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Atmospheric photooxidation of isoprene part I: The hydroxyl radical and ground state atomic oxygen reactions

Paulson, Suzanne E. and Flagan, Richard C. and Seinfeld, John H. (1992) Atmospheric photooxidation of isoprene part I: The hydroxyl radical and ground state atomic oxygen reactions. International Journal of Chemical Kinetics, 24 (1). pp. 79-101. ISSN 0538-8066. doi:10.1002/kin.550240109. https://resolver.caltech.edu/CaltechAUTHORS:20150805-111659703

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Abstract

The OH reaction with isoprene is studied. Methyl nitrite photolysis experiments were carried out in an outdoor smog chamber in an attempt to identify as completely as possible OH-isoprene product distribution. Emphasis was placed on identification and quantification of oxygenated products. A Tenax-based cryo-trap thermal desorber used to trap, concentrate, and dry chamber samples for identification on a GC/MS is described. Analysis of the products revealed that O(^3P) can form in reaction systems designed to study OH reactions that include high concentrations of NO, and consequently NO_2, hence, this reaction is also examined. The yields of methacrolein and methyl vinyl ketone are determined as 25 ± 3 and 35.5 ± 4%, respectively, with an additional 4 ± 2% as 3-methyl furan, totaling 65 ± 4%. These results, combined with those of previous studies allow 80% of isoprene's products to be explicitly identified, and the general structure of the remaining products to be ascertained. The O(^3P) reaction produces 84 ± 8% epoxides, and 8 ± 3% species which result in production of HO_2, and subsequently, OH. A heretofore unidentified product of the O(^3P) reaction, 2-methyl 2-butenal, is identified. The rate constant of the NO_2-isoprene reaction is measured.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1002/kin.550240109DOIArticle
http://onlinelibrary.wiley.com/doi/10.1002/kin.550240109/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, Inc. 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 W.P.L. Carter and R. Atkinson 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.550240109
Record Number:CaltechAUTHORS:20150805-111659703
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150805-111659703
Official Citation:Paulson, S. E., Flagan, R. C. and Seinfeld, J. H. (1992), Atmospheric photooxidation of isoprene part I: The hydroxyl radical and ground state atomic oxygen reactions. Int. J. Chem. Kinet., 24: 79–101. doi: 10.1002/kin.550240109
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59224
Collection:CaltechAUTHORS
Deposited By: Irina Meininger
Deposited On:06 Nov 2015 00:04
Last Modified:10 Nov 2021 22:17

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