Nitration nitrogen pentoxide

The i factors of ethyl nitrate, nitrogen pentoxide, and nitrogen tetroxide in sulfuric acid are 5, 6, and 6, indicating that these substances ionize to form nitryl ions according to the equations... 

The only method utilized commercially is vapor-phase nitration of propane, although methane (70), ethane, and butane also can be nitrated quite readily. The data in Table 5 show the typical distribution of nitroparaffins obtained from the nitration of propane with nitric acid at different temperatures (71). Nitrogen dioxide can be used for nitration, but its low boiling point (21°C) limits its effectiveness, except at increased pressure. Nitrogen pentoxide is a powerful nitrating agent for alkanes however, it is expensive and often gives polynitrated products. 

Unpiotonated hydioxylamine is oxidized rapidly by ozone, / = 2.1 X 10 (39). The reaction of ozone with the lower oxides of nitrogen (NO and NO2) is also rapid and quantitative the end product is nitrogen pentoxide, which is also a catalyst for the decomposition of ozone (45). Nitrous oxide, however, reacts slowly (k < 10 ) (39). Nitrogen-containing anions, eg, nitrite and cyanide, also ate oxidized by ozone (39). Nitrite is oxidized to nitrate (fc = 3.7 X 10 and cyanide is oxidized rapidly to cyanate (fc = 2.6 X 10 (46) and 10 -10 (39)). Cyanate, however, is oxidized slowly. 

At room temperature, Htde reaction occurs between carbon dioxide and sodium, but burning sodium reacts vigorously. Under controUed conditions, sodium formate or oxalate may be obtained (8,16). On impact, sodium is reported to react explosively with soHd carbon dioxide. In addition to the carbide-forrning reaction, carbon monoxide reacts with sodium at 250—340°C to yield sodium carbonyl, (NaCO) (39,40). Above 1100°C, the temperature of the DeviHe process, carbon monoxide and sodium do not react. Sodium reacts with nitrous oxide to form sodium oxide and bums in nitric oxide to form a mixture of nitrite and hyponitrite. At low temperature, Hquid nitrogen pentoxide reacts with sodium to produce nitrogen dioxide and sodium nitrate. 

Nitrates. Anhydrous zirconium tetranitrate [12372-57-5] Zr(N02)4, is prepared from zirconium tetrachloride and nitrogen pentoxide (201). The hydrated compounds are obtained from aqueous nitric acid (165) Zr0(N02)2 2H20 [20213-65-4] is most commonly used Zr(N02)4 5H20 [12372-57-5] can be produced from strong nitric acid. 

Salpetersaure. /. nitric acid, -anhydrid, n. nitric anhydride, (di)nitrogen pentoxide, nitrogen(V) oxide, -ather, m. nitric ether (ethyl nitrate), -bad, n. nitric acid bath, -dampf, m. nitric acid vapor or fume. 

In the solid state, dinitrogen pentoxide is ionic, existing as N02+N03 and sometimes called nitronium nitrate. The same is true of dinitrogen pentoxide in polar solvents like nitric acid where complete ionization to nitronium and nitrate ions is observed. In the vapour phase, and in nonpolar solvents, a covalent structure is observed. This dichotomy of behavior in both physical state and in solution means that no single nitrating agent is as diverse and versatile as nitrogen pentoxide. 

The furazan-based heterocycle (12) is iV-nitrated to the corresponding nitramine (13) with nitrogen pentoxide in nitric acid without chloride catalyst because of the inherent low basicity of the methylenediamine functionality." ... 

Nitrogen pentoxide dissolved in chloroform is used as a nitrating agent in organic synthesis. 

Reaction with liquid nitrogen pentoxide at low temperatures forms sodium nitrate and nitrogen dioxide ... 

This involved treating the corresponding lactones with Liquid anmonia and nitration of the products by nitrogen pentoxide, as described by Caesar Goldfrank(Re 3). Methods of prepn of individual compds are given in Ref 6... 

Refs l)Beil 3, 2 2)J.Glattfeld D.Mac-millan, J ACS 56,2481 2( 1934) (Preparation of aldonic and saccharic acid amines in liquid ammonia) 3)G.V.Caesar M.Gold-frank, J ACS 68,372-5(1946)(Nitration of starches with nitrogen pentoxide in presence of sodium fluoride) 4)Karrer( 1950), 325 ... 

Thus, Bouchonnet [48] nitrated cellulose in a solution of nitrogen pentoxide in carbon tetrachloride, to obtain a stable cellulose trinitrate of 14.1% N. Similar... 

T. Urbanski and Janiszewski [56] have confirmed the results of their predecessors, using nitrogen pentoxide plus a small amount of nitric acid, intended for preparing a liquid nitrating solution. Within 40 min at 20°C or after 35 min at 45°C, a product containing 14.0% N was reached. This kind of nitrocellulose is characterized by its high stability. 

The nitration of polysaccharides with nitrogen pentoxide in the gaseous phase has the advantage of not degrading the large molecule (Vollmert [73]). 

Nitrogen pentoxide dissolved in chloroform is an excellent O-nitrating agent (Oldham [17]). Montgomery and Clark [18] obtained 1,2,4,5-di-O-isopropylidene-D-fructose 3-nitrate in that way. According to Bell and Synge [15] below 0°C methyl-4,6-0-ethylidene-/S-D-glucoside was transformed mainly into 2,3-dinitrate within about 5 min. 

Rice and Getz J made a very complete study of the matter from this point of view. At 65° C. they found k = 0-286, compared with the value 0-292 of Daniels and Johnston. In order to test the possibility that the reaction might depend on catalysis by dust, they compared the velocity constants for filtered and unfiltered nitrogen pentoxide and for gas which had been passed through an electrical dust precipitator. In some experiments the gas was dried with phosphorus pentoxide, in others not. In some it was prepared by the dehydration of nitric acid with phosphorus pentoxide and in others by the action of chlorine on silver nitrate. Nitric acid was found to have no catalytic effect on the decomposition. Some of the principal results are summarized below, all data referring to 65° C. 

The very low value of Ashmore and Burnett is difficult to explain. It is easy to demonstrate that the discrepancy is not resolved by assuming the N03 intermediate in nitrogen dioxide decomposition is the pernitrite radical, in contradistinction to the symmetric nitrate radical. Their calculation of k5 depended on an experimentally obtained value for k 5 and an equilibrium constant K5- 5 calculated from thermodynamic properties for N03 measured by Schott and Davidson and Ray and Ogg. These results, obtained in a nitrogen pentoxide system, pertain to the nitrate radical, not the pernitrite radical. Guillory and Johnston176 reported an equilibrium constant based on estimated... 

Jilulc HNO, and concentrating the solution. The compound deliquesces in moist air and effloresces in dry air. The pink anhydrous cobaltous nitrate cannot he formed by dehydrating Ihe hexahydrate but by treating Ihe salt with nitrogen pentoxide gas (or in solution in concentrated HNOi). The salt is used mainly in the preparation of catalysts. 

Nitrogen pentoxide can be made by dehydration of anhydrous nitric acid with phosphorus pentoxide and sublimation from the mixture at about 40°. Resublimation with ozone and more phosphorus pentoxide gives pure white crystals which rattle around in the reaction chamber after slight evacuation. Direct oxidation with ozone of nitrogen dioxide prepared by heating lead nitrate is a somewhat better way of making the material. 

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