The atmospheric degradation pathways of BrCH2O2: computational calculation on mechanisms of the reaction with HO2.
The atmospheric degradation pathways of BrCH2O2: computational calculation on mechanisms of the reaction with HO2.
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DOI：
10.1016/j.chemosphere.2014.04.068
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发表时间：
2014-09
期刊：
影响因子：
8.8
通讯作者：
Yizhen Tang;Jingyu Sun;Yunju Zhang;Rongshun Wang
中科院分区：
文献类型：
--
作者：
Yizhen Tang;Jingyu Sun;Yunju Zhang;Rongshun Wang
采用量子化学方法研究了BrCH 2 O2 + HO 2的大气降解反应机理。结果表明，主要产物为BrCH_2OOH + O_2（3摩尔）。而CH_2O + HBr + O_3、BrCHO + OH + HO_2和CH_2O + Br + HO_3在大气中存在一定程度的竞争。同时，在大气条件下，新生产物-BrCH_2 OOH容易与OH自由基反应，再次生成BrCH_2 O_2。OH自由基在BrCH_2 OOH → BrCHO + H_2 O的净反应中起催化作用。因此，实验中提出的产物BrCHO + H2O + O2可能是由BrCH 2 OOH与额外OH自由基反应生成的。比较表明，卤素取代效应对大气中XCH_2 O_2（X= H，F，Cl和Br）+HO_2反应的贡献较小。
Mechanisms for the atmospheric degradation reaction of BrCH2O2+ HO2were investigated using quantum chemistry methods. The result indicates that the dominant product is BrCH2OOH + O2(3Σ). While CH2O + HBr + O3, BrCHO + OH + HO2and CH2O + Br + HO3will be competitive to a certain extent in the atmosphere. Meanwhile, the nascent product – BrCH2OOH reacts easily with OH radicals leading to BrCH2O2again under the atmospheric conditions. Moreover, OH radicals could act as a catalyst in the net reaction of BrCH2OOH → BrCHO + H2O. Thus the proposed product BrCHO + H2O + O2in the experiment might be generated from the subsequent reaction of BrCH2OOH with extra OH radicals. Comparisons indicate that halogen substitution effect makes minor contributions to theXCH2O2(X= H, F, Cl and Br) + HO2reactions in the atmosphere.