Chlorine dioxide, reaction

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. 

Ni, Y. Wang, X. (1996) Mechanism and kinetics of chlorine dioxide reaction with hydrogen peroxide under acidic conditions. Canadian Journal of Chemical Engineering, 75, 31-36. 

Wang P, He Y-L, Huang C-H (2010) Oxidation of fluoroquinolone antibiotics and structurally related amines by chlorine dioxide reaction kinetics, product and pathway evaluation. Water Res 44 5989-5998... 

Rav-AchaC. 1998. Transformation of aqueous pollutants by chlorine dioxide Reaction, mechanisms and products. In Handbook of environmental chemistry. Vol. 5, 143-175. 

Ch. Rav-Acha, Transformation of aqueous poUutants by chlorine dioxide reactions, mechanisms and products , in Handbook of Environmental Chemistry, Vol. 5, Part C, Quality and Treatment of Drinking Water (Ed. J. Hrubec), Springer-Verlag, Berhn, Heidelberg, 1998, p. 62. S. Franke, S. Hildebrandt, J. Schwarzbauer, M. Link and W. Franke, Fresenius Z. Anal Chem., 353, 39 (1995). 

Two reactions are known for generation of chlorine dioxide (reactions (11) and... 

Reaction (11), the disproportionation of the C102 ion to CIO2 and Cl , affords chlorine-free chlorine dioxide. Reaction (12) is less useful when CIO2 is being used to combat taste and odor, since the product is inevitably contaminated with hypochlorous acid, thus defeating the objective of using a chlorine substitute. The precursor in either case is sodium chlorite, NaC102, which is a powerful oxidizer, and has to be stored carefully. 

Lengyel I, Rabai G and Epstein I R Experimental and modelling study of oscillations in the chlorine dioxide-iodine-malonic acid reaction J. Am. Chem. See. 112 9104-10... 

Liquid chlorine dioxide, ClOj, boils at 284 K to give an orange-yellow gas. A very reactive compound, it decomposes readily and violently into its constituents. It is a powerful oxidising agent which has recently found favour as a commercial oxidising agent and as a bleach for wood pulp and flour. In addition, it is used in water sterilisation where, unlike chlorine, it does not produce an unpleasant taste. It is produced when potassium chlorate(V) is treated with concentrated sulphuric acid, the reaction being essentially a disproportionation of chloric(V) acid ... 

Only chloric(III) acid, HCIO2, is definitely known to exist. It is formed as one of the products of the reaction of water with chlorine dioxide (see above). Its salts, for example NaClOj, are formed together with chlorates)V) by the action of chlorine dioxide on alkalis. Sodium chlorate(III) alone may be obtained by mixing aqueous solutions of sodium peroxide and chlorine dioxide ... 

Conversion of Aromatic Rings to Nonaromatic Cyclic Structures. On treatment with oxidants such as chlorine, hypochlorite anion, chlorine dioxide, oxygen, hydrogen peroxide, and peroxy acids, the aromatic nuclei in lignin typically ate converted to o- and -quinoid stmctures and oxinane derivatives of quinols. Because of thein relatively high reactivity, these stmctures often appear as transient intermediates rather than as end products. Further reactions of the intermediates lead to the formation of catechol, hydroquinone, and mono- and dicarboxyhc acids. 

Chlorine heptoxide is more stable than either chlorine monoxide or chlorine dioxide however, the CX C) detonates when heated or subjected to shock. It melts at —91.5°C, bods at 80°C, has a molecular weight of 182.914, a heat of vapori2ation of 34.7 kj/mol (8.29 kcal/mol), and, at 0°C, a vapor pressure of 3.2 kPa (23.7 mm Hg) and a density of 1.86 g/mL (14,15). The infrared spectmm is consistent with the stmcture O CIOCIO (16). Cl O decomposes to chlorine and oxygen at low (0.2—10.7 kPa (1.5—80 mm Hg)) pressures and in a temperature range of 100—120°C (17). It is soluble in ben2ene, slowly attacking the solvent with water to form perchloric acid it also reacts with iodine to form iodine pentoxide and explodes on contact with a flame or by percussion. Reaction with olefins yields the impact-sensitive alkyl perchlorates (18). 

At present, thionyl chloride is produced commercially by the continuous reaction of sulfur dioxide (or sulfur trioxide) with sulfur monochloride (or sulfur dichloride) mixed with excess chlorine. The reaction is conducted in the gaseous phase at elevated temperature over activated carbon (178). Unreacted sulfur dioxide is mixed with the stoichiometric amount of chlorine and allowed to react at low temperature over activated carbon to form sulfuryl chloride, which is fed back to the main thionyl chloride reactor. 

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. 

Chlorine dioxide, CIO2, is another chlorine derivative. This unstable, potentially explosive gas must be generated at the point of appHcation. The most common method of generating CIO2 is through the reaction of chlorine gas with a solution of sodium chlorite. 

Hypochlorous acid can also be used, but the reaction is slower. Chlorine dioxide is also made by adding acid to sodium chlorite solutions by the overall reaction in equation 11 ... 

Some chlorine and chlorate also form through competing reactions. Chlorine dioxide is also evolved from mixtures of powdered sodium chlorite and acidic clays or alumina. 

This reaction is very slow in acid but rapid above pH 10. Chlorine dioxide solutions are also decomposed by light. 

Chlorine dioxide gas is a strong oxidizer. The standard reversible potential is determined by the specific reaction chemistry. The standard potential for gaseous CIO2 in aqueous solution reactions where a chloride ion is the product is —1.511 V, but the potential can vary as a function of pH and concentration (26) ... 

Thermal Decomposition of GIO2. Chloiine dioxide decomposition in the gas phase is chaiacteiized by a slow induction period followed by a rapid autocatalytic phase that may be explosive if the initial concentration is above a partial pressure of 10.1 kPa (76 mm Hg) (27). Mechanistic investigations indicate that the intermediates formed include the unstable chlorine oxide, CI2O2. The presence of water vapor tends to extend the duration of the induction period, presumably by reaction with this intermediate. When water vapor concentration and temperature are both high, the decomposition of chlorine dioxide can proceed smoothly rather than explosively. Apparently under these conditions, all decomposition takes place in the induction period, and water vapor inhibits the autocatalytic phase altogether. The products of chlorine dioxide decomposition in the gas phase include chlorine, oxygen, HCl, HCIO, and HCIO. The ratios of products formed during decomposition depend on the concentration of water vapor and temperature (27). 

Photochemical Reactions. The photochemistry of chlorine dioxide is complex and has been extensively studied (29—32). In the gas phase, the primary photochemical reaction is the homolytic fission of the chlorine—oxygen bond to form CIO and O. These products then generate secondary products such as chlorine peroxide, ClOO, chlorine, CI2, oxygen, O2, chlorine trioxide [17496-59-2] CI2O2, chlorine hexoxide [12442-63-6] and... 

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. 

A process for producing chlorine-free chlorine dioxide, called the 01 PROCESS technology, was aimounced by Olin Corp. in early 1992 (72). The process uses a pure chloric acid feedstock and proprietary catalysts that uti1i2e water as the reducing agent. The overall reaction chemistry of the process is... 

The stoichiometric relationship between chlorine dioxide added and color removed during bleaching is nonlinear, but it is independent of temperature, pH, and pulp concentration under conditions normally used. Models used to explain the kinetics and stoichiometry show a strong dependence on chromophore concentration that probably results from differences in the reaction rates of the various chromophores present in the pulps (80). 

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