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Stopped-Flow Kinetic Investigation of Manganese-based Chemiluminescence Oxidation Reactions

Otamonga, Jean Paul (2013) Stopped-Flow Kinetic Investigation of Manganese-based Chemiluminescence Oxidation Reactions. Doctoral thesis, University of Huddersfield.

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Abstract

In order to better understand the mechanism of solution manganese-based chemilumines-cence, the kinetics of a number of chemiluminescent oxidations by manganese species were studied using stopped-flow spectrophotometry. Both the kinetics of the decay of the oxi-dant and the chemiluminescence emission were followed for oxidations by permanganate, manganese dioxide sol and Mn3+(aq) of a range of organic compounds.

The most detailed studies were carried out on the oxidation of the relatively simple compounds including glyoxylic acid and glyoxal under pseudo first order conditions and an acidic medium at 25oC. For permanganate under these conditions, the decay is sigmoidal consistent with autocatalysis and for managanese dioxide sol and Mn3+ pseudo first order. Simple mechanisms are suggested and compared with the experimental kinetic data. For per-manganate CL system, the following chemical kinetic model was considered:

MnO4- + xsR  MnO2 (k1)
MnO2 + xsR  Mn3+ (k2)
MnO4- + 3Mn3+  4MnO2 (k3)
Mn3+ + xsR  (Mn2+)*

Item Type: Thesis (Doctoral)
Subjects: Q Science > QD Chemistry
Schools: School of Applied Sciences
Depositing User: Gail Hurst
Date Deposited: 06 Aug 2013 15:33
Last Modified: 01 Dec 2016 04:25
URI: http://eprints.hud.ac.uk/id/eprint/18054

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