Abstract
An approximate theory for anodic stripping voltammetry with a plane, thin (⩽ 100 micron) mercury-film electrode is presented. This approximate theory is valid only for slow rates of linear potential scan during the stripping of the reduced metal from the mercury, and for thin mercury films. There are important differences between anodic stripping peaks obtained with a thin mercury-film electrode and the peaks obtained under the conditions of the Ševčik-Randles theory. In the latter case the peak potential and the peak width are independent of the rate of potential change v, and of the mercury-film, thickness l (which is supposed to be infinite), but the peaks obtained with a mercury-film electrode show a variation of both the peak potential and the peak width with varying v and l. The peak width can be very small ( ca. 40 mV), permitting a sharp separation of metals with closely adjacent half-wave potentials. For very thin mercury-films (⩽ 25 micron) the peak current is nearly proportional to the rate of potential change.
Published Version
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