Measurements of the liquid-liquid phase diagrams of solutions of the ionic liquids (ILs) 1-dodecyl-3-methylimidazolium chloride (C12mimCl) in arenes (benzene, toluene, o-xylene, tetraline) and 1-tetradecyl-3-methylimidazolium chloride (C14mimCl) in CCl4 are reported and compared with those of solutions of trihexyl-tetradecyl-phosphonium halides (P666 14Cl, P666 14Br) in hydrocarbons and 1-alkyl-3-methylimidazolium tetrafluoroborates (CnmimBF4) in alcohols and water. The phase diagrams of solutions of tetrapentyl-ammonium bromide (N5555Br) in water and KI in SO2 are also discussed. Except for the KI/SO2 system, which features a lower critical solution point (LCSP), all systems have an upper critical solution point (UCSP) and show corresponding-states behavior. The experimental data are compared with results from simulations and theory concerning the model fluid of charged hard spheres in a dielectric continuum, termed restricted primitive model (RPM). The analysis in terms of of RPM variables shows agreement with the location of the critical point (CP) of the model with noticeable systematic deviations. However, for protic solvents, the CP becomes an LCSP, while in aprotic solvents the CP is a UCSP as expected for Coulomb systems. This indicates that in aprotic solvents, the phase transition is essentially determined by the Coulomb interactions, while in the solutions in protic solvents with hydrogen bonds, both Coulomb and solvophobic interactions are important.

The room temperature ionic liquids (RTIL) trihexyl-tetradecyl phosphonium chloride (P 666 14 Cl) and the bromide (P 666 14 Br) are soluble in hydrocarbons. The investigated solutions in heptane, octane, nonane and decane show liquid-liquid phase separation with an upper critical solution point at ambient temperatures at molar fractions near 0.03 of the salt. Phase diagrams are reported and analysed presuming Ising criticality. The critical temperatures and the critical densities increase with the chain length of the hydrocarbons, where the figures corresponding to the bromides are above that of the chlorides. Scaled by the critical data the phase diagrams show corresponding state behaviour. In accordance with the prediction of the restricted primitive model (RPM), which is a model fluid of equal sized, charged hard spheres in a dielectric continuum, the critical points are located at low temperature and low concentration, when the corresponding state variables of this model are used. However, the critical temperature T * c and the critical density ρ * c are well below the figures of the RPM prediction. Comparison is made with the phase diagrams of alcohol solutions of imidazolium ionic liquids and with simulation results of the RPM.

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