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Thermochemical factors affecting the dehalogenation of aromatics.
Sadowsky, Daniel; McNeill, Kristopher; Cramer, Christopher J.
Afiliación
  • Sadowsky D; Institute of Biogeochemistry and Pollutant Dynamics, ETH Zurich , 8092 Zurich, Switzerland.
Environ Sci Technol ; 47(24): 14194-203, 2013 Dec 17.
Article en En | MEDLINE | ID: mdl-24237268
Halogenated aromatics are one of the largest chemical classes of environmental contaminants, and dehalogenation remains one of the most important processes by which these compounds are degraded and detoxified. The thermodynamic constraints of aromatic dehalogenation reactions are thus important for understanding the feasibility of such reactions and the redox conditions necessary for promoting them. Accordingly, the thermochemical properties of the (poly)fluoro-, (poly)chloro-, and (poly)bromobenzenes, including standard enthalpies of formation, bond dissociation enthalpies, free energies of reaction, and the redox potentials of Ar-X/Ar-H couples, were investigated using a validated density functional protocol combined with continuum solvation calculations when appropriate. The results highlight the fact that fluorinated aromatics stand distinct from their chloro- and bromo- counterparts in terms of both their relative thermodynamic stability toward dehalogenation and how different substitution patterns give rise to relevant properties, such as bond strengths and reduction potentials.
Asunto(s)

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Halogenación / Hidrocarburos Aromáticos Tipo de estudio: Prognostic_studies Idioma: En Revista: Environ Sci Technol Año: 2013 Tipo del documento: Article País de afiliación: Suiza Pais de publicación: Estados Unidos

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Halogenación / Hidrocarburos Aromáticos Tipo de estudio: Prognostic_studies Idioma: En Revista: Environ Sci Technol Año: 2013 Tipo del documento: Article País de afiliación: Suiza Pais de publicación: Estados Unidos