Page:Scientific Papers of Josiah Willard Gibbs.djvu/401

Rh analytical processes from the general condition of equilibrium (2). The condition of equilibrium which relates to the dissolving of the solid at a surface where it meets a fluid may be expressed by the equation where $$\epsilon, \eta, v$$, and $$m_{1}$$ denote respectively the energy, entropy, volume, and mass of the solid, if it is homogeneous in nature and state of strain,—otherwise, of any small portion which may be treated as thus homogeneous,—$$\mu_{1}$$ the potential in the fluid for the substance of which the solid consists, $$p$$ the pressure in the fluid and therefore one of the principal pressures in the solid, and $$t$$ the temperature. It will be observed that when the pressure in the solid is isotropic, the second member of this equation will represent the potential in the solid for the substance of which it consists {see (9)}, and the condition reduces to the equality of the potential in the two masses, just as if it were a case of two fluids. But if the stresses in the solid are not isotropic, the value of the second member of the equation is not entirely determined by the nature and state of the solid, but has in general three different values (for the same solid at the same temperature, and in the same state of strain) corresponding to the three principal pressures in the solid. If a solid in the form of a right parallelepiped is subject to different pressures on its three pairs of opposite sides by fluids in which it is soluble, it is in general necessary for equilibrium that the composition of the fluids shall be different.

The fundamental equations which have been described above are limited, in their application to solids, to the case in which the stresses in the solid are isotropic. An example of a more general form of fundamental equation for a solid, is afforded by an equation between the energy and entropy of a given quantity of the solid, and the quantities which express its state of strain, or by an equation between $$\psi$$ {see (3)} as determined for a given quantity of the solid, the temperature, and the quantities which express the state of strain.

Capillarity.—The solution of the problems which precede may be regarded as a first approximation, in which the peculiar state of thermodynamic equilibrium about the surfaces of discontinuity is neglected. To take account of the condition of things at these surfaces, the following method is used. Let us suppose that two homogeneous fluid masses are separated by a surface of discontinuity, i.e., by a very thin non-homogeneous film. Now we may imagine a state of things in which each of the homogeneous masses extends without variation of the densities of its several components, or of the densities of energy and entropy, quite up to a geometrical surface (to be called the dividing surface) at which the masses meet. We may suppose this surface to be sensibly coincident with the physical surface