Enthalpies of interaction of ketones with organic solvents

Abstract

Enthalpies of solution (ΔHS) of a series of ketones (acetone, 2-butanone, 2-heptanone, 2-nonanone, 5-nonanone, 2,2,4,4-tetramethyl-3-pentanone, cyclohexanone) and alkane model compounds (n-heptane, n-nonane, 2,2,4,4-tetramethylpentane, cyclohexane) have been determined in 17 organic solvents (n-heptane, cyclohexane, CCl4, α,α,α,-trifluorotoluene, 1,2-dichloroethane, triethylamine, butyl ether, ethyl acetate, DMF, DMSO, benzene, toluene, mesitylene, 1-octanol, methanol, t-butyl alcohol, 2,2,2-trifluoroethanol), and combined with heats of vaporization to give enthalpies of transfer from vapor to solvent (ΔH(v → S)). These values have been used to evaluate ketone–solvent polar interactions (ΔΔH(v → S) = ΔH(v → S)(ketone) − ΔH(v → S)(alkane)). The linear relationships between ΔΔH(v → S) and solvent dipolarity-polarizability (Taft-Kamlet π* parameters) are derived. Based on the deviations from these correlations, ketone–CF3CH2OH enthalpies of hydrogen bond formation have been evaluated. The other alcohol solvents show no evidence of exothermic H-bond formation with ketones.