Pure and Applied Chemistry

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 (P_{666 14}Cl, P_{666 14}Br) in hydrocarbons and 1-alkyl-3-methylimidazolium tetrafluoroborates (C_nmimBF₄) 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.