Part V – May 1969 - Communications - On the Near-Surface Effect in Tracer Diffusion

Two recent papers in this journal1,2 contain experimental evidence for an anomaly in the concentration gradient for tracer diffusion. In both papers, the authors suggest that this anomaly is due to a Gibbs' absorption effect. Their hypothesis is that surface active tracer elements tend to remain in or near the surface adsorption layer, thereby altering the diffusion flux and concentration gradient. It is not clear how the anomaly can be explained in terms of an adsorption effect. Surface tension forces act parallel rather than perpendicular to a surface and therefore should affect only the rate of spreading of surface active agents tangentially across a surface. Frenkel3 has given a short treatment of surface tension as a driving force for surface diffusion. While the equilibrium concentration of a surface active agent at the surface of a solution is known to be higher than in the bulk, its chemical potential is necessarily the same. It is difficult to see how adsorption can result in an anomaly in the chemical potential gradient, which is the driving force for diffusion. A more detailed explanation by the authors of the adsorption mechanism is in order. A similar anomaly does not seem to arise where