Gas-Phase Ozonolysis of Selected Olefins: The Yield of Stabilized Criegee Intermediate and the Reactivity toward SO2

被引：87

作者：

Berndt, Torsten ^{[1
]}

Jokinen, Tuija ^{[2
]}

Mauldin, Roy L., III ^{[2
,3
]}

Petaja, Tuukka ^{[2
]}

Herrmann, Hartmut ^{[1
]}

Junninen, Heikki ^{[2
]}

Paasonen, Pauli ^{[2
]}

Worsnop, Douglas R. ^{[2
,4
,5
]}

Sipila, Mikko ^{[2
]}

机构：

[1] Leibniz Inst Tropospher Res, Leipzig, Germany

[2] Univ Helsinki, Dept Phys, Helsinki, Finland

[3] Univ Colorado, Boulder, CO 80309 USA

[4] Univ Eastern Finland, Kuopio, Finland

[5] Aerodyne Res Inc, Billerica, MA 01821 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2012年 / 3卷 / 19期

基金：

芬兰科学院; 欧洲研究理事会;

关键词：

OZONE-ALKENE REACTION; RATE CONSTANTS; SULFURIC-ACID; HOX FORMATION; MECHANISM; PRESSURE; ETHENE; DEPENDENCE; OXIDATION; KINETICS;

D O I：

10.1021/jz301158u

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：

The gas-phase reaction of ozone with olefins represents an important path for the conversion of unsaturated hydrocarbons in the atmosphere. The current interest is focused on the formation of stabilized Criegee intermediates (sCI) and possible further reactions of sCI. We report results from the ozonolysis of 2,3-dimethyl-2-butene (TME), trans-2-butene and 1-methyl-c-yclohexene (MCH) carried out in an atmospheric pressure flow tube at 293 +/- 0.5 K and RH = 50% using chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometry to detect H2SO4 produced from SO2 oxidation by sCI. The yields of sCI were found to be in good agreement with recently observed data: 0.62 +/- 0.28 (TME), 0.53 +/- 0.24 (trans-2-butene) and 0.16 +/- 0.07 (MCH). The rate coefficients for sCI + SO2 from our experiment, (0.9-7.7) X 10(-13) cm(3) molecule(-1) s(-1), are within the range of recommendations from indirect determinations as given so far in the literature. Our study helps to assess the importance of sCI in atmospheric chemistry, especially for the oxidation of SO2 to H2SO4.

引用

页码：2892 / 2896

页数：5

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