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Application of gas chromatography-tandem mass spectrometry to the analysis of inhibition of dimerisation of tributylphosphate under radiolysis. Identification of isomeric tributylphosphate-alkylbenzene inhibitor coupling products.

Authors
Type
Published Article
Journal
Journal of Chromatography A
0021-9673
Publisher
Elsevier
Publication Date
Volume
917
Issue
1-2
Pages
261–275
Identifiers
PMID: 11403478
Source
Medline

Abstract

Tributylphosphate (TBP), solvent used as extractant for reprocessing spent nuclear fuel, can dimerise under radiolysis. This occurs by radical radical recombination, leading to 10 isomeric dimers (TBP-TBP). These species are complexation agents and are responsible of fission product retention in the organic phase that increases the solvent degradation. In order to limit their formation two free radical inhibitors (In), isopropyl and 1,4-diisopropylbenzenes, were used. These additives reduce by about 50% the concentration of TBP-TBP dimers but this reduction is not strictly followed by TBP regeneration as mixed coupling products from TBP and inhibitor are detected. By using GC-MS-MS and selectively deuterated compounds, the identification of these different isomers (TBP-In) has been realised. From these identifications and from the analysis of the proportion of the different isomers, the major primary TBP radical generated under radiolysis was determined.

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