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An Introduction to Chemical Kinetics

ISBN: 978-1-84821-302-9
480 pages
July 2011, Wiley-ISTE
An Introduction to Chemical Kinetics (1848213026) cover image
This book is a progressive presentation of kinetics of the chemical reactions. It provides complete coverage of the domain of chemical kinetics, which is necessary for the various future users in the fields of Chemistry, Physical Chemistry, Materials Science, Chemical Engineering, Macromolecular Chemistry and Combustion. It will help them to understand the most sophisticated knowledge of their future job area.
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 non-steady-state processes of combustion and explosion are treated in the final chapter.
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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 Quasi-steady State Modes 135

7.1. Pseudo-steady state mode 135

7.2. Pseudo-steady state sequences with constant volume (or surface) – quasi-steady state 147

7.3. Pseudo- and quasi-steady state of diffusion 150

7.4. Application to the calculation of speeds in pseudo-steady state or quasi-steady state 151

7.5. Pseudo-steady state and open or closed systems 159

7.6. Conclusion 162

7.7. Important figure in pseudo-steady state 163

Chapter 8. Modes with Rate-determining Steps 165

8.1. Mode with one determining step 166

8.2. Pseudo-steady 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 rate-determining 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 non-branch 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. Physico-chemical growth models 384

14.7. Conclusion on heterogeneous reactions 386

14.8. Important figures in reaction kinetics 387

Chapter 15. Kinetics of Non-pseudo-steady State Modes 389

15.1. Partial pseudo-steady 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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