Citation: Jiao-Xue YANG, Guo-Chun LV, Yan WANG, Ze-Hua WANG, Xiao-Min SUN, Zhi-Qiang LI. Mechanism Studies on the Degradation of Hexachlorocyclopentadiene in the Atmosphere[J]. Chinese Journal of Structural Chemistry, ;2020, 39(11): 1925-1932. doi: 10.14102/j.cnki.0254–5861.2011–2833 shu

Mechanism Studies on the Degradation of Hexachlorocyclopentadiene in the Atmosphere

a.
Environment Research Institute, Shandong University, Qingdao 266237, China
b.
Center for Optics Research and Engineering (CORE), Shandong University, Qingdao 266237, China

Corresponding author: Xiao-Min SUN, Zhi-Qiang LI,
Received Date: 2 April 2020
Accepted Date: 27 May 2020

Fund Project: the National Natural Science Foundation of China 21976109Natural Science Foundation of Shandong Province ZR2018MB043the Fundamental Research Funds of Shandong University 2018JC027Shandong Province Key Research and Development Program 2019GSF109037

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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.
- hexachlorocyclopentadiene,
- theoretical calculations,
- mechanism,
- rate constant
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