Page:Scientific Papers of Josiah Willard Gibbs.djvu/350

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314
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.

tension in the film are mainly due is a component of the liquid masses on each side of the air film, the necessary differences of the potential of this substance cannot be permanently maintained, and these films have little persistence compared with films of soap-water in air. In this respect, the case of these air-films is analogous to that of liquid films in an atmosphere containing substances by which their tension is greatly reduced. Compare pages 310, 311.


Surfaces of Discontinuity between Solids and Fluids.

We have hitherto treated of surfaces of discontinuity on the supposition that the contiguous masses are fluid. This is by far the most simple case for any rigorous treatment, since the masses are necessarily isotropic both in nature and in their state of strain. In this case, moreover, the mobility of the masses allows a satisfactory experimental verification of the mechanical conditions of equilibrium. On the other hand, the rigidity of solids is in general so great, that any tendency of the surfaces of discontinuity to variation in area or form may be neglected in comparison with the forces which are produced in the interior of the solids by any sensible strains, so that it is not generally necessary to take account of the surfaces of discontinuity in determining the state of strain of solid masses. But we must take account of the nature of the surfaces of discontinuity between solids and fluids with reference to the tendency toward solidification or dissolution at such surfaces, and also with reference to the tendencies of different fluids to spread over the surfaces of solids.

Let us therefore consider a surface of discontinuity between a fluid and a solid, the latter being either isotropic or of a continuous crystalline structure, and subject to any kind of stress compatible with a state of mechanical equilibrium with the fluid. We shall not exclude the case in which substances foreign to the contiguous masses are present in small quantities at the surface of discontinuity, but we shall suppose that the nature of this surface (i.e., of the non-homogeneous film between the approximately homogeneous masses) is entirely determined by the nature and state of the masses which it separates, and the quantities of the foreign substances which may be present. The notions of the dividing surface, and of the superficial densities of energy, entropy, and the several components, which we have used with respect to surfaces of discontinuity between fluids (see pages 219 and 224), will evidently apply without modification to the present case. We shall use the suffix with reference to the substance of the solid, and shall suppose the dividing surface to be determined so as to make the superficial density of this substance vanish. The superficial densities of energy, of entropy, and of the