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

Electrochemical reactions where the variation of supporting electrolyte concentration is mechanistically revealing: ECE-DISP1 processes in which the chemical step is an isomerisation

“…An irregular spatial grid was used, with a high density of regularly spaced points close to the electrode, which then expanded proportionally to R past a switching point R s . This grid has been used in previous studies [1,8,13,33]. Defining R 0 to be equal to 1, the point at the electrode surface, the grid can be expressed mathematically as follows:…”

“…This investigation uses a model based on this, with homogeneous kinetics included, also developed previously [1,16]. Table 2.…”

“…Instead, the model makes use of the zero field approximation, which negates the need to model the electrical double layer. This theoretical framework has successfully been used to model chronoamperometic [9,13] and voltammetric responses [1,8,14].…”

“…Performing voltammetric experiments under conditions of weak support has been shown to be a useful tool in probing electrochemical mechanisms [1][2][3][4][5][6]. Electrolysis of a solution transfers charge from the electrode into the solution, and will result in an electric field extending away from the electrode.…”

Theory of Square-wave Voltammetry of Kinetically Controlled Two-step Electrode Reactions

“…[1][2][3][4][5][6] For electroreduction two peaks appear if the standard potential of the second electron transfer is more than hundred millivolts lower than the standard potential of the first electron transfer. [7][8][9][10] Otherwise the response is a single peak.…”