Acid, hypochlorous

Acide hypocMoreux. Unterehlorige Saure.—When chlorine gas is passed through a cold diluted solution of an alkali, compounds are formed, which are known as bleaching compounds, and have been considered to consist of chlorine and metallic oxides, such as the so-called chlorides of lime and soda. They are, however, in reality, mixtures of chloride of the metal with hypochlorite of the oxide. Thus 2 eq. soda and 2 eq. chlorine, instead of combining together, act on each other as follows — 

The true bleaching compound of soda contains, therefore, 1 eq. of chloride of sodium 4-1 eq. hypochlorite of soda. 

To obtain hypoohlorous acid in the free state, red oxide of mercury and water are agitated with chlorine when there are formed a compound of perchloride and peroxide of mercury, which is insoluble, and hypochlorous acid which dissolves in the water. 

By rectification, a stronger solution may be obtained and if this be placed in a retort with an excess of dry nitrate of, limei, 

It is a gas of a strong yellow colour, and a peculiar penetrating smell. It is very easily decomposed into two vol. chlorine, and one vol. oxygen, exploding by the mere contact of many combustible substances, or by a gentle heat. Experiments with it require the greatest caution. 

Maximum concentrations of hypochlorous acid are obtained by treating pure liquid chlorine(I) oxide with water at 0°. Lower concentrations result from use of the gaseous oxide under reduced pressure or from use of solutions of the oxide in carbon tetrachloride. The last procedure is convenient for acid concentrations up to 5 M. The reaction is nearly quantitative, the equilibrium concentrations of hypochlorous acid and chlorine (I) oxide in the two phases at 0° being calculated from the data of 

Yost and Felt5 and of Secoy and Cady Concentration of HOC1 in water, mol/1 6 as 1 2 3 4 5 

The concentration of chlorine(I) oxide-in carbon tetrachloride and the volume of the solution are first determined. Then the quantity of water that must be added to give a solution of hypochlorous acid of the desired concentration is calculated from the expression 

Both the carbon tetrachloride solution of chlorine(I) oxide and the water are cooled nearly to 0°. The liquids are then added to a separatory funnel of suitable size  

Hypochlorous acid solutions undergo decomposition to chlorine, oxygen, and some chloric acid. The reaction rate is dependent upon hydrogen-ion concentration, reaching a maximum at pH 6.7 and a minimum at pH 13.1.7 The decomposition of the acid is very slow at —20°. At Dry Ice temperatures, no liquid is present, and the solid phases are ice and the compound H0Ch2H20. Hypochlorous acid solutions should be stored in the dark and at low temperatures to minimize decomposition. 

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Sulphites are oxidised by chlorine water and solutions con-tainingchloric(I) (hypochlorous)acid or the chlorate(I) (hypochlorite) ion... 

Figure 2-41. Six different possibilities for numbering the atoms in a hypochlorous acid molecule.

Upon the addition of a weak acid (e.g., acetic acid), it reacts with the liberated hypochlorous acid giving NA -dichloro-p-toluenesulphonamide (dichloramine-T) which, being insoluble in water, crystallises rapidly ... 

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. 

HCIO hypochlorous acid H2Re04 rhenic acid... 

Dry chlorine reacts with most metals combustively depending on temperature alurninum, arsenic, gold, mercury, selenium, teUerium, and tin react with dry CI2 in gaseous or Hquid form at ordinary temperatures carbon steel ignites at about 250°C depending on the physical shape and titanium reacts violendy with dry chlorine. Wet chlorine is very reactive because of the hydrochloric acid and hypochlorous acid (see eq. 37). Metals stable to wet chlorine include platinum, silver, tantalum, and titanium. Tantalum is the most stable to both dry and wet chlorine. 

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). 

Lithium Hypochlorite. Lithium hypochlorite [13840-33-0], LiOCl, is obtained from reaction of chlorine and an aqueous solution of lithium hydroxide. The soHd is usually obtained as a dry stable product containing other alkaH haHdes and sulfates (64). A product containing 35% available chlorine is used for sanitizing appHcations in swimming pools and in food preparation areas where its rapid and complete dissolution is important. The salt can also be obtained in higher purity by reaction of lithium hydroxide and hypochlorous acid (65). 

HCIO hypochlorous acid HCIO2 chlorous acid HCIO chloric acid HCIO4 perchloric acid... 

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... 

In the reaction of aEyl alcohol with an aqueous chlorine solution, addition of hypochlorous acid to the double bond of aEyl alcohol yields glycerol monochlorohydrin and as a by-product, glycerol dichlorohydrin. Thus, a poor yield of glycerol monochlorohydrin is obtained (8). To improve the yield of glycerol monochlorohydrin, addition of sodium carbonate in an amount equivalent to that of the hydrogen chloride in the aqueous chlorine solution, has been proposed (9). 

In two proposed alternative processes, the chlorine is replaced in the hypochlorination reaction by hypochlorous acid [7790-92-3] HOCl, or tert-huty hypochlorite. In the first, a concentrated (>10% by weight) aqueous solution of hypochlorous acid, substantially free of chloride, chlorate, and alkah metal ions, is contacted with propylene to produce propylene chlorohydrin (113). The likely mechanism of reaction is the same as that for chlorine, as chlorine is generated in situ through the equiUbrium of chlorine and hypochlorous acid (109). 

In the second proposed alternative process, tert-huty hypochlorite, formed from the reaction of chlorine and tert-huty alcohol, reacts with propylene and water to produce the chlorohydrin. The alcohol is a coproduct and is recycled to generate the hypochlorite (114—116). No commercialisation of the hypochlorous acid and tert-huty hypochlorite processes for chlorohydrin production is known. 

V-Chlorosuccinimide [128-09-6] mp 150—151°C, forms orthorhombic crystals and has a chlorine-like odor it is prepared from succinimide and hypochlorous acid (114,115). Because of its powerhil germicide properties, it is used ia disiafectants for drinking water. Like its bromine derivative, it is also a halogenating agent. 

Chlorine Vehicle ndStabilizer. Sulfamic acid reacts with hypochlorous acid to produce /V-ch1orosu1famic acids, compounds in which the chlorine is stiU active but more stable than in hypochlorite form. The commercial interest in this area is for chlorinated water systems in paper mills, ie, for slimicides, cooling towers, and similar appHcations (54) (see INDUSTRIALANTIMICROBIALAGENTS). 

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. 

Antimicrobial efficacy is also affected by demand in the cooling water system, specifically demand exerted by ammonia. Chlorine reacts with ammonia to form chloramines, which are not as efficacious as hypochlorous acid or the hypochlorite ion in microbiological control. Bromine reacts with ammonia to form bromamines. Unlike chloramines, bromamines are unstable and reform hypobromous acid. 

Sodium hypochlorite and calcium hypochlorite are chlorine derivatives formed by the reaction of chlorine with hydroxides. The appHcation of hypochlorite to water systems produces the hypochlorite ion and hypochlorous acid, just as the appHcation of chlorine gas does. 

The dissociation of hypochlorous acid depends upon pH and, to a much lesser extent, temperature (6). At 25°C, it is - 0% at pH 5, about 50% at pH 7.5, and - 100% at pH 10, see Figure 1. Because of the acidity formed by chlorine gas, addition of soda ash (Na2C02) or sodium sesquicarbonate (Na2C03-NaHC03) is necessary to maintain the proper pH and to replenish alkalinity. 

NaOH for stabiUty which has only a small effect on pool pH. It is a commonly used sanitizer for swimming pools. In pool water, it produces hypochlorite ion and hypochlorous acid ... 

Calcium Hypochlorite. This chemical, marketed since 1928, is one of the most widely used swimming-pool water sanitizers. Calcium hypochlorite, a crystalline sofld, is a convenient source of available chlorine and is sold in granular or tablet form for use in home, semiprivate, and commercial pools. When dissolved in water, Ca(OCl)2 forms hypochlorous acid and hypochlorite ion similar to NaOCl. It contains small amounts of stabilizing Ca(OH)2, which has a very small effect on pool pH (7). Calcium hypochlorite has superior storage stabiUty and much higher available CI2 concentration than Hquid bleach, which reduces storage requirements and purchasing frequency. 

In solutions, the concentration of available chlorine in the form of hypochlorite or hypochlorous acid is called free-available chlorine. The available chlorine in the form of undissociated A/-chloro compounds is called combined-available chlorine. Several analytical methods can be used to distinguish between free- and combined-available chlorine (8). Bleaches that do not form hypochlorite in solution like chlorine dioxide and nonchlorine bleaches can be characterized by thek equivalent available chlorine content. This can be calculated from equation 5 by substituting the number of electrons accepted divided by two for the number of active chlorine atoms. It can also be measured by iodomettic titration. 

Solutions of available chlorine bleaches decompose on standing at a rate that depends on the conditions described below. Hypochlorous acid [7790-92-3] and hypochlorite anions decompose according to equations 6 and 7 (20,21) ... 

Chlorine gas is usually used, but electrolysis of alkaline salt solutions in which chlorine is generated in situ is also possible and may become more important in the future. The final pH of solutions to be sold or stored is always adjusted above 11 to maximize stabiUty. The salt is usually not removed. However, when the starting solution contains more than 20.5% sodium hydroxide some salt precipitates as it is formed. This precipitate is removed by filtration to make 12—15% NaOCl solutions with about one-half of the normal amount of salt. Small amounts of such solutions are sold for special purposes. Solutions with practically no salt can be made by reaction of high purity hypochlorous acid with metal hydroxides. 

Hypochlorous Acid. Hypochlorous acid [7790-92-3] solutions are made for immediate use as chemical intermediates from chlorine monoxide or in bleaching and water disinfection by adjusting the pH of hypochlorite solutions. Salt-free hypochlorous acid solutions have been economically made... 

Hypochlorous acid can also be used, but the reaction is slower. Chlorine dioxide is also made by adding acid to sodium chlorite solutions by the overall reaction in equation 11 ... 

For optimum disinfection in swimming pools, the pH is maintained in the 7.2 to 7.6 range where HOCl represents 69—47% of the FAC. By contrast, the HOBr fraction varies from 97 to 93%. Nevertheless, the bactericidal effectiveness of HOCl is greater than that of HOBr below pH 8 on a molar basis (8). However, above pH 8 the superiority of HOCl is overcome by the fact that the concentration of C10 exceeds that of HOCl above pH 7.5, whereas the concentration of HOBr stiU exceeds that of BrO up to pH 8.7. Hypochlorous acid is a better viricide than HOBr, but HOBr is more effective against certain algae (9). 

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