Abstract
Analysis of electron-transfer-chemical reaction-electron-transfer (ECE) mechanisms by polarography and linear sweep voltammetry is discussed in the case where two well separated successive waves are observed. With polarography it is shown that for moderately fast first-order chemical reactions the limiting current of the second wave is inversely proportional to the square root of the mercury column height. With linear sweep voltammetry the same relation holds between peak current and sweep rate. These can be used as diagnostic criteria for ECE mechanisms. Furthermore, a new method using double potential scan is proposed for kinetic analysis of ECE systems. It allows second-order reaction kinetics as well as first-order ones to be readily determined.
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