Chemical reactions corrosion

In corrosion, adsorbates react directly with the substrate atoms to fomi new chemical species. The products may desorb from the surface (volatilization reaction) or may remain adsorbed in fonning a corrosion layer. Corrosion reactions have many industrial applications, such as dry etching of semiconductor surfaces. An example of a volatilization reaction is the etching of Si by fluorine [43]. In this case, fluorine reacts with the Si surface to fonn SiF gas. Note that the crystallinity of the remaining surface is also severely disrupted by this reaction. An example of corrosion layer fonnation is the oxidation of Fe metal to fonn mst. In this case, none of the products are volatile, but the crystallinity of the surface is dismpted as the bulk oxide fonns. Corrosion and etching reactions are discussed in more detail in section A3.10 and section C2.9. 

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. 

Unique system characteristics and special design features, e.g., corrosion, foaming, chemical reaction, and fouling, and designs to overcome such problems. 

Thus in all corrosion reactions one (or more) of the reaction products will be an oxidised form of the metal, aquo cations (e.g. Fe (aq.), Fe (aq.)), aquo anions (e.g. HFeO aq.), Fe04"(aq.)), or solid compounds (e.g. Fe(OH)2, Fej04, Fe3 04-H2 0, Fe203-H20), while the other reaction product (or products) will be the reduced form of the non-metal. Corrosion may be regarded, therefore, as a heterogeneous redox reaction at a metal/non-metal interface in which the metal is oxidised and the non-metal is reduced. In the interaction of a metal with a specific non-metal (or non-metals) under specific environmental conditions, the chemical nature of the non-metal, the chemical and physical properties of the reaction products, and the environmental conditions (temperature, pressure, velocity, viscosity, etc.) will clearly be important in determining the form, extent and rate of the reaction. 

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. 

The standard electrode potentials , or the standard chemical potentials /X , may be used to calculate the free energy decrease —AG and the equilibrium constant /T of a corrosion reaction (see Appendix 20.2). Any corrosion reaction in aqueous solution must involve oxidation of the metal and reduction of a species in solution (an electron acceptor) with consequent electron transfer between the two reactants. Thus the corrosion of zinc ( In +zzn = —0-76 V) in a reducing acid of pH = 4 (a = 10 ) may be represented by the reaction ... 

In view of the importance of the hydronium ion, HjO, and dissolved oxygen as electron acceptors in corrosion reactions, some values of the redox potentials E and chemical potentials n for the equilibria... 

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. 

A considerable amount of work has been carried out into the corrosion of steels in the gases produced during the combustion of fossil fuel due to extensive use of low alloy steels as heat exchanger tubes in power generation. Combustion gases contain many species, such as CO, CO2, SO2, SO3, H2S and HCl, arising from elements within the fuel. The many different combinations of operating temperature and chemical stoichiometry of combustion reactions lead to many possible complex corrosion reactions. 

Although the term fretting corrosion implies chemical reaction, it has often been used even when the latter is absent. Campbell has suggested that to avoid confusion the word fretting be used to describe the wear process, and that the expression fretting corrosion be applied in those cases where one or both of the surfaces, or the wear particles from them, react with their environment. 

Lead coatings are mainly applied by cladding and find principal use in the chemical industry for resistance to sulphuric acid, for cable sheathing resistant to attack by soils and in architectural applications where resistance to industrial atmospheres is particularly good. They rely for their protective action on the formation of insoluble corrosion products which stifle the corrosion reaction and lead to very long service lives, but the corrosion resistance is impaired when chlorides are present. 

Deposit control is important because porous deposits, under the influence of heat flux, can induce the development of high concentrations of boiler water solutes far above their normally beneficial bulk values with correspondingly increased corrosion rates. This becomes an increasingly important feature with increase in boiler saturation temperature. In addition, deposits can cause overheating owing to loss of heat transfer. Finally, carryover of boiler water solutes, which can be either mechanical or chemical, can lead to consequential corrosion in the circuit, either on-load or off-load. Material so transported can result in corrosion reactions far from its point of origin, with costly penalties. It is therefore preferably dealt with by a policy of prevention rather than cure. 

The total index is divided into Chemical and Process Inherent Safety Index. The previous is formed of subindices for reaction heats, flammability, explosiveness, toxicity, corrosiveness and chemical interaction. The latter is formed of subindices for inventory, process temperature, pressure and the safety of equipment and process structure. 

The CMT method is based on the direct measurement of chemical change, and a number ofrestrictions may arise due to the chemistry of the corrosion reactions and the electrolyte solution. The simple relation (4) in accordance with reactions (l)-(3) is not always valid because of complications connected with either the anodic or the cathodic reactions. 

A corrosion-inhibiting admixture is a chemical compound which, when added in small concentrations to concrete or mortar, effectively checks or retards corrosion. These admixtures can be grouped into three broad classes, anodic, cathodic and mixed, depending on whether they interfere with the corrosion reaction preferentially at the anodic or cathodic sites or whether both are involved [48]. Six types of mechanisms, viz. anodic (oxidizing passivators), anodic (non-oxidizing passivators), cathodic, precipitation... 

The type of attack that occurs in liquid media is highly dependent on the chemical nature of the liquid—that is, molten metal, molten ceramic, or aqueous solution. We will consider two industrially important cases attack by molten metals and attack by aqueous media. The attack of most metal oxide ceramics by molten metals involves a simple exchange of one metal ion for another. For example, silicon dioxide in contact with molten aluminum is susceptible to the following corrosion reaction ... 

---