Energetics of C-F, C-Cl, C-Br, and C-I bonds in 2-haloethanols.: Enthalpies of formation of XCH2CH2OH (X = F, Cl, Br, I) compounds and of the 2-hydroxyethyl radical

The energetics of the C-F, C-Cl, C-Br, and C-I bonds in 2-haloethanols was investigated by using a combination of experimental and theoretical methods. The standard molar enthalpies of formation of 2-chloro-, 2-bromo-, and 2-iodoethanol, at 298.15 K, were determined as Delta(f)(ClCH2CH2OH, l) = -315.5 +/- 0.7 kJ center dot mol(-1), Delta(f)(BrCH2CH2OH, l) = -275.8 +/- 0.6 kJ center dot mol(-1), Delta(f)(ICH2CH2OH, l) = -207.3 +/- 0.7 kJ center dot mol(-1), by rotating-bomb combustion calorimetry. The corresponding standard molar enthalpies of vaporization, Delta(vap)(ClCH2CH2OH) = 48.32 +/- 0.37 kJ center dot mol(-1), Delta(vap)(BrCH2CH2OH) = 54.08 +/- 0.40 kJ center dot mol(-1), and Delta(vap)(ICH2CH2OH) = 57.03 +/- 0.20 kJ center dot mol(-1) were also obtained by Calvet-drop microcalorimetry. The condensed phase and vaporization enthalpy data lead to Delta(f)(ClCH2CH2OH, g) = -267.2 +/- 0.8 kJ center dot mol(-1), Delta(f)(BrCH2CH2OH, g) = -221.7 +/- 0.7 kJ center dot mol(-1), and Delta(f)(ICH2CH2OH, g) = -150.3 +/- 0.7 kJ center dot mol(-1). These values, together with the enthalpy of selected isodesmic and isogyric gas-phase reactions predicted by density functional theory (B3LYP/cc-pVTZ) and CBS-QB3 calculations were used to derive the enthalpies of formation of gaseous 2-fluoroethanol, Delta(f)(FCH2CH2OH, g) = -423.6 +/- 5.0 kJ center dot mol(-1), and of the 2-hydroxyethyl radical, Delta(f)(CH2CH2OH, g) = -28.7 +/- 8.0 kJ center dot mol(-1). The obtained thermochemical data led to the following carbon-halogen bond dissociation enthalpies: DHo(X-CH2CH2OH) = 474.4 +/- 9.4 kJ center dot mol(-1) (X = F), 359.9 +/- 8.0 kJ center dot mol(-1) (X = Cl), 305.0 +/- 8.0 kJ center dot mol(-1) (X = Br), 228.7 +/- 8.1 kJ center dot mol(-1) (X = I). These values were compared with the corresponding C-X bond dissociation enthalpies in XCH2COOH, XCH3, XC2H5, XCHCH2, and XC6H5. In view of this comparison the computational methods mentioned above were also used to obtain Delta(f)(FCH2COOH, g) = -594.0 +/- 5.0 kJ center dot mol(-1) from which DHo(F-CH2COOH) = 435.4 +/- 5.4 kJ center dot mol(-1). The order DHo(C-F) > DHo(C-Cl) > DHo(C-Br) > DHo(C-I) is observed for the haloalcohols and all other RX compounds. It is finally concluded that the major qualitative trends exhibited by the C-X bond dissociation enthalpies for the series of compounds studied in this work can be predicted by Pauling's electrostatic-covalent model.