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Article: A Computational Chemistry Investigation of the Mechanism of the Water-Assisted Decomposition of Trichloroethylene Oxide

TitleA Computational Chemistry Investigation of the Mechanism of the Water-Assisted Decomposition of Trichloroethylene Oxide
Authors
Issue Date2014
Citation
The Journal of Physical Chemistry A, 2014, v. 118, p. 1557-1567 How to Cite?
AbstractTrichloroethylene oxide is a downstream product in the oxidative metabolism of trichloroethylene (TCE) and it may be involved in cytochrome P450 inactivation, protein function destruction, and nucleic acid base alkalization. To explore the hydrolysis mechanism of the decomposition of TCE oxide, an investigation using Second-order Møller–Plesset perturbation theory in conjunction with density functional theory has been conducted to analyze the effect of the water solvation shell on probable reaction steps. The decomposition of TCE oxide is accelerated by coordinated water molecules (up to seven), which reveals that water molecules can help to solvate the TCE oxide molecule and activate the release of the Cl– leaving group. After the opening of the epoxide ring, several pathways are proposed to account for the dehalogenation step along with the formation of CO as well as three carboxylic acids (formic acid, glyoxylic acid, and dichloroacetic acid). The predominant pathways were examined by comparing the computed activation energies for the formation of the products to each other for the possible reaction steps examined in this work. After rationally analyzing the computational results, the ring-opening reaction has been identified as the rate-determining step. The rate constant estimated for the TCE oxide decomposition from the calculations performed here was found to be reasonably consistent with previous experimental observations reported in the literature.
Persistent Identifierhttp://hdl.handle.net/10722/202570

 

DC FieldValueLanguage
dc.contributor.authorHuang, Jen_US
dc.contributor.authorYeung, CSen_US
dc.contributor.authorMa, Jen_US
dc.contributor.authorGayner, ERen_US
dc.contributor.authorPhillips, DLen_US
dc.date.accessioned2014-09-19T08:41:23Z-
dc.date.available2014-09-19T08:41:23Z-
dc.date.issued2014en_US
dc.identifier.citationThe Journal of Physical Chemistry A, 2014, v. 118, p. 1557-1567en_US
dc.identifier.urihttp://hdl.handle.net/10722/202570-
dc.description.abstractTrichloroethylene oxide is a downstream product in the oxidative metabolism of trichloroethylene (TCE) and it may be involved in cytochrome P450 inactivation, protein function destruction, and nucleic acid base alkalization. To explore the hydrolysis mechanism of the decomposition of TCE oxide, an investigation using Second-order Møller–Plesset perturbation theory in conjunction with density functional theory has been conducted to analyze the effect of the water solvation shell on probable reaction steps. The decomposition of TCE oxide is accelerated by coordinated water molecules (up to seven), which reveals that water molecules can help to solvate the TCE oxide molecule and activate the release of the Cl– leaving group. After the opening of the epoxide ring, several pathways are proposed to account for the dehalogenation step along with the formation of CO as well as three carboxylic acids (formic acid, glyoxylic acid, and dichloroacetic acid). The predominant pathways were examined by comparing the computed activation energies for the formation of the products to each other for the possible reaction steps examined in this work. After rationally analyzing the computational results, the ring-opening reaction has been identified as the rate-determining step. The rate constant estimated for the TCE oxide decomposition from the calculations performed here was found to be reasonably consistent with previous experimental observations reported in the literature.en_US
dc.languageengen_US
dc.relation.ispartofThe Journal of Physical Chemistry Aen_US
dc.titleA Computational Chemistry Investigation of the Mechanism of the Water-Assisted Decomposition of Trichloroethylene Oxideen_US
dc.typeArticleen_US
dc.identifier.emailPhillips, DL: phillips@hku.hken_US
dc.identifier.authorityPhillips, DL=rp00770en_US
dc.identifier.doi10.1021/jp501310zen_US
dc.identifier.hkuros237029en_US
dc.identifier.volume118en_US
dc.identifier.spage1557en_US
dc.identifier.epage1567en_US

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