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2-糠醛基肉桂醛的大气化学研究。

Study of the atmospheric chemistry of 2-formylcinnamaldehyde.

机构信息

Air Pollution Research Center, University of California Riverside, California 92521, United States.

出版信息

J Phys Chem A. 2013 Aug 22;117(33):7876-86. doi: 10.1021/jp404994w. Epub 2013 Aug 7.

Abstract

2-Formylcinnamaldehyde is a significant product of the reaction of naphthalene with OH radicals, and its photolysis and gas-phase reactions with O3, NO3 radicals, and OH radicals have been investigated in this work. 2-Formylcinnamaldehyde was observed to undergo photolysis by black lamps, with a photolysis rate of 0.14 × J(NO2), where J(NO2) is the NO2 photolysis rate. The measured rate constants for the reactions of 2-formylcinnamaldehyde with O3, NO3 radicals, and OH radicals (in units of cm(3) molecule(-1) s(-1)) were 1.8 × 10(-18), 4.3 × 10(-14), and 2.1 × 10(-11), respectively, with those for the O3 and NO3 reactions being for the E-isomer. 2-Formylcinnamaldehyde was observed to undergo significant adsorption and desorption from the reaction chamber Teflon film walls, and the photolysis rate and rate constants are subject to significant uncertainties. In the atmosphere, the dominant chemical loss processes for 2-formylcinnamaldehyde will be photolysis during daylight hours and reaction with NO3 radicals during nighttime. Phthaldialdehyde and glyoxal were observed as products of the OH radical and O3 reactions, and photolysis of E-2-formylcinnamaldehyde led to formation of Z-2-formylcinnamaldehyde plus two other molecular weight 160 isomers. The present results are compared with previous literature data, and reaction mechanisms are discussed.

摘要

2-甲酰肉桂醛是萘与 OH 自由基反应的重要产物,本工作研究了其光解以及与 O3、NO3 自由基和 OH 自由基的气相反应。2-甲酰肉桂醛在黑光灯下发生光解,光解速率为 0.14×J(NO2),其中 J(NO2)为 NO2 光解速率。实验测量得到 2-甲酰肉桂醛与 O3、NO3 自由基和 OH 自由基的反应速率常数(单位为 cm3 分子-1 s-1)分别为 1.8×10-18、4.3×10-14和 2.1×10-11,这些速率常数针对的是 E-异构体。实验观察到 2-甲酰肉桂醛在反应腔特氟龙壁上发生显著的吸附和解吸,光解速率和速率常数存在较大的不确定性。在大气中,2-甲酰肉桂醛的主要化学损耗过程将是日光下的光解以及夜间与 NO3 自由基的反应。实验还观测到邻苯二甲醛和乙二醛是 OH 自由基和 O3 反应的产物,E-2-甲酰肉桂醛的光解导致 Z-2-甲酰肉桂醛和另外两种分子量为 160 的异构体的生成。本文结果与以往文献数据进行了比较,并对反应机制进行了讨论。

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