Theoretical structural and thermochemical characterization of partially fluorinated alcohols.

[Display omitted] • Conformers of nine fluorinated alcohols were determined by theoretical calculations. • Standard enthalpies of formation were predicted from isodesmic reactions. • Enthalpy changes of H-abstraction reactions by OH radicals were computed. • H-abstraction from CH 2 group is the channel thermodynamically most favorable. Molecular conformations, harmonic vibrational frequencies and standard enthalpies of formation for CH 3-n F n CF 2 CH 2 OH, CH 3-n F n CH 2 OH and CH 3-n F n OH (n = 1,2,3) partially fluorinated alcohols were computed at different levels of theory using isodesmic and isogiric work reactions. The lack of data and large uncertainties in the reported thermodynamic properties motivated the present study. As average at the G4 and CBSQB3 levels of theory, standard enthalpies of formation at 298 K of −313.9±1.8, −258.2±1.8 and −208.4±1.8 kcal mol⁻¹ were computed for CF 3 CF 2 CH 2 OH, CHF 2 CF 2 CH 2 OH and CH 2 FCF 2 CH 2 OH, respectively; values of −213.0±1.7, −154.5±1.7 and −100.4±1.7 kcal mol⁻¹ were obtained for CF 3 CH 2 OH, CHF 2 CH 2 OH and CH 2 FCH 2 OH; while −216.9±1.2, −159.8±1.2 and −100.9±1.7 kcal mol⁻¹ were derived for CF 3 OH, CHF 2 OH and CH 2 FOH. The corresponding enthalpies of formation presented here for CF 3 CF 2 CH 2 OH and CH 2 FCF 2 CH 2 OH were predicted for the first time. Hydrogen abstraction reactions enthalpies by OH radicals were also estimated and comparisons with previously reported results were performed. [ABSTRACT FROM AUTHOR]