Abstract
An important source of thermodynamic data is measurement of the halfwave potentials of reversible polarographic or voltammetric waves. Usually such potentials are determined by performing a “log plot” analysis on experimental current—voltage data. The theory of such analyses is based on planar electrodes but in practice mercury spheres are the favourite electrodes. The prediction that sphericity affects the intercept (and, to a lesser extent, the slope) of the log plot without destroying its linearity has been verified experimentally for the reduction of Cd(II) in 1.0 M KCl at a static mercury drop electrode. Three methods of correcting for sphericity are examined and are shown to yield time-independent halfwave potentials of thermodynamic validity. Applications to chronoamperometry, normal pulse voltammetry, classical polarography and normal pulse polarography are discussed.
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