The kinetics of the reaction of OH With COS
Identifieur interne : 001538 ( Istex/Corpus ); précédent : 001537; suivant : 001539The kinetics of the reaction of OH With COS
Auteurs : Andreas Wahner ; A. R. RavishankaraSource :
- Journal of Geophysical Research: Atmospheres [ 0148-0227 ] ; 1987-02-20.
Abstract
The laser/flash‐photolysis laser‐induced fluorescence technique was employed to study the reaction of OH with carbonyl sulfide (COS) in various buffer gases (He, N2, and SF6). In order to determine the relevance of this reaction to tropospheric chemistry the influence of O2 on the rate constant was investigated. To avoid secondary reactions, especially the photolysis of COS, different photolytic OH precursors (H2O2, HNO3, and HONO) with different photolysis light sources (Xe flash lamp, ArF laser, fourth‐harmonic Nd: YAG laser, XeF laser, and third‐harmonic Nd: YAG laser) were used. The rate constant (1.92±0.25)×10−15 cm3 s−1 for the reaction of OH with COS at room temperature was found (after correcting for H2S impurity) to be independent of the pressure and the buffer gas. Addition of O2 was found to have no influence on the measured rate constant. Certain experiments were carried out at 298 K and 245 K to ascertain the mechanism for this reaction. Our results suggest that the degradation pathway involving homogeneous gas phase reaction of COS with OH is of minor importance in the troposphere.
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DOI: 10.1029/JD092iD02p02189
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Ravishankara</name></author></analytic><monogr></monogr><series><title level="j">Journal of Geophysical Research: Atmospheres</title><title level="j" type="abbrev">J. Geophys. Res.</title><idno type="ISSN">0148-0227</idno><idno type="eISSN">2156-2202</idno><imprint><publisher>Blackwell Publishing Ltd</publisher><date type="published" when="1987-02-20">1987-02-20</date><biblScope unit="volume">92</biblScope><biblScope unit="issue">D2</biblScope><biblScope unit="page" from="2189">2189</biblScope><biblScope unit="page" to="2194">2194</biblScope></imprint><idno type="ISSN">0148-0227</idno></series><idno type="istex">52174110CB10DF095DF5BB8309038A0A07ACFF89</idno><idno type="DOI">10.1029/JD092iD02p02189</idno><idno type="ArticleID">6D0632</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0148-0227</idno></seriesStmt></fileDesc><profileDesc><textClass></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract">The laser/flash‐photolysis laser‐induced fluorescence technique was employed to study the reaction of OH with carbonyl sulfide (COS) in various buffer gases (He, N2, and SF6). In order to determine the relevance of this reaction to tropospheric chemistry the influence of O2 on the rate constant was investigated. To avoid secondary reactions, especially the photolysis of COS, different photolytic OH precursors (H2O2, HNO3, and HONO) with different photolysis light sources (Xe flash lamp, ArF laser, fourth‐harmonic Nd: YAG laser, XeF laser, and third‐harmonic Nd: YAG laser) were used. The rate constant (1.92±0.25)×10−15 cm3 s−1 for the reaction of OH with COS at room temperature was found (after correcting for H2S impurity) to be independent of the pressure and the buffer gas. Addition of O2 was found to have no influence on the measured rate constant. Certain experiments were carried out at 298 K and 245 K to ascertain the mechanism for this reaction. Our results suggest that the degradation pathway involving homogeneous gas phase reaction of COS with OH is of minor importance in the troposphere.</div></front></TEI><istex><corpusName>wiley</corpusName><author><json:item><name>Andreas Wahner</name></json:item><json:item><name>A. R. Ravishankara</name></json:item></author><articleId><json:string>6D0632</json:string></articleId><language><json:string>eng</json:string></language><abstract>The laser/flash‐photolysis laser‐induced fluorescence technique was employed to study the reaction of OH with carbonyl sulfide (COS) in various buffer gases (He, N2, and SF6). In order to determine the relevance of this reaction to tropospheric chemistry the influence of O2 on the rate constant was investigated. To avoid secondary reactions, especially the photolysis of COS, different photolytic OH precursors (H2O2, HNO3, and HONO) with different photolysis light sources (Xe flash lamp, ArF laser, fourth‐harmonic Nd: YAG laser, XeF laser, and third‐harmonic Nd: YAG laser) were used. The rate constant (1.92±0.25)×10−15 cm3 s−1 for the reaction of OH with COS at room temperature was found (after correcting for H2S impurity) to be independent of the pressure and the buffer gas. Addition of O2 was found to have no influence on the measured rate constant. Certain experiments were carried out at 298 K and 245 K to ascertain the mechanism for this reaction. 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R.</givenNames> <familyName>Ravishankara</familyName></author> (<pubYear year="1987">1987</pubYear>), <articleTitle>The kinetics of the reaction of OH With COS</articleTitle>, <journalTitle>J. Geophys. Res.</journalTitle>, <vol>92</vol>(<issue>D2</issue>), <pageFirst>2189</pageFirst>–<pageLast>2194</pageLast>, doi:<accessionId ref="info:doi/10.1029/JD092iD02p02189">10.1029/JD092iD02p02189</accessionId>.</citation></selfCitationGroup><linkGroup><link type="toTypesetVersion" href="file:JGRD.JGRD669.pdf"></link></linkGroup></publicationMeta><contentMeta><titleGroup><title type="main">The kinetics of the reaction of OH With COS</title><title type="shortAuthors">Wahner and Ravishankara</title></titleGroup><creators><creator xml:id="jgrd669-cr-0001"><personName><givenNames>Andreas</givenNames><familyName>Wahner</familyName></personName></creator><creator xml:id="jgrd669-cr-0002"><personName><givenNames>A. R.</givenNames><familyName>Ravishankara</familyName></personName></creator></creators><abstractGroup><abstract type="main"><p xml:id="jgrd669-para-0001">The laser/flash‐photolysis laser‐induced fluorescence technique was employed to study the reaction of OH with carbonyl sulfide (COS) in various buffer gases (He, N<sub>2</sub>, and SF<sub>6</sub>). In order to determine the relevance of this reaction to tropospheric chemistry the influence of O<sub>2</sub> on the rate constant was investigated. To avoid secondary reactions, especially the photolysis of COS, different photolytic OH precursors (H<sub>2</sub>O<sub>2</sub>, HNO<sub>3</sub>, and HONO) with different photolysis light sources (Xe flash lamp, ArF laser, fourth‐harmonic Nd: YAG laser, XeF laser, and third‐harmonic Nd: YAG laser) were used. The rate constant (1.92±0.25)×10<sup>−15</sup> cm<sup>3</sup> s<sup>−1</sup> for the reaction of OH with COS at room temperature was found (after correcting for H<sub>2</sub>S impurity) to be independent of the pressure and the buffer gas. Addition of O<sub>2</sub> was found to have no influence on the measured rate constant. Certain experiments were carried out at 298 K and 245 K to ascertain the mechanism for this reaction. Our results suggest that the degradation pathway involving homogeneous gas phase reaction of COS with OH is of minor importance in the troposphere.</p></abstract></abstractGroup></contentMeta></header></component></istex:document></istex:metadataXml><mods version="3.6"><titleInfo lang="en"><title>The kinetics of the reaction of OH With COS</title></titleInfo><titleInfo type="alternative" contentType="CDATA" lang="en"><title>The kinetics of the reaction of OH With COS</title></titleInfo><name type="personal"><namePart type="given">Andreas</namePart><namePart type="family">Wahner</namePart></name><name type="personal"><namePart type="given">A. R.</namePart><namePart type="family">Ravishankara</namePart></name><typeOfResource>text</typeOfResource><genre type="article" displayLabel="article"></genre><originInfo><publisher>Blackwell Publishing Ltd</publisher><dateIssued encoding="w3cdtf">1987-02-20</dateIssued><dateCaptured encoding="w3cdtf">1986-08-01</dateCaptured><dateValid encoding="w3cdtf">1986-10-24</dateValid><edition>Wahner, A., and A. R. Ravishankara (1987), The kinetics of the reaction of OH With COS, J. Geophys. Res., 92(D2), 2189–2194, doi:10.1029/JD092iD02p02189.</edition><copyrightDate encoding="w3cdtf">1987</copyrightDate></originInfo><language><languageTerm type="code" authority="rfc3066">en</languageTerm><languageTerm type="code" authority="iso639-2b">eng</languageTerm></language><physicalDescription><internetMediaType>text/html</internetMediaType></physicalDescription><abstract>The laser/flash‐photolysis laser‐induced fluorescence technique was employed to study the reaction of OH with carbonyl sulfide (COS) in various buffer gases (He, N2, and SF6). In order to determine the relevance of this reaction to tropospheric chemistry the influence of O2 on the rate constant was investigated. To avoid secondary reactions, especially the photolysis of COS, different photolytic OH precursors (H2O2, HNO3, and HONO) with different photolysis light sources (Xe flash lamp, ArF laser, fourth‐harmonic Nd: YAG laser, XeF laser, and third‐harmonic Nd: YAG laser) were used. The rate constant (1.92±0.25)×10−15 cm3 s−1 for the reaction of OH with COS at room temperature was found (after correcting for H2S impurity) to be independent of the pressure and the buffer gas. Addition of O2 was found to have no influence on the measured rate constant. Certain experiments were carried out at 298 K and 245 K to ascertain the mechanism for this reaction. Our results suggest that the degradation pathway involving homogeneous gas phase reaction of COS with OH is of minor importance in the troposphere.</abstract><relatedItem type="host"><titleInfo><title>Journal of Geophysical Research: Atmospheres</title></titleInfo><titleInfo type="abbreviated"><title>J. Geophys. 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