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Iron(II,III) oxide

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Iron(II,III) oxide, or black iron oxide, is the chemical compound with formula Fe3O4. It occurs in nature as the mineral magnetite. It is one of a number of iron oxides, the others being iron(II) oxide (FeO), which is rare, and iron(III) oxide (Fe2O3) which also occurs naturally as the mineral hematite. It contains both Fe2+ and Fe3+ ions and is sometimes formulated as FeO ∙ Fe2O3. This iron oxide is encountered in the laboratory as a black powder. It exhibits permanent magnetism and is ferrimagnetic, but is sometimes incorrectly described as ferromagnetic.[4] Its most extensive use is as a black pigment (see: Mars Black). For this purpose, it is synthesized rather than being extracted from the naturally occurring mineral as the particle size and shape can be varied by the method of production.[5]

Iron(II,III) oxide
Names
IUPAC name
iron(II) iron(III) oxide
Other names
ferrous ferric oxide, ferrosoferric oxide, iron(II,III) oxide, magnetite, black iron oxide, lodestone, rust, iron(II) diiron(III) oxide
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.013.889 Edit this at Wikidata
UNII
  • InChI=1S/3Fe.4O checkY
    Key: SZVJSHCCFOBDDC-UHFFFAOYSA-N checkY
  • InChI=1/3Fe.4O/rFe3O4/c1-4-2-6-3(5-1)7-2
    Key: SZVJSHCCFOBDDC-QXRQKJBKAR
  • O1[Fe]2O[Fe]O[Fe]1O2
Properties
Fe3O4

FeO.Fe2O3

Molar mass 231.533 g/mol
Appearance solid black powder
Density 5 g/cm3
Melting point 1,597 °C (2,907 °F; 1,870 K)
Boiling point 2,623[1] °C (4,753 °F; 2,896 K)
2.42[2]
Hazards
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 0: Exposure under fire conditions would offer no hazard beyond that of ordinary combustible material. E.g. sodium chlorideFlammability 0: Will not burn. E.g. waterInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazard OX: Oxidizer. E.g. potassium perchlorate
0
0
1
OX
Thermochemistry
-1120.89 kJ·mol−1[3]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Preparation

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Heated iron metal interacts with steam to form iron oxide and hydrogen gas.

 

Under anaerobic conditions, ferrous hydroxide (Fe(OH)2) can be oxidized by water to form magnetite and molecular hydrogen. This process is described by the Schikorr reaction:

 

This works because crystalline magnetite (Fe3O4) is thermodynamically more stable than amorphous ferrous hydroxide (Fe(OH)2 ).[6]

The Massart method of preparation of magnetite as a ferrofluid, is convenient in the laboratory: mix iron(II) chloride and iron(III) chloride in the presence of sodium hydroxide.[7]

A more efficient method of preparing magnetite without troublesome residues of sodium, is to use ammonia to promote chemical co-precipitation from the iron chlorides: first mix solutions of 0.1 M FeCl3·6H2O and FeCl2·4H2O with vigorous stirring at about 2000 rpm. The molar ratio of the FeCl3:FeCl2 should be about 2:1. Heat the mix to 70 °C, then raise the speed of stirring to about 7500 rpm and quickly add a solution of NH4OH (10 volume %). A dark precipitate of nanoparticles of magnetite forms immediately.[8]

In both methods, the precipitation reaction relies on rapid transformation of acidic iron ions into the spinel iron oxide structure at pH 10 or higher.

Controlling the formation of magnetite nanoparticles presents challenges: the reactions and phase transformations necessary for the creation of the magnetite spinel structure are complex.[9] The subject is of practical importance because magnetite particles are of interest in bioscience applications such as magnetic resonance imaging (MRI), in which iron oxide magnetite nanoparticles potentially present a non-toxic alternative to the gadolinium-based contrast agents currently in use. However, difficulties in controlling the formation of the particles, still frustrate the preparation of superparamagnetic magnetite particles, that is to say: magnetite nanoparticles with a coercivity of 0 A/m, meaning that they completely lose their permanent magnetisation in the absence of an external magnetic field. The smallest values currently reported for nanosized magnetite particles is Hc = 8.5 A m−1,[10] whereas the largest reported magnetization value is 87 Am2 kg−1 for synthetic magnetite.[11][12]

Pigment quality Fe3O4, so called synthetic magnetite, can be prepared using processes that use industrial wastes, scrap iron or solutions containing iron salts (e.g. those produced as by-products in industrial processes such as the acid vat treatment (pickling) of steel):

  • Oxidation of Fe metal in the Laux process where nitrobenzene is treated with iron metal using FeCl2 as a catalyst to produce aniline:[5]
C6H5NO2 + 3 Fe + 2 H2O → C6H5NH2 + Fe3O4
  • Oxidation of FeII compounds, e.g. the precipitation of iron(II) salts as hydroxides followed by oxidation by aeration where careful control of the pH determines the oxide produced.[5]

Reduction of Fe2O3 with hydrogen:[13][14]

3Fe2O3 + H2 → 2Fe3O4 +H2O

Reduction of Fe2O3 with CO:[15]

3Fe2O3 + CO → 2Fe3O4 + CO2

Production of nano-particles can be performed chemically by taking for example mixtures of FeII and FeIII salts and mixing them with alkali to precipitate colloidal Fe3O4. The reaction conditions are critical to the process and determine the particle size.[16]

Iron(II) carbonate can also be thermally decomposed into Iron(II,III):[17]

3FeCO3 → Fe3O4 + 2CO2 + CO

Reactions

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Reduction of magnetite ore by CO in a blast furnace is used to produce iron as part of steel production process:[4]

 

Controlled oxidation of Fe3O4 is used to produce brown pigment quality γ-Fe2O3 (maghemite):[18]

 

More vigorous calcining (roasting in air) gives red pigment quality α-Fe2O3 (hematite):[18]

 

Structure

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Fe3O4 has a cubic inverse spinel group structure which consists of a cubic close packed array of oxide ions where all of the Fe2+ ions occupy half of the octahedral sites and the Fe3+ are split evenly across the remaining octahedral sites and the tetrahedral sites.

Both FeO and γ-Fe2O3 have a similar cubic close packed array of oxide ions and this accounts for the ready interchangeability between the three compounds on oxidation and reduction as these reactions entail a relatively small change to the overall structure.[4] Fe3O4 samples can be non-stoichiometric.[4]

The ferrimagnetism of Fe3O4 arises because the electron spins of the FeII and FeIII ions in the octahedral sites are coupled and the spins of the FeIII ions in the tetrahedral sites are coupled but anti-parallel to the former. The net effect is that the magnetic contributions of both sets are not balanced and there is a permanent magnetism.[4]

In the molten state, experimentally constrained models show that the iron ions are coordinated to 5 oxygen ions on average.[19] There is a distribution of coordination sites in the liquid state, with the majority of both FeII and FeIII being 5-coordinated to oxygen and minority populations of both 4- and 6-fold coordinated iron.

Properties

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Sample of magnetite, naturally occurring Fe3O4.

Fe3O4 is ferrimagnetic with a Curie temperature of 858 K (585 °C). There is a phase transition at 120 K (−153 °C), called Verwey transition where there is a discontinuity in the structure, conductivity and magnetic properties.[20] This effect has been extensively investigated and whilst various explanations have been proposed, it does not appear to be fully understood.[21]

While it has much higher electrical resistivity than iron metal (96.1 nΩ m), Fe3O4's electrical resistivity (0.3 mΩ m [22]) is significantly lower than that of Fe2O3 (approx kΩ m). This is ascribed to electron exchange between the FeII and FeIII centres in Fe3O4.[4]

Uses

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Ferumoxytol
Clinical data
Trade namesFeraheme, Rienso
AHFS/Drugs.comMonograph
MedlinePlusa614023
License data
Routes of
administration		Intravenous infusion
ATC code
  • None
Legal status
Legal status
Identifiers
  • iron(2+);iron(3+);oxygen(2-)
CAS Number
DrugBank
UNII
KEGG
ChEBI
CompTox Dashboard (EPA)
ECHA InfoCard100.013.889  
Chemical and physical data
FormulaFe3O4
Molar mass231.531 g·mol−1
3D model (JSmol)
  • [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3]
  • InChI=1S/3Fe.4O/q+2;2*+3;4*-2
  • Key:WTFXARWRTYJXII-UHFFFAOYSA-N

Fe3O4 is used as a black pigment and is known as C.I pigment black 11 (C.I. No.77499) or Mars Black.[18]

Fe3O4 is used as a catalyst in the Haber process and in the water-gas shift reaction.[26] The latter uses an HTS (high temperature shift catalyst) of iron oxide stabilised by chromium oxide.[26] This iron–chrome catalyst is reduced at reactor start up to generate Fe3O4 from α-Fe2O3 and Cr2O3 to CrO3.[26]

Bluing is a passivation process that produces a layer of Fe3O4 on the surface of steel to protect it from rust. Along with sulfur and aluminium, it is an ingredient in steel-cutting thermite.[citation needed]

Medical uses

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Nano particles of Fe3O4 are used as contrast agents in MRI scanning.[27]

Ferumoxytol, sold under the brand names Feraheme and Rienso, is an intravenous Fe3O4 preparation for treatment of anemia resulting from chronic kidney disease.[23][24][28][29] Ferumoxytol is manufactured and globally distributed by AMAG Pharmaceuticals.[23][29]

Biological occurrence

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Magnetite has been found as nano-crystals in magnetotactic bacteria (42–45 nm)[5] and in the beak tissue of homing pigeons.[30]

References

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  1. ^ Magnetite (Fe3O4): Properties, Synthesis, and Applications Archived 2017-07-20 at the Wayback Machine Lee Blaney, Lehigh Review 15, 33-81 (2007). See Appendix A, p.77
  2. ^ Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN 0-07-049439-8
  3. ^ Chase MW (1998). "NIST-JANAF Themochemical Tables". NIST (Fourth ed.): 1–1951.
  4. ^ a b c d e f Greenwood NN, Earnshaw A (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  5. ^ a b c d Cornell RM, Schwertmann U (2007). The Iron Oxides: Structure, Properties, Reactions, Occurrences and Uses. Wiley-VCH. ISBN 978-3-527-60644-3.
  6. ^ Ma M, Zhang Y, Guo Z, Gu N (January 2013). "Facile synthesis of ultrathin magnetic iron oxide nanoplates by Schikorr reaction". Nanoscale Research Letters. 8 (1): 16. Bibcode:2013NRL.....8...16M. doi:10.1186/1556-276X-8-16. PMC 3598988. PMID 23294626.
  7. ^ Massart R (1981). "Preparation of aqueous magnetic liquids in alkaline and acidic media". IEEE Transactions on Magnetics. 17 (2): 1247–1248. Bibcode:1981ITM....17.1247M. doi:10.1109/TMAG.1981.1061188.
  8. ^ Keshavarz S, Xu Y, Hrdy S, Lemley C, Mewes T, Bao Y (2010). "Relaxation of Polymer Coated Fe3O4 Magnetic Nanoparticles in Aqueous Solution". IEEE Transactions on Magnetics. 46 (6): 1541–1543. doi:10.1109/TMAG.2010.2040588. S2CID 35129018.
  9. ^ Jolivet JP, Chanéac C, Tronc E (March 2004). "Iron oxide chemistry. From molecular clusters to extended solid networks". Chemical Communications (5): 481–7. doi:10.1039/B304532N. PMID 14973569.
  10. ^ Ström V, Olsson RT, Rao KV (2010). "Real-time monitoring of the evolution of magnetism during precipitation of superparamagnetic nanoparticles for bioscience applications". Journal of Materials Chemistry. 20 (20): 4168. doi:10.1039/C0JM00043D.
  11. ^ Fang M, Ström V, Olsson RT, Belova L, Rao KV (2011). "Rapid mixing: A route to synthesize magnetite nanoparticles with high moment". Applied Physics Letters. 99 (22): 222501. Bibcode:2011ApPhL..99v2501F. doi:10.1063/1.3662965.
  12. ^ Fang M, Ström V, Olsson RT, Belova L, Rao KV (April 2012). "Particle size and magnetic properties dependence on growth temperature for rapid mixed co-precipitated magnetite nanoparticles". Nanotechnology. 23 (14): 145601. Bibcode:2012Nanot..23n5601F. doi:10.1088/0957-4484/23/14/145601. PMID 22433909. S2CID 34153665.
  13. ^ US 2596954, Heath TD, "Process for reduction of iron ore to magnetite", issued 13 May 1952, assigned to Dorr Company 
  14. ^ Pineau A, Kanari N, Gaballah I (2006). "Kinetics of reduction of iron oxides by H2 Part I: Low temperature reduction of hematite". Thermochimica Acta. 447 (1): 89–100. doi:10.1016/j.tca.2005.10.004.
  15. ^ Hayes PC, Grieveson P (1981). "The effects of nucleation and growth on the reduction of Fe2O3 to Fe3O4". Metallurgical and Materials Transactions B. 12 (2): 319–326. Bibcode:1981MTB....12..319H. doi:10.1007/BF02654465. S2CID 94274056.
  16. ^ Arthur T. Hubbard (2002) Encyclopedia of Surface and Colloid Science CRC Press, ISBN 0-8247-0796-6
  17. ^ "FeCO3 = Fe3O4 + CO2 + CO | The thermal decomposition of iron(II) carbonate". chemiday.com. Retrieved 2022-10-14.
  18. ^ a b c Gunter Buxbaum, Gerhard Pfaff (2005) Industrial Inorganic Pigments 3d edition Wiley-VCH ISBN 3-527-30363-4
  19. ^ Shi C, Alderman OL, Tamalonis A, Weber R, You J, Benmore CJ (2020). "Redox-structure dependence of molten iron oxides". Communications Materials. 1 (1): 80. Bibcode:2020CoMat...1...80S. doi:10.1038/s43246-020-00080-4. S2CID 226248368.
  20. ^ Verwey EJ (1939). "Electronic Conduction of Magnetite (Fe3O4) and its Transition Point at Low Temperatures". Nature. 144 (3642): 327–328 (1939). Bibcode:1939Natur.144..327V. doi:10.1038/144327b0. S2CID 41925681.
  21. ^ Walz F (2002). "The Verwey transition - a topical review". Journal of Physics: Condensed Matter. 14 (12): R285–R340. doi:10.1088/0953-8984/14/12/203. S2CID 250773238.
  22. ^ Itai R (1971). "Electrical resistivity of Magnetite anodes". Journal of the Electrochemical Society. 118 (10): 1709. Bibcode:1971JElS..118.1709I. doi:10.1149/1.2407817.
  23. ^ a b c "Feraheme- ferumoxytol injection". DailyMed. 9 July 2020. Retrieved 14 September 2020.
  24. ^ a b "Rienso EPAR". European Medicines Agency. 17 September 2018. Retrieved 14 September 2020.
  25. ^ "Ferumoxytol (Feraheme) Use During Pregnancy". Drugs.com. 15 May 2020. Retrieved 14 September 2020.
  26. ^ a b c Sunggyu Lee (2006) Encyclopedia of Chemical Processing CRC Press ISBN 0-8247-5563-4
  27. ^ Babes L, Denizot B, Tanguy G, Jallet P (April 1999). "Synthesis of Iron Oxide Nanoparticles Used as MRI Contrast Agents: A Parametric Study". Journal of Colloid and Interface Science. 212 (2): 474–482. Bibcode:1999JCIS..212..474B. doi:10.1006/jcis.1998.6053. PMID 10092379.
  28. ^ Schwenk MH (January 2010). "Ferumoxytol: a new intravenous iron preparation for the treatment of iron deficiency anemia in patients with chronic kidney disease". Pharmacotherapy. 30 (1): 70–79. doi:10.1592/phco.30.1.70. PMID 20030475. S2CID 7748714.
  29. ^ a b "Drug Approval Package: Feraheme (Ferumoxytol) Injection NDA #022180". U.S. Food and Drug Administration (FDA). Retrieved 14 September 2020.
    Rieves D (June 23, 2009). "Application Number: 22-180" (PDF) (Summary Review). Center for Drug Evaluation and Research.
  30. ^ Hanzlik M, Heunemann C, Holtkamp-Rötzler E, Winklhofer M, Petersen N, Fleissner G (December 2000). "Superparamagnetic magnetite in the upper beak tissue of homing pigeons". Biometals. 13 (4): 325–31. doi:10.1023/A:1009214526685. PMID 11247039. S2CID 39216462.
edit
  • "Ferumoxytol". Drug Information Portal. U.S. National Library of Medicine.
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