"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)
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.
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.
Preface xxiList 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
9.2. Direction of the development of phase B during the growth 311
9.3. Modes and models for growth 312
9.4. Relationship between the motion velocities of the interfaces and the chemical growth rate 315
9.5. Methodology to model growth 318
9.6. Expressions of the space functions for the growth of a grain 320
Chapter 10. Transformation by Surface Nucleation and Growth 337
10.1. Nucleation, growth, and experimental rate 338
10.2. One-process model with instantaneous nucleation and slow growth 339
10.3. Two-process models: nucleation and growth 347
10.4. Two-process model with surface nucleation-radial anisotropic growth 351
10.5. Two-process model with surface nucleation and isotropic growth 361
10.6. Non-isobaric and/or non-isothermal kinetics 370
10.7. Powders with granular distributions 375
10.8. Return to the first and second kind of changes of laws 376
10.9. Conclusion 377
Chapter 11. Modeling and Experiments 379
11.1. The adequacy between the experimental conditions and modeling 379
11.2. Expressions of experimental speeds 381
11.3. Derivation of the kinetic curves 388
11.4. The experimental verification of the assumptions 388
11.5. Determination of the morphological model for growth 395
11.6. Calculations of the reactivity of growth and the specific frequency of nucleation 398
11.7. Variations of the kinetic properties with the intensive variables 399
11.8. Methodology of a study 402
Chapter 12. Granular Coalescence 407
12.1. Qualitative description of the model 408
12.2. Morphological modeling 409
12.3. Structure of the coalescence mechanism 413
12.4. Determination of the space functions 416
12.5. Rate constants and radius of curvature 420
12.6. Reactivity of coalescence of a solid with a single component 423
12.7. Extensions to the coalescence of solids with several components 436
12.8. Relations between experiments and modeling 443
12.9. Oswald ripening and reduction in porosity 448
Chapter 13. Decomposition Reactions of Solids 449
13.1. Classifications of decomposition reactions 450
13.2. Extent measurement with the change of the mass 451
13.3. Observed experimental results 456
13.4. Kinetics of growth in decomposition reactions of solids 462
13.5. Nucleation in decomposition reactions of solids 478
13.6. Total kinetic curves 484
13.7. Influence of the granular distribution 484
13.8. Normal and abnormal growth 486
Chapter 14. Reactions Between Solids 489
14.1. Classification of the reactions between solids 490
14.2. The modeling assumptions 492
14.3. The experimental measure of the extent of the reactions 493
14.4. Reactivities of reactions between solids 494
14.5. Rates of the reactions between powders 508
14.6. Conclusion 541
Chapter 15. Gas-Solid Reactions 543
15.1. Classification of gas-solid reactions 544
15.2. Pure metal gas reactions 546
15.3. Growth process in the reduction of metallic oxides by hydrogen 585
15.4. Growth process of oxidation of metals by water vapor 596
Chapter 16. Transformations of Solid Solutions 603
16.1. General information on transformations of solid solutions 603
16.2. Oxidation of metal alloys 606
16.3. Variations of the composition of a solid solution with gas formation 640
16.4. Superposition of a variation of stoichiometry and decomposition 648
Chapter 17. Modeling of Mechanisms 651
17.1. Non-stoichiometry of iron oxide 651
17.2. Stability of calcium carbonate 658
17.3. Thermodynamics of a solid-solid reactions 665
17.4. Hydrates of alumina 669
17.5. Point defects in a metal sulfide 679
17.6. Point defects of an alkaline bromide 689
17.7. Diffusion of a metal into another metal 694
17.8. Generation of atmospheres with very low pressures 701
Chapter 18. Mechanisms and Kinetic Laws 709
18.1 Coalescence of anatase grains 709
18.2. Reaction of a cubic sample 713
18.3. Anisotropic growth 723
18.4. Gas-solid reaction with one-process model 732
18.5. The direction of the development of a layer 738
18.6. Mampel modeling by way of the point of inflection 747
18.7. Nucleation in a reaction of dehydration 753
18.8. Influence of particle size in nucleation-growth approach 759
18.9. Decomposition with slow nucleation and slow anisotropic growth determined by diffusion 767
19. Mechanisms and Reactivity 779
19.1. Competition oxidation – volatilization by TGA 779
19.2. Controlled rate thermal analysis (CRTA) 783
19.3. Sulfurization of a metal 789
19.4. Oxidation of a metal and some of its alloys 794
19.5. Reduction of octo-oxide of triuranium by dihydrogen 804
19.6. Dehydration of kaolinite 813
19.7. Decomposition of a carbonate of a metal 823
19.8. Reaction between two solids 837
Appendix 1 845
Appendix 2 847
Appendix 3 849
Appendix 4 853
Appendix 5 861
Appendix 6 867
Appendix 7 873
Appendix 8 875
Appendix 9 881
Appendix 10 899
Appendix 11 911
Bibliography 913
Index 919