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

Abstract

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.

Authors:
; ;  [1]
  1. National Inst. of Standards and Technology, Gaithersburg, MD (United States)
Publication Date:
OSTI Identifier:
6868414
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry; (United States)
Additional Journal Information:
Journal Volume: 99:1; Journal ID: ISSN 0022-3654
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHEMICAL REACTIONS; CHEMICAL REACTION KINETICS; CHLORPROMAZINE; PEROXY RADICALS; ABSORPTION SPECTRA; SYNTHESIS; AROMATICS; BUTANOLS; COMPILED DATA; METHANOL; ORGANIC BROMINE COMPOUNDS; OXIDATION; OXYGEN; SOLUTIONS; SOLVATED ELECTRONS; ALCOHOLS; AMINES; AZINES; CENTRAL NERVOUS SYSTEM DEPRESSANTS; DATA; DISPERSIONS; DRUGS; ELECTRONS; ELEMENTARY PARTICLES; ELEMENTS; FERMIONS; HETEROCYCLIC COMPOUNDS; HYDROXY COMPOUNDS; HYPNOTICS AND SEDATIVES; INFORMATION; KINETICS; LEPTONS; MIXTURES; NONMETALS; NUMERICAL DATA; ORGANIC CHLORINE COMPOUNDS; ORGANIC COMPOUNDS; ORGANIC HALOGEN COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; ORGANIC SULFUR COMPOUNDS; PHENOTHIAZINES; PS; RADICALS; REACTION KINETICS; SPECTRA; TRANQUILIZERS; 400201* - Chemical & Physicochemical Properties; 400102 - Chemical & Spectral Procedures

Citation Formats

Alfassi, Z B, Khaikin, G I, and Neta, P. Arylperoxyl radicals. Formation, absorption spectra, and reactivity in aqueous alcohol solutions. United States: N. p., 1995. Web. doi:10.1021/j100001a041.
Alfassi, Z B, Khaikin, G I, & Neta, P. Arylperoxyl radicals. Formation, absorption spectra, and reactivity in aqueous alcohol solutions. United States. https://doi.org/10.1021/j100001a041
Alfassi, Z B, Khaikin, G I, and Neta, P. 1995. "Arylperoxyl radicals. Formation, absorption spectra, and reactivity in aqueous alcohol solutions". United States. https://doi.org/10.1021/j100001a041.
@article{osti_6868414,
title = {Arylperoxyl radicals. Formation, absorption spectra, and reactivity in aqueous alcohol solutions},
author = {Alfassi, Z B and Khaikin, G I and Neta, P},
abstractNote = {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.},
doi = {10.1021/j100001a041},
url = {https://www.osti.gov/biblio/6868414}, journal = {Journal of Physical Chemistry; (United States)},
issn = {0022-3654},
number = ,
volume = 99:1,
place = {United States},
year = {Thu Jan 05 00:00:00 EST 1995},
month = {Thu Jan 05 00:00:00 EST 1995}
}