The enthalpies of vaporisation of ionic liquids: new measurements and predictions.

The enthalpies of vaporisation, Δ(vap)H(298), of seven ionic liquids (ILs) (four imidazoliums, a pyridinium, a phosphonium and an isouronium) have been determined by temperature programmed desorption using line of sight mass spectrometry. They were: 1-ethyl-3-methylimidazolium bis(pentafluoroethyl)phosphinate, [C(2)C(1)Im][PO(2)(C(2)F(5))(2)]; 1-butyl-3-methylimidazolium octylsulfate, [C(4)C(1)Im][C(8)OSO(3)]; 1-butyl-3-methylimidazolium tetrafluoroborate, [C(4)C(1)Im][BF(4)]; 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, [C(6)C(1)Im][FAP]; 1-butylpyridinium methylsulfate, [C(4)Py][C(1)OSO(3)]; trihexyl(tetradecyl)phosphonium tetrafluoroborate, [P(6,6,6,14)][BF(4)] and O-ethyl-N,N,N',N'-tetramethylisouronium trifluoromethanesulfonate, [C(2)(C(1))(4)iU][TfO]. The values were found to be consistent with a previously proposed, predictive, model in which Δ(vap)H(298) is decomposed into a Coulombic component (computable from the IL density) and van der Waals components from the anion and cation. Two previously predicted values of Δ(vap)H(298) were found to be within 6 kJ mol(-1) of the measured experimental values. Values for the van der Waals components are tabulated for eleven cations and twelve anions. Predictions are made for Δ(vap)H(298) for 13 ILs with as yet unmeasured Δ(vap)H(298) values (using experimental molar volumes), and for a further 44 ILs using estimated molar volumes.