The theoretical and practical possibilities of the determination of elementary kinetic parameters k(1), alpha(1), k(2), alpha(2) for sequence A --> B-k1,B-alpha1 --> C-kf --> D-k2,D-alpha2 were examined for various k(2)/k(1), ratios on the basis of electrochemical simulations. The errors of the kinetic parameters evaluated from theoretical CV curves or from those with artificial noise added were calculated and discussed. The subject is important for the modelling of the ECE mechanism and other consecutive reaction steps. The work demonstrates quantitatively the relations that are qualitatively familiar to chemists: a precise determination of second stage kinetic parameters in a consecutive process is impossible if their magnitude is much higher than that in the first stage. (C) 2003 Elsevier Science Ireland Ltd. All rights reserved.