An Introduction to Chemical Kinetics

Name: An Introduction to Chemical Kinetics
Brand: Wiley-ISTE
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Michel Soustelle(Autor*in)

Wiley-ISTE (Verlag)

Erschienen am 7. Februar 2013

480 Seiten

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978-1-118-60422-9 (ISBN)

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Cover
Title Page
Copyright Page
Table of Contents
Preface
PART 1. BASIC CONCEPTS OF CHEMICAL KINETICS
Chapter 1. Chemical Reaction and Kinetic Quantities
1.1. The chemical reaction
1.1.1. The chemical equation and stoichiometric coefficients
1.1.2. The reaction components
1.1.3. Reaction zones
1.2. Homogeneous and heterogeneous reactions
1.2.1. Single zone reaction
1.2.2. Multizone reaction
1.3. Extent and speed of a reaction
1.3.1. Stoichiometric abundance of a component in a reaction mixture
1.3.2. Extent of a reaction
1.3.3. Speed of a reaction
1.4. Volumetric and areal speed of a monozone reaction
1.5. Fractional extent and rate of a reaction
1.5.1. The fractional extent of a reaction
1.5.2. Rate of a reaction
1.5.3. Expression of the volumetric speed (areal) from variations in the amount of a component
1.6. Reaction speeds and concentrations
1.6.1. Concentration of a component in a zone
1.6.2. Relationship between concentration and fractional extent in a closed environment
1.7. Expression of volumetric speed according to variations in concentration in a closed system
1.8. Stoichiometric mixtures and progress
1.9. Factors influencing reaction speeds
1.9.1. Influence of temperature
1.9.2. Influence of the concentratios (or partial pressures of gases)
1.9.3. Other variables
Chapter 2. Reaction Mechanisms and Elementary Steps
2.1. Basic premise of kinetics
2.2. Reaction mechanism
2.2.1. Definition
2.2.2. Examples of mechanisms
2.3. Reaction intermediates
2.3.1. Excited atoms (or molecules)
2.3.2. Free radicals
2.3.3. Ions
2.3.4. Adsorbed species
2.3.5. Point defects
2.3.6. The effect of intermediates on extent and speeds
2.4. Reaction sequences and Semenov representation
2.4.1. Semenov diagram
2.4.2. Linear sequences and multipoint sequences
2.5. Chain reactions
2.5.1. Definition
2.5.2. The different categories of chain reactions
2.5.3. The steps in a chain reaction
2.5.4. Sequence of chain reactions
2.5.5. Reactions of macromolecule formation
2.6. Catalytic reactions
2.6.1. Homogeneous catalysis
2.6.2. Heterogeneous catalysis
2.7. Important figures in reaction mechanisms
Chapter 3. Kinetic Properties of Elementary Reactions
3.1. Space function of an elementary reaction
3.2. Reactivity and rate of an elementary step
3.3. Kinetic constants of an elementary step
3.3.1. Expression of reactivity as a function of concentrations
3.3.2. Rate factor of an elementary reaction
3.4. Opposite elementary reactions
3.4.1. Reactivity of two opposite elementary reactions
3.4.2. Distance from equilibrium conditions
3.4.3. Principle of partial equilibria
3.5. Influence of temperature on the reactivities of elementary steps
3.5.1. Influence of temperature near the equilibrium
3.5.2. Activation energies of opposite elementary reactions and reaction enthalpy
3.6. Modeling of a gas phase elementary step
3.6.1. Collision theory
3.6.2. Theory of activated complex
3.7. A particular elementary step: diffusion
3.7.1. The diffusion phenomenon
3.7.2. Diffusion flux and Fick's first law
3.7.3. Diffusion flux in a steady state system
3.7.4. Reactivity and diffusion space function
3.7.5. Diffusion in solids
3.7.6. Interdiffusion of gases
3.7.7. Diffusion of a gas in a cylindrical pore
3.8. Gases adsorption onto solids
3.8.1. Chemisorption equilibrium: Langmuir model
3.8.2. Dissociative adsorption and the Langmuir model
3.8.3. Chemisorption of gas mixtures in the Langmuir model
3.8.4. Chemisorption kinetic in the Langmuir model
3.9. Important figures in the kinetic properties of elementary reactions
Chapter 4. Kinetic Data Acquisition
4.1. Experimental kinetic data of a reaction
4.2. Generalities on measuring methods
4.3. Chemical methods
4.4. Physical methods
4.4.1. Methods without separation of components
4.4.2. Physical methods with separation of components
4.4.3. Study of fast reactions
4.5. Researching the influence of various variables
4.5.1. Ostwald's isolation method
4.5.2. Variables separation
Chapter 5. Experimental Laws and Calculation of Kinetic Laws of Homogeneous Systems
5.1. Experimental laws in homogeneous kinetics
5.1.1. Influence of concentrations
5.1.2. Influence of temperature
5.2. Relationship between the speed of a reaction and the speeds of its elementary steps
5.3. Mathematical formulation of speed from a mechanism and experimental conditions
5.3.1. Example of resolution of a mechanism in a closed system
5.3.2. Example of resolution of a mechanism in an open system with constant concentrations
5.4. Mathematical formulation of a homogeneous reaction with open sequence
5.4.1. Mathematical formulation in a closed system
5.4.2. Mathematical formulation of a system with constant concentrations
5.5. Mathematical formulation of chain reactions
5.5.1. Mathematical formulation of a simple homogeneous chain reaction
5.5.2. Mathematical formulation of a reaction forming a macromolecule through polymerization
Chapter 6. Experimental Data and Calculation of Kinetic Laws of Heterogeneous Reactions
6.1. Heterogeneous reactions
6.1.1. Distinctive nature of heterogeneous systems
6.1.2. Rate of a heterogeneous reaction
6.1.3. Different kinetic classes of heterogeneous reactions
6.2. Experimental kinetic data of heterogeneous reactions
6.2.1. Catalytic reactions
6.2.2. Stoichiometric heterogeneous gas-solid reactions
6.3. Involvement of diffusion in matter balances
6.3.1. Balance in a slice of a volume zone
6.3.2. Balance in a 2D zone
6.3.3. Application of balances to the elementary steps of a sequence of reactions
6.3.4. Application to Fick's second law
6.4. Example of mathematical formulation of a heterogeneous catalytic reaction
6.5. Example of the mathematical formulation of an evolution process of a phase
6.5.1. Balance of intermediates
6.5.2. Expressions of the reactivities of elementary chemical steps
6.5.3. Expressions of the concentrations of species at the interfaces
6.5.4. Diffusion equations of the defects
6.5.5. Expressions of the variations in sizes of the zones involved in the reaction
6.5.6. Evolution law of the rate chosen to characterize the speed
Chapter 7. Pseudo- and Quasi-steady State Modes
7.1. Pseudo-steady state mode
7.1.1. Definition
7.1.2. Uniqueness of the reaction speed in pseudo-steady state mode
7.1.3. Linear sequences in pseudo-steady state modes
7.1.4. Multipoint sequences in pseudo-steady state mode
7.1.5. Experimental research into the pseudo-steady state
7.2. Pseudo-steady state sequences with constant volume (or surface) - quasi-steady state
7.2.1. Quasi-steady state sequences
7.2.2. Linear sequences in quasi-steady state mode
7.2.3. Speed of a homogeneous linear sequence in quasi-steady state mode with invariant volume
7.2.4. Multipoint sequences in quasi-steady state mode
7.3. Pseudo- and quasi-steady state of diffusion
7.4. Application to the calculation of speeds in pseudo-steady state or quasi-steady state
7.4.1. Principle of the method
7.4.2. Example 1: dinitrogen pentoxide decomposition
7.4.3. Example 2: hydrogen bromide synthesis
7.4.4. Example 3: polymerization
7.4.5. Example 4: application of the pseudo-steady state to a heterogeneous catalytic reaction
7.5. Pseudo-steady state and open or closed systems
7.5.1. Kinetics law in homogeneous closed systems
7.5.2. Kinetics law in heterogeneous closed systems
7.5.3. Kinetic laws of open systems with constant concentrations
7.6. Conclusion
7.7. Important figure in pseudo-steady state
Chapter 8. Modes with Rate-determining Steps
8.1. Mode with one determining step
8.1.1. Definition
8.1.2. Concentrations theorem for linear sequences
8.1.3. Reactivity of the rate-determining step
8.1.4. Rate of reaction
8.1.5. Calculation of speed of a linear sequence in pure mode determined by one step
8.1.6. Pure modes away from equilibrium for linear sequences
8.1.7. Influence of temperature on linear sequences
8.1.8. Cyclic sequences
8.1.9. Conclusion on modes with a single determining step
8.2. Pseudo-steady state mode with two determining steps
8.2.1. Definition
8.2.2. Mathematical formulation of a mixed pseudo-steady state mode
8.2.3. Linear sequences: inverse rate law or the law of slowness
8.2.4. Cyclic sequences
8.2.5. Law of characteristic times
8.3. Generalization to more than two determining steps
8.4. Conclusion to the study of modes with one or several rate-determining steps
8.5. First order mode changes
8.6. Conclusion
PART 2. REACTION MECHANISMS AND KINETIC PROPERTIES
Chapter 9. Establishment and Resolution of a Reaction Mechanism
9.1. Families of reaction mechanisms
9.2. Different categories of elementary steps
9.2.1. Homolytic bond breaking
9.2.2. Heterolytic bond breaking
9.2.3. Ion dissociation
9.2.4. Radical reactions
9.2.5. Ion-molecule reactions
9.2.6. Reactions between ions
9.2.7. Interface reactions
9.2.8. Reaction between structure elements in the solid state
9.2.9. Reactions between adsorbed species and point defects
9.3. Establishment of a reaction mechanism
9.3.1. Methodology
9.3.2. Rule no. 1: the law of elimination of intermediates
9.3.3. Rule no. 2: the rule of the least change of structure (in the case of a single bond)
9.3.4. Rule no. 3: the rule of the greatest simplicity of elementary reactions (bimolecular)
9.3.5. Rule no. 4: the rule involving a single jump into the solid state
9.3.6. Rule no. 5: the law of micro-reversibility
9.4. Research into a mechanism: intermediary reactions
9.4.1. Reaction filiations: primary and non-primary products
9.4.2. Labile intermediates
9.5. Back to the modes and laws of kinetics
9.5.1. Modes with a single rate-determining step
9.5.2. Modes with multiple rate-determining steps
9.5.3. Pseudo-steady state modes
9.5.4. Link between the form of the rate equation and the presence of some elementary steps
9.6. Experimental tests
9.6.1. Experimental methods
9.6.2. The pseudo-steady state mode test
9.6.3. Research into the uniqueness of the space function mechanism or ?E test
9.7. Looking for the type of rate law
9.7.1. Research into the influence of concentrations
9.7.2. Research into the influence of temperature
Chapter 10. Theory of the Activated Complex in the Gas Phase
10.1. The notion of molecular energy: the energy of a group of atoms
10.1.1. Energy of a group of two atoms
10.1.2. Energy of an even number of atoms
10.2.3. Energy of an odd number of atoms
10.2. Bimolecular reactions in the gas phase
10.2.1. Postulate of the activated molecular collision
10.2.2. Potential energy surface
10.2.3. Reaction pathways and the equivalent "mass point"
10.2.4. Absolute expression of the reaction rate
10.2.5. Partition functions of the activated complex
10.2.6. Evaluation of the pre-exponential factor
10.2.7. Activation energies
10.2.8. Units and other forms of the reaction rate coefficient
10.3. Monomolecular reactions in the gas phase
10.4. Photochemical elementary reactions
10.4.1. Grotthus-Draper quantitative law
10.4.2. Energetic paths of molecule dissociation
10.4.3. Einstein's quantitative law
10.4.4. Influence of temperature on photochemical reactions
10.5. The theory of activated complexes
Chapter 11. Modeling Elementary Reactions in Condensed Phase
11.1. Elementary reaction in the liquid phase
11.1.1. Generic expression of an elementary-step reaction rate in the liquid phase: the Brønstedt-Bjerrum law
11.1.2. Influence of the environment
11.1.3. Comparison of the reaction rate in solution and gas phases
11.1.4. Reactions between ions in diluted solution
11.1.5. Reactions in concentrated solutions: the acidity factor
11.2. Elementary reaction in the solid state
11.2.1. Potential energy of a solid
11.2.2. Reaction pathway
11.2.3. Rate of an elementary jump
11.2.4. Diffusion in solids
11.3. Interphase reactions
11.3.1. Gas-solid interphases: adsorption, desorption
11.3.2. Solid-solid interface: the concept of epitaxy
11.4. Electrochemical reactions
11.4.1. Definition
11.4.2. Reactivity of an electrochemical reaction
11.4.3. The De Donder-Pourbaix inequality
11.4.4. Polarization curves
11.4.5. Polarization curve equation
11.5. Conclusion
Chapter 12. The Kinetics of Chain Reactions
12.1. Definition of a chain reaction
12.2. The kinetic characteristics of chain reactions
12.3. Classification of chain reactions
12.3.1. Straight or non-branched chain reactions
12.3.2. Reactions with direct branching
12.3.3. Reactions with indirect branching
12.4. Chain reaction sequences
12.4.1. Initiation of a chain reaction
12.4.2. Propagation of a chain reaction
12.4.3. Chain breaking
12.4.4. Branching chain reaction
12.5. Kinetic study of straight chain or non-branch chain reactions
12.5.1. Mean length of the chains
12.5.2. Expression of the reaction rate
12.5.3. Calculation of the rate and mean length of chains in the reactor
12.5.4. Variation of reaction rate with temperature
12.5.5. Permanency of the pseudo-steady state mode and reactant consumption
12.6. Kinetic study of chain reactions with direct branching
12.6.1. Simplified representation of reactions with direct branching
12.6.2. Mean chain lengths: condition of the appearance of a pseudo-steady state
12.6.3. Example of a chain reaction with both linear branching and breaking in the bulk
12.6.4. Example of the calculation of the measures related to a branching chain reaction
12.7. Semenov and the kinetics of chain reactions
Chapter 13. Catalysis and Catalyzed Reactions
13.1. Homogenous catalysis
13.1.1. Specific acid-base catalysis by H+ and OH- ions
13.1.2. Generic acid-base catalysis
13.1.3. Catalysis by Lewis acids
13.1.4. Redox catalysis
13.1.5. Autocatalytic reactions
13.1.6. Enzymatic catalysis
13.2. Heterogeneous catalysis reactions
13.2.1. Experimental laws in heterogeneous catalysis
13.2.2. Structure of the mechanism of heterogeneous catalysis
13.2.3. Kinetics of the catalytic act
13.2.4. Example of the kinetics of catalysis on a porous support
13.2.5. Influence of the catalyst surface area: poisoning
13.3. Gas-solid reactions leading to a gas
13.4. Conclusion on catalysis
13.5. Langmiur and Hinshelwood
Chapter 14. Kinetics of Heterogeneous Stoichiometric Reactions
14.1. Extent versus time and rate versus extent curves
14.2. The global model with two processes
14.3. The ?E law
14.4. Morphological modeling of the growing space function
14.4.1. The hypothesis
14.4.2. Types of model involving one or two processes
14.4.3. Experimental research on the type of morphological model
14.5. The nucleation process
14.5.1. Description of the nucleation process
14.5.2. Thermodynamics of nucleation
14.5.3. The nucleation mechanism
14.5.4. The nucleation rate
14.5.5. Surface and nucleation frequencies
14.6. Physico-chemical growth models
14.7. Conclusion on heterogeneous reactions
14.8. Important figures in reaction kinetics
Chapter 15. Kinetics of Non-pseudo-steady State Modes
15.1. Partial pseudo-steady state modes
15.2. The paralinear law of metal oxidation
15.3. Thermal runaway and ignition of reactions
15.4. Chemical ignition of gaseous mixtures
15.4.1. Branched chains with linear branching and chain breaking in the bulk
15.4.2. Branched chains with linear branching and breaking in the bulk and heterogeneous breaking on the walls
APPENDICES
Appendix 1: Point Defects and Structure Elements of Solids
A1.1. Point defects of solids
A1.2. Definition of a structural element
A1.3. Symbolic representation of structure elements
A1.4. Reactions involving structure elements in quasi-chemical reactions
A1.5. Equilibria and reactivities of quasi-chemical reactions
Appendix 2: Notions of Microscopic Thermodynamics
A2.1. Molecule distribution between the different energy states
A2.2. Partition functions
A2.3. Degrees of freedom of a molecule
A2.4. Elementary partition functions
A2.4.1. Vibration partition function
A2.4.2. Rotation partition function
A2.4.3. Translation partition function
A2.4.4. Order of magnitude of partition functions
A2.5. Expression of thermodynamic functions from partition functions
A2.5.1. Internal energy
A2.5.2. Entropy
A2.5.3. Free energy
A2.6. Equilibrium constant and partition functions
Appendix 3: Vibration Frequency of the Activated Complex
Notations and Symbols
Bibliography
Index

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