Voltammetric Studies of Parallel Electrode Processes Under Low Ionic Strength Conditions. Influence of Convection

It is known that either a very strong enhancement or an almost complete depression of the height of one of two waves can be obtained when two analytes (one appropriately charged and one uncharged) are present in a quiet solution containing no supporting electrolyte. In this paper we examine whether these effects can be extended for solutions with forced convection. Three two‐analyte mixtures were examined voltammetrically under conditions of no added supporting electrolyte and added convection. The first mixture (1,1′‐ferrocenedimethanol and ferrocenesulfonate anion) changes its total charge from −1 to +1 after electrooxidation of both components. Under all applied conditions, the introduction of convection caused an increase of both waves without changing the wave height ratio. A similar behavior was observed for the mixture of ferrocene and 1,1′‐ferrocenedimethanol. For this system the total charge changes from 0 to +2. A substantial influence of convection on the ratio of two waves was found for the third mixture: ferrocene and ferrocenylmethyltrimethylammonium cation (total charge changes from +1 to +3). For this system the convection strongly depressed the migrational effects. The obtained experimental results were verified with simulations using software MIOTRAS. This software is capable of modeling diffusion, migration, convection and following homogenous reactions. The agreement between experiment and simulations was fairly good.