Thermodynamic, Spectroscopic, and Computational Studies of f -Element Complexation by N -Hydroxyethyl-diethylenetriamine- N,N ', N ", N"-tetraacetic Acid
Abstract
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 mixturesmore »
- Authors:
-
[1];
[2];
[2];
[2];
- 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
- Publication Date:
- Research Org.:
- 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 Org.:
- USDOE Office of Science (SC); USDOE Office of Nuclear Energy (NE)
- OSTI Identifier:
- 1427625
- Grant/Contract Number:
- AC05-00OR22725; AC07-05ID14517; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 56; Journal Issue: 3; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS
Citation Formats
Grimes, Travis S., Heathman, Colt R., Jansone-Popova, Santa, Bryantsev, Vyacheslav S., Goverapet Srinivasan, Sriram, Nakase, Masahiko, and Zalupski, Peter R. Thermodynamic, Spectroscopic, and Computational Studies of f -Element Complexation by N -Hydroxyethyl-diethylenetriamine- N,N ', N ", N"-tetraacetic Acid. United States: N. p., 2017.
Web. doi:10.1021/acs.inorgchem.6b02897.
Grimes, Travis S., Heathman, Colt R., Jansone-Popova, Santa, Bryantsev, Vyacheslav S., Goverapet Srinivasan, Sriram, Nakase, Masahiko, & Zalupski, Peter R. Thermodynamic, Spectroscopic, and Computational Studies of f -Element Complexation by N -Hydroxyethyl-diethylenetriamine- N,N ', N ", N"-tetraacetic Acid. United States. https://doi.org/10.1021/acs.inorgchem.6b02897
Grimes, Travis S., Heathman, Colt R., Jansone-Popova, Santa, Bryantsev, Vyacheslav S., Goverapet Srinivasan, Sriram, Nakase, Masahiko, and Zalupski, Peter R. Tue .
"Thermodynamic, Spectroscopic, and Computational Studies of f -Element Complexation by N -Hydroxyethyl-diethylenetriamine- N,N ', N ", N"-tetraacetic Acid". United States. https://doi.org/10.1021/acs.inorgchem.6b02897. https://www.osti.gov/servlets/purl/1427625.
@article{osti_1427625,
title = {Thermodynamic, Spectroscopic, and Computational Studies of f -Element Complexation by N -Hydroxyethyl-diethylenetriamine- N,N ', N ", N"-tetraacetic Acid},
author = {Grimes, Travis S. and Heathman, Colt R. and Jansone-Popova, Santa and Bryantsev, Vyacheslav S. and Goverapet Srinivasan, Sriram and Nakase, Masahiko and Zalupski, Peter R.},
abstractNote = {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.},
doi = {10.1021/acs.inorgchem.6b02897},
journal = {Inorganic Chemistry},
number = 3,
volume = 56,
place = {United States},
year = {Tue Jan 24 00:00:00 EST 2017},
month = {Tue Jan 24 00:00:00 EST 2017}
}
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