Acoustic,volumetric and osmotic properties of binary mixtures containing the ionic liquid 1-butyl-3-methylimidazolium dicyanamide mixed with primary and secondary alcohols

In this paper, densities and speeds of sound for five binary systems {alcohol + 1-butyl-3-methylimidazolium dicyanamide} were measured from T = (293.15 to 323.15) K and atmospheric pressure. From these experimental data, apparent molar volume and apparent molar isentropic compression have been calculated and fitted to a Redlich–Meyer type equation. This fit was also used to calculate the apparent molar volume and apparent molar isentropic compression at infinite dilution for the studied binary mixtures. Moreover, the osmotic and activity coefficients and vapor pressures of these binary mixtures were also determined at T = 323.15 K using the vapor pressure osmometry technique. The experimental osmotic coefficients were correlated using the Extended Pitzer model of Archer. The mean molal activity coefficients and the excess Gibbs free energy for the studied mixtures were calculated from the parameters obtained in the correlation.     

Excess molar properties for binary systems of alkylimidazolium-based ionic liquids + nitromethane. Experimental results and ERAS-model calculations

Density, isobaric molar heat capacity, and excess molar enthalpy were experimentally determined at atmospheric pressure for a set of binary systems ionic liquid + nitromethane. The studied ionic liquids were: 1-butyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-ethyl-3-methylimidazolium ethylsulfate, 1-butyl-3-methylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, and 1-butyl-3-methylimidazolium trifluoromethanesulfonate. Density and heat capacity were obtained within the temperature range (293.15 to 318.15) K whereas excess molar enthalpy was measured at 303.15 K; excess molar volume and excess molar isobaric heat capacity were calculated from experimental data. The ERAS-model was applied in order to study the microscopic mechanisms involved in the mixing process. Although the studied compounds are not self-associated, ERAS-model describe adequately the experimental results if cross-association between both compounds is considered.     

Heat capacities of the mixtures of ionic liquids with methanol at temperatures from 283.15 K to 323.15 K

The molar isobaric heat capacities of (methanol + 1-hexyl-3-methylimidazolium tetrafluoroborate) and (methanol + 1-methyl-3-octylimidazolium tetrafluoroborate) mixtures have been determined over the temperature range from 283.15 K to 323.15 K within the whole composition range. The excess molar heat capacities of investigated mixtures have been fitted to the Redlich–Kister equation at several selected temperatures. Positive deviations from the additivity of molar heat capacities have been observed in both examined systems. The results obtained have been discussed in terms of molecular interactions in binary mixtures.     

(Vapor + liquid) equilibria of binary mixtures containing light alcohols and ionic liquids

This work presents (vapor + liquid) equilibrium (VLE) of binary mixtures containing methanol or ethanol and three imidazolium based ionic liquids: 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium acetate, and 1-butyl-3-methylimidazolium hydrogen sulfate. VLE measurements were carried out over the whole range of composition between (283.15 and 298.15) K using a static apparatus. Activity coefficients γ_i of these solvents in the ionic liquids have been determined from the VLE data and correlated using the NRTL model. The results show that the NRTL model can be applied successfully with systems containing ionic liquids.     

Osmotic and apparent molar properties of binary mixtures alcohol + 1-butyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid

In this work, physical properties (densities and speeds of sound) for the binary systems {1-propanol, or 2-propanol, or 1-butanol, or 2-butanol, or 1-pentanol + 1-butyl-3-methylimidazolium trifluoromethanesulfonate} were experimentally measured from T = (293.15 to 323.15) K and at atmospheric pressure. These data were used to calculate the apparent molar volume and apparent molar isentropic compression which were fitted to a Redlich–Meyer type equation. This fit was used to obtain the corresponding apparent molar properties at infinite dilution. On the other hand, the osmotic and activity coefficients and vapor pressures of these binary mixtures were also determined at T = 323.15 K using the vapor pressure osmometry technique. The Extended Pitzer model of Archer was employed to correlate the experimental osmotic coefficients. From the parameters obtained in the correlation, the mean molal activity coefficients and the excess Gibbs free energy for the studied mixtures were calculated.     

Volumetric properties,viscosities and refractive indices of binary liquid mixtures of tetrafluoroborate-based ionic liquids with methanol at several temperatures

Densities, speeds of sound, viscosities and refractive indices of two binary systems 1-butyl-3-methylimidazolium tetrafluoroborate [bmim][BF₄] + methanol and 1-ethyl-3-methylimidazolium tetrafluoroborate [emim][BF₄] + methanol, as well as of all pure components, have been measured covering the whole range of compositions at T = (278.15 to 318.15) K and p = 101 kPa. From this data, excess molar volumes, excess isentropic compressibilities, viscosity deviations and refractive index deviations were calculated and fitted to extended versions of the Redlich–Kister equation. Estimated coefficients of these equations taking into account the dependence on composition and temperature simultaneously were also presented.     

Excess enthalpy,density, and heat capacity for binary systems of alkylimidazolium-based ionic liquids + water

Experimental measurements of excess molar enthalpy, density, and isobaric molar heat capacity are presented for a set of binary systems ionic liquid + water as a function of temperature at atmospheric pressure. The studied ionic liquids are 1-butyl-3-methylpyridinium tetrafluoroborate, 1-ethyl-3-methylimidazolium ethylsulfate, 1-butyl-3-methylimidazolium methylsulfate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, and 1-ethyl-3-methylimidazolium trifluoromethanesulfonate. Excess molar enthalpy was measured at 303.15 K whereas density and heat capacity were determined within the temperature range (293.15 to 318.15) K. From experimental data, excess molar volume and excess molar isobaric heat capacity were calculated. The analysis of the excess properties reveals important differences between the studied ionic liquids which can be ascribed to their capability to form hydrogen bonds with water molecules.     

Phase equilibria study of the binary systems (N-butyl-3-methylpyridinium tosylate ionic liquid + an alcohol)

Isothermal (vapour + liquid) equilibrium data, (VLE) have been measured by an ebulliometric method for the binary mixtures of ionic liquid (IL) {N-butyl-4-methylpyridinium tosylate (p-toluenesulfonate) [BMPy][TOS] + ethanol, 1-propanol, and 1-butanol} at T = 373.15 K over the pressure range from p = 0 kPa to p = 110 kPa. (Solid + liquid) phase equilibria (SLE) for the binary systems: ionic liquid (IL) {N-butyl-4-methylpyridinium tosylate (p-toluenesulfonate) [BMPy][TOS] + ethanol and 1-propanol} have been determined at ambient pressure. A dynamic method was used over a broad range of mole fractions and temperatures from (320 to 390) K. For the binary systems containing alcohol, it was noticed that with increasing chain length of alcohol vapour pressure of the mixture and the solubility of the IL decreases. Well-known Wilson, NRTL, and UNIQUAC equations have been used to correlate simultaneously the experimental VLE and SLE data sets with the same parameters. The excess molar Gibbs free energy, G^E function in general was negative in all systems at high temperature (VLE) and positive at low temperatures (SLE).     

Thermophysical properties of binary mixtures of {ionic liquid 2-hydroxy ethylammonium acetate + (water,methanol, or ethanol)}

In this work, density and speed of sound data of binary mixtures of an ionic liquid consisting of {2-hydroxy ethylammonium acetate (2-HEAA) + (water, methanol, or ethanol)} have been measured throughout the entire concentration range, from the temperature of (288.15 to 323.15) K at atmospheric pressure. The excess molar volumes, variations of the isentropic compressibility, the apparent molar volume, isentropic apparent molar compressibility, and thermal expansion coefficient were calculated from the experimental data. The excess molar volumes were negative throughout the whole composition range. Compressibility data in combination with low angle X-ray scattering and NMR measurements proved that the presence of micelles formed due to ion pair interaction above a critical concentration of the ionic liquid in the mixtures. The Peng–Robinson equation of state coupled with the Wong–Sandler mixing rule and COSMO–SAC model was used to predict densities and the calculated deviations were lower than 3%, for binary mixtures in all composition range.     

Osmotic coefficients of binary mixtures of 1-butyl-3-methylimidazolium methylsulfate and 1,3-dimethylimidazolium methylsulfate with alcohols at T = 323.15 K

Measurements of osmotic coefficients of BMimMSO₄ (1-butyl-3-methylimidazolium methylsulfate) and MMimMSO₄ (1,3-dimethylimidazolium methylsulfate) with ethanol, 1-propanol, and 2-propanol at T = 323.15 K are reported in this work. Vapour pressure and activity values for the binary systems studied are obtained from experimental results. The osmotic coefficients are correlated using the extended Pitzer model modified by Archer and the modified NRTL (MNRTL) model. The standard deviations obtained with both models are lower than 0.013 and 0.060, respectively. The parameters obtained with the extended Pitzer model of Archer are used to calculate the mean molal activity coefficients and the excess Gibbs free energy of the binary mixtures.     

Densities and viscosities for ionic liquids mixtures containing [eOHmim][BF4], [bmim][BF4] and [bpy][BF4]

Densities and viscosities of binary ionic liquids mixtures, 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate ([eOHmim][BF₄]) + 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]), 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate ([eOHmim][BF₄]) + N-butylpyridinium tetrafluoroborate ([bpy][BF₄]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]) + N-butylpyridinium tetrafluoroborate ([bpy][BF₄]) were measured over the entire mole fraction from T = (298.15 to 343.15) K. The excess molar volumes were calculated and correlated by Redlich–Kiser polynomial expansions. The viscosities for pure ionic liquids were analyzed by means of the Vogel–Tammann–Fulcher equation and ideal mixing rules were applied for the ILs mixtures.     

Excess thermodynamic properties of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate and N-octyl-2-pyrrolidone from T = (298.15 to 323.15) K at atmospheric pressure

Density (ρ), refractive index (n_D) and speed of sound (u) values are measured for the binary mixture of 1-butyl-3-methylimidazolium tetrafluoroborate and N-octyl-2-pyrrolidone over the entire range of mole fraction at temperatures from T = (298.15 to 323.15) K under atmospheric pressure. Using the basic experimental data, various acoustic and excess thermodynamic parameters are calculated and are discussed in terms of molecular interactions between the present investigated binary system. The excess values are fitted to Redlich–Kister polynomial equation to estimate the binary coefficients and standard deviation between the experimental and calculated values. Further, the molecular interactions in the binary mixture system are analysed using the experimental FT-IR spectrum recorded at room temperature.     

Thermodynamic and transport properties of (1,2-ethanediol + 1-nonanol) at temperatures from (298.15 to 313.15) K

Densities and kinematic viscosities have been measured for (1,2-ethanediol + 1-nonanol) over the temperature range from (298.15 to 313.15) K. The speeds of sound in those mixtures within the temperature range from (293.15 to 313.15) K have been measured as well. Using the measurement results, the molar volumes, isentropic compressibility coefficients, molar isentropic compressibilities, and the corresponding excess and deviation values (excess molar volumes, excess isentropic compressibility coefficients, excess molar isentropic compressibilities, differently defined deviations of the speed of sound, and dynamic viscosity deviations) were calculated. The excess Gibbs free energies estimated by the use of the UNIQUAC model are also reported. The excess molar volumes and Gibbs free energies are positive, whereas the compressibility excesses are s-shaped. The excess and deviation values are expressed by Redlich–Kister polynomials and discussed in terms of variations of the structure of the system caused by the participation of two different alcohol molecules in the dynamic intermolecular association process through hydrogen bonding. The effect of temperature is discussed. The predictive abilities of the McAllister equation for viscosities of the mixtures under test have also been examined.     

Thermodynamic study of binary mixtures containing 1-butylpyridinium tetrafluoroborate and methanol, or ethanol

Densities and speeds of sound have been determined for the binary mixture (1-butylpyridinium tetrafluoroborate + methanol, or ethanol) over the temperature range 293.15 K to 323.15 K. From experimental values, excess volume and excess isentropic compressibility have been calculated. The mixtures give negative values for the excess properties. Besides, (vapour + liquid) equilibrium in isothermal conditions has been obtained for these systems at T = 303.15 K and T = 323.15 K, which has allowed us to derive activity coefficients and excess Gibbs functions. Positive deviations from Raoult’s law have been found. A detailed analysis and interpretation of results have been carried out in structural and energetic terms using thermodynamic information of the pure compounds.     

Micropolarity and aggregation behavior in ionic liquid + organic solvent solutions

UV–vis spectroscopy and conductivity measurement techniques were used to study the physicochemical and structural properties of the binary or ternary mixtures of 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]) + organic solvent and 1-n-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]) + organic solvent systems. The solvents involved were acetonitrile, water, ethanol, ethyl acetate, and tetrahydrofuran. It was indicated that the micropolarity and the aggregation behavior of the mixtures depend strongly on the dielectric constants of the solvents and the composition of the mixtures.     

Density and surface tension of pure ionic liquid 1-butyl-3-methyl-imidazolium l-lactate and its binary mixture with alcohol and water

The density and surface tension of the pure ionic liquid 1-butyl-3-methyl-imidazolium l-lactate were measured from T (293.15 to 343.15) K. The coefficient of thermal expansion, molecular volume, standard entropy, lattice energy, surface entropy, surface enthalpy, and enthalpy of vaporization were calculated from the experimental values. Density and surface tension were also determined for binary mixtures of {1-butyl-3-methyl-imidazolium l-lactate + water/alcohol (methanol, ethanol, and 1-butanol)} systems over the whole composition range from T (298.15 to 318.15) K at atmospheric pressure. The partial molar volume, excess partial molar volume and apparent molar volume of the component IL and alcohol/water in the binary mixtures were discussed as well as limiting properties at infinite dilution and the thermal expansion coefficients of the four binary mixtures. The surface properties of the four binary mixtures were also discussed.     

Ethanol extraction from its azeotropic mixture with hexane employing different ionic liquids as solvents

In this work, the ionic liquids 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [EMim][NTf₂], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [BMim][NTf₂], 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, [BMpy][NTf₂], 1-butyl-3-methylpyridinium trifluoromethanesulfonate, [BMpy][TfO], have been investigated for their use as solvents in extraction processes for the ethanol removal from its azeotropic mixture with hexane. Therefore, the experimental determination of the liquid + liquid equilibrium for the ternary systems {hexane (1) + ethanol (2) + [EMim][NTf₂] (3)}, {hexane (1) + ethanol (2) + [BMim][NTf₂] (3)}, {hexane (1) + ethanol (2) + [BMpy][NTf₂] (3)} and {hexane (1) + ethanol (2) + [BMpy][TfO] (3)} was carried out at T = 298.15 K and atmospheric pressure. Classical parameters such as selectivity and solute distribution ratio, derived from the tie-line data, were calculated and afterwards, the structural influence of the ionic liquids on the extraction process was analyzed. Finally, the experimental LLE data were correlated by means of the NRTL and UNIQUAC models.     

Viscosities and refractive indices of binary mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-2,3-dimethylimidazolium tetrafluoroborate with water at 298 K

Viscosities and refractive indices have been determined for (water + 1-butyl-3-methylimidazolium tetrafluoroborate) and (water + 1-butyl-2,3-dimethylimidazolium tetrafluoroborate) mixtures at 298.15 K, over the whole composition range. The refractive indices were compared with the predictions of the Lorentz–Lorenz, Wiener, and Gladstone–Dale equations. Viscosity deviations (Δη) and refractive index deviations (Δn_D) have been calculated and fitted to the Redlich–Kister polynomial equations. Δn_D are positive whereas Δη are negative over the entire mixture composition for the two salts. The influence of the structure of imidazolium cation on the above physicochemical properties was discussed.     

Experimental methodology for precise determination of density of RTILs as a function of temperature and pressure using vibrating tube densimeters

A specific calibration procedure that allows the accurate determination of densities of room temperature ionic liquids, RTILs, as a function of temperature and pressure using vibrating tube densimeters is presented. This methodology overcomes the problems of common calibration methods when they are used to determine the densities of high density and high viscosity fluids such as RTILs. The methodology is applied for the precise density determination of RTILs 1-ethyl-3-methylimidazolium tetrafluoroborate [Emim][BF₄], 1-butyl-3-methylimidazolium tetrafluoroborate [Bmim][BF₄], 1-hexyl-3-methylimidazolium tetrafluoroborate [Hmim][BF₄], and 1-octyl-3-methylimidazolium tetrafluoroborate [Omim][BF₄] in the temperature and pressure intervals (283.15 to 323.15) K and (0.1 to 60) MPa, respectively. The viscosities of these substances, needed for the estimation of the viscosity-induced errors, were estimated at the same conditions from the experimental measurements in the intervals (283.15 to 323.15) K and (0.1 to 14) MPa and from a specific extrapolation procedure. The uncertainty in the density measurements was estimated in ±0.30 kg · m^?3 which is an excellent value in the working intervals. The results of these RTILs have demonstrated that viscosity-induced errors are relevant and they must be taken into account for a precise density determination. Finally, an alternative tool for a simpler application of this procedure is presented.     

Density and viscosity of three (2,2,2-trifluoroethanol + 1-butyl-3-methylimidazolium) ionic liquid binary systems

Densities and viscosities were determined for binary mixtures of 2,2,2-trifluoroethanol (TFE) and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]), 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]) or 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([bmim][NTf₂]) over the entire range of composition. The experimental measurements were carried out at temperatures ranging from 278.15 K to 333.15 K, at atmospheric pressure. The densities and viscosities of the pure ionic liquids and their mixtures with TFE were described successfully by an empirical third-order polynomial and by the Vogel–Fulcher–Tammann equation, respectively. In addition, excess molar volumes and viscosity deviations were determined from densities and viscosities of mixtures, respectively, and fitted by using the Redlich–Kister equation.