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Excess enthalpies of mixing of piperidinium ionic liquids with short-chain alcohols: measurements and PC-SAFT modeling.

This work is a continuation of our systematic study on thermodynamic properties of 1-n-alkyl-1-methylpiperdinium bis[(trifluoromethyl)sulfonyl]imides homologous series of ionic liquids ([CnC1Pip][NTf2]). Excess enthalpies of mixing (H(E)) of four binary systems containing two ionic liquids, namely [C4C1Pip][NTf2] and [C6C1Pip][NTf2], and two short-chain alcohols, namely ethanol and 1-propanol, were measured by isothermal titration calorimetry. Alcohol-to-ionic liquid and ionic liquid-to-alcohol titration experiments were carried out at temperature T = 298.15 K and atmospheric pressure. The experimental data were modeled in terms of perturbed-chain statistical associating fluid theory (PC-SAFT). Wolbach-Sandler combining rules were adopted in order to account for ionic liquid-alcohol cross-association. The model was applied in a conventional manner (i.e., without any binary corrections) as well as in a novel predictive mode developed previously by our group [Paduszyński, K.; Domańska, U. J. Phys. Chem. B 2012, 116, 5002-5018; Domańska et al. J. Phys. Chem. B 2012, 116, 8191-8200]. The latter approach employs temperature-dependent binary correction fitted to experimental limiting activity coefficient of alcohol in ionic liquid.