Catalysis of DBP-Precursor Bromination by Halides and Hypochlorous Acid

Sivey, John D.; Bickley, Mark A; Victor, Daniel A.

doi:10.1021/bk-2015-1190.ch014

Cited by 3 publications

(1 citation statement)

References 64 publications

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“…Br 2 may be influential when [Br – ] > [free chlorine] and when bromide-containing waters are ozonated (e.g., disinfected ballast water). , Compared to other exotic bromine(+1) species, Br 2 is perhaps the most studied. For additional discussions of Br 2 , see refs and . H 2 OBr + has also been proposed as a reactive brominating agent in solutions of free bromine, , but the feasibility of H 2 OBr + serving as a brominating agent has been debated. , If H 2 OBr + were present in solutions containing Cl – , its contribution to bromination rates could be complicated by the co-occurrence of BrCl (eq ), whose concentration is also first-order in [H + ] in the absence of Br – .…”

Section: Bromine Speciesmentioning

confidence: 99%

Exotic Electrophiles in Chlorinated and Chloraminated Water: When Conventional Kinetic Models and Reaction Pathways Fall Short

Rose

Lau

Prasse

et al. 2020

Environ. Sci. Technol. Lett.

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Halogenation and oxidation of organic matter in chlorinated and chloraminated water are typically attributed to the most abundant electrophiles present. This interpretation sometimes fails to explain laboratory observations, including halogenation kinetics and product distributions. Exotic electrophiles, species commonly overlooked in the environmental literature, can help to resolve these discrepancies. Herein, we review evidence demonstrating the significance of lesser-studied electrophilic chlorinating (Cl2 and Cl2O), brominating (BrCl, BrOCl, and Br2O), and iodinating (H2OI+ and ICl) agents in chlor(am)inated water. The evidence includes reaction rate dependencies on [Cl–], [H+], and [HOCl] that cannot be attributed to the reactivity of hypohalous acids or hypohalites alone. For example, enhancement of chlorination and bromination rates by Cl– implicates Cl2 and BrCl, respectively, as active halogenating agents. Herein, we discuss a new method for quantifying the sensitivity of halogenation to rate enhancement by Cl–. We also discuss complexities that Cl– can impart on iodination kinetics. In addition, we highlight recent insights into radical-mediated reaction pathways and unexpected organic electrophiles in chlorinated water. Finally, we discuss practical implications, identify research needs, and offer recommendations to improve the design of future halogenation experiments. Overall, this review aims to spur new research into underappreciated electrophiles in chlor(am)inated water.

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Section: Bromine Speciesmentioning

confidence: 99%

Exotic Electrophiles in Chlorinated and Chloraminated Water: When Conventional Kinetic Models and Reaction Pathways Fall Short

Rose

Lau

Prasse

et al. 2020

Environ. Sci. Technol. Lett.

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Kinetic Role of Reactive Intermediates in Controlling the Formation of Chlorine Dioxide in the Hypochlorous Acid–Chlorite Ion Reaction

2023

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An advanced experimental protocol is reported for studying the kinetics and mechanism of the complex redox reaction between chlorite ion and hypochlorous acid under acidic condition. The formation of ClO2 is followed directly by the classical two-component stopped-flow method. In sequential stopped-flow experiments, the target reaction is chemically quenched using NaI solution and the concentration of each reactant and product is monitored as a function of time by utilizing the principles of kinetic discrimination. Thus, in contrast to earlier studies, not only the formation of one of the products but the decay of the reactants was also directly followed. This approach provides a firm basis for postulating a detailed mechanism for the interpretation of the experimental results under a variety of conditions. The intimate details of the reaction are explored by simultaneously fitting 78 kinetic traces, i.e., the concentration vs. time profiles of ClO2 –, HOCl, and ClO2, to an 11-step kinetic model. The most important reaction steps were identified, and it was shown that two reactive intermediates have a pivotal role in the mechanism. While chlorate ion predominantly forms via the reaction of Cl2O, chlorine dioxide is exclusively produced in reaction steps involving Cl2O2. This study leads to clear conclusions on how to control the stoichiometry of the reaction and achieve optimum conditions to produce chlorine dioxide and to reduce the formation of the toxic chlorate ion in practical applications.

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Structural effects on the bromination rate and selectivity of alkylbenzenes and alkoxybenzenes in aqueous solution

Schammel

Martin-Culet

Taggart

et al. 2021

Phys. Chem. Chem. Phys.

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Catalysis of DBP-Precursor Bromination by Halides and Hypochlorous Acid

Cited by 3 publications

References 64 publications

Exotic Electrophiles in Chlorinated and Chloraminated Water: When Conventional Kinetic Models and Reaction Pathways Fall Short

Exotic Electrophiles in Chlorinated and Chloraminated Water: When Conventional Kinetic Models and Reaction Pathways Fall Short

Kinetic Role of Reactive Intermediates in Controlling the Formation of Chlorine Dioxide in the Hypochlorous Acid–Chlorite Ion Reaction

Structural effects on the bromination rate and selectivity of alkylbenzenes and alkoxybenzenes in aqueous solution

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