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Kinetics and selectivity of permanganate chemiluminescence: A study of hydroxyl and amino disubstituted benzene positional isomers


Slezak, T and Smith, ZM and Adcock, JL and Hindson, CM and Barnett, NW and Nesterenko, PN and Francis, PS, Kinetics and selectivity of permanganate chemiluminescence: A study of hydroxyl and amino disubstituted benzene positional isomers, Analytica Chimica Acta, 707, (1-2) pp. 121-127 . ISSN 0003-2670 (2011) [Refereed Article]

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DOI: doi:10.1016/j.aca.2011.09.024


Examination of the chemiluminescence reactions of dihydroxybenzenes, aminophenols and phenylenediamines with acidic potassium permanganate has provided a new understanding of the relationships between analyte structure, reaction conditions, kinetics of the light-producing pathway and emission intensity, with broad implications for this widely utilised chemiluminescence detection system. Using a permanganate reagent prepared in a polyphosphate solution and adjusted to pH 2.5, large differences in the rate of reaction with different positional isomers were observed, with the meta-substituted forms reacting far slower and therefore exhibiting much lower chemiluminescence intensities in flow analysis systems. The preliminary partial reduction of permanganate to form significant concentrations of Mn(III) increased the rate of reaction with all analytes tested, resulting in comparable or (in the case of aminophenol and phenylenediamine) even greater emission intensities for the meta-isomers, demonstrating the opportunity to tune the selectivity of the reagent towards certain classes of compound or even specific positional isomers of the same compound. Using more acidic permanganate reagents, in which polyphosphates are not required, the discrepancy between the chemiluminescence intensities was still observed, but was less prominent due to the generally faster rates of reaction. The enhancement of these chemiluminescence reactions by on-line addition of formic acid or formaldehyde can in part also be attributed to the generation of significant pools of the key Mn(III) precursor to the emitting species.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Analytical chemistry
Research Field:Separation science
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Nesterenko, PN (Professor Pavel Nesterenko)
ID Code:73775
Year Published:2011
Web of Science® Times Cited:14
Deposited By:Chemistry
Deposited On:2011-10-25
Last Modified:2017-10-26

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