摘要
Hexachlorocyclopentadiene(HCCP) is one of the chlorinated and highly reactive pollutants, which can be released into the atmosphere and undergo chemical transformations. In this paper, the initiated reaction mechanisms of HCCP with typical atmospheric oxidants(·NO3, ·HO2, ·OH, and O3) were theoretically investigated. The results mean that all initiated reactions are exothermic, and the energy barriers do not exceed 16 kcal×mol-1. The rate constants of HCCP reaction triggered by ·NO3, ·HO2, ·OH, and O3 are 2.49 × 10-12, 2.44 × 10-22, 2.46 × 10-13 and 1.33 × 10-20 cm3×molecule-1×s-1 at 298 K, respectively. It can be concluded that the reaction of ·NO3 and ·OH with HCCP more likely occurs according to the rate constants. Then the subsequent reactions of the ·NO3/·OH-initiated intermediates with O2 and NO were calculated, resulting in that the cyclopentadiene is ruptured completely. And the results show that the Criegee intermediates created in the ozonization reactions of HCCP can react with O2, NO2 and SO2. This study gives more insight into the chemical transformation mechanisms of HCCP in the atmosphere.
基金
supported by the National Natural Science Foundation of China (21976109)
Natural Science Foundation of Shandong Province (ZR2018MB043)
the Fundamental Research Funds of Shandong University (2018JC027)
Shandong Province Key Research and Development Program (2019GSF109037)。
