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Journal of Solution Chemistry

, Volume 48, Issue 1, pp 15–30 | Cite as

Synergism in the Solvent Extraction of Europium(III) with Thenoyltrifluoroacetone and CMPO in Methylimidazolium Ionic Liquids

  • Maria AtanassovaEmail author
  • Vanya Kurteva
Article
  • 18 Downloads

Abstract

The solvent extraction of Eu(III) from an aqueous chloride phase into hydrophobic ionic liquids (ILs), 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides ([C1Cnim+][Tf2N], n = 4, 6, 8 and 10), by β-diketone 2-thenoyltrifluoroacetone (HTTA) alone and in combination with N,N-diisobutyl-2-(octylphenylphosphoryl)acetamide (CMPO) was investigated. The interaction between the two extractants (acidic/neutral) in deuterochloroform has been studied by 1H, 13C, 19F and 31P NMR spectra and NOESY experiments. 1H and 19F Q-NMR analytical techniques were also applied for determination of [C1C4im+] and [Tf2N] entities transferred into the aqueous phase. Eu(III) was efficiently extracted by HTTA/[C1Cnim+][Tf2N] and HTTA/CMPO/[C1Cnim+][Tf2N] systems but a relatively small synergism was established. A cation extraction mechanism was proposed via the log–log slope analysis method. The effect of the IL cation alkyl chain length on the extraction process was studied as well.

Keywords

Synergism Ionic liquids Lanthanoids Thenoyltrifluoroacetone CMPO Q-NMR 

Notes

Acknowledgements

The authors are grateful to FP7-PEOPLE-Marie Curie Actions-IEF for the support of the Project INNOVILLN (622,906: 2014/2015) as well as the Grants 11602/2016 and 11714/2017 from UCTM.

Supplementary material

10953_2019_844_MOESM1_ESM.docx (398 kb)
Supplementary material 1 (DOCX 398 kb)

References

  1. 1.
    Atanassova, M., Kurteva, V.: Peculiar synergistic extraction behavior of Eu(III) in ionic liquids: benzoylacetone and CMPO fusion. Sep. Purif. Technol. 183, 226–236 (2017)CrossRefGoogle Scholar
  2. 2.
    De, A.K., Khopkar, S.: Analytical application of thenoyltrifluoroacetone. J. Sci. Industr. Des. 21A, 131–135 (1962)Google Scholar
  3. 3.
    Sekine, T., Ono, M.: Studies of the liquid–liquid partition systems. IV. The solvent extraction study of europium(III) adduct chelate complexes with six acetylacetone derivatives and tributylphosphate. Bull. Chem. Soc. Jpn. 38, 2067–2094 (1965)CrossRefGoogle Scholar
  4. 4.
    Komatsu, Y., Fujiki, Y., Michine, Y., Yajima, Y., Sasaki, T.: Solvent extraction separation of alkaline earth metal ions with thenoyltrifluoroacetone and trioctylphosphine oxide in carbon tetrachloride. Solv. Extr. Ion Exch. 9, 471–479 (1991)CrossRefGoogle Scholar
  5. 5.
    Akki, S.B., Khopkar, J.M.: Solvent extraction of selenium(IV) with 2-thenoyltrifluoroacetone. Sep. Sci. Technol. 6, 455–460 (1971)Google Scholar
  6. 6.
    De, A., Rahaman, M.: Extraction and spectroscopic determination of platinium(IV) and palladium(II) with 2-thenoyltrifluoroacetone. Analyst 89, 795–799 (1964)CrossRefGoogle Scholar
  7. 7.
    Poskanzer, A.M., Foreman, B.M.: A summary of TTA extraction coefficients. J. Inorg. Nucl. Chem. 16, 323–336 (1961)CrossRefGoogle Scholar
  8. 8.
    Alstad, J., Augustson, L.H., Farbu, L.H.: Solvent extraction of rare earth metal ions with thenoyltrifluoroacetone in carbon tetrachloride. J. Inorg. Nucl. Chem. 36, 899–903 (1974)CrossRefGoogle Scholar
  9. 9.
    Stary, J., Freiser, H.: Equilibrium constants of liquid distribution reactions: Part IV. Chelating extractants. IUPAC Chemical Data Series, vol. 18. Pergamon, Oxford (1975)Google Scholar
  10. 10.
    Cary, S., Livshits, M., Cross, J., Ferrie, M., Mocko, V., Stein, B., Kozimor, S., Scott, B., Rack, J.: Advancing understanding of the +4 metal extractant thenoyltrifluoroacetone (TTA); synthesis and structure of MIVTTA4 (MIV = Zr, Hf, Ce, Th, U, Np, Pu) and MIII(TTA)4 (MIII = Ce, Nd, Sm, Yb). Inorg. Chem. 57, 3782–3797 (2018)CrossRefGoogle Scholar
  11. 11.
    Ensor, D.D., Nicks, M., Pruett, D.: Extraction of uranyl ions by synergistic mixtures of thenoyltrifluoroacetone and macrocyclic donors. Solvent Extr. Ion Exch. 6, 621–629 (1988)CrossRefGoogle Scholar
  12. 12.
    Reddy, A.S., Reddy, L.K.: Solvent extraction separation of some actinides and lanthanides with 2-thenoyltrifluoroacetone. Sep. Sci. Technol. 15, 1263–1269 (1980)CrossRefGoogle Scholar
  13. 13.
    Mathur, J.N.: Synergism of trivalent lanthanides and actinides. Solv. Extr Ion Exch. 1, 349–412 (1983)CrossRefGoogle Scholar
  14. 14.
    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-pyrazoline using diphenylsulphoxide as synergistic agent. J. Solution Chem. 38, 289–301 (2009)CrossRefGoogle Scholar
  15. 15.
    Zhang, A., Wanyan, G., Kumagai, M.: Association behavior of 4-acylpyrazolone derivative and tertiary amine of high molecular weight in antagonistic synergistic extraction of palladium. J. Solution Chem. 33, 1017–1028 (2004)CrossRefGoogle Scholar
  16. 16.
    Marklik, E., Vaňura, P., Ruzza, P.: Synergistic extraction of some univalent cations from water into nitrobenzene using sodium dicarbolylcobaltate and antamanide. J. Solution Chem. 46, 1121–1130 (2017)CrossRefGoogle Scholar
  17. 17.
    Hasegawa, Y., Nakako, T., Choppin, G.: Synergistic extraction of europium(III) with benzoic acid and thenoyltrifluoroacetone. Solvent Ext. Ion Exch. 1, 745–753 (1983)CrossRefGoogle Scholar
  18. 18.
    El-Reefy, J.A., Dessouky, N.A., Aly, H.F.: Extraction of Am(III) and Eu(III) from nitrate medium by thenoyltrifluoroacetone mixed with some soft donor ligands. Solvent Extr. Ion Exch. 11, 19–32 (1993)CrossRefGoogle Scholar
  19. 19.
    Ensor, D.D., Shah, A.H.: Extraction of trivalent lanthanides and actinides by a synergistic mixture of thenoyltrifluoroacetone and a linear polyether. Solvent Extr. Ion Exch. 2, 591–605 (1984)CrossRefGoogle Scholar
  20. 20.
    Khopkar, P., Mathur, J.: Synergistic extraction of trivalent actinides by mixtures of thenoyltrifluoroacetone and neutral oxo donors. Sep. Sci. Technol. 16, 957–969 (1981)CrossRefGoogle Scholar
  21. 21.
    Ramaknishna, V., Patil, S., Hara Prakas, B.: Solvent extraction and spectrophotometric studies on synergistic extraction of plutonium(IV) by mixtures of thenoyltrifluoroacetone (HTTA) and tri-n-butylphosphate (TBP) in benzene. Sep. Sci. Technol. 14, 571–589 (1979)CrossRefGoogle Scholar
  22. 22.
    Irving, H., Edgington, D.N.: Synergic effects in the solvent extraction of the actinides I–uranium(VI). J. Inorg. Nucl. Chem. 15, 158–170 (1960)CrossRefGoogle Scholar
  23. 23.
    Healy, T.V.: Synergism with thenoyltrifluoroacetone in the solvent extraction of metallic species. Nucl. Sci. Eng. 16, 413–420 (1963)CrossRefGoogle Scholar
  24. 24.
    Atanassova, M., Lachkova, V., Vassilev, N., Shivachev, B., Varbanov, S., Dukov, I.: Effect of p-tert-butylcalix[4]aene fitted with phosphinoyl pendant arms as synergistic agent in the solvent extraction of trivalent lanthanides with 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione and structural study of solid complexes by IR. NMR and X-ray. Polyhedron 27, 3306–3312 (2008)Google Scholar
  25. 25.
    Dukov, I., Atanassova, M.: High molecular weight amines and quaternary ammonium salts as synergistic agents in the solvent extraction of metal ions with chelating extractants (Chap. 7). In: Morrison, D.A. (ed.) Handbook of Inorganic Chemistry Research. Nova Science, Hauppauge (2010)Google Scholar
  26. 26.
    Atanassova, M.: Synergistic solvent extraction and separation of lanthanide(III) ions with 4-benzoyl-3-phenyl-5-isoxazolone and the quaternary ammonium salt. Solvent Extr. Ion Exch. 27, 159–171 (2009)CrossRefGoogle Scholar
  27. 27.
    Akiba, K., Wada, M., Kanno, T.: Effect of diluent on synergic extraction of europium by thenoyltrifluoroacetone and tri-n-octyl phosphine oxide. J. Inorg. Nucl. Chem. 43, 1031–1034 (1981)CrossRefGoogle Scholar
  28. 28.
    Murthy, K., Krupadam, R., Auganeynly, Y.: Studies on the solvent extraction of trivalent lanthanides with hexafluoroacetylacetone (HFAA) and tri-n-octylphosphine oxide (TOPO). Proc. Indian Acad. Sci. Chem. Sci. 110, 83–88 (1998)Google Scholar
  29. 29.
    Mathur, J., Pai, S., Khopkar, P., Sumramanian, M.: Thermodynamics of synergistic extraction of europium(III) by mixtures of thenoyltrifluoroacetone and some neutral oxo-donors. J. Inorg. Nucl. Chem. 39, 653–657 (1977)CrossRefGoogle Scholar
  30. 30.
    Sekine, T., Dyrssen, D.: Solvent extraction of metal ions with mixed ligands. IV Extraction of Eu(III) with chelating acids and neutral adduct-forming ligands. J. Inorg. Nucl. Chem. 29, 1475–1480 (1967)CrossRefGoogle Scholar
  31. 31.
    Dukov, I., Genov, L.: On the mechanism of the synergistic extraction of lanthanides with thenoyltrifluoroacetone and Aliquat-336S. Acta Chim. Acad. Sci. Hung. 104, 329–335 (1980)Google Scholar
  32. 32.
    Atanassova, M., Jordanov, V., Dukov, I.: Effect of the quaternary ammonium salt Aliquat 336 on the solvent extraction of lanthanoid(III) ions with thenoyltrifluoroacetone. Hydrometallurgy 63, 41–47 (2002)CrossRefGoogle Scholar
  33. 33.
    Dukov, I., Atanassova, M.: Effect of diluents on the synergistic solvent extraction of some lanthanides with thenoyltrifluoroacetone and quaternary ammonium salt. Hydrometallurgy 68, 89–96 (2003)CrossRefGoogle Scholar
  34. 34.
    Atanassova, M., Dukov, I.: Synergistic solvent extraction and separation of trivalent lanthanide metals with mixtures of 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one and Aliquat 336. Sep. Purif. Technol. 40, 171–176 (2004)CrossRefGoogle Scholar
  35. 35.
    Brunette, J.P., Lakkis, Z., Lakkis, M., Leroy, M.J.F.: Effect of inorganic aqueous anions on the synergic extraction of cadmium and zinc with 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one (HPMBP) and lipophilic ammonium salts. Polyhedron 4, 577–582 (1985)CrossRefGoogle Scholar
  36. 36.
    Mikkola, J.-P., Virtanen, P., Sjöholm, R.: Aliquat 336-a versatile and affordable cation source for an entirely new family of hydrophobic ionic liquids. Green Chem. 8, 250–255 (2006)CrossRefGoogle Scholar
  37. 37.
    Kolaric, Z.: Ionic liquids: how far do they extend the potential of solvent extraction of f-elements? Solv. Extr. Ion Exch. 31, 24–60 (2013)CrossRefGoogle Scholar
  38. 38.
    Jensen, M., Neuefeind, J., Beitz, J., Skanthakumar, S., Soderholm, L.: Mechanism of metal ion transfer into room-temperature ionic liquids: the role of anion exchange. J. Am. Chem. Soc. 125, 15466–15473 (2003)CrossRefGoogle Scholar
  39. 39.
    Fu, J., Chen, Q., Sun, T., Shen, Y.: Extraction of Th(IV) from aqueous solution by room temperature ionic liquids and coupled with supercritical carbon dioxide. Sep. Purif. Technol. 119, 66–71 (2013)CrossRefGoogle Scholar
  40. 40.
    Hirayama, N., Okamura, H., Kidani, K., Imura, H.: Ionic liquid synergistic cation-exchange system for the selective extraction of lanthanum(III) using 2-thenoyltrifluoroacetone and 18-crown-6. Anal. Sci. 24, 697–699 (2008)CrossRefGoogle Scholar
  41. 41.
    Jensen, M., Borkowski, M., Laszak, I., Beitz, J., Rickert, P., Dietz, M.: Anion effects in the extraction of lanthanide 2-thenoyltrifluoroacetone complexes into an ionic liquid. Sep. Sci. Technol. 47, 233–243 (2012)CrossRefGoogle Scholar
  42. 42.
    Ranjbar, L., Yamini, Y., Saleh, A., Seidi, J., Faraji, M.: Ionic liquid based dispersive liquid–liquid microextraction combined with ICP–OES for the determination of trace quantities of cobald, copper, manganese, nickel and zinc in environmental water samples. Microchim. Acta 177, 119–127 (2012)CrossRefGoogle Scholar
  43. 43.
    Pandey, S., Baker, G., Sze, L., Pandey, S., Kamath, G., Zhao, H., Baker, S.: Ionic liquids containing fluorinated β-diketonate anions: synthesis, characterization and potential applications. New J. Chem. 37, 909–919 (2013)CrossRefGoogle Scholar
  44. 44.
    Kidani, K., Imura, H.: Solvent effect of ionic liquids on the distribution constants of 2-thenoyltrifluoroacetone and its nickel(II) and copper(II) chelates and the evaluation of the solvent properties based on the regular solution theory. Talanta 83, 299–304 (2010)CrossRefGoogle Scholar
  45. 45.
    Rout, A., Venkatesan, K., Srinivasan, T., Vasudeva Rao, P.: Ionic liquid extractants in molecular diluents: extraction behavior of plutonium(IV) in 1,3-diketone ionic liquids. Solvent Extr. Ion Exch. 29, 602–618 (2011)CrossRefGoogle Scholar
  46. 46.
    Okamura, H., Sakae, H., Kidani, K., Hirayama, N., Aoyagi, N., Saito, T., Shimojo, K., Naganawa, H., Imura, H.: Laser-induced fluorescence and infrared spectroscopic studies on the specific solvation of tris(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)europium(III) in an ionic liquid. Polyhedron 31, 748–753 (2012)CrossRefGoogle Scholar
  47. 47.
    Atanassova, M.: Investigation of synergism and selectivity using mixture of two neutral extractants in IL media for lanthanoids extraction. Sep. Purif. Technol. 169, 253–261 (2016)CrossRefGoogle Scholar
  48. 48.
    Atanassova, M., Mazan, V., Billard, I.: Modulating the solubilities of ionic liquid components in aqueous–ionic liquid biphasic systems: a Q-NMR investigation. Chem. Phys. Chem. 16, 1703–1711 (2015)CrossRefGoogle Scholar
  49. 49.
    Okamura, H., Takagi, H., Isomura, T., Morita, K., Nagatani, H., Imura, H.: Highly selective synergism for the extraction of lanthanoid(III) ions with β-diketones and trioctylphosphine oxide in an ionic liquid. Anal. Sci. 30, 323–325 (2014)CrossRefGoogle Scholar
  50. 50.
    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)CrossRefGoogle Scholar
  51. 51.
    Sekine, T., Koike, Y., Hasegawa, Y.: Studies of actinium(III) in various solutions. II. Distribution behavior of lanthanum(III) and actinium(III) in some chelate extraction systems. Bull. Chem. Soc. Jpn 42, 432–436 (1969)CrossRefGoogle Scholar
  52. 52.
    Albinsson, Y., Mahmood, A., Majdan, M., Rydberg, J.: Solvent extraction studies of lanthanide acetylacetonates complexes formed by La, Nd, Sm and Eu. Radiochim. Acta 48, 49–57 (1989)CrossRefGoogle Scholar
  53. 53.
    Atanassova, M., Kurteva, V., Billard, I.: Coordination chemistry of europium(III) ion towards acylpyrazolone ligands. Anal. Sci. 31, 917–922 (2015)CrossRefGoogle Scholar
  54. 54.
    Sekine, T., Koizumi, A., Sakairi, M.: Studies of scandium in various solutions. III The solvent extraction and complex formation of scandium(III) with acetylacetone and thenoyltrifluoroacetone. Bull. Chem. Soc. Jpn 39, 2681–2684 (1966)CrossRefGoogle Scholar
  55. 55.
    Noro, J., Sekine, T.: Separation factor of lanthanides by solvent extraction of their ternary complexes. J. Alloys Compd. 192, 132–134 (1993)CrossRefGoogle Scholar
  56. 56.
    Hirayama, N., Deguchi, M., Kawasumi, H., Honjo, T.: Use of 1-alkyl-3-methylimidazolium hexafluorophosphate room temperature ionic liquids as chelate extraction solvent with 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione. Talanta 65, 255–260 (2005)CrossRefGoogle Scholar
  57. 57.
    Hirayama, N.: Chelate extraction of metals into ionic liquids. Solv. Extr. Res. Dev. Jpn. 18, 1–14 (2011)CrossRefGoogle Scholar
  58. 58.
    Kumar, P., Vincent, T., Khanna, A.: Extraction of UO2 2+ into ionic liquids using TTA and TBP as extractants. Sep. Sci. Technol. 50, 2668–2675 (2015)Google Scholar
  59. 59.
    Janssen, C., Macias-Ruvalcaba, N., Aguilar-Martinez, M., Kobrak, M.: Metal extraction to ionic liquids: the relationship between structure, mechanism and application. Int. Reviews. Phys. Chem. 34, 591–622 (2015)CrossRefGoogle Scholar
  60. 60.
    Okamura, H., Aoyagi, N., Shimojo, K., Naganawa, H., Imura, H.: Role of Tf2N anions in the ionic liquid–water distribution of europium(III) chelates. RSC Adv. 7, 7610–7618 (2017)CrossRefGoogle Scholar
  61. 61.
    Atanassova, M., Dukov, I.: Crown ethers as synergistic agents in the solvent extraction of trivalent lanthanoids with thenoyltrifluoroacetone. Sep. Sci. Technol. 40, 1103–1113 (2005)CrossRefGoogle Scholar
  62. 62.
    Atanassova, M.: Lanthanoid complexes with thenoyltrifluoroacetone and 4-tert-butylcalix[4]arene-tetraacetic acid tetraethyl ester: synergistic extraction and separation. Microchim. Acta 174, 175–181 (2011)CrossRefGoogle Scholar
  63. 63.
    Favaro, D., Atalla, L.: Interaction effect between thenoyltrifluorocetone and tri-n-octylphosphine oxide in the synergistic extraction of trivalent lanthanides. Determination of the composition of the extracted species. J. Radioanal. Nucl. Chem. 111, 81–94 (1987)CrossRefGoogle Scholar
  64. 64.
    Atanassova, M., Kurteva, V.: Synergism as a phenomenon in solvent extraction of 4f-elements with calixarenes. RSC Adv. 6, 11303–11324 (2016)CrossRefGoogle Scholar
  65. 65.
    Atanassova, M., Kurteva, V., Dukov, I.: The interaction of extractants during synergistic solvent extraction of metals Is it an important reaction? RSC Adv. 6, 81250–81265 (2016)CrossRefGoogle Scholar
  66. 66.
    Sekine, T., Saito, T., Iga, H.: Association of β-diketones with trioctylphosphine oxide in solvent extraction systems. Bull. Chem. Soc. Jpn 56, 700–704 (1983)CrossRefGoogle Scholar
  67. 67.
    Zhao, Z., Baba, Y., Kubota, F., Kamiya, N., Goto, M.: Synergistic extraction of rare-earth metals and separation of scandium using 2-thenoyltrifluoroacetone and tri-n-octylphosphine oxide in an ionic liquid system. J. Chem. Eng. Jpn 47, 656–662 (2014)CrossRefGoogle Scholar
  68. 68.
    Atanassova, M., Kaloyanova, S., Deligeorgiev, T.: Application of 4,4,4-trifluoro-1-(biphenyl-4-yl)butane-1,3-dione as a chelating extractant in the solvent extraction and separation of light lanthanoids in combination with phosphine oxides. Acta Chim. Slov. 57, 821–827 (2010)Google Scholar
  69. 69.
    Petrova, M.A., Kurteva, V.B., Lubenov, L.A.: Synergistic effect in the solvent extraction and separation of lanthanoids by 4-(4-fluorobenoyl)-3-methyl-1-phenyl-pyrazol-5-one in the presence of monofunctional neutral organophosphorus extractants. Ind. Eng. Chem. Res. 50, 12170–12176 (2011)CrossRefGoogle Scholar
  70. 70.
    Singh, S., Dhami, P., Dakshinamoorthy, A., Sundersanan, M.: Studies on the recovery of uranium from phosphoric acid medium using synergistic mixture of 2-ethyl hexyl hydrogen 2-ethyl hexyl phosphonate and octyl(phenyl)-N,N-diisobutyl carbamoyl methyl phosphine oxide. Sep. Sci. Technol. 44, 491–505 (2009)CrossRefGoogle Scholar
  71. 71.
    Atanassova, M., Kurteva, V., Lubenov, L., Billard, I.: Comparing extraction, synergism and separation of lanthanoids using acidic and neutral compounds in chloroform and one ionic liquid: is the latter always “better”? RSC Adv. 4, 38820–38829 (2014)CrossRefGoogle Scholar
  72. 72.
    Zhu, M., Zhao, J., Li, Y., Mehio, N., Qi, Y., Liu, H., Dai, S.: An ionic-liquid-based synergistic extraction strategy for rare earths. Green Chem. 5, 2981–2993 (2015)CrossRefGoogle Scholar

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Authors and Affiliations

  1. 1.Department of General and Inorganic ChemistryUniversity of Chemical Technology and MetallurgySofiaBulgaria
  2. 2.Institute of Organic Chemistry with Centre of PhytochemistryBulgarian Academy of SciencesSofiaBulgaria

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