Nitrogen explosive compounds

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. 

Organic Solids A few organic compounds decompose before melting, mostly nitrogen compounds azides, diazo compounds, and nitramines. The processes are exothermic, classed as explosions, and may follow an autocatalytic law. Temperature ranges of decomposition are mostly 100 to 200°C (212 to 392°F). Only spotty results have been obtained, with no coherent pattern. The decomposition of malonic acid has been measured for both the solid and the supercooled liquid. The first-order specific rates at 126.3°C (259.3°F) were 0.00025/min for solid and 0.00207 for liquid, a ratio of 8 at II0.8°C (23I.4°F), the values were 0.000021 and 0.00047, a ratio of 39. The decomposition of oxalic acid (m.p. I89°C) obeyed a zero-order law at 130 to I70°C (266 to 338°F). 

Exothermic Decompositions These decompositions are nearly always irreversible. Sohds with such behavior include oxygen-containing salts and such nitrogen compounds as azides and metal styphnates. When several gaseous products are formed, reversal would require an unlikely complex of reactions. Commercial interest in such materials is more in their storage properties than as a source of desirable products, although ammonium nitrate is an important explosive. A few typical exampes will be cited to indicate the ranges of reaction conditions. They are taken from the review by Brown et al. ( Reactions in the Solid State, in Bamford and Tipper, Comprehensive Chemical Kinetics, vol. 22, Elsevier, 1980). 

A potentially liazardous by-product of chlorine manufacture is nitrogen trichloride, which is unstable and liigldy explosive. It can be formed from a combination of chlorine with nitrogen compounds in the brine feed, ammonia in... 

Of the eight nonmetals listed in Table 21.1, nitrogen is by far the least reactive. Its inertness is due to the strength of the triple bond holding the N2 molecule together (B.E. N=N = 941 kj/mol). This same factor explains why virtually all chemical explosives are compounds of nitrogen (e.g., nitroglycerin, trinitrotoluene, ammonium nitrate,... 

Explosions involving flammable gases, vapours and dusts are discussed in Chapter 5. In addition, certain chemicals may explode as a result of violent self-reaction or decomposition when subjected to mechanical shock, friction, heat, light or catalytic contaminants. Substances containing the atomic groupings listed in Table 6.7 are known from experience to be thermodynamically unstable, or explosive. They include acetylides and acetylenic compounds, particular nitrogen compounds, e.g. azides and fulminates, peroxy compounds and vinyl compounds. These unstable moieties can be classified further as in Table 6.8 for peroxides. Table 6.9 lists a selection of potentially explosive compounds. 

A very shock sensitive explosive, containing nearly 90 wt% of nitrogen. See other high-nitrogen compounds, non-metal azides... 

Wilier, R. L. et al., J. Heterocycl. Chem., 1992, 29(7), 1835 An explosive of moderate sensitivity, thermally decomposing (non-explosively) from 120°C. The 4-nitro analogue was also explosive and decomposed from 90°C. See Other A-NITRO COMPOUNDS, HIGH NITROGEN COMPOUNDS... 

Violence of the reaction, sometimes explosive, with e.g., acetic acid, benzene, ether, is associated with both their carbon and hydrogen contents. If nitrogen is also present, explosive fluoroamino compounds may be involved. Fibrous mate-rials-cotton, paper, wood-invariably ignite. 

See entry thermal explosions See other high-nitrogen compounds... 

Electrolysis of sodium chloride in presence of nitrogenous compounds to produce chlorine may lead to formation of explosive nitrogen trichloride. Precautions are detailed. 

It is a toxic colourless gas which is dangerously explosive in the gaseous, liquid and solid states [1]. It is produced dining electrolysis of nitrogenous compounds in hydrogen fluoride [2], Later work (perhaps with purer material ) did not show the explosive instability [3], The shock-sensitivity is confirmed [4],... 

Ammonia solutions react with iodine (or potassium iodide) to produce highly explosive addition compounds of nitrogen triiodide and ammonia. 

As mentioned earlier, there are many nitrogen compounds that are either explosives or propellants. That is one reason why nitrates and nitric acid have been so important throughout several centuries of history. 

For a study of nitrophenylbenzotriazoles as explosives, the triazole ring conferring impact sensitivity, see [1]. Simpler nitro- and azido-triazoles also find explosive use. On heating to above 260°C, 1,2,3-triazole halides explode violently [2], Several examples of instability among this group of relatively high-nitrogen compounds may be found under the entries ... 

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