Chemical Kinetics - 1st Edition - ISBN: 9780444521866, 9780080469348

Chemical Kinetics

1st Edition

From Molecular Structure to Chemical Reactivity

Authors: Luis Arnaut Sebastiao Formosinho Hugh Burrows
Hardcover ISBN: 9780444521866
eBook ISBN: 9780080469348
Imprint: Elsevier Science
Published Date: 8th December 2006
Page Count: 562
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Description

1. Introduction Includes a historical perspective of chemical kinetics and basic physical-chemistry information (Boltzmann distribution law, harmonic oscillator, equilibrium constants, etc). 2. Reaction rate laws Definition. Factors that influence the rates (nature of the reactants, concentration of the reactants, temperature, light, catalysts, medium). 3. Experimental methods Conventional analytical techniques, including procedures for their application in examples of first and second order reactions, complex reactions, and enzyme catalysis. Fast reaction methods, including relaxation techniques, stopped flow, NMR, flash photolysis, single photon counting, time-resolved photoacoustic calorimetry, femtochemistry. Most of these techniques are illustrated with data collected in the authors’ labs. 4. Rate constants and reaction orders First, second and zero-order reactions, complex reaction mechanisms (parallel, consecutive and reversible reactions), methods to solve kinetic equations (Laplace transforms, matrix, Runge-Kutta, Markov chain, Monte Carlo), simplification of reaction mechanisms (isolation method, pre-equilibrium approximation, steady-state hypothesis). 5. Collisions and molecular dynamics Simple collisions theory, reaction cross-sections, classical trajectories, avoided crossings in potential energy surfaces, molecular dynamics. 6. Reactivity in thermalized systems Transition-state theory, including semi-classical treatments of zero-point energy and tunnelling. Intersecting-state model. 7. Structure-Reactivity Relationships Linear and quadratic free-energy relationships, Brönsted, Hammett and Taft relationships. Hammond postulate, reactivity-selectivity principle, Ritchie equation. 8.Unimolecular Reactions Lindemann, Hinshelwood and RRKM approaches. 9. Reaction in solution Solvent effects, diffusion control, reactivity control in solution (internal pressure, ionic strength, hydrostatic pressure). 10. Reactions in surfaces Adsorption, Adsorption isotherms with or without dissociation. Competitive adsorption. Multilayer adsorption. Bimolecular reactions in surfaces. Velocity of adsorption and desorption. Velocity of reaction of adsorbed species. 11. Nucleophilic substitution reactions SN1 and SN2 reactions. Langford-Gray classification. Methyl transfers in the gas phase and in solution. Shaik-Pross correlation diagrams. 12. Chain reactions Halogen – molecular hydrogen reactions. Pyrolysis. Combustion and explosions. 13. Acid-base catalysis and proton-transfer reactions Mechanisms (Arrhenius and van't Hoff intermediates). Specific and general acid-base catalysis. Catalytic activity and acid-base strength. Salt effects. Acidity functions. Proton transfer reactions (Eigen mechanism, carbon acids and bases, solvent effects, kinetic isotope effects). 14. Enzyme catalysis Michaelis-Menten mechanism, competition and inhibition, pH and temperature effects. Molecular models of enzyme catalysis. 15. Transitions between electronic states Golden-Rule of quantum mechanics. Franck-Condon factors. Radiationless transitions. Electronic coupling. 16. Electron transfers Self-exchange reactions. Marcus theory and ISM. Spin and distance dependence of nonadiabatic electron transfers. Inverted regions. Electron transfers in proteins. Electrochemistry. 17. Fractals, chaos and oscillatory reactions.

Key Features

  • Looking at atoms and molecules, and how molecular structures change with time.
  • Providing practical examples and detailed theoretical calculations
  • Of special interest to Industrial Chemistry and Biochemistry

Readership

For students, researchers and practitioners in the field of kinetics

Table of Contents

1. Introduction Includes a historical perspective of chemical kinetics and basic physical-chemistry information (Boltzmann distribution law, harmonic oscillator, equilibrium constants, etc). 2. Reaction rate laws Definition. Factors that influence the rates (nature of the reactants, concentration of the reactants, temperature, light, catalysts, medium). 3. Experimental methods Conventional analytical techniques, including procedures for their application in examples of first and second order reactions, complex reactions, and enzyme catalysis. Fast reaction methods, including relaxation techniques, stopped flow, NMR, flash photolysis, single photon counting, time-resolved photoacoustic calorimetry, femtochemistry. Most of these techniques are illustrated with data collected in the authors’ labs. 4. Rate constants and reaction orders First, second and zero-order reactions, complex reaction mechanisms (parallel, consecutive and reversible reactions), methods to solve kinetic equations (Laplace transforms, matrix, Runge-Kutta, Markov chain, Monte Carlo), simplification of reaction mechanisms (isolation method, pre-equilibrium approximation, steady-state hypothesis). 5. Collisions and molecular dynamics Simple collisions theory, reaction cross-sections, classical trajectories, avoided crossings in potential energy surfaces, molecular dynamics. 6. Reactivity in thermalized systems Transition-state theory, including semi-classical treatments of zero-point energy and tunnelling. Intersecting-state model. 7. Structure-Reactivity Relationships Linear and quadratic free-energy relationships, Brönsted, Hammett and Taft relationships. Hammond postulate, reactivity-selectivity principle, Ritchie equation. 8.Unimolecular Reactions Lindemann, Hinshelwood and RRKM approaches. 9. Reaction in solution Solvent effects, diffusion control, reactivity control in solution (internal pressure, ionic strength, hydrostatic pressure). 10. Reactions in surfaces Adsorption, Adsorption isotherms with or without dissociation. Competitive adsorption. Multilayer adsorption. Bimolecular reactions in surfaces. Velocity of adsorption and desorption. Velocity of reaction of adsorbed species. 11. Nucleophilic substitution reactions SN1 and SN2 reactions. Langford-Gray classification. Methyl transfers in the gas phase and in solution. Shaik-Pross correlation diagrams. 12. Chain reactions Halogen – molecular hydrogen reactions. Pyrolysis. Combustion and explosions. 13. Acid-base catalysis and proton-transfer reactions Mechanisms (Arrhenius and van't Hoff intermediates). Specific and general acid-base catalysis. Catalytic activity and acid-base strength. Salt effects. Acidity functions. Proton transfer reactions (Eigen mechanism, carbon acids and bases, solvent effects, kinetic isotope effects). 14. Enzyme catalysis Michaelis-Menten mechanism, competition and inhibition, pH and temperature effects. Molecular models of enzyme catalysis. 15. Transitions between electronic states Golden-Rule of quantum mechanics. Franck-Condon factors. Radiationless transitions. Electronic coupling. 16. Electron transfers Self-exchange reactions. Marcus theory and ISM. Spin and distance dependence of nonadiabatic electron transfers. Inverted regions. Electron transfers in proteins. Electrochemistry. 17. Fractals, chaos and oscillatory reactions.

Details

No. of pages:
562
Language:
English
Copyright:
© Elsevier Science 2006
Published:
Imprint:
Elsevier Science
eBook ISBN:
9780080469348
Hardcover ISBN:
9780444521866

About the Author

Luis Arnaut

Affiliations and Expertise

Chemistry Department, University of Coimbra, Portugal

Sebastiao Formosinho

Affiliations and Expertise

Chemistry Department, University of Coimbra, Portugal

Hugh Burrows

Affiliations and Expertise

Chemistry Department, University of Coimbra, Portugal