Overall rate constant measurements of the reactions of alkene-derived hydroxyalkylperoxy radicals with nitric oxide

Title:
Overall rate constant measurements of the reactions of alkene-derived hydroxyalkylperoxy radicals with nitric oxide
Authors:
Miller, Angela M.; Kiep, Annastassja C.; Elrod, Matthew J.; Yeung, Laurence Y.
Abstract:
The overall rate constants of the NO reaction with hydroxyalkylperoxy radicals derived from the OH-initiated oxidation of several atmospherically abundant alkenes- ethene, propene, 1-butene, 2-butene, 2-methyl propene, 1,3-butadiene, and isoprene (2-methyl-1,3-butadiene)-were determined using the turbulent flow technique and pseudo first-order kinetic conditions with high pressure chemical ionization mass spectrometry for the direct detection of hydroxyalkylperoxy radical reactants. The individual 100 Torr, 298 K rate constants for each alkene system were found to be identical within the 95% confidence interval associated with each separate measurement. The average overall rate constant for the reaction of all alkene-derived hydroxyalkylperoxy radicals with NO was determined to be 9.1 ± 0.5 (2WEIRD"O")*10^{-12}cm^{3} molecule^{-1}s^{-1}. Previous studies of this reaction for the ethene, 2-methyl propene and isoprene systems reported varying rate constant values that ranged from a factor of two lower to a factor of two higher than the present result. However, the invariant nature and value of the present rate constant determination closely parallels the results obtained in the measurement of rate constants for the reactions of several alkane-derived peroxy radicals with NO.
Citation:
Miller, A.M., L.Y. Yeung, A.C. Kiep, and M.J. Elrod. 2004. "Overall Rate Constant Measurements of the Reactions of Alkene-Derived Hydroxyalkylperoxy Radicals with Nitric Oxide." Physical Chemistry Chemical Physics 6(13): 3402-3407.
Publisher:
The Royal Society of Chemistry
DATE ISSUED:
2004-07
Department:
Chemistry
Type:
article
PUBLISHED VERSION:
10.1039/b402110j
PERMANENT LINK:
http://hdl.handle.net/11282/309796

Full metadata record

DC FieldValue Language
dc.contributor.authorMiller, Angela M.en_US
dc.contributor.authorKiep, Annastassja C.en_US
dc.contributor.authorElrod, Matthew J.en_US
dc.contributor.authorYeung, Laurence Y.en_US
dc.date.accessioned2013-12-23T16:18:05Zen
dc.date.available2013-12-23T16:18:05Zen
dc.date.issued2004-07en
dc.identifier.citationMiller, A.M., L.Y. Yeung, A.C. Kiep, and M.J. Elrod. 2004. "Overall Rate Constant Measurements of the Reactions of Alkene-Derived Hydroxyalkylperoxy Radicals with Nitric Oxide." Physical Chemistry Chemical Physics 6(13): 3402-3407.en_US
dc.identifier.issn1463-9076en_US
dc.identifier.urihttp://hdl.handle.net/11282/309796en
dc.description.abstractThe overall rate constants of the NO reaction with hydroxyalkylperoxy radicals derived from the OH-initiated oxidation of several atmospherically abundant alkenes- ethene, propene, 1-butene, 2-butene, 2-methyl propene, 1,3-butadiene, and isoprene (2-methyl-1,3-butadiene)-were determined using the turbulent flow technique and pseudo first-order kinetic conditions with high pressure chemical ionization mass spectrometry for the direct detection of hydroxyalkylperoxy radical reactants. The individual 100 Torr, 298 K rate constants for each alkene system were found to be identical within the 95% confidence interval associated with each separate measurement. The average overall rate constant for the reaction of all alkene-derived hydroxyalkylperoxy radicals with NO was determined to be 9.1 ± 0.5 (2WEIRD"O")*10^{-12}cm^{3} molecule^{-1}s^{-1}. Previous studies of this reaction for the ethene, 2-methyl propene and isoprene systems reported varying rate constant values that ranged from a factor of two lower to a factor of two higher than the present result. However, the invariant nature and value of the present rate constant determination closely parallels the results obtained in the measurement of rate constants for the reactions of several alkane-derived peroxy radicals with NO.en_US
dc.language.isoen_USen_US
dc.publisherThe Royal Society of Chemistryen_US
dc.identifier.doi10.1039/b402110jen
dc.subject.departmentChemistryen_US
dc.titleOverall rate constant measurements of the reactions of alkene-derived hydroxyalkylperoxy radicals with nitric oxideen_US
dc.typearticleen_US
dc.identifier.journalPhysical Chemistry Chemical Physicsen_US
dc.subject.keywordOH-initiated oxidationen_US
dc.subject.keywordPeroxy radicalsen_US
dc.subject.keywordTemperature dependenceen_US
dc.subject.keywordBranching channelen_US
dc.subject.keywordReaction systemen_US
dc.subject.keywordKineticsen_US
dc.subject.keywordHydrocarbonen_US
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