The theoretical treatment of derivative potentiometric stripping analysis and differential potentiometric stripping analysis is presented. The latter term refers to the technique employing the derivative of time with respect to potential vs. the potential function as the measured signal. The mathematical expressions obtained were also verified experimentally.

The theoretical treatment of potentiometric stripping analysis is presented for the cases of reversible and quasi-reversible electrode reactions. The experimental results were found to be in good agreement with calculated data. Derivations based on different assumptions (e.g., stripping in stirred solutions, diffusion layer of constant thickness) are compared.

The resolution of differential potentiometric stripping analysis has been evaluated in terms of the difference in the half-wave potentials, the number of electrons involved in the electrode reactions and the concentration ratio of the ions to be determined simultaneously. The asymmetry of the dt/dE vs. E function was found to affect the resolution considerably. In other words the interference is considerably enhanced when the half-wave potential of the interfering ion is more cathodic than that of the measured one while in the reverse case the resolution is much improved