The galvanostatic double-pulse method in the study of the kinetics of stepwise electrode processes involving the adsorption of intermediates

Pulsed Anodization for Control of Porosity Gradients and Interface Roughness in Porous Silicon

“…The very nature of the anodization technique used in this work, in which constant current is repeatedly pulsed, enables the observation of reaction kinetics via galvanostatic relaxation throughout the anodization process. Previous reaction kinetic studies [37][38][39][40] are summarized schematically in Fig. 9, which qualitatively illustrates the response of the potential relaxation to a galvanostatic pulse and the concentration of adsorbed intermediates.…”

“…The inferred high concentration of Si͑I͒ abs at the instant the pulse turns on suggests that the first step is slow compared to the second step in the dissolution reaction, hence k 1 Ͻ k 2 . 38 This galvanostatic analysis also applies when additional electrochemical steps are considered, [40][41][42] as is the case here, where a second intermediate Si͑II͒ abs is possible for the oxidation Reaction 3. In this situation the potential response is still dependent on the concentration of the first intermediate Si͑I͒ abs .…”

Theory of square wave voltammetry of three step electrode reaction

“…In voltammetry the response may consist of one, two or three peaks, depending on the stability of intermediates [4,5]. The theory of this type of reactions is developed for the single and double pulse chronoamperometry [6][7][8], chronopotentiometry [9,10], polarography [11][12][13], cyclic voltammetry [14][15][16] and square wave voltammetry [17]. Electrode reactions of bismuth [18][19][20][21][22][23][24][25][26] and antimony [27] were analyzed.…”

Theory of Square-Wave Voltammetry of Two-Electron Reduction with the Adsorption of Intermediate

“…Thermodynamically unstable intermediate can be kinetically stabilized if the second charge transfer is slow [1,3,4]. Furthermore, the intermediate can be stabilized by the adsorption to the electrode surface [7][8][9][10][11]. This phenomenon was observed in electroreduction of hydrogen [8,9], chloropyridines [12], and paraquet [13], in electrooxidation of bismuth [7], aluminum [14], and methanol [15], in the passivation of cobalt electrode [16], and in the anodic evolution of oxygen [17].…”

“…Furthermore, the intermediate can be stabilized by the adsorption to the electrode surface [7][8][9][10][11]. This phenomenon was observed in electroreduction of hydrogen [8,9], chloropyridines [12], and paraquet [13], in electrooxidation of bismuth [7], aluminum [14], and methanol [15], in the passivation of cobalt electrode [16], and in the anodic evolution of oxygen [17]. The theory of two-electron reaction complicated by the adsorption of intermediate is developed for pulse and differential pulse polarography [18][19][20][21][22][23] and for impedance measurements [24][25][26], and in this paper the theory is extended to squarewave voltammetry [27][28][29].…”