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Atmospheric photooxidation of isoprene part II: The ozone-isoprene reaction

Paulson, Suzanne E. and Flagan, Richard C. and Seinfeld, John H. (1992) Atmospheric photooxidation of isoprene part II: The ozone-isoprene reaction. International Journal of Chemical Kinetics, 24 (1). pp. 103-125. ISSN 0538-8066. doi:10.1002/kin.550240110. https://resolver.caltech.edu/CaltechAUTHORS:20150805-111822807

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Abstract

A series of experiments have been performed to study the ozone-isoprene reaction in a smog chamber by adding externally produced O_3 to the hydrocarbon in the dark. A chemical tracer, methyl cyclohexane, was added to probe the OH formation in the system. O(^3P) formation was also examined using the known distribution of products that are unique to the O(^3P)-isoprene reaction (part I). The results provide clear evidence that both OH and O(^3P) are produced by the O_3-isoprene reaction directly in large quantities; about 0.68 ± 0.15 and 0.45 ± 0.20 per O_3-isoprene reaction, respectively. These additional radicals severely complicate the analysis of the O_3 reaction, hence, computer kinetic modeling was necessary to ascertain the products of the O_3 reaction itself, corrected for OH and O(^3P) reactions. The product distribution, which differs dramatically from that published previously, is: 67 ± 9% methacrolein, 26 ± 6% methyl vinyl ketone, and 7 ± 3% propene, accounting for 100 ± 10% of the reacted isoprene. Applicability of these results to the gas-phase O_3 reaction with other unsaturated hydrocarbons is briefly discussed.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1002/kin.550240110DOIArticle
http://onlinelibrary.wiley.com/doi/10.1002/kin.550240110/abstractPublisherArticle
ORCID:
AuthorORCID
Paulson, Suzanne E.0000-0003-0855-7615
Flagan, Richard C.0000-0001-5690-770X
Seinfeld, John H.0000-0003-1344-4068
Additional Information:© 1992 John Wiley & Sons. Received July 9, 1991; Accepted August 7, 1991. This work was supported by National Science Foundation Grant ATM-9003186. One of the authors (S.E.P.) gratefully acknowledges the support of a Dissertation Fellowship from the American Association of University Women. The authors also appreciate helpful discussions with R. Atkinson and W P. L. Carter of the University of California at Riverside.
Funders:
Funding AgencyGrant Number
NSFATM-9003186
American Association of University WomenUNSPECIFIED
Issue or Number:1
DOI:10.1002/kin.550240110
Record Number:CaltechAUTHORS:20150805-111822807
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150805-111822807
Official Citation:Paulson, S. E., Flagan, R. C. and Seinfeld, J. H. (1992), Atmospheric photooxidation of isoprene part II: The ozone-isoprene reaction. Int. J. Chem. Kinet., 24: 103–125. doi: 10.1002/kin.550240110
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59225
Collection:CaltechAUTHORS
Deposited By: Irina Meininger
Deposited On:09 Dec 2015 21:51
Last Modified:10 Nov 2021 22:17

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