Square Wave Anodic Stripping Voltammetry at the Mercury Film Electrode: Theoretical Treatment

The theoretical treatment of square wave anodic stripping voltammetry at a mercury film electrode Is presented. Numerlcal calculations, using the step method, show that the dlfferentlal current voltammograms are symmetrical and the peak potentlal, E,, shlfts to more negaflve potentials (anEd8 log A = 59.2 mV) with decreasing film thickness parameter A = / / ( D R ~ ) " * . For A < 0.3, peak current Is proportional only lo square wave (SW) frequency ( f ) and amount of metal depostted In the mercury layer ( 9 R ) and glves a response 6 tlmes as great as other stllpping waveforms (A/, = o.M8f#qRf under typical condltkns wlth a 5O-mV SW amplitude, a 10mV step height, and n = 1). The peak wldth changes from a constant 124 mV for A > 3 to 99 mV for A < 0.3.