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Issue 42, 2015
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The structures of CyMe4-BTBP complexes of americium(iii) and europium(iii) in solvents used in solvent extraction, explaining their separation properties

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Abstract

Separation of trivalent actinoid (An(III)) and lanthanoid (Ln(III)) ions is extremely challenging due to their similar ionic radii and chemical properties. Poly-aromatic nitrogen compounds acting as tetradentate chelating ligands to the metal ions in the extraction, have the ability to sufficiently separate An(III) from Ln(III). One of these compounds, 6,6′-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzol[1,2,4]triazin-3-yl)[2,2]bipyridine, CyMe4-BTBP, has proven to be resistant towards acidic environments and strong radiation from radioactive decomposition. EXAFS studies of the dicomplexes of CyMe4-BTBP with americium(III) and europium(III) in nitrobenzene, cyclohexanone, 1-hexanol, 1-octanol and malonamide (DMDOHEMA) in 1-octanol have been carried out to get a deeper understanding of the parameters responsible for the separation. The predominating complexes independent of solvent used are [Am(CyMe4-BTBP)2(NO3)]2+ and [Eu(CyMe4-BTBP)2]3+, respectively, which are present as outer-sphere ion-pairs with nitrate ions in the studied solvents with low relative permittivity. The presence of a nitrate ion in the first coordination sphere of the americium(III) complex compensates the charge density of the complex considerably in comparison when only outer-sphere ion-pairs are formed as for the [Eu(CyMe4-BTBP)2]3+ complex. The stability and solubility of a complex in a solvent with low relative permittivity increase with decreasing charge density. The [Am(CyMe4-BTBP)2(NO3)]2+ complex will therefore be increasingly soluble and stabilized over the [Eu(CyMe4-BTBP)2]3+ complex in solvents with decreasing relative permittivity of the solvent. The separation of americium(III) from europium(III) with CyMe4-BTBP as extraction agent will increase with decreasing relative permittivity of the solvent, and thereby also with decreasing solubility of CyMe4-BTBP. The choice of solvent is therefore a balance of a high separation factor and sufficient solubility of the CyMe4-BTBP ligand.

Graphical abstract: The structures of CyMe4-BTBP complexes of americium(iii) and europium(iii) in solvents used in solvent extraction, explaining their separation properties

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Publication details

The article was received on 25 Jul 2015, accepted on 15 Sep 2015 and first published on 16 Sep 2015


Article type: Paper
DOI: 10.1039/C5DT02859K
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Dalton Trans., 2015,44, 18395-18402

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    The structures of CyMe4-BTBP complexes of americium(III) and europium(III) in solvents used in solvent extraction, explaining their separation properties

    C. Ekberg, E. Löfström-Engdahl, E. Aneheim, M. R. StJ. Foreman, A. Geist, D. Lundberg, M. Denecke and I. Persson, Dalton Trans., 2015, 44, 18395
    DOI: 10.1039/C5DT02859K

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