CHAPTER 1. METALS AND ALLOYS
1.1 The Metallic State ......................................... 2
1.2 The Metallic Surface ...................................... 14
1.3 Alloys .................................................... 24
References ..................................................... 31
CHAPTER 2. SMALL METAL PARTICLES AND SUPPORTED METAL CATALYSTS
2.1 Introduction .............................................. 36
2.2 Preparation of Unsupported Metal Particles ................ 39
2.3 Supported Metal Catalysts ................................. 40
2.4 Measurement of the Size and Shape of Small Metal
Particles ................................................. 47
2.5 Properties of Small Metal Particles ....................... 60
2.6 Metal-Support Interactions ................................ 69
2.7 Promoters and Selective Poisons ........................... 75
2.8 Sintering and Redispersion ................................ 77
References ..................................................... 78
CHAPTER 3. CHEMISORPTION AND REACTIONS OF HYDROGEN
3.1 The Interaction of Hydrogen with Metals ................... 94
3.2 Chemisorption of Hydrogen on Unsupported Metals and
Alloys .................................................... 97
3.3 Chemisorption of Hydrogen on Supported Metals ............ 114
3.4 Reactions of Hydrogen .................................... 140
References .................................................... 142
CHAPTER 4. THE CHEMISORPTION OF HYDROCARBONS
4.1. Introduction ............................................. 154
4.2 The Chemisorption of Hydrocarbons: An Overview ........... 156
4.3 The Techniques ........................................... 158
4.4 Identification of Adsorbed Hydrocarbon Species ........... 161
4.5 Structures and Properties of Chemisorbed Hydrocarbons .... 176
4.6 Thermal Decomposition of Chemisorbed Hydrocarbons ........ 186
4.7 Theoretical Approaches ................................... 190
4.8 Chemisorption of Alkanes ................................. 196
4.9 The Final Stage: Carbonaceous Deposits ................... 197
References .................................................... 198
CHAPTER 5. INTRODUCTION TO THE CATALYSIS OF HYDROCARBON
REACTIONS
5.1 The Essential Nature of Catalysis ........................ 210
5.2 The Formulation of Kinetic Expressions ................... 214
5.3 The Concept of Reaction Mechanism ........................ 227
5.4 The Idea of the Active Centre ............................ 229
5.5 The Use of Bimetallic Catalysts .......................... 234
5.6 The Phenomenon of 'Compensation' ......................... 239
5.7 The Temkin Equation: Assumptions and Implications ........ 246
5.8 Techniques ............................................... 247
References .................................................... 251
CHAPTER 6. EXCHANGE OF ALKANES WITH DEUTERIUM
6.1 Introduction ............................................. 257
6.2 Equilibration of Linear and Branched Alkanes with
Deuterium ................................................ 260
6.3 Equilibration of Cycloalkanes with Deuterium ............. 275
6.4 Interalkane Exchange ..................................... 285
6.5 Conclusions .............................................. 285
References .................................................... 287
CHAPTER 7. HYDROGENATION OF ALKENES AND RELATED PROCESSES
7.1 Introduction ............................................. 292
7.2 Hydrogenation of Ethene and Propene ...................... 297
7.3 Reactions of the Butenes with Hydrogen and with
Deuterium ................................................ 328
7.4 Reactions of Higher Alkenes with Hydrogen and with
Deuterium ................................................ 336
7.5 Hydrogenation of Cycloalkenes ............................ 338
References .................................................... 348
CHAPTER 8. HYDROGENATION OF ALKADIENES AND POLY-ENES
8.1 Introduction ............................................. 357
8.2 Hydrogenation of 1, 2-Alkadienes (Allenes) ............... 360
8.3 Hydrogenation of 1,3-Butadiene ........................... 365
8.4 Hydrogenation of Higher Alkadienes ....................... 382
References .................................................... 390
CHAPTER 9. HYDROGENATION OF ALKYNES
9.1 Introduction ............................................. 395
9.2 Hydrogenation of Ethyne: 1, In Static Systems ............ 400
9.3 Hydrogenation of Ethyne: 2, in Dynamic System with
Added Ethene ............................................. 411
9.4 Use of Bimetallic Catalysts for Ethyne Hydrogenation ..... 418
9.5 Hydrogenation of Higher Alkynes .......................... 421
9.6 Conclusion ............................................... 430
References .................................................... 431
CHAPTER 10. HYDROGENATION OF THE AROMATIC RING
10.1 Introduction ............................................ 438
10.2 Kinetics and Mechanism of Aromatic Ring Hydrogenation ... 440
10.3 Hydrogenation of Alkyl-Substituted Benzenes ............. 458
10.4 Hydrogenation of Multiple Aromatic Ring Systems ......... 461
References .................................................... 468
CHAPTER 11. HYDROGENATION OF SMALL ALICYCLIC RINGS
11.1 Introduction ............................................ 473
11.2 Hydrogenation and Hydrogenolysis of Cyclopropane ........ 477
11.3 Hydrogenation of Alkylcyclopropanes ..................... 484
11.4 Hydrogenation of Cyclopropanes Having Other
Unsaturated Groups ...................................... 491
11.5 Hydrogenation of Alkylcyclobutanes and Related
Molecules ............................................... 494
References .................................................... 499
CHAPTER 12. DEHYDROGENATION OF ALKANES
12.1 Introduction ............................................ 501
12.2 Dehydrogenation of Acyclic Alkanes ...................... 504
12.3 Dehydrogenation of Cycloalkanes ......................... 509
12.4 The Chemisorption of Hydrogen on Platinum ............... 514
12.5 The Formation, Structure, and Function of Carbonaceous
Deposits ................................................ 516
12.6 The Homologation of Methane ............................. 519
References .................................................... 520
CHAPTER 13. REACTIONS OF THE LOWER ALKANES WITH HYDROGEN
13.1. Introduction ............................................ 526
13.2 Hydrogenolysis of the Lower Alkanes on Single Metal
Catalysts: Rates, Kinetics, and Mechanisms .............. 531
13.3 Structure-Sensitivity of Rates of Alkane
Hydrogenolysis .......................................... 552
13.4 Selectivity of Product Formation in Alkane
Hydrogenolysis .......................................... 555
13.5 Mechanisms Based on Product Selectivities ............... 562
13.6 Hydrogenolysis of Alkanes on Ruthenium Catalysts ........ 565
13.7 Effects of Additives and the Strong Metal-Support
Interaction on Alkane Hydrogenolysis .................... 569
13.8 Hydrogenolysis of Alkanes on Bimetallic Catalysts ....... 574
13.9 Apologia ................................................ 583
References .................................................... 583
CHAPTER 14. REACTIONS OF HIGHER ALKANES WITH HYDROGEN
14.1 Introduction: Petroleum Reforming and Reactions of
Higher Alkanes with Hydrogen ............................ 592
14.2 Reactions of Higher Alkanes with Hydrogen: Rates and
Product Selectivities ................................... 599
14.3 Mechanisms of Alkane Transformations .................... 624
14.4 Structure-Sensitivity ................................... 629
14.5 Modification of the Active Centre ....................... 634
References .................................................... 647
INDEX ......................................................... 657
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