An introduction to chemical kinetics

 Content: 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   OE 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