Voltammetry

Voltammetry is a category of electroanalytical methods used in analytical chemistry and various industrial processes. In voltammetry, information about an analyte is obtained by measuring the current as the potential is varied.

Voltammetry experiments investigate the half-cell reactivity of an analyte. Voltammetry is the study of current as a function of applied potential. These curves I = f(E) are called voltammograms. The potential is varied arbitrarily either step by step or continuously, and the actual current value is measured as the dependent variable. The opposite, i.e., amperometry, is also possible but not common. The shape of the curves depends on the speed of potential variation (nature of driving force) and on whether the solution is stirred or quiescent (mass transfer). Most experiments control the potential (volts) of an electrode in contact with the analyte while measuring the resulting current (amperes).

To conduct such an experiment one requires at least two electrodes. The working electrode, which makes contact with the analyte, must apply the desired potential in a controlled way and facilitate the transfer of charge to and from the analyte. A second electrode acts as the other half of the cell. This second electrode must have a known potential with which to gauge the potential of the working electrode, furthermore it must balance the charge added or removed by the working electrode. While this is a viable setup, it has a number of shortcomings. Most significantly, it is extremely difficult for an electrode to maintain a constant potential while passing current to counter redox events at the working electrode.

To solve this problem, the roles of supplying electrons and providing a reference potential are divided between two separate electrodes. The reference electrode is a half cell with a known reduction potential. Its only role is to act as reference in measuring and controlling the working electrode's potential and at no point does it pass any current. The auxiliary electrode passes all the current needed to balance the current observed at the working electrode. To achieve this current, the auxiliary will often swing to extreme potentials at the edges of the solvent window, where it oxidizes or reduces the solvent or supporting electrolyte. These electrodes, the working, reference, and auxiliary make up the modern three electrode system.

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