Is Voltammetric Current Proportional to the Number of Transferred Electrons for Multi‐Charged Ions or to 3/2 Power of the Number?

Particles with a large number of electrons to transfer, such as nanoparticles and colloidal redox particles, give voltammetrric currents that were demonstrated theoretically to be proportional directly to the number of the electrons, n , rather than to n 3/2 . The latter quantity is included in the conventional expression for voltammetric peak currents of multi‐charge transfer processes. This apparent contradiction appears depending on whether the charge transfer occurs concurrently ( n 3/2 ) or consecutively ( n ). The expression for the linear sweep voltammetric current was derived from a combination of the diffusion equation for large particles with n electrons and the Nernst equation for the n ‐time consecutive one‐electron reactions at the electrode. The power in n for the peak currents, in several voltammetric techniques, was demonstrated to be ascribed to the convolution of the Nernst equation and the diffusion equation.