Ion Transport through Monolayers and Interfacial Films.

Ion transport through monolayers and through several molecules of thick films at the mercury/water interface is discussed. The permeability of the monolayer is described by a rate constant, k(c). The permeability of a thin but not monomolecular film is expressed as a function of the thickness of the film, the diffusion coefficient of the permeant in the film, and the distribution coefficient between the film and the bulk of the solution. The rate constant k(c) is expressed in terms of absolute rate processes. In the absence of specific interactions, the activation energy is composed of three terms: (a) electrostatic interaction between the permeating ion and the charged monolayer, (b) monolayer compression work of forming a hole for passage of the ions, and (c) energy of boundary line formation between the monolayer and the hole. The contribution of the third term is especially marked in condensed monolayers. Ions are bound weakly to the monolayers of the dipolar ion lecithin, which complicates the transport problem in this system. The retardation of oxygen reduction by the lecithin monolayer is of particular interest.