Document Detail


Correlation of stoichiometries for rb(+) extraction determined by mass spectrometry and electrochemistry at liquid|liquid interfaces.
MedLine Citation:
PMID:  22816784     Owner:  NLM     Status:  In-Data-Review    
Abstract/OtherAbstract:
The electrochemical extraction of rubidium at micro water|1,2-dichloroethane (w|DCE) and water|room-temperature ionic liquid (w|RTIL) interfaces housed at the tip of a 25-μm capillary using octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) in the TRans Uranic EXtraction (TRUEX) process, was examined. Rubidium is of great interest in a modern spent nuclear fuel cycle as well as toward myocardial perfusion imaging utilizing (82)Sr/(82)Rb isotopic generators. The ligand-to-metal stoichiometry (n:1) and overall complexation constant (β) for interfacial complexation reactions induced by an applied potential were determined by the interfacial electrochemistry. One stoichiometry, n = 2, was observed at the w|DCE interface with β = 3.3 × 10(4). In the w|RTIL system, two rubidium salt solutions were employed: RbNO(3) and RbNO(3) plus Rb(2)SO(4). The former demonstrated a stoichiometry of n = 2 and β = 2.4 × 10(6), while the latter showed n = 4 and β = 3.3 × 10(12). These stoichiometries of the reaction were confirmed by electrospray ionization mass spectrometry, using an emulsion generated by shaking water and DCE phases containing the dissolved metal and ligand, respectively. Both RbCMPO(+) and RbCMPO(2)(+) complexes were observed. The influence of ion pair interactions in this system will be discussed.
Authors:
Tom J Stockmann; Anne-Marie Montgomery; Zhifeng Ding
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Publication Detail:
Type:  Journal Article     Date:  2012-07-03
Journal Detail:
Title:  Analytical chemistry     Volume:  84     ISSN:  1520-6882     ISO Abbreviation:  Anal. Chem.     Publication Date:  2012 Jul 
Date Detail:
Created Date:  2012-07-23     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0370536     Medline TA:  Anal Chem     Country:  United States    
Other Details:
Languages:  eng     Pagination:  6143-9     Citation Subset:  IM    
Affiliation:
Department of Chemistry, The University of Western Ontario , Chemistry Building, 1151 Richmond Street, London, Ontario, Canada N6A 5B7.
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