Complexation of NpO2+ with (2-Hydroxyethyl)ethylenediaminetriacetic Acid (HEDTA) in Aqueous Solutions: Thermodynamic Studies and Structural Analysis

Li, Xingliang; Zhang, Zhicheng; Martin, Leigh R; Luo, Shunzhong; Rao, Linfeng

doi:10.1039/C6RA17818A

Complexation of NpO2+ with (2-Hydroxyethyl)ethylenediaminetriacetic Acid (HEDTA) in Aqueous Solutions: Thermodynamic Studies and Structural Analysis

Journal Article · Fri Dec 02 04:00:00 EST 2016 · RSC Advances

DOI:https://doi.org/10.1039/C6RA17818A· OSTI ID:1337050

Li, Xingliang ^[1]; Zhang, Zhicheng ^[1]; Martin, Leigh R ^[2]; Luo, Shunzhong ^[1]; Rao, Linfeng ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

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, NpO₂L^2-, 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)₂L₂^6- complex, two Np(V) atoms are bridged by two hydroxides and each HEDTA maintains the tridentate coordination mode.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1337050

Journal Information:: RSC Advances, Journal Name: RSC Advances Vol. 6; ISSN 2046-2069

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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