Formation and reactivity of phenylperoxyl radicals in aqueous solutions

Journal Article · Thu Aug 18 00:00:00 EDT 1994 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100084a017· OSTI ID:7015208

Alfassi, Z B; Marguet, S; Neta, P ^[1]

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1. National Inst. of Standards and Technology, Gaithersburg, MD (United States)

The reaction of phenyl radicals with oxygen, to produce phenylperoxyl radicals, and the reactions of several phenylperoxyl radicals with a number of organic compounds in aqueous solutions have been studied by pulse radiolysis. Phenyl radicals were produced by reduction of aryl halides with hydrated electrons. The rate constant for the reaction of 4-carboxyphenyl with O[sub 2] was determined from the rate of buildup of the peroxyl radical absorption at 520 nm as a function of [O[sub 2]] and found to be 1.6 x 10[sup 9] L mol[sup [minus]1] s[sup [minus]1]. Phenyl radicals react with 2-PrOH by H abstraction; a rate constants of 4 x 10[sup 6] L mol[sup [minus]1] s[sup [minus]1] was determined for 4-carboxyphenyl by competition with the reaction of this radical with O[sub 2]. Phenylperoxyl radicals react with 4-methoxyphenolate ions, trolox C(6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid), ascorbate ions, chlorpromazine, and ABTS [2,2[prime]-azinobis(3-ethylbenzothiazoline-6-sulfonate ion)] by one-electron oxidation. The rate constants for such reactions, determined from the rate of formation of the one-electron oxidation product as a function of substrate concentration, were found to be near 10[sup 8]-10[sup 9] L mol[sup [minus]1] s[sup [minus]1]. 24 refs., 4 figs., 1 tab.

• OSTI ID: 7015208
• Journal Information: Journal of Physical Chemistry; (United States), Vol. 98:33; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ORGANIC COMPOUNDS
CHEMICAL REACTION KINETICS
OXYGEN
RADICALS
AQUEOUS SOLUTIONS
OXIDATION
PHENOLS
PHENYL RADICALS
PROPANOLS
RADIOLYSIS
SOLVATED ELECTRONS
ALCOHOLS
AROMATICS
ARYL RADICALS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
DECOMPOSITION
DISPERSIONS
ELECTRONS
ELEMENTARY PARTICLES
ELEMENTS
FERMIONS
HYDROXY COMPOUNDS
KINETICS
LEPTONS
MIXTURES
NONMETALS
RADIATION EFFECTS
REACTION KINETICS
SOLUTIONS
400600* - Radiation Chemistry
400201 - Chemical & Physicochemical Properties