Automatic elucidation of electrode mechanisms by a knowledge-based system: Part 2: Staircase voltammetry, convolutive voltammetry and chronocoulometry applied to simple mechanisms

An improved expert system for the automatic elucidation of electrode reaction mechanisms is presented. The system is coupled to the electrochemical instrument, designs the experiment, controls it and collects the results automatically. The approximate logic concept is used to handle situations when inconsistent or conflicting information is obtained. Cyclic staircase voltammetry, chronocoulometry/chronoamperometry and convolution voltammetry are used at this stage of development. In the elucidation process, general information and characteristics of particular reaction steps are delivered, and are finally combined in an answer about the mechanism of the electrode reaction. The present set of rules allows full elucidation of ten simple mechanisms. For more complicated mechanisms, all stages of the elucidation except the final combination of all gathered knowledge, are output. The performance of the expert system was checked with four well-known electrochemical systems. In all cases, the answer about the reaction mechanisms was correct. The typical time for a full elucidation cycle was about 25 min.