Abstract
The kinetic and mechanism factors in the electrochemical reduction of ketones were investigated by observation of the following relations for the reduction of benzophenone and p-bromobenzophenone over the pH range of 2 to 7: variation of E1/2 with pH, ethanol concentration, and droptime; vaniation of current wtth time at vanious points on the polarographic waves; and variation of the heterogeneous rate constant with pH, ethanol concentration, and temperature. The pinacol produced by dimerization of the free radical formed in the first one- electron wave may form an insoluble (adsorbed?) film at the interface which has marked effects on the obserwed behavior. The wave I electron-transfer process is quite rapid, but the subsequent irreversible chemical process (dimerization) causes the net reaction to appear irreversible. The process producing the second one-electron wave (reduction of free ducing the second one-electron wave (reduction of free radical to carbinol) is quasi-reversible. The combined wave, observed above - pH 5, is controlled at first by the wave II process; with increasing pH, control shifts to the wave I process. The cause of the heretofore unobserved slight pH-dependency of wave II is discussed. (auth)
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