Uses of Chlorates

Sodium chlorate is used for oxidation in organic industries and for the manufacture of perchlorates. Very often it is used as a 2 per cent solution, to destroy 

Potassium chlorate is used as an oxidizing agent in vat dyeing, for printed ealico, for pyrotechnical purposes but mainly in the manufacture of matches. For pharmaceutical use, the so called santonine form of fine, scale shaped crystals is sometimes demanded. These are formed by the saturated solutions when they are slowly cooled. 

In Czechoslovakia, various grades of chlorate are manufactured as per technical specifications indicated in Table 18. 

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It should be noted that the use of chlorate has not been limited to Bali. Two more attacks using chlorate-based improvised explosives occurred in Indonesia followed the Bali bombing. On August 5, 2003, the J.W. Marriott hotel was bombed in Jakarta. In an even bolder attack the Australian Embassy in Jakarta was bombed on September 9, 2004. This continued reliance on a highly sensitive main charge in Indonesia illustrates that terrorists will utilize whatever tools are at their disposal regardless of the risks. 

The use of chlorate or perchlorate oxidizers (KCIO 3> KC10 , etc.) is one way to introduce chlorine atoms into the pyrotechnic flame. Another method is to incorporate a chlorine-rich organic compound into the mixture. Table 7.8 lists some of the chlorine donors commonly used in pyrotechnic mixtures. A dramatic increase in color quality can be achieved by the addition of a small percentage of one of these materials into a mixture. Shimizu recommends the addition of 2-3% organic chlorine donor into compositions that don t contain a metallic fuel, and the addition of 10-15% chlorine donor into the high temperature mixtures containing metallic fuels [11]. 

Uses of Chlorate Explosives, Most chlorate expls have been used for industrial purposes, but during WWI WWII some were used by the French, Russians, Italians, Japanese and Germans for loading mines, torpedoes, hand grenades depth charges(but not in artillery shells). Many expls contg chlorate have been used in primers and detonators (See also under individual expls, such as CHEDDITES)... 

According to Brock, the use of chlorate in pyrotechnic mixtures, initiating the modern epoch in the art, first occurred about 1830. Lieut. Hippert of the Belgian artillery published at Bruxelles in 1836 a French translation, Pyrotechnie raisonnee, of a work by Prussian artillery Captain Moritz Meyer in which one chapter is devoted to colored fires, and listed several com-... 

Although Meyer s formulas are somewhat incoherent, they represent a definite advance. Equally significant with the use of chlorate is his use of the nitrates of strontium and barium. 

Various anecdotal accounts are given of incendiary mishaps consequent upon former use of chlorate throat lozenges [5]. 

Caution in the use of Chlorate Of Potassa. This substance should never be kept in admixture with any inflammable matter, especially sulphur or phosphorus, as they oxplode with terrific violenco by tho most trivial causes, and not unfrcquently spontaneously. All pounding and nibbing must be avoided. 

This consists of a mixture, used for adding to illumination mixtures, of 125 parts of potassium chlorate and 3S parts of sulphur. The use of chlorates is restricted in mixtures on account of their sensitiveness and has been made illegal in some countries,... 

The use of chlorates, gallic acid, picrates, sulfur and sulfides should be avoided. 

These can be prepared by electrolytic oxidation of chlorates(V) or by neutralisation of the acid with metals. Many chlorates(VII) are very soluble in water and indeed barium and magnesium chlorates-(VII) form hydrates of such low vapour pressure that they can be used as desiccants. The chlorate(VII) ion shows the least tendency of any negative ion to behave as a ligand, i.e. to form complexes with cations, and hence solutions of chlorates (VII) are used when it is desired to avoid complex formation in solution. 

Most of the chlorine produced is used in the manufacture of chlorinated compounds for sanitation, pulp bleaching, disinfectants, and textile processing. Further use is in the manufacture of chlorates, chloroform, carbon tetrachloride, and in the extraction of bromine. 

Peroxides, superoxides, and chlorates are oxidising compounds and should not contact organic materials, eg, oil, greases, etc. This is especially tme while oxygen is being produced. Caustic residues that may remain after use of peroxides and superoxides require disposal appropriate to alkaH metal hydroxides. Spent candles containing barium may require special disposal considerations. 

The standard potential for the anodic reaction is 1.19 V, close to that of 1.228 V for water oxidation. In order to minimize the oxygen production from water oxidation, the cell is operated at a high potential that requires either platinum-coated or lead dioxide anodes. Various mechanisms have been proposed for the formation of perchlorates at the anode, including the discharge of chlorate ion to chlorate radical (87—89), the formation of active oxygen and subsequent formation of perchlorate (90), and the mass-transfer-controUed reaction of chlorate with adsorbed oxygen at the anode (91—93). Sodium dichromate is added to the electrolyte ia platinum anode cells to inhibit the reduction of perchlorates at the cathode. Sodium fluoride is used in the lead dioxide anode cells to improve current efficiency. 

Use of mercuric catalysts has created a serious pollution problem thereby limiting the manufacture of such acids. Other catalysts such as palladium or mthenium have been proposed (17). Nitration of anthraquinone has been studied intensively in an effort to obtain 1-nitroanthraquinone [82-34-8] suitable for the manufacture of 1-aminoanthraquinone [82-45-1]. However, the nitration proceeds so rapidly that a mixture of mono- and dinitroanthraquinone is produced. It has not been possible, economically, to separate from this mixture 1-nitroanthraquinone in a yield and purity suitable for the manufacture of 1-aminoanthraquinone. Chlorination of anthraquinone cannot be used to manufacture 1-chloroanthraquinone [82-44-0] since polychlorinated products are formed readily. Consequentiy, 1-chloroanthraquinone is manufactured by reaction of anthraquinone-l-sulfonic acid [82-49-5] with sodium chlorate and hydrochloric acid (18). 

Pyrotechnic mixtures may also contain additional components that are added to modify the bum rate, enhance the pyrotechnic effect, or serve as a binder to maintain the homogeneity of the blended mixture and provide mechanical strength when the composition is pressed or consoHdated into a tube or other container. These additional components may also function as oxidizers or fuels in the composition, and it can be anticipated that the heat output, bum rate, and ignition sensitivity may all be affected by the addition of another component to a pyrotechnic composition. An example of an additional component is the use of a catalyst, such as iron oxide, to enhance the decomposition rate of ammonium perchlorate. Diatomaceous earth or coarse sawdust may be used to slow up the bum rate of a composition, or magnesium carbonate (an acid neutralizer) may be added to help stabilize mixtures that contain an acid-sensitive component such as potassium chlorate. Binders include such materials as dextrin (partially hydrolyzed starch), various gums, and assorted polymers such as poly(vinyl alcohol), epoxies, and polyesters. Polybutadiene mbber binders are widely used as fuels and binders in the soHd propellant industry. The production of colored flames is enhanced by the presence of chlorine atoms in the pyrotechnic flame, so chlorine donors such as poly(vinyl chloride) or chlorinated mbber are often added to color-producing compositions, where they also serve as fuels. 

The cleavage products of several sulfonates are utilized on an industrial scale (Fig. 3). The fusion of aromatic sulfonates with sodium hydroxide [1310-73-2J and other caustic alkalies produces phenohc salts (see Alkylphenols Phenol). Chlorinated aromatics are produced by treatment of an aromatic sulfonate with hydrochloric acid and sodium chlorate [7775-09-9J. Nitriles (qv) (see Supplement) can be produced by reaction of a sulfonate with a cyanide salt. Arenesulfonates can be converted to amines with the use of ammonia. This transformation is also rather facile using mono- and dialkylamines. 

Uses. The dominant use of sulfur dioxide is as a captive intermediate for production of sulfuric acid. There is also substantial captive production in the pulp and paper industry for sulfite pulping, and it is used as an intermediate for on-site production of bleaches, eg, chlorine dioxide or sodium hydrosulfite (see Bleaching agents). There is a substantial merchant market for sulfur dioxide in the paper and pulp industry. Sulfur dioxide is used for the production of chlorine dioxide at the paper (qv) mill site by reduction of sodium chlorate in sulfuric acid solution and also for production of sodium dithionite by the reaction of sodium borohydride with sulfur dioxide (315). This last appHcation was growing rapidly in North America as of the late 1990s. 

Several common acid treatments for sample decomposition include the use of concentrated nitric acid, aqua regia, nitric—sulfuric acids, and nitric perchloric acids. Perchloric acid is an effective oxidant, but its use is ha2ardous and requkes great care. Addition of potassium chlorate with nitric acid also assists in dissolving any carbonaceous matter. 

Yokagawa Electric Works has developed a thermometer based on the nuclear quadmpole resonance of potassium chlorate, usable over the range from —184 to 125°C. This thermometer makes use of the fundamental properties of the absorption frequency of the Cl nucleus, and its caUbration is itself a constant of nature. 

An integrated process for producing chlorine dioxide that can consume chlorine (46) involves the use of hydrochloric acid as the reductant. The spent chlorine dioxide generator Hquor is used as feed for chlorate production, and hydrogen gas from chlorate production is burned with chlorine to produce hydrochloric acid. The principal disadvantage in the integrated hydrochloric acid-based processes is that the chlorine dioxide gas contains Y2 mole of chlorine for each mole of chlorine dioxide produced. A partial purification is achieved by absorption in chilled water in which the solubiHty of chlorine is less than chlorine dioxide however, this product stiU contains 10—15% chlorine on the basis of total chlorine and chlorine dioxide. 

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