Production of Hydroxyl Radical via the Activation of Hydrogen Peroxide by Hydroxylamine

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College of Biology and the Environment, Nanjing Forestry University, Nanjing 210037, China
§ School of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou 310018, China
College of Architecture and Environment, Sichuan University, Chengdu 610065, China
School of Environmental Science and Engineering, Sun Yat-sen University, Guangzhou 510275, China
State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, China
*(L.C.) Phone: +86-025-85427479; fax: +86-025-85418873; e-mail: [email protected]
*(J.M.) Phone: +86-451-86282292; fax: +86-451-8628-3010; e-mail: [email protected]
Cite this: Environ. Sci. Technol. 2015, 49, 17, 10373–10379
Publication Date (Web):August 14, 2015
https://doi.org/10.1021/acs.est.5b00483
Copyright © 2015 American Chemical Society
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Abstract

The production of the hydroxyl radical (HO·) is important in environmental chemistry. This study reports a new source of HO· generated solely from hydrogen peroxide (H2O2) activated by hydroxylamine (HA). Electron paramagnetic resonance analysis and the oxidation of a HO· probe, benzoic acid, were used to confirm the production of HO·. The production of HO· increased with increasing concentrations of either HA or H2O2 as well as decreasing pH. The second-order rate constant for the reaction was (2.2 ± 0.2) × 10–4 M–1 s–1. HO· was probably produced in two steps: the activation of H2O2 by protonated HA and then reaction between the H2O2 and the intermediate protonated aminoxyl radical generated in the first step. Such a two-step oxidation can possibly be ascribed to the ionizable hydroxyl moiety in the molecular structure of HA, as is suggested by comparing the reactivity of a series of HA derivatives in HO· production. The results shed light on a previously unknown source of HO· formation, which broadens the understanding of its role in environmental processes.

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