III Perchlorate

Gallium Halogenates. The anhydrous galhum(III) perchlorate [19854-31-0], Ga(Q0 2 is obtained by reaction of chlorine peroxide, 0120, on GaCl at —180° C (34). The product is a white sohd and is stable at room temperature. 

Perchlorates. Iron(II) perchlorate hexahydrate [13922-23-8], Fe(C10 2 6H20, is prepared by dissolving iron in cold, dilute perchloric acid or by dissolving FeS in perchloric acid. It crystallizes in hygroscopic, light green hexagonal prisms which are stable in dry air and extremely soluble (0.978 g/mL H2O at 0°C) in water and alcohol. It is susceptible to air oxidation in aqueous solution and decomposes above 100°C. Yellow iron(III) perchlorate... 

Bismuth Triperchlorate Pentahydrate. Bismuth(III) perchlorate pentahydrate [66172-92-7], Bi(C10 2 5H20, is prepared by dissolving Bi202 in 70% HCIO4. Anhydrous bismuth triperchlorate [14059-45-1], Bi(C10 2> maybe prepared by heating bismuthyl perchlorate monohydrate [66172-93-8], BiOClO H2O, between 80 and 100°C. Attempts to dissolve bismuth metal in concentrated perchloric acid have resulted in explosions. Treatment of bismuth or with dilute solutions of perchloric acid yields hydrates of bismuthyl perchlorate. 

The materials of construction, from the cupboard to the fan, should be inorganic and resistant to attack by perchloric acid. For the cupboard itself suitable materials include stainless steel of types, 316 or 317, solid epoxy resin, and rigid PVC. Stainless steel has been popular for this application as it is easy to form, weld, and polish. It is, however, attacked by the acid, which causes discoloration of the metal surface and the formation of iron(III) perchlorate, which can be explosive. Ductwork, separate from other extract systems, is usually made from stainless steel or plastic materials. Fire regulations may preclude the use of plastic ductwork or require it to be sheathed in an outer casing of metal or GRP. The fan casing and impeller can both be made of plastic. 

Chromium in steel Discussion. The chromium in the steel is oxidised by perchloric acid to the dichromate ion, the colour of which is intensified by iron (III) perchlorate which is itself colourless. The coloured solution is compared with a blank in which the dichromate is reduced with ammonium iron(II) sulphate. The method is not subject to interference by iron or by moderate amounts of alloying elements usually present in steel. 

A particle size effect has been detected by Chou and Olson [486] in the isothermal decomposition of isothiocyanatopentammine cobalt(III) perchlorate. Below a = 0.09, the larger crystals decompose relatively more rapidly than the smaller, whereas for a > 0.09, the reverse is true. This behaviour was attributed to enhanced nucleation in the larger particles due to strain, but this favourable factor was later offset by the inhibiting influence of the product ammonia which accumulated in the larger crystals. 

Wiberg and Koch 167) also disagreed with Littler s results, and found that the major product (75%) obtained on treatment of cyclohexanone with aqueous thallium(III) perchlorate was cyclopentanecarboxylic acid (XL). 2-Hydroxycyclohexanone was isolated in only 3 % yield unchanged starting material accounted for the remainder of the product. Wiberg and Koch were unable to detect any cyclohexane-1,2-dione in the product mixture, but did prove that 2-hydroxycyclohexanone did not function as the precursor to the ring-contracted acid. From the results obtained from a study of the oxidation of 2,2,6,6-[Pg.196]

A stopped-flow examination of the Oo(III) perchlorate oxidation produced kinetics ... 

The Co(III) perchlorate oxidation of hydrogen peroxide affords a rate law... 

Mn(III) perchlorate in HCIO4 oxidises H2O2 with a stoichiometry of 2 Mn(III) 1 H202 . Stopped-flow studies show the reaction to be approximately first-order in both reactants but that the second-order rate coefficient k2 varies as follows... 

The kinetics of oxidation of propionic acid in aqueous perchloric acid by Co(III) perchlorate are ... 

Oxidation by Co(III) perchlorate shows the same kinetics as that of saturated carboxylic acids (p. 384) namely... 

Iron(III) complexes of 2-acetylpyridine Af-oxide iV-methyl- and 3-azabicyclo[3.2.2.]nonylthiosemicarbazone, 24 and 25, respectively, have been isolated from both iron(III) perchlorate and chloride [117], The perchlorate salt yields low spin, octahedral, monovalent, cationic complexes involving two deprotonated, tridentate thiosemicarbazone ligands coordinated via the N-oxide oxygen, azomethine nitrogen and thiol sulfur based on infrared spectral studies. Their powder ESR g-values are included in Table 1 and indicate that bonding is less covalent than for the analogous thiosemicarbazones prepared from 2-acetylpyridine, 3a and 4. Starting with iron (III) chloride, compounds with the same cations, but with tetrachloroferrate(III) anions, were isolated. 

Mixtures of the sulfoxide with metal salts of oxoacids are powerful explosives. Examples are aluminium perchlorate, sodium perchlorate and iron(III) nitrate [1], The water in hydrated oxosalts (aluminium perchlorate, iron(III) perchlorate, iron(III) nitrate) may be partially or totally replaced by dimethyl (or other) sulfoxide to give solvated salts useful as explosives [2], Metal nitrates and perchlorates solvated with DMSO are generally powerfully explosive, and under certain conditions a violent reaction is easily triggered [3], Several other explosions involving perchlorates and the sulfoxide have been reported. 

See Chromium(III) perchlorate. 6 dimethyl sulfoxide Magnesium perchlorate Dimethyl sulfoxide Mercury(II) perchlorate. 6(or 4)dimethyl sulfoxide Silver perchlorate Dimethyl sulfoxide See Perchloric acid Sulfoxides... 

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