Oxidation in corrosion

The breakdown of protective coating systems on structures often leads to this form of corrosion. Dulling of a bright or poUshed surface, etching by acid cleaners, or oxidation (discoloration) of steel are examples of surface corrosion. Corrosion-resistant alloys and stainless steels can become tarnished or oxidized in corrosive environments. Surface corrosion can indicate a breakdown in the protective coating system, however, and should be examined closely for more advanced attack. If surface corrosion is permitted to continue, the surface may become rough and surface corrosion can lead to more serious types of corrosion. 

I. Hutcheon 1998. The potential role of pyrite oxidation in corrosion and reservoir souring. Journal... 

Oxygen is one of the most important oxidants in corrosion reactions. Often only a thin electrolyte film is covering the metal surface, which may easily be saturated with dissolved oxygen. With a bulk concentration = 2 x 10 M, D = 10 cm s", n = 4,... 

The kinetics of reactions in which a new phase is formed may be complicated by the interference of that phase with the ease of access of the reactants to each other. This is the situation in corrosion and tarnishing reactions. Thus in the corrosion of a metal by oxygen the increasingly thick coating of oxide that builds up may offer more and more impedance to the reaction. Typical rate expressions are the logarithmic law,... 

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. 

The material should be stored in corrosion-resistant containers, away from alkaline or strong oxidizing materials. In the event of a spill or leak, nonsparking equipment should be used, and dusty conditions should be avoided. Spills should be covered with soda ash, then flushed to drain with large amounts of water (5). 

Another attractive commercial route to MEK is via direct oxidation of / -butenes (34—39) in a reaction analogous to the Wacker-Hoechst process for acetaldehyde production via ethylene oxidation. In the Wacker-Hoechst process the oxidation of olefins is conducted in an aqueous solution containing palladium and copper chlorides. However, unlike acetaldehyde production, / -butene oxidation has not proved commercially successflil because chlorinated butanones and butyraldehyde by-products form which both reduce yields and compHcate product purification, and also because titanium-lined equipment is required to withstand chloride corrosion. 

Sulfamic acid at concentrations of 2—6%, in conjunction with the proper proprietary inhibitor, can be effective in removing zinc oxides and corrosion by-products without attacking the zinc metal. 

Copper and tin phosphides are used as deoxidants in the production of the respective metals, to increase the tensile strength and corrosion resistance in phosphor bronze [12767-50-9] and as components of brazing solders (see Solders and brazing alloys). Phosphor bronze is an alloy of copper and 1.25—11 wt % tin. As tin may be completely oxidized in a copper alloy in the form of stannic oxide, 0.03—0.35 wt % phosphoms is added to deoxidize the alloy. Phosphor copper [12643-19-5] is prepared by the addition of phosphoms to molten copper. Phosphor tin [66579-64-4] 2.5—3 wt % P, is made for the deoxidation of bronzes and German silver. 

Most talc sold to paper, ceramics, and other industrial customers is manufactured to specifications agreed to between the producer and consumer. In paper, properties such as color, abrasion, surface area, and tint ate most important, whereas in ceramics, oxide chemistry, fired color, pressing characteristics, and alkaH metal content ate mote important. There ate some military specifications for talc used in corrosive coatings (6) and for cosmetic talc products used for cleaning of personnel in chemical warfare zones (7). 

These equations are based on the thermodynamically stable species. Further research is needed to clarify the actual intermediate formed during overcharge. In reahty, the oxygen cycle can not be fully balanced because of other side reactions, that include gtid corrosion, formation of residual lead oxides in the positive electrode, and oxidation of organic materials in the cell. As a result, some gases, primarily hydrogen and carbon dioxide (53), are vented. 

The metallurgy of the cyclone equipment has in recent years focused primarily on type 304 H stainless steel. The 304 H material is durable and easy to fabricate and repair, withstands the high regenerator temperatures, and is oxidation- and corrosion-resistant. Essentially all internal surfaces of the cyclone that are subject to erosion are protected with a 2 cm layer of erosion-resistant lining. When installed and cured, most refractory linings are highly resistant to erosion. 

The ease with which the ferrous ion can be oxidized to a ferric ion in the electrowinning cell furthers this reaction. Attack on the copper is most apparent at the solution line, where it results in corrosion of the loops supporting the cathodes, leading to dropped cathodes. 

Ores are mined and are then refined in an energy intensive process to produce pure metals, which in turn are combined to make alloys (see Metallurgy Mineral RECOVERY and processing). Corrosion occurs because of the tendency of these refined materials to return to a more thermodynamically stable state (1—4). The key reaction in corrosion is the oxidation or anodic dissolution of the metal to produce metal ions and electrons... 

The environment plays several roles in corrosion. It acts to complete the electrical circuit, ie, suppHes the ionic conduction path provide reactants for the cathodic process remove soluble reaction products from the metal surface and/or destabili2e or break down protective reaction products such as oxide films that are formed on the metal. Some important environmental factors include the oxygen concentration the pH of the electrolyte the temperature and the concentration of anions. 

Impurities in a corrodent can be good or bad from a corrosion standpoint. An impurity in a stream may act as an inhibitor and actually retard corrosion. However, if this impurity is removed by some process change or improvement, a marked rise in corrosion rates can result. Other impurities, of course, can have very deleterious effec ts on materials. The chloride ion is a good example small amounts of chlorides in a process stream can break down the passive oxide film on stainless steels. The effects of impurities are varied and complex. One must be aware of what they are, how much is present, and where they come from before attempting to recommena a particular material of construction. 

Stainless steels tend to pit in acid solutions. Pits form local areas of metal loss associated with breakdown of a protective oxide layer. Breakdown is stimulated by low pH as well as by the decrease of dissolved oxygen in occluded regions. Small, active pit sites form and remain stable because of the large ratio of cathodic surface area (unattacked metal surface) to the pit area. Active corrosion in the pit cathodically protects immediately adjacent areas. If conditions become very severe, pitting will give way to general attack as more and more of the surface becomes actively involved in corrosion. 

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