On the influence of RRC and RSC dimerizations on the shape of semi-integrated voltammograms : a mixed asymptotic and numerical analysis

With the ultimate purpose of determining experimentally whether rate-determining adsorption effects are involved in the electroreduction of vinylic monomers in electropolymerization synthesis, we have examined whether the diagnosis of adsorption proposed by Bowling and McCreery is still valid when dimerization reactions (RRC and RSC) are coupled to the charge transfer. The analysis we made in a previous work suggests that maxima are likely to occur on systems in which the coupled chemistry directly or indirectly consumes the depolarizer, enough to cause a significant and non-electrochemical depletion of this compound in the diffusion layer. The overall result of this study is that the RSC scheme is responsible for maxima on the convolved currents in most regions of the kinetic zones diagram even when adsorption effects are absent, while the diagnosis remains unconditionally valid for the RRC scheme. The issue as to whether these maxima are detectable experimentally is also considered.