title: DFT Studies of SN2 Dechlorination of Polychlorinated Biphenyls.
abstract: Nucleophilic dechlorination of all 209 PCBs congeners by ethylene glycol anion has been studied theoretically at the DFT level. The obtained Gibbs free energies of activation are in the range 7-22 kcal/mol. The reaction Gibbs free energies indicate that all reactions are virtually irreversible. Due to geometric constrains these reactions undergo rather untypical attack with attacking oxygen atom being nearly perpendicular to the attacked C-Cl bond. The most prone to substitution are chlorine atoms that occupy ortho- (2, 2', 6, 6') positions. These results provide extensive information on the PEG/KOH dependent PCBs degradation. They can also be used in further developments of reaction class transition state theory (RC-TST) for description of complex reactive systems encountered for example in combustion processes.
authors.affiliation: Institute of Applied Radiation Chemistry, Lodz University of Technology , Zeromskiego 116, 90-924 Lodz, Poland.
authors.forename: Agnieszka
authors.initials: A
authors.lastname: Krzemińska
authors.affiliation: Institute of Applied Radiation Chemistry, Lodz University of Technology , Zeromskiego 116, 90-924 Lodz, Poland.
authors.forename: Piotr
authors.initials: P
authors.lastname: Paneth
mesh_terms: D002713:Chlorine / Q000737:chemistry; D054879:Halogenation; D011078:Polychlorinated Biphenyls / Q000378:metabolism*
chemical_list: D002713:Chlorine; D011078:Polychlorinated Biphenyls