title: Mechanism and rate constants for complete series reactions of 19 fluorophenols with atomic H.
abstract: Fluorine-containing halogenated fluorophenol may have effect as intermediate species involved in the formation of polyfluorinated dibenzo-p-dioxin/dibenzofurans (PFDDs/Fs). The mechanism for the atomic H initiated reactions with complete series of nineteen fluorophenol congeners was studies using the density functional theory. At the MPWB1K/6-31+G(d,p) level, the geometries and frequencies of reactants, transition states, and products were obtained, and the accurate energetic values were acquired at the MPWB1K/6-311+G(3df,2p) level. The rate constants were evaluated by the canonical variational transition-state theory with the small curvature tunneling contribution over a wide temperature range of 600-1000 K. The study shows that the intramolecular hydrogen-bond in the ortho-substituted FPs as well as the inductive effect of the electron-withdrawing fluorine and steric repulsion of multiple substitutions may ultimately be responsible for the relative strength of the O-H bonds in FPs. The results can be used for further studies on PFDD/Fs formation mechanism.
authors.forename: Rui
authors.initials: R
authors.lastname: Gao
authors.forename: Xiaoyan
authors.initials: X
authors.lastname: Sun
authors.forename: Wanni
authors.initials: W
authors.lastname: Yu
authors.forename: Qingzhu
authors.initials: Q
authors.lastname: Zhang
authors.forename: Wenxing
authors.initials: W
authors.lastname: Wang
mesh_terms: D001572:Benzofurans / Q000737:chemistry*; D002733:Chlorophenols / Q000737:chemistry; D004147:Dioxins / Q000737:chemistry*; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007700:Kinetics; D010636:Phenols / Q000737:chemistry*
chemical_list: D001572:Benzofurans; D002733:Chlorophenols; D004147:Dioxins; D006845:Hydrocarbons, Fluorinated; D010636:Phenols; D006859:Hydrogen; C023614:dibenzofuran; C020887:dibenzo(1,4)dioxin