Mechanism Studies on the Degradation of Hexachlorocyclopentadiene in the Atmosphere

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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.

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	杨娇雪
	吕国春
	王研
	王泽华
	孙孝敏
	李志强

关键词 ： hexachlorocyclopentadiene, theoretical calculations, mechanism, rate constant

Abstract：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.

Key words： hexachlorocyclopentadiene theoretical calculations mechanism rate constant

收稿日期: 2020-04-02 出版日期: 2020-11-09

基金资助:This project was 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),and Shandong Province Key Research and Development Program (2019GSF109037)

通讯作者: sxmwch@sdu.edu.cn E-mail: sxmwch@sdu.edu.cn

引用本文:

杨娇雪;吕国春;王研;王泽华;孙孝敏;李志强. Mechanism Studies on the Degradation of Hexachlorocyclopentadiene in the Atmosphere[J]. 结构化学, 2020, 39(11): 1925-1932.
YANG Jiao-Xue;LV Guo-Chun;WANG Yan;WANG Ze-Hua;SUN Xiao-Min;LI Zhi-Qiang. Mechanism Studies on the Degradation of Hexachlorocyclopentadiene in the Atmosphere. CHINESE JOURNAL OF STRUCTURAL CHEMISTRY, 2020, 39(11): 1925-1932.

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http://manu30.magtech.com.cn/jghx/CN/ 或 http://manu30.magtech.com.cn/jghx/CN/Y2020/V39/I11/1925

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