Solubility of CO2 in room temperature ionic liquid [hmim][Tf2N

Solubility measurements of carbon dioxide in 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide have been performed with a gravimetric microbalance at temperatures of about 282, 297, 323, and 348 K and pressures up to about 2 MPa. Two different sources for the ionic liquid are examined in this work: an ultrapure sample from NIST (the IUPAC task force sample) and a commercially available sample. Both samples show nearly identical solubility behaviors, being undistinguishable within experimental uncertainties. Solubility (pressure-temperature-composition) data have been well correlated with an equation-of-state (EOS) model used in our previous works. The EOS model calculations are compared with experimental solubility data for the same system in the literature. The present EOS has predicted partial immiscibility at the CO2-rich side solutions. To prove this prediction, vapor-liquid-liquid equilibrium experiments have been made, and our predictions have been confirmed.     

Solubility of tetrafluoromethane in the ionic liquid [hmim][Tf2N

Experimental results for the solubility of tetrafluoromethane (CF4, R14) in the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([hmim][Tf2N]) are presented for temperatures between 293.3 and 413.3 K, at pressures (gas molalities) up to 9.6 MPa (0.22 mol kg-1). The experimental results were determined with a high-pressure view-cell technique operating on the synthetic method. The experimental data were used to determine Henry's constant of tetrafluoromethane in [hmim][Tf2N]. The results for the Henry's constant (at zero pressure) are correlated (on the molality scale) within the experimental uncertainty (i.e., about 1.1%) by ln(k(0)(H,CF4)/MPa) = 7.537 - 893.8/(T/K) - 0.003977(T/K). Henry's law was also extended to describe the gas solubility at higher pressures. Furthermore, a cubic equation of state was used to correlate the gas solubility over the entire range of experimentally investigated temperature and pressure. Both methods proved suited for a reliable correlation of the new experimental data.     

Solubility of H2S in ionic liquids [hmim][PF6], [hmim][BF4], and [hmim][Tf2N]

The solubility of hydrogen sulphide in three ionic liquids, viz. 1-hexyl-3-methylilmidazolium hexafluorophosphate ([hmim][PF₆]), 1-hexyl-3-methylimidazolium tetrafluoroborate ([hmim][BF₄]), and 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([hmim][Tf₂N]), at temperatures ranging from 303.15 K to 343.15 K and pressures up to 1.1 MPa were determined. The solubility values were correlated using the Krichevsky–Kasarnovsky equation and Henry’s constants were obtained at different temperatures. Partial molar thermodynamic functions of solvation such as standard Gibbs free energy, enthalpy, and entropy were calculated from the solubility results. Comparison of the values obtained show that the solubility of H₂S in these three ionic liquids was in the sequence: [hmim][BF₄] > [hmim][PF₆] ≈ [hmim][Tf₂N].     

Palladium-catalyzed regiospecific aminocarbonylation of alkynes in the ionic liquid [bmim][Tf2N

[Structure: see text] Regiospecific construction of 2-substituted acrylamides was achieved by palladium-catalyzed aminocarbonylation of alkynes in the ionic liquid [bmim][Tf2N] without any acid additive under relatively mild conditions. The ionic liquid was used as the reaction medium and also acted as a promoter. Acrylamides were obtained in moderate to excellent yields, and an important feature is that the catalyst system can be recycled five times without loss of catalytic activity.     

Autocatalytic sonolysis of iron pentacarbonyl in room temperature ionic liquid [BuMeIm][Tf2N

The autocatalytic sonochemical reaction of Fe(CO)(5) decomposition in [BuMeIm][Tf(2)N] provides iron nanoparticles in higher yields than in tetralin. Such a difference is explained by the higher decomposition of the intermediate Fe(3)(CO)(12) according to the two-sites model of the sonochemical reactions and the specific properties of the ionic liquid.     

Spectroscopic and electrochemical studies of U(IV)-hexachloro complexes in hydrophobic room-temperature ionic liquids [BuMeIm][Tf2N] and [MeBu3N][Tf2N

The behavior of U(IV) octahedral complexes [cation]2[UCl6], where the [cation]+ is [BuMeIm]+ and [MeBu3N]+, is studied using UV/visible spectroscopy, cyclic staircase voltammetry, and rotating disk electrode voltammetry in hydrophobic room-temperature ionic liquids (RTILs) [BuMeIm][Tf2N] and [MeBu3N][Tf2N], where BuMeIm+ and MeBu3N+ are 1-butyl-3-methylimidazolium and tri-n-butylmethylammonium cations, respectively, and Tf2N- is the bis(trifluoromethylsulfonyl)imide anion. The absorption spectra of [cation]2[UCl6] complexes in the RTIL solutions are similar to the diffuse solid-state reflectance spectra of the corresponding solid species, indicating that the octahedral complex UCl6(2-) is the predominant chemical form of U(IV) in Tf2N--based hydrophobic ionic liquids. Hexachloro complexes of U(IV) are stable to hydrolysis in the studied RTILs. Voltammograms of UCl(6)2- at the glassy carbon electrode in both RTILs and at the potential range of -2.5 to +1.0 V versus Ag/Ag(I) reveal the following electrochemical couples: UCl6-/UCl6(2-) (quasi-reversible system), UCl(6)2-/UCl6(3-) (quasi-reversible system), and UCl(6)2-/UCl6(Tf2N)x-3+x (irreversible reduction). The voltammetric half-wave potential, Ep/2, of the U(V)/U(IV) couple in [BuMeIm][Tf2N] is positively shifted by 80 mV compared with that in [MeBu3N][Tf2N]. The positive shift in the Ep/2 value for the quasi-reversible U(IV)/U(III) couple is much greater (250 mV) in [BuMeIm][Tf2N]. Presumably, the potential shift is due to the specific interaction of BuMeIm+ with the uranium-hexachloro complex in ionic liquid. Scanning the negative potential to -3.5 V in [MeBu3N][Tf2N] solutions of UCl6(2-) reveals the presence of an irreversible cathodic process at the peak potential equal to -3.12 V (at 100 mV/s and 60 degrees C), which could be attributed to the reduction of U(III) to U(0).     

Liquid/solid interface of ultrathin ionic liquid films: [C1C1Im][Tf2N] and [C8C1Im][Tf2N] on Au(111)

Ultrathin films of two imidazolium-based ionic liquids (IL), [C(1)C(1)Im][Tf(2)N] (= 1,3-dimethylimidazolium bis(trifluoromethyl)imide) and [C(8)C(1)Im][Tf(2)N] (= 1-methyl-3-octylimidazolium bis(trifluoromethyl)imide) were prepared on a Au(111) single-crystal surface by physical vapor deposition in ultrahigh vacuum. The adsorption behavior, orientation, and growth were monitored via angle-resolved X-ray photoelectron spectroscopy (ARXPS). Coverage-dependent chemical shifts of the IL-derived core levels indicate that for both ILs the first layer is formed from anions and cations directly in contact with the Au surface in a checkerboard arrangement and that for [C(8)C(1)Im][Tf(2)N] a reorientation of the alkyl chain with increasing coverage is found. For both ILs, geometry models of the first adsorption layer are proposed. For higher coverages, both ILs grow in a layer-by-layer fashion up to thicknesses of at least 9 nm (>10 ML). Moreover, beam damage effects are discussed, which are mainly related to the decomposition of [Tf(2)N](-) anions directly adsorbed at the gold surface.     

Solubility of CO2, CO, and H2 in the ionic liquid [bmim][PF6] from Monte Carlo simulations

This work reports predictions from molecular simulation results for the solubility of the single gases carbon dioxide, carbon monoxide, and hydrogen in the ionic liquid 1-N-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim][PF6]) at temperatures from 293 to 393 K and at pressures up to 9 MPa. The predictions are achieved by Gibbs ensemble Monte Carlo simulations at constant pressure and temperature (NpT-GEMC). The intermolecular forces are approximated by effective pair potentials for the pure gases and by a quantum-chemistry-based pair potential for [bmim][PF6]. The interactions between unlike groups are described using common mixing rules without any adjustable binary interaction parameter. The simulation results for the solubility of hydrogen agree within their statistical uncertainty with experimental data, whereas the results for carbon monoxide and carbon dioxide reveal somewhat larger deviations.     

Mixing and decomposition behavior of {[4bmpy][Tf2N] + [emim][EtSO4]} and {[4bmpy][Tf2N] + [emim][TFES]} ionic liquid mixtures

Mixing ionic liquids (ILs) has been revealed as a useful way to finely tune the properties of IL-based solvents. The scarce available studies on IL mixtures have shown a quasi-ideal behavior of their physical properties. In this work, we have performed a thermophysical characterization of two binary IL mixtures, namely {4-methyl-N-butylpyridinium bis(trifluoromethylsulfonyl)imide ([4bmpy][Tf₂N]) + 1-ethyl-3-methylimidazolium ethylsulfate ([emim][EtSO₄])} and {[4bmpy][Tf₂N] + 1-ethyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate [emim][TFES]}. Both binary IL mixtures have been recently proposed as promising solvents in the (liquid + liquid) extraction of aromatic hydrocarbons from mixtures with alkanes. Densities, viscosities, refractive indices, thermal stability, and specific heats of the {[4bmpy][Tf₂N] + [emim][EtSO₄]} and {[4bmpy][Tf₂N] + [emim][TFES]} IL mixtures have been measured as a function of both temperature and composition. Dynamic viscosities, refractive indices, and thermal stability of the {[4bmpy][Tf₂N] + [emim][EtSO₄]} mixture have exhibited strong deviations from the ideality, in contrast with the quasi-ideal properties of the {[4bmpy][Tf₂N] + [emim][TFES]} mixture and the behavior of the imidazolium and pyridinium-based IL mixtures studied hitherto. The reliability of predictive methods of the thermophysical properties of the mixtures has also been evaluated.     

Investigations with infrared spectroscopy on films of the ionic liquid [EMIM]Tf2N

The reflection-absorption infrared (RAIRS) spectra of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM]Tf 2N) are presented as a function of temperature between 114 and 292 K. A comparison is made with the corresponding infrared spectra (obtained with transmission spectroscopy) from bulk [EMIM]Tf 2N. The liquid and amorphous films show rather similar spectra, indicating that the film structure is similar in both cases. On the other hand, these spectra differ considerably from those of crystalline films. Characteristic differences seen between the film and bulk spectra are attributed to the different structures of the respective networks. There are, however, indications that under all studied conditions the cation-anion interaction is between the C-H groups of the [EMIM] ring and the SO 2 groups of the anion.     

Uranyl complexation by chloride ions. Formation of a tetrachlorouranium(VI) complex in room temperature ionic liquids [Bmim][Tf2N] and [MeBu3N][Tf2N

The tetrachlorouranium(VI) complex is formed in [Bmim][Tf2N] and [MeBu3N][Tf2N] from a uranium(VI) solution in the presence of a stoichiometric quantity of chloride ions. The [UVIO2Cl4]2- absorption and emission spectra show bands splitting in comparison with the [UVIO2]2+ spectra, as observed in the solid state, organic solvents, and chloroaluminate-based ionic liquids. The fluorescence lifetime of [UO2Cl4]2- in [MeBu3N][Tf2N] is 0.7 +/- 0.1 mus. The reduction potential of this complex is -1.44 and -1.8 V vs Ag/Ag+ respectively in [Bmim][Tf2N] and [MeBu3N][Tf2N] and does not depend on the chloride concentration. The mechanism proposed for the redox process is a monoelectronic reduction to form [UVO2Cl4]3-, followed by a chemical reaction. The tetrachlorouranium(V) complex seems more stable in [Bmim][Tf2N] than in [MeBu3N][Tf2N]. The electrochemical analysis put in evidence specific interactions of the ionic liquid cation with the uranium anionic species.     

Acetyl nitrate nitrations in [bmpy][N(Tf)2] and [bmpy][OTf], and the recycling of ionic liquids

In this work we have examined the nitration by acetyl nitrate of a range of activated and deactivated aromatic substrates in two ionic liquids and compared the results to the same reaction in dichloromethane. Both ionic liquids are stable to the reaction conditions, and in both ionic liquids the yields of reaction are higher after unit time than the same reactions in dichloromethane, although the regioselectivity is little affected by solvent choice. This result gives further support to the suggestion that in the ionic liquid, acetyl nitrate dissociates to give the nitronium ion, and that this is the effective nitrating agent here. However, it is shown that [bmpy][N(Tf)(2)] is a better solvent for aromatic nitration than [bmpy][OTf]. This is due to the ease of formation of nitronium ion in the former ionic liquid, and is consistent with the fact that [bmpy][N(Tf)(2)] is a weaker hydrogen bond acceptor solvent than [bmpy][OTf]. Finally, a method by which [bmpy][N(Tf)(2)] may be recovered and reused for aromatic nitration has been demonstrated.     

Stability of [MeBu3N][Tf2N] under gamma irradiation

The stability of the ionic liquid [MeBu3N][Tf2N], dry or after contact with water (where [MeBu3N]+ is the methyltributylammonium cation and [Tf2N](-) is the bistriflimide anion), was studied under 137Cs gamma irradiation in argon and in air. In a quantitative study with an absorbed dose of 2 MGy this ionic liquid was highly stable regardless of the radiolysis conditions. The radiolytic disappearance yields determined by ESI-MS were -0.38 and -0.25 micromol J(-1) for the cation and anion, respectively. ESI-MS, NMR, and liquid chromatography coupled with ESI-MS identified a large number of degradation products in very small quantities for the same dose. The cation radicals were formed by the loss of a Bu group, the Me group, or two H atoms to form a double bond with the butyl chain. Radiolysis of the anion produced mainly F and CF3 radicals. The anion radicals recombined with the cation to form a wide range of secondary degradation products regardless of the radiolysis conditions.     

Characterization of the interfaces between Au(hkl) single crystal basal plane electrodes and [Emmim][Tf2N] ionic liquid

The interface between Au(hkl) basal planes and the ionic liquid 1-Ethyl-2,3-dimethyl imidazolium bis(trifluoromethyl)sulfonil imide was investigated by using both cyclic voltammetry and laser-induced temperature jump. Cyclic voltammetry showed characteristic features, revealing surface sensitive processes at the interfaces Au(hkl)/[Emmim][Tf₂N]. From laser-induced heating the potential of maximum entropy (pme) is determined. Pme is close to the potential of zero charge (pzc) and, therefore, the technique provides relevant interfacial information. The following order for the pme values has been found: Au(111) > Au(100) > Au(110). This order correlates well with work function data and values of pzc in aqueous solutions.     

Atomistic simulation of the absorption of carbon dioxide and water in the ionic liquid 1-n-Hexyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide ([hmim][Tf2N

The solubility of water and carbon dioxide in the ionic liquid 1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([hmim][Tf2N]) is computed using atomistic Monte Carlo simulations. A newly developed biasing algorithm is used to enable complete isotherms to be computed. In addition, a recently developed pairwise damped electrostatic potential calculation procedure is used to speed the calculations. The computed isotherms, Henry's Law constants, and partial molar enthalpies of absorption are all in quantitative agreement with available experimental data. The simulations predict that the excess molar volume of CO2/ionic liquid mixtures is large and negative. Analysis of ionic liquid conformations shows that the CO2 does not perturb the underlying liquid structure until very high CO2 concentrations are reached. At the highest CO2 concentrations, the alkyl chain on the cation stretches out slightly, and the distance between cation and anion centers of mass increases by about 1 angstroms. Water/ionic liquid mixtures have excess molar volumes that are also negative but much smaller in magnitude than those for the case of CO2.     

Crystal engineering in ionic liquids. The crystal structures of [Mppyr]3[NdI6] and [Bmpyr]4[NdI6][Tf2N

Single crystals of [mppyr][NdI6] and [bmpyr][NdI6][Tf2N] are the first surprising examples of how the cation of an ionic liquid determines the compound formation from an ionic liquid. Depending upon the variation of the length of the alkyl chain of the quaternary pyrrolidinium cation (C3 and C4, respectively), incorporation of the anion of the ionic liquid, [Tf2N]-, can either be evoked or suppressed.     

The [BMI][Tf2N] ionic liquid/water binary system: a molecular dynamics study of phase separation and of the liquid-liquid interface

We report molecular dynamics (MD) simulations of the aqueous interface of the hydrophobic [BMI][Tf2N] ionic liquid (IL), composed of 1-butyl-3-methylimidazolium cations (BMI+) and bis(trifluoromethylsulfonyl)imide anions (Tf2N-). The questions of water/IL phase separation and properties of the neat interface are addressed, comparing different liquid models (TIP3P vs TIP5P water and +1.0/-1.0 vs +0.9/-0.9 charged IL ions), the Ewald vs the reaction field treatments of the long range electrostatics, and different starting conditions. With the different models, the "randomly" mixed liquids separate much more slowly (in 20 to 40 ns) than classical water-oil mixtures do (typically, in less than 1 ns), finally leading to distinct nanoscopic phases separated by an interface, as in simulations which started with a preformed interface, but the IL phase is more humid. The final state of water in the IL thus depends on the protocol and relates to IL heterogeneities and viscosity. Water mainly fluctuates in hydrophilic basins (rich in O(Tf2N) and aromatic CH(BMI) groups), separated by more hydrophobic domains (rich in CF3(Tf2N) and alkyl(BMI) groups), in the form of monomers and dimers in the weakly humid IL phase, and as higher aggregates when the IL phase is more humid. There is more water in the IL than IL in water, to different extents, depending on the model. The interface is sharper and narrower (approximately 10 A) than with the less hydrophobic [BMI][PF6] IL and is overall neutral, with isotropically oriented molecules, as in the bulk phases. The results allow us to better understand the analogies and differences of aqueous interfaces with hydrophobic (but hygroscopic) ILs, compared to classical organic liquids.     

Modeling the solubility behavior of CO(2), H(2), and Xe in [C(n)-mim][Tf(2)N] ionic liquids

We present here a new model for the imidazolium-based ionic liquids (ILs) with the bis(trifluoromethylsulfonyl)imide anion [Tf(2)N](-) in the context of the soft-SAFT EoS. The model is used to predict the solubility of several compounds in these ILs, and results are compared to available experimental data. Since in the soft-SAFT EoS an associating site is used to represent a short-range and highly directional attractive force among molecules, we have used this feature to mimic the main interactions between the anion and the cation for the alkylimidazolium-[Tf(2)N] ILs. The members of the alkylimidazolium-[Tf(2)N] family are modeled as Lennard-Jones chains with three associating sites in each molecule (one "A" site and two "B" sites). An "A" site represents the nitrogen atom interactions with the cation, and a "B" site represents the delocalized charge due the oxygen molecules on the anion. Each type of associating site is identically defined, but only AB interactions between different IL molecules are allowed. Model parameters for the ionic liquids were estimated with experimental density data from different authors, following a similar approach taken in our previous work [Andreu and Vega, J. Phys. Chem. C 2007, 111, 16028]. The new set of parameters was used to study the solubility behavior of hydrogen, carbon dioxide, and xenon in these ILs over a wide range of temperature and pressure. It has been observed that no binary parameters are needed to correlate the solubility of hydrogen in [C(6)-mim][Tf(2)N] at different temperatures, and predictions up to 100 MPa are presented here. The model is able to correlate with very good agreement the experimental data for the systems [C(n)-mim][Tf(2)N] + CO(2) with only one temperature-independent mixture parameter, while two temperature-independent mixture parameters are needed to correlate the experimental solubility data for the systems IL + Xe, attaining an excellent agreement in a wide range of temperatures. The work presented here reinforces previous results, proving that a reasonable simple model for the IL within the framework of soft-SAFT is able to describe the physical absorption of different gases in ILs with good accuracy, in spite of the most complex nature of the anion, without the need of further parameters or terms. In addition, since these parameters do not depend on the particular conditions at which they were fitted, soft-SAFT is used then to analyze the solubility dependence of these gases in ILs, according to the anion nature and the alkyl chain length of the imidazolium cation by the use of the models developed within this approach.