Open circuit reactions complicating the electroprecipitation of poly(vinylferricinium) films from methylene chloride

We describe an electrochemical quartz crystal microbalance interfacial gravimetric study of the electroprecipitation and dissolution of PVF+ClO4- (PVF = poly(vinylferrocene)) films exposed to methylene chloride solutions. Film deposition is diffusion controlled by the supply of PVF from the solution. Film solvent content is markedly dependent upon the deposition potential. The self-exchange process between surface-bound ferricinium sites and solution-phase ferrocene sites, which is responsible for film deposition under conditions of positive applied potential, is also responsible for film dissolution under open circuit conditions. Dependent upon the deposition potential, releasing the electrode from potential control may (not) result in transient deposition processes that temporarily increase surface coverage. Under all conditions, opening the circuit ultimately leads to reductive stripping of the film by solution-phase PVF. The dissolution rate is independent of applied potential, and is not limited by electron transfer at the outer film interface or by electron (and coupled ion) transport within the film; we speculate that polymer-based processes, such as chain disentanglement, are rate limiting.