Steady-State or Transient Techniques

Voltammetric techniques may be broadly divided into steady-state techniques, such as channel flow cell [36,37], rotating disk [38,39], or microelectrode [40] voltammetry at sufficiently low potential scan rate to give a current re- 

Transient spectroelectrochemical studies are possible with modern and fast spectroscopic probes, e.g. based on diode array spectrometers [46]. Compared to steady-state techniques, the design of transient spectroelectrochemical ex- 

The experiment was based on a channel flow cell system (see Fig. II.6.2) with UV/Vis detection downstream of the working electrode (Fig. II.6.2D). Switching the electrode potential from the potential region with no faradaic current into a region with diffusion-limited faradaic current allowed the transient change in the UV/Vis absorption to be monitored. The data analysis for this transient UV/Vis response was based on a computer simulation model, which allowed D(TMPD) and D(TMPD ) to be varied independently. Interestingly, the difference in D(TMPD) and D(TMPD ) was relatively high in water and ethanol (15% slower diffusion of the radical cation) and considerably lower (5%) in the less polar solvent acetonitrile. This example demonstrates the ability of transient spectroelectrochemical experiments, in conjunction with computer simulation based data analysis, to unravel even complex processes. 

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