Fundamental reactions of free radicals relevant to pyrolysis reactions

Free-radical mechanisms are ubiquitous for pyrolysis of organic substrates. Background information is supplied to assist in the interpretation of such reactions by dissection into the elementary radical-forming, radical-consuming, and radical-interconverting reactions that form the building blocks of overall mechanisms. Particular attention is given to homolysis, hydrogen abstraction, beta-scission-addition, and rearrangement steps, and to bond-breaking and bond-forming processes. Since the thermochemistry of such elementary reactions is dependent on the stability of the radicals involved, the major influences of structural changes on radical stability are reviewed. Kinetics of prototypical elementary reactions and their responses to structural changes are rationalized in terms of their Arrhenius parameters. The fundamental relationships between thermochemical parameters and kinetic parameters are summarized, and the use of these to estimate rate constants for cases where data is not available is demonstrated. Some kinetic consequences of the combination of elementary reactions to produce chain reactions are reviewed. Critical structural and kinetic features that determine the selectivity among product types and the response of reactions to temperature and substrate concentration are indicated. (C) 2000 Published by Elsevier Science B.V.