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

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.

1H and 2H NMR Studies of Mixtures 2,6-Lutidine/Water Near the Lower Critical Solution Point

Deuteron spin-lattice relaxation time (TJ measurements of binary mixtures 2,6-lutidine/D20 have been done near the lower critical solution point (TC, L), ε = (T - TC, L)/TC, L ≧10-5. Singularities are observed at TC, L. The changes in the slope of T1 (2H) = ƒ ( T ) can be interpreted as due to the effect of concentration changes on Ty and simultaneously strong overlaping of 2H NMR signals from coexisting phases. In the two-phase region, ca. 2°C above TC, L two D2O signals with very strong temperature evolution have been detected. Similar doubling of 2,6-lutidine 1H NMR signals has been observed already at T - TC, L ≦ 1 °C. It is shown that the two signals arise from the nuclei in two coexisting phases; they are not due to pecularities of hydrogen bond. The difference between chemical shifts of both D2O signals δ’ - δ” possess the property of an order parameter, i.e. δ’ - δ” ~ εβ with β = 0.336±0.030