Corrosion reactions cathodic

A process resulting in a decrease in touglmess or ductility of a metal due to absorjDtion of hydrogen. This atomic hydrogen can result, for instance, in the cathodic corrosion reaction or from cathodic protection. 

Many of the by-products of microbial metaboHsm, including organic acids and hydrogen sulfide, are corrosive. These materials can concentrate in the biofilm, causing accelerated metal attack. Corrosion tends to be self-limiting due to the buildup of corrosion reaction products. However, microbes can absorb some of these materials in their metaboHsm, thereby removing them from the anodic or cathodic site. The removal of reaction products, termed depolari tion stimulates further corrosion. Figure 10 shows a typical result of microbial corrosion. The surface exhibits scattered areas of localized corrosion, unrelated to flow pattern. The corrosion appears to spread in a somewhat circular pattern from the site of initial colonization. 

In a battery, the anode and cathode reactions occur ia different compartments, kept apart by a separator that allows only ionic, not electronic conduction. The only way for the cell reactions to occur is to mn the electrons through an external circuit so that electrons travel from the anode to the cathode. But ia the corrosion reaction the anode and cathode reactions, equations 8 and 12 respectively, occur at different locations within the anode. Because the anode is a single, electrically conductive mass, the electrons produced ia the anode reaction travel easily to the site of the cathode reaction and the 2iac acts like a battery where the positive and negative terminals are shorted together. 

In most aqueous systems, the corrosion reaction is divided into an anodic portion and a cathodic portion, occurring simultaneously at discrete points on metallic surfaces. Flow of electricity from the anodic to the cathodic areas may be generated by local cells set up either on a single metallic surface (because of local point-to-point differences on the surface) or between dissimilar met s. 

The concept of the corrosion process, derived from the Latin corrodere (to eat away, to destroy), first appeared in the Philosophical Transactions in 1667 [2]. It was discussed in a German translation from the French on the manufacture of white lead in 1785 and was mentioned in 1836 in the translation of an English paper by Davy on the cathodic protection of iron in seawater [3]. However, almost until the present day, the term was used indiscriminately for corrosion reaction, corrosion effects, and corrosion damage. Only in DIN 50900, Part I, were these terms distinguished and defined [4] (see Section 2.1). 

Inhibitors are materials that reduce either one or both of the partial corrosion reactions as in Fig. 2-5. Anodic or cathodic inhibitors inhibit the anodic or cathodic reaction respectively so that the rest potential becomes either more positive or more negative. Most inhibitors, however, inhibit the anodic partial reaction. This is because the transfer of metal ions can be more easily restricted than that of electrons. 

Nascent atomic hydrogen released at metal surfaces by chemical reactions between the process environment and the metal (corrosion or cathodic protection reactions)... 

All these types of polarisation will be present to a greater or lesser extent in most corrosion reactions, but if one is more significant than the others it will control the rate of the reaction. This leads to a classification of corrosion reactions according to whether the cathodic or anodic reaction is rate... 

The graphical method of showing how the corrosion rate is dependent on the extent of the polarisation of the anodic and cathodic reactions constituting the corrosion reaction was due originally to Evanswho used... 

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... 

It follows from the electrochemical mechanism of corrosion that the rates of the anodic and cathodic reactions are interdependent, and that either or both may control the rate of the corrosion reaction. It is also evident from thermodynamic considerations (Tables 1.9 and 1.10) that for a species in solution to act as an electron acceptor its redox potential must be more positive than that of the M /M equilibrium or of any other equilibrium involving an oxidised form of the metal. 

It follows from this that the limiting current density / l is the most significant parameter in a corrosion reaction in which oxygen is the cathodic reactant, and that any factor that increases / l will increase the corrosion rate, since at E ... 

Corrosion reactions involving two simultaneous cathodic processes have already been referred to, and it is now appropriate to consider the graphical method of representing the corrosion rate. It should be noted that although the simultaneous reduction of HjO and dissolved oxygen occurs frequently this does not exhaust the possibilities, and reactions such as Fe - Fe, -> Cu, CI2 Cl may accompany either or both of the... 

It should be noted that since the rust is formed at a position in between the anodic and cathodic sites it will not influence the kinetics of the corrosion reaction. 

Although Table 2.16 shows which metal of a couple will be the anode and will thus corrode more rapidly, little information regarding the corrosion current, and hence the corrosion rate, can be obtained from the e.m.f. of the cell. The kinetics of the corrosion reaction will be determined by the rates of the electrode processes and the corrosion rates of the anode of the couple will depend on the rate of reduction of hydrogen ions or dissolved oxygen at the cathode metal (Section 1.4). 

Equation 10.2, which involves consumption of the metal and release of electrons, is termed an anodic reaction. Equation 10.3, which represents consumption of electrons and dissolved species in the environment, is termed a cathodic reaction. Whenever spontaneous corrosion reactions occur, all the electrons released in the anodic reaction are consumed in the cathodic reaction no excess or deficiency is found. Moreover, the metal normally takes up a more or less uniform electrode potential, often called the corrosion or mixed potential (Ecotr)-... 

It is possible to envisage what might happen if an electrical intervention was made in the corrosion reaction by considering the impact on the anodic and cathodic reactions. For example, if electrons were withdrawn from the metal surface it might be anticipated that reaction 10.2 would speed up (to replace the lost electrons) and reaction 10.3 would slow down, because of the existing shortfall of electrons. It follows that the rate of metal consumption would increase. 

The corrosion reaction may also be represented on a polarisation diagram (Fig. 10.4). The diagram shows how the rates of the anodic and cathodic reactions (both expressed in terms of current flow, I) vary with electrode potential, E. Thus at , the net rate of the anodic reaction is zero and it increases as the potential becomes more positive. At the net rate of the cathodic reaction is zero and it increases as the potential becomes more negative. (To be able to represent the anodic and cathodic reaction rates on the same axis, the modulus of the current has been drawn.) The two reaction rates are electrically equivalent at E , the corrosion potential, and the... 

It was indicated earlier that the cathodic current was a poor indicator of adequate protection. Whilst, to a first approximation the protection potential is a function of the metal, the current required for protection is a function of the environment and, more particularly, of the cathodic kinetics it entails. From Fig. 10.4 it is apparent that any circumstance that causes the cathodic kinetics to increase will cause both the corrosion rate and the current required for full (/") or partial (1/ — /, ) protection to rise. For example, an increase in the limiting current in Fig. 10.5 produced by an increase in environmental oxygen concentration or in fluid flow rate will increase the corrosion rate and the cathodic protection current. Similarly, if the environment is made more acid the hydrogen evolution reaction is more likely to be involved in the corrosion reaction and it also becomes easier and faster this too produces an increased corrosion rate and cathodic current demand. 

Because of the many variables which can influence the corrosion reaction, the use of the e.m.f. series of metals to predict the behaviour of galvanic couples in a given service environment can be hazardous and misleading. Numerous examples of coatings expected to act cathodically which have, in fact, been anodic have been reported in the literature and specialised lists of galvanic couples in different environments have been compiled. ... 

The potential difference across the electric double layer A. This cannot be determined in absolute terms but must be defined with reference to another charged interface, i.e. a reference electrode. In the case of a corroding metal the potential is the corrosion potential which arises from the mutual polarisation of the anodic and cathodic reactions constituting the overall corrosion reaction see Section 1.4). 

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