Chlorine dioxide reduction

A more permanent removal of color has been described by Lin (6), and by Dilling and Sarjeant (7), for lignin derivatives in which the phenolic functionality has been partially blocked. These largely non-phenolic (and sulphonated) lignin derivatives were bleached in homogeneous aqueous phase with hydrogen peroxide and chlorine dioxide. Reductions in color of 80-93% were reported for these water soluble derivatives (6,7). 

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. 

Large-Scale Industrial Production. Large amounts of chlorine dioxide ate used in pulp bleaching and smaller quantities ate used for the manufacture of sodium chlorite. In these appHcations, sodium chlorate is the only commercially available taw material. Chlorine dioxide production from sodium chlorate is achieved by the reduction of the chlorate ion in the presence of strong acid. The reaction consumes acid, so that acid and reducing agents must be constantly added to maintain the reaction. 

Chloride Reductant. Processes prior to 1945 used hydrochloric acid as both the acid and reducing agent. Hydrochloric acid is oxidized to chlorine gas and chlorate is reduced to chlorine dioxide. The overall stoichiometry produces a 2 1 molar ratio of chlorine dioxide to chlorine. Sodium chloride is a by-product ... 

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. 

Sulfur Dioxide Reductant. The Mathieson process uses sulfur dioxide, sodium chlorate, and sulfuric acid to produce chlorine dioxide gas with a much lower chlorine content. The sulfur dioxide gas reductant is oxidized to make sulfuric acid, reducing the overall acid requirement of the process. Air is used to dilute the chlorine dioxide produced by this process. The exit gases flow through a scmbber to which chlorate is added in order to remove any unreacted sulfur dioxide. Spent Hquor, containing some unreacted chlorate, sulfuric acid, and sodium sulfate, continuously overflows from this process. 

Chlorine dioxide produced from the methanol reductant processes contains carbon dioxide and small amounts of formic acid. For this reason, sulfur dioxide and chloride-based chlorine dioxide processes are stih used for sodium chlorite production. This problem has been addressed by recycling a portion of the vapor from methanol-based generators so that formic acid further reacts to carbon dioxide ... 

Improvements to the methanol reductant processes may be found in the patent Hterature. These include methods of operation to reduce acidity in the crystallisation 2one of the generator to promote crystallisation of sodium sulfate and to reduce sulfuric acid consumption (48). Other improvements sought are the elimination of formic acid and chlorine impurities from the chlorine dioxide, as weU as methods of recovering acid and sodium hydroxide, or acid and neutral sodium sulfate from the soHd sodium sesquisulfate salt waste stream (48—52). 

The commercial manufacture of sodium chlorite is based almost entirely on the reduction of chlorine dioxide gas in a sodium hydroxide solution containing hydrogen peroxide [7722-84-1] as the reducing agent. The chlorine dioxide is generated from the chemical or electrochemical reduction of sodium chlorate under acidic conditions. 

Reaction between arsenic(tll) and chlorate is fairly slow. Although the reaction can be markedly accelerated by osmium tetroxide as catalyst , the quantitative reduction of chlorates takes nearly an hour. In the case of the induced reaction it was assumed that arsenic(III) is oxidized to arsenic(IV) by 1-equivalent oxidizing agents. Chlorate is reduced to chlorine dioxide by the arsenic(IV) intermediate, viz. 

Then, in fast consecutive steps, chlorine dioxide is reduced to chloride. The induced reduction of chlorate is quantitative within a few minutes. At the beginning of the titration not only the special smell but also the faint-yellowish colour of chlorine dioxide can be observed after the complete disappearance of the cerium(IV) reagent. 

The use of chlorine dioxide in water systems results in its reduction to chlorite and chloride. In the UK the Drinking Water Inspectorate (DWI) restricts the use of chlorine dioxide in potable water supplies to a maximum of 0.5ppm total oxidants expressed as chlorine dioxide. This ensures that chlorite (and any chlorate) concentrations do not reach levels of potential harm to humans. 

Redox titrants (mainly in acetic acid) are bromine, iodine monochloride, chlorine dioxide, iodine (for Karl Fischer reagent based on a methanolic solution of iodine and S02 with pyridine, and the alternatives, methyl-Cellosolve instead of methanol, or sodium acetate instead of pyridine (see pp. 204-205), and other oxidants, mostly compounds of metals of high valency such as potassium permanganate, chromic acid, lead(IV) or mercury(II) acetate or cerium(IV) salts reductants include sodium dithionate, pyrocatechol and oxalic acid, and compounds of metals at low valency such as iron(II) perchlorate, tin(II) chloride, vanadyl acetate, arsenic(IV) or titanium(III) chloride and chromium(II) chloride. 

Persson A process for making chlorine dioxide by reducing sodium chlorate with chromium (III) in the presence of sulfuric acid. The chromium (III) becomes oxidized to chromium (VI) and is then reduced back to chromium (III) with sulfur dioxide. This cyclic redox process with chromium avoids complications that would occur if sulfur dioxide itself were used as the reductant. Installed at the Stora Kopparbergs paper mill, Sweden, in 1946. Sheltmire, W. H., in Chlorine, its Manufacture, Properties and Uses, Sconce, J. S., Ed., Reinhold Publishing, New York, 1962,275,538. 

Oral gavage of rat pups with 14mg/kg/day ftom posmatal day 5 through 20 caused reductions in serum thyroxine levels that correlated with depressed behavioral parameters. Further studies using the same protocol reported decreased cell proliferation in the cerebellum and forebrain on postnatal days 11 and 21, respectively. In yet another study, 14mg/day of chlorine dioxide on posmatal days 1-20 was associated with some neurotoxicity (decreased forebrain weight and reduced synapse formation on day 35), but the neurotoxicity was not correlated with any antithyroid activity of this chemical. ... 

Both chlorine dioxide and chlorite, being strong oxidizing agents, are most likely rapidly reduced in biological systems mainly to chloride ion. Bercz et al. (1982) demonstrated this reduction for chlorine dioxide that was introduced into saliva obtained from anesthetized monkeys. 

Gilbert Gordon We have been studying the reduction of various halogenates, such as chlorate, chlorine dioxide, chlorite, hypochlorite, and chlorine by metal ions. In contrast to the comments of Richard Yalman, there does appear to be some order. 

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