Mechanism of permanganate chemiluminescence

Hindson, Christopher M., Francis, Paul S., Hanson, Graeme R., Adcock, Jacqui L. and Barnett, Neil W. 2010, Mechanism of permanganate chemiluminescence, Analytical chemistry, vol. 82, no. 10, pp. 4174-4180.

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Title Mechanism of permanganate chemiluminescence
Author(s) Hindson, Christopher M.
Francis, Paul S.
Hanson, Graeme R.
Adcock, Jacqui L.
Barnett, Neil W.
Journal name Analytical chemistry
Volume number 82
Issue number 10
Start page 4174
End page 4180
Total pages 7
Publisher American Chemical Society
Place of publication Washington, D.C.
Publication date 2010-05-15
ISSN 0003-2700
1520-6882
Summary Spectroscopic 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.
Language eng
Field of Research 030101 Analytical Spectrometry
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1 Refereed article in a scholarly journal
HERDC collection year 2010
Copyright notice ©2010, American Chemical Society
Persistent URL http://hdl.handle.net/10536/DRO/DU:30031412

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