from water by exposure to sulphuric acid, to a pressure of about
four atmospheres, when the same yellow fluid was produced
(Phil. Trans., 1823, 113, pp. 160-165). He proceeded to experiment
with a number of other gases subjected in sealed tubes to
the pressure caused by their own continuous production by
chemical action, and in the course of a few weeks liquefied
sulphurous acid, sulphuretted hydrogen, carbonic acid, euchlorine,
nitrous acid, cyanogen, ammonia and muriatic acid, the last
of which, however, had previously been obtained by Davy.
But he failed with hydrogen, oxygen, fluoboric, fluosilicic and
phosphuretted hydrogen gases (Phil. Trans., ib. pp. 189-198).
Early in the following year he published an “Historical statement
respecting the liquefaction of gases” (Quart. Journ. Sci., 1824,
16, pp. 229-240), in which he detailed several recorded cases in
which previous experimenters had reduced certain gases to
their liquid state.
In 1835 Thilorier, by acting on bicarbonate of soda with sulphuric acid in a closed vessel and evacuating the gas thus obtained under pressure into a second vessel, was able to accumulate large quantities of liquid carbonic acid, and found that when the liquid was suddenly ejected into the air a portion of it was solidified into a snow-like substance (Ann. chim. phys., 1835, 60, pp. 427-432). Four years later J. K. Mitchell in America, by mixing this snow with ether and exhausting it under an air pump, attained a minimum temperature of 146° below zero F., by the aid of which he froze sulphurous acid gas to a solid.
Stimulated by Thilorier’s results and by considerations arising out of the work of J. C. Cagniard de la Tour (Ann. chim. phys., 1822, 21, pp. 127 and 178, and 1823, 22, p. 410), which appeared to him to indicate that gases would pass by some simple law into the liquid state, Faraday returned to the subject about 1844, in the “hope of seeing nitrogen, oxygen and hydrogen either as liquid or solid bodies, and the latter probably as a metal” (Phil. Trans., 1845, 135, pp. 155-157). On the basis of Cagniard de la Tour’s observation that at a certain temperature a liquid under sufficient pressure becomes a vapour or gas having the same bulk as the liquid, he inferred that “at this temperature or one a little higher, it is not likely that any increase of pressure, except perhaps one exceedingly great, would convert the gas into a liquid.” He further surmised that the Cagniard de la Tour condition might have its point of temperature for oxygen, nitrogen, hydrogen, &c., below that belonging to the bath of solid carbonic acid and ether, and he realized that in that case no pressure which any apparatus would be able to bear would be able to bring those gases into the liquid or solid state, which would require a still greater degree of cold. To fulfil this condition he immersed the tubes containing his gases in a bath of solid carbonic acid and ether, the temperature of which was reduced by exhaustion under the air pump to −166° F., or a little lower, and at the same time he subjected the gases to pressures up to 50 atmospheres by the use of two pumps working in series. In this way he added six substances, usually gaseous, to the list of those that could be obtained in the liquid state, and reduced seven, including ammonia, nitrous oxide and sulphuretted hydrogen, into the solid form, at the same time effecting a number of valuable determinations of vapour tensions. But he failed to condense oxygen, nitrogen and hydrogen, the original objects of his pursuit, though he found reason to think that “further diminution of temperature and improved apparatus for pressure may very well be expected to give us these bodies in the liquid or solid state.” His surmise that increased pressure alone would not suffice to bring about change of state in these gases was confirmed by subsequent investigators, such as M. P. E. Berthelot, who in 1850 compressed oxygen to 780 atmospheres (Ann. chim. phys., 1850, 30, p. 237), and Natterer, who a few years later subjected the permanent gases to a pressure of 2790 atmospheres, without result; and in 1869 Thomas Andrews (Phil. Trans., 11) by his researches on carbonic acid finally established the conception of the “critical temperature” as that temperature, differing for different bodies, above which no gas can be made to assume the liquid state, no matter what pressure it be subjected to (see Condensation of Gases).
About 1877 the problem of liquefying the permanent gases was taken up by L. P. Cailletet and R. P. Pictet, working almost simultaneously though independently. The former relied on the cold produced by the sudden expansion of the gases at high compression. By means of a specially designed pump he compressed about 100 cc. of oxygen in a narrow glass tube to about 200 atmospheres, at the same time cooling it to about −29° C., 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
