Page:Scientific Papers of Josiah Willard Gibbs.djvu/346

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EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.

The energy of the suction which produces these effects may be inferred from the following considerations. The pressure in the slender liquid mass which encircles the film is of course variable, being greater in the lower portions than in the upper, but it is everywhere less than the pressure of the atmosphere. Let us take a point where the pressure is less than that of the atmosphere by an amount represented by a column of the liquid one centimeter in height. (It is probable that much greater differences of pressure occur.) At a point near by in the interior of the film the pressure is that of the atmosphere. Now if the difference of pressure of these two points were distributed uniformly through the space of one centimeter, the intensity of its action would be exactly equal to that of gravity. But since the change of pressure must take place very suddenly (in a small fraction of a millimeter), its effect in producing a current in a limited space must be enormously great compared with that of gravity.

Since the process just described is connected with the descent of the liquid in the mass encircling the film, we may regard it as another example of the downward tendency of the interior of the film. There is a third way in which this descent may take place, when the principal component of the interior is volatile, viz., through the air. Thus, in the case of a film of soap-water, if we suppose the atmosphere to be of such humidity that the potential for water at a level mid- way between the top and bottom of the film has the same value in the atmosphere as in the film, it may easily be shown that evaporation will take place in the upper portions and condensation in the lower. These processes, if the atmosphere were otherwise undisturbed, would occasion currents of diffusion and other currents, the general effect of which would be to carry the moisture downward. Such a precise adjustment would be hardly attainable, and the processes described would not be so rapid as to have a practical importance.

But when the potential for water in the atmosphere differs considerably from that in the film, as in the case of a film of soap-water in a dry atmosphere, or a film of soap- water with glycerine in a moist atmosphere, the effect of evaporation or condensation is not to be neglected. In the first case, the diminution of the thickness of the film will be accelerated, in the second, retarded. In the case of the film containing glycerine, it should be observed that the water condensed cannot in all respects replace the fluid carried down by the internal current but that the two processes together will tend to wash out the glycerine from the film.

But when a component which greatly diminishes the tension of the film, although forming but a small fraction of its mass (therefore