Overpotential total

Faraday s constant (96,487 C/mol) overpotential total current current density exchange current density ratio of ohmic constriction to inter-facial resistance surface exchange coefficient volume-specific interfacial resistance in a composite thickness utilization length characteristic length of a porous microstructure... 

Surface to volume fraction of catalyst atoms Total catalyst utilization Local overpotential Total overpotential of CCL Wetting angle of water on CCL pore walls Surface coverage of COacovered fraction of active sites... 

Fig. 10.12 Schematic representation of a pipewall subject to cathodic protection (see text), t , = overpotential at x 7) = overpotential at x = 0 7)p,oi = overpotential at x = a/2 1, - current line at x = current density entering line at x / = current in line at x = 0 from one side of drain point (2/ = total current drain) a = distance between the drain points...

According to the discussion at the end of Section III.5, at the steady state, the total overpotential of anodic dissolution is determined by the ohmic drop, so that the A mo/s(jc, y, t) is assumed to be approximately zero at steady state ... 

The autocorrelation distance is determined by the total overpotential (0Q) of the double layer, which is measured from the critical pitting potential and the coverage 0 of the passive film. From the experimental results which will be discussed later, the actual function form is determined as... 

It is very important to develop a high performance cathode catalyst, because a sluggish ORR causes a large overpotential at low temperatures. With respect to the total performance of activity and stability, the cathode catalyst material is limited to Pt or its alloys at present. In acidic media such as Nation electrolyte or aqueous acid solutions, four-electron reduction is dominant at Pt-based electrodes ... 

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... 

The total overpotential in limiting-current measurements is therefore represented as the sum of these three components ... 

Potentiostatic current sources, which allow application of a controlled overpotential to the working electrode, are used widely by electrochemists in surface kinetic studies and find increasing use in limiting-current measurements. A decrease in the reactant concentration at the electrode is directly related to the concentration overpotential, rj0 (Eq. 6), which, in principle, can be established directly by means of a potentiostat. However, the controlled overpotential is made up of several contributions, as indicated in Section III,C, and hence, the concentration overpotential is by no means defined when a given overpotential is applied its fraction of the total overpotential varies with the current in a complicated way. Only if the surface overpotential and ohmic potential drop are known to be negligible at the limiting current density can one assume that the reactant concentration at the electrode is controlled by the applied potential according to Eq. (6). 

The second bracket contains the aspect ratio. The group in the first bracket is a measure of the approach to the limiting current modified by a total overpotential. The authors describe this group as a ratio of mass-transfer resistance to kinetic resistance. 

Worked Example 6.1 introduces us to an important result, namely that below a certain overpotential, not all of the analyte at the surface of the electrode will be electromodified. At or above a crucial value of q, all of the material around the electrode is converted. The associated current, if conversion is total, is then... 

Figure 19. Liquid saturation and current density of the cathode as a function of position for the case of dry air fed at 60 °C. (a) Liquid saturation in the gas-diffusion layer where the channel goes from x = 0 to 0.05 cm and the rib is the rest the total cathode overpotential is —0.5 V. (b) Current-density distributions for different channel/rib arrangements. (Reproduced with permission from ref 56. Copyright 2001 The Electrochemical Society, Inc.)...

Processes at metal/metal-ion electrodes include crystallization partial reactions. These are processes by which atoms are either incorporated into or removed from the crystal lattice. Hindrance of these processes results in crystallization overpotential The slowest partial reaction is rate determining for the total overall reaction. However, several partial reactions can have low reaction rates and can be rate determining. 

Thus, four different kinds of overpotential are distinguished and the total overpotential rj can be considered to be composed of four components ... 

Figure 6.14. Cell Voltage vs. Cell Current profile of a hydrogen - oxygen fuel cell under idealized (dotted-dashed curve) and real conditions. Under real conditions the cell voltage suffers from a severe potential loss (overpotential) mainly due to the activation overpotential associated with the electroreduction process of molecular oxygen at the cathode of the fuel cell. Smaller contributions to the total overpotential losses (resistance loss and mass transport) are indicated.

There is a good economic reason for this. Look back at the Butler Volmer equation (Eq. 7.24) the larger the ifl (Le., the better the catalysis), the smaller the overpotential needed to get a given rate of reaction. However, the smaller the overpotential, the less the total cell potential, and hence the kilowatt hours, to produce a given amount of a substance in an electrochemical reactor. 

It is now necessary to take a more unified view by considering situations in which the rate of the electrodic process at the interface is subject both to activation and to transport limitations. One refers to a combined activation-transport control of the electrodic reaction. Under such conditions, there will be, in addition to the overpotential T)c produced by the concentration change (from c° to c ) at the interface, an activation overpotential because the charge-transfer reaction is not at equilibrium. The total overpotential rj is the difference between the interfacial-potential difference... 

Now the overpotentials Tjj and t 2 are the total overpotentials at the two interfaces. They must include the activation overpotentials Tja and concentration overpotentials Tlc. Thus, Eq. (7.321) can be written... 

It is an experimental fact that whenever mass transfer limitations are excluded, the rate of charge transfer for a given electrochemical reaction varies exponentially with the so-called overpotential rj, which is the potential difference between the equilibrium potential F0 and the actual electrode potential E (t) = E — Ed). Since for the electrode reaction Eq. (1) there exists a forward and back reaction, both of which are changed by the applied overpotential in exponential fashion but in an opposite sense, one obtains as the effective total current density the difference between anodic and cathodic partial current densities according to the generalized Butler-Volmer equation ... 

---