Page:Scientific Papers of Josiah Willard Gibbs.djvu/348

312 which go on can be watched. It is apparent even to a very superficial observation that a film of which the tint is approaching the black exhibits a remarkable instability. The continuous change of tint is interrupted by the breaking out and rapid extension of black spots. That in the formation of these black spots a separation of different substances takes place, and not simply an extension of a part of the film, is shown by the fact that the film is made thicker at the edge of these spots.

This is very distinctly seen in a plane vertical film, when a single black spot breaks out and spreads rapidly over a considerable area which was before of a nearly uniform tint approaching the black. The edge of the black spot as it spreads is marked as it were by a string of bright beads, which unite together on touching, and thus becoming larger, glide down across the bands of color below. Under favorable circumstances, there is often quite a shower of these bright spots. They are evidently small spots—very much thicker apparently many times thicker—than the part of the film out of which they are formed. Now if the formation of the black spots were due to a simple extension of the film, it is evident that no such appearance would be presented. The thickening of the edge of the film cannot be accounted for by contraction. For an extension of the upper portion of the film and contraction of the lower and thicker portion, with descent of the intervening portions, would be far less resisted by viscosity, and far more favored by gravity than such extensions and contractions as would produce the appearances described. But the rapid formation of a thin spot by an internal current would cause an accumulation at the edge of the spot of the material forming the interior of the film, and necessitate a thickening of the film in that place.

That which is most difficult to account for in the formation of the black spots is the arrest of the process by which the film grows thinner. It seems most natural to account for this, if possible, by passive resistance to motion due to a very viscous or gelatinous condition of the film. For it does not seem likely that the film, after becoming unstable by the flux of matter from its interior, would become stable (without the support of such resistance) by a continuance of the same process. On the other hand, gelatinous properties are very marked in soap-water which contains somewhat more soap than is best for the formation of films, and it is entirely natural that, even when such properties are wanting in the interior of a mass or thick film of a liquid, they may still exist in the immediate vicinity of the surface (where we know that the soap or some of its components exists in excess), or throughout a film which is so thin that the interior has ceased to have the properties of matter