An Introduction to Chemical KineticsISBN: 9781848213029
480 pages
July 2011, WileyISTE

Over 15 chapters, this book present the fundamentals of chemical kinetics, its relations with reaction mechanisms and kinetic properties. Two chapters are then devoted to experimental results and how to calculate the kinetic laws in both homogeneous and heterogeneous systems. The following two chapters describe the main approximation modes to calculate these laws. Three chapters are devoted to elementary steps with the various classes, the principles used to write them and their modeling using the theory of the activated complex in gas and condensed phases. Three chapters are devoted to the particular areas of chemical reactions, chain reactions, catalysis and the stoichiometric heterogeneous reactions. Finally the nonsteadystate processes of combustion and explosion are treated in the final chapter.
Preface xvii
PART 1. BASIC CONCEPTS OF CHEMICAL KINETICS 1
Chapter 1. Chemical Reaction and Kinetic Quantities 3
1.1. The chemical reaction 3
1.2. Homogeneous and heterogeneous reactions 8
1.3. Extent and speed of a reaction 9
1.4. Volumetric and areal speed of a monozone reaction 12
1.5. Fractional extent and rate of a reaction 14
1.6. Reaction speeds and concentrations 18
1.7. Expression of volumetric speed according to variations in concentration in a closed system 19
1.8. Stoichiometric mixtures and progress 20
1.9. Factors influencing reaction speeds 21
Chapter 2. Reaction Mechanisms and Elementary Steps 25
2.1. Basic premise of kinetics 25
2.2. Reaction mechanism 26
2.3. Reaction intermediates 29
2.4. Reaction sequences and Semenov representation 32
2.5. Chain reactions 34
2.6. Catalytic reactions 37
2.7. Important figures in reaction mechanisms 41
Chapter 3. Kinetic Properties of Elementary Reactions 43
3.1. Space function of an elementary reaction 43
3.2. Reactivity and rate of an elementary step 44
3.3. Kinetic constants of an elementary step 45
3.4. Opposite elementary reactions 47
3.5. Influence of temperature on the reactivities of elementary steps 49
3.6. Modeling of a gas phase elementary step 51
3.7. A particular elementary step: diffusion 58
3.8. Gases adsorption onto solids 64
3.9. Important figures in the kinetic properties of elementary reactions 71
Chapter 4. Kinetic Data Acquisition 73
4.1. Experimental kinetic data of a reaction 73
4.2. Generalities on measuring methods 74
4.3. Chemical methods 74
4.4. Physical methods 75
4.5. Researching the influence of various variables 87
Chapter 5. Experimental Laws and Calculation of Kinetic Laws of Homogeneous Systems 91
5.1. Experimental laws in homogeneous kinetics 91
5.2. Relationship between the speed of a reaction and the speeds of its elementary steps 95
5.3. Mathematical formulation of speed from a mechanism and experimental conditions 96
5.4. Mathematical formulation of a homogeneous reaction with open sequence 99
5.5. Mathematical formulation of chain reactions 101
Chapter 6. Experimental Data and Calculation of Kinetic Laws of Heterogeneous Reactions 109
6.1. Heterogeneous reactions 109
6.2. Experimental kinetic data of heterogeneous reactions 112
6.3. Involvement of diffusion in matter balances 119
6.4. Example of mathematical formulation of a heterogeneous catalytic reaction 124
6.5. Example of the mathematical formulation of an evolution process of a phase 127
Chapter 7. Pseudo and Quasisteady State Modes 135
7.1. Pseudosteady state mode 135
7.2. Pseudosteady state sequences with constant volume (or surface) – quasisteady state 147
7.3. Pseudo and quasisteady state of diffusion 150
7.4. Application to the calculation of speeds in pseudosteady state or quasisteady state 151
7.5. Pseudosteady state and open or closed systems 159
7.6. Conclusion 162
7.7. Important figure in pseudosteady state 163
Chapter 8. Modes with Ratedetermining Steps 165
8.1. Mode with one determining step 166
8.2. Pseudosteady state mode with two determining steps 185
8.3. Generalization to more than two determining steps 189
8.4. Conclusion to the study of modes with one or several ratedetermining steps 190
8.5. First order mode changes 190
8.6. Conclusion 191
PART 2. REACTION MECHANISMS AND KINETIC PROPERTIES 193
Chapter 9. Establishment and Resolution of a Reaction Mechanism 195
9.1. Families of reaction mechanisms 195
9.2. Different categories of elementary steps 196
9.3. Establishment of a reaction mechanism 201
9.4. Research into a mechanism: intermediary reactions 205
9.5. Back to the modes and laws of kinetics 210
9.6. Experimental tests 212
9.7. Looking for the type of rate law 218
Chapter 10. Theory of the Activated Complex in the Gas Phase 223
10.1. The notion of molecular energy: the energy of a group of atoms 223
10.2. Bimolecular reactions in the gas phase 227
10.3. Monomolecular reactions in the gas phase 243
10.4. Photochemical elementary reactions 248
10.5. The theory of activated complexes 252
Chapter 11. Modeling Elementary Reactions in Condensed Phase 253
11.1. Elementary reaction in the liquid phase 253
11.2. Elementary reaction in the solid state 268
11.3. Interphase reactions 276
11.4. Electrochemical reactions 280
11.5. Conclusion 290
Chapter 12. The Kinetics of Chain Reactions 291
12.1. Definition of a chain reaction 291
12.2. The kinetic characteristics of chain reactions 292
12.3. Classification of chain reactions 293
12.4. Chain reaction sequences 295
12.5. Kinetic study of straight chain or nonbranch chain reactions 299
12.6. Kinetic study of chain reactions with direct branching 311
12.7. Semenov and the kinetics of chain reactions 321
Chapter 13. Catalysis and Catalyzed Reactions 323
13.1. Homogenous catalysis 324
13.2. Heterogeneous catalysis reactions 335
13.3. Gas–solid reactions leading to a gas 351
13.4. Conclusion on catalysis 352
13.5. Langmiur and Hinshelwood 352
Chapter 14. Kinetics of Heterogeneous Stoichiometric Reactions 353
14.1. Extent versus time and rate versus extent curves 354
14.2. The global model with two processes 355
14.3. The ÖE law 356
14.4. Morphological modeling of the growing space function 357
14.5. The nucleation process 373
14.6. Physicochemical growth models 384
14.7. Conclusion on heterogeneous reactions 386
14.8. Important figures in reaction kinetics 387
Chapter 15. Kinetics of Nonpseudosteady State Modes 389
15.1. Partial pseudosteady state modes 389
15.2. The paralinear law of metal oxidation 392
15.3. Thermal runaway and ignition of reactions 395
15.4. Chemical ignition of gaseous mixtures 397
APPENDICES 405
Appendix 1. Point Defects and Structure Elements of Solids 407
Appendix 2. Notions of Microscopic Thermodynamics 413
Appendix 3. Vibration Frequency of the Activated Complex 425
Notations and Symbols 431
Bibliography 439
Index 441
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