The principle of detailed balancing, the iron-catalyzed disproportionation of hydrogen peroxide, and the Fenton reaction

Abstract

The iron-catalyzed disproportionation of H₂O₂ has been investigated for over a century, as has been its ability to induce the oxidation of other species present in the system (Fenton reaction). The mechanisms of these reactions have been under consideration at least since 1932. Unfortunately, little or no attention has been paid to ensuring the conformity of the proposed mechanisms and rate constants with the constraints of the principle of detailed balancing. Here we identify more than 200 publications having mechanisms that violate the principle of detailed balancing. These violations occur through the use of incorrect values for certain rate constants, the use of incorrect forms of the rate laws for certain steps in the mechanisms, and the inclusion of illegal loops. A core mechanism for the iron-catalyzed decomposition of H₂O₂ is proposed that is consistent with the principle of detailed balancing and includes both the one-electron oxidation of H₂O₂ by Fe(III) and the Fe(II) reduction of HO₂˙.