In this paper we report an investigation on the interactions between dioxouranium(VI) and citrate using potentiometry (H+-glass electrode) and UV-spectrophotometry. Potentiometric measurements were carried out in NaCl and KNO3 aqueous solutions at t = 25 °C in a wide range of experimental conditions (concentrations, ligand/metal molar ratio, pH, titrants). Measurements in NaCl were carried out at different ionic strength values (0.1 ≤ I/mol L-1 ≤ 1.0); different procedures were employed for the acquisition of experimental data and careful analysis of these data performed. In all cases the speciation model that best fits experimental data takes into account the formation of the following species: UO2(Cit)-, (UO2)2(Cit)22-, (UO2)2(Cit)2(OH)24-, (UO2)2(Cit)2(OH)3-, (UO2)2(Cit)(OH)2-, (UO2)2(Cit)(OH)0, (UO2)3(Cit)2(OH)55-. The dependence on ionic strength of formation constants was taken into account by using both a simple Debye-Hückel type equation and the SIT (Specific ion Interaction Theory) approach. Moreover, a visible absorption spectrum for each complex reaching a significant percentage of formation in solution (KNO3 medium) has been calculated to characterise the compounds found by pH-metric refinement. Recommended values for the uranyl-citrate species were proposed for each ionic strength values in NaCl aqueous solution. Comparison with literature stability constants is reported too.

Potentiometric and spectrophotometric characterization of the UO22+-citrate complexes in aqueous solution, at different concentrations, ionic strengths and supporting electrolytes

BERTO, Silvia;DANIELE, Pier Giuseppe;PRENESTI, Enrico;
2012

Abstract

In this paper we report an investigation on the interactions between dioxouranium(VI) and citrate using potentiometry (H+-glass electrode) and UV-spectrophotometry. Potentiometric measurements were carried out in NaCl and KNO3 aqueous solutions at t = 25 °C in a wide range of experimental conditions (concentrations, ligand/metal molar ratio, pH, titrants). Measurements in NaCl were carried out at different ionic strength values (0.1 ≤ I/mol L-1 ≤ 1.0); different procedures were employed for the acquisition of experimental data and careful analysis of these data performed. In all cases the speciation model that best fits experimental data takes into account the formation of the following species: UO2(Cit)-, (UO2)2(Cit)22-, (UO2)2(Cit)2(OH)24-, (UO2)2(Cit)2(OH)3-, (UO2)2(Cit)(OH)2-, (UO2)2(Cit)(OH)0, (UO2)3(Cit)2(OH)55-. The dependence on ionic strength of formation constants was taken into account by using both a simple Debye-Hückel type equation and the SIT (Specific ion Interaction Theory) approach. Moreover, a visible absorption spectrum for each complex reaching a significant percentage of formation in solution (KNO3 medium) has been calculated to characterise the compounds found by pH-metric refinement. Recommended values for the uranyl-citrate species were proposed for each ionic strength values in NaCl aqueous solution. Comparison with literature stability constants is reported too.
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Dioxouranium(VI)-Citrate; Speciation; Sequestering ability; Dependence on ionic strength; SIT equation
Silvia Berto; Francesco Crea; Pier Giuseppe Daniele; Concetta De Stefano; Enrico Prenesti; Silvio Sammartano
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2318/91063
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