Oxidizers chlorites

Chlorine dioxide is a relatively stable free radical it is paramagnetic because it contains an unpaired electron. It can be prepared by oxidizing chlorite, 0102", for example, by peroxosulfate or CI2. The reaction with CI2 is... 

Alteration (oxidization, chloritization, epidotization, weathering, tectonization). 

Calcium oxide Chlorite Chlorodiphenyl (54% Cl) Copper powder Feldspar Graphite Jute Melamine-formaldehyde resin Molybdenum disulfide PEG-4 dimethacrylate Sucrose distearate Urethane-acrylate resin Vinyltriethoxysilane Zeolite Zinc oxide Zinc stearate... 

Chlorine dioxide is conveniently prepared in the laboratory by oxidizing chlorite with, for example, molecular chlorine ... 

Figure 2. Species boundaries according to Hey [1954]. Tetrahedral and octahedral cations allocated on the basis of 14 oxygens (anhydrous), (a) OrthocUorites (b) oxidized chlorites. From Mineral Mag. 30 280 (1954).

Figure 24. Modified graph of Hey [1954] relating refractive index (w), birefringence ( - w). and specific gravity (D) to orthochlorite composition. For oxidized chlorites, the o> and D values will be higher, and e - co will be lower than indicated, in proportion to the percentage of Fe203 present.

Chatterjee, N. D., 1966. On the widespread occurrence of oxidized chlorites in the Pennine zone of the Western Alps. Contrib. Min. Petr. 12 325. 

Ammonia, anhydrous Mercury, halogens, hypochlorites, chlorites, chlorine(I) oxide, hydrofluoric acid (anhydrous), hydrogen peroxide, chromium(VI) oxide, nitrogen dioxide, chromyl(VI) chloride, sulflnyl chloride, magnesium perchlorate, peroxodisul-fates, phosphorus pentoxide, acetaldehyde, ethylene oxide, acrolein, gold(III) chloride... 

Chlorite ion is oxidized rapidly to chlorine dioxide by ozone at pH 4, yielding one mol CIO2 per mol O3 when chlorite is in excess (k > lO" (39). The oxidation of bromite to bromate by ozone is too rapid to measure. Chlorine dioxide is oxidized rapidly to chlorate. Chlorate, bromate, and iodate ions do not react with ozone. 

HCIO4, one of the strongest of the mineral acids. The perchlorates are more stable than the other chlorine oxyanions, ie, chlorates, CIO chlorites, CIO or hypochlorites, OCf (3) (see Chlorine oxygen acids and salts). Essentially, all of the commercial perchlorate compounds are prepared either direcdy or indirectly by electrochemical oxidation of chlorine compounds (4—8) (see Alkali and chlorine products Electrochemical processing). 

Oxidation. Oxidation of the -amyl alcohols produces aldehydes, which after continued oxidation can yield acids. This route to aldehydes has httle merit. However, oxidative esterifications with alkah metal hypohaUtes (eg, calcium chlorite, Ca(OCl)2) (49), bromates (eg, sodium bromate, NaBrO )... 

Sodium chlorite oxidation of com and rice starches is recommended for the production of textile sizes (101) and oxidized starch is recommended as a hardening agent in the immobilization of microbial cells within gelatin (102). 

The oxo-anions of chlorine are weaker oxidants than the corresponding acids. Because they are also more stable, it is not too difficult to isolate certain salts of those acids that can be obtained only in aqueous solution. Hypochlorites and chlorites are hydroly2ed in aqueous solution since HOCl and HCIO2 have acid dissociation constants of 10 and 10 , respectively however, aqueous chloric and perchloric acids are hiUy iorrhed. 

Reagents similai to those used in the analysis of chloiine are commonly employed in the quantitation of gaseous and aqueous chloiine dioxide as well as its reaction coproducts chlorine, chlorite, and chlorate. The volatihty of the gas from aqueous solutions as well as its reactivity to light must be considered for accurate analysis. Other interferences that must be taken into account include other oxidizers such as chloramine, hydrogen peroxide, permanganate, and metal impurities such as ferrous and ferric iron. 

Many of the metal chlorites are not particularly stable and will explode or detonate when stmck or heated. These include the salts of Hg", Tl", Pb ", Cu", and Ag". Extremely fast decomposition with high heat evolution has been noted for barium chlorite [14674-74-9] Ba(Cl02)2, at 190°C, silver chlorite [7783-91-7] AgC102, at 120°C, and lead chlorite [13453-57-17, at 103°C (109). Sodium chlorite can be oxidized by ozone to form chlorine dioxide under acidic conditions (110) ... 

Sodium chlorite is used to produce chlorine dioxide by chemical oxidation, electrochemical oxidation methods, or by acidification with acids. Most of the commercial methods employ chlorine or sodium hypochlorite. 

The pH of the chlorine dioxide reaction mixture must be maintained in the 2.8—3.2 pH range, otherwise decreased conversion yields of chlorite to chlorine dioxide are obtained with by-product formation of chlorate. Generator efficiencies of 93% and higher have been demonstrated. A disadvantage of this system is the limited storage life of the sodium hypochlorite oxidant solution. 

Electrochemical Generation of Chlorine Dioxide from Chlorite. The electrochemical oxidation of sodium chlorite is an old, but not weU-known method of generating chlorine dioxide. Concentrated aqueous sodium chlorite, with or without added conductive salts, is oxidized at the anode of an electrolytic cell having a porous diaphragm-type separator between the anode and cathode compartments (122—127). The anodic reaction is... 

Mechanisms in Chlorine Dioxide Generation from Chlorite. The reactions between sodium chlorite and chloriue-based oxidizers and acids are complex and involve the formation of the proposed unsymmetrical intermediate, [CI2O2] (16,18,22,36,108,135—140). 

Organic Reactions. The chlorite ion, CIO,, is mosdy a weak and slow oxidizer in alkaline aqueous solutions. Aldehydes (qv) can be readily oxidized to the corresponding carboxyhc acids in neutral or weakly acidic solutions. Mixing sohd sodium chlorite with combustible organic materials can result in explosions and fire on shock, exposure to heat, or dames. 

Sodium chlorite is not Hsted by the USEPA or any regulatory authority as a carcinogen. Studies conducted ia mice and rats did not show an increase in tumors in animals exposed to sodium chlorite in thek drinking water. Sodium chlorite has been found to have mutagenic activity in some in vitro test systems such as the Ames Salmonella reverse mutation assay without the presence of metaboHc activators. The significance of these test results in regard to human health is not clear because of the oxidizing effects of the chlorite ion (149). 

Industrial Processes. The use of sodium chlorite as an oxidizer in NO and SO combustion flue gas scmbber systems has been described... 

Sodium chlorite has also been used for treatment and removal of toxic and odorous gases such as hydrogen sulfide and mercaptans. Chlorine dioxide from chlorite is also useful for microbial and slime control in paper mills and alkaline paper machine systems (164,165). The use of sodium chlorite in textile bleaching and stripping is well known. Cotton is not degraded by sodium chlorite because the oxidation reactions are specific for the hemiceUulose and lignin components of the fibers. 

Chlorine dioxide gas generated from chlorite has been used as a chemosterilizing agent substitute for ethylene oxide in medical appHcations (174,175). Aqueous foam compositions containing chlorine dioxide have also been developed for the sanitization of hard surfaces (176). 

The final solution should be checked for absence of free cyanide. The hypochlorite or CI2 + NaOH method is by far the most widely used commercially (45). However, other methods are oxidation to cyanate using hydrogen peroxide, o2one, permanganate, or chlorite electrolysis to CO2, NH, and cyanate hydrolysis at elevated temperatures to NH and salts of formic acid air or steam stripping at low pH biological decomposition to CO2 and N2 chromium... 

Appropriate pyrido[2,3-d]pyrimidin-5-ones with formyl groups in the 6-position have been oxiized to piromidic (68) and pipemidic (69) acids, or to intermediates for these, using moist silver oxide, chromium trioxide (potassium dichromate), potassium permanganate or, alternatively, sodium chlorite/hydroxylamine-O-sulfonic acid. 6-Acetyl groups have been similarly oxidized using sodium hypobromite in aqueous dioxane, whilst 2-acetyl groups give dimethylaminomethylene derivatives en route to 2-pyrazolylpyrido[2,3-d]pyrimidines. 

O-X Alkyl perchlorates. Chlorite salts. Halogen oxides, Hypohalites, Perchloric acid, Perchloryl Compounds... 

Chlorine dioxide, discovered in 1811 by Davy, was prepared from the reaction of potassium chlorate with hydrochloric acid. Early experimentation showed that chlorine dioxide exhibited strong oxidizing and bleaching properties. In the 1930s, the Mathieson Alkali Works developed the first commercial process for preparing chlorine dioxide from sodium chlorate. By 1939, sodium chlorite was established as a commercial product for the generation of chlorine dioxide. 

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