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

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• 作者：Torsten Berndt ; Tuija Jokinen ; Roy L. Mauldin ; III ; Tuukka Pet盲j盲 ; Hartmut Herrmann ; Heikki Junninen ; Pauli Paasonen ; Douglas R. Worsnop ; Mikko Sipil盲
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2012
• 出版时间：October 4, 2012
• 年：2012
• 卷：3
• 期：19
• 页码：2892-2896
• 全文大小：306K
• 年卷期：v.3,no.19(October 4, 2012)
• ISSN：1948-7185

文摘

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-cyclohexene (MCH) carried out in an atmospheric pressure flow tube at 293 卤 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 卤 0.28 (TME), 0.53 卤 0.24 (trans-2-butene) and 0.16 卤 0.07 (MCH). The rate coefficients for sCI + SO₂ from our experiment, (0.9鈥?.7) 脳 10^鈥?3 cm³ molecule^鈥? s^鈥?, 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.

Keywords:

gas-phase ozonolysis; Criegee intermediate; stabilization; atmospheric H₂SO₄ formation; CI-APi-TOF mass spectrometry