The salting-out effect and phase separation in aqueous solutions of tri-sodium citrate and 1-butyl-3-methylimidazolium bromide

The aim of this work is to obtain further evidence about the salting-out effect produced by the addition of tri-sodium citrate to aqueous solutions of water miscible ionic liquid 1-butyl-3-methylimidazolium bromide ([C₄mim][Br]) by evaluating the effect of tri-sodium citrate on the thermodynamic properties of aqueous solutions of this ionic liquid. Experimental measurements of density and sound velocity at different temperatures ranging from (288.15 to 308.15) K, the refractive index at 308.15 K and the liquid–liquid phase diagram at different temperatures ranging from (288.15 to 338.15) K for aqueous solutions containing 1-butyl-3-methylimidazolium bromide ([C₄mim][Br]) and tri-sodium citrate (Na₃Cit) are taken. The apparent molar volume of transfer of [C₄mim][Br] from water to aqueous solutions of Na₃Cit have positive values and it increases by increasing salt molality. Although at high IL molality, the apparent molar isentropic compressibility shows similar behaviour with that of the apparent molar volume. However at low concentrations of IL, the apparent molar isentropic compressibility of transfer of [C₄mim][Br] from water to aqueous solutions of Na₃Cit have negative values. The effects of temperature and the addition of Na₃Cit and [C₄mim][Br] on the liquid–liquid phase diagram of the investigated system have been studied. It was found that an increase in temperature caused the expansion of the one-phase region. The presence of Na₃Cit triggers a salting-out effect, leading to significant upward shifts of the liquid–liquid de-mixing temperatures of the system. The effect of temperature on the phase-forming ability in the system investigated has been studied based on a salting-out coefficient obtained from fitting the binodal values to a Setschenow-type equation for each temperature. Based on cloud point values, the energetics of the clouding process have been estimated and it was found that both of entropy and enthalpy are the driving forces for biphasic formation.     

(Vapour + liquid) equilibria,volumetric and compressibility behaviour of binary and ternary aqueous solutions of 1-hexyl-3-methylimidazolium chloride,methyl potassium malonate,and ethyl potassium malonate

(Vapour + liquid) equilibrium data (water activity, vapour pressure, osmotic coefficient, and activity coefficient) of binary aqueous solutions of 1-hexyl-3-methylimidazolium chloride ([C₆mim][Cl]), methyl potassium malonate, and ethyl potassium malonate and ternary {[C₆mim][Cl] + methyl potassium malonate} and {[C₆mim][Cl] + ethyl potassium malonate} aqueous solutions were obtained through the isopiestic method at T = 298.15 K. These results reveal that the ionic liquid behaves as surfactant-like and aggregates in aqueous solutions at molality about 0.4 mol · kg⁻¹. The constant water activity lines of all the ternary systems investigated show small negative deviations from the linear isopiestic relation (Zdanovskii–Stokes–Robinson rule) derived using the semi-ideal hydration model. The density and speed of sound measurements were carried out on solutions of methyl potassium malonate and ethyl potassium malonate in water and of [C₆mim][Cl] in aqueous solutions of 0.25 mol · kg⁻¹ methyl potassium malonate and ethyl potassium malonate at T = (288.15 to 308.15) K at atmospheric pressure. From the experimental density and speed of sound data, the values of the apparent molar volume, apparent molar isentropic compressibility and excess molar volume were evaluated and from which the infinite dilution apparent molar volume and infinite dilution apparent molar isentropic compressibility were calculated at each temperature. Although, there are no clear differences between the values of the apparent molar volume of [C₆mim][Cl] in pure water and in methyl potassium malonate or ethyl potassium malonate aqueous solutions, however, the results show a positive transfer isentropic compressibility of [C₆mim][Cl] from pure water to the methyl potassium malonate or ethyl potassium malonate aqueous solutions. The results have been interpreted in terms of the solute–water and solute–solute interactions.     

Effect of sodium phosphate salts on the thermodynamic properties of aqueous solutions of poly(ethylene oxide) 6000 at different temperatures

Precise density, sound velocity, water activity, and phase diagram measurements have been carried out on polyethylene oxide (PEO) in aqueous solutions of sodium di-hydrogen phosphate, di-sodium hydrogen phosphate, and tri-sodium phosphate over a range of temperatures at atmospheric pressure. The experimental density and sound velocity data are used to calculate the apparent specific volume and isentropic compressibility as a function of temperature and concentration. It was found that both of the apparent specific volume and isentropic compressibility of PEO in aqueous solutions increase by increasing temperature and charge on the anion of electrolytes. The results show that the slope of constant water activity lines increased with increasing the temperature and charge on the anion of electrolytes and the vapour pressure depression for an aqueous (PEO + sodium phosphate) system is more than the sum of those for the corresponding binary solutions. Furthermore, the effect of temperature and type of anion of salt on the salting-out effect of polyethylene oxide by sodium phosphate salts has been studied.     

Volumetric and viscosity studies of interactions between sodium phosphate salts and poly(propylene glycol) 400 in aqueous solutions at different temperatures

Density and sound velocity at the 288.15–313.15 K and viscosity at the 298.15–313.15 K temperature range at 5 K intervals for polypropylene glycol (PPG) in aqueous solutions of sodium di-hydrogen phosphate, di-sodium hydrogen phosphate and tri-sodium phosphate with salt mass fractions 0.00, 0.010 and 0.020 are reported at atmospheric pressure. From the experimental density and sound velocity data, the apparent specific volume, excess specific volume, isentropic compressibility and isentropic compressibility deviation values have been determined. The infinite dilution apparent specific volume and isentropic compressibility values of PPG have been obtained and from which the infinite dilution apparent specific volumes of transfer of PPG from water to aqueous sodium phosphate solutions have been obtained for the investigated salt concentrations and temperatures. The excess specific volume, isentropic compressibility and viscosity deviation are negative and decrease in magnitude as temperature, concentration of sodium phosphate and charge on the anion of electrolyte increases.     

Effect of tri-potassium phosphate on volumetric,acoustic, and transport behaviour of aqueous solutions of 1-ethyl-3-methylimidazolium bromide at T = (298.15 to 318.15) K

Density, sound velocity, and viscosity of 1-ethyl-3-methylimidazolium bromide, [Emim][Br], in aqueous solutions of tri-potassium phosphate with salt weight fractions (w_s = 0.00, 0.10, 0.15, and 0.20) have been measured as a function of concentration of [Emim][Br] at atmospheric pressure and T = (298.15, 303.15, 308.15, 313.15, and 318.15) K. The apparent molar volume, isentropic compressibility, apparent isentropic compressibility, and relative viscosity values have been evaluated from the experimental data. The partial molar volume and isentropic compressibility at infinite dilution, and viscosity B-coefficient obtained from these data have been used to calculate the corresponding transfer parameters for the studied IL from water to the aqueous tri-potassium phosphate solutions. Also, an empirical equation was satisfactorily used to correlate the experimental viscosity data.     

Effect of alkyl chain length and temperature on the thermodynamic properties of ionic liquids 1-alkyl-3-methylimidazolium bromide in aqueous and non-aqueous solutions at different temperatures

The alkyl chain length of 1-alkyl-3-methylimidazolium bromide ([Rmim][Br], R = propyl (C₃), hexyl (C₆), heptyl (C₇), and octyl (C₈)) was varied to prepare a series of room-temperature ionic liquids (RTILs), and experimental measurements of density and speed of sound at different temperatures ranging from (288.15 to 308.15) K for their aqueous and methanolic solutions in the dilute concentration region (0.01 to 0.30) mol · kg^?1 were taken. The values of the compressibilities, expansivity and apparent molar properties for [C_nmim][Br] in aqueous and methanolic solutions were determined at the investigated temperatures. The obtained apparent molar volumes and apparent molar isentropic compressibilities were fitted to the Redlich–Mayer and the Pitzer’s equations from which the corresponding infinite dilution molar properties were obtained. The values of the infinite dilution molar properties were used to obtain some information about solute–solvent and solute–solute interactions. The thermodynamic properties of investigated ionic liquids in aqueous solutions have been compared with those in methanolic solutions. Also, the comparison between thermodynamic properties of investigated solutions and those of electrolyte solutions, polymer solutions, cationic surfactant solutions and tetraalkylammonium salt solutions have been made.     

Thermodynamic properties of solutions of sodium di-hydrogen phosphate in (1-propanol + water) mixed-solvent media over the temperature range of (283.15 to 303.15) K

The apparent molar volume and apparent molar isentropic compressibility of solutions of sodium di-hydrogen phosphate (NaH₂PO₄) in (1-propanol + water) mixed-solvent media with alcohol mass fractions of 0.00, 0.05, 0.10, and 0.15 are reported over the range of temperature (283.15 to 303.15) K at 5 K intervals. The results were fitted to a Redlich–Mayer type equation from which the apparent molar volume and apparent molar isentropic compressibility of the solutions at the infinite dilution were also calculated at the working temperature. The results show a positive transfer volume of NaH₂PO₄ from an aqueous solution to an aqueous 1-propanol solution. The apparent molar isentropic compressibility of NaH₂PO₄ in aqueous 1-propanol solutions is negative and it increases with increasing the concentration of NaH₂PO₄, 1-propanol, and temperature. Electrical conductivity and refractive index of the solutions are also studied at T = 298.15 K. The effects of the electrolyte concentration and relative permittivity of the medium on the molar conductivity were also investigated.     

Apparent molar volume, isentropic compressibility and conductivity of di-sodium hydrogen phosphate in water and in aqueous solutions of 1-propanol

Precise measurements on the density and sound velocity of solutions of di-sodium hydrogen phosphate in 1-propanol + water mixed-solvent media with alcohol mass fractions of 0.00, 0.05, 0.10 and 0.15 are reported in the 283.15–303.15 K temperature range at 5 K intervals. Electrical conductivity and refractive index of the solutions are studied at 298.15 K. From the experimental density and sound velocity data, the apparent molar volume and isentropic compressibility values of di-sodium hydrogen phosphate have been evaluated. The results show a positive transfer volume of di-sodium hydrogen phosphate from an aqueous 1-propanol solution to a more concentrated 1-propanol solution. The apparent molar isentropic compression of di-sodium hydrogen phosphate in aqueous 1-propanol solutions is negative and it increases with increasing the concentration of 1-propanol and temperature. The negative values of apparent molar isentropic compression imply that the water molecules around the di-sodium hydrogen phosphate are less compressible than the water molecules in the bulk solutions. The effects of the electrolyte concentration and relative permittivity of the medium on the molar conductivity were also investigated.     

Study on the Conductivities of Pure and Aqueous Bromide-Based Ionic Liquids at Different Temperatures

Electrical conductivities were measured for the pure ionic liquids [C₆mim][Br] (1-hexyl-3-methylimidazolium bromide) and [C₈mim][Br] (1-octyl-3-methylimidazolium bromide) at 0.1 MPa from 293.15 to 333.15 K. Conductivity measurements were also made for the binary water + [C₆mim][Br] and water + [C₈mim][Br] systems and their ternary water + [C₆mim][Br] + [C₈mim][Br] system at 0.1 MPa and 293.15, 298.15, and 303.15 K. The conductivity data of the pure ionic liquids were correlated by the VFT (Vogel-Tamman-Fulcher) equation, and the fitting parameters and mean absolute deviations were determined. New explanations are presented for the molality-dependent behavior of the conductivity of the binary water + [C₆mim][Br] and water + [C₈mim][Br] systems. The generalized Young’s rule and the semi-ideal solution theory for conductivity were used to predict the conductivities of the ternary water + [C₆mim][Br] + [C₈mim][Br] system from the conductivities of its corresponding binary water + [C₆mim][Br] and water + [C₈mim][Br] subsystems. The predictions are in good agreement with the measured values.     

Thermodynamic properties of surfactant sodium n-heptyl sulfonate in water and in aqueous solutions of poly(ethylene glycol) at different temperatures

The volumetric, compressibility and electrical conductivity properties of sodium n-heptyl sulfonate (C₇SO₃Na) in pure water and in aqueous poly(ethylene glycol) (PEG) solutions were determined at different temperatures below and above the micellar composition range. At each temperature, the infinite dilution apparent molar volumes of the monomer and micellar state of C₇SO₃Na in aqueous PEG solutions respectively are smaller and larger than those in pure water. However, the values of the infinite dilution apparent molar isentropic compressibility of both monomer and micellar states of C₇SO₃Na in aqueous PEG solutions are larger than those in pure water. Thermodynamic parameters of micellization of investigated surfactant in water and in aqueous solutions of PEG at different temperatures were estimated and it was found that the micelle formation process is endothermic and therefore, this process must be driven by entropy increase. The calculated Gibbs free energies of micellization for aqueous PEG solutions are more negative than those for pure water and become more negative by increasing temperature. The variation of the critical micelle concentration (CMC) of C₇SO₃Na in water and in aqueous PEG solutions with temperature was obtained and a comparison between the CMC of C₇SO₃Na obtained from different thermodynamic properties was also made.     

Effect of additives on the surface active and morphological features of 1-octyl-3-methylimidazolium halide aggregates in aqueous media

The influence of two salts as additives namely sodium chloride and sodium sulphate and a nonelectrolyte, 2-butoxyethanol on surface chemical and aggregation characteristics of ionic liquids (IL) of 1-octyl-3-methylimidazolium chloride, [C₈mim][Cl], 1-octyl-3-methylimidazolium bromide, [C₈mim][Br], and 1-octyl-3-methylimidazolium iodide, [C₈mim][I] in aqueous media were monitored through surface tension and small angle neutron scattering measurements. The addition of salts drastically decreased the critical aggregation concentration (CAC) and increased the area per adsorbed IL molecule. The co-ions of salts modify the surface of IL molecules and aggregates through various interactions such as charge neutralization, specific interactions and dehydration The results obtained by analyzing the SANS curves in the whole Q range showed that the oblate ellipsoidal shape of the aggregates of ionic liquids is un-altered upon the addition of additives. However the additives facilitate the growth of the aggregates in to microstructures with cubic packing at high salt concentrations.     

Apparent molar volumes and compressibilities of electrolytes and ions in γ-butyrolactone

The densities of tetraphenylphosphonium bromide, sodium tetraphenylborate, lithium perchlorate, sodium perchlorate and lithium bromide in γ-butyrolactone at (288.15, 293.15, 298.15, 303.15, 308.15 and 313.15) K and speed of sound at 298.15 K have been measured. From these data apparent molar volumes V_Φ at (288.15, 293.15, 298.15, 303.15, 308.15 and 313.15) K and the apparent molar isentropic compressibility K_S,Φ, at T = 298.15 K of the salts have been determined. The apparent molar volumes and the apparent molar isentropic compressibilities were fitted to the Redlich, Rosenfeld and Mayer equation as well as to the Pitzer and Masson equations yielding infinite dilution data. The obtained limiting values have been used to estimate the ionic data of the standard partial molar volume and the standard partial isentropic compressibility in γ-butyrolactone solutions.     

Conductivity,apparent molar volume and isentropic compressibility of 12-tungstosilicic acid and potassium 12-tungstosilicate in aqueous solutions at different temperatures

12-Tungstosilicic acid and potassium 12-tungstosilicate were synthesized and conductivities, densities and ultrasound velocities of their aqueous solutions were studied in the 283.15–303.15 K temperature range at 5 K intervals. Apparent molar volume and apparent molar isentropic compressibility of 12-tungstosilicic acid and potassium 12-tungstosilicate and isentropic compressibility of the studied aqueous solutions have been determined from the experimental density and sound velocity data.     

Volumetric and isentropic compressibility behaviour of aqueous solutions of (polyvinylpyrrolidone + sodium citrate) at T = (283.15 to 308.15) K

The apparent specific volumes and isentropic compressibilities have been determined for polyvinylpyrrolidone in aqueous solutions of sodium citrate by density and sound velocity measurements at T = (283.15 to 308.15) K at atmospheric pressure. The results show a positive transfer volume of PVP from an aqueous solution to an aqueous sodium citrate solution. For low concentrations of PVP, the apparent specific volumes of PVP in water increased along with an increase in the polymer mass fraction, while in aqueous sodium citrate solutions decreased along with an increase in the polymer mass fraction. For high concentrations of PVP, the apparent specific volumes of PVP in water and in aqueous sodium citrate solutions were independent of the polymer mass fraction. The apparent specific isentropic compressibility of PVP is negative at T = (283.15 and 288.15) K, which imply that the water molecules around the PVP molecules are less compressible than the water molecules in the bulk solutions. The positive values of apparent specific isentropic compressibility at T = (298.15, 303.15, and 308.15) K imply that the water molecules around the PVP molecules are more compressible than the water molecules in the bulk solutions. Finally, it was found that the apparent specific isentropic compressibility of PVP increases as the concentration of sodium citrate increases.     

288.15-318.15K温度范围内离子液体[C5mim][Pro]水溶液的体积和表面性质

在288.15-318.15 K温度范围内,测定了不同浓度离子液体1-戊基-3-甲基咪唑丙酸盐([C5mim][Pro])水溶液的密度和表面张力,计算了不同温度下不同浓度的溶液热膨胀系数、表观摩尔体积和溶液等张比容;根据密度实验数据计算得到溶质表观膨胀率,并与Harned和Owen提供的理论方程计算结果作了比较,两者计算结果能够很好一致;另外,本文还验证了预测溶液表面张力的经验方程,用其预测溶液的表面张力,不仅与溶液表面张力实验值在误差范围内很好一致,也与用等张比容方法预测的结果一致.     

Conductivities, volumes, fluorescence, and aggregation behavior of ionic liquids [C4mim][BF4] and [C(n)mim]Br (n = 4, 6, 8, 10, 12) in aqueous solutions

Densities, conductivities, and polarity indexes of pyrene for aqueous solutions of a series of ionic liquids [C(n)mim]Br (n = 4, 6, 8, 10, 12) and [C4mim][BF4] have been determined at 298.15 K as a function of ionic liquid concentrations. It was shown that possible aggregation appeared for the ionic liquids in aqueous solutions except for [C4mim]Br. The critical aggregation concentration (CAC) of the ionic liquids, the ionization degree of aggregates (beta), the standard Gibbs energy of aggregation (Delta G(m)(o)), the limiting molar conductivity (Lambda(m)(o)), and the standard partial molar volume (V(m)(o)) for the ionic liquids were derived from the experimental data. The dependence of the CAC, Delta G(m)(o), Lambda(m)(o), and V(m)(o) on the length of the alkyl chain of the cations was examined. It was further suggested from volumetric data that a micelle was formed for [C8mim]Br, [C10mim]Br, and [C12mim]Br in aqueous solutions. Their apparent molar volumes at the critical micelle concentration (V Phi,CMC), apparent molar volumes in the micelle phase (V(Phi)(mic)), and the change of their apparent molar volume upon micellization (Delta V Phi,m) were calculated by application of the pseudophase model of micellization. In addition, the average aggregation number of [C(n)mim]Br (n = 8, 10, 12) has been determined by the steady-state fluorescence quenching technique, and predicted from a simple geometrical mode. It is found that the experimental values are in good agreement with the predicted ones.     

Modulation of the aggregation behaviour and physicochemical properties of 1-dodecyl-3-methylimidazolium bromide in aqueous solutions by β-CD

The modulation of aggregation behaviour of ionic liquids (ILs) in aqueous media is one of the important research topics. In the present work, aggregation behaviour of 1-dodecyl-3-methylimidazolium bromide ([C₁₂mim]Br) modulated by beta-cyclodextrin (β-CD) has been investigated by using conductivity, volume, fluorescence, dynamic light scattering and transmission electron microscopy techniques. The results suggested that the addition of β-CD significantly affects the aggregation of [C₁₂mim]Br in aqueous solutions. For example, the apparent critical micelle concentration increases with the increase of β-CD concentration; the average micellar size reduced with the increasing concentration of β-CD, and the process for micelle formation of [C₁₂mim]Br in aqueous β-CD solution is driven by entropy at lower temperature, while driven by enthalpy at higher temperature. It is expected that findings in this study would shed light on the potential applications of IL in supramolecular chemistry.     

Interactions of Imidazolium Based Ionic Liquids with Water Studied by Density and Speed of Sound Measurements: Effect of the Chain Length of an Alkyl Substituent on the Imidazolium Ion

Densities and speeds of sound of three ionic liquids (ILs), 1-ethyl-3-methyl imidazoliumtetrafluoroborate (C₂mimBF₄), 1-butyl-3-methylimidazoliumtetrafluoroborate (C₄mimBF₄) and 1-hexyl-3-methylimidazoliumtetrafluoroborate (C₆mimBF₄) were measured in aqueous solutions at (288.15, 293.15, 298.15, 303.15 and 308.15) K. These data were used to calculate the volumetric properties apparent molar volume and apparent molar isentropic compression as a function of molality. Infinite dilution values for these properties were evaluated by an extrapolation procedure based on Redlich–Meyer type equations. Apparent molar isobaric expansions at infinite dilution were also obtained from the slopes of the apparent molar volume at infinite dilution versus temperature. All these properties are interpreted in terms of IL–water interactions. The hydrolysis of the \( {\text{BF}}_{4}^{ - } \) anion of the ILs and its effects on the results is discussed.     

Thermophysical and Spectroscopic Studies of Pure 1-Butyl-3-methylimidazolium Tetrafluoroborate and Its Aqueous Mixtures

Intermolecular interactions in the aqueous mixtures of the room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF₄]), have been studied. The thermophysical properties: density ρ, speed of sound u, specific conductivity κ and refractive index n _D have been measured over the whole composition range at different temperatures (293.15–323.15 K) and are discussed. The results from thermophysical measurements are explained with the help of spectroscopy. In order to interpret the nature of molecular interactions occurring between [BMIM][BF₄] and water molecules, as well as to identify the moieties in which interactions are taking place, ¹H, ¹³C NMR and FT-IR spectra of the solutions have been studied. Excess molar volume V ^E, excess molar isentropic compressibility $ K_{S}^{\text{E}} $ , partial molar excess volume $ V_{i}^{\text{E}} $ , partial molar excess isentropic compressibility $ K_{S,i}^{\text{E}} $ , deviation in specific conductivity ?κ, and deviation in refractive index ?R have also been determined and analyzed to have a better understanding of the interactions taking place between the different components. Additionally, the excess ultrasonic speed u ^E and excess isentropic compressibility $ k_{S}^{\text{E}} $ , in terms of volume fractions, have been calculated and analyzed. It has been observed that temperature has a significant effect on the thermophysical properties of the studied system. Spectroscopic measurements confirm the disruption of ion-pair interactions of [BMIM][BF₄] and hydrogen-bonded network of water in the aqueous mixture of [BMIM][BF₄].     

Effect of KCl on the volumetric and transport properties of aqueous tri-potassium citrate solutions at different temperatures

Density, speed of sound and viscosity measurements of binary aqueous solutions of tri-potassium citrate were performed from dilute up to near saturated concentration range at T = (293.15, 298.15, 303.15, 308.15, and 313.15) K. Volumetric and transport properties of ternary aqueous solutions of (tri-potassium citrate + KCl) have also been measured within the molality range of KCl (0.05, 0.15, 0.25, 0.35, 0.45, and 0.55) at different temperatures. Apparent molar volume and apparent molar isentropic compressibility have been calculated from the density and speed of sound for binary and ternary aqueous solutions of tri-potassium citrate. Apparent molar volume and apparent molar isentropic compressibility of ternary aqueous solutions of (tri-potassium citrate + KCl) have been correlated with the Redlich–Mayer equation. Viscosity values of ternary aqueous solutions of (tri-potassium citrate + KCl) have been fitted with the Jones–Dole equation. The results obtained have been interpreted in elucidating the effect of tri-potassium citrate on the interaction of KCl–H₂O. Density and viscosity values of ternary aqueous solutions of (tri-potassium citrate + KCl) have been predicted successfully using the methods proposed by Laliberte (2007), Laliberte and Cooper (2004) [9], [10] and Zafarani-Moattar and Majdan-Cegincara (2009) [11].