Moreover, it appeared from his theory that the coefficient of viscosity should be independent of the number of molecules of gas present, so that it is not altered by varying the density. This result Maxwell characterises as startling, and he instituted an elaborate series of experiments a few years later with a view of testing it. The reason for this result will appear if we remember that, when the density is decreased, the mean free path is increased; relatively, then, to the total number of molecules present, the number which cross the surface in a given time is increased. And it appears from Maxwell’s result that this relative increase is such that the total number crossing remains unchanged. Hence the momentum conveyed across each unit area per second remains the same, in spite of the decrease in density.
Another consequence of the same investigation is that the coefficient of viscosity is proportional to the mean velocity of the molecules. Since the absolute temperature is proportional to the square of the velocity, it follows that the coefficient of viscosity is proportional to the square root of the absolute temperature.
The second part of the paper deals with the process of diffusion of two or more kinds of moving particles among one another.
If two different gases are placed in two vessels separated by a porous diaphragm such as a piece of unglazed earthenware, or connected by means of a narrow tube, Graham had shewn that, after sufficient time has elapsed, the two are mixed together. The same process takes place when two gases of different density are placed together in the same vessel. At first the denser gas may be at the bottom, the less dense above, but after a time the two are found to be uniformly distributed throughout.
Maxwell attempted to calculate from his theory the rate at which the diffusion takes place in these cases. The conditions of most of Graham’s experiments were too complicated to admit of direct comparison with the theory, from which it appeared that there is a relation between the mean free path and the rate of diffusion. One experiment, however, was found, the conditions of which could be made the subject of calculation, and from it Maxwell obtained as the value of the mean free path in air 1/389000 of an inch.
The number was close enough to that found from the viscosity to afford some confirmation of his theory.
However, a few years later Clausius criticised the details of this part of the paper, and Maxwell, in his memoir of 1866, admits the calculation to have been erroneous. The main principles remained unaffected, the molecules pass from one gas to the other, and this constitutes diffusion.
Now, suppose we have two sets of particles in contact of such a nature that the mean kinetic energy of the one set is different from that of the other; the temperatures of the two will then be different. These two sets will diffuse into each other, and the diffusing particles will carry with them their kinetic energy, which will gradually pass from those which have the greater energy to those which have the less, until the average kinetic energy is equalised throughout. But the kinetic energy of translation is the heat of the particles. This diffusion of kinetic energy is a diffusion of heat by conduction, and we have here the mechanical theory of the conduction of heat in a gas.
Maxwell obtained an expression, which, however, he afterwards modified, for the conductivity of a gas in terms of the mean free path. It followed from this that the conductivity of air was only about 1/7000 of that of copper.
Thus the diffusion of gases, the viscosity of gases, and the conduction of heat in gases, are all connected with the diffusion of the particles carrying with them their momenta and their energy; while values of the mean free path can be obtained from observations on any one of these properties.