Corrosion potential cathodic reactions

Dissimilar metals. Galvanic corrosion occurs when two metals with different electrochemical potentials are in contact in the same solution [Figures 6.7 and 6.8]. In both cases, the corrosion of iron (steel) is exothermic and the cathodic reaction is controlling the corrosion rate. The more noble metal, copper increases the corrosion through cathodic reaction of hydrogen ion reduction and hydrogen evolution A passive oxide film on stainless steel for example can accelerate hydrogen reduction reaction. 

FIGURE 15.4 Schematic Evans diagram illustrating the concepts of corrosion potential, cathodic protection, and anodic protection. (H+/H2) reversible potential for the hydrogen reduction reaction (HRR) %(h /h2)> exchange current density for the HRR on the metal surface con and Wr are the corrosion potential and corrosion current, respectively. See text for discussion of the other quantities. 

Oxygen evolution is the counter electrode reaction in several electrolytic processes (e.g. metal extraction, chromium plating, several organic electrosyntheses) while oxygen reduction is the desired cathode reactions in fuel cells and metalair batteries, a potential cathode reaction in improved chlor-alkali cells and a component reaction in corrosion. 

Again, the Kelvin probe can be used to monitor the local corrosion potential of a partly coated metal surfece in a humid atmosphere. If, for example, the presence of the organic molecule changes the kinetics of the metal dissolution reaction, then this is reflected in a change of the corrosion potential an acceleration of the metal dissolution will shift the corrosion potential cathodically, a retardation will shift the corrosion potential anodically. As an example. Figure 22 shows a map of the corrosion potential of an iron surface that is partly coated by one monolayer of octadecylsilanol as measured with the Kelvin probe in a humid atmosphere [87]. The corrosion potential changes locally by several 100 mV due to the presence or absence of the film and it has been proved that the anodic potentials correspond to the areas that are coated by the polymer [53]. The potential plot of Figure 22 is therefore a representation of the inhibition of the anodic metal dissolution in a humid atmosphere. 

In the original derivation of the Wagner-Traud polarization equation, it was assumed that the anodic and cathodic partial reactions of the corrosion process proceed only in the forward direction. This is a good approximation as long as the corrosion potential is far from the equilibrium potential of both partial reactions. If one or both of the equilibrium potentials is close to the corrosion potential, the reaction(s) occurring in the reverse direction must be taken into account. The polarization equation for this case was derived by Mansfeld and Oldham ... 

The thermodynamic data pertinent to the corrosion of metals in aqueous media have been systematically assembled in a form that has become known as Pourbaix diagrams (11). The data include the potential and pH dependence of metal, metal oxide, and metal hydroxide reactions and, in some cases, complex ions. The potential and pH dependence of the hydrogen and oxygen reactions are also suppHed because these are the common corrosion cathodic reactions. The Pourbaix diagram for the iron—water system is given as Figure 1. 

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). 

Equation (2-38) is valid for every region of the surface. In this case only weight loss corrosion is possible and not localized corrosion. Figure 2-5 shows total and partial current densities of a mixed electrode. In free corrosion 7 = 0. The free corrosion potential lies between the equilibrium potentials of the partial reactions and U Q, and corresponds in this case to the rest potential. Deviations from the rest potential are called polarization voltage or polarization. At the rest potential = ly l, which is the corrosion rate in free corrosion. With anodic polarization resulting from positive total current densities, the potential becomes more positive and the corrosion rate greater. This effect is known as anodic enhancement of corrosion. For a quantitative view, it is unfortunately often overlooked that neither the corrosion rate nor its increase corresponds to anodic total current density unless the cathodic partial current is negligibly small. Quantitative forecasts are possible only if the Jq U) curve is known. 

Inhibitors are materials that reduce either one or both of the partial corrosion reactions as in Fig. 2-5. Anodic or cathodic inhibitors inhibit the anodic or cathodic reaction respectively so that the rest potential becomes either more positive or more negative. Most inhibitors, however, inhibit the anodic partial reaction. This is because the transfer of metal ions can be more easily restricted than that of electrons. 

It follows from the electrochemical mechanism of corrosion that the rates of the anodic and cathodic reactions are interdependent, and that either or both may control the rate of the corrosion reaction. It is also evident from thermodynamic considerations (Tables 1.9 and 1.10) that for a species in solution to act as an electron acceptor its redox potential must be more positive than that of the M /M equilibrium or of any other equilibrium involving an oxidised form of the metal. 

Fig. 1.40 Schematic anodic polarisation curve for a passivatable metal (solid line), shown together with three alternative cathodic reactions (broken line). Open-circuit corrosion potentials are determined by the intersection between the anodic and cathodic reaction rates. Cathode a intersects the anodic curve in the active region and the metal corrodes. Cathode b intersects at three possible points for which the metal may actively corrode or passivate, but passivity could be unstable. Only cathode c provides stable passivity. The lines a, b and c respectively could represent different cathodic reactions of increasing oxidizing power, or they could represent the same oxidizing agent at increasing concentration.

Graphic estimation of the corrosion rate and corrosion potential of a metal immersed in a corrosive high-conductivity electrolyte, from the intersection of the polarisation curves for the appropriate anodic and cathodic reactions, has been proposed and explained by several authorities. These polarisation curves can be further used to illustrate the effect of imposing additional anodic or cathodic potentials on to a corroding metal (see also Sections 1.4 and 10.1). 

Equation 10.2, which involves consumption of the metal and release of electrons, is termed an anodic reaction. Equation 10.3, which represents consumption of electrons and dissolved species in the environment, is termed a cathodic reaction. Whenever spontaneous corrosion reactions occur, all the electrons released in the anodic reaction are consumed in the cathodic reaction no excess or deficiency is found. Moreover, the metal normally takes up a more or less uniform electrode potential, often called the corrosion or mixed potential (Ecotr)-... 

The corrosion reaction may also be represented on a polarisation diagram (Fig. 10.4). The diagram shows how the rates of the anodic and cathodic reactions (both expressed in terms of current flow, I) vary with electrode potential, E. Thus at , the net rate of the anodic reaction is zero and it increases as the potential becomes more positive. At the net rate of the cathodic reaction is zero and it increases as the potential becomes more negative. (To be able to represent the anodic and cathodic reaction rates on the same axis, the modulus of the current has been drawn.) The two reaction rates are electrically equivalent at E , the corrosion potential, and the... 

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