Page:Scientific Papers of Josiah Willard Gibbs.djvu/284

From Wikisource
Jump to navigation Jump to search
This page has been proofread, but needs to be validated.
248
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.

attribute in its initial state the same homogeneous masses and surfaces of discontinuity which belong to the real system. We shall also suppose that the homogeneous masses and surfaces of discontinuity of this system, which we may call the imaginary system, have the same fundamental equations as those of the real system. But the imaginary system is to differ from the real in that the variations of its state are limited to such as do not violate the conditions of equilibrium relating to temperature and the potentials, and that the fundamental equations of the surfaces of discontinuity hold true for these varied states, although the condition of equilibrium expressed by equation (500) may not be satisfied.

Before proceeding farther, we must decide whether we are to examine the question of stability under the condition of a constant external temperature, or under the condition of no transmission of heat to or from external bodies, and in general, to what external influences we are to regard the system as subject. It will be convenient to suppose that the exterior of the system is fixed, and that neither matter nor heat can be transmitted through it. Other cases may easily be reduced to this, or treated in a manner entirely analogous.

Now if the real system in the given state is unstable, there must be some slightly varied state in which the energy is less, but the entropy and the quantities of the components the same as in the given state, and the exterior of the system unvaried. But it may easily be shown that the given state of the system may be made stable by constraining the surfaces of discontinuity to pass through certain fixed lines situated in the unvaried surfaces. Hence, if the surfaces of discontinuity are constrained to pass through corresponding fixed lines in the surfaces of discontinuity belonging to the varied state just mentioned, there must be a state of stable equilibrium for the system thus constrained which will differ infinitely little from the given state of the system, the stability of which is in question, and will have the same entropy, quantities of components, and exterior, but less energy. The imaginary system will have a similar state, since the real and imaginary systems do not differ in respect to those states which satisfy all the conditions of equilibrium for each surface of discontinuity. That is, the imaginary system has a state, differing infinitely little from the given state, and with the same entropy, quantities of components, and exterior, but with less energy.

Conversely, if the imaginary system has such a state as that just described, the real system will also have such a state. This may be shown by fixing certain lines in the surfaces of discontinuity of the imaginary system in its state of less energy and then making the energy a minimum under the conditions. The state thus determined