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作为 NO2 浓度的函数,气相 OH 自由基引发的甲苯、二甲苯和均三甲苯反应生成乙二醛和甲基乙二醛的生成率。

Formation yields of glyoxal and methylglyoxal from the gas-phase OH radical-initiated reactions of toluene, xylenes, and trimethylbenzenes as a function of NO2 concentration.

机构信息

Air Pollution Research Center, University of California, Riverside, California 92521, USA.

出版信息

J Phys Chem A. 2010 Sep 23;114(37):10140-7. doi: 10.1021/jp105112h.

DOI:10.1021/jp105112h
PMID:20804209
Abstract

Aromatic hydrocarbons comprise 20% of non-methane volatile organic compounds in urban areas and are transformed mainly by atmospheric chemical reactions with OH radicals during daytime. In this work we have measured the formation yields of glyoxal and methylglyoxal from the OH radical-initiated reactions of toluene, xylenes, and trimethylbenzenes over the NO2 concentration range (0.2-10.3) × 1013 molecules cm(-3). For toluene, o-, m-, and p-xylene, and 1,3,5-trimethylbenzene, the yields showed a dependence on NO2, decreasing with increasing NO2 concentration and with no evidence for formation of glyoxal or methylglyoxal from the reactions of the OH-aromatic adducts with NO2. In contrast, for 1,2,3- and 1,2,4-trimethylbenzene the glyoxal and methylglyoxal formation yields were independent of the NO2 concentration within the experimental uncertainties. Extrapolations of our results to NO2 concentrations representative of the ambient atmosphere results in the following glyoxal and methylglyoxal yields, respectively: for toluene, 26.0 ± 2.2% and 21.5 ± 2.9%; for o-xylene, 12.7 ± 1.9% and 33.1 ± 6.1%; for m-xylene, 11.4 ± 0.7% and 51.5 ± 8.5%; for p-xylene, 38.9 ± 4.7% and 18.7 ± 2.2%; for 1,2,3-trimethylbenzene, 4.7 ± 2.4% and 15.1 ± 3.3%; for 1,2,4-trimethylbenzene, 8.7 ± 1.6% and 27.2 ± 8.1%; and for 1,3,5-trimethylbenzene, 58.1 ± 5.3% (methylglyoxal).

摘要

芳香烃占城市中非甲烷挥发性有机化合物的 20%,主要通过大气化学反应与羟基自由基在白天转化。在这项工作中,我们测量了在二氧化氮浓度范围内(0.2-10.3)×1013 分子 cm(-3) 下,甲苯、二甲苯和三甲苯与羟基自由基反应生成乙二醛和甲基乙二醛的生成率。对于甲苯、邻二甲苯、间二甲苯和对二甲苯以及 1,3,5-三甲苯,产率随二氧化氮浓度的增加而降低,没有证据表明羟基-芳香加合物与二氧化氮反应生成乙二醛或甲基乙二醛。相比之下,对于 1,2,3-和 1,2,4-三甲苯,乙二醛和甲基乙二醛的生成率在实验不确定度内与二氧化氮浓度无关。将我们的结果外推到代表环境大气的二氧化氮浓度,得到以下乙二醛和甲基乙二醛的产率,分别为:对于甲苯,26.0±2.2%和 21.5±2.9%;对于邻二甲苯,12.7±1.9%和 33.1±6.1%;对于间二甲苯,11.4±0.7%和 51.5±8.5%;对于对二甲苯,38.9±4.7%和 18.7±2.2%;对于 1,2,3-三甲苯,4.7±2.4%和 15.1±3.3%;对于 1,2,4-三甲苯,8.7±1.6%和 27.2±8.1%;对于 1,3,5-三甲苯,58.1±5.3%(甲基乙二醛)。

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