Page:Scientific Papers of Josiah Willard Gibbs.djvu/309

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EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
273

effect of extending the surface will be to raise its temperature. In either case, it will be observed, the immediate effect of extending the surface is to increase its tension. A contraction of the surface will of course have the opposite effect. But the time necessary for the reestablishment of sensible thermal equilibrium after extension or contraction of the surface must in most cases be very short.

In regard to the formation or extension of a surface between two coexistent phases of more than two components, there are two extreme cases which it is desirable to notice. When the superficial density of each of the components is exceedingly small compared with its density in either of the homogeneous masses, the matter (as well as the heat) necessary for the formation or extension of the normal surface can be taken from the immediate vicinity of the surface without sensibly changing the properties of the masses from which it is taken. But if any one of these superficial densities has a considerable value, while the density of the same component is very small in each of the homogeneous masses, both absolutely and relatively to the densities of the other components, the matter necessary for the formation or extension of the normal surface must come from a considerable distance. Especially if we consider that a small difference of density of such a component in one of the homogeneous masses will probably make a considerable difference in the value of the corresponding potential {see eq. (217)}, and that a small difference in the value of the potential will make a considerable difference in the tension (see eq. (508)}, it will be evident that in this case a considerable time will be necessary after the formation of a fresh surface or the extension of an old one for the reestablishment of the normal value of the superficial tension. In intermediate cases, the reestablishment of the normal tension will take place with different degrees of rapidity.

But whatever the number of component substances, provided that it is greater than one, and whether the reestablishment of equilibrium is slow or rapid, extension of the surface will generally produce increase and contraction decrease of the tension. It would evidently be inconsistent with stability that the opposite effects should be produced. In general, therefore, a fresh surface between coexistent phases has a greater tension than an old one.[1] By the use of fresh surfaces, in experiments in capillarity, we may sometimes avoid the effect of minute quantities of foreign substances, which may be

  1. When, however, homogeneous masses which have not coexistent phases are brought into contact, the superficial tension may increase with the course of time. The superficial tension of a drop of alcohol and water placed in a large room will increase as the potential for alcohol is equalized throughout the room, and is diminished in the vicinity of the surface of discontinuity.