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Dalton Trans., 2006, 4829 - 4837, DOI: 10.1039/b605321a
Thermodynamics and the structural aspects of the ternary complexes of Am(III), Cm(III) and Eu(III) with Ox and EDTA + Ox
Punam Thakur, Jagdish N. Mathur, Cleveland J. Dodge, Arokiasamy J. Francis and Gregory R. Choppin
The stability constants and the associated thermodynamic parameters of formation of the binary and the ternary complexes of Am3+, Cm3+ and Eu3+ were determined by a solvent extraction to measure the variation in the distribution coefficient with temperature (0–60 °C) for aqueous solutions of I = 6.60 m (NaClO4). The formation of ternary complexes is favored by both the enthalpy (exothermic) and the entropy (endothermic) values. 13 C NMR, TRLFS and EXAFS spectral data was used to study the coordination modes of the ternary complexes. In the formation of the complex M(EDTA)(Ox)3–, the EDTA retained all its coordination sites with Ox binding via two carboxylates and with one water of hydration remaining attached to the M3+. In the complex M(EDTA)(Ox)25–, one carboxylate, either from EDTA or Ox, is not bounded to M3+ and there were no water of hydration attached to these cations
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