

1.1.Introduction3

1.2.Definitions of catalysts and catalysed reactions6

1.3.Catalysts and reversible reactions10

1.4.Simple general mechanisms for catalysed reactions13

1.5.Activation energies of catalysed reactions17

PART ⅡHOMOGENEOUS CATALYSIS25

2.HOMOGENEOUS CATALYSIS BY PROTON TRANSFER27

2.1.Introduction27

2.2.Early work on acid-base reactions and catalyses28

2.3.General acid-base catalysis in dilute aqueous solution33

2.4.Proton transfer reactions38

2.5.Reaction mechanisms of some acid-base catalysed reactions40

2.6.Hydrolysis of esters45

2.7.Summary of simple mechanisms46

2.8.Metal ions as acid catalysts47

2.9.Catalytic activity of concentrated acids47

2.10.Catalysis in non-aqueous solvents52

2.11.Friedel-Crafts syntheses and related rcactions53

3.HOMOGENEOUS CATALYSIS BY GROUP OR ELECTRON TRANSFER58

3.1.Group and clectron transfer in solution58

3.1.1.Introduction58

3.1.2.Catalysis of electron-transfer reactions60

3.1.3.Rcductions by moleccular hydrogen in solution63

3.2.Catalysis by atom transfer in non-chain gas reaactions66

4.ENZYME-CATALYSED REACTIONS74

4.1.Introduction74

4.2.Intermediate complexes77

4.3.Kinetic mechanisms for single substrate reactions(Scheme Ⅰ)79

4.4.Inhibitors of single suhstrate reactions84

4.5.Bimolecular reactions between substrates(Schemes Ⅱ and Ⅲ)88

4.6.The influence of hydrogen ion concentration91

4.7.The influence of temperature on enzyme-catalysed reactions95

4.8.The effectiveness of enzymes97

4.9.The active centres98

PART ⅢHETEROGENEOUS CATALYSIS105

5.HETEROGENEOUSLY CATALYSED REACTIONS107

5.1.Introduction107

5.2.Rates of surface reactions of gases111

5.3.Heterogeneous catalysts113

5.4.Physical characterization of heterogeneous catalysts116

5.4.1.Particle size of catalysts117

5.4.2.The surface area of catalysts117

5.4.3.Structure of porous catalysts121

6.HETEROGENEOUS CATALYSIS AND CHEMISORPTION126

6.1.Introduction126

6.2.Chemisorption of gases on metals128

6.2.1.Preparation of single crystal faces130

6.2.2.Preparation of evaporated films132

6.2.3.Infra-red spectra of chemisorbed species137

6.3.Chemisorption on oxides139

6.3.1.The insulator oxides139

6.3.2.Semiconductor oxides140

6.4.Heats of adsorption142

6.4.1.The fall in heat of chemisorption with increasing coverage148

6.5.Derivation of adsorption isotherms149

6.6.Rates of adsorption152

6.6.1.Experimental measurements of the rates of adsorption on plane surfaces156

6.6.2.Slow activated chemisorptions162

6.7.Rates of desorption167

7.MECHANISMS OF HETEROGENEOUSLY CATALYSED REACTIONS Ⅰ174

7.1.Introduction174

7.2.Reactions proceeding by Langmuir-Hinshelwood mechanisms176

7.3.Velocity constants of surface reactions183

7.4.Inhibition of surface reactions188

7.5.On active sites192

8.MECHANISMS OF HETEROGENEOUSLY CATALYSED REACTIONS Ⅱ196

8.1.The orthohydrogen-parahydrogen conversion and thehydrogen-deuterium exchange196

8.2.Hydrogenation-dehydrogenation reactions200

8.2.1.Hydrogenation and exchange reactions with ethylene202

8.2.2.Hydrogenation and dehydrogenation of cyclic com-pounds206

8.3.Synthesis and decomposition of ammonia210

8.4.Fischer-Tropsch and related syntheses220

8.5.The synthesis of methanol227

8.6.Heterogeneous catalysis of oxidations231

8.6.1.Oxidation of ammonia232

8.6.2.Oxidation of sulphur dioxide235

8.6.3.Oxidation of carbon monoxide238

8.6.4.Oxidation of hydrocarbons240

8.7.Catalytic cracking and related reactions243

8.7.1.Cracking and reforming reactions244

8.7.2.Bifunctional reforming catalysts247

PART ⅣCATALYSIS AND INHIBITION OF CHAIN REACTIONS255

9.THE RATES OF CHAIN REACTIONS257

9.1.Introduction257

9.2.Stationary-state rates260

9.3.Inhibitors and induction periods261

9.4.Induction periods in branched-chain reactions264

9.5.Catalysis and inhibition of some chain reactions of chlorine266

9.5.1.Introduction266

9.5.2.Hydrogen and chlorine267

9.5.3.Carbon monoxide and chlorine273

9.5.4.Chlorination of hydrocarbons and their derivatives275

9.6.Catalysis and inhibition of(chain)thermal decompositions277

9.6.1.Introduction277

9.6.2.Inhibitors of decompositions279

9.6.3.Decomposition of organic peroxides,hydroperoxides and other chain initiators282

10.CATALYSIS,INITIATION AND INHIBITION OF POLYMERIZATION REACTIONS289

10.1.Introduction289

10.2.Free-radical polymerizations292

10.2.1.Introduction292

10.2.2.Homolytic initiators293

10.2.3.Redox initiators300

10.2.4.Inbibitors and retarders304

10.2.5.Auto-acceleration312

10.2.6.Emulsion polymerization315

10.3.Ionic polymerization316

10.4.Heterogeneous catalysis of polymerization320

11.CATALYSIS AND INHIBITION OF SOME CHAIN REACTIONS OF OXYOEN329

11.1.Introduction329

11.2.Low-temperature auto-oxidations335

11.3.Oxidation of gaseous hydrocarbons344

11.3.1.Methane344

11.3.2.Ethane,propane and butane348

11.3.3.Higher hydrocarbons350

11.4.Sensitized ignitions of hydrogen and oxygen354

Appendix Ⅰ:Derivation of adsorption isotherms for uniform surfaces363

Appendix Ⅱ:Derivation of adsorption isotherms for non-uniform surfaces366

SUBJECT INDEX369