Liquid-liquid phase transition in solutions of ionic liquids with halide anions: Criticality and corresponding states

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Abstract 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.