Cyclic voltammetric studies on [SMo12O40]2- and [SMo12O40]3- at macrodisk electrodes in acetonitrile with and without added supporting electrolyte

Abstract

The polyoxomolybdate [(C6H13)4N]2[SMo12O 40] while soluble in acetonitrile (>2.5 g L-1) precipitates from this solvent when tetraalkylammonium salts are added as the supporting electrolyte at the usual 0.1 M concentration levels used in electrochemical investigations. Although conventional conditions cannot be used, this study demonstrates that application of cyclic voltammetry in the absence of added supporting electrolyte is viable for studies on the [SMo12O40]2-/3- and [SMo12O40]3-/4- reduction processes. Thus, there is excellent agreement between voltammetric experiments and theory based on mass transport by both migration and diffusion, after problems associated with Ohmic drop are over..