Chloramines reactivity

Potassium peroxymonosulfate, introduced in the late 1980s, is finding increasing use as an auxiUary oxidant for shock treatment and oxidation of chloramines. Sodium peroxydisulfate is also being sold for shock treatment, however, it is less reactive than peroxymonosulfate. Mixtures of sodium peroxydisulfate and calcium hypochlorite can be used for shock treatment (28). Disadvantages of peroxymonosulfate and peroxydisulfate are they do not provide a disinfectant residual and peroxymonosulfate oxidizes urea and chloramines to nitrate ion, which is a nutrient for algae. 

Reagents similai to those used in the analysis of chloiine are commonly employed in the quantitation of gaseous and aqueous chloiine dioxide as well as its reaction coproducts chlorine, chlorite, and chlorate. The volatihty of the gas from aqueous solutions as well as its reactivity to light must be considered for accurate analysis. Other interferences that must be taken into account include other oxidizers such as chloramine, hydrogen peroxide, permanganate, and metal impurities such as ferrous and ferric iron. 

The amount of HOCl plus OCl in wastewater is referred to as the free available chlorine. Chlorine is a very active oxidizing agent and is therefore highly reactive with readily oxidized compounds such as ammonia. Chlorine readily reacts with ammonia in water to form chloramines. 

Reactive chloramine derivatives are produced in the first reaction step as a result of chlorination of the nitrogen by the /erf-butyl hypochlorite in the presence of potassium... 

Primary and secondary amines and amides are first chlorinated at nitrogen by the chlorine released by the gradually decomposing calcium hypochlorite. Excess chlorine gas is then selectively reduced in the TLC layer by gaseous formaldehyde. The reactive chloramines produced in the chromatogram zones then oxidize iodide to iodine, which reacts with the starch to yield an intense blue iodine-starch inclusion complex. 

Reactive carbon behaves as a chemical reactor for chloramine destruction, with a first order rate constant of around 0.011 s 1 under the conditions tested in the study. 

Figure 12.3 The strong oxidant chloramine-T can react with iodide anion in aqueous solution to form a highly reactive mixed halogen species. 125IC1 then can modify tyrosine and histidine groups in proteins to form radiolabeled products.

Whilst chloramines are less reactive than HOC1, they are longer-lived and so can diffuse away from their site of production. Those formed from lipophilic amines are especially toxic because they can permeate membranes. Chloramines are toxic for a number of reasons they can oxidise sulphydryl or sulphur-ether groups, they are unstable and can be hydrolysed to release chlorine in the form of HOC1 or NH2C1, they can react with iodide to form iodine and they can covalently bind proteins. 

Primary amino acids will react with o-phthalaldehyde in the presence of the strongly reducing 2-mercaptoethanol (pH 9-11) to yield a fluorescent product (emission maximum, 455 nm excitation maximum, 340 nm). Peptides are less reactive than a-amino acids and secondary amines do not react at all. As a result, proline and hydroxyproline must first be treated with a suitable oxidizing agent such as chloramine T (sodium A-chloro-p-toluene-sulphonamide) or sodium hypochlorite, to convert them into compounds which will react. Similarly cystine and cysteine should also be first oxidized to cysteic acid. 

Grey shock AE, Vikesland PJ (2006) Triclosan reactivity in chloraminated waters. Environ Sci Technol 40 2615-2622... 

If one considers the hydration of the hydroxide and remembers that the hydroxide once it goes into an activated complex has to peel off its water of hydration, a completely different picture emerges. We looked at the reactivity of the hydroxide in the bimolecular base-catalyzed substitutions both in the case of chloramine and of ethyl iodide (7, 8). Investigating these systems in concentrated hydroxide solutions and calculating the concentration of the so called free hydroxide ions shows that the hydroxide ion is much more reactive than its form in dilute solution. This means, in the kind of sticky mechanisms where you introduce the hydroxide into the complex, it is likely to be much less reactive than one expects from such a strong base. 

It seems safe to say that coordination will generally decrease the reactivity of donor atoms in the first row of the periodic table through steric effects. With some reactions the extent of this steric hindrance may be small. Ammonia can be transformed into chloramines when coordinated (34), and aromatic acid chlorides coordinated to A1C13 or TiCl4 may be esterified even when the functional group is a hindered one, as in mesitylene carbonyl chloride (47). These last reactions may proceed through a very reactive carbonium ion, whose existence is rendered possible by the polarization of the ligand which it suffers as a result of coordination. 

Figure 265 IODO-BEADS contains immobilized Chloramine-T functional groups that can react with radioactive iodide in aqueous solution to form a highly reactive intermediate. The active species may be an iodosulfonamide derivative, which then can iodinate tyrosine or histidine residues in proteins.

In the oxidation of alkanethiols to disulfides with chloramine-T (CAT), in alkaline solution, the proposed reactive species are hypochlorous acid and TsNCl- anion. A correlation of reaction rate with Taft s dual substituent parameter equation yielded p = -5.28 and 5 = -2.0, indicating the rate-enhancing effect of electron-donating substituents.133 Michaelis-Menten-type kinetics have been observed in the oxidation of atenolol with CAT in alkaline solutions. TsNHCl is assumed to be reactive species. A mechanism has been suggested and the activation parameters for the rate-determining step were calculated.134 The Ru(III)-catalysed oxidation of diphenyl... 

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