Mechanism Studies on the Degradation of Hexachlorocyclopentadiene in the Atmosphere

作     者：YANG Jiao-Xue LV Guo-Chun WANG Yan WANG Ze-Hua SUN Xiao-Min LI Zhi-Qiang YANG Jiao-Xue;LV Guo-Chun;WANG Yan;WANG Ze-Hua;SUN Xiao-Min;LI Zhi-Qiang

作者机构：Environment Research InstituteShandong UniversityQingdao 266237China Center for Optics Research and Engineering(CORE)Shandong UniversityQingdao 266237China 

出 版 物：《Chinese Journal of Structural Chemistry》 (结构化学（英文）)

年 卷 期：2020年第39卷第11期

页      面：1925-1932页

核心收录：

学科分类：090403[农学-农药学(可授农学、理学学位）] 07[理学] 070602[理学-大气物理学与大气环境] 09[农学] 0706[理学-大气科学] 0904[农学-植物保护] 

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) 

主　　题：hexachlorocyclopentadiene theoretical calculations mechanism rate constant 

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.