Issue 115, 2016

Complexation of NpO2+ with (2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA) in aqueous solutions: thermodynamic studies and structural analysis

Abstract

Complexation of Np(V) with N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA) was studied in aqueous solution (I = 1.0 mol L−1 NaClO4, t = 25 °C) by spectrophotometry, microcalorimetry and Extended X-ray absorption fine structure (EXAFS) spectroscopy. Equilibrium constants for the formation of three complexes, NpO2L2−, NpO2(HL), and (NpO2)2(OH)2L26−, were determined to be (6.91 ± 0.06), (4.28 ± 0.03) and −(4.93 ± 0.03), respectively. The enthalpies of complexation were determined to be −(8.0 ± 2.0) kJ mol−1 for NpO2L2− and −(2.2 ± 2.0) kJ mol−1 for NpO2(HL). Thermodynamic data of the complexation of Np(V) with HEDTA were compared to those of Np(V) with other aminopolycarboxylic acids, gaining insight into the possible coordination modes of the complexes. The EXAFS studies provided further structural information on those modes. In both NpO2L2− and NpO2(HL) complexes, HEDTA coordinates to Np(V) in a tridentate mode through two oxygens of two carboxylic groups and one nitrogen of the amine group. In the (NpO2)2(OH)2L26− complex, two Np(V) atoms are bridged by two hydroxides and each HEDTA maintains the tridentate coordination mode.

Graphical abstract: Complexation of NpO2+ with (2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA) in aqueous solutions: thermodynamic studies and structural analysis

Supplementary files

Article information

Article type
Paper
Submitted
12 Jul 2016
Accepted
01 Dec 2016
First published
02 Dec 2016

RSC Adv., 2016,6, 114916-114926

Complexation of NpO2+ with (2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA) in aqueous solutions: thermodynamic studies and structural analysis

X. Li, Z. Zhang, L. R. Martin, S. Luo and L. Rao, RSC Adv., 2016, 6, 114916 DOI: 10.1039/C6RA17818A

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