Page:Scientific Papers of Josiah Willard Gibbs.djvu/201

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EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
165

and also denoting functions of the temperature. Therefore

(296)

It will be seen (if we disregard the difference of notation) that this equation is equivalent in form to (216), which was deduced from a priori considerations as a probable relation between the quantity and the potential of a small component. When a liquid absorbs several gases at once, there will be several equations of the form of (296), which will hold true simultaneously, and which we may regard as equivalent to equations (217), (218). The quantities and in (216), with the corresponding quantities in (217), (218), were regarded as functions of the temperature and pressure, but since the potentials in liquids are but little affected by the pressure, we might anticipate that these quantities in the case of liquids might be regarded as functions of the temperature alone.

In regard to equations (216), (217), (218), we may now observe that by (264) and (276) they are shown to hold true in ideal gases or gas-mixtures, not only for components which form only a small part of the whole gas-mixture, but without any such limitation, and not only approximately but absolutely. It is noticeable that in this case quantities and are functions of the temperature alone, and do not even depend upon the nature of the gaseous mass, except upon the particular component to which they relate. As all gaseous bodies are generally supposed to approximate to the laws of ideal gases when sufficiently rarefied, we may regard these equations as approximately valid for gaseous bodies in general when the density is sufficiently small. When the density of the gaseous mass is very great, but the separate density of the component in question is small, the equations will probably hold true, but the values of and may not be entirely independent of the pressure, or of the composition of the mass in respect to its principal components. These equations will also apply, as we have just seen, to the potentials in liquid bodies for components of which the density in the liquid is very small, whenever these components exist also in the gaseous state, and conform to the law of Henry. This seems to indicate that the law expressed by these equations has a very general application.


Considerations relating to the Increase of Entropy due to the Mixture of Gases by Diffusion.

From equations (278) we may easily calculate the increase of entropy which takes place when two different gases are mixed by diffusion, at a constant temperature and pressure. Let us suppose