Dissolution active

Impedance spectroscopy has been applied extensively in the analysis of the mechanism of corrosion of iron and other metals in aqueous solutions. Typical work of this kind is that reported by Keddam et al. [1981], who sought to distinguish between various mechanisms that had been proposed for the electrodissolution of iron in acidified sodium sulfate solutions. Since this particular study provides an excellent 

As the result of analyzing a large number of possible mechanisms for the dissolution of iron, Keddam et al. [1981] concluded that the most viable mechanism for this reaction involves three intermediate species 

Mass balance relationships involving the adsorbed species results in the following expressions for the time dependencies of 0, 02, ft, and O.  

In order to derive the faradic impedance (Zp) we note that for sinusoidal variations in the potential and in the surface coverages of reaction intermediates we may write 

The faradic impedance is readily obtained by first deriving expressions for dOi/dt. This is done by taking the total differentials of Eqs (32)-(35). For example in the case of Eq. (33) we write 

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In the following, the most typical modes of corrosion—other than the above discussed unifonn dissolution (active corrosion) and localized pitting and crevice corrosion (local active dissolution)—are briefly presented. 

Firstly, they might be expected to have an effect when corrosion occurs under conditions of active (film-free) anodic dissolution and is not limited by the diffusion of oxygen or some other species in the environment. However, if the rate of active dissolution is controlled by the rate of oxygen diffusion, or if, in general terms, the rate-controlling process does not take place at the metal surface, the effect of crystal defects might be expected to be minimal. 

Active Dissolution and Crystal Defects—Energy Considerations... 

Fig. 1.39 Schematic anodic polarisation curve for a metal. Region AB describes active dissolution of the metal. BC is the active/passive transition, with passivation commencing at B. Passivation is complete only at potentials higher than C. The metal is passive over the range CD...

The form of Figure 1.43 is common among many metals in solutions of acidic to neutral pH of non-complexing anions. Some metals such as aluminium and zinc, whose oxides are amphoteric, lose their passivity in alkaline solutions, a feature reflected in the potential/pH diagram. This is likely to arise from the rapid rate at which the oxide is attacked by the solution, rather than from direct attack on the metal, although at low potential, active dissolution is predicted thermodynamically The reader is referred to the classical work of Pourbaix for a full treatment of potential/pH diagrams of pure metals in equilibrium with water. 

With regard to the anodic dissolution under film-free conditions in which the metal does not exhibit passivity, and neglecting the accompanying cathodic process, it is now generally accepted that the mechanism of active dissolution for many metals results from hydroxyl ion adsorption " , and the sequence of steps for iron are as follows ... 

Since the hydroxyl anion is involved in the mechanism given before, the implication is that other anions may also take part in the dissolution process, and that the effect of various chemicals may be interpreted in the light of the effect of each anion species. Most studies have been in solutions of sulphuric and hydrochloric acids and typically the reaction postulated for active dissolution in the presence of sulphuric acid is ... 

In de-aerated 10sulphuric acid (Fig. 3.45) the active dissolution of the austenitic irons occurs at more noble potentials than that of the ferritic irons due to the ennobling effect of nickel in the matrix. This indicates that the austenitic irons should show lower rates of attack when corroding in the active state such as in dilute mineral acids. The current density maximum in the active region, i.e. the critical current density (/ ii) for the austenitic irons tends to decrease with increasing chromium and silicon content. Also the current densities in the passive region are lower for the austenitic irons... 

Similar curves determined in 50 Vo sodium hydroxide solution at 60°C show (Fig. 3.46) that the austenitic irons exhibit more noble active dissolution and also lower current densities in the active and passive regions than the ferritic irons the current densities in both regions decrease markedly with increasing nickel content (Fig. 3.47). 

Amorphous alloys are in a thermodynamically metastable state, and hence essentially they are chemically more reactive than corresponding thermodynamically stable crystalline alloyIf an amorphous alloy crystallises to a single phase having the same composition as the amorphous phase, crystallisation results in a decrease in the activity of the alloy related to the active dissolution rate of the alloy . 

As can be seen in Fig. 3.67, the corrosion resistance of amorphous alloys changes with the addition of metalloids, and the beneficial effect of a metaU loid in enhancing corrosion resistance based on passivation decreases in the order phosphorus, carbon, silicon, boron (Fig. 3.72). This is attributed partly to the difference in the speed of accumulation of passivating elements due to active dissolution prior to passivation... 

Let us mention some examples, that is, the passivation potential at which a metal surface suddenly changes from an active to a passive state, and the activation potential at which a metal surface that is passivated resumes active dissolution. In these cases, a drastic change in the corrosion rate is observed before and after the characteristic value of electrode potential. We can see such phenomena in thermodynamic phase transitions, e.g., from solid to liquid, from ferromagnetism to paramagnetism, and vice versa.3 All these phenomena are characterized by certain values... 

Plonski, I.-H. Effects of Surface Structure and Adsorption Phenomena on the Active Dissolution of Iron in Acid Media 29... 

Phenomena on the Active Dissolution of Iron in Acid Media... 

In solutions containing different anions, as seen in Fig. 17, the sudden rise in the anodic current density mentioned earlier [see Section 111(2)] and characteristic of initiation of active dissolution occurs at different potentials. It was shown108 that, at least with halides, this potential is a linear function of the crystalline radius of the ion. 

While the above effect must play a significant role in the active dissolution under the influence of halide ions, there are reasons to believe that some additional effects must be involved. They are ... 

The linear dependence of the pitting potential on ionic radius is likely a reflection of the similarly linear relationship between the latter and the free energy of formation of aluminum halides.108 It is reasonable to assume that the energy of adsorption of a halide on the oxide is also related to the latter. Hence, one could postulate that the potential at which active dissolution takes place is the potential at which the energy of adsorption overcomes the energy of coulombic repulsion so that the anions get adsorbed. 

The depth profiling technique used on samples with a barrier film before and after the addition of chloride to the buffering borate electrolyte showed no indication of either chloride penetration or significant reduction of the average oxide layer thickness.123 This, of course, does not rule out the possibility of the formation, by any of the mechanisms suggested above, of pinholes with radii much smaller than that of the ion-gun beam, through which the entire active dissolution could take place, or the possibility that the beam missed pits formed sporadically across the surface. If pinholes which are not visible were formed, the dissolution should proceed in them with extremely high true current densities. 

In nonalloyed metal, impurities affect the OCP and the corrosion behavior, while they have little effect on the potential plateau of active dissolution. 

The fact that impurities do not affect the active dissolution in chloride solutions at current densities larger than 0.01mA/ cm2 shows that the inhomogeneity resulting in a pitting mechanism of dissolution is unrelated to impurities and is an inherent property of the metal. 

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