Digital simulation of migrational voltammetry.

Steady-state voltammetry at a microdisc electrode in the absence of excess supporting electrolyte for reversible, quasi-reversible and irreversible electrode kinetics

“…The value of the diffusion coefficient for [Ru(NH 3 ) 6 ] 2+ is obtained by fitting the voltammetric current at a steady-state using the numerical simulation. 24 The value of the diffusion coefficient for [Ru(NH 3 ) 6 ] 2+ is 8.6 Â 10 À10 m 2 s À1 , in good agreement with the literature value. 41 The steady-state value becomes smaller with increasing support ratio.…”

“…22 Consequently, the use of hemispherical electrodes in experimental work is also popular. 17,23,24 However, such studies are restricted because hemispheres are only easily fabricated using mercury: the electrode must be made and characterised before every experiment in order to maintain a clean surface; mercury is toxic; mercury reacts with many common ions, most notably halides and sulphides; mercury often limits the potential window of the experiment in the oxidative direction; finally, the surface tension of mercury, and its potential dependence, limits the range of radii over which the electrode is truly hemispherical. In order to strike a compromise between theoretical and experimental work, many workers rely on the so-called 'hemispherical approximation': the voltammetry obtained at a microdisc, of radius r e , is presumed to be identical to that obtained at a hemisphere, of radius 2 p r e .…”

Cyclic Voltammetry in the Absence of Excess Supporting Electrolyte Offers Extra Kinetic and Mechanistic Insights: Comproportionation of Anthraquinone and the Anthraquinone Dianion in Acetonitrile

“…[5,6,[12][13][14][15][16] Most publications to date have only considered systems at steady state; this was the case for the EE studies (E stands for an electron-transfer step) noted above. [5,6,[12][13][14][15][16] Most publications to date have only considered systems at steady state; this was the case for the EE studies (E stands for an electron-transfer step) noted above.…”

Cyclic Voltammetry in the Absence of Excess Supporting Electrolyte Offers Extra Kinetic and Mechanistic Insights: Comproportionation of Anthraquinone and the Anthraquinone Dianion in Acetonitrile

“…Several theories have been developed to account for electrochemistry at low support. [5,6,[12][13][14][15][16] Most publications to date have only considered systems at steady state; this was the case for the EE studies (E stands for an electron-transfer step) noted above. [8][9][10][11] Work under transient conditions has been done exclusively for the E mechanism.…”