Electron transfer cathodic polarization

Reductive dissolution may be more complex than the two previous mechanisms in that it involves electron transfer processes. Formation of Fe" via reductive dissolution can be effected by adsorption of an electron donor, cathodic polarization of an electrode supporting the iron oxide and by transfer of an electron from within a ternary surface complex to a surface Fe ". Addition of Fe" to a system containing a ligand such as EDTA or oxalate promotes electron transfer via a surface complex and markedly accelerates dissolution. 

Thus, in the region of very high anodic or cathodic polarization, the RDS is always the first step in the reaction path. The transfer coefficient of the full reaction which is equal to that of this step is always smaller than unity (for a one-electron RDS), while slope i in the Tafel equation is always larger than 0.06 V. When the potential is outside the region of low polarization, a section will appear in the polarization curve at intermediate values of anodic or cathodic polarization where the transfer coefficient is larger than unity and b is smaller than 0.06 V. This indicates that in this region the step that is second in the reaction path is rate determining. 

In electrochemistry, the electrode at which no transfer of electrons and ions occurs is called the polarizable electrode, and the electrode at which the transfer of electrons and/or ions takes place is called the nonpolarizable electrode as shown in Fig. 4-4. The term of polarization in electrochemistry, different from dipole polarization in physics, indicates the deviation in the electrode potential from a specific potential this specific potential is usually the potential at which no electric current flows across the electrode interface. To polarize" means to shift the electrode potential from a specific potential in the anodic (anodic polarization) or in the cathodic (cathodic polarization) direction. 

Such an interfacial degeneracy of electron energy levels (quasi-metallization) at semiconductor electrodes also takes place when the Fermi level at the interface is polarized into either the conduction band or the valence band as shown in Fig. 5-42 (Refer to Sec. 2.7.3.) namely, quasi-metallization of the electrode interface results when semiconductor electrodes are polarized to a great extent in either the anodic or the cathodic direction. This quasi-metallization of electrode interfaces is important in dealing with semiconductor electrode kinetics, as is discussed in Chap. 8. It is worth noting that the interfacial quasi-metallization requires the electron transfer to be in the state of equilibrimn between the interface and the interior of semiconductors this may not be realized with wide band gap semiconductors. 

Figures 8-5 and 8-6 are energy diagrams, as functions of electron energy e imder anodic and cathodic polarization, respectively, for the electron state density Dyf.t) in the metal electrode the electron state density AtEDox(c) in the redox particles and the differential reaction current ((e). From these figures it is revealed that most of the reaction current of redox electron transfer occurs in a narrow range of energy centered at the Fermi level of metal electrode even in the state of polarization. Further, polarization of the electrode potential causes the ratio to change between the occupied electron state density Dazc/itnu md the imoccupied...

Fig. 8-5. Electron state density in a metal electrode and in hydrated redox particles, and anodic and cathodic currents of redox electron transfer under cathodic polarization n s cathodic overvoltage (negative) i = anodic current i = cathodic current. [From (lerischer, I960.]...

It is characteristic of metal electrodes that the reaction current of redox electron transfer, under the anodic and cathodic polarization conditions, occurs mostly at the Fermi level of metal electrodes rather than at the Fermi level of redox particles. In contrast to metal electrodes, as is discussed in Sec. 8.2, semiconductor electrodes exhibit no electron transfer current at the Fermi level of the electrodes. 

Next, we consider the anodic reaction current of redox electron transfer via the conduction band, of which the exchange reaction current has been shown in Fig. 8-16. Application of a slight anodic polarization to the electrode lowers the Fermi level of electrode fix>m the equilibrium level (Ep(sc)( n = 0) = eiiOTSDca)) to a polarized level (ep(8C)( n) = ep(REDox)- n)withoutchanging at the electrode interface the electron level relative to the redox electron level (the band edge level pinning) as shown in Fig. 8-20. As a result of anodic polarization, the concentration of interfacial electrons, n, in the conduction band decreases, and the concentration of interfadal holes, Pm, in the valence band increases. Thus, the cathodic transfer current of redox electrons, in, via the conduction band decreases (with the anodic electron im ection current, ii, being constant), and the anodic transfer current of redox holes, (p, via the valence band increases (with the cathodic hole injection... 

As the polarization (the overvoltage t) ) increases of a redox reaction that requires the transport of minority charge carriers towards the electrode interface (anodic hole transfer at n-type and cathodic electron transfer at p-type electrodes), the transport overvoltage, t)t, increases from zero at low reaction currents to infinity at high reaction current at this condition the reaction current is controlled by the limiting diffusion current (iu.)tm or ip.um) of minority charge carriers as shown in Fig. 8-25. 

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 ...

Charge transfer reactions on semiconductor electrodes proceed under the condition of anodic and cathodic polarization in which the Fermi level epfsc) is different either from the Fermi level Eputicox) of redox electron transfer reactions or from the equivalent Fermi level ep,ioN) of ion transfer reactions. For redox electron transfer reactions, thermodynamic requirement for the anodic and cathodic reactions to proceed is given by the following inequalities ... 

Figure 10-16 shows polarization curves observed for the anodic ox en reaction (anodic hole transfer) and for the cathodic hydrogen reaction (cathodic electron transfer) on an n-type semiconductor electrode of titanium oxide. The data in Fig. 10-16 show that the anodic current due to the transfer of holes (minority... 

Figure 10-17 shows the polarization ciirves for the cathodic hydrogen reaction (cathodic electron transfer) on a p-type semiconductor electrode of galliiun phosphide. The onset potential of cathodic photoexcited hydrogen reaction shifts significantly from the equilibrium electrode potential of the same hydrogen reaction toward the flat band potential of the p-type electrode (See Fig. 10-15.). 

In another paper, they confirmed that the absorbance of solutions of NaB(CaHs)4 and KB(C6He)4 and of NaAl(C2H5)4 was strictly proportional to the number of electrons transfer at the electrode. And from the observation that mixing of the anode and cathode solutions resulted in a destruction of the living ends, they reversed the polarity of the electrodes and found a stoichiometric destruction of the living ends of a-methystyrene tetramer and a decrease in absorbance directly dependent on the charge transferred 13). Exactly same quantity of charge was... 

Because the flow of electric current always involves the transport of matter in solution and chemical transformations at the solution-electrode interface, local behavior can only be approached. It can be approximated, however, by a reference electrode whose potential is controlled by a well-defined electron-transfer process in which the essential solid phases are present in an adequate amount and the solution constituents are present at sufficiently high concentrations. The electron transfer is a dynamic process, occurring even when no net current flows and the larger the anodic and cathodic components of this exchange current, the more nearly reversible and nonpolarizable the reference electrode will be. A large exchange current increases the slope of the current-potential curve so that the potential of the electrode is more nearly independent of the current. The current-potential curves (polarization curves) are frequently used to characterize the reversibility of reference electrodes. 

Reversible step transfer of up to 6 electrons per one molecule to form anion radicals is observed in the cathodic polarization of C6o fullerene solutions [6], Anion particles are stable in aprotic media, however in the general case anion stability decreases with increasing charge [7]. The number of observed steps depends on the medium and experimental conditions. The literature analysis [8-10] has revealed that the use of different solvent systems, base electrolytes and electrodes results in considerable variations in redox potentials for the most extensively studied pairs of C(JC , C(,fC(f2, C(,fCeo"3. 

It is well known that ACN reacts with active metals (Li, Ca) to form polymers [48], These polymers are products of condensation reactions in which ACIST radical anions are formed by the electron transfer from the active metal and attack, nucleophilically, more solvent molecules. Species such as CH3C=N(CH3)C=N are probably intermediates in this polymerization. ACN does not react on noble metal electrodes in the same way as with active metals. For instance, well-re-solved Li UPD peaks characterize the voltammograms of noble metal electrodes in ACN/Li salt solutions. This reflects a stability of the Li ad-layers that are formed at potentials above Li deposition potentials. Hence, the cathodic limit of noble metal electrodes in ACN solutions is the cation reduction process (either TAA or active metal cations). As discussed in the previous sections, with TAA-based solutions it is possible that the electrode surfaces remain bare. When the cations are metallic (e.g., Li+), it is expected that the electrode surfaces become covered with surface films originating from atmospheric contaminants reduction if the electrodes are polarized below 1.5 V (Li/Li+). As Mann found [13], in the presence of Na salts the polarization of metal electrodes in ACN solutions to sodium deposition potentials leads to solvent decomposition, with evolution of H2, CH4 and sodium cyanide (due to reaction with metallic sodium). 

A second related issue is the asymmetry in the E-i response near Ecelectron transfer reaction that is different from the metal oxidation reaction. Therefore there is no fundamental reason why pa and pc should be equal, and they should be expected to differ. The extent of their difference defines the degree of asymmetry. Asymmetry matters because the extent of the region where Eq. (2) is a good approximation of Eq. (1) then differs for anodic and cathodic polarization (29). The errors in assuming 10 mV linearity using both the tangent to the E-i data at Econ and for +10 or -10 mV potentiostatic polarizations have been defined for different Tafel slopes (30). 

The electrochemical insertion process includes - charge transfer (red-ox reaction) by electrons and ions and -> diffusion of ions in the host to theirs sites. The inserted species can be cations (upon cathodic polarization), anions (upon anodic polarization), atoms, and molecules. Insertion of ions can be accompanied by co-insertion of solvent molecules from the -> solvation shell of the ions, which are dragged to the host together with the ions as the electrical field is applied. Insertion electrodes are highly important for the filed of - Li batteries, as most of the electrodes used in Li/Li-ion batteries are in fact insertion electrodes. Thereby, this entry concentrates mainly on Li ion insertion electrodes. 

A similar cathodic limiting current has also been observed for the electroreduction of peroxide on LaNi03 (Fig. 18) [48] and this behavior occurs at potentials where the reduction of the solid surface takes place changing the potential distribution at the oxide-electrolyte interface. This change of surface properties is quite similar to the behavior of NiO [347] under cathodic polarization and is also reflected in the inhibition of electron transfer to or from redox couples in solution [81] and capacitance Mott-Schottky type plots [87, 290, 291] of these interfaces. 

The two types of electron transfer in a redox reaction at semiconductors can be distinguished by a number of experimental methods (12,13,14). The mechanisms of some redox reactions at germanium electrodes are summarized In Table I. It is seen that the mechanism of redox reactions with positive normal potentials is associated with the valence band, whereas the mechanism of redox reactions with more negative normal potentials is associated with the conduction band if there is any reaction at all. The situation remains the same when the electrode is moderately polarized in the anodic or cathodic direction. An example is shown in Fig. 11 using a redox system with properties equivalent to those assumed In Fig. 10. 

Another type of hot electron transfer from a metal-covered n-Si electrode to a redox system ([Fe(CN)6] ) was studied by Chen and Freese [170, 171]. The hot electrons were actually produced in the metal by transfer from the conduction band of n-Si during cathodic polarization. In sufficiently thin layers (< 500 A) they were transported to the metal/liquid interface without essential thermalization. 

If the cathodic current - / is plotted as ordinate and the cathodic polarization — t) as abscissa, then the quantity iotiFIRT is the slope (dildrj)i=o of the current-potential curve at the point of zero current (the equilibrium potential). Its reciprocal RTInFi has the dimensions of resistance (ohms) and is often called the polarization resistance. It is the effective resistance imposed at the electrode surface by the finite rate of the electron-transfer process (Section 12-9). 

Since the externally applied voltage occurs only across the Helmholtz layer at the metal electrolyte interface, the energy levels on both sides of the interface are shifted against each other as illustrated in Fig. 7.5. Upon cathodic polarization, an electron transfer occurs from the occupied states in the metal where the latter overlap with the... 

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