Electrode of the third kind is a metal electrode assembly with the equilibrium potential being a function of the concentration of a cation, other than the cation of the electrode metal, in the solution. The assembly consists of a metal in contact with two slightly soluble salts (one containing the cation of the solid metal, the other the cation to be determined, with both salts having a common anion) immersed in a solution containing a salt of the second metal (e.g., zinc metal--zinc oxalate--calcium oxalate--calcium salt solution). The potential of the metal is controlled by the concentration of its cation in the solution, but this is controlled by the anion concentration in the solution through the solubility product of the slightly soluble metal salt, which, in turn is controlled by the concentration of the cation of the second slightly soluble salt. These electrodes are very sluggish and unstable due to a series of equilibria to be established to produce a stable potential.
Generalic, Eni. "Electrode of the third kind." Croatian-English Chemistry Dictionary & Glossary. 29 June 2022. KTF-Split. {Date of access}. <https://glossary.periodni.com>.
Glossary
Periodic Table