The polarization of a calomel electrode
The object of this paper is to define, for electro-physiological purposes, the limits within which a calomel electrode is unaffected by electric current passing through it. The calomel half-cell, though always known as a non-polarizable electrode, is in fact polarizable in the same way as all other electrodes. The only difference between it and a notoriously polarizable electrode such as Pt is in degree. Since it is incorrect to talk of a calomel half-cell as a non-polarizable electrode, a definition of polarization is necessary: when a metal dips into a solution, there is a p. d. between it and the solution. Provided that (1) the composition of the electrode does not alter, (2) the activities of the components of the solution do not alter, and (3) no current flows through the system, the p. d. between the metal and the solution remains constant. If equilibrium does not exist between the metal and the solution, the p. d. does not remain constant and the metal becomes polarized. Thus polarization may be defined as the production of a thermodynamically irreversible potential at the surface of an electrode.