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Oxidation of Dihydroxybenzenes in Aerated Aqueous Suspensions of Birnessite

Published online by Cambridge University Press:  02 April 2024

M. B. McBride
M. B. McBride*
Affiliation:
Department of Agronomy, Cornell University, Ithaca, New York 14853
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Abstract

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The oxidation of 1,2- and 1,4-dihydroxybenzenes (1,2-DHB and 1,4-DHB) by unbuffered aerated suspensions of synthetic bimessite was studied by continuously monitoring the H+, Mn2+, dissolved O2, and organic radical concentration of the aqueous phase during the reaction. The reaction rapidly generated a very high pH, attributed to oxide dissolution, and the alkaline conditions prevented Mn2+ release into solution over the entire reaction period. Semiquinone radical anions accumulated early in the reaction and then diminished. A secondary radical product appeared in solution during the reaction of the oxide with 1,2-DHB, and was tentatively identified as an hydroxylated semiquinone. The oxide/DHB ratio controlled the maximum concentration and persistence of these radicals in solution as well as the degree to which O2 was consumed as an electron donor. In general, low oxide/DHB ratios promoted O2 uptake by the system, consistent with the subordinate role of O2 as a competing electron acceptor in the presence of excess Mn oxide. Soluble phosphate suppressed O2 consumption, but the mechanism by which it interacted with the reaction system was not determined.

Keywords

BimessiteDihydroxybenzeneElectron spin resonanceManganeseOxidation
Type
Research Article
Information
Clays and Clay Minerals , Volume 37 , Issue 4 , August 1989 , pp. 341 - 347
Copyright
Copyright © 1989, The Clay Minerals Society

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