Question

Cyclic voltammograms for a Fe(CN)₆^3- solution are obtained when the solution is stirred and when it is unstirred. Explain why the stirred cyclic voltammogram looks different from the unstirred one. Why is the signal noisy and consider what happens to the product when formed at the electrode.

Answer 1

The electrodes are immobile and sit in unstirred solutions during cyclic voltammetry. This "still" solution method gives rise to cyclic voltammetry's characteristic diffusion-controlled peaks. This method also allows a portion of the analyte to remain after reduction or oxidation so that it may display further redox activity. Stirring the solution between cyclic voltammetry traces is important in order to supply the electrode surface with fresh analyte for each new experiment. The solubility of an analyte can change drastically with its overall charge; as such it is common for reduced or oxidized analyte species to precipitate out onto the electrode. This layering of analyte can insulate the electrode surface, display its own redox activity in subsequent scans, or otherwise alter the electrode surface in a way that affects the CV measurements. For this reason it is often necessary to clean the electrodes between scans.To run cyclic voltammetry experiments at very high scan rates a regular working electrode is insufficient. High scan rates create peaks with large currents and increased resistances, which result in distortions. Ultramicroelectrodes can be used to minimize the current and resistance.