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Study of mass spectrometric fragmentations of tributyl phosphate via collision‐induced dissociation

2001; Wiley; Volume: 15; Issue: 20 Linguagem: Inglês

10.1002/rcm.467

1097-0231

Denis Lesage, H. Virelizier, Jean Claude Tabet, Christopher K. Jankowski,

Chemical Synthesis and Characterization

Abstract Tributyl phosphate (TBP) fragmentation mechanisms were studied by mass spectrometry (MS) and tandem mass spectrometry (MS/MS), using electron impact (EI) or chemical (CI) ionisation of the parent compound and its deuterated analogues. The study of this simple compound is essential for the analysis of complex post‐radiolysis mixtures and the identification of particular effects arising from the radiolysis or acid hydrolysis of TBP during nuclear fuel reprocessing. Energy‐resolved mass spectrometry (ERMS) and isotopic labelling helped to establish the fragment ion connectivities by distinct identification of the competitive and consecutive mechanisms. An ion‐dipole intermediate hypothesis, proposed previously in the case of alkyl phosphates and phosphonates in order to explain the mobility of hydrogen atoms from the alkyl chains, is rejected on the basis of the identification of competitive mechanisms in the TBP fragmentation pathways. Copyright © 2001 John Wiley & Sons, Ltd.