Page:Scientific Papers of Josiah Willard Gibbs.djvu/223

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EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
187

the whole body, we shall obtain the value of the variation of the total energy of the body, when this is supposed invariable in substance. But if we suppose the body to be increased or diminished in substance at its surface (the increment being continuous in nature and state with the part of the body to which it is joined), to obtain the complete value of the variation of the energy of the body, we must add the integral

in which denotes an element of the surface measured in the state of reference, and the change in position of this surface (due to the substance added or taken away) measured normally and outward in the state of reference. The complete value of the variation of the intrinsic energy of the solid is therefore

(357)

This is entirely independent of any supposition in regard to the homogeneity of the solid.

To obtain the conditions of equilibrium for solid and fluid masses in contact, we should make the variation of the energy of the whole equal to or greater than zero. But since we have already examined the conditions of equilibrium for fluids, we need here only seek the conditions of equilibrium for the interior of a solid mass and for the surfaces where it comes in contact with fluids. For this it will be necessary to consider the variations of the energy of the fluids only so far as they are immediately connected with the changes in the solid. We may suppose the solid with so much of the fluid as is in close proximity to it to be enclosed in a fixed envelop, which is impermeable to matter and to heat, and to which the solid is firmly attached wherever they meet. We may also suppose that in the narrow space or spaces between the solid and the envelop, which are filled with fluid, there is no motion of matter or transmission of heat across any surfaces which can be generated by moving normals to the surface of the solid, since the terms in the condition of equilibrium relating to such processes may be cancelled on account of the internal equilibrium of the fluids. It will be observed that this method is perfectly applicable to the case in which a fluid mass is entirely enclosed in a solid. A detached portion of the envelop will then be necessary to separate the great mass of the fluid from the small portion adjacent to the solid, which alone we have to consider. Now the variation of the energy of the fluid mass will be, by equation (13),

(358)

where denotes an integration extending over all the elements of