Chemical Kinetics

From Molecular Structure to Chemical Reactivity

2nd Edition - June 22, 2021
Author: Luis Arnaut
Language: English
Paperback ISBN:
9 7 8 - 0 - 4 4 4 - 6 4 0 3 9 - 0
eBook ISBN:
9 7 8 - 0 - 4 4 4 - 6 4 0 4 0 - 6

Chemical Kinetics: From Molecular Structure to Chemical Reactivity, Second Edition, explains how molecular structures change with time. It offers a comprehensive and coherent… Read more

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Chemical Kinetics: From Molecular Structure to Chemical Reactivity, Second Edition, explains how molecular structures change with time. It offers a comprehensive and coherent coverage of the rates of chemical transformations.

The book is written for both undergraduate chemistry students, and for the specialist. The newcomer will find the fundamental concepts, the simple experiments, and the underlying theories. For the seasoned specialist, it presents sophisticated experimental and theoretical methods, offering a panorama of time-dependent molecular phenomena connected by a new rationale. The gap between the two is bridged by a logical path that leads the reader from a phenomenological approach of molecular changes, to the formalism of chemical reaction rates, and then to state-of-the-art calculations of rate constants of the most prevalent reactions: atom transfers, catalysis, proton transfers, substitution reactions, energy transfers and electron transfers. In the process, the reader is presented with the details of collision and transition state theories. The coverage includes unimolecular reactions in the gas phase, reactions in solution and reactions on surfaces.

Cover image
Title page
Table of Contents
Copyright
Preface
Chapter 1. Introduction
Abstract
1.1 Introduction
1.2 Initial difficulties in the development of chemical kinetics in the twentieth century
1.3 Chemical kinetics: the current view
References
Chapter 2. Reaction rate laws
Abstract
2.1 Reaction rates
2.2 Factors that influence the velocities of reactions
References
Chapter 3. Experimental methods
Abstract
3.1 Application of conventional techniques to study reactions
3.2 Application of special techniques for fast reactions
References
Chapter 4. Reaction order and rate constants
Abstract
4.1 Rates of elementary reactions
4.2 Rates of complex reactions
4.3 Methods for solving kinetic equations
4.4 Simplification of kinetic schemes
4.5 Global and target analysis of kinetic data
References
Chapter 5. Collisions and molecular dynamics
Abstract
5.1 Simple collision theory
5.2 Improved collision theory
5.3 Collision cross section
5.4 Calculation of classical trajectories
5.5 PES crossings
5.6 Molecular dynamics
References
Chapter 6. Reactivity in thermalised systems
Abstract
6.1 Transition-state theory
6.2 Semi-classical treatments
6.3 Intersecting-state model
References
Chapter 7. Relationships between structure and reactivity
Abstract
7.1 Quadratic free-energy relationships
7.2 Linear free-energy relationships
7.3 Other kinds of relationships between structure and reactivity
References
Chapter 8. Unimolecular reactions
Abstract
8.1 Lindemann–Christiansen mechanism
8.2 Hinshelwood’s treatment
8.3 Rice–Ramsperger–Kassel–Marcus treatment
8.4 Local random matrix theory
8.5 Energy barriers in the isomerisation of cyclopropane
References
Chapter 9. Elementary reactions in solution
Abstract
9.1 Solvent effects on reaction rates
9.2 Effect of diffusion
9.3 Diffusion constants
9.4 Spin-statistical factors in diffusion-controlled reactions
9.5 Reaction control
References
Chapter 10. Reactions on surfaces
Abstract
10.1 Adsorption
10.2 Adsorption isotherms
10.3 Kinetics on surfaces
10.4 Transition-state theory for reactions on surfaces
10.5 Model systems
References
Chapter 11. Substitution reactions
Abstract
11.1 Mechanisms of substitution reactions
11.2 SN2 and SN1 reactions
11.3 Langford–Gray classification
11.4 Symmetrical methyl group transfers in the gas-phase
11.5 State correlation diagrams of Pross and Shaik
11.6 Intersecting-state model
11.7 Cross-reactions in methyl group transfers in the gas phase
11.8 Solvent effects in methyl group transfers
References
Chapter 12. Chain reactions
Abstract
12.1 Hydrogen–bromine reaction
12.2 Reaction between molecular hydrogen and chlorine
12.3 Reaction between molecular hydrogen and iodine
12.4 Calculation of energy barriers for elementary steps in hydrogen–halogen reactions
12.5 Comparison of the mechanisms of the hydrogen–halogen reactions
12.6 Pyrolysis of hydrocarbons
12.7 Explosive reactions
12.8 Polymerisation reactions
References
Chapter 13. Acid–base catalysis and proton-transfer reactions
Abstract
13.1 General catalytic mechanisms
13.2 General and specific acid–base catalysis
13.3 Mechanistic interpretation of the pH dependence of the rates
13.4 Catalytic activity and acid–base strength
13.5 Salt effects
13.6 Acidity functions
13.7 Hydrated proton mobility in water
13.8 Proton-transfer rates in solution
13.9 Proton-transfer model system
References
Chapter 14. Enzymatic catalysis
Abstract
14.1 Terminology
14.2 Factors that accelerate enzymatic action
14.3 Michaelis–Menten equation
14.4 Mechanisms with two enzyme–substrate complexes
14.5 Inhibition of enzymes
14.6 Effects of pH
14.7 Temperature effects
14.8 Isomerisation of dihydroxyacetone phosphate to glyceraldehyde 3-phosphate catalysed by triose-phosphate isomerase
14.9 Hydroperoxidation of linoleic acid catalysed by soybean lipoxygenase-1
14.10 Enzymes in drug design
References
Chapter 15. Pharmacokinetics
Abstract
15.1 Origins and current use of pharmacokinetics
15.2 Drug administration and absorption
15.3 Drug distribution
15.4 Drug metabolism and excretion
15.5 Pharmacokinetics models
References
Chapter 16. Transitions between electronic states
Abstract
16.1 Mechanisms of energy transfer
16.2 The “Golden Rule” of quantum mechanics
16.3 Radiative and radiationless rates
16.4 Franck–Condon factors
16.5 Radiationless transition within a molecule
16.6 Triplet energy (or electron) transfer between molecules
16.7 Electronic coupling
16.8 Triplet energy transfer rates
References
Chapter 17. Electron-transfer reactions
Abstract
17.1 Rate laws for outer-sphere electron exchanges
17.2 Theories of electron-transfer reactions
17.3 ISM and electron-transfer reactions
17.4 Non-adiabatic self-exchanges of transition-metal complexes
17.5 Electron self-exchanges of organic molecules
17.6 Inverted regions
17.7 Electron transfer at electrodes
References
Chapter 18. Oscillatory reactions
Abstract
18.1 Non-linear systems
18.2 Chaos
18.3 Oscillatory reactions
18.4 The Coimbrator
References
Appendix 1. General data
Appendix 2. Statistical thermodynamics
Appendix 3. Parameters employed in ISM calculations
Appendix 4. Semi-classical interacting state model
A4.1 Vibrationally adiabatic path
A4.2 Tunnelling corrections
A4.3 Semi-classical rate constants
Appendix 5. The Lippincott–Schroeder potential
A5.1 Lippincott–Schroeder potential
A5.2 The LS–ISM reaction path
A5.3 Rate constants for proton transfer along a H bond
Appendix 6. Quantum-mechanical radiationless transition theory
A6.1 The strong coupling limit
A6.2 The weak coupling limit
A6.3 Energy and electron-transfer rates
Appendix 7. Problems
Answers
Index

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