Corrosion chromium anodic reaction

In deaerated 1 N H2SO4 (pH = 0.56), hydrogen-ion reduction is the cathodic reaction with the cathodic polarization curve intersecting the iron, nickel, and chromium curves in the active potential region. Hence, active corrosion occurs with hydrogen evolution, and the corrosion rates would be estimated by the intersections of the curves. The curves predict that the titanium will be passivated. However, the position ofthe cathodic hydrogen curve relative to the anodic curves for titanium and chromium indicates that if the exchange current density for the hydro-... 

The sequence of reactions involved in the overall reduction of nitric acid is complex, but direct measurements confirm that the acid has a high oxidation/reduction potential, -940 mV (SHE), a high exchange current density, and a high limiting diffusion current density (Ref 38). The cathodic polarization curves for dilute and concentrated nitric acid in Fig. 5.42 show these thermodynamic and kinetic properties. Their position relative to the anodic curves indicate that all four metals should be passivated by concentrated nitric acid, and this is observed. In fact, iron appears almost inert in concentrated nitric acid with a corrosion rate of about 25 pm/year (1 mpy) (Ref 8). Slight dilution causes a violent iron reaction with corrosion rates >25 x 1()6 pm/year (106 mpy). Nickel also corrodes rapidly in the dilute acid. In contrast, both chromium and titanium are easily passivated in dilute nitric acid and corrode with low corrosion rates. 

Ferrous ion, a product of the corrosion reaction in Eq. (12.6), reacts with nitrate immediately to form a barrier oxide film through Eq. (12.13). The resulting potential would then be the potential of Fe203 in water. The anodic potential shift is due to protective film surface coverage. The observed performance improvement of chromium-containing alloys suggests that the inhibitor helps stabifize both the iron and chromium oxide layer. Nitrite ions act as anodic inhibitors by increasing barrier oxide film formation rate. 

For metals such as chromium and alloys such as stainless steel, the plot of potential versus corrosion rate above the range is shown in Figure 20.67. Figure 20.68 shows a sudden sharp drop in corrosion above some critical potential. Despite a high level of anode polarization above V, the corrosion rate drops precipitously due to the formation of a thin, protective oxide film as a barrier to the anodic dissolution reaction. Resistance to corrosion above is termed passivity. The drop in corrosion rate above can be as much as 10 to 10 times below the maximum rate in the active state. With increasing corrosion potential, the low corrosion rate remains constant until at a relatively high potential the passive film break down, and the normal increase in corrosion rate resumes in a transpassive region. 

Examples of metals that are passive under Definition 1, on the other hand, include chromium, nickel, molybdenum, titanium, zirconium, the stainless steels, 70%Ni-30% Cu alloys (Monel), and several other metals and alloys. Also included are metals that become passive in passivator solutions, such as iron in dissolved chromates. Metals and alloys in this category show a marked tendency to polarize anodicaUy. Pronounced anodic polarization reduces observed reaction rates, so that metals passive under Definition 1 usually conform as well to Definition 2 based on low corrosion rates. The corrosion potentials of metals passive by Definition 1 approach the open-circuit cathode potentials (e.g., the oxygen electrode) hence, as components of galvanic cells, they exhibit potentials near those of the noble metals. 

If the cathodic polarization curves of Fig. 6.5 intersect the anodic curve at a still more noble potential, within the transpassive region, the corrosion rate of, for example, stainless steel, is greatly increased over the corrosion rate at less noble potentials within the passive region, and the corrosion products become Cr207 and Fe ". Transpassivity occurs not only with stainless steels, but also with chromium, for which the potential for the reaction... 

For passivation, the passivation current density ipjs must be applied either by means of an anodic current (polarisation) or in the reaction vith an oxidant at passivation potential Upas. In the active and passive range, trivalent chromium (Cr ) is dissolved. Above the transpassive breakthrough potential Ua, i.e. after the transition to the transpassive range, the current density, and with it the rate of corrosion, rises once again, since at this high oxidation potential chromium then dissolves in hexa-valent form (Cr ) as chromate. 

Corrosion reactions may be minimized by essentially two means. Firstly, by covering the surfaces of metals with protective films and secondly, by exploiting inhibition processes. Steel, for example, may be protected by surface layers of chromium, nickel, zinc or tin. Cracks in a surface film of a more noble metal than the one being offered protection, can give rise to local cells in which the exposed base metal becomes an anode and the protective layer a cathode. Local corrosion then sets in. 

For more than a century, a number of different aluminum alloys have been commonly used in the aircraft industry These substrates mainly contain several alloying elements, such as copper, chromium, iron, nickel, cobalt, magnesium, manganese, silicon, titanium and zinc. It is known that these metals and alloys can be dissolved as oxides or other compounds in an aqueous medium due to the chemical or electrochemical reactions between their metal surfaces and the environment (solution). The rate of the dissolution from anode to cathode phases at the metal surfaces can be influenced by the electrical conductivity of electrolytic solutions. Thus, anodic and cathodic electron transfer reactions readily exist with bulk electrolytes in water and, hence, produce corrosive products and ions. It is known that pure water has poor electrical conductivity, which in turn lowers the corrosion rate of materials however, natural environmental solutions (e g. sea water, acid rains, emissions or pollutants, chemical products and industrial waste) are highly corrosive and the environment s temperature, humidity, UV light and pressure continuously vary depending on time and the type of process involved. ... 

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