Issue 6, 2022

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˙.

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

Supplementary files

Article information

Article type
Perspective
Submitted
27 Okt. 2021
Accepted
06 Janv. 2022
First published
06 Janv. 2022

Dalton Trans., 2022,51, 2135-2157

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

D. M. Stanbury, Dalton Trans., 2022, 51, 2135 DOI: 10.1039/D1DT03645A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements