Exchange current.

For a more general reaction of the fonn Ox + ne Red, with differing concentrations of Ox and Red, the exchange current density is given by... 

Some values for and (3 for electrochemical reactions of importance are given in table A2.4.6, and it can be seen that the exchange currents can be extremely dependent on the electrode material, particularly for more complex processes such as hydrogen oxidation. Many modem electrochemical studies are concerned with understanding the origin of tiiese differences in electrode perfomiance. 

The exchange current is directiy related to the reaction rate constant, to the activities of reactants and products, and to the potential drop across the double layer. The larger the more reversible the reaction and, hence, the lower the polarization for a given net current flow. Electrode reactions having high exchange currents are favored for use in battery apphcations. 

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...

The sohd line in Figure 3 represents the potential vs the measured (or the appHed) current density. Measured or appHed current is the current actually measured in an external circuit ie, the amount of external current that must be appHed to the electrode in order to move the potential to each desired point. The corrosion potential and corrosion current density can also be deterrnined from the potential vs measured current behavior, which is referred to as polarization curve rather than an Evans diagram, by extrapolation of either or both the anodic or cathodic portion of the curve. This latter procedure does not require specific knowledge of the equiHbrium potentials, exchange current densities, and Tafel slope values of the specific reactions involved. Thus Evans diagrams, constmcted from information contained in the Hterature, and polarization curves, generated by experimentation, can be used to predict and analyze uniform and other forms of corrosion. Further treatment of these subjects can be found elsewhere (1—3,6,18). 

The exchange current density, depends on temperature, the composition of the electrolyte adjacent to the electrode, and the electrode material. The exchange current density is a measure of the kinetic resistance. High values of correspond to fast or reversible kinetics. The three parameters, a, a. ... 

In this equation /g, is th equilibrium exchange current, and the arrow convention adopted is that / g represents the rate of cathodic reduction... 

If the areas of the electrodes are assumed to be 1 cm, and taking the equilibrium exchange current density /g for the Ag /Ag equilibrium to be 10 A cm", then /g will be 10 A, which is a very high rate of charge transfer. A similar situation will prevail at electrode II, and rates of exchange of silver ions and the potential will be the same as for electrode I. 

It is evident from these expressions that since in the Tafel region / (the current density actually determined) must be greater than /(, (the equilibrium exchange current density), the signs of the overpotentials will conform to equations 1.60 and 1.61, i.e. will be negative and will be positive. 

Fig, 1.24 Tafel lines for a single exchange process. The following should be noted (a) linear f-log I curves are obtained only at overpotentials greater than 0-052 V (at less than 0-052 V E vs. i is linear) b) the extrapolated anodic and cathodic -log / curves intersect at tg the equilibrium exchange current density and (c) /, and the anodic and cathodic current densities... 

The standard electrode trotential, Ep, 2+ Pb = —Q.126V . shows that lead is thermodynamically unstable in acid solutions but stable in neutral. solutions. The exchange current for the hydrogen evolution reaction on lead is very small (-10 - 10"" Acm ), but control of corrosion is usually due to mechanical passivation of the local anodes of the corrosion cells as the majority of lead salts are insoluble and frequently form protective films or coatings. 

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 ... 

The most significant parameter in the relationships given above is the equilibrium exchange current density io, which can be evaluated by extra-p>olating the linear t/ vs. log / curve to tj = 0, at which log / = log io. Alternatively, /q may be evaluated from the linear Ep vs. log / curve by extrapolating the curve to the equilibrium potential. ... 

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