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NMR Study on the Possible Interactions Between Imidazolium Based Ionic Liquids and Extractants Widely Applied in Solvent Extraction and Separation of f-Ions

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Abstract

A detailed NMR study on the possible interactions between a series of imidazolium based ionic liquids (1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide, RmimTf2N, n = 4, 6, 8, 10), and compounds commonly applied in the solvent extraction and separation of 4f and 5f-ions as acidic chelating agents and neutral extractants is presented. The analytical techniques applied are 1H, 13C, 19F and 31P NMR spectra and NOESY experiments. Investigation of the types and strengths of the solvent–solute interactions is necessary for a better understanding of the chemical solubility, reactivity and selectivity, as ILs have a strong influence on the solvent extraction mechanism of metal ions. The goal of the scientific research is to gain insight on the role of ILs as a perspective efficient “green” medium in the solvent extraction processes. The experimental results show that no IL–ligand interactions occurred in chloroform solution independently on the length of the imidazolium alkyl chain or on the structure and acidity of the ligand.

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References

  1. Roger, R.D., Seddon, K.R. (eds.): Ionic Liquids as Green Solvents. Progress and Prospects. American Chemical Society, Washington, DC (2003)

    Google Scholar 

  2. Kirchner, B. (ed.): Ionic Liquids. Springer, Berlin (2009)

    Google Scholar 

  3. Rogers, R.D., Seddon, K.R. (eds.): Ionic Liquids: Industrial Applications for Green Chemistry. American Chemical Society, Washington, DC (2002)

    Google Scholar 

  4. Plechkova, N.V., Seddon, K.R.: Applications of ionic liquids in the chemical industry. Chem. Soc. Rev. 37, 123–150 (2008)

    Article  CAS  Google Scholar 

  5. Kolarik, Z.: Ionic liquids: how far do they extend the potential of solvent extraction of f-elements? Solvent Extr. Ion Exch. 31, 24–60 (2013)

    Article  CAS  Google Scholar 

  6. Fernández, J.F., Neumann, J., Thöming, J.: Regeneration, recovery and removal of ionic liquids. Curr. Org. Chem. 15, 1992–2014 (2011)

    Article  Google Scholar 

  7. Abu-Eishah, S.I.: Ionic liquids recycling for reuse. In: Handy, S.T. (ed.) Ionic Liquids—Classes and Properties, pp. 239–272. InTech, Rijeka (2011)

    Google Scholar 

  8. Mai, N.L., Ahn, K., Koo, Y.-M.: Methods for recovery of ionic liquids–a review. Process Biochem. 49, 872–881 (2014)

    Article  CAS  Google Scholar 

  9. Dzyuba, S.V., Kollar, K.D., Sabnis, S.S.: Synthesis of imidazolium room-temperature ionic liquids. Exploring green chemistry and click chemistry paradigms in undergraduate organic chemistry laboratory. J. Chem. Educ. 86(2009), 56–858 (2009)

    Google Scholar 

  10. Wasserscheid, P., Welton, T. (eds.): Ionic Liquids in Synthesis. Wiley, Weinheim (2003)

    Google Scholar 

  11. Rantwijk, F.V., Sheldon, R.A.: Biocatalysis in ionic liquids. Chem. Rev. 107, 2757–2785 (2007)

    Article  Google Scholar 

  12. Dietz, M.L.: Ionic liquids as extraction solvents: where do we stand? Sep. Sci. Technol. 41, 2047–2063 (2006)

    Article  CAS  Google Scholar 

  13. Binnemans, K.: Lanthanides and actinides in ionic liquids. Chem. Rev. 107, 2592–2614 (2007)

    Article  CAS  Google Scholar 

  14. Billard, I.: Ionic liquids: new hopes for efficient lanthanide/actinide extraction and separation? In: Bünzli, J.C.G, Pecharsky, V.K. (eds.) Handbook on the Physics and Chemistry of Rare Earths, vol. 43, Chapter 256, pp. 213–273. Elsevier, New York (2013)

  15. Dzyuba, S.V., Bartsch, R.A.: Influence of structural variations in 1-alkyl(aralkyl)-3-methylimidazolium hexafluorophosphates and bis(trifluoromethylsulfonyl)imides on physical properties of the ionic liquids. ChemPhysChem 3, 161–166 (2002)

    Article  CAS  Google Scholar 

  16. Atanassova, M., Mazan, V., Billard, I.: Modulating the solubilities of ionic liquid components in aqueous–ionic liquid biphasic systems: a Q-NMR investigation. ChemPhysChem 16, 1703–1711 (2015)

    Article  CAS  Google Scholar 

  17. Billard, I., Gaillard, C.: Actinide and lanthanide speciation in imidazolium-based ionic liquids. Radiochim. Acta 97, 355–359 (2009)

    Article  CAS  Google Scholar 

  18. Gaillard, C., Azzi, A.E., Billard, I., Bolvin, H., Hennig, C.: Uranyl complexation in fluorinated acids (HF, HBF4, HPF6, HTf2N): a combined experimental and theoretical study. Inorg. Chem. 44, 852–861 (2005)

    Article  CAS  Google Scholar 

  19. Gaillard, C., Billard, I., Chaumont, A., Mekki, S., Ouadi, A., Denecke, M.A., Moutiers, G., Wipff, G.: Europium(III) and its halides in anhydrous room-temperature imidazolium-based ionic liquids: a combined TRES, EXAFS, and molecular dynamics study. Inorg. Chem. 44, 8355–8367 (2005)

    Article  CAS  Google Scholar 

  20. Ferreira, R., Garcia, H., Sousa, A.F., Petkovic, M., Lamosa, P., Freire, C.S.R., Silvestre, A.J.D., Rebelo, L.P.N., Pereira, C.S.: Suberin isolation from cork using ionic liquids: characterisation of ensuing products. New J. Chem. 36, 2014–2024 (2012)

    Article  CAS  Google Scholar 

  21. Zirbs, R., Strassl, K., Gaertner, P., Schroder, C., Bica, K.: Exploring ionic liquid–biomass interactions: towards the improved isolation of shikimic acid from star anise pods. RSC Adv. 3, 26010–26016 (2013)

    Article  CAS  Google Scholar 

  22. Ribeiro, B.D., Coelho, M.A.Z., Rebelo, L.P.N., Marrucho, I.M.: Ionic liquids as additives for extraction of saponins and polyphenols from mate (Ilex paraguariensis) and tea (Camellia sinensis). Ind. Eng. Chem. Res. 52, 12146–12153 (2013)

    Article  CAS  Google Scholar 

  23. Passos, H., Freire, M.G., Coutinho, J.A.P.: Ionic liquid solutions as extractive solvents for value-added compounds from biomass. Green Chem. 16, 4786–4815 (2014)

    Article  CAS  Google Scholar 

  24. Strehmel, V., Berdzinski, S., Rexhausen, H.: Interactions between ionic liquids and radicals. J. Mol. Liq. 192, 153–170 (2014)

    Article  CAS  Google Scholar 

  25. Atanassova, M., Kurteva, V., Lubenov, L., Billard, I.: Comparing extraction, synergism and separation of lanthanoids by use of acidic and neutral compounds in chloroform and one ionic liquid: is the latter always “better”? RSC Adv. 4, 38820–38829 (2014)

    Article  CAS  Google Scholar 

  26. Billard, I., Georg, S.: Reactivity towards europium(III) of the radiolysis products of the ionic liquid 1-methyl-3-butyl-1H-imidazolium bis[(trifluoromethyl)sulfonyl]amide (C4-mimTf2N) and effect of water: a TRLFS (Time-Resolved Laser-Induced Fluorescence Spectroscopy) preliminary study. Helv. Chim. Acta 92, 2227–2237 (2009)

    Article  CAS  Google Scholar 

  27. Giernoth, R., Bröhl, A., Brehm, M., Lingscheid, Y.: Interactions in ionic liquids probed by in situ NMR spectroscopy. J. Mol. Liq. 192, 55–58 (2014)

    Article  CAS  Google Scholar 

  28. Fumino, K., Ludwig, R.: Analyzing the interaction energies between cation and anion in ionic liquids: the subtle balance between Coulomb forces and hydrogen bonding. J. Mol. Liq. 192, 94–102 (2014)

    Article  CAS  Google Scholar 

  29. Stark, A.: Shaping micro- and macroscopic properties of ionic liquid–solute systems: multi-functional task-specific agents. J. Mol. Liq. 192, 144–152 (2014)

    Article  CAS  Google Scholar 

  30. Khatun, S., Castner Jr, E.W.: Ionic liquid–solute interactions studied by 2D NOE NMR spectroscopy. J. Chem. Phys. B 119, 9225–9235 (2015)

    Article  CAS  Google Scholar 

  31. Atanassova, M., Billard, I.: Determination of pK aIL values of three chelating extractants in ILs: consequences for the extraction of 4f elements. J. Solution Chem. 44, 606–620 (2015)

    Article  CAS  Google Scholar 

  32. Marcus, Y., Kertes, A.S.: Synergistic extraction. In: Ion Exchange and Solvent Extraction of Metal Complexes, Chapter 11, pp. 815–858. Wiley Interscience, New York (1969)

  33. Atanassova, M., Dukov, I.: A comparative study of the solvent extraction of the trivalent elements of the lanthanoid series with thenoyltrifluoroacetone and 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one using diphenylsulphoxide as synergistic agent. J. Solution Chem. 38, 289–301 (2009)

    Article  CAS  Google Scholar 

  34. Petrova, M.A., Dukov, I.: Effect of crown ethers on the solvent extraction and separation of lanthanide(III) ions with 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one. Chem. Pap. 62, 207–214 (2008)

    Article  CAS  Google Scholar 

  35. Zhang, A.: Study of the antagonistic extraction of palladium(II) with 1-phenyl-3-methyl-4-propionylpyrazolone-5-one and an organic amine. Solvent Extr. Ion Exch. 19, 925–938 (2001)

    Article  CAS  Google Scholar 

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Acknowledgments

The financial support by FP7-PEOPLE-Marie Curie Actions-IEF, Project INNOVILLN (622906) 2014-2016, is gratefully acknowledged.

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Correspondence to Vanya Kurteva.

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Kurteva, V., Atanassova, M. & Billard, I. NMR Study on the Possible Interactions Between Imidazolium Based Ionic Liquids and Extractants Widely Applied in Solvent Extraction and Separation of f-Ions. J Solution Chem 44, 2416–2430 (2015). https://doi.org/10.1007/s10953-015-0420-3

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  • DOI: https://doi.org/10.1007/s10953-015-0420-3

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