Complexation of uranium(VI) and samarium(III) with oxydiacetic acid: Temperature effect and coordination modes
- LBNL Library
The complexation of uranium(VI) and samarium(III) with oxydiacetate in 1.05 mol kg{sup -1} NaClO{sub 4} is studied at variable temperatures (25-70 C). Three U(VI)/O DA complexes (UO{sub 2}L, UO{sub 2}L{sub 2}{sup 2-}, and UO{sub 2}HL{sub 2}{sup -}) and three Sm(III)/ODA complexes (SmL{sub j}{sup (3-2j)+} 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 ({Delta}C{sub p}{sup o} in J K{sup -1} mol{sup -1}) are 95 {+-} 6, 297 {+-} 14, and 162 {+-} 19 for UO{sub 2}L, UO{sub 2}L{sub 2}{sup 2-}, and UO{sub 2}HL{sub 2}{sup -}, and 142 {+-} 6, 198 {+-} 14 and 157 {+-} 19 for SmL{sup +}, SmL{sub 2}{sup -}, and SmL{sub 3}{sup 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.
- Research Organization:
- Ernest Orlando Lawrence Berkeley National Laboratory, Berkeley, CA (US)
- Sponsoring Organization:
- USDOE Director, Office of Science. Basic Energy Sciences (US)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 815351
- Report Number(s):
- LBNL--52011
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 11 Vol. 42; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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