Friday, June 01, 2007
Nitroglycerin explosion
Nitroglycerin (NG), also known as nitroglycerine, trinitroglycerin, and glyceryl trinitrate, is a chemical compound. It is a heavy, colorless, oily, explosive liquid obtained by nitrating glycerol. It is used in the manufacture of explosives, specifically dynamite, and as such is employed in the construction and demolition industries, and as a plasticizer in some solid propellants. It is also used medically as a vasodilator to treat heart conditions. Nitroglycerin is a venous dilator that decreases preload.
In its pure form, it is a contact explosive (physical shock can cause it to explode) and degrades over time to even more unstable forms. This makes it highly dangerous to transport or use. In this undiluted form it is one of the most powerful high explosives, comparable to the military explosives RDX and PETN (which are not used in munitions at full concentration because of their sensitivity) as well as the plastic explosive C-4.
Early in the history of this explosive it was discovered that liquid nitroglycerin can be "desensitized" by cooling to 5 to 10 °C (40 to 50 °F), at which temperature it freezes, contracting upon solidification. However, later thawing can be extremely sensitizing, especially if impurities are present or if warming is too rapid. It is possible to chemically "desensitize" nitroglycerin to a point where it can be considered approximately as "safe" as modern high explosive formulations, by the addition of approximately 10-30% ethanol, acetone, or dinitrotoluene (percentage varies with the desensitizing agent used). Desensitization requires extra effort to reconstitute the "pure" product. Failing this, it must be assumed that desensitized nitroglycerin is substantially more difficult to detonate, possibly rendering it useless as an explosive for practical application.
A serious problem in the use of nitroglycerin results from its high freezing point (13 °C [55 °F]). Solid nitroglycerin is much less sensitive to shock than the liquid, a feature common in explosives; in the past it was often shipped in the frozen state, but this resulted in a high number of accidents during the thawing process by the end user just prior to use. This disadvantage is overcome by using mixtures of nitroglycerin with other polynitrates; for example, a mixture of nitroglycerin and ethylene glycol dinitrate freezes at -29 °C (-20 °F).
Nitroglycerin and any or all of the dilutents used can certainly deflagrate or burn. However, the explosive power of nitroglycerin is derived from detonation: energy from the initial decomposition causes a pressure gradient that detonates the surrounding fuel. This can generate a self-sustained shock-wave that propagates through the fuel-rich medium at or above the speed of sound as a cascade of near-instantaneous pressure-induced decomposition of the fuel into gas. This is quite unlike deflagration, which depends solely upon available fuel, regardless of pressure or shock.
Nitroglycerin is prepared by nitration of glycerol (also known as glycerin). In the process, glycerin is slowly tipped into a mix of full concentration nitric acid and sulfuric acid (about 50% sulfuric acid, 40% nitric acid, and 5-10% glycerin). The mixed acid must be cooled to approximately room temperature before the glycerin is added because they will exotherm (heat up) greatly when combined. The solution is slowly stirred. A few seconds after mixing, the vessel must be immersed in a jacket of ice water to prevent the exothermic reaction from overheating it, causing nitric acid decomposition or even an explosion. The temperature should never exceed 10 °C (50 °F), but the chemicals must not be cooled by the ice water before mixing, or the nitrating reaction will not take place.
If the reaction is successful, the nitroglycerin will form a slightly yellow or straw colored liquid which will float to the top of the acid mix. The mix is then carefully poured into a large container of water. The nitroglycerin will settle to the bottom (it is water insoluble) and should be neutralized with sodium carbonate and water mix until its pH becomes neutral.
Another method of producing nitroglycerin is to mix the glycerin and sulfuric acid first, which produces heat, but at this stage is not dangerous. After cooling, the nitric acid can be added reasonably quickly to the mix, but it can still cause uncontrolled nitration. It can also cause the acid to splash. Therefore it should be avoided, and the nitration mixture should be added very slowly to the glycerol. The then nitrated glycerin and acid solution has to be left for the nitroglycerin to float to the top, since this method can sometimes produce the nitroglycerin in fine quantities. The waiting period is a day or less, but the prolonged exposure to the acids may cause the decomposition or even the explosion of the nitroglycerin, although the latter will only occur in large batches. If a milky colour is seen, it is only because of water in the mix. From this point, continue as above. This method was used in the time of Nobel, although it was not his own.
The industrial manufacturing process often uses a nearly 50:50 mixture of sulfuric acid and nitric acid. This can be produced by mixing white fuming nitric acid (quite costly pure nitric acid in which oxides of nitrogen have been removed, as opposed to red fuming nitric acid) and concentrated sulfuric acid. More often, this mixture is attained by the cheaper method of mixing fuming sulfuric acid (sulfuric acid containing excess sulfur trioxide) and azeotropic nitric acid (consisting of around 70% nitric acid, the rest being water).
The sulfuric acid produces protonated nitric acid species, which are attacked by glycerin's nucleophilic oxygen atoms. The nitro group is thus added as an ester C-O-NO2 and water is produced. This is different from an aromatic nitration reaction in which nitronium ions are the active species in an electrophilic attack of the molecules ring system.
The addition of glycerin results in an exothermic reaction (i.e., heat is produced), as usual for mixed acid nitrations. However, if the mixture becomes too hot, it results in runaway, a state of accelerated nitration accompanied by the destructive oxidizing of organic materials of nitric acid and the release of very poisonous brown nitrogen dioxide gas at high risk of an explosion. Thus, the glycerin mixture is added slowly to the reaction vessel containing the mixed acid (not acid to glycerin). The nitrator is cooled with cold water or some other coolant mixture and maintained throughout the glycerin addition at about 22 °C, much below which the esterification occurs too slowly to be useful. The nitrator vessel, often constructed of iron or lead and generally stirred with compressed air, has an emergency trap door at its base, which hangs over a large pool of very cold water and into which the whole reaction mixture (called the charge) can be dumped to prevent an explosion, a process referred to as drowning. If the temperature of the charge exceeds about 10 °C (actual value varying by country) or brown fumes are seen in the nitrators vent, then it is immediately drowned.
Because of the great dangers associated with its production, most nitroglycerin production facilities are in offshore rigs or very remote locations.
