Spectroelectrochemistry for the study of reversible electrode reactions with complex stoichiometries

The value of spectroelectrochemistry (SPEC) for the elucidation of electrode reactions with complex stoichiometries (aO + ne(-)reversible arrow bR) is investigated theoretically. The analytical equations presented enable the modelling of the absorbance response in both normaland parallel-beam modes and any potential-controlled technique. As a proof of concept, the SPEC signals of the 1:2 and 2:1 stoichiometries in chronoamperometry and cyclic voltammetry are studied and compared with the 1:1 case, demonstrating how SPEC can assist the simultaneous and unambiguous determination of the stoichiometric coefficients of the redox species.

Automated summary

The theoretical investigation on the value of spectroelectrochemistry for elucidating electrode reactions with complex stoichiometries is presented. The analytical equations allow for modeling absorbance response in various modes and potential-controlled techniques, with a demonstration on how SPEC can assist in determining stoichiometric coefficients of redox species concurrently and unequivocally.