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Ionic liquids (ILs) have been proposed as extractants for separation of metals, including rare earth elements. In particular, protonated betaine bis(trifluoromethylsulfonyl)imide ([HBet][TFSI]) exhibits liquid–liquid phase behavior with water that can be tuned by complexation with various metals. Here we show that previously undetected neutral zwitterionic betaine formed during the IL synthesis can affect the phase behaviour. [ABSTRACT FROM AUTHOR]

Separation of olefins from their paraffin analogs relies on energy‐intensive cryogenic distillation. Facilitated transport‐based membranes that reversibly and selectively bind olefins, but not paraffins, could save considerable amounts of energy. However, the chemical instability of the silver ion olefin‐binding carriers in such membranes has been a longstanding roadblock for this approach. We discovered long‐term carrier stability against extended exposure to hydrogen, a common contaminant in such streams. Based on UV/Vis absorption and Raman spectroscopy, along with XRD analysis results, certain ionic liquids solubilize silver ions, and anion aggregates surrounding the silver ion carriers greatly attenuate their reduction by hydrogen. Here, we report the stability of olefin/paraffin separation properties under continuous exposure to high pressure hydrogen, which addresses a critical technical roadblock in membrane‐based olefin/paraffin separation. [ABSTRACT FROM AUTHOR]

Separation of olefins from their paraffin analogs relies on energy‐intensive cryogenic distillation. Facilitated transport‐based membranes that reversibly and selectively bind olefins, but not paraffins, could save considerable amounts of energy. However, the chemical instability of the silver ion olefin‐binding carriers in such membranes has been a longstanding roadblock for this approach. We discovered long‐term carrier stability against extended exposure to hydrogen, a common contaminant in such streams. Based on UV/Vis absorption and Raman spectroscopy, along with XRD analysis results, certain ionic liquids solubilize silver ions, and anion aggregates surrounding the silver ion carriers greatly attenuate their reduction by hydrogen. Here, we report the stability of olefin/paraffin separation properties under continuous exposure to high pressure hydrogen, which addresses a critical technical roadblock in membrane‐based olefin/paraffin separation. [ABSTRACT FROM AUTHOR]

While phosphonium phosphate ionic liquids (ILs) have been evaluated as additives for engine oils owing to their excellent physico‐chemical properties, miscibility with hydrocarbon fluids, and promising tribological properties, their lubrication mechanism is still not established. Here, atomic force microscopy (AFM) nanotribological experiments are performed using diamond‐like carbon‐coated silicon tips sliding on air‐oxidized steel in neat trihexyltetradecylphosphonium bis(2‐ethylhexyl)phosphate IL. The AFM results indicate a reduction in friction only after the removal of the native oxide layer from steel. Laterally resolved analyses of the steel surface chemistry reveal a higher concentration of bis(2‐ethylhexyl)phosphate ions adsorbed on regions where the native oxide is mechanically removed together with a change in surface electrostatic potential. These surface modifications are proposed to be induced by a change in adsorption configuration of bis(2‐ethylhexyl)phosphate anions on metallic iron compared to their configuration on iron oxide together with a reduction of surface roughness, which lead to the formation of a densely packed, lubricious boundary layer only on metallic iron. [ABSTRACT FROM AUTHOR]

We study ion dissociation in four aqueous 1-alkyl-3-methyl-imidazolium chloride ([amim][Cl]) (where a = alkyl) ionic liquids (ILs) focusing on the effects of microstructure formation. We calculate ion dissociation using precise density, viscosity, and ionic conductivity measurements taken in this work as well as values reported by Rogac et al. (M. Bešter-Rogač, M. V. Fedotova, S.E. Kruchinin, and M. Klähn, Mobility and association of ions in aqueous solutions: The case of imidazolium based ionic liquids, Phys. Chem. Chem. Phys. 18, 28594–28605 (2016); R. Toma, A. Tot, J. Kuhar, and M. Be, Interactions in aqueous solutions of imidazolium chloride ionic liquids [C n mim][Cl] (n=0, 1, 2, 4, 6, 8) from volumetric properties, viscosity B-coefficients and molecular dynamics simulations, 254, 267–271 (2018)) in conjunction with our estimation framework presented previously (O. Nordness, L.D. Simoni, M.A. Stadtherr, and J.F. Brennecke, Characterization of Aqueous 1-Ethyl-3-Methylimidazolium Ionic Liquids for Calculation of Ion Dissociation, J. Phys. Chem. B 123, 1348–1358 (2019); L.D. Simoni, Predictive Modeling of Fluid Phase Equilibria for Systems Containing Ionic Liquids (University of Notre Dame, Notre Dame, IN, 2009)). We first consider ion dissociation at dilute IL concentrations below the critical aggregate concentrations (cac). We introduce a combined Stokes radii term calculated from limiting molar conductivity data, which more accurately estimates ion dissociation in dilute IL systems than radii estimated from a group contribution method. Incorporating the new radii term in the existing model, we study ion dissociation across a wide IL concentration range. Even if prior knowledge of aggregation were not available, as is the case for aqueous [amim][Cl] systems, aggregation is apparent from this analysis because the increased viscous forces of microstructure formation lead to unrealistic estimates of ion dissociation. [ABSTRACT FROM AUTHOR]

A rigorous and generally applicable method for computing solid-liquid coexistence is presented. The method overcomes some of the technical difficulties associated with other solid-liquid simulation procedures and can be implemented within either a molecular dynamics or Monte Carlo framework. The method consists of three steps: First, relative Gibbs free energy curves are created for the solid and liquid phases using histogram reweighting. Next, the free energy difference between the solid and liquid phases is evaluated at a single state point by integrating along a pseudosupercritical transformation path that connects the two phases. Using this result, the solid and liquid free energy curves are referenced to a common point, allowing a single coexistence point to be determined. Finally, Gibbs-Duhem integration is used to determine the full coexistence curve. To evaluate its utility, this method is applied to the Lennard-Jones and NaCl systems. Results for solid-liquid coexistence agree with previous calculations for these systems. In addition, it is shown that the NaCl model does not correctly describe solid-liquid coexistence at high pressures. An analysis of the accuracy of the method indicates that the results are most sensitive to the transformation free energy calculation.© 2005 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Carbon dioxide has been shown to be an effective antisolvent gas for separating organic compounds from ionic liquids (ILs) by inducing a liquid-vapour to liquid-liquid-vapour transition. Using carbon dioxide, toluene can be separated from imidazolium, phosphonium and pyridinum cation-based ILs with the bis(trifluoromethylsulfonyl)imide anion, which is relatively hydrophobic and has a high toluene solubility. A new IL with relatively low viscosity is tested here for the same toluene separation process: 1-n-butylthiolanium bis(trifluoromethylsulfonyl)imide. Carbon dioxide solubility in binary and ternary systems containing toluene and 1-n-butylthiolanium bis(trifluoromethylsulfonyl)imide is measured at 298.15 and 313.15K up to 7.4 MPa. Solubility behaviour in this IL is similar to imidazolium-based ILs with the same anion. However, phase split pressures are lower when 1-n-butylthiolanium bis (trifluoromethylsulfonyl)imide is used instead of 1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide at the same conditions of temperature and initial composition of toluene in the IL. Solubility data are modelled with the conductor-like screening model for real solvents combined with the Soave-Redlich-Kwong equation of state, which provides good qualitative results. [ABSTRACT FROM AUTHOR]

High pressure carbon dioxide was dissolved in ionic liquid + toluene mixtures to obtain the conditions of pressure and composition where a liquid-liquid phase split occurs at constant temperature. Ionic liquids (ILs) with four different cations paired with the bis(trifluoromethylsulfonyl)imide ([Tf2N]−) anion were selected: 1-hexyl-3-methylimidazolium ([hmim]+), 1-hexyl-3-methylpyridinium ([hmpy]+), triethyloctylphosphonium ([P2228]+), and tetradecyltrihexylphosphonium ([P66614]+). The solubility of CO2 was measured in the liquid mixtures at temperatures between 298 and 333 K and at pressures up to 8 MPa, or until the second liquid phase appeared, for initial liquid phase compositions of 0.30, 0.50, and 0.70 mole fraction of IL. Ternary isotherms were compared with the binary solubility of CO2 in each IL and pure toluene. The lowest pressure for separating toluene in a second liquid phase was achieved by decreasing the temperature of the system, increasing the amount of toluene in the initial liquid mixture and using [hmim][Tf2N]. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2968-2976, 2015 [ABSTRACT FROM AUTHOR]

We show that phosphonium azolide ionic liquids of interest for CO2 capture applications react with CO2 both through the normal anion channel and, at elevated temperatures, through a previously unrecognized cation channel. The reaction is caused by an interaction between the anion and cation that allows proton transfer, and involves a phosphonium ylide intermediate. The cation reaction can be mitigated by using ammonium rather than phosphonium cations. Thus, phosphonium and ammonium cations paired with aprotic heterocyclic anions (AHAs) react with CO2 through different mechanisms at elevated temperatures. This work shows that careful consideration of both physical properties and chemical reactivity of ILs based on AHA anions is needed when designing ionic liquids for CO2 separations. [ABSTRACT FROM AUTHOR]

Capture me! The first report of an N‐heterocyclic carbene (NHC) as a solid‐state carbon capture reagent is presented. Experimental and theoretical measurements demonstrate the ability of the NHC to react rapidly and stoichiometrically with CO2 at low partial pressures (see scheme). [ABSTRACT FROM AUTHOR]

Recommendations are given for reporting in the primary scientific literature of measurements involving phase equilibrium. The focus is on documentation issues, and many of the recommendations may also be applied to the more general fields of thermodynamic and transport properties. The historical context of the work and specific plans for implementation of the recommendations are discussed. [ABSTRACT FROM AUTHOR]

Carbon dioxide has received significant attention as a potential environmentally benign medium to replace hazardous organic compounds, but is a relatively poor solvent. The addition of siloxane substituents provides an attractive and inexpensive means to solubilize a wide variety of compounds in CO2. By synthesizing and testing a family of gem-diphosphonate ligands that have been rendered CO2-philic by incorporation of a number of related, discrete dimethylsiloxane oligomers, we show that small variations in substituents have a significant effect on the CO2-philicity of the ligand. To our knowledge, this is the first systematic study of the effect of siloxane substituent size, branching, and position on the affinity of a ligand for CO2. In addition, we present a general approach to the preparation of novel gem-diphosphonate ligands. [ABSTRACT FROM AUTHOR]

Ionic liquids (ILs) have been explored as a surface modification strategy to promote the oxygen reduction reaction (ORR) on Pt/C and their chemical structures were identified to have strong influence on the ORR activities. To better understand the roles of anion and cation of ILs on the catalytic reaction, two cations ([MTBD]+ and [bmim]+) were paired with three anions ([TFSI]−, [beti]−, and [C4F9SO3]−) to form various IL structures. By systematically varying the IL combinations and studying their effects on the electrochemical behaviors, such as electrochemical surface area and specific ORR activities, it was found that cation structure had a higher influence than anion, and the impact of the [MTBD]+ series was stronger than the [bmim]+ series. In addition to the investigation in the half-cell, studies were also extended to the membrane electrode assembly (MEA). Considerable performance enhancements were demonstrated in both the kinetic region and high current density region with the aid of IL. This work suggests that IL modification can provide a complementary approach to improve the performance of proton exchange membrane fuel cells. [ABSTRACT FROM AUTHOR]

Describes the details of the construction of a high-pressure optical cell and flow apparatus for the study of pulse-radiolytically induced reactions in supercritical fluids. Optical cell design; Flow and support apparatus; Pulse radiolysis; Sample preparation; Absorption spectrum observed.

The carboxyl-functionalized phosphonium ionic liquid (IL), [HCTMP][Tf2N], enabled the directed nucleation of monomeric or dimeric uranyl(vi) compounds. This new IL is the first carboxyl-functionalized IL which is liquid at room temperature and exhibits a wider electrochemical window and lower melting point than its ammonium analogue. [ABSTRACT FROM AUTHOR]

Presents research which showed how a fluorinated dendrimer can be used to extract hydrophilic compounds from water into liquid carbon dioxide. Research in September 25, 1997 edition of `Nature'; Expansion of carbon dioxide as a solvent; Carbon dioxide and so-called green chemistry intertwined; Attractions of carbon dioxide; Supercritical fluids allowing single-phase reactions; Solutions to limited-solubility challenge; Extracting metals into carbon dioxide; Industrial applications.