Stanbury David M
Department of Chemistry and Biochemistry, Auburn University, Auburn, AL 36849, USA.
Dalton Trans. 2022 Feb 8;51(6):2135-2157. doi: 10.1039/d1dt03645a.
The iron-catalyzed disproportionation of HO 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 HO is proposed that is consistent with the principle of detailed balancing and includes both the one-electron oxidation of HO by Fe(III) and the Fe(II) reduction of HO˙.
HO的铁催化歧化反应已经被研究了一个多世纪,其诱导系统中其他物质氧化的能力(芬顿反应)也是如此。至少从1932年起,人们就一直在考虑这些反应的机理。不幸的是,对于确保所提出的机理和速率常数符合细致平衡原理的约束,几乎没有给予关注。在这里,我们确定了200多篇具有违反细致平衡原理的机理的出版物。这些违反情况是通过对某些速率常数使用不正确的值、对机理中某些步骤使用不正确形式的速率定律以及包含非法循环而发生的。提出了一个与细致平衡原理一致的铁催化HO分解的核心机理,该机理包括Fe(III)对HO的单电子氧化和HO˙的Fe(II)还原。
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