Page:Scientific Papers of Josiah Willard Gibbs.djvu/285

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EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
249

will satisfy all the conditions of equilibrium for each surface of discontinuity, and the real system will therefore have a corresponding state, in which the entropy, quantities of components, and exterior will be the same as in the given state, but the energy less.

We may therefore determine whether the given system is or is not unstable, by applying the general criterion of instability (7) to the imaginary system.

If the system is not unstable, the equilibrium is either neutral or stable. Of course we can determine which of these is the case by reference to the imaginary system, since the determination depends upon states of equilibrium, in regard to which the real and imaginary systems do not differ. We may therefore determine whether the equilibrium of the given system is stable, neutral, or unstable, by applying the criteria (3)–(7) to the imaginary system.

The result which we have obtained may be expressed as follows:—In applying to a fluid system which is in equilibrium, and of which all the small parts taken separately are stable, the criteria of stable, neutral, and unstable equilibrium, we may regard the system as under constraint to satisfy the conditions of equilibrium relating to temperature and the potentials, and as satisfying the relations expressed by the fundamental equations for masses and surfaces, even when the condition of equilibrium relating to pressure {equation (500)} is not satisfied.

It follows immediately from this principle, in connection with equations (501) and (86), that in a stable system each surface of tension must be a surface of minimum area for constant values of the volumes which it divides, when the other surfaces bounding these volumes and the perimeter of the surface of tension are regarded as fixed; that in a system in neutral equilibrium each surface of tension will have as small an area as it can receive by any slight variations under the same limitations; and that in seeking the remaining conditions of stable or neutral equilibrium, when these are satisfied, it is only necessary to consider such varied surfaces of tension as have similar properties with reference to the varied volumes and perimeters.

We may illustrate the method which has been described by applying it to a problem but slightly different from one already (pp. 244, 245) discussed by a different method. It is required to determine the conditions of stability for a system in equilibrium, consisting of two different homogeneous masses meeting at a surface of discontinuity, the perimeter of which is invariable, as well as the exterior of the whole system, which is also impermeable to heat.

To determine what is necessary for stability in addition to the condition of minimum area for the surface of tension, we need only