Non-metal redox kinetics: hypochlorite and hypochlorous acid reactions with cyanide

Gerritsen, Cynthia M.; Margerum, Dale W.

doi:10.1021/ic00340a010

Cited by 83 publications

(73 citation statements)

References 2 publications

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“…Such correlation in the chlorination of inorganic compounds has been demonstrated to suggest that the nucleophilicity of the compounds determines the reactivity of HOCl (Gerritsen and Margerum, 1990) (Fig. 13B).…”

Section: Mechamismsmentioning

confidence: 72%

Oxidation of inorganic contaminants by ferrates (VI, V, and IV)–kinetics and mechanisms: A review

Sharma

2011

Journal of Environmental Management

255

143

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Section: Mechamismsmentioning

confidence: 72%

Oxidation of inorganic contaminants by ferrates (VI, V, and IV)–kinetics and mechanisms: A review

Sharma

2011

Journal of Environmental Management

255

143

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“…(1) the reaction related to OCl À could be neglected due to a much lower reactivity of OCl À than HOCl (Gerritsen and Margerum, 1990;Rebenne et al, 1996); and (2) the protonated amine was unreactive towards HOCl/OCl À , just as it does not react with other electrophilic oxidants such as ozone and ferrate (Pryor et al, 1984;Qiang and Adams, 2004;Sharma et al, 2006). Therefore, the reaction of DPD with FC occurred predominantly between the neutral (i.e.…”

Section: Determination Of Chlorination Rate Constants Of Dpd By Sfs Tmentioning

confidence: 99%

Determination of rapid chlorination rate constants by a stopped-flow spectrophotometric competition kinetics method

et al. 2014

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a b s t r a c tFree chlorine is extensively used for water and wastewater disinfection nowadays. However, it still remains a big challenge to determine the rate constants of rapid chlorination reactions although competition kinetics and stopped-flow spectrophotometric (SFS) methods have been employed individually to investigate fast reaction kinetics. In this work, we proposed an SFS competition kinetics method to determine the rapid chlorination rate constants by using a common colorimetric reagent, N,N-diethyl-p-phenylenediamine (DPD), as a reference probe. A kinetic equation was first derived to estimate the reaction rate constant of DPD towards chlorine under a given pH and temperature condition. Then, on that basis, an SFS competition kinetics method was proposed to determine directly the chlorination rate constants of several representative compounds including tetracycline, ammonia, and four a-amino acids. Although Cl 2 O is more reactive than HOCl, its contribution to the overall chlorination kinetics of the test compounds could be neglected in this study. Finally, the developed method was validated through comparing the experimentally measured chlorination rate constants of the selected compounds with those obtained or calculated from literature and analyzing with Taft's correlation as well.This study demonstrates that the SFS competition kinetics method can measure the chlorination rate constants of a test compound rapidly and accurately.ª 2014 Elsevier Ltd. All rights reserved. IntroductionChlorine is the most widely used chemical disinfectant around the world. It is cheap, stable and effective against many pathogens including bacteria and viruses. Hence, despite the formation of harmful chlorinated disinfection byproducts, chlorine will still act as a primary disinfectant in many countries. In recent years, the transformation and fate of various organic micropollutants during water chlorination have attracted increasing attentions (Deborde and von Gunten, 2008;Sharma, 2008;Sedlak and von Gunten, 2011). As a prerequisite, the kinetic rate constants of a micropollutant reacting towards chlorine should be determined, * Corresponding author. Tel.: þ86 10 62849128; fax: þ86 10 62923541. E-mail address: hjliu@rcees.ac.cn (H. Liu).Available online at www.sciencedirect.com ScienceDirect journal homepage: www.else vier.com/locate /wa tres w a t e r r e s e a r c h 5 5 ( 2 0 1 4 ) 1 2 6 e1 3 2 0043-1354/ ª

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“…Cyanogen chloride, a highly toxic cyanide species, was observed in the chlorination of cyanide in a preceding study. 42,43 Cysteine may also react with hypochloric acid or/and hypochlorite to produce cysteinyl chloride according to eq 2. 44…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Derivatization Method of Free Cyanide Including Cyanogen Chloride for the Sensitive Analysis of Cyanide in Chlorinated Drinking Water by Liquid Chromatography-Tandem Mass Spectrometry

Kang

Shin²

2014

Anal. Chem.

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A novel derivatization method of free cyanide (HCN + CN(-)) including cyanogen chloride in chlorinated drinking water was developed with d-cysteine and hypochlorite. The optimum conditions (0.5 mM D-cysteine, 0.5 mM hypochlorite, pH 4.5, and a reaction time of 10 min at room temperature) were established by the variation of parameters. Cyanide (C(13)N(15)) was chosen as an internal standard. The formed β-thiocyanoalanine was directly injected into a liquid chromatography-tandem mass spectrometer without any additional extraction or purification procedures. Under the established conditions, the limits of detection and the limits of quantification were 0.07 and 0.2 μg/L, respectively, and the interday relative standard deviation was less than 4% at concentrations of 4.0, 20.0, and 100.0 μg/L. The method was successfully applied to determine CN(-) in chlorinated water samples. The detected concentration range and detection frequency of CN(-) were 0.20-8.42 μg/L (14/24) in source drinking water and 0.21-1.03 μg/L (18/24) in chlorinated drinking water.

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Non-metal redox kinetics: hypochlorite and hypochlorous acid reactions with cyanide

Cited by 83 publications

References 2 publications

Oxidation of inorganic contaminants by ferrates (VI, V, and IV)–kinetics and mechanisms: A review

Oxidation of inorganic contaminants by ferrates (VI, V, and IV)–kinetics and mechanisms: A review

Determination of rapid chlorination rate constants by a stopped-flow spectrophotometric competition kinetics method

Derivatization Method of Free Cyanide Including Cyanogen Chloride for the Sensitive Analysis of Cyanide in Chlorinated Drinking Water by Liquid Chromatography-Tandem Mass Spectrometry

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