Handbook of Heterogenous 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 degree level while also carrying out research in this topic.

• Preface xxiList of Symbols xxvChapter 1. Definitions and Experimental Approach 11.1. Thermal transformations of solids 11.2. Classification of transformations 21.3. Speed and rate of reaction 61.4. Reaction zones of a transformation 101.5. Chemical characterizations 121.6. Structural characterizations of the solids 131.7. Textural characterizations of the solids 141.8. Characterization of the evolution of the systems 171.9. Influence of various variables on speed 26Chapter 2. The Real Solid: Structure Elements and Quasi-Chemical Reactions 292.1. Structure elements of a solid 302.2. Structure elements of a stoichiometric binary solid 352.3. Structure elements of a non-stoichiometric binary solid 362.4. Extension to non-binary compounds 442.5. Quasi-chemical reactions 462.6. Introduction of foreign elements into a solid 53Chapter 3. Thermodynamics of Heterogenous Systems 593.1. Introduction: aims of thermodynamics 593.2. General survey of thermodynamics of equilibrium 603.3. Phenomena leading to solid-gas equilibriums 693.4. Thermodynamic approach of solid-gas systems 713.5. Thermodynamics of systems containing solid phases only 763.6. Specific study of quasi-chemical equilibriums 773.7. Thermodynamics of systems: water vapor-hydrated salts 853.8. Sequence of transformations, juxtaposition of stability area 933.9. Equilibrium of the formation of a solid from a solution 963.10. Variations in the equilibrium conditions with sizes of solid phases 100Chapter 4. Elementary Steps in Heterogenous Reactions 1054.1. Nature of elementary steps 1074.2. Elementary reactions at solid-solid interfaces 1144.3. Elementary reactions at gas-solid interfaces 1224.4. The apparent energies of activation of interface reactions 1304.5. The areal speed of an interface reaction 130Chapter 5. Chemical Diffusion 1315.1. Introduction: nature of diffusing particles in a solid 1315.2. Flux of diffusion and velocity of diffusing particles 1355.3. The laws of Fick1365.4. Steady state obstructed diffusion 1505.5. Diffusion under electric field 1535.6. Diffusion in two mediums separated by a mobile interface 161Chapter 6. Chemical Adsorption1696.1. Definitions: physical adsorption and chemical adsorption 1696.2. Adsorption thermodynamics and chemisorption equilibrium 1706.3. Kinetics of chemisorption 1786.4. Chemisorption and structure elements 181Chapter 7. Mechanisms and Kinetics of a Process 1957.1. Speeds and reactivities of reactions taking place in only a single zone 1957.2. Transformations with several zones 2017.3. Linear reaction mechanisms 2107.4. Linear mechanisms in pseudo-steady state modes 2137.5. Pure modes or modes with a rate-determining step 2207.6. Mixed modes 2347.7. Generalization, rate of a linear mechanism in pseudo-steady state mode 2417.8. Mixed non-pseudo-steady state modes 2427.9. Equivalent reaction of a linear subset in local pseudo-steady state mode 2457.10. Reactions with separable rates 2487.11. Influence of intensive variables on the kinetic laws 2507.12. Distance from equilibrium for a reaction 2527.13. Processes concerned in a heterogenous reaction 255Chapter 8. Nucleation of a New Solid Phase 2578.1. Clusters 2588.2. Examples of nucleation diagram 2588.3. Interfacial energy 2608.4. Formation molar Gibbs energy of clusters 2728.5. Kinetics of nucleation 285Chapter 9. Growth of a Solid Phase 3099.1. Description of the zones of growth 3099.2. Direction of the development of phase B during the growth 3119.3. Modes and models for growth 3129.4. Relationship between the motion velocities of the interfaces and the chemical growth rate 3159.5. Methodology to model growth 3189.6. Expressions of the space functions for the growth of a grain 320Chapter 10. Transformation by Surface Nucleation and Growth 33710.1. Nucleation, growth, and experimental rate 33810.2. One-process model with instantaneous nucleation and slow growth 33910.3. Two-process models: nucleation and growth 34710.4. Two-process model with surface nucleation-radial anisotropic growth 35110.5. Two-process model with surface nucleation and isotropic growth 36110.6. Non-isobaric and/or non-isothermal kinetics 37010.7. Powders with granular distributions 37510.8. Return to the first and second kind of changes of laws 37610.9. Conclusion 377Chapter 11. Modeling and Experiments 37911.1. The adequacy between the experimental conditions and modeling 37911.2. Expressions of experimental speeds 38111.3. Derivation of the kinetic curves 38811.4. The experimental verification of the assumptions 38811.5. Determination of the morphological model for growth 39511.6. Calculations of the reactivity of growth and the specific frequency of nucleation 39811.7. Variations of the kinetic properties with the intensive variables 39911.8. Methodology of a study 402Chapter 12. Granular Coalescence 40712.1. Qualitative description of the model 40812.2. Morphological modeling 40912.3. Structure of the coalescence mechanism 41312.4. Determination of the space functions 41612.5. Rate constants and radius of curvature 42012.6. Reactivity of coalescence of a solid with a single component 42312.7. Extensions to the coalescence of solids with several components 43612.8. Relations between experiments and modeling 44312.9. Oswald ripening and reduction in porosity 448Chapter 13. Decomposition Reactions of Solids 44913.1. Classifications of decomposition reactions 45013.2. Extent measurement with the change of the mass 45113.3. Observed experimental results 45613.4. Kinetics of growth in decomposition reactions of solids 46213.5. Nucleation in decomposition reactions of solids 47813.6. Total kinetic curves 48413.7. Influence of the granular distribution 48413.8. Normal and abnormal growth 486Chapter 14. Reactions Between Solids 48914.1. Classification of the reactions between solids 49014.2. The modeling assumptions 49214.3. The experimental measure of the extent of the reactions 49314.4. Reactivities of reactions between solids 49414.5. Rates of the reactions between powders 50814.6. Conclusion 541Chapter 15. Gas-Solid Reactions 54315.1. Classification of gas-solid reactions 54415.2. Pure metal gas reactions 54615.3. Growth process in the reduction of metallic oxides by hydrogen 58515.4. Growth process of oxidation of metals by water vapor 596Chapter 16. Transformations of Solid Solutions 60316.1. General information on transformations of solid solutions 60316.2. Oxidation of metal alloys 60616.3. Variations of the composition of a solid solution with gas formation 64016.4. Superposition of a variation of stoichiometry and decomposition 648Chapter 17. Modeling of Mechanisms 65117.1. Non-stoichiometry of iron oxide 65117.2. Stability of calcium carbonate 65817.3. Thermodynamics of a solid-solid reactions 66517.4. Hydrates of alumina 66917.5. Point defects in a metal sulfide 67917.6. Point defects of an alkaline bromide 68917.7. Diffusion of a metal into another metal 69417.8. Generation of atmospheres with very low pressures 701Chapter 18. Mechanisms and Kinetic Laws 709 18.1 Coalescence of anatase grains 70918.2. Reaction of a cubic sample 71318.3. Anisotropic growth 72318.4. Gas-solid reaction with one-process model 73218.5. The direction of the development of a layer 73818.6. Mampel modeling by way of the point of inflection 74718.7. Nucleation in a reaction of dehydration 75318.8. Influence of particle size in nucleation-growth approach 75918.9. Decomposition with slow nucleation and slow anisotropic growth determined by diffusion 76719. Mechanisms and Reactivity 77919.1. Competition oxidation – volatilization by TGA 77919.2. Controlled rate thermal analysis (CRTA) 78319.3. Sulfurization of a metal 78919.4. Oxidation of a metal and some of its alloys 79419.5. Reduction of octo-oxide of triuranium by dihydrogen 80419.6. Dehydration of kaolinite 81319.7. Decomposition of a carbonate of a metal 82319.8. Reaction between two solids 837Appendix 1 845Appendix 2 847Appendix 3 849Appendix 4 853Appendix 5 861Appendix 6 867Appendix 7 873Appendix 8 875Appendix 9 881Appendix 10 899Appendix 11 911Bibliography 913Index 919

"Soustelle (emeritus, heterogenous kinetics, Ecole Nationale Supérieure des Mines, France) offers an extensive overview of the theoretical and experimental basis of heterogenous kinetics and its application to the study of solids reactivity. The field integrates physical, theoretical, and computational elements of chemistry and materials science. The book's contents are based on courses given for undergraduates and master's students in chemical engineering." (Book News, September 2010)