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COMPLEXATION DU PROTACTINIUM(V) PAR LES ACIDES OXALIQUE ET DIETHYLENETRIAMINEPENTAACETIQUE

Abstract : The present work is devoted to complexation of Pa(V) with oxalic acid and DTPA. Structural data on the limiting complex have been collected by combining X-ray absorption Spectroscopy, Capillary Electrophoresis (CE-ICP-MS) and DFT calculations. Thermodynamic data have been deduced from solvent extraction experiments. XAS data registered on samples of Pa(V) in oxalic acid have revealed the presence of one single Pa-O oxo bond and 3 oxalate in a bidentate mode in the complex of maximum order. The structure optimization, performed through DFT calculations indicate that 2 oxalate lie in the equatorial plane of the Pa=O bond, whereas one oxygen of the third oxalate goes in the prolongation of the oxo bond. Stability constants of the three successive complexes were determined by solvent extraction in the TTA/toluene/H2O/Pa(V)/NaClO4/HClO4/H2C2O4 system at different temperatures and 3 M ionic strength. The stability of the complexes was proved to increase with their order. CE-ICP-MS measurements on Pa/DTPA samples have indicated the formation of a neutral (1:1) limiting complex. This complex can therefore be written as Pa(DTPA). The optimized structure determined by DFT calculations allowed one to conclude that all eight donor atoms (5 O and 3 N) of the DTPA ligand are involved in the coordination of protactinium. The formation constant of this complex has been determined for different values of ionic strength and temperature. The complexation reaction of Pa(V) with DTPA was proved to be entropy-controlled.
keyword : Protactinium(V)
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M. Mendes. COMPLEXATION DU PROTACTINIUM(V) PAR LES ACIDES OXALIQUE ET DIETHYLENETRIAMINEPENTAACETIQUE. Physique Nucléaire Théorique [nucl-th]. Université Paris Sud - Paris XI, 2010. Français. ⟨tel-00557119⟩

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