Tafel anodic

Pa = Anodic polarization constant (Tafel anodic slope) (V)... 

This constant /3 wiU be derived in the next section In fact, this method requires knowledge of the Tafel anodic and cathodic slopes in order to calculate P, and subsequently predict ieorr using eq. (3.29). This Wr expression is simple, but essential in corrosion measurements since iayrr can be converted to corrosion rate in units of mm/y, which are more convenient for engineering purposes after 0 and Rp are determined, finally, the values of these slopes are < 1 vdt and Pc[Pg.85]

Criterion This is a criterion that requires known Tafel anodic constant (slope) /3 of the metal to be protected cathodicaUy. According to Jones [138] and the overpotential required to reduce corrosion rate can be graphically determined as shown in Figure 8.4. However, the same results can be mathematically estimated using eq. (3.20a). 

Figure 8.4 Effect of Tafel anodic constant on overpotential for cathodic...

For a fixed polarization current density (tp), the only changing variable is the Tafel anodic slope / . In this case, the overpotential becomes... 

The effect of Tafel anodic constant for the h5 thetical case shown in Figure 8.4 is calculated below as well as the half-cell potential, E = Ecorr - v- Thus,... 

Hi) Surface blockers. Type 1 tlie inliibiting molecules set up a geometrical barrier on tlie surface (mostly by adsorjDtion) such as a variety of ionic organic molecules. The effectiveness is directly related to tlie surface coverage. The effect is a lowering of tlie anodic part of tlie polarization curve witliout changing tlie Tafel slope. 

Type 2 tlie inliibiting species takes part in tlie redox reaction, i.e. it is able to react at eitlier catliodic or anodic surface sites to electroplate, precipitate or electropolymerize. Depending on its activation potential, tlie inliibitor affects tlie polarization curve by lowering tlie anodic or catliodic Tafel slope. 

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). 

This limit is called linear kinetics. On the other hand, if the surface overpotential is large, one of the exponential terms is negligible. This limit is called Tafel kinetics. The relationship was found empirically. In the anodic Tafel region... 

Tafel Extrapolation Corrosion is an elec trochemical reac tion of a metal and its environment. When corrosion occurs, the current that flows between individual small anodes and cathodes on the metal surface causes the electrode potential for the system to change. While this current cannot be measured, it can be evaluated indirectly on a metal specimen with an inert electrode and an external electrical circuit. Pmarization is described as the extent of the change in potential of an electrode from its equilibrium potential caused by a net current flow to or from the electrode, galvanic or impressed (Fig. 28-7). 

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... 

If it is assumed that anodic polarisation of the more negative metal of the couple is insignificant, then it can be shown from the Tafel relationship for the hydrogen evolution reaction that... 

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 values of h, and b, i.e. The Tafel constants of the anodic and cathodic polarisation curves, first have to be measured directly in the laboratory or deduced by correlating values of AE/Ai measured on the plant with values deduced from corrosion coupons. The criticism is that the K value is likely to be inaccurate and/or to change markedly as conditions in the process stream change, i.e. the introduction of an impurity into a process stream could not only alter i but also the K factor which is used to calculate it. 

The effects of adsorbed inhibitors on the individual electrode reactions of corrosion may be determined from the effects on the anodic and cathodic polarisation curves of the corroding metaP . A displacement of the polarisation curve without a change in the Tafel slope in the presence of the inhibitor indicates that the adsorbed inhibitor acts by blocking active sites so that reaction cannot occur, rather than by affecting the mechanism of the reaction. An increase in the Tafel slope of the polarisation curve due to the inhibitor indicates that the inhibitor acts by affecting the mechanism of the reaction. However, the determination of the Tafel slope will often require the metal to be polarised under conditions of current density and potential which are far removed from those of normal corrosion. This may result in differences in the adsorption and mechanistic effects of inhibitors at polarised metals compared to naturally corroding metals . Thus the interpretation of the effects of inhibitors at the corrosion potential from applied current-potential polarisation curves, as usually measured, may not be conclusive. This difficulty can be overcome in part by the use of rapid polarisation methods . A better procedure is the determination of true polarisation curves near the corrosion potential by simultaneous measurements of applied current, corrosion rate (equivalent to the true anodic current) and potential. However, this method is rather laborious and has been little used. 

Blocking of reaction sites The interaction of adsorbed inhibitors with surface metal atoms may prevent these metal atoms from participating in either the anodic or cathodic reactions of corrosion. This simple blocking effect decreases the number of surface metal atoms at which these reactions can occur, and hence the rates of these reactions, in proportion to the extent of adsorption. The mechanisms of the reactions are not affected and the Tafel slopes of the polarisation curves remain unchanged. Behaviour of this type has been observed for iron in sulphuric acid solutions containing 2,6-dimethyl quinoline, /3-naphthoquinoline , or aliphatic sulphides . 

Participation in the electrode reactions The electrode reactions of corrosion involve the formation of adsorbed intermediate species with surface metal atoms, e.g. adsorbed hydrogen atoms in the hydrogen evolution reaction adsorbed (FeOH) in the anodic dissolution of iron . The presence of adsorbed inhibitors will interfere with the formation of these adsorbed intermediates, but the electrode processes may then proceed by alternative paths through intermediates containing the inhibitor. In these processes the inhibitor species act in a catalytic manner and remain unchanged. Such participation by the inhibitor is generally characterised by a change in the Tafel slope observed for the process. Studies of the anodic dissolution of iron in the presence of some inhibitors, e.g. halide ions , aniline and its derivatives , the benzoate ion and the furoate ion , have indicated that the adsorbed inhibitor I participates in the reaction, probably in the form of a complex of the type (Fe-/), or (Fe-OH-/), . The dissolution reaction proceeds less readily via the adsorbed inhibitor complexes than via (Fe-OH),js, and so anodic dissolution is inhibited and an increase in Tafel slope is observed for the reaction. 

Adsorbed species may also accelerate the rate of anodic dissolution of metals, as indicated by a decrease in Tafel slope for the reaction. Thus the presence of hydrogen sulphide in acid solutions stimulates the corrosion of iron, and decreases the Tafel slope The reaction path through... 

The controversy that arises owing to the uncertainty of the exact values of and b and their variation with environmental conditions, partial control of the anodic reaction by transport, etc. may be avoided by substituting an empirical constant for (b + b /b b ) in equation 19.1, which is evaluated by the conventional mass-loss method. This approach has been used by Makrides who monitors the polarisation resistance continuously, and then uses a single mass-loss determination at the end of the test to obtain the constant. Once the constant has been determined it can be used throughout the tests, providing that there is no significant change in the nature of the solution that would lead to markedly different values of the Tafel constants. 

The corrosion current (it is also assumed that the area of the metal is 1 cm so that - ho ) occurs at a value within the Tafel region for the anodic and cathodic reaction, i.e. transport overpotential is negligible. 

Figure 19.10a shows a theoretical plot of the right-hand side of equation 19.16 vs. AE in which the cathodic Tafel slope has been assumed to be constant at 120 mV and the anodic Tafel slope to have the arbitrary slopes of 40, 60 and 120 mV. It can be seen that linearity over a range of positive and negative potentials AE is achieved only when b = and that linearity is confined to AE 0 when b and b differ. 

Attention should be drawn to the signs in equations 20.66 and 20.67 and it should be noted that the Tafel slope b is always positive for an anodic process and negative for a cathodic process and that the constant a is of opposite sign to the slope. 

FIGURE 1-8 Tafel plots for the cathodic and anodic branches of the current-potential curve. 

Average from cathodic and anodic Tafel lines. 

The exact calculation of icorr for a given time requires simultaneous measurements of Rp and anodic and cathodic Tafel slopes (/> and be). Computer programs have been developed for the determination of precise values of /corr according to Eqs. (2) and (3). Experimental values of Rp (2p contain a contribution from the uncompensated solution resistance... 

Thus, in the region of very high anodic or cathodic polarization, the RDS is always the first step in the reaction path. The transfer coefficient of the full reaction which is equal to that of this step is always smaller than unity (for a one-electron RDS), while slope i in the Tafel equation is always larger than 0.06 V. When the potential is outside the region of low polarization, a section will appear in the polarization curve at intermediate values of anodic or cathodic polarization where the transfer coefficient is larger than unity and b is smaller than 0.06 V. This indicates that in this region the step that is second in the reaction path is rate determining. 

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