Premium
Rate constants for the combination of trichloromethyl radicals and the electron‐transfer reaction between hydroxymethyl radicals and carbon tetrachloride in solution
Author(s) -
Paul H.
Publication year - 1979
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550110504
Subject(s) - chemistry , radical , reaction rate constant , carbon tetrachloride , hydroxymethyl , electron transfer , kinetics , photochemistry , methanol , electron paramagnetic resonance , organic chemistry , nuclear magnetic resonance , physics , quantum mechanics
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.