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This paper studies the wetting properties of seven phosphonium cation-based ionic liquids: trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl) phosphinate [P66614][(iC8)2PO2], trihexyltetradecylphosphonium bis(2-ethylhexyl)phosphate [P66614][BEHP], trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl) imide [P66614][NTf2], tributyltetradecylphosphonium dodecylbenzenesulfonate [P44414][DBS], tributylethylphosphonium diethylphosphate [P4442][DEP], trihexyltetradecylphosphonium dicyanamide [P66614][DCA], and trihexyltetradecylphosphonium chloride [P66614][Cl]. The surface tension was analyzed using the Gibbs free energy in a temperature range of 293-353 K, obtaining the expected linear decrease with temperature rise. The contact angle was measured on four different surfaces (AISI 52100 steel, CrN, TiN, and ZrN) and all liquids with high surface tensions interacting with hydrophobic systems displayed high contact angles as expected. The polarity fraction (PF) and the spreading parameter (SP) were estimated to complete and improve the wetting characterization of these ionic liquids, finding TiN-[P66614][BEHP] and TiN-[P66614][(iC8)2PO2] as the most favorable surface-ionic liquid combinations from a wetting point of view. [ABSTRACT FROM AUTHOR]

Description of the local microscopic structure in ionic liquids (ILs) is a prerequisite to obtain a comprehensive understanding of the influence of the nature of ions on the properties of ILs. The local structure is mainly determined by the spatial arrangement of the nearest neighboring ions. Therefore, the main interaction patterns in ILs, such as cation-anion H-bond-like motifs, cation-cation alkyl tail aggregation, and ring stacking, were considered within the framework of the nearest-neighbor approach with respect to each particular interaction site. We employed classical molecular dynamics (MD) simulations to study in detail the spatial, radial, and orientational relative distribution of ions in a set of imidazolium-based ILs, in which the 1-butyl-3-methylimidazolium (C4mim+) cation is coupled with the acetate (OAc-), chloride (Cl-), tetrafluoroborate (BF4 -), hexafluorophosphate (PF6 -), trifluoromethanesulfonate (TfO-), or bis(trifluoromethanesulfonyl)amide (TFSA-) anion. It was established that several structural properties are strongly anion-specific, while some can be treated as universally applicable to ILs, regardless of the nature of the anion. Namely, strongly basic anions, such as OAc- and Cl-, prefer to be located in the imidazolium ring plane next to the C-H2/4-5 sites. By contrast, the other four bulky and weakly coordinating anions tend to occupy positions above/below the plane. Similarly, the H-bond-like interactions involving the H² site are found to be particularly enhanced in comparison with the ones at H4-5 in the case of asymmetric and/or more basic anions (C4mimOAc, C4mimCl, C4mimTfO, and C4mimTFSA), in accordance with recent spectroscopic and theoretical findings. Other IL-specific details related to the multiple H-bond-like binding and cation stacking issues are also discussed in this paper. The secondary H-bonding of anions with the alkyl hydrogen atoms of cations as well as the cation-cation alkyl chain aggregation turned out to be poorly sensitive to the nature of the anion. [ABSTRACT FROM AUTHOR]

Thermal conductivity is an importantthermophysical propertyof ionic liquids (ILs). In this paper, a database for the thermalconductivity of ILs was established by collecting experimental datafrom literature covering the period from 2007 to 2013, including 359data points, 45 ILs. The influences of temperature and the alkyl chainlength of the cation on thermal conductivity were also discussed.A topological index method was proposed to estimate the thermal conductivityof ILs based on collected data which were divided into training (299data points, 38 ILs) and testing (60 data points, 7 ILs) sets. Thetotal average absolute deviation between the calculated and literaturedata was found to be 2.3%, with 2.1% for the training set and 2.9%for the testing set. The topological index method guarantees satisfactoryprecision with a simple form and can be easily expanded to new kindsof ILs. [ABSTRACT FROM AUTHOR]

Supportedionic liquid membranes (SILMs) are promising tools for the separationof carbon dioxide from other gases. In this paper, new imidazolium,pyrrolidinium, piperidinium, and morpholinium ionic liquids with atriethylene glycol side chain and tosylate anions, as well as theirsymmetrical dicationic analogues, have been synthesized and incorporatedinto SILMs. The selectivities for CO2/N2andCO2/CH4separations have been measured. Theselectivities exhibited by the dicationic ionic liquids are up totwo times higher than the values of the corresponding monocationicionic liquids. Quantum chemical calculations have been used to investigatethe difference in the interaction of carbon dioxide with monocationicand dicationic ionic liquids. The reason for the increased gas separationselectivity of the dicationic ionic liquids is two-fold: (1) a decreasein permeance of nitrogen and methane through the ionic liquid layer,presumably due to their less favorable interactions with the gases,while the permeance of carbon dioxide is reduced much less; (2) anincrease in the number of interaction sites for the interactions withthe quadrupolar carbon dioxide molecules in the dicationic ionic liquids,compared to the monocationic analogues. [ABSTRACT FROM AUTHOR]

Room temperature ionic liquids (ILs) are effective matrices in secondary ion mass spectrometry (SIMS) and matrix assisted laser desorption ionization (MALDI). In this paper, we examine the role of proton transfer in the mechanism of secondary ion enhancement using IL matrices in SIMS. We employ hydrogenated and deuterated 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) as analytes to investigate the origin of proton transfer. The data indicate that protons from the IL anion transfer to the analyte in solution leading to an increase in the secondary ion intensity of the protonated molecular ion. The chemical identity of the matrix cation also affects analyte signal intensities. Using deuterated DPPC we observe that protons (deuterium) from the DPPC tail group react with the cation of the IL liquid leading to an increase in (cation + D) ion intensities. Further, the data suggest that the transfer kinetics of deuterium (hydrogen) is correlated with the secondary ion enhancements observed. The highest secondary ion enhancements are observed for the least sterically hindered cation. Neither the proton affinity nor the pK of the IL cation have a large effect on the analyte ion intensities, suggesting that steric factors are important in determining the efficacy of IL matrices for a given analyte. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]