Gamma Radiolysis of Phenyl-Substituted TODGAs: Part II

Zarzana, Christopher A.; McAlpine, Jack; Wilden, Andreas; Hupert, Michelle; Stärk, Andrea; Iqbal, Mudassir; Verboom, Willem; Vandevender, Aspen N.; Mincher, Bruce J.; Groenewold, Gary S.; Modolo, Giuseppe

doi:10.1080/07366299.2023.2221290

Gamma Radiolysis of Phenyl-Substituted TODGAs: Part II

Journal Article · Thu Jul 06 00:00:00 EDT 2023 · Solvent Extraction and Ion Exchange

DOI:https://doi.org/10.1080/07366299.2023.2221290· OSTI ID:1997483

^[1]; McAlpine, Jack ^[2]; ^[3]; ^[3]; Stärk, Andrea ^[3]; ^[4]; ^[5]; Vandevender, Aspen N. ^[2]; ^[1]; ^[1]; ^[3]

Idaho National Laboratory (INL), Idaho Falls, ID (United States)
University of Idaho, Moscow, ID (United States); Idaho National Laboratory (INL), Idaho Falls, ID (United States)
Forschungszentrum Jülich GmbH (Germany)
National University of Sciences and Technology (NUST), Islamabad (Pakistan)
University of Twente, Enschede (Netherlands)

The radiolytic degradation chemistry of three phenylated analogs of $N,N,N’,N’$-tetraoctyl diglycolamide (TODGA) was investigated: 2-(2-(di-$$n$$-octylamino)-2-oxoethoxy)-$N,N$-di-$$n$$-octyl-2-phenylacetamide (PhTODGA), which has a phenyl substituent bound to a central methylene, 2-(2-(di-$$n$$-octylamino)-2-oxo-1-phenylethoxy)-$N,N$-di-$$n$$-octylpropanamide (PhMeTODGA), which also contains a methyl substituent bound to the methylene on the other side of the ether moiety, and, 2-(2-$$N$$-$$n$$-hexyl-$$N$$-phenylamino)-2-oxoethoxy)-$$N$$-$$n$$-hexyl-$$N$$-phenylacetamide (DHDPDGA), which has phenyl substituents located on the amide groups instead of the central methylenes. In Part II of this series of papers radiolytic degradation products were identified after separation with liquid chromatography by High Resolution, Accurate-Mass mass spectrometry and collision-induced dissociation. At least twenty-two radiolytic degradation products were identified for PhTODGA, twenty-nine for PhMeTODGA, and over three dozen for DHDPDGA. The suite of radiolytic degradation products of these three investigated ligands was significantly larger than has been reported for previously studied diglycolamides, owing to their asymmetric nature, and to the identification of several new degradation mechanisms, including addition of methyl, hydroxyl, and nitrogen oxide radicals, that have not been previously reported for diglycolamides. Degradation products that contained addition of a NO₂ or NO₃ group were particularly prevalent for DHDPDGA, likely due to the phenyl side-groups. In conclusion, several of these newly observed mechanisms do not appear to depend on the presence of the phenyl groups, suggesting these novel mechanisms may apply to other diglycolamides.

View Accepted Manuscript (DOE)

Research Organization:: Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE), Nuclear Fuel Cycle and Supply Chain. Fuel Cycle Research and Development Program

Grant/Contract Number:: AC07-05ID14517

OSTI ID:: 1997483

Report Number(s):: INL/JOU-23-70901-Rev000

Journal Information:: Solvent Extraction and Ion Exchange, Journal Name: Solvent Extraction and Ion Exchange Journal Issue: 5 Vol. 41; ISSN 0736-6299

Publisher:: Taylor and FrancisCopyright Statement

Country of Publication:: United States

Language:: English

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