Voltammetry of surface redox processes perturbed by a father-son reaction

ssThe theory for surface redox processes perturbed by a father-son reaction under linear voltammetric conditions, and in the absence of mass transport complications, has been extended to remove the kinetic restrictions of pre vious treatments. The solution of the initial value problem, when reactants and products remain in the adsorbed state, is shown to be closely related to that corresponding to reactants equilibrated with the bulk solution at a ny potential. Analytical expressions for the voltammetric waves are derived for the fast reversible and irreversible kinetic limits, and empirical equ ations are developed to relate the peak coordinates with experimental varia bles when only numerical solutions are available. Bidirectional kinetics of the father-son reaction leads to two voltammetric waves, even when a singl e electron is being exchanged in the redox process. A comparison is made wi th previous results derived for a surface DIM1 electrodimerization mechanis m, and diagnostic criteria are outlined in terms of the peak parameter valu es. (C) 2000 Elsevier Science Ltd. All rights reserved.