Published in

Wiley, Chinese Journal of Chemistry, 7(20), p. 657-662, 2010

DOI: 10.1002/cjoc.20020200707

Links

Tools

Export citation

Search in Google Scholar

On the criteria of instability for electrochemical systems

This paper was not found in any repository; the policy of its publisher is unknown or unclear.
This paper was not found in any repository; the policy of its publisher is unknown or unclear.

Full text: Unavailable

Green circle
Preprint: archiving allowed
Orange circle
Postprint: archiving restricted
Red circle
Published version: archiving forbidden
Data provided by SHERPA/RoMEO

Abstract

Both cyclic-voltammetry-based and impedance-based experimental criteria that have been developed recently for the oscillatory electrochemical systems are critically appraised with two typical categories of oscillators. Consistent conclusions can be drawn by the two criteria for the category of oscillators that involve the coupling of charge transfer mainly with surface steps (e. g. ad- and desorption) such as in the electrooxidation of C, organic molecules. Whereas, impedance-based criterion is not applicable to the category of oscillators that involve the coupling of charge transfer mainly with mass transfer ( e. g. diffusion and convection) such as in the Fe(CN)(6)(3-) reduction accompanying periodic hydrogen evolution. The mason is that the negative impedance cannot include the feedback information of convection mass transfer induced by the hydrogen evolution. However, both positive and negative nonlinear feedbacks, i. e., the diffusion-limited depletion and convection-enhanced replenishment of the Fe(CN)(6)(3-) surface concentration, that coexist between the bistability, i. e., Fe(CN)(6)(3-) reduction With and without hydrogen evolution at lower and higher potential sides respectively, are all reflected in the crossed cyclic voltammogram (CCV). It can be concluded that the voltammetry-based criterion (in time domain) Is more intuitive, less time-consuming and has a wider range of applications than the impedance-based one (in frequency domain).