liquid in an open vessel, owing to its low specific gravity and the
rapidity of the gas-current, still the general type of the arrangement
seemed so promising that in the next two years there
was laid down in the laboratories of the Royal Institution
a large plant—it weighs 2 tons and contains 3000 ft. of pipe—which
Fig. 4.—Bottom
of Vacuum Vessel.
is designed on precisely the same principles, although
its construction is far more elaborate. The one important
novelty, without which it is practically impossible to succeed,
is the provision of a device to surmount the difficulty of withdrawing
the liquefied hydrogen after it has
been made. The desideratum is really a
means of forming an aperture in the bottom
of a vacuum vessel by which the contained
liquid may be run out. For this purpose the
lower part of the vacuum vessel (D in fig. 3)
containing the jet is modified as shown in
fig. 4; the inner vessel is prolonged in a
fine tube, coiled spirally, which passes
through the outer wall of the vacuum vessel,
and thus sufficient elasticity is obtained to
enable the tube to withstand without fracture
the great contraction consequent on the
extreme cold to which it is subjected. Such
peculiarly shaped vacuum vessels were made by Dewar’s
directions in Germany, and have subsequently been supplied to
and employed by other experimenters.
With the liquefying plant above referred to liquid hydrogen was for the first time collected in an open vessel on the 10th of May 1898. The gas at a pressure of 180 atmospheres was cooled to −205° C. by means of liquid air boiling in vacuo, and was then passed through the nozzle of the regenerative coil, which was enclosed in vacuum vessels in such a way as to exclude external heat as perfectly as possible. In this way some 20 cc. of the liquid had been collected when the experiment came to a premature end, owing to the nozzle of the apparatus becoming blocked by a dense solid—air-ice resulting from the congelation of the air which was present to a minute extent as an impurity in the hydrogen. This accident exemplifies what is a serious trouble encountered in the production of liquid hydrogen, the extreme difficulty of obtaining the gas in a state of sufficient purity, for the presence of 1% of foreign matters, such as air or oxygen, which are more condensible than hydrogen, is sufficient to cause complete stoppage, unless the nozzle valve and jet arrangement is of special construction. In subsequent experiments the liquid was obtained in larger quantities—on the 13th of June 1901 five litres of it were successfully conveyed through the streets of London from the laboratory of the Royal Institution to the rooms of the Royal Society—and it may be said that it is now possible to produce it in any desired amount, subject only to the limitations entailed by expense. Finally, the reduction of hydrogen to a solid state was successfully undertaken in 1899. A portion of the liquid carefully isolated in vacuum-jacketed vessels was suddenly transformed into a white mass resembling frozen foam, when evaporated under an air-pump at a pressure of 30 or 40 mm., and subsequently hydrogen was obtained as a clear transparent ice by immersing a tube containing the liquid in this solid foam.
Liquefaction of Helium.—The subjection of hydrogen completed the experimental proof that all gases can be reduced to the liquid and solid states by the aid of pressure and low temperature, at least so far as regards those in the hands of the chemist at the beginning of the last decade of the 19th century. But a year or so before hydrogen was obtained in the liquid form, a substance known to exist in the sun from spectroscopic researches carried out by Sir Edward Frankland and Sir J. Norman Lockyer was shown by Sir William Ramsay to exist on the earth in small quantities. Helium (q.v.), as this substance was named, was found by experiment to be a gas much less condensable than hydrogen. Dewar in 1901 expanded it from a pressure of 80-100 atmospheres at the temperature of solid hydrogen without perceiving the least indication of liquefaction. Olszewski repeated the experiment in 1905, using the still higher initial compression of 180 atmospheres, but he equally failed to find any evidence of liquefaction, and in consequence was inclined to doubt whether the gas was liquefiable at all, whether in fact it was not a truly “permanent” gas. Other investigators, however, took a different and more hopeful view of the matter. Dewar, for instance (Pres. Address Brit. Assoc., 1902), basing his deductions on the laws established by van der Waals and others from the study of phenomena at much higher temperatures, anticipated that the boiling-point of the substance would be about 5° absolute, so that the liquid would be about four times more volatile than liquid hydrogen, just as liquid hydrogen is four times more volatile than liquid air; and he expressed the opinion that the gas would succumb on being subjected to the process that had succeeded with hydrogen, except that liquid hydrogen, instead of liquid air, evaporating under exhaustion must be employed as the primary cooling agent, and must also be used to surround the vacuum vessel in which the liquid was collected.
Various circumstances combined to prevent Dewar from actually carrying out the operation thus foreshadowed, but his anticipations were justified and the sufficiency of the method he indicated practically proved by Dr H. Kamerlingh Onnes, who, working with the splendid resources of the Leiden cryogenic laboratory, succeeded in obtaining helium in the liquid state on the 10th of July 1908. Having prepared 200 litres of the gas (160 litres in reserve) from monazite sand,[1] he cooled it with exhausted liquid hydrogen to a temperature of 15 or 16° abs., and expanded it through a regenerative coil under a pressure of 50 to 100 atmospheres, making use of the most elaborate precautions to prevent influx of heat and securing the absence of less volatile gases that might freeze and block the tubes of the apparatus by including in the helium circuit charcoal cooled to the temperature of liquid air. Operations began at 5.45 in the morning with the preparation of the necessary liquid hydrogen, of which 20 litres were ready by 1.30. The circulation of the helium was started at 4.30 in the afternoon and was continued until the gas had been pumped round the circuit twenty times; but it was not till 7.30, when the last bottle of liquid hydrogen had been brought into requisition, that the surface of the liquid was seen, by reflection of light from below, standing out sharply like the edge of a knife against the glass wall of the vacuum vessel. Its boiling-point has been determined as being 4° abs., its critical temperature 5°, and its critical pressure not more than three atmospheres. The density of the liquid is found to be 0.015 or about twice that of liquid hydrogen. It could not be solidified even when exhausted under a pressure of 2 mm., which in all probability corresponds to a temperature of 2° abs. (see Communications from the physical laboratory at the University of Leiden, 1908–1909).
The following are brief details respecting some of the more important liquid gases that have become available for study within recent years. (For argon, neon, krypton, &c., see Argon.)
Oxygen.—Liquid oxygen is a mobile transparent-liquid, possessing a faint blue colour. At atmospheric pressure it boils at −181.5° C.; under a reduced pressure of 1 cm. of mercury its temperature falls to −210° C. At the boiling point it has a density of 1.124 according to Olszewski, or of 1.168 according to Wroblewski; Dewar obtained the value 1.1375 as the mean of twenty observations by weighing a number of solid substances in liquid oxygen, noting the apparent relative density of the liquid, and thence calculating its real density, Fizeau’s values for the coefficients of expansion of the solids being employed. The capillarity of liquid oxygen is about one-sixth that of water; it is a non-conductor of electricity, and is strongly magnetic. By its own evaporation it cannot be reduced to the solid state, but exposed to the temperature of liquid hydrogen it is frozen
- ↑ It may be noted that now that the commercial production of oxygen is effected by the liquefaction of air, with separation of its constituents in what is essentially a Coffey still, the chemist has at his command large quantities not only of the less volatile constituents, krypton and xenon, but also of the more volatile ones, neon and helium. Roughly a million volumes of air contain 20 volumes of neon and helium, about 15 of the former to 5 of the latter, approximately 1 volume of hydrogen being associated with them, so that in view of the enormous amounts of oxygen that are produced, helium can be obtained in practically any quantity directly from the atmosphere.
