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Rate constants for the combination of trichloromethyl radicals and the electron-transfer reaction between hydroxymethyl radicals and carbon tetrachloride in solution

✍ Scribed by H. Paul

Publisher
John Wiley and Sons
Year
1979
Tongue
English
Weight
728 KB
Volume
11
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

The rate constant for the bimolecular combination of trichloromethyl radicals in methanol is determined as a function of temperature by steady‐state kinetics and electron‐spin resonance with modulated radical initiation. The rate constant is in accord with the Smoluchowski equation and indicates a diffusion‐controlled radical termination. The temperature dependence of the rate constant for the electron‐transfer reaction between hydroxymethyl radicals and carbon tetrachloride in methanol is determined, and is found to disagree with predictions of the Marcus theory. This disagreement is tentatively ascribed to the structure of the transition state.

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