Nitration Nitrogen dioxide

N-nitrosomethlyphenylamine N-nitrosomethlyphenylamine TV-nitroso compounds nitric oxide nitrogen dioxide nitrate radical nitrite radical nitrogen trioxide... 

Keywords arenes, nitrogen dioxide, nitration, gas-solid reaction... 

Magnesium Mg Brown fumes of nitrogen dioxide nitrate oxide oxide ... 

Nitrogen dioxide Nitrate Nitrite Ozone Photochemistry Quantum yield Rate law... 

As is known (Vol. I). alkanes can be nitrated in vapour phase by nitric acid or nitrogen dioxide. Nitration with nitric acid at temperatures of 400-435 C (method of Hass, Vol. I. p. 86) became a well established commercial method of making nitroalkanes. A considerable number of papers mainly by Hass and co-workers (Vol. 1) and Titov (Vol. I) gave both theoretical and practical foundations for this remarkable process and subsequently less theoretical work has appeared. Less attention was paid to the nitration of alkanes with nitrogen... 

Nitrogen dioxide is prepared by heating the nitrate of a heavy metal, usually that of lead(ll) ... 

If this reaction takes place in air, the evolved nitrogen monoxide is oxidised to the dioxide and this dissolves again as in equation (9.1) hence virtually complete conversion of nitrogen dioxide to nitric acid can occur (see nitric acid, below). With alkalis, a mixture of nitrite and nitrate is formed ... 

The nitrates of other metals give nitrogen dioxide, oxygen and the metal oxide, unless the latter is unstable to heat, in which case the metal and oxygen are formed (for example from nitrates of silver and mercury) ... 

Like all nitrates, it is soluble in water on heating it decomposes evolving nitrogen dioxide and oxygen, but leaving the metal, and not, as is usual with other nitrates, the oxide ... 

It is also possible to use more powerful reagents to nitrate thiazoles for example, 2-methylthiazole has been nitrated using nitronium tetrafluorobo-rate and the complex nitrogen dioxide-boron tn fluoride (240). The overall yield is about 50 to 60%. 

Lead nitrate [10099-74-8] Pb(N02)2, mol wt 331.23, sp gr 4.53, forms cubic or monoclinic colorless crystals. Above 205°C, oxygen and nitrogen dioxide are driven off, and basic lead nitrates are formed. Above 470°C, lead nitrate is decomposed to lead monoxide and Pb O. Lead nitrate is highly soluble in water (56.5 g/100 mL at 20°C 127 g/100 mL at 100°C), soluble in alkalies and ammonia, and fairly soluble in alcohol (8.77 g/100 mL of 43% aqueous ethanol at 22°C). Lead nitrate is readily obtained by dissolving metallic lead, lead monoxide, or lead carbonate in dilute nitric acid. Excess acid prevents the formation of basic nitrates, and the desired lead nitrate can be crystallized by evaporation. 

Reactions 8 and 9 are important steps for the Hquid-phase nitration of paraffins. The nitric oxide which is produced is oxidized with nitric acid to reform nitrogen dioxide, which continues the reaction. The process is compHcated by the presence of two Hquid phases consequentiy, the nitrogen oxides must transfer from one phase to another. A large interfacial area is needed between the two phases. 

The vapor-phase process of SocifitH Chemique de la Grande Paroisse for production of nitroparaffins employs propane, nitrogen dioxide, and air as feedstocks (34). The yields of nitroparaffins based on both propane and nitrogen dioxide are relatively high. Nitric oxide produced during nitration is oxidized to nitrogen dioxide, which is adsorbed in nitric acid. Next, the nitric dioxide is stripped from the acid and recirculated. 

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. 

Industrial. Nitric acid is itself the starting material for ammonium nitrate, nitroglycerin [55-63-0] trinitrotoluene [118-96-7]., nitroceUulose [9004-70-0] and other nitrogen compounds used in the manufacture of explosives (see Explosives and propellants). Nitric acid is made by oxidation of ammonia to nitrogen dioxide [10102-44-0] which is subsequently absorbed by water. 

The Kestner-Johnson dissolver is widely used for the preparation of silver nitrate (11). In this process, silver bars are dissolved in 45% nitric acid in a pure oxygen atmosphere. Any nitric oxide, NO, produced is oxidized to nitrogen dioxide, NO2, which in turn reacts with water to form more nitric acid and nitric oxide. The nitric acid is then passed over a bed of granulated silver in the presence of oxygen. Most of the acid reacts. The resulting solution contains silver at ca 840 g/L (12). This solution can be further purified using charcoal (13), alumina (14), and ultraviolet radiation (15). 

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. 

Efforts to raise the alpha-selectivity have been made. Thus nitration of anthraquinone using nitrogen dioxide and ozone has been reported (17). l-Amino-4-bromoanthraquinone-2-sulfonic acid (bromamine acid) [116-81 -4] (8) is the most important intermediate for manufacturing reactive and acid dyes. Bromamine acid is manufactured from l-aminoanthraquinone-2-sulfonic acid [83-62-5] (19) by bromination in aqueous medium (18—20), or in concentrated sulfuric acid (21). l-Aminoanthraquinone-2-sulfonic acid is prepared from l-aminoanthraquinone by sulfonation in an inert, high boiling point organic solvent (22), or in oleum with sodium sulfate (23). 

Nitric oxide, NO, results from high-temperature combustion, both in stationary sources such as power plants or industrial plants in the production of process heat and in internal combustion engines in vehicles. The NO is oxidized in the atmosphere, usually rather slowly, or more rapidly if there is ozone present, to nitrogen dioxide, NO2. NO2 also reacts further with other constituents, forming nitrates, which is also in fine parhculate form. 

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