Automatic polarographic elucidation of electrode mechanisms by means of a knowledge-based system Part 1. Sampled d.c. polarography

A knowledge-based system has been developed for the automatic eluctdatton of electrochemical mechanisms The system IS based on sampled drrect current (or Tast) polarography at a droppmg mercury electrode as a technrque for collectmg experimental mformatton and consists of a general expert system shell for the reasonmg process, the spectftc set of rules and expenmental modules The set of rules allows the eluctdatton of eight relatively simple electrode reactton mechamsms fully atomattcally The computer system has been validated with chermcal systems the electrochermcal behaviour of which ts well established. All parts of the program are wntten m FORTH language for Apple II mrcrocomputers. Thts expert system has an open character and new rules can be added to extend the set of mechamsms that can be determmed Investigations of electrochemtcal reaction mechanisms are of importance for many branches of chemistry, especially in analytical chemistry, where the choice of a technique for the electrochemical determination of compounds of interest and the proper adjustment of the relevant variables is based on the mechanism of the reaction at the electrode. Recently, attention has been paid to the automation of the elucidation of these mechanisms, but this problem is hampered by the large number of simultaneous processes that can take place at the metal-solution interface and in its vicinity, e.g., multi-step electrochemical processes, adsorptton, homogeneous reactions and equilibna involving electroacttve species, electrocrystallizatton and layer formation. General strategies for the elucidation of mechanisms do not exist, so efficient mechamstic studies rely mostly on the expenence and knowledge of the scientist. It is to be expected that in this situation the use of soft0003-2670/90/$03 50