Electrode potential limitations

In contrast to Ru, Ir proved to be quite stable in the fuel cell envirrMunent. As presented in Fig. 22.8, the three consecutive scans to 1.55 V practically overlapped, and, as a result, the OER activity of Ir at 1.55 V was 18 times higher than that of Ru, albeit that Ru had a much higher initial OER activity. Kotz and Stucki estimated the Ir dissolution rate proceeded at only 1 % of the total current during the OER test [35]. Unlike for Ru, we have not observed any quantitative changes in the electrochemical performance for Ir. The electrode potential limit for Ir stability beyond 1.65 V will be presented later (see Sect. 22.4). 

The change of the electronic resistance of PPy as a function of electrode potential in solutions of various compositions is shown in Figure 60. Because of the selected electrode potential limits, onfy a reversible increase/decrease was found no evidence of overoxidation was observed [73]. With a polymer transistor manufactured with a film of PPy as the active material, Ofer et al. [645] found a limited electrode potential window wherein PPy has a high electronic conductivity. 

FIGURE 43. SNIFTIRS spectra of 0.1 M tetrabutylammonium tetrafluoroborate in anhydrous acetonitrile for different potential pulses (Pt electrode, potential limits of the pulse in volts as indicated), according to Pons et... 

At low currents, the rate of change of die electrode potential with current is associated with the limiting rate of electron transfer across the phase boundary between the electronically conducting electrode and the ionically conducting solution, and is temied the electron transfer overpotential. The electron transfer rate at a given overpotential has been found to depend on the nature of the species participating in the reaction, and the properties of the electrolyte and the electrode itself (such as, for example, the chemical nature of the metal). 

In Section 8, the material on solubility constants has been doubled to 550 entries. Sections on proton transfer reactions, including some at various temperatures, formation constants of metal complexes with organic and inorganic ligands, buffer solutions of all types, reference electrodes, indicators, and electrode potentials are retained with some revisions. The material on conductances has been revised and expanded, particularly in the table on limiting equivalent ionic conductances. 

Mass Transport. Probably the most iavestigated physical phenomenon ia an electrode process is mass transfer ia the form of a limiting current. A limiting current density is that which is controlled by reactant supply to the electrode surface and not the appHed electrode potential (42). For a simple analysis usiag the limiting current characteristics of various correlations for flow conditions ia a parallel plate cell, see Reference 43. 

Further, as the current density of the fuel cell increases, a point is inevitably reached where the transport of reactants to or products from the surface of the electrode becomes limited by diffusion. A concentration polarization is estabhshed at the elec trode, which diminishes the cell operating potential. The magnitude of this effect depends on many design and operating variables, and its value must be obtained empirically. 

Ion-selective electrodes are a relatively cheap approach to analysis of many ions in solution. The emf of the selective electrode is measured relative to a reference electrode. The electrode potential varies with the logarithm of the activity of the ion. The electrodes are calibrated using standards of the ion under investigation. Application is limited to those ions not subject to the same interference as ion chromatography (the preferred technique), e.g. fluoride, hydrogen chloride (see Table 10.3). 

As shown in Figure 3.6-1, GC and Pt exhibit anodic and cathodic potential limits that differ by several tenths of volts. However, somewhat fortuitously, the electrochemical potential windows for both electrodes in this ionic liquid come out to be 4.7 V. What is also apparent from Figure 3.6-1 is that the GC electrode exhibits no significant background currents until the anodic and cathodic potential limits are reached, while the Pt working electrode shows several significant electrochemical processes prior to the potential limits. This observed difference is most probably due to trace amounts of water in the ionic liquid, which is electrochemically active on Pt but not on GC (vide supra). 

Ideally, one would prefer to compare anodic and cathodic potential limits instead of the overall ionic liquid electrochemical window, because difference sets of anodic and cathodic limits can give rise to the same value of electrochemical window (see Figure 3.6-1). However, the lack of a standard reference electrode system within and between ionic liquid systems precludes this possibility. Gonsequently, significant care must be taken when evaluating the impact of changes in the cation or anion on the overall ionic liquid electrochemical window. 

If the electrode potential is further reduced to h-350 mV, a hexagonal superstructure with a periodicity of 2.4 0.2 nm is observed. With respect to the interatomic distances in the Au(lll) structure at the surface, this corresponds - within the error limits - to an 8 X 8 superstructure (Figure 6.2-9). 

Turning now to the acidic situation, a report on the electrochemical behaviour of platinum exposed to 0-1m sodium bicarbonate containing oxygen up to 3970 kPa and at temperatures of 162 and 238°C is available. Anodic and cathodic polarisation curves and Tafel slopes are presented whilst limiting current densities, exchange current densities and reversible electrode potentials are tabulated. In weak acid and neutral solutions containing chloride ions, the passivity of platinum is always associated with the presence of adsorbed oxygen or oxide layer on the surface In concentrated hydrochloric acid solutions, the possible retardation of dissolution is more likely because of an adsorbed layer of atomic chlorine ... 

Steady-state potential comparable with Types 4 and 5 reversible electrodes Potential of metal depends on pH of solution, although the dependence is confined to a limited range of pH and does not conform precisely to the Nernst equation. Ni in H2SO4 (Ni/Hj, H + ) Cu in NaOH (Cu/CujO/OH")... 

Other situations may also occur that allow a simple determination of the sensitivity factor. When, for example, a sufficiently negative electrode potential forces all minority carriers to drift into the interior of the semiconductor electrode, where they recombine subject to the bulk lifetime Tfr we will see a limiting PMC signal (given a sufficiently thick electrode). Knowing the photonflux /0 (corrected for reflection), we may expect the following formula to hold ... 

In principle, the oxidation of proceeds at an electrode potential that is more negative by about 0.7 V than the anodic decomposition paths in the above cases however, because of the adsorption shift, it is readily seen that practically there is no energetic advantage compared to CdX dissolution in competing for photogenerated holes. Similar effects are observed with Se and Te electrolytes. As a consequence of specific adsorption and the fact that the X /X couples involve a two-electron transfer, the overall redox process (adsorption/electron trans-fer/desorption) is also slow, which limits the degree of stabilization that can be attained in such systems. In addition, the type of interaction of the X ions with the electrode surface which produces the shifts in the decomposition potentials also favors anion substitution in the lattice and the concomitant degradation of the photoresponse. 

The changes in surface concentrations of the components caused by current flow have two important effects They produce a change in electrode potential, and they imply that there is an upper limit to the cell currents when the diffusion flux attains its iimiting value. The first of these effects is considered in Section 6.3 the second, in the present section. 

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