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Mixed Ligand Complexes of Am3+, Cm3+ and Eu3+ with HEDTA and HEDTA + NTA—Complexation Thermodynamics and Structural Aspects

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Abstract

The stability constants and the associated thermodynamic parameters of formation for the 1:1 binary complexes of Am3+, Cm3+ and Eu3+ with N-(2-hydroxyethyl) ethylenediaminetriacetate (HEDTA) and their 1:1:1 ternary complexes with HEDTA + NTA (nitrilotriacate) were determined by distribution ratio measurements using solvent extraction in aqueous solutions of I=0.10 mol⋅L−1 (NaClO4) at temperatures of 0–45 °C. Formation of these complexes is favored by both the enthalpy (exothermic) and the entropy (endothermic) terms. Luminescence lifetime measurements with Cm and Eu were used to study the coordination environment of these complexes over a range of concentrations and pH values. In the binary complexes M(HEDTA), HEDTA is a hexadentate ligand with three waters of hydration, while in the ternary complexes M(HEDTA)(NTA)3− we propose that the HEDTA retaines hexadentate coordination with NTA binding via three sites, depending on the pH of the solution, with the observation that the complex may contain a single water of hydration.

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Acknowledgements

This research was supported by a grant from the USDOE Environmental Management Science Program.

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  1. P. Thakur

    Present address: Carlsbad Environmental Monitoring & Research Center, 1400 University Drive, Carlsbad, NM, 88220, USA

Authors and Affiliations

  1. Department of Chemistry & Biochemistry, Florida State University, Tallahassee, FL, 32306, USA

    P. Thakur & G. R. Choppin

  2. Center of Laboratory Science, RJ Lee Group Inc., 2710 North 20th Avenue, Pasco, WA, 99301, USA

    J. L. Conca

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  1. P. Thakur
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  2. J. L. Conca
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  3. G. R. Choppin
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Correspondence to P. Thakur.

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Thakur, P., Conca, J.L. & Choppin, G.R. Mixed Ligand Complexes of Am3+, Cm3+ and Eu3+ with HEDTA and HEDTA + NTA—Complexation Thermodynamics and Structural Aspects. J Solution Chem 41, 599–615 (2012). https://doi.org/10.1007/s10953-012-9826-3

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