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1 Polish Journal of Chemistry

1 2004

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On the Role of Specific Characteristics of the Streaming Mercury Electrode in the Generation of the Ni=onlinear Electrochemical Dynamical Phenomena

Orlik M., Jurczakowski R.

Polish Journal of Chemistry

2004

Vol. 78 / nr 9

1221-1234

The streaming mercury electrode was recently found by us a very powerful electrode type for the observation of sustained oscillations and multistability accompanying the electrode processes with the region of the negative differential resistance (NDR) in their I-E characteristics. Following our earlier experimental and theoretical studies of the electroreduction of the pseudohalogenide complexes of nickel(II) at the streaming mercury electrode, we discuss the conditions for the onset of oscillations and multistability in these processes, taking into account the dependence of the double layer capacitance on the electrode potential. The improved stability criteria, involving both the differentialCd and integral K capacitances are derived and compared with our earlier simplified theory. Based on the experimental characteristics of the Ni(II)-SCN- electroreduction it is quantitatively shown, how the two factors specific to the streaming electrodes: the permanent flow of the capacitive current and - in particular - the relatively small thickness of the diffusion layer determine the characteristics of the bistable and oscillatory behaviour.