Alkaline perchlorate

When hot, ammonia and compounds, which contain nitrogen-hydrogen bonds eg ammonium salts and cyanides react violently with chlorates and alkaline perchlorates. Diammonlum sulphate, ammonium chloride, hydroxyl-amine, hydrazine, sodamide, sodium cyanide and ammonium thiocyanate have been cited. So far as hydrazine is concerned, the danger comes from the formation of a complex with sodium or lithium perchlorate, which is explosive when ground. Many of these interactions are explosive but the factors which determine the seriousness of the accident are not known. 

Occurrence Formed locally in air from lightning, in stratosphere by UV radiation. Also occurs in automobile engines and by electrolysis of alkaline perchlorate solutions. Commercial mixtures containing up to 2% ozone are produced by electronic irradiation of air. It is usually manufactured on the spot because it is too expensive to ship. Tonnage quantities are used. 

F. Accascina, R. De Lise, and M. Goffredi, Electrochim. Acta, 16, 1209 (1970). The conductance behavior of some alkaline perchlorates in water-<-Butanol mixtures at 25°C. 

The reduction potentials for the actinide elements ate shown in Figure 5 (12—14,17,20). These ate formal potentials, defined as the measured potentials corrected to unit concentration of the substances entering into the reactions they ate based on the hydrogen-ion-hydrogen couple taken as zero volts no corrections ate made for activity coefficients. The measured potentials were estabhshed by cell, equihbrium, and heat of reaction determinations. The potentials for acid solution were generally measured in 1 Af perchloric acid and for alkaline solution in 1 Af sodium hydroxide. Estimated values ate given in parentheses. 

The AsF ion is very stable toward hydrolysis in aqueous solution. It is not hydroly2ed by boiling a strongly basic solution almost to dryness (26), although it is hydroly2ed in sulfuric acid (27) or in boiling perchloric acid (26). The hydrolysis of AsF in concentrated sulfuric acid (27) and in base (28) at 193—222°C is first order in AsF . The hydrolysis of AsF in alkaline solution is slower than either PF or SbF . ... 

For many years fluorine has been deterrnined by the Willard-Winters method in which finely ground ore, after removal of organic matter, is distilled with 72% perchloric acid in glass apparatus. The distillate, a dilute solution of fluorosiUcic acid, is made alkaline to release fluoride ion, adjusted with monochloroacetic acid at pH 3.4, and titrated with thorium nitrate, using sodium a1i2arine sulfonate as indicator. 

The preferred method of determining water in glycerol is by the Kad Fischer volumetric method (18). Water can also be determined by a special quantitative distillation in which the distilled water is absorbed by anhydrous magnesium perchlorate (19). Other tests such as ash, alkalinity or acidity, sodium chloride, and total organic residue are included in AOCS methods (13,16,18). 

Cesium perchlorate [13454-84-7], CsClO, mol wt 232.35 and theoretical cesium content hi.25/q, is a crystalline powder that decomposes at 250°C Cesium fluoride [13400-13-0], CsF, mol wt 151.90, theoretical cesium content 87.49%, has a melting point of 682—703°C and a boiling point of 1253°C. Cesium fluoride is an extremely hygroscopic, colorless, crystalline soUd it has a solubUity of 3.665 kg/L of water at 18°C. Cesium fluoride is made by exactly neutrali2ing cesium hydroxide with hydrofluoric acid and evaporating the resultant solution to dryness at 400°C. Excess HE results in a bifluoride salt that does not decompose at 400°C, and carbonate in the starting material gives an alkaline product. 

No attempt should be made to purify perchlorates, except for ammonium, alkali metal and alkaline earth salts which, in water or aqueous alcoholic solutions are insensitive to heat or shock. Note that perchlorates react relatively slowly in aqueous organic solvents, but as the water is removed there is an increased possibility of an explosion. Perchlorates, often used in non-aqueous solvents, are explosive in the presence of even small amounts of organic compounds when heated. Hence stringent care should be taken when purifying perchlorates, and direct flame and infrared lamps should be avoided. Tetra-alkylammonium perchlorates should be dried below 50° under vacuum (and protection). Only very small amounts of such materials should be prepared, and stored, at any one time. 

An important class of expl materials contains metallic fuels and inorganic oxidants. Examples are Tritonal (TNT/A1, 80/20), Amatols (TNT/AN, 28/80 80/20), and Minol-2 (TNT/AN/A1, 40/40/20). Oxidants other than nitrates, such as chlorates and perchlorates, may be employed. Water solns containing these cations are highly corrosive to metals. Alkaline metal salts, for example, in the presence of moisture, will pit A1 quickly (Ref 6)... 

Ammonium, and Alkaline Earth Perchlorates in J.C. Schumacher Perchlorates, their Properties, Manufacture, and Uses , ACS Monograph 146, Reinhold, NY (1960), 30 6) L.W. Fagg,... 

The intensity of a flare is largely determined by its temp, which in turn depends on the stability of the reaction products. In order to generate grey body radiation which encompasses the spectral sensitivity of the human eye (0.4— 0.74pm), 3000°K should be exceeded. Whereas this is possible using nitrates and perchlorates with alkaline earth metals as well as Zr, Ti and Hf (Ref 34) (H, C, B, Si and P form oxides which dissociate at high temps), in practice Mg and A1 are found to be best in terms of heat output, cost, and transparency to visible radiation... 

Sodium hypochlorite could also be dangerous when hot, and alkaline chlorites also in this case however it is not guaranteed that the acid character of this example is sufficient to form chlorine dioxide. Caution is still required when handling these mixtures to which chlorates and perchlorates can be added. 

It violently reacts with strong oxidants such as ammonium perchlorate (ignition in contact with copper pip ), alkaline chlorates (detonation by heating, impact or friction powdered copper), ammonium nitrate (detonation molten ammonium nitrate and powdered copper) and potassium superoxide (copper glows). 

Catalytically active species derived from 4. Spectrophotometric titration of the backbone ligand of the sngar discriminating dinuclear copper(ll) complex N, N-bis[(2-pyridylmethyl)-l,3-diaminopropan-2-olato] (//-acetato) dicoppeftll) perchlorate (Cu2(bpdpo), 4) in the presence of two equivalents of copper(ll) ions with sodium hydroxide indicates successive replacement of the bridging acetate anion bound in the sohd state with two hydroxyl ions and two water molecnles in alkaline aqneons solntion (eqs. 2 and 3) (20-22). Two species, [Cu2(L h)(OH)] (4a) and [Cn2(L h)(OH)2] (4b), are thus observed in a pH-dependent equihbrium (20). 

The quantity dyl3 In a2 at the potential of the electrocapillary maximum is of basic importance. As the surface charge of the electrode is here equal to zero, the electrostatic effect of the electrode on the ions ceases. Thus, if no specific ion adsorption occurs, this differential quotient is equal to zero and no surface excess of ions is formed at the electrode. This is especially true for ions of the alkali metals and alkaline earths and, of the anions, fluoride at low concentrations and hydroxide. Sulphate, nitrate and perchlorate ions are very weakly surface active. The remaining ions decrease the surface tension at the maximum on the electrocapillary curve to a greater or lesser degree. 

As a safer alternative to digestion of vegetable matter with perchloric acid, alkaline oxidation of sulfur compounds to sulfate by sodium hypobromite, and reduction of sulfate to hydrogen sulfide by hydriodic acid/formaldehyde/phosphinic acid is recommended. 

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