Purely chemical explosives like nitro-glycerine, gun-cotton, the picrites, and the fulminates, present a terrible danger from the unknown mode of the new union of atoms, and reaction of the particles within themselves, in spontaneous explosions happening in irregular manner. Some curious circumstances attend the manufacture and use of gun-cotton,[1] nitro-glycerine, and dynamite. Baron von Link, in his system of the artillery use of gun-cotton, diminishes the danger of sudden explosion by twisting the prepared cotton into cords or weaving it into cloth, thereby securing a more uniform density. Mr. Abel's mode of making gun-cotton, which explosive is now used more than any other by the British government, includes drying the damp prepared cotton upon hot plates, freely open to the air. If ignited by a flame, however, in an unconfined place, gun-cotton only burns with a strong blaze, but if confined where the temperature reaches 340° F., it explodes with terrific violence. Somewhat similar is the action of nitro-glycerine and dynamite, which simply burn if ignited in the open air, while the same substance will explode through a very slight concussion or by the application of the electric spark; a red-hot iron, also, if applied, will explode them when a flame will not. With care, nitro-glycerine can be kept many years without deterioration; and it has been heated in a sand-bath to 80° C. for a whole day without explosion or alteration. One curious experiment is deserving of mention: If a broad-headed nail be partly driven into pine wood, and then some pieces of dynamite placed on the head of the nail, the latter may be struck hard blows with a wooden mallet without exploding the dynamite so long as the nail will continue to enter the wood.
[Footnote 1: The purest gun-cotton may be regarded as a cellulose, in which three atoms of hydrogen are replaced by three molecules of peroxide of nitrogen.]
Taking gunpowder as the unit, picrate of potash (picric acid and potassium) has five times more force, gun-cotton seven and a half times, and nitro-glycerine ten times more force. There are others still more powerful, but less known and used, and some explosives are quite uncontrollable and useless.
But the particular object of these remarks is to refer to articles of merchandise non-explosive under general conditions, but so in particular circumstances, as the two fire-extinguishers, water and salt, are explosive under given conditions. The memorable fire which, in July, 1850, destroyed three hundred buildings in Philadelphia, upon Delaware avenue, Water, Front, and Vine streets, was largely extended by explosions of possibly concealed or unknown materials, the presence of the generally recognized explosives being denied by the owners of the properties.
"The germ of the first knowledge of an explosive was probably the accidental discovery, ages ago, of the deflagrating property of the natural saltpeter when in contact with incandescent charcoal."[1] Although much manipulation is deemed necessary to form the close mechanical mixture of the materials of gunpowder, it has never been proved that such intimate previous union is necessary to precede the chemical reaction causing explosion; indeed, some explosions in powder works, before the mixture of the materials, or just at its commencement, seem to point to the contrary. It is also certain that in the manufacture of gunpowder the usual nitrate of potassium (saltpeter) can be replaced by the nitrates of soda, baryta, and ammonia, also by the chloride of potassium; charcoal by sawdust, tan, resin, and starch; and though a substitute for sulphur is not easily found, the latter, or a similar substance, is not an absolute necessity in the composition of gunpowder.[2]
[Footnote 1: Encyclopædia Britannica, new edition, viii, p. 806.]
[Footnote 2: Vide Abel's Experiments in Gunpowder, as detailed in Phil. Trans. Eoy. Soc, 1874.--Vide also Bull. Soc. d'Encouragement, Nov., 1880, p. 633, Sur les Explosives.]
The generally received theory of the chemical action which makes gunpowder explosive is that it is due to the superior affinity of the oxygen of the niter (KNO3) for the carbon of the charcoal, and the production of carbonic acid gas (CO2) and carbonic oxide (CO) suddenly and in great volume. The latter extinguishes flame as well as the former, unless its own flammability is supported by the oxygen of the atmosphere until the degree of oxygenation CO2 is reached. Considering that water (H2O) is composed of two volumes of hydrogen and one of oxygen, and that under an enormously high temperature and the excessive affinity of oxygen gas for potassium or sodium (freed from nitrate union), dissociation of the water may be possible, aided by its being in the form of spray and steam, we would hesitate to deny that an explosive union of suitable crude salts could occur during the burning of a building containing them when water for extinguishment was put on. Any one who has seen the brilliance with which potassium and sodium burn upon water can easily imagine how such strong affinity of oxygen for these substances might aid in severing its union in water in their presence and under extraordinary heat. It might be safe so say that the presence of water under very high temperature may be as aidful to form an explosive among such salts as have been named, as sulphur is for the rapid combustion of gunpowder.
In the review for August, 1862 (Saltpeter Deflagrations in Burning Buildings and Vessels--Water as an Explosive Agency), it was shown that Mr. Boyden's experiments in 1861-62 proved that explosions would occur when water was put upon niter heated alone, and stronger explosion from niter, drywood, and sulphur; also explosion when melted niter was poured on water. The following points we reproduce for comparison: If common salt be heated separately to a bright heat, and water at 150° F. poured on it, an explosion will occur. Niter mixed with common salt, placed upon burning charcoal, and water added, produce a stronger explosion than salt alone. Heating caustic potash to a white heat, and adding warm or hot water, produces explosion. At a Boston fire small explosions were observed upon water touching culinary salt highly heated. Anthracite coal and niter heated in a crucible exploded when sea water was poured on them.
The production of explosion by the putting of water on nitrate of potassium and chloride of sodium arises from the union, at high temperature, of the oxygen of the water with the potash and soda. Of the three liberated gases, hydrogen only is inflammable, and the other two suffocative of flame; but together the nitrogen and chlorine are not to be undervalued, for chloride of nitrogen is ranked as the most terrible and unmanageable of all explosives. Chlorine is a great water separator, but in the present case its affinity for hydrogen would result in hydrochloric acid, a fire extinguisher.