Organic Reactions book cover

Organic Reactions

Equilibria, Kinetics and Mechanism

This book begins with a brief survey of non-kinetic methods, and continues with kinetic methods used for the elucidation of reaction mechanisms. It is method oriented and therefore deals with the following topics: basic principles of reaction kinetics; Structure and reactivity relationships; isotope effects; acids, bases, electrophiles and nucleophiles; and concludes with homogeneous catalysis.

Rigorous mathematical descriptions of the basic principles are provided in a clear and easily understandable form. The book is more comprehensive than many physical organic texts and it is supported by an extensive list of references. It also contains a valuable collection of problems.

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Published: April 1994

Imprint: Elsevier

ISBN: 978-0-444-88174-8

Contents

  • 1. Introduction. 2. Nonkinetic Method for the Elucidation of Reaction Mechanisms. Stoichiometry and reaction mechanisms. Structure of products. Structure of intermediates. Stereochemical experiments. Isotopic labeling experiments. Crossover experiments. 3. Energetics of Chemical Reactions. Nomenclature of thermodynamic potential functions. Thermodynamic requirements for chemical reactions. Kinetic requirements for chemical reactions. The principle of microscopic reversibility. Kinetic and thermodynamic control. 4. Kinetics of Elementary Reactions. Basic principles of reaction kinetics. The integrated rate equation. Pseudo-orders of simplified rate equations. Numerical determination of reaction order and rate constants from experimental data. 5. Kinetics of Complex Reactions. Reversible reactions. Parallel reactions. Consecutive reactions. Approximate methods for analyzing complex reactions. Conclusions. Examples. 6. Theories of Chemical Reactions. Temperature dependence of chemical equilibria. Temperature dependence of reaction rates. Collision theory. Transition-state theory. Structure of activated complexes. Entropy of activation. Enthalpy of activation. The isokinetic relationship. Volume of activation. 7. Structure and Reactivity Relationships. The Hammett equation. The linear free-enthalpy relationship. The application of Hammett equation to multistep reactions. The &sgr;+, &sgr;-, and &sgr;0 substituent constants; the Yukawa-Tsuno equation. Separation of inductive and resonance effects. Separation of electronic and steric effects. 8. Isotope Effects. Isotope effects on equilibria. Theory of kinetic isotope effect. Primary kinetic isotope effect. Secondary kinetic isotope effects. Solvent isotope effect. 9. Environmental Effects. The structure of liquids. Solvation. Solvent effects in chemical equilibria. Solvent effect in chemical kinetics. Solvent effect on reaction rates. Specific solvation effects on reaction rates. Empirical solvent-polarity parameters. Salt effects. 10. Acids, Bases, Electrophiles and Nucleophiles. Strengths of Brønsted acids and bases. Structural effects on Brønsted acidity and basicity. Solvent effect on acidity and basicity. Acidity of solvents and acidity functions. Very weak acids. Superacids. Lewis acids and Lewis bases. Nucleophiles and electrophiles. 11. Homogeneous Catalysis. Acid-base catalysis. Rates of proton-transfer reactions. Brønsted's law of catalysis. Reactions in strongly acidic media. Nucleophilic catalysis. Electrophilic catalysis. Neighboring group participation and intramolecular catalysis. Micellar catalysis. Enzymic catalysis.

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