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Title: Gamma-radiolytic stability of new methylated TODGA derivatives for minor actinide recycling

Abstract

The stability against gamma radiation of MeTODGA (methyl tetraoctyldiglycolamide) and Me2TODGA (dimethyl tetraoctyldiglycolamide), derivatives from the well-known extractant TODGA (N,N,N',N';-tetraoctyldiglycolamide), were studied and compared. Solutions of MeTODGA and Me2TODGA in alkane diluents were subjected to 60Co γ-irradiation in the presence and absence of nitric acid and analyzed using LC-MS to determine their rates of radiolytic concentration decrease, as well as to identify radiolysis products. The results of product identification from three different laboratories are compared and found to be in good agreement. The diglycolamide (DGA) concentrations decreased exponentially with increasing absorbed dose. The MeTODGA degradation rate constants (dose constants) were uninfluenced by the presence of nitric acid, but the acid increased the rate of degradation for Me2TODGA. The degradation products formed by irradiation are also initially produced in greater amounts in acid-contacted solution, but products may also be degraded by continued radiolysis. As a result, the identified radiolysis products suggest that the weakest bonds are those in the diglycolamide center of these molecules.

Authors:
 [1];  [2];  [3];  [1];  [3];  [4];  [4];  [1];  [4];  [3];  [2];  [2]
  1. Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas (CIEMAT), Madrid (Spain)
  2. Idaho National Lab. (INL), Idaho Falls, ID (United States)
  3. Forschungszentrum Julich GmbH, Institut fur Energie-und Klimaforschung -Nukleare Entsorgung und Reaktorsicherheit (IEK), Julich (Germany)
  4. Univ. of Twente, Enschede (The Netherlands)
Publication Date:
Research Org.:
Idaho National Lab. (INL), Idaho Falls, ID (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1294500
Report Number(s):
INL/JOU-15-35577
Journal ID: ISSN 1477-9226; ICHBD9
Grant/Contract Number:  
AC07-05ID14517
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 44; Journal Issue: 41; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; radiation chemistry; free radicals; minor actinides; degradation products; diglycolamides

Citation Formats

Galan, Hitos, Zarzana, Christopher A., Wilden, Andreas, Nunez, Ana, Schmidt, Holger, Egberink, Richard J. M., Leoncini, Andrea, Cobos, Joaquin, Verboom, Willem, Modolo, Giuseppe, Groenewold, Gary S., and Mincher, Bruce J. Gamma-radiolytic stability of new methylated TODGA derivatives for minor actinide recycling. United States: N. p., 2015. Web. doi:10.1039/C5DT02484F.
Galan, Hitos, Zarzana, Christopher A., Wilden, Andreas, Nunez, Ana, Schmidt, Holger, Egberink, Richard J. M., Leoncini, Andrea, Cobos, Joaquin, Verboom, Willem, Modolo, Giuseppe, Groenewold, Gary S., & Mincher, Bruce J. Gamma-radiolytic stability of new methylated TODGA derivatives for minor actinide recycling. United States. doi:10.1039/C5DT02484F.
Galan, Hitos, Zarzana, Christopher A., Wilden, Andreas, Nunez, Ana, Schmidt, Holger, Egberink, Richard J. M., Leoncini, Andrea, Cobos, Joaquin, Verboom, Willem, Modolo, Giuseppe, Groenewold, Gary S., and Mincher, Bruce J. Tue . "Gamma-radiolytic stability of new methylated TODGA derivatives for minor actinide recycling". United States. doi:10.1039/C5DT02484F. https://www.osti.gov/servlets/purl/1294500.
@article{osti_1294500,
title = {Gamma-radiolytic stability of new methylated TODGA derivatives for minor actinide recycling},
author = {Galan, Hitos and Zarzana, Christopher A. and Wilden, Andreas and Nunez, Ana and Schmidt, Holger and Egberink, Richard J. M. and Leoncini, Andrea and Cobos, Joaquin and Verboom, Willem and Modolo, Giuseppe and Groenewold, Gary S. and Mincher, Bruce J.},
abstractNote = {The stability against gamma radiation of MeTODGA (methyl tetraoctyldiglycolamide) and Me2TODGA (dimethyl tetraoctyldiglycolamide), derivatives from the well-known extractant TODGA (N,N,N',N';-tetraoctyldiglycolamide), were studied and compared. Solutions of MeTODGA and Me2TODGA in alkane diluents were subjected to 60Co γ-irradiation in the presence and absence of nitric acid and analyzed using LC-MS to determine their rates of radiolytic concentration decrease, as well as to identify radiolysis products. The results of product identification from three different laboratories are compared and found to be in good agreement. The diglycolamide (DGA) concentrations decreased exponentially with increasing absorbed dose. The MeTODGA degradation rate constants (dose constants) were uninfluenced by the presence of nitric acid, but the acid increased the rate of degradation for Me2TODGA. The degradation products formed by irradiation are also initially produced in greater amounts in acid-contacted solution, but products may also be degraded by continued radiolysis. As a result, the identified radiolysis products suggest that the weakest bonds are those in the diglycolamide center of these molecules.},
doi = {10.1039/C5DT02484F},
journal = {Dalton Transactions},
number = 41,
volume = 44,
place = {United States},
year = {2015},
month = {9}
}

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    Works referencing / citing this record:

    Unprecedented Inversion of Selectivity and Extraordinary Difference in the Complexation of Trivalent f  Elements by Diastereomers of a Methylated Diglycolamide
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