to that of 1 atmosphere the value of the mechanical equivalent
of heat obtained was 821.89 foot-pounds. Between 10 atmospheres
and 1 it was 815.875 foot-pounds, and between 23 and 14
atmospheres 761.74 foot-pounds.
But, unlike Mayer and Séguin, Joule was not content with assuming that when air is compressed or allowed to expand the heat generated or absorbed is the equivalent of the work done and of that only, no change being made in the internal energy of the air itself when the temperature is kept constant. To test this two vessels similar to that used in the last experiment were placed in the same calorimeter and connected by a tube with a stop-cock. One contained air at a pressure of 22 atmospheres, while the other was exhausted. On opening the stop-cock no work was done by the expanding air against external forces, since it expanded into a vacuum, and it was found that no heat was generated or absorbed. This showed that Mayer’s assumption was true. On repeating the experiment when the two vessels were placed in different calorimeters, it was found that heat was absorbed by the vessel containing the compressed air, while an equal quantity of heat was produced in the calorimeter containing the exhausted vessel. The heat absorbed was consumed in giving motion to the issuing stream of air, and was reproduced by the impact of the particles on the sides of the exhausted vessel. The subsequent researches of Dr Joule and Lord Kelvin (Phil. Trans., 1853, p. 357, 1854, p. 321, and 1862, p. 579) showed that the statement that no internal work is done when a gas expands or contracts is not quite true, but the amount is very small in the cases of those gases which, like oxygen, hydrogen and nitrogen, can only be liquefied by intense cold and pressure.
For a long time the final result deduced by Joule by these varied and careful investigations was accepted as the standard value of the mechanical equivalent of heat. Recent determinations by H. A. Rowland and others, necessitated by modern requirements, have shown that it is in error, but by less than 1%. The writings of Joule, which thus occupy the place of honour in the practical establishment of the conservation of energy, have been collected into two volumes published by the Physical Society of London. On the theoretical side the greatest stimulus came from the publication in 1847, without knowledge of Mayer or Joule, of Helmholtz’s great memoir, Über die Erhaltung der Kraft, followed immediately (1848–1852) by the establishment of the science of thermodynamics (q.v.), mainly by R. Clausius and Lord Kelvin on the basis of “Carnot’s principle” (1824), modified in expression so as to be consistent with the conservation of energy (see Energetics).
Though we can convert the whole of the energy possessed by any mechanical system into heat, it is not in our power to perform the inverse operation, and to utilize the whole of the heat in doing mechanical work. Thus we see that different forms of energy are not equally valuable for conversion into work. The ratio of the portion of the energy of a system which can under given conditions be converted into mechanical work to the whole amount of energy operated upon may be called the “availability” of the energy. If a system be removed from all communication with anything outside of itself, the whole amount of energy possessed by it will remain constant, but will of its own accord tend to undergo such transformations as will diminish its availability. This general law, known as the principle of the “dissipation of energy,” was first adequately pointed out by Lord Kelvin in 1852; and was applied by him to some of the principal problems of cosmical physics. Though controlling all phenomena of which we have any experience, the principle of the dissipation of energy rests on a very different foundation from that of the conservation of energy; for while we may conceive of no means of circumventing the latter principle, it seems that the actions of intelligent beings are subject to the former only in consequence of the rudeness of the machinery which they have at their disposal for controlling the behaviour of those ultimate portions of matter, in virtue of the motions or positions of which the energy with which they have to deal exists. If we have a weight capable of falling through a certain distance, we can employ the mutual forces of the system consisting of the earth and weight to do an amount of useful work which is less than the full amount of potential energy possessed by the system only in consequence of the friction of the constraints, so that the limit of availability in this case is determined only by the friction which is unavoidable. Here we have to deal with a transformation with which we can grapple, and which can be controlled for our purposes. If, on the other hand, we have to deal with a system of molecules of whose motions in the aggregate we become conscious only by indirect means, while we know absolutely nothing either of the motions or positions of any individual molecule, it is obvious that we cannot grasp single molecules and control their movements so as to derive the full amount of work from the system. All we can do in such cases is to place the system under certain conditions of transformation, and be content with the amount of work which it is, as it were, willing to render up under those conditions. Thus the principle of Carnot involves the conclusion that a greater proportion of the heat possessed by a body at a high temperature can be converted into work than in the case of an equal quantity of heat possessed by a body at a low temperature, so that the availability of heat increases with the temperature.
Clerk Maxwell supposed two compartments, A and B, to be filled with gas at the same temperature, and to be separated by an ideal, infinitely thin partition containing a number of exceedingly small trap-doors, each of which could be opened or closed without any expenditure of energy. An intelligent creature, or “demon,” possessed of unlimited powers of vision, is placed in charge of each door, with instructions to open the door whenever a particle in A comes towards it with more than a certain velocity V, and to keep it closed against all particles in A moving with less than this velocity, but, on the other hand, to open the door whenever a particle in B approaches it with less than a certain velocity v, which is not greater than V, and to keep it closed against all particles in B moving with a greater velocity than this. By continuing this process every unit of mass which enters B will carry with it more energy than each unit which leaves B, and hence the temperature of the gas in B will be raised and that of the gas in A lowered, while no heat is lost and no energy expended; so that by the application of intelligence alone a portion of gas of uniform pressure and temperature may be sifted into two parts, in which both the temperature and the pressure are different, and from which, therefore, work can be obtained at the expense of heat. This shows that the principle of the dissipation of energy has control over the actions of those agents only whose faculties are too gross to enable them to grapple individually with the minute portions of matter which are the seat of energy.
In 1875 Lord Rayleigh published an investigation on “the work which may be gained during the mixing of gases.” In the preface he states the position that “whenever, then, two gases are allowed to mix without the performance of work, there is dissipation of energy, and an opportunity of doing work at the expense of low temperature heat has been for ever lost.” He shows that the amount of work obtainable is equal to that which can be done by the first gas in expanding into the space occupied by the second (supposed vacuous) together with that done by the second in expanding into the space occupied by the first. In the experiment imagined by Lord Rayleigh a porous diaphragm takes the place of the partition and trap-doors imagined by Clerk Maxwell, and the molecules sort themselves automatically on account of the difference in their average velocities for the two gases. When the pressure on one side of the diaphragm thus becomes greater than that on the other, work may be done at the expense of heat in pushing the diaphragm, and the operation carried on with continual gain of work until the gases are uniformly diffused. There is this difference, however, between this experiment and the operation imagined by Maxwell, that when the gases have diffused the experiment cannot be repeated; and it is no more contrary to the dissipation of energy than is the fact that work may be derived at the expense of heat when a gas expands into a vacuum, for the working substance is not finally restored to its original condition; while Maxwell’s “demons” may operate without limit.
