Free energy circuits

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Within the stagnant diffusion layer, only diffusion contributes to the flux of the reacting species; outside the diffusion layer, no concentration gradients exist and convection is the only transport mechanism for the reacting species. The role convection plays for the rate of the electrode reaction can be understood by considering that convection determines the thickness of the stagnant diffusion layer; the higher the prevailing convection rate, the smaller the thickness of the Nernst diffusion layer and the higher, therefore, the flux of the reacting species at the electrode surface.

3 Kinetics of Electrolytic Corrosion Reactions Pt Fe Ecorr, Pt SCE Ecorr, Fe vs SCE vs SCE Solution potential Potential distribution between uncoupled Fe and Pt electrodes. Fig. 14 This is because the corrosion potential is measured by a voltmeter connected to the back of the metal electrode and the back of the reference electrode. The corrosion potential of the Pt is higher than that of the Fe, but the measured potentials do not depend on the position of the reference electrode within the solution because the solution potential is constant.

In order to perform Tafel extrapolation, it is necessary to polarize the electrode to large potentials on either side of the corrosion potential. It is also possible to determine corrosion rate experimentally using much smaller polarization from the corrosion potential, as is shown in this section. Equation (41) represents the measured or net current as a function of applied potential. For small E − Ecorr = dE: exp E − Ecorr b dE ∼ =1+ b (45) For small differences in potential from Ecorr , dE, the measured net currents will be small, di.

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