Overpotential Oxidation, current density

In the derivations of Eq 3.14 and 3.19 for the metal oxidation current density, iox M, and the metal-ion reduction current density, ired M, it was not necessary to restrict the half-cell potential to its equilibrium value. Deviation from E M will occur if the potential of either the metal or the solution is changed, resulting in an overpotential defined in general by Eq 3.1. More specifically, small deviations are associated with charge-transfer polarization, and the overpotential is designated as ... 

With an oxidation overpotential, the removal of electrons from the electrode makes it more positive relative to the solution, an effect that the electrode attempts to counteract by increasing the rate of transfer of ions from metal to solution (i.e., ioxM is increased and iredM is decreased relative to their equilibrium value, i0 M), giving a net oxidation current density. 

Electroplating passive alloys Another application of strike baths reverses the case illustrated in the previous example. The strike is used to promote a small amount of cathode corrosion. When the passivation potential of a substrate lies below the cathode potential of a plating bath, deposition occurs onto the passive oxide film, and the coating is non-adherent. Stainless steel plated with nickel in normal baths retains its passive film and the coating is easily peeled off. A special strike bath is used with a low concentration of nickel and a high current density, so that diffusion polarisation (transport overpotential) depresses the potential into the active region. The bath has a much lower pH than normal. The low pH raises the substrate passivation potential E pa, which theoretically follows a relation... 

The behaviour of hydrogen and methanol at constant oxidation rates can be compared in Fig. 2.1. Using platinized platinum anodes a constant current density was applied in a 0.5mol/L-1 H2S04 solution containing (a) H2 p — 1 bar) and (b) ImolL-1 CH3OH solution. While no more than 20 mV overpotential are... 

Significant advances have been made in this decade in electrochemical H2 separation, mostly through the use of solid polymer electrolytes. Since the overpotentials for H2 reduction and oxidation are extremely low at properly constructed gas diffusion electrodes, very high current densities are achievable at low total polarization. Sedlak [13] plated thin layer of Pt directly on Nafion proton conductors 0.1-0.2cm in thickness, and obtained nearly 1200 mA/cm2 at less than 0.3 V. The... 

Oxidant The oxidant composition and utilization are parameters that affect the cathode performance, as evident in Figure 2-3. Air, which contains -21% Oi, is the oxidant of choice for PAFCs. The use of air with -21% Oi instead of pure Oi results in a decrease in the current density of about a factor of three at constant electrode potential. The polarization at the cathode increases with an increase in Oi utilization. Experimental measurements (38) of the change in overpotential (Aric) at a PTFE-bonded porous electrode in 100% H3PO4 (191°C, atmospheric pressure) as a function of O2 utilization is plotted in Figure 5-4 in accordance with Equation (5-7) ... 

The slowest step, or rate-determining step, can be either (a) electron transfer at the electrode-solution interface or (b) formation of atoms at the electrode surface. The activation polarization component of the overpotential, r)a, is related to the actual rate of oxidation or reduction, i, and the exchange current density ... 

Given that the rates of oxidation and reduction of the half-reactions are controlled by activation polarization only, that = 4-0.07 and = —0.08, and that the exchange current densities for both the oxidation of Fe and reduction of hydrogen in acidic solution are identical, use the data in Tables 3.3 and 3.4 to determine the following quantities. Recall that the potential for each half-cell is the sum of the equilibrium potential and the corresponding overpotential, in this case, r]a-... 

In practice, one often has cases where the course of the cathodic and anodic current densities across the electrode with change of overpotential is symmetrical (except for the signs for the same numerical value of T)). It will be seen in the next section that this is so if the symmetry factor, P, is exactly 0.50. More often, the anodic and cathodic curves are nearly symmetrical. However, sometimes they are importantly and even dramatically different. For example, the anodic current is oxidizing and could provoke... 

The dissolution reaction is Pt - Pt2+ + 2e and the value of its reversible thermodynamic potential is 1.2 V on the normal hydrogen scale. The evolution of O2 in acid solution at a current density of, say, 100 mA cm, needs an overpotential on platinum of nearly 1.0 V, i.e., the electrode potential would be >2.0 V. It follows feat at these very anodic potentials platinum would tend to dissolve, although its dissolution would be slowed down by fee fact feat it forms an oxide film at fee potentials concerned. Nevertheless, fee facts stated show feat fee alleged stability of Pt may be more limited than is often thought. This is an important practical conclusion because dissolved Pt from an anode may deposit on fee cathode of fee cell, and instead of having fee surface one started wife as fee cathode, it becomes in fact what is on its surface, platinum. 

Figure 25 shows the evolution of cell voltage with time of Raney-nickel anodes that are deliberately operated at too high current densities so that the effectively applied overpotential was above the threshhold for nickel oxidation, which amounts to +80 mV vs the reversible hydrogen electrode. Evidently at a current density of 400 mA/cm2 and at 80°C the oxidation of Raney nickel proceeds within hours and at 300 mA/cm2 still within a week. 

At lower temperature and still lower current density and anodic overpotential, respectively (50°C, 100 mA/cm2, r = +40 mV), the observed decline of the current density with time signals physical and not chemical deterioration of the catalyst as the overpotential is not sufficient for nickel oxidation. 

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