Page:Scientific Papers of Josiah Willard Gibbs.djvu/233

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EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
197

adapt our language to what we may regard as the most general case, viz., that in which the fluids contain the substance of the solid but are not wholly composed of that substance), the fluids in equilibrium with the solid are all supersaturated with respect to the substance of the solid, except when the solid is in a state of hydrostatic stress; so that if there were present in any one of these fluids any small fragment of the same kind of solid subject to the hydrostatic pressure of the fluid, such a fragment would tend to increase. Even when no such fragment is present, although there must be perfect equilibrium so far as concerns the tendency of the solid to dissolve or to increase by the accretion of similarly strained matter, yet the presence of the solid which is subject to the distorting stresses, will doubtless facilitate the commencement of the formation of a solid of hydrostatic stress upon its surface, to the same extent, perhaps, in the case of an amorphous body, as if it were itself subject only to hydrostatic stress. This may sometimes, or perhaps generally, make it a necessary condition of equilibrium in cases of contact between a fluid and an amorphous solid which can be formed out of it, that the solid at the surface where it meets the fluid shall be sensibly in a state of hydrostatic stress.

But in the case of a solid of continuous crystalline structure, subjected to distorting stresses and in contact with solutions satisfying the conditions deduced above, although crystals of hydrostatic stress would doubtless commence to form upon its surface (if the distorting stresses and consequent supersaturation of the fluid should be carried too far), before they would commence to be formed within the fluid or on the surface of most other bodies, yet within certain limits the relations expressed by equations (393)–(395) must admit of realization, especially when the solutions are such as can be easily supersaturated.[1]

It may be interesting to compare the variations of , the pressure in the fluid which determines in part the stresses and the state of strain of the solid, with other variations of the stresses or strains in the solid, with respect to the relation expressed by equation (388). To examine this point with complete generality, we may proceed in the following manner.

Let us consider so much of the solid as has in the state of reference the form of a cube, the edges of which are equal to unity, and parallel to the co-ordinate axes. We may suppose this body to be homogeneous in nature and in state of strain both in its state of

  1. The effect of distorting stresses in a solid on the phenomena of crystallization and liquefaction, as well as the effect of change of hydrostatic pressure common to the solid and liquid, was first described by Professor James Thomson. See Trans. R. S. Edin., vol. xvi, p. 575; and Proc. Roy. Soc., vol. xi, p. 473, or Phil. Mag., ser. 4, vol. xxiv, p. 395.