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Title: The Chemistry of Separations Ligand Degradation by Organic Radical Cations

Solvent based extractions of used nuclear fuel use designer ligands in an organic phase extracting ligand complexed metal ions from an acidic aqueous phase. These extractions will be performed in highly radioactive environments, and the radiation chemistry of all these complexants and their diluents will play a major role in determining extraction efficiency, separation factors, and solvent-recycle longevity. Although there has been considerable effort in investigating ligand damage occurring in acidic water radiolysis conditions, only minimal fundamental kinetic and mechanistic data has been reported for the degradation of extraction ligands in the organic phase. Extraction solvent phases typically use normal alkanes such as dodecane, TPH, and kerosene as diluents. The radiolysis of such diluents produce a mixture of radical cations (R •+), carbon-centered radicals (R ), solvated electrons, and molecular products such as hydrogen. Typically, the radical species will preferentially react with the dissolved oxygen present to produce relatively inert peroxyl radicals. This isolates the alkane radical cation species, R •+ as the major radiolytically-induced organic species that can react with, and degrade, extraction agents in this phase. Here we report on our recent studies of organic radical cation reactions with various ligands. Elucidating these parameters, and combining them withmore » the known acidic aqueous phase chemistry, will allow a full, fundamental, understanding of the impact of radiation on solvent extraction based separation processes to be achieved.« less
Authors:
 [1] ;  [1] ;  [2] ;  [2] ;  [3] ;  [3]
  1. California State Univ., Long Beach, CA (United States)
  2. Idaho National Lab. (INL), Idaho Falls, ID (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
Publication Date:
Report Number(s):
BNL-113885-2017-JA
Journal ID: ISSN 1876-6196; R&D Project: CO-004; KC0301010
Grant/Contract Number:
SC0012704; AC07-05ID14517; NE0008406
Type:
Accepted Manuscript
Journal Name:
Procedia Chemistry
Additional Journal Information:
Journal Volume: 21; Journal ID: ISSN 1876-6196
Publisher:
Elsevier
Research Org:
California State Univ., Long Beach, CA (United States); Brookhaven National Lab. (BNL), Upton, NY (United States); Idaho National Lab. (INL), Idaho Falls, ID (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Nuclear Energy (NE)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; amides; free radicals; mass spectrometry; pulse radiolysis; radiation chemistry; solvent extraction
OSTI Identifier:
1358034