Solid–Liquid Equilibria for Hexafluorophosphate-Based Ionic Liquid Quaternary Mixtures and Their Corresponding Subsystems

The present work describes an experimental study and the thermodynamic modeling for the solid–liquid phase diagram of an ionic liquid quaternary system constituted by hexafluorophosphate ([PF6]−) as the common anion and by 1-methyl-3-propylimidazolium ([C3mim]+), 1-methyl-1-propylpyrrolidinium ([C3mpyrr]+), 1-methyl-3-propylpyridinium ([C3mpy]+), or 1-methyl-1-propylpiperidinium ([C3mpip]+) as the cations. The Modified Quasichemical Model was used to model the liquid solution, and the Compound Energy Formalism was used for the relevant solid solutions. The liquidus projections of the four ternary subsystems (1) [C3mim]­[PF6]–[C3mpip]­[PF6]–[C3mpyrr]­[PF6], (2) [C3mpy]­[PF6]–[C3mpip]­[PF6]–[C3mpyrr]­[PF6], (3) [C3mpip]­[PF6]–[C3mpy]­[PF6]–[C3mim]­[PF6], and (4) [C3mpyrr]­[PF6]–[C3mpy]­[PF6]–[C3mim]­[PF6] were predicted using a standard symmetric (for systems 3 and 4) or asymmetric (for systems 1 and 2) interpolation method. In order to test the accuracy of the thermodynamic model, two isoplethal sections were experimentally measured in each of the four ternary systems using differential scanning calorimetry. Overall, agreement was very satisfactory, not requiring fitting of any ternary interaction parameters for the liquid solution model. In each of the four calculated ternary liquidus projections, the region of composition corresponding to room temperature ionic liquid mixtures was determined. The global minimum of the liquidus temperature in the complete composition space was calculated to be about −16 °C, with a mole percentage composition of (33.8% [C3mpyrr]­[PF6] + 33.9% [C3mpy]­[PF6] + 32.3% [C3mim]­[PF6]).