The Detroit Post
Thursday, 21 October, 2021

Is Rust Green

David Lawrence
• Tuesday, 15 December, 2020
• 10 min read

The crystal structure of green rust can be understood as the result of inserting the foreign anions and water molecules between Bruce -like layers of iron(II) hydroxide, Fe(OH) 2. The latter has a hexagonal structure, with layer sequence Aback..., where A and B are planes of hydroxide ions, and c those of Fe 2+ (iron (II), ferrous) cations.

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Each triple layer ACB, which is electrically neutral in the hydroxide, becomes positively charged. Oxidation of the carbonate variety can be retarded by wetting the material with hydroxyl -containing compounds such as glycerol or glucose, even though they do not penetrate the structure.

Depending on the cations in the solution, the nitrate anions replaced the sulfate in the intercalation layer, before the reduction. It was conjectured that green rust may be formed in the reducing alkaline conditions below the surface of marine sediments and may be connected to the disappearance of oxidized species like nitrate in that environment.

Suspensions of carbonate green rust and orange -FeOOH in water will react over a few days produce a black precipitate of magnetite Fe 3 O 4. Green rust compounds were identified in green corrosion crusts that form on iron and steel surfaces, in alternating aerobic and anaerobic conditions, by water containing anions such as chloride, sulfate, carbonate, or bicarbonate.

Hexagonal crystals of green rust (carbonate and/or sulfate) have also been obtained as a byproduct of bio reduction of ferric hydroxides by dissimulator iron-reducing bacteria, such as Shewanella putrefaction, that couple the reduction of Fe 3+ with the oxidation of organic matter. In one experiment, a 160 m suspension of orange lepidocrocite -FeOOH in a solution containing format (HBO 2), incubated for 3 days with a culture of S. putrefaction, turned dark green due to the conversion of the hydroxide to GR(CO 2 3), in the form of hexagonal platelets with diameter ~7 µm.

Then the sodium salt of the third anion is added, and the suspension is oxidized by stirring in air. For example, carbonate green rust can be prepared by mixing solutions of iron(II) sulfate Peso 4 and sodium hydroxide; then adding sufficient amount of sodium carbonate Na 2 CO 3 solution, followed by the air oxidation step.

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A more direct method combines a solution of iron(II) sulfate Peso 4 with NaOH, and proceeding to the oxidizing step. The suspension must have a slight excess of Peso 4 (in the ratio of 0.5833 Fe 2+ for each HO ) for the green rust to form; however, too much of it will produce instead an insoluble basic iron sulfate, iron(II) sulfate hydroxide Fe 2 SO 4 (OH) 2 · n H 2 O.

Refit, L. Simon, and S. H. Crisis (1998): “Preparation and Eh-pH diagrams of Fe(II)-Fe(III) green rust compounds; hyper fine interaction characteristics and stoichiometry of hydrochloride, sulfate and –carbonate”. Hyper fine Interactions, volume 111, pages 313-318. Doi : 10.1023/A:1012638724990 ^ a b c P. P. Stamp fl (1969): “EIN banishes Risen II-III Carbonate in Most.

Refit, S. H. Crisis, J. P. Mile, and J.-M. R. Lenin (1996): “Conversion electron Mössbauer spectroscopy and X-ray diffraction studies of the formation of carbonate-containing green rust one by corrosion of metallic iron in NaHCO3 and (NaHCO3 + NaCl) solutions”. Corrosion Science, volume 38, pages 623-633. Doi : 10.1016/0010-938X(95)00153-B ^ a b c d M. Abdelmoula, F. Toward, G. Bourrèe and J.-M. R. Lenin (1998): “Evidence of the Fe(II)–Fe(III) green rust `forgeries' mineral occurrence in a homomorphic soil and its transformation with depth”.

Hyper fine Interactions, volume 111, pages 231-238. Doi : 10.1023/A:1010802508927 ^ a b W. Feitknecht and G. Keller (1950): “Uber die dunkelgrünen Hydroxyverbindungen DES Risen”. Zeitschrift fur anorganische UND allegiance Cherie, volume 262, pages 61-68. Doi : 10.1002/zaac.19502620110 ^ a b c d J. D. Vernal, D. R. Disrupt, and A. L. Mackay (1959): “The oxides and hydroxides of iron and their structural inter-relationships”.

A. Lowe, B. Reside, N. D. Benbouzid-Rollet, M. Content and D. Proof (1993): “Identification of sulfate green rust 2 compound produced as a result of microbial induced corrosion of steel sheet piles in harbor”. ^ L. Wins, J. Sub rt, V. Capital, and F. Heinous (1987): “Preparation and properties of green rust type substances”.

rust deviantart

Reduction of SEO 4 2 Anions and Anoxic Formation of Iron(II)iron(III) Hydroxy-Selenate Green Rust. , 2000, 34 (5), pp 819–825 DOI : 10.1021/es990376g ^ a b I. R. McGill, B. McEnany, and D. C. Smith (1976): “Crystal structure of green rust formed by corrosion of cast iron”.

Nature, volume 259, pages 1521-1529. Doi : 10.1038/259200a0 ^ a b c d Ludovic Legrand, Léo Gazelles and Annie Chassé (2004): “The oxidation of carbonate green rust into ferric phases: Solid-state reaction or transformation via solution”. ^ Hans C. B. Hansen, Christian Bender Koch, Anne Nancke-Krogh, Ole K. Bodyguard and Jan Sorenson (1996): “Abiotic nitrate reduction to ammonium: Key role of green rust “.

Environmental Science & Technology, volume 30, pages 2053-2056. Doi : 10.1021/es950844w ^ Christian Bender Koch and Hans C. B. Hansen (1997): “Reduction of nitrate to ammonium by sulfate green rust “. ^ a b Hans C. B. Hansen and Christian Bender Koch (1998): “Reduction of nitrate to ammonium by sulfate green rust : activation energy and reaction mechanism”.

Clay Minerals, volume 33, pages 87-101. Doi : 10.1180/000985598545453 ^ a b c G. Ona-Nguema, M. Abdelmoula, F. Jo rand, O. Bengali, A. Behind, J. C. Block, and J.-M. R. Lenin (2002): “Iron(II, III) hydroxycarbonate green rust formation and stabilization from lepidocrocite bio reduction”. ^ G. Butler and J. G. Canon (1967): “The corrosion of mild steel in boiling salt solutions”.

Corrosion Science 7, pages 385-404. Doi : 10.1016/S0010-938X(67)80052-0 ^ Pascal M. Benin, Wojciech Federal, Marek S. Odziemkowski, and Robert W. Gilliam (2000): “Electrochemical and Roman spectroscopic studies of the influence of chlorinated solvents on the corrosion behavior of iron in borate buffer and in simulated groundwater”. Corrosion Science 42, pages 1921-1939. Doi : 10.1016/S0010-938X(00)00027-5 ^ S. Savoy, L. Legrand, G. Wagon, S. Become, A. Chassé, R. Messina, and P. Toughest (2001): “Experimental investigations on iron Zorro- sion products formed in bicarbonate/carbonate-containing solutions at 90 °C.

rust collections

^ F. Toward, J.-M. R. Lenin, M. Abdelmoula, G. Bourrèe, B. Hubert, and A. Bertillon (1997): “Identity phi cation of a green rust mineral in a reductomorphic soil by Mössbauer and Roman spectroscopes. ^ J. K. Fredrickson, J. M. Zachary, D. W. Kennedy, H. Dong, T. C. Stott, N. Binman, and S. M. Li (1998): “Bionic iron mineralization accompanying the dissimulator reduction of hydrous ferric oxide by a groundwater bacterium”.

Geochemical ET Cosmochimica ACTA, volume 62, issues 19-20, pages 3239-3257. Doi : 10.1016/S0016-7037(98)00243-9 ^ J. Detour nay, R. Derive, and M. Those (1976): “Étude DE l’oxidation par aeration DE Fe(OH)2 en milieu closure”. Zeitschrift fur anorganische UND allegiance Cherie, volume 427, pages 265-273. Doi : 10.1002/zaac.654270311 ^ pH.

Refit and J.-M. R. Lenin (1993): “The oxidation of Fe(II) hydroxide in chloride-containing aqueous media and Roubaix diagrams of green rust I. ^ J. Detour nay, L. DE Miranda, R. Derive, and M. Those (1975): “The region of stability of green rust II in the electrochemical potential-pH diagram in sulfate medium”.

A. Lowe and J.-M. R. Lenin (1991): “The mechanism of oxidation of Fe(II) hydroxide in sulfate aqueous media: importance of the initial ratio of the reactants”. Refit, and L. Simon (1996): “On the stoichiometry and Roubaix diagram of Fe(II)-Fe(III) hydroxy-sulphate or sulphate-containing green rust 2: An electrochemical and Mössbauer spectroscopy study”.

Corrosion Science, volume 38, pages 1751-1762. Doi : 10.1016/S0010-938X(96)00072-8 ^ a b c A. Behind, C. Ruby, M. Abdelmoula, O. Bengali, J. Ghana, pH. Refit, and J.-M. R. Lenin (2002): “Synthesis of Fe(II-III) hydroxylate green rust by coprecipitation”.


Solid State Science, volume 4, pages 61-66. Doi : 10.1016/S1293-2558(01)01219-5 ^ a b L. Legrand, S. Savoy, A. Chassé, and R. Messina (2000): “Study of oxidation products formed on iron in solutions containing bicarbonate/carbonate”. Electrochemical ACTA, volume 46, issue 1, pages 111-117. Doi : 10.1016/S0013-4686(00)00563-6 ^ a b S. H. Crisis, pH.

Refit, M. Abdelmoula, and J.-M. R. Lenin (1995): “The preparation and thermodynamic properties of Fe(II)-Fe(III) hydroxide-carbonate (green rust 1); Roubaix diagram of iron in carbonate-containing aqueous media”. A. Lowe, B. Patron, J.-M. R. Lenin (1991): “The influence of temperature on the oxidation of ferrous hydroxide in sulfate aqueous medium: Activation energies of formation of the products and hyper fine structure of magnetite” Corrosion Science, volume 32, issue 9, pages 985-1001. Doi : 10.1016/0010-938X(91)90017-J ^ pH.

Refit, L. Simon, and J.-M. R. Lenin (2000): “Reduction of SEO 4 2 anions and anoxic formation of iron(II)-iron(III) hydroxy-selenate green rust. Given sufficient time, any iron mass, in the presence of water and oxygen, could eventually convert entirely to rust.

Surface rust is commonly flaky and friable, and provides no passivation protection to the underlying iron, unlike the formation of patina on copper surfaces. Rusting is the common term for corrosion of elemental iron and its alloys such as steel.

Many other metals undergo similar corrosion, but the resulting oxides are not commonly called rust “. Other forms of rust include the result of reactions between iron and chloride in an environment deprived of oxygen.

rust archive

Rapid oxidation occurs when heated steel is exposed to air Rust is a general name for a complex of oxides and hydroxides of iron, which occur when iron or some alloys that contain iron are exposed to oxygen and moisture for a long period of time. Over time, the oxygen combines with the metal forming new compounds collectively called rust.

Although rust may generally be termed as “oxidation”, that term is much more general and describes a vast number of processes involving the loss of electrons or increased oxidation state, as part of a reaction. Many other oxidation reactions exist which do not involve iron or produce rust.

Iron or steel structures might appear to be solid, but water molecules can penetrate the microscopic pits and cracks in any exposed metal. The hydrogen atoms present in water molecules can combine with other elements to form acids, which will eventually cause more metal to be exposed.

If chloride ions are present, as is the case with saltwater, the corrosion is likely to occur more quickly. As the atoms combine, they weaken the metal, making the structure brittle and crumbly.

Iron metal is relatively unaffected by pure water or by dry oxygen. The conversion of the passivating ferrous oxide layer to rust results from the combined action of two agents, usually oxygen and water.

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Under these corrosive conditions, iron hydroxide species are formed. Unlike ferrous oxides, the hydroxides do not adhere to the bulk metal.

As they form and flake off from the surface, fresh iron is exposed, and the corrosion process continues until either all the iron is consumed or all of the oxygen, water, carbon dioxide, or sulfur dioxide in the system are removed or consumed. When iron rusts, the oxides take up more volume than the original metal; this expansion can generate enormous forces, damaging structures made with iron.

O 2 + 4 e + 2 H2O 4 OH Because it forms hydroxide ions, this process is strongly affected by the presence of acid. Likewise, the corrosion of most metals by oxygen is accelerated at low pH.

Providing the electrons for the above reaction is the oxidation of iron that may be described as follows: With limited dissolved oxygen, iron(II)-containing materials are favored, including Few and black lodestone or magnetite (Fe 3 O 4).

High oxygen concentrations favor ferric materials with the nominal formulae Fe(OH) 3 x O x 2. The nature of rust changes with time, reflecting the slow rates of the reactions of solids.

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Furthermore, these complex processes are affected by the presence of other ions, such as Ca 2+, which serve as electrolytes which accelerate rust formation, or combine with the hydroxides and oxides of iron to precipitate a variety of Ca, Fe, O, OH species. The onset of rusting can also be detected in the laboratory with the use of ferry indicator solution.

Cor-Ten is a special iron alloy that rusts, but still retains its structural integrityBecause of the widespread use and importance of iron and steel products, the prevention or slowing of rust is the basis of major economic activities in a number of specialized technologies. A brief overview of methods is presented here; for detailed coverage, see the cross-referenced articles.

Special weathering steel alloys such as Cor-Ten rust at a much slower rate than normal, because the rust adheres to the surface of the metal in a protective layer. Interior rusts in old galvanized iron water pipes can result in brown and black waterGalvanization consists of an application on the object to be protected of a layer of metallic zinc by either hot-dip galvanizing or electroplating.

Zinc is traditionally used because it is cheap, adheres well to steel, and provides cathodic protection to the steel surface in case of damage to the zinc layer. In more corrosive environments (such as salt water), cadmium plating is preferred.

Galvanization often fails at seams, holes, and joints where there are gaps in the coating. In some cases, such as very aggressive environments or long design life, both zinc and a coating are applied to provide enhanced corrosion protection.

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Typical galvanization of steel products which are to be subjected to normal day-to-day weathering in an outside environment consists of a hot-dipped 85 µm zinc coating. Cathodic protection is a technique used to inhibit corrosion on buried or immersed structures by supplying an electrical charge that suppresses the electrochemical reaction.

The sacrificial anode must be made from something with a more negative electrode potential than the iron or steel, commonly zinc, aluminum, or magnesium. The sacrificial anode will eventually corrode away, ceasing its protective action unless it is replaced in a timely manner.

Flaking paint, exposing a patch of surface rust on sheet metal Rust formation can be controlled with coatings, such as paint, lacquer, varnish, or wax tapes that isolate the iron from the environment. As a closely related example, iron bars were used to reinforce stonework of the Parthenon in Athens, Greece, but caused extensive damage by rusting, swelling, and shattering the marble components of the building.

When only temporary protection is needed for storage or transport, a thin layer of oil, grease, or a special mixture such as Coastline can be applied to an iron surface. Such treatments are extensively used when mothballing a steel ship, automobile, or other equipment for long-term storage.

Special antiseize lubricant mixtures are available, and are applied to metallic threads and other precision machined surfaces to protect them from rust. These compounds usually contain grease mixed with copper, zinc, or aluminum powder, and other proprietary ingredients.

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They are not effective when air circulation disperses them, and brings in fresh oxygen and moisture. An example of this is the use of silica gel packets to control humidity in equipment shipped by sea.

It was the cause of the collapse of the Minus river bridge in 1983, when the bearings rusted internally and pushed one corner of the road slab off its support. The Kinda Bridge in Pennsylvania was blown down by a tornado in 2003, largely because the central base bolts holding the structure to the ground had rusted away, leaving the bridge anchored by gravity alone.

It is one of the most common failure modes of reinforced concrete bridges and buildings. In music, literature, and art, rust is associated with images of faded glory, neglect, decay, and ruin.

Rust Never Sleeps: Recognizing Metals and Their Corrosion Products” (PDF). ^ Ramsay, Hosahalli S.; Marlette, Michele; Pastry, Sudhir; Abderrahim, Khalid (2014-02-14).

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