Nitroglycerines

Nitroglycerine [N03CH2CHN03 CH2N03 Structure (2.3)] is prepared by reacting glycerine with a mixture of sulfuric and nitric acid under carefully controlled CH2 — ON02 

Nitroglycerine. Nitroglycerine (C3H5N3O9) (2.6) was first prepared by the Italian, Ascanio Sobrero in 1846 by adding glycerol to a mixture of sulfuric and nitric acids. In 1863, a laboratory plant was set up to manufacture nitroglycerine by the Nobel family. In 1882, the Boutmy-Faucher process for the manufacture of 

Colour Light colourless or pale yellow crystalline solid 

The Nobel family suffered many set backs in marketing nitroglycerine because it was prone to accidental initiation, and its initiation in bore holes by blackpowder was unreliable. There were many accidental explosions, one of which destroyed the Nobel factory in 1864 and killed Alfred s brother, Emil. Alfred Nobel in 1864 invented the metal blasting cap detonator which greatly improved the initiation of blackpowder. The detonator contained mercury fulminate [Hg(CNO)2] and was able 

Examples of secondary explosives are TNT, tetryl, picric acid, nitrocellulose, nitroglycerine, nitroguanidine, RDX, HMX and TATB. Examples of commercial secondary explosives are blasting gelatine, guhr dynamite and 60% gelatine dynamite. 

Mercury fulminate (C2N2Q.2Hg)(2il) is.,obtained by treating a solution of mercuric nitrate with alcohol in.nitric.acid. 

This reaction, together with HSjpi jucj Jbas,been studied by a number of chemists, including Liebig., wl a. elah- account of the elementary chemical composition of mechanism of the 

The most important exi)lpsive t)ropet,lyvpf,mercury fulminate is that after initiation it will easily,detonalej On,detonation, it decomposes to 

Lead azide can exist in two allotropic forms the more stable a-form which is orthorhombic, and the -form which is monoclinic. The a-form is prepared by rapidly stirring a solution of sodium azide with a solution of lead acetate or lead nitrate whereas the /7-form is prepared by slow diffusion of sodium azide in lead nitrate solutions. The fi-form has a tendency to revert to the a-form when its crystals are added to a solution containing either the a-form crystals or a lead salt. If the /7-form crystals are left at a temperature of 160 C they will also convert to the a-form. Some of the properties of lead azide are presented in Table 2.3. 

---

QHsNjO, OCCH CH.ONO ),. Formed by the nitration of diethyleneglycol. Viscous, colourless, odourless liquid m.p. — ll-5" C. Used to replace nitroglycerin as a propellant. 

We also found N-nitropyridinium salts such as C5HjN N02BF4 as convenient transfer nitrating reagents in selective, clean reaetions. Transfer nitrations are equally applicable to C- as well as to 0-nitra-tions, allowing, for example, safe, acid-free preparation of alkyl nitrates and polynitrates from alcohols (including nitroglycerine). 

Exothermic oxidation—reduction reactions provide the energy released in both propellant burning and explosive detonation. The reactions are either internal oxidation—reductions, as in the decomposition of nitroglycerin and pentaerythritol tetranitrate, or reactions between discrete oxidizers and fuels in heterogeneous mixtures. 

Nitroglycerin. Nitroglycerin (NG), glyceryl trinitrate [55-63-0] is primarily used as an explosive in dynamites and as a plasticizer... 

Pure nitroglycerin is a stable Hquid at temperate conditions. It decomposes above 60°C to form nitric oxides which in turn catalyze further decomposition. Moisture increases the rate of decomposition under these conditions. Double- and multibase propellants containing nitroglycerin have substantially shorter stabiHty Hves at 65 and 80°C than do single-base propellants. The decomposition of nitroglycerin proceeds as... 

Safety has been greatly increased by use of the continuous nitration processes. The quantity of nitroglycerin in process at any one time is greatly reduced, and emulsification of nitroglycerin with water decreases the likelihood of detonation. Process sensors (qv) and automatic controls minimize the likelihood of mnaway reactions. Detonation traps may be used to decrease the likelihood of propagation of an accidental initiation eg, a tank of water into which the nitrated product flows and settles on the bottom. 

Other Glycol Nitrates. Other Hquid nitrates have been used as explosive plasticizers for nitroceUulose (Table 8). These may be made by mixed-acid nitration using procedures similar to those used for nitroglycerin. 

Trimethylolethane trinitrate (metriol trinitrate) is not satisfactory as a plasticizer for nitrocellulose, and must be used with other plasticizers such as metriol triacetate. Mixtures with nitroglycerin tend to improve the mechanical properties of double-base cast propellants at high and low temperatures. Metriol trinitrate has also been used in combination with triethylene glycol dinitrate as a plasticizer for nitrocellulose. Its physical properties are Hsted in Table 7 (118-122). 

Military. The single-component explosives most commonly used for military compositions are TNT, RDX or HMX, nitrocellulose, and nitroglycerin. The last two are used almost exclusively to make propellants. The production volume of TNT far exceeds that of any other explosive. It is used as manufactured, as a base of biaary slurries with other high melting explosives, or ia ternary systems generally containing a biaary mix and aluminum. 

P. Naoum, Nitroglycerin and Nitroglycerin Explosives, WiUiams and Wilkins Co., Baltimore, Md., 1928. 

C. Boyars, "Sensitivity and Desensitization of Nitroglycerin," ia Proceedings of 2nd Symposium on Chemical Problems Connected with the Stability of... 

O. E. Wating and G. Krastins, The Kinetics and Mechanism of Thermal Decomposition of Nitroglycerin, Report 5746, NOL, White Oaks, Md., 1958. 

Worldwide Technology Assessment of Nitroglycerin Manufacture, 4 Vols., (Proprietary Information) Mason and Hanger, Silas Mason, 1985. 

---