Adsorption kinetics of tetrabutylammonium cations on Bi() plane

Adsorption kinetics of tetrabutylammonium cations on Bi() plane

“…It should be noted that these conclusions are in a good agreement with the results in literature [33 -37, 71] devoted to the conception of so-called "ideally polarizable electrode" [1][2][3][4][5]. The main results established can be reviewed as a conclusion that there is no ideally polarizable electrodes if α ≠ 1.0 [33,70,71]. Thus, from the physical point of view there are problems with the conception of "ideally polarizable electrode" for the solid electrodes but the classical conception takes into account only the fact that the Faradaic current has to be minimal [71].…”

“…However, there is an additional maximum in the phase angle vs. log f plots for the data obtained in the region of maximal adsorption, which is probably due to the formation (or dissipating) of the twodimensionally associated layers at some parts of the electrode surface. |δ| decreases somewhat at the negative potentials (E ≤ -1.45 V) and at very low frequencies, which may be connected mainly with a partial charge transfer process or very slow Faradaic processes, occurring at very low frequencies [2][3][4][5]70]. The shape of the δ,logf-curves is practically independent of electrode potential at f ≥ 100 Hz (except E ≤ -1.65 V and E ≥ -0.…”

“…In the case of lower concentrations (c cat < 1×10 -5 M) the influence of C n and R n on the coincidence of fitted and experimental curves is very small. [70] The double layer capacitance values C dl are minimal in the regions of TBN + adsorption and increase with desorption of TBN + at E < -1.65 V or if the adsorption of Ianions begins at E > -0.65 V (Fig. 6 (c)).…”

“…at the ideally polarizable electrodes [7,11]. The C ad values increase very quickly with the decrease of ω at E ≤ -1.45 V as well as at E ≥ -0.65 V, where the value of ( µ θ E ∂ ∂ ) is high [70]. At very high frequencies as well as in the region of maximal adsorption, C ad has a tendency to approach zero.…”

Adsorption of camphor and 2,2′-bipyridine on Bi(111) electrode surface

“…4a and 6a)) and Bode phase angle and complex impedance versus log f plots (Figs. 4b and 6b) [32,33,[35][36][37][38][39][40][41][42][43] shows that, in the region of ac frequency from 500 to 10 Hz, the camphor adsorption is limited mainly by the rate of the heterogeneous adsorption step and adsorption of 2,2 -BP is limited mainly by the mixed kinetics (slow heterogeneous adsorption and diffusion steps) because the phase angle values are lower than −75 • like for uracil adsorption on Bi(h k l) [33]. The characteristic relaxation time τ max = (2πf max ) −1 varies from 0.7 s (at E = −1.2 V) to 0.43 s (at E = −0.80 V) for camphor and τ max is over 0.3 s for 2,2 -BP at E = −1.3 V. At E > −1.3 V it is impossible to obtain τ max values because of the very slow adsorption kinetics of 2,2 -BP.…”