Important explosives

The commercially important explosive pentaerythritol tetranitrate [78-11-5] (PETN), C HgN40 2>... 

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). 

Aromatic nitro compounds include both important explosives and a number of agrochemicals. Concern with their fate has motivated extensive examination of their reduction to amines under a range of conditions. 

These are readily produced by nitration of aromatic compounds and are important explosives. The amines formed by reduction are able to undergo a nnmber of reactions, and have a wide range of application in the production of agrochemicals, dyestnffs, and pharmaceuticals. 

The most important explosives of this class are the ammon gelignites, so called because they are based essentially on ammonium nitrate which is the cheapest and most powerful source of oxygen. Sodium nitrate is sometimes added as well in order to improve the oxygen balance for certain types of these explosives. The ammon gelignites are explosives with... 

Mercury fulminate (C2N202Hg) is one of the most important primary explosives. It is usually found in the form of a gray powder, is sensitive to impact and friction, and is easily detonated by sparks and flames. It is desensitized by the addition of water, but is very sensitive to sunlight. It reacts with metals in moist environments. It is created by treating a solution of mercuric nitrate with alcohol in nitric acid. Its most important explosive property is that it easily detonates after initiation.10... 

The major advantage of the TNA technology is that it can produce a nitrogen map and many important explosives have a high nitrogen content. The neutrons... 

The replacement of amine and amide hydrogen with a nitro group via direct nitration is an important route to A-nitro functionality. However, the cleavage of other bonds is also important. In the case of C-N bond cleavage the process is known as nitrolysis and is an invaluable route to many energetic materials (Section 5.6). The nitrolysis of hexamine and the syntheses of the important explosives HMX and RDX are discussed in Section 5.15. This area of chemistry could easily demand a separate chapter of its own and is the most complex and diverse in the field of nitramine chemistry. 

A number of important explosives contain nitramino functionality in conjunction with nitrate ester or C-nitro functionality. A-Nitrodiethanolamine dinitrate (DINA) (7) is a powerful explosive which can be melt-cast into charges. A,2,4,6-Tetranitro-A-methylaniline (tetryl) (8) exhibits high brisance (VOD 7920 m/s, d = 1.73 g/cm ) and has found application in both detonators and boosters, in addition to being a component of some composite high explosives. 

Two other derivatives of toluene are the important explosive trinitrotoluene (TNT) and the polyurethane monomer toluene diisocyanate (TDI). TNT requires complete nitration of toluene. TDI is derived from a mixture of dinitrotoluenes (usually 80% o,p and 20% o,o) by reduction to the diamine and reaction with phosgene to the diisocyanate. TDI is made into flexible foam polyurethanes for cushioning in furniture (35%), transportation (25%), carpet underlay (20%), and bedding (10%). A small amount is used in polyurethane coatings, rigid foams, and elastomers. 

Other explosives, discovered in the nineteenth century, were nitroglycerine, a liquid that is absorbed in a solid to make dynamite, and nitrocellulose, a solid that produces less smoke (smokeless powder). They are made by heating glycerine and cellulose with nitric acid, a process that adds nitro (-NO2) groups. Another important explosive is trinitrotoluene, made by heating (very carefully) toluene in nitric acid,... 

Cyclonite is a very important explosive. The outstanding properties of RDX as an explosive are high chemical stability, not much lower than aromatic nitro compounds and high explosive power which considerably surpasses that of aromatic nitro compounds such as TNT and picric acid. RDX has a detonation velocity of8600 ms"1 and a detonation pressure of 33.8 GPa at a density of 1.77 gem"3. RDX is used in mixtures with TNT (Hexotols, Cyclotols, Compn. B) wax (Composition A) aluminum (Hexals) aluminum and TNT (HBX, Hexotonal, Torpex) etc. 

This substance is an intermediate product of the decomposition of the important explosive nitroguanidine. It is also present in an aqueous solution of nitrourea or a sulphuric acid solution of nitrourea (Davis and Blanchard [7]). 

The most important explosive property of mercury fulminate is that after initiation it will easily detonate. On detonation, it decomposes to stable products as shown in Reaction 2.5. 

TNT is by far the most important explosive for blasting charges. It is widely used in commercial explosives and is much safer to produce and handle than nitroglycerine and picric acid. A lower grade of TNT can be used for commercial explosives, whereas the military grade is very pure. 

Uses, AN is one of the most widely used components of explosives. The most important explosives contg high percentages of AN include amatols, ammonals, ammonites, dynamites, dynammons, Favier type explor sives, grisounites, grisoutines, schneiderites etc.. In addition, AN and mixts containing it have been used extensively as fertilizers... 

The nitration of chlorobenzene is easier than the nitration of benzene and more difficult than the nitration of toluene. Trinitro-chlorobenzene (picryl chloride) can be prepared on the plant scale by the nitration of dinitrochlorobenzene, but the process is expensive of acid and leads to but few valuable explosives which cannot be procured more cheaply and more simply from dinitrochlorobenzene by other processes. Indeed, there are only two important explosives, namely TNB and hexanitrobiphenyl, for the preparation of which picryl chloride could be used advantageously if it were available in large amounts. In the laboratory, picryl chloride is best prepared by the action of phosphorus pentachloride on picric acid. 

ANFO alone represents about three fourths of the current volume of commercial explosives in use today around the world. Because of this, ANFO is commonly used as a reference when defining and comparing explosive properties. Some of these important explosive properties include density, detonation velocity, and energy release. 

IMO = Intergovernmental Maritime Consultative Organization 72 185 IME = Institute of Makers of Explosives 185 immobilization 185 impact sensitivity 44 185 268 important explosives 134 impulse 190 impulse specifique 295 incendiary 190 incompatibility 61 365 Industrial explosvies -+ commercial explosives 61 inert 190 to inflame 190... 

TNT is by far the most important explosive for blasting charges of all weapons. It is very stable, neutral, and does not attack metals it can be charged by casting as well by pressing it is insensitive and needs no phlegmatizers. It can be applied pure and mixed with ammonium nitrate (-> Amatols), aluminum powder (-> Tritonal), with RDX (-> Cy-clonite and -> Composition B), and combinations (-> Torpex, -> HBX, -> Trialenes). Furthermore, TNT is an important component of industrial explosives. 

Fig.3.93 shows the data on the sensitivity of ammonium nitrate, which is an important explosive material. There is a difference in the sensitivity level between crystalline and prilled ammonium nitrate (AN (Prill)), which has many holes in the porous grains that make it more sensitive. The porous prills do not explode completely at a PETN equivalent 1.2g, but they do in the 50/60 steel tube test with an initial explosive booster of 50 g of RDX. 

Symbols usually refer to U. S. and Chemical Warfare designations for some of the more important explosives and warfare agents some of the foreign symbols are also listed. 

With no claim for completeness, an earnest effort has been made to list all of the more important explosives, explosive mixtures, modifying and addition agents, and particularly those which are actually heing used or which have been used as far back as World War 1. Some of the older explosives and compositions have also heen included in order to give a picture of the gradual development of the field or because they are of particular historic interest. 

RDX forms orthorhombic crystals with a melting point of 206 Celsius. 1 Gram dissolves in 25 milliliters of acetone, but its solubility in alcohol, ether, ethyl acetate, and glacial acetic acid is even less. It is insoluble in water, carbon tetrachloride, and carbon disulfide. RDX is one of the most important military explosives known to man. It is highly versatile, being resistant to heat, shock and percussion, and is capable of being alloyed with many different secondary explosives. RDX is very well known in several of the most important explosives compositions. These compositions include semtex, C4, and composition B, all of which are widely used in military operations. RDX is by far one of the most important explosives in occurrence, and it is manufactured on an industrial scale. 

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