Autoxidation of Organic Compounds in the Atmosphere

被引：458

作者：

Crounse, John D. ^{[1
]}

Nielsen, Lasse B. ^{[3
]}

Jorgensen, Solvejg ^{[3
]}

Kjaergaard, Henrik G. ^{[3
]}

Wennberg, Paul O. ^{[1
,2
]}

机构：

[1] CALTECH, Div Geol & Planetary Sci, Pasadena, CA 91125 USA

[2] CALTECH, Div Engn & Appl Sci, Pasadena, CA 91125 USA

[3] Univ Copenhagen, Dept Chem, DK-2100 Copenhagen O, Denmark

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2013年 / 4卷 / 20期

基金：

美国国家科学基金会;

关键词：

OH RADICALS; AEROSOL; OXIDATION; POLYPHENOLS; PARTICLES; CHEMISTRY; MECHANISM; EVOLUTION; PRODUCTS; KETONES;

D O I：

10.1021/jz4019207

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

We present a hypothesis that autoxidation (inter- and intramolecular hydrogen abstraction by peroxy radicals) plays an important role in the oxidation of organic compounds in the atmosphere, particularly organic matter associated with aerosol. In the laboratory, we determine the rate of this process at room temperature for a model system, 3-pentanone. We employ ab initio calculations to investigate H-shifts within a broader group of substituted organic compounds. We show that the rate of abstraction of hydrogen by peroxy radicals is largely determined by the thermochemistry of the nascent alkyl radicals and thus is highly influenced by neighboring substituents. As a result, autoxidation rates increase rapidly as oxygen-containing functional groups (carbonyl, hydroxy, and hydroperoxy) are added to organic compounds. This mechanism is consistent with formation of the multifunctional hydroperoxides and carbonyls often found in atmospheric aerosol particles.

引用

页码：3513 / 3520

页数：8

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