Collect. Czech. Chem. Commun. 1988, 53, 732-742

Effect of surface active cations undergoing interfacial rearrangements on deposition type electrode reactions

Anastos Anastopoulos and Anastasia Christodoulou

Laboratory of Physical Chemistry, Chemistry Department, University of Thessaloniki, 54006 Thessaloniki, Greece


The influence of the adsorption of methyltriphenyl- and cyclopropyltriphenylphosphonium cations on simple deposition reactions of Cd2+ and Zn2+ at the dropping mercury electrode, is studied by polarographic techniques. The size parameters of the activated complex, r, and adsorbate particles, ri, are determined and discussed. It is shown that for substances undergoing interfacial rearrangements, i.e. condensation and reorientation, the values of the size ratio r/ri can hardly be correlated to independently determined values of r and ri. Electrode coverages are related to formal rate constants and an elucidation of the inhibition mechanism is attempted.