Calcium hypochlorite reactions

Lithium ferf-butylperoxide has been used effectively as an epoxidising agent with electron deficient alkenes (Scheme 40) [91, 92]. However, application of this methodology to systems containing fluorine has only recently been explored, and it is now established that this can be a very successful procedure with fluoroalkenes. Indeed, the Lithium tert-butylperoxide system worked in some cases where the calcium hypochlorite reaction was ineffective [93,94]. 

Precaution Ignition will cause class B fire sudden reaction and Are may result if mixed with an oxidizing agent incompat. with oxidizers, sodium or calcium hypochlorite reaction with peroxides may cause violent decomp., possible explosion... 

Prepare a solution containing about 100 g, of potassium hypochlorite from commercial calcium hypochlorite ( H.T.H. ) as detailed under -Dimethylacrylic Acid, Section 111,142, Note 1, and place it in a 1500 ml. three-necked flask provided with a thermometer, a mechanical stirrer and a reflux condenser. Warm the solution to 55° and add through the condenser 85 g, of p-acetonaphthalene (methyl p-naphthyl ketone) (1). Stir the mixture vigorously and, after the exothermic reaction commences, maintain the temperature at 60-70° by frequent cooling in an ice bath until the temperature no longer tends to rise (ca. 30 minutes). Stir the mixture for a further 30 minutes, and destroy the excess of hypochlorite completely by adding a solution of 25 g. of sodium bisulphite in 100 ml. of water make sure that no hypochlorite remains by testing the solution with acidified potassium iodide solution. Cool the solution, transfer the reaction mixture to a 2-litre beaker and cautiously acidify with 100 ml. of concentrated hydrochloric acid. Filter the crude acid at the pump. 

Hoffman Degradation. Polyacrylamide reacts with alkaline sodium hypochlorite [7681-52-9], NaOCl, or calcium hypochlorite [7778-54-3], Ca(OCl)2, to form a polymer with primary amine groups (58). Optimum conditions for the reaction include a slight molar excess of sodium hypochlorite, a large excess of sodium hydroxide, and low temperature (59). Cross-linking sometimes occurs if the polymer concentration is high. High temperatures can result in chain scission. 

Thiol spills are handled ia the same manner that all chemical spills are handled, with the added requirement that the odor be eliminated as rapidly as possible. In general, the leak should be stopped, the spill should be contained, and then the odor should be reduced. The odor can be reduced by sprayiag the spill area with sodium hypochlorite (3% solution), calcium hypochlorite solution (3%), or hydrogen peroxide (3—10% solution). The use of higher concentrations of oxidant gives strongly exothermic reactions, which iacrease the amount of thiol ia the vapor, as well as pose a safety ha2ard. The apphcation of an adsorbent prior to addition of the oxidant can be quite helpful and add to the ease of cleanup. 

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. 

Dichlorides and e2thers are the main by-products in this reaction. Treatment with base produces propylene oxide. Specialty epoxides, eg, butylene oxide, are also produced on an industrial scale by means of HOCl generated from calcium hypochlorite and acetic acid followed by dehydrohalogenation with base. 

Reaction of HOCl, formed from calcium hypochlorite and CO2, with highly substituted alkenes in CH2CI2 is a convenient route to aHyUc chlorides (111). Ketones are chlorinated to a-chloroketones by reaction with HOCl Acetone initially gives CH2COCH2CI (112). Methyl ethyl ketone gives 78% CH3CHCICOCH3, 15% CH3CH2COCH2CI, and 7% dichlorides (113). 

Calcium hypochlorite can also be prepared by reaction of soHd lime (212), quicklime (213), or CaCl2 (214) with CI2O chlorate formation is a competing side reaction. 

The dissociation of hypochlorous acid depends on the pH. The unionized acid is present in greater quantities in acid solution, although in strongly acid solution the reaction with water is reversed and chlorine is Hberated. In alkaline solutions the hypochlorite ion OCL is increasingly Hberated as the pH is increased. The pH is important because unionized hypochlorous acid is largely responsible for the antimicrobial action of chlorine in water. Chlorine compounds are therefore more active in the acid or neutral range. The hypochlorites most commonly employed are sodium hypochlorite [7681-52-9] or calcium hypochlorite [7778-54-3]. 

Chemical Reactivity - Reactivity with Water No reaction Reactivity with Common Materials Can catch fire when in contact with porous materials such as wood, asbestos, cloth, soil, or rusty metals Stability During Transport Stable at ordinary temperatures, however when heated this material can decompose to nitrogen and ammonia gases. The decomposition is not generally hazardous unless it occurs in confined spaces Neutralizing Agents for Acids and Caustics Flush with water and neutralize the resulting solution with calcium hypochlorite Polymerization Not pertinent Inhibitor of Polymerization Not pertinent. 

The calcium hypochlorite or sodium dichloroisocyanurate used to disinfect swimming pools also bleaches hair, although contrary to popular belief it does not turn the hair green. It simply allows the green copper sulfate from the water to show up in the hair. The copper sulfate comes from the reaction of the copper pipes in the plumbing to the sulfuric acid used to neutralize the alkalies in the chlorination chemicals. 

This oxide catalyses the violent or even explosive decomposition of hydrogen peroxide. This reaction explains the numerous accidents mentioned involving the contact of hydrogen peroxide with rusted iron. Two accidents of this nature dealt with mixtures of hydrogen peroxide with ammonia and an alkaline hydroxide The detonations took place after a period of induction of respectively several hours and four minutes. Iron (III) oxide also catalyses the explosive decomposition of calcium hypochlorite. 

Nitromethane gives rise to an extremely violent reaction with calcium hypochlorite. 

There was an attempt to treat spreadings of organic sulphides or thiols with calcium hypochlorite in the solid state. These treatments usually ended with a violent reaction followed by the compounds igniting. Nevertheless, this does not represent any danger when using sodium hypochlorite solutions at 15%. 

When acids and bases are mixed, a neutralization reaction occurs. Not all acids and bases should be mixed, however. Bleach, which is a solution of sodium or calcium hypochlorite, for example, should never be mixed with any kind of acid because the resulting chemical reaction creates the deadly gas chlorine. Chlorine gas was used as a chemical weapon in World War I, and breathing it can destroy lung tissue. The lungs fill with fluid, and the unfortunate victim eventually dies by suffocation. 

A jug containing calcium hypochlorite (probably as moist solid) was used as a disposal receptacle for cyanide wastes from student preparations of benzoin. When a little acetic acid residue was inadvertently added, an explosion occurred, attributed to a cyanide-chlorine redox reaction. 

The chlorination of water is usually carried out by adding chlorine gas, sodium hypochlorite, or calcium hypochlorite to the water in low concentrations. The active antibacterial agent in each case is hypochlorous acid, HClO(aq). For example, when chlorine gas is added to water, hypochlorous acid is formed by the following reaction. 

Oxidizers may not themselves be combustible, but they may provide reaction pathways to accelerate the oxidation of other combustible materials. Combustible solids and liquids should be segregated from oxidizers. Certain oxidizers undergo dangerous reactions with specific noncombustible materials. Some oxidizers, such as calcium hypochlorite, decompose upon heating or contamination and self-react with violent heat output. Oxidizers include nitrates, nitric acid, nitrites, inorganic peroxides, chlorates, chlorites, dichromates, hypochlorites, perchlorates, permanganates, persulfates and the halogens. 

Calcium hypochlorite is an oxidizing agent. It undergoes vigorous to violent reactions with reducing agents and organics. In aqueous solution, it dissociates to calcium and hypochlorite ions. The hypochlorite ions form hypochlor-ous acid and molecular chlorine, which coexist in equilibrium. 

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... 

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