E.s.r. investigations of short-lived intermediates in electrochemical reactions

Abstract

In the e.s.r. investigation of electrochemically generated radicals, some limitations with respect to the lifetime of these radicals result, for the intra muros technique, from the unfavourable geometry of the sample cell which allows only for limited currents.

This drawback has been overcome to some extent by dividing the generating electrode into several independent strips each of which has its individual current supply, thus largely eliminating the interfering ohmic drop across the sample cell. In this way, the generating current and the e.s.r. signal intensity could be increased considerably under well-defined steady-state conditions.

This technique has been applied to a kinetic study of the reaction of the anion radical SO^–₂, formed upon the reduction of sulphur dioxide, with organic halides, resulting in the electrosynthesis of sulphones.