Handbook of Heterogenous Kinetics

This book presents all the theoretical and practical basements of heterogeneous kinetics and reactivity of solids. It applies the new concepts of reactivity and spatial function, introduced by the author, for both nucleation and growth processes, with a unified presentation of the reactivity of bulk and powder solids, including gas-solid reactions, thermal decompositions, solid-solid reactions, reactions of solid solutions, and coalescence of solid grains. It also contains many exercises and problems with solutions included, allowing readers to understand and use all the concepts and methods discussed therein.

Auteur

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.

Contenu

Preface xxi

List of Symbols xxv

Chapter 1. Definitions and Experimental Approach 1

1.1. Thermal transformations of solids 1

1.2. Classification of transformations 2

1.3. Speed and rate of reaction 6

1.4. Reaction zones of a transformation 10

1.5. Chemical characterizations 12

1.6. Structural characterizations of the solids 13

1.7. Textural characterizations of the solids 14

1.8. Characterization of the evolution of the systems 17

1.9. Influence of various variables on speed 26

Chapter 2. The Real Solid: Structure Elements and Quasi-Chemical Reactions 29

2.1. Structure elements of a solid 30

2.2. Structure elements of a stoichiometric binary solid 35

2.3. Structure elements of a non-stoichiometric binary solid 36

2.4. Extension to non-binary compounds 44

2.5. Quasi-chemical reactions 46

2.6. Introduction of foreign elements into a solid 53

Chapter 3. Thermodynamics of Heterogenous Systems 59

3.1. Introduction: aims of thermodynamics 59

3.2. General survey of thermodynamics of equilibrium 60

3.3. Phenomena leading to solid-gas equilibriums 69

3.4. Thermodynamic approach of solid-gas systems 71

3.5. Thermodynamics of systems containing solid phases only 76

3.6. Specific study of quasi-chemical equilibriums 77

3.7. Thermodynamics of systems: water vapor-hydrated salts 85

3.8. Sequence of transformations, juxtaposition of stability area 93

3.9. Equilibrium of the formation of a solid from a solution 96

3.10. Variations in the equilibrium conditions with sizes of solid phases 100

Chapter 4. Elementary Steps in Heterogenous Reactions 105

4.1. Nature of elementary steps 107

4.2. Elementary reactions at solid-solid interfaces 114

4.3. Elementary reactions at gas-solid interfaces 122

4.4. The apparent energies of activation of interface reactions 130

4.5. The areal speed of an interface reaction 130

Chapter 5. Chemical Diffusion 131

5.1. Introduction: nature of diffusing particles in a solid 131

5.2. Flux of diffusion and velocity of diffusing particles 135

5.3. The laws of Fick136

5.4. Steady state obstructed diffusion 150

5.5. Diffusion under electric field 153

5.6. Diffusion in two mediums separated by a mobile interface 161

Chapter 6. Chemical Adsorption169

6.1. Definitions: physical adsorption and chemical adsorption 169

6.2. Adsorption thermodynamics and chemisorption equilibrium 170

6.3. Kinetics of chemisorption 178

6.4. Chemisorption and structure elements 181

Chapter 7. Mechanisms and Kinetics of a Process 195

7.1. Speeds and reactivities of reactions taking place in only a single zone 195

7.2. Transformations with several zones 201

7.3. Linear reaction mechanisms 210

7.4. Linear mechanisms in pseudo-steady state modes 213

7.5. Pure modes or modes with a rate-determining step 220

7.6. Mixed modes 234

7.7. Generalization, rate of a linear mechanism in pseudo-steady state mode 241

7.8. Mixed non-pseudo-steady state modes 242

7.9. Equivalent reaction of a linear subset in local pseudo-steady state mode 245

7.10. Reactions with separable rates 248

7.11. Influence of intensive variables on the kinetic laws 250

7.12. Distance from equilibrium for a reaction 252

7.13. Processes concerned in a heterogenous reaction 255

Chapter 8. Nucleation of a New Solid Phase 257

8.1. Clusters 258

8.2. Examples of nucleation diagram 258

8.3. Interfacial energy 260

8.4. Formation molar Gibbs energy of clusters 272

8.5. Kinetics of nucleation 285

Chapter 9. Growth of a Solid Phase 309 9.1. Description of the zones of growth 309&l...