THEORY OF SQUARE WAVE VOLTAMMETRY

When the sum of a synchronized square wave and staircase potential is applied to a stationary electrode, the double layer charging current may be made negligible by measurement at a suitable time after the pulses occur. The staircase allows the electrode potential to be swept over the useful potential range. The theory for a reversible system predicts that the resulting current-time behavior should be symmetrical and bellshaped with a peak at E1/2. The peak current is a linear function of concentration and the square root of the square wave frequency. The peak current is a more complicated function of square wave amplitude, measurement time, and staircase amplitude. The similarity between this technique and square wave polarography is discussed. © 1969, American Chemical Society. All rights reserved.