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Thermodynamic Study of the Complexation of Protactinium(V) with Diethylenetriaminepentaacetic Acid

Abstract : The complex formation of protactinium(V) with DTPA was studied at different temperatures (25-50 °C) and ionic strengths (0.1-1 M) with the element at tracer scale. Irrespective of the temperature and ionic strength studied, only one neutral complex with (1:1) stoichiometry was identified from solvent extraction and capillary electrophoresis coupled to ICP-MS (CE-ICP-MS) experiments. Density Functional Theory (DFT) calculations revealed that two complexes can be considered: Pa(DTPA) and PaO(H2DTPA). The associated formation constants were determined from solvent extraction data at different ionic strengths and temperatures and then extrapolated to zero ionic strength by SIT methodology. These constants are valid, regardless of complex form, Pa(DTPA) or PaO(H2DTPA). The standard thermodynamic data determined with these extrapolated constants revealed a very stable complex formed energetically by an endothermic contribution which is counter balanced by a strong entropic contribution. Both, the positive enthalpy and entropy energy terms suggest the formation of an inner sphere complex.
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http://hal.in2p3.fr/in2p3-00865789
Contributor : Sophie Heurteau <>
Submitted on : Wednesday, September 25, 2013 - 10:18:37 AM
Last modification on : Thursday, November 19, 2020 - 8:06:01 AM

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M. Mendes, S. Leguay, C. Le Naour, S. Hamadi, J. Roques, et al.. Thermodynamic Study of the Complexation of Protactinium(V) with Diethylenetriaminepentaacetic Acid. Inorganic Chemistry, American Chemical Society, 2013, 52, pp.7497-7507. ⟨10.1021/ic400378t⟩. ⟨in2p3-00865789⟩

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