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Int. J. Mol. Sci. 2015, 16(9), 20449-20467; doi:10.3390/ijms160920449

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

Environment Research Institute, Shandong University, Jinan 250100, China
Author to whom correspondence should be addressed.
Academic Editor: Henry Chermette
Received: 13 August 2015 / Revised: 26 August 2015 / Accepted: 26 August 2015 / Published: 28 August 2015
(This article belongs to the Section Physical Chemistry, Theoretical and Computational Chemistry)
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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. View Full-Text
Keywords: 2,4-dithiochlorophenol; 2,4,6-Trithiochlorophenol; PCTA/DT; formation mechanism; rate constants 2,4-dithiochlorophenol; 2,4,6-Trithiochlorophenol; PCTA/DT; formation mechanism; rate constants

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Xu, F.; Shi, X.; Li, Y.; Zhang, Q. Mechanistic and Kinetic Studies on the Homogeneous Gas-Phase Formation of PCTA/DTs from 2,4-Dichlorothiophenol and 2,4,6-Trichlorothiophenol. Int. J. Mol. Sci. 2015, 16, 20449-20467.

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