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Sequestering Ability of Dicarboxylic Ligands Towards Dioxouranium(VI) in NaCl and KNO3 Aqueous Solutions at T=298.15 K

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Abstract

The formation constants of dioxouranium(VI)-2,2′-oxydiacetic acid (diglycolic acid, ODA) and 3,6,9-trioxaundecanedioic acid (diethylenetrioxydiacetic acid, TODA) complexes were determined in NaCl (0.1≤I≤1.0 mol⋅L−1) and KNO3 (I=0.1 mol⋅L−1) aqueous solutions at T=298.15 K by ISE-[H+] glass electrode potentiometry and visible spectrophotometry. Quite different speciation models were obtained for the systems investigated, namely: ML0, MLOH−, ML 2−2 , M2L2(OH)−, and M2L2(OH) 2−2 , for the dioxouranium(VI)–ODA system, and ML0, MLH+, and MLOH− for the dioxouranium(VI)–TODA system (M=UO 2+2 and L = ODA or TODA), respectively. The dependence on ionic strength of the protonation constants of ODA and TODA and of both metal-ligand complexes was investigated using the SIT (Specific Ion Interaction Theory) approach. Formation constants at infinite dilution are [for the generic equilibrium pUO 2+2 +q(L2−)+rH+ ⇌(UO 2+2 ) p (L) q H (2p−2q+r) r ;β pqr ]: log 10 β 110=6.146, log 10 β 11−1=0.196, log 10 β 120=8.360, log 10 β 22−1=8.966, log 10 β 22−2=3.529, for the dioxouranium(VI)–ODA system and log β 110=3.636, log 10 β 111=6.650, log 10 β 11−1=−1.242 for dioxouranium(VI)–TODA system. The influence of etheric oxygen(s) on the interaction towards the metal ion was discussed, and this effect was quantified by means of a sigmoid Boltzman type equation that allows definition of a quantitative parameter (pL 50) that expresses the sequestering capacity of ODA and TODA towards UO 2+2 ; a comparison with other dicarboxylates was made. A visible absorption spectrum for each complex reaching a significant percentage of formation in solution (KNO3 medium) has been calculated to better characterize the compounds found by pH-metric refinement.

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Authors and Affiliations

  1. Dipartimento di Chimica Analitica dell’Università, Via Pietro Giuria 5, 10125, Torino, Italy

    Silvia Berto, Pier Giuseppe Daniele & Enrico Prenesti

  2. Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica dell’Università, Salita Sperone 31, 98166, Messina (Vill. S. Agata), Italy

    Francesco Crea, Concetta De Stefano & Silvio Sammartano

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  1. Silvia Berto
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  2. Francesco Crea
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  3. Pier Giuseppe Daniele
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  4. Concetta De Stefano
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  5. Enrico Prenesti
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  6. Silvio Sammartano
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Correspondence to Francesco Crea or Pier Giuseppe Daniele.

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Berto, S., Crea, F., Daniele, P.G. et al. Sequestering Ability of Dicarboxylic Ligands Towards Dioxouranium(VI) in NaCl and KNO3 Aqueous Solutions at T=298.15 K. J Solution Chem 38, 1343–1356 (2009). https://doi.org/10.1007/s10953-009-9452-x

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  • DOI: https://doi.org/10.1007/s10953-009-9452-x

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