Liquid-Phase Reaction Rate Constants

ISBN-13: 9781468483024 / Angielski / Miękka / 2012 / 772 str.

E. T. Denisov; E. T. Denisov

Opis

The past 25 years in chemical kinetics have seen major advances in studyiqg the mechanisms of complex chemical re actions, in particular free radical reactions. Many differ ent methods have been developed for quantitative studies of elementary chemical reactions. Thousands of rate constants have been measured, for hundreds of diverse chemical reac tions. It is becoming more and more difficult for the chemist to orient himself in the voluminous and rapidly growing liter ature of chemical reaction kinetics. This leads to major expenditures of time in searching out, collecting. and eval uating quantitative kinetic data; to unnecessary repetition (duplication) of research; and to a situation in which the rich material already accumulated in the field of chemical kinetics is very often not fully utilized in comparing, interpreting, and analyzing new experimental data. There is a pressing need for the creation of a series of handbooks on reaction rate constants. Such work was begun several years ago at the initiative of V. N. Kondrat'ev, and is now going forward under his direction at the Institute of Chemical Physics of the USSR Academy of Sciences. This book is devoted to liquid-phase, homolytic reactions. Part One contains data on monomolecular reactions in which molecules decompose to form radicals, as well as data on bi molecular and trimolecular reactions that form free radicals."

Spis treści

one — Reactions of Molecules.- I. Monomolecular reactions.- 1. Methods for Measuring Rate Constants of Monomolecular Reactions.- 2. Rate Constants for Decomposition of Peroxide Compounds.- 3. Decomposition of Azo Compounds.- 4. Decomposition at C — C, N-N, N-C,N-O, and C-Metal Bonds.- 5. Decomposition of Iodobenzene Dichloride.- 6. Correlation Equations.- 7. Effect of Pressure and Solvent on Monomolecular Reactions.- II. Bimolecular and Trimolecular Reactions.- 1. Methods for Measuring Rate Constants of Bimoleeular Reactions.- 2. Diels-Alder Reaction.- 3. Bimolecular Reactions with Peroxide Participation.- 4. Oxidation-Reduction Reactions with Participation of CIO2, O2, and CI2.- 5. Reactions with Rupture of Metal-Carbon Bond.- 6. Trimolecular Reactions.- III. The cage effect.- 1. Questions of Theory.- 2. Methods for Measuring Initiator Efficiency.- 3. Initiator Efficiency.- Literature Cited (Part One).- Two — Reactions of free Atoms and Radicals.- IV. Methods for Measuring Rate Constants of Radical Reactions.- 1. Measurement of Relative Rate Constants of Radical Reactions.- 2. Measurement of Absolute Rate Constants of Reactions of Atoms and Radicals.- V. Isomerization and Decomposition of Free Radicals.- 1. Isomerization of Free Radicals.- 2. Decomposition of Free Radicals.- VI. Radical Substitution Reactions.- 1. Reactions of Atoms.- 2. Reactions of Radicals Having Free Valence on Oxygen.- 3. Reactions of Radicals Having Free Valence on Carbon.- 4. Chain Transfer in Radical Polymerization.- 5. Reactions of Radicals Having Free Valence on Nitrogen.- 6. Correlation Equations for Radical Substitution Reactions.- VII. Addition Reactions of Atoms and Radicals.- 1. Addition of Atoms and Radicals to Molecular Oxygen.- 2. Addition at C = C Bond.- 3. Addition to Aromatic Compounds.- 4. Addition to Quinones, Carbonyl Compounds, Nitriles, and Nitro Compounds.- VIII. Recombination and Disproportionate of Free Atoms and Radicals.- 1. Recombination of Atoms.- 2. Disproportionation and Recombination of Alkyl and RO? Radicals.- 3. Reactions between Peroxy Radicals.- 4. Reactions of Radicals Having Free Valence on Nitrogen or Tin.- 5. Reactions between Free Radicals of Different Types.- IX. Effect of Solvent on Free Radical Reactions.- 1. Solvent Viscosity.- 2. Internal Pressure of Liquid.- 3. Nonspecific Solvation.- 4. Hydrogen Bond between Molecules.- 5. Radical Hydrogen Bond.- 6. Formation of ? -Complexes.- Literature Cited (Part Two).- Three — Ionic Homolytic Reactions.- X. Oxidation-Reduction Reactions of Ions With Molecules.- Oxidation of Organic Compounds by Variable-Valence Metal Ions.- Reaction of Variable-Valence Metal Ions with Oxygen, Peroxides, and Quinones.- XI. Reactions of Atoms and Radicals with Ions.- 1. Reactions of Hydrogen Atom.- 2. Reactions of Free Radicals.- XII. Reactions of Ion-Radicals and Solvated Electrons.- 1. Reactions of Ion-Radicals.- 2. Solvated Electron.- XIII. Ionic Oxidation-Reduction Reactions.- 1. Methods for Measuring Reaction Rates for Electron Transfer from Ion to Ion.- 2. Electron Exchange Reactions.- 3. Oxidation-Reduction Reactions between Ions.- Literature Cited (Part Three).