Page:Scientific Papers of Josiah Willard Gibbs.djvu/115

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EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
79

are familiar examples. Such an equilibrium will, however, be practically unstable. By this is meant that, although, strictly speaking, an infinitely small disturbance or change may not be sufficient to destroy the equilibrium, yet a very small change in the initial state, perhaps a circumstance which entirely escapes our powers of perception, will be sufficient to do so. The presence of a small portion of the substance for which the condition (53) does not hold true, is sufficient to produce this result, when this substance forms a variable component of the original homogeneous masses. In other cases, when, if the new substances are formed at all, different kinds must be formed simultaneously, the initial presence of the different kinds, and that in immediate proximity, may be necessary.

It will be observed, that from (56) and (53) we can at once obtain (50) and (51), viz., by applying (53) to bodies differing infinitely little from the various homogeneous parts of the given mass. Therefore, the condition (56) (relating to the various homogeneous parts of the given mass) and (53) (relating to any bodies which can be formed of the given matter) with (43) are always sufficient for equilibrium, and always necessary for an equilibrium which shall be practically stable. And, if we choose, we may get rid of limitation in regard to equations (43). For, if we compare these equations with (38), it is easy to see that it is always immaterial, in applying the tests (56) and (53) to any body, how we consider it to be composed. Hence, in applying these tests, we may consider all bodies to be composed of the ultimate components of the given mass. Then the terms in (56) and (53) which relate to other components than these will vanish, and we need not regard the equations (43). Such of the constants as relate to the ultimate components, may be regarded, like T and P, as unknown quantities subject only to the conditions (56) and (53).

These two conditions, which are sufficient for equilibrium and necessary for a practically stable equilibrium, may be united in one, viz. (if we choose the ultimate components of the given mass for the component substances to which relate), that it shall be possible to give such values to the constants in the expression (57) that the value of the expression for each of the homogeneous parts of the mass in question shall be as small as for any body whatever made of the same components.


Effect of Solidity of any Part of the given Mass.

If any of the homogeneous masses of which the equilibrium is in question are solid, it will evidently be proper to treat the proportion of their components as invariable in the application of the criterion