Quantum Chemical and Kinetic Study on Radical/Molecule Formation Mechanism of Pre-Intermediates for PCTA/PT/DT/DFs from 2-Chlorothiophenol and 2-Chlorophenol Precursors
文献类型：期刊论文
| 作者 | Zuo, Chenpeng; Wang, Hetong; Pan, Wenxiao; Zheng, Siyuan; Xu, Fei; Zhang, Qingzhu |
| 刊名 | INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
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| 出版日期 | 2019-03-27 |
| 卷号 | 20期号:7页码:- |
| 关键词 | PCTA PT DTs formation mechanism radical molecule coupling density functional theory rate constant |
| ISSN号 | 1422-0067 |
| 英文摘要 | Polychlorinated phenoxathiins (PCPTs), polychlorinated dibenzothiophenes (PCDTs), and polychlorinated thianthrenes (PCTAs) are sulfur analogues of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/DFs). Chlorothiophenols (CTPs) and chlorophenols (CPs) are key precursors for the formation of PCTA/PT/DTs, which can react with H or OH to form chloro(thio)phenoxy radical, sulfydryl/hydroxyl-substituted phenyl radicals, and (thio)phenoxyl diradicals. However, previous radical/radical PCTA/DT formation mechanisms in the literature failed to explain the higher concentration of PCDTs than that of PCTAs under the pyrolysis or combustion conditions. In this work, a detailed thermodynamics and kinetic calculations were carried out to investigate the pre-intermediate formation for PCTA/PT/DTs from radical/molecule coupling of the 2-C(T)P with their key radical species. Our study showed that the radical/molecule coupling mechanism explains the gas-phase formation of PCTA/PT/DTs in both thermodynamic and kinetic perspectives. The S/C coupling modes to form thioether-(thio)enol intermediates are preferable over the O/C coupling modes to form ether-(thio)enol intermediates. Thus, although the radical/molecule coupling of chlorophenoxy radical with 2-C(T)P has no effect on the PCDD/PT formation, the radical/molecule coupling of chlorothiophenoxy radical with 2-C(T)P plays an important role in the PCTA/PT formation. Most importantly, the pre-PCDT intermediates formation pathways from the couplings of sulfydryl/hydroxyl-substituted phenyl radical with 2-C(T)P and (thio)phenoxyl diradicals with 2-C(T)P are more favorable than pre-PCTA/PT intermediates formation pathways from the coupling of chlorothiophenoxy radical with 2-C(T)P, which provides reasonable explanation for the high PCDT-to-PCTA ratio in the environment. |
| 源URL | [http://ir.rcees.ac.cn/handle/311016/42998]  |
| 专题 | 生态环境研究中心_环境化学与生态毒理学国家重点实验室 |
| 作者单位 | 1.Shandong Univ, Environm Res Inst, Qingdao 266237, Shandong, Peoples R China 2.Chinese Acad Sci, State Key Lab Environm Chem & Ecotoxicol, Res Ctr Ecoenvironm Sci, Beijing 100085, Peoples R China 3.Shandong Univ, Shenzhen Res Inst, Shenzhen 518057, Peoples R China |
| 推荐引用方式 GB/T 7714 | Zuo, Chenpeng,Wang, Hetong,Pan, Wenxiao,et al. Quantum Chemical and Kinetic Study on Radical/Molecule Formation Mechanism of Pre-Intermediates for PCTA/PT/DT/DFs from 2-Chlorothiophenol and 2-Chlorophenol Precursors[J]. INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES,2019,20(7):-. |
| APA | Zuo, Chenpeng,Wang, Hetong,Pan, Wenxiao,Zheng, Siyuan,Xu, Fei,&Zhang, Qingzhu.(2019).Quantum Chemical and Kinetic Study on Radical/Molecule Formation Mechanism of Pre-Intermediates for PCTA/PT/DT/DFs from 2-Chlorothiophenol and 2-Chlorophenol Precursors.INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES,20(7),-. |
| MLA | Zuo, Chenpeng,et al."Quantum Chemical and Kinetic Study on Radical/Molecule Formation Mechanism of Pre-Intermediates for PCTA/PT/DT/DFs from 2-Chlorothiophenol and 2-Chlorophenol Precursors".INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES 20.7(2019):-. |
入库方式： OAI收割
来源：生态环境研究中心
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