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Spectroscopy
Volume 13 (1997), Issue 4, Pages 275-290
http://dx.doi.org/10.1155/1997/565194

Identification of minor products obtained during radiolysis of tributylphosphate (TBP)

Denis Lesage,1 Henri Virelizier,1 Christophe K. Jankowski,3 and Jean Claude Tabet2

1DCC/DPE/SPEA/SAIS, Centre d’Etudes Nucléaires de Saclay, 91191 Gif-sur-Yvette, France
2Laboratoire de Chimie Structurale Organique et Biologique, EP103, Université P. et M. Curie, 4 place Jussieu, 75252 Paris Cedex 05, France
3Faculté des Études Supérieures et de la Recherche, Université de Moncton>, Moncton N.-B., E1A3E9, Canada

Received 11 November 1996; Accepted 20 August 1997

Copyright © 1997 Hindawi Publishing Corporation. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

The structure identification of the fraction of minor products obtained during radiolysis of tributylphosphate (TBP), the solvent used in reprocessing of nuclear fuel, is reported. These results were realised from the distillation residue of the EDIT loop. The primary radiolysis formed TBP radical dimerises and is transformed under oxidative nitric acid conditions into several butyl chains substituted hydroxy or nitro phosphates as well as alkylated TBP. The butyl chain hydroxylated phosphate is leading to ketones, ethers and O-ester derivatives. The structures were determined by tandem mass spectrometry (MS–MS) and isotopic labelling techniques as well as by ion filiation and isotopic exchange studies. The analytical method developed consisted of the use of the integrated GC–MS, or GC–MS–MS, isotopic labelling technique. The combination of these techniques enabled to identify and to semi-quantify most of highly functionalised TBP without their prior separation from the post radiolysis mixtures.