Square-wave voltammetry of an adsorbed reactant

Theoretical study of a surface electrode reaction preceded by a homogeneous chemical reaction under conditions of square-wave voltammetry

“…One of the most intriguing features of the SW voltammetric response of a surface electrode reactions is the ''quasireversible maximum'' [13,14,[28][29][30][31][32][33]35], which is manifested as a parabolic dependence of the dimensionless net peak current on the logarithm of the redox kinetic parameter k. The origin and properties of the quasireversible maximum has been elaborated in detail [28,29,35]. Its importance stems from the fact that it can be exploited for estimation of the electron transfer kinetics [13,14,[28][29][30][31][32][33]35].…”

“…This is due to its feasibilities for relatively easy consideration of diverse reaction mechanisms [14,[24][25][26]. In the last two decades, however, square-wave voltammetry (SWV) replaces considerably CV in analytically oriented studies or studies concerned with the mechanism of the electrode reaction [27][28][29][30][31][32][33][34][35]. The SWV is capable to discriminate the charging current as well as to provide an insight into both half-electrode reactions, making this technique particularly suitable for studying the electrode mechanism [27][28][29][30][31][32][33][34][35].…”

“…In the last two decades, however, square-wave voltammetry (SWV) replaces considerably CV in analytically oriented studies or studies concerned with the mechanism of the electrode reaction [27][28][29][30][31][32][33][34][35]. The SWV is capable to discriminate the charging current as well as to provide an insight into both half-electrode reactions, making this technique particularly suitable for studying the electrode mechanism [27][28][29][30][31][32][33][34][35]. Several electrode mechanisms involving chemical reactions under semi-infinite diffusion mass transfer in SWV have been studied by Osteryoung and OÕDea [2,4] and others [16][17][18][19][20]22,23].…”

“…Beside the diffusion controlled electrode reactions, significant attention has also been paid to the diffusionless electrode reactions, e.g., the surface electrode reactions [3,13,14,21,[24][25][26][28][29][30][31][32][33][34][35]. It has been shown that the voltammetric responses of a surface electrode reaction possess unique features such as a ''quasireversible maximum'' [13,14,[28][29][30][31][32][33][34][35] and ''split SW peaks'' [13,14,31,34], which both can be utilized for the determination of the kinetics of the electrode reaction. Moreover, in recent papers, the properties of a surface catalytic electrode reaction were elaborated in detail, establishing criteria for measuring the kinetics of the catalytic reaction [13,14].…”

Adsorptive Stripping Voltammetric Behavior of Probucole. Experimental and Theoretical Treatment

“…4, within the same frequency interval, the relationship between peak currents and the SW frequency deviates signi®cantly from linearity which is a consequence of the speci®c properties of the SWV response of surface processes. According to the theoretical predictions [3,8], the SW peak current depends parabolically on the signal frequency over the large frequency interval. Within the quasireversible region, the peak current gains a maximum value, and this property of the surface redox reactions is known as à`q uasireversible maximum''.…”