Page:Scientific Papers of Josiah Willard Gibbs.djvu/182

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146
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.

requires that the pressure shall be a function of the height alone, and that the density shall be equal to the first derivative of this function, divided by .

Conditions (227) contain all that is characteristic of chemical equilibrium. To satisfy these conditions it is necessary and sufficient that

(234)

The expressions denote quantities which we have called the potentials for the several components, and which are entirely determined at any point in a mass by the nature and state of the mass about that point. We may avoid all confusion between these quantities and the potential of the force of gravity, if we distinguish the former, when necessary, as intrinsic potentials. The relations indicated by equations (234) may then be expressed as follows:—

When a fluid mass is in equilibrium under the influence of gravity, and has the same independently variable components throughout, the intrinsic potentials for the several components are constant in any given level, and diminish uniformly as the height increases, the difference of the values of the intrinsic potential for any component at two different levels being equal to the work done by the force of gravity when a unit of matter falls from the higher to the lower level.

The conditions expressed by equations (228), (233), (234) are necessary and sufficient for equilibrium, except with respect to the possible formation of masses which are not approximately identical in phase with any previously existing about the points where they may be formed. The possibility of such formations at any point is evidently independent of the action of gravity, and is determined entirely by the phase or phases of the matter about that point. The conditions of equilibrium in this respect have been discussed on pages 74–79.

But equations (228), (233), and (234) are not entirely independent. For with respect to any mass in which there are no surfaces of discontinuity (i.e., surfaces where adjacent elements of mass have finite differences of phase), one of these equations will be a consequence of the others. Thus by (228) and (234), we may obtain from (97), which will hold true of any continuous variations of phase, the equation

(235)

{{MathForm2|(236)|or which will therefore hold true in any mass in which equations (228) and (234) are satisfied, and in which there are no surfaces of discontinuity. But the condition of equilibrium expressed by equation