Formation of benzofuran and chlorobenzofuran from 1,3-dichloropropene: A quantum chemical investigation

Ahubelem, Nwakamma; Shah, Kalpit; Moghtaderi, Behdad; Page, Alister J.

doi:10.1002/qua.25010

Cited by 2 publications

(2 citation statements)

References 64 publications

(115 reference statements)

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“…There is close correlation between the concentrations of PCDT and PCTA, and their dioxin analogues, indicating that similar chemical mechanisms dictate their formation during combustion [13]. Furthermore, since chlorinated hydrocarbons (1,3-dichloropropene [14][15][16] and particularly chlorophenols [17]) are known to be key precursors of PCDD and PCDF during combustion, it is likely that chlorothiophenol is a precursor for the formation of the PCDT and PCTA analogues. A previous report has demonstrated that the presence of sulfur in the precursor moiety, as opposed to oxygen, lowers enthalpic barriers in this respect [18].…”

Section: Introductionmentioning

confidence: 97%

Formation of persistent organic pollutants from 2,4,5-trichlorothiophenol combustion: a density functional theory investigation

et al. 2016

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Polychlorinated dibenzothiophene (PCDT) and polychlorinated thianthrene (PCTA) are sulfur analogues of dioxins, such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F). In this work, we present a detailed mechanistic and kinetic analysis of PCDT and PCTA formation from the combustion of 2,4,5-trichlorothiophenol. It is shown that the formation of these persistent organic pollutants is more favourable, both kinetically and thermodynamically, than their analogous dioxin counterparts. This is rationalised in terms of the different influences of the S-H and O-H moieties in the 2,4,5-trichlorothiophenol and 2,4,5-trichlorophenol precursors. Kinetic parameters also indicate that the yield of PCDT should exceed that of PCDD. Finally, we demonstrate here that the degree and pattern of chlorination on the 2,4,5-trichlorothiophenol precursor leads to subtle thermodynamic and kinetic changes to the PCDT/PCTA formation mechanisms. Graphical abstract Formation mechanisms of persistant organic pollutants, PCDT and PCTA, from 2,4,5-trichlorothiophenol combustion, has been investigated using density functional theory.

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Section: Introductionmentioning

confidence: 97%

Formation of persistent organic pollutants from 2,4,5-trichlorothiophenol combustion: a density functional theory investigation

et al. 2016

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“…The TST triggered the development of a variety of improved approaches: Important variants include the variational TST [28], the Marcus theory of electron transfer [29], and quantum [30] and path integral [31,32] versions. However, the variants of TST require additional information of the potential energy surface rendering formidable the task of estimating kinetic parameters as the size of molecular systems increases: Examples are the degradation kinetics of organic pollutants in aquatic, soil, and atmospheric environments [33,34,35,36,37,38].…”

Section: Introductionmentioning

confidence: 99%

“Transitivity”: A Code for Computing Kinetic and Related Parameters in Chemical Transformations and Transport Phenomena

et al. 2019

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The Transitivity function, defined in terms of the reciprocal of the apparent activation energy, measures the propensity for a reaction to proceed and can provide a tool for implementing phenomenological kinetic models. Applications to systems which deviate from the Arrhenius law at low temperature encouraged the development of a user-friendly graphical interface for estimating the kinetic and thermodynamic parameters of physical and chemical processes. Here, we document the Transitivity code, written in Python, a free open-source code compatible with Windows, Linux and macOS platforms. Procedures are made available to evaluate the phenomenology of the temperature dependence of rate constants for processes from the Arrhenius and Transitivity plots. Reaction rate constants can be calculated by the traditional Transition-State Theory using a set of one-dimensional tunneling corrections (Bell (1935), Bell (1958), Skodje and Truhlar and, in particular, the deformed (d-TST) approach). To account for the solvent effect on reaction rate constant, implementation is given of the Kramers and of Collins–Kimball formulations. An input file generator is provided to run various molecular dynamics approaches in CPMD code. Examples are worked out and made available for testing. The novelty of this code is its general scope and particular exploit of d-formulations to cope with non-Arrhenius behavior at low temperatures, a topic which is the focus of recent intense investigations. We expect that this code serves as a quick and practical tool for data documentation from electronic structure calculations: It presents a very intuitive graphical interface which we believe to provide an excellent working tool for researchers and as courseware to teach statistical thermodynamics, thermochemistry, kinetics, and related areas.

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Formation of benzofuran and chlorobenzofuran from 1,3-dichloropropene: A quantum chemical investigation

Cited by 2 publications

References 64 publications

Formation of persistent organic pollutants from 2,4,5-trichlorothiophenol combustion: a density functional theory investigation

Formation of persistent organic pollutants from 2,4,5-trichlorothiophenol combustion: a density functional theory investigation

“Transitivity”: A Code for Computing Kinetic and Related Parameters in Chemical Transformations and Transport Phenomena

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