Skip to main content
SpringerLink
Log in

Highly Efficient Solvent Extraction of Americium and Europium by Using Hydrogen Dicarbollylcobaltate and N,N′-Diethyl-N,N′-bis(4-ethylphenyl)-1,10-phenanthroline-2,9-dicarboxamide

  • Published:
Journal of Solution Chemistry Aims and scope Submit manuscript

Abstract

Solvent extraction of microamounts of Eu3+ and Am3+ from water into nitrobenzene by means of a mixture of hydrogen dicarbollylcobaltate (H+B−) and N,N′-diethyl-N,N′-bis(4-ethylphenyl)-1,10-phenanthroline-2,9-dicarboxamide (L) was studied. The equilibrium data were explained assuming that the species HL+, \( \text{HL}_{\text{2}}^{ + } \), \( \text{ML}_{2}^{3 + } \), and \( \text{ML}_{\text{3}}^{{\text{3} + }} \) (M3+ = Eu3+, Am3+; L = N,N′-diethyl-N,N′-bis(4-ethylphenyl)-1,10-phenanthroline-2,9-dicarboxamide) are extracted into the organic phase. Extraction and stability constants of the cationic complex species in nitrobenzene saturated with water were determined and are discussed. The reached separation factors SFAm/Eu in this two-phase system are in the range of 19–99. From the experimental results it is apparent that this very effective N,N′-diethyl-N,N′-bis(4-ethylphenyl)-1,10-phenanthroline-2,9-dicarboxamide receptor for the Eu3+ and Am3+ cations could be considered as a potential extraction agent for nuclear waste treatment.

Graphical Abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Scheme 2

Similar content being viewed by others

References

  1. Retegan, T., Berthon, L., Ekberg, C., Fermvik, A., Skarnemark, G., Zorz, N.: Electrospray ionization mass spectrometry investigation of BTBP–lanthanide(III) and actinide(III) complexes. Solvent Extr. Ion Exch. 27, 663–682 (2009)

    Article  CAS  Google Scholar 

  2. Fermvik, A., Ekberg, C., Englund, S., Foreman, M.R.S.J., Modolo, G., Retegan, T., Skarnemark, G.: Influence of dose rate on the radiolytic stability of a BTBP solvent for actinide (III)/lanthanide(III) separation. Radiochim. Acta 97, 319–324 (2009)

    Article  CAS  Google Scholar 

  3. Magnusson, D., Christiansen, B., Malmbeck, R., Glatz, J.-P.: Investigation of the radiolytic stability of a CyMe4-BTBP based SANEX solvent. Radiochim. Acta 97, 497–502 (2009)

    CAS  Google Scholar 

  4. Magnusson, D., Christiansen, B., Foreman, M.R.S., Geist, A., Glatz, J.-P., Malmbeck, R., Modolo, G., Serrano-Purroy, D., Sorel, C.: Demonstration of a SANEX process in centrifugal contactors using the CyMe4-BTBP molecule on a genuine fuel solution. Solvent Extr. Ion Exch. 27, 97–106 (2009)

    Article  CAS  Google Scholar 

  5. Lewis, F.W., Harwood, L.M., Hudson, M.J., Drew, M.G.B., Desreux, J.F., Vidick, G., Bouslimani, N., Modolo, G., Wilden, A., Sypula, M., Vu, T.-H., Simonin, J.-P.: Highly efficient separation of actinides from lanthanides by a phenanthroline-derived bis-triazine ligand. J. Am. Chem. Soc. 133, 13093–13102 (2011)

    Article  CAS  Google Scholar 

  6. Hudson, M.J., Harwood, L.M., Laventine, D.M., Lewis, F.W.: Use of soft heterocyclic N-donor ligands to separate actinides and lanthanides. Inorg. Chem. 52, 3414–3428 (2013)

    Article  CAS  Google Scholar 

  7. Bremer, A., Whittaker, D.M., Sharrad, C.A., Geist, A., Panak, P.J.: Complexation of Cm(III) and Eu(III) with CyMe4-BTPhen and CyMe4-BTBP studied by time resolved laser fluorescence spectroscopy. Dalton Trans. 43, 2684–2694 (2014)

    Article  CAS  Google Scholar 

  8. Lewis, F.W., Hudson, M.J., Harwood, L.M.: Development of highly selective ligands for separations of actinides from lanthanides in the nuclear fuel cycle. Synlett 18, 2609–2632 (2011)

    Google Scholar 

  9. Panak, P.J., Geist, A.: Complexation and extraction of trivalent actinides and lanthanides by triazinylpyridine N-donor ligands. Chem. Rev. 113, 1199–1236 (2013)

    Article  CAS  Google Scholar 

  10. Cuillerdier, C., Musikas, C., Hoel, P., Nigond, L., Vitart, X.: Malonamides as new extractants for nuclear waste solutions. Sep. Sci. Technol. 26, 1229–1244 (1991)

    Article  CAS  Google Scholar 

  11. Manchanda, V.K., Pathak, P.N.: Amides and diamides as promising extractants in the back end of the nuclear fuel cycle: an overview. Sep. Pur. Technol. 35, 85–103 (2004)

    Article  CAS  Google Scholar 

  12. Sasaki, Y., Choppin, G.R.: Solvent extraction of Eu, Th, U, Np and Am with N,N′-dimethyl-N,N′-dihexyl-3-oxapentanediamide and its analogous compounds. Anal. Sci. 12, 225–230 (1996)

    Article  CAS  Google Scholar 

  13. Sasaki, Y., Sugo, Y., Suzuki, S., Tachimori, S.: The novel extractants, diglycolamides, for the extraction of lanthanides and actinides in HNO3–n-dodecane system. Solvent Extr. Ion Exch. 19, 91–103 (2001)

    Article  CAS  Google Scholar 

  14. Sasaki, Y., Tachimori, S.: Extraction of actinides(III), (IV), (V), (VI), and lanthanides(III) by structurally tailored diamides. Solvent Extr. Ion Exch. 20, 21–34 (2002)

    Article  CAS  Google Scholar 

  15. Sasaki, Y., Sugo, Y., Suzuki, S., Kimura, T.: A method for the determination of extraction capacity and its application to N,N,N′,N′-tetraalkylderivatives of diglycolamide–monoamide/n-dodecane-media. Anal. Chim. Acta 543, 31–37 (2005)

    Article  CAS  Google Scholar 

  16. Ansari, S.A., Pathak, P.N., Manchanda, V.K., Husain, M., Prasad, A.K., Parmar, V.S.: N, N, N′, N′-tetraoctyl diglycolamide (TODGA): a promising extractant for actinide partitioning from high level waste (HLW). Solvent Extr. Ion Exch. 23, 463–479 (2005)

    Article  CAS  Google Scholar 

  17. Horwitz, E.P., McAlister, D.R., Bond, A.H., Barrans Jr., R.E.: Novel extraction of chromatographic resins based on tetraalkyl diglycolamides: characterization and potential applications. Solvent Extr. Ion Exch. 23, 319–344 (2005)

    Article  CAS  Google Scholar 

  18. Iqbal, M., Mohapatra, P.K., Ansari, S.A., Huskens, J., Verboom, W.: Preorganization of diglycolamides on the calix[4]arene platform and its effect on the extraction of Am(III)/Eu(III). Tetrahedron 68, 7840–7847 (2012)

    Article  CAS  Google Scholar 

  19. Mohapatra, P.K., Iqbal, M., Raut, D.R., Verboom, W., Huskens, J., Godbole, S.V.: Complexation of novel diglycolamide functionalized calix[4]arenes: unusual extraction behaviour, transport, and fluorescence studies. Dalton Trans. 41, 360–363 (2012)

    Article  CAS  Google Scholar 

  20. Raut, D.R., Mohapatra, P.K., Ansari, S.A., Godbole, S.V., Iqbal, M., Manna, D., Ghanty, T.K., Huskens, J., Verboom, W.: Complexation of trivalent lanthanides and actinides with several novel diglycolamide functionalized calix[4]arenes: solvent extraction, luminescence and theoretical studies. RSC Advances 3, 9296–9303 (2013)

    Article  CAS  Google Scholar 

  21. Mohapatra, P.K., Raut, D.R., Iqbal, M., Huskens, J., Verboom, W.: Evaluation of several multiple diglycolamide functionalized calix[4]arene ligands for the isolation of carrier free 90Y from 90Sr. Appl. Radiat. Isot. 85, 133–138 (2014)

    Article  CAS  Google Scholar 

  22. Makrlík, E., Vaňura, P.: Applications of the dicarbollylcobaltate(III) anion in the water/nitrobenzene extraction system. Talanta 32, 423–429 (1985)

    Article  Google Scholar 

  23. Makrlík, E., Vaňura, P., Selucký, P.: Stability constants of some univalent cation complexes of 2,3-naphtho-15-crown-5 in nitrobenzene saturated with water. J. Solution Chem. 38, 1129–1138 (2009)

    Article  Google Scholar 

  24. Makrlík, E., Vaňura, P., Selucký, P.: Solvent extraction of calcium and strontium into nitrobenzene by using hydrogen dicarbollylcobaltate in the presence of dibutyl diethylcarbamoylmethylene phosphonate. J. Solution Chem. 39, 692–700 (2010)

    Article  Google Scholar 

  25. Makrlík, E., Vaňura, P., Selucký, P., Babain, V.A., Smirnov, I.V.: Extractive properties of synergistic mixture of hydrogen dicarbollylcobaltate and N, N, N′, N′-tetraisobutyl-2,6-dipicolinamide in the water–nitrobenzene system with regard to Eu3+ and Am3+. Acta Chim. Slov. 56, 718–722 (2009)

    Google Scholar 

  26. Makrlík, E., Vaňura, P., Sedláková, Z.: Extraction of europium and cerium into nitrobenzene using synergistic mixture of hydrogen dicarbollylcobaltate and polyethylene glycol PEG 600. J. Radioanal. Nucl. Chem. 283, 157–161 (2010)

    Article  Google Scholar 

  27. Makrlík, E., Spíchal, Z., Vaňura, P., Selucký, P.: Synergistic extraction of europium and americium into nitrobenzene by using hydrogen dicarbollylcobaltate and bis(diphenylphosphino)methane dioxide. J. Radioanal. Nucl. Chem. 295, 2135–2140 (2013)

    Article  Google Scholar 

  28. Romanovskiy, V.N., Smirnov, I.V., Babain, V.A., Todd, T.A., Herbst, R.S., Law, J.D., Brewer, K.N.: The universal solvent extraction (UNEX) process. I. Development of the UNEX process solvent for the separation of cesium, strontium and the actinides from acidic radioactive waste. Solvent Extr. Ion Exch. 19, 1–21 (2001)

    Article  CAS  Google Scholar 

  29. Law, J.D., Herbst, R.S., Todd, T.A., Romanovskiy, V.N., Babain, V.A., Esimantovskiy, V.M., Smirnov, I.V., Zaitsev, B.N.: The universal solvent extraction (UNEX) process. II. Flowsheet development and demonstration of the UNEX process for the separation of cesium, strontium and actinides from actual acidic radioactive waste. Solvent Extr. Ion Exch. 19, 23–36 (2001)

    Article  CAS  Google Scholar 

  30. Wu, L., Fang, Y., Jia, Y., Yang, Y., Liao, J., Liu, N., Yang, X., Feng, W., Ming, J., Yuan, L.: Pillar[5]arene-based diglycolamides for highly efficient separation of americium(III) and europium(III). Dalton Trans. 43, 3835–3838 (2014)

    Article  CAS  Google Scholar 

  31. Li, C., Wu, L., Chen, L., Yuan, X., Cai, Y., Feng, W., Liu, N., Ren, Y., Sengupta, A., Murali, M.S., Mohapatra, P.K., Tao, G., Zeng, H., Ding, S., Yuan, L.: Highly efficient extraction of actinides with pillar[5]arene-derived diglycolamides in ionic liquids via a unique mechanism involving competitive host-guest interactions. Dalton Trans. 45, 19299–19310 (2016)

    Article  CAS  Google Scholar 

  32. Galletta, M., Scaravaggi, S., Macerata, E., Famulari, A., Mele, A., Panzeri, W., Sansone, F., Casnati, A., Mariani, M.: 2,9-Dicarbonyl-1,10-phenanthroline derivatives with an unprecedented Am(III)/Eu(III) selectivity under highly acidic conditions. Dalton Trans. 42, 16930–16938 (2013)

    Article  CAS  Google Scholar 

  33. Manna, D., Mula, S., Bhattacharyya, A., Chattopadhyay, S., Ghanty, T.K.: Actinide selectivity of 1,10-phenanthroline-2,9-dicarboxamide and its derivatives: a theoretical prediction followed by experimental validation. Dalton Trans. 44, 1332–1340 (2015)

    Article  CAS  Google Scholar 

  34. Hawthorne, M.F., Young, D.C., Andrews, T.D., Howe, D.V., Pilling, R.L., Pitts, A.D., Reintjes, M., Warren, L.F., Wegner, P.A.: π-Dicarbollyl derivatives of the transition metals: metallocene analogs. J. Am. Chem. Soc. 90, 879–896 (1968)

    Article  CAS  Google Scholar 

  35. Makrlík, E.: Hydration of complexes of some univalent cations with polyethylene glycol ligands in nitrobenzene saturated with water. Collect. Czech. Chem. Commun. 57, 289–295 (1992)

    Article  Google Scholar 

  36. Vaňura, P., Rais, J., Selucký, P., Kyrš, M.: Extraction of strontium with dicarbolide in the presence of polyethylene glycol. Collect. Czech. Chem. Commun. 44, 157–166 (1979)

    Article  Google Scholar 

  37. Makrlík, E., Vaňura, P., Spíchal, Z., Selucký, P.: Synergistic extraction of europium and americium into nitrobenzene by using hydrogen dicarbollylcobaltate and 1,3-bis(diphenylphosphino)propane dioxide. J. Radioanal. Nucl. Chem. 298, 243–248 (2013)

    Article  Google Scholar 

  38. Vaňura, P., Makrlík, E., Rais, J., Kyrš, M.: Extraction of strontium and barium by nitrobenzene solution of dicarbolide in the presence of polyethylene glycols. Collect. Czech. Chem. Commun. 47, 1444–1464 (1982)

    Article  Google Scholar 

  39. Vaňura, P., Makrlík, E.: The extraction of strontium and barium with a solution of bis-1,2-dicarbollylcobaltate in nitrobenzene in the presence of 18-crown-6. Collect. Czech. Chem. Commun. 58, 1324–1336 (1993)

    Article  Google Scholar 

  40. Sillén, L.G., Warnqvist, B.: High-speed computers as a supplement to graphical methods. VI. A strategy for two-level LETAGROP adjustment of common and “group” parameters. Features that avoid divergence. Arkiv Kemi 31, 315–339 (1969)

    Google Scholar 

  41. Rais, J., Šebestová, E., Selucký, P., Kyrš, M.: Synergistic effect of polyethylenglycols in extraction of alkaline earth cations by nitrobenzene. J. Inorg. Nucl. Chem. 38, 1742–1744 (1976)

    Article  CAS  Google Scholar 

  42. Rais, J., Tachimori, S.: Extraction separation of tervalent americium and lanthanides in the presence of some soft and hard donors and dicarbollide. Sep. Sci. Technol. 29, 1347–1365 (1994)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Grant Agency of Faculty of Environmental Sciences, Czech University of Life Sciences, Prague, Project No. 42900/1312/3114 entitled “Environmental Aspects of Sustainable Development of Society,” by the Czech Ministry of Education, Youth, and Sports, Project MSMT No. 20/2015, and finally, by the Government of Russian Federation, Grant No. 074-U01.

Author information

Authors and Affiliations

  1. Faculty of Environmental Sciences, Czech University of Life Sciences, Prague, Kamýcká 129, 165 21, Prague 6 – Suchdol, Czech Republic

    Emanuel Makrlík

  2. Department of Analytical Chemistry, University of Chemistry and Technology, Prague, Technická 5, 166 28, Prague 6, Czech Republic

    Petr Vaňura

  3. Nuclear Research Institute, 250 68, Řež, Czech Republic

    Pavel Selucký

  4. ThreeArc Mining Ltd, 5, Stary Tolmachevskiy pr., Moscow, Russia, 115184

    Vasily Babain

  5. ITMO University, 49, Kronverksky pr., St. Petersburg, Russia, 197101

    Vasily Babain & Mikhail Alyapyshev

  6. Polymetal International, Narodnogo Opolcheniya 2, St. Petersburg, Russia, 198216

    Mikhail Alyapyshev

  7. Institute of Chemistry, St. Petersburg State University, 7-9, Universitetskaya nab., St. Petersburg, Russia, 199034

    Dmitriy Dar’in

Authors
  1. Emanuel Makrlík
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Petr Vaňura
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Pavel Selucký
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Vasily Babain
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Mikhail Alyapyshev
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Dmitriy Dar’in
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Emanuel Makrlík.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Makrlík, E., Vaňura, P., Selucký, P. et al. Highly Efficient Solvent Extraction of Americium and Europium by Using Hydrogen Dicarbollylcobaltate and N,N′-Diethyl-N,N′-bis(4-ethylphenyl)-1,10-phenanthroline-2,9-dicarboxamide. J Solution Chem 46, 1475–1489 (2017). https://doi.org/10.1007/s10953-017-0651-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-017-0651-6

Keywords

Search

Navigation