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Evidence of Different Stoichiometries for the Limiting Carbonate Complexes across the Lanthanide(III) Series

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Abstract

The stoichiometries of limiting carbonate complexes of lanthanide(III) ions were investigated by solubility measurements of hydrated NaLn(CO3)2 solid compounds (Ln = La, Nd, Eu and Dy) at room temperature in aqueous solutions of high ionic strength (3.5 mol⋅kg−1 NaClO4) and high \(\mathrm{CO_{3}^{2-}}\) concentrations (0.1 to 1.5 mol⋅kg−1). The results were interpreted by considering the stability of carbonate complexes, with limiting species found to be \(\mathrm{La(CO_{3})_{4}^{5-}}\), \(\mathrm{Nd(CO_{3})_{4}^{5-}}\), \(\mathrm{Eu(CO_{3})_{3}^{3-}}\) and \(\mathrm{Dy(CO_{3})_{3}^{3-}}\). TRLFS measurements on the Eu and Dy solutions confirmed the predominance of a single aqueous complex in all the samples. Equilibrium constants were determined for the reaction \(\mathrm{Ln(CO_{3})_{3}^{3-}}+\mathrm{CO_{3}^{2-}}\) ⇌ \(\mathrm{Ln(CO_{3})_{4}^{5-}}\): \(\log_{10}K\mathrm{^{3.5m\:NaClO_{4}}_{4,La}=0.7\pm0.3}\), \(\log_{10}K\mathrm{^{3.5m\:NaClO_{4}}_{4,Nd}=1.3\pm0.3}\), and for Ln = Eu and Dy, \(\log_{10}K\mathrm{^{3.5m\:NaClO_{4}}_{4,Ln}\leq-0.4}\). These results suggest that tetracarbonato complexes are stable only for the light lanthanide ions in up to 1.5 molal \(\mathrm{CO_{3}^{2-}}\) aqueous solutions, in agreement with our recent capillary electrophoresis study. Comparison with literature results indicates that analogies between actinide(III) and lanthanide(III) ions of similar ionic radii do not hold in concentrated carbonate solutions. \(\mathrm{Am(CO_{3})_{3}^{3-}}\) was previously evidenced by solubility measurements, whereas we have observed that \(\mathrm{Nd(CO_{3})_{4}^{5-}}\) predominates in similar conditions. We may speculate that small chemical differences between Ln(III) and An(III) could result in macroscopic differences when their coordination sphere is complete.

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  1. V. Philippini

    Present address: Laboratoire de Radiochimie, Sciences Analytiques et Environnement (LRSAE), Institut de Chimie de Nice (ICN), Université de Nice Sophia-Antipolis, 28 avenue Valrose, 06108, Nice Cedex 2, France

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  1. CEA Saclay DEN/DPC/SECR Laboratoire de spéciation des radionucléides et des molécules, 91191, Gif-sur-Yvette, France

    V. Philippini, T. Vercouter & P. Vitorge

  2. Laboratoire Analyse et Modélisation pour la Biologie et l’Environnement UMR 8587, Bâtiment Maupertuis, Université d’Evry Val d’Essonne—CNRS, Boulevard François Mitterrand, 91025, Evry cedex, France

    P. Vitorge

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Philippini, V., Vercouter, T. & Vitorge, P. Evidence of Different Stoichiometries for the Limiting Carbonate Complexes across the Lanthanide(III) Series. J Solution Chem 39, 747–769 (2010). https://doi.org/10.1007/s10953-010-9539-4

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