Page:Scientific Papers of Josiah Willard Gibbs.djvu/81

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THERMODYNAMIC PROPERTIES OF SUBSTANCES.
45

Phil. Trans., vol. 159, p. 575, has obtained by his experiments with carbonic acid is that, in the case of this substance at least, the derived surface which represents a compound of liquid and vapor is terminated as follows: as the tangent plane rolls upon the primitive surface, the two points of contact approach one another and finally fall together. The rolling of the double tangent plane necessarily comes to an end. The point where the two points of contact fall together is the critical point. Before considering farther the geometrical characteristics of this point and their physical significance, it will be convenient to investigate the nature of the primitive surface which lies between the lines which form the limite of absolute stability.

Between two points of the primitive surface which have a common tangent plane, as those represented by and in figure 2, if there is no gap in the primitive surface, there must evidently be a region where the surface is concave toward the tangent plane in one of its principal curvatures at least, and therefore represents states of unstable equilibrium in respect to continuous as well as discontinuous changes (see pages 42, 43).[1] If we draw a line upon the primitive surface, dividing it into parts which represent respectively stable and unstable equilibrium, in respect to continuous changes, i.e., dividing the surface which is concave upward in both its principal curvatures from that which is concave downward in one or both, this line, which may be called the limit of essential instability, must have a form somewhat like that represented by in figure 2. It touches the limite of absolute stability at the critical point . For we may take a pair of points in and having a common tangent plane as near to as we choose, and the line joining them upon the primitive surface made by a plane section perpendicular to the tangent plane, will pass through an area of instability.

The geometrical properties of thecritical point in our surface may be made more clear by supposing the lines of curvature drawn upon the surface for one of the principal curvatures, that one, namely, which has different signs upon different sides of the limit of essential instability. The lines of curvature which meet this line will in general cross it. At any point where they do so, as the sign of their curvature changes, they evidently cut a plane tangent to the surface, and therefore the surface itself cuts the tangent plane. But where one of these lines of curvature touches the limit of essential instability without crossing it, so that its curvature remains always positive (curvatures being considered positive when the concavity is on the upper side of the surface), the surface evidently does not cut the

  1. This is the same result as that obtained by Professor J. Thomson in connectino with the surface referred to in the note on page 34.