Effect of the Supporting Electrolyte on the Adsorption of Octanoic Acid at the Mercury/Electrolyte Interface

The adsorption and the changes in the interfacial composition of octanoic acid at the mercury/electrolyte interface was studied by measuring the differential capacitance at different concentrations of the supporting electrolyte, at various supporting electrolyte systems and at various temperatures. The adsorption was followed by means of capacity-potential curves in the short-term region and capacity-time transients in the long-term region at selected potentials, in all the potential ranges. A decrease of the capacitance with time was observed in most cases, followed either by a constant capacitance value or by its increase. In the short-term region, anion-surfactant complexes are formed, where the anions act as bridges between the perpendicularly oriented surfactant molecules. The larger is the negative charge of the anion, the more negative will be the charge of the anion-surfactant complex leading to a shift of the potential of maximal adsorption to more positive values. The formation of metastable condensed films is best when the hydration of the anion and its size are not too large. In the long-term region the observed increase of the capacity with time can be explained as an exchange of the metastable condensed film by a hemimicellar surface state. Here, the anions act as cores of the hemimicelles, and the hydrophilic acid groups of the amphiphiles contact the solution. Two contrary effects determine the formation of the hemimicelles. The greater is the specific adsorption of the anions, the larger is the formation of hemimicelles and the increase of the capacity. With an increase in the ability of the anions to break the water structure (lyotropic or Hofmeister series), the formation of hemimicelles will be decreased. Copyright 2000 Academic Press.