Efficient Coupling of Reaction Pathways of Criegee Intermediates and Free Radicals in the Heterogeneous Ozonolysis of Alkenes

被引：16

作者：

Zeng, Meirong ^{[1
]}

Wilson, Kevin R. ^{[1
]}

机构：

[1] Lawrence Berkeley Natl Lab, Div Chem Sci, Berkeley, CA 94720 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2020年 / 11卷 / 16期

关键词：

HYDROXYL RADICALS; OXIDATION; OH; SQUALENE; AEROSOL; PRODUCTS; OZONE; HYDROPEROXIDES; NANOPARTICLES; AUTOXIDATION;

D O I：

10.1021/acs.jpclett.0c01823

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：

In the gas phase, ozonolysis of olefins is known to be a significant source of free radicals. However, for heterogeneous and condensed phase ozone reactions, the importance of reaction pathways that couple Criegee intermediates (CI) with hydroxyl (OH), alkoxy, and peroxy free radicals remains uncertain. Here we report experimental evidence for substantial free radical oxidation during the heterogeneous reaction of O-3 with cis-9-tricosene (Tri) aerosol. A kinetic model with three coupled submechanisms that include O-3, CI, and free radical reactions is used to explain how the observed Tri reactivity and its product distributions depend upon [O-3], [OH], and the presence of CI scavengers. During multiphase ozonolysis, the kinetic model predicts that only similar to 30% of the alkene is actually consumed by O-3, while the remaining similar to 70% is consumed by free radicals that cycle through pathways involving CI. These results reveal the importance of free radical oxidation during heterogeneous ozonolysis, which has been previously difficult to isolate due to the complex coupling of CI and OH reaction pathways.

引用

页码：6580 / 6585

页数：6

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