Complexation of Uranium(VI) and Samarium(III) with Oxydiacetic Acid:  Temperature Effect and Coordination Modes

• Published in: Inorganic chemistry 2003-06, Vol.42 (11), p.3685-3692
• Main Authors: Rao, Linfeng, Garnov, Alexander Yu, Jiang, Jun, Di Bernardo, Plinio, Zanonato, PierLuigi, Bismondo, Arturo
• Format: Article
• Language: English
• Subjects: CALORIMETRY; ELECTROSTATICS; ENTHALPY; ENTROPY; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; POTENTIOMETRY; SOLVENTS; SPECIFIC HEAT; SPECTROSCOPY; TEMPERATURE DEPENDENCE; THERMODYNAMICS; URANIUM
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic034227h

The complexation of uranium(VI) and samarium(III) with oxydiacetate (ODA) in 1.05 mol kg-1 NaClO4 is studied at variable temperatures (25−70 °C). Three U(VI)/ODA complexes (UO2L, UO2L2 2-, and UO2HL2 -) and three Sm(III)/ODA complexes (SmL j (3-2 j )+ with j = 1, 2, 3) are identified in this temperature range. The formation constants and the molar enthalpies of complexation are determined by potentiometry and calorimetry. The complexation of uranium(VI) and samarium(III) with oxydiacetate becomes more endothermic at higher temperatures. However, the complexes become stronger due to increasingly more positive entropy of complexation at higher temperatures that exceeds the increase in the enthalpy of complexation. The values of the heat capacity of complexation (ΔC p° in J K-1 mol-1) are 95 ± 6, 297 ± 14, and 162 ± 19 for UO2L, UO2L2 2-, and UO2HL2 -, and 142 ± 6, 198 ± 14, and 157 ± 19 for SmL+, SmL2 -, and SmL3 3-, respectively. The thermodynamic parameters, in conjunction with the structural information from spectroscopy, help to identify the coordination modes in the uranium oxydiacetate complexes. The effect of temperature on the thermodynamics of the complexation is discussed in terms of the electrostatic model and the change in the solvent structure.