Arylperoxyl radicals. Formation, absorption spectra, and reactivity in aqueous alcohol solutions

Journal Article · Thu Jan 05 04:00:00 EST 1995 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100001a041· OSTI ID:6868414

Alfassi, Z B; Khaikin, G I; Neta, P ^[1]

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

Aryl radicals (phenyl, 4-biphenylyl, 2-naphthyl, 1-naphthyl, and 9-phenanthryl) were produced by the reaction of the corresponding aryl bromide with solvated electrons and reacted rapidly with oxygen to produce the arylperoxyl radicals. These radicals exhibit optical absorptions in the visible range, with [lambda][sub max] at 470, 550, 575, 650, and 700 nm, respectively. Arylperoxyl radicals react with 2,2[prime]-azinobis(3-ethylbenzothiazoiine-6-sulfonate ion) (ABTS), chlorpromazine, and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox C) by one-electron oxidation. The rate constants k for these reactions, determined from the rate of formation of the one-electron oxidation products as a function of substrate concentration, vary between 4 [times] 10[sup 6] and 2 [times] 10[sup 9] L mol[sup [minus]1] s[sup [minus]1] and increase in the order phenyl-, 4-biphenyl-, 2-naphthyl-, 1-naphthyl-, and 9-phenanthrylperoxyl, the same order as the absorption peaks of these radicals. Good correlation was found between log k and the energy of the absorption peak. 16 refs., 2 figs., 2 tabs.

• OSTI ID: 6868414
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 99:1; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTRA
ALCOHOLS
AMINES
AROMATICS
AZINES
BUTANOLS
CENTRAL NERVOUS SYSTEM DEPRESSANTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHLORPROMAZINE
COMPILED DATA
DATA
DISPERSIONS
DRUGS
ELECTRONS
ELEMENTARY PARTICLES
ELEMENTS
FERMIONS
HETEROCYCLIC COMPOUNDS
HYDROXY COMPOUNDS
HYPNOTICS AND SEDATIVES
INFORMATION
KINETICS
LEPTONS
METHANOL
MIXTURES
NONMETALS
NUMERICAL DATA
ORGANIC BROMINE COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXIDATION
OXYGEN
PEROXY RADICALS
PHENOTHIAZINES
PS
RADICALS
REACTION KINETICS
SOLUTIONS
SOLVATED ELECTRONS
SPECTRA
SYNTHESIS
TRANQUILIZERS