METHOD OF ANALYSIS.
Walter Crum[5] describes a method of analysing bodies containing nitric acid, applicable to the nitro-compounds; when nitrate of potash is used, it is previously purified by crystallization, and fused at little more than its melting heat. Nitro-Glycerin, gun-cotton, etc., must be deprived of moisture.
A glass jar eight inches long and an inch and a quarter in diameter, is filled with and inverted over mercury; a single lump of time fused nitrate, weighing about six grains, is let up through the mercury into the inverted jar, and afterwards fifty grains of water. As soon as the nitrate is dissolved, 125 grains of sulphuric acid, ascertained to be free from nitric acid, are added. By the action of the mercury upon the liberated nitric acid, deutoxide of nitrogen soon begins to be evolved, and, usually in about two hours, without the application of heat, the whole of the nitric acid is converted into that gas. Sometimes agitation is necessary, and it is easily performed by giving a jerking horizontal motion to the upper part of the jar. The surface of the sulphuric acid is then marked, and three-fourths of an inch of solution of sulphate of iron recently boiled, let up into the jar. The gas is rapidly absorbed, except a small portion at last, which must be left several hours to the action of the solution, or be well agitated in a smaller tube with a fresh portion of it. No correction of the nitric oxide has to be made for moisture, for the mixture of acid and water employed has no perceptible vapor tension.
In one experiment, 5.40 grains of nitrate of potash yielded 4.975 cubic inches of gas, at 60°F, and barometer 30 inches.
The residue not absorbed by the sulphate of iron, was 0.015 cubic inch, leaving
4.96 cubic inches of nitric oxide = 1.594 grains NO², and which correspond to 2.869 grains nitric acid, or 53.13 of the nitrate of potash.
| Four consecutive experiments yielded | |||
| 53.13 | |||
| 53.14 | |||
| 53.73 | |||
| 53.29 | |||
| Mean | 53.32 | or leaving out the third experiment. | |
| Mean | 53.19 | ||
The calculated percentage of nitric acid in nitrate of potash, the acid being represented by 6.75, and the potash by 5.8992, is 53.36. Thomson gives for percentage of nitric acid in nitrate of potash 52.94, and Berzelius 53.44.
Salts in powder, which are difficult to pass through mercury without loss, may be enclosed in small glass cylinders. Nitro-Glycerin may be made into pellets with powdered glass, and congealed at 45°F, or simply congealed by taking great care it is not partially thawed during manipulation.
Mr. Theron Skeel, of Albany, has furnished me with the following extract from the Engineering Journal of the 17th Nov., 1871, being an explanation of M. L. Hote’s method of analysing the gases produced by the explosion of Nitro-Glycerin. He uses Ure’s graduated electric eudiometer, made out of a green glass organic analysis tube. Introduce into the apparatus ten centimeters of the gases evolved from water by voltaic electricity, then introduce small globules of thin glass, containing from five to six milligrammes of the explosive; an electric spark being passed through the mixed gases by means of the platina points melted in the upper part of the eudiometer, explodes the gases, breaks the small glass globules and explodes the Nitro-Glycerin. The gases evolved are colorless, and contain a proportion of binoxide of nitrogen. Submitted to the proper absorbents, for moisture, binoxide of nitrogen and carbonic acid, there remains nitrogen. Thus:
| 1 gramme | Nitro-Glycerin gave at temp. | 0 | Cent. |
| 29.7 | barom. press., | ||
| of these gases 284 c.c. | |||
| One hundred parts by volume contained | |||
| Carbonic acid, | 45.72 | ||
| Binoxide of Nitrogen, | 20.36 | ||
| Nitrogen, | 33.92 | ||
| 100.00 | |||
Martin[6] has devised a method of ascertaining the percentage of nitric acid, by its conversion into ammonia. Nitric acid when mixed with sulphuric or muriatic acids, in the presence of metallic zinc, is converted into ammonia (Gmelin I, 828). By placing some zinc in a mixture of the two acids, there is no disengagement of gas, whilst the nitric acid is converted into ammonia. Hydrogen in its nascent state combines with the oxygen of the nitrogen compound, produced by the nitric acid alone.
Metallic zinc, with dilute nitric acid, gives protoxide of nitrogen; and by taking one equivalent of this gas and four equivalents of hydrogen, water and ammonia may be formed.
NO + 4H = NH³ + HO.
The nitric acid, acting gradually and slowly on the zinc, is transformed into ammonia, equivalent for equivalent. When this reaction has ceased, then follows a disengagement of hydrogen gas from the zinc, which is permitted for a few seconds. It now remains to ascertain the percentage of ammonia. The ammonia may be distilled off and then absorbed by a normal or previously ascertained quantitative solution of oxalic acid, and afterwards to ascertain the quantity of oxalic acid not taken up; deduct this from the original quantity contained in the absorbing solution, and the result gives the percentage of oxalic acid neutralized by the absorption of the ammonia; from this the ammonia is calculated. Mohr’s apparatus for the disengagement of ammonia may be used with advantage in this operation. See Mohr’s Traite d’analyse chimique, supplement, p. 402, Paris, 1857.
Tilberg[7] analysed the Stockholm Nitro-Glycerin with the following results: C³H⁵(NO²)O³ (the Carbon atoms being estimated as 12, Hydrogen 1, Oxygen 16,) and regarded it as Mono-Nitro-Glycerin.
In proof of the fact of Nitro-Glycerin being explosive by concussion effected at a distance, if proof were needed, I instance a small can containing about 4 lbs. of Nitro-Glycerin left by the blaster about 350 feet from the heading, and partially protected by the rail which was curved upwards to prevent the cars running over the dump, was exploded, when a full charge of 16 holes was fired in the heading at the West End of the Hoosac Tunnel. It will be noted that there could be no heat developed 350 feet from the primary explosion, and being enclosed in an ordinary kerosene can, it appears a striking instance of the possibility of explosion from induced concussion.
Again, in April, 1872, a cartridge of Nitro-Glycerin was left in the cartridge chest, containing about 2 lbs. Nitro-Glycerin, whilst 20 charges of blasting powder were fired in the heading, 200 feet distant; the explosion of the powder was unusually heavy, and the Nitro-Glycerin exploded, tearing the chest to pieces, fracturing the air main and disrupting the track. This indubitably proves the explosion of Nitro-Glycerin by concussion, and should warn every operator to be careful to place any surplus explosive away from exploders, and as far distant as possible from where an explosion is intended, and particularly in such position that if it should explode, a contingency possible, there may be no one near the vessel containing such surplus.
[8]The experiments of February 17, 1870, described by Professors Barker and S. W. Johnson, where water and glass intervened to receive the heat and concussion, confirm the fact of Nitro-Glycerin being explosive by concussion, without heat or pressure; in these instances neither heat nor pressure were admitted, yet the explosion blew the tub into fragments, cutting off the staves level with the hoops, smashing and fracturing the bottom of the tub on the rock serving as a pedestal, and sending the water up so that it descended in a shower seventy feet from the point of explosion.
It is proper I should here announce that, after a series of experiments, during my leisure hours, extending over several years, with nitro-mannite, nitro-sugar, nitro-dextrin, nitro-starch, and nitro-naphthalin, with a view to obtain a homogeneous compound convertible wholly into gaseous matter, and miscible with liquid Nitro-Glycerin, which would not explode under ordinary conditions, I have succeeded in obtaining such a mixture, viz.:
Nitro-Glycerin, thirty parts.
Nitro-Toluol, ten parts.
Mixed, this will not explode when struck on an anvil, burns when thrown on to the fire, and can only be exploded with very heavily charged exploders, containing, say, fifteen grains of fulminate, better and more surely, however, with twenty grains. To this I know but one drawback: it does not solidify at a moderate (45°F) temperature, and, if the containing vessel should leak, a too frequent source of accident with inferior Nitro-Glycerin that cannot be congealed, the nitro-toluol is liable to evaporate, and the Nitro-Glycerin is then left with its usually dangerous properties unimpaired.
This was patented by C. Volney, who formerly blasted for me, and for the Lake Shore N. G. Co., and assigned to me for a consideration.
