Kinetic modelling of the bromine-ammonia system: Formation and decomposition of bromamines. 2022

Anette T Mensah, and Florence Berne, and Sébastien Allard, and Sylvie Soreau, and Hervé Gallard
Institut de Chimie des Milieux et des Matériaux de Poitiers IC2MP UMR 7285 CNRS Université de Poitiers, ENSI Poitiers, 1 rue Marcel Doré TSA 41105, 86 073 Cedex 9, Poitiers, France.

Bromamines i.e. monobromamine (NH2Br), dibromamine (NHBr2), and tribromamine (NBr3) can be formed during oxidative treatment of waters containing bromide and ammonia. The formation and decomposition of bromamines in aqueous solution was investigated and a comprehensive kinetic model of the bromine-ammonia system was developed at 23 ± 1 °C. Determination of rate constants and model validation were primarily performed at pH 8.0 - 8.3 for subsequent application to seawater disinfection. The rate constant of NHBr2 self-decomposition was determined by second-order rate law linearization with k9 = 5.5 (± 0.8) M-1s-1 at pH 8.10. The rate constant of NBr3 self-decomposition increased proportionately to the concentration of hydroxide ions (OH-) according to the equation k10 = 4.4 (± 0.1) × 107. [OH-] over the pH range 6.0 - 8.5, which gave k10 = 56 (± 1) M-1s-1 at pH 8.10. The rate constants of NHBr2 and NBr3 formation were obtained by fitting model-predicted data to the experimental results and were found to be k3 = 2.3 (± 0.2) × 104M-1s-1 and k5 = 4.0 (± 0.6) × 103M-1s-1, respectively at pH 8.10. NBr3 was also found to react with NHBr2 with k11 = 3.4 (± 0.2) × 103M-1s-1 at pH 8.10. A kinetic model was proposed based on these experimental rate constants and literature values, which provided a good prediction of bromamines formation and decomposition for various initial bromine and ammonia concentrations. The kinetic model was also used to accurately predict the total oxidant concentration and the speciation of bromamines during breakpoint bromination. This study provides kinetic data to model more complex oxidative systems such as seawater chlorination in the presence of ammonia.

UI MeSH Term Description Entries
D007700 Kinetics The rate dynamics in chemical or physical systems.
D001965 Bromides Salts of hydrobromic acid, HBr, with the bromine atom in the 1- oxidation state. (From McGraw-Hill Dictionary of Scientific and Technical Terms, 4th ed) Bromide
D001966 Bromine A halogen with the atomic symbol Br, atomic number 35, and atomic weight 79.904. It is a volatile reddish-brown liquid that gives off suffocating vapors, is corrosive to the skin, and may cause severe gastroenteritis if ingested. Bromine-79,Bromine 79
D002713 Chlorine An element with atomic symbol Cl, atomic number 17, and atomic weight 35, and member of the halogen family. Chlorine Gas,Chlorine-35,Cl2 Gas,Chlorine 35,Gas, Chlorine,Gas, Cl2
D000641 Ammonia A colorless alkaline gas. It is formed in the body during decomposition of organic materials during a large number of metabolically important reactions. Note that the aqueous form of ammonia is referred to as AMMONIUM HYDROXIDE.
D016877 Oxidants Electron-accepting molecules in chemical reactions in which electrons are transferred from one molecule to another (OXIDATION-REDUCTION). Oxidant,Oxidizing Agent,Oxidizing Agents,Agent, Oxidizing,Agents, Oxidizing
D018508 Water Purification Any of several processes in which undesirable impurities in water are removed or neutralized; for example, chlorination, filtration, primary treatment, ion exchange, and distillation. It includes treatment of WASTEWATER to provide potable and hygienic water in a controlled or closed environment as well as provision of public drinking water supplies. Waste Water Purification,Waste Water Treatment,Wastewater Purification,Wastewater Treatment,Water Treatment,Purification, Waste Water,Purification, Wastewater,Purification, Water,Treatment, Waste Water,Treatment, Wastewater,Treatment, Water,Waste Water Purifications,Waste Water Treatments,Water Purification, Waste

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