Electrolytic Reduction of Oxygen in Dimethyl Sulfoxide, N, N-Dimethylformamide and Acetonitrile in the Presence of Lanthanoid Ions

Abstract

The electrolytic reduction of oxygen in dimethyl sulf oxide (DMSO), N, N-dimethylformamide (DMF) and acetonitorile(AN) in the presence of lanthanoid ions and 0.05 molg NaCl04 was investigated with particular attention to the nature of electrolytic process in DMSO.
In these solvents, oxygen was reduced to an oxygen radical, 02-, which would readily pair with lanthanoid ions. The lanthanoid superoxide would in turn disproportion on the mercury electrode to form lanthanoid peroxide in DMSO.
Stable compounds of lanthanoid superoxide and peroxide of the formula M(02)3DMS0 (for the platinum electrode, in DMSO), M(02)3 (for the platinum and mercury electrodes, in DMF) and M2(02)3 DMSO (for the mercury electrode, in DMSO) have been prepared by the controlled current electrolysis. Their infra-red spectra are also reported.