Ferric oxalate

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Ferric oxalate
Ferric oxalate.svg
Names
Systematic IUPAC name
iron(3+) ethanedioate (2:3)
Other names
Iron(III) oxalate
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.019.047 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 220-951-7
PubChem CID
UNII
  • InChI=1S/3C2H2O4.2Fe/c3*3-1(4)2(5)6;;/h3*(H,3,4)(H,5,6);;/q;;;2*+3/p-6
  • [Fe+3].[Fe+3].O=C([O-])C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O
Properties
C6Fe2O12
Molar mass 375.747 g/mol
AppearancePale yellow solid (anhydrous)
Lime green solid (hexahydrate)
Odor odorless
Melting point 365.1 °C (689.2 °F)
slightly soluble
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Ferric oxalate, also known as iron(III) oxalate, refers to inorganic compounds with the formula Fe2(C2O4)3(H2O)x but could also refer to salts of [Fe(C2O4)3]3-. Fe2(C2O4)3(H2O)x are coordination polymers with varying degrees of hydration. The coordination complex with the formula [Fe(C2O4)3]3- forms a variety of salts, a well-known example being potassium ferrioxalate. This article emphasizes the coordination polymers.

Contents

Structure

Tetrahydrate

Structure of hydrated ferric oxalate Color code: red=O, white = H, blue = Fe, gray = C. Fe2(ox)3hydrate.jpg
Structure of hydrated ferric oxalate Color code: red=O, white = H, blue = Fe, gray = C.
Room temperature Mossbauer spectrum of
Fe2(C2O4)3*4H2O Mossbauer spectrum.jpg
Room temperature Mössbauer spectrum of Fe2(C2O4)3·4H2O

According to X-ray crystallography of the tetrahydrate Fe2(C2O4)3· 4 H2O, iron is octahedral. The oxalate ligands are bridging. Some through all four oxygen atoms, some with two oxygen atoms. Half of the water is lattice water, being situated between chains of Fe oxalates. Mössbauer spectrum of Fe2(C2O4)3· 4 H2O exhibits an isomer shift of 0.38 mm/s and a quadrupole splitting of 0.40 mm/s, suggesting a high spin Fe3+ in octahedral coordination. [1] [2]

Production

Ferric oxalate may be produced by reaction of iron(III) hydroxide and solution of oxalic acid:

2Fe(OH)3 + 3H2C2O4 → Fe2(C2O4)3 + 6H2O

Uses

Dentistry

Like many oxalates, ferric oxalate has been investigated as a short-term treatment for dentin hypersensitivity. [3] It is used in certain toothpaste formulations; however, its effectiveness has been questioned. [4]

Photography

Ferric oxalate is used as the light-sensitive element in the Kallitype photographic printing process; and the platinotype process Platinum/Palladium Printing.

Batteries

Ferric oxalate tetrahydrate has been investigated as a possible cheap material for the positive electrode of lithium-iron batteries. It can intercalate lithium ions at an average potential of 3.35 V, and has shown a sustainable capacity of 98 mAh/g. [1]

Organic synthesis

Ferric oxalate hexahydrate is used with sodium borohydride for radical Markovnikov hydrofunctionalization reactions of alkenes. [5]

See also

A number of other iron oxalates are known:-

Related Research Articles

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

In chemistry, iron(III) refers to the element iron in its +3 oxidation state. The adjective ferric or the prefix ferri- is often used to specify such compounds, as in ferric chloride 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">Ferrous</span> Metal compound containing iron

In chemistry, the adjective ferrous indicates a compound that contains iron(II), meaning iron in its +2 oxidation state, possibly as the divalent cation Fe2+. It is opposed to ferric, or iron(III), meaning iron in its +3 oxidation state, such as the trivalent cation Fe3+. This usage has been largely replaced by the IUPAC nomenclature, which calls for the oxidation state being indicated by Roman numerals in parentheses, such as iron(II) oxide for ferrous oxide (FeO), iron(III) oxide for ferric oxide (Fe2O3), and iron(II,III) oxide for the oxide Fe3O4 that contains both forms of iron.

<span class="mw-page-title-main">Calcium oxalate</span> Calcium salt of oxalic acid

Calcium oxalate (in archaic terminology, oxalate of lime) is a calcium salt of oxalic acid with the chemical formula CaC2O4 or Ca(COO)2. It forms hydrates CaC2O4·nH2O, where n varies from 1 to 3. Anhydrous and all hydrated forms are colorless or white. The monohydrate CaC2O4·H2O occurs naturally as the mineral whewellite, forming envelope-shaped crystals, known in plants as raphides. The two rarer hydrates are dihydrate CaC2O4·2H2O, which occurs naturally as the mineral weddellite, and trihydrate CaC2O4·3H2O, which occurs naturally as the mineral caoxite, are also recognized. Some foods have high quantities of calcium oxalates and can produce sores and numbing on ingestion and may even be fatal. Cultural groups with diets that depend highly on fruits and vegetables high in calcium oxalate, such as those in Micronesia, reduce the level of it by boiling and cooking them. They are a constituent in 76% of human kidney stones. Calcium oxalate is also found in beerstone, a scale that forms on containers used in breweries.

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.

In chemistry, water(s) of crystallization or water(s) of hydration are water molecules that are present inside crystals. Water is often incorporated in the formation of crystals from aqueous solutions. In some contexts, water of crystallization is the total mass of water in a substance at a given temperature and is mostly present in a definite (stoichiometric) ratio. Classically, "water of crystallization" refers to water that is found in the crystalline framework of a metal complex or a salt, which is not directly bonded to the metal cation.

<span class="mw-page-title-main">Double salt</span> Type of salt

A double salt is a salt that contains two or more different cations or anions. Examples of double salts include alums (with the general formula MIMIII(SO4)2·12H2O) and Tutton's salts (with the general formula (MI)2MII(SO4)2·6H2O). Other examples include potassium sodium tartrate, ammonium iron(II) sulfate (Mohr's salt), potassium uranyl sulfate (used to discover radioactivity) and bromlite BaCa(CO3)2. The fluorocarbonates contain fluoride and carbonate anions. Many coordination complexes form double salts.

<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.

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

Manganese(II) sulfate usually refers to the inorganic compound with the formula MnSO4·H2O. This pale pink deliquescent solid is a commercially significant manganese(II) salt. Approximately 260,000 tonnes of manganese(II) sulfate were produced worldwide in 2005. It is the precursor to manganese metal and many other chemical compounds. Manganese-deficient soil is remediated with this salt.

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

Potassium ferrioxalate, also called potassium trisoxalatoferrate or potassium tris(oxalato)ferrate(III) is a chemical compound with the formula K3[Fe(C2O4)3]. It often occurs as the trihydrate K3[Fe(C2O4)3]·3H2O. Both are crystalline compounds, lime green in colour.

<span class="mw-page-title-main">Iron(II)</span> The element iron in its +2 oxidation state

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+.

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

Ferrous oxalate (iron(II) oxalate) are inorganic compound with the formula FeC2O4(H2O)x where x is 0 or 2. These are orange compounds, poorly soluble in water.

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

Sodium ferrioxalate are inorganic compounds with the formula Na3Fe(C2O4)3(H2O)n. The pentahydrate has been characterized by X-ray crystallography. In contrast the potassium, ammonium, and rubidium salts crystallize from water as their trihydrates.

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

Cobalt(II) oxalate is the inorganic compound with the formula of CoC2O4. Like other simple inorganic oxalates, it is a coordination polymer. The oxalate ligands bridge of Co(OH2)2 centres. Each cobalt adopts octahedral coordination geometry.

<span class="mw-page-title-main">Ferric ammonium oxalate</span> Chemical compound

Ferric ammonium oxalate is the ammonium salt of the anionic trisoxalato coordination complex of iron(III). It is a precursor to iron oxides, diverse coordination polymers, and Prussian Blue. The latter behavior is relevant to the manufacture of blueprint paper. Ferric ammonium oxalate has also been used in the synthesis of superconducting salts with bis(ethylene)dithiotetrathiafulvalene (BEDT-TTF), see Organic superconductor.

Potassium ferrooxalate, also known as potassium bisoxalatoferrate(II), is a salt with the formula K2Fe(C2O4)2(H2O)x. The anion is a transition metal oxalate complex, consisting of an atom of iron in the +2 oxidation state bound to oxalate (C
2
O2−
4
) ligands and water.

<span class="mw-page-title-main">Ferrioxalate</span> Ion

Ferrioxalate or trisoxalatoferrate(III) is a trivalent anion with formula [Fe(C2O4)3]3−. It is a transition metal complex consisting of an iron atom in the +3 oxidation state and three bidentate oxalate ions C2O2−4 anions acting as ligands.

<span class="mw-page-title-main">Transition metal oxalate complex</span>

Transition metal oxalate complexes are coordination complexes with oxalate (C2O42−) ligands. Some are useful commercially, but the topic has attracted regular scholarly scrutiny. Oxalate (C2O42-) is a kind of dicarboxylate ligand. As a small, symmetrical dinegative ion, oxalate commonly forms five-membered MO2C2 chelate rings. Mixed ligand complexes are known, e.g., [Co(C2O4)(NH3)4]κ+.

<span class="mw-page-title-main">Yttrium oxalate</span> Chemical compound

Yttrium oxalate is an inorganic compound, a salt of yttrium and oxalic acid with the chemical formula Y2(C2O4)3. The compound does not dissolve in water and forms crystalline hydrates—colorless crystals.

An oxalate chloride or oxalato chloride is a mixed anion compound contains both oxalate and chloride anions.

References

  1. 1 2 Ahouari, Hania; Rousse, Gwenaëlle; Rodríguez-Carvajal, Juan; Sougrati, Moulay-Tahar; Saubanère, Matthieu; Courty, Matthieu; Recham, Nadir; Tarascon, Jean-Marie (2015). "Unraveling the Structure of Iron(III) Oxalate Tetrahydrate and Its Reversible Li Insertion Capability". Chemistry of Materials. 27 (5): 1631–1639. doi:10.1021/cm5043149.
  2. Rousse, G.; Rodríguez-Carvajal, J. (2016). "Oxalate-mediated long-range antiferromagnetism order in Fe2(C2O4)3·4H2O". Dalton Transactions. 45 (36): 14311–14319. doi:10.1039/C6DT02740G. PMID   27539964.
  3. Gillam, D. G.; Newman, H. N.; Davies, E. H.; Bulman, J. S.; Troullos, E. S.; Curro, F. A. (2004). "Clinical evaluation of ferric oxalate in relieving dentine hypersensitivity". Journal of Oral Rehabilitation. 31 (3): 245–250. doi:10.1046/j.0305-182X.2003.01230.x. PMID   15025657.
  4. Cunha-Cruz, J.; Stout, J. R.; Heaton, L. J.; Wataha, J. C. (29 December 2010). "Dentin Hypersensitivity and Oxalates: a Systematic Review". Journal of Dental Research. 90 (3): 304–310. doi:10.1177/0022034510389179. PMC   3144108 . PMID   21191127.
  5. Barker, Timothy (2001-04-15). "Ferric Oxalate Hexahydrate". Encyclopedia of Reagents for Organic Synthesis (1 ed.). Wiley. pp. 1–4. doi:10.1002/047084289X.rn02346. ISBN   978-0-471-93623-7. S2CID   225482606.