Theory for cyclic reciprocal derivative chronopotentiometry with power and exponential programmed currents applied to electrodes coated with reversible electroactive molecular films

Theoretical expressions corresponding to the responses of adsorbed redox molecules exhibiting reversible charge transfer in cyclic reciprocal derivative chronopotentiometry with programmed currents of the form I(t)=(−1)i+1I0tiu and I(t)=(−1)i+1I0 eωti are presented. The effects of the interfacial potential distribution are considered in both cases by using the Smith and White model (Anal. Chem. 64 (1992) 2398). These equations become those previously deduced by Honeychurch (J. Electroanal. Chem. 445 (1998) 63) in reciprocal derivative chronopotentiometry with constant current on making u=0 and ω=0. The total analogy between the reciprocal derivative chronopotentiograms (dtiu+1/dE versus E or d eωti/dE versus E curves) and the cyclic voltammograms (I/E curves) is proved.