Auxiliary electrode Auxiliary electrode The auxiliary electrode, often also called the counter electrode, is an electrode used in a three electrode electrochemical cell for voltammetric analysis or other reactions in which an electric current is expected to flow. The auxiliary electrode is distinct from the reference electrode, which establishes the electrical potential against which other potentials may be measured, and the working electrode, at which the cell reaction takes place. In a two-electrode system, either a known current or potential is applied between the working and auxiliary electrodes and the other variable may be measured. The auxiliary electrode functions as a cathode
Standard electrode potential 0.00 V and any electrode, for which the electrode potential is not yet known, can be paired with SHE—to form a galvanic cell—and the galvanic cell potential gives the unknown electrode's potential. Using this process, any electrode with an unknown potential can be paired with either the SHE or another electrode for which the potential has already been derived and that unknown value can be established. Since the electrode potentials are conventionally defined as reduction potentials, the sign of the potential for the metal electrode being oxidized must be reversed when calculating the overall cell potential. Note that the electrode