Applications of small iridium-based mercury electrodes to high concentrations of depolarizers

Voltammetric and microscopic data on the analytical properties of small iridium-based (127- μm diameter) mercury film electrodes are presented. A method of estimating and controlling the size of the deposit is described. The voltammetric behaviour of electrodes with mercury deposits varying from a film to a near-hemisphere is discussed for linear-scan, differential- and normal- pulse voltammetry. The systems Pb²⁺/Pb, Fe³⁺/Fe²⁺ and Co²⁺/Co, are used to show that, by changing the size of the deposit, either time-dependent or almost time-independent (steady-state) voltammograms can be obtained under the same instrumental conditions. Possible applications to the determination of high concentrations of depolarizers are outlined; voltammetric data for the determination of lead in the range 10–120 mM are presented. The evaluation of diffusion coefficients is discussed.