The energetics of the hydrogenolysis, dehydrohalogenation, and hydrolysis of 4,4′-Dichloro-diphenyl-trichloroethane from ab initio electronic structure theory

Eric J. Bylaska, David A. Dixon, Andrew R. Felmy, Edoardo Aprà, Theresa L. Windus, Chang Guo Zhan, Paul Tratnyek

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Abstract

Electronic structure methods were used to calculate the aqueous reaction energies for hydrogenolysis, dehydrochlorination, and nucleophilic substitution by OH - of 4,4′-DDT. Thermochemical properties ΔH° f (298.15 K), S° (298.15 K, 1 bar), ΔG s (298.15 K, 1 bar) were calculated by using ab initio electronic structure calculations, isodesmic reactions schemes, gas-phase entropy estimates, and continuum solvation models for a series of DDT type structures (p-C 6H 4Cl) 2-CH-CCl 3, (p-C 6H 4Cl) 2-CH-CCl 2̇, (p-C 6H 4Cl) 2-CH-CHCl 2, (p-C 6H 4Cl) 2-C=CCl 2, (p-C 6H 4Cl) 2-CH-CCl 2OH, (p-C 6H 4Cl) 2-CH-CCl(=O), and (p-C 6H 4-Cl) 2-CH-COOH. On the basis of these thermochemical estimates, the overall aqueous reaction energetics of hydrogenolysis, dehydrochlorination, and hydrolysis of 4,4′-DDT were estimated. The results of this investigation showed that the dehydrochlorination and hydrolysis reactions have strongly favorable thermodynamics in the standard state, as well as under a wide range of pH conditions. For hydrogenolysis with the reductant aqueous Fe(II), the thermodynamics are strongly dependent on pH, and the stability region of the (p-C 6H 4Cl) 2-CH-CCl 2̇ (aq) species is a key to controlling the reactivity in hydrogenolysis. These results illustrate the use of ab initio electronic structure methods to identify the potentially important environmental degradation reactions by calculation of the reaction energetics of a potentially large number of organic compounds with aqueous species in natural waters.

Original languageEnglish (US)
Pages (from-to)5883-5893
Number of pages11
JournalJournal of Physical Chemistry A
Volume108
Issue number27
DOIs
Publication statusPublished - Jul 8 2004

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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