Ammonium azide with ammonia

This primary explosive is created by adding lead acetate to a solution of sodium or ammonium azide. Lead azide has a good shelf life in dry conditions but is unstable in the presence of moisture, oxidizing agents, and ammonia. It is less sensitive to impact than mercury fulminate, but more sensitive to friction. Since lead azide is a nonconductor, it may be mixed with flaked graphite to form a conductive mixture for use in low-energy electronic detonators. 

Several explosive salts including the acetylide, azide, borate, bromate, chlorate, chromate, iodate (and ammonium iodate double salt), nitrite, perchlorate (and ammonium perchlorate double salt), periodate, permanganate, picrate and trinitrobenzoate were prepared. The 3 latter salts and the acetylide, azide and bromate are impact-sensitive detonators [1], It appears probable that many of the explosively unstable compounds [2], formed in various ways from interaction of mercury or its compounds with ammonia or its salts, may have the common polymeric structure now recognised for Millon s base [3], This is a silica-like network of N+ and Hg in 4- and 2-coordination, respectively, with OH and water in the interstitial spaces. Individually indexed compounds are Poly(dimercuryimmonium acetylide)... 

Trinitromethyl)tetrazole (166) and 5-(dinitrofluoromethyl)tetrazole (167) have been synthesized and isolated as their ammonium salts from the reactions of trimethylsilyl azide with the corresponding nitriles followed by reaction with ammonia in diethyl ether. ... 

Ammonium Azide Ammonates, Ammonium azide forms with ammonia addition products a)Monoammonate, NH4N3-NHa, its existence was established from a study of the system ammonium azide-ammonia (Refs 7 8) b) Diammonate, NH4Na 2NH3, clear, col elongated plates stable at -33°, but incapable of existence at 0° (Ref 7) c)Tetrammonate,... 

Fusion of ammonium thiocyanate,6,6 either alone or in the presence of heavy metal salts, at 180°C., gives guanidine thiocyanate. This procedure has been modified by heating lead nitrate with a solution of ammonium thiocyanate in liquid ammonia at 120°.7 Lead sulfide is formed, and guanidine nitrate recovered. Other methods of formation involve the hydrolysis of dicyandiamide8-10 and the nitridation11 of methyl amine by means of ammonium azide in liquid ammonia. 

Summary Ammonium azide is easily prepared by mixing solutions of sodium azide, and aqueous ammonia. The mixture is then treated with carbon dioxide gas to precipitate sodium ion as sodium bicarbonate. The remaining ammonium azide stays in solution, and can be recrystallized from the reaction mixture. The collected crystals should then be dried in a desiccator as vacuum drying may result in loss of product from volatization air-drying the solid may also lead to loss in product. 

Earlier, Turrentine (Ref 4) obtained ferric azide in soln by electrolysis of a dil sodium azide soln using iron electrodes and later by Browne et al (Ref 6) on using iron electrodes in liq amm solns of ammonium azide, but the product was ammonolyzed to an Ammono-Basic Ferric Azide. Curtius et al (Refs 1 2), with ferric alum and NaN, obtained ferric azide in soln and they also repotted that iron dissolved in dil aq hydrazoic acid to form the azide, but the soln decompd on evapn giving either the basic azide or hydroxide. In 1934 Franklin (Ref 9) noted that aq hydrazoic acid reacts on iron to form ferric azide, nitrogen and ammonia together with a small amt of hydrazine. According to Franklin Ferrous Azide, Fe(Nj), is formed first and oxidizes to ferric azide when the soln is warmed with excess hydrazoic acid present. Ricca (Ref 11) studied the reactions of the ferric ion with hydrazoic acid on electrolysis of their solns and obtained results which would indicate that ferric azide has the structure [Fe(Nj)](Nj)2... 

Ammonium azide is a colorless, crystalline substance. Some of its properties are given in Table 19. No phase transitions are found between 90 and 348 K. Sublimation of ammonium azide begins at 406 K, recondensation of the vapors at 418 K. Ammonium azide vapors decompose, similar to other ammonium salts, to ammonia and HN3 at 418 K (A// = -1-67.7 kJmol ). In the solid state, all ammonium ions are tetrahedrally connected to azide ions via hydrogen bonds with an NH -N distance of 297.5(4) and 296.7(3) pm. ... 

Ammonium azide is synthesized either by reacting solntions of HN3 with ammonia ... 

The preparation of ammonium azide by the interaction of ammonia with hydrazoic acid in ethereal solution has been described by Frierson. A second preparative method using ammonium nitrate or sulfate is also described in the same reference. Both methods have disadvantages, in that the former requires the preparation of hydrazoic acid, whereas the latter is limited to small quantities because of explosion hazards. 

Two German patents by Muller describe preparative methods which avoid the use of hydrazoic acid by heating sodium azide with ammonium chloride or sulfate in aqueous solution. A recent Japanese patent describes a reaction between sodium azide and ammonium carbamate in liquid ammonia to give ammonium azide. Evans, Yoffe, and Gray have suggested the reaction of sodium azide with ammonium chloride in iV,iV-dimethylformamide. A modification of the last method has been made it involves the reaction of sodium azide and ammonium sulfate in dimethyl-formamide to give anhydrous ammonium azide of high purity. 

Diazido-l,3,5-triazin-2-amine was formed by treating 2,4,6-triazido-l,3,5-triazine with gaseous ammonia in diethyl ether the ammonium azide was separated by water extraction.153... 

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