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Int. J. Mol. Sci. 2015, 16(8), 18714-18731; doi:10.3390/ijms160818714

Formation of Chlorotriophenoxy Radicals from Complete Series Reactions of Chlorotriophenols with H and OH Radicals

Environment Research Institute, Shandong University, Jinan 250100, China
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Author to whom correspondence should be addressed.
Academic Editor: Habil. Mihai V. Putz
Received: 23 June 2015 / Revised: 16 July 2015 / Accepted: 17 July 2015 / Published: 11 August 2015
(This article belongs to the Special Issue Chemical Bond and Bonding 2015)
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Abstract

The chlorothiophenoxy radicals (CTPRs) are key intermediate species in the formation of polychlorinated dibenzothiophenes/thianthrenes (PCDT/TAs). In this work, the formation of CTPRs from the complete series reactions of 19 chlorothiophenol (CTP) congeners with H and OH radicals were investigated theoretically by using the density functional theory (DFT) method. The profiles of the potential energy surface were constructed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution at 600–1200 K. The present study indicates that the structural parameters, thermal data, and rate constants as well as the formation potential of CTPRs from CTPs are strongly dominated by the chlorine substitution at the ortho-position of CTPs. Comparison with the study of formation of chlorophenoxy radicals (CPRs) from chlorophenols (CPs) clearly shows that the thiophenoxyl-hydrogen abstraction from CTPs by H is more efficient than the phenoxyl-hydrogen abstraction from CPs by H, whereas the thiophenoxyl-hydrogen abstraction from CTPs by OH is less impactful than the phenoxyl-hydrogen abstraction from CPs by OH. Reactions of CTPs with H can occur more readily than that of CTPs with OH, which is opposite to the reactivity comparison of CPs with H and OH. View Full-Text
Keywords: chlorothiophenols; chlorothiophenoxy radicals; H radicals; OH radicals; reaction mechanism; rate constants chlorothiophenols; chlorothiophenoxy radicals; H radicals; OH radicals; reaction mechanism; rate constants
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MDPI and ACS Style

Xu, F.; Shi, X.; Zhang, Q.; Wang, W. Formation of Chlorotriophenoxy Radicals from Complete Series Reactions of Chlorotriophenols with H and OH Radicals. Int. J. Mol. Sci. 2015, 16, 18714-18731.

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