Products of the gas-phase reaction of O3 with cyclohexene
Products of the gas-phase reaction of O3 with cyclohexene
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DOI：
10.1021/jp022122e
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发表时间：
2003-04-03
影响因子：
2.9
通讯作者：
Atkinson, R
中科院分区：
文献类型：
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作者：
Aschmann, SM;Tuazon, EC;Atkinson, R
采用气相色谱-火焰离子化检测、气相色谱-质谱联用、原位傅里叶变换红外光谱和原位大气压电离质谱仪(API-MS)研究了03与环己烯和环己烯-d(10)在羟基自由基清除剂存在下的气相反应产物。实验中使用了环己烷和环己烷-d(12)作为OH自由基清除剂，通过API-MS分析，可以将03与环己烯和环己烯-d(10)反应生成的产物与OH自由基与环己烷和环己烷-d(12)反应生成的产物区分开来。在OH自由基清除剂的存在下，O-3与环己烯反应的气相产物是戊醛(23.6+/-1.8%)；OH自由基(54+/-8%)；甲酸(3.5%的初始产率)；戊二醛[HC(O)CH2CH2CH2CH2CHO]；己二醛[HC(O)CH2CH2CH2CH2CH2CHO]，属于次要臭氧的C6H1003产物；C5H7O2(OOH)产物，分子量130羟基二羰基；和分子量116羰基化合物。O-3与环己烯d(10)反应生成正戊醛d(10)、OD自由基和DC(O)OH的产率分别为16.4+/-1.4%、50+/-7%和1.6%(初始)。我们的数据表明，Criegee中间体生成戊醛(+CO2)和OH自由基+有机自由基副产物的反应占反应路径的78+/-9%，其中有机自由基副产物反应生成(部分)戊二醛。乙二醛可以由加热的Criegee中间体(可能是抗中间体)与水蒸气反应生成。O-3与丙烯(40+/-6%)、丙烯-d(6)(27+/-4%)、α-品烯(86+/-13%)和2，3-二甲基-2-丁烯(107+/-16%)的反应生成OH(或OD)自由基。
Products of the gas-phase reactions of 03 with cyclohexene and cyclohexene-d(10) were investigated in the presence of OH radical scavengers by gas chromatography with flame ionization detection, combined gas chromatography-mass spectrometry, in situ Fourier transform infrared spectroscopy, and in situ atmospheric pressure ionization mass spectrometry (API-MS). Cyclohexane and cyclohexane-d(12) were used as OH radical scavengers in the experiments using API-MS analyses to allow products formed from the 03 reactions with cyclohexene and cyclohexene-d(10) to be differentiated from those from the reactions of OH radicals with cyclohexane and cyclohexane-d(12). The gas-phase products observed from the reaction of O-3 with cyclohexene in the presence of an OH radical scavenger were pentanal (23.6 +/- 1.8%); OH radicals (54 +/- 8%); formic acid (3.5% initial yield); glutaraldehyde [HC(O)CH2CH2CH2CHO]; adipaldehyde [HC(O)CH2CH2CH2CH2CHO], a C6H10O3 product attributed to the secondary ozonide; a C5H7O2(OOH) product, a molecular weight 130 hydroxydicarbonyl; and a molecular weight 116 carbonyl compound. Yields of pentanal-d(10), OD radicals, and DC(O)OH from the reaction of O-3 with cyclohexene-d(10), of 16.4 +/- 1.4%, 50 +/- 7%, and 1.6% (initial), respectively, were obtained. Our data indicate that reactions of the Criegee intermediate to form pentanal (plus CO2) and an OH radical plus organic radical coproduct account for 78 +/- 9% of the reaction pathways, with the organic radical coproduct reacting to form (in part) glutaraldehyde. Adipaldehyde can be formed from reaction of the thermalized Criegee intermediate (presumably the anti-intermediate) with water vapor. OH (or OD) radical formation yields were also measured from the reactions of O-3 with propene (40 +/- 6%), propene-d(6) (27 +/- 4%) alpha-pinene (86 +/- 13%), and 2,3-dimethyl-2-butene (107 +/- 16%).