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Mechanism of permanganate chemiluminescence
journal contribution
posted on 2010-05-15, 00:00 authored by Christopher Hindson, Paul FrancisPaul Francis, G Hanson, Jacqui AdcockJacqui Adcock, Neil BarnettNeil BarnettSpectroscopic and synthetic methods have been exploited to deduce the mechanism for acidic potassium permanganate chemiluminescence. We have employed electron paramagnetic resonance (EPR) spectroscopy with a continuous flow assembly to monitor the formation of radical intermediates in real time generated from substrate oxidation by manganese(VII). These transient species react with manganese(III) in solution to produce the previously characterized manganese(II)* emission source. Using UV-vis, EPR, attenuated total reflection (ATR)-FTIR, and chemiluminescence spectroscopies, we have established that there are two distinct enhancement mechanisms that in combination afford a 50-fold increase in emission intensity when the reaction is conducted in the presence of phosphate oligomers. In addition to preventing disproportionation of the manganese(III) precursor, the phosphate oligomers form protective "cagelike” structures around the manganese(II)* emitter, thus preventing nonradiative relaxation pathways.
History
Journal
Analytical chemistryVolume
82Issue
10Pagination
4174 - 4180Publisher
American Chemical SocietyLocation
Washington, D.C.Publisher DOI
ISSN
0003-2700eISSN
1520-6882Language
engPublication classification
C1 Refereed article in a scholarly journalCopyright notice
2010, American Chemical SocietyUsage metrics
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