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Oxidative degradation of bis(2,4,4-trimethylpentyl)dithiophosphinic acid in nitric acid studied by electrospray ionization mass spectrometry.
MedLine Citation:
PMID:  22956310     Owner:  NLM     Status:  In-Data-Review    
Abstract/OtherAbstract:
RATIONALE: The selective separation of the minor actinides (Am, Cm) from the lanthanides is a topic of ongoing nuclear fuel cycle research, and dithiophosphinic acids are candidate ligands in these processes. Ligand instability has been noted under radiolytic and harsh acid conditions but explicit degradation pathways for ligands such as bis(2,4,4-trimethylpentyl)-dithiophosphinic acid (CyxH), the major compound in the commercial product Cyanex 301, have been elusive.
METHODS: Organic solutions of CyxH were contacted with aqueous solutions of HNO(3) , and their degradation was studied by analyzing samples from these experiments by direct infusion electrospray ionization mass spectrometry. Ions were identified using accurate mass measurement and collision-induced dissociation.
RESULTS: The positive ion spectra contained cationized CyxH cluster ions, and oxidatively coupled species (designated Cyx(2) ) cationized by either H or Na. The Cyx(2) -derived ions increased with acid contact time. The negative ion spectra consisted almost entirely of the CyxH conjugate base. The negative ion spectra of the HNO(3) -contacted samples also contained conjugate bases corresponding to the dioxo and perthio derivatives of CyxH.
CONCLUSIONS: CyxH is oxidized by acid contact to form the coupled species Cyx(2) , and the dioxo species arise from subsequent oxidation of Cyx(2) . Oxidative coupling increases with contact time, and with higher HNO(3) concentrations. The direct infusion measurements provided a simple approach for assessing degradation pathways and kinetics. Copyright © 2012 John Wiley & Sons, Ltd.
Authors:
Gary S Groenewold; Dean R Peterman; John R Klaehn; Laetitia H Delmau; Philippe Marc; Radu Custelcean
Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  Rapid communications in mass spectrometry : RCM     Volume:  26     ISSN:  1097-0231     ISO Abbreviation:  Rapid Commun. Mass Spectrom.     Publication Date:  2012 Oct 
Date Detail:
Created Date:  2012-09-07     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  8802365     Medline TA:  Rapid Commun Mass Spectrom     Country:  England    
Other Details:
Languages:  eng     Pagination:  2195-203     Citation Subset:  IM    
Copyright Information:
Copyright © 2012 John Wiley & Sons, Ltd.
Affiliation:
Idaho National Laboratory, 2351 North Boulevard, Idaho Falls, ID, 83415-2208, USA. gary.groenewold@inl.gov.
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From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


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