Ionic liquid analogues formed from hydrated metal salts

A dark green, viscous liquid can be formed by mixing choline chloride with chromium(III) chloride hexahydrate and the physical properties are characteristic of an ionic liquid. The eutectic composition is found to be 1:2 choline chloride/chromium chloride. The viscosity and conductivity are measured as a function of temperature and composition and explained in terms of the ion size and liquid void volume. The electrochemical response of the ionic liquid is also characterised and it is shown that chromium can be electrodeposited efficiently to yield a crack-free deposit. This approach could circumvent the use of chromic acid for chromium electroplating, which would be a major environmental benefit. This method of using hydrated metal salts to form ionic liquids is shown to be valid for a variety of other salt mixtures with choline chloride.     

Application of ionic liquids to the electrodeposition of metals

The electrodeposition of most of technologically important metals has been shown to be possible from a wide range of room temperature molten salts, more commonly known today as 'ionic liquids'. These liquids are currently under intense scrutiny for a wide variety of applications some of which have already been commercialized. Despite the fact that electrodeposition was the first application studied in these liquids no metal deposition processes have as yet been developed to an industrial scale. This review addresses the practical and theoretical aspects that need to be considered when choosing ionic liquids for metal deposition. It details the current understanding of the physical and chemical properties of these interesting fluids and highlights the areas that need to be considered to develop practical electroplating systems. The effect of composition and temperature on viscosity and conductivity are discussed together with the fundamental approaches required to synthesise new liquids.     

The effect of the anion on the physical properties of trihalide-based N,N-dialkylimidazolium ionic liquids

Low viscosity, high density trihalide-based 1-n-butyl-3-methylimidazolium ionic liquids have been prepared and characterised. Key physical properties (density, conductivity, melting point, refractive index, surface tension and diffusion coefficient) of the ionic liquids have been determined and are compared with those of other 1,3-dialkylimidazolium molten salts. The relationship between anion identity and the physical properties of the ionic liquids under investigation is discussed.     

Eutectic-based ionic liquids with metal-containing anions and cations

Eutectic mixtures of zinc chloride and donor molecules such as urea and acetamide are described and it is proposed that these constitute a new class of ionic liquids. FAB-MS analysis shows that the liquids are made up of metal-containing anions and cations in which the donor is coordinated to the cation. Data on the viscosity, conductivity, density, phase behaviour and surface tension are presented and these are shown to be significantly different to other related ionic liquids that incorporate quaternary ammonium salts. The conductivity and viscosity are comparable with other ionic liquids and the data fit well to the Hole theory model recently proposed.     

Density, viscosity and electrical conductivity of protic alkanolammonium ionic liquids

Ionic liquids are molten salts with melting temperatures below the boiling point of water, and their qualification for applications in potential industrial processes does depend on their fundamental physical properties such as density, viscosity and electrical conductivity. This study aims to investigate the structure-property relationship of 15 ILs that are primarily composed of alkanolammonium cations and organic acid anions. The influence of both the nature and number of alkanol substituents on the cation and the nature of the anion on the densities, viscosities and electrical conductivities at ambient and elevated temperatures are discussed. Walden rule plots are used to estimate the ionic nature of these ionic liquids, and comparison with other studies reveals that most of the investigated ionic liquids show Walden rule values similar to many non-protic ionic liquids containing imidazolium, pyrrolidinium, tetraalkylammonium, or tetraalkylphosphonium cations. Comparison of literature data reveals major disagreements in the reported properties for the investigated ionic liquids. A detailed analysis of the reported experimental procedures suggests that inappropriate drying methods can account for some of the discrepancies. Furthermore, an example for the improved presentation of experimental data in scientific literature is presented.     

New ionic liquids with tris(perfluoroalkyl)trifluorophosphate (FAP) anions

The synthesis of new ionic liquids with tris(perfluoroalkyl)trifluorophosphate (FAP) anions is described. The physico-chemical properties (conductivity, viscosity, electrochemical and thermal stability) of this new generation of ionic liquids (molten salts) are discussed. FAP-ionic liquids show an excellent hydrolytic stability, low viscosity and high electrochemical and thermal stability that makes them attractive for use in electrochemical devices and as a new media for application in modern technologies and chemical synthesis.     

锕系元素在熔盐体系中的电化学及萃取特性研究进展

熔融盐是一类非水溶剂,分为高温熔盐、室温熔盐和低温熔盐。 作为反应介质和电解介质,因其优良性能,可以溶解很多难溶于水的活泼金属。 近年来,该领域的研究热点是将熔盐作为干法后处理的电解质分离和回收锕系元素。 本文综述了锕系元素在高温熔盐中的电化学行为、热力学等物理特性,介绍了近几年室温离子液体(RTILs)的研究进展及锕系元素在RTILs中萃取特性的最新研究成果,展望了熔盐体系未来的研究方向。     

Ionic Liquids Made with Dimethyl Carbonate: Solvents as well as Boosted Basic Catalysts for the Michael Reaction

This article describes 1) a methodology for the green synthesis of a class of methylammonium and methylphosphonium ionic liquids (ILs), 2) how to tune their acid–base properties by anion exchange, 3) complete neat‐phase NMR spectroscopic characterisation of these materials and 4) their application as active organocatalysts for base‐promoted carbon–carbon bond‐forming reactions. Methylation of tertiary amines or phosphines with dimethyl carbonate leads to the formation of the halogen‐free methyl‐onium methyl carbonate salts, and these can be easily anion‐exchanged to yield a range of derivatives with different melting points, solubility, acid–base properties, stability and viscosity. Treatment with water, in particular, yields bicarbonate‐exchanged liquid onium salts. These proved strongly basic, enough to efficiently catalyse the Michael reaction; experiments suggest that in these systems the bicarbonate basicity is boosted by two orders of magnitude with respect to inorganic bicarbonate salts. These basic ionic liquids used in catalytic amounts are better even than traditional strong organic bases. The present work also introduces neat NMR spectroscopy of the ionic liquids as a probe for solute–solvent interactions as well as a tool for characterisation. Our studies show that high catalytic efficacy of functional ionic liquids can be achieved by integrating their green synthesis, along with a fine‐tuning of their structure. Demonstrating that ionic liquid solvents can be made by a truly green procedure, and that their properties and reactivity can be tailored to the point of bridging the gap between their use as solvents and as catalysts.     

Protic ionic liquids: solvents with tunable phase behavior and physicochemical properties

The phase behavior, including glass, devitrification, solid crystal melting, and liquid boiling transitions, and physicochemical properties, including density, refractive index, viscosity, conductivity, and air-liquid surface tension, of a series of 25 protic ionic liquids and protic fused salts are presented along with structure-property comparisons. The protic fused salts were mostly liquid at room temperature, and many exhibited a glass transition occurring at low temperatures between -114 and -44 degrees C, and high fragility, with many having low viscosities, down to as low as 17 mPa.s at 25 degrees C, and ionic conductivities up to 43.8 S/cm at 25 degrees C. These protic solvents are easily prepared through the stoichiometric combination of a primary amine and Br?nsted acid. They have poor ionic behavior when compared to the far more studied aprotic ionic liquids. However, some of the other physicochemical properties possessed by these solvents are highly promising and it is anticipated that these, or analogous protic solvents, will find applications beyond those already identified for aprotic ionic liquids. This series of protic fused salts was employed to determine the effect of structural changes on the physicochemical properties, including the effect of hydroxyl groups, increasing alkyl chain lengths, branching, and the differences between inorganic and organic anions. It was found that simple structural modifications provide a mechanism to manipulate, over a wide range, the temperature at which phase transitions occur and to specifically tailor physicochemical properties for potential end-use applications.     

Novel halogen-free chelated orthoborate-phosphonium ionic liquids: synthesis and tribophysical properties

We report on the synthesis, characterisation, and physical and tribological properties of halogen-free ionic liquids based on various chelated orthoborate anions with different phosphonium cations, both without halogen atoms in their structure. Important physical properties of the ILs including glass transition temperatures, density, viscosity and ionic conductivity were measured and are reported here. All of these new halogen-free orthoborate ionic liquids (hf-BILs) are hydrophobic and hydrolytically stable liquids at room temperature. As lubricants, these hf-BILs exhibit considerably better antiwear and friction reducing properties under boundary lubrication conditions for steel-aluminium contacts as compared with fully formulated (15W-50 grade) engine oil. Being halogen free these hf-BILs offer a more environmentally benign alternative to ILs being currently developed for lubricant applications.     

Synthesis and characterization of new pyrrolidinium based protic ionic liquids. Good and superionic liquids

New pyrrolidinium-cation-based protic acid ionic liquids (PILs) were prepared through a simple and atom-economic neutralization reactions between pyrrolidine and Br?nsted acids, HX, where X is NO 3 (-), HSO 4 (-), HCOO (-), CH 3COO (-) or CF 3COO (-) and CH 3(CH 2) 6COO (-). The thermal properties, densities, electrochemical windows, temperature dependency of dynamic viscosity and ionic conductivity were measured for these PILs. All protonated pyrrolidinium salts studied here were liquid at room temperature and possess a high ionic conductivity (up to 56 mS cm (-1)) at room temperature. Pyrrolidinium based PILs have a relatively low cost, a low toxicity and exhibit a large electrochemical window as compared to other protic ionic liquids (up 3 V). Obtained results allow us to classify them according to a classical Walden diagram and to determinate their "Fragility". Pyrrolidinium based PILs are good or superionic liquids and shows extremely fragility. They have wide applicable perspectives for fuel cell devices, thermal transfer fluids, and acid-catalyzed reaction media as replacements of conventional inorganic acids.     

Cyclic quaternary ammonium ionic liquids with perfluoroalkyltrifluoroborates: synthesis, characterization, and properties

New cyclic quaternary ammonium salts, composed of N-alkyl(alkyl ether)-N-methylpyrrolidinium, -oxazolidinium, -piperidinium, or -morpholinium cations (alkyl = nC4H9, alkyl ether = CH3OCH2, CH3OCH2CH2) and a perfluoroalkyltrifluoroborate anion ([R(F)BF3]-, R(F) = CF3, C2F5, nC3F7, nC4F9), were synthesized and characterized. Most of these salts are liquids at room temperature. The key properties of these salts--phase transitions, thermal stability, density, viscosity, conductivity, and electrochemical windows--were measured and compared to those of their corresponding [BF4]- and [(CF3SO2)2N]- salts. The structural effect on all the above properties was intensively studied in terms of the identity of the cation and anion, variation of the side chain in the cation (i.e., alkyl versus alkyl ether), and change in the length of the perfluoroalkyl group (R(F)) in the [R(F)BF3]- ion. The reduction of Li+ ions and reoxidation of Li metal took place in pure N-butyl-N-methylpyrrolidinium pentafluoroethyltrifluoroborate as the supporting electrolyte. Such comprehensive studies enhance the knowledge necessary to design and optimize ionic liquids for many applications, including electrolytes. Some of these new salts show desirable properties, including low melting points, high thermal stabilities, low viscosities, high conductivities, and wide electrochemical windows, and may thus be potential candidates for use as electrolytes in high-energy storage devices. In addition, many salts are ionic plastic crystals.     

Ionische Flüssigkeiten: Innovative Lösungsmittel für die Zweiphasenkatalyse

Ionic liquids are low melting salts which represent a new class of non-molecular, ionic solvents. By combining different cations and anions a large number of liquids with very different physical and chemical properties can be obtained. It is possible to optimize the ionic medium for a specific application by the careful choice of the ion combination. Ionic liquids are interesting substitutes for organic solvent in catalytic reactions for many reasons: Besides their non-volatile nature offering significant engineering advantages, the unusual solubility properties of these liquids enable new multiphasic catalytic reactions.     

Choline-derivative-based ionic liquids

A total of sixty-three choline derivative-based ionic liquids in the forms of chlorides, acesulfamates, and bis(trifluoromethylsulfonyl)imides have been prepared and their physical properties (density, viscosity, solubility, and thermal stability) have been determined. Thirteen of these salts are known chlorides: precursors to the 26 water-soluble acesulfamates, 12 acesulfamates only partially miscible with water, and 12 water-insoluble imides. The crystal structures for two of the chloride salts-(2-hydroxyethyl)dimethylundecyloxymethylammonium chloride and cyclododecyloxymethyl(2-hydroxyethyl)dimethylammonium chloride-were determined. The antimicrobial (cocci, rods, and fungi) activities of the new hydrophilic acesulfamate-based ILs were measured and 12 were found to be active. The alkoxymethyl(2-hydroxyethyl)dimethylammonium acesulfamates have been shown to be insect feeding deterrents and thus open up a new generation of synthetic deterrents based on ionic liquids. The alkoxymethyl(2-decanoyloxyethyl)dimethylammonium bis(trifluoromethylsulfonyl)imides have also been shown to act as fixatives for soft tissues and can furthermore be used as substitutes for formalin and also preservatives for blood.     

Ionic liquids based upon metal halide/substituted quaternary ammonium salt mixtures

The synthesis of ionic liquids based upon functionalized quaternary ammonium salts and metal salts of zinc, tin, or iron is demonstrated. The freezing point of these ionic liquids was studied as a function of the quaternary ammonium cation. The complex anions were identified and quantified using mass spectrometry and potentiometry. It is shown that the primary zinc anion is Zn(2)Cl(5)(-) with Zn(3)Cl(7)(-) becoming more abundant in more Lewis basic solutions. Similar results were observed for ionic liquids containing SnCl(2). The surface tension was also measured and was used to explain the high viscosity of the ionic liquids in terms of the large ion:hole size ratio and the small probability of finding a hole of suitable dimensions adjacent to a given ion to permit movement. The phase behavior of a variety of quaternary ammonium halides/ZnCl(2) mixtures is characterized and it is shown that the depression of freezing point is related to the increase in size of the component ions.     

Synthesis and properties of chiral ammonium-based ionic liquids

New chiral ammonium-based ionic liquids containing the (1R,2S,5R)-(-)-menthyl group can be easily and efficiently prepared under ambient conditions. The preparation and characterization of trialkyl[(1R,2S,5R)-(-)-menthoxymethyl]ammonium salts is reported. The salts have been demonstrated to be air- and moisture-stable under ambient conditions and can be readily used in a variety of standard experimental procedures. The single-crystal X-ray structure of butyldimethyl[(1R,2S,5R)-(-)-menthoxymethyl]ammonium chloride has been determined. The chiral, room-temperature ionic liquids have been characterized by physical properties such as specific rotation, density, viscosity, thermal degradation, and glass transition temperature. Trialkyl[(1R,2S,5R)-(-)-menthoxymethyl]ammonium chloride prototype ionic liquids have also been found to exhibit strong antimicrobial and high antielectrostatic activities.     

Towards large-scale, fully ab initio calculations of ionic liquids

Ionic liquids have attracted a substantial amount of interest as replacement of traditional electrolytes in high efficiency electrochemical devices for generation and storage of energy due to their superior physical and chemical properties, especially low volatility and high electrochemical stability. For enhanced performance of the electrochemical devices ionic liquids are required to be highly conductive and low viscous. Long-range Coulomb and short-range dispersion interactions between ions affect physical and chemical properties of ionic liquids in a very complex way, thus preventing direct correlations to the chemical structure. Considering a vast combination of available cations and anions that can be used to synthesize ionic liquids, development of predictive theoretical approaches that allow for accurate tailoring of their physical properties has become crucial to further enhance the performance of electrochemical devices such as lithium batteries, fuel and solar cells. This perspective article gives a thorough overview of current theoretical approaches applied for studying thermodynamic (melting point and enthalpy of vapourisation) and transport (conductivity and viscosity) properties of ionic liquids, emphasizing their reliability and limitations. Strategies for improving predictive power and versatility of existing theoretical approaches are also outlined.     

Ionic-Liquid-Based Nanofluids and Their Heat-Transfer Applications: A Comprehensive Review

Due to the improved thermophysical characteristics of ionic liquids (ILs), such as their strong ionic conductivity, negligible vapor pressure, and thermal stability at high temperatures, they are being looked at viable contender for future heat transfer fluids. Additionally, the dispersing nanoparticles can further improve the thermophysical characteristics and thermal performance of ionic liquids, which is one of the emerging research interests to increase the heat transfer rates of the thermal devices. The latest investigations about the utilization of ionic liquid nanofluids as a heat transfer fluid is summarized in this work. These summaries are broken down into three types: (a) the thermophysical parameters including thermal conductivity, viscosity, density, and specific heat of ionic liquids (base fluids), (b) the thermophysical properties like thermal conductivity, viscosity, density, and viscosity of ionic liquids based nanofluids (IL nanofluids), and (iii) utilization of IL nanofluids as a heat transfer fluid in the thermal devices. The techniques for measuring the thermophysical characteristics and the synthesis of IL nanofluids are also covered. The suggestions for potential future research directions for IL nanofluids are summarized.     

Density scaling of the transport properties of molecular and ionic liquids

Casalini and Roland [Phys. Rev. E 69, 062501 (2004); J. Non-Cryst. Solids 353, 3936 (2007)] and other authors have found that both the dielectric relaxation times and the viscosity, η, of liquids can be expressed solely as functions of the group (TV?(γ)), where T is the temperature, V is the molar volume, and γ a state-independent scaling exponent. Here we report scaling exponents γ, for the viscosities of 46 compounds, including 11 ionic liquids. A generalization of this thermodynamic scaling to other transport properties, namely, the self-diffusion coefficients for ionic and molecular liquids and the electrical conductivity for ionic liquids is examined. Scaling exponents, γ, for the electrical conductivities of six ionic liquids for which viscosity data are available, are found to be quite close to those obtained from viscosities. Using the scaling exponents obtained from viscosities it was possible to correlate molar conductivity over broad ranges of temperature and pressure. However, application of the same procedures to the self-diffusion coefficients, D, of six ionic and 13 molecular liquids leads to superpositioning of poorer quality, as the scaling yields different exponents from those obtained with viscosities and, in the case of the ionic liquids, slightly different values for the anion and the cation. This situation can be improved by using the ratio (D∕T), consistent with the Stokes-Einstein relation, yielding γ values closer to those of viscosity.