Hypochlorous acid, oxidation

The hypochlorous acid oxidizes the cell walls and kills bacteria. Solid calcium hypochlorite, Ca(OCl)2, and liquid solutions of sodium hypochlorite, NaOCl, can be used to generate hypochlorous acid in place of chlorine gas, for example, in chlorinating swimming pools. The hypochlorite ion generated from Ca(OCl)2 and NaOCl forms an equilibrium with water represented by the equation ... 

Sodium hypochlorites (and calcium hypochlorite s) disinfection property is due to its ability to form hypochlorous acid, HOC1. The hypochlorous acid oxidizes the cell walls and kills bacteria. Sodium hypochlorite generates hypochlorous acid according to the reaction NaOCl( H2offi —> HOCl + NaOH(Ml. The hypochlorite ion generated from NaOCl exists... 

This is essentially a two-step reaction, with hypochlorous acid being generated from the reaction of bleach with water and then the hypochlorous acid oxidizing the sodium bromide component. 

Bergt C, Fu X, Huq NP, Kao J, Heinecke JW (2004) Lysine Residues Direct the Chlorination of Tyrosines in YXXK Motifs of Apolipoprotein A-I When Hypochlorous Acid Oxidizes High Density Lipoprotein. J Biol Chem 279 7856... 

Bergt, C., S. Peimathur, X. Fu, J. Byun, K. O Brien, T. O. McDonald, P. Singh et al. 2004. The myeloperoxidase product hypochlorous acid oxidizes HDL in the human artery wall and impairs ABC Al-dependent cholesterol transport. 

A similar intramolecular oxidation, but for the methyl groups C-18 and C-19 was introduced by D.H.R. Barton (1979). Axial hydroxyl groups are converted to esters of nitrous or hypochlorous acid and irradiated. Oxyl radicals are liberated and selectively attack the neighboring axial methyl groups. Reactions of the methylene radicals formed with nitrosyl or chlorine radicals yield oximes or chlorides. 

Ethylene glycol was originally commercially produced in the United States from ethylene chlorohydrin [107-07-3J, which was manufactured from ethylene and hypochlorous acid (eq. 8) (see Chlorohydrins). Chlorohydrin can be converted direcdy to ethylene glycol by hydrolysis with a base, generally caustic or caustic/bicarbonate mix (eq. 9). An alternative production method is converting chlorohydrin to ethylene oxide (eq. 10) with subsequent hydrolysis (eq. 11). 

Chlorine and Bromine Oxidizing Compounds. The organo chlorine compounds shown in Table 6 share chemistry with inorganic compounds, such as chlorine/77< 2-3 (9-j5y and sodium hypochlorite/7 )< /-j5 2-5 7. The fundamental action of chlorine compounds involves hydrolysis to hypochlorous acid (see Cm ORiNE oxygen acids and salts). 

Highly pure perchloric acid can also be produced by a patented electrochemical process ia which 22% by weight hypochlorous acid is oxidized to chloric acid ia a membrane-separated electrolyzer, and then additionally oxidized to perchloric acid (8,84). The desired electrochemical oxidation takes place ia two stages ... 

Perchlorates. Historically, perchlorates have been produced by a three-step process (/) electrochemical production of sodium chlorate (2) electrochemical oxidation of sodium chlorate to sodium perchlorate and (4) metathesis of sodium perchlorate to other metal perchlorates. The advent of commercially produced pure perchloric acid directly from hypochlorous acid means that several metal perchlorates can be prepared by the reaction of perchloric acid and a corresponding metal oxide, hydroxide, or carbonate. 

Oxidation. There are 10 types of oxidative reactions in use industriaHy (80). Safe reactions depend on limiting the concentration of oxidi2ing agents or oxidants, or on low temperature. The foUowing should be used with extreme caution salts of permanganic acid hypochlorous acid and salts sodium... 

Cooling water pH affects oxidizing antimicrobial efficacy. The pH determines the relative proportions of hypochlorous acid and hypochlorite ion or, in systems treated with bromine donors, hypobromous acid and hypobromite ion. The acid forms of the halogens are usually more effective antimicrobials than the dissociated forms. Under some conditions, hypochlorous acid is 80 times more effective in controlling bacteria than the hypochlorite ion. Hypochlorous acid predominates below a pH of 7.6. Hypobromous acid predominates below pH 8.7, making bromine donors more effective than chlorine donors in alkaline cooling waters, especially where contact time is limited. 

Dichlorine monoxide is the anhydride of hypochlorous acid the two nonpolar compounds are readily interconvertible in the gas or aqueous phases via the equilibrium CI2 O + H2 0 2H0Cl. Like other chlorine oxides, CI2O has an endothermic heat of formation and is thus thermodynamically unstable with respect to decomposition into chlorine and oxygen. Dichlorine monoxide typifies the chlorine oxides as a highly reactive and explosive compound with strong oxidhing properties. Nevertheless, it can be handled safely with proper precautions. 

Cyanate can be further oxidized by HOCl to nitrogen and bicarbonate along with small amounts of N2O and NCl. Hypochlorous acid reacts with peroxide with evolution of oxygen by the postulated intermediate formation of peroxyhypochlorous acid (99). 

Hypochlorous acid reacts very rapidly and quantitatively with a slight excess of free ammonia forming monochloramine, NH2CI, which reacts at a slower rate with additional HOCl forming dichloramine, NHCI2. Trichloramine is formed when three moles of HOCl are added per mole of ammonia between pH 3—4 (100). Hypochlorous acid in the form of chlorine or hypochlorite is used in water treatments to oxidize ammonia by the process of break-point chlorination, which is based on formation of unstable dichloramine. The instabiHty of NHCI2 is caused by presence of HOCl and NCl (101,102). The reaction is most rapid at a pH of about 7.5 (103). Other nitrogen compounds such as urea, creatinine, and amino acids are also oxidized by hypochlorous acid, but at slower rates. Unstable iV-chloro compounds are intermediates in deammination of amino acids (104,105). 

Hypochlorous acid undergoes a variety of reactions with organic substances including addition, oxidation, C- and iV-chlorination, and ester formation. On an industrial scale, hypochlorous acid, generated m situ via chlorine hydrolysis, reacts with propylene forming primarily the a-propjlene chlorohydrin isomer. 

Some hypochlorites, either as solutions or soflds, are much more stable than hypochlorous acid, and because of thek high oxidation potential and ready hydrolysis to the parent acid, find wide use in bleaching and sanitizing appHcations. One of the novel uses of hypochlorites was for disinfection of ApoUo Eleven on its return from the moon (136). 

Molten sodium cyanide reacts with strong oxidizing agents such as nitrates and chlorates with explosive violence. In aqueous solution, sodium cyanide is oxidized to sodium cyanate [917-61 -3] by oxidizing agents such as potassium permanganate or hypochlorous acid. The reaction with chlorine in alkaline solution is the basis for the treatment of industrial cyanide waste Hquors (45) ... 

Ethylene oxide has been produced commercially by two basic routes the ethylene chlorohydrin and direct oxidation processes. The chlorohydrin process was first iatroduced dufing World War I ia Germany by Badische Anilin-und Soda-Eabfik (BASE) and others (95). The process iavolves the reaction of ethylene with hypochlorous acid followed by dehydrochlofination of the resulting chlorohydrin with lime to produce ethylene oxide and calcium chloride. Union Carbide Corp. was the first to commercialize this process ia the United States ia 1925. The chlorohydrin process is not economically competitive, and was quickly replaced by the direct oxidation process as the dominant technology. At the present time, all the ethylene oxide production ia the world is achieved by the direct oxidation process. 

Chlorination of thiiranes in hydroxylic solvents gives /3-chloroethylsulfonyl chlorides due to further oxidation of the intermediate sulfenyl chloride by chlorine or hypochlorous acid (Scheme 40). Polymer is usually obtained also unless the reaction is done in concentrated hydrochloric acid, which causes rapid ring cleavage to 2-chloroethylthiols which are subsequently oxidized to the sulfonyl chlorides. An 85% yield of (37) is obtained in concentrated hydrochloric acid-HCl(g) whereas only a 15% yield is obtained in CCI4-H2O. 

Because a considerable part of the anodically evolved chlorine is carried away by the flowing water, the amount of hypochlorous acid is small and therefore the removal of graphite is less than in fresh water or soil, where direct oxidation according to Eq. (7-3) predominates. 

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. 

It should be noted that although BrCl is mainly a brominating agent that is eompetitive with bromine, its ehemieal reaetivity makes its action similar to that of ehlorine (that is, disinfection, oxidation, and a bleaching agent). BrCl hydrolyzes exelusively to hypobromous aeid, and if any hydrobromie aeid (HBr) is formed by hydrolysis of the dissociated bromine, it quickly oxidizes to hydrobromous acid via hypochlorous acid. 

The main method to obtain propylene oxide is chlorohydrination followed by epoxidation. This older method still holds a dominant role in propylene oxide production. Chlorohydrination is the reaction between an olefin and hypochlorous acid. When propylene is the reactant, propylene chlorohydrin is produced. The reaction occurs at approximately 35°C and normal pressure without any catalyst ... 

The hypochlorous acid, HCIO, formed by this reaction is a powerful oxidizing agent (E a = +1.630 V) it kills bacteria, apparently by destroying certain enzymes essential to their metabolism. The taste and odor that we associate with chlorinated water are actually due to compounds such as CH3NHC1, produced by the action of hypochlorous acid on bacteria. 

Iodoxybenzene has been prepared by the disproportionation of iodosobenzene,4Hi by oxidation of iodosobenzene with hypo-chlorous add or bleaching powder,7 and by oxidation of iodobenzene with hypochlorous acid or with sodium hydroxide and bromine.8 Other oxidizing agents used with iodobenzene include air,3 chlorine in pyridine,9 Caro s acid,19-11 concentrated chloric acid,15 and peracetic acid solution.13 Hypochlorite oxidation of iodobenzene dichloride has also been employed.14... 

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