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Title: The yield for hydroxyl radical from the decomposition of peroxynitrous acid

Abstract

Mechanistic predictions, based upon the assumption that free {sm{underscore}bullet}OH and {sm{underscore}bullet}NO{sub 2} radicals are formed as intermediates during the ONOOH decay, were tested using inorganic radical scavengers. Both the rates and the yields of Fe(CN){sub 6}{sup 4{minus}} and IRcl{sub 6}{sup 3{minus}} oxidation by ONOOH were independent of their concentrations in submillimolar range. A 55 {+-} 7% Fe(CN){sub 6}{sup 3{minus}} yield and 25 {+-} 3% IrCl{sub 6}{sup 2{minus}} were measured at pH 5.7, 22 C. A yields ratio close to 2 is expected, because, of the two radicals produced, only {sm{underscore}bullet}OH can rapidly oxidize IRCl{sub 6}{sup 3{minus}}. The competition kinetic studies demonstrated that the relative reactivities of the oxidizing intermediate generated by ONOOH toward IrCl{sub 6}{sup 3{minus}} and NO{sub 2}{sup {minus}} were identical with the reactivities of the authentic {sm{underscore}bullet}OH radical generated by pulse radiolysis. It is concluded that ONOOH decomposes via its peroxo bond homolysis producing a pair of discrete {sm{underscore}bullet}OH and {sm{underscore}bullet}NO{sub 2} radicals with 28 {+-} 4% yield. A bimolecular reaction between ONOOH and Fe(CN){sub 6}{sup 4{minus}} with the rate constant (8.2 {+-} 0.4) M{sup {minus}1} s{sup {minus}1} significantly increases both oxidation yield and rate at high [Fe(CN){sub 6}{sup 4{minus}}].

Authors:
;
Publication Date:
Research Org.:
Brookhaven National Lab., Upton, NY (US)
Sponsoring Org.:
USDOE
OSTI Identifier:
20003189
DOE Contract Number:  
AC02-98CH10886
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 38; Journal Issue: 19; Other Information: PBD: 20 Sep 1999
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; DECOMPOSITION; HYDROXYL RADICALS; CHEMICAL REACTION YIELD; PEROXY RADICALS; NITROGEN OXIDES; KINETICS

Citation Formats

Gerasimov, O.V., and Lymar, S.V. The yield for hydroxyl radical from the decomposition of peroxynitrous acid. United States: N. p., 1999. Web. doi:10.1021/ic990384y.
Gerasimov, O.V., & Lymar, S.V. The yield for hydroxyl radical from the decomposition of peroxynitrous acid. United States. doi:10.1021/ic990384y.
Gerasimov, O.V., and Lymar, S.V. Mon . "The yield for hydroxyl radical from the decomposition of peroxynitrous acid". United States. doi:10.1021/ic990384y.
@article{osti_20003189,
title = {The yield for hydroxyl radical from the decomposition of peroxynitrous acid},
author = {Gerasimov, O.V. and Lymar, S.V.},
abstractNote = {Mechanistic predictions, based upon the assumption that free {sm{underscore}bullet}OH and {sm{underscore}bullet}NO{sub 2} radicals are formed as intermediates during the ONOOH decay, were tested using inorganic radical scavengers. Both the rates and the yields of Fe(CN){sub 6}{sup 4{minus}} and IRcl{sub 6}{sup 3{minus}} oxidation by ONOOH were independent of their concentrations in submillimolar range. A 55 {+-} 7% Fe(CN){sub 6}{sup 3{minus}} yield and 25 {+-} 3% IrCl{sub 6}{sup 2{minus}} were measured at pH 5.7, 22 C. A yields ratio close to 2 is expected, because, of the two radicals produced, only {sm{underscore}bullet}OH can rapidly oxidize IRCl{sub 6}{sup 3{minus}}. The competition kinetic studies demonstrated that the relative reactivities of the oxidizing intermediate generated by ONOOH toward IrCl{sub 6}{sup 3{minus}} and NO{sub 2}{sup {minus}} were identical with the reactivities of the authentic {sm{underscore}bullet}OH radical generated by pulse radiolysis. It is concluded that ONOOH decomposes via its peroxo bond homolysis producing a pair of discrete {sm{underscore}bullet}OH and {sm{underscore}bullet}NO{sub 2} radicals with 28 {+-} 4% yield. A bimolecular reaction between ONOOH and Fe(CN){sub 6}{sup 4{minus}} with the rate constant (8.2 {+-} 0.4) M{sup {minus}1} s{sup {minus}1} significantly increases both oxidation yield and rate at high [Fe(CN){sub 6}{sup 4{minus}}].},
doi = {10.1021/ic990384y},
journal = {Inorganic Chemistry},
number = 19,
volume = 38,
place = {United States},
year = {1999},
month = {9}
}