Page:Scientific Papers of Josiah Willard Gibbs.djvu/310

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274
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.

present without our knowledge or desire, in the fluids which meet at the surface investigated.

When the establishment of equilibrium is rapid, the variation of the tension from its normal value will be manifested especially during the extension or contraction of the surface, the phenomenon resembling that of viscosity, except that the variations of tension arising from variations in the densities at and about the surface will be the same in all directions, while the variations of tension due to any property of the surface really analogous to viscosity would be greatest in the direction of the most rapid extension.

We may here notice the different action of traces in the homogeneous masses of those substances which increase the tension and of those which diminish it. When the volume-densities of a component are very small, its surface-density may have a considerable positive value, but can only have a very minute negative one.[1] For the value when negative cannot exceed (numerically) the product of the greater volume-density by the thickness of the non-homogeneous film. Each of these quantities is exceedingly small. The surface-density when positive is of the same order of magnitude as the thickness of the non-homogeneous film, but is not necessarily small compared with other surface-densities because the volume-densities of the same substance in the adjacent masses are small. Now the potential of a substance which forms a very small part of a homogeneous mass certainly increases, and probably very rapidly, as the proportion of that component is increased. {See (171) and (217).} The pressure, temperature, and the other potentials, will not be sensibly affected. {See (98).} But the effect on the tension of this increase of the potential will be proportional to the surface-density, and will be to diminish the tension when the surface-density is positive. {See (508).} It is therefore quite possible that a very small trace of a substance in the homogeneous masses should greatly diminish the tension, but not possible that such a trace should greatly increase it.[2]

  1. It is here supposed that we have chosen for components such substances as are incapable of resolution into other components which are independently variable in the homogeneous masses. In a mixture of alcohol and water, for example, the components must be pure alcohol and pure water.
  2. From the experiments of M. E. Duclaux (Annales de Chimie et de Physique, ser. 4, vol. xxi, p. 383), it appears that one per cent. of alcohol in water will diminish the superficial tension to .933, the value for pure water being unity. The experiments do not extend to pure alcohol, but the difference of the tensions for mixtures of alcohol and water containing 10 and 20 per cent. water is comparatively small, the tensions being .322 and .336 respectively.
    According to the same authority (page 427 of the volume cited), one 3200th part of Castile soap will reduce the superficial tension of water by one-fourth; one 800th part of soap by one-half. These determinations, as well as those relating to alcohol and