Mechanistic and Kinetic Studies on the Homogeneous Gas-Phase Formation of PCTA/DTs from 2,4-Dichlorothiophenol and 2,4,6-Trichlorothiophenol

International Journal of Molecular Sciences

Fei Xu¹  Xiangli Shi¹  Yunfeng Li¹  Qingzhu Zhang² 

[1] Environment Research Institute, Shandong University, Jinan 250100, China;

关键词: 2;    4-dithiochlorophenol;    2;    4;    6-Trithiochlorophenol;    PCTA/DT;    formation mechanism;    rate constants;   

DOI  :  10.3390/ijms160920449

来源: mdpi

【 摘 要 】

Polychlorinated thianthrene/dibenzothiophenes (PCTA/DTs) are sulfur analogues compounds to polychlorinated dibenzo-p-dioxin/dibenzofurans (PCDD/Fs). Chlorothiophenols (CTPs) are key precursors to form PCTA/DTs. 2,4-DCTP has the minimum number of Cl atoms to form 2,4,6,8-tetrachlorinated dibenzothiophenes (2,4,6,8-TeCDT), which is the most important and widely detected of the PCDTs. In this paper, quantum chemical calculations were carried out to investigate the homogeneous gas-phase formation of PCTA/DTs from 2,4-DCTP and 2,4,6-TCTP precursors at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. Several energetically feasible pathways were revealed to compare the formation potential of PCTA/DT products. The rate constants of the crucial elementary reactions were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) correction over a wide temperature range of 600–1200 K. This study shows that pathways that ended with elimination of Cl step were dominant over pathways ended with elimination of the H step. The water molecule has a negative catalytic effect on the H-shift step and hinders the formation of PCDTs from 2,4-DCTP. This study, together with works already published from our group, clearly illustrates an increased propensity for the dioxin formation from CTPs over the analogous CPs.

【 授权许可】

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