Polarography

Polarography is a type of voltammetry where the working electrode is a dropping mercury electrode (DME) or a static mercury drop electrode (SMDE), which are useful for their wide cathodic ranges and renewable surfaces. It was invented in 1922 by Czech chemist Jaroslav Heyrovský, for which he won the Nobel prize in 1959. The main advantages of mercury as electrode material are as follows:

1. a large voltage window: ca. from +0.2 V to -1.8 V vs reversible hydrogen electrode (RHE). Hg electrode is particularly well-suited for studying electroreduction reactions.
2. very reproducible electrode surface, since mercury is liquid.
3. very easy cleaning of the electrode surface by making a new drop of mercury from a large Hg pool connected by a glass capillary. Polarography played a major role as an experimental tool in the advancement of both Analytical Chemistry and Electrochemistry until the 1990s (see figure below), when it was supplanted by other methods that did not require the use of mercury. Polarography is an electrochemical voltammetric technique that employs (dropping or static) mercury drop as a working electrode. In its most simple form polarography can be used to determine concentrations of electroactive species in liquids by measuring their mass-transport limiting currents. In such an experiment the potential of the working mercury drop electrode is linearly changed in time, and the electrode current is recorded at a certain time just before the mercury drop dislodges from a glass capillary from where the stream of mercury emerges. A plot of the current vs. potential in a polarography experiment shows the current oscillations corresponding to the drops of Hg falling from the capillary. If the maximum currents of each drop were connected, a sigmoidal shape would result. The limiting current (the plateau on the sigmoid), is called the diffusion-limited current because diffusion is the principal contribution to the flux of the electroactive material at this point of the Hg drop life.