The New Physics and Its Evolution

by Lucien Poincaré

Thus, below fifty to thirty millionths of a millimetre the properties of matter depend on its thickness. There are then, no doubt, only a few molecules to be met with, and it may be concluded, in consequence, that the discontinuous elements of bodies—that is, the molecules—have linear dimensions of the order of magnitude of the millionth of a millimetre. Considerations regarding more complex phenomena, for instance the phenomena of electricity by contact, and also the kinetic theory of gases, bring us to the same conclusion.

The idea of the discontinuity of matter forces itself upon us for many other reasons. All modern chemistry is founded on this principle; and laws like the law of multiple proportions, introduce an evident discontinuity to which we find analogies in the law of electrolysis. The elements of bodies we are thus brought to regard might, as regards solids at all events, be considered as immobile; but this immobility could not explain the phenomena of heat, and, as it is entirely inadmissible for gases, it seems very improbable it can absolutely occur in any state. We are thus led to suppose that these elements are animated by very complicated movements, each one proceeding in closed trajectories in which the least variations of temperature or pressure cause modifications.

The atomistic hypothesis shows itself remarkably fecund in the study of phenomena produced in gases, and here the mutual independence of the particles renders the question relatively more simple and, perhaps, allows the principles of mechanics to be more certainly extended to the movements of molecules.

The kinetic theory of gases can point to unquestioned successes; and the idea of Daniel Bernouilli, who, as early as 1738, considered a gaseous mass to be formed of a considerable number of molecules animated by rapid movements of translation, has been put into a form precise enough for mathematical analysis, and we have thus found ourselves in a position to construct a really solid foundation. It will be at once conceived, on this hypothesis, that pressure is the resultant of the shocks of the molecules against the walls of the containing vessel, and we at once come to the demonstration that the law of Mariotte is a natural consequence of this origin of pressure; since, if the volume occupied by a certain number of molecules is doubled, the number of shocks per second on each square centimetre of the walls becomes half as much. But if we attempt to carry this further, we find ourselves in presence of a serious difficulty. It is impossible to mentally follow every one of the many individual molecules which compose even a very limited mass of gas. The path followed by this molecule may be every instant modified by the chance of running against another, or by a shock which may make it rebound in another direction.

The difficulty would be insoluble if chance had not laws of its own. It was Maxwell who first thought of introducing into the kinetic theory the calculation of probabilities. Willard Gibbs and Boltzmann later on developed this idea, and have founded a statistical method which does not, perhaps, give absolute certainty, but which is certainly most interesting and curious. Molecules are grouped in such a way that those belonging to the same group may be considered as having the same state of movement; then an examination is made of the number of molecules in each group, and what are the changes in this number from one moment to another. It is thus often possible to determine the part which the different groups have in the total properties of the system and in the phenomena which may occur.

Such a method, analogous to the one employed by statisticians for following the social phenomena in a population, is all the more legitimate the greater the number of individuals counted in the averages; now, the number of molecules contained in a limited space—for example, in a centimetre cube taken in normal conditions—is such that no population could ever attain so high a figure. All considerations, those we have indicated as well as others which might be invoked (for example, the recent researches of M. Spring on the limit of visibility of fluorescence), give this result:—that there are, in this space, some twenty thousand millions of molecules. Each of these must receive in the space of a millimetre about ten thousand shocks, and be ten thousand times thrust out of its course. The free path of a molecule is then very small, but it can be singularly augmented by diminishing the number of them. Tait and Dewar have calculated that, in a good modern vacuum, the length of the free path of the remaining molecules not taken away by the air-pump easily reaches a few centimetres.

By developing this theory, we come to consider that, for a given temperature, every molecule (and even every individual particle, atom, or ion) which takes part in the movement has, on the average, the same kinetic energy in every body, and that this energy is proportional to the absolute temperature; so that it is represented by this temperature multiplied by a constant quantity which is a universal constant.

This result is not an hypothesis but a very great probability. This probability increases when it is noted that the same value for the constant is met with in the study of very varied phenomena; for example, in certain theories on radiation. Knowing the mass and energy of a molecule, it is easy to calculate its speed; and we find that the average speed is about 400 metres per second for carbonic anhydride, 500 for nitrogen, and 1850 for hydrogen at 0° C. and at ordinary pressure. I shall have occasion, later on, to speak of much more considerable speeds than these as animating other particles.

The kinetic theory has permitted the diffusion of gases to be explained, and the divers circumstances of the phenomenon to be calculated. It has allowed us to show, as M. Brillouin has done, that the coefficient of diffusion of two gases does not depend on the proportion of the gases in the mixture; it gives a very striking image of the phenomena of viscosity and conductivity; and it leads us to think that the coefficients of friction and of conductivity are independent of the density; while all these previsions have been verified by experiment. It has also invaded optics; and by relying on the principle of Doppler, Professor Michelson has succeeded in obtaining from it an explanation of the length presented by the spectral rays of even the most rarefied gases.

But however interesting are these results, they would not have sufficed to overcome the repugnance of certain physicists for speculations which, an imposing mathematical baggage notwithstanding, seemed to them too hypothetical. The theory, moreover, stopped at the molecule, and appeared to suggest no idea which could lead to the discovery of the key to the phenomena where molecules exercise a mutual influence on each other. The kinetic hypothesis, therefore, remained in some disfavour with a great number of persons, particularly in France, until the last few years, when all the recent discoveries of the conductivity of gases and of the new radiations came to procure for it a new and luxuriant efflorescence. It may be said that the atomistic synthesis, but yesterday so decried, is to-day triumphant.