Oxidizers bromates

Use standard reduction potentials to analyze the thermodynamic possibility of using peroxydisulfate to oxidize bromate to perbromate. Hint Use Table 12.2, p. 332.)... 

This makes XeF2 so strong an oxidizing agent that it can even be used to oxidize bromate to perbromate. It also will oxidize a variety of other substances, including chromium(III) to chromate and chloride to chlorine, as shown in Equations (19.13) and (19.14) ... 

The existence of chaotic oscillations has been documented in a variety of chemical systems. Some of tire earliest observations of chemical chaos have been on biochemical systems like tire peroxidase-oxidase reaction [12] and on tire well known Belousov-Zhabotinskii (BZ) [13] reaction. The BZ reaction is tire Ce-ion-catalyzed oxidation of citric or malonic acid by bromate ion. Early investigations of the BZ reaction used tire teclmiques of dynamical systems tlieory outlined above to document tire existence of chaos in tliis reaction. Apparent chaos in tire BZ reaction was found by Hudson et a] [14] aiid tire data were analysed by Tomita and Tsuda [15] using a return-map metliod. Chaos was confinned in tire BZ reaction carried out in a CSTR by Roux et a] [16, E7] and by Hudson and... 

Copper Acetylene and alkynes, ammonium nitrate, azides, bromates, chlorates, iodates, chlorine, ethylene oxide, fluorine, peroxides, hydrogen sulflde, hydrazinium nitrate... 

Neutralizing Lotion. The principal active ingredient of cold wave neutralizers is usually an oxidizing agent. The most popular is hydrogen peroxide [7722-84-1J, employed at a concentration of 1—2% it continues to find widespread use. Aqueous solutions of sodium bromate [7789-38-0] at a concentration of 10—20% occasionally are used and are technically preferred over the peroxide formulations because of excellent stabiUty and absence of hair bleaching. Neutralizing powders appear to be on the decline but formulations stiU in use consist of sodium perborate [7632-04-4] combined with hexametaphosphates to improve solubiUty in hard water. 

The pH must be kept at 7.0—7.2 for this method to be quantitative and to give a stable end poiut. This condition is easily met by addition of soHd sodium bicarbonate to neutralize the HI formed. With starch as iudicator and an appropriate standardized iodine solution, this method is appHcable to both concentrated and dilute (to ca 50 ppm) hydraziue solutious. The iodiue solutiou is best standardized usiug mouohydraziuium sulfate or sodium thiosulfate. Using an iodide-selective electrode, low levels down to the ppb range are detectable (see Electro analytical techniques) (141,142). Potassium iodate (143,144), bromate (145), and permanganate (146) have also been employed as oxidants. 

Iodine can be oxidized to iodate in acid solutions by concentrated nitric acid and, in more dilute solutions, by permanganate, bromates, chlorates, and even chlorine and bromine. 

Potassium iodate [7758-05-6] KIO, mol wt 214.02, 59.30% I, forms white, odorless crystals or a crystalline powder. It has a density 3.98 g/mL and mp of 560°C with partial decomposition. Potassium iodate is rapidly formed when potassium iodide is fused with potassium chlorate, bromate, or perchlorate. The solubihty in water is 9.16 g/100 g H2O at 25°C and 32.2 g/100 g H2O at 100°C. KIO is extensively used as an oxidizing agent in analytical chemistry and as amaturing agent and dough conditioner (see Bakery processes and leavening agents). 

The chlorides, bromides, nitrates, bromates, and perchlorate salts ate soluble in water and, when the aqueous solutions evaporate, precipitate as hydrated crystalline salts. The acetates, iodates, and iodides ate somewhat less soluble. The sulfates ate sparingly soluble and ate unique in that they have a negative solubitity trend with increasing temperature. The oxides, sulfides, fluorides, carbonates, oxalates, and phosphates ate insoluble in water. The oxalate, which is important in the recovery of lanthanides from solutions, can be calcined directly to the oxide. This procedure is used both in analytical and industrial apptications. 

Ferrous Sulfdte Titration. For deterrnination of nitric acid in mixed acid or for nitrates that are free from interferences, ferrous sulfate titration, the nitrometer method, and Devarda s method give excellent results. The deterrnination of nitric acid and nitrates in mixed acid is based on the oxidation of ferrous sulfate [7720-78-7] by nitric acid and may be subject to interference by other materials that reduce nitric acid or oxidize ferrous sulfate. Small amounts of sodium chloride, potassium bromide, or potassium iodide may be tolerated without serious interference, as can nitrous acid up to 50% of the total amount of nitric acid present. Strong oxidizing agents, eg, chlorates, iodates, and bromates, interfere by oxidizing the standardized ferrous sulfate. 

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. 

Potassium bromate [7758-01-7] is much less soluble than the bromide and can mostly be removed by filtration the remaining bromate is reduced with iron. After filtration of the iron oxide, the KBr is crystallized. 

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 )... 

Bromates are stable in storage. They have various uses based on their oxidizing power. Bromates can be formed by the disproportionation of bromine in basic solution ... 

Boiling the solution speeds the conversion of intermediate hypobromites and bromites to bromate. The less soluble bromate can be separated from the hahde by fractional crystallization. A method that is often more economical is the oxidation of bromides into bromates by hypochlorites in aqueous solution. This can be done by passing chlorine into an alkaline bromide solution (75) ... 

Bromates represent a potential fire and explosion hazard if heated, subjected to shock, or acidified. They should not be allowed to contact reactive organic matter, including paper and wood. Industrial quantities are packed in fiber dmms with polyethylene liners or in metal dmms. Laboratory quantities are supphed in glass bottles. For shipment, a yellow oxidizer label is required under DOT regulations. 

Disproportionation of X2 in hot alkaline solution has long been used to synthesize chlorates and bromates (see oxidation state diagrams, p. 855) ... 

Bromates and iodates are prepared on a much smaller scale, usually by chemical oxidation. For example, Br is oxidized to Br03 by aqueous hypochlorite (conveniently effected by passing... 

The modes of thermal decomposition of the halates and their complex oxidation-reduction chemistry reflect the interplay of both thermodynamic and kinetic factors. On the one hand, thermodynamically feasible reactions may be sluggish, whilst, on the other, traces of catalyst may radically alter the course of the reaction. In general, for a given cation, thermal stability decreases in the sequence iodate > chlorate > bromate, but the mode and ease of decomposition can be substantially modified. For example, alkali metal chlorates decompose by disproportionation when fused ... 

For bromates and iodates, disproportionation to halide and perhalate is not thermodynamically feasible and decomposition occurs either with formation of halide and liberation of O2 (as in the catalysed decomposition of CIOs just considered), or by formation of the oxide ... 

The oxidizing power of the halate ions in aqueous solution, as measured by their standard reduction potentials (p. 854), decreases in the sequence bromate > chlorate > iodate but the rates of reaction follow the sequence iodate > bromate > chlorate. In addition, both the thermodynamic oxidizing power and the rate of reaction depend markedly on the hydrogen-ion concentration of the solution, being substantially greater in acid than in alkaline conditions (p, 855). 

The various reactions of bromates and iodates are summarized in the. schemes on p. 866. The oxidation of halates to perhalates is considered further in the next section. 

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