CHOICE OF EXPERIMENTAL-METHOD INDUCED BY STRUCTURAL-PROPERTIES OF MECHANISMS

The interest of checking structural properties of reaction mechanisms prior to any attempt at estimating their kinetic parameters is illustr ated by considering the identifiability of the parameters of the Volme r-Heyrovsky mechanism. The technique employed applies to any of the sm all-signal methods used for the study of electrochemical mechanisms, a s well as to signals involving large deviations. It turns out that ste ady-state measurements, electrochemical impedance spectroscopy and lin ear sweep voltammetry do not make it possible to estimate the kinetic parameters unambiguously, even from noise-free data, contrary to elect rogravimetry. This type of analysis, which seems still largely ignored among electrochemists, can be used for the choice of experimental pro cedures to be employed.