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 NO₂, 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 HO₂, and subsequently, OH. A heretofore unidentified product of the O(³P) reaction, 2-methyl 2-butenal, is identified. The rate constant of the NO₂-isoprene reaction is measured.
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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. | ||||||||
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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: | 19 Apr 2023 23:14 |
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