The current decrease after the peak occurs because the thickness of the diffusion layer

increases with time (see 3)). Even if the potential scan is stopped after the peak, the current
continues to decrease with time in the same way.

Nowadays, most of the instruments for polarography and

voltammetry are three-electrode devices. In the case of two-electrode devices, there
is a relation V=(EDME–EREF)+iR, where V is the voltage applied to the cell, EDME
and EREF are the potentials of the DME and the counter electrode with a constant
potential, R is the cell resistance, and i is the current through the cell. If R or |i|
is large, the current-potential curve is distorted due to the influence of the ohmic
(iR) drop. In the case of three-electrode devices, the influence of the iR drop is
eliminated to a considerable extent (see Section 5.9).

Fig. 5.8 Schematic diagram of polarographic (or voltammetric) circuits for

two-electrode (a) and three-electrode (b) systems. WE(DME): indicator or
working electrode (dropping mercury electrode in the case of polarography);
RE: reference electrode; CE: counter electrode; DC voltage (V): DC voltage
source; Current (i): current measuring device.