Kb. Oldham, LIMITING CURRENTS FOR STEADY-STATE ELECTROLYSIS OF AN EQUILIBRIUM MIXTURE, WITH AND WITHOUT SUPPORTING INERT ELECTROLYTE, Analytical chemistry, 69(3), 1997, pp. 446-453
An exact treatment derives the steady-state limiting current of a one-
electron reduction for the N reversible arrow O+ + A(-) mixture at a h
emispherical microelectrode. Either or both of the neutral N and catio
nic O+ species may be electroactive, A supporting salt is present at a
ny concentration, including zero or excess; its ions are electropassiv
e acid do not interact with the other solutes or each other. The vario
us species are treated as having distinct diffusivities, linked to the
ir mobilities through the Nernst-Einstein relationship, Universal elec
troneutrality is assumed, The predictions of the model are compared wi
th published experimental data on the reduction of aqueous weak acids;
agreement is excellent at intermediate, but poor at low, support rati
os. Analysis of the unsupported case shows that the neutral N species
dissociates in a narrow zone close to the electrode, and the injection
of ions there serves to increase the electric field in the outer regi
on of the transport zone, This enhances cationic migration enormously,
leading to an unsupported limiting current that is much more than dou
ble the supported value, However, the limiting current is drastically
diminished by traces of foreign electrolyte. Curiously, the limiting c
urrent with full support adopts the same value when equilibration is f
ast as when it:is very slow, although the mechanisms are totally diffe
rent.