2C_{6}H_{2}(NO_{2}){3}OH + O{10} = 12CO_{2} + 3H_{2} + 3N_{2}.
The percentage composition of picric acid is—Nitrogen, 18.34; oxygen, 49.22; hydrogen, 1.00; and carbon, 31.44, equal to 60.26 per cent. of NO_{2}. The products of decomposition are carbonic acid, carbonic oxide, carbon, hydrogen, and nitrogen, and the heat liberated, according to Berthelot, would be 130.6 cals., or 570 cals. per kilogramme. The reduced volume of the gases would be 190 litres per equivalent, or 829 litres per kilogramme. To obtain a total combustion of picric acid it is necessary to mix with it an oxidising agent, such as a nitrate, chlorate, &c. It has been proposed to mix picric acid (10 parts) with sodium nitrate (10 parts) and potassium bichromate (8.3 parts). These proportions would furnish a third of oxygen in excess of the necessary proportion.
Picric acid was not considered to be an explosive, properly so called, for a long time after its discovery, but the disastrous accident which occurred at Manchester (vide Gov. Rep. No. LXXXI., by Colonel (now Sir V.D.) Majendie, C.B.), and some experiments made by Dr Duprè and Colonel Majendie to ascertain the cause of the accident, conclusively proved that this view was wrong. The experiments of Berthelot (Bull. de la Soc. Chim. de Paris, xlix., p. 456) on the explosive decomposition of picric acid are also deserving of attention in this connection. If a small quantity of picric acid be heated in a moderate fire, in a crucible, or even in an open test tube, it will melt (at 120° C. commercial acid), then give off vapours which catch fire upon contact with air, and burn with a sooty flame, without exploding. If the burning liquid be poured out upon a cold slab, it will soon go out. A small quantity carefully heated in a tube, closed at one end, can even be completely volatilised without apparent decomposition. It is thus obvious that picric acid is much less explosive than the nitric ethers, such as nitro-glycerol and nitro-cellulose, and very considerably less explosive than the nitrogen compounds and fulminates.
It would, however, be quite erroneous to assume that picric acid cannot explode when simply heated. On the contrary, Berthelot has proved that this is not the case. If a glass tube be heated to redness, and a minute quantity of picric acid crystals be then thrown in, it will explode with a curious characteristic noise. If the quantity be increased so that the temperature of the tube is materially reduced, no explosion will take place at once, but the substance will volatilise and then explode, though with much less violence than before, in the upper part of the tube. Finally, if the amount of picric acid be still further increased under these conditions, it will undergo partial decomposition and volatilise, but will not even deflagrate. Nitro-benzene, di-nitrobenzene, and mono-, di-, and tri-nitro-naphthalenes behave similarly.
The manner in which picric acid will decompose is thus dependent upon the initial temperature of the decomposition, and if the surrounding material absorb heat as fast as it is produced by the decomposition, there will be no explosion and no deflagration. If, however, the absorption is not sufficient to prevent deflagration, this may so increase the temperature of the surrounding materials that the deflagration will then end in explosion. Thus, if an explosion were started in an isolated spot, it would extend throughout the mass, and give rise to a general explosion.
In the manufacture of picric acid the first obvious and most necessary precaution is to isolate the substance from other chemicals with which it might accidentally come into contact. If pure materials only are used, the manufacture presents no danger. The finished material, however, must be carefully kept from contact with nitrates, chlorates, or oxides. If only a little bit of lime or plaster become accidentally mixed with it, it may become highly dangerous. A local explosion may occur which might have the effect of causing the explosion of the whole mass. Picric acid can be fired by a detonator, 5-grain fulminate, and M. Turpin patented the use of picric acid, unmixed with any other substance, in 1885. The detonation of a small quantity of dry picric acid is sufficient to detonate a much larger quantity containing as much as 17 per cent. of water.
It is chiefly due to French chemists (and to Dr Sprengel) that picric acid has come to the front as an explosive. Melinite,[A] a substance used by the French Government for filling shells, was due to M. Turpin, and is supposed to be little else than fused picric acid mixed with gun-cotton dissolved in some solvent (acetone or ether-alcohol). Sir F.A. Abel has also proposed to use picric acid, mixed with nitrate of potash (3 parts) and picrate of ammonia (2 parts) as a filling for shells. This substance requires a violent blow and strong confinement to explode it. I am not aware, however, that it has ever been officially adopted in this country. Messrs Désignolles and Brugère have introduced military powders, consisting of mixtures of potassium and ammonium picrates with nitrate of potassium. M. Désignolles introduced three kinds of picrate powders, composed as follows:—
___________________________________________________________________ | | | | | | | For Torpedoes | For Guns. | For Small | | | and Shells. | Ordinary. Heavy. | Arms. | |___________________|_______________|___________________|___________| | | | | | | | Picrate of Potash | 55-50 | 16.4- 9.6 | 9 | 28.6-22.9 | | Saltpetre | 45-50 | 74.4-79.7 | 80 | 65.0-69.4 | | Charcoal | … | 9.2-10.7 | 11 | 6.4- 7.7 | |___________________|_______________|___________|_______|___________|
They were made much like ordinary gunpowder, 6 to 14 per cent. of moisture being added when being milled. The advantages claimed over gunpowder are greater strength, and consequently greater ballistic or disruptive effect, comparative absence of smoke, and freedom from injurious action on the bores of guns, owing to the absence of sulphur. Brugère's powder is composed of ammonium picrate and nitre, the proportions being 54 per cent. picrate of ammonia and 46 per cent. potassic nitrate. It is stable, safe to manufacture and handle, but expensive. It gives good results in the Chassepôt rifle, very little smoke, and its residue is small, and consists of carbonate of potash. It is stated that 2.6 grms. used in a rifle gave an effect equal to 5.5 grms. of ordinary gunpowder.
[Footnote A: The British Lydite and the Japanese Shimose are said to be identical with Melinite.]