Page:Scientific Papers of Josiah Willard Gibbs.djvu/342

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306
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.

cases in which the film exhibits a decided viscosity. That is, the relations (618), (614), (615) will hold true, when by or we understand the tension of the film regarded as a simple surface of discontinuity (this is equivalent to the sum of the tensions of the two surfaces of the film), and by its mass per unit of area diminished by the mass of gas which would occupy the same space if the film should be suppressed and the gases should meet at its surface of tension. This surface of tension of the film will evidently divide the distance between the surfaces of tension for the two surfaces of the film taken separately, in the inverse ratio of their tensions. For practical purposes, we may regard F simply as the mass of the film per unit of area. It will be observed that the terms containing in (613) and (614) are not to be neglected in our present application of these equations.

But the mechanical conditions of equilibrium for the film regarded us an approximately homogeneous mass in the form of a thin sheet bounded by two surfaces of discontinuity are not necessarily satisfied when the film is in a state of apparent rest. In fact, these conditions cannot be satisfied (in any place where the force of gravity has an appreciable intensity) unless the film is horizontal. For the pressure in the interior of the film cannot satisfy simultaneously condition (612), which requires it to vary rapidly with the height , and condition (613) applied separately to the different surfaces, which makes it a certain mean between the pressures in the adjacent gas-masses. Nor can these conditions be deduced from the general condition of mechanical equilibrium (606) or (611), without supposing that the interior of the film is free to move independently of the surfaces, which is contrary to what we have supposed.

Moreover, the potentials of the various components of the film will not in general satisfy conditions (617), and cannot (when the temperature is uniform) unless the film is horizontal. For if these conditions were satisfied, equation (612) would follow as a consequence. (See page 283.)

We may here remark that such a film as we are considering cannot form any exception to the principle indicated on page 284,—that when a surface of discontinuity which satisfies the conditions mechanical equilibrium has only one component which is not found in the contiguous masses, and these masses satisfy all the conditions of equilibrium, the potential for the component mentioned must satisfy the law expressed in (617), as a consequence of the condition of mechanical equilibrium (614). Therefore, as we have just seen that it is impossible that all the potentials in a liquid film which is not horizontal should conform to (617) when the temperature is uniform it follows that if a liquid film exhibits any persistence which is