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Bimolecular self-reactions of ketyl radicals of acetophenone and diphenylaminyl radicals

✍ Scribed by I.V. Khudyakov; L.L. Koroli

Book ID: 103023068
Publisher: Elsevier Science
Year: 1984
Tongue: English
Weight: 509 KB
Volume: 103
Category: Article
ISSN: 0009-2614
DOI: 10.1016/0009-2614(84)80325-5

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✦ Synopsis

The rate wnstants of selfxactions of ketyl radicals of acetophenone in n-heptane [2k = (3.2 2 05) x 109 hl-1 s-t] and diphenylaminyl radicals in toluene [2k = (3.3 f 05) x lo7 11-t s-l ] hat= been determined at 298 K using the flash photolysis technique-The rate constant of ketyl radicals is equal to the calculated diffusion constant and, therefore, this reaction isdiffusioncontrolled.Theaminyl radical recombination rate is independent of the viscosity of the toluene/vaseline oil binary mixture (055 < rl S 12 cP) and thip reaction is activationcontrolled-

Reactivity anisotropy axzxjng due to the cage effect has been considered for ketyl and some other radicals. On the basis of the analysis it has been proposed that ketyl recombination involves formation of not only pinaml, but also iso-pinacols.

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