Oxidizers iodates

Periodates are best obtained by oxidizing iodate (or even I" or I2) electrolytically or with Cl2 in strongly basic solution to give Na3H2IC>6, or by thermal disproportionation of an iodate ... 

BRONZE POWDER (7440-50-8) The powder forms the friction-, heat-, or shock-sensitive explosive detonator, copper acetylide, with acetylene, acetylene compounds. Potentially violent reaction when finely dispersed powder comes into contact with strong oxidizers, ammonium nitrate, alkynes, azides, bromine vapor, bromates, calcium carbide, chlorates, chlorine, ethylene oxide, iodates, hydrazine mononitrate, hydrogen peroxide, hydrogen sulfide, iodates, finely divided iodine, lead azide, potassium peroxide, sodium peroxide, sulfuric acid. Incompatible with acids, anhydrous ammonia. 

Boiling alkaline [S208] " oxidizes iodate to periodate ... 

Andrews deration An important titration for the estimation of reducing agents. The reducing agent is dissolved In concentrated hydrochloric acid and titrated with potassium iodale(V) solution. A drop of carbon tetrachloride is added to the solution and the end point is indicated by the disappearance of the iodine colour from this layer. The reducing agent is oxidized and the iodate reduced to ICl, i.e. a 4-eiectron change. 

Laughing gas, see Nitrogen(I) oxide Lautarite, see Calcium iodate Lawrencite, see Iron(II) chloride Lechatelierite, see Silicon dioxide Lime, see Calcium oxide Litharge, see Lead(II) oxide... 

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

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. 

Subsequendy, the hypoiodite is oxidized to iodate, and this reaction is not induenced by the alkah concentration, temperature, or iodate concentration. 

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. 

In alkaline solutions, iodine can be oxidized to iodate by sodium hypochlorite or hypobromite, whereas chlorine passed into a solution of iodine and alkah oxidizes ah the way to periodate. 

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. 

Silver compounds, available from commercial suppHers, are expensive. Reagent grades of sHver(I) carbonate, cyanide, diethjldithiocarbamate, iodate, nitrate, oxide, phosphate, and sulfate are available. Standardized solutions of silver nitrate are also available for analytical uses. Purified grades of sHver(I) acetate, bromide, cyanide, and iodide can be purchased silver nitrate is also made as a USP XX grade for medicinal uses (6). 

Many silver compounds are unstable to light, and are thus shipped ia brown glass or opaque plastic bottles. Silver compounds that are oxidants, eg, silver nitrate and iodate, must be so identified according to U.S. Department of Transportation (DOT) regulations. Compounds such as silver cyanide, which is toxic owiag to its cyanide content, must carry a poison label. However, most silver compounds are essentially nontoxic. 

Iodized Salt. Iodized table salt has been used to provide supplemental iodine to the U.S. population since 1924, when producers, in cooperation with the Michigan State Medical Society (24), began a voluntary program of salt iodization in Michigan that ultimately led to the elimination of iodine deficiency in the United States. More than 50% of the table salt sold in the United States is iodized. Potassium iodide in table salt at levels of 0.006% to 0.01% KI is one of two sources of iodine for food-grade salt approved by the U.S. Food and Dmg Administration. The other, cuprous iodide, is not used by U.S. salt producers. Iodine may be added to a food so that the daily intake does not exceed 225 p.g for adults and children over four years of age. Potassium iodide is unstable under conditions of extreme moisture and temperature, particularly in an acid environment. Sodium carbonate or sodium bicarbonate is added to increase alkalinity, and sodium thiosulfate or dextrose is added to stabilize potassium iodide. Without a stabilizer, potassium iodide is oxidized to iodine and lost by volatilization from the product. Potassium iodate, far more stable than potassium iodide, is widely used in other parts of the world, but is not approved for use in the United States. 

The Chilean nitrate deposits are located in the north of Chile, in a plateau between the coastal range and the Andes mountains, in the Atacama desert. These deposits are scattered across an area extending some 700 km in length, and ranging in width from a few kilometers to about 50 km. Most deposits are in areas of low rehef, about 1200 m above sea level. The nitrate ore, caUche, is a conglomerate of insoluble and barren material such as breccia, sands, and clays (qv), firmly cemented by soluble oxidized salts that are predominandy sulfates, nitrates, and chlorides of sodium, potassium, and magnesium. Cahche also contains significant quantities of borates, chromates, chlorates, perchlorates, and iodates. 

Analytical Methods. A classical and stiU widely employed analytical method is iodimetric titration. This is suitable for determination of sodium sulfite, for example, in boiler water. Standard potassium iodate—potassium iodide solution is commonly used as the titrant with a starch or starch-substitute indicator. Sodium bisulfite occurring as an impurity in sodium sulfite can be determined by addition of hydrogen peroxide to oxidize the bisulfite to bisulfate, followed by titration with standard sodium hydroxide (279). 

The determination of tin in metals containing over 75 wt % tin (eg, ingot tin) requites a special procedure (17). A 5-g sample is dissolved in hydrochloric acid, reduced with nickel, and cooled in CO2. A calculated weight of pure potassium iodate (dried at 100°C) and an excess of potassium iodide (1 3) are dissolved in water and added to the reduced solution to oxidize 96—98 wt % of the stannous chloride present. The reaction is completed by titration with 0.1 Af KIO —KI solution to a blue color using starch as the indicator. 

Bromide ndIodide. The spectrophotometric determination of trace bromide concentration is based on the bromide catalysis of iodine oxidation to iodate by permanganate in acidic solution. Iodide can also be measured spectrophotometricaHy by selective oxidation to iodine by potassium peroxymonosulfate (KHSO ). The iodine reacts with colorless leucocrystal violet to produce the highly colored leucocrystal violet dye. Greater than 200 mg/L of chloride interferes with the color development. Trace concentrations of iodide are determined by its abiUty to cataly2e ceric ion reduction by arsenous acid. The reduction reaction is stopped at a specific time by the addition of ferrous ammonium sulfate. The ferrous ion is oxidi2ed to ferric ion, which then reacts with thiocyanate to produce a deep red complex. 

Developed methods have been checked up by analysis of kitchen salt which contains potassium iodate. Preliminary oxidation of iodate in the salt to periodate was performed by hydrogen peroxide in the acidic solution. The results of analysis coincide with certificate data of iodinated kitchen salt. 

Section 16.16 Oxidation of sulfides yields sulfoxides, then sulfones. Sodium metaper-iodate is specific for the oxidation of sulfides to sulfoxides, and no further. Hydrogen peroxide or peroxy acids can yield sulfoxides (1 mole of oxidant per mole of sulfide) or sulfone (2 moles of oxidant per mole of sulfide). 

Periodic acid oxidation (Section 15.12) finds extensive use as an analytical method in carbohydrate chemistry. Structural information is obtained by measuring the number of equivalents of periodic acid that react with a given compound and by identifying the reaction products. A vicinal diol consumes one equivalent of per-iodate and is cleaved to two carbonyl compounds ... 

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 ... 

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