Corrosion reactions, process

Since metals have very high conductivities, metal corrosion is usually electrochemical in nature. The tenn electrochemical is meant to imply the presence of an electrode process, i.e. a reaction in which free electrons participate. For metals, electrochemical corrosion can occur by loss of metal atoms tluough anodic dissolution, one of the fiindamental corrosion reactions. As an example, consider a piece of zinc, hereafter referred to as an electrode, inunersed in water. Zinc tends to dissolve in water, setting up a concentration of Zn ions very near the electrode... 

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. 

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. 

Passive corrosion caused by chemically inert substances is the same whether the substance is living or dead. The substance acts as an occluding medium, changes heat conduction, and/or influences flow. Concentration cell corrosion, increased corrosion reaction kinetics, and erosion-corrosion can he caused by biological masses whose metabolic processes do not materially influence corrosion processes. Among these masses are slime layers. 

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). 

The principle of electrochemical corrosion protection processes is illustrated in Figs. 2-2 and 2-5. The necessary requirement for the protection process is the existence of a potential range in which corrosion reactions either do not occur or occur only at negligibly low rates. Unfortunately, it cannot be assumed that such a range always exists in electrochemical corrosion, since potential ranges for different types of corrosion overlap and because in addition theoretical protection ranges cannot be attained due to simultaneous disrupting reactions. 

The examples already discussed lead to the conclusion that any reaction of a metal with its environment must be regarded as a corrosion process irrespective of the extent of the reaction or of the rates of the initial and subsequent stages of the reaction. It is not illogical, therefore, to regard passivity, in which the reaction product forms a very thin protective film that controls rate of the reaction at an acceptable level, as a limiting case of a corrosion reaction. Thus both the rapid dissolution of active titanium in 40% H2SO4 and the slow dissolution of passive titanium in that acid must be... 

The classification given in Table 1.2 is based on the various forms that corrosion may take, but the terminology used in describing corrosion phenomena frequently places emphasis on the environment or cause of attack rather than the form of attack. Thus the broad classification of corrosion reactions into wet or dry is now generally accepted, and the nature of the process is frequently made more specific by the use of an adjective that indicates type or environment, e.g. concentration—cell corrosion, crevice corrosion, bimetallic corrosion and atmospheric corrosion. 

Corrosion reactions in aggressive organic solvents are becoming a more frequent occurrence owing to developments in the chemical and petrochemical industries, and these reactions can lead to the deterioration of the metal and to undesirable changes in the solvent. This aspect of corrosion has recently been the subject of an extensive review by Heitz who has considered the mechanisms of the reactions, the similarities between corrt ion in organic solvents and in aqueous solutions, the methods of study and the occurrence of the phenomenon in industrial processes. 

The study of corrosion is essentially the study of the nature of the metal reaction products (corrosion products) and of their influence on the reaction rate. It is evident that the behaviour of metals and alloys in most practical environments is highly dependent on the solubility, structure, thickness, adhesion, etc. of the solid metal compounds that form during a corrosion reaction. These may be formed naturally by reaction with their environment (during processing of the metal and/or during subsequent exposure) or as a result of some deliberate pretreatment process that is used to produce thicker films or to modify the nature of existing films. The importance of these solid reaction products is due to the fact that they frequently form a kinetic barrier that isolates the metal from its environment and thus controls the rate of the reaction the protection afforded to the metal will, of course, depend on the physical and chemical properties outlined above. 

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... 

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... 

Bearing in mind the importance of the rate determining process and because of the complex situation in corrosion reactions of having two electrode processes, the effect of temperature is best illustrated by reference to specific situations. 

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). 

Hardly any quantitative results on the effect of movement on corrosion of steel are available. Water movement can markedly affect the corrosion process in controlling the rate of transport of reactants to the corrosion site, and the removal of the corrosion reaction products. 

In certain applications it has not always been easy to hnd suitable metallic container materials, particularly in the nuclear-energy industry, where, for certain applications, corrosion resistance of the same order as that required by the fine chemical industry has to be achieved in order to prevent contamination of the process stream. Such difflculties have stimulated the study of corrosion in fused salts and have led to a fairly high degree of understanding of corrosion reactions in these media. 

Mechanism The mechanism of cracking has not been established. Even the corrosion reaction that is responsible for the initial attack has not been determined. Early work led to the suggestion that chlorine gas was generated and could cause fracture by a cyclic process requiring the formation and decomposition of TiCl2 ... 

Particularly in theoretical studies of corrosion processes, it has been useful to measure the progress of corrosion in terms of the rate or extent of consumption of oxygen in the corrosion reactions. This technique has been very useful in following the progress of wet corrosion or of oxidation in its initial stages... 

Some investigatorshave advocated a type of accelerated test in which the specimens are coupled in turn to a noble metal such as platinum in the corrosive environment and the currents generated in these galvanic couples are used as a measure of the relative corrosion resistance of the metals studied. This method has the defects of other electrolytic means of stimulating anodic corrosion, and, in addition, there is a further distortion of the normal corrosion reactions and processes by reason of the differences between the cathodic polarisation characteristics of the noble metal used as an artificial cathode and those of the cathodic surfaces of the metal in question when it is corroding normally. 

These considerations show the essentially thermodynamic nature of and it follows that only those metals that form reversible -i-ze = A/systems, and that are immersed in solutions containing their cations, take up potentials that conform to the thermodynamic Nernst equation. It is evident, therefore, that the e.m.f. series of metals has little relevance in relation to the actual potential of a metal in a practical environment, and although metals such as silver, mercury, copper, tin, cadmium, zinc, etc. when immersed in solutions of their cations do form reversible systems, they are unlikely to be in contact with environments containing unit activities of their cations. Furthermore, although silver when immersed in a solution of Ag ions will take up the reversible potential of the Ag /Ag equilibrium, similar considerations do not apply to the NaVNa equilibrium since in this case the sodium will react with the water with the evolution of hydrogen gas, i.e. two exchange processes will occur, resulting in an extreme case of a corrosion reaction. 

Partial Reactions anodic reaction (reactions) and cathodic reaction (reactions) constituting a single exchange process or a corrosion reaction. 

The corrosion reactions may be slowed down by using zinc alloys (with lead and cadmium, also improving the mechanical properties of zinc to simplify the production process) instead of the pure metal, or by amalgamating the inner surface of the can by adding a small amount of a mercury compound to the electrolyte. 

Some measure of control over corrosion also is obtained by limiting the salinity in the boiler (primarily the ions of sodium, chloride, and sulfate). These ions all increase the conductivity of boiler water electrolyte and thus enhance corrosion reaction rates. Also, chloride and sulfate ions affect the passivation process. 

Phase transition occurs at a state of thermodynamic equilibrium, inducing a change in the microstructure of atoms. However, corrosion is a typical nonequilibrium phenomenon accompanied by diffusion and reaction processes. We can also observe that this phenomenon is characterized by much larger scales of length than an atomic order (i.e., masses of a lot of atoms), which is obvious if we can see the morphological change in the pitted surface. 

Moreover, fluctuations of this kind are important, not only because they provide a useful method for describing such a complex system, but also because they actually exist in the reaction process. Thus it can be said that the corrosion reaction progresses according to the formation of nonequilibrium fluctuations. The most important point is that there is complete reciprocity between reactions and fluctuations a reaction is controlled by the fluctuations, while the fluctuations are controlled by the reaction itself. Therefore, we can again point out that the reactivity in corrosion is determined, not by its distance from the reaction equilibrium, but by the growth process of the nonequilibrium fluctuations. 

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