Corrosion metal dissolution

This is essentially a corrosion reaction involving anodic metal dissolution where the conjugate reaction is the hydrogen (qv) evolution process. Hence, the rate depends on temperature, concentration of acid, inhibiting agents, nature of the surface oxide film, etc. Unless the metal chloride is insoluble in aqueous solution eg, Ag or Hg ", the reaction products are removed from the metal or alloy surface by dissolution. The extent of removal is controUed by the local hydrodynamic conditions. 

The most common form of corrosion is uniform corrosion, in which the entire metal surface degrades at a near uniform rate (1 3). Often the surface is covered by the corrosion products. The msting of iron (qv) in a humid atmosphere or the tarnishing of copper (qv) or silver alloys in sulfur-containing environments are examples (see also SiLVERAND SILVER ALLOYS). High temperature, or dry, oxidation, is also usually uniform in character. Uniform corrosion, the most visible form of corrosion, is the least insidious because the weight lost by metal dissolution can be monitored and predicted. 

Fig. 1.30 Corrosion of a metal in an acid in which both metal dissolution and hydrogen evolution are under activation control so that the .log i curves are linear, (a) Effect of pH on and I o Hi increase in pH (decrease in an + ) lowers E and decreases / o (b) Effect of...

Film is locally removed by dissolution, surface shear stress or particle/bubble impact but it can repassivate. Erosion corrosion rate is a function of the frequency of film removal, bare metal dissolution rate and subsequent repassivation rate. 

Film is removed and underlying metal surface is mechanically damaged which contributes to overall metal loss i.e. erosion corrosion rate is equal to bare metal dissolution rate plus possibly synergistic effect of mechanical damage. 

The explicit aims of boiler and feed-water treatment are to minimise corrosion, deposit formation, and carryover of boiler water solutes in steam. Corrosion control is sought primarily by adjustment of the pH and dissolved oxygen concentrations. Thus, the cathodic half-cell reactions of the two common corrosion processes are hindered. The pH is brought to a compromise value, usually just above 9 (at 25°C), so that the tendency for metal dissolution is at a practical minimum for both steel and copper alloys. Similarly, by the removal of dissolved oxygen, by a combination of mechanical and chemical means, the scope for the reduction of oxygen to hydroxyl is severely constrained. 

In addition to the basic corrosion mechanism of attack by acetic acid, it is well established that differential oxygen concentration cells are set up along metals embedded in wood. The gap between a nail and the wood into which it is embedded resembles the ideal crevice or deep, narrow pit. It is expected, therefore, that the cathodic reaction (oxygen reduction) should take place on the exposed head and that metal dissolution should occur on the shank in the wood. 

The determination of polarisation curves of metals by means of constant potential devices has contributed greatly to the knowledge of corrosion processes and passivity. In addition to the use of the potentiostat in studying a variety of mechanisms involved in corrosion and passivity, it has been applied to alloy development, since it is an important tool in the accelerated testing of corrosion resistance. Dissolution under controlled potentials can also be a precise method for metallographic etching or in studies of the selective corrosion of various phases. The technique can be used for establishing optimum conditions of anodic and cathodic protection. Two of the more recent papers have touched on limitations in its application and differences between potentiostatic tests and exposure to chemical solutions. ... 

As mentioned, corrosion is complexly affected by the material itself and the environment, producing various kinds of surface films, e.g., oxide or hydroxide film. In the above reactions, both active sites for anodic and cathodic reactions are uniformly distributed over the metal surface, so that corrosion proceeds homogeneously on the surface. On the other hand, if those reaction sites are localized at particular places, metal dissolution does not take place uniformly, but develops only at specialized places. This is called local corrosion, pitting corrosion through passive-film breakdown on a metal surface is a typical example. 

Corrosion (spontaneous dissolution) of the catalyticaUy active material, and hence a decrease in the quantity present. Experience shows that contrary to widespread belief, marked corrosion occurs even with the platinum metals. For smooth platinum in sulfuric acid solutions at potentials of 0.9 to 1.0 V (RHE), the steady rate of self-dissolution corresponds to a current density of about 10 A/cm. Also, because of enhanced dissolution of ruthenium from the surface layer of platinum-ruthenium catalysts, their exceptional properties are gradually lost, and they are converted to ordinary, less active platinum catalysts. 

The rotating hemispherical electrode (RHSE) was originally proposed by the author in 1971 as an analytical tool for studying high-rate corrosion and dissolution reactions [13]. Since then, much work has been published in the literature. The RHSE has a uniform primary current distribution, and its surface geometry is not easily deformed by metal deposition and dissolution reactions. These features have made the RHSE a complementary tool to the rotating disk electrode (RDE). 

Corrosion is a mixed-electrode process in which parts of the surface act as cathodes, reducing oxygen to water, and other parts act as anodes, with metal dissolution the main reaction. As is well known, iron and ferrous alloys do not dissolve readily even though thermodynamically they would be expected to, The reason is that in the range of mixed potentials normally encountered, iron in neutral or slightly acidic or basic solutions passivates, that is it forms a layer of oxide or oxyhydroxide that inhibits further corrosion. 

For the corresponding equations in alkaline solutions, see Chapter 9. The metal surface attains a mixed potential corrosion potential, such that the anodic current of the metal dissolution is exactly balanced by the cathodic current of one or more reduction reactions. The corrosion potential is given by Eq. (11.41), and the corrosion current density by Eq. (11.42). 

As described in Sec. 11.3, the spontaneous corrosion potential of a corroding metal is represented by the intersection of the anodic polarization curve of metal dissolution with the cathodic polarization curve of oxidant reduction (Figs. 11—5 and 11-6). Then, whether a metal electrode is in the active or in the passive state is determined by the intersection of the anodic and cathodic polarization curves. 

An examination of the theoretical models proposed for metal dissolution and for the general Impedance behavior of electrodes enables the rate-determining step of the corrosion reaction to be Identified. It Is then possible to separately study the rate determining step In order to find a suitable Inhibitor or a suitable surface coating. 

Thus it appears that by incorporating parameters such as pore resistance and coating capacitance to the existing theoretical impedance model dealing with metal dissolution one would obtain valuable overall information (14,27). Complemented by results from regular immersion and salt spray tests it should be possible to find satisfactory solutions to corrosion problems of coated metals (9 ). 

Fig. 13. (a) Schematic representation of the formation of mixed potential, M, at an inert electrode with two simultaneous redox processes (I) and (II) with formal equilibrium potentials E j and E2. Observed current density—potential curve is shown by the broken line, (b) Representation of the formation of corrosion potential, Econ, by simultaneous occurrence of metal dissolution (I), hydrogen evolution, and oxygen reduction. Dissolution of metal M takes place at far too noble potentials and hence does not contribute to EC0Ir and the oxygen evolution reaction. The broken line shows the observed current density—potential curve for the system. 

The basic mechanism for the instability of ultrapure metals was suggested by Wagner and Traud in a classic paper in 1938.1 The essence of their view is that for corrosion to occur, there need not exist spatially separated electron-sink and -source areas on the corroding metal. Hence, impurities or other heterogeneities on the surface are not essential for the occurrence of corrosion. The necessary and sufficient condition for corrosion is that the metal dissolution reaction and some electronation reaction proceed simultaneously at the metal/environment interface. For these two processes to take place simultaneously, it is necessary and sufficient that the corrosion potential be more positive than the equilibrium potential of the M, + + ne M reaction and more negative than the equilibrium potential of the electronation (cathodic) reaction A + ne — D involving electron acceptors contained in the electrolyte (Fig. 12.8). 

Hence, the present view is a unified one. When the electron-sink and -source areas are distinct in space and stable in time, one has the local-cell, or heterogeneous, theory of corrosion [Fig. 12.9(a)], On the other hand, when the metal-dissolution and electronation reactions occur randomly over the surface with regard to both space and... 

Fig. 12.8. Corrosion can always occur when the reversible potential of the metal dissolution is more negative than the actual potential of the metal, and that of the electronation reactions is more positive.

A very important aspect of the corrosion of metal has been only touched upon so far. This aspect concerns the electronation (cathodic) reaction required to complete the corrosion circuit by consuming the electrons transferred to the metal from the metal-dissolution reaction. The question is What is the electronation (cathodic) reaction ... 

Consider a system consisting of a metal corroding in an electrolyte. The corrosion process involves a metal-dissolution deelectronation (anodic) reaction at electron-sink areas on the metal and an electronation (cathodic) reaction at electron-source areas. (This picture is applicable to a metal s corroding by a Wagner-Traud mechanism provided one imagines the sink and source areas shrunk to atomic-sized dimensions and considers the situation at one instant of time.)... 

The rate of corrosion of the metal is obviously given directly by the rate of metal dissolution hence, the corrosion current /corr is equal to the metal-dissolution current... 

Two fundamental ideas have been developed. First, the rate of corrosion, a quantity of great practical significance, is given by the corrosion current /corr, which is equal to the metal-dissolution, deelectronation current /M and to the negative of the electronation (cathodic) current /so at the electron-source areas, i.e.,... 

Second, there is a uniform potential difference, namely, the corrosion potential d0corr> all over the surface of the corroding metal. It is this corrosion potential that is associated with both the metal-dissolution and electronation currents, i.e.,... 

To obtain quantitative expressions for the corrosion current and the corrosion potential, one has to substitute the proper expression for the metal-dissolution- and electronation-current densities. If no oxide films form on the surface of the corroding metal and neither of the current densities is controlled by mass transport, i.e., there is no concentration overpotential, one can insert the Butler-Volmer expression for the deelectronation- and electronation-current densities. Thus,... 

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