Theoretical expressions and mathematical analysis in cyclic reciprocal derivative chronopotentiometry (CRDCP) are presented for totally irreversible electrode processes corresponding to the application of symmetrical and unsymmetrical programmed currents. For two successive unsymmetrical programmed currents, the effect of the currents ratio b (b= vertical bar I-2(t)/I-1(t)vertical bar) on the (dt/dE)-Ecurves is discussed. The electrochemical behavior of totally irreversible electrode processes has been studied corresponding to the application of the unique unsymmetrical programmed phi(m)(I-0) proposed recently. CRDCP characteristic parameters obtained for totally irreversible electrode processes are different from those of reversible electrode processes. Therefore, a comparison of CRDCP between both mechanisms is presented. Based on the mathematical derivation, alternative methods for kinetic measuring are described. It is prospected that CRDCP is convenient and applicable for studying the reversibility of the electrode processes in form of CRDCP characteristic parameters. (C) 2007 Elsevier Ltd. All rights reserved.