“boiled” after being formed. It is found that the ingot of calcium carbide formed in the furnace, although itself consisting of pure crystalline calcium carbide, is nearly always surrounded by a crust which contains a certain proportion of imperfectly converted constituents, and therefore gives a lower yield of acetylene than the carbide itself. In breaking up and sending out the carbide for commercial work, packed in air-tight drums, the crust is removed by a sand blast. A statement of the amount made per kilowatt hour may be misleading, since a certain amount of loss is of necessity entailed during this process. For instance, in practical working it has been found that a furnace return of 0·504 ℔ per kilowatt hour is brought down to 0·406 ℔ per kilowatt hour when the material has been broken up, sorted and packed in air-tight drums. In the tapping process a fixed crucible is used, lined with carbon, the electrode is nearly as big as the crucible and a much higher current density is used. The carbide is heated to complete liquefaction and tapped at short intervals. There is no unreduced material, and the process is considerably simplified, while less expensive plant is required. The run carbide, however, is never so rich as the ingot carbide, since an excess of lime is nearly always used in the mixture to act as a flux, and this remaining in the carbide lowers its gas-yielding power. Many attempts have been made to produce the substance without electricity, but have met with no commercial success.
Calcium carbide, as formed in the electric furnace, is a beautiful crystalline semi-metallic solid, having a density of 2·22, and showing a fracture which is often shot with iridescent colours. It can be kept unaltered in dry air, but the smallest trace of moisture in the atmosphere leads to Properties
of calcium carbide.the evolution of minute quantities of acetylene and gives it a distinctive odour. It is infusible at temperatures up to 2000° C., but can be fused in the electric arc. When heated to a temperature of 245° C. in a stream of chlorine gas it becomes incandescent, forming calcium chloride and liberating carbon, and it can also be made to burn in oxygen at a dull red heat, leaving behind a residue of calcium carbonate. Under the same conditions it becomes incandescent in the vapour of sulphur, yielding calcium sulphide and carbon disulphide; the vapour of phosphorus will also unite with it at a red heat. Acted upon by water it is at once decomposed, yielding acetylene and calcium hydrate. Pure crystalline calcium carbide yields 5·8 cubic feet of acetylene per pound at ordinary temperatures, but the carbide as sold commercially, being a mixture of the pure crystalline material with the crust which in the electric furnace surrounds the ingot, yields at the best 5 cubic feet of gas per pound under proper conditions of generation. The volume of gas obtained, however, depends very largely upon the form of apparatus used, and while some will give the full volume, other apparatus will only yield, with the same carbide, 334 feet.
Impurities. The purity of the carbide entirely depends on the purity of the material used in its manufacture, and before this fact had been fully grasped by manufacturers, and only the purest material obtainable employed, it contained notable quantities of compounds which during its decomposition by water yielded a somewhat high proportion of impurities in the acetylene generated from it. Although at the present time a marvellous improvement has taken place all round in the quality of the carbide produced, the acetylene nearly always contains minute traces of hydrogen, ammonia, sulphuretted hydrogen, phosphuretted hydrogen, silicon hydride, nitrogen and oxygen, and sometimes minute traces of carbon monoxide and dioxide. The formation of hydrogen is caused by small traces of metallic calcium occasionally found free in the carbide, and cases have been known where this was present in such quantities that the evolved gas contained nearly 20% of hydrogen. This takes place when in the manufacture of the carbide the material is kept too long in contact with the arc, since this overheating causes the dissociation of some of the calcium carbide and the solution of metallic calcium in the remainder. The presence of free hydrogen is nearly always accompanied by silicon hydride formed by the combination of the nascent hydrogen with the silicon in the carbide. The ammonia found in the acetylene is probably partly due to the presence of magnesium nitride in the carbide.
On decomposition by water, ammonia is produced by the action of steam or of nascent hydrogen on the nitride, the quantity formed depending very largely upon the temperature at which the carbide is decomposed. The formation of nitrides and cyanamides by actions of this kind and their easy conversion into ammonia is a useful method for fixing the nitrogen of the atmosphere and rendering it available for manurial purposes. Sulphuretted hydrogen, which is invariably present in commercial acetylene, is formed by the decomposition of aluminium sulphide. A. Mourlot has shown that aluminium sulphide, zinc sulphide and cadmium sulphide are the only sulphur compounds which can resist the heat of the electric furnace without decomposition or volatilization, and of these aluminium sulphide is the only one which is decomposed by water with the evolution of sulphuretted hydrogen. In the early samples of carbide this compound used to be present in considerable quantity, but now rarely more than 110% is to be found. Phosphuretted hydrogen, one of the most important impurities, which has been blamed for the haze formed by the combustion of acetylene under certain conditions, is produced by the action of water upon traces of calcium phosphide found in carbide. Although at first it was no uncommon thing to find 12% of phosphuretted hydrogen present in the acetylene, this has now been so reduced by the use of pure materials that the quantity is rarely above 0·15%, and it is often not one-fifth of that amount.
In the generation of acetylene from calcium carbide and water, all that has to be done is to bring these two compounds into contact, when they mutually react upon each other with the formation of lime and acetylene, while, if there be sufficient water present, the lime combines with it toGeneration of acetylene from carbide. form calcium hydrate.
| Calcium carbide. Water. Acetylene. Lime. |
| CaC2+H2O = C2H2 + CaO |
| Lime. Water. Calcium hydrate. |
| CaO +H2O = Ca(HO)2 |
The decomposition of the carbide by water may be brought about either by bringing the water slowly into contact with an excess of carbide, or by dropping the carbide into an excess of water, and these two main operations again may be varied by innumerable ingenious devices by which the rapidity of the contact may be modified or even eventually stopped. The result is that although the forms of apparatus utilized for this purpose are all based on the one fundamental principle of bringing about the contact of the carbide with the water which is to enter into double decomposition with it, they have been multiplied in number to a very large extent by the methods employed in order to ensure control in working, and to get away from the dangers and inconveniences which are inseparable from a too rapid generation.
In attempting to classify acetylene generators some authorities have divided them into as many as six different classes, but this is hardly necessary, as they may be divided into two main classes—first, those in which water is brought in contact with the carbide, the carbide being in Generators.excess during the first portion of the operation; and, second, those in which the carbide is thrown into water, the amount of water present being always in excess. The first class may again be subdivided into generators in which the water rises in contact with the carbide, in which it drips upon the carbide, and in which a vessel full of carbide is lowered into water and again with-drawn as generation becomes excessive. Some of these generators are constructed to make the gas only as fast as it is consumed at the burner, with the object of saving the expense and room which would be involved by a storage-holder. Generators with devices for regulating and stopping at will the action going on are generally termed “automatic.” Another set merely aims at developing the gas from the carbide and putting it into a storage-holder with as little loss as possible, and these are termed
