Formation and reactions of halogenated phenylperoxyl radicals in aqueous alcohol solutions

G. I. Khaikin, Z. B. Alfassi, P. Neta

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14 Scopus citations


Halogenated phenylperoxyl radicals were produced in irradiated aqueous alcohol solutions by reductive dehalogenation of dihalo- and polyhalobenzenes with solvated electrons and subsequent reaction of the halophenyl radicals with oxygen. Phenylperoxyl radicals oxidize 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonate ion) (ABTS2-) with rate constants between 3 × 107 and 3 × 109 L mol-1 s-1, depending on the structure of the peroxyl radical and the alcohol concentration. For monohalogenated phenylperoxyl radicals, the reactivity changed in the order F < Cl < Br and p < m < o. The reactivity increased on going from the (monohalophenyl)- to the (dihalophenyl)- and (trihalophenyl)peroxyl radicals. The rate constants were correlated with the substituent constants and with the pKa values of similarly halogenated phenols. The reduction potential for PhOO·/PhOO- was estimated to be near 0.7 V vs NHE; that for the trichloro derivative, near 0.9 V. The rate constants in various solvent mixtures were correlated with the cohesive pressure of the medium.

Original languageEnglish
Pages (from-to)11447-11451
Number of pages5
JournalJournal of Physical Chemistry
Issue number29
StatePublished - 1 Jan 1995
Externally publishedYes

ASJC Scopus subject areas

  • General Engineering
  • Physical and Theoretical Chemistry


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