A kinetic study of the enhancement of solution chemiluminescence of glyoxylic acid oxidation by manganese species

In order to study the mechanism of the enhancement of solution chemiluminescence, the kinetics of the decay of the oxidant and the chemiluminescence emission were followed for oxidations by permanganate, manganese dioxide sol and Mn³⁺_(aq) of glyoxylic acid, using stopped‐flow spectrophotometry. Results are reported for the glyoxylic acid oxidized under pseudo first‐order conditions and in an acidic medium at 25 °C. For permanganate under these conditions, the decay is sigmoidal, consistent with autocatalysis, and for manganese dioxide sol and Mn³⁺ it is pseudo first order. The effects of the presence of aqueous formaldehyde and Mn²⁺ were observed and a fit to a simple mechanism is discussed. It is concluded that chemiluminescent enhancement in these systems is best explained by reaction kinetics. Copyright © 2014 John Wiley & Sons, Ltd.