Interionic Interactions in Imidazolic Ionic Liquids Probed by Soft X-ray Absorption Spectroscopy

This work investigates pure ionic liquids (ILs) derived from an imidazolium ring with different carbonic chains and halides or bis(trifluoromethanesulfonilimide) (TFSI-) as anions, using X-ray absorption near edge spectroscopy (XANES) at different energies (N, S, O, F, and Cl edges) to probe the interionic interactions. XANES data show that the interaction with the anion is weaker when the cation is an imidazolium than when the salt is formed by smaller cations, as lithium, independently of the length of the carbonic chain attached to the imidazolium cation. The results also show that, for all studied as, it is not observed any influence of the anion on the XANES spectra of the cation, nor the opposite. 1-Methylimidazolium with Cl-, a small and strongly coordinating anion, presents in the N K XANES spectrum a splitting of the band corresponding to nitrogen in the imidazolic ring, indicating two different chemical environments. For this cation with TFSI-, on the contrary, this splitting was not observed, showing that the anion has a weaker interaction with the imidazolic ring, even without a lateral carbonic chain.

Solvation in aqueous binary mixtures: consequences of the hydrophobic character of the ionic liquids and the solvatochromic probes

Information on the solvation in mixtures of water, W, and the ionic liquids, ILs, 1-allyl-3-R-imidazolium chlorides; R = methyl, 1-butyl, and 1-hexyl, has been obtained from the responses of the following solvatochromic probes: 2,6-dibromo-4-[(E)-2-(1-R-pyridinium-4-yl)ethenyl] phenolate, R = methyl, MePMBr2; 1-octyl, OcPMBr(2), and the corresponding quinolinium derivative, MeQMBr(2). A model developed for solvation in binary mixtures of W and molecular solvents has been extended to the present mixtures. Our objective is to assess the relevance to solvation of hydrogen-bonding and the hydrophobic character of the IL and the solvatochromic probe. Plots of the medium empirical polarity, E-T(probe) versus its composition revealed non-ideal behavior, attributed to preferential solvation by the IL and, more efficiently, by the IL-W hydrogen-bonded complex. The deviation from linearity increases as a function of increasing number of carbon atoms in the alkyl group of the IL, and is larger than that observed for solvation by W plus molecular solvents (1-propanol and 2-(1-butoxy)ethanol) that are more hydrophobic than the ILs investigated. This enhanced deviation is attributed to the more organized structure of the ILs proper, which persists in their aqueous solutions. MeQMBr(2) is more susceptible to solvent lipophilicity than OcPMBr(2), although the former probe is less lipophilic. This enhanced susceptibility agrees with the important effect of annelation on the contributions of the quinonoid and zwitterionic limiting structures to the ground and excited states of the probe, hence on its response to both medium composition and lipophilicity of the IL.

LONG TIME CORRELATIONS OF NONLINEAR LUTTINGER LIQUIDS

An overview is given of the limitations of Luttinger liquid theory in describing the real time equilibrium dynamics of critical one-dimensional systems with nonlinear dispersion relation. After exposing the singularities of perturbation theory in band curvature effects that break the Lorentz invariance of the Tomonaga-Luttinger model, the origin of high frequency oscillations in the long time behaviour of correlation functions is discussed. The notion that correlations decay exponentially at finite temperature is challenged by the effects of diffusion in the density-density correlation due to umklapp scattering in lattice models.

High Viscosity of Imidazolium Ionic Liquids with the Hydrogen Sulfate Anion: A Raman Spectroscopy Study

Ionic liquids based on 1-alkyl-3-methylimidazolium cations and the hydrogen sulfate (or bisulfate) anion, HSO4-, are much more viscous than ionic liquids with alkyl sulfates, RSO4-. The structural origin of the high viscosity of HSO4- ionic liquids is unraveled from detailed comparison of the anion Raman bands in 1-ethyl-3-methylimidazolium hydrogen sulfate and 1-butyl-3-methylimidazolium hydrogen sulfate with available data for simple HSO(4)(-) salts in crystalline phase, molten phase, and aqueous solution. Two Raman bands at 1046 and 1010 cm(-1) have been assigned as symmetric stretching modes nu(s)(S = O) of HSO4-, the latter being characteristic of chains of hydrogen-bonded anions. The intensity of this component increases in the supercooled liquid phase. For comparison purposes, Raman spectra of 1-ethyl-3-methylimidazolium ethyl sulfate and 1-butyl-3-methylimidazolium methyl sulfate have been also obtained. There is no indication of difference in the strength of hydrogen bond interactions of imidazolium cations with HSO4- or RSO4- anions. Raman spectra at high pressures, up to 2.6 GPa, are also discussed. Raman spectroscopy provides evidence that hydrogen-bonded anions resulting in anion-anion interaction is the reason for the high viscosity of imidazolium ionic liquids with HSO4-. If the ionic liquid is exposed to moisture, these structures are disrupted upon absorption of water from the atmosphere.

Magnetic Ionic Liquids Produced by the Dispersion of Magnetic Nanoparticles in 1-n-Butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMI.NTf2)

This paper reports on the advancement of magnetic ionic liquids (MILs) as stable dispersions of surface-modified gamma-Fe2O3, Fe3O4, and CoFe2O4 magnetic nanoparticles (MNPs) in a hydrophobic ionic liquid, 1-n-butyl 3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMI.NTf2). The MNPs were obtained via coprecipitation and were characterized using powder X-ray diffraction, transmission electron microscopy, Raman spectroscopy and Fourier transform near-infrared (FT-NIR) spectroscopy, and magnetic measurements. The surface-modified MNPs (SM-MNPs) were obtained via the silanization of the MNPs with the aid of 1-butyl-3[3-(trimethoxysilyl)propyl]imidazolium chloride (BMSPI.Cl). The SM-MNPs were characterized by Raman spectroscopy and Fourier trail: form infrared attenuated total reflectance (FTIR-ATR) spectroscopy and by magnetic measurements. The FTIR-ATR spectra of the SM-MNPs exhibited characteristic absorptions of the imidazolium and those of the Fe-O-Si-C moieties, confirming the presence of BMSPI.Cl on the MNP surface. Thermogravimetric analysis (TGA) showed that the SM-MNPs were modified by at least one BMSPI.Cl monolayer. The MILs were characterized using Raman spectroscopy, differential scanning calorimetry (DSC), and magnetic measurements. The Raman and DSC results indicated an interaction between the SM-MNPs and the IL. This interaction promotes the formation of a supramolecular structure close to the MNP surface that mimics the IL structure and is responsible for the stability of the MIL. Magnetic measurements of the MILs indicated no hysteresis. Superparamagnetic behavior and a saturation magnetization of similar to 22 emu/g could be inferred from the magnetic measurements of a sample containing 50% w/w gamma-Fe2O3 SM-MNP/BMI-NTf2.

An electrochemical gas sensor based on paper supported room temperature ionic liquids

A sensitive and fast-responding membrane-free amperometric gas sensor is described, consisting of a small filter paper foil soaked with a room temperature ionic liquid (RTIL), upon which three electrodes are screen printed with carbon ink, using a suitable mask. It takes advantage of the high electrical conductivity and negligible vapour pressure of RTILs as well as their easy immobilization into a porous and inexpensive supporting material such as paper. Moreover, thanks to a careful control of the preparation procedure, a very close contact between the RTIL and electrode material can be achieved so as to allow gaseous analytes to undergo charge transfer just as soon as they reach the three-phase sites where the electrode material, paper supported RTIL and gas phase meet. Thus, the adverse effect on recorded currents of slow steps such as analyte diffusion and dissolution in a solvent is avoided. To evaluate the performance of this device, it was used as a wall-jet amperometric detector for flow injection analysis of 1-butanethiol vapours, adopted as the model gaseous analyte, present in headspace samples in equilibrium with aqueous solutions at controlled concentrations. With this purpose, the RTIL soaked paper electrochemical detector (RTIL-PED) was assembled by using 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide as the wicking RTIL and printing the working electrode with carbon ink doped with cobalt(II) phthalocyanine, to profit from its ability to electrocatalyze thiol oxidation. The results obtained were quite satisfactory (detection limit: 0.5 mu M; dynamic range: 2-200 mu M, both referring to solution concentrations; correlation coefficient: 0.998; repeatability: +/- 7% RSD; long-term stability: 9%), thus suggesting the possible use of this device for manifold applications.

Novel polymer electrolytes based on gelatin and ionic liquids

This study describes the results of the characterization of polymer electrolytes using gelatin matrix doped with europium triflate and/or different ionic liquids. Samples of solvent-free electrolytes were prepared and characterized by ionic conductivity measurements, thermal analysis, electrochemical stability, X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectroscopy. Electrolyte samples are thermally stable up to approximately 220 degrees C. All the materials synthesized are totally amorphous. The room temperature conductivity maximum of this electrolyte system is based on ionic liquid 1-ethyl-3-methylimidazolium acetate, (C(2)mim)(OAc) (1.18 x 10(-4) S cm(-1) at 30 degrees C). The electrochemical stability domain of all samples is about 2.0 V versus Li/Li+. This new series of materials represents a promising alternative in polymer electrolytes research field. The preliminary studies carried out with electrochromic devices (ECDs) incorporating optimized compositions have confirmed that these materials may perform as satisfactory multifunctional component layers in the field of "smart windows". This new materials, will open a land of promising applications in many areas: optics, energy, medicine for example as membranes and separation devices, ECD-based devices, sensors, etc. (C) 2012 Elsevier B.V. All rights reserved.

The Equilibrium Structure of Lithium Salt Solutions in Ether-Functionalized Ammonium Ionic Liquids

Molecular dynamics simulations have been performed for ionic liquids based on a ternary mixture of lithium and ammonium cations and a common anion, bis(trifluoromethylsulfonyl)imide, [Tf2N](-). We address structural changes resulting from adding Li+ in ionic liquids with increasing length of an ether-functionalized chain in the ammonium cation. The calculation of static structure factors reveals the lithium effect on charge ordering and intermediate range order in comparison with the neat ionic liquids. The charge ordering is modified in the lithium solution because the coordination of [Tf2N](-) toward Li+ is much stronger than ammonium cations. Intermediate range order is observed in neat ionic liquids based on ammonium cations with a long chain, but in the lithium solutions, there is also a nonhomogenous distribution of Li+ cations. The presence of Li+ enhances interactions between the ammonium cations due to correlations between the oxygen atom of the ether chain and the nitrogen atom of another ammonium cation.

Usable work of macro-scale cavities in liquids

It is shown that the generation of cavities in a liquid can produce usable work, which is illustrated by the stretching of a string. This work is done during the expansion of the cavity, and not with its collapse. Basic equations are presented for the movement of a device moved by the so called cavity events. A theoretical solution is also proposed, which uses polynomial functions relating the so called "excess of pressure" in the cavity and time. Evaluations of the force generated during the expansion of the cavity showed a mean peak value of about 58 N for the moving container, while measurements with the container fixed to a support showed a peak value of 476 N, considered somewhat overestimated, because high frequency oscillations seem to superpose the mean behavior. Simultaneous phenomena occurring during the cavity events are also described. Series of pictures of the experiments are presented.