Behavior and prediction of photochemical degradation of chlorinated polycyclic aromatic hydrocarbons in cyclohexane.
Behavior and prediction of photochemical degradation of chlorinated polycyclic aromatic hydrocarbons in cyclohexane.
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DOI：
10.1016/j.chemosphere.2007.08.064
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发表时间：
2008-02
期刊：
影响因子：
8.8
通讯作者：
T. Ohura;T. Amagai;M. Makino
中科院分区：
文献类型：
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作者：
T. Ohura;T. Amagai;M. Makino
研究了11种氯代多环芳烃(ClPAHs)及其对应的5种母体多环芳烃(PAHs)的光化学降解，模拟了该化合物在气溶胶表面的去向。所有ClPAHs和PAHs的降解均符合一级反应速率动力学。氯代多环芳烃的光解速率因多环芳烃骨架的不同而有很大差异，氯代菲和1-氯基吡喃的光解速率高于相应的母体多环芳烃，而氯荧蒽、7-氯苯并[a]菲和6-氯苯并[a]芘的光解速率比相应的母体多环芳烃更稳定。考虑到检测到的ClPhes的光产物，氧化可能立即发生在前沿电子密度最高的位置。最后，建立了氯代环芳烃和母体多环芳烃的直接光解半衰期和平均量子产率的定量结构-性质关系模型，其中影响光解的显著因素分别为ELUMO+1、总能量和表面积，以及ELUMO、ELUMO−EHOMO和总能量。
The photochemical degradation of 11 chlorinated polycyclic aromatic hydrocarbons (ClPAHs) and the corresponding 5 parent PAHs was examined to simulate the compound’s fate on aerosol surfaces. All the ClPAHs and PAHs decayed according to the first-order reaction rate kinetics. The photolysis rates of ClPAHs varied greatly according to the skeleton of PAHs; the rates of chlorophenanthrenes (ClPhes) and 1-chloropyrene were higher than those of corresponding parent PAHs, whereas chlorofluoranthenes, 7-chlorobenz[a]anthracene and 6-chlorobenzo[a]pyrene were more stable under irradiation compared to respective parent PAH. Considering the photoproducts of ClPhes detected, the oxidation could occur immediately at positions of the highest frontier electron density. Finally, the quantitative structure-property relationship models were developed for direct photolysis half-lives and average quantum yields of the ClPAHs and parent PAHs, in which the significant factors affecting photolysis were ELUMO+1, total energy and surface area, and ELUMO, ELUMO−EHOMOand total energy, respectively.