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Home , Ionic liquid

What’s an Ionic ?

by Keith E. Johnson “When I use a word,” Humpty Dumpty said, in rather a scornful tone, “it means just what I choose it to mean – neither more nor less.” “The question is,” said Alice, “whether you can make words mean so many different things.” Lewis Carroll, Through the Looking

Introduction to the Phrase “Ionic ” scheduling of groups of papers. One property that we emphasized EUCHEM 2006 dealt with Molten recently is the molarity of the liquid6 he Structure and Properties Salts and Ionic Liquids with the (a straightforward quantity except of Ionic Melts” was the content of each session usually for mixed systems such as a basic Ttitle of a Faraday Society mixed. chloroaluminate containing both Cl- “ - Discussion held in Liverpool in 1961; and AlCl4 in significant amounts). it dealt exclusively with molten Modern Ionic Liquids The molarity is important regarding inorganic salts.1 “Ionic Liquids” kinetic measurements, including was the title of Chapter 6 of the The properties of a modern conductivities. textbook Modern Electrochemistry ionic liquid are summarized in Table II indicates a range of by Bockris and Reddy, published in Table I. Particularly significant molarities of many liquids from 1 1970: it discussed liquids ranging are (i.) the low vapor pressures to 60, with at 55, liquid alkali from alkali silicates and halides to in most instances which contrast halides up to 35 (LiCl) and most tetraalkylammonium salts.2 The the environmental problems of organic salts less than 10. Specific modern era of ionic liquids stems volatile organic and (ii.) conductivities span a far greater range from the work on alkylpyridinium moderate specific conductivities, from the metal through and dialkylimidazolium salts in usually in the same range as molten inorganic salts in the Scm-1 region to organic salts (the modern ionic liquids) and aqueous solutions Table I. Modern ionic liquids. in the mScm-1 region and finally A Cation and or anion quite large to the near non-conducting but ionizing acetic and water at Freezing point Preferably below 100°C µScm-1. Combining these data into molar conductances is illuminating. Liquidus range Often > 200°C We see comparable values for simple Thermal stability Usually high inorganic salts alone and in aqueous solutions* but much smaller values Normally < 100 cP, workable for the low temperature semi-organic Dielectric constant Implied < 30 and organic systems. Thus these modern ionic liquids must consist of Polarity Moderate AND PAIRS, (undissociated ), while liquid alkali halides Specific conductivity Usually < 10 mScm-1, “Good” are purely IONIC and aqueous Molar conductivity < 10 Scm2 mol-1 electrolytes behave as a mixture of hydrated ions and the molecular Electrochemical window > 2V, even 4.5 V, except for Brønsted acidic systems water. Figure 1 attempts to Solvent and/or catalyst Excellent for many organic reactions picture these differences.

Vapor pressure Usually negligible Acid- Properties and Water Interactions

3 Colorado in the late 1970s. The term those of aqueous . It is While simple salts such as KCl can 4 ionic liquids was introduced to cover found that many such systems are be thought of as the product of an systems below 100°C, one reason excellent solvents or catalysts for electron transfer between elements, being to avoid the words “molten organic reactions3 and some simple organic salts can be traced to a salts” in phrases such as “ambient processes such as electrodeposition.5 transfer between an acid and base. temperature molten salts,” another Unfortunately, one finds reports of Cations such as emim+ and n-bupy+ to create an impression of freshness new “ionic liquids” without data on result from the of the bases and a third, perhaps, for patent conductivities, which would establish purposes. The first “Conference on that they are dissociated to some Ionic Liquids” took place in Salzburg extent at least into ions. in 2005, Molten Salts 7 in Toulouse in 2005 had one of ten sessions Liquids Comparisons * Extrapolation of aqueous solution devoted to Ionic Liquids; but the molar or equivalent conductances to International Symposia on Molten How do these ionic liquids infinite dilution, at which ion pairing is Salts of ECS from 1976 to the present eliminated, gives many values in the 100 compare with other liquids, especially to 150 Scm2 mol-1 range,11 the exceptions have not shown discrimination on those which conduct electricity? Table involving H+ and OH- for which the the basis of temperature, beyond II presents some illustrative data. Grotthus mechanism operates.2

38 The Electrochemical Society Interface • Spring 2007 Table II. Properties of various liquids.

Table II. Properties of various liquids.

Compound Temp. Molarity Spec Cond Molar Cond Visc. Ref. °C Mol L-1 Scm-1 Scm2 mol-1 cP Ionic Liquids

NaCl 900 25.3 3.88 154 1.05 2 LiCl 780 35 7.59 217 2

NaNO3 450 21.4 0.72 34 6.9 2

Na2SiO3 1750 ~ 18 4.8 ~270 2

AlCl3 (63%) – NaCl 175 5.8 0.24 41 3.85 7 LiCl-KCl 450 29.7 1.57 53 2.44 7

[(CH3)3S][ HBr2] 25 7.3 0.034 4.7 20.5 8

emimCl(60%)-AlCl3 25 5.3 0.0065 1.2 47 8

emim Al2Cl7 25 3.4 0.015 4.4 14 8

bmim CF3CO2 20 5.1 0.0032 0.6 73 8

bupy BF4 25 5.5 0.0019 0.3 103 8

emim[(CF3SO2)2N] 25 3.7 0.0057 1.5 31 8

Others

a -8 -7 H2O 25 55.3 4 x 10 7 x 10 0.895 2 0.1 M aq. KCl 25 0.1b 0.013 129 0.9 2 Na 100 40.4 1.04 x 105 2.6 x 106 1.058 2 b H2SO4 25 0.049 0.0104 212 24.55 9 a -9 -7 CH3COOH 25 17.5 8 x 10 4.6 x 10 1.056 10 HF 0 50.1a 1 x 10-6 2 x 10-5 0.256 9 a = total molarity • b = ionic molarity • emim = 1-ethyl-3-methyl-1H-imidazolium • a = bmimtotal molarity = 1-butyl-3-methyl-1 • b = ionic molarityH-imidazolium • emim •= bupy1-ethyl-3-methyl-1H-imidazolium = 1-butylpyridinium • bmim = 1-butyl-3-methyl-1H-imidazolium • bupy = 1-butylpyridinium

+ + - Hmim and py . Anions such as NO3 , liquids related to proton chemistry What happens when water is - - AlCl4 and PF6 derive from Lewis acid in water? added to an ionic liquid or not – base reactions: First, acidic in ionic completely removed at some stage in liquids often occur as anions, e.g., its preparation? 2- - - O + N O t 2NO - - - - 2 5 3 HCl2 , HBr2 , H2Br3 , rather than 1. Some anions such as AlCl - - - 4 Cl + AlCl3 t AlCl4 cations. Second, protons bonded and HCl - are irreversibly - - - 2 F + PF5 t PF6 ­ to bases such as and l- decomposed. methylimidazole are not labile.13 Do 2. Water may bind strongly to one It is also possible for Lewis neutral these bases behave in line with their of the ions. ions to add further Lewis to form pkb’s in water? No. Bases in ionic 3. Water may dissolve the liquid - - - acidic ions, e.g., Al2Cl7 , Sb2F11 , HBr2 . liquids appear to act in accordance until it forms a saturated salt As a result we can obtain Lewis with their gas phase proton affinities solution; unlike the case of basic, neutral or acidic ionic liquids, (l-methylimidazole > pyridine > dissolving a solid salt, the other exemplified by the well-researched ammonia).14 The complicating factor phase will be liquid and it may haloaluminates. In addition we can of course is in water. One or may not contain water. make protic acidic liquids which are can, however, obtain Hammett 4. At high temperatures, species 12 simultaneously of any Lewis aspect. + - acidity data for some systems which such as Li(H2O) Cl may How is proton chemistry in ionic make fair chemical sense.15 decompose to LiOH and HCl7. (continued on next page)

(a) (b) (c)

Fig. 1. Representation of (a) liquid NaCl, (b) molten bmim PF6, and (c) aqueous NaCl. Courtesy of A. East and Q. Li

The Electrochemical Society Interface • Spring 2007 39 Conclusion Table III. ElectrodeTable III. processes Electrode of ionicprocesses liquid ofsolvents. ionic liquid solvents. An ionic liquid is characterized Process Examples by a specific conductivity in the mScm-1 range as a minimum, together with a molar conductivity 1. Cation Reduction K+ + e- t K probably exceeding 0.1 Scm2 mol-1. In addition, the liquid should only bmim+ + e- t bmim t bmim t 2 contain ions with lesser numbers of ion pairs or parent molecules. Ionic 2. Anion Reduction - - - 2- NO3 + 2e t NO2 + O liquids tend to have low dielectric 2- - - 2- } constants, which means they are O + NO3 t NO2 + O2 2- - 2- not ionizing solvents. One can CO3 + 4e t C + 3O assign an ionicity to an ionic liquid - - - - Al2Cl7 + 3e t Al + AlCl4 + 3Cl in terms of its conductivity and, presumably one might attempt to 3. Anion Oxidation 2- - describe any liquid in this manner SO4 - 2e t SO3 + ½ O2 2- - but ignoring the chemical properties CO3 - 2e t CO2 + ½ O2 of excess solvent molecules could - - BF4 - e t BF3 + ½ F2 lead to significant errors. F + bmim+ t C F } Thus in answer to the opening 2 n n+2 question, “What is an ionic liquid?” I prefer the answer, “Just a liquid salt 4. Proton Reactions - - - NO3- + H2O + 2e t NO2 + 2OH consisting of ions and ion pairs.” n - - HCl2 + e t ½ H2 + 2Cl Acknowledgments

The long-term support of NSERC Electrochemistry of Ionic Liquids— Clue #2 /H NMR spectra show (Canada) and recent contributions The General Situation downfield shift of HA’s of the Petroleum Technology proton with B addition: Research Centre (Regina) and the Once we have established BHA is ionized to BH+A- Saskatchewan Research Council are from conductivity measurements Clue #3 Some mixtures show s appreciated. that a liquid is ionic (not ionic/ values in the mScm-1 molecular), its temperature and range, far greater than for References complexity should not pose special the components: BH+A- problems for using it as a solvent dissociates 1. The Structure and Properties of for electrochemistry. Table III lists Ionic Melts, Discuss. Faraday Soc., 32, the types of electrode processes one The overall chemistry University Press, Aberdeen (1962). 2. J. O’M Bockris and A. K. N. encounters.16 With inorganic cations, B + HA } BH+A- } BH+ + A- Reddy, Modern Electrochemistry, the of a metal in its salt may Plenum, New York (1970). arise while the reduction of organic is then governed by the ionization and 3. J. S. Wilkes, in ACS Symposium 818, R. cations is complex and irreversible. dissociation constants D. Rogers and K. R. Seddon, Editors, Following chemical reactions such Washington, DC, p. 214 (2002); J. S. [BH + A - ]­ as attack of an electrode reaction K = Wilkes, J. Mol. Cat. A: Chemical, 214, i [B][­AH]­ product on the opposite ion in the and 11 (2004). +17 [BH + ][­A - ]­ 4. K. R. Seddon, J. Chem. Tech. system can also occur (F2 vs. bmim , Kd = Biotechnol., 68, 351 (1997). O2- vs. NO -). [BH + A - ]­ 3 5. Q. Zhu and C. L. Hussey, J. with the ionic liquid containing the Electrochem. Soc., 149, C268 (2002). Detecting Your Ionic Liquid ions BH+ and A- and the ion-pair 6. L. Xiao, J. S. Wilkes, and K. E. BH+A-.20-22 In practice, one may also Johnson, in Molten Salts XIII, H. C. The following (Scheme 1) is a have to include the self-ionization Delong, et al., Editors, PV 2002-19, sequence of steps prompted by finding of HA and the formation of p. 964, The Electrochemical Society th Proceedings Series, Pennington, NJ two 19 century pieces of work: (a) hydrogenates H A -. Gardner’s observation18 of maximum- n n+1 (2002). 7. J. A. Plambeck, Encyclopedia of boiling point compositions for mixtures (b) For the salt MX or BRA where R = of several bases with (he Electrochemistry of the Elements, Vol. : X: Fused Salt Systems, Marcel Dekker, incorrectly called these specific mixtures New York (1976); G. J. Janz, Molten compounds not azeotropes); and (b) Clue #1 Very low vapor pressures: Salts Handbook, Academic Press, New Zawidzki’s vapor pressure studies19 of stable compound in York (1967). Both give considerable pyridine mixed with formic, acetic and liquid amounts of data regarding high propionic acids (good data even if some Clue #2 NMR data less dramatic: temperature systems. fine details are questionable). may suggest BR+A- 8. P. C. Trulove and R. C. Mantz, in Ionic Clue #3 s values at least in the Liquids in Synthesis, P. Wasserscheid Scheme 1. Detecting an ionic liquid. mScm-1 range: MX or and T. Welton, Editors, Wiley-VCH, + - Weinheim, p. 112 (2003). Data are BR A dissociation tabulated, with references for more (a) For an acid-base system HA + B: For the acid-base systems the vapor than 500 systems at temperatures of 20-35°C. Clue #1 Vapor pressures of some may consist of the or 23 9. T. O’Donnell, Superacids and Acidic mixtures show large the original components, whereas the Melts, VCH, Weinheim, p. 8 (1993). + - negative deviation from breakdown of BR A (e.g., emimCl) into B 10. I. M. Kolthoff and A. Willman, J. Am. Raoult’s law: compound and RA is probably irreversible.24,25 The Chem. Soc., 56, 1007 (1934). forms behavior of the vapor should correlate with the gas phase proton affinities.

40 The Electrochemical Society Interface • Spring 2007 11. P. Vanysek, CRC Handbook of Chemistry and Physics, 82nd Edition, CRC Press, Boca Raton (2001-2002). 12. J. L. E. Campbell and K. E. Johnson, J. Am. Chem. Soc., 117, 7791 (1995). 13. G. Driver and K. E. Johnson, Green THE ELECTROCHEMICAL SOCIETY Chem., 5, 163 (2003). 14. K. E. Johnson and G. Driver, Proc. Int. Symp. on Ionic Liquids, in Honor of M. Gaune Escard, Norwegian Univ. Sci. Tech., Trondheim, p. 233 (2003). Monograph Series 15. G. P. Smith, A. S. Dworkin, R. M. Pagni, and S. P. Zingg, J. Am. Chem. The following volumes are sponsored by ECS, and published Soc., 111, 5075 (1989). 16. K. E. Johnson, L. Xiao, and G. Driver, by John Wiley & Sons, Inc. They should be ordered from: in ACS Symposium 818, R. D. Rogers and K. R. Seddon, Editors, Washington, ECS, 65 South Main St., Pennington, NJ 08534-2839, USA. DC, p. 230 (2002). 17. L. Xiao and K. E. Johnson, J. Electrochem. Soc., 150, E307 (2003). 18. J. A. Gardner, Ber. Dtsch. Chem. Ges., 23, 1587 (1890). Just Published! 19. J. von Zawidzki, Z. Phys. Chem., 35, Fundamentals of Electrochemical Deposition (2nd Edition) 129 (1900). Edited by M. Paunovic and M. Schlesinger (2006) 20. I. M. Kolthoff and S. Bruckenstein, J. Am. Chem. Soc., 78, 1 (1956). 373 pages. ISBN 0-471-71221-3. 21. G. Charlot and B. Tremillon, Chemical Reactions in Solvents and Melts, Fundamentals of Electrochemistry (2nd Edition) Pergamon, Oxford (1969). Edited by V. S. Bagotsky (2005) 22. H. A. Laitinen, Chemical Analysis, 722 pages. ISBN 0-471-70058-4. McGraw Hill, New York, p. 57 (1960). 23. R. G. Treble, K. E. Johnson, and E.Tosh, Can. J. Chem., 84, 915 (2006). Electrochemical Systems (3rd edition) 24. M. J. Earle, J. M. S. S. Esperanca, M. by John Newman and Karen E. Thomas-Alyea (2004) A. Gilea, J. N. Canongia Lopes, L. P. 647 pages. ISBN 0-471-47756-7. N. Rebelo, J. W. Magee, K. R. Seddon, and J. A. Widegren, Nature, 439, 831 (2006). Modern Electroplating (4th edition) 25. M. Yoshizawa, W. Xu, and C.A. Angell, by M. Schlesinger and M. Paunovic (2000) J. Am. Chem. Soc., 125, 15411 (2003). 832 pages. ISBN 0-471-16824-6.

Atmospheric Corrosion (2nd edition) About the Author by C. Leygraf and T. Graedel (2000) 354 pages. ISBN 0-471-37219-6. Keith E. Johnson is a Professor Emeritus of Chemistry and a Research Fellow in Energy and Environment at Uhlig’s Corrosion Handbook (2nd edition) the University of Regina, Canada. A by R. Winston Revie (2000) graduate of Imperial College, London, 1300 pages. ISBN 0-471-15777-5. he has worked with ionic liquids of various types for 50 years. He is the Semiconductor Wafer Bonding author or co-author of over 100 papers, mostly in this field and has directed the by Q. -Y. Tong and U. Gösele (1998) research of 37 graduate students and 297 pages. ISBN 0-471-57481-3. postdoctoral fellows. He joined the ECS in 1960. He may be reached at: Keith. Fundamentals of Electrochemical Deposition [email protected]. by M. Paunovic and M. Schlesinger (1998) 301 pages. ISBN 0-471-16820-3.

Corrosion of Stainless Steels (2nd edition) by A. J. Sedriks (1996) 437 pages. ISBN 0-471-00792-7.

Synthetic Diamond: Emerging CVD Science and Technology Edited by K. E. Spear and J. P. Dismukes (1994) 688 pages. ISBN 0-471-53589-3.

Electrochemical Oxygen Technology by K. Kinoshita (1992) 444 pages. ISBN 0-471-57043-5.

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The Electrochemical Society Interface • Spring 2007 41