Titration curves in complexometric titrations with the redox system Fe(III)/Fe(II).

Potentiometric titrations of metal ions with EDTA have been carried out with a platinum or graphite electrode and the Fe(III)/Fe(II) redox system. In the absence of oxygen and for pH < 2 the titration curves may be described by an equation similar to that given previously for titrations with silver and mercury electrodes. Titration curves for bismuth and indium, which are more strongly complexed than iron, are asymmetrical and useful for analytical purposes. When the titrated ions are complexed less strongly than iron(III) ions the kinetics of metal complexation have a pronounced effect. The titration curves of thorium and copper, which react more rapidly than iron, are analytically useful. The curves recorded rapidly after titrant additions have a better end-point break than those which correspond to thermodynamic equilibrium. When a metal, e.g., nickel, is weakly bound by EDTA, and reacts more slowly than iron, a very small end-point break or none at all is observed.