Page:EB1911 - Volume 01.djvu/169

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138
ACETYLENE
  

fire as they reach the surface, and if a jet of acetylene be passed up into a bottle of chlorine it takes fire and burns with a heavy red flame, depositing its carbon in the form of soot. If chlorine be bubbled up into a jar of acetylene standing over water, a violent explosion, attended with a flash of intense light and the deposition of carbon, at once takes place. When the gas is kept in a small glass holder exposed to direct sunlight, the surface of the glass soon becomes dimmed, and W. A. Bone has shown that when exposed for some time to the sun’s rays it undergoes certain polymerization changes which lead to the deposition of a film of heavy hydrocarbons on the surface of the tube. It has also been observed by L. Cailletet and later by P. Villard that when allowed to stand in the presence of water at a low temperature a solid hydrate is formed.The polymer-ization of acetylene. Acetylene is readily decomposed by heat, polymerizing under its influence to form an enormous number of organic compounds; indeed the gas, which can itself be directly prepared from its constituents, carbon and hydrogen, under the influence of the electric arc, can be made the starting point for the construction of an enormous number of different organic compounds of a complex character. In contact with nascent hydrogen it builds up ethylene; ethylene acted upon by sulphuric acid yields ethyl sulphuric acid; this can again be decomposed in the presence of water to yield alcohol, and it has also been proposed to manufacture sugar from this body. Picric acid can also be obtained from it by first treating acetylene with sulphuric acid, converting the product into phenol by solution in potash and then treating the phenol with fuming nitric acid.

Acetylene is one of those bodies the formation of which is attended with the disappearance of heat, and it is for this reason termed an “endothermic” compound, in contradistinction to those bodies which evolve heat in their formation, and which are called “exothermic.” Such endothermic bodies are nearly always found to show Endothermic nature of acetylene.considerable violence in their decomposition, as the heat of formation stored up within them is then liberated as sensible heat, and it is undoubtedly this property of acetylene gas which leads to its easy detonation by either heat or a shock from an explosion of fulminating mercury when in contact with it under pressure. The observation that acetylene can be resolved into its constituents by detonation is due to Berthelot, who started an explosive wave in it by firing a charge of 0·1 gram of mercury fulminate. It has since been shown, however, that unless the gas is at a pressure of more than two atmospheres this wave soon dies out, and the decomposition is only propagated a few inches from the detonator. Heated in contact with air to a temperature of 480° C., acetylene ignites and burns with a flame, the appearance of which varies with the way in which it is brought in contact with the air. With the gas in excess a heavy lurid flame emitting dense volumes of smoke results, whilst if it be driven out in a sufficiently thin sheet, it burns with a flame of intense brilliancy and almost perfect whiteness, by the light of which colours can be judged as well as they can by daylight. Having its ignition point below that of ordinary gas, it can be ignited by any red-hot carbonaceous matter, such as the brightly glowing end of a cigar. For its complete combustion a volume of acetylene needs approximately twelve volumes of air, forming as products of combustion carbon dioxide and water vapour. When, however, the air is present in much smaller ratio the combustion is incomplete, and carbon, carbon monoxide, carbon dioxide, hydrogen and water vapour are produced. This is well shown by taking a cylinder one-half full of acetylene and one-half of air; on applying a light to the mixture a lurid flame runs down the cylinder and a cloud of soot is thrown up, the cylinder also being thickly coated with it, and often containing a ball of carbon. If now, after a few moments’ interval to allow some air to diffuse into the cylinder, a taper again be applied, an explosion takes place, due to a mixture of carbon monoxide and air. It is probable that when a flame is smoking badly, distinct traces of carbon monoxide are being produced, but when an acetylene flame burns properly the products are as harmless as those of coal gas, and, light for light, less in amount. Mixed with air, like every other combustible gas, acetylene forms an explosive mixture. F. Clowes has shown that it has a wider range of explosive proportions when mixed with air than any of the other combustible gases, the limiting percentages being as follows:—

Acetylene . . . . . . . 3 to 82
Hydrogen . . . . . . . 5 to 72
Carbon monoxide . . . . 13 to 75
Ethylene . . . . . . . . 4 to 22
Methane . . . . . . . . 5 to 13

The methods which can be and have been employed from time to time for the formation of acetylene in small quantities are exceedingly numerous. Before the commercial production of calcium carbide made it one of the most easily obtainable gases, the processes which were most Methods of production.largely adopted for its preparation in laboratories were:-first, the decomposition of ethylene bromide by dropping it slowly into a boiling solution of alcoholic potash, and purifying the evolved gas from the volatile bromethylene by washing it through a second flask containing a boiling solution of alcoholic potash, or by passing it over moderately heated soda lime; and, second, the more ordinarily adopted process of passing the products of incomplete combustion from a Bunsen burner, the flame of which had struck back, through an ammoniacal solution of cuprous chloride, when the red copper acetylide was produced. This on being washed and decomposed with hydrochloric acid yielded a stream of acetylene gas. This second method of production has the great drawback that, unless proper precautions are taken to purify the gas obtained from the copper acetylide, it is always contaminated with certain chlorine derivatives of acetylene. Edmund Davy first made acetylene in 1836 from a compound produced during the manufacture of potassium from potassium tartrate and charcoal, which under certain conditions yielded a black compound decomposed by water with considerable violence and the evolution of acetylene. This compound was afterwards fully investigated by J. J. Berzelius, who showed it to be potassium carbide. He also made the corresponding sodium compound and showed that it evolved the same gas, whilst in 1862 F. Wöhler first made calcium carbide, and found that water decomposed it into lime and acetylene. It was not, however, until 1892 that the almost simultaneous discovery was made by T. L. Willson in America and H. Moissan in France that if lime and carbon be fused together at the temperature of the electric furnace, the lime is reduced to calcium, which unites with the excess of carbon present to form calcium carbide.Manufacture of calcium carbide. The cheap production of this material and the easy liberation by its aid of acetylene at once gave the gas a position of commercial importance. In the manufacture of calcium carbide in the electric furnace, lime and anthracite of the highest possible degree of purity are employed. A good working mixture of these materials may be taken as being 100 parts by weight of lime with 68 parts by weight of carbonaceous material. About 1.8 ℔ of this is used up for each pound of carbide produced. The two principal processes utilized in making calcium carbide by electrical power are the ingot process and the tapping process. In the former, the anthracite and lime are ground and carefully mixed in the right proportions to suit the chemical actions involved. The arc is struck in a crucible into which the mixture is allowed to flow, partially filling it. An ingot gradually builds up from the bottom of the crucible, the carbon electrode being raised from time to time automatically or by hand to suit the diminution of resistance due to the shortening of the arc by the rising ingot. The crucible is of metal and considerably larger than the ingot, the latter being surrounded by a mass of unreduced material which protects the crucible from the intense heat. When the ingot has been made and the crucible is full, the latter is withdrawn and another substituted. The process is not continuous, but a change of crucibles only takes two or three minutes under the best conditions, and only occurs every ten or fifteen hours. The essence of this process is that the coke and lime are only heated to the point of combination, and are not