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Titel: The electronic structure of anionic halide complexes of element 105 in aqueous solutions and their extraction by aliphatic amines
Autor(en): Pershina, Valerija G.Fricke, BurkhardKratz, Jens V.Ionova, Galina V.
Klassifikation (DDC): 530 - Physik (Physics)
Erscheinungsdatum: 1994
Zitierform: In: Radiochimica acta. - Muenchen : Oldenbourg, 64.1994. - S.37-48
Zusammenfassung: To study the complex formation of group 5 elements (Nb, Ta, Ha, and pseudoanalog Pa) in aqueous HCI solutions of medium and high concentrations the electronic structures of anionic complexes of these elements [MCl_6]^-, [MOCl_4]^-, [M(OH)-2 Cl_4]^-, and [MOCl_5]^2- have been calculated using the relativistic Dirac-Slater Discrete-Variational Method. The charge density distribution analysis has shown that tantalum occupies a specific position in the group and has the highest tendency to form the pure halide complex, [TaCl_6-. This fact along with a high covalency of this complex explains its good extractability into aliphatic amines. Niobium has equal trends to form pure halide [NbCl_6]^- and oxyhalide [NbOCl_5]^2- species at medium and high acid concentrations. Protactinium has a slight preference for the [PaOCl_5]^2- form or for the pure halide complexes with coordination number higher than 6 under these conditions. Element 105 at high HCl concentrations will have a preference to form oxyhalide anionic complex [HaOCl_5]^2- rather than [HaCl_6]^-. For the same sort of anionic oxychloride complexes an estimate has been done of their partition between the organic and aqueous phases in the extraction by aliphatic amines, which shows the following succession of the partition coefficients: P_Nb < P_Ha < P_Pa.
URI: urn:nbn:de:hebis:34-2008102024609
ISSN: 0033-8230

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