Ionic liquids as entrainers for water + ethanol,water + 2-propanol,and water + THF systems: A quantum chemical approach

Ionic liquids (ILs) are used as entrainers in azeotropic systems such as water + ethanol, water + 2-propanol, and water + tetrahydrofuran (THF). Ionic liquids consisting of a cation and an anion has limitless combinations, thereby making experimentation expensive and time taking. For the prediction of the liquid phase nonidealities resulting from molecular interactions, “COnductor-like Screening MOdel for Real Solvents” (COSMO-RS) approach is used in this work for the screening of potential ionic liquids. Initially benchmarking has been done on 12 reported isobaric IL based ternary systems with an absolute average deviation of 4.63% in vapor phase mole fraction and 1.07% in temperature. After successful benchmarking, ternary vapor + liquid equilibria for the azeotropic mixture of (a) ethanol + water, (b) 2-propanol + water, and (c) THF + water with combinations involving 10 cations (imidazolium, pyridinium, quinolium) and 24 anions were predicted. The VLE prediction, which gave the relative volatility, showed that the imidazolium based ionic liquid were the best entrainer for the separation of the three systems at their azeotropic point. ILs with [MMIM] cation in combination with acetate [OAc], chloride [Cl], and bromide [Br] anion gave the highest relative volatility.     

Application of a group contribution equation of state for the thermodynamic modeling of binary systems (gas + ionic liquids) with bis[(trifluoromethyl)sulfonyl]imide anion

The properties of ionic liquids (ILs) can be modified by appropriate selection of cations and anions. Even if an infinite number of ionic liquids can be generated, only a limited number of families of anions and cations are used. The group contribution equation of state (GC-EoS) is a promising method for calculating the phase behavior of systems with ILs. If the parameters of the characteristic functional group of a IL family are fitted by using data of a reduced number of ILs of the family, then the phase behavior of all the ILs of the same family can be predicted using exclusively the data of the pure components. Previously, the parameters of the IL families with an imidazolium-based cation and the anions PF₆, BF₄NO₃, and Tf₂N were fitted to experimental data [19], and some ternary systems (CO₂ + organics + ionic liquid [bmim][BF₄]) were also modeled [22]. In this work, the GC-EoS was used to calculate phase behavior of gases {(CO₂, O₂, or SO₂) + ionic liquids} with Tf₂N anion and cations of the families 2,3-dimethyl-imidazolium, 1-alkyl-1-methyl-pyrrolidinium, and 1-alkyl-3-methyl-pyridinium. The GC-EoS was able to reproduce experimental data with deviations of the same order of experimental uncertainty. With the correlated parameters it will be possible to predict the phase behavior of systems with ILs of the families considered in this work.     

Experimental investigation on the dissociation conditions of methane hydrate in the presence of imidazolium-based ionic liquids

In this work, the performance of nine ionic liquids (ILs) as thermodynamic hydrate inhibitors is investigated. The dissociation temperature is determined for methane gas hydrates using a high pressure micro deferential scanning calorimeter between (3.6 and 11.2) MPa. All the aqueous IL solutions are studied at a mass fraction of 0.10. The performance of the two best ILs is further investigated at various concentrations. Electrical conductivity and pH of these aqueous IL solutions (0.10 mass fraction) are also measured. The enthalpy of gas hydrate dissociation is calculated by the Clausius–Clapeyron equation. It is found that the ILs shift the methane hydrate (liquid + vapour) equilibrium curve (HLVE) to lower temperature and higher pressure. Our results indicate 1-(2-hydroxyethyl) 3-methylimidazolium chloride is the best among the ILs studied as a thermodynamic hydrate inhibitor. A statistical analysis reveals there is a moderate correlation between electrical conductivity and the efficiency of the IL as a gas hydrate inhibitor. The average enthalpies of methane hydrate dissociation in the presence of these ILs are found to be in the range of (57.0 to 59.1) kJ ⋅ mol⁻¹. There is no significant difference between the dissociation enthalpy of methane hydrate either in the presence or in absence of ILs.     

Thermodynamic properties of the N-octylquinolinium bis{(trifluoromethyl)sulfonyl}imide

This work is a continuation of our wide ranging investigation on quinolinium based ionic liquids (ILs). The study includes specific basic characterisation of the synthesized compounds N-octylquinolinium bromide, [OQuin][Br] and N-octylquinolinium bis{(trifluoromethyl)sulfonyl}imide [OQuin][NTf₂] by NMR spectra, elementary analysis and water content. Differential scanning calorimetry (DSC) measurements gave us properties of the pure [OQuin][NTf₂] i.e. melting and glass-transition temperatures, the enthalpy of fusion as well as heat capacity at the glass transition. Densities and viscosities were determined as a function of temperature. The temperature-composition phase diagrams of 10 binary mixtures composed of organic solvent dissolved in the IL: {[OQuin][NTf₂] + aromatic hydrocarbon (benzene, or thiophene, or toluene, or ethylbenzene, or n-propylbenzene), or an alcohol (1-butanol, or 1-hexanol, or 1-octanol, or 1-decanol, or 1-dodecanol)} were measured at ambient pressure. A dynamic method was used over a broad range of mole fractions and temperatures from (250 to 370) K. For mixtures with benzene and alkylbenzenes, the immiscibility gap in the liquid phase in a low mole fraction of the IL was observed with upper critical solution temperature (UCST) higher than the boiling point of the solvent. In the system with thiophene, the immiscibility gap is lower and UCST was measured. For binary mixtures with alcohols, complete miscibility in the liquid phase was observed for 1-butanol and 1-hexanol. In the systems with longer chain alcohols, the immiscibility gap with UCST was noted. Typical behaviour for ILs was observed with an increase of the chain length of an alcohol the solubility decreases. The well-known NRTL equation was used to correlate experimental (solid + liquid), SLE and (liquid + liquid), LLE phase equilibrium data sets.     

Ionic liquids in microemulsions: Formulation and characterization

In the last few decades ionic liquids (ILs) have been widely considered as a “green solvents” and they are used in various fields. ILs can be used in the formation of microemulsion as a dispersed medium, polar domain and recently as a surfactant. In this particular review our discussion is about the novel IL-based aqueous and non-aqueous microemulsions which are quite fascinating and interesting research field for scientists. Synthesis of double and triple chain containing surface active ionic liquid (SAILs) and formation of microemulsion as a surfactant with ILs as a polar core have been elaborated in this review. ILs with a certain surface activity having long alkyl chain substituents can self-aggregate and form ILs microemulsion with high-temperature stability and temperature insensitivity. Characterization of these ILs in oil microemulsion and different ultrafast processes which are performed inside these characterized systems are documented very well. We have highlighted the similarities and differences between the nonaqueous microemulsions and the aqueous microemulsions. Addition of water and effect of temperature are quite important in case of the ILs containing microemulsions.     

Thermodynamic properties of the N-butylisoquinolinium bis(trifluoromethylsulfonyl)imide

A new isoquinolinium ionic liquid (IL) has been synthesised as a continuation of our work with quinolinium-based ionic liquids (ILs). The work includes specific basic characterization of synthesized compounds: N-isobutylquinolinium bromide, [BiQuin][Br] and N-isobutylquinolinium bis{(trifluoromethyl)sulfonyl}imide [BiQuin][NTf₂] by NMR spectra, elementary analysis and water content. The basic thermal properties of the pure [BiQuin][NTf₂], i.e. melting and glass-transition temperatures, the enthalpy of fusion as well as heat capacity at glass transition have been measured using a differential scanning microcalorimetry technique (DSC). Densities and viscosities were determined as a function of temperature. The temperature-composition phase diagrams of 8 binary mixtures composed of organic solvent dissolved in the IL: {[BiQuin][NTf₂] + aromatic hydrocarbon (benzene, or toluene, or ethylbenzene, or n-propylbenzene), or an alcohol (1-butanol, or 1-hexanol, or 1-octanol, or 1-decanol)} were measured at ambient pressure. A dynamic method was used over a broad range of mole fraction and temperature from (270 to 320) K. For all the binary systems with benzene and alkylbenzenes, the eutectic diagrams were observed with an immiscibility gap in the liquid phase existing at low mole fraction of the IL with a very high upper critical solution temperature (UCST). For mixtures with alcohols, complete miscibility was observed for 1-butanol and also an immiscibility gap with UCST in the liquid phase for the remaining alcohols. The typical dependence was observed that with increasing chain length of an alcohol, the solubility decreases. The well-known NRTL equation was used to correlate experimental (solid + liquid), SLE and (liquid + liquid), LLE phase equilibrium data sets.     

New dicationic piperidinium hexafluorophosphate ILs,synthesis, characterization and dielectric measurements

A new class of dicationic ionic liquids (ILs) were synthesized for electrochemical applications at high temperatures. The syntheses are based on a dialkylation reaction of N-alkylpiperidine followed by anion exchange. The structures of ILs, based on piperidinium combined with hexafluorophosphate anion, were identified by using ¹H, ¹³C, ¹⁹F, ³¹P NMR and FT-IR spectroscopy. ILs’ thermal properties were investigated in the temperature range from −50 to 350 °C by using differential scanning calorimetry (DSC). In the frequency of 10⁻²–10⁶ Hz range, dielectric measurements were performed on ILs’ samples at various temperatures from −80 to 20 °C, i.e. around the glass transition temperature. The peak relaxation was observed near to this temperature. Also, the conductivity was investigated and the energy activation determined. The temperature dependence of the relaxation times was shown to be governed by the Arrhenius equation.     

Effect of ionic liquids on (vapor + liquid) equilibrium behavior of (water + 2-methyl-2-propanol)

Isobaric T, x, y data were reported for ternary systems of {water + 2-methyl-2-propanol (tert-butyl alcohol, TBA) + ionic liquid (IL)} at p = 100 kPa. When the mole fraction of TBA on IL-free basis was fixed at 0.95, measurements were performed at IL mass fractions from 0.6 down to 0.05, in a way of repeated synthesis. The vapor-phase compositions were obtained by analytical methods and the liquid-phase compositions were calculated with the aid of mass balances. Activity coefficients of water and TBA were obtained without the need of a thermodynamic model of the liquid-phase. Six ILs, composed of an anion chosen from [OAc]^? or [Cl]^?, and a cation from [emim]⁺, or [bmim]⁺, or [hmim]⁺, were studied. Relative volatility and activity coefficients were presented in relation with the IL mole fraction, showing the effect of the ILs on a molar basis. The effect of the ILs on relative volatility of TBA to water was depicted by the effect of anions and cations on, respectively, the activity coefficients of water and TBA. The results indicated that, among the six ILs studied, [emim][Cl] has the most significant effect on enhancement of the relative volatility, which reaches a value of 7.2 at an IL mass fraction of 0.58. Another IL, [emim][OAc], has also significant effect, with an appreciable value of 5.2 for the relative volatility when the IL mass fraction is 0.6. Considering the relatively low viscosity and melting point of [emim][OAc], it might be a favorable candidate as solvent for the separation of water and TBA by extractive distillation. Simultaneous correlation by the NRTL model was presented for both systems of (water + ethanol + IL) and (water + TBA + IL), using consistent binary parameters for water and IL.     

The role of additional solvents in transition metal complex catalyzed asymmetric reductions in ionic liquid containing systems

When ionic liquids (ILs) are employed as solvents for transition metal complex (TMC) catalyzed reductions, a second solvent can be added to increase the efficiency of the catalytic cycle and the solubility of the reactant in the IL phase. Two industrially relevant asymmetric hydrogenations, the enantioselective reductions of methyl 2-acetamidoacrylate with Rh-EtDuPHOS and methyl acetoacetate with Ru-BINAP, were performed in different catalytic systems including 1-butyl-3-methylimidazolium hexafluorophosphate/ tetrafluoroborate as ILs. Product separation and TMC recycling was performed by extracting the product from the reaction mixture. This can be accomplished by cooling the system, by adding an excess of the second solvent or by adding a third solvent. A high solubility of the second solvent in the IL catalytic phase favors the reaction activity, but can induce leaching of the IL and TMC.     

Solvation of ionic liquids based on N-methyl-N-alkyl morpholinium cations in dimethylsulfoxide – volumetric and compressibility studies

The density and sound velocity of the solutions of ionic liquids based on N-alkyl-N-methyl-morpholinium cations, N-ethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, N-butyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, N-methyl-N-octyl-morpholinium bis(trifluoromethanesulfonyl)imide and N-decyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide in dimethylsulfoxide were measured at T = (298.15 to 318.15) K and at atmospheric pressure. The apparent molar volume and apparent molar compressibility values were evaluated from density and sound velocity values and fitted to the Masson equation from which the partial molar volume and partial molar isentropic compressibility of the ILs at infinite dilution were also calculated at working temperatures. By using the density values, the limiting apparent molar expansibilities were estimated. The effect of the alkyl chain length of the ILs and experimental temperature on these thermodynamic properties is discussed. In addition, molecular dynamics simulations were used to interpret the measured properties in terms of interactions of ILs with solvent molecules. Both, volumetric measurements results and molecular dynamics simulations for ionic liquids in dimethylsulfoxide were compared and discussed with results obtained for the same IL in acetonitrile.     

Excess molar volumes of binary mixtures (an ionic liquid + water): A review

This review covers recent developments in the area of excess molar volumes for mixtures of {ILs (1) + H₂O (2)} where ILs refers to ionic liquids involving cations: imidazolium, pyridinium, pyrrolidinium, piperidinium, morpholinium and ammonium groups; and anions: tetraborate, triflate, hydrogensulphate, methylsulphate, ethylsulphate, thiocyanate, dicyanamide, octanate, acetate, nitrate, chloride, bromide, and iodine. The excess molar volumes of aqueous ILs were found to cover a wide range of values for the different ILs (ranging from −1.7 cm³ · mol⁻¹ to 1.2 cm³ · mol⁻¹). The excess molar volumes increased with increasing temperature for all systems studied in this review. The magnitude and in some cases the sign of the excess molar volumes for all the aqueous ILs mixtures, apart from the ammonium ILs, were very dependent on temperature. This was particularly important in the dilute IL concentration region. It was found that the sign and magnitude of the excess molar volumes of aqueous ILs (for ILs with hydrophobic cations), was more dependent on the nature of the anion than on the cation.     

An electrically heated ionic-liquid/multi-wall carbon nanotube composite electrode and its application to electrochemiluminescent detection of ascorbic acid

A heated composite electrode consisted of multi-wall carbon nanotube (MWNT) and ionic liquids (ILs) was designed and fabricated. The non-conductive binders were replaced by a conductive IL, n-octylpyridinum hexafluorophosphate (OPFP). This heated OPFP/MWNT composite electrode was applied for electrochemiluminescent (ECL) sensor, and the performance of ECL sensor was evaluated by ascorbic acid (AA)/lucigenin ECL system. The new heated electrode combines the advantages of ILs/CNT and heated electrode, showing high thermal stability and conductivity, simple heating setups, improved reproducibility, renewable surface, simplicity of fabrication and enhanced sensitivity with detection limit (S/N = 3) of 0.01 μmol/L for AA.     

Evaluation of the ionic liquids 1-alkyl-3-methylimidazolium hexafluorophosphate as a solvent for the extraction of benzene from cyclohexane: (Liquid + liquid) equilibria

In the catalytic hydrogenation of benzene to cyclohexane, the separation of unreacted benzene from the product stream is inevitable and essential for an economically viable process. In order to evaluate the separation efficiency of ionic liquids (ILs) as a solvent in this extraction processes, the ternary (liquid + liquid) equilibrium of 1-alkyl-3-methylimidazolium hexafluorophosphate, [C_nmim][PF₆] (n = 4, 5, 6), with benzene and cyclohexane was studied at T = 298.15 K and atmospheric pressure. The reliability of the experimentally determined tie-line data was confirmed by applying the Othmer–Tobias equation. The solute distribution coefficient and solvent selectivity for the systems studied were calculated and compared with literature data for other ILs and sulfolane. It turns out that the benzene distribution coefficient increases and solvent selectivity decreases as the length of the cation alkyl chain grows, and the ionic liquids [C_nmim][PF₆] proved to be promising solvents for benzene–cyclohexane extractive separation. Finally, an NRTL model was applied to correlate and fit the experimental LLE data for the ternary systems studied.     

Use of selective ionic liquids and ionic liquid/salt mixtures as entrainer in a (vapor + liquid) system to separate n-heptane from toluene

During the last years, a large number of studies have evaluated the ability of ionic liquids (ILs) to separate aromatic from aliphatic hydrocarbons by liquid extraction. Nevertheless, in order to design a global process, a post-extraction step based on the aromatic recovery from the extract stream and the regeneration of the IL is required. Taking into account the negligible vapor pressure of the ILs, the use of separation units based on the difference of volatility among the components of the extract could be an appropriate way. However, that requires additional (vapor + liquid) equilibrium (VLE) data, which are scarce today. In this work, the isothermal VLE data for {n-heptane + toluene + 1-ethyl-3-methylimidazolium thiocyanate ([EMim][SCN])} and {n-heptane + toluene + 1-butyl-3-methylimidazolium thiocyanate ([BMim][SCN])} mixtures were experimentally measured at T = (323.2, 343.2 and 363.2) K over the whole composition range within the rich-IL miscibility region. For that, a static headspace gas chromatograph (HS-GC) was used. In addition, the non-random two liquids (NRTL) thermodynamic model was satisfactory applied to correlate the experimental VLE data.Finally, the effect of thiocyanate-based inorganic salts (AgSCN, Co(SCN)₂ and CuSCN) on the phase behavior of the above mentioned mixtures were also analyzed through the experimental determination of the isothermal VLE of the pseudo-ternary systems {n-heptane + toluene + [EMim][SCN]/salt mixture}.The obtained results show that the use of pure thiocyanate-based ILs as entrainer increases the n-heptane relative volatility from toluene whereas the addition of inorganic salts has not led to an improvement of these results.     

Studies on the micropolarities of bmimBF4/TX-100/toluene ionic liquid microemulsions and their behaviors characterized by UV-visible spectroscopy

Ionic liquids (ILs), 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4), were substituted for polar water and formed nonaqueous microemulsions with toluene by the aid of nonionic surfactant TX-100. The phase behavior of the ternary system was investigated, and microregions of bmimBF4-in-toluene (IL/O), bicontinuous, and toluene-in-bmimBF4 (O/IL) were identified by traditional electrical conductivity measurements. Dynamic light scattering (DLS) revealed the formation of the IL microemulsions. The micropolarities of the IL/O microemulsions were investigated by the UV-vis spectroscopy using the methyl orange (MO) and methylene blue (MB) as absorption probes. The results indicated that the polarity of the IL/O microemulsion increased only before the IL pools were formed, whereas a relatively fixed polar microenvironment was obtained in the IL pools of the microemulsions. Moreover, UV-vis spectroscopy has also shown that ionic salt compounds such as Ni(NO3)2, CoCl2, CuCl2, and biochemical reagent riboflavin could be solubilized into the IL/O microemulsion droplets, indicating that the IL/O microemulsions have potential application in the production of metallic or semiconductor nanomaterials, and in biological extractions or as solvents for enzymatic reactions. The IL/O microemulsions may have some expected effects due to the unique features of ILs and microemulsions.     

Removal of ionic liquids and ibuprofen by adsorption on a microporous activated carbon: Kinetics,isotherms, and pore sites

Ionic liquids (ILs) are considered as emergent pollutants as their synthesis and further use at a large scale might generate environmental problems. The adsorption on activated carbons represents one of the most effective methods to remove ionic liquids and other micropollutants from wastewater. In this work, the adsorption properties on an activated carbon cloth of two pyridinium ionic liquids (4-tert-butyl-1-propylpyridinium bromide (IL1) and 4-tert-butyl-1-(2-carboxyethyl)pyridinium bromide (IL2)) newly synthesized, were compared with the ones of ibuprofen. The adsorption kinetics and isotherms were studied at pH 3 and 7.5. The adsorption thermodynamic parameters calculated from the isotherms indicate an exothermic process, typical of physisorption. The adsorption kinetics of a mixture of the molecules show a competition between ibuprofen and IL2. The location of each adsorbed ionic liquid and ibuprofen into the porosity of the activated carbon cloth was determined from N₂ (at 77 K) and CO₂ adsorption isotherms (at 273 K). The purification process of an effluent containing the ionic liquids and the ibuprofen in mixture or in single solute could be workable by adsorption on an activated cloth.     

Phase equilibrium study of the binary systems (N-hexyl-3-methylpyridinium tosylate ionic liquid + water,or organic solvent)

The (solid + liquid) phase equilibrium (SLE) and (liquid + liquid) phase equilibrium (LLE) for the binary systems ionic liquid (IL) N-hexyl-3-methylpyridinium tosylate (p-toluenesulfonate), {([HM³Py][TOS] + water, or an alcohol (1-butanol, or 1-hexanol, or 1-octanol, or 1-decanol), or an aromatic hydrocarbon (benzene, toluene, or ethylbenzene, or propylbenzene), or an alkane (n-hexane, n-heptane, n-octane)} have been determined at ambient pressure using a dynamic method. Simple eutectic systems with complete miscibility in the liquid phase were observed for the systems involving water and alcohols. The phase equilibrium diagrams of IL and aromatic or aliphatic hydrocarbons exhibit eutectic systems with immiscibility in the liquid phase with an upper critical solution temperature as for most of the ILs. The correlation of the experimental data has been carried out using the UNIQUAC, Wilson and the non-random two liquid (NRTL) correlation equations. The results reported here have been compared with analogous phase diagrams reported by our group previously for systems containing the tosylate-based ILs.     

Measurement of heat capacities of ionic liquids by differential scanning calorimetry

Heat capacities for nine ionic liquids (IL) have been determined with the “three-step” method using two different differential scanning calorimeters (DSC). In addition, the heat capacities of these ionic liquids have been studied by the modulated-temperature differential scanning calorimetry (MDSC™). The measurements cover a temperature range from 315 to 425 K.     

Studies on the thermodynamic properties of new ionic liquids: 1-Methyl-3-pentylimidazolium salts containing metal of group III

This paper reports that new ionic liquids (ILs) have been prepared by directly mixing the chloride of group III and 1-methyl-3-pentylimidazolium chloride (PMIC) with molar ratio 1/1 under dry argon atmosphere. The densities and surface tension of these ILs were determined at temperature range of 273.15 K to 343.15 ± 0.1 K. The properties for the ionic liquids were discussed by interstice model and Glasser’s theory.     

(Liquid + liquid) equilibrium for the ternary systems {heptane + toluene + 1-allyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide} and {heptane + toluene + 1-methyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide} ionic liquids

The (liquid + liquid) equilibrium (LLE) data for two systems containing heptane, toluene, and 1-methyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide ([mpim][Tf₂N]) or 1-allyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([amim][Tf₂N]) ionic liquids (ILs) were determined at T = 313.2 K and atmospheric pressure. The effect of a double bond in an alkyl side chain in the imidazolium cation was evaluated in terms of selectivity and extractive capacity. The results show a decrease of the amount of toluene and heptane dissolved in the IL with the allyl group. Thus, the distribution ratios of toluene and heptane of [mpim][Tf₂N] IL are higher than those of [amim][Tf₂N] IL. On the other hand, the separation factor of the [amim][Tf₂N] IL increases comparing to [mpim][Tf₂N] IL. The NRTL model was used to correlate satisfactorily the experimental LLE data for the two studied ternary systems.