Solid–liquid equilibria for systems containing 1-butyl-3-methylimidazolium chloride

The solubility of 1-butyl-3-methylimidazolium chloride [C₄mim][Cl] in alcohols {ethanol, 1-butanol, 1-hexanol, 1-octanol, 1-decanol, 1-dodecanol, 2-butanol, 2-methyl-2-propanol (tert-butanol)} has been measured by a dynamic method from 270 K to the melting point of the ionic liquid or to the boiling point of the solvent. The melting point, enthalpy of fusion, and the temperature of the glass phase transition were determined by differential scanning calorimetry.The solubility data were correlated by means of the Wilson, UNIQUAC ASM and modified NRTL1 equations utilizing parameters derived from the solid–liquid equilibrium data. The root-mean-square deviations of the solubility temperatures for all calculated data were higher than 0.9 K and depended on the particular equation used.     

Electrochemical properties of the system of Ag—1-butyl-3-methylimidazolium bromide low-temperature ionic liquid—silver bromide

The methods of potentiometry, electrochemical impedance spectroscopy, cyclic voltammetry, and gravimetry were used to study the electrochemical behavior of a silver electrode in low-temperature ionic liquids of BMImBr and BMImBr—AgBr, and also the process of cathodic reduction of Ag(I) compounds out of a BMImBr—AgBr melt. It is shown that an AgBr film is formed on the silver surface and its properties are determined by the ionic liquid composition. It is found that the process of silver electrodeposition from a BMImBr—AgBr binary alloy occurs irreversibly, at a high current efficiency (up to 100%) and a good quality of the deposit at low current densities. At 70°C, the transfer coefficients of the cathodic process (α = 0.56 and 0.16) and diffusion coefficients (D _Ag(I) = 0.48 × 10⁻⁷ cm²/s and 3.3 × 10⁻⁷ cm²/s) of silver-containing ions are determined in ionic liquids with the AgBr concentration of 0.81 and 1.53 mol/kg BMImBr, accordingly.     

Liquid–liquid equilibria of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate and sodium citrate/tartrate/acetate aqueous two-phase systems at 298.15 K: Experiment and correlation

Binodal curves of the aqueous 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF₄) + sodium citrate (Na₃C₆H₅O₇), [Bmim]BF₄ + sodium tartrate (Na₂C₄H₄O₆) and [Bmim]BF₄ + sodium acetate (NaC₂H₃O₂) systems have been determined experimentally at 298.15 K. The Merchuk equation was used to correlate the binodal data. The effective excluded volume (EEV) values obtained from the binodal model for these three systems were determined. The binodal curves and EEV both indicate that the salting-out abilities of the three salts follow the order: Na₃C₆H₅O₇ > Na₂C₄H₄O₆ > NaC₂H₃O₂. The liquid–liquid equilibrium (LLE) data were obtained by density determination and binodal curves correlation of these systems. Othmer–Tobias and Bancraft, and Setschenow equations were used for the correlation of the tie-line data. Good agreement was obtained with the experimental tie-line data with both models.     

Improvement of the Friedel–Crafts benzoylation by using bismuth trifluoromethanesulfonate in 1-butyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid under microwave irradiation

Bismuth trifluoromethanesulfonate (bismuth triflate) catalyzed the Friedel–Crafts benzoylation of activated aromatic compounds when dissolved in 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([BMIM]OTf) ionic liquid. Immobilization of bismuth triflate (5 mol %) in [BMIM]OTf allowed the synthesis of aryl ketones in good to excellent yields with short reaction times under microwave irradiation. This catalytic system was easily recovered and reused several times without any significant loss of the activity.     

Corrosion behaviors of materials in aluminum chloride–1-ethyl-3-methylimidazolium chloride ionic liquid

The corrosion properties of carbon steel (CS), 304 stainless steel (304 SS), and pure titanium (Ti) are first studied in aluminum chloride–1-ethyl-3-methylimidazolium chloride ionic liquid (IL). An active-to-passive transition behavior was clearly observed for CS. The 304 SS exhibited the best stability among the materials; no considerable corrosion was recognized even in this high-chloride environment. In contrast, although Ti resists corrosion in ambient environments, it was not passivated in the IL and became severely corroded under an anodic applied potential. The material corrosion behaviors and mechanisms in the non-aqueous, low-oxygen, and high-halogen-containing IL are completely different from those in traditional aqueous solutions.     

Properties of room temperature ionic liquid—3-ethyl-1-methylimidazolium ethyl sulfate

This paper reports densities of aqueous of liquid (IL) 3-ethyl-1-methylimidazolium ethyl sulfate (EMISE). The apparent molal volume, partial molal volume and Pitzer’s parameters of EMISE were obtain.     

Local structure of ionic liquid–monohydric alcohol solutions

The method of molecular dynamics is used to investigate the effect of monohydric alcohols on the formation of the local structure of ionic liquids based on the dimethylimidazolium cation at T = 400 K. The intermolecular interaction energies are analyzed to find that the increase in the length of the alkyl chain in the alcohol molecule reduces the influence of the solute molecule on the formation of the local structure of the dmim⁺/Cl^––solute molecule systems. An analysis of the radial distribution function shows that the change in the structure and physical characteristics of the solute molecule does not affect the interaction between the hydroxyl group proton of the alcohol molecule and the ionic liquid anions, whose interactions form the hydrogen bond H^alcohol…Cl^– with a length of 2.3 Å.     

Nanostructuring of 1-butyl-4-methylpyridinium chloride in ionic liquid–iron oxide nanofluids

Journal of Thermal Analysis and Calorimetry - Understanding the behavior of ionic liquids (ILs) in ionic liquid-based nanofluids has great significance for its proper application. The phase changes...     

Hybrid material based on 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and Dawson polyoxoanion [P2Mo18O62]6−. Part II: further characterizations and catalytic oxidation of the NADH coenzyme

In this account, [BMIM]₆P₂Mo₁₈O₆₂ hybrid material was further characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and Raman spectroscopy. XRD illustrated that compared to the parent K₆P₂Mo₁₈O₆₂·nH₂O, where 92 % of the structure is crystalline, 84 % of the structure of [BMIM]₆P₂Mo₁₈O₆₂ hybrid material is fine-grain amorphous and only 16 % is crystalline. This was attributed to the replacement of most of the protons and constitution water molecules in K₆P₂Mo₁₈O₆₂·nH₂O by [BMIM]⁺ cations. TEM showed that K₆P₂Mo₁₈O₆₂·nH₂O has uniform and spherical nanoparticles with an average diameter of ~100 nm. However, the hybrid material displayed less uniform morphology with spherical and variously shaped nanoparticles with diameters varying from ~10 to 100 nm. Raman spectroscopy of [BMIM]₆P₂Mo₁₈O₆₂ illustrated that peaks of the Dawson [P₂Mo₁₈O₆₂]^6? unit in [BMIM]₆P₂Mo₁₈O₆₂ hybrid material are not obvious due to the overlap with the peaks of [BMIM]⁺. The latter was related to the large number of [BMIM]⁺ cations surrounding the Dawson unit in the hybrid material. [BMIM]₆P₂Mo₁₈O₆₂ was immobilized on glassy carbon electrode and studied by electrochemistry. Linear sweep voltammetry illustrated that unlike the parent polyoxoanion [P₂Mo₁₈O₆₂]^6? which showed no particular catalytic activity towards the oxidation of the NADH coenzyme, the hybrid material [BMIM]₆P₂Mo₁₈O₆₂ is found to efficiently catalyze the oxidation of the NADH coenzyme at low overpotentials. Amperometry revealed high sensitivities (~1.97 μA?mM^?1?mm^?2) and extended linearity (~9.1 mM) of [BMIM]₆P₂Mo₁₈O₆₂/GC electrode towards the oxidation of the NADH coenzyme.     

Electrodeposition of nanocrystalline aluminium, copper, and copper–aluminium alloys from 1-butyl-1-methylpyrrolidinium trifluoromethylsulfonate ionic liquid

In this paper, we show that nanocrystalline aluminium, copper, and copper–aluminium alloys can be electrodeposited from the ionic liquid 1-butyl-1-methylpyrrolidinium trifluoromethylsulfonate, [Py_1,4]TfO. Furthermore, Al deposition was studied in 1-ethyl-3-methylimidazolium trifluoromethylsulfonate, [EMIm]TfO for comparison. The two employed ionic liquids exhibit different concentration-dependent phase behaviour with AlCl₃. This study comprises cyclic voltammetry, potentiostatic electrolysis, scanning electron microscopy, X-ray diffraction, atomic absorption spectroscopy, and inductively coupled plasma optical emission spectroscopy. Thick (in micrometre regime) and uniform layers of aluminium deposits were obtained from 2.75?M AlCl₃ in [Py_1,4]TfO at 100?°C. The average crystallite size of aluminium was found to be around 40 to 50?nm. However, a coarse and cubic-shaped Al deposit with crystal sizes in the micrometre regime was obtained from [EMIm]TfO. Electrodeposition of copper was investigated in [Py_1,4]TfO-containing Cu(TfO)₂ at 100?°C. The average grain size of the copper deposit obtained from the electrolysis is around 20 to 40?nm. Electrodeposition of copper–aluminium alloys was successful in the same ionic liquid at 100?°C. Thick layers of copper–aluminium alloys were obtained from the employed ionic liquid. XRD analysis of the obtained deposits from electrolysis experiments revealed that Cu₃Al alloy was formed. SEM analysis indicated that the nanocrystalline copper–aluminium deposits have an average grain size of 60 to 70?nm.     

A Bloembergen–Purcell–Pound <Superscript>13</Superscript>C NMR relaxation study of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

The molecular structure and rotational motion of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) were studied over a wide temperature range using the Bloembergen–Purcell–Pound ¹³C NMR spin–lattice relaxation method and NOE factors. Examination of the spin–lattice relaxation times (T ₁) and the rates (R ₁=1/T ₁) of the 1-butyl-3-methylimidazolium cation reveals the relative motions of each carbon in the imidazolium cation. The rotational characteristics of the [BMIM] cation are supported by ab-initio molecular structures of [BMIM][PF6] using density functional theory (DFT) and Hartree–Fock (HF) methods. The ab-initio gas phase structures of [BMIM][PF6] indicate that the 1-butyl-3-methylimidazolium C2 hydrogen, the ring methyl group, and the butyl side-chain hydrogen atoms form hydrogen bonds with the hexafluorophosphate anion.     

Dissolution of zinc oxide in a protic ionic liquid with the 1-methylimidazolium cation and electrodeposition of zinc from ZnO/ionic liquid and ZnO/ionic liquid–water mixtures

We show that zinc oxide can be dissolved in the protic ionic liquid 1-methylimidazolium trifluoromethylsulfonate, [MIm]TfO at quite a high concentration (~ 2.5 mol/L). FTIR and Raman spectra revealed the association of zinc ions with 1-methylimidazole. The ZnO/[MIm]TfO solutions and their mixtures with water were employed as electrolytes for the electrodeposition of zinc. High current density electrodeposition of zinc can be achieved in the employed electrolytes. Spongy-like zinc structures with a high porosity were obtained in ZnO/[MIm]TfO and the formation of Au_1.2Zn_8.8 alloy was observed. Compact and hexagonal zinc deposits were found in the presence of water. The present results show the potential of ionic liquids as electrolytes for rechargeable zinc–air batteries.     

Viscosity reduction of cellulose + 1-butyl-3-methylimidazolium acetate in the presence of CO2

Viscosities of microcrystalline cellulose + 1-butyl-3-methylimidazolium acetate ([bmIm][Ac]) solutions (0.6–1.2 wt%) in contact with CO₂ were measured at 312 K with a resonant vibrational viscometer. At 4 MPa and 312 K, the CO₂ could reduce the viscosity of 1.2 wt% cellulose + [bmIm][Ac] solution by about 80 %, whereas N₂ at the same conditions gave less than a 10 % reduction in viscosity. The viscosity-averaged degree of polymerization and IR spectrum showed that cellulose did not decompose during experiments and that [bmIm][Ac] acted as a non-derivatizing solvent during the dissolution and viscosity reduction process. Further, although CO₂ does react with [bmIm][Ac] to form 1-butyl-3-methylimidazolium-2-carboxylate, the reaction seems to be reversible and it does not affect the cellulose. Thus, [bmIm][Ac] with CO₂ provides an effective solvent for cellulose and the solvent system can probably be recycled or reused.     

Influence of the reticular polymeric gel—electrolyte structure on ionic and molecular mobility of an electrolyte system salt—ionic liquid: LiBF4—1-ethyl-3-methylimidazolium tetrafluoroborate

Russian Chemical Bulletin - Peculiarities of the formation of a reticular polymeric gel—electrolyte matrix based on polyethylene glycol diacrylate in a medium of ionic liquid...     

Activity coefficients at infinite dilution of organic solutes in the ionic liquid 1-butyl-3-methylimidazolium hexafluoroantimonate using gas–liquid chromatography at T = (313.15, 323.15, and 333.15) K

Activity coefficients at infinite dilution were determined for 27 solutes: n-alkanes, alk-1-enes, alk-1-ynes, cycloalkanes, alkylbenzenes, alcohols, and ketones in the ionic liquid 1-butyl-3-methylimidazolium hexafluoroantimonate, [BMIM][SbF₆], by gas–liquid chromatography at three different temperatures, T = (313.15, 323.15, and 333.15) K. The results are compared to published data on related compounds. The partial molar excess enthalpy values at infinite dilution were calculated from the experimental data over the same temperature range. Selectivities and capacities at infinite dilution were calculated for the hexane/benzene and methanol/benzene systems from experimental infinite dilution activity coefficients and compared to the literature values for related ionic liquids, as well as to data on industrial molecular solvents.     

Prediction of liquid–liquid equilibrium for ternary systems containing ionic liquids with the tetrafluoroborate anion using ASOG

Liquid–liquid equilibrium (LLE) data for different systems involving ionic liquids are essential for design, optimization and operation of separation processes, such as recovery of valuable products and remotion of polluting agents in effluents. In this work, the ASOG model for the activity coefficient is used to predict LLE data for 32 ternary systems at 101.3 kPa and several temperatures; all the systems are formed by ionic liquids including the tetrafluoroborate anion plus alkanes, alkenes, cycloalkanes, alkanols, ketones, carboxylic acids, esters and aromatics. New group interaction parameters were determined by using a modified Simplex method, minimizing a composition-based objective function. The results, in terms of mean deviation between the experimental and calculated compositions, are satisfactory, with rms deviations of about 4%.