Evidence of a phase transition in water-1-butyl-3-methylimidazolium tetrafluoroborate and water-1-butyl-2,3-dimethylimidazolium tetrafluoroborate mixtures at 298 K: determination of the surface thermal coefficient, bT,P

We studied the aggregation behavior of two short-chain room-temperature ionic liquids. Previous surface tension studies have shown that 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)) aggregates in water. We observed the same behavior for another ionic liquid, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (bdmimBF(4)). We carried out a thermodynamic study of the mixtures between water and the two butylimidazolium salts to investigate this unusual behavior for cations with short chains by determining the surface thermal coefficient, b(T,P). Plotting b(T,P) as a function of the molar fraction (X) of the two salts showed a clear discontinuity at X = 0.016 for bmimBF(4) and X = 0.004 for bdmimBF(4). This discontinuity could be attributed to a transition such as an aggregation.     

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 volumetric properties of binary mixtures of the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate with benzaldehyde at T = (298.15 to 313.15) K

The densities of the binary mixtures formed by 1-butyl-3-methylimidazolium tetrafluoroborate [bmim][BF₄] with aromatic compound (benzaldehyde) have been determined over the full range of compositions at the temperature range from (298.15 to 313.15) K and at atmospheric pressure using a vibrating-tube densimeter (DMA4500). Excess molar volumes $(V_{\text{m}}^{\text{E}})$ have been obtained from these experimental results, and been fitted by the fourth-order Redlich–Kister equation. In addition, partial molar volumes, apparent molar volumes, and partial molar volumes at infinite dilution have been calculated for each component. Our results show $V_{\text{m}}^{\text{E}}$ decreases slightly when temperature increases in the systems studied. The results have been interpreted in terms of ion–dipole interactions and structural factors of the ionic liquid and these organic molecular liquids.     

Cloud point measurements of 1-butyl-2,3-dimethylimidazolium tetrafluoroborate with alcohols

Mutual solubility data of imidazolium-based ionic liquid, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate ([bmmim][BF₄]) with the alcohols, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, and 1-hexanol were obtained by a cloud point method. The upper critical solution temperatures of the ionic liquid and alcohol mixtures were determined from the mutual solubility data. The upper critical solution temperature of the binary mixtures gradually increased as the chain length of the alcohol increased. The mutual solubility data of binary systems ([bmmim][BF₄] + alcohols) have been correlated by the original UNIQUAC model as well as the extended and modified form of the UNIQUAC model. The temperature dependence of the mutual solubility data could be represented in terms of the temperature dependence of the binary energy parameters obtained from the correlation. Additionally the influence of water contamination on the ionic liquid mixture was shown experimentally by adding pure water into the binary mixture ([bmmim][BF₄] + 1-butanol).     

The nature of associates of 1,4-dinitrobenzene dianion with 1-butyl-3-methylimidazolium and 1-butyl-2,3-dimethylimidazolium cations

Association of 1,4-dinitrobenzene (1,4-DNB) dianion (DA) with 1-butyl-3-methylimidazolium (bmim⁺) and 1-butyl-2,3-dimethylimidazolium (bdmim⁺) cations, whose salts are widely used as ionic liquids, was studied by cyclic voltammetry. In 0.1 M solution of Bu₄NClO₄ in DMF, associates with the number of coordinated cations up to four in the case of bmim⁺ and two in the case of bdmim⁺ are formed. The partial stability constant values for the associates of bmim⁺ are 40, 20, 5, and 3.2 L mol⁻¹, of bdmim⁺ − 24 and 1.9 L mol⁻¹. The higher number of coordinated bmim+ cations is attributed to the formation of, along with ion pairs, hydrogen bonds between 1,4-DNB DA and bmim⁺ due to the labile hydrogen atom at position 2 of the imidazole ring, in contrast to bdmim⁺, which is involved only into the ion-pair interactions.     

Part I: Thermodynamic analysis of volumetric properties of concentrated aqueous solutions of 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate,and ethylammonium nitrate based on pseudo-lattice theory

This study concerns volumetric behaviour of mixtures between water and three ionic liquids: 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF₄), 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (bdmimBF₄), and ethylammonium nitrate (EAN). We report that the pseudo-lattice theory proposed by Bahe and recently supplemented by Varela et al. can suitably describe the partial molar volume of ionic liquids throughout the composition scale from the infinitely dilute state to the pure room temperature molten salt. In this approach, the ions of 1:1 electrolytes in concentrated solutions are supposed to be distributed in a face-centred-cubic structure. The main advantage of this approach is that, contrary to Debye–Hückel approach, it widens the range of composition that can be described to high concentration salt solutions (several times molar) and also the most diluted salt solutions.     

Structural change of 1-butyl-3-methylimidazolium tetrafluoroborate + water mixtures studied by infrared vibrational spectroscopy

Mixtures of ionic liquid (IL, 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF4]) and water with varying concentrations were studied by attenuated total reflection infrared absorption and Raman spectroscopy. Changes in the peak intensities and peak positions of CHx (x = 1, 2, 3) vibration modes of the cation of the IL and OH vibration modes of the water molecules were investigated. Peaks from normal-mode stretch vibrations of CH bonds belonging to the imidazolium ring of the cation did not change their positions, while those from the terminal methyl group of the butyl chain blueshifted by approximately 10 cm-1 with the addition of water. On the other hand, change in the spectral shape in the OH stretch vibration region shows hydrogen-bonding network of water molecules breaking down rapidly as the IL is added. Trends in the change of the peak positions and the peak intensities suggested qualitative change of the intermolecular structure in the [BMIM][BF4] + H2O mixture at 32 +/- 2 and 45 +/- 2 mol/L of water concentration.     

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.     

A new force field model of 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and acetonitrile mixtures

Recently, we introduced a new force field (FF) to simulate transport properties of imidazolium-based room-temperature ionic liquids (RTILs) using a solid physical background. In the present work, we apply this FF to derive thermodynamic, structure, and transport properties of the mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF(4)], and acetonitrile (ACN) over the whole composition range. Three approaches to derive a force field are formulated based on different treatments of the ion-ion and ion-molecule Coulomb interactions: unit-charge, scaled-charge and floating-charge approaches. The simulation results are justified with the help of experimental data on specific density and shear viscosity for these mixtures. We find that a phenomenological account (particularly, a simple scaled-charge model) of electronic polarization leads to the best-performing model. Remarkably, its validity does not depend on the molar fraction of [BMIM][BF(4)] in the mixture. The derived FF is so far the first molecular model which is able to simulate all transport properties of the mixtures, comprising RTIL and ACN, fully realistically.     

Liquid structures of 1-butyl-3-methylimidazolium tetrafluoroborate and carbon dioxide mixtures by X-ray diffraction measurements

X-ray diffraction measurements for the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF₄], mixed with CO₂ were carried out at high pressures using our developed polymer cell. The intermolecular distribution functions obtained for [BMIM][BF₄]–CO₂ mixtures showed that CO₂ molecules are preferentially solvated to the [BF₄]⁻ anion. The similar preferential solvation was previously observed in analogous 1-btuyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF₆], with a different anion, which is in harmony with the present results in [BMIM][BF₄]–CO₂.     

Isotope effects on miscibility of 1-butyl-3-methylimidazolium tetrafluoroborate with butanols

The liquid-liquid miscibility temperatures as a function of composition and deuterium substitution have been experimentally determined for the binary mixtures of 1-butyl-3-methylimidazolium tetrafluroborate with 1-butanol, isobutyl alcohol, 2-butanol, and tert-butyl alcohol and their deuterated forms (OH/OD substitution). All systems exhibit upper critical solution temperatures (UCSTs) with a visible effect of branching in alcohols. Deuteration of alcohols in the hydroxyl group results in a decrease of the UCST of the given system and the largest shift is observed for tert-butyl alcohol. These solvent isotope effects nicely correlate with the polarity expressed by dielectric constants or E(T)(30) parameters of alcohols. The effect of the isotope substitution on the miscibility of ILs with butanols can be rationalized by using the statistical-mechanical theory of the isotope effects coupled with a phenomenological g(E) model. Following this procedure one finds that the isotope shift of UCST is associated mainly with the zero-point energy contribution.     

Physical properties of the ternary system (ethanol + water + 1-butyl-3-methylimidazolium methylsulphate) and its binary mixtures at several temperatures

In this paper, we report experimental densities, dynamic viscosities, and refractive indices and their derived properties of the ternary system (1-butyl-3-methylimidazolium methylsulphate + ethanol + water) at T = 298.15 K and of its binary systems 1-butyl-3-methylimidazolium methylsulphate with ethanol and with water at several temperatures T = (298.15, 313.15, 328.15) K. These physical properties have been measured over the whole composition range and at 0.1 MPa. Excess molar volumes, viscosity deviations, and excess free energy of activation for the binary systems at the abovementioned temperatures, were calculated and fitted to the Redlich–Kister equation to determine the fitting parameters and the root-mean-square deviations and for the ternary systems were calculated and fitted to Cibulka, Singh et al., and Nagata and Sakura equations. The ternary excess properties were predicted from binary contributions using geometrical solution models. Refractive indices were measured from T = 298.15 K over the whole composition range for the binary and ternary systems. The results were used to calculate deviations in the refractive index.     

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.     

Electrochemistry of water in 1-butyl-3-methylimidazolium tetrafluoroborate at nickel electrode: application to hydrogen peroxide production and water sensing

The electrochemistry of water dissolved in 1-butyl-3-methylimidazolium tetrafluoroborate ([C₄mim][BF₄]) was studied by cyclic voltammetry and electrochemical impedance spectroscopy using a nickel electrode. Hydrogen peroxide is being produced by direct electrolysis of water in a cooperative process between the nickel electrode and [C₄mim][BF₄]. There is linear response between the concentration of water and the oxidation peak current at 1.60 V. Impedance decreases significantly with increasing concentration of water. The findings resulted in two promising applications: The first is the production of hydrogen peroxide, and the second is in water sensing. Both methods are environmentally friendly and convenient.     

Synthesis and micellar properties of 1-decyl-2,3-dimethylimidazolium bromide surfactant in water and water-ethanolamine mixtures at 298.15 K

1-Decyl-2,3-dimethylimidazolium bromide (ddmimBr) has been synthesized by the reaction of 1,2-dimethylimidazole and 1-bromodecane. Micellization of ddmimBr surfactant in water (W) and water-ethanolamine (W-EA) with the weight percent of EA changing within the range 0-39.79%, has been investigated at 298.15 K. Information about the influence of the added EA on the critical micelle concentration (CMC) was obtained through density and surface tension measurements. This last provides information about the dependence of the surface excess concentration, the minimum area per surfactant molecule and the surface pressure at the CMC on the added weight percentage of organic solvent. The effect of binary aqueous mixtures of W-EA on the apparent molar volume (phi V) of the ddmimBr has been investigated. The apparent molar volume upon aggregation (Delta phi V) shows a maximum at about 15 wt% of EA, this behavior is discussed in terms of the changes of the solvent structure. Partial specific volume data, obtained by density measurements, indicate that the fraction of solvent molecules interact with the surfactant remained roughly constant.     

Thermodynamic investigations of 1-ethyl-3-methylimidazolium tetrafluoroborate and cycloalkanone mixtures

The densities, ρ, speeds of sound, u, and heat capacities, (C _P)_mix, for binary 1-ethyl-3-methylimidazolium tetrafluoroborate (1) + cyclopentanone or cyclohexanone (2) mixtures within temperature range (293.15–308.15 K) and excess molar enthalpies, H ^E, at 298.15 K have been measured over the entire composition range. The excess molar volumes, V ^E, excess isentropic compressibilities, \( \kappa_{\text{S}}^{\text{E}}, \) and excess heat capacities, \( C_{\text{P}}^{\text{E}}, \) have been computed from the experimental results. The V ^E, \( \kappa_{\text{S}}^{\text{E}} \) , H ^E, and \( C_{\text{P}}^{\text{E}} \) values have been calculated and compared with calculated values from Graph theory. It has been observed that V ^E, \( \kappa_{\text{S}}^{\text{E}} \) , H ^E, and \( C_{\text{P}}^{\text{E}} \) values were predicted by Graph theory compare well with their experimental values. The V ^E, \( \kappa_{\text{S}}^{\text{E}}, \) and H ^E thermodynamic properties have also been analyzed in terms of Prigogine–Flory–Patterson theory.     

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.     

Experimental densities,refractive indices,and speeds of sound of 12 binary mixtures containing alkanes and aromatic compounds at T = 313.15 K

Densities, speeds of sound, and refractive indices of 12 binary systems of alkanes (hexane, heptane, octane, and nonane) with aromatics (benzene, or toluene, or ethylbenzene) at T = 313.15 K and at atmospheric pressure were determined over the whole composition range, and are presented in this paper. From the experimental results, the derived and excess properties (isentropic compressibility, excess molar volumes, and excess molar isentropic compressibility) at T = 313.15 K were calculated and satisfactorily fitted to the Redlich–Kister equation.