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Rate constants for the reaction of tert-butyl radicals with chloroform in solution

✍ Scribed by H.-R. Dütsch; H. Fischer

Publisher
John Wiley and Sons
Year
1981
Tongue
English
Weight
699 KB
Volume
13
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

The decay of photochemically generated tert‐butyl radicals in methylcyclopentane solutions containing chloroform is studied by time‐resolved ESR spectroscopy. In the pure solvent it perfectly follows the second‐order rate law for radical self‐termination. Increasing chloroform concentrations cause increasing admixture of a pseudo‐first‐order decay from which the rate constant of the title reaction is obtained. For 273 K ≦ T ≦ 323 K,
where θ = 2.303__RT__ kcal/mol. CIDNP studies of the reaction mechanism and NMR product yields show H and Cl abstractions to occur with the temperature‐independent ratio k~H~/k~Cl~ = 1.4 ± 0.1. The results point to polar effects in the transfer reactions of tert‐butyl. The potential of time‐resolved ESR spectroscopy in studies of first‐ and pseudo‐first‐order reaction rates is discussed.

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