Issue 5, 2024

Kinetics of the reaction of ferrous ions with hydroxyl radicals in the temperature range 25–300 °C

Abstract

The kinetics and mechanism of the reaction between OH radicals and ferrous ions in the temperature range 25–300 °C were studied using pulse radiolysis. At temperatures <150 °C the rate of reaction is essentially independent of temperature, while at temperatures >150 °C the activation energy is 45.8 ± 3.0 kJ mol−1. The change in activation energy is attributed to a change in the dominant mechanism from hydrogen atom transfer (HAT) to dissociative ligand interchange. The kinetic isotope effect (KIE) was measured by repeating experiments in heavy water. A value of 2.9 was measured at room temperature where HAT is the dominant mechanism. The KIE decreases to zero at temperatures > 150 °C as ligand interchange becomes dominant and the O–H bond is no longer involved in the reaction.

Graphical abstract: Kinetics of the reaction of ferrous ions with hydroxyl radicals in the temperature range 25–300 °C

Article information

Article type
Paper
Submitted
10 Aug 2023
Accepted
08 Jan 2024
First published
11 Jan 2024

Phys. Chem. Chem. Phys., 2024,26, 4278-4283

Kinetics of the reaction of ferrous ions with hydroxyl radicals in the temperature range 25–300 °C

L. Barr, J. K. Conrad, C. McGregor, R. Perron, P. A. Yakabuskie and C. R. Stuart, Phys. Chem. Chem. Phys., 2024, 26, 4278 DOI: 10.1039/D3CP03819J

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