Chlorates, solubility

KCIO3. Not very soluble in water, deposited from chlorate(V) solutions (CI2 plus Ca(OH)2 or electrolysis of aqueous NaCl). On heating gives KCl and KCIO4 but decomposes to KCl at high temperatures. 

Generally the solubility of a given metal halate decreases from chlorate(V) to iodatef and many heavy metal iodates(V) are quantitatively insoluble. Like their parent acids, the halates(V) are strong oxidising agents, especially in acid solution their standard electrode potentials are given below (in volts) ... 

These can be prepared by electrolytic oxidation of chlorates(V) or by neutralisation of the acid with metals. Many chlorates(VII) are very soluble in water and indeed barium and magnesium chlorates-(VII) form hydrates of such low vapour pressure that they can be used as desiccants. The chlorate(VII) ion shows the least tendency of any negative ion to behave as a ligand, i.e. to form complexes with cations, and hence solutions of chlorates (VII) are used when it is desired to avoid complex formation in solution. 

Originally, general methods of separation were based on small differences in the solubilities of their salts, for examples the nitrates, and a laborious series of fractional crystallisations had to be carried out to obtain the pure salts. In a few cases, individual lanthanides could be separated because they yielded oxidation states other than three. Thus the commonest lanthanide, cerium, exhibits oxidation states of h-3 and -t-4 hence oxidation of a mixture of lanthanide salts in alkaline solution with chlorine yields the soluble chlorates(I) of all the -1-3 lanthanides (which are not oxidised) but gives a precipitate of cerium(IV) hydroxide, Ce(OH)4, since this is too weak a base to form a chlorate(I). In some cases also, preferential reduction to the metal by sodium amalgam could be used to separate out individual lanthanides. 

The carbonates, sulfates, nitrates, and haUdes of lead (except the yeUow iodide) are colodess. Bivalent lead forms a soluble nitrate, chlorate, and acetate a slightly soluble chloride and an insoluble sulfate, carbonate, chromate, phosphate, molybdate, and sulfide. Highly crystalline basic lead salts of both anhydrous and hydrated types are readily formed. Tetrabasic lead sulfate [52732-72-6] 4PbO PbSO, and the hydrated tribasic salt [12397-06-7] ... 

Only three simple silver salts, ie, the fluoride, nitrate, and perchlorate, are soluble to the extent of at least one mole per Hter. Silver acetate, chlorate, nitrite, and sulfate are considered to be moderately soluble. AH other silver salts are, at most, spatingly soluble the sulfide is one of the most iasoluble salts known. SHver(I) also forms stable complexes with excess ammonia, cyanide, thiosulfate, and the haUdes. Complex formation often results ia the solubilization of otherwise iasoluble salts. Silver bromide and iodide are colored, although the respective ions are colorless. This is considered to be evidence of the partially covalent nature of these salts. 

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. 

Quantitatively, sulfur in a free or combined state is generally determined by oxidizing it to a soluble sulfate, by fusion with an alkaH carbonate if necessary, and precipitating it as insoluble barium sulfate. Oxidation can be effected with such agents as concentrated or fuming nitric acid, bromine, sodium peroxide, potassium nitrate, or potassium chlorate. Free sulfur is normally determined by solution in carbon disulfide, the latter being distilled from the extract. This method is not useful if the sample contains polymeric sulfur. 

The water solubiUty of zinc compounds varies greatly, as shown in Table 1. Water-soluble compounds not Hsted are zinc formate [557-41-5] chlorate [10361-95-2] fluorosihcate [16871 -71 -9] and thiocyanate [557-42-6]. Also, the water-soluble amino and cyanide complexes have many uses. 

The flow sheet in Figure 3 iHustrates cadmium recovery from cadmium-bearing fumes. Depending on composition, the fume may have to be roasted with or without sulfuric acid or oxidi2ed using sodium chlorate or chlorine in order to convert cadmium into a water- or acid-soluble form and to... 

Manufacture. Most chlorate is manufactured by the electrolysis of sodium chloride solution in electrochemical cells without diaphragms. Potassium chloride can be electroly2ed for the direct production of potassium chlorate (35,36), but because sodium chlorate is so much more soluble (see Fig. 2), the production of the sodium salt is generally preferred. Potassium chlorate may be obtained from the sodium chlorate by a metathesis reaction with potassium chloride (37). 

Lithium chlorate [13453-71 -9] LiClO, has rhombic needles mp 124—129°C decomposes on heating to 270°C. It is one of the most soluble salts known and it is very hygroscopic. LiClO is prepared by adding lithium chloride [7447-41-8] to sodium chlorate solution. Sodium chloride precipitates, the hquor is concentrated, and the lithium chlorate is filtered and dried. It has limited use in pyrotechnics. 

For example, J. von Liebig developed the technical preparation of KCIO3 by passing CI2 into a warm suspension of Ca(OH)2 and then adding KCl to enable the less-soluble chlorate to crystallize on cooling ... 

Urea possesses negligible basic properties (Kb = 1.5 x 10 l4), is soluble in water and its hydrolysis rate can be easily controlled. It hydrolyses rapidly at 90-100 °C, and hydrolysis can be quickly terminated at a desired pH by cooling the reaction mixture to room temperature. The use of a hydrolytic reagent alone does not result in the formation of a compact precipitate the physical character of the precipitate will be very much affected by the presence of certain anions. Thus in the precipitation of aluminium by the urea process, a dense precipitate is obtained in the presence of succinate, sulphate, formate, oxalate, and benzoate ions, but not in the presence of chloride, chlorate, perchlorate, nitrate, sulphate, chromate, and acetate ions. The preferred anion for the precipitation of aluminium is succinate. It would appear that the main function of the suitable anion is the formation of a basic salt which seems responsible for the production of a compact precipitate. The pH of the initial solution must be appropriately adjusted. 

Discussion. These anions are both determined as silver bromide, AgBr, by precipitation with silver nitrate solution in the presence of dilute nitric acid. With the bromate, initial reduction to the bromide is achieved by the procedures described for the chlorate (Section 11.56) and the iodate (Section 11.63). Silver bromide is less soluble in water than is the chloride. The solubility of the former is 0.11 mg L 1 at 21 °C as compared with 1.54 mg L 1 for the latter hence the procedure for the determination of bromide is practically the same as that for chloride. Protection from light is even more essential with the bromide than with the chloride because of its greater sensitivity (see Section 11.57). 

Determination of nitrate as nitron nitrate Discussion. The mono-acid base nitron, C20H16N4, forms a fairly insoluble crystalline nitrate, C20H 16N4,HN03 (solubility is 0.099 g L 1 at about 20 °C), which can be used for the quantitative determination of nitrates [see Section 11.11(E)]. The sulphate and acetate are soluble so that precipitation may be made in sulphuric or acetic (ethanoic) acid solution. Perchlorates (0.08 g), iodides (0.17 g), thiocyanates (0.4 g), chromates (0.6 g), chlorates (1.2g), nitrites (1.9 g), bromides (6.1 g), hexacyanoferrate(II), hexacyanoferrate(III), oxalates, and considerable quantities of chlorides interfere, and should be absent. The figures in parentheses are the approximate solubilities of the nitron salts in g L-1 at about 20 °C. 

Potassium chlorate is less satisfactory because of its lower solubility. 

Exhaustive oxidation of sulphones to sulphate using a mixture of potassium chlorate, sodium peroxide and sugar in a bomb has also been recommended220. This procedure is known as the Parr method and produces a mixture of soluble alkali sulphates. 

Upon heating anthraquinone with fuming sulphuric acid at 160° for about 1 hour, the main product Is anthraquinone-p-sulphonic acid, which is isolated as the sparingly soluble sodium salt. The latter when heated imder pressure with sodium hydroxide solution and an oxidising agent (sodium or potassium chlorate) yields first the corresponding hydroxy compound further hydroxy-lation occurs in the a-position through oxidation by the chlorate and 1 2-di-hydroxyanthraquinone (alizarin) is formed. 

The latter cleaning method would have removed completely the sodium chlorate, which is soluble in water but not in halogenated solvents [5],... 

Oxidation of l,2,5,6-tetraacetoxyhexene-3 led to the formation of dulcitol tetraacetate. In a typical experiment 22 g. of the tetraacetate was oxidized with 4.4 g. of silver chlorate and 0.1 g. of osmic acid and yielded a sirujj which did not crystallize. The sirup was acetylated again and yielded the corresponding hexitol hexaacetate. The crystals which deposited first were collected and recrystallized from methanol, in which they are difficultly soluble in the cold. The product melted at 166-166.5° and analyzed correctly for a hexitol hexaacetate. Now there was found in the collections of the Ecole Normale Sup rieure an old bottle containing dulcitol hexaacetate, m. p. 167-168°. A mixture of the new and the old hexaacetates was found to melt at 166.5-167.5° the identity of the two compounds was thus beyond doubt. 

Tetraphosphorus trisulfide (P4S3) which is also called phosphorus sesquisulfide, can be obtained by heating a stoichiometric mixture of phosphorus and sulfur at 180 °C in an inert atmosphere. The compound (m.p. 174 °C) is soluble in toluene, carbon disulfide, and benzene, and it is used with potassium chlorate, sulfur, and lead dioxide in matches. 

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