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:
-
- Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas (CIEMAT), Madrid (Spain)
- Idaho National Lab. (INL), Idaho Falls, ID (United States)
- Forschungszentrum Julich GmbH, Institut fur Energie-und Klimaforschung -Nukleare Entsorgung und Reaktorsicherheit (IEK), Julich (Germany)
- 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. https://doi.org/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. https://doi.org/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 = {Tue Sep 15 00:00:00 EDT 2015},
month = {Tue Sep 15 00:00:00 EDT 2015}
}
Web of Science
Works referenced in this record:
Assessment of the environmental footprint of nuclear energy systems. Comparison between closed and open fuel cycles
journal, May 2014
- Poinssot, Ch.; Bourg, S.; Ouvrier, N.
- Energy, Vol. 69
A review of the demonstration of innovative solvent extraction processes for the recovery of trivalent minor actinides from PUREX raffinate
journal, August 2012
- Modolo, Giuseppe; Wilden, A.; Geist, Andreas
- Radiochimica Acta, Vol. 100, Issue 8-9
Direct Selective Extraction of Actinides (III) from PUREX Raffinate using a Mixture of CyMe 4 BTBP and TODGA as 1-cycle SANEX Solvent Part III: Demonstration of a Laboratory-Scale Counter-Current Centrifugal Contactor Process
journal, March 2013
- Wilden, Andreas; Modolo, Giuseppe; Schreinemachers, Christian
- Solvent Extraction and Ion Exchange, Vol. 31, Issue 5
Laboratory-Scale Counter-Current Centrifugal Contactor Demonstration of an Innovative-SANEX Process Using a Water Soluble BTP
journal, October 2014
- Wilden, Andreas; Modolo, Giuseppe; Kaufholz, Peter
- Solvent Extraction and Ion Exchange, Vol. 33, Issue 2
The Actinide-Lanthanide Separation Concept
journal, May 2014
- Lumetta, Gregg J.; Gelis, Artem V.; Carter, Jennifer C.
- Solvent Extraction and Ion Exchange, Vol. 32, Issue 4
Implementation of Americium Separation from a PUREX Raffinate
journal, January 2012
- Bollesteros, Marie-Jordane; Calor, Jean-Noël; Costenoble, Sylvain
- Procedia Chemistry, Vol. 7
Chemistry of Diglycolamides: Promising Extractants for Actinide Partitioning
journal, November 2011
- Ansari, Seraj A.; Pathak, Priyanath; Mohapatra, Prasanta K.
- Chemical Reviews, Vol. 112, Issue 3
THE NOVEL EXTRACTANTS, DIGLYCOLAMIDES, FOR THE EXTRACTION OF LANTHANIDES AND ACTINIDES IN HNO 3 – n -DODECANE SYSTEM
journal, January 2001
- Sasaki, Yuji; Sugo, Yumi; Suzuki, Shinichi
- Solvent Extraction and Ion Exchange, Vol. 19, Issue 1
Demonstration of a TODGA based Extraction Process for the Partitioning of Minor Actinides from a PUREX Raffinate: Part III: Centrifugal Contactor Run using Genuine Fuel Solution
journal, January 2009
- Magnusson, Daniel; Christiansen, Birgit; Glatz, Jean‐Paul
- Solvent Extraction and Ion Exchange, Vol. 27, Issue 1
Plutonium Loading of Prospective Grouped Actinide Extraction (GANEX) Solvent Systems based on Diglycolamide Extractants
journal, March 2012
- Brown, Jamie; McLachlan, Fiona; Sarsfield, Mark
- Solvent Extraction and Ion Exchange, Vol. 30, Issue 2
Development of a New Flowsheet for Co-Separating the Transuranic Actinides: The “EURO-GANEX” Process
journal, June 2014
- Carrott, Michael; Bell, Katie; Brown, Jamie
- Solvent Extraction and Ion Exchange, Vol. 32, Issue 5
ACSEPT—Partitioning technologies and actinide science: Towards pilot facilities in Europe
journal, September 2011
- Bourg, S.; Hill, C.; Caravaca, C.
- Nuclear Engineering and Design, Vol. 241, Issue 9
Synthesis and Am/Eu extraction of novel TODGA derivatives
journal, August 2010
- Iqbal, Mudassir; Huskens, Jurriaan; Verboom, Willem
- Supramolecular Chemistry, Vol. 22, Issue 11-12
Modified Diglycolamides for the An(III) + Ln(III) Co-separation: Evaluation by Solvent Extraction and Time-Resolved Laser Fluorescence Spectroscopy
journal, January 2014
- Wilden, Andreas; Modolo, Giuseppe; Lange, Steve
- Solvent Extraction and Ion Exchange, Vol. 32, Issue 2
Influence of diluent on radiolysis of amides in organic solution
journal, May 2007
- Sugo, Yumi; Izumi, Yoshinobu; Yoshida, Yoichi
- Radiation Physics and Chemistry, Vol. 76, Issue 5
Radiolytic Stability of TODGA: Characterization of Degraded Samples under Different Experimental Conditions
journal, January 2012
- Galán, Hitos; Núñez, Ana; Espartero, Amparo G.
- Procedia Chemistry, Vol. 7
A Comparison of the γ -Radiolysis of TODGA and T(EH)DGA Using UHPLC-ESI-MS Analysis
journal, March 2015
- Zarzana, Christopher A.; Groenewold, Gary S.; Mincher, Bruce J.
- Solvent Extraction and Ion Exchange, Vol. 33, Issue 5
Review: The Effects of Radiation Chemistry on Solvent Extraction 4: Separation of the Trivalent Actinides and Considerations for Radiation-Resistant Solvent Systems
journal, June 2010
- Mincher, Bruce J.; Modolo, Giuseppe; Mezyk, Stephen P.
- Solvent Extraction and Ion Exchange, Vol. 28, Issue 4
Comparative evaluation of two substituted diglycolamide extractants for ‘actinide partitioning’
journal, February 2010
- Gujar, R. B.; Ansari, S. A.; Murali, M. S.
- Journal of Radioanalytical and Nuclear Chemistry, Vol. 284, Issue 2
Development of a TODGA based Process for Partitioning of Actinides from a PUREX Raffinate Part I: Batch Extraction Optimization Studies and Stability Tests
journal, October 2007
- Modolo, Giuseppe; Asp, Hanna; Schreinemachers, Christian
- Solvent Extraction and Ion Exchange, Vol. 25, Issue 6
Studies on hydrolysis and radiolysis of N,N,N′,N′-tetraoctyl-3-oxapentane-1,5-diamide
journal, January 2002
- Sugo, Y.; Sasaki, Y.; Tachimori, S.
- Radiochimica Acta, Vol. 90, Issue 3
Hydrolysis and Radiation Stability of m-Xylylene Bis-diglycolamide: Synthesis and Quantitative Study of Degradation Products by HPLC-APCI+
journal, June 2011
- Galán, Hitos; Murillo, María Teresa; Sedano, Rosa
- European Journal of Organic Chemistry, Vol. 2011, Issue 20-21
Studies on hydrolytic and radiolytic stability of N , N , N ´, N ´-tetra-(2-ethylhexyl) thiodiglycolamide T(2EH)TDGA
journal, January 2012
- Ruhela, R.; Sharma, J. N.; Tomar, B. S.
- Radiochimica Acta, Vol. 100, Issue 1
Radiolytic Stability of N,N,N ′ ,N ′-Tetraoctyl Diglycolamide (TODGA) in the Presence of Phase Modifiers Dissolved in n -Dodecane
journal, May 2012
- Gujar, R. B.; Ansari, S. A.; Bhattacharyya, A.
- Solvent Extraction and Ion Exchange, Vol. 30, Issue 3
Considerations for choice of a kinetic fig. of merit in process radiation chemistry for waste treatment
journal, February 2000
- Mincher, Bruce J.; Curry, Randy D.
- Applied Radiation and Isotopes, Vol. 52, Issue 2
Extraction of Nitric Acid into Alcohol: Kerosene Mixtures
journal, August 2010
- Geist, Andreas
- Solvent Extraction and Ion Exchange, Vol. 28, Issue 5
The Radiation Chemistry of CMPO: Part 1. Gamma Radiolysis
journal, September 2013
- Mincher, Bruce J.; Mezyk, Stephen P.; Elias, Gracy
- Solvent Extraction and Ion Exchange, Vol. 31, Issue 7
Diamex Process for Minor Actinide Partitioning: Hydrolytic and Radiolytic Degradations of Malonamide Extractants
journal, June 2001
- Berthon, L.; Morel, J. M.; Zorz, N.
- Separation Science and Technology, Vol. 36, Issue 5-6
Development and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular model
journal, June 1985
- Dewar, Michael J. S.; Zoebisch, Eve G.; Healy, Eamonn F.
- Journal of the American Chemical Society, Vol. 107, Issue 13
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
journal, March 2019
- Wilden, Andreas; Kowalski, Piotr M.; Klaß, Larissa
- Chemistry – A European Journal, Vol. 25, Issue 21
Application of quantum mechanical simulations for studying the radiolytic stability of prospective extractants in the nuclear fuel cycle
journal, October 2018
- Koubský, Tomáš; Luštinec, Jakub
- Journal of Radioanalytical and Nuclear Chemistry, Vol. 318, Issue 3
Radiolytic degradation of hydrophilic PyTri ligands for minor actinide recycling
journal, September 2019
- Mossini, Eros; Macerata, Elena; Brambilla, Luigi
- Journal of Radioanalytical and Nuclear Chemistry, Vol. 322, Issue 3
Ligands for f-element extraction used in the nuclear fuel cycle
journal, January 2017
- Leoncini, Andrea; Huskens, Jurriaan; Verboom, Willem
- Chemical Society Reviews, Vol. 46, Issue 23
A Study of the γ-Radiolysis of N,N -Didodecyl- N′,N′ -Dioctyldiglycolamide Using UHPLC-ESI-MS Analysis
journal, June 2016
- Roscioli-Johnson, Kristyn M.; Zarzana, Christopher A.; Groenewold, Gary S.
- Solvent Extraction and Ion Exchange, Vol. 34, Issue 5
Radiation chemistry of the branched-chain monoamide di-2-ethylhexyl-isobutyramide
journal, September 2017
- Drader, J.; Saint-Louis, G.; Muller, J. M.
- Solvent Extraction and Ion Exchange, Vol. 35, Issue 7
Actinide–lanthanide co-extraction by rigidified diglycolamides
journal, December 2017
- Macerata, Elena; Ossola, Annalisa; Panzeri, Walter
- Solvent Extraction and Ion Exchange, Vol. 36, Issue 1
Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides
journal, June 2018
- Wilden, Andreas; Mincher, Bruce J.; Mezyk, Stephen P.
- Solvent Extraction and Ion Exchange, Vol. 36, Issue 4
Gamma Radiolysis of TODGA and CyMe 4 BTPhen in the Ionic Liquid Tri- n -Octylmethylammonium Nitrate
journal, January 2020
- Zsabka, Peter; Van Hecke, Karen; Wilden, Andreas
- Solvent Extraction and Ion Exchange, Vol. 38, Issue 2
Radiation chemistry of the branched-chain monoamide di-2-ethylhexyl-isobutyramide
text, January 2017
- Drader, J.; Saint-Louis, G.; Muller, J. M.
- Taylor & Francis
Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides
text, January 2018
- Wilden, Andreas; Mincher, Bruce J.; Mezyk, Stephen P.
- Taylor & Francis
Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides
text, January 2018
- Wilden, Andreas; Mincher, Bruce J.; Mezyk, Stephen P.
- Taylor & Francis
Radiation chemistry of the branched-chain monoamide di-2-ethylhexyl-isobutyramide
text, January 2017
- Drader, J.; Saint-Louis, G.; Muller, J. M.
- Taylor & Francis
Actinide–lanthanide co-extraction by rigidified diglycolamides
text, January 2017
- Macerata, Elena; Ossola, Annalisa; Panzeri, Walter
- Taylor & Francis
Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides
text, January 2018
- Wilden, Andreas; Mincher, Bruce J.; Mezyk, Stephen P.
- Taylor & Francis