Thermodynamic, Spectroscopic, and Computational Studies of f -Element Complexation by N -Hydroxyethyl-diethylenetriamine- N,N ', N ", N"-tetraacetic Acid

Grimes, Travis S.; Heathman, Colt R.; Jansone-Popova, Santa; Bryantsev, Vyacheslav S.; Goverapet Srinivasan, Sriram; Nakase, Masahiko; Zalupski, Peter R.

doi:10.1021/acs.inorgchem.6b02897

Title: Thermodynamic, Spectroscopic, and Computational Studies of f -Element Complexation by N -Hydroxyethyl-diethylenetriamine- N,N ', N ", N"-tetraacetic Acid

Journal Article · Tue Jan 24 00:00:00 EST 2017 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.6b02897· OSTI ID:1427625

^[1]; Heathman, Colt R. ^[1];

^[2];

^[2]; Nakase, Masahiko ^[3]; Zalupski, Peter R. ^[1]

Idaho National Lab. (INL), Idaho Falls, ID (United States). Aqueous Separations and Radiochemistry Dept.
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Japan Atomic Energy Agency (JAEA)-Material Science Research Center, Hyogo (Japan). Actinide Chemistry Group

Potentiometric and spectroscopic techniques were combined with DFT calculations to probe the coordination environment and determine thermodynamic features of trivalent f-element complexation by N-hydroxyethyl-diethylenetriamine-N,N',N",N"-tetraacetic acid, HEDTTA. Ligand protonation constants and lanthanide stability constants were determined using potentiometry. Five protonation constants were accessible in I = 2.0 M (H⁺/Na⁺)ClO₄. UV–vis spectroscopy was used to determine stability constants for Nd³⁺ and Am³⁺ complexation with HEDTTA. Luminescence spectroscopy indicates two water molecules in the inner coordination sphere of the Eu/HEDTTA complex, suggesting HEDTTA is heptadentate. Luminescence data was supported by DFT calculations, which demonstrate that substitution of the acetate pendant arm by a N-hydroxyethyl group weakens the metal–nitrogen bond. This bond elongation is reflected in HEDTTA’s ability to differentiate trivalent actinides from trivalent lanthanides. The trans-lanthanide Ln/HEDTTA complex stability trend is analogous to Ln/DTPA complexation; however, the loss of one chelate ring resulting from structural substitution weakens the complexation by ~3 orders of magnitude. Successful separation of trivalent americium from trivalent lanthanides was demonstrated when HEDTTA was utilized as aqueous holdback complexant in a liquid–liquid system. Time-dependent extraction studies for HEDTTA were compared to diethylenetriamine-N,N,N',N",N"-pentaacetic acid (DTPA) and N-hydroxyethyl-ethylenediamine-N,N',N'-triacetic acid (HEDTA). The results presented here indicate substantially enhanced phase-transfer kinetic rates for mixtures containing HEDTTA.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Idaho National Lab. (INL), Idaho Falls, ID (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC); USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: AC05-00OR22725; AC07-05ID14517; AC02-05CH11231

OSTI ID:: 1427625

Journal Information:: Inorganic Chemistry, Vol. 56, Issue 3; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 16 works

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