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The Schikorr reaction formally describes the conversion of the iron(II) hydroxide (Fe(OH)2) into iron(II,III) oxide (Fe3O4). This transformation reaction was first studied by Gerhard Schikorr. The global reaction follows:
It is of special interest in the context of the serpentinization, the formation of hydrogen by the action of water on a common mineral. [1]
The Schikorr reaction can be viewed as two distinct processes:
The global reaction can thus be decomposed in half redox reactions as follows:
to give:
Adding to this reaction one intact iron(II) ion for each two oxidized iron(II) ions leads to:
Electroneutrality requires the iron cations on both sides of the equation to be counterbalanced by 6 hydroxyl anions (OH−):
For completing the main reaction, two companion reactions have still to be taken into account:
The autoprotolysis of the hydroxyl anions; a proton exchange between two OH−, like in a classical acid–base reaction:
it is then possible to reorganize the global reaction as:
Considering then the formation reaction of iron(II,III) oxide:
it is possible to write the balanced global reaction:
in its final form, known as the Schikorr reaction:
The Schikorr reaction can occur in the process of anaerobic corrosion of iron and carbon steel in various conditions.
Anaerobic corrosion of metallic iron to give iron(II) hydroxide and hydrogen:
followed by the Schikorr reaction:
give the following global reaction:
At low temperature, the anaerobic corrosion of iron can give rise to the formation of "green rust" (fougerite) an unstable layered double hydroxide (LDH). In function of the geochemical conditions prevailing in the environment of the corroding steel, iron(II) hydroxide and green rust can progressively transform in iron(II,III) oxide, or if bicarbonate ions are present in solution, they can also evolve towards more stable carbonate phases such as iron carbonate (FeCO3), or iron(II) hydroxycarbonate (Fe2(OH)2(CO3), chukanovite) isomorphic to copper(II) hydroxycarbonate (Cu2(OH)2(CO3), malachite) in the copper system.
Anaerobic oxidation of iron and steel commonly finds place in oxygen-depleted environments, such as in permanently water-saturated soils, peat bogs or wetlands in which archaeological iron artefacts are often found.
Anaerobic oxidation of carbon steel of canisters and overpacks is also expected to occur in deep geological formations in which high-level radioactive waste and spent fuels should be ultimately disposed. Nowadays, in the frame of the corrosion studies related to HLW disposal, anaerobic corrosion of steel is receiving a renewed and continued attention. Indeed, it is essential to understand this process to guarantee the total containment of HLW waste in an engineered barrier during the first centuries or millennia when the radiotoxicity of the waste is high and when it emits a significant quantity of heat.
The question is also relevant for the corrosion of the reinforcement bars (rebars) in concrete (Aligizaki et al., 2000). This deals then with the service life of concrete structures, amongst others the near-surface vaults intended for hosting low-level radioactive waste.
The slow but continuous production of hydrogen in deep low-permeability argillaceous formations could represent a problem for the long-term disposal of radioactive waste (Ortiz et al., 2001; Nagra, 2008; recent Nagra NTB reports). Indeed, a gas pressure build-up could occur if the rate of hydrogen production by the anaerobic corrosion of carbon-steel and by the subsequent transformation of green rust into magnetite should exceed the rate of diffusion of dissolved H2 in the pore water of the formation. The question is presently the object of many studies (King, 2008; King and Kolar, 2009; Nagra Technical Reports 2000–2009) in the countries (Belgium, Switzerland, France, Canada) envisaging the option of disposal in clay formation.
When nascent hydrogen is produced by anaerobic corrosion of iron by the protons of water, the atomic hydrogen can diffuse into the metal crystal lattice because of the existing concentration gradient. After diffusion, hydrogen atoms can recombine into molecular hydrogen giving rise to the formation of high-pressure micro-bubbles of H2 in the metallic lattice. The trends to expansion of H2 bubbles and the resulting tensile stress can generate cracks in the metallic alloys sensitive to this effect also known as hydrogen embrittlement. Several recent studies (Turnbull, 2009; King, 2008; King and Kolar, 2009) address this question in the frame of the radioactive waste disposal in Switzerland and Canada.
Rust is an iron oxide, a usually reddish-brown oxide formed by the reaction of iron and oxygen in the catalytic presence of water or air moisture. Rust consists of hydrous iron(III) oxides (Fe2O3·nH2O) and iron(III) oxide-hydroxide (FeO(OH), Fe(OH)3), and is typically associated with the corrosion of refined iron.
Redox is a type of chemical reaction in which the oxidation states of a reactant change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a decrease in the oxidation state.
In chemistry, iron (III) refers to the element iron in its +3 oxidation state. In ionic compounds (salts), such an atom may occur as a separate cation (positive ion) denoted by Fe3+.
Iron(III) oxide or ferric oxide is the inorganic compound with the formula Fe2O3. It is one of the three main oxides of iron, the other two being iron(II) oxide (FeO), which is rare; and iron(II,III) oxide (Fe3O4), which also occurs naturally as the mineral magnetite. As the mineral known as hematite, Fe2O3 is the main source of iron for the steel industry. Fe2O3 is readily attacked by acids. Iron(III) oxide is often called rust, since rust shares several properties and has a similar composition; however, in chemistry, rust is considered an ill-defined material, described as hydrous ferric oxide.
Wüstite is a mineral form of mostly iron(II) oxide found with meteorites and native iron. It has a grey colour with a greenish tint in reflected light. Wüstite crystallizes in the isometric-hexoctahedral crystal system in opaque to translucent metallic grains. It has a Mohs hardness of 5 to 5.5 and a specific gravity of 5.88. Wüstite is a typical example of a non-stoichiometric compound.
Iron(II,III) oxide, or black iron oxide, is the chemical compound with formula Fe3O4. It occurs in nature as the mineral magnetite. It is one of a number of iron oxides, the others being iron(II) oxide (FeO), which is rare, and iron(III) oxide (Fe2O3) which also occurs naturally as the mineral hematite. It contains both Fe2+ and Fe3+ ions and is sometimes formulated as FeO ∙ Fe2O3. This iron oxide is encountered in the laboratory as a black powder. It exhibits permanent magnetism and is ferrimagnetic, but is sometimes incorrectly described as ferromagnetic. Its most extensive use is as a black pigment (see: Mars Black). For this purpose, it is synthesized rather than being extracted from the naturally occurring mineral as the particle size and shape can be varied by the method of production.
Serpentinite is a rock composed predominantly of one or more serpentine group minerals formed by near to complete serpentinization of mafic to ultramafic rocks. Its name originated from the similarity of the texture of the rock to that of the skin of a snake. Serpentinite has been called serpentine or serpentine rock, particularly in older geological texts and in wider cultural settings.
Pitting corrosion, or pitting, is a form of extremely localized corrosion that leads to the random creation of small holes in metal. The driving power for pitting corrosion is the depassivation of a small area, which becomes anodic while an unknown but potentially vast area becomes cathodic, leading to very localized galvanic corrosion. The corrosion penetrates the mass of the metal, with a limited diffusion of ions.
Iron(II) hydroxide or ferrous hydroxide is an inorganic compound with the formula Fe(OH)2. It is produced when iron(II) salts, from a compound such as iron(II) sulfate, are treated with hydroxide ions. Iron(II) hydroxide is a white solid, but even traces of oxygen impart a greenish tinge. The air-oxidised solid is sometimes known as "green rust".
The hydrogen cycle consists of hydrogen exchanges between biotic (living) and abiotic (non-living) sources and sinks of hydrogen-containing compounds.
Iron shows the characteristic chemical properties of the transition metals, namely the ability to form variable oxidation states differing by steps of one and a very large coordination and organometallic chemistry: indeed, it was the discovery of an iron compound, ferrocene, that revolutionalized the latter field in the 1950s. Iron is sometimes considered as a prototype for the entire block of transition metals, due to its abundance and the immense role it has played in the technological progress of humanity. Its 26 electrons are arranged in the configuration [Ar]3d64s2, of which the 3d and 4s electrons are relatively close in energy, and thus it can lose a variable number of electrons and there is no clear point where further ionization becomes unprofitable.
The Haber–Weiss reaction generates •OH (hydroxyl radicals) from H2O2 (hydrogen peroxide) and superoxide (•O2−) catalyzed by iron ions. It was first proposed by Fritz Haber and his student Joseph Joshua Weiss in 1932.
In geology, a redox buffer is an assemblage of minerals or compounds that constrains oxygen fugacity as a function of temperature. Knowledge of the redox conditions (or equivalently, oxygen fugacities) at which a rock forms and evolves can be important for interpreting the rock history. Iron, sulfur, and manganese are three of the relatively abundant elements in the Earth's crust that occur in more than one oxidation state. For instance, iron, the fourth most abundant element in the crust, exists as native iron, ferrous iron (Fe2+), and ferric iron (Fe3+). The redox state of a rock affects the relative proportions of the oxidation states of these elements and hence may determine both the minerals present and their compositions. If a rock contains pure minerals that constitute a redox buffer, then the oxygen fugacity of equilibration is defined by one of the curves in the accompanying fugacity-temperature diagram.
The surface color of the planet Mars appears reddish from a distance because of rusty atmospheric dust. From close up, it looks more of a butterscotch, and other common surface colors include golden, brown, tan, and greenish, depending on minerals.
Bacterial anaerobic corrosion is the bacterially-induced oxidation of metals. Corrosion of metals typically alters the metal to a form that is more stable. Thus, bacterial anaerobic corrosion typically occurs in conditions favorable to the corrosion of the underlying substrate. In humid, anoxic conditions the corrosion of metals occurs as a result of a redox reaction. This redox reaction generates molecular hydrogen from local hydrogen ions. Conversely, anaerobic corrosion occurs spontaneously. Anaerobic corrosion primarily occurs on metallic substrates but may also occur on concrete.
Anaerobic corrosion is a form of metal corrosion occurring in anoxic water. Typically following aerobic corrosion, anaerobic corrosion involves a redox reaction that reduces hydrogen ions and oxidizes a solid metal. This process can occur in either abiotic conditions through a thermodynamically spontaneous reaction or biotic conditions through a process known as bacterial anaerobic corrosion. Along with other forms of corrosion, anaerobic corrosion is significant when considering the safe, permanent storage of chemical waste.
For chemical reactions, the iron oxide cycle (Fe3O4/FeO) is the original two-step thermochemical cycle proposed for use for hydrogen production. It is based on the reduction and subsequent oxidation of iron ions, particularly the reduction and oxidation between Fe3+ and Fe2+. The ferrites, or iron oxide, begins in the form of a spinel and depending on the reaction conditions, dopant metals and support material forms either Wüstites or different spinels.
In chemistry, iron(II) refers to the element iron in its +2 oxidation state. In ionic compounds (salts), such an atom may occur as a separate cation (positive ion) denoted by Fe2+.
Iron oxide nanoparticles are iron oxide particles with diameters between about 1 and 100 nanometers. The two main forms are composed of magnetite and its oxidized form maghemite. They have attracted extensive interest due to their superparamagnetic properties and their potential applications in many fields including molecular imaging.
Green rust is a generic name for various green crystalline chemical compounds containing iron(II) and iron(III) cations, the hydroxide (HO−
) anion, and another anion such as carbonate (CO2−
3), chloride (Cl−
), or sulfate (SO2−
4), in a layered double hydroxide structure. The most studied varieties are
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(help)For detailed reports on iron corrosion issues related to high-level waste disposal, see the following links: