Organic electrochemical mechanisms—II. Effects of tetra-n-alkylammonium ions on the polarographic reductions of organic depolarizers

✍ Scribed by J.P. Petrovich

• Publisher: Elsevier Science
• Year: 1967
• Tongue: English
• Weight: 453 KB
• Volume: 12
• Category: Article
• ISSN: 0013-4686
• DOI: 10.1016/0013-4686(67)80056-2

✦ Synopsis

The reduction potentials, Ells, of ethyl cinnamate, ethyl crotonate, triphenylcyanopropylphosphonium bromide and cycle-octatetraene have been determined polarographically in dimethylfor-man-ride solvent as a function of the size of the tetra-n-alkylammonium cation used as a supporting electrolyte.

The electrocapillary curves for these salts in dimethylformamide have also been determined. Both anodic and cathodic shifts in Ells were observed with increasing size of the cation of the electrolyte depending on the nature of the depolarizer. All of the depolarizers reduce on the cathodic side of the electrocapillary maxima. The data are interpreted on the basis of the energy required to remove a cation from the electrode surface and on the relative ability of the cation to stabilize the anions formed in electrolytic reductions.