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Updated: Aug 24, 2026

Light-driven Enzymatic Decarboxylation
Published on: May 22, 2016
Kinetics and mechanism of chromate reduction with hydrogen peroxide in base
Douglas A Vander Griend1, Joshua S Golden, Charles A Arrington
1Department of Chemistry, Furman University, 3300 Poinsett Highway, Greenville, South Carolina 29613-1120, USA. dougvg@calvin.edu
Abstract:
[Cr(VI)O(4)](2)(-) is reduced to [Cr(V)(O(2))(4)](3)(-) by hydrogen peroxide in strongly basic media where the acid dissociation of H(2)O(2) (pK(a) = 11.65) is appreciable. The reaction is first order in chromium(VI) and inhibited by hydroxide. The hydrogen peroxide dependence is defined by the form of the effective pseudo-first-order rate constant: k(eff) = [H(2)O(2)](3)/(K(1) + K(2)[H(2)O(2)] + K(3)[HO(2)(-)]) with K(1) = 175(43) s x M(3), K(2) = 403(18) s x M(2), and K(3) = 1422(34) s x M(2). Hydrogen peroxide anion initially attacks chromate, and subsequent equilibrium steps that exchange oxo groups for three peroxo groups precede a rate-determining, one-electron, intramolecular reduction step.
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