Chloramine oxidation

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.

During the iodination with the oxidizer chloramine T, all reactants are present in solution (one-phase system). Pierce offers oxidizers that were applied to a solid phase (two-phase system iodobeads, iodogen). lodobeads are N-chlorobenzene sulfonamides attached to polystyrene beads. Iodogen is a hydrophobic chloramine T derivative applied to the wall of the reaction vessel. After the reaction with iodobeads and iodogen, the solid phase with the oxidizer can easily be separated from the reaction mixture. Hence, the addition of reducing agent (bisulfite) is unnecessary, which spares the sensitive disulfide bridges of some proteins. In addition, N-chlorobenzene sulfonamide is a milder oxidizer than chloramine T. 

This reaction is slow and requires elevated temperatures of 120—150°C under pressure. The kinetics (93,94) and mechanism (95,96) of these reactions have been studied. An undesirable competing reaction is the further oxidation of hydrazine by chloramine ... 

KetaZine Processes. The oxidation of ammonia by chlorine or chloramine in the presence of ahphatic ketones yields hydrazones (36), ketazines (37), or diaziddines (38), depending on the pH, ketone ratios, and reaction conditions (101). 

Because of the time and expense involved, biological assays are used primarily for research purposes. The first chemical method for assaying L-ascorbic acid was the titration with 2,6-dichlorophenolindophenol solution (76). This method is not appHcable in the presence of a variety of interfering substances, eg, reduced metal ions, sulfites, tannins, or colored dyes. This 2,6-dichlorophenolindophenol method and other chemical and physiochemical methods are based on the reducing character of L-ascorbic acid (77). Colorimetric reactions with metal ions as weU as other redox systems, eg, potassium hexacyanoferrate(III), methylene blue, chloramine, etc, have been used for the assay, but they are unspecific because of interferences from a large number of reducing substances contained in foods and natural products (78). These methods have been used extensively in fish research (79). A specific photometric method for the assay of vitamin C in biological samples is based on the oxidation of ascorbic acid to dehydroascorbic acid with 2,4-dinitrophenylhydrazine (80). In the microfluorometric method, ascorbic acid is oxidized to dehydroascorbic acid in the presence of charcoal. The oxidized form is reacted with o-phenylenediamine to produce a fluorescent compound that is detected with an excitation maximum of ca 350 nm and an emission maximum of ca 430 nm (81). 

In reahty the chemistry of breakpoint chlorination is much more complex and has been modeled by computer (21). Conversion of NH/ to monochloramine is rapid and causes an essentially linear increase in CAC with chlorine dosage. Further addition of chlorine results in formation of unstable dichloramine which decomposes to N2 thereby causing a reduction in CAC (22). At breakpoint, the process is essentially complete, and further addition of chlorine causes an equivalent linear increase in free available chlorine. Small concentrations of combined chlorine remaining beyond breakpoint are due primarily to organic chloramines. Breakpoint occurs slightly above the theoretical C1 N ratio (1.75 vs 1.5) because of competitive oxidation of NH/ to nitrate ion. Organic matter consumes chlorine and its oxidation also increases the breakpoint chlorine demand. Cyanuric acid does not interfere with breakpoint chlorination (23). 

Urea (24), amino acids (25), and creatinine (26) are also decomposed during superchlorination or shock treatment, with formation of N2 and other oxidation products. However, the process is slower than with ammonium ion (see Chloramines and BROMAMINEs). Urea is the principal nitrogen-containing compound in swimming pools. Since it is an amide, it reacts slowly with chlorine, yielding N2, NCl, and NO/ (27). 

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 parent compound, cyclic diazomethane , was first obtained from formaldehyde, ammonia and chloramine by dichromate oxidation of the initially formed higher molecular diaziridine-formaldehyde condensation product (61TL612). Further syntheses of (44) started from Schiff bases of formaldehyde, which were treated with either difluoramine or dichloramine to give (44) in a one-pot procedure. Dealkylation of nitrogen in the transient diaziridine was involved (65JOC2108). 

Chlorine is desirable as a bulk pretreatment biocide for inlet water, but its subsequent removal upstream of the membrane is absolutely necessary ana difficult. NaHSO,3 is a common additive to dechlorinate before membranes. It is customarily added at 3-5 mg/1, an excess over the stoichiometric requirement. NH3 is sometimes added to convert the chlorine to chloramine, a much less damaging biocide. Heavy metals present in seawater seem to amplify the damaging effects of chlorine and other oxidants. 

Disinfection - water completely free of suspended sediment, is treated with a powerful oxidizing agent usually chlorine, chlorine and ammonia (chloramine), or ozone. A residual disinfectant is left in the water to prevent reinfection. Chlorine can form harmful byproducts and has suspected links to stomach cancer and miscarriages. 

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. 

Hypochlorous acid and hypochlorite ion are known as free available chlorine. The chloramines are known as combined available chlorine and are slower than free chlorine in killing microorganisms. For identical conditions of contact time, temperature, and pH in the range of 6 to 8, it takes at least 25 times more combined available chlorine to produce the same germicidal efficiency. The difference in potency between chloramines and HOCl can be explained by the difference in their oxidation potentials, assuming the action of chloramine is of an electrochemical nature rather than one of diffusion, as seems to be the case for HOCl. 

Combined available chlorine The concentration of chlorine which is combined with ammonia (NH3) as chloramine or as other chloro derivatives, yet is still available to oxidize organic matter. 

For the preparation of the parent substance, cyclic diazomethane (67), formaldehyde, chloramine, and ammonia were reacted. Diaziri-dine formation was successful in about 20% yield the diaziridine condensed with further formaldehyde to high molecular weight products the diaziridine detected by its oxidizing power was nonvolatile. Oxidation with dichromate in dilute sulfuric acid led to gaseous diazirine (67) [Eq. (56)]. It was only investigated in solution. 

Hydrazine is produced by the oxidation of ammonia using the Rashig process. Sodium hypochlorite is the oxidizing agent and yields chloramine NH2CI as an intermediate. Chloramine further reacts with ammonia producing hydrazine ... 

Other oxidants may be used in place of PTAB chloramine-T efficiently azir-idinates a range of alkenes in the presence of H202 (Scheme 4.20) [25]. 

The commercially available chloramine-T trihydrate (TsNNaCl 3H20) could also be used directly as the oxidant, although slightly more dilute concentrations (0.2 m vs. 0.5 m) had to be employed to ensure comparable yields. The applicability of this trihydrate version to large-scale syntheses was demonstrated by the aziridination of cyclopentene on a 0,5 mol scale reaction, providing 6-tosylazabicyclo-[3.1.0]hexane in 80% isolated yield (Scheme 12.14). 

Despite the effectiveness of chloramine-T in this new method, removal of the toluenesulfonyl group from the newly introduced nitrogen substituent requires harsh conditions. The finding that the N-chloramine salt of tert-butylsulfonamide is also an efficient nitrogen source and the terminal oxidant for aziridination of... 

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