Ferrous

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Iron(II) chloride tetrahydrate, .mw-parser-output .template-chem2-su{display:inline-block;font-size:80%;line-height:1;vertical-align:-0.35em}.mw-parser-output .template-chem2-su>span{display:block;text-align:left}.mw-parser-output sub.template-chem2-sub{font-size:80%;vertical-align:-0.35em}.mw-parser-output sup.template-chem2-sup{font-size:80%;vertical-align:0.65em} FeCl2*4H2O. Eisen(II)-chlorid-Tetrahydrat.jpg
Iron(II) chloride tetrahydrate, FeCl2·4H2O.

In chemistry, iron(II) refers to the element iron in its +2 oxidation state. The adjective ferrous or the prefix ferro- is often used to specify such compounds, as in ferrous chloride for iron(II) chloride (FeCl2). The adjective ferric is used instead for iron(III) salts, containing the cation Fe3+. The word ferrous is derived from the Latin word ferrum , meaning "iron".

Contents

In ionic compounds (salts), such an atom may occur as a separate cation (positive ion) abbreviated as Fe2+, although more precise descriptions include other ligands such as water and halides. Iron(III) centres occur in coordination complexes, such as in the anion ferrocyanide, [Fe(CN)6]4−, where six cyanide ligands are bound the metal centre; or, in organometallic compounds, such as the ferrocene [Fe(C2H5)2], where two cyclopentadienyl anions are bound to the FeII centre.

Iron(II) in biology

All known forms of life require iron. [1] Many proteins in living beings contain iron(III) centers. Examples of such metalloproteins include hemoglobin, ferredoxin, and the cytochromes. In many of these proteins, Fe(II) converts reversibly to Fe(III) [2]

Insufficient iron in the human diet causes anemia. Animals and humans can obtain the necessary iron from foods that contain it in assimilable form, such as meat. Other organisms must obtain their iron from the environment. However, iron tends to form highly insoluble iron(III) oxides/hydroxides in aerobic (oxygenated) environment, especially in calcareous soils. Bacteria and grasses can thrive in such environments by secreting compounds called siderophores that form soluble complexes with iron(III), that can be reabsorbed into the cell. (The other plants instead encourage the growth around their roots of certain bacteria that reduce iron(III) to the more soluble iron(II).) [3]

In contrast to iron(III) aquo complexes, iron(II) aquo complexes are soluble in water near neutral pH.[ citation needed ] Ferrous iron is however oxidized by the oxygen in air, converting to iron(III). [4]

Pourbaix diagram of aqueous iron Pourbaix Diagram of Iron.svg
Pourbaix diagram of aqueous iron

Iron(II) salts and complexes

Redox reaction of [Fe(bipyridine)3] . Fe(bipy)3 redox.svg
Redox reaction of [Fe(bipyridine)3] .

Typically iron(II) salts, like the "chloride" are aquo complexes with the formulas [Fe(H2O)6]2+, as found in ferrous ammonium sulfate. [5]

The aquo ligands on iron(II) complexes are labile. It reacts with 1,10-phenanthroline to give the blue iron(II) derivative:

When metallic iron (oxidation state 0) is placed in a solution of hydrochloric acid, iron(II) chloride is formed, with release of hydrogen gas, by the reaction

Fe0 + 2 H+ → Fe2+ + H2

Iron(II) is oxidized by hydrogen peroxide to iron(III), forming a hydroxyl radical and a hydroxide ion in the process. This is the Fenton reaction. Iron(III) is then reduced back to iron(II) by another molecule of hydrogen peroxide, forming a hydroperoxyl radical and a proton. The net effect is a disproportionation of hydrogen peroxide to create two different oxygen-radical species, with water (H+ + OH−) as a byproduct. [6]

Fe2+ + H2O2 → Fe3+ + HO• + OH−

 

 

 

 

(1)

Fe3+ + H2O2 → Fe2+ + HOO• + H+

 

 

 

 

(2)

The free radicals generated by this process engage in secondary reactions, which can degrade many organic and biochemical compounds.

Iron(II) minerals and other solids

Iron(II) oxide (ferrous oxide), FeO, is a very complicated material that contains iron(II). Iron(II) oxide.jpg
Iron(II) oxide (ferrous oxide), FeO, is a very complicated material that contains iron(II).

Iron(II) is found in many minerals and solids. Examples include the sulfide and oxide, FeS and FeO. These formulas are deceptively simple because these sulfides and oxides are often nonstoichiometric. For example, "ferrous sulfide" can refer to the 1:1 species (mineral name troilite) or a host of Fe-deficient derivatives (pyrrhotite). The mineral magnetite ("lode stone") is a mixed-valence compound with both Fe(II) and Fe(III), Fe3O4.

Bonding

Iron(II) is a d6 center, meaning that the metal has six "valence" electrons in the 3d orbital shell. The number and type of ligands bound to iron(II) determine how these electrons arrange themselves. With so-called "strong field ligands" such as cyanide, the six electrons pair up. Thus ferrocyanide ([Fe(CN)6]4− has no unpaired electrons. It is low-spin. With so-called "weak field ligands" such as water, the four of the six electrons are unpaired. Thus aquo complex ([Fe(H2O)6]2+ is paramagnetic. It is high-spin. With chloride, iron(III) forms tetrahedral complexes, e.g. [FeCl4]2−. Tetrahedral complexes are high spin.

d-orbital splitting scheme for low- and high spin octahedral Fe(II) complexes. L.s. vs h.s. d6 octahedral.svg
d-orbital splitting scheme for low- and high spin octahedral Fe(II) complexes.

See also

Related Research Articles

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<span class="mw-page-title-main">Ferric</span> The element iron in its +3 oxidation state

In chemistry, Ferric refers to the element iron in its +3 oxidation state. Ferric chloride is an alternative name for iron(III) chloride (FeCl3). The adjective ferrous is used instead for iron(II) salts, containing the cation Fe2+. The word ferric is derived from the Latin word ferrum, meaning "iron".

<span class="mw-page-title-main">Potassium ferricyanide</span> Chemical compound

Potassium ferricyanide is the chemical compound with the formula K3[Fe(CN)6]. This bright red salt contains the octahedrally coordinated [Fe(CN)6]3− ion. It is soluble in water and its solution shows some green-yellow fluorescence. It was discovered in 1822 by Leopold Gmelin.

In chemistry, a reducing agent is a chemical species that "donates" an electron to an electron recipient . Examples of substances that are common reducing agents include hydrogen, the alkali metals, formic acid, oxalic acid, and sulfite compounds.

Iron(III) chloride describes the inorganic compounds with the formula FeCl3(H2O)x. Also called ferric chloride, these compounds are some of the most important and commonplace compounds of iron. They are available both in anhydrous and in hydrated forms which are both hygroscopic. They feature iron in its +3 oxidation state. The anhydrous derivative is a Lewis acid, while all forms are mild oxidizing agents. It is used as a water cleaner and as an etchant for metals.

Iron(II) chloride, also known as ferrous chloride, is the chemical compound of formula FeCl2. It is a paramagnetic solid with a high melting point. The compound is white, but typical samples are often off-white. FeCl2 crystallizes from water as the greenish tetrahydrate, which is the form that is most commonly encountered in commerce and the laboratory. There is also a dihydrate. The compound is highly soluble in water, giving pale green solutions.

<span class="mw-page-title-main">Pitting corrosion</span> Form of insidious localized corrosion in which a pit develops at the anode site

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–sulfur proteins are proteins characterized by the presence of iron–sulfur clusters containing sulfide-linked di-, tri-, and tetrairon centers in variable oxidation states. Iron–sulfur clusters are found in a variety of metalloproteins, such as the ferredoxins, as well as NADH dehydrogenase, hydrogenases, coenzyme Q – cytochrome c reductase, succinate – coenzyme Q reductase and nitrogenase. Iron–sulfur clusters are best known for their role in the oxidation-reduction reactions of electron transport in mitochondria and chloroplasts. Both Complex I and Complex II of oxidative phosphorylation have multiple Fe–S clusters. They have many other functions including catalysis as illustrated by aconitase, generation of radicals as illustrated by SAM-dependent enzymes, and as sulfur donors in the biosynthesis of lipoic acid and biotin. Additionally, some Fe–S proteins regulate gene expression. Fe–S proteins are vulnerable to attack by biogenic nitric oxide, forming dinitrosyl iron complexes. In most Fe–S proteins, the terminal ligands on Fe are thiolate, but exceptions exist.

<span class="mw-page-title-main">Tin(II) chloride</span> Chemical compound

Tin(II) chloride, also known as stannous chloride, is a white crystalline solid with the formula SnCl2. It forms a stable dihydrate, but aqueous solutions tend to undergo hydrolysis, particularly if hot. SnCl2 is widely used as a reducing agent (in acid solution), and in electrolytic baths for tin-plating. Tin(II) chloride should not be confused with the other chloride of tin; tin(IV) chloride or stannic chloride (SnCl4).

<span class="mw-page-title-main">Iron(II) hydroxide</span> Chemical compound

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".

<span class="mw-page-title-main">Ferricyanide</span> Anion in which a Fe3+ ion is complexed by 6 CN− ions

Ferricyanide is the anion [Fe(CN)6]3−. It is also called hexacyanoferrate(III) and in rare, but systematic nomenclature, hexacyanidoferrate(III). The most common salt of this anion is potassium ferricyanide, a red crystalline material that is used as an oxidant in organic chemistry.

<span class="mw-page-title-main">Ferrocyanide</span> Anion in which a Fe2+ ion is complexed by 6 CN− ions

Ferrocyanide is the name of the anion [Fe(CN)6]4−. Salts of this coordination complex give yellow solutions. It is usually available as the salt potassium ferrocyanide, which has the formula K4Fe(CN)6. [Fe(CN)6]4− is a diamagnetic species, featuring low-spin iron(II) center in an octahedral ligand environment. Although many salts of cyanide are highly toxic, ferro- and ferricyanides are less toxic because they tend not to release free cyanide. It is of commercial interest as a precursor to the pigment Prussian blue and, as its potassium salt, an anticaking agent.

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Pentetic acid or diethylenetriaminepentaacetic acid (DTPA) is an aminopolycarboxylic acid consisting of a diethylenetriamine backbone with five carboxymethyl groups. The molecule can be viewed as an expanded version of EDTA and is used similarly. It is a white solid with limited solubility in water.

<span class="mw-page-title-main">Iron(III) nitrate</span> Chemical compound

Iron(III) nitrate, or ferric nitrate, is the name used for a series of inorganic compounds with the formula Fe(NO3)3.(H2O)n. Most common is the nonahydrate Fe(NO3)3.(H2O)9. The hydrates are all pale colored, water-soluble paramagnetic salts.

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.

<span class="mw-page-title-main">Sodium ferrocyanide</span> Chemical compound

Sodium ferrocyanide is the sodium salt of the coordination compound of formula [Fe(CN)6]4−. In its hydrous form, Na4Fe(CN)6 · 10 H2O (sodium ferrocyanide decahydrate), it is sometimes known as yellow prussiate of soda. It is a yellow crystalline solid that is soluble in water and insoluble in alcohol. The yellow color is the color of ferrocyanide anion. Despite the presence of the cyanide ligands, sodium ferrocyanide has low toxicity (acceptable daily intake 0–0.025 mg/kg body weight). The ferrocyanides are less toxic than many salts of cyanide, because they tend not to release free cyanide. However, like all ferrocyanide salt solutions, addition of an acid or exposure to UV light can result in the production of hydrogen cyanide gas, which is extremely toxic.

<span class="mw-page-title-main">Iron(III) sulfate</span> Chemical compound

Iron(III) sulfate (or ferric sulfate), is a family of inorganic compounds with the formula Fe2(SO4)3(H2O)n. A variety of hydrates are known, including the most commonly encountered form of "ferric sulfate". Solutions are used in dyeing as a mordant, and as a coagulant for industrial wastes. Solutions of ferric sulfate are also used in the processing of aluminum and steel.

Organoiron chemistry is the chemistry of iron compounds containing a carbon-to-iron chemical bond. Organoiron compounds are relevant in organic synthesis as reagents such as iron pentacarbonyl, diiron nonacarbonyl and disodium tetracarbonylferrate. Although iron is generally less active in many catalytic applications, it is less expensive and "greener" than other metals. Organoiron compounds feature a wide range of ligands that support the Fe-C bond; as with other organometals, these supporting ligands prominently include phosphines, carbon monoxide, and cyclopentadienyl, but hard ligands such as amines are employed as well.

In situ chemical oxidation (ISCO), a form of advanced oxidation process, is an environmental remediation technique used for soil and/or groundwater remediation to lower the concentrations of targeted environmental contaminants to acceptable levels. ISCO is accomplished by introducing strong chemical oxidizers into the contaminated medium to destroy chemical contaminants in place. It can be used to remediate a variety of organic compounds, including some that are resistant to natural degradation. The in situ in ISCO is just Latin for "in place", signifying that ISCO is a chemical oxidation reaction that occurs at the site of the contamination.

References

  1. ↑ "Iron integral to the development of life on Earth – and the possibility of life on other planets". University of Oxford. 7 December 2021. Retrieved 9 May 2022.
  2. ↑ Berg, Jeremy Mark; Lippard, Stephen J. (1994). Principles of bioinorganic chemistry. Sausalito, Calif: University Science Books. ISBN   0-935702-73-3.
  3. ↑ H. Marschner and V. Römheld (1994): "Strategies of plants for acquisition of iron". Plant and Soil, volume 165, issue 2, pages 261–274. doi : 10.1007/BF00008069
  4. ↑ Petsch, S.T. (2014). "10.11 - The Global Oxygen Cycle". In Holland, H.D.; Turekian, K.K. (eds.). Treatise on Geochemistry. Reference Module in Earth Systems and Environmental Sciences. Vol. 10 (Second ed.). Elsevier. pp. 437–473. doi:10.1016/B978-0-08-095975-7.00811-1. ISBN   978-0-08-095975-7.
  5. ↑ Earnshaw, A.; Greenwood, N. N. (1997). Chemistry of the elements (2nd ed.). Oxford: Butterworth-Heinemann. ISBN   0-7506-3365-4.
  6. ↑ Tang, Zhongmin; Zhao, Peiran; Wang, Han; Liu, Yanyan; Bu, Wenbo (2021). "Biomedicine Meets Fenton Chemistry". Chemical Reviews. 121 (4): 1981–2019. doi:10.1021/acs.chemrev.0c00977. PMID   33492935. S2CID   231712587.
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