Author:
Korcek S.,Chenier J. H. B.,Howard J. A.,Ingold K. U.
Abstract
The rate constants, kp, for the abstraction of a hydrogen atom from a wide variety of organic substrates at 30° have been correlated with the strengths of the C—H bond that are broken, D[R—H] (in units of kcal/mol). Two empirical relations have been derived, one for tertiary peroxy radicals,[Formula: see text]and one for secondary peroxy radicals,[Formula: see text]These equations hold extremely well for hydrocarbons and reasonably well for substrates containing heteroatoms. The activation energies and pre-exponential factors for the oxidation of some hydrocarbons by t-butylperoxy radicals have been measured and the empirical relation[Formula: see text]derived. If D[t-ROO—H] is taken as 88 kcal/mol, this yields the Polanyi equation,[Formula: see text]where ΔH is the heat of the hydrogen abstraction reaction. These empirical equations permit the calculation of the rate constants for chain propagation in the autoxidation of many organic substrates at 30° and also at other temperatures.
Publisher
Canadian Science Publishing
Subject
Organic Chemistry,General Chemistry,Catalysis
Cited by
290 articles.
订阅此论文施引文献
订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献