The Kinetic Theory of Gases

Abstract

THE difficulty of reconciling line spectra with the kinetic theory of gases, has been referred to by Prof. Fitzgerald (NATURE, January 3, p. 221). The following considerations show that it is possible under certain suppositions to have a number of spectral rays with a very restricted number of degrees of freedom. Most of us, I believe, now accept a definite atomic charge of electricity, and if each charge is imagined to be capable of moving along the surface of an atom, it would represent two degrees of freedom. If a molecule is capable of sending out a homogeneous vibration, it means that there must be a definite position of equilibrium of the “electron.” If there are several such positions, the vibrations may take place in several periods. Any one molecule may perform for a certain time a simple periodic oscillation about one position of equilibrium, and owing to some impact the electron may be knocked over into a new position. The vibrations under these circumstances would not be quite homogeneous, but if the electron oscillates about any one position sufficiently long to perform a few thousand oscillations, we should hardly notice the want of homogeneity. Each electron at a given time would only send out vibrations which in our instruments would appear as homogeneous. Each molecule could thus successively give rise to a number of spectral rays, and at any one time the electron in the different molecules would, by the laws of probability, be distributed over all possible positions of equilibrium, so that we should always see all the vibrations which any one molecule of the gas is capable of sending out. The probability of an electron oscillating about one of its positions of equilibrium need not be the same in all cases. Hence a line may be weak not because the vibration has a smaller amplitude, but because fewer molecules give rise to it. The fact that the vibrations of a gas are not quite homogeneous, is borne out by experiment. If impacts become more frequent by increased pressure, we should expect from the above views that the time during which an electron performs a certain oscillation is shortened; hence the line should widen, which is the case. I have spoken, for the sake of simplicity, as if an electron vibrating about one position of equilibrium could only do so in one period. If the forces called into play, by a displacement, depend on the direction of the displacement, there would be two possible frequencies. If the surface is nearly symmetrical, we should have double lines.