Heterogeneous Kinematics Handbook

Name: Heterogeneous Kinematics Handbook
Brand: Wiley-ISTE
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Michel Soustelle(Autor*in)

Wiley-ISTE (Verlag)

Erschienen am 4. März 2013

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Cover
Handbook of Heterogenous Kinetics
Title Page
Copyright Page
Table of Contents
Preface
List of Symbols
Chapter 1. Definitions and Experimental Approach
1.1. Thermal transformations of solids
1.2. Classification of transformations
1.2.1. Transformation without formation of a new solid phase
1.2.2. Transformation with formation of a new solid phase
1.3. Speed and rate of reaction
1.3.1. Speed of reaction
1.3.2. Fractional extent and rate of a reaction
1.3.3. Volumes of the phases and coefficient of expansion of the reaction
1.4. Reaction zones of a transformation
1.4.1. Definition
1.4.2. Classification
1.4.3. Sizes of a reaction zone
1.5. Chemical characterizations
1.5.1. Analyses of the gas phases
1.5.2. Elementary analyses of the solids
1.6. Structural characterizations of the solids
1.7. Textural characterizations of the solids
1.7.1. The marker method
1.7.2. The cavity method
1.8. Characterization of the evolution of the systems
1.8.1. Curves of evolution: definitions
1.8.2. Curves of evolution: experimental obtaining
1.8.3. Curves of evolution: obtained laws
1.9. Influence of various variables on speed
1.9.1. Influence of temperature
1.9.2. Influence of partial pressures of gases
1.9.3. Influence of the shapes and sizes of solid particles
Chapter 2. The Real Solid: Structure Elements and Quasi-Chemical Reactions
2.1. Structure elements of a solid
2.1.1. Definition of a structure element
2.1.2. Binary solids
2.1.3. Symbolic notation of structure elements
2.1.4. Building unit of a solid
2.1.5. Description and composition of a solid
2.2. Structure elements of a stoichiometric binary solid
2.2.1. Schottky disorder
2.2.2. Frenkel disorder
2.2.3. Antistructure disorder
2.2.4. S.A. disorder
2.3. Structure elements of a non-stoichiometric binary solid
2.3.1. Distance from stoichiometry and structure element
2.3.2. The approximation of Wagner of the prevalent defect for ionic solids
2.3.3. More complex binary compounds
2.4. Extension to non-binary compounds
2.4.1. The pseudo-binary approximation
2.4.2. Generalization of the approximation of the prevalent defect
2.5. Quasi-chemical reactions
2.5.1. Definition and characteristics of quasi-chemical reactions
2.5.2. Homogenous quasi-chemical reactions in the solid
2.5.3. The interphase reactions
2.5.4. Reactions of solid destruction
2.6. Introduction of foreign elements into a solid
2.6.1. Concepts of impurity and doping agent
2.6.2. The controlled atomic imperfection in stoichiometric solids
2.6.3. The controlled electronic imperfection in non-stoichiometric solids
2.6.4. Concept of induced valence
Chapter 3. Thermodynamics of Heterogenous Systems
3.1. Introduction: aims of thermodynamics
3.2. General survey of thermodynamics of equilibrium
3.2.1. Chemical potential of a component in a phase
3.2.2. Variance of a system at equilibrium
3.2.3. Associated extensive properties of a transformation, partial molar properties
3.2.4. Chemical potential of an ion or a structure element
3.2.5. Feasibility of chemical reactions: De Donder inequality
3.2.6. Law of mass action for equilibriums
3.3. Phenomena leading to solid-gas equilibriums
3.3.1. Systems with variance p - 1
3.3.2. Systems with variance p
3.3.3. Systems with variance p + 1
3.4. Thermodynamic approach of solid-gas systems
3.4.1. Univariant systems
3.4.2. Divariant systems
3.4.3. Trivariant systems
3.5. Thermodynamics of systems containing solid phases only
3.5.1. Non-variant systems
3.5.2. Univariant systems
3.6. Specific study of quasi-chemical equilibriums
3.6.1. Equilibrium between an oxide and oxygen: the Wagner prevalent defect approximation
3.6.2. General equilibrium of an oxide with oxygen in the Brouwer approximation of majority defects
3.6.3. Doping a solid with foreign elements: quantitative aspect
3.7. Thermodynamics of systems: water vapor-hydrated salts
3.7.1. Experimental approach of equilibriums between water vapor and hydrated salts
3.7.2. Study of the equilibriums with variance 1
3.7.3. Study of hydrates with variance 2
3.8. Sequence of transformations, juxtaposition of stability area
3.9. Equilibrium of the formation of a solid from a solution
3.9.1. Solubility product and supersaturation
3.9.2. Extension to formation of a real solid
3.9.3. Extension to the transformation of a solid into another solid
3.10. Variations in the equilibrium conditions with sizes of solid phases
3.10.1. Variation in equilibrium constant with curvature radii
3.10.2. Influence of curvature radii on tension of vapor
3.10.3. Influence of curvature radii on point defect concentrations
Chapter 4. Elementary Steps in Heterogenous Reactions
4.1. Nature of elementary steps
4.1.1. The postulate of the activated jump
4.1.2. Voluminal speed of an elementary jump
4.1.3. Total voluminal speed of an elementary step
4.2. Elementary reactions at solid-solid interfaces
4.2.1. The phenomenon of epitaxy
4.2.2. Creation of an M interstitial cation in MG
4.2.3. Creation of a G vacancy anion in MG
4.2.4. Consumption of a G interstitial anion of MG
4.2.5. Consumption of an M vacancy cation of MG
4.2.6. Creation of the point defects created in the initial solid
4.3. Elementary reactions at gas-solid interfaces
4.3.1. Consumption of an M interstitial cation of MG
4.3.2. Consumption of a G vacancy anion of MG
4.3.3. Creation of a G interstitial anion in MG
4.3.4. Creation of an M vacancy cation in MG
4.4. The apparent energies of activation of interface reactions
4.5. The areal speed of an interface reaction
Chapter 5. Chemical Diffusion
5.1. Introduction: nature of diffusing particles in a solid
5.1.1. Origin of the diffusion in a solid
5.1.2. Mechanisms of diffusion in a solid
5.2. Flux of diffusion and velocity of diffusing particles
5.3. The laws of Fick
5.3.1. First law of Fick
5.3.2. Second law of Fick
5.3.3. Expression of the laws of Fick in various axes systems
5.3.4. Solutions of the laws of Fick
5.3.5. Self-diffusion and diffusion of the associated defect
5.4. Steady state obstructed diffusion
5.5. Diffusion under electric field
5.5.1. Expression of flux
5.5.2. Electric conductivity and diffusion
5.5.3. Diffusion in a semiconductor with electronic conduction under null current and without accumulation
5.6. Diffusion in two mediums separated by a mobile interface
5.6.1. Danckwerts solution
5.6.2. Example of application
5.6.3. Wagner pseudo-steady state approximation
Chapter 6. Chemical Adsorption
6.1. Definitions: physical adsorption and chemical adsorption
6.2. Adsorption thermodynamics and chemisorption equilibrium
6.2.1. Experimental results on adsorption equilibrium
6.2.2. The Langmuir model of chemisorption equilibrium
6.2.3. Dissociative adsorption and the Langmuir model
6.2.4. Chemisorption of gas mixtures in the Langmuir model
6.2.5. Adsorption isotherms that do not follow the Langmuir model
6.3. Kinetics of chemisorption
6.3.1. Velocity equation
6.3.2. Role of temperature on the kinetics of adsorption
6.4. Chemisorption and structure elements
6.4.1. Ways of chemisorption modeling
6.4.2. The concepts used in the quasi-chemical description of adsorption
6.4.3. Modes of adsorption
6.4.4. Modifications of the properties of adsorption of a solid
Chapter 7. Mechanisms and Kinetics of a Process
7.1. Speeds and reactivities of reactions taking place in only a single zone
7.1.1. Voluminal speed in a zone
7.1.2. Reactivity of a transformation in a given zone
7.2. Transformations with several zones
7.2.1. Postulate of the decomposition of a reaction in elementary steps
7.2.2. Reaction mechanism
7.2.3. Material balance in a reaction zone
7.2.4. Setting in the equation of mechanism - example
7.3. Linear reaction mechanisms
7.3.1. Definition and classification of the linear mechanisms
7.3.2. Multiplying coefficients of a linear mechanism
7.4. Linear mechanisms in pseudo-steady state modes
7.4.1. Definitions
7.4.2. Theorem of "the equality of rates" of a linear mechanism in pseudo-steady state modes
7.4.3. Relations between various forms of the rates (speed) of reactions with a linear mechanism in pseudo-steady state modes
7.4.4. Volumes of the phases and coefficient of expansion of a reaction with a linear mechanism in pseudo-steady state modes
7.4.5. Setting in equation of a linear mechanism in pseudo-steady state modes
7.5. Pure modes or modes with a rate-determining step
7.5.1. Definition
7.5.2. Theorem of the concentrations in pure mode
7.5.3. Reactivity of the rate-determining step in pure mode
7.5.4. Application of the method of the pure modes
7.5.5. Rate of the reaction in pure modes
7.5.6. Examples of resolutions of pure modes
7.5.7. Pure modes far from equilibrium
7.6. Mixed modes
7.6.1. Definition: pseudo-steady state mixed modes
7.6.2. Solving a pseudo-steady state mixed mode
7.7. Generalization, rate of a linear mechanism in pseudo-steady state mode
7.8. Mixed non-pseudo-steady state modes
7.9. Equivalent reaction of a linear subset in local pseudo-steady state mode
7.9.1. Local pseudo-steady state modes
7.9.2. Application to the "elementary" steps
7.10. Reactions with separable rates
7.11. Influence of intensive variables on the kinetic laws
7.11.1. The first kind of changes of laws
7.11.2. The second kind changes of laws
7.11.3. The third kind changes of laws
7.12. Distance from equilibrium for a reaction
7.12.1. Distance of an elementary step from equilibrium
7.12.2. Pseudo-steady state mode with a rate-determining step
7.13. Processes concerned in a heterogenous reaction
Chapter 8. Nucleation of a New Solid Phase
8.1. Clusters
8.2. Examples of nucleation diagram
8.3. Interfacial energy
8.3.1. Definition of interfacial energy
8.3.2. Microscopic interpretation
8.3.3. Effective interfacial energy
8.3.4. Relation between energy and the interfacial area
8.4. Formation molar Gibbs energy of clusters
8.4.1. Assumptions
8.4.2. Homogenous nucleation within a liquid phase: Volmer approach
8.4.3. Homogenous nucleation within a solid phase
8.4.4. Heterogenous primary nucleation starting from a fluid phase
8.4.5. Heterogenous primary nucleation starting from a solid phase
8.5. Kinetics of nucleation
8.5.1. Reaction pathway and localization of the phenomena
8.5.2. Rate and frequency of nucleation
8.5.3. Various considered modes
8.5.4. Kinetics of pseudo-steady state modes of condensation
8.5.5. Kinetics of pseudo-steady state modes of condensation on potential nuclei
8.5.6. Intervention of diffusion in the process of nucleation
Chapter 9. Growth of a Solid Phase
9.1. Description of the zones of growth
9.1.1. The initial solid is a single reactant
9.1.2. The initial solid reacts with another phase
9.2. Direction of the development of phase B during the growth
9.2.1. The initial solid is a single reactant
9.2.2. The initial solid reacts with another phase
9.3. Modes and models for growth
9.3.1. Modes of the growth of a crystal of B on support A
9.3.2. Modeling the growth
9.4. Relationship between the motion velocities of the interfaces and the chemical growth rate
9.4.1. Inward development of formed solid
9.4.2. Outward development of the formed solid
9.5. Methodology to model growth
9.5.1. Modeling the space function of growth
9.5.2. Modeling the reactivity of growth
9.6. Expressions of the space functions for the growth of a grain
9.6.1. Space functions in isotropic growth
9.6.2. Space functions in radial anisotropic growth
9.6.3. Introduction of a dimensionless time
Chapter 10. Transformation by Surface Nucleation and Growth
10.1. Nucleation, growth, and experimental rate
10.2. One-process model with instantaneous nucleation and slow growth
10.2.1. Reaction of a single grain (or massive material)
10.2.2. Case of a monodispersed powder
10.2.3. Shapes of kinetic and rate curves
10.2.4. One-process model with slow nucleation and instantaneous growth
10.2.5. Reaction of a single grain
10.2.6. Reaction of a powder
10.3. Two-process models: nucleation and growth
10.3.1. General expression for the rate
10.3.2. Influence of the past on the transformation rate
10.4. Two-process model with surface nucleation-radialanisotropic growth
10.4.1. Reaction of a single grain
10.4.2. Construction of the model of evolution of a powder
10.4.3. Calculation of the free area (space function) for nucleation
10.4.4. Calculation of the rates and the fractional extents according to time
10.4.5. Dimensionless rate
10.4.6. Conclusion on the surface nucleation and radial anisotropic growth model
10.5. Two-process model with surface nucleation and isotropic growth
10.5.1. Qualitative approach
10.5.2. Quantitative approach
10.5.3. Modeling the evolution of a grain
10.5.4. Modeling the evolution of a collection of grains
10.5.5. Application to the spherical grains: model of Johnson-Mehl and Mampel
10.6. Non-isobaric and/or non-isothermal kinetics
10.6.1. One-process models
10.6.2. Two-process models
10.7. Powders with granular distributions
10.8. Return to the first and second kind of changes of laws
10.8.1. First kind of changes of laws
10.8.2. Second kind of changes of laws
10.9. Conclusion
Chapter 11. Modeling and Experiments
11.1. The adequacy between the experimental conditions and modeling
11.2. Expressions of experimental speeds
11.2.1. Thermogravimetry
11.2.2. Microcalorimetry
11.2.3. Manometry
11.2.4. Measurement of the amounts of solids A with X-ray diffraction
11.2.5. Measurement of the amounts of the formed solid B
11.2.6. Thickness of the layer of a planar sample of B
11.2.7. Relationships between experimental speeds
11.3. Derivation of the kinetic curves
11.4. The experimental verification of the assumptions
11.4.1. The pseudo-steady state mode test
11.4.2. The test of the separable rate or the f? test
11.5. Determination of the morphological model for growth
11.5.1. Choice of the category of models: one-process or two-process model?
11.5.2. Determination of the model and its parameters
11.6. Calculations of the reactivity of growth and the specific frequency of nucleation
11.7. Variations of the kinetic properties with the intensive variables
11.7.1. Determination of the variation in the reactivity of growth starting from the morphological model
11.7.2. Direct determination of the variation in the reactivity of growth starting from the experiment
11.7.3. Comparison of the two obtained variations: new verification of the morphological model
11.8. Methodology of a study
11.8.1. Identification of the reaction
11.8.2. The separation of the models
11.8.3. Methodical approach of a study
Chapter 12. Granular Coalescence
12.1. Qualitative description of the model
12.2. Morphological modeling
12.2.1. Assumptions
12.2.2. Geometry of the neck
12.2.3. Relation between the fractional extent and the radius x of the bridge
12.3. Structure of the coalescence mechanism
12.3.1. Transport phenomenon and groups of elementary steps
12.3.2. Various kinetic modes with rate-determining steps
12.3.3. Definition of the reactivity of coalescence
12.4. Determination of the space functions
12.4.1. Mode with an interface reaction as the rate-determining step
12.4.2. Modes with diffusion as rate-determining step
12.4.3. Recapitulation of the space functions
12.5. Rate constants and radius of curvature
12.6. Reactivity of coalescence of a solid with a single component
12.6.1. Case of vacancies diffusion in the solid
12.6.2. Case of gas diffusion
12.6.3. Summary of the reactivities
12.7. Extensions to the coalescence of solids with several components
12.7.1. Coalescence of anatase in the presence of water vapor
12.7.2. Coalescence of anatase in the presence of oxygen and hydrogen chloride with or without water vapor
12.7.3. Coalescence of ceria in presence of oxygen and water vapor
12.8. Relations between experiments and modeling
12.8.1. Experimental measurement of coalescence
12.8.2. Determination of the variations of the reactivity with intensive quantities
12.8.3. Relation between experiment and space function in the model of tangential spheres
12.9. Oswald ripening and reduction in porosity
Chapter 13. Decomposition Reactions of Solids
13.1. Classifications of decomposition reactions
13.1.1. Classification according to the sign of the enthalpy
13.1.2. Classification according to the origin of the gas molecule
13.2. Extent measurement with the change of the mass
13.2.1. Stoichiometric solids
13.2.2. The produced solid is not stoichiometric
13.2.3. The initial solid is not stoichiometric
13.3. Observed experimental results
13.3.1. Rate-time and extent-time curves
13.3.2. Influences of the gas pressures
13.3.3. Influence of temperature
13.3.4. Non-isothermal decomposition reactions
13.4. Kinetics of growth in decomposition reactions of solids
13.4.1. Qualitative analysis of the growth
13.4.2. Basic growth mechanism with gaseous diffusion
13.4.3. Basic mechanism of growth with diffusions of defects
13.4.4. Smith-Topley's Effect
13.5. Nucleation in decomposition reactions of solids
13.5.1. Experimental approach of nucleation
13.5.2. Example of the dehydration of kaolinite
13.5.3. Nucleation and Smith-Topley's effect
13.6. Total kinetic curves
13.7. Influence of the granular distribution
13.8. Normal and abnormal growth
Chapter 14. Reactions Between Solids
14.1. Classification of the reactions between solids
14.1.1. Simple addition reactions
14.1.2. Addition reactions involving decomposition
14.1.3. Addition reactions involving a redox reaction
14.1.4. Exchange reactions or double decompositions
14.2. The modeling assumptions
14.3. The experimental measure of the extent of the reactions
14.4. Reactivities of reactions between solids
14.4.1. Position of the problem and experimental approach
14.4.2. Structures of the reaction mechanism of growth
14.4.3. Expression of the reactivities, reaction of titanium dioxide with barium carbonate
14.5. Rates of the reactions between powders
14.5.1. Problems of designs
14.5.2. Rates of a two-grain level
14.5.3. Rate of a granular cell
14.5.4. Rates on the scale of the powder
14.6. Conclusion
Chapter 15. Gas-Solid Reactions
15.1. Classification of gas-solid reactions
15.1.1. Class 1: synthesis reactions
15.1.2. Class 2: double-decomposition reactions
15.2. Pure metal gas reactions
15.2.1. Experimental data of oxidation of metals
15.2.2. Reaction zones and elementary reactions
15.2.3. Pure modes with interface rate determining step
15.2.4. Pure diffusion modes
15.2.5. Mixed modes
15.3. Growth process in the reduction of metallic oxides by hydrogen
15.3.1. Mechanism with diffusion of gases through the pores
15.3.2. Mechanisms with diffusion of defect in the formed solid phase
15.3.3. Conclusion about the reduction of oxides by hydrogen
15.3.4. Example of the reduction of a uranium oxide
15.4. Growth process of oxidation of metals by water vapor
15.4.1. General approach of mechanism
15.4.2. n-type formed oxide with interstitial cations
15.4.3. n-type formed oxide with anion vacancies
15.4.4. p-type formed oxide with cation vacancies
15.4.5. p-type formed oxide with interstitial anions
Chapter 16. Transformations of Solid Solutions
16.1. General information on transformations of solid solutions
16.1.1. Various types of transformations of solid solutions
16.1.2. Variations of concentrations in solid solution
16.2. Oxidation of metal alloys
16.2.1. Selective oxidation of single-phase binary metal alloys
16.2.2. Internal oxidation of single-phase binary alloys
16.2.3. Oxidation of single-phase binary alloys with miscibility of formed oxides
16.2.4. Oxidation of single-phase binary alloys with formation of two superimposed oxide layers
16.3. Variations of the composition of a solid solution with gas formation
16.3.1. Fractional extent and rate
16.3.2. Spatial structure of the model
16.3.3. Pure diffusion mode
16.3.4. Example: variation of stoichiometry of an oxide by reaction with hydrogen
16.4. Superposition of a variation of stoichiometry and decomposition
Chapter 17. Modeling of Mechanisms
17.1. Non-stoichiometry of iron oxide
17.1.1. Key words
17.1.2. Problem
17.1.3. Data
17.1.4. Solution
17.2. Stability of calcium carbonate
17.2.1. Key words
17.2.2. Problem
17.2.3. Data
17.2.4. Solution
17.3. Thermodynamics of a solid-solid reactions
17.3.1. Key words
17.3.2. Problem
17.3.3. Data
17.3.4. Solution
17.4. Hydrates of alumina
17.4.1. Key words
17.4.2. Problem
17.4.3. Data
17.4.4. Solution
17.5. Point defects in a metal sulfide
17.5.1. Key words
17.5.2. Problem
17.5.3. Data
17.5.4. Solution
17.6. Point defects of an alkaline bromide
17.6.1. Key words
17.6.2. Problem
17.6.3. Data
17.6.4. Solution
17.7. Diffusion of a metal into another metal
17.7.1. Key words
17.7.2. Problem
17.7.3. Data
17.7.4. Solution
17.8. Generation of atmospheres with very low pressures
17.8.1. Key words
17.8.2. Problem
17.8.3. Data
17.8.4. Solution
Chapter 18. Mechanisms and Kinetic Laws
18.1 Coalescence of anatase grains
18.1.1. Key words
18.1.2. Problem
18.1.3. Data
18.1.4. Solution
18.2. Reaction of a cubic sample
18.2.1. Key words
18.2.2. Problem
18.2.3. Data
18.2.4. Solution
18.3. Anisotropic growth
18.3.1. Key words
18.3.2. Problem
18.3.3. Data
18.3.4. Solution
18.4. Gas-solid reaction with one-process model
18.4.1. Key words
18.4.2. Problem
18.4.3. Data
18.4.4. Solution
18.5. The direction of the development of a layer
18.5.1. Key words
18.5.2. Problem
18.5.3. Data
18.5.4. Solution
18.6. Mampel modeling by way of the point of inflection
18.6.1. Key words
18.6.2. Problem
18.6.3. Data
18.6.4. Solution
18.7. Nucleation in a reaction of dehydration
18.7.1. Key words
18.7.2. Problem
18.7.3. Data
18.7.4. Solution
18.8. Influence of particle size in nucleation-growth approach
18.8.1. Key words
18.8.2. Problem
18.8.3. Data
18.8.4. Solution
18.9. Decomposition with slow nucleation and slow anisotropic growth determined by diffusion
18.9.1. Key words
18.9.2. Problem
18.9.3. Data
18.9.4. Solution
19. Mechanisms and Reactivity
19.1. Competition oxidation - volatilization by TGA
19.1.1. Key words
19.1.2. Problem
19.1.3. Data
19.1.4. Solution
19.2. Controlled rate thermal analysis (CRTA)
19.2.1. Key words
19.2.2. Problem
19.2.3. Data
19.2.4. Solution
19.3. Sulfurization of a metal
19.3.1. Key words
19.3.2. Problem
19.3.3. Data
19.3.4. Solution
19.4. Oxidation of a metal and some of its alloys
19.4.1. Key words
19.4.2. Problem
19.4.3. Data
19.4.4. Solution
19.5. Reduction of octo-oxide of triuranium by dihydrogen
19.5.1. Key words
19.5.2. Problem
19.5.3. Data
19.5.4. Solution
19.6. Dehydration of kaolinite
19.6.1. Key words
19.6.2. Problem
19.6.3. Data
19.6.4. Solution
19.7. Decomposition of a carbonate of a metal
19.7.1. Key words
19.7.2. Problem
19.7.3. Data
19.7.4. Solution
19.8. Reaction between two solids
19.8.1. Key words
19.8.2. Problem
19.8.3. Data
19.8.4. Solution
Appendix 1
Appendix 2
Appendix 3
Appendix 4
Appendix 5
Appendix 6
Appendix 7
Appendix 8
Appendix 9
Appendix 10
Appendix 11
Bibliography
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