Kinetics of the reaction between hydrogen peroxide and hypobromous acid: Implication on water treatment and natural systems

doi:10.1016/S0043-1354(96)00368-5

Water Research

Volume 31, Issue 4, April 1997, Pages 900-906

https://doi.org/10.1016/S0043-1354(96)00368-5 Get rights and content

Abstract

HOBr can be formed in various oxidation processes in engineered and natural systems. The rate of HOBr reduction by H₂O₂ is decisive to avoid formation of brominated organic compounds and bromate during ozone or hydrogen peroxide-based advanced or naturally occurring oxidation processes. From the pH dependence of this rate that was determined by stopped-flow measurements we conclude that either OBr⁻ and H₂O₂ or HOBr and HO⁻₂ react with each other. Assuming that either one of the reactions takes place the corresponding second-order rate constants were determined to be k_{OBr⁻·H₂O₂} = (1.2 ± 0.2)·10⁶M⁻¹s⁻¹ and k_{HOBr·HO⁻₂} = (7.6 ± 1.3)·10⁸M⁻¹s⁻¹. Mechanistic considerations lead to the conclusion that a nucleophilic attack of HO⁻₂ on HOBr must be the dominant reaction in the system. From the determined rate constants it can be estimated that the half-life for HOBr is less than a few seconds for a H₂O₂ concentration of 0.1 mg L⁻¹ (3 μM) at pH 8. However, at a lower pH of 5, as encountered in cloud waters, the half-life of HOBr is several hours for the same H₂O₂ concentration.

References (22)

H. Bader et al.
Photometric method for the determination of low concentrations of hydrogen peroxide by the peroxidase catalyzed oxidation of N,N-diethyl-p-phenylenediamine (DPD)
Wat. Res.
(1988)
W.R. Haag et al.
Improved ammonia oxidation by ozone in the presence of bromide ion during water treatment
Wat. Res.
(1984)
G.V. Buxton et al.
The radiolysis of aqueous solutions of oxybromine compounds; the spectra and reactions of BrO and BrO₂
H. Ellis
IS-1 Rapid Software Suite
(1991)
Vorschlag für eine Richtlinie des Rates über die Qualität von Wasser für den menschlichen Gebrauch
Amtsblatt der Europäischen Gemeinschaften
(1995)
W.R. Haag et al.
Ozonation of bromide-containing waters: kinetics of formation of hypobromous acid and bromate
Environ. Sci. Technol.
(1983)
A.M. Held et al.
Mechanisms of chlorine oxidation of hydrogen peroxide
J. Am. Chem. Soc.
(1978)
A.F. Holleman et al.
Lehrbuch der Anorganischen Chemie
(1985)
B. Langlais et al.
Ozone in Water Treatment: Application and Engineering
(1991)

F.G. Lee

Kinetics of reactions between chlorine and phenolic compounds

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Kinetics of the reaction between hydrogen peroxide and hypobromous acid: Implication on water treatment and natural systems

Abstract

Wat. Res.

Wat. Res.

The radiolysis of aqueous solutions of oxybromine compounds; the spectra and reactions of BrO and BrO2

IS-1 Rapid Software Suite

Vorschlag für eine Richtlinie des Rates über die Qualität von Wasser für den menschlichen Gebrauch

Amtsblatt der Europäischen Gemeinschaften

Ozonation of bromide-containing waters: kinetics of formation of hypobromous acid and bromate

Environ. Sci. Technol.

Mechanisms of chlorine oxidation of hydrogen peroxide

J. Am. Chem. Soc.

Lehrbuch der Anorganischen Chemie

Ozone in Water Treatment: Application and Engineering

Kinetics of reactions between chlorine and phenolic compounds

The radiolysis of aqueous solutions of oxybromine compounds; the spectra and reactions of BrO and BrO₂