Electroanalytical simulations. 10. The simulation of fast second order reactions in electrochemical systems

Two methods for the simulation of fast chemical second order reactions coupled to an electron transfer at an electrode are used in conjunction with orthogonal collocation to calculate theoretical cyclic voltammograms: spline collocation and the technique of the heterogeneous equivalent. The techniques prove to produce reliable numerical results for the model of an electro-chemically induced irreversible dimerization reaction after the application of a non-linear space coordinate transformation. Also, simulations of the ece/disp model (two electron transfers coupled by a chemical equilibrium and a disproportionation reaction) with the spline collocation method are discussed. It is shown in this case that the assumption about the DISP equilibrium usually required for the solution of the model equations can be dropped and the spline algorithm can be used throughout the parameter space.