Giving physical insight into the Butler–Volmer model of electrode kinetics: Application of asymmetric Marcus–Hush theory to the study of the electroreductions of 2-methyl-2-nitropropane, cyclooctatetraene and europium(III) on mercury microelectrodes

Giving physical insight into the Butler–Volmer model of electrode kinetics: Part 2 – Nonlinear solvation effects on the voltammetry of heterogeneous electron transfer processes

“…As suggested by several authors [8,21,22,[26][27][28][29], a reasonable explanation is related to asymmetric Gibbs energy curves for the initial and final species (oxidized and reduced forms) as a result of the change of charge in the ET process. Consequently, the vibrational modes and the interactions with the surroundings may differ significantly between the oxidized and reduced species.…”

“…In the last few years the validity of the MH model has been questioned on the basis of experimental deviations documented for solution-phase and surface-bound electrode processes [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23]. Spectroscopic measurements have also shown discrepancies with respect to the Marcus picture of electron transfer [24,25].…”

Square‐Wave Voltammetry: A Review on the Recent Progress

“…In the reviewed period significant contributions in the theory of SWV have been done by the research groups of Lovric [18][19][20][22][23][24][25][26][27][28][29], Molina [17,[30][31][32][33][34][35], Compton [36][37][38][39], Mirceski [40][41][42][43], Gulaboski [44][45][46][47], and others [48][49][50]. The theory refers to a variety of electrode mechanisms including dissolved or immobilized redox couples at macroscopic planar or microelectrodes, as well as processes undergoing in a restricted diffusion space.…”

“…Due to their relevance for biochemical systems, multistep, consecutive electron transfers [17, 22-24, 33, 44] and catalytic mechanisms [30,31,34,45] have received considerable attention. Importantly, a series of works have been dedicated to the study the electrode processes in the frame of Marcus-Hush electron transfer kinetic model [36][37][38][39]. In addition, several works have been published addressing general methodological issues in SWV such as the role of the scan rate [27] and the influence of the ohmic drop effect [51,52].…”

Measuring the Electrode Kinetics of Surface Confined Electrode Reactions at a Constant Scan Rate

“…The application of square-wave voltammetry (SWV) [1] for mechanistic and kinetic studies [2][3][4][5][6][7][8] of electrode processes increases permanently in the last decade, due to the intensive development of the theory of the technique for a variety of electrode mechanisms and electrode geometries [9][10][11][12][13][14][15][16][17]. A plethora of intriguing studies has been conducted in relation to the kinetics of charge transfer processes at liquid/liquid interfaces [18][19][20][21][22][23], electrochemistry of immobilized proteins [24,25], and catalytic mechanisms [26][27][28], revealing that SWV is highly suited for both mechanistic and kinetic characterization of electrode reactions, besides its excellent analytical performances [29][30][31][32][33][34] and its appropriateness for bioanalytical applications [35][36][37][38][39][40][41].…”