DeutschesFachbuch.de : Concepts of Modern Catalysis and Kinetics Von I. Chorkendorff, J. W. Niemantsverdriet

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Contents
PrefaceXV
1 Introduction to Catalysis 1
1.1 What is Catalysis?2
1.2 Catalysts Can Be Atoms, Molecules, Enzymes and Solid Surfaces 4
1.2.1 Homogeneous Catalysis 4
1.2.2 Biocatalysis 5
1.2.3 Heterogeneous Catalysis 6
1.3 Why is Catalysis Important?8
1.3.1 Catalysis and Green Chemistry 8
1.3.2 Atom Efficiency, E Factors and Environmental Friendliness 9
1.3.3 The Chemical Industry 11
1.4 Catalysis as a Multidisciplinary Science 15
1.4.1 The Many Length Scales of a "Catalyst"15
1.4.2 Time Scales in Catalysis 17
1.5 The Scope of This Book 17
1.6 Catalysis in Journals 18
1.7 General References to Textbooks in Catalysis 21
2 Kinetics 23
2.1 Introduction 23
2.2 The Rate Equation and Power Rate Laws 25
2.3 Reactions and Thermodynamic Equilibrium 28
2.3.1 Example of Chemical Equilibrium: The Ammonia Synthesis 31
2.3.2 Chemical Equilibrium for a Non-ideal Gas 34
2.4 Temperature Dependence of the Rate 36
2.5 Integrated Rate Equations: Time Dependence of Concentrations in Reactions...
2.6 Coupled Reactions in Flow Reactors: The Steady-state Approximation 41
2.7 Coupled Reactions in Batch Reactors 46
2.8 Catalytic Reactions 48
2.8.1 The Mean-field Approximation 52
2.9 Langmuir Adsorption Isotherms 53
2.9.1 Associative Adsorption 53
2.9.2 Dissociative Adsorption 55
2.9.3 Competitive Adsorption 55
2.10 Reaction Mechanisms 56
2.10.1 Langmuir-Hinshelwood or Eley-Rideal Mechanisms 56
2.10.2 Langmuir-Hinshelwood Kinetics 57
2.10.3 The Complete Solution 58
2.10.4 The Steady State Approximation 59
2.10.5 The Quasi-equilibrium Approximation 59
2.10.6 Steps with Similar Rates 61
2.10.7 Irreversible Step Approximation 61
2.10.8 The MARI Approximation 62
2.10.9 Nearly Empty Surface 62
2.10.10 Reaction Order 63
2.10.11 Apparent Activation Energy 65
2.11 Entropy, Entropy Production, Auto Catalysis and Oscillating Reactions 69
2.12 Kinetics of Enzyme-catalyzed Reactions 73
3 Reaction Rate Theory 79
3.1 Introduction 79
3.2 The Boltzmann Distribution and the Partition Function 80
3.3 Partition Functions of Atoms and Molecules 83
3.3.1 The Boltzmann Distribution 84
3.3.1.1 Justification for Equating y 2 with 1/T 86
3.3.2 Maxwell-Boltzmann Distribution of Velocities 87
3.3.3 Total Partition Function of System 87
3.3.3.1 Translational Partition Function 88
3.3.3.2 Vibrational Partition Function 90
3.3.3.3 Rotational (and Nuclear) Partition Function 91
3.3.3.4 Electronic and Nuclear Partition Functions 92
3.4 Molecules in Equilibrium 93
3.5 Collision Theory 101
3.5.1 Rate of Surface Collisions 103
3.5.2 Reaction Probability 104
3.5.3 Fundamental Objection Against Collision Theory 106
3.6 Activation of Reacting Molecules by Collisions: The Lindemann Theory 107
3.7 Transition State Theory 108
3.7.1 Thermodynamic Form of the Rate Transition State Expression 110
3.8 Transition State Theory of Surface Reactions 113
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Index
Aab initio method 269
acidic site 369
acidity 202, 370
activation energy 2-4, 8, 36
ammonia synthesis 297
apparent 37, 38, 42, 64, 65, 68, 212, 214, 297
- desorption 279
active sites 7, 49
activity 29, 167
adsorbate 184
adsorbate site 173
adsorbent 184
adsorption 271
associative 53, 54
- competitive 55, 198
- direct 116
- dissociative 55
- indirect 114, 119
- molecular 119
- of atom 113
- precursor-mediated 119
adsorptive 184
aerosol 192
air pollution 381, 382
alcohol dehydrogenase 6 alkylation 372, 373
alloy catalyst 312, 313
alloy formation 181
ALPO 201, 203
alumina 193, 194
aluminophosphate 201
amino acid 74
ammonia slip 401
ammonia synthesis 31-35, 264, 267, 295-303, 331-339
adiabatic two-bed reactor 335
- by enzymes 332
- history 331
- process description 331, 332
- reactor 335
ammoxidation 376-378
Arrhenius equation 2, 36, 79, 206
- comparison with collision theory 105
Arrhenius plot 275, 291
- CO + NO reaction 394
- transport limitation 215
atmospheric chemistry 4 atom efficiency 9, 10
atomic force microscopy 164, 165
attrition 167, 184
Auger electron 134, 135
- nomenclature 136
Auger process 134
auto catalysis 69, 70
automotive exhaust
- composition 382
- converter 386
automotive exhaust catalysis 7, 66, 381-397
- CO + NO reaction 392
- mechanism 389
- NOx storage 395, 396
Bback donation 246
backscattering factor 141
band gap 234, 235
band narrowing 234
band structure 233, 234
bandwidth 234
basal planes 171
Belouzhov-Zabothinsky reaction 70
BET isotherm 185-190
bifunctional catalysis 368-372
bimetallic systems 181
binding energy 135
biomass 399
Bloch Theorem 233
blocking 341, 342
body-centered cubic 170
Boltzmann distribution 80, 81, 84, 229
bonding in molecules 221
boson 229
Bragg's law 131, 133
Bravais lattices 174
Br 0 nsted acid 202
Bronsted base 177, 178
Bronsted-Evans-Polany relation 266, 267, 285, 289, 338
broken-bond calculations 179
bulb experiment 275
Ccarbenium ion 368, 371, 373
carbonaceous deposit 358
carbon filaments 309, 310
carbon formation 309
carbonium ion 368
carbon support 195
Carnot efficiency 350
catalysis
- biocatalysis 4, 5
- heterogeneous 4, 6
- history 23, 24
- homogeneous 4, 5, 10
- journals 18-20
catalyst
- activity 207
characterization 129-166
- eggshell 198
- fluid catalytic cracking 367
- for hydrotreating 359
- fuel cell 347, 348
- fused 199
- optimum use 338
- preparation 196 ff
- requirements 167
- selective catalytic reduction 399
- shaping 195
- testing 204-215
catalytic cycle 2, 7, 48, 57, 123
- hydrodesulfurization 362
- selective catalytic reduction 402
catalytic partial oxidation 315
cetane number 365
chain reaction 44
chemical bonding 220
chemical engineering 17
chemical industry 8
- processes 11
- producers 13
- products 11
chemical potential 28, 29, 94
chemical shift 137
chemisorption 257
CO on metal 253-255, 260
- of atoms 249
- of molecules 253
- theory 237-261
- trends 249, 253
cohesive energy 179, 227, 237
coke 358, 366, 369
collision theory 79, 100-106, 115
- activation energy 105
combustion 397
compensation effect 282, 283
competitive adsorption 55, 198
competitive inhibition 78
conduction band 234, 235
coordination numbers 140
core level 227
Cossee-Arlman mechanism 380
crack-gas 315
crude oil 353, 354
crystal planes 170
CSTR 205
Dd-band shift model 255
deactivation 167
degrees of freedom 121
dehydrogenation 371
delocalized orbitals 227
density-functional theory 258, 268, 285
density of states 229
- in scanning tunneling microscopy 163
deposition precipitation 199
desorption 123, 125, 278-283
- preexponential factor 126
diatomic molecule 221, 222
diesel 354
diffusion limitation 295
dispersion 134, 139
- from XPS 138
dissociation 8, 223, 257
- heterolytic 178
- of NO 393
dissociative adsorption 55, 258, 259
d-orbitals 226
EE-factor 9, 10
effectiveness factor 211
efficiency factor 213
electric double layer 230
electric quadrupole splitting 148
electronegativity 137
electron mean free path 135
electron microscopy 143-147
electrostatic effects 246
elementary steps 286
- CO + NO reaction 393
Eley-Rideal mechanism 56
emission standards 382, 383
energy barrier 79, 105, 109
energy carriers 349, 352
energy-dispersive X-ray analysis 145
entropy 69, 84
entropy production 69
environmental
- catalysis 381-404
- catalyst 381
- friendliness 9
- impact 11
enzyme 4-6, 73-78, 315, 332
enzyme-catalyzed reaction 73-78
epichlorohydrine process 9 epoxidation 9, 374-376
equilibrium 94
equilibrium constant 3, 26, 29, 30
- dissociation 96-100
extended X-ray absorption fine structure 139-143
extrusion 196
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