| OH radical initiated oxidation of 1,3-butadiene: isomeric selective study of the dominant addition channel. | |
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MedLine Citation:
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PMID: 20361769 Owner: NLM Status: MEDLINE |
Abstract/OtherAbstract:
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We report the first isomeric selective kinetic study of the dominant isomeric pathway in the OH initiated oxidation of 1,3-butadiene in the presence of O(2) and NO using the laser photolysis-laser induced fluorescence (LP-LIF) technique. The photodissociation of the precursor 2-iodo-but-3-en-1-ol results exclusively in the dominant OH-butadiene addition product, permitting important insight into the OH initiated oxidation mechanism. On the basis of analysis of the time dependent OH/OD signals, we have determined a rate constant for O2 addition to the hydroxyalkyl radical of 7.0(-3.0)(+7.0) x 10(-13) cm(3) s(-1), and we find a value of 1.5(-0.6)(+1.0) x 10(-11) cm(3) s(-1) for the overall reaction rate constant of the hydroxy peroxy radical with NO. We also report the first clear experimental evidence of the (E) form of the delta-hydroxyalkoxy channel through isotopic labeling experiments and provide an upper bound of 13 +/- 5% to its branching ratio. This species provides a mechanistic pathway for the formation of 4-hydroxy-2-butenal, which has been identified as a first generation end product. This isomeric selective kinetic study, together with a previous study on the minor channel of the 1,3-butadiene oxidation, yields a comprehensive picture of butadiene oxidation under high NOx conditions relevant to most regions in the continental US. |
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Authors:
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Buddhadeb Ghosh; Alejandro Bugarin; Brian T Connell; Simon W North |
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Publication Detail:
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Type: Journal Article; Research Support, U.S. Gov't, Non-P.H.S. |
Journal Detail:
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Title: The journal of physical chemistry. A Volume: 114 ISSN: 1520-5215 ISO Abbreviation: J Phys Chem A Publication Date: 2010 Apr |
Date Detail:
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Created Date: 2010-04-22 Completed Date: 2010-07-12 Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 9890903 Medline TA: J Phys Chem A Country: United States |
Other Details:
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Languages: eng Pagination: 5299-305 Citation Subset: IM |
Affiliation:
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Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842, USA. |
Export Citation:
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| MeSH Terms | |
Descriptor/Qualifier:
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Butadienes
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chemistry* Hydroxyl Radical / chemistry* Isomerism Kinetics Lasers Molecular Structure Nitric Oxide / chemistry Oxidation-Reduction Oxygen / chemistry* |
| Chemical | |
Reg. No./Substance:
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0/Butadienes; 10102-43-9/Nitric Oxide; 106-99-0/1,3-butadiene; 3352-57-6/Hydroxyl Radical; 7782-44-7/Oxygen |
From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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