Hydrogen peroxide decomposition in bicarbonate solution catalyzed by divalent manganese species*This article has a companion paper in this issue (doi: 10.1139/v11-078).

Abstract

The peroxymonocarbonate mono- and di-anions (HCO4– and CO42–) are known to be generated from H2O2/HCO3–. They are promising oxidants for wood pulp bleaching, but peroxide decomposition catalyzed by Mn(II) species may be significant for pulp samples with unusually high Mn contents. This investigation aimed to see if HCO3– addition caused destabilization of the peroxygen system owing to its partial conversion to HCO4–. This anionic peracid is a much stronger oxidant than H2O2 and could lead to a higher rate of Mn(II) oxidation to Mn(III) and (or) Mn(IV). For most free radical chain mechanisms, an increase in Mn(II) oxidation results in a higher rate of peroxide decomposition. Peroxide decomposition catalyzed by Mn(II) was investigated in H2O2/HCO3 in the pH ranges 8.5–8.7 and 7.4–7.9. The rate equation for peroxide decomposition was first order in [H2O2] and [Mn(II)] in both pH ranges, but close to second order in [HCO3–] in the higher pH range and close to third order in the lower pH range. Free radical chain mechanisms were proposed for both pH ranges and with all the correct reaction orders. Contrary to mechanisms previously proposed, it was concluded that HCO4– is the principal oxidizer of Mn(II) in the pH 7.4–7.9 range.