QUANTITATIVE RESOLUTION OF OVERLAPPED PEAKS IN PROGRAMMED POTENTIAL-STEP VOLTAMMETRY

Several methods for the quantitative resolution enhancement of overlapped vottammetric data were evaluated. Square wave voltammetry was selected as the quantitative technique of choice because of the low limits of detection obtainable, symmetric current-voltage peaks, and ease of implementation by a digital computer. Differences in half-wave potentials, (ΔE1/2)n, of overlapped systems were less than 150 mV. Approaches such as derlvatizaticn of square wave data and real-time modification of applied potential waveforms proved to be only moderately effective in increasing resolvability. Numerical deconvolution by means of multilinear least-squares regression proved to be an effective quantitative analysis tool for peak separations as small as 30 mV. The regression approach yielded accurate (<3% relative error) and rapid (<2 min 5-10 iterations) quantitative analysis of mixtures. © 1979, American Chemical Society. All rights reserved.