Page:Encyclopædia Britannica, Ninth Edition, v. 3.djvu/53

Rh are not, the method of dialysis, as employed by Graham, would enable us to separate the molecules of smaller mass from those of greater, as they would stream through porous substances with greater velocity. We should thus be able to separate a gas, say hydrogen, into two portions, having different densities and other physical properties, different combining weights, and probably different chemical properties of other kinds. As no chemist has yet obtained specimens of hydrogen differing in this way from other specimens, we conclude that all the molecules of hydrogen are of sensibly the same mass, and not merely that their mean mass is a statistical constant of great stability.

But as yet we have not considered the phenomena which enable us to form an estimate of the actual mass and dimensions of a molecule. It is to Clausius that we owe the first definite conception of the free path of a molecule and of the mean distance travelled by a molecule between successive encounters. He showed that the number of encounters of a molecule in a given time is proportional to the velocity, to the number of molecules in unit of volume, and to the square of the distance between the centres of two molecules when they act on one another so as to have an encounter. From this it appears that if we call this distance of the centres the diameter of a molecule, and the volume of a sphere having this diameter the volume of a molecule, and the sum of the volumes of all the molecules the molecular volume of the gas, then the diameter of a molecule is a certain multiple of the quantity obtained by diminishing the free path in the ratio of the molecular volume of the gas to the whole volume of the gas. The numerical value of this multiple differs slightly, according to the hypothesis we assume about the law of distribution of velocities. It also depends on the definition of an encounter. When the molecules are regarded as elastic spheres we know what is meant by an encounter, but if they act on each other at a distance by attractive or repulsive forces of finite magnitude, the distance of their centres varies during an encounter, and is not a definite quantity. Nevertheless, the above statement of Clausius enables us, if we know the length of the mean path and the molecular volume of a gas, to form a tolerably near estimate of the diameter of the sphere of the intense action of a molecule, and thence of the number of molecules in unit of volume and the actual mass of each molecule. To complete the investigation we have, therefore, to determine the mean path and the molecular volume. The first numerical estimate of the mean path of a gaseous molecule was made by the present writer from data derived from the internal friction of air. There are three phenomena which depend on the length of the free path of the molecules of a gas. It is evident that the greater the free path the more rapidly will the molecules travel from one part of the medium to another, because their direction will not be so often altered by encounters with other molecules. If the molecules in different parts of the medium are of different kinds, their progress from one part of the medium to another can be easily traced by analysing portions of the medium taken from different places. The rate of diffusion thus found furnishes one method of estimating the length of the free path of a molecule. This kind of diffusion goes on not only between the molecules of different gases, but among the molecules of the same gas, only in the latter case the results of the diffusion the molecules of different gases, but among the molecules of the same gas, only in the latter case the results of the diffusion cannot be traced by analysis. But the diffusing molecules carry with them in their free paths the momentum and the energy which they happen at a given instant to have. The diffusion of momentum tends to equalise the apparent motion of different parts of the medium, and constitutes the phenomenon called the internal friction or viscosity of gases. The diffusion of energy tends to equalise the temperature of different parts of the medium, and constitutes the phenomenon of the conduction of heat in gases.

These three phenomena the diffusion of matter, of motion, and of heat in gases have been experimentally investigated, the diffusion of matter by Graham and Loschmidt, the diffusion of motion by Oscar Meyer and Clerk Maxwell, and that of heat by Stefan.

These three kinds of experiments give results which in the present imperfect state of the theory and the extreme difficulty of the experiments, especially those on the conduction of heat, may be regarded as tolerably consistent with each other. At the pressure of our atmosphere, and at the temperature of melting ice, the mean path of a molecule of hydrogen is about the 10,000th of a millimetre, or about the fifth part of a wave-length of green light. The mean path of the molecules of other gases is shorter than that of hydrogen.

The determination of the molecular volume of a gas is subject as yet to considerable uncertainty. The most obvious method is that of compressing the gas till it assumes the liquid form. It seems probable, from the great resistance of liquids to compression, that their molecules are at about the same distance from each other as that at which two molecules of the same substance in the gaseous form act on each other during an encounter. If this is the case, the molecular volume of a gas is somewhat less than the volume of the liquid into which it would be condensed by pressure, or, in other words, the density of the molecules is somewhat greater than that of the liquid.

Now, we know the relative weights of different molecules with great accuracy, and, from a knowledge of the mean path, we can calculate their relative diameters approximately. From these we can deduce the relative densities of different kinds of molecules. The relative densities so calculated have been compared by Lorenz Meyer with the observed densities of the liquids into which the gases may be condensed, and he finds a remarkable correspondence between them. There is considerable doubt, however, as to the relation between the molecules of a liquid and those of its vapour, so that till a larger number of comparisons have been made, we must not place too much reliance on the calculated densities of molecules. Another, and perhaps a more refined, method is that adopted by M. Van der Waals, who deduces the molecular volume from the deviations of the pressure from Boyle's law as the gas is com pressed.

The first numerical estimate of the diameter of a molecule was that made by Loschmidt in 1865 from the mean path and the molecular volume. Independently of him and of each other, Mr Stoney, in 1868, and Sir W. Thomson, in 1870, published results of a similar kind those of Thomson being deduced not only in this way, but from considerations derived from the thickness of soap bubbles, and from the electric action between zinc and copper.

The diameter and the mass of a molecule, as estimated by these methods, are, of course, very small, but by no means infinitely so. About two millions of molecules of hydrogen in a row would occupy a millimetre, and about two hundred million million million of them would weigh a milligramme. These numbers must be considered as exceedingly rough, guesses ; they must be corrected by more extensive and accurate experiments as science advances ; but the main result, which appears to be well established, is that the determination of the mass of a molecule is a legitimate object of scientific research, and that this mass is by no means immeasurably small.

Loschmidt illustrates these molecular measurements by a comparison with the smallest magnitudes visible by means of a microscope. Nobert, he tells us, can draw 4000 lines in the breadth of a millimetre. The intervals between 