Passivity mixed potential theory

Solution pH, velocity, and oxidizer concentration change the properties of the anodic curve of the active-passive metal. For example, the equilibrium potential of the cathodic reaction shifts according to the Nemst equation in the noble direction by increasing the oxidizer concentration. Mixed potential theory, in this case, may predict the intersection of the cathodic and anodic Tafel fines and corrosion rate or extent of passivation of the metal. 

Mixed potential theory and the Levich equation are used to construct the anodic and cathodic polarization curve of the active-passive alloy and to estimate the value of the oxygen limiting diffusion current when a spontaneous passive film is formed on the surface. Figure 4.11 correlates the relationship between potential and current for the... 

E4.1. Calctilate and construct, using mixed potential theory, the critical passivation current density (a) potentiostatic and (b) galvanostatic polarization curve for anodic dissolution for active-passive metal that has the following electrochemical parameters Ecorr= 0-5 V vs. SCE, Epp= — 0.4 V vs. SCE, 4orr= 10 A/cm, K = 0.05,. , = 10 A/cm andEtr= + l-0V vs. SCE. 

E4.3. Construct an anodic polarization curve and calculate the critical passivation current density of an active-passive alloy using mixed potential theory with the following electrochemical parameters Econ = 0-b5V vs. SCE /corr= 10 " A/cm fca = 0.1, Epp= —0.3 V vs. SCE and /pass = 10 A/cm, Etr = + 0.9 V. 

Mixed potential theory is used to estimate the galvanic current and the galvanic potential in an active-passive metal that passivates at potentials less noble than the reversible hydrogen potential. A galvanic couple between titanium and platinum of equal area of 1 cm is exposed to 1 M HCl. The electrochemical parameters for the active-passive alloy are eeq xi = —163 V vs. SHE anodic Tafel, b Ti = 0.1 exchange current density, ixi= 10 A/cm passivation potential, pp= —0.73 V passivation current, 7pass= 10 A/cm transpassive potential, = 0.4 V vs. SHE and activity of dissolved species [Ti ] = 1 M. The exchange current densities, i°, on platinum and titanium... 

Using the given parameters, the anodic polarization curve was constructed (Fig. E4.3) and the critical passivation current density was calculated using mixed potential theory. 

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