A potential that must be applied in an electrolytic cell in addition to the theoretical potential required to liberate a given substance at an electrode. The value depends on the electrode material and on the current density. It occurs because of the significant activation energy for electron transfer at the electrodes, and is particularly important for the liberation of such gases as hydrogen and oxygen. For example, in the electrolysis of a solution of zinc ions, hydrogen (E⦵ = 0.00 V) would be expected to be liberated at the cathode in preference to zinc (E⦵ = −0.76 V). In fact, the high overpotential of hydrogen on zinc (about 1 V under suitable conditions) means that zinc can be deposited instead.
Subjects: Chemistry — Physics.