A VOLTAMMETRIC ANALYSIS OF THE ELECTROCHEMICAL-BEHAVIOR OF ONIUM SALTS AT A MERCURY-ELECTRODE

An analysis of the cyclic voltammograms of the reduction of various onium salt at mercury, produced more detailed information concerning the nature of the reaction pathway, in terms of adsorption, amalgam formation and kinetics of electron transfer, and lead to an interpretation of the characteristic ″inverted peak″ . An ″auto-catalytic″ reaction mechanism was indicated, and in conjunction with the preparative experiments a full reduction scheme proposed for the sulphonium salt ( left bracket Ph//2S** plus CH//3 right bracket ClO//4** minus ) and the phosphonium salt ( left bracket Ph//2P** plus (CH//3)//2 right bracket Br** minus ).