Orientation and mutual location of ions at the surface of ionic liquids
14 Oct 2010-Physical Chemistry Chemical Physics (The Royal Society of Chemistry)-Vol. 12, Iss: 41, pp 13816-13827
TL;DR: The structure of the liquid-vacuum interface in room temperature ionic liquids (ILs) is investigated using angle-resolved X-ray photoelectron spectroscopy (ARXPS) and synchrotron SXPS and it is shown unequivocally that this layer is not due to the presence of impurities.
Abstract: The structure of the liquid–vacuum interface in room temperature ionic liquids (ILs) is investigated using angle-resolved X-ray photoelectron spectroscopy (ARXPS) and synchrotron X-ray photoelectron spectroscopy (SXPS). By varying the polar angle and comparing the results for the chosen ionic liquids, we identify the presence of a surface layer that is chemically different to the bulk. In particular, this layer: (i) is enriched by aliphatic carbon atoms from the saturated carbon chains of the anions and cations, and (ii) contains an unequal distribution of cations and anions in a direction normal to the surface. This unequal distribution creates a potential gradient which extends from the surface into the liquid. We show unequivocally that this layer is not due to the presence of impurities.
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1,656 citations
TL;DR: One of the advantages of RTILs as compared to their high-temperature molten salt (HTMS) “sister-systems” is that the dissolved molecules are not imbedded in a harsh high temperature environment which could be destructive for many classes of fragile (organic) molecules.
Abstract: Until recently, “room-temperature” (<100–150 °C) liquid-state electrochemistry was mostly electrochemistry of diluted electrolytes(1)–(4) where dissolved salt ions were surrounded by a considerable amount of solvent molecules. Highly concentrated liquid electrolytes were mostly considered in the narrow (albeit important) niche of high-temperature electrochemistry of molten inorganic salts(5-9) and in the even narrower niche of “first-generation” room temperature ionic liquids, RTILs (such as chloro-aluminates and alkylammonium nitrates).(10-14) The situation has changed dramatically in the 2000s after the discovery of new moisture- and temperature-stable RTILs.(15, 16) These days, the “later generation” RTILs attracted wide attention within the electrochemical community.(17-31) Indeed, RTILs, as a class of compounds, possess a unique combination of properties (high charge density, electrochemical stability, low/negligible volatility, tunable polarity, etc.) that make them very attractive substances from fundamental and application points of view.(32-38) Most importantly, they can mix with each other in “cocktails” of one’s choice to acquire the desired properties (e.g., wider temperature range of the liquid phase(39, 40)) and can serve as almost “universal” solvents.(37, 41, 42) It is worth noting here one of the advantages of RTILs as compared to their high-temperature molten salt (HTMS)(43) “sister-systems”.(44) In RTILs the dissolved molecules are not imbedded in a harsh high temperature environment which could be destructive for many classes of fragile (organic) molecules.
1,076 citations
TL;DR: This work reviews the available literature of mixtures of ionic liquid mixtures to identify how their properties change and the possibility for their application.
Abstract: Simple ionic liquids have long been held to be designer solvents, based upon the ability to independently vary their cations and anions. The formation of mixtures of ionic liquids increases this synthetic flexibility. We review the available literature of these ionic liquid mixtures to identify how their properties change and the possibility for their application.
504 citations
TL;DR: This critical review analyses most of the surface tension data reported between 2001 and 2010 (187 references) and concludes that ionic liquids present characteristic surface behavior and distinctive trends of their surface tension versus temperature.
Abstract: Some of the most active scientific research fronts of the past decade are centered on ionic liquids These fluids present characteristic surface behavior and distinctive trends of their surface tension versus temperature One way to explore and understand their unique nature is to study their surface properties This critical review analyses most of the surface tension data reported between 2001 and 2010 (187 references)
360 citations
TL;DR: The results indicate that ionic liquids screen charged surfaces through the formation of both bound (Stern) and diffuse electric double layers, where the diffuse double layer is comprised of effectively dissociated ionic liquid ions.
Abstract: We combine direct surface force measurements with thermodynamic arguments to demonstrate that pure ionic liquids are expected to behave as dilute weak electrolyte solutions, with typical effective dissociated ion concentrations of less than 0.1% at room temperature. We performed equilibrium force–distance measurements across the common ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]) using a surface forces apparatus with in situ electrochemical control and quantitatively modeled these measurements using the van der Waals and electrostatic double-layer forces of the Derjaguin–Landau–Verwey–Overbeek theory with an additive repulsive steric (entropic) ion–surface binding force. Our results indicate that ionic liquids screen charged surfaces through the formation of both bound (Stern) and diffuse electric double layers, where the diffuse double layer is comprised of effectively dissociated ionic liquid ions. Additionally, we used the energetics of thermally dissociating ions in a dielectric medium to quantitatively predict the equilibrium for the effective dissociation reaction of [C4mim][NTf2] ions, in excellent agreement with the measured Debye length. Our results clearly demonstrate that, outside of the bound double layer, most of the ions in [C4mim][NTf2] are not effectively dissociated and thus do not contribute to electrostatic screening. We also provide a general, molecular-scale framework for designing ionic liquids with significantly increased dissociated charge densities via judiciously balancing ion pair interactions with bulk dielectric properties. Our results clear up several inconsistencies that have hampered scientific progress in this important area and guide the rational design of unique, high–free-ion density ionic liquids and ionic liquid blends.
356 citations
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...These observations are consistent with studies of ionic liquids at the free vacuum interface, where the size, polarity, and shape asymmetry of ionic liquid cations and anions are shown to differently impact their structuring at the free vacuum interface, with ionic liquids forming increasingly charge-separated electric double layers at the ionic liquid–vacuum interface as the degree of cation–anion asymmetry is increased (33, 34)....
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TL;DR: In this paper, a compilation of all published measurements of electron inelastic mean free path lengths in solids for energies in the range 0-10 000 eV above the Fermi level is presented.
Abstract: A compilation is presented of all published measurements of electron inelastic mean free path lengths in solids for energies in the range 0–10 000 eV above the Fermi level. For analysis, the materials are grouped under one of the headings: element, inorganic compound, organic compound and adsorbed gas, with the path lengths each time expressed in nanometers, monolayers and milligrams per square metre. The path lengths are vary high at low energies, fall to 0.1–0.8 nm for energies in the range 30–100 eV and then rise again as the energy increases further. For elements and inorganic compounds the scatter about a ‘universal curve’ is least when the path lengths are expressed in monolayers, λm. Analysis of the inter-element and inter-compound effects shows that λm is related to atom size and the most accuratae relations are λm = 538E−2+0.41(aE)1/2 for elements and λm=2170E−2+0.72(aE)1/2 for inorganic compounds, where a is the monolayer thickness (nm) and E is the electron energy above the Fermi level in eV. For organic compounds λd=49E−2+0.11E1/2 mgm−2. Published general theoretical predictions for λ, valid above 150 eV, do not show as good correlations with the experimental data as the above relations.
4,486 citations
TL;DR: The first systematic study of the effect of impurities and additives (e.g., water, chloride, and cosolvents) on the physical properties of room-temperature ionic liquids was performed in this article.
Abstract: We report here the first systematic study of the effect of impurities and additives (e.g., water, chloride, and cosolvents) on the physical properties of room-temperature ionic liquids. Remarkably, it was discovered that the viscosity of mixtures was dependent mainly on the mole fraction of added molecular solvents and only to a lesser extent upon their iden- tity, allowing viscosity changes during the course of a reaction to be entirely predictable. While the addition of such molecular solvents decreases the viscosity and density, chloride impurities, arising from the preparation of the ionic liquids, increase viscosity dramatically. The commonly used methods of preparation were validated with respect to chloride impurity.
2,105 citations
TL;DR: As the length of the alkyl chain increases, the nonpolar domains become larger and more connected and cause swelling of the ionic network, in a manner analogous to systems exhibiting microphase separation.
Abstract: Nanometer-scale structuring in room-temperature ionic liquids is observed using molecular simulation. The ionic liquids studied belong to the 1-alkyl-3-methylimidazolium family with hexafluorophosphate or with bis(trifluoromethanesulfonyl)amide as the anions, [Cnmim][PF6] or [Cnmim][(CF3SO2)2N], respectively. They were represented, for the first time in a simulation study focusing on long-range structures, by an all-atom force field of the AMBER/OPLS_AA family containing parameters developed specifically for these compounds. For ionic liquids with alkyl side chains longer than or equal to C4, aggregation of the alkyl chains in nonpolar domains is observed. These domains permeate a tridimensional network of ionic channels formed by anions and by the imidazolium rings of the cations. The nanostructures can be visualized in a conspicuous way simply by color coding the two types of domains (in this work, we chose red = polar and green = nonpolar). As the length of the alkyl chain increases, the nonpolar domai...
1,668 citations