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قراءة كتاب Encyclopaedia Britannica, 11th Edition, "Liquid Gases" to "Logar" Volume 16, Slice 7
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Encyclopaedia Britannica, 11th Edition, "Liquid Gases" to "Logar" Volume 16, Slice 7
and on suddenly releasing the pressure he saw momentarily in the interior of the tube a mist (brouillard), from which he inferred the presence of a vapour very near its point of liquefaction. A few days later he repeated the experiment with hydrogen, using a pressure of nearly 300 atmospheres, and observed in his tube an exceedingly fine and subtle fog which vanished almost instantaneously. At the time when these experiments were carried out it was generally accepted that the mist or fog consisted of minute drops of the liquefied gases. Even had this been the case, the problem would not have been completely solved, for Cailletet was unable to collect the drops in the form of a true stable liquid, and at the best obtained a “dynamic” not a “static” liquid, the gas being reduced to a form that bears the same relation to a true liquid that the partially condensed steam issuing from the funnel of a locomotive bears to water standing in a tumbler. But subsequent knowledge showed that even this proximate liquefaction could not have taken place, and that the fog could not have consisted of drops of liquid hydrogen, because the cooling produced by the adiabatic expansion would give a temperature of only 44° abs., which is certainly above the critical temperature of hydrogen. Pictet again announced that on opening the tap of a vessel containing hydrogen at a pressure of 650 atmospheres and cooled by the cascade method (see Condensation of Gases) to −140° C., he saw issuing from the orifice an opaque jet which he assumed to consist of hydrogen in the liquid form or in the liquid and solid forms mixed. But he was no more successful than Cailletet in collecting any of the liquid, which—whatever else it may have been, whether ordinary air or impurities associated with the hydrogen—cannot have been hydrogen because the means he employed were insufficient to reduce the gas to what has subsequently been ascertained to be its critical point, below which of course liquefaction is impossible. It need scarcely be added that if the liquefaction of hydrogen be rejected a fortiori Pictet’s claim to have effected its solidification falls to the ground.
After Cailletet and Pictet, the next important names in the history of the liquefaction of gases are those of Z. F. Wroblewski and K. S. Olszewski, who for some years worked together at Cracow. In April 1883 the former announced to the French Academy that he had obtained oxygen in a completely liquid state and (a few days later) that nitrogen at a temperature of −136° C., reduced suddenly from a pressure of 150 atmospheres to one of 50, had been seen as a liquid which showed a true meniscus, but disappeared in a few seconds. But with hydrogen treated in the same way he failed to obtain even the mist reported by Cailletet. At the beginning of 1884 he performed a more satisfactory experiment. Cooling hydrogen in a capillary glass tube to the temperature of liquid oxygen, he expanded it quickly from 100 atmospheres to one, and obtained the appearance of an instantaneous ebullition. Olszewski confirmed this result by expanding from a pressure of 190 atmospheres the gas cooled by liquid oxygen and nitrogen boiling under reduced pressure, and even announced that he saw it running down the walls of the tube as a colourless liquid.
Wroblewski, however, was unable to observe this phenomenon, and Olszewski himself, when seven years later he repeated the experiment in the more favourable conditions afforded by a larger apparatus, was unable to produce again the colourless drops he had previously reported: the phenomenon of the appearance of sudden ebullition indeed lasted longer, but he failed to perceive any meniscus such as would have been a certain indication of the presence of a true liquid. Still, though neither of these investigators succeeded in reaching the goal at which they aimed, their work was of great value in elucidating the conditions of the problem and in perfecting the details of the apparatus employed. Wroblewski in particular devoted the closing years of his life to a most valuable investigation of the isothermals of hydrogen at low temperatures. From the data thus obtained he constructed a van der Waals equation which enabled him to calculate the critical temperature, pressure and density of hydrogen with very much greater certainty than had previously been possible. Liquid oxygen, liquid nitrogen and liquid air—the last was first made by Wroblewski in 1885—became something more than mere curiosities of the laboratory, and by the year 1891 were produced in such quantities as to be available for the purposes of scientific research. Still, nothing was added to the general principles upon which the work of Cailletet and Pictet was based, and the “cascade” method, together with adiabatic expansion from high compression (see Condensation of Gases), remained the only means of procedure at the disposal of experimenters in this branch of physics.
In some quarters a certain amount of doubt appears to have arisen as to the sufficiency of these methods for the liquefaction of hydrogen. Olszewski, for example, in 1895 pointed out that the succession of less and less condensible gases necessary for the cascade method breaks down between nitrogen and hydrogen, and he gave as a reason for hydrogen not having been reduced to the condition of a static liquid the non-existence of a gas intermediate in volatility between those two. By 1894 attempts had been made in the Royal Institution laboratories to manufacture an artificial gas of this nature by adding a small proportion of air to the hydrogen, so as to get a mixture with a critical point of about −200° C. When such a mixture was cooled to that temperature and expanded from a high degree of compression into a vacuum vessel, the result was a white mass of solid air together with a clear liquid of very low density. This was in all probability hydrogen in the true liquid state, but it was not found possible to collect it owing to its extreme volatility. Whether this artificial gas might ultimately have enabled liquid hydrogen to be collected in open vessels we cannot say, for experiments with it were abandoned in favour of other measures, which led finally to a more assured success.
Vacuum Vessels.—The problem involved in the liquefaction of hydrogen was in reality a double one. In the first place, the gas had to be cooled to such a temperature that the change to the liquid state was rendered possible. In the second, means had to be discovered for protecting it, when so cooled, from the influx of external heat, and since the rate at which heat is transferred from one body to another increases very rapidly with the difference between their temperatures, the question of efficient heat insulation became at once more difficult and more urgent in proportion to the degree of cold attained. The second part of the problem was in fact solved first. Of course packing with non-conducting materials was an obvious expedient when it was not necessary that the contents of the apparatus should be visible to the eye, but in the numerous instances when this was not the case such measures were out of the question. Attempts were made to secure the desired end by surrounding the vessel that contained the cooled or liquid gas with a succession of other vessels, through which was conducted the vapour given off from the interior one. Such devices involved awkward complications in the arrangement of the apparatus, and besides were not as a rule very efficient, although some workers, e.g. Dr Kamerlingh Onnes, of Leiden, reported some success with their use. In 1892 it occurred to Dewar that the principle of an