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748
LIQUID GASES


immediately by the destruction of this mechanical energy through friction and its consequent reconversion into heat. Thus the net result would be nil so far as change of temperature through the performance of external work was concerned. But the conditions in such an arrangement resemble that in the experiments of Thomson and Joule on the thermal changes which occur in a gas when it is forced under pressure through a porous plug or narrow orifice, and those experimenters found, as the former of them had predicted, that a change of temperature does take place, owing to internal work being done by the attraction of the gas molecules. Hence the effective result obtainable in practice by such an attempt at continuous adiabatic expansion as that suggested above is to be measured by the amount of the “Thomson-Joule effect,” which depends entirely on the internal, not the external, work done by the gas. To Linde belongs the credit of having first seen the essential importance of this effect in connexion with the liquefaction of gases by adiabatic expansion, and he was, further, the first to construct an industrial plant for the production of liquid air based on the application of this principle.

Fig. 2.—Laboratory Liquid Air Machine.

A, Air or oxygen inlet.
B, Carbon dioxide inlet.
C, Carbon dioxide valve.
D, Regenerator coils.
F, Air or oxygen expansion valve.
G, Vacuum vessel with liquid air or oxygen.
H, Carbon dioxide and air outlet.
O, Air coil.
O, Carbon dioxide coil.

The change of temperature due to the Thomson-Joule effect varies in amount with different gases, or rather with the temperature at which the operation is conducted. At ordinary temperatures oxygen and carbonic acid are cooled, while hydrogen is slightly heated. But hydrogen also is cooled if before being passed through the nozzle or plug it is brought into a thermal condition comparable to that of other gases at ordinary temperatures—that is to say, when it is initially cooled to a temperature having the same ratio to its critical point as their temperatures have to their critical points—and similarly the more condensible gases would be heated, and not cooled, by passing through a nozzle or plug if they were employed at a temperature sufficiently above their critical points. Each gas has therefore a point of inversion of the Thomson-Joule effect, and this temperature is, according to the theory of van der Waals, about 6.75 times the critical temperature of the body. Olszewski has determined the inversion-point in the case of hydrogen, and finds it to be 192.5° absolute, the theoretical critical point being thus about 28.5° absolute. The cooling effect obtained is small, being for air about ¼° C. per atmosphere difference of pressure at ordinary temperatures. But the decrement of temperature is proportional to the difference of pressure and inversely as the absolute temperature, so that the Thomson-Joule effect increases rapidly by the combined use of a lower temperature and greater difference of gas pressure. By means of the “regenerative” method of working, which was described by C. W. Siemens in 1857, developed and extended by Ernest Solvay in 1885, and subsequently utilized by numerous experimenters in the construction of low temperature apparatus, a practicable liquid air plant was constructed by Linde. The gas which has passed the orifice and is therefore cooled is made to flow backwards round the tube that leads to the nozzle; hence that portion of the gas that is just about to pass through the nozzle has some of its heat abstracted, and in consequence on expansion is cooled to a lower temperature than the first portion. In its turn it cools a third portion in the same way, and so the reduction of temperature goes on progressively until ultimately a portion of the gas is liquefied. Apparatus based on this principle has been employed not only by Linde in Germany, but also by Tripler in America and by Hampson and Dewar in England. The last-named experimenter exhibited in December 1895 a laboratory machine of this kind (fig. 2), which when supplied with oxygen initially cooled to −79° C., and at a pressure of 100–150 atmospheres, began to yield liquid in about a quarter of an hour after starting. The initial cooling is not necessary, but it has the advantage of reducing the time required for the operation. The efficiency of the Linde process is small, but it is easily conducted and only requires plenty of cheap power. When we can work turbines or other engines at low temperatures, so as to effect cooling through the performance of external work, then the economy in the production of liquid air and hydrogen will be greatly increased.

Fig. 3.—Hydrogen Jet Apparatus. A, Cylinder containing compressed hydrogen. B and C, Vacuum vessels containing carbonic acid under exhaustion and liquid air respectively. D, Regenerating coil in vacuum vessel. F, Valve. G, Pin-hole nozzle.

This treatment was next extended to hydrogen. For the reason already explained, it would have been futile to experiment with this substance at ordinary temperatures, and therefore as a preliminary it was cooled to the temperature of boiling liquid air, about −190° C. At this temperature it is still 2½ times above its critical temperature, and therefore its liquefaction in these circumstances would be comparable to that of air, taken at +60° C., in an apparatus like that just described. Dewar showed in 1896 that hydrogen cooled in this way and expanded in a regenerative coil from a pressure of 200 atmospheres was rapidly reduced in temperature to such an extent that after the apparatus had been working a few minutes the issuing jet was seen to contain liquid, which was sufficiently proved to be liquid hydrogen by the fact that it was so cold as to freeze liquid air and oxygen into hard white solids. Though with this apparatus, a diagrammatic representation of which is shown in fig. 3, it was now found possible at the time to collect the