Total and free charge densities on mercury coated with self-assembled phosphatidylcholine and octadecanethiol monolayers and octadecanethiol/phosphatidylcholine bilayers

The thermodynamic ‘total’ charge density is the charge to be supplied to the electrode to keep the applied potential constant when the electrode surface is increased by unity, while the extrathermodynamic ‘free’ charge density is the charge actually experienced by the diffuse layer ions. The total charge density at dioleoylphosphatidylcholine (DOPC) and octadecanethiol (ODT) monolayers and mixed ODT/DOPC bilayers self-assembled on mercury from aqueous solutions was determined from chronocoulometric single potential steps to a final potential negative enough to cause complete desorption of the film. The effect of different alkali metal ions and of tetramethylammonium on DOPC desorption was examined. The total charge for ODT monolayers and ODT/DOPC bilayers, +56±3 μC cm⁻², agrees with the value obtained by integration of the current under the reductive desorption voltammetric peaks, only provided the scan rate is higher than 100 mV s⁻¹. An approximate model of the interface of the ODT-coated electrode, which accounts for partial charge transfer from sulfur to mercury and for the degree of dissociation of the sulfhydryl group upon self-assembly, was employed to estimate the free charge density.