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 arrangement he had used nearly twenty years before for some calorimetric experiments on the physical constants of hydrogenium, which was a natural deduction from the work of Dulong and Petit on radiation, might be employed with advantage as well to protect cold substances from heat as hot ones from cold. He therefore tried the effect of surrounding his liquefied gas with a highly exhausted space. The result was entirely successful. Experiment showed that liquid air contained in a glass vessel with two walls, the space between which was a high vacuum, evaporated at only one fifth the rate it did when in an ordinary vessel surrounded with air at atmospheric pressure, the convective transference of heat by means of the gas particles being enormously reduced owing to the vacuum. But in addition these vessels lent themselves to an arrangement by which radiant heat could still further be cut off, since it was found that when the inner wall was coated with a bright deposit of silver, the influx of heat was diminished to one-sixth of the amount existing without the metallic coating. The total effect, therefore, of the high vacuum and silvering is to reduce the in-going heat to one-thirtieth part. In making such vessels a mercurial vacuum has been found very satisfactory. The vessel in which the vacuum is to be produced is provided with a small subsidiary vessel joined by a narrow tube with the main vessel, and connected with a powerful air-pump. A quantity of mercury having been placed in it, it is heated in an oil- or air-bath to about 200° C., so as to volatilize the mercury, the vapour of which is removed by the pump. After the process has gone on for some time, the pipe leading to the pump is sealed off, the vessel immediately removed from the bath, and the small subsidiary part immersed in some cooling agent such as solid carbonic acid or liquid air, whereby the mercury vapour is condensed in the small vessel and a vacuum of enormous tenuity left in the large one. The final step is to seal off the tube connecting the two. In this way a vacuum may be produced having a vapour pressure of about the hundred-millionth of an atmosphere at 0° C. If, however, some liquid mercury be left in the space in which the vacuum is produced, and the containing part of the vessel be filled with liquid air, the bright mirror of mercury which is deposited on the inside wall of the bulb is still more effective than silver in protecting the chamber from the influx of heat, owing to the high refractive index, which involves great reflecting power, and the bad heat-conducting powers of mercury.
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| Fig. 1.—Metallic Vacuum Vessel. |
With the discovery of the remarkable power of gas absorption possessed by charcoal cooled to a low temperature (see below), it became possible to make these vessels of metal. Previously this could not be done with success, because gas occluded in the metal gradually escaped and vitiated the vacuum; but now any stray gas may be absorbed by means of charcoal so placed in a pocket within the vacuous space that it is cooled by the liquid in the interior of the vessel. Metal vacuum vessels (fig. 1), of a capacity of from 2 to 20 litres, may be formed of brass, copper, nickel or tinned iron, with necks of some alloy that is a bad conductor of heat, silvered glass vacuum cylinders being fitted as stoppers. Such flasks, when properly constructed, have an efficiency equal to that of the chemically-silvered glass vacuum vessels now commonly used in low temperature investigations, and they are obviously better adapted for transport. The principle of the Dewar vessel is utilized in the Thermos flasks which are now extensively manufactured and employed for keeping liquids warm in hospitals, &c.
Thermal Transparency at Low Temperatures.—The proposition, once enunciated by Pictet, that at low temperatures all substances have practically the same thermal transparency, and are equally ineffective as non-conductors of heat, is based on erroneous observations. It is true that if the space between the two walls of a double-walled vessel is packed with substances like carbon, magnesia, or silica, liquid air placed in the interior will boil off even more quickly than it will when the space merely contains air at atmospheric pressure; but in such cases it is not so much the carbon, &c., that bring about the transference of heat, as the air contained in their interstices. If this air be pumped out such substances are seen to exert a very considerable influence in stopping the influx of heat, and a vacuum vessel which has the space between its two walls filled with a non-conducting material of this kind preserves a liquid gas even better than one in which that space is simply exhausted of air. In experiments on this point double-walled glass tubes, as nearly identical in shape and size as possible, were mounted in sets of three on a common stem which communicated with an air-pump, so that the degree of exhaustion in each was equal. In two of each three the space between the double walls was filled with the powdered material it was desired to test, the third being left empty and used as the standard. The time required for a certain quantity of liquid
