LEPMI - Saint Martin d'Hères

Some properties are reported for hydrophobic ionic liquids (IL) containing 1-methyl-1-propyl pyrrolidinium [MPPyrro] + , 1-methyl-1-butyl pyrrolidinium [MBPyrro] + , 1-methyl-1-propyl piperidinium [MPPip] + , 1-methyl-1-butyl piperidinium [MBPip] + , 1-methyl-1octylpyrrolidinium [MOPyrro] + and 1-methyl-1-octylpiperidinium [MOPip] + cations. These liquids provide new alternatives to pyridinium and imidazolium ILs. High thermal stability of an ionic liquid increases safety in applications like rechargeable lithium-ion batteries and

In vitro cytotoxicities were measured for ionic liquids (ILs) containing various cations and anions using the MCF7 human breast cancer cell line. We measured the cytotoxicities of ionic liquids containing the cations pyridinium, pyrrolidinium, piperidinium, or imidazolium with various alkyl chain lengths, and the anions bromide, bis(trifluoromethanesulfone)imide (Tf 2 N), trifluoromethylsulfonate (TfO), or nonafluoromethylsulfonate (NfO). Three new hydrophobic, task-specific ionic liquids (TSILs), namely, [MBCNPip] 1 [Tf 2 N] 2 , [MPS 2 Pip] 1 [Tf 2 N] 2 , and [MPS 2 Pyrro] 1 [Tf 2 N] 2 designed for metal-ion extraction were also evaluated. IC 50 values of the ionic liquids toward the MCF7 cells ranged from 8 lM to 44 mM. The toxicity depended significantly on the nature of the cations and anions, especially when the cations contained a long side chain. TSILs studied in this work were less toxic than the classical ILs. # 2008 Wiley Periodicals, Inc. Environ Toxicol 24: 388-395, 2009.

Literature data for the solubility of lithium chloride salts (anhydrous LiCl, LiCl‚H 2 O, LiCl‚2H 2 O, LiCl‚ 3H 2 O, and LiCl‚5H 2 O) in pure water have been compiled and critically evaluated. These data have been represented by empirical temperature-molality expressions from which the coordinates of the eutectics and of the peritectics have been calculated. The thermodynamic properties of the LiCl salts have been calculated from their solubilities in pure water using two different models of aqueous LiCl solutions (Pitzer's ion interaction model and the mean spherical approximation model) which allow the calculation of the activity of water and of the LiCl(aq) activity coefficient to very low temperatures (199 K) and/or very high concentrations (up to 30 M), characteristic of the LiCl + H 2 O system. The water-ice equilibrium constant has been determined to 199 K. Results of the Pitzer-Holmes-Mesmer ion interaction model are reliable only for LiCl molalities below 11 M. At higher molalities (corresponding to the solubilities of LiCl‚2H 2 O(s), of LiCl‚H 2 O(s), and of anhydrous LiCl for temperatures between 273 and 433 K), the mean spherical approximation model has been used. Entropies and standard enthalpies of formation of the various solids have been retrieved from fits of their solubility products with respect to temperature. Our values are in good agreement with the NBS values. There is a linear correlation between the entropies and standard enthalpies of formation and the number of water molecules in the LiCl hydrates, as already reported for MgCl 2 ‚nH 2 O, MgSO 4 ‚nH 2 O, and Na 2 CO 3 ‚nH 2 O.

In this letter, we report for the first time lanthanum electrodeposition in ambient atmosphere using 1octyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquid. This electrolyte exhibits an electrochemical window of 4.8 V with a strong cathodic stability and a low hygroscopic character that allows electrodeposition without the need of an inert atmosphere. A 350 nm thick lanthanum film was obtained after 2 h potentiostatic deposition.

Precise vapor pressure data for pure acetonitrile and (LiBr + acetonitrile) are given for temperatures ranging from T ¼ (298.15 to 343.15) K. The molality range is from m ¼ (0.0579 to 0.8298) mol Á kg À1 . The osmotic coefficients are calculated by taking into account the second virial coefficient of acetonitrile. The parameters of the extended Pitzer ion interaction model of Archer and the mole fractionbased thermodynamic model of Clegg-Pitzer are evaluated. These models accurately reproduce the available osmotic coefficients. The parameters of the extended Pitzer ion interaction model of Archer are used to calculate the mean molal activity coefficients.

The mean spherical approximation is used to describe the vapor pressure over aqueous solutions containing an electrolyte and carbon dioxide. Three electrolytes have been studied: NaOH, NaCl, and acetic acid. A good representation is obtained with a reduced number of parameters as compared to previous models. These parameters account for the concentration and temperature dependence of the solute sizes and the relative permittivity of solution. The numerical values of these physically interpretable parameters are in a reasonable range. Figure 6. Plot of the pressure over aqueous CO2 solutions up to 433 K. Experimental values taken from ref 33. (b): 373.15 K. (1): 393.15 K. (+): 413.15 K. (9): 453.15 K. (×): 473.15 K.

The capability of the MSA-NRTL model to describe heat effects for binary aqueous electrolyte and nonelectrolyte solutions, with a relatively reduced number of parameters, is examined. The thermodynamic properties described include the osmotic coefficient, φ, the apparent relative molar enthalpy, Φ L , and the apparent molar heat capacity, Φ C P . The MSA-NRTL model consists of the mean spherical approximation (MSA) for the long-range electrostatic contribution to the Gibbs energy (for ionic solutions) and a local composition model, the non-random two-liquid (NRTL) model for the short-range contribution.

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Extraction of tetrachloroaurate or tetrabromoaurate anions has been carried out at acidic pHs (1 and 4) with several ionic liquids bearing halide or bis(trifluoromethanesulfonyl)imide NTf 2 − anions and cations 1-octyl-3-methylimidazolium, 1-octylpyridinium or 1-methyl-1-octylpyrrolidinium. The removal of gold anionic moieties from water was first studied by mixing aqueous solutions containing gold complexes and water soluble halide (chloride or bromide) ionic liquids. This lead to the formation of either a solid precipitate or a liquid phase corresponding to a hydrophobic ionic liquid based on a tetrahalogenoaurate anion. Values below 10 −6 for the solubility products of gold-bearing ionic liquids were obtained. Liquidliquid extraction of anionic gold complexes with hydrophobic ionic liquids was also carried out. Gold was successfully extracted from water whatever the pH and the ionic liquid used. Distribution coefficients ranged from 3 × 10 2 to 3 × 10 4 . Investigation on the extraction mechanism revealed an anion exchange between one anionic gold complex and one NTf 2 − anion.

The electrochemistry of AuBr4- complexes extracted into ionic liquids [C8PYR][NTf2] or [C8MIM][NTf2]
saturated with water and gas has been studied by cyclic voltammetry on a glassy carbon macro electrode and by linear voltammetry on a platinum microelectrode. Unlike AuCl4-, the reduction of AuBr4- to Au(0) is achieved following a one reduction step involving three electrons. The deposition of Au(0) from AuBr4- is carried out at a potential above that of water, leading to the simple and easy
deposition of gold and subsequently to the extraction of AuBr4À into an ionic liquid.

Development of a simple route for the catalytic conversion of starch-based industrial waste (potato peels) and potato starch into reducing sugars was investigated in two ionic liquids for comparison -1-allyl-3methylimidazolium chloride [AMIM]Cl and 1-(4-sulfobutyl)-3-methylimidazolium chloride [SBMIM]Cl. Over a two hour period, a 20 wt% solution containing up to 43% and 98% of reducing sugars at low temperature in aqueous [SBMIM]Cl was achieved for the starch-based waste and the potato starch, respectively. In addition, the use of microwave and low frequency ultrasound to perform the depolymerisation of the raw starch-based material was explored and compared with conventional heating processes.