Corrosion Evans diagram

The two dashed lines in the upper left hand corner of the Evans diagram represent the electrochemical potential vs electrochemical reaction rate (expressed as current density) for the oxidation and the reduction form of the hydrogen reaction. At point A the two are equal, ie, at equiUbrium, and the potential is therefore the equiUbrium potential, for the specific conditions involved. Note that the reaction kinetics are linear on these axes. The change in potential for each decade of log current density is referred to as the Tafel slope (12). Electrochemical reactions often exhibit this behavior and a common Tafel slope for the analysis of corrosion problems is 100 millivolts per decade of log current (1). A more detailed treatment of Tafel slopes can be found elsewhere (4,13,14). 

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). 

A typical Evans diagrams for the corrosion of a single metal is illustrated in Fig. 1.26a (compare with Fig. 1.23 for two separable electrodes), and it can be seen that the E -I and E -I curves are drawn as straight lines that intersect at a point that defines and (it is assumed that the resistance for the solution is negligible). E can of course be determined by means of a reference electrode, but since the anodic and cathodic sites are inseparable direct determination of /co by means of an ammeter is not... 

Fig. 1.27 Evans diagrams illustrating (a) cathodic control, (b) anodic control, (c) mixed control, (d) resistance control, (e) how a reaction with a higher thermodynamic tendency ( r, ii) may result in a smaller corrosion rate than one with a lower thermodynamic tendency and (/) how gives no indication of the corrosion rate...

The equilibrium potentials and E, can be calculated from the standard electrode potentials of the H /Hj and M/M " " equilibria taking into account the pH and although the pH may be determined an arbitrary value must be used for the activity of metal ions, and 0 1 = 1 is not unreasonable when the metal is corroding actively, since it is the activity in the diffusion layer rather than that in the bulk solution that is significant. From these data it is possible to construct an Evans diagram for the corrosion of a single metal in an acid solution, and a similar approach may be adopted when dissolved O2 or another oxidant is the cathode reactant. 

Figures 1.27a to d show how the Evans diagram can be used to illustrate how the rate may be controlled by either the polarisation of one or both of the partial reactions (cathodic, anodic or mixed control) constituting corrosion reaction, or by the resistivity of the solution or films on the metal surface (resistance control). Figures 1. lie and/illustrate how kinetic factors may be more significant than the thermodynamic tendency ( , u) and how provides no information on the corrosion rate.

Over the years the original Evans diagrams have been modified by various workers who have replaced the linear E-I curves by curves that provide a more fundamental representation of the electrode kinetics of the anodic and cathodic processes constituting a corrosion reaction (see Fig. 1.26). This has been possible partly by the application of electrochemical theory and partly by the development of newer experimental techniques. Thus the cathodic curve is plotted so that it shows whether activation-controlled charge transfer (equation 1.70) or mass transfer (equation 1.74) is rate determining. In addition, the potentiostat (see Section 20.2) has provided... 

Fig. 1.28 Evans diagram illustrating a corrosion process (e.g. a bimetallic couple) in which the area of the cathode is not equal to that of the anode, (o) so that and (b) > S(,...

Evans Diagram diagram in which the E vs. I relationships for the cathodic and anodic reactions of a corrosion reaction are drawn as straight lines intersecting at the corrosion potential, thus indicating the corrosion current associated with the reaction. 

Any fundamental classification of corrosion control must be based on the electrochemical mechanism of corrosion, and Evans diagrams may be constructed (Fig. 1.27, Section 1.4) illustrating... 

Fig. 12.17. The Evans diagrams are plots of the potentials of the two reactions (a) vs. the magnitude of the two currents or (b) vs. their logarithms. The intersections of the curves define the corrosion current and corrosion potential.

The less well known (so-called) Evans diagrams involve kinetics and allow one to make a rough first cut at the order of magnitude of a corrosion rate (for a pure surface without blocking oxide films). 

The above two methods ofpreventing corrosion can be understood easily with an Evans diagram (Fig. 12.39 see Section 12.19). (These diagrams it will be recalled, result from the superposition of the potential-current curves of the electronation and... 

With the help of the Evans diagram (Fig. E12.1) explain the influence of an inhibitor on the corrosion potential and corrosion current. Assume that the inhibitor decreases the exchange current density for the cathodic reaction. (Contractor)... 

It is well known that Pourbaix diagrams give the thermodynamic limits of corrosion. However, it is possible that corrosion in a system may be limited by kinetics to rates so low that corrosion that is thermodynamically possible can be neglected under practical circumstances. In this light, (a) construct an Evans diagram, i.e., a plot of the actual relevant electrode potentials against log i for... 

Consider an Evans diagram in a general way. The anodic dissolution reaction is to be represented in the Tafel region the same applies for the cathodic partner reaction, (a) Draw the two Tafel lines and show the region of intersection Oanodic= Cathodic)- Indicate on the graph the corrosion rate and corrosion potential. 

Fig. 16.3. Evans diagram for metallic corrosion in acid medium. The concentrations are adjusted for eq to be equal for the three metals.

The corrosion rate of the iron can be directly predicted from the Evans diagram by considering two facts ... 

Figure 25 Evans diagram for Fe in acid showing use of conservation of charge to determine Eom and corrosion rate (7corr), given complete knowledge of the kinetic parameters involved.

Consider the two materials whose polarization curves are shown in Fig. 31. Both the polarization curves and the Evans lines are shown for both materials. Material 1 is the more noble material (i.e., it has a more positive Ec0II) and has a lower circuit corrosion rate when it is uncoupled. If the surface area of the two materials is the same and the materials are coupled, then the two material-solution interfaces must come to the same potential. In a manner identical to that used for the example of iron in acid used to introduce Evans diagrams, the potential and current at which this condition is met can be found by applying the conservation of charge to the sysytem ... 

A metal is passive if it substantially resists corrosion in an environment where there is a large thermodynamic driving force for its oxidation (also known as thick film passivity). The Evans diagram for this type of behavior is shown in Fig. 1. 

In the presence of oxidizing species (such as dissolved oxygen), some metals and alloys spontaneously passivate and thus exhibit no active region in the polarization curve, as shown in Fig. 6. The oxidizer adds an additional cathodic reaction to the Evans diagram and causes the intersection of the total anodic and total cathodic lines to occur in the passive region (i.e., Ecmi is above Ew). The polarization curve shows none of the characteristics of an active-passive transition. The open circuit dissolution rate under these conditions is the passive current density, which is often on the order of 0.1 j.A/cm2 or less. The increased costs involved in using CRAs can be justified by their low dissolution rate under such oxidizing conditions. A comparison of dissolution rates for a material with the same anodic Tafel slope, E0, and i0 demonstrates a reduction in corrosion rate... 

Figure 11 Schematic Evans diagram illustrating the effect of a change in the cathodic reaction kinetics on the corrosion conditions. Case 1 would be representative of Fig. 5. Case 3 would lead to the polarization behavior described in Fig. 6. Case 2 would lead to the polarization behavior shown in Fig. 8. (After Ref. 71.)...

Figure 24 Schematic Evans diagram and polarization curve illustrating the origin of the negative hysteresis observed upon cyclic polarization for materials that do not pit. Line a represents the (unchanging) cathodic Evans line. Line b represents the anodic Evans line during the anodically directed polarization, while line c represents the anodic Evans line for the material after its passive film has thickened because of the anodic polarization. The higher corrosion potential observed for the return scan (E (back)) is due to the slowing of the anodic dissolution kinetics.

Figure 27 Schematic (a) Evans diagram and (b) corrosion potential vs. time behavior for localized corrosion stabilization. Line a on the Evans diagram represents the electrochemical behavior of the material before localized corrosion initiates, while line b represents the electrochemical behavior of the material in the localized corrosion site. Due to the low Tafel slope of the active site, the corrosion potential of the passive surface/local-ized corrosion site falls. If repassivation occurs, the anodic behavior reverts back to line a, and the corrosion potential increases again (line c). If repassivation does not occur, the corrosion potential will remain low (line d).

The information required to predict electrochemical reaction rates (i.e., experimentally determined by Evans diagrams, electrochemical impedance, etc.) depends upon whether the reaction is controlled by the rate of charge transfer or by mass transport. Charge transfer controlled processes are usually not affected by solution velocity or agitation. On the other hand, mass transport controlled processes are strongly influenced by the solution velocity and agitation. The influence of fluid velocity on corrosion rates and/or the rates of electrochemical reactions is complex. To understand these effects requires an understanding of mixed potential theory in combination with hydrodynamic concepts. 

Figure 2 Evans diagram illustrating the influence of solution velocity on corrosion rate for a cathodic reaction under mixed charge transfer-mass transport control. The anodic reaction shown is charge transfer controlled.

A preliminary knowledge of which reaction steps could be key in determining the overall corrosion rate can be assessed by measurements of Corr as a function of important system parameters, e.g., oxidant concentration, solution composition, temperature. The proximity of ACOrr to either eM/Mn+ or /Red can indicate which of the two half-reactions may be rate determining. This is illustrated in Fig. 3A, which shows an Evans diagram for the combination of a fast anodic reaction coupled to a slow cathodic one. The corrosion of iron or carbon steel in aerated neutral solution would be an example of such a combination. The anodic reaction requires only a small overpotential (1) = /Mn+ - Ecorr) to sustain the corrosion current, /COrr, compared to the much larger overpotential required to sustain the cathodic reaction at this current. The anodic reaction would... 

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