James Clerk Maxwell (1831-1879)

Limitation of the Second Law of Thermodynamics

Before I conclude, I wish to direct attention to an aspect of the molecular theory which deserves consideration.

One of the best established facts in thermodynamics is that it is impossible in a system enclosed in an envelope which permits neither change of volume nor passage of heat, and in which both the temperature and the pressure are everywhere the same, to produce any inequality of temperature or of pressure without the expenditure of work. This is the second law of thermodynamics, and it is undoubtedly true as long as we can deal with bodies only in mass, and have no power of perceiving or handling the separate molecules of which they are made up. But if we conceive a being whose faculties are so sharpened that he can follow every molecule in its course, such a being, whose attributes are still as essentially finite as our own, would be able to do what is at present impossible to us. For we have seen that the molecules in a vessel full of air at uniform temperature are moving with velocities by no means uniform, though the mean velocity of any great number of them, arbitrarily selected, is almost exactly uniform. Now let us suppose that such a vessel is divided into two portions, A and B, by a division in which there is a small hole, and that a being, who can see the individual molecules, opens and closes this hole, so as to allow only the swifter molecules to pass from A to B, and only the swifter molecules to pass from A to B, and only the slower ones to pass from B to A. He will thus, without expenditure of work, raise the temperature of B and lower that of A, in contradiction to the second law of thermodynamics.

This is only one of the instances in which conclusions which we have drawn from our experience of bodies consisting of an immense number of molecules may be found not to be applicable to the more delicate observations and experiments which we may suppose made by one who can perceive and handle the individual molecules which we deal with only in large masses.

In dealing with masses of matter, while we do not perceive the individual molecules, we are compelled to adopt what I have described as the statistical method of calculation, and to abandon the strict dynamical method, in which we follow every motion by the calculus.

It would be interesting to enquire how far those ideas about the nature and methods of science which have been derived from examples of scientific investigation in which the dynamical method is followed are applicable to our actual knowledge of concrete things, which, as we have seen, is of an essentially statistical nature, because no one has yet discovered any practical method of tracing the path of a molecule, or of identifying it at different times.

I do not think, however, that the perfect identity which we observe between different portions of the same kind of matter can be explained on the statistical principle of the stability of the averages of large numbers of quantities each of which may differ from the mean. For if of the molecules of some substance such as hydrogen, some were of slightly greater mass than others, we have the means of producing a separation between molecules of different masses, and in this way we should be able to produce two kinds of hydrogen, one of which would be somewhat denser than the other. As this cannot be done, we must admit that the equality which we assert to exist between the molecules of hydrogen applies to each individual molecule, and not merely to the average of groups of millions of molecules.