Osmotic coefficients of binary mixtures of four ionic liquids with ethanol or water at T = (313.15 and 333.15) K

Measurements of osmotic coefficients of BmimCl (1-butyl-3-methylimidazolium chloride) and HmimCl (1-hexyl-3-methylimidazolium chloride) with ethanol and EmimEtSO₄ (1-ethyl-3-methylimidazolium ethylsulfate) and EmpyEtSO₄ (1-ethyl-3-methylpyridinium ethylsulfate) with water at T = (313.15 and 333.15) K are reported in this work. Vapour pressure and activity results of the studied binary systems are obtained from experimental measurements. The results for 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 also given. The parameters obtained with the extended Pitzer model of Archer are used to calculate the mean molal activity coefficients.     

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.     

Measurement and modeling of osmotic coefficients of binary mixtures (alcohol + 1,3-dimethylpyridinium methylsulfate) at T = 323.15 K

Measurement of osmotic coefficients of binary mixtures containing several primary and secondary alcohols (1-propanol, 2-propanol, 1-butanol, 2-butanol, and 1-pentanol) and the pyridinium-based ionic liquid 1,3-dimethylpyridinium methylsulfate were performed at T = 323.15 K using the vapor pressure osmometry technique, and from experimental data, vapor pressure, and activity coefficients were determined. The extended Pitzer model modified by Archer, and the NRTL model modified by Jaretun and Aly (MNRTL) were used to correlate the experimental osmotic coefficients, obtaining standard deviations lower than 0.017 and 0.054, respectively. From the parameters obtained with the extended Pitzer model modified by Archer, the mean molal activity coefficients and the excess Gibbs free energy for the studied binary mixtures were calculated. The effect of the cation is studied comparing the experimental results with those obtained for the ionic liquid 1,3-dimethylimidazolium methylsulfate.     

Vapour pressures,osmotic and activity coefficients for binary mixtures containing (1-ethylpyridinium ethylsulfate + several alcohols) at T = 323.15 K

Osmotic coefficients of binary mixtures containing several primary and secondary alcohols (1-propanol, 2-propanol, 1-butanol, 2-butanol, and 1-pentanol) and the pyridinium-based ionic liquid 1-ethylpyridinium ethylsulfate were determined at T = 323.15 K using the vapour pressure osmometry technique. From the experimental results, vapour pressure and activity coefficients can be determined. For the correlation of osmotic coefficients, the extended Pitzer model modified by Archer, and the modified NRTL (MNRTL) model were used, obtaining deviations lower than 0.017 and 0.047, respectively. The mean molal activity coefficients and the excess Gibbs free energy for the binary mixtures studied were determined from the parameters obtained with the extended Pitzer model modified by Archer.     

Determination and modelling of osmotic coefficients and vapour pressures of binary systems 1- and 2-propanol with CnMimNTf2 ionic liquids (n = 2, 3, and 4) at T = 323.15 K

The osmotic and activity coefficients and vapour pressures of binary mixtures containing 1-propanol, or 2-propanol and imidazolium-based ionic liquids with bis(trifluoromethylsulfonyl)imide as anion (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, C₂MimNTf₂, 1-methyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide, C₃MimNTf₂, and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, C₄MimNTf₂) were determined at T = 323.15 K using the vapour pressure osmometry technique. The experimental osmotic coefficients were correlated using the extended Pitzer model modified by Archer and the MNRTL model, obtaining standard deviations lower than 0.033 and 0.064, respectively. The mean molal activity coefficients and the excess Gibbs free energy for the mixtures studied were calculated from the parameters of the extended Pitzer model modified by Archer. Besides the effect of the alkyl-chain of the cation, the effect of the anion can be assessed comparing the experimental results with those previously obtained for imidazolium ionic liquids with sulphate anions.     

Osmotic and activity coefficients in the binary solutions of 1-butyl-3-methylimidazolium chloride and bromide in methanol or ethanol at T = 298.15 K from isopiestic measurements

Osmotic coefficients of the binary solutions of two room-temperature ionic liquids (1-butyl-3-methylimidazolium chloride and bromide) in methanol and ethanol have been measured at T = 298.15 K by the isopiestic method. The experimental osmotic coefficient data have been correlated using a forth-order polynomial in terms of (molality)^0.5, with both, ion interaction model of Pitzer and electrolyte non-random two liquid (e-NRTL) model of Chen. The values of vapor pressures of above-mentioned solutions have been calculated from the osmotic coefficients. The model parameters fitted to the experimental osmotic coefficients have been used for prediction of the mean ionic activity coefficients of those ionic liquids in methanol and ethanol.     

Mean activity coefficient measurement and thermodynamic modelling of the ternary mixed electrolyte (MgCl2 + glucose + water) system at T = 298.15 K

In this work, the mean activity coefficients of MgCl₂ in pure water and (glucose + water) mixture solvent were determined using a galvanic cell without liquid junction potential of type: (Mg²⁺ + ISE)|MgCl₂ (m), glucose (wt.%), H₂O (100 wt.%)|AgCl|Ag. The measurements were performed at T = 298.15 K. Total ionic strengths were from (0.0010 to 6.0000) mol · kg⁻¹. The various (glucose + water) mixed solvents contained (0, 10, 20, 30 and 40)% mass fractions percentage of glucose respectively. The mean activity coefficients measured were correlated with Pitzer ion interaction model and the Pitzer adjustable parameters were determined. Then these parameters were used to calculate the thermodynamics properties for under investigated system. The results showed that Pitzer ion interaction model can satisfactory describe the investigated system. The modified three-characteristic-parameter correlation (TCPC) model was applied to correlate the experimental activity coefficient data for under investigation electrolyte system, too.     

Determination of thermodynamic properties of aqueous mixtures of RbCl and Rb2SO4 by the EMF method at T=298.15 K

The thermodynamic properties, including activity coefficients, osmotic coefficients and excess Gibbs free energy for RbCl and Rb₂SO₄ aqueous mixtures at T=298.15 K and in 0.01 mol · kg⁻¹ to 5 mol · kg⁻¹ ionic strength, were determined by emf measurements. The Rb–ISE and Ag–AgCl electrodes used in this work were prepared in our laboratory and had a reasonably good Nernst response. The experimental data were fitted by using the Harned rule and Pitzer model. The Harned coefficients and the Pitzer binary and ternary interaction parameters for the system have been evaluated. The experimental results obey the Harned rule. The Pitzer model can be used to describe this aqueous system satisfactorily.     

Hygrometric determination of the water activities and the osmotic and activity coefficients of (ammonium chloride + sodium chloride + water) atT = 298.15 K

The mixed aqueous electrolyte system of ammonium and sodium chlorides has been studied by the hygrometric method at the temperature 298.15 K. The relative humidities of this system were measured at total molalities from 0.3mol · kg ^− 1 to 6 mol · kg ^− 1for different ionic-strength fractions of NH ₄Cl with y =  (0.33, 0.50, and 0.67). The data obtained allow the deduction of new water activities and osmotic coefficients. The experimental results are compared with the predictions of the extended composed additivity model proposed in our previous work, the Robinson–Stokes, Reilly–Wood–Robinson, and Lietzke–Stoughton models. From these measurements, the new Pitzer mixing ionic parameters were determined and used to predict the solute activity coefficients in the mixture.     

Thermodynamic properties of (NaCl + KCl + LiCl + H2O) at T = 298.15 K: Water activities,osmotic and activity coefficients

The water activities of aqueous electrolyte mixture (NaCl + KCl + LiCl + H₂O) were experimentally determined at T = 298.15 K by the hygrometric method at total ionic-strength from 0.4 mol · kg⁻¹ to 6 mol · kg⁻¹ for different ionic-strength fractions y of NaCl with y = 1/3, 1/2, and 2/3. The data allow the deduction of new osmotic coefficients. The results obtained were correlated by Pitzer’s model and Dinane’s mixing rules ECA I and ECA II for calculations of the water activity in mixed aqueous electrolytes. A new Dinane–Pitzer model is proposed for the calculation of osmotic coefficients in quaternary aqueous mixtures using the newly ternary and quaternary ionic mixing parameters of this studied system. The solute activity coefficients of component in the mixture are also determined for different ionic-strength fractions y of NaCl.     

Activity coefficients of CaCl2 in (maltose + water) and (lactose + water) mixtures at 298.15 K

Activity coefficients of CaCl₂ in disaccharide {(maltose, lactose) + water} mixtures at 298.15 K were determined by cell potentials. The molalities of CaCl₂ ranged from about 0.01 mol · kg^?1 to 0.20 mol · kg^?1, the mass fractions of maltose from 0.05 to 0.25, and those of lactose from 0.025 to 0.125. The cell potentials were analyzed by using the Debye–Hückel extended equation and the Pitzer equation. The activity coefficients obtained from the two theoretical models are in good agreement with each other. Gibbs free energy interaction parameters (g_ES) and salting constants (k_S) were also obtained. These were discussed in terms of the stereo-chemistry of saccharide molecules and the structural interaction model.     

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.     

Isopiestic study of (calcium chloride + water) and (calcium chloride + magnesium chloride + water) atT = 313.15 K

The osmotic coefficients of aqueous calcium chloride solutions were experimentally determined atT =  313.15 K by the isopiestic method. Magnesium chloride served as the isopiestic standard for the calculation of osmotic coefficients. The molality range covered in this study correspond to about 0.1mol · kg ^− 1to 3.0mol · kg ^− 1. In addition, the osmotic coefficients of aqueous mixtures of calcium chloride and magnesium chloride were determined over the range of ionic strength levels of about 0.1mol · kg ^− 1to 9mol · kg ^− 1and at various mole fractions. The results obtained were correlated by the Pitzer equation.     

Hygrometric determination of water activities,osmotic and activity coefficients of (NaCl + KCl)(aq) at T = 298.15 K

The purpose of this study is to present a model for the prediction of water activity in multicomponent aqueous solutions containing a common ion from available binary data. The hygrometric method has been used to measure relative humidities for the aqueous electrolyte mixture (NaCl  +  KCl)(aq) at total molalities ranging from 0.2 mol · kg ^− 1to saturation for different molal ratiosr of NaCl(aq) to KCl(aq) with r =  (0.2, 0.5, 1, 2, 3, and 4) at T =  298.15 K. The data obtained have been used to determine water activities and osmotic coefficients. The results show that the values of water activities and osmotic coefficients calculated with the proposed model are close to the experimental ones. This model is also compared with four other models (RS, Pitzer, RWR, and LS II) over the range of the studied total molalities. From the measurements, the activity coefficients of NaCl(aq) and KCl(aq) in the mixture have also been determined.     

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.     

Thermodynamic properties of {(NH4)2SO4(aq) + Li2SO4(aq)} and {(NH4)2SO 4(aq) + Na2SO4(aq)} at a temperature of 298.15 K

The water activities and osmotic coefficients of aqueous solutions of {(NH₄ )₂SO ₄ +  Li ₂SO ₄} and {(NH₄ )₂SO ₄ +  Na ₂SO ₄} have been determined at a temperature of 298.15 K with a hygrometric method, at molalities in the region 0.2 mol · kg ^− 1 to saturation of the solutes for different fractional ionic-strengthsy =  0.2, 0.5, and 0.8 of (NH ₄)₂SO ₄. The experimental results are compared with the predictions obtained from our extended compared additivity model, as well as the models reported by Zdanovskii, Stokes and Robinson, Pitzer, and Lietzke-Stoughton. From these measurements, parameters of Pitzers model have been determined. These were used to predict solute activity coefficients in the mixture and calculate the excess Gibbs function at total molalities for different y for these systems.     

Activity coefficients of CaCl2 in (serine or proline + water) mixtures at T = 298.15 K

Activity coefficients for the (CaCl₂ + amino acid + water) system were determined at a temperature of 298.15 K using ion-selective electrodes. The range of molalities of CaCl₂ is (0.01 to 0.20) mol · kg^?1, and that of amino acids is (0.10 to 0.40) mol · kg^?1. The activity coefficients obtained from the Debye–Hückel extended equation and the Pitzer equation are in good agreement with each other. Results show that the interactions between CaCl₂ and amino acid are controlled mainly by the electrostatic interactions (attraction). Gibbs free energy interaction parameters (g_EA) and salting constants (k_S) are positive, indicating that these amino acids are salted out by CaCl₂. These results are discussed based on group additivity model.     

Water activities,osmotic and activity coefficients in aqueous chloride solutions atT = 298.15 K by the hygrometric method

Water activities of aqueous electrolyte solutions of HCl(aq), LiCl(aq), NaCl(aq), KCl(aq), CsCl(aq), NH₄Cl(aq), MgCl₂(aq), CaCl₂(aq), and BaCl₂(aq) have been determined at T =  298.15 K by the hygrometric method, and at molalities ranging from 0.2 mol · kg ^− 1to saturation. From measurements of droplets diameters of reference NaCl(aq) or LiCl(aq), the dependence of relative humidity on solute concentration was determined. The data on the relative humidities allow the deduction of water activities and the osmotic coefficients at different molalities. Osmotic coefficient data have been described by the ion interaction model of Pitzer. The ion interaction parameters were also determined for each of the studied salts. With these parameters, the solute activity coefficients can be predicted. Our present results have been compared with reported thermodynamic data.     

Osmotic coefficients of aqueous solutions of four ionic liquids at T = (313.15 and 333.15) K

Measurements of osmotic coefficients of BmimCl (1-butyl-3-methylimidazolium chloride), HmimCl (1-hexyl-3-methylimidazolium chloride), MmimMeSO₄ (1,3-dimethylimidazolium methylsulfate), and BmimMeSO₄ (1-butyl-3-methylimidazolium methylsulfate) with water at T = (313.15 and 333.15) K are reported in this work. Vapour pressure and activity data of all the studied binary systems are obtained from experimental data. The osmotic coefficients data are correlated using the extended Pitzer model of Archer and the modified NRTL (MNRTL) model and standard deviations obtained with both models are given too. The parameters obtained with the extended Pitzer model of Archer are used to calculate the mean molal activity coefficients.