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Eye, respiratory and skin irritant. |Hazards_ref = <ref>{{cite web |title=5936-11-8 - Potassium trioxalatoferrate(III) trihydrate - Potassium iron(III) oxalate - 31124 - Alfa Aesar |url=https://www.alfa.com/en/catalog/031124/ |website=www.alfa.com}}</ref> |GHSPictograms = {{GHS07}} |GHSSignalWord = Warning |HPhrases = {{H-phrases|302|312}} |PPhrases = {{P-phrases|280|301+330+331|302+353|312|330|363|403|501}} }} |Section5 = {{Chembox Related |OtherAnions = [[Sodium ferrioxalate]] |OtherFunction_label = compounds |OtherFunction = [[Iron(II) oxalate]]<br>[[Iron(III) oxalate]] }} }} '''Potassium ferrioxalate,''' also called '''potassium trisoxalatoferrate''' or '''potassium tris(oxalato)ferrate(III)'''<ref name="sari" /> is a chemical compound with the formula {{chem2|K3[Fe(C2O4)3]|auto=1}}. It often occurs as the [[trihydrate]] {{chem2|K3[Fe(C2O4)3]*3H2O}}. Both are crystalline compounds, lime green in colour.<ref name=JCB/> The compound is a [[salt (chemistry)|salt]] consisting of [[ferrioxalate]] [[anion]]s, {{chem2|[Fe(C2O4)3](3-)}}, and [[potassium]] cations {{chem2|K(+)}}. The anion is a [[transition metal oxalate complex]] consisting of an [[iron]] atom in the +3 oxidation state and three [[bidentate]] [[oxalate]] {{chem2|C2O4(2-)}} [[ligands]]. Potassium is a [[counterion]], balancing the −3 charge of the complex. In solution, the salt dissociates to give the ferrioxalate anion, {{chem2|[Fe(C2O4)3](3-)}}, which appears fluorescent green in color. The salt is available in anhydrous form<ref name=sari>A. Saritha, B. Raju, M. Ramachary, P. Raghavaiah, and K. A. Hussain (2012) "Synthesis, Crystal Structure and Characterization of Chiral, Three-Dimensional Anhydrous Potassium Tris(oxalato)ferrate(III)", ''Physica B: Condensed Matter'', volume 407, issue 21, pages 4208-4213. {{doi|10.1016/j.physb.2012.07.005}}</ref> as well as a [[water of crystallization|trihydrate]].<ref name=Junk/> The ferrioxalate anion is quite stable in the dark, but it is decomposed by light and high-energy [[electromagnetic radiation]]. ==Preparation== The complex can be synthesized by the reaction between [[iron(III) sulfate]], [[barium oxalate]] and [[potassium oxalate]]:<ref name=JCB>{{cite journal|first1=John C. |last1=Bailar, Jr. |first2=Eldon M. |last2=Jones |title=Trioxalato Salts (Trioxalatoaluminiate, -ferriate, -chromiate, and -cobaltiate) |journal=[[Inorganic Syntheses]] |date=1939 |volume=1 |pages=35–38|doi=10.1002/9780470132326.ch13|isbn=9780470132326}}</ref> : {{chem2|Fe2(SO4)3 + 3 BaC2O4 + 3 K2C2O4 → 2 K3[Fe(C2O4)3] + 3 BaSO4}} As can be read in the reference above, iron(III) sulfate, barium oxalate and potassium oxalate are combined in water and digested for several hours on a steam bath. Oxalate ions from barium oxalate will then replace the sulfate ions in solution, removing them as {{chem2|BaSO4}} which can then be filtered and the pure material can be crystallized. ==Structure== The structures of the trihydrate and of the anhydrous salt have been extensively studied.<ref name=Junk>{{cite journal|title=Supramolecular Interactions in the X-ray Crystal Structure of Potassium Tris(oxalato)ferrate(III) Trihydrate|last=Junk |first=Peter C. |journal=J. Coord. Chem. |date=2005 |volume=58|issue=4 |pages=355–361 |doi=10.1080/00958970512331334250|s2cid=216142329}}</ref> which indicates that the Fe(III) is [[high spin]]; as the low spin complex would display [[Jahn–Teller distortion]]s. The ammonium and mixed sodium-potassium salts are [[isomorphous]], as are related complexes with {{chem2|Al(3+), Cr(3+), and V(3+)}}. 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).<ref>{{Greenwood&Earnshaw}}</ref> [[File:2-isomers-of-ferrioxalate.svg|300px|frameless|center]] ==Reactions== ===Photoreduction=== The ferrioxalate anion is sensitive to light and to high-energy electromagnetic radiation, including [[X-rays]] and [[gamma rays]]. Absorption of a photon causes the decomposition of one oxalate ion to [[carbon dioxide]] {{chem2|CO2}} and reduction of the iron(III) atom to iron(II).<ref name=hatch/> This photo-sensitive property is used for chemical [[actinometry]], the measure of luminous flux, and for preparation of [[blueprint]]s. This light-catalyzed redox reaction once formed the basis of some photographic processes. However due to their insensitivity and ready availability of advanced digital photography, these processes are obsolete. ===Thermal decomposition=== The trihydrate loses the three water molecules at 113&nbsp;°C.<ref name=ladr>J. Ladriere (1992): "Mössbauer Study on the Thermal Decomposition of Potassium Tris(oxalato)ferrate(III) Trihydrate and Bis(oxalato) ferrate(II) Dihydrate". ''Hyperfine Interactions'', volume 70, issue 1, pages 1095–1098. {{doi|10.1007/BF02397520}}</ref> At 296&nbsp;°C, the anhydrous salt decomposes into the iron(II) complex potassium ferrioxalate, potassium oxalate, and [[carbon dioxide]]:<ref name=ladr/> : {{chem2|2 K3[Fe(C2O4)3] → 2 K2[Fe(C2O4)2] + K2C2O4 + 2 CO2}} ==Uses== ===Photometry and actinometry=== The discovery of the efficient [[photolysis]] of the ferrioxalate anion was a landmark for chemical [[photochemistry]] and [[actinometry]]. The potassium salt was found to be over 1000 times more sensitive than [[uranyl oxalate]], the compound previously used for these purposes.<ref name=hatch>{{cite journal|title=A new sensitive chemical actinometer. II. Potassium ferrioxalate as a standard chemical actinometer|author1=Hatchard, C. G. |author2=Parker, C. A. |journal=Proceedings of the Royal Society of London|year=1956|volume=235|issue=1203|pages=518–36|doi=10.1098/rspa.1956.0102|bibcode=1956RSPSA.235..518H|s2cid=98652159}}</ref><ref>{{cite journal|title=New Insight into Photochemistry of Ferrioxalate |first1=Ivan P. |last1=Pozdnyakov |first2=Oksana V. |last2=Kel |first3=Victor F. |last3=Plyusnin |first4=Vyacheslav P. |last4=Grivin |first5=Nikolai M. |last5=Bazhin |journal=J. Phys. Chem. A |date=2008 |volume=112 |issue=36 |pages=8316–8322 |doi=10.1021/jp8040583|pmid=18707071 |bibcode=2008JPCA..112.8316P}}</ref> ===Chemistry education=== The synthesis and thermal decomposition of potassium ferrioxalate is a popular exercise for high school, college or undergraduate university students, since it involves the chemistry of transition metal complexes, visually observable photochemistry, and [[thermogravimetry]].<ref name=olmsted>John Olmsted (1984): "Preparation and analysis of potassium tris(oxalato)ferrate(III)trihydrate: A general chemistry experiment". ''Journal of Chemical Education'', volume 61, issue 12, page 1098. {{doi|10.1021/ed061p1098}}</ref> ===Blueprints=== Before the ready availability of wide [[ink-jet printer|ink-jet]] and [[laser printer]]s, large-size engineering drawings were commonly reproduced by the [[cyanotype]] method. That was a simple contact-based photographic process that produced a "negative" white-on-blue copy of the original drawing—a [[blueprint]]. The process is based on the photolysis of an iron(III) complex which gets converted into an insoluble iron(II) version in areas of the paper that were exposed to light. The complex used in cyanotype is mainly [[ammonium ferric citrate]], but potassium ferrioxalate is also used.<ref name=fiorito>Pablo Alejandro Fiorito and André Sarto Polo (2015): "A New Approach toward Cyanotype Photography Using Tris-(oxalato)ferrate(III): An Integrated Experiment". ''Journal of Chemical Education'', volume 92, issue 10, pages 1721–1724. {{doi|10.1021/ed500809n}}</ref><ref name=ware>Mike Ware (2014): ''[https://www.academia.edu/10303227/Cyanomicon_The_History_Science_and_Art_of_Cyanotype_photographic_printing_in_Prussian_blue Cyanomicon - History, Science and Art of Cyanotype: photographic printing in Prussian blue]''. Online document at www.academia.edu, published by www.mikeware.co.uk, accessed on 2019-03-29.</ref> ==See also== A number of other iron oxalates are known: * [[Iron(II) oxalate]] * [[Iron(III) oxalate]] * [[Sodium ferrioxalate]] See [[transition metal oxalate complex]]. ==References== {{reflist}} {{Potassium compounds}} [[Category:Iron complexes]] [[Category:Iron(III) compounds]] [[Category:Potassium compounds]] [[Category:Oxalato complexes]] [[Category:Ferrates]] </textarea><div class="templatesUsed"><div class="mw-templatesUsedExplanation"><p><span id="templatesused">Pages transcluded onto the current version of this page<span class="posteditwindowhelplinks"> (<a href="/wiki/Help:Transclusion" title="Help:Transclusion">help</a>)</span>:</span> </p></div><ul> <li><a href="/wiki/Template:Abbr" title="Template:Abbr">Template:Abbr</a> (<a href="/w/index.php?title=Template:Abbr&action=edit" title="Template:Abbr">view source</a>) (protected)</li><li><a href="/wiki/Template:Button" 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