Popular Science Monthly/Volume 26/December 1884/Liquefaction of the Elementary Gases
|LIQUEFACTION OF THE ELEMENTARY GASES.|
THE earlier experiments of MM. Cailletet and Raoul Pictet in the liquefaction of gases, and the apparatus by means of which they performed the process, were described in "The Popular Science Monthly," March and May, 1878. The experiments have since been continued and improved upon by MM. Cailletet and Pictet, and others, with more complete results than had been attained at the time the first reports were published, and with the elucidation of some novel properties of gases, and the disclosure of relations, previously not well understood, between the gaseous and the liquid condition. The experiments of Faraday, in the compression of gases by the combined agency of pressure and extreme cold, left six gases, which still refused to enter into the liquid state. They were the two elements of the atmosphere (oxygen and nitrogen), nitric oxide, marsh-gas, carbonic oxide, and hydrogen. Many new experiments were tried before the principle that governs the change from the gaseous to the liquid, or from the liquid to the gaseous form, was discovered. Aimé sank manometers filled with air into the sea till the pressure upon them was equal to that of four hundred atmospheres; Berthelot, by the expansion of mercury in a thermometer-tube, succeeded in exerting a pressure of seven hundred and eighty atmospheres upon oxygen. Both series of experiments were without result. M. Cailletet, having fruitlessly subjected air and hydrogen to a pressure of one thousand atmospheres, came to the conclusion that it was impossible to liquefy those gases at the ordinary temperature by pressure alone. Previously it had been thought that the obstacle to condensing gases by pressure alone lay in the difficulty of obtaining sufficient pressure, or in that of finding a vessel suitable for manipulation that would be capable of resisting it. M. Cailletet's thought led to the discovery of another fundamental property of gases.
The experiments of Despretz and Regnault had shown that the scope of Mariotte's law (that the volume of gases increases or diminishes inversely as the pressure upon them) was limited, and that its limits were different with different substances. Andrews confirmed the observations of these investigators, and extended them. Compressing carbonic acid at 13° C. (55° Fahr.), he found that the rate of diminution in volume increased more rapidly than Mariotte's law demanded, and at a progressive rate. At fifty atmospheres the gas all at once assumed the liquid form, became very dense, and fell to the bottom of the vessel, where it remained separated from its vapor by a clearly defined surface, like that which distinguishes water in the air. Experimenting in the same way with the gas at a higher temperature (21° C, or 70° Fahr.), he found that the same result was produced, but more slowly; and it seemed to be heralded in advance by a more rapid diminution in volume previous to the beginning of the change, which continued after the process had been accomplished; as if an anticipatory preparation for the liquid state were going on previous to the completion of the change. Performing the experiment again at 32° C. (90° Fahr.), the anticipatory preparation and the after continuation of the contraction were more marked, and, instead of a separate and distinct liquid, wavy and mobile striæ were perceived on the sides of the vessel as the only signs of a change of state which had not yet been effected. At temperatures above 32° C. (90° Fahr,), there were neither striæ nor liquefaction, but there seemed to be a suggestion of them, for, under a particular degree of pressure, the density of the gas was augmented, and its volume diminished at an increasing rate. The temperature of 32° C. (90° Fahr.) is, then, a limit, marking a division between the temperatures which permit and those which prevent liquefaction; it is the critical point, at which is defined the separation, for carbonic acid, between two very distinct states of matter. Below this point, the particular matter may assume the aspect of a liquid; above it, the gas can not change its appearance, but enters into the opposite constitution from that of a liquid.
Generally, a liquid has considerably greater density than its vapor. But, if a vessel containing both is heated, the liquid experiences a dilatation which is gradually augmented till it equals and even exceeds that of the gas; whence, of course, an equal volume of the liquid will weigh less and less. On the other hand, a constantly larger quantity of vapor is formed, which accumulates above the liquid and becomes heavier and heavier. Now, if the density of the vapor increases, and that of the liquid diminishes, they will reach a point, under a suitable temperature, when they will be the same. There will then be no reason for the liquid to sink or the vapor to rise, or for the existence of any line of separation between them, and they will be mixed and confounded. They will no longer be distinguishable by their heat of constitution. It is true that, in passing into the state of a vapor, a liquid absorbs a great deal of latent heat, but that is employed in scattering the molecules and keeping them at a distance; and there will be none of it if the distance does not increase. We are then, at this stage of our experiments, in the presence of a critical point, at which we do not know whether the matter is liquid or gaseous; for, in either condition, it has the same density, the same heat of constitution, and the same properties. It is a new state, the gaso-liquid state. An experiment of Cagniard-Latour re-enforced this explanation of the phenomena. Heating ether in closed vessels to high temperatures, he brought it to a point where the liquid could be made wholly to disappear, or to be suddenly reformed on the slightest elevation or the slightest depression of temperature, accordingly as it was raised just above or cooled to just below the critical point. The discovery of these properties suggested an explanation of the failure of previous attempts to liquefy air. Air at ordinary low temperatures is in the gaso-liquid condition, and its liquefaction is not possible except when a difference exists between the density of the vapor and that of the liquid greater than it is possible to produce under any conditions than can exist then. It was necessary to reduce the temperature to below the critical point; and it was by adopting this course that MM. Cailletet and Raoul Pictet achieved their success. The rapid escape of the compressed gas itself from a condition of great condensation at an extremely low temperature was employed as the agent for producing a greater degree of cold than it had been possible before to obtain. M. Cailletet used oxygen escaping at -29° C. from a pressure of three hundred atmospheres; M. Raoul Pictet, the same gas escaping at -140° from a pressure of three hundred and twenty atmospheres; and both obtained oxygen and nitrogen, and M. Pictet hydrogen in what they thought was a liquid, and possibly even in a solid form.
Still, it could not be asserted that hydrogen and the elements of the air had been completely liquefied. These gases had not yet been seen collected in the static condition at the bottom of a tube and separated from their vapors by the clearly defined concave surface, which is called a meniscus. The experiments had, however, proved that liquefaction is possible at a temperature of below -120° C. (-184° Fahr.). To make the process practicable, it was only necessary to find sufficiently powerful refrigerants; and these were looked for among gases that had proved more refractory than carbonic acid and protoxide of nitrogen. M. Cailletet selected ethylene, a hydrocarbon of the same composition as illuminating gas, which, when liquefied by the aid of carbonic acid and a pressure of thirty-six atmospheres, boils at -103° C. (-153° Fahr.). M. Wroblewski, of Cracow, who had witnessed some of M. Cailletet's experiments, and obtained his apparatus, and M. Olzewski, in association with him, also experimented with ethylene, and had the pleasure of recording their first complete success early in April, 1883. Causing liquid ethylene to boil in an air-pump vacuum at -103° C, they were able to produce a temperature of -1,50° C. (-238° Fahr.), the lowest that had ever been observed. Oxygen, having been previously compressed in a glass tube, became a permanent liquid, with a clearly defined meniscus. It presented itself, like the other liquefied gases, under the form of a transparent and colorless substance, resembling water, but a little less dense. Its critical point was marked at -113° C. (-171° Fahr.), below which the liquid could be formed, but never above it; while it boiled rapidly at -186° C. (-303° Fahr.). A few days afterward, the Polish professors obtained the liquefaction of nitrogen, a more refractory gas, under a pressure of thirty-six atmospheres, at -146° C. (-231° Fahr.). Long, difficult, and expensive operations were required to produce this result, for the extreme degree of cold it demanded had to be produced by boiling large quantities of ethylene in a vacuum. M. Cailletet devised a cheaper process, by employing another hydrocarbon that rises from the mud of marshes, and is called formene. It is less easily liquefied than ethylene, but for that very reason can be boiled in the air at a lower temperature, or at -160° C. (-256° Fahr.); and at this temperature nitrogen and oxygen can be liquefied in a bath of formene as readily as sulphurous acid in the common freezing mixture.
MM. Cailletet, Wroblewski, and Olzewski have continued their experiments in liquefaction and acquired increased facility in the handling of liquid ethylene, formene, atmospheric air, oxygen, and nitrogen. M. Olzewski was able to report to the French Academy of Sciences, on the 21st of July, 1884, that by placing liquefied nitrogen in a vacuum he had succeeded in producing a temperature of -213° C. (-351° Fahr.), under which hydrogen was liquefied. Contrary to the suppositions founded on the metallic behavior of this element, that it would present the appearance of a molten metal, like mercury, the liquid had the mobile behavior and the transparency of the hydrocarbons.