Ferrioxalate

Last updated
Ferrioxalate
Ferrioxalate.svg
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/3C2H2O4.Fe/c3*3-1(4)2(5)6;/h3*(H,3,4)(H,5,6);/q;;;+3/p-6
    Key: FYJLUEWYCIBBGT-UHFFFAOYSA-H
  • C(=O)(C(=O)[O-])[O-].C(=O)(C(=O)[O-])[O-].C(=O)(C(=O)[O-])[O-].[Fe+3]
Properties
C6FeO123−
Molar mass 319.901 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

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.

Contents

The ferrioxalate anion gives a lime green color to salts, and in solution it is fluorescent. The anion is sensitive to light and higher-energy electromagnetic radiation, which causes the decomposition of one oxalate to carbon dioxide (CO2) and reduction of the iron(III) atom to iron(II). This property is exploited for actinometry.

The most common and most-studied salt is potassium ferrioxalate, but the sodium, ammonium, and lithium salts have also received some attention.

Properties

Potassium ferrioxalate crystals. Potassium trioxalatoferrate(III) large crystals.jpg
Potassium ferrioxalate crystals.

Stability

In the absence of light or other radiation, the ferrioxalate complex is quite stable. The potassium and sodium salts and their solutions can be heated to near 100 °C for hours without significant decomposition.

Molecular structure

The complex is held together by dative covalent bonds, due to the oxygen atoms in the oxalate anions (the "ligands") donating a lone pair to the p and d orbitals of the iron atom (the "center" of the complex). The center has three electrons in its d orbitals, leaving 13 empty places in the remaining d and p orbitals. Twelve of these are filled by electrons from the ligands.

The iron center in the ferrioxalate anion has a distorted octahedral geometry. The ferrioxalate complex has D3 molecular symmetry, within which the six Fe–O bond distances all close to 2.0 Å [1] which indicates that the Fe(III) is high spin; as the low spin complex would display Jahn–Teller distortions. The ammonium and mixed sodium-potassium salts are isomorphous, as are related complexes with Al3+, Cr3+, and V3+.

Chirality

The ferrioxalate complex displays helical chirality as it can form two non-superimposable geometries. In accordance with the IUPAC convention, the isomer with the left-handed screw axis is assigned the Greek symbol Λ (lambda). Its mirror image with the right-handed screw axis is given the Greek symbol Δ (delta). [2]

2-isomers-of-ferrioxalate.svg

Reactions

Photoreduction

In solution, the ferrioxalate complex undergoes photoreduction. In this process, the complex absorbs a photon of light and subsequently decomposes to form Fe(C
2O
4)2−
2 and CO
2. The iron centre is reduced (gains an electron) from the +3 to the +2 oxidation state, while an oxalate ion is oxidised to carbon dioxide:

2 [Fe(C
2O
4)
3]3− + hν → 2 [Fe(C
2O
4)
2]2− + 2 CO
2 + C
2O2−
4

This reaction provides an efficient chemical method for photometry and actinometry, the measurement of light and higher-energy electromagnetic radiation. Potassium ferrioxalate is over 1000 times more sensitive than uranyl oxalate, the compound previously used for these purposes. [3] [4] While the complex itself is insensitive to neutrons, the lithium salt can be used to measure them. A lithium-6 nucleus can absorb a neutron and emit alpha particle 4He2+ and a triton 3H+ with high energies, which presumably decompose the nearby ferrioxalate. [5]

See also

Related Research Articles

<span class="mw-page-title-main">Alkali metal</span> Group of highly reactive chemical elements

The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), and francium (Fr). Together with hydrogen they constitute group 1, which lies in the s-block of the periodic table. All alkali metals have their outermost electron in an s-orbital: this shared electron configuration results in their having very similar characteristic properties. Indeed, the alkali metals provide the best example of group trends in properties in the periodic table, with elements exhibiting well-characterised homologous behaviour. This family of elements is also known as the lithium family after its leading element.

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

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".

<span class="mw-page-title-main">Actinometer</span> Instrument for measuring thermal radiation

An actinometer is an instrument that can measure the heating power of radiation. Actinometers are used in meteorology to measure solar radiation as pyranometers, pyrheliometers and net radiometers.

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

Sodium perchlorate is an inorganic compound with the chemical formula NaClO4. It consists of sodium cations Na+ and perchlorate anions ClO−4. It is a white crystalline, hygroscopic solid that is highly soluble in water and ethanol. It is usually encountered as sodium perchlorate monohydrate NaClO4·H2O. The compound is noteworthy as the most water-soluble of the common perchlorate salts.

<span class="mw-page-title-main">Ferrate(VI)</span> Ion

Ferrate(VI) is the inorganic anion with the chemical formula [FeO4]2−. It is photosensitive, contributes a pale violet colour to compounds and solutions containing it and is one of the strongest water-stable oxidizing species known. Although it is classified as a weak base, concentrated solutions containing ferrate(VI) are corrosive and attack the skin and are only stable at high pH. It is similar to the somewhat more stable permanganate.

<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">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">Barium ferrate</span> Chemical compound

Barium ferrate is the chemical compound of formula BaFeO4. This is a rare compound containing iron in the +6 oxidation state. The ferrate(VI) ion has two unpaired electrons, making it paramagnetic. It is isostructural with BaSO4, and contains the tetrahedral [FeO4]2− anion.

<span class="mw-page-title-main">Croconic acid</span> Chemical compound

Croconic acid is a chemical compound with formula C5H2O5 or (C=O)3(COH)2. It has a cyclopentene backbone with two hydroxyl groups adjacent to the double bond and three ketone groups on the remaining carbon atoms. It is sensitive to light, soluble in water and ethanol and forms yellow crystals that decompose at 212 °C.

<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">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.

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

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.

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
2O2−
4) ligands and water.

<span class="mw-page-title-main">Hydromelonic acid</span> Chemical compound

Hydromelonic acid, is an elusive chemical compound with formula C
9H
3N
13 or (HNCN)
3(C
6N
7), whose molecule would consist of a heptazine H3(C
6N
7) molecule, with three cyanamido groups H–N=C=N– or N≡C–NH– substituted for the hydrogen atoms.

The borate oxalates are chemical compounds containing borate and oxalate anions. Where the oxalate group is bound to the borate via oxygen, a more condensed anion is formed that balances less cations. These can be termed boro-oxalates, bis(oxalato)borates, or oxalatoborates or oxalate borates. The oxalatoborates are heterocyclic compounds with a ring containing -O-B-O-. Bis(oxalato)borates are spiro compounds with rings joined at the boron atom.

<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+.

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

References

  1. ↑ Junk, Peter C. (2005). "Supramolecular interactions in the X-ray crystal structure of potassium tris(oxalato)ferrate(III) trihydrate". J. Coord. Chem. 58 (4): 355–361. doi:10.1080/00958970512331334250. S2CID   216142329.
  2. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.
  3. ↑ Hatchard, C. G.; Parker, C. A. (1956). "A new sensitive chemical actinometer. II. Potassium ferrioxalate as a standard chemical actinometer". Proceedings of the Royal Society of London. 235 (1203): 518–36. Bibcode:1956RSPSA.235..518H. doi:10.1098/rspa.1956.0102. S2CID   98652159.
  4. ↑ Pozdnyakov, Ivan P.; Kel, Oksana V.; Plyusnin, Victor F.; Grivin, Vyacheslav P.; Bazhin, Nikolai M. (2008). "New Insight into Photochemistry of Ferrioxalate". J. Phys. Chem. A. 112 (36): 8316–8322. Bibcode:2008JPCA..112.8316P. doi:10.1021/jp8040583. PMID   18707071.
  5. ↑ Junko Akashi, Yoshio Uchida, Tomoko Kojima, Motomi Katada, and Hirotoshi Sano (1984): "Mössbauer Spectroscopic Studies of the Effects of the 6Li(n, α)T Reaction in Lithium Tris(oxalato)ferrate(III)". Bulletin of the Chemical Society of Japan, volume 57, issue 4, pages 1076-1078. doi : 10.1246/bcsj.57.1076
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