Surfactant aggregation within room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

On the basis of the response of solvatochromic probes [Reichardt's betaine dye, pyrene, and 1,3-bis(1-pyrenyl)propane], we have investigated the aggregation behavior of common anionic, cationic, and nonionic surfactants when solubilized within a low-viscosity room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (emimTf2N). We observed possible aggregate formation by all nonionic surfactants included in the study (Brij-35, Brij-700, Tween-20, and Triton X-100), while no aggregation was observed for the cationic surfactant cetyltrimethylammonium bromide. The anionic surfactant sodium dodecyl sulfate does not appear to solubilize within emimTf2N at ambient conditions.     

Infinite dilution activity coefficients and gas-to-liquid partition coefficients of organic solutes dissolved in 1-sec-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and in 1-tert-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Inverse gas chromatography was used to measure infinite dilution activity coefficients and gas-to-liquid partition coefficients for 48 organic solute probes in either 1-sec-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-tert-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide in the temperature range from 323.15 to 373.15 K. Partial molar excess enthalpies of solution were calculated from the variation of the infinite dilution activity coefficients with temperature. Abraham model correlations were also derived from the experimental partition coefficient data. The derived Abraham model correlations describe the observed partition coefficients to within 0.11 log units.     

Nuclear magnetic relaxation and diffusion study of the ionic liquids 1-ethyl- and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide confined in porous glass

The molecular dynamics of the room-temperature ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (Bmim Tf2N) confined in porous glass is studied by nuclear magnetic resonance (NMR) relaxometry and diffusometry and is compared with the bulk dynamics over a wide temperature range. The molecular reorientation processes for anions and cations alike are found to be significantly affected by the presence of the glass interface at high temperatures. In this respect, the ionic liquid behaves similarly to polar liquids where proton NMR relaxation is governed by reorientations mediated by translational displacements (RMTDs). This process becomes less significant towards lower temperatures when the characteristic translational correlation times of the ions approach a timescale comparable with those of the RMTD process, and the relaxation dispersions in bulk and in confinement become similar below a temperature corresponding to about 1.2T_g, a value where the onset of dynamic heterogeneity has been observed before. The self-diffusion coefficient, on the other hand, is found to be strongly reduced than the bulk within the accessible temperature range of 248 K and above and is significantly slower than expected from the tortuosity effect, suggesting that ion–surface interactions affect the macroscopic properties.     

Low-temperature heat capacity of room-temperature ionic liquid, 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Heat capacities of liquid, stable crystal, and liquid-quenched glass of a room-temperature ionic liquid (RTIL), 1-hexyl-3-methylimidazolium bis(trifluromethylsulfonyl)imide were measured between 5 and 310 K by adiabatic calorimetry. Heat capacity of the liquid at 298.15 K was determined for an IUPAC project as (631.6 +/- 0.5) J K(-1) mol(-1). Fusion was observed at T(fus) = 272.10 K for the stable crystalline phase, with enthalpy and entropy of fusion of 28.34 kJ mol(-1) and 104.2 J K(-1) mol(-1), respectively. The purity of the sample was estimated as 99.83 mol % by the fractional melting method. The liquid could be supercooled easily and the glass transition was observed around T(g) approximately 183 K, which was in agreement with the empirical relation, T(g) approximately ((2)/(3)) T(fus). The heat capacity of the liquid-quenched glass was larger than that of the crystal as a whole. In the lowest temperature region, however, the difference between the two showed a maximum around 6 K and a minimum around 15 K, at which the heat capacity of the glass was a little smaller than that of crystal.     

Anion conformation of low-viscosity room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) imide

Anion conformation of a low-viscosity room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) imide (EMI+FSI-) has been studied by Raman spectra and theoretical DFT calculations. Three strong Raman bands were found at 293, 328, and 360 cm(-1), which are ascribed to the FSI- ion. These Raman bands show significant temperature dependence, implying that two FSI- conformers coexist in equilibrium. This is supported by theoretical calculations that the FSI- ion is present as either C2 (trans) or C1 (cis) conformer; the former gives the global minimum, and the latter has a higher SCF energy of about 4 kJ mol(-1). Full geometry optimizations followed by normal frequency analyses show that the observed bands at 293, 328, and 360 cm(-1) are ascribed to the C2 conformer. The corresponding vibrations at 305, 320, and 353 cm(-1) were extracted according to deconvolution of the observed Raman bands in the range280-400 cm(-1 )and are ascribed to the C1 conformer. The enthalpy DeltaH degrees of conformational change from C2 to C1 was experimentally evaluated to be ca. 4.5 kJ mol(-1), which is in good agreement with the predicted value by theoretical calculations. The bis(trifluoromethanesulfonyl) imide anion (TFSI-) shows a conformational equilibrium between C1 and C2 analogues (DeltaH degrees = 3.5 kJ mol(-1)). However, the profile of the potential energy surface of the conformational change for FSI- (the F-S-N-S dihedral angle) is significantly different from that for TFSI- (the C-S-N-S dihedral angle).     

Ion-pair formation in the ionic liquid 1-ethyl-3-methylimidazolium bis(triflyl)imide as a function of temperature and concentration.

The structures and ion-pair formation in the ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide are studied by a combination of FTIR measurements and DFT calculations. We could clearly distinguish imidazolium cations that are completely H-bonded to anions from those that are single H-bonded in ion pairs. Ion-pair formation already occurs in the neat IL and rises with temperature. Ion-pair formation is strongly promoted by dilution of the IL in chloroform. In these weakly polar environments ion pairs H-bonded via C(2)H are strongly favored over those H-bonded via C(4,5)H. This finding is in agreement with DFT (gas phase) calculations, which show a preference for ion pairs H-bonded via C(2)H as a result of the acidic C(2)H bond.     

Enhancement of oxygen and methane solubility in 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide using carbon dioxide

The presence of CO(2) increases the solubility of O(2) and CH(4) in 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide at 25 degrees C and pressures to 13 bar.     

Changes of the near-surface chemical composition of the 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide room temperature ionic liquid under the influence of irradiation

Radiation induced degradation effects are studied for a model ionic liquid (IL)--[EMIm]Tf(2)N--in order to distinguish in which way the results of X-ray based material analysis methods can be falsified by the radiation supplied by typical X-ray sources itself. Photoelectron spectroscopy is commonly used for determining the electronic structure of ionic liquids. Degradation effects, which often occur e.g. in organic materials during X-ray or electron irradiation, are potentially critical for the interpretation of data obtained from ionic liquids. The changes of the chemical composition as well as the radiation-induced desorption of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm]Tf(2)N) fragments are analysed by X-ray photoelectron spectroscopy (XPS) as well as quadrupole mass spectroscopy (QMS) upon exposure to monochromated or non-monochromated AlKα X-rays from typical laboratory sources. During the irradiation of [EMIm]Tf(2)N, an increasing carbon concentration is observed in both cases and especially the [Tf(2)N](-) ion is strongly altered. This observation is supported by the results from the QMS analysis which revealed a variety of different IL fragments that are desorbed during X-ray irradiation. It is shown that the decomposition rate is directly linked to the photon flux on the sample and hence has to be considered when planning an XPS experiment. However, for typical experiments on this particular IL the measurements suggest that the changes are on a larger time scale as typically required for spectra acquisition, in particular if monochromated X-ray sources are used.     

Determination of ammonia based on the electro-oxidation of hydroquinone in dimethylformamide or in the room temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

The results detail a novel methodology for the electrochemical determination of ammonia based on its interaction with hydroquinone in DMF. It has been shown that ammonia reversibly removes protons from the hydroquinone molecules, thus facilitating the oxidative process with the emergence of a new wave at less positive potentials. The analytical utility of the proposed methodology has been examined with a linear range from 10 to 95 ppm and corresponding limit-of-detection of 4.2 ppm achievable. Finally, the response of hydroquinone in the presence of ammonia has been examined in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluormethylsulfonyl)imide, [EMIM][N(Tf)₂]. Analogous voltammetric waveshapes to that observed in DMF were obtained, thereby confirming the viability of the method in either DMF or [EMIM][N(Tf)₂] as solvent.     

Phase behavior of ionic liquids 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides with halogenated benzenes

(Liquid + liquid) miscibility temperatures as a function of composition have been determined experimentally for the binary systems formed by imidazolium based ionic liquids with bis(trifluoromethylsulfonyl)imide ([C_nMIM][NTf₂]: n = 3 to 10) with fluorobenzene, chlorobenzene, bromobenzene, iodobenzene and 1,2-dichlorobenzene. In addition, the phase diagrams for deuterated chlorobenzene, bromobenzene and 1,2-dichlorobenzene have been obtained. All the measured systems show the limited miscibility with the upper critical solution temperature behavior. Similarly to the other systems with the imidazolium cation the increase of the alkyl chain length in this cation improves the miscibility. The impact of the halogenobenzene is also very visible. The miscibility is improving in the order: iodobenzene < bromobenzene < chlorobenzene < fluorobenzene. This arrangement corresponds to the decreasing molar volume of the substituted benzenes. The disubstituted chlorobenzene is a better solvent for ionic liquids than chlorobenzene. The replacement of hydrogen for deuterium in halogenobenzenes in all cases improves the miscibility and the isotope shifts of the UCSTs are very large.     

1-Alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids as solvents in the separation of azeotropic mixtures

(Liquid + liquid) equilibrium data for the ionic liquids 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [EMim][NTf₂], 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [PMim][NTf₂], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [BMim][NTf₂], and 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [HMim][NTf₂], mixed with ethanol and heptane were studied at T = 298.15 K and atmospheric pressure. The ability of these ionic liquids as solvents for the extraction of ethanol from heptane was evaluated in terms of selectivity and solute distribution ratio. Moreover, density and refractive index values over the miscible region for the ternary mixtures were also measured at T = 313.15 K. Finally, the experimental data were correlated with the Non Random Two Liquids (NRTL) and UNIversal QUAsi Chemical (UNIQUAC) thermodynamic models, and an exhaustive comparison with available literature data of the studied systems was carried out.     

Vapour permeation and sorption in fluoropolymer gel membrane based on ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide

The emissions of hydrocarbons from fossil fuels into atmosphere entail both an economic loss and an environmental pollution. Membrane separations can be used for vapour recovery and/or vapour removal from the permanent gas stream, given that the appropriate membrane is identified. A neat poly(vinylidene fluoride-co-hexafluoropropylene) membrane is impermeable to both the representatives of aliphatic hydrocarbons and branched hydrocarbons, namely hexane and isooctane, whereas the permeation flux is enhanced by the presence of 80 mass % of the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide in the membrane, as detailed in this work. The permeabilities of hydrocarbon vapours were determined from the binary mixture containing hydrocarbon and nitrogen to simulate the real input of an air stream containing a condensable hydrocarbon. The diffusion coefficient determined from sorption measurements was higher for hexane, as would be expected for a smaller molecule, whereas both the sorption isotherms and permeabilities of the hydrocarbons studied were found to be almost identical. It is possible that the sorption effect predominates in the transport mechanism for VOCs/N₂ separations.     

Viscosity of (C2-C14) 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ionic liquids in an extended temperature range

Dynamic viscosities of several members of the 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, [C_nmim][NTf₂], ionic liquids family, with the cation alkyl side-chain length varying from 2 to 14 carbon atoms, have been measured in the 278.15 K to 393.15 K temperature range using two different apparatuses. To the best of our knowledge, it is the first time that such an extensive assessment of viscosity - in terms of the number of compounds of a single ionic liquid homologous series, of the broad range of temperature covered, and the use of two different experimental techniques - is reported. The use of two different instruments, using different methodologies, provides information about the uncertainties in the measurement of viscosity of ionic liquids, including its dependence on the presence of traces of water and other impurities. An extensive critical analysis of the deviations between the data measured in this work and those reported in literature has been carried out.     

Solubility of carbon dioxide in 1-ethyl-3-methylimidazolium 2-(2-methoxyethoxy) ethylsulfate

Experimental results for the solubility of carbon dioxide in the ionic liquid 1-ethyl-3-methylimidazolium 2-(2-methoxyethoxy) ethylsulfate are not reported in the literature. To this end, we present in this work new solubility data for carbon dioxide in 1-ethyl-3-methylimidazolium 2-(2-methoxyethoxy) ethylsulfate for temperatures ranging from (303.2 to 343.2) K and pressures up to 6.7 MPa using a thermogravimetric microbalance. The carbon dioxide solubility was determined from absorption saturation (equilibrium) data at each fixed temperature and pressure. The buoyancy effect was accounted in the evaluation of the carbon dioxide solubility. Highly accurate equations of states for carbon dioxide and for ionic liquids were employed to determine the effect of buoyancy on carbon dioxide solubility. The solubility measurements are presented as a function of temperature and pressure. The present experimental solubility results have been successfully correlated using an extended Henry’s law equation.     

High pressure volumetric properties of 1-ethyl-3-methylimidazolium ethylsulfate and 1-(2-methoxyethyl)-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide

In order to select the most suitable ionic liquids (ILs) for certain applications it is necessary to know some of their thermophysical properties, such as density or viscosity. In this work we have performed density measurements of two ILs 1-ethyl-3-methylimidazolium ethylsulfate and 1-(2-methoxyethyl)-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide in a broad range of temperature and pressure ((278.15 to 398.15) K and up to 120 MPa). From these measurements we have obtained other volumetric properties such as isothermal compressibility and isobaric thermal expansivity. In addition, density values were predicted using the method proposed by Gardas and Coutinho and also that proposed by Jacquemin et al., obtaining a good agreement with experimental values.     

Electrodeposition of Al in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ionic liquids: in situ STM and EQCM studies

In the present paper, the electrodeposition of Al on flame-annealed Au(111) and polycrystalline Au substrates in two air- and water-stable ionic liquids namely, 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide, [Py(1,4)]Tf(2)N, and 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)amide, [EMIm]Tf(2)N, has been investigated by in situ scanning tunneling microscopy (STM), electrochemical quartz crystal microbalance (EQCM), and cyclic voltammetry. The cyclic voltammogram of aluminum deposition and stripping on Au(111) in the upper phase of the biphasic mixture of AlCl(3)/[EMIm]Tf(2)N at room temperature (25 degrees C) shows that the electrodeposition process is completely reversible as also evidenced by in situ STM and EQCM studies. Additionally, a cathodic peak at an electrode potential of about 0.55 V vs Al/Al(III) is correlated to the aluminum UPD process that was evidenced by in situ STM. A surface alloying of Al with Au at the early stage of deposition occurs. It has been found that the Au(111) surface is subject to a restructuring/reconstruction in the upper phase of the biphasic mixture of AlCl(3)/[Py(1,4)]Tf(2)N at room temperature (25 degrees C) and that the deposition is not fully reversible. Furthermore, the underpotential deposition of Al in [Py(1,4)]Tf(2)N is not as clear as in [EMIm]Tf(2)N. The frequency shift in the EQCM experiments in [Py(1,4)]Tf(2)N shows a surprising result as an increase in frequency and a decrease in damping with bulk aluminum deposition at potentials more negative than -1.8 V was observed at room temperature. However, at 100 degrees C there is a frequency decrease with ongoing Al deposition. At -2.0 V vs Al/Al(III), a bulk aluminum deposition sets in.     

Ion-Pair Formation of the Ionic Liquid 1-Ethyl-3-methylimidazolium bis(trifyl)imide in Low Dielectric Media

A proton nuclear magnetic resonance (¹H NMR) study of the ionic liquid, 1-ethyl-3-methylimidazolium bis(trifyl)imide, dilute in low dielectric constant solvent media is presented. Equilibrium species are directly observed in the ¹H NMR spectrum as two sets of resonance features, thus displaying unusually long lifetimes. In mixed solvent systems the species mole fractions are directly proportional to the bulk dielectric constant of the solution. The two sets of resonance features are assigned to the freely dissolved ions and ion-pair aggregates. The assignment is supported by measured spin lattice relaxation rates, and the observed temperature and concentration dependencies of the equilibrium. The thermodynamic quantities G _m , S _m , and H _m are also evaluated from the temperature-dependent data.     

Measurement and correlation of solubility of carbon dioxide in 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids

The solubility of carbon dioxide in the ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate and 1-nonyl-3-methylimidazolium hexafluorophosphate was measured at temperatures of 293.15 and 298.15 K and pressure up to 4 MPa using a stoichiometric phase equilibrium apparatus. The measured data for 1-butyl-3-methylimidazolium hexafluorophosphate were in good agreement with existing literature data and new solubility data were reported for 1-nonyl-3-methylimidazolium hexafluorophosphate. The measured data were correlated using the group contribution non-random lattice fluid equation of state (GC-NLF EoS) proposed by Lee and co-workers. The group parameters for CG-NLF EoS were slightly modified at limited range to accommodate recent experimental data and better prediction at high pressure and long alkyl chains.     

Vapor pressures and activity coefficients of binary mixtures of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide with acetonitrile and tetrahydrofuran

A new apparatus for the determination of VLE has been constructed which works for absolute pressure measurements as well as for measuring differential pressures. The first results obtained are (vapor + liquid) equilibria (VLE) of binary mixtures containing acetonitrile or tetrahydrofuran and the ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMIm][NTf2] by using the absolute pressures method. VLE measurements were carried out over the whole concentration range at four different temperatures between 293.15 K and 313.15 K. Activity coefficients (γ₁) of the solvents in [EMIm][NTf2] and their osmotic coefficients (ϕ₁) have been determined from the VLE data.