Nitrosyl perchlorate

It was first prepared by K. A. Hofmann and Zedtwitz [26] by passing a mixture of nitric oxide and nitrogen dioxide into 72% perchloric acid. The acid was then evaporated to 140°C and on cooling the hydrate of nitrosyl perchlorate N0C104-H20 crystallized out. The product was dehydrated in vacuo over phosphorous pentoxide. 

When heated below 100°C it decomposes [27] according to the equation  

At higher temperature the decomposition follows a different course  

It is a strongly endothermic compound with a heat of formation -AH = 41.79 0.08 kcal/mole [27]. 

It reacts with water with evolution of nitrogen oxides. Ethanol, acetone, dry ether and primary amines react violently with nitrosyl perchlorate causing ignition or explosion. 

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Nitrosyl perchlorate Acetones, amines, diethyl ether, metal salts, organic materials... 

Nitrosyl Perchlorate. NOCIO4, mw 129-47, N 10,82% white cryst, decomps on heating, hygroscopic, d 2.169g/cc, unstable... 

Preparation. The anhyd salt is prepd in good yield by heating a mixt of solid Ba chloride and nitrosyl perchlorate (Ref 15), by heating an intimate mixt of AP and Ba carbonate (Ref 8), or by dehydration of the trihydrate in a vacuum at 140—70° (Ref 5)... 

Preparation. It was first prepd by passing a mixt of N monoxide and N dioxide into 72% perchloric ac, the mixt evapd until the temp rose to 140° and dense white fumes were evolved, and cooled. The solid which sepd was found to be a monohydrate of nitrosyl perchlorate which was dried in a vacuum over P pentoxide to give the anhyd salt (Ref 2). More recently it was obtained by the action of an excess of liq dinitrogen tetroxide on anhyd Mg perchlorate (Ref 5)... 

Thepnal Decomposition. Workers at the Hebrew Univ, Israel found that the thermal decompn of nitrosyl perchlorate at 100-140° results in an equilibrium being established with nitryl perchlorate and the decompn prods of both compds (nitronium). N dioxide, Cl dioxide, and O were found to be the final decompn prods isolated (Ref 6)... 

Preparation. It was first prepd by dissolving Ag oxide in aq perchloric ac followed by evapn of the soln until ciysts form (Ref 3). More recent procedures for the prepn of the anhyd salt are by the addn of anhyd perchloric ac to the soln of a Ag salt in trifluoroacetic ac (Ref 9) by the interaction of solid nitrosyl perchlorate and Ag bromide (Ref 10) or by the addn of the monohydrate to et bz. Two phases are formed, the upper phase contg only et bz and Ag perchlorate, This phase is treated with a satd hydrocarbon to give anhyd Ag perchlorate (Ref 13). Last traces of w can be removed by azeotropic distn with bz (Ref 11)... 

Preparation. The anhyd salt has only recently been prepd by heating a mixt of Zn oxide and nitrosyl perchlorate in a vacuum at ca 180° (Ref 11)... 

Morkovnik et al. (1989) found experimentally that the addition of an equimolar amount of 4-morpholino- or 4-dimethylaminoaniline to a suspension of nitrosyl perchlorate in 100 % acetic acid, dioxan, or acetonitrile yields a mixture of the diazonium perchlorate and the perchlorate salt of the amine radical cation, with liberation of gaseous nitric oxide. Analogous results in benzene, including evidence for radicals by ESR spectroscopy and by spin trapping experiments, were obtained by Reszka et al. (1990). 

Nitrosyl perchlorate Organic materials Perchloric acid Alcohols Permanganic acid Organic materials Peroxodisulfuric acid Organic liquids Potassium dioxide Ethanol Potassium perchlorate Ethanol Potassium permanganate Ethanol, etc. Ruthenium(VIII) oxide Organic materials Silver perchlorate Aromatic compounds Sodium peroxide Hydroxy compounds Uranium hexafluoride Aromatic hydrocarbons, etc. Uranyl perchlorate Ethanol See v-halomides Alcohols... 

Nitrosyl perchlorate Organic materials Oxygen (Gas) Acetylene, Acetone Peroxomonosulfuric acid Acetone... 

Hydrogen peroxide Organic compounds (reference 2) Nitric acid Aromatic amines Nitrosyl perchlorate Organic materials Ozone Aromatic compounds Perchloric acid Aniline, etc. 

Nitropropane Nitrosyl fluoride Nitrosyl perchlorate Nitrourea Nitrous acid Nitryl chloride Oxalic acid See under Nitromethane chlorosulfonic acid, oleum Haloalkenes, metals, nonmetals Acetones, amines, diethyl ether, metal salts, organic materials Mercury(II) and silver salts Phosphine, phosphorus trichloride, silver nitrate, semicarbazone Ammonia, sulfur trioxide, tin(IV) bromide and iodide Furfuryl alcohol, silver, mercury, sodium chlorate, sodium chlorite, sodium hypochlorite... 

Al-Nitrosodiethanolamine, 2 449, 450 Nitroso dyes, 9 263-264 Nitro soluble dyes, 7 373t Nitroso soluble dyes, 7 373t Nitrosomonas, use in recirculating aquaculture biofiltration, 3 196 P-Nitrostyrenes, preparation by nitration of styrenes, 16 581 Nitrosyl chloride, 20 634 Nitrosyl complexes, osmium, 19 642 Nitrosyl perchlorate, 18 279 Nitrosyl tetrafluoroborate, 4 144t n-Nitrotoluene, 17 263... 

It has been found possible (K. A. Hofmann and Zedtwitz [5]) to obtain the esters of perchloric acid by treating alcohols with nitrosyl perchlorate, N0C104-H20. Nitrosyl perchlorate is a stable, crystalline substance that reacts explosively on contact with aromatic amines. In the presence of alcohol the perchlorate and alkyl nitrite are produced. 

Other Group 15 perchlorates include nitronium perchlorate, NO2CIO4, also called nitryl or nitroxyl perchlorate nitrosyl perchlorate, [CAS 15605-28-4], NOCIO4. and phosphonium perchlorate, P(0H)4C10i. 

Nitrosyl perchlorate, N0C104, is generally considered stable at room temperature and,by itself, should be completely safe. Decomposition begins just below 100 t, above IOOt (II5°-120ct) low order explosions occur (Ref 103) p-Nitrotoluene - HzSO4 mixtures explode when heated to 160°C... 

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