No. XXI.
Several U. S. patents have been recently granted to James Weir Graydon for inventions which relate to the use of high explosives for war purposes. U. S. Patent No. 399882, March 19, 1889, is for "A Revolving Air-Gun" for throwing dynamite or other high explosive projectiles, the object of the invention being the production of a gun in which, by the simple turning of a crank, the projectiles may be automatically placed in the barrels, the barrels revolved, and the projectiles discharged under a predetermined regulated degree of air pressure.
U. S. Patent No. 399883, March 19, 1889, is for a "High Explosive Charge," which is to be made by soaking woolen or cotton cloth or like fabric in nitro-glycerine until saturated, and coating the whole with paraffined paper, which is cemented to the cloth, or with shellac or any coating which will prevent the exudation of the nitro-glycerine. The cloth may be in sheets or in ribbons, and the charges may be made up by rolling up the fabric into cylinders. When in ribbons, the charge may be made up by placing the tape-like disks on one another.
U. S. Patent No. 399881, March 19, 1889, is for a "Shell" for use with powder-guns. This shell is to be charged with the tape-like disks (described in the last mentioned patent) of" dynamite cloth," as the inventor calls it, the shell having been previously lined with finely pulverized niter placed between two layers of cloth or other suitable fabric, which are protected from the moisture of the atmosphere by shellac or other similar material. The niter is used because, while it will "prevent heat engendered by the explosion of the propelling charge in the gun from reaching the bursting charge," it will also, "when subjected to the very much higher degree of heat produced by the explosion of the bursting charge, be converted into a gas, thus adding to the force of said charge." The niter is stated to resist a temperature of over 600° F., but when subjected to a temperature of above 644° F. it evolves oxygen gas freely, and this gas, mingling with the gases produced by the high explosive, will render the latter very much more effective.
Besides this and other features there is a flexible porous sack cemented to the point of the shell, and this sack is filled with oil. When the shell moves, the air pressure forces the oil out so as to lubricate the gun and shell and reduce the friction.
U. S. Patent No. 399877, March 9, 1889, is for a" High-Explosive Shell" for air-guns, the object being to provide a projectile which can be readily loaded and unloaded, and in which the density of the bursting charge may be equalized throughout the length of the charge chamber. He seeks to secure this by means of a perforated metal tube which fits in the center of the shell and runs the entire length, and which has secured to its exterior surface and throughout its entire length a continuous spiral sheet-metal flange or vane, this vane being also perforated. The interior of the tube contains the fulminate charge, while the high-explosive charge is coiled between the spiral vanes.
This high-explosive charge is the subject of another application, Serial No. 287630, October 9, 1888, and it consists of a flexible tube of some absorbent material, such as cotton or linen, which is filled with the dynamite or other high explosive. It is stated that when the charge thus put up is required for use, it is preferable to saturate the tube with nitric acid in order to convert it also into an explosive. This form of explosive is designed both for torpedo and artillery purposes.
U. S. Patent No. 399876, March 19, 1889, is for a "Circuit-Closing Device for Electrical Torpedo Fuzes," the peculiarity of which resides in the fact that it is to be operated by the pressure of the water when the torpedo has reached a predetermined depth.
U. S. Letters Patent No. 401851, April 23, 1889, has been granted H. W. Parsons for a "Distributor for Explosive Bombs," which consists of a frame carrying the desired number of bombs, and which is so controlled by electricity that any desired number of the bombs can be released at any desired time. It is intended that the distributor shall be attached to a balloon or float suspended in mid-air and operated from the ground.
From a private communication we learn that the insensitive nitroglycerine employed by Mr. S. D. Smolianinoff in the experiments described in these Notes (Proc. Nay. Inst. 13, 573; 1887) is now styled Americanite.
U. S. Letters Patent No. 396739, January 29, 1889, were granted . G. C. Gillespie, of Brooklyn, N. Y., for a "Machine or Engine for the Application of Explosive Energy to Mechanical Power," in which he states that the primary object to be attained in the construction of any machine operated by the sudden generation of high-pressure gas—as, for example, when gun-cotton is exploded—is to provide a means of controlling the power at the outset, and thus preserve the apparatus from any destructive shock. This object he claims to accomplish by the use of a cylinder and plunger, both of which are movable instead of one being fixed, as in the case of ordinary steam or gas engines.
Another important point, he states, to be provided for is the prevention of overheating, and this he claims to accomplish by the use of single-action cylinders which are drawn completely away from the plungers at each downward stroke, thereby enabling the gaseous products of the explosion to escape freely, and thus exert a cooling effect by their expansion.
A lecture on "Recent Inventions in Gunpowder and other Explosives" was delivered on Friday, the 5th of April, 1889, at the Royal United Service Institution, by Mr. W. H. Deering, F. C. S., F. I. C., Chief Assistant Chemist to War Department. The author referred first to brown or cocoa powder, which was introduced in Germany, in 1882, in the well known form of a hexagonal prism with a central cylindrical hole. Its composition differs widely from the black powders then in use, being 79 per cent potassium nitrate, 3 per cent sulphur, and 18 per cent of a very lightly baked brown charcoal. Prismatic brown powder, which is used in the larger English breech loading guns, is of this composition, very slightly carbonized straw being used for the brown charcoal. For the same muzzle energy, this powder causes less pressure and less smoke than black gunpowder of the old composition. From investigations into the products of combustion in each case, it is found that in the brown powder there is present more of the oxidizing niter absolutely and relatively to the reducing charcoal and sulphur than in the black powder; thus the residue of the former is fully oxidized, and the gases contain only 7 per cent by volume of unoxidized or imperfectly oxidized constituents, while the residue of the black powder contains some 24 per cent of unoxidized constituents, and the gases 22 per cent. The volume of the gases produced in each case is about the same, but the 'temperature in the case of the brown is greater than in that of the black powder; hence it follows that the diminished pressures produced by the former must have been due to its slower rate of burning, which depends on its chemical composition.
Sir F. Abel and Captain A. Nobel have experimented with a mining powder, which is interesting as an example of the influence of a change of composition in the opposite direction to that of brown prismatic powder. Its ingredients are: niter, 61.92 per cent; sulphur, 15.06 per cent; charcoal, 21.41 per cent; and water, 1.61 per cent. The products of combustion are much richer in unoxidized products than those of the pebble powder, and the temperature is less. They have come to the conclusion that the gunpowder which gives most gas and least heat causes the least erosion in steel tubes. In view of this statement, it would be interesting to know how a powder of the composition of this mining powder, in the form of prisms of the usual shape and size, would behave as a gunpowder, and whether satisfactory ballistic results and less erosion would be obtained with it.
The lecturer next dealt with nitrate of ammonium gunpowder, and referred to the so-called amide powder of Mr. F. Gaens, which has the following composition: 101 parts by weight of ordinary niter, 80 parts nitrate of ammonium, and 40 parts charcoal. It is claimed that in ignition, potassamine (KH2N) is formed, which is volatile at high temperature and increases the useful effect of the explosive; that there is very little residue; that no injurious gases are generated, and that little smoke is produced. It is, however, open to question whether the potassamine is really produced, or whether the products of combustion are not similar to those obtained from ordinary gunpowder. The powders referred to in Krupp's last report (No. 53, October, 1888) probably contain nitrate of ammonium, as may be deduced from the published accounts of their trial. Both those for small and large guns gave better results than the German service brown powder, and they were all very hygroscopic. A similar powder seems to have been used with the Swiss Hebler rifle. E. X. E. powder and S. B. C. powder were also mentioned as having been tried against English brown prismatic powder for heavy guns, with more or less satisfactory results. Perforated cake powders were mentioned as applications of the principles introduced by the American General Rodman in 1862, as also the efforts that have been made to obtain a charcoal of uniform chemical composition, either by the method of blending or by using uncharred turf or bog stuff.
Next, the interesting subject of smokeless powders was reached. Within the last three or four years, several preparations which have been stated to give practically no smoke have been proposed as substitutes for the old niter, sulphur and charcoal powders. They consist essentially of nitro-cotton or other kind of nitro-cellulose, specially treated with a view of producing a slower burning substance; or of nitro-glycerine and nitro-cotton. It was to be noted, however, that the presence of metallic nitrates would be incompatible with their smokelessness. This the lecturer exemplified by experiment. By the use of a suitable preparation of nitro-cellulose, or similar chemical compound, a practically smokeless powder is attainable, giving, with less weight of charge than ordinary gunpowder, very high velocity to the bullet, and making the cartridge of the small-bore rifle a little lighter. Vieille's powder (or "Poudre B"), which is used for the French Lebel rifle of 0.315-inch caliber, is stated to give to the bullet, which weighs 231 gr., a muzzle velocity of 1968 ft. sec., or, according to another statement, 2034 ft. sec., and to produce little or no smoke. Several patents have been taken out in England for various methods by which it is sought to slow down ordinary service gun-cotton (trinitro-cellulose) so that it can be used in a firearm without producing enormous initial pressures. Thus, in the Johnson-Borland powder the salient feature consists in forming nitro-cellulose into grains or prisms, which, after being dried, are saturated with a solution of camphor in a volatile solvent such as will evaporate below 100° C. This solvent is distilled off by a gentle heat and recovered, and the camphor is left in the solid state, intimately mixed with the nitro-cellulose. The material is then heated in a closed vessel, when the camphor exercises a remarkable gelatinizing effect on the nitrocellulose, the hardness being regulated by the amount of camphor used, and not being merely on the surface, but extending throughout the mass. This peculiar property of camphor has long been utilized in the manufacture of celluloid. Engel, Glaser, and Turpin have also patented processes, and in all three the nitro-cellulose is dissolved or gelatinized in a solvent, by which treatment the fibrous character of the material is destroyed and a horny product obtained, burning in the rifle or gun at a slower rate than in the fibrous condition. Another powder of this class is that of Mr. A. Nobel, the founder of the nitro-glycerine industry. It is a horny preparation, composed of nitro-glycerine, nitro-cotton, and camphor. It is a kind of blasting gelatine, with the proportion of nitro-cotton greatly increased, and with the addition of camphor. The resulting product resembles celluloid in appearance, is easily formed into grains or pellets of any shape, and, it is claimed, burns in firearms slowly enough to render it a fit substitute for gunpowder, over which it is said to have the advantage of greater power, of leaving no residue, and of being practically smokeless. The permissible range of variation of the constituents is a wide one. Two examples of mixtures are given, representing the extremes of variation. In 100 parts by weight of nitro-glycerine, 10 parts of camphor are to be dissolved and 200 parts of benzol added. In this mixture, 50 parts of dry soluble nitrocotton pulp are to be steeped. The benzol is then evaporated, and the material mixed by passing between rollers, which are hollow, and heated by steam to 500 C. or 600 C. When uniform, it is rolled out into sheets, and cut up into grains or moulded. Or, when it is required to reduce the amount of nitro-glycerine as far as practicable, 100 parts by weight of nitro-glycerine, 10 to 25 parts of camphor, and 200 to 400 parts of acetate of amyl are mixed, and zoo parts of dry soluble nitro-cotton pulp are steeped in the liquid. The material is then kneaded into a paste, the solvent is removed by heat, and the dry material cut up into grains, as before.
The lecturer concluded by referring to the picrates. After mentioning the powders of Abel and Turpin, he proceeded to say that picric acid is the predominating constituent of "melinite," introduced into service use in France, in 1886-87, for charging shells. It is probable that ether is one of its constituents, its use being to cement together picric acid grains by means of collodion, a solution of dinitro-cotton in ether and alcohol. It is questionable whether the quantities of carbolic acid available for the manufacture of picric acid would be sufficient to meet large and continued demands for the latter. The available supplies of cotton for making gun-cotton, and even of glycerine for nitro-glycerine, are much less likely to be affected by a run upon them than those of carbolic acid, which depend upon the amount of coal tar produced, mainly in gas making. From French and German statements it appears that a vault of concrete 10 'feet thick, not covered with earth, which would act as tamping to the explosive, may be considered as almost invulnerable to the attack of melinite shells.
A short discussion followed the lecture. Mr. Nordenfelt said that it was not a question as to whether we should adopt a smokeless powder, but which smokeless powder should we adopt. Sir F. Abel pointed out the difficulties in selection, and the caution that is necessary; while the chairman wound up the discussion by reporting some extremely interesting ballistic results, transmitted to him from Elswick. It appears that the "velocity pressure curve" obtained there with the Chillworth special powder is almost ideal in its perfection. With the 4.7-inch gun, firing a 45-pound projectile, a muzzle velocity of 1990 ft. sec. was obtained with I3f tons pressure. In our new rifle, the black pellet powder is to give a velocity of 18to ft. sec. with 18 to 19 tons pressure; but with a powder known as the R. C. P., employed at Elswick, with the same pressure, a velocity of 2050 ft. sec. was reached.—(Industries 6, 426-427; 1889.)
The valuable paper by Sir Frederick Abel and Colonel Maitland, on the "Erosion of Gun-barrels by Powder-products," which was published in the Jour. Iron and Steel. Inst., No. 2, 1886, has been reprinted in full in the Notes on the Construction of Ordnance, No. 46, published by the Ordnance Department, U. S. A.
English Patent 13656, September 21, 1888, has been granted C. F. Hengst for an "Improved Safety Smokeless Gunpowder," which is produced by nitrating pulped straw, and after removal of all traces of acid, granulating the product, with or without the addition of oxidizing agents.
English Patent 7608, May 25, 1887, has been granted Wohanka & Co. for "Improvements in the Manufacture of Explosives," which consist in adding cellulose to the liquid explosives, made by dissolving in concentrated nitric acid the nitro-derivatives of the hydrocarbons of the aromatic phenol series. The cellulose becomes nitrated and swells up, forming with the explosives a plastic mass resembling gelatin.
English Patent 18362, December 15, 1888, has been granted J. W. Skoglund for "Improvements in the Manufacture of Explosive Compounds," which invention relates to the manufacture of explosive compounds consisting of nitro-cellulose or trinitrophenol; together with the radical of carbonic, oxalic, or carbamic acids, in combination with ammonium or another volatile radical base or hydroxyl.
English Patent No. 5270, April 9, 1888, has been granted Le Vicomte Hilaire de Chardonnet for a "Process for Denitrating and Dyeing Pyroxilin," which consists in treating nitro-celluloses with nitric acid of a density of 1.32, whereby in a few hours they lose part of their nitrogen and become reduced below the state of the "tetranitrate," at the same time beginning to soften and being rendered more easy of treatment in dyeing and other operations.
English Patent 8253, June 8, 1887, has been granted F. Crane for "Improvements in Pyroxyline Compounds and Varnishes," in which propyl and butyl acetates alone, together, or mixed with benzene, light petroleum, acetone, methyl and ethyl alcohols, and amyl acetate, are used as solvents for pyroxyline for the manufacture of varnishes and lacquers and for the production of celluloid.
The advantages claimed for the propyl or butyl acetates are their good solvent powers, the sufficient but not too great rapidity with which they evaporate, their non-hygroscopic character, the ease with which they mix with the other substances mentioned above, and their comparatively agreeable odor.
English Patent 2694, February 21, 1887, was granted M. P. E. Gerard, Paris, for a composition capable of being formed into threads, films, sheets, slabs, or moulded articles, or used as a varnish., the composition of which is: Ten parts gun-cotton and five parts gelatin are separately dissolved in acetic acid, then mixed together. A small quantity of glycerine and castor oil, or in other cases a little gluten, glucose, or honey, is added to improve the corn position. The addition of a trace of calcium chloride renders it uninflammable. The product can be used as a varnish for wood, etc., and especially for plaster, and can also be moulded into articles of great delicacy of structure.
English Patent 5824, April 21, 1887, has been granted J. W. Knight and W. D. Gall for "Improvements in the Manufacture of Carbolic Acid and other Tar Acids," by which the carbolic oil is treated with lime and agitated with a hot solution of sodium sulphate, the carbolate of lime first produced being converted into carbolate of soda, with simultaneous formation of calcium sulphate. The watery liquid containing carbolate of soda is drawn off and decomposed with sulphuric acid. The carbolic acid rising to the top is then separated from the lower liquid, which consists of a solution of sodium sulphate ready to use for another treatment with a fresh quantity of oil. The exhausted oil may be passed through filters in order to remove the calcium sulphate.
U. S. Letters Patent No. 403749, May 21, 1889, have been granted J. A. Halbmayr for a method of "Manufacturing Explosives" from tar-oils, which consists in conducting the oils into a body of nitrating acid from below the surface of the latter in a state of division, and at the same time introducing cold air under pressure at the same point with the oils. This is accomplished by using a series of tall waterjacketed tanks filled two thirds full of fuming nitric acid, and reservoirs for the tar-oils which are placed at higher levels than the converting tanks, so that the oils can by gravity be forced into the bottom of the converting tanks, cold air being introduced under pressure at the same point. The nitro-derivatives rise to the top of the liquids in the converting tanks, and by suitable overflow pipes they may be removed. By using a series of these converters at different levels, the operations may be repeated so as to ensure more complete and thorough conversion of the lower or the production of the higher nitro-derivatives.
The Favier Company, in Belgium, have recently brought out a new explosive which consists of a mixture of mononitronaphthalene and ammonium nitrate. The cartridges which are made with this explosive are made waterproof by dipping in molten paraffin.
One molecule of nitronaphthalene requires, theoretically, 2I molecules of ammonium nitrate in order to burn to carbonic acid, water and nitrogen. But if both the 4.41 per cent of paraffin and the 6.86 per cent of nitronaphthalene are oxidized completely, 144.62 per cent of ammonium nitrate is required, whereas the amount of ammonium nitrate present (88 per cent) is only sufficient to oxidize the carbon to carbonic oxide. Such an explosive is unsuitable for underground blasting. The new explosive is indifferent to concussion, and burns with difficulty. In order to cause it to explode, two grams of fulminate are required, but as this priming is about six times as expensive as the priming of a dynamite cartridge, it is questionable whether Favier's explosive can ever hope to compete with dynamite. Favier failed in obtaining a patent in Germany, nor has he been more successful in finding capitalists in that country inclined to work his "invention."—(J. Soc. Ch. Ind. 8, 519 ; 188g; from Chem. Jour. 241.)
English Patent No. 8929, June 22, 1887, has been granted H. Gtittler for an "Improvement in the Manufacture of Charcoal for Explosives and other Purposes, and Apparatus for that Purpose." In the apparatus described, the material is suitably contained in an air-tight cylinder, which is fitted with a pressure gauge and pyrometer and heated by means of a muffle. The carbonization takes place in a current of heated carbon dioxide, and the pressure of the same in the cylinder can be varied at will. The temperature is regulated by admitting cold air to the muffle and by varying the supply of heated gas to the cylinder. After the charring is complete, cold air is rapidly drawn through the muffle, and cooled carbon dioxide passed through the charcoal, which rapidly cools and absorbs the carbon dioxide in its pores. Charcoal treated in this manner is said to be proof against spontaneous ignition.
The Jour. Soc. Chem. Ind. 7, 488-489; 1888, contains a detailed account of the visit of the society to Nobel's Dynamite Works, near Stevenson, Ayrshire, and of the experiments with dynamite and blasting gelatin which were made on this occasion. On pages 490-493 of the same journal is a paper on the "Manufacture of Explosives as carried on by Nobel's Explosives Company." Besides nitroglycerine, dynamite and blasting gelatin, this company manufacture detonators and fulminate of mercury. It was claimed that the Stevenson factory was the largest dynamite factory in the world, and produced about eight tons of explosives daily.
U. S. Letters Patent No. 397285, February 5, 1889, have been granted to G. E. F. Griine for a method of "Preparing Dynamite," which consists in first mixing kieselguhr with sugar, starch, cellulose and like substances, or blood, glue, casein and the like, then compressing the mixture into cartridges, which are then carbonized so as to obtain an intimate mixture of carbon and kieselguhr. These cartridges are then immersed in nitroglycerine until saturated, whereby they are converted into dynamite. It is claimed that this dynamite is water-resisting, and that these cartridges may be kept and transported under water without producing any diminution in their explosive power.
U. S. Letters Patent No. 398559, February 26, 1889, have been granted to J. Waffen for a "Dynamite." In manufacturing this explosive he first makes a mixture of
Sodium nitrate, 22.50 parts.
Decayed wood (well dried), 36.00
Picric acid, 25
Sulphur, 1.00
Sodium carbonate, 25
Next he mixes together
Nitroglycerine, 94.00
Collodion, 6.00
and then he takes 60 parts of the first mixture and 40 parts of the second and mixes the whole together until the mass presents the appearance of a uniformly fatty substance.
English Patent 758, January 18,1886, has been granted W. D. Borland for "Improvements in Explosive Substances and Absorbent Materials therefor." It is stated that the most porous forms of charcoal at present known will not absorb more than from 5-6 times their weight of nitroglycerol, in consequence of which large proportion of charcoal in the explosive, the gases produced by explosion contain too much carbonic oxide. By this improved process, a carbonaceous material is prepared capable of absorbing as much as 35 times its weight of nitroglycerol. The inventor carbonizes small pieces of cork waste or any form of cork in a convenient and suitable manner. "When properly prepared the carbonaceous substance readily absorbs from 7-8 times its weight of nitroglycerol, giving a pulverulent mixture; from 10-12 times, giving a plastic-like mass; and is capable of absorbing even so much as from 30-35 times its weight, yielding a stiff paste of homogeneous appearance from which no nitroglycerol separates, even after many months' immersion in water."
The mixture of 7-8 parts of nitroglycerol with one of the carbonaceous material is excellent for cartridges, and may be safely moulded under water. Mixed with one-fourth its weight of water it becomes absolutely uninflammable, but may be detonated. A mixture of 75 parts of nitroglycerol, 3 parts of the carbonaceous substance, 2 of alkaline carbonate, and zo of kieselguhr is extremely dry to the touch, less affected by freezing and thawing than ordinary kieselguhr dynamite, and may be immersed in water for an indefinite length of time without showing signs of exudation.
English Patent 3759, March to, 1888, has been granted E. Kubin and A. Siersch for "Improvements in Explosives." "The object of this invention is to provide an explosive which, on being detonated, will prevent danger of ignition of fire-damp or coal-dust in mines."
For this purpose chloride or sulphate of ammonia, or the two salts together, are mixed with dynamite, blasting powder, or other explosive, in proportions varying from 10 to 50 per cent. On the detonation of the explosive the ammonia salts are decomposed into noninflammable gases, which have the effect of reducing the temperature and rarefying the explosive gases. At the commencement of 1888 "The Flameless Explosives Company, Limited," was started in London. The flameless powder is the invention of Hermann Schoneweg, of Dudweiler, near Saarbriicken, Germany. His invention consists in surrounding a blasting cartridge with a casing containing oxalic acid or oxalates, with the addition of oxygen-carriers, for the purpose of extinguishing the flame of the fuze and increasing the explosive power of the cartridge. It is mentioned in the prospectus of the company, that if an equal amount of the Schoneweg mixture (consisting of 75 per cent of ammonium oxalate and 25 per cent of potassium nitrate) be added to dynamite, blasting gelatine, or similar substances, no flame is produced on explosion; but this assertion has not been sufficiently tested. Besides, dynamite requires a far larger amount of potassium nitrate and ammonium oxalate than has been added in order to burn to carbonic acid, water and nitrogen, and, in the absence of these oxidizing agents, a large quantity of carbonic oxide, ammonia, and perhaps hydrocyanic acid would be given off. For this reason the author does not anticipate a great future for the flameless powder. Schoneweg did not succeed in having a patent granted to him in Germany. He has also conferred the working of his securite patent to the company mentioned. Securite consists of dinitrobenzol and ammonium nitrate. The Royal Mining Inspector, Margraf, testifies in the prospectus of the company to its being absolutely safe in the presence of marsh -gas and coal-dust, whereas the experiments of the Royal Saxon mining authorities gave the very opposite result.—(Jour. Soc. Ch. Incl. 7, 519; 1888.)
English Patent No. 5949, April 21, 1888, has been granted A. Kuhnt and R. Deissler for an "Improvement in Explosive Compounds," which consists in substituting for the water-cartridge at present in use in coal mines one made of nitroglycerine mixed with ammonium carbonate or chloride. "By the addition of this carbonate of ammonium (or chloride), the temperature of the explosive gases is so small that flashing of the gases is prevented."
U. S. Letters Patent No. 397440, February 5, 1889, have been granted L. Plom and J. d'Andrimont for a "Method of Blasting," which consists in making a cavity near to the end and on either side of the bore-hole, filling the lower part of this lateral cavity with the explosive, and plugging the bore-hole with a wooden plug which carries the fuze. It is claimed that the explosive will thus be rendered more efficient, and that any tendency to blow out through the borehole will be prevented.
J. R. Eaton states that after making hydrogen phosphide in the usual way by boiling phosphorus in potassium hydroxide, he allowed the apparatus to remain in stain quo for three days, in order to show his class that the phosphorus remained in the liquid state after cooling, and at the end of this time finding it liquid, he lifted the flask and gave it a slight shake, when it immediately exploded and the phosphorus solidified at once. He suggests that it was due to gas being condensed by adhesion around the phosphorus as the solution cooled, and that the shaking caused a rapid evolution of this gas.
He states that nitrogen iodide will explode when wet, if it has been allowed to stand twenty-four hours in aqua ammonia, and that when freshly prepared, if partially dried and then scattered over the surface of a tank of water, it will repeatedly explode for hours after by slightly agitating the water.
He many years ago used a mixture of potassium chlorate and phosphorus by placing the powdered salt (no more than will cover a nickel, if exploded within doors) upon a board, and wetting it with a solution of phosphorus in carbont disulphide (an inch of phosphorus will dissolve in an ounce and a half of carbon disulphide in a few minutes). In from five to ten minutes, or as soon as the mixture is dry, touch it with a long pole, or even stamp on the floor, and a loud explosion will ensue. A quantity sufficient to cover a dollar will shatter a thick plank and make a considerable hole in the ground.—(Science 13, 449, 1889.)
The high temperatures attainable with Dr. Hare's oxyhydrogen blowpipe have long been known to chemists, and its practical use in the "lime light" has been quite common. Formerly the gases were stored for use in tin gas-holders or rubber bags, and were forced out under a moderate pressure, but within the last decade it has become the custom to store the gases up in stout steel or wrought iron cylinders, under a pressure of many hundred pounds, and the supplying of these compressed gases has become a very considerable industry.
With the cheapening in the cost of the production of oxygen, the substitution of compressed coal gases for hydrogen, the continual improvements in methods and means for compression of the gases, and in the form and proportions of the blowpipe, it is not surprising to learn that new commercial applications are continually being found for it, and that in its present form it bids fair to rival in cheapness and to surpass in convenience the various electric methods which have recently been devised for autogenic welding. An account of some of the most recent advances will be found in a paper by Thos. Fletcher (Jour. Soc. Chem. bid. 7, 182-185; 1888) on a "New Commercial Application of Oxygen."
The explosiveness of these gaseous mixtures is one of the well known facts of chemistry, and several examples of accidental explosions have already been cited in these Notes, but as the use of the compressed gases is increasing very rapidly and bids fair to become widely extended, we quote the following "Notes on the Explosion of Gas Cylinder," by W. N. Hartley, from the Chem. News 59, 75-76; 1889:
On January 28 a lamentable and fatal accident happened to Mr. Thomas Arthur Bewley, by the explosion of a cylinder of compressed gas at the shipbuilding yard of Messrs. Bewley & Webb, East Wall, Dublin. The deceased gentleman established machinery for the compression of gases, and supplied the trade with compressed coalgas and oxygen in wrought-iron cylinders. Owing to the uncertainty of the exact cause of the explosion, a good deal of anxiety has been excited amongst the public.
The combustible gas, whether hydrogen or coal-gas, was stored in cylinders painted red and the oxygen in cylinders painted black. This rule was intended to be invariable. On December 27, Mr. Chancellor, of Sackville Street, sent an urgent request for a bottle of oxygen, but there being none of the black cylinders available, owing to the excess of business at Christmas time, Mr. Chancellor was informed that he could be accommodated with oxygen in a red cylinder. This cylinder was returned on January 15. Afterwards, an application was made for a bottle of hydrogen and one of oxygen. It had been forgotten by the deceased that this bottle was charged with oxygen, and, being red, it was simply filled up and sent out as hydrogen.
It was attached to a lime-light apparatus when the discovery was made that it contained mixed gases, for the india-rubber connecting tube was blown off as soon as the gas was ignited at the burner. It was placed on one side and labeled "mixed gases." Two days afterwards the bottle was sent back to Mr. Bewley and was placed on a table in the drawing office, where it remained until the fatal occurrence.
Instead of allowing the gas to blow off, he tested a small quantity of the gas in a tube in presence of one of his foremen, who described the "spirt" with which it went off when a lighted match was applied to the mouth of the tube. The flame seen was a small blue one. He stated to the foreman that, as the amount of inflammable gas was so small, he intended to use the cylinder himself as an oxygen cylinder. As the pressure was higher than he required, a portion of the gas was allowed to pass into another black cylinder, which reduced its tension from 800 to 400 pounds (the breaking strain of the bottle is well over 2000 or 2500 pounds). It must be remarked that the connecting tube did not fit satisfactorily, and that at the time (2 o'clock) a small gas-jet was burning in the room. At 4.25 the explosion occurred, but as no one had been in the drawing office but Mr. Bewley himself, the conditions under which the explosion took place are not precisely known. The evidence, however, is fairly conclusive.
In the first place, it must be stated that the metal of the cylinder was perfectly sound, and in the interior there was no appearance either of oil or of rust. While the upper part of the cylinder was blown to pieces, the body of it struck the arch over a window and caused the wall to bulge; it then ricocheted apparently against the wall, and passed through a window opposite to where it had first struck. The upper end of the cylinder was found at a much greater distance from the building.
One witness, who saw a gauge on the bottle marking 800 pounds, believed that the cylinder had been overcharged, and that disruption occurred simply by the elastic force of the gas. Having examined the premises, I was in a position to state at the inquest that the nature of the explosion was most certainly that of a detonation. The table and drawers were splintered into match-wood, and the glass from the window, as it lay on the ground, presented the peculiarities of fracture which are characteristic of such an explosion.
The examination of the top of the cylinder just below the shoulder showed that the fractured metal at this part had a different appearance from the other fractured surfaces. Instead of being bright it was burnt all the way round, that is to say, covered with magnetic oxide. Moreover, the medical evidence showed that death was caused by shock, and the force of the explosion threw the body out of the room. While the left hand was severed from the arm at four inches above the wrist, the right was charred, and singeing was noticed on the right leg, and the hair was crisp from the same cause. Without doubt the explosion occurred from the detonation of mixed gases within the cylinder.
The valves of both cylinders, which had been connected by a tube previously, were found wide open. The ignition of the gases was most probably caused, not by any chemical action spontaneously taking place within the cylinder, but either by a leakage which was tested by applying a match, or, the leakage being serious, the gases were fired by a lighted gas-jet. It must be remembered that what was believed to be the same gas had previously exploded in the lime-light apparatus, merely blowing off the india-rubber tube, but the valve being but slightly open, the explosion was not communicated to the interior of the cylinder because the pressure was higher and the issuing gas was traveling at too great speed for the temperature of ignition to be maintained in the stream issuing from the small orifice in so large a mass of metal.
For the better understanding of this explanation I will refer to a very simple experiment. Carbon monoxide stored in a gas-holder under a pressure of six inches of water, cannot be burnt from an ordinary gas jet, but if the size of the orifice is enlarged to 1/16 or 1/8 of an inch, it can be made to burn when the pressure is somewhat reduced. There is no material alteration in the conditions of the experiment if the gas be mixed with air or oxygen. In fact, the temperature of ignition cannot be maintained in contact with the cooling mass which surrounds a small orifice, or with the gas under a very rapid rate of flow.
We cannot precisely ascertain the temperature of ignition or the rapidity of explosion of the mixture of gases contained in the cylinder, but it certainly contained a large excess of oxygen, and the conditions under which it was first found to be dangerous were different and less favorable to explosion than after the pressure was reduced.
The verdict of accidental death was coupled with a recommendation that the public should be protected from similar accidents by a Government stamp being fixed to all cylinders used for such purposes. But greater safety would be secured by making the fittings for hydrogen and oxygen cylinders so entirely different that it would be practically impossible to charge a cylinder with the wrong gas.
In Ding. Poly. Jour. 267, 416-419; 1888, is an article by L. Jawein and S. Lamansky, on the "Decrease of the Illuminating Power of Naphtha Gas by Admixture of Air, and the Explosibility of such Mixtures," which contains the results of an examination of such naphtha gas as is manufactured in Russia from naphtha and naphtha residues, for illuminating purposes. Owing to the difficulty of obtaining a general average sample of the gas, the experiments were all made on one day; the required amount of gas being led into a small gasholder, which also contained the air for mixing. The explosibility of the different mixtures was ascertained by subjecting them in a eudiometer to the action of an electric spark, and the following results were thus obtained:
Vol. of Gas. Vol. of Air. Explosion.
1 4.9 — 5-2 None.
1 5.6 — 5.8 Feeble.
1 6.0— 6.5 Violent.
1 7.0— 9.0 Very violent.
1 10.0 — 13.0 Violent
1 14.0 — 16.6 Feeble.
1 17.0 — 17.7 Very Feeble.
1 18.0— 22.0 None.
A mixture of naphtha gas and air is therefore explosive if gas and air be in the proportion of i to 5.6 — 17.7 by volume, or i to 85 — 94.4 by weight. Of course these figures are only accurate for the sample of naphtha gas experimented upon. After all, it is not likely that the figures will vary much with different naphtha gases, the proportion for marsh gas being 1 vol. of gas to 6—16 vol. of air.
We have already recorded in these Notes the suggestion which has been made to employ a mixture of powdered magnesium and. gun-cotton for use as a flash-light in photography, and we have since watched for the accidents which it seemed inevitable must follow. Recently we have learned through private channels that such an accident occurred in New York on the evening of May 1, 1889, while a photographer was attempting to take a picture of the Centennial Arch. For this purpose he employed from six to seven ounces of the mixture, which was placed in a tin tube about six inches long and three and one half to four inches long. This tube was fastened on the end of a wooden handle, so it could be held above the head at arm's length, like a torch. On igniting the mixture and raising the holder above the head, an explosion ensued which was accompanied with a violent report. The photographer was thrown down and rendered unconscious, but fortunately (and probably because of the position in which the tube was held) he escaped with only severe burns on the face, arm and hand.
The Journal of the Society of Chemical Industry 7, 244; 1888, gives the following account of the trade in explosives in France in 1885-1886, as rendered by Her Majesty's Attaché:
"As regards imports, we should remember that gunpowder, guncotton, nitro-glycerine, picrates, and fulminate are all prohibited; that dynamite is allowed to enter at a duty of 2 francs 50 centimes per kilo under special regulations; and that loaded cartridges are admitted, under special arrangements, at a duty of 25 francs per too kilos.
"The imports of dynamite and loaded cartridges into France in 1886 were as follows: From Belgium, 68,605 kilos of dynamite, and cartridges, nil; from England, dynamite, nil, and 133 kilos of cartridges; from Italy, dynamite, nil, and 18 kilos of cartridges; from Switzerland, dynamite, nil, and 1458 kilos of cartridges; giving totals of 68,605 kilos of dynamite and 1609 kilos of cartridges.
"Belgium is the sole importer of dynamite.
"The exports of explosives have been as follows: Military powder, 994 kilos in 1886, and nil in 1885; sporting powder, 30,018 kilos and 13,924 kilos; mining and foreign trade powder, 833,164 kilos and 817,779 kilos.
"The production of dynamite and gunpowder is controlled by the Excise, and official returns show the sales to have been as follows: Sporting powder, 433,518 kilos in 1886 and 490,562 kilos in 1885 ; mining powder, 2,559,128 kilos and 2,815,258 kilos; military powder, 164,286 kilos and 171,888 kilos; powders sold of all kinds on the Swiss and Italian frontier districts of Corsica, Monaco, and Tunisia, 148,967 kilos and 100,193 kilos; dynamite, 396,618 kilos and 447,359 kilos; nitro-glycerine, 668 kilos and 774 kilos.
"The total amount of gunpowder that paid excise was 4,169,081 kilos in 1886, and 4,409,604 kilos in 1885.
"The excise on gunpowder gave 12,970,255 francs (£518,808) in 1886, as against 13,862,441 francs (£554,496) in 1885."
The British consul at Palermo reports that the very unsatisfactory state of the sulphur trade, and of the low prices this article finds in the market, are causing great anxiety to the owners of sulphur mines and to those who trade in sulphur. For the last five years the prices have been steadily decreasing; and whereas at one time merchants insisted on a profit varying from 21 to 42 centimes, they are now only too glad to obtain a profit of 4 and sometimes 2 centimes. The reason for this is to be found in the fact that the production of the mineral during the last thirty years has been excessive, and at present the annual production has been from 600,000 to 700,000 quintals over and above the ordinary consumption. The consequence is that the sulphur accumulates at the mines and at the outports, thereby causing the owners to get rid of their produce at any price. Another circumstance that has tended to depreciate the value of sulphur is that Sicilians cannot be brought to bind themselves into companies or associations; and so the opportunity of being able to close their mines for a few years until the stock is all disposed of at a fair profit is lost.
The French Bulletin du Ministere des Travaux Publics, for November last, says that the total quantity of sulphur contained in the Sicilian mines before workings were commenced is estimated at 65,000,000 tons. The quantity produced from 1831 to 1885 is stated to be 8,353,091 tons, and previous to this period about two millions, making a total of 10,353,091. When it is considered that to obtain this quantity about fifteen million tons were turned over (as generally a third is lost in the treatment), it results that the quantity still available is at least 50 million tons, and supposing that the average production for the future should be maintained at about the same proportion as in past years, the Sicilian mines may continue to be worked for another century.—(Jour. Soc. Chem. Ind. 7, 139, 140; 1889.)
The yield of the sulphur mines in Northern Italy was 21,663 tons in 1887, as against 23,274 tons in 1886. The decrease is partly due to the diminished yield of the Boratella pits, which have been partly worked out, and to the collapse of the Cesena Sulphur Company, Limited, which has pretty well exhausted the basin of the Romagna. The company has spent large sums in the search for new places of production, and in the attempt to work further those commenced by its predecessors, but without avail; and after a few years the company saw itself confined to the pits at Boratella. The production of the company of the Romagna shows a slight increase. The Montivecchio shaft, which belongs to this company, is not yet complete.
Permanent progress is noticeable in the provinces of Pesaro and Urbino. The new shaft in the mine of San Lorenzo, in Zolfinelli, has increased the daily yield of the latter to 200 tons of ore. The loss of work in the Boratella mines has caused many of the workmen to turn again to the old Casalbono mines, which they work in small gangs. The yield has so far only been moderate.
The treatment of the crude sulphur has undergone little modification. A new refinery with three ovens and 34 refining kilns has been erected at Porto Corsini, near Ravenna. It turns out 6000 tons a year. In 1887 the various refineries have produced 24,000 tons of ground sulphur, an increase of 3516 tons over last year. The exact quantity of finely ground sulphur produced is not known, but it probably represents 1 2 of the total refined sulphur. The Albani Pit Company produces special preparations, and to meet the increased demand, especially for their acid sulphur, has induced them to enlarge their new mill at Fano. During the last wine season the Pesaro manufactory turned out 9500 tons of acid sulphur containing 0.22 percent of sulphuric acid, and 1105 tons sulphur containing between one and eight per cent of copper sulphate.
The presence of the above quantity of sulphuric acid has been found the most suitable in the treatment of the vine disease. This acid is not added, as is done in some parts of Italy, but is a natural adjunct of the preparation. Artificial acidification does not yet appear to have been introduced in the factories.
Though almost the whole production was disposed of during the wine season, prices have been kept low by Sicilian competition.
The average price per centner for the year has been:
Crude sulphur, 8.75 francs
Refined in loaves, 10.40 francs
Sulphur in sticks, 13.00 francs
Coarsely powdered, 13.10 francs
Sublimed, 14.50 francs
Acidified powdered, 17.65 francs
Powdered and containing copper, 21.50 francs
Flowers of sulphur, washed, 35.00 francs
The Bulletin du Musee Commercial, March 24, 1888, states that there are in Chili about 50 manufactories of nitrates. The total production of 47 of these factories during the month of December, 1887, amounted to 659,464 metric quintals, or 65,946 tons; it was 67,745 for the month of November. Assuming that these figures were maintained for the other months, there would be produced in 1887 about 800,000 tons. This is almost double the amount exported by Chili in 1886 and 1885, when the syndicate of manufacturers decided to diminish the production.
The Journal of the Society of Chemical Industry 8, 152-153; 1889, states that the shipments of nitrate to the United States during 1888 were 472,500 bags, against 555,000 bags in 1887, 522,750 in 1886, 270,323 in 1885, and 437,234 in 1884. The quantity to arrive for Atlantic ports is 224,000 bags, against 239,000 in 1888, 238,500 in 1887. The total visible supply is 310,000 bags, against 301,940 in 1888, 311,266 in 1887. The quantity to arrive in Europe is 2,527,000, making the visible supply there 3,112,000 bags, against 2,927,500 bags in 1888, and 2,070,000 in 1887. The deliveries at San Francisco during last year were 6o,000 bags, making the total deliveries in this country 515,000 bags, as against 534,347 in 1887 and 454,760 in 1886. In Europe the deliveries were 4,712,000 bags, making the total for the world 5,227,000, as against 4,164,347 in 1887, 3,522,260 in 1886, 3,278,686 in 1885, and 3,974,071 in 1884. Tables are given showing the condition of the trade with the United States and Europe annually from 1883 to 1889. —(Eng. and Mining Journal.)
A. Muntz and V. Marcano have been studying the "Proportion of Nitrates contained in the Rain in Tropical Regions," and they have examined 121 specimens from Caracas, Venezuela, which have yielded them the following average weights of nitric acid per liter: Specimens from July, 1883, to July, 1884, 2.45 mgr.; specimens from January, 1885, to December, 1885, 2.01 mgr.; or for a general mean, 2.23 mgr. The richest specimen of rain (taken October 19, 1883) gave the enormous quantity of 16.25 mgr. and the poorest 0.20 mgr. Comparing these results with those obtained in Europe we find that Boussingault obtained an average of 0.18 mgr. at Liebfrauenberg, Alsace, and Lawes and Gilbert obtained an average of 0.42 mgr. at Rothamsted, England.
The authors attribute the great richness of the rains in the equatorial regions to the high electrical tension and frequent discharges which occur there, and which serve to oxidize the atmospheric nitrogen.—(Compt. rend. 108, 1062-1064; 1889.)
A second edition of "Les Explosifs Modernes," by P. F. Chalon, has appeared, which has been augmented by over one hundred pages, which are devoted to a dictionary, or rather an encyclopedia, of explosives, and which adds very much to the value of the book.
A new book by Lieutenant Max von Forster, superintendent of the gun-cotton factory of Wolff & Co. at Walsrode, is announced under the title " Schiesswolle in ihrer militarischen Verwendung," Berlin, 1888.
The "Lectures on Chemistry and Explosives," which were delivered by Charles E. Munroe to the officers under instruction at the Torpedo Station in i888, have been issued from the Station press in the form of a large octavo of some 320 pages, together with plates illustrating the methods of manufacture of gun-cotton.