Quantum Chemical Study on Formation of PCDT/TA from 2-Chlorothiophenol Precursor

Abstract

This contribution investigates the thermochemical and kinetic parameters pertinent to the homogeneous gas-phase formation of two groups of pollutants, polychlorinated dibenzothiophenes (PCDT) and polychlorinated thianthrenes (PCTA) from their 2-chlorothiophenol (2-CTP) precursor. We compare the enthalpic profiles of the formation mechanism of PCDT/TA with the corresponding reactions involved in the gas-phase synthesis of PCDD/F (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans, also known as dioxins). Overall, the presence of sulfur atoms greatly reduces the activation enthalpies of the rate determining steps in reference to the oxygenated system of PCDD/F. The rate constants of all elementary reactions are calculated using the transition state theory (TST) over a wide temperature range of 300-1200 K. We performed kinetic calculations for the formation of chlorinated dibenzothiophenes and chlorinated thianthrenes that could be applied to predict yields of these pollutants from 2-CTP up to ∼1200 K, that is, prior to the emergence of dechlorination and oxidation reactions. The results presented herein provide a greatly improved understanding of the gas-phase formation of the sulfur analogs of the notorious dioxins compounds.