Kinetic studies by cyclic voltammetry at low temperatures using microelectrodes

Comparative studies of the reduction of 2-naphthaldehyde, 9,9′-spirobi-(9H-fluorene)-2-carboxaldehyde and 2-fluorenecarboxaldehyde in nonaqueous solvents

“…Calibration of the electrode for purposes of the determination of diffusion coefficients has been described [10]. The electrolyte solution consisted of 0.10 M Bu 4 NPF 6 in anhydrous acetonitrile (resistivity, q, of 109 X cm) or anhydrous dimethylformamide (q = 219 X cm) [11]. The experiments were conducted at 298 K. All reported potentials are referenced to the potential of the ferrocenium ion/ ferrocene (Fc + /Fc) couple as measured in the electrolyte solution.…”

Application of Global Analysis for the measurement of electrochemical parameters with disk electrodes

“…Recognition that errors due to uncompensated resistance and RC time constants could be minimized by reducing the size of an electrode has greatly improved the accuracy of kinetic measurement using cyclic voltammetry [11]. However, for the inlaid disk, which is the most popular form of electrode geometry, decreasing the size of the electrode at a particular scan rate results in enhanced mass transport due to an increased contribution of the convergent diffusion component that occurs at the electrode's edge [12].…”

Effects Due to Uncompensated Resistance and Capacitance

“…The LSV curve becomes distorted and such a correction does not retrieve the shape of the curve as it would be in the absence of an iR effect. The reason is that the varying current during the sweep changes the electrode potential by a varying amount iR u , and thus the potential program, that was intended to be linear with time, is no longer so.Bowyer et al [5] and Strutwolf [6] show examples of such distorted potentialtime relations and also distorted LSV curves, see also below.The simulation literature deals with this problem sporadically, although it is often simply ignored. The iR effect introduces nonlinear boundary conditions (see below), and these have been dealt with in various ways.…”

“…The work of Bowyer et al [5] is interesting. Recognising that iR effects will distort the LSV signal from the nominal linear change, they took account of the measured current and knowing the resistance, calculated the resulting distorted potential sweep signal, and fed this into the simulation.…”

“…Some have taken the easy way out and used explicit methods [15][16][17][18], others used hopscotch [12,19], ADI (for a two-dimensional problem) [20,21] and other methods [4,5,[22][23][24][25][26]. Bieniasz [27] used the Rosenbrock method (see Chap.…”