AbstractSome characteristics of bi‐ligand systems, important for the design and performance of studies on mixed‐ligand complex formation, are given. The problem of the optimum ligand concentration is discussed using published results. In the experimental work the concentration range of the stronger complexant (at a constant level of the weaker) seems to be critical. The measurements should start under conditions where the increase in the half‐wave potential shift (with respect to the situation in the presence of only the weaker ligand) is virtually absent and finish at concentrations where it is pronounced. Small changes at the beginning reflect the ‘contribution’ of ternary species to the composite signal, whereas the big shifts at higher concentrations are mainly produced by simple species with only a minor contribution from mixed‐ligan
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