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The interest of checking structural properties of reactional mechanisms prior to any attempt at estimating their kinetic parameters is illustrated by considering the identifiability of the parameters of the Volmer-Heyrovsky mechanism. The technique employed applies to any of the small-signal methods used for the study of electrochemical mechanisms. It turns out that the stationary method and electrochemical impedance spectroscopy do not make it to estimate the kinetic parameters unambiguously, even from noise-free data, contrary to the use of the electrogravimetric transfer function.
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