Introduction to Chemical Kinetics

Michel Soustelle is a chemical engineer and Emeritus Professor at Ecole des Mines de Saint-Etienne in France. He taught chemical kinetics from postgraduate to Master's levels while also carrying out research in this topic.

• Preface xviiPART 1. BASIC CONCEPTS OF CHEMICAL KINETICS 1Chapter 1. Chemical Reaction and Kinetic Quantities 31.1. The chemical reaction 31.2. Homogeneous and heterogeneous reactions 81.3. Extent and speed of a reaction 91.4. Volumetric and areal speed of a monozone reaction 121.5. Fractional extent and rate of a reaction 141.6. Reaction speeds and concentrations 181.7. Expression of volumetric speed according to variations in concentration in a closed system 191.8. Stoichiometric mixtures and progress 201.9. Factors influencing reaction speeds 21Chapter 2. Reaction Mechanisms and Elementary Steps 252.1. Basic premise of kinetics 252.2. Reaction mechanism 262.3. Reaction intermediates 292.4. Reaction sequences and Semenov representation 322.5. Chain reactions 342.6. Catalytic reactions 372.7. Important figures in reaction mechanisms 41Chapter 3. Kinetic Properties of Elementary Reactions 433.1. Space function of an elementary reaction 433.2. Reactivity and rate of an elementary step 443.3. Kinetic constants of an elementary step 453.4. Opposite elementary reactions 473.5. Influence of temperature on the reactivities of elementary steps 493.6. Modeling of a gas phase elementary step 513.7. A particular elementary step: diffusion 583.8. Gases adsorption onto solids 643.9. Important figures in the kinetic properties of elementary reactions 71Chapter 4. Kinetic Data Acquisition 734.1. Experimental kinetic data of a reaction 734.2. Generalities on measuring methods 744.3. Chemical methods 744.4. Physical methods 754.5. Researching the influence of various variables 87Chapter 5. Experimental Laws and Calculation of Kinetic Laws of Homogeneous Systems 915.1. Experimental laws in homogeneous kinetics 915.2. Relationship between the speed of a reaction and the speeds of its elementary steps 955.3. Mathematical formulation of speed from a mechanism and experimental conditions 965.4. Mathematical formulation of a homogeneous reaction with open sequence 995.5. Mathematical formulation of chain reactions 101Chapter 6. Experimental Data and Calculation of Kinetic Laws of Heterogeneous Reactions 1096.1. Heterogeneous reactions 1096.2. Experimental kinetic data of heterogeneous reactions 1126.3. Involvement of diffusion in matter balances 1196.4. Example of mathematical formulation of a heterogeneous catalytic reaction 1246.5. Example of the mathematical formulation of an evolution process of a phase 127Chapter 7. Pseudo- and Quasi-steady State Modes 1357.1. Pseudo-steady state mode 1357.2. Pseudo-steady state sequences with constant volume (or surface) – quasi-steady state 1477.3. Pseudo- and quasi-steady state of diffusion 1507.4. Application to the calculation of speeds in pseudo-steady state or quasi-steady state 1517.5. Pseudo-steady state and open or closed systems 1597.6. Conclusion 1627.7. Important figure in pseudo-steady state 163Chapter 8. Modes with Rate-determining Steps 1658.1. Mode with one determining step 1668.2. Pseudo-steady state mode with two determining steps 1858.3. Generalization to more than two determining steps 1898.4. Conclusion to the study of modes with one or several rate-determining steps 1908.5. First order mode changes 1908.6. Conclusion 191PART 2. REACTION MECHANISMS AND KINETIC PROPERTIES 193Chapter 9. Establishment and Resolution of a Reaction Mechanism 1959.1. Families of reaction mechanisms 1959.2. Different categories of elementary steps 1969.3. Establishment of a reaction mechanism 2019.4. Research into a mechanism: intermediary reactions 2059.5. Back to the modes and laws of kinetics 2109.6. Experimental tests 2129.7. Looking for the type of rate law 218Chapter 10. Theory of the Activated Complex in the Gas Phase 22310.1. The notion of molecular energy: the energy of a group of atoms 22310.2. Bimolecular reactions in the gas phase 22710.3. Monomolecular reactions in the gas phase 24310.4. Photochemical elementary reactions 24810.5. The theory of activated complexes 252Chapter 11. Modeling Elementary Reactions in Condensed Phase 25311.1. Elementary reaction in the liquid phase 25311.2. Elementary reaction in the solid state 26811.3. Interphase reactions 27611.4. Electrochemical reactions 28011.5. Conclusion 290Chapter 12. The Kinetics of Chain Reactions 29112.1. Definition of a chain reaction 29112.2. The kinetic characteristics of chain reactions 29212.3. Classification of chain reactions 29312.4. Chain reaction sequences 29512.5. Kinetic study of straight chain or non-branch chain reactions 29912.6. Kinetic study of chain reactions with direct branching 31112.7. Semenov and the kinetics of chain reactions 321Chapter 13. Catalysis and Catalyzed Reactions 32313.1. Homogenous catalysis 32413.2. Heterogeneous catalysis reactions 33513.3. Gas–solid reactions leading to a gas 35113.4. Conclusion on catalysis 35213.5. Langmiur and Hinshelwood 352Chapter 14. Kinetics of Heterogeneous Stoichiometric Reactions 35314.1. Extent versus time and rate versus extent curves 35414.2. The global model with two processes 35514.3. The ?ÖE law 35614.4. Morphological modeling of the growing space function 35714.5. The nucleation process 37314.6. Physico-chemical growth models 38414.7. Conclusion on heterogeneous reactions 38614.8. Important figures in reaction kinetics 387Chapter 15. Kinetics of Non-pseudo-steady State Modes 38915.1. Partial pseudo-steady state modes 38915.2. The paralinear law of metal oxidation 39215.3. Thermal runaway and ignition of reactions 39515.4. Chemical ignition of gaseous mixtures 397APPENDICES 405Appendix 1. Point Defects and Structure Elements of Solids 407Appendix 2. Notions of Microscopic Thermodynamics 413Appendix 3. Vibration Frequency of the Activated Complex 425Notations and Symbols 431Bibliography 439Index 441