In this article, we study the behavior of an ionic liquid (IL) derived from pyridinium, 1-butyl-3-methylpyridinium tetrafluoroborate [b3mpy][BF4], in mixtures with water and with the first alkanols of the series from methanol to butan-1-ol, at the temperatures of (298.15 and 318.15) K. First, the miscibility regions with the alkanols were established at these two temperatures, determining experimentally the liquid−liquid equilibria and the upper critical solution temperature (UCST) for each binary mixture, confirming the quasiexponential variation of the UCST with the alkanol chain. The enthalpies were determined experimentally with a newly designed calorimetric cell, and the excess molar volumes were determined from densities, at (298.15 and 318.15) K. In all cases, the are positive with (d /dT)p > 0, whereas the are negative for mixtures with alkanols but positive for the mixture of IL + water. The thermal coefficient (d /dT)p > 0 was also positive in all cases. All data were correlated with a suitable polynomial equation, and the area and volume parameters of [b3mpy][BF4] were calculated. Finally, we give an interpretation of the results and of the behavior of the mixtures.

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This work analyzes the utility of a new model to correlate thermodynamic properties of solutions, the foundations of which have been published in a previous study. The model is applied to a set of experimental data for several properties of binary systems of methanol with four butyl alkanoates (vapor-liquid equilibria at p ) 141.32 kPa and excess enthalpies and volumes at 298.15 and 318.15 K). Vapor-liquid equilibrium data (VLE) indicate that the four binary systems deviate positively from Raoult's law and do not present azeotrope. Excess enthalpies (h E ) are positive for the entire range of compositions and decrease regularly with increasing length of the ester chain, with (∂h E /∂T) p,x > 0. The excess volumes (V E ) decrease regularly with the length of the acid chain; they are positive for the binary systems of methanol with butyl (methanoate, ethanoate, and propanoate) and become negative for the system with butyl butanoate, with (∂V E /∂T) p,x > 0. The new model can be used to obtain a satisfactory correlation for Gibbs function g E ) g E (p, T, x i ), and for its derivatives. Correlation procedures for the data are described for the stages (x, h E ) f [x, g E (T)] for the isobaric data reported here and (x, V E ) f [x, g E (p)] for isothermal data reported in the literature. The new method allows a better correlation than the one obtained with the classical models of Wilson, NRTL, and UNIQUAC. We also present a unique correlation of all the properties of the methanol + butyl ethanoate system in the form of an analytical expression (p, T, x, y) ) 0 and conclude that, on the whole, its implementation can be considered an advance in the data treatment of the properties of liquid solutions.

Here we present experimental data of different properties for a set of binary mixtures composed of water or alkanols (methanol to butanol) with an ionic liquid (IL), butylpyridinium tetrafluoroborate [bpy][BF(4)]. Solubility data (x(IL),T) are presented for each of the mixtures, including water, which is found to have a small interval of compositions in IL, x(IL), with immiscibility. In each case, the upper critical solubility temperature (UCST) is determined and a correlation was observed between the UCST and the nature of the compounds in the mixtures. Miscibility curves establish the composition and temperature intervals where thermodynamic properties of the mixtures, such as enthalpies H(m)(E) and volumes V(m)(E), can be determined. Hence, at 298.15 and 318.15 K these can only be found with the first four alkanols. All mixing properties are correlated with a suitable equation ξ (x(IL),T,Y(m)(E) = 0. An analysis on the influence of the temperature in the properties is shown, likewise a comparison between the results obtained here and those of analogous mixtures, discussing the position of the -CH(3) group in the pyridinic ring. The (1)H NMR spectra are determined to analyze the molecular interactions present, especially those due to hydrogen bonds. Additional information about the molecular interactions and their influence on the mixing properties is obtained by quantum chemistry calculations.