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Kinetic and Mechanistic Aspects of the Reactions of Iodide and Hypoiodous Acid with Permanganate: Oxidation and Disproportionation.
Environ Sci Technol. 2016 Apr 19; 50(8):4358-65.ES

Abstract

Oxidation kinetics of iodide and HOI/OI(-) by permanganate were studied in the pH range of 5.0-10.0. Iodide oxidation and iodate formation were faster at lower pH. The apparent second-order rate constants (k(obs)) for iodide oxidation by permanganate decrease with increasing pH from 29 M(-1) s(-1) at pH 5.0 and 6.9 M(-1) s(-1) at pH 7.0 to 2.7 M(-1) s(-1) at pH 10.0. k(obs) for HOI abatement are 56 M(-1) s(-1) at pH 5.0, 2.5 M(-1) s(-1) at pH 7.0, and 173 M(-1) s(-1) at pH 10.0. Iodate yields over HOI abatement decrease from 98% at pH 6.0 to 33% for pH ≥ 9.5, demonstrating that HOI disproportionation dominates HOI transformation by permanganate at pH ≥ 8.0. MnO2 formed as a product from permanganate reduction, oxidizes HOI to iodate for pH < 8.0, and promotes HOI disproportionation for pH ≥ 8.0. The rate of HOI oxidation or disproportionation induced by MnO2 is much lower than for permanganate. During treatment of iodide-containing waters, the potential for iodinated disinfection byproducts (I-DBPs) formation is highest at pH 7.0-8.0 due to the long lifetime of HOI. For pH < 6.0, HOI/I2 is quickly oxidized by permanganate to iodate, whereas for pH ≥ 8.0, HOI/OI(-) undergoes a fast permanganate-mediated disproportionation.

Authors+Show Affiliations

State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology , Harbin 150090, China. Eawag, Swiss Federal Institute of Aquatic Science and Technology , Ueberlandstrasse 133, CH-8600 Dübendorf, Switzerland.Eawag, Swiss Federal Institute of Aquatic Science and Technology , Ueberlandstrasse 133, CH-8600 Dübendorf, Switzerland.State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology , Harbin 150090, China.State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology , Harbin 150090, China.Eawag, Swiss Federal Institute of Aquatic Science and Technology , Ueberlandstrasse 133, CH-8600 Dübendorf, Switzerland. School of Architecture, Civil and Environmental Engineering (ENAC), Ecole Polytechnique Fédérale de Lausanne (EPFL) , CH-1015 Lausanne, Switzerland.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

27003721

Citation

Zhao, Xiaodan, et al. "Kinetic and Mechanistic Aspects of the Reactions of Iodide and Hypoiodous Acid With Permanganate: Oxidation and Disproportionation." Environmental Science & Technology, vol. 50, no. 8, 2016, pp. 4358-65.
Zhao X, Salhi E, Liu H, et al. Kinetic and Mechanistic Aspects of the Reactions of Iodide and Hypoiodous Acid with Permanganate: Oxidation and Disproportionation. Environ Sci Technol. 2016;50(8):4358-65.
Zhao, X., Salhi, E., Liu, H., Ma, J., & von Gunten, U. (2016). Kinetic and Mechanistic Aspects of the Reactions of Iodide and Hypoiodous Acid with Permanganate: Oxidation and Disproportionation. Environmental Science & Technology, 50(8), 4358-65. https://doi.org/10.1021/acs.est.6b00320
Zhao X, et al. Kinetic and Mechanistic Aspects of the Reactions of Iodide and Hypoiodous Acid With Permanganate: Oxidation and Disproportionation. Environ Sci Technol. 2016 Apr 19;50(8):4358-65. PubMed PMID: 27003721.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Kinetic and Mechanistic Aspects of the Reactions of Iodide and Hypoiodous Acid with Permanganate: Oxidation and Disproportionation. AU - Zhao,Xiaodan, AU - Salhi,Elisabeth, AU - Liu,Huiling, AU - Ma,Jun, AU - von Gunten,Urs, Y1 - 2016/04/07/ PY - 2016/3/23/entrez PY - 2016/3/24/pubmed PY - 2016/12/15/medline SP - 4358 EP - 65 JF - Environmental science & technology JO - Environ. Sci. Technol. VL - 50 IS - 8 N2 - Oxidation kinetics of iodide and HOI/OI(-) by permanganate were studied in the pH range of 5.0-10.0. Iodide oxidation and iodate formation were faster at lower pH. The apparent second-order rate constants (k(obs)) for iodide oxidation by permanganate decrease with increasing pH from 29 M(-1) s(-1) at pH 5.0 and 6.9 M(-1) s(-1) at pH 7.0 to 2.7 M(-1) s(-1) at pH 10.0. k(obs) for HOI abatement are 56 M(-1) s(-1) at pH 5.0, 2.5 M(-1) s(-1) at pH 7.0, and 173 M(-1) s(-1) at pH 10.0. Iodate yields over HOI abatement decrease from 98% at pH 6.0 to 33% for pH ≥ 9.5, demonstrating that HOI disproportionation dominates HOI transformation by permanganate at pH ≥ 8.0. MnO2 formed as a product from permanganate reduction, oxidizes HOI to iodate for pH < 8.0, and promotes HOI disproportionation for pH ≥ 8.0. The rate of HOI oxidation or disproportionation induced by MnO2 is much lower than for permanganate. During treatment of iodide-containing waters, the potential for iodinated disinfection byproducts (I-DBPs) formation is highest at pH 7.0-8.0 due to the long lifetime of HOI. For pH < 6.0, HOI/I2 is quickly oxidized by permanganate to iodate, whereas for pH ≥ 8.0, HOI/OI(-) undergoes a fast permanganate-mediated disproportionation. SN - 1520-5851 UR - https://www.unboundmedicine.com/medline/citation/27003721/Kinetic_and_Mechanistic_Aspects_of_the_Reactions_of_Iodide_and_Hypoiodous_Acid_with_Permanganate:_Oxidation_and_Disproportionation_ L2 - https://dx.doi.org/10.1021/acs.est.6b00320 DB - PRIME DP - Unbound Medicine ER -