Comparison of Absolute Scale with Scale of Air Thermometer
The comparison which Joule and Thomson carried out of the absolute thermodynamic scale with the scale of the constant pressure gas thermometer has already been referred to, and it has been shown that the two scales would exactly agree, that is, absolute temperature would be simply proportional to the volume of the gas in a gas thermometer kept at the temperature to be measured, if the internal energy of the gas were not altered by an alteration of volume without alteration of temperature, that is, if the de − ∂e of p. [107] above were zero. Joule tested whether this was the case by immersing two vessels, connected by a tube which could be opened or closed by a stopcock, in the water of a calorimeter, ascertaining the temperature with a very sensitive thermometer, and then allowing air which had already been compressed into one of the vessels to flow into the other, which was initially empty. It was found that no alteration of temperature of the water of the calorimeter that could be observed was produced. But the volume of the air had been doubled by the process, and if any sensible alteration of internal energy had taken place it would have shown itself by an elevation or a lowering of the temperature of the water, according as the energy had been diminished or increased.
Thomson suggested that the gas to be examined should be forced through a pipe ending in a fine nozzle, or, preferably, through a plug of porous material placed in a pipe along which the gas was forced by a pump, and observations made of the temperature in the steady stream on both sides of the plug. The experiments were carried out with a plug of compressed cotton-wool held between two metal disks pierced with holes, in a tube of boxwood surrounded also by cotton-wool, and placed in a bath of water closely surrounding the supply pipe. This was of metal, and formed the end of a long spiral all immersed in the bath. Thus the temperature of the gas approaching the plug was kept at a uniform temperature determined by a delicate thermometer; another thermometer gave the temperature in the steady stream beyond the plug.
In the case of hydrogen the experiments showed a slight heating effect of passage through the plug; air, oxygen, nitrogen and carbonic acid were cooled by the passage.
The theory of the matter is set forth in the original papers, and in a very elegant manner in the article on Heat. The result of the analysis shows that if ∂w be the positive or negative work-value of the heat which will convert one gramme of the gas after passage to its original temperature; and T be absolute temperature, and v volume of a gramme of the gas at pressure p, and the difference of pressure on the two sides of the plug be dp, the equation which holds is
It was found by Joule and Thomson that ∂w was proportional to dp for values of dp up to five or six atmospheres. At different temperatures, however, in the case of hydrogen the heating effect was found to diminish with rise of temperature, being .100 of a degree centigrade at 4° or 5° centigrade, and .155 at temperatures of from 89° to 93° centigrade for a difference of pressure due to 100 inches of mercury.
If there is neither heating nor cooling ∂w = 0, and we obtain by integration T = Cv, where C is a constant.
Elaborate discussions of the theory of this experiment will be found in modern treatises on thermodynamics, and in various recent memoirs, and the differential equation has been modified in various ways, and integrated on various suppositions, which it would be out of place to discuss here.
The cooling effect of passing a gas such as air or oxygen through a narrow orifice has been used to liquefy the gas. The stream of gas is pumped along a pipe towards the opening, and that which has passed the orifice and been slightly cooled is led on its way back to the pump along the outside of the pipe by which more gas is approaching the orifice, and so cools slightly the advancing current. The gas which emerges later is thus cooler than that which emerged before, and the process goes on until the issuing gas is liquefied and falls down into the lower part of the pipe surrounding the orifice, whence it can be drawn off into vessels constructed to receive and preserve it.
It is possible thus to liquefy hydrogen, which shows that at the low temperature at which the process is usually started (an initial cooling is applied) the passage through the orifice has a cooling effect as in the other cases.
Another idea, that of thermodynamic motivity, on which Thomson suggested might be founded a fruitful presentation of the subject of thermodynamics, may be mentioned here. It was set forth in a letter written to Professor Tait in May 1879. If a system of bodies be given, all at different temperatures, it is possible to reduce them to a common temperature, and by doing so to extract a certain amount of mechanical energy from them. The temperatures must for this purpose be equalised by perfect thermodynamic engines working between the final temperature T0, say, and the temperatures of the different parts of the system. This process is one of the levelling up and the levelling down of temperature; and the temperature T0 is such that exactly the heat given out at T0 by certain engines, receiving heat from bodies of higher temperature than T0, is supplied to the engines which work between T0 and bodies at lower temperatures. The whole useful work obtained in this way was called by Thomson the motivity of the system. Of course equalisation of temperature may be obtained by conduction, and in this case the energy which might be utilised is lost. With two equal and similar bodies at absolute temperatures T, T' the temperature to which they are reduced when their motivity is extracted is √(TT'). If the temperatures are equalised by conduction the resulting temperature is higher, being ½(T + T'). Thus, if only the two bodies are available for engines to work between, the motivity is the measure of the energy lost when conduction brings about equalisation of temperature.
A very suggestive paper on the subject was published by Lord Kelvin in the Trans. R.S.E., vol. 28, 1877-8.