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so that the current density / and limiting current density jx for A:c o follow the equations nr jl/nF=k1pcA kc +kxK (5.6.24)

n = 0, 2, 4

Fig. 5.38 Reduction of 10~ 3 M phenylglyoxylic acid at the mercury streaming electrode in acetate and phosphate buffers containing 1 M KNO3: (1) pH 5.02, (2) pH 5.45, (3) pH 5.85, (4) pH 6.25. The curves 2, 3 and 4 are shifted by 0.2 V, 0.4 V and 0.6 V with respect to curve 1. The first wave is controlled by the surface protonation reaction while the second is a direct reduction of the acid anion. (According to J. Koryta)

15

352 j-E curve with a peak is obtained. This phenomenon is typical for a number of cases where the protonized electroactive form is formed by a surface reaction with protons (see Fig. 5.38).

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References Bard, A. J., and L. R. Faulkner, see page 290. Brdicka, R., V. Hanus, and J. Koutecky, General theoretical treatment of polarographic kinetic currents, in Progress in Polarography (Eds P. Zuman and I. M. Kolthoff), Vol. 1, p. 145, Interscience, New York, 1962. Heyrovsky, J., and Kuta, see page 343. Gerischer, H., and K. J. Vetter, Reaction overpotential (in German), Z. Physik. Chemie, 197, 92 (1951). Koryta, J., Diffusion and kinetic currents at the streaming mercury electrode, Coll. Czech. Chem. Comm., 19, 433 (1954). Koryta, J., Electrochemical kinetics of metal complexes, AEy 6, 289 (1967). Koutecky, J., and J. Koryta, The general theory of polarographic kinetic currents, Electrochim. Acta, 3, 318 (1961). Southampton Electrochemistry Group, see page 253. 5.7 Adsorption and Electrode Processes

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nanocomposite lm by monitoring the steady-state oxidative current at constant potential for the reactions (Fig 1316) taking place on the working electrode surface (ITO) By performing chronoamperometry under UV or visible light exposure, changes in the transport due to photoisomerization are re ected as changes in current The concept of this experiment is illustrated in Fig 1317 An ITO electrode is coated with a photoresponsive nanoporous lm At constant potential, the effective pore size limits the diffusion rates of the probe molecules (FDM, FDMDG, and FDMTG) to the electrode surface during electrolysis (as the probes are uncharged molecules, the electromigration effect can be ignored) Under dark conditions, the azobenzene moieties are predominately in their extended trans form Upon UV irradiation (l = 360 nm), the azobenzene moieties isomerize to the more compact cis form, which should increase the diffusion rate and correspondingly the oxidative current.

As mentioned in Section 5.1, adsorption of components of the electrolysed solution plays an essential role in electrode processes. Adsorption of reagents or products or of the intermediates of the electrode reaction or other components of the solution that do not participate directly in the electrode reaction can sometimes lead to acceleration of the electrode reaction or to a change in its mechanism. This phenomenon is termed electrocatalysis. It is typical of electrocatalytic electrode reactions that they depend strongly on the electrode material, on the composition of the electrode-solution interphase, and, in the case of single-crystal electrodes, on the crystallographic index of the face in contact with the solution. Adsorption can also have the opposite effect on the rate of the electrode reaction, i.e. it can retard it. This is termed inhibition of the electrode

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