Polarization curves metal electrodes

Figure 4.38 Potentiokinetic polarization curve and electrode potential values at which stress corrosion cracking appears. (From Jones, R.H. BatteUe Pacific Northwest Laboratory, Ricker, R.E. N.B.S., Metals Handbook, 13, ASM. Reproduced by kind permission of ASM, Metals Park, Ohio, USA)...

Corrosion protection of metals can take many fonns, one of which is passivation. As mentioned above, passivation is the fonnation of a thin protective film (most commonly oxide or hydrated oxide) on a metallic surface. Certain metals that are prone to passivation will fonn a thin oxide film that displaces the electrode potential of the metal by +0.5-2.0 V. The film severely hinders the difflision rate of metal ions from the electrode to tire solid-gas or solid-liquid interface, thus providing corrosion resistance. This decreased corrosion rate is best illustrated by anodic polarization curves, which are constructed by measuring the net current from an electrode into solution (the corrosion current) under an applied voltage. For passivable metals, the current will increase steadily with increasing voltage in the so-called active region until the passivating film fonns, at which point the current will rapidly decrease. This behaviour is characteristic of metals that are susceptible to passivation. 

Fig. 3. Hypothetical Evans diagram and polarization curve for a metal corroding in an acidic solution, where point A represents the current density, /q, for the hydrogen electrode at equiUbrium point B, the exchange current density at the reversible or equiUbrium potential, for M + 2e and point...

In the polarization curve for anodic dissolution of iron in a phosphoric acid solution without CP ions, as shown in Fig. 3, we can see three different states of metal dissolution. The first is the active state at the potential region of the less noble metal where the metal dissolves actively, and the second is the passive state at the more noble region where metal dissolution barely proceeds. In the passive state, an extremely thin oxide film called a passive film is formed on the metal surface, so that metal dissolution is restricted. In the active state, on the contrary, the absence of the passive film leads to the dissolution from the bare metal surface. The difference of the dissolution current between the active and passive states is quite large for a system of an iron electrode in 1 mol m"3 sulfuric acid, the latter value is about 1/10,000 of the former value.6... 

Figure 11. Schematic diagram of anodic polarization curve of passive-metal electrode when sweeping electrode potential in the noble direction. The dotted line indicates the polarization curve in the absence of Cl-ions, whereas the solid line is the polarization curve in the presence of Cl ions.7 Ep, passivation potential Eb, breakdown potential Epit> the critical pitting potential ETP, transpassive potential. (From N. Sato, J, Electrochem. Soc. 129, 255, 1982, Fig. 1. Reproduced by permission of The Electrochemical Society, Inc.)...

The form of the kinetic equation depends on the way in which the surface potential X varies with electrode potential E. When the surface potential is practically constant, the first factor in Eq. (14.24) will also be constant, and the potential dependence of the reaction rate is governed by the second factor alone. The slope b of the polarization curve will be RT/ F (i.e., has the same value as that found when the same reaction occurs at a metal electrode). When in another case a change in electrode potential E produces an equally large change in surface potential (i.e., E = x + const), while there is practically no change in interfacial potential. Then Eq. (14.24) changes into... 

Figure 15.2 shows polarization curves for hydrogen evolution at electrodes of different metals in acidic electrolyte solutions. The results of polarization measurements are highly sensitive to the experimental conditions, in particular to the degree of solution and electrode surface purification for this reason, marked differences exist among the data reported by different workers. The curves shown still provide the correct picture of the common features. 

Theoretically, at a low Uappl the counteraction would be expected to result in full polarization of the electrodes, i.e., would become equal to Eappl, so no current will be passed however, the actual pc,2 at the electrode surface is continuously diminished by diffusion of the Cl2 gas into the solution and so there results a residual current, i = (2 appl - E fR. The amount of the latter increases more or less gradually with increasing Uappl, because the actual pC 2 increases until it finally becomes 1 atm, where Cl2 gas starts to escape from the solution. In the meantime, the anode has been completely covered with Zn metal, so that [Zn] has become unity. In fact, E has now attained a constant maximum value, the so-called decomposition potential, where electrolysis really breaks through. Any further increase in app) would, according to first expectations, cause a linear current increase, i = ( app, - Edecomp )IR. However, Fig. 3.2 shows that the experimental current curve deviates more and... 

The anodic evolution of oxygen takes place at platinum and other noble metal electrodes at high overpotentials. The polarization curve obeys the Tafel equation in the potential range from 1.2 to 2.0 V with a b value between 0.10 and 0.13. Under these conditions, the rate-controlling process is probably the oxidation of hydroxide ions or water molecules on the surface of the electrode covered with surface oxide ... 

As demonstrated in Section 5.2, the electrode potential is determined by the rates of two opposing electrode reactions. The reactant in one of these reactions is always identical with the product of the other. However, the electrode potential can be determined by two electrode reactions that have nothing in common. For example, the dissolution of zinc in a mineral acid involves the evolution of hydrogen on the zinc surface with simultaneous ionization of zinc, where the divalent zinc ions diffuse away from the electrode. The sum of the partial currents corresponding to these two processes must equal zero (if the charging current for a change in the electrode potential is neglected). The potential attained by the metal under these conditions is termed the mixed potential Emix. If the polarization curves for both processes are known, then conditions can be determined such that the absolute values of the cathodic and anodic currents are identical (see Fig. 5.54A). The rate of dissolution of zinc is proportional to the partial anodic current. 

Figure 3 shows polarization curves for the anodic oxidation of H2CO at various metal electrodes recorded by Ohno et al. [38] in a solution maintained at 25 °C and containing EDTA (a commonly used complexant in electroless Cu solutions) and maintained at a pH = 12.5. After exhibiting exceptional activity at potentials less than -0.8 Y (SCE)2, the activity of Cu decreases at ca. 0.3 Y (SCE) this region of activity is more than adequate for electroless deposition of Cu. Although they... 

The distribution of the exchange transfer current of redox electrons o(e), which corresponds to the state density curves shown in Fig. 8-11, is illustrated for both metal and semiconductor electrodes in Fig. 8-12 (See also Fig. 8-4.). Since the state density of semiconductor electrons available for electron transfer exists only in the conduction and valence bands fairly away from the Fermi level nsc), and since the state density of redox electrons available for transfer decreases remarkably with increasing deviation of the electron level (with increasing polarization) from the Fermi level CFciiEDax) of the redox electrons, the exchange transfer current of redox electrons is fairly small at semiconductor electrodes compared with that at metal electrodes as shown in Fig. 8-12. 

Figure 8-42 illustrates the anodic and cathodic polarization curves observed for an outer-sphere electron transfer reaction with a typical thick film on a metallic niobium electrode. The thick film is anodically formed n-type Nb206 with a band gap of 5.3 eV and the redox particles are hydrated ferric/ferrous cyano-complexes. The Tafel constant obtained from the observed polarization curve is a- 0 for the anodic reaction and a" = 1 for the cathodic reaction these values agree with the Tafel constants for redox electron transfers via the conduction band of n-lype semiconductor electrodes already described in Sec. 8.3.2 and shown in Fig. 8-27. 

Fig. 8-42. Anodic and cathodic polarization curves observed for electron transfer of hydrated redox particles at an electrode of metallic niobium covered with a thick niobium oxide NbsOs film (12 nm thick) in acidic solution reaction is an electron transfer of hydrated redox particles, 0.25MFe(CN)6 /0.25M Fe(CN)g, in 0.1 M acetic add buffer solution of pH 4.6 at 25 C. =...

Figure S-4S shows the polarization curves observed, as a function of the film thickness, for the anodic and cathodic transfer reactions of redox electrons of hydrated ferric/ferrous cyano-complex particles on metallic tin electrodes that are covered with an anodic tin oxide film of various thicknesses. The anodic oxide film of Sn02 is an n-type semiconductor with a band gap of 3.7 eV this film usually contains a donor concentration of 1x10" ° to lxl0 °cm °. For the film thicknesses less than 2.5 nm, the redox electron transfer occurs directly between the redox particles and the electrode metal the Tafel constant, a, is close to 0.5 both in the anodic and in the cathodic curves, indicating that the film-covered tin electrode behaves as a metallic tin electrode with the electron transfer current decreasing with increasing film thickness.

Fig. 8-43. Anodic and cathodic polarization curves observed for a redox electron transfer at metallic tin electrodes covered with an anodic oxide Sn02 film of various thicknesses d in a basic solution reaction is a redox electron transfer of 0.25 M Fe(CN)6 A).25 M Fe(CN)6 in 0.2 M borate buffer solution of pH 9.1 at 25°C. d = film thickness dj = 2 nm ...

Fig. 9-3. Polarization curves estimated for a simple electrode reaction of metallic ion transfer i = reaction current to - exchange reaction current in reaction equilibrium = symmetric factor (0 < 3 < 1).

Figure 9—4 shows the polarization curves observed for the transfer reaction of cadmium ions (Cd Cd ) at a metallic cadmium electrode in a sulfuric acid solution. It has been proposed in the literature that the transfer of cadmium ions is a single elemental step involving divalent cadmium ions [Conway-Bockris, 1968]. The Tafel constant, a, obtained from the observed polarization curves in Fig. 9-4 agrees well with that derived for a single transfer step of divalent ions the Tafel constant is = (1- P) 1 in the anodic transfer and is a = z p = 1 in the cathodic transfer. 

Fig. 9-4. Anodic and cathodic polarization curves measured for transfer of divalent cadmium ions (dissolution-deposition) at a metallic cadmium electrode in a sulfate solution (0.005MCd + 0.4MS04 ) i (i )= anodic (cathodic) reaction current a = Tafel constant (transfer coefficient). [From Lorenz, 1954.]...

Fig. 9-5. Anodic and cathodic polarization curves observed for transfer of divalent iron ions (dissolution-deposition) at a metallic iron electrode in a sulfuric add solution at pH 4 (0.5MFesS04-)-0.5MKaS04) = anodic iron dissolution (cathodic iron...

Fig. 10-14. Energy levels and polarization curves (current vs. potential) for anodic transfer ofphotoexdted holes in oxygen reaction (2 HgO. -t- 4h O24 4 H. ) on a metal electrode and on an n-type semiconductor electrode j = anodic reaction current ep(02 20)- Fermi level of oxygen electrode reaction dCpi, = gain of photoenergy q = potential for the onset of anodic photoexdted ox en reacti . 4 pi, (=-Ae.. le) = shift of potential for the onset of anodic oxygen reaction from equilibrium oxygen potential in the negative direction due to gain of photoenergy in an n-type electrode Eib = flat band potential of an n-type electrode.

Fig. 10-lS. Ehietgy levels and polarization curves of cathodic hydrogen reaction at a metal electrode and at a photoexdted p-type semiconductor electrode = cathodic current ... 

Fig. 10-28. Polarization curves for cell reactions of photoelectrolytic decomposition of water at a photoezcited n-type anode and at a metal cathode solid curve M = cathodic polarization curve of hydrogen evolution at metal cathode solid curve n-SC = anodic polarization curve of oxygen evolution at photoezcited n-type anode (Fermi level versus current curve) dashed curve p-SC = quasi-Fermi level of interfadal holes as a ftmction of anodic reaction current at photoezcited n-type anode (anodic polarization curve r re-sented by interfacial hole level) = electrode potential of two operating electrodes in a photoelectrolytic cell p. sc = inverse overvoltage of generation and transport ofphotoezcited holes in an n-type anode.

Fig. 11-6. Polarization curves of anodic metal dissolution and of cathodic oxidant reduction at a corroding metallic electrode (mixed electrode) s equilibrium...

The polarization curve (polarization current i, versus polarization potential E) of a corroding metallic electrode can be measured by polarizing the electrode in the anodic and cathodic directions. In the range of electrode potential a short distance away from the corrosion potential, the polarization curve follows the Tafel relation as shown in Fig. 11-6. Here, the polarization current, ip, in the anodic direction equals the dissolution current of the metal i and the polarization current, ip, in the cathodic direction equals the reduction current of the oxidant i. In the range of potential near the corrosion potential, however, the polarization current, ip, is the difference between the anodic dissolution current of the metal... 

Fig. 11-6. Polarization curves that can be observed with a corroding metallic electrode (solid curve) compared with anodic and cathodic reaction currents (dashed curve) as Amctions of electrode potential ip (ip ) = anodic (cathodic) polarization current i (i ) = anodic (cathodic) reaction current.

Figure 11-7 shows the polarization curve of an iron electrode in an acidic solution in which the anodic reaction is the anodic transfer of iron ions for metal dissolution (Tafel slope 40 mV/decade) the cathodic reaction is the cathodic transfer of electrons for reduction of hydrogen ions (Tafel slope 120 mV /decade) across the interface of iron electrode. 

Fig. 11-8. Polarization curves for a corroding metallic electrode of which corrosion rate is controlled by diffusion of oxidants in aqueous solution solid curve = observable polarization curve.

Fig. 11-9. Anodic polarization curve of a metallic electrode for active dissolution, passivation, and transpassivation in aqueous acidic solution > u = anodic current of metal dissolution = passivation potential = transpassivation potential = maximum metal...

Fig. 11-10. Anodic polarization curves observed for metallic iron, nickel, and chromium electrodes in a sulfuric acid solution (0.5 M H 2SO 4) at 25°C solid curve = anodic metal dissolution current dot-dash curve s anodic oxygen evolution current [Sato-Okamoto, 1981.]...

Fig. 11-13. Anodic polarization curve of a metallic nickel electrode in a sulfuric add solution transpassivation arises at a potential relatively dose to the flat band potential because of p-type nature of the passive oxide film. [From Sato, 1982.]...

As described in Sec. 11.3, the spontaneous corrosion potential of a corroding metal is represented by the intersection of the anodic polarization curve of metal dissolution with the cathodic polarization curve of oxidant reduction (Figs. 11—5 and 11-6). Then, whether a metal electrode is in the active or in the passive state is determined by the intersection of the anodic and cathodic polarization curves. 

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