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DOI | 10.5194/acp-19-5021-2019 |
Aqueous reactions of organic triplet excited states with atmospheric alkenes | |
Kaur, Richie1,2; Hudson, Brandi M.3; Draper, Joseph1,4; Tantillo, Dean J.3; Anastasio, Cort1,2 | |
2019-04-12 | |
发表期刊 | ATMOSPHERIC CHEMISTRY AND PHYSICS
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ISSN | 1680-7316 |
EISSN | 1680-7324 |
出版年 | 2019 |
卷号 | 19期号:7页码:5021-5032 |
文章类型 | Article |
语种 | 英语 |
国家 | USA |
英文摘要 | Triplet excited states of organic matter are formed when colored organic matter (i. e., brown carbon) absorbs light. While these " triplets" can be important photooxidants in atmospheric drops and particles (e. g., they rapidly oxidize phenols), very little is known about their reactivity toward many classes of organic compounds in the atmosphere. Here we measure the bimolecular rate constants of the triplet excited state of benzophenone ((BP)-B-3*), a model species, with 17 water-soluble C-3-C-6 alkenes that have either been found in the atmosphere or are reasonable surrogates for identified species. Measured rate constants (k(ALK+3BP*)) vary by a factor of 30 and are in the range of (0.24-7.5) x 109M 1 s 1. Biogenic alkenes found in the atmosphere -e. g., cis-3hexen- 1-ol, cis-3-hexenyl acetate, and methyl jasmonate react rapidly, with rate constants above 1 x 10(9) M-1 s(-1). Rate constants depend on alkene characteristics such as the location of the double bond, stereochemistry, and alkyl substitution on the double bond. There is a reasonable correlation between k(ALK+3BP*) and the calculated one-electron oxidation potential (OP) of the alkenes (R-2 = 0: 58); in contrast, rate constants are not correlated with bond dissociation enthalpies, bond dissociation free energies, or computed energy barriers for hydrogen abstraction. Using the OP relationship, we estimate aqueous rate constants for a number of unsaturated isoprene and limonene oxidation products with 3BP* : values are in the range of (0.080-1.7) x 10(9) M-1 s(-1), with generally faster values for limonene products. Rate constants with less reactive triplets, which are probably more environmentally relevant, are likely roughly 25 times slower. Using our predicted rate constants, along with values for other reactions from the literature, we conclude that triplets are probably minor oxidants for isoprene-and limonene-related compounds in cloudy or foggy atmospheres, except in cases in which the triplets are very reactive. |
领域 | 地球科学 |
收录类别 | SCI-E |
WOS记录号 | WOS:000464352500005 |
WOS关键词 | SET MODEL CHEMISTRY ; DENSITY-FUNCTIONAL THERMOCHEMISTRY ; AEROSOL FORMATION ; RATE CONSTANTS ; HYDROGEN-PEROXIDE ; EPOXIDE FORMATION ; PHASE REACTIONS ; SINGLET OXYGEN ; TOTAL ENERGIES ; ISOPRENE |
WOS类目 | Environmental Sciences ; Meteorology & Atmospheric Sciences |
WOS研究方向 | Environmental Sciences & Ecology ; Meteorology & Atmospheric Sciences |
引用统计 | |
文献类型 | 期刊论文 |
条目标识符 | http://119.78.100.173/C666/handle/2XK7JSWQ/182312 |
专题 | 地球科学 |
作者单位 | 1.Univ Calif Davis, Dept Land Air & Water Resources, Davis, CA 95616 USA; 2.Univ Calif Davis, Agr & Environm Chem Grad Grp, Davis, CA 95616 USA; 3.Univ Calif Davis, Dept Chem, Davis, CA 95616 USA; 4.Fresno Metropolitan Flood Control Dist, Fresno, CA 93727 USA |
推荐引用方式 GB/T 7714 | Kaur, Richie,Hudson, Brandi M.,Draper, Joseph,et al. Aqueous reactions of organic triplet excited states with atmospheric alkenes[J]. ATMOSPHERIC CHEMISTRY AND PHYSICS,2019,19(7):5021-5032. |
APA | Kaur, Richie,Hudson, Brandi M.,Draper, Joseph,Tantillo, Dean J.,&Anastasio, Cort.(2019).Aqueous reactions of organic triplet excited states with atmospheric alkenes.ATMOSPHERIC CHEMISTRY AND PHYSICS,19(7),5021-5032. |
MLA | Kaur, Richie,et al."Aqueous reactions of organic triplet excited states with atmospheric alkenes".ATMOSPHERIC CHEMISTRY AND PHYSICS 19.7(2019):5021-5032. |
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