Bates, Kelvin H. and Crounse, John D. and St. Clair, Jason M. and Bennett, Nathan B. and Nguyen, Tran B. and Seinfeld, John H. and Stoltz, Brian M. and Wennberg, Paul O. (2014) Gas Phase Production and Loss of Isoprene Epoxydiols. Journal of Physical Chemistry A, 118 (7). pp. 1237-1246. ISSN 1089-5639. https://resolver.caltech.edu/CaltechAUTHORS:20140210-145231305
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Abstract
Isoprene epoxydiols (IEPOX) form in high yields from the OH-initiated oxidation of isoprene under low-NO conditions. These compounds contribute significantly to secondary organic aerosol formation. Their gas-phase chemistry has, however, remained largely unexplored. In this study, we characterize the formation of IEPOX isomers from the oxidation of isoprene by OH. We find that cis-β- and trans-β-IEPOX are the dominant isomers produced, and that they are created in an approximate ratio of 1:2 from the low-NO oxidation of isoprene. Three isomers of IEPOX, including cis-β- and trans-β, were synthesized and oxidized by OH in environmental chambers under high- and low-NO conditions. We find that IEPOX reacts with OH at 299 K with rate coefficients of (0.84 ± 0.07) × 10^(–11), (1.52 ± 0.07) × 10^(–11), and (0.98 ± 0.05) × 10^(–11) cm^3 molecule^(–1) s^(–1) for the δ1, cis-β, and trans-β isomers. Finally, yields of the first-generation products of IEPOX + OH oxidation were measured, and a new mechanism of IEPOX oxidation is proposed here to account for the observed products. The substantial yield of glyoxal and methylglyoxal from IEPOX oxidation may help explain elevated levels of those compounds observed in low-NO environments with high isoprene emissions.
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Additional Information: | © 2014 American Chemical Society. Received: November 1, 2013; Revised: January 28, 2014; Published: January 29, 2014. The authors would like to thank Prof. Jason D. Surratt for correspondence regarding the synthesis of IEPOX and the National Science Foundation (AGS 1240604) for their support of this research. | ||||||||||||||
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Issue or Number: | 7 | ||||||||||||||
Record Number: | CaltechAUTHORS:20140210-145231305 | ||||||||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20140210-145231305 | ||||||||||||||
Official Citation: | Gas Phase Production and Loss of Isoprene Epoxydiols Kelvin H. Bates, John D. Crounse, Jason M. St. Clair, Nathan B. Bennett, Tran B. Nguyen, John H. Seinfeld, Brian M. Stoltz, and Paul O. Wennberg The Journal of Physical Chemistry A 2014 118 (7), 1237-1246 | ||||||||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||||
ID Code: | 43756 | ||||||||||||||
Collection: | CaltechAUTHORS | ||||||||||||||
Deposited By: | Ruth Sustaita | ||||||||||||||
Deposited On: | 10 Feb 2014 23:22 | ||||||||||||||
Last Modified: | 09 Mar 2020 13:19 |
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