期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 118, 期 7, 页码 1237-1246出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp4107958
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资金
- National Science Foundation [AGS 1240604]
- Div Atmospheric & Geospace Sciences
- Directorate For Geosciences [1240604] Funding Source: National Science Foundation
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-beta- and trans-beta-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-beta- and trans-beta, 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) x 10(-11), (1.52 +/- 0.07) x 10(-11), and (0.98 +/- 0.05) x 10(-11) cm(3) molecule(-1) s(-1) for the delta 1, cis-beta, and trans-beta 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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