Whether atoms really exist, and their arrangement in the particles of bodies can be deduced from the phenomena, or not, the fact is undeniable that these ideas have given chemists a wonderful grasp of the facts of their science. The consistency and completeness of the explanation afforded by these theories are ever being extended by modifications which enable them to embrace more and more facts. Some of the properties of the substance we are now considering confirm in a remarkable manner the theoretical views which are expressed in its constitutional formula. We may first consider the nature of gunpowder, and by comparing it with nitro-glycerine, endeavour to explain the greater power of the latter substance. Gunpowder is a mixture of charcoal, sulphur, and nitre, the latter constituting three-fourths of its weight. Nitre supplies oxygen for the combustion of the charcoal, which is thus converted into carbonic acid, and the sulphur, which is added to increase the rapidity of the combustion, is also oxidized. The products of the action are, however, numerous and complicated, but the important result is the sudden generation of a quantity of carbonic acid, nitrogen, carbonic oxide, hydrogen, and other gases, which at the oxidizing temperature and pressure of the air would occupy a space 300 times greater than the powder from which they are set free; but the intense heat attending the chemical action dilates the gases, so that at the moment of explosion they would occupy a space at least 1,500 times greater than the gunpowder. The materials of which gunpowder is composed are finely powdered, in order that each portion shall be in immediate contact with others, which shall act upon it. Plainly, the more thorough the incorporation of the materials—that is, the more finely ground and intimately mixed they are—the more rapid will be the inflammation of the powder.
Looking now at the crude formula of nitro-glycerine, C3H5N3O9, the reader will remark that the molecule contains more than sufficient oxygen to form carbonic acid with all the carbon atoms, and water with all the hydrogen atoms; for the C6 in two molecules of nitro-glycerine would take only O12 to form 6CO2; and the H10, to be converted into 5H2O, would only need O5; thus there would be an excess of oxygen. Now, it may occur to the reflective reader that in every molecule of nitro-glycerine the carbon and hydrogen are already associated with as much oxygen as they can take up: that they are, in fact, already burnt, and that no further union is possible. But from chemical considerations it has been deduced that in the nitro-glycerine molecule the oxygen atoms, except only three, which are partially and imperfectly joined to carbon, are united to nitrogen atoms only. The constitution of the molecule may be represented by arranging, as below, the letters which stand for the atoms, and by joining them with lines, which shall stand for the bonds by which the atoms are united.
We see here that the hydrogen atoms are completely, and the carbon atoms partially, detached from the oxygen atoms; and therefore these atoms are in the condition of the separated carbon and oxygen atoms in gunpowder. Only the pieces of matter which lie side by side in gunpowder are in size to the molecules of nitro-glycerine as mountains to grains of sand. The mixture of the materials is then so much more intimate in nitro-glycerine, since atoms which can rush together are actually within the limits of the molecules; and these molecules have such a degree of minuteness, that 25 millions, at least, could be placed in a row within the length of an inch. We know that the finer the grains and the more intimate the mixture, the quicker will gunpowder inflame; but here we have a mixture far surpassing in minute subdivision anything we can imagine as existing in gunpowder. Hence the combination in the case of nitro-glycerine must be instantaneous, whereas that in gunpowder, quick though it be, must still require a certain interval. If it take a thousandth of a second for the gases to be completely liberated from a mass of gunpowder, and only one-millionth of a second for a vast quantity of carbonic acid, nitrogen, and steam to be set free from nitro-glycerine, the destructive effect will be much greater in the latter case. Again, the volume of the gases liberated from nitro-glycerine in its detonation have at least 5,000 times the bulk of the substance. We have entered into these chemical considerations, at some risk of wearying the reader, with the desire of affording him a clue to the singular properties of nitro-glycerine and gun-cotton, which we are about to describe.
The nature of the chemical changes which may be set up in an explosive substance, and the rapidity with which these changes proceed throughout a mass of the material, are greatly modified by the conditions under which the action takes place. If a red-hot wire be applied to a small loose tuft of gun-cotton, it goes off with a bright flash without leaving any smoke or any other residue. Thus, when the substance is quite unconfined, no explosion occurs. If the cotton-wool be made into a thread, and laid along the ground, it will burn at the rate of about 6 in. per second; if it be twisted into a yarn, the combustion will run along at the rate of 6 ft. per second; but if the yarn be enclosed in an Indian-rubber tube, the ignition proceeds at the rate of 30 ft. in a second. If to a limited surface of gun-cotton, such as one end of a length of gun-cotton yarn, a source of heat is applied—the temperature of which is high enough to set up a chemical change, but not high enough to inflame the resulting gases (carbonic oxide, hydrogen, &c.)—the cotton burns comparatively slowly, rather smouldering than inflaming. If, however, a flame be applied, the gun-cotton flashes off with great rapidity, because the heat applied sets fire to the gaseous products of the chemical action. But if the gun-cotton be confined so that the gases cannot escape, the combustion becomes rapid however set up. The reason is that if the gases escape into the air, they carry off so much of the heat produced by the smouldering gun-cotton, that the temperature does not rise to the extent required to produce the flaming ignition, in which the products are completely oxidized. If a mass of gun-cotton be enclosed in a capacious vessel from which the air has been removed, and the gun-cotton be ignited by means of a wire made hot by electricity, the cotton will at first only burn in the slow way without flame; but as the gases accumulate and exert a pressure which retards the abstraction of heat accompanying their formation, the temperature will rise and attain the degree necessary for the complete and rapid chemical changes involved in the flaming combustion. Thus, the more resistance is offered to the escape of the gases, the more rapid and perfect is the combustion and explosive force produced by the ignition. Now, the explosion of gun-cotton has been found to be too rapid when it is packed into the powder-chamber of a gun, for its tendency is to burst the gun before the ball has been fairly started. Hence a material like gunpowder, in which the combustion is more gradual, is better suited for artillery. The ignition of gunpowder, though rapid, is not instantaneous, and therefore we can speak of it as more or less gradual. Indeed, in even the most violent explosives, some time is doubtless required for the propagation of the action from particle to particle. This extreme rapidity of combustion, and consequent rending power, which is so objectionable in a gun-chamber, makes gun-cotton a most powerful bursting charge for shells, and, when it is enclosed in strong receptacles, for torpedoes also.
But by the researches of Nobel, Professor Abel, and others, it has been discovered—and this is, perhaps, the most remarkable discovery in connection with explosives—that gun-cotton, nitro-glycerine, and other explosive bodies, are capable of producing explosions in a manner quite different from that which attends their ignition by heat. The violence of this kind of explosion is far greater than that due to ordinary ignition, for the action takes place with far greater rapidity throughout the mass, and is, indeed, practically instantaneous. It appears to be produced by the mere mechanical agitation or vibrations which are communicated to the particles of the substance. Turning back to the representation of the molecule of nitro-glycerine on page [744], it will not be difficult to imagine that this may be an unstable kind of structure; that the atoms of oxygen are prevented from rushing into union with those of hydrogen and carbon only by the interposition of the nitrogen; and that an agitation of the structure might shake all the atoms loose, and leave them free to re-combine according to their strongest affinities. Nitro-glycerine is by no means so ready to inflame as is gun-cotton: it is said that the flame of a match may be safely extinguished by plunging it into the liquid; and when a sufficient heat is applied to a quantity of the liquid in the open air, it will burn quietly and without explosion. Even when nitro-glycerine is confined, the application of heat cannot always be made to produce its explosion; or, at least, the circumstances under which it can do so are not accurately known, and the operation is difficult and uncertain. On the other hand, nitro-glycerine explodes violently even when freely exposed to the air if there be exploded in contact with it a confined charge of gunpowder, or a detonating compound such as fulminating powder. Gun-cotton possesses the same property of exploding by concussion, which appears indeed to be a general one belonging to all explosive bodies. According to recent researches, even gunpowder is capable of a detonative explosion. A mass of gunpowder confined with a certain proportion of gun-cotton, which is itself set off by fulminate of mercury, is said to exert an explosive force four times greater than that developed by the ignition of the gunpowder in the ordinary manner. It has also been found that wet gun-cotton can be exploded by concussion, and the force of the explosion is unimpaired even when the material is saturated with water. This makes it possible to use gun-cotton with greater safety, as it may be transported and handled in the wet condition without risk, and it preserves its properties for an indefinite period without being deteriorated by the water. Some experiments illustrating the extraordinary force of the detonative explosions of gun-cotton and nitro-glycerine will give the reader an idea of their power.
A palisade, constructed by sinking 4 ft. into the ground trunks of trees 18 in. in diameter, was completely destroyed in some experiments at Stowmarket by the explosion of only 15 lbs. of gun-cotton. Huge logs were sent bounding across the field to great distances, and some of the trees were literally reduced to match-wood. The gun-cotton, be it observed, was simply laid on the ground exposed to the air. The destructive powers of nitro-glycerine are even greater. A tin canister, containing only a few ounces of nitro-glycerine, is placed, without being in any way confined, on the top of a smooth boulder stone of several tons weight; it is exploded by a fuse containing fulminating powder, which is fired from a distance by electricity. There is a report, and the stone is found in a thousand fragments. The last experiment shows one of the advantages of nitro-glycerine over gunpowder as a blasting material, beyond its far greater power, which is about ten times that of gunpowder. A charge of gunpowder inserted in a vertical hole tends to force out a conical mass, the apex of which is at the space occupied by the charge. With nitro-glycerine, and also with gun-cotton, which last has almost six times the force of gunpowder, a powerful rending action is exerted below as well as above the charge. Again, in blasting with gunpowder the charge must be confined, and the hole is filled in above the charge with tightly rammed materials, forming what is termed the tamping. But nitro-glycerine requires no tamping: a small, thin metallic core containing the charge is simply placed in the drill-hole, or the liquid itself is poured in, and a little water placed above it. The effect of the explosion of nitro-glycerine in “striking down,” when apparently no resistance is offered, will seem very strange to the reader who is oblivious of certain fundamental principles of mechanics. The force of the explosion is due entirely to the sudden production of an enormous volume of gas, which at the ordinary pressure would occupy several thousand times the bulk of the material from which it is produced. This gas, by the law of the equality of action and reaction, presses down upon the stone with the same force that it exerts to raise the superincumbent atmosphere. The pressure of the gas at the moment of its liberation is enormous; but the atmosphere cannot instantaneously yield to this, for time is required to set the mass of air in motion, and the wave of compression advances slowly compared with the rapidity of the explosion. Hence the air acts, practically, like a mass of solid matter, against which the gases press, and which yields less readily than the rock, so that the blow which is struck takes visible effect on the latter. Now, with gunpowder, the evolution of gas is less rapid, the atmosphere has time to yield, and the reaction has not the same violence. The rapidity of the evolution of gas from the exploding nitro-glycerine is so great, that the gases, though apparently unconfined, are not so in reality; for the atmosphere acts as a real and very efficient tamping.
When nitro-glycerine first came into use for blasting purposes, it was used in the liquid form under the name of “blasting oil;” but the dangers attending the handling of the substance in this state are so great, that it is now usual to mix the liquid with some powdered substance which is itself without action, and merely serves as a vehicle for containing the nitro-glycerine. To mixtures of this kind the names “dynamite,” “dualine,” “lithofracteur” &c., have been given.
It is now hardly necessary to point out that the discovery of these new explosives has largely extended our power over the rocks, enabling works to be executed which would have been considered impracticable with less powerful agents. It is true that the most fearful disasters have been accidentally produced by the new explosives; but such occasional devastation is the price exacted for the possession of powerful agents. And just as in other cases—steam, for example—where great forces are dealt with, so these new powers must be managed with unceasing care, and placed in the hands of only skilful and intelligent men.
The products of the combustion of gunpowder are not all gaseous, but include solid compounds, such as carbonate and sulphate of potassium. It is these that give rise to the smoke seen when a gun is discharged, and which, in rapid firing, soon obscures the sight of the objects aimed at. They are also the causes of the fouling of the bore. Gun-cotton is quite unexceptionable in these respects, and that prompted the attempts made soon after its introduction to use it instead of gunpowder in fire-arms. But the explosion of gun-cotton was found too sudden and violent for guns and rifles, so that many serious accidents in consequence occurred. The next thing done was to lessen the rapidity of the explosion by using gun-cotton mixed with ordinary cotton, or twisted in threads round some inert substance—in fact, to mitigate the violence of the shock by some mechanical disposition of the material. The introduction of rapid firing guns and repeating rifles forced on the problem of a smokeless powder; and as the plan of replacing nitrate of potassium, in ordinary gunpowder, by nitrate of ammonium was found to be attended with loss of the keeping quality of the powder, other materials, such as picric acid, which forms also the basis of the explosive called mélinite, have been proposed. The composition of mélinite was long a mystery, and that of the smokeless powder adopted by the French was so carefully concealed that many experiments had to be made by other nations to discover some similar preparation, which was found possible by combining certain substances with gun-cotton so as to modify the violence of its explosion, and produce a manageable material having the required properties. The British Government, after many experiments and much careful testing, decided to adopt cordite, made of nitro-glycerine, in which, by the aid of volatile solvent, di-nitro-cellulose is dissolved, together with a little mineral oil. The semi-fluid composition, forced through a round hole or die, comes out like a thread or cord, which the evaporation of the volatile solvent leaves with very much the appearance of common brown window-cord. This material has the several advantages of keeping well, of being uniform in its propulsive powers, of being capable of imparting as high a velocity as a much larger charge of the ordinary black gunpowder, while at the same time exercising a less pressure on the chase of the gun.