Stable free radicals — N-oxides of 2,2,6,6-tetramethylpiperidone and 2,2,6,6-tetramethylpiperidine — are irreversibly reduced on a dropping mercury electrode to the corresponding hydroxylamine derivatives, giving one-electron, one-stage diffusion waves.
The heights of the waves do not depend on the pH; E1/2 of the waves are determined by the kinetic volume protonation of the radicals, preceding the strictly electrochemical step. The introduction of adsorbed anions (Cl−, Br−) into the solution, produces a displacement of E1/2 of the waves, equal to the change in the ψ1-potential.
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Neimann, M.B., Mairanovskii, S.G., Kovarskaya, B.M. et al. Polarographic study of certain N-oxide free radicals. Russ Chem Bull 13, 1424–1426 (1964). https://doi.org/10.1007/BF00850350
- Free Radical
- Mercury Electrode
- Drop Mercury Electrode