Addition hypochlorites

Cyanide destmction by alkaline chlorination is a widely used process. With alkaline chlorination, cyanide is first converted to cyanate with hypochlorite [7681-52-9] at a pH greater than 10. A high pH is required to prevent the formation of cyanogen chloride [506-77-4] which is toxic and may evolve in gaseous form at a lower pH. With additional hypochlorite, cyanate is then oxidized to bicarbonate, nitrogen gas, and chloride. The pH for this second stage is 7—9.5 (6). 

To the other aliquot, add calcium hypochlorite solution (5 g/100 mL) drop-wise while maintaining the pH between 11 and 12 with caustic soda solution. Perform a test for residual chlorine using Kl-starch paper. The presence of excess chlorine is indicated from the iodide-starch paper turning to a distinct blue color when a drop of the solution is poured on the paper. If required, add additional hypochlorite solution. 

Only a limited number of materials are suitable for use in a bleach plant. Hypochlorite needs to be protected from contacting nickel, cobalt, copper, and alloys that contain these metals since enough of these metals can be adsorbed from piping and equipment to decrease stability. In addition, hypochlorite corrodes these and many other metals such as aluminum, tin, zinc, iron, and stainless steel. 

Reaction mechanism proposed to proceed via radical addition.. ..hypochlorite. 

If a bromomethyl- or vinyl-substituted cyclopropane carbon atom bears a hydroxy group, the homoallyiic rearrangement leads preferentially to cyclobutanone derivatives (J. Sa-laun, 1974). Addition of amines to cydopropanone (N. J. Turro, 1966) yields S-lactams after successive treatment with tert-butyl hypochlorite and silver(I) salts (H.H. Wasserman, 1975). For intramolecular cyclopropane formation see section 1.16. 

A solution of 2-aminobenzophenone (98 g, 0.50 mol) and methyl 2-(methyl-thio)propanoate (74 g, 0,50 mol) in CH Clj (21) was cooled to —70 C and 95% 7-butyl hypochlorite (56 g, 0.5 mol) was added dropwise at such a rate that the temperature did not rise above — 65 C. One hour after the addition was complete, EtjN was added and the mixture was allowed to come to room temperature. The solution w as mixed with 3 N HCl (800 ml) and stirred for 1 h. The organic layer was separated, dried (Na2S04 ) and filtered. The solution was evaporated in vacuo and the residue triturated with ether. Filtration gave the 3-(methylthio)oxindole intermediate (92 g) in 62% yield. 

Bis(azol-2-5l)stilbenes (2(i]ll such as (4) have been prepared. 4,4 -Dihydrazinostilbene-2,2 -disulfonic acid, obtained from the diamino compound, on treatment with 2 moles of oximinoacetophenone and subsequent ring closure, leads to the formation of (4) [23743-28 ]. Such compounds are used chiefly as washing powder additives for the brightening of cotton fabrics, and exhibit excellent light- and hypochlorite-stabiUty. 

Comparison to the Raschig Process. The economics of this peroxide process in comparison to the Raschig or hypochlorite—ketazine processes depend on the relative costs of chlorine, caustic, and hydrogen peroxide. An inexpensive source of peroxide would make this process attractive. Its energy consumption could be somewhat less, because the ketazine in the peroxide process is recovered by decantation rather than by distillation as in the hypcochlorite process. A big advantage of the peroxide process is the elimination of sodium chloride as a by-product this is important where salt discharge is an environmental concern. In addition to Elf Atochem, Mitsubishi Gas (Japan) uses a peroxide process. 

The estimated world production capacity for hydrazine solutions is 44,100 t on a N2H4 basis (Table 6). About 60% is made by the hypochlorite—ketazine process, 25% by the peroxide—ketazine route, and the remainder by the Raschig and urea processes. In addition there is anhydrous hydrazine capacity for propellant appHcations. In the United States, one plant dedicated to fuels production (Olin Corp., Raschig process), has a nominal capacity of 3200 t. This facihty also produces the two other hydrazine fuels, monomethyUiydrazine and unsymmetrical dimethyUiydrazine. Other hydrazine fuels capacity includes AH in the PRC, Japan, and Russia MMH in France and Japan and UDMH in France, Russia, and the PRC. 

The anhydride can be made by the Hquid-phase oxidation of acenaphthene [83-32-9] with chromic acid in aqueous sulfuric acid or acetic acid (93). A postoxidation of the cmde oxidation product with hydrogen peroxide or an alkaU hypochlorite is advantageous (94). An alternative Hquid-phase oxidation process involves the reaction of acenaphthene, molten or in alkanoic acid solvent, with oxygen or acid at ca 70—200°C in the presence of Mn resinate or stearate or Co or Mn salts and a bromide. Addition of an aHphatic anhydride accelerates the oxidation (95). 

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. 

Superchlorination typically refers to a dding FAC equal to 10 x ppm CAC, whereas shock treatment generally involves addition of 10 ppm FAC. The frequency of superchlorination or shock treatment depends on bather load and temperature. Calcium hypochlorite, because of its convenience, is widely used for superchlorination and shock treatment. Sodium hypochlorite, LiOCl, or chlorine gas are also used. Chloroisocyanurates are not recommended since their use would result in excessive cyanuric acid concentrations. 

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). 

Other processes also use the dibasic salt as an intermediate. Dibasic calcium hypochlorite can be prepared from filtrates from chlorinated lime slurries in various ways. In one process, the filtrate is returned to the slurry being chlorinated to keep it thin. This is designed to improve crystal growth. The dibasic crystals, together with water, are added to the slurry during chlorination and some dibasic salt is prepared by chlorination in addition to the dibasic salt made from filtrates (188). In another process, dibasic crystals are separated, slurried in water, and chlorinated to obtain a slurry of neutral Ca(OCl)2 2H20 in a mother Hquor of reduced calcium chloride content which is then filtered and air dried (191,192). 

Dibasic Magnesium Hypochlorite. Basic magnesium hypochlorite [64131 -05-1], av CI2 40-45%, has been known for over 100 years and was once an item of commerce. Dibasic magnesium hypochlorite was first synthesized in 1969 by addition of either a NaOCl or Ca(OCl)2 solution to an excess of aqueous MgCl2 or Mg(N03)2 (225). SoHd hydrates or slurries can also be employed as reactants (226). The reaction proceeds as follows ... 

Dibasic magnesium hypochlorite is more thermally stable than neutral or dibasic calcium hypochlorite. In addition, its decomposition, which starts at - 325° C, is endothermic rather than exothermic as in the case of the Ca compounds. 

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