Ionic liquid

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Overview

File:Bmim.svg
A 1-butyl-3-methylimidazolium (BMIM) salt.

An ionic liquid is a liquid that contains essentially only ions. Some ionic liquids, such as ethylammonium nitrate are in a dynamic equilibrium where at any time more than 99.99% of the liquid is made up of ionic rather than molecular species. In the broad sense, the term includes all molten salts, for instance, sodium chloride at temperatures higher than 800 °C. Today, however, the term "ionic liquid" is commonly used for salts whose melting point is relatively low (below 100 °C). In particular, the salts that are liquid at room temperature are called room-temperature ionic liquids, or RTILs. There also exist mixtures of substances which have low melting points, called Deep eutectic solvent, or DES, that have many similarities with ionic liquids.

History

The date of discovery, as well as discoverer, of the "first" ionic liquid is disputed. Ethanolammonium nitrate (m.p. 52-55 °C) was reported in 1888 by Gabriel.[1] However, one of the earlier known truly room temperature ionic liquids was [EtNH3]+ [NO3]- (m.p. 12 °C), the synthesis of which was published in 1914.[2] Much later, series of ionic liquids based on mixtures of 1,3-dialkylimidazolium or 1-alkylpyridinium halides and trihalogenoaluminates, initially developed for use as electrolytes, were to follow.[3][4] An important property of the imidazolium halogenoaluminate salts was that they were tuneable – viscosity, melting point and the acidity of the melt could be adjusted by changing the alkyl substituents and the ratio of imidazolium or pyridinium halide to halogenoaluminate.[5]

A major drawback was their moisture sensitivity and, though to a somewhat lesser extent, their acidity/basicity, the latter which can sometimes be used to an advantage. In 1992, Wilkes and Zawarotko reported the preparation of ionic liquids with alternative, 'neutral', weakly coordinating anions such as hexafluorophosphate ([PF6]-) and tetrafluoroborate ([BF4])-, allowing a much wider range of applications for ionic liquids.[6] It was not until recently that a class of new, air- and moisture stable, neutral ionic liquids, was available that the field attracted significant interest from the wider scientific community.

More recently, people have been moving away from [PF6]- and [BF4]- since they are highly toxic, and towards new anions such as bistriflimide [(CF3SO2)2N]- or even away from halogenated compounds completely. Moves towards less toxic cations have also been growing, with compounds like ammonium salts (such as choline) being just as flexible a scaffold as imidazole.

Characteristics

Ionic liquids are electrically conductive and have extremely low vapor pressure. (Their noticeable odours are likely due to impurities.) Their other properties are diverse. Many have low combustibility, excellent thermal stability, a wide liquid range, and favorable solvating properties for diverse compounds. Many classes of chemical reactions, such as Diels-Alder reactions and Friedel-Crafts reactions, can be performed using ionic liquids as solvents. Recent work has shown that ionic liquids can serve as solvents for biocatalysis [7]. The miscibility of ionic liquids with water or organic solvents varies with sidechain lengths on the cation and with choice of anion. They can be functionalized to act as acids, bases or ligands, and have been used as precursor salts in the preparation of stable carbenes. Because of their distinctive properties, ionic liquids are attracting increasing attention in many fields, including organic chemistry, electrochemistry, catalysis, physical chemistry, and engineering; see for instance magnetic ionic liquid.

Despite their extremely low vapor pressures, some ionic liquids can be distilled under vacuum conditions at temperatures near 300 °C.[8] Some ionic liquids (such as 1-butyl-3-methylimidazolium nitrate) generate flammable gases on thermal decomposition. Thermal stability and melting point depend on the components of the liquid. Thermal stability of various RTILs are available. The thermal stability of a task-specific ionic liquid, protonated betaine bis(trifluoromethanesulfonyl)imide is of about 534 K and N-Butyl-N-Methyl pyrrolidinium bis(trifluoromethanesulfonyl)imide was thermally stable up to 640 K [9]

The solubility of different species in imidazolium ionic liquids depends mainly on polarity and hydrogen bonding ability. Simple aliphatic compounds are generally only sparingly soluble in ionic liquids, whereas olefins show somewhat greater solubility, and aldehydes can be completely miscible. This can be exploited in biphasic catalysis, such as hydrogenation and hydrocarbonylation processes, allowing for relatively easy separation of products and/or unreacted substrate(s). Gas solubility follows the same trend, with carbon dioxide gas showing exceptional solubility in many ionic liquids, carbon monoxide being less soluble in ionic liquids than in many popular organic solvents, and hydrogen being only slightly soluble (similar to the solubility in water) and probably varying relatively little between the more popular ionic liquids. (Different analytical techniques have yielded somewhat different absolute solubility values.)

Room temperature ionic liquids

Room temperature ionic liquids consist of bulky and asymmetric organic cations such as 1-alkyl-3-methylimidazolium, 1-alkylpyridinium, N-methyl-N-alkylpyrrolidinium and ammonium ions. A wide range of anions is employed, from simple halides, which generally inflect high melting points, to inorganic anions such as tetrafluoroborate and hexafluorophosphate and to large organic anions like bistriflimide, triflate or tosylate. There are also many interesting examples of uses of ionic liquids with simple non-halogenated organic anions such as formate, alkylsulfate, alkylphosphate or glycolate. As an example, the melting point of 1-butyl-3-methylimidazolium tetrafluoroborate or [bmim][BF4] with an imidazole skeleton is about -80 °C, and it is a colorless liquid with high viscosity at room temperature.

It has been pointed out that in many synthetic processes using transition metal catalyst, metal nanoparticles play an important role as the actual catalyst or as a catalyst reservoir. It also been shown that ionic liquids (ILs) are an appealing medium for the formation and stabilization of catalytically active transition metal nanoparticles. More importantly, ILs can be made that incorporate co-ordinating groups,[10], for example, with nitrile groups on either the cation or anion (CN-IL). In various C-C coupling reactions catalyzed by palladium catalyst, it has been found the palladium nanoparticles are better stabilized in CN-IL compared to non-functionalized ionic liquids; thus enhanced catalytic activity and recyclability are realized. [11]

Low temperature ionic liquids

Low temperature ionic liquids (below 130 kelvins) have been proposed as the fluid base for an extremely large diameter spinning liquid mirror telescope to be based on the earth's moon.[12] Low temperature is advantageous in imaging long wave infrared light which is the form of light (extremely red-shifted) that arrives from the most distant parts of the visible universe. Such a liquid base would be covered by a thin metallic film that forms the reflective surface. A low volatility is important for use in the vacuum conditions present on the moon.

Food science

Ionic liquids have been used in food science. [bmim]Cl for instance is able to completely dissolve freeze dried banana pulp and the solution with an additional 15% DMSO lends itself to Carbon-13 NMR analysis. In this way the entire banana compositional makeup of starch, sucrose, glucose, and fructose can be monitored as a function of banana ripening.[13]

Applications

Nowadays ionic liquids find a number of industrial applications which vary greatly in character. A few of their industrial applications are briefly described below; more detailed information can be found in a recent review article.[14]

BASIL

The first major industrial application of ILs was the BASIL (Biphasic Acid Scavenging utilizing Ionic Liquids) process by BASF, in which a 1-alkylimidazole was used to scavenge the acid from an existing process. This then results in the formation of an IL which can easily be removed from the reaction mixture.[15] But the easier removal of an unwanted side-product (as an IL rather than as a solid salt) is not the only advantage of the IL based process. By using an IL it was possible to increase the space/time yield of the reaction by a factor of 80,000. It should, however, be kept in mind that improvements of such scale are rare.[citation needed]

Cellulose Processing

Occurring at a volume of some 700 billion tons, cellulose is the earth’s most widespread natural organic chemical and, thus, highly important as a bio-renewable resource. But even out of the 40 billion tons nature renews every year, only approx. 0.2 billion tons are used as feedstock for further processing. A more intensive exploitation of cellulose as a biorenewable feedstock has to date been prevented by the lack of a suitable solvent that can be used in chemical processes. Robin Rogers and co-workers at the University of Alabama have found that by means of ionic liquids, however, real solutions of cellulose can now be produced for the first time at technically useful concentrations [16]. This new technology therefore opens up great potential for cellulose processing.

For example, making cellulosic fibers from so-called dissolving pulp currently involves the use, and subsequent disposal, of great volumes of various chemical auxiliaries, esp. carbon disulfide (CS2). Major volumes of waste water are also produced for process reasons and need to be disposed of. These processes can be greatly simplified by the use of ionic liquids, which serve as solvents and are nearly entirely recycled. The “Institut für Textilchemie und Chemiefasern” (ITCF) in Denkendorf and BASF are jointly investigating the properties of fibers spun from an ionic liquid solution of cellulose in a pilot plant setup. [17]

Eastman chemical’s DHF plant

Eastman operated an ionic liquid-based plant for the synthesis of 2,5-dihydrofuran from 1996 to 2004. However, the plant is now defunct because demand for the product has ceased.[citation needed]

Dimersol - Difasol

The dimersol process is a traditional way to dimerise short chain alkenes into branched alkenes of higher molecular weight. Nobel laureate Yves Chauvin and Hélène Olivier-Bourbigou at IFP (France) have developed an ionic liquid-based add-on to this process called the Difasol process. However, while may be licensed it has as yet not been put into commercial practice.

Petrochina

Petrochina have announced the implementation of an ionic liquid-based process called Ionikylation. This process, the alkylation of C4 olefins with iso-butane, is retrofitted into a 65,000 tonne per year alkylation plant, making it the biggest industrial application of ILs to date.

Degussa paint additives

Ionic liquids can enhance the finish, appearance and drying properties of paints. Degussa are marketing such ILs under the name of TEGO Dispers. These products are also added to the Pliolite paint range.

Air products - ILs as a transport medium for reactive gases

Air products make use of ILs as a medium to transport reactive gases in. Reactive gases such as trifluoroborane, phosphine or arsine, BF3, PH3 or AsH3, respectively, are stored in suitable ILs at sub-ambient pressure. This is a significant improvement over pressurised cylinders. The gases are easily withdrawn from the containers by applying a vacuum.

Linde's IL 'piston'

Whereas Air Product’s Gasguard system relies on the solubility of some gases in ILs, Linde are exploiting other gases’ insolubility in ILs. As mentioned above, the solubility of Hydrogen in ILs is very low. Linde now make use of this insolubility by using a body of ionic liquid to compress Hydrogen in filling stations; and in so doing they reduced the number of moving parts from about 500 in a conventional piston pump engine down to 8.

Nuclear industry

RTILs are extensively explored for various innovative applications in nuclear industry. It includes application of ionic liquid as extractant/diluent in solvent extraction systems, as alternate electrolyte media for the high temperature pyrochemical processing, etc. Fundamental studies on the extraction cum electrodeposition of fission products like uranium, palladium etc., from spent nuclear fuel using RTILs as extractants are reported. Reports on employing using Ionic liquids as non-aquoues electrolyte media for the recovery of uranium [18]and useful fission products like palladium [19] and rhodium [20] from spent nuclear fuel are also available.Studies on the electrochemical behavior of uranium(VI) in ionic liquid, 1-butyl-3-methylimidazolium chloride and also the recovery of valuable fission products from tissue paper waste was studied in room temperature ionic liquids.[21].

Safety

Due to their non-volatility, effectively eliminating a major pathway for environmental release and contamination, ionic liquids have been considered as having a low impact on the environment and human health, and thus recognized as solvents for green chemistry. However, this is distinct from toxicity, and it remains to be seen how 'environmentally-friendly' ILs will be regarded once widely used by industry. Research into IL aquatic toxicity has shown them to be as toxic or more so than many current solvents already in use [22]. A review paper on this aspect has been published in 2007.[23] Available research also shows that mortality isn't necessarily the most important metric for measuring their impacts in aquatic environments, as sub-lethal concentrations have been shown to change organisms' life histories in meaningful ways. According to these researchers balancing between zero VOC emissions, and avoiding spills into waterways (via waste ponds/streams, etc.) should become a top priority. However, with the enormous diversity of substituents available to make useful ILs, it should be possible to design them with useful physical properties and less toxic chemical properties.

With regard to the safe disposal of ionic liquids, a 2007 paper has reported the use of ultrasound to degrade solutions of imidazolium-based ionic liquids with hydrogen peroxide and acetic acid to relatively innocuous compounds.[24]

Despite their low vapor pressure many ionic liquids have also found to be combustible and therefore require careful handling [25]. Brief exposure (5 to 7 seconds) to a flame torch will ignite these IL's and some of them are even completely consumed by combustion.

See also

References

  • F. Endres, S. Zein El Abedin (2006). "Air and water stable ionic liquids in physical chemistry". Phys. Chem. Chem. Phys. 8: 2101. doi:10.1039/b600519p.
  • S. Fujita, H. Kanamaru, H. Senboku and M. Arai (2006). "Preparation of Cyclic Urethanes from Amino Alcohols and Carbon Dioxide Using Ionic Liquid Catalysts with Alkali Metal Promoters" (open access). Int. J. Mol. Sci. 2006 (7): 438–450.
  1. ↑ S. Gabriel, J. Weiner (1888). "Ueber einige Abkömmlinge des Propylamins". Ber. 21 (2): 2669–2679. doi:10.1002/cber.18880210288.
  2. ↑ P. Walden, Bull. Acad. Sci. St. Petersburg 1914, 405-422
  3. ↑ H. L. Chum, V. R. Koch, L. L. Miller, R. A. Osteryoung (1975). "Electrochemical scrutiny of organometallic iron complexes and hexamethylbenzene in a room temperature molten salt". J. Am. Chem. Soc. 97: 3264. doi:10.1021/ja00844a081.
  4. ↑ J. S. Wilkes, J. A. Levisky, R. A. Wilson, C. L. Hussey (1982). "Dialkylimidazolium chloroaluminate melts: a new class of room-temperature ionic liquids for electrochemistry, spectroscopy and synthesis". Inorg. Chem. 21: 1263–1264. doi:10.1021/ic00133a078.
  5. ↑ R. J. Gale, R. A. Osteryoung (1979). "Potentiometric investigation of dialuminum heptachloride formation in aluminum chloride-1-butylpyridinium chloride mixtures". Inorganic Chemistry. 18: 1603. doi:10.1021/ic50196a044.
  6. ↑ J. S. Wilkes, M. J. Zaworotko Chemical Communications 1992, 965-967
  7. ↑ Adam J. Walker and Neil C. Bruce (2004). "Cofactor-dependent enzyme catalysis in functionalized ionic solvents". Chemical Communications. 2004: 2570. doi:10.1039/b410467f.
  8. ↑ Martyn J. Earle, José M.S.S. Esperança, Manuela A. Gilea, José N. Canongia Lopes, Luís P.N. Rebelo, Joseph W. Magee, Kenneth R. Seddon and Jason A. Widegren (2006 volume = 439). "The distillation and volatility of ionic liquids". Nature: 831. doi:10.1038/nature04451. Check date values in: |year= (help)
  9. ↑ Ch.Jagadeeswara Rao, R. Venkata krishnan, K. A. Venkatesan, K. Nagarajan, 332 - 334, Feb. 4-6, Sixteenth national symposium on thermal analysis(Thermans 2008)
  10. ↑ X. Li, D. Zhao, Z. Fei, L. Wang (2006). "Applications of Functionalized Ionic Liquids". Science in China: B. 35: 181. doi:10.1007/s11426-006-2020-y.
  11. ↑ Zhao, D.; Fei, Z.; Geldbach, T. J.; Scopelliti, R.; Dyson, P. J. (2004). "Nitrile-Functionalized Pyridinium Ionic Liquids: Synthesis, Characterization, and Their Application in Carbon-Carbon Coupling Reactions". J. Am. Chem. Soc. 126: 15876. doi:10.1021/ja0463482.
  12. ↑ E. F. Borra, O. Seddiki, R. Angel, D. Eisenstein, P. Hickson, K. R. Seddon and S. P. Worden (2007). "Deposition of metal films on an ionic liquid as a basis for a lunar telescope". Nature. 447 (7147): 979–981. doi:10.1038/nature05909.
  13. ↑ Fort, D.A, Swatloski, R.P., Moyna, P., Rogers, R.D., Moyna, G. Chem. Commun. 2006, 714
  14. ↑ Plechkova, N.V., Seddon, K.R., 2008, Chem. Soc. Rev., 123
  15. ↑ "BASF to present BASIL™ ionic liquid process at technology transfer forum" (Press release). BASF. 2004-05-10.
  16. ↑ Richard P. Swatloski, Scott K. Spear, John D. Holbrey, and Robin D. Rogers (2002). "Dissolution of Cellose with Ionic Liquids". Journal of the American Chemical Society. 124/18: 4974–4975. doi:10.1021/ja025790m.
  17. ↑ Frank Hermanutz, Frank Gähr, Klemens Massonne, Eric Uerdingen, oral presentation at the 45th Chemiefasertagung, Dornbirn, Austria, September 20th – 22nd, 2006
  18. ↑ Electrochemical behavior of uranium(VI) in 1-butyl-3-methylimidazolium chloride and thermal characterization of uranium oxide deposit, Electrochimica Acta, Volume 52, Issue 9, 15 February 2007, Pages 3006-3012, P. Giridhar, K.A. Venkatesan, T.G. Srinivasan and P.R. Vasudeva Rao
  19. ↑ Electrochemical behavior of fission palladium in 1-butyl-3-methylimidazolium chloride Electrochimica Acta, Volume 52, Issue 24, 1 August 2007, Pages 7121-7127, M. Jayakumar, K.A. Venkatesan and T.G. Srinivasan, http://dx.doi.org/10.1016/j.electacta.2007.05.049
  20. ↑ Electrochemical behavior of rhodium(III) in 1-butyl-3-methylimidazolium chloride ionic liquid, Electrochimica Acta, Volume 53, Issue 6, 15 February 2008, Pages 2794-2801 M. Jayakumar, K.A. Venkatesan and T.G. Srinivasan, http://dx.doi.org/10.1016/j.electacta.2007.10.056
  21. ↑ Ch. Jagadeeswara Raoa, K.A. Venkatesana, K. Nagarajana, T.G. Srinivasana and P.R. Vasudeva Rao (2007). "Treatment of tissue paper containing radioactive waste and electrochemical recovery of valuables using ionic liquids". Electrochimica Acta. 53 (4): 1911–1919. doi:10.1016/j.electacta.2007.08.043.
  22. ↑ C Pretti, C Chiappe, D Pieraccini, M Gregori, F Abramo, G Monni and L Intorre (2006). "Acute toxicity of ionic liquids to the zebrafish (Danio rerio)". Green Chem. 8: 238–240. doi:10.1039/b511554j.
  23. ↑ D. Zhao, Y. Liao and Z. Zhang (2007). "Toxicity of Ionic Liquids". CLEAN - Soil, Air, Water. 35 (1): 42–48. doi:10.1002/clen.200600015.
  24. ↑ Xuehui Li, Jinggan Zhao, Qianhe Li, Lefu Wang and Shik Chi Tsang (2007). "Ultrasonic chemical oxidative degradations of 1,3-dialkylimidazolium ionic liquids and their mechanistic elucidations". Dalton Trans.: 1875. doi:10.1039/b618384k.
  25. ↑ Marcin Smiglak, W. Mathew Reichert, John D. Holbrey, John S. Wilkes, Luyi Sun, Joseph S. Thrasher, Kostyantyn Kirichenko, Shailendra Singh, Alan R. Katritzky and Robin D. Rogers (2006). "Combustible ionic liquids by design: is laboratory safety another ionic liquid myth?". Chemical Communications. 2006: 2554–2556. doi:10.1039/b602086k.

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