Journal of Electroanalytical Chemistry, Vol.493, No.1-2, 117-122, 2000
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+1)I(0)t(i)(u) and I(t) = (- 1)(i+) 1I(0) e(omega ti) 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 omega = 0. The total analogy between the reciprocal derivative chronopotentiograms (dt(i)(u+1)/dE versus E or d e(omega ti)/dE versus E curves) and the cyclic voltammograms (IIE curves) is proved.
Keywords:cyclic reciprocal derivative chronopotentiometry;programmed currents;interfacial potential distribution;adsorption