Protonation and Complexation of Isosaccharinic Acid with U(VI) and Fe(III) in Acidic Solutions: Potentiometric and Calorimetric Studies
Protonation and complexation of {alpha}-isosaccharinic acid with U(VI) and Fe(III) have been studied in acidic solutions at t=25 C and I=1.0 mol dm{sup -3} NaClO{sub 4}. From the potentiometric titrations, the protonation constant of the carboxylate group is calculated to be 3.65 {+-} 0.05 and the data are consistent with the presence of three and four successive mononuclear complexes for U(VI) and Fe(III), respectively. The formation constants of the complexes, log {beta}{sub j}for the reactions of M+L=ML{sub j} where j=1-3 for U(VI), j=1-4 for Fe(III) and L stands for isosaccharinate, are determined to be 2.91 {+-} 0.15 (UO{sub 2}L), 5.37 {+-} 0.07 (UO{sub 2}L{sub 2}), 7.25 {+-} 0.18 (UO{sub 2}L{sub 3}), 5.06 {+-} 0.17 (FeL), 8.51 {+-} 0.15 (FeL{sub 2}), 11.00 {+-} 0.16 (FeL{sub 3}), and 12.99 {+-} 0.17 (FeL{sub 4}). From the calorimetric titrations, the enthalpy of protonation of the carboxylate group is determined to be -(7.94 {+-} 0.03)kJ mol{sup -1}, similar to that of other ?-hydroxycarboxylates. The enthalpies of complexation between U(VI) and isosaccharinate are quite small: {Delta} H{sub 1} = -(1.0 {+-} 1.0)kJ mol{sup -1}, {Delta} H{sub 2}=1.4 {+-} 1.8 kJ mol{sup -1} and {Delta} H{sub 3}=-(6.2 {+-} 3.0)kJ mol{sup -1}, typical of the interactions between carboxylates and hard-acid cations. The complexation between U(VI) and isosaccharinate is mainly entropy-driven. In comparison, the enthalpies of complexation for FeL{sub 3} and FeL{sub 4} are large and exothermic, contributing significantly to the stability of the complexes.
- Research Organization:
- Pacific Northwest National Lab., Richland, WA (US)
- Sponsoring Organization:
- US Department of Energy (US)
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 15015152
- Report Number(s):
- PNNL-SA-44876; RAACAP; KP1301020; TRN: US0501874
- Journal Information:
- Radiochimica Acta, Vol. 92, Issue 9-11; Other Information: PBD: 1 Dec 2004; ISSN 0033-8230
- Country of Publication:
- United States
- Language:
- English
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