KINETICS AND MECHANISM FOR THE ELECTROCHEMICAL REDUCTION OF BENZOPHENONE IN ACIDIC MEDIA. Report No. 53
The kinetic and mechanism factors in the electrochemical reduction of ketones were investigated by observation of the relations for the reduction of benzophenone and pbromobenzophenone over the pH range of 2 to 7 such as variation of half-wave potential, E/sub 1/2, with pH, ethanol concentration and drop-time; variation of current with time at potentials selected at various regions of 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 film at the interface which has marked effects on the observed behavior. The electron- transfer process for the first wave is very rapid, but the subsequent irreversible chemical process (dimerization) causes the net reaction to appear irreversible. The process producing the second oneelectron wave (reduction of free radical to carbinol) is quaeireversible. The rate of the combined wave, observed above ca. 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 pHdependency of wave II is discussed. (auth)
- Research Organization:
- Michigan. Univ., Ann Arbor
- NSA Number:
- NSA-14-012532
- OSTI ID:
- 4170731
- Report Number(s):
- TID-5711
- Country of Publication:
- United States
- Language:
- English
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