Sodium perchlorate, dehydration

In dry acetonitiile/sodium perchlorate, however, sodium methanesulfonate and CO is obtained. A methylthiomethyl cation 159, (Eq. (220) ), is believed to be an intermediate, which is hydrolyzed to formaldehyde and methyl mercaptane. Both products are subsequently oxidized by C1207, formed by dehydration of perchloric acid, to CO and NaS03CH3 465 In spite of the fact that epe was conducted well below the discharge potential of the supporting electrolyte complications arose (Eq. (220) ), that were attributed to anodically generated C104 This observation asks for caution in the use of perchlorates as supporting electrolytes in apro-tic solvents. If possible, tetrafluoroborates or hexafluorophosphates should be used instead. 

The UV absorption spectra of sodium nitrite in aqueous solutions of sulfuric and perchloric acids were recorded by Seel and Winkler (1960) and by Bayliss et al. (1963). The absorption band at 250 nm is due either to the nitrosoacidium ion or to the nitrosyl ion. From the absorbancy of this band the equilibrium concentrations of HNO2 and NO or H20 —NO were calculated over the acid concentration ranges 0-100% H2S04 (by weight) and 0-72% HC104 (by weight). For both solvent systems the concentrations determined for the two (or three) equilibrium species correlate with the acidity function HR. This acidity function is defined for protonation-dehydration processes, and it is usually measured using triarylcarbinol indicators in the equilibrium shown in Scheme 3-15 (see Deno et al., 1955 Cox and Yates, 1983). 

ALCOHOL, DEHYDRATED (64-17-5) Forms explosive mixture with air [flash point 55°F/13"C 68°F/20°C (80%) 72°F/22°C (60%) 79°F/26°C (40%)]. Reacts, possibly violently, with strong oxidizers, bases, acetic anhydride, acetyl bromide, acetyl chloride, aliphatic amines, bromine pentafluoride, calcium oxide, cesium oxide, chloryl perchlorate, disulfuryl difluoride, ethylene glycol methyl ether, iodine heptafluoride, isocyanates, nitrosyl perchlorate, perchlorates, platinum, potassium-te/7-butoxide, potassium, potassium oxide, potassium peroxide, phosphorus Ill) oxide, silver nitrate, silver oxide, sulfuric acid, oleum, sodium, sodium hydrazide,. sodium peroxide, sulfmyl cyanamide, tetrachlorosilane, i-tri-azine-2,4,6-triol, triethoxydialuminum tribromide, triethylaluminum, uranium fluoride, xenon tetranuoride. Mixture with mercury nitrate(II) forms explosive mercury fulminate. Forms explosive complexes with perchlorates, magnesium perchlorate (forms ethyl perchlorate), silver perchlorate. Flow or agitation of substance may generate electrostatic charges due to low conductivity. 

Some dehydration reactions of sulfuric acid can be very vigorous. For example, the reaction with perchloric acid produces unstable CI2O7, and a violent explosion can result. Concentrated sulfuric acid produces dangerous or toxic products with a number of other substances such as toxic carbon monoxide (CO) from reaction with oxalic acid, H2C2O4 toxic bromine and sulfur dioxide (Bf2 and SO2) from reaction with sodium bromide, NaBr and toxic, unstable chlorine dioxide (CIO2) from reaction with sodium chlorate, NaClOj. 

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