Hypochlorite solutions

When treated with alkaline hypochlorite solution anthranilic acid is obtained. This reaction, the first stage in the indigo synthesis, is the most important commercial outlet for phthalimide. 

IODOFORM FROM ACETONE. (Semi-micro Scale.) Required Acetone, 0 5 ml. 10% potassium iodide solution, 20 ml. 10% sodium hydroxide solution, 8 ml. zM sodium hypochlorite solution, 20 ml. 

Iodoform reaction. To i ml. of the aldehyde solution, add 3 ml. of 10% KI solution and 10 ml. of freshly prepared sodium hypochlorite solution. Yellow crystals of iodoform, CHI3, soon separate. 

Lead dioxide. A convenient method of preparation is to oxidi.se a plumbous salt in an alkaline medium with a hypochlorite solution ... 

The commercial 10-14 per cent, sodium hypochlorite solution should be diluted with an equal volume of water. 

By treatment of an amide with sodium hypobromite or sodium hypochlorite solution (or with the halogen and alkali), the amine of one less carbon atom is produced, the net result being the elimination of the carbonyl group. An example is ... 

Anthranilic acid. This substance, the ortho amino derivative of benzoic acid, may be conveniently prepared by the action of sodium hypobromite (or sodium hypochlorite) solution upon phthalimide in alkaline solution at 80°. The ring in phthalimide is opened by hydrolysis to phthalamidic acid and the latter undergoes the Hofmann reaction (compare Section 111,116) ... 

Dichloramine-T and chloramine-T. When p toluenesulphonamide is dissolved in excess of sodium (01 calcium) hypochlorite solution, it is converted into the soluble salt of the N-monochloro derivative ... 

Dichloranrine-T (p-toluenesulphondichloramide). Prepare about 200 ml. of a saturated solution of calcium hjrpochlorite by grinding a fresh sample of bleaching powder with water and filtering with shght suction. Dissolve 5 g. of p-toluenesulphonamide in as small a volume of the calcium hypochlorite solution as possible (about 150 ml.) and filter the solution if necessary. Cool in ice, and add about 50 ml. of a mixture of equal volumes of glacial acetic acid and water slowly and with stirring until precipitation is complete. The dichloramine T separates out first as a fine emulsion, which rapidly forms colourless crystals. Filter the latter... 

NOTE In order to make this as painless as possible, please observe the following recommendations 1) Keep the mixing bowl temperature as close to OC or less as possible 2) Keep the Hypochlorite solution as it is being added as close to OC or less as possible 3) After half the Hypochlorite solution has been added, place a plastic bag with 50-1 OOg ice/salt/water mix into the bowl to help keep temperatures low (use this instead of directly adding ice to the reactants, which adds a considerable volume of water making the process less volumetric ally efficient) 4) Purchase an 81b bag of ice ahead of time ... 

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 Solution. Sodium hypochlorite (Uquid bleach) is usually bottled as a 10—15% available CI2 solution, containing... 

Commercially important soHd available chlorine bleaches are usually more stable than concentrated hypochlorite solutions. They decompose very slowly in sealed containers. But most of them decompose quickly as they absorb moisture from air or from other ingredients in a formulation. This may release hypochlorite that destroys other ingredients as well. 

A 5—6% sodium hypochlorite solution is sold for household purposes, of which the largest use is in laundry. Solutions of 10—15% NaOCl are sold for swimming pool disinfection, institutional laundries, and industrial purposes. Solutions of various strengths are used in household and industrial and institutional (I I) cleaners, disinfectants, and mildewcides. A small amount is used in textile mills. Sodium hypochlorite is also made on site with 30—40 g/L available chlorine for pulp bleaching, but its use is decreasing in order to reduce chloroform emissions (see Chlorine oxygen acids and salts). 

Historically, bleaching powder and tropical bleach were significant sources of available chlorine but very Httle are used today. This is because of the greater availabiUty of sodium hypochlorite solutions and the development of calcium hypochlorite. They are stiU used to sanitize fields, drainage ditches, and reservoirs where its insoluble portion is not important. And, they are important sources of available chlorine within some less developed tropical countries. 

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... 

Other Cellulosics. Rayon is bleached similarly to cotton but under milder conditions since the fibers are more easily damaged and since there is less colored material to bleach. Cellulose acetate and triacetate are not usually bleached. They can be bleached like rayon, except a slightly lower pH is used to prevent hydrolysis. The above fibers are most commonly bleached with hydrogen peroxide. Linen, dax, and jute requite more bleaching and mil der conditions than cotton, so multiple steps are usually used. Commonly an acidic or neutral hypochlorite solution is followed by alkaline hypochlorite, peroxide, chlorite, or permanganate, or a chlorite step is done between two peroxide steps. A one-step process with sodium chlorite and hydrogen peroxide is also used. 

In Solution. Although hypochlorite solutions ate much mote stable than HOCl, they ate subject to decomposition, which is influenced by concentration, ionic strength, pH, temperature, light, and impurities. Decomposition occurs in two ways ... 

Saturated hydrocarbons can be chlorinated in moderate yields under mild conditions in a biphasic system consisting of alkaline hypochlorite solution and CH2CI2 containing Ni(Il) bis(saHcyHdene)ethylenediamine as chlorination catalyst and bexadecyltrimetbylammonium bromide as phase-transfer catalyst (166). 

Ana.lysls. The available chlorine (av CI2) in hypochlorite solutions or soHds is deterrnined by reaction with aqueous KI, followed by acidification with either acetic or sulfutic acid and titration of the Hberated iodine with standard thiosulfate. The av CI2 in a hypochlorite is a measure of the oxidi2ing capacity expressed in terms of elemental chlorine one hypochlorite ion is equivalent to one CI2 molecule. Thus pure Ca(OCl)2 has an av CI2 of 2 x mol wt... 

Hypochlorite solutions are prepared in near quantitative yield by chlorination of dilute caustic or a lime slurry. 

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