Iron(II,III) oxide: Difference between revisions
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| IUPACName = iron(II) diiron(III) oxide |
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| OtherNames = ferrous ferric oxide, ferroso ferric oxide, iron(II,III) oxide, magnetite, black iron oxide, lodestone |
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| Section1 = {{Chembox Identifiers |
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| CASNo = 1317-61-9 <br />1309-38-2 |
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| Section2 = {{Chembox Properties |
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| Formula = Fe<sub>3</sub>O<sub>4</sub> |
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| MolarMass = 231.533 g/mol |
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| Appearance = black powder |
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| Density = 5.17 g/cm3 |
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'''Iron(II,III) oxide''' is the chemical compound Fe<sub>3</sub>O<sub>4</sub>. It is found in nature as the mineral [[magnetite]]. It contains both Fe<sup>2+</sup> and Fe<sup>3+</sup> ions and is sometimes formulated as FeO.Fe<sub>2</sub>O<sub>3</sub>. It is encountered in the laboratory as a black powder. It exhibits permanent magnetism and is [[ferrimagnetic]], but is sometimes incorrectly described as [[ferromagnetic]].<ref name = "Greenwood">{{Greenwood&Earnshaw}}</ref> Its most extensive use is as a black pigment which is synthesised rather than being extracted from the naturally occurring mineral as the particle size and shape can be varied by the method of production.<ref name = "Cornell">Rochelle M. Cornell, Udo Schwertmann 2007 ''The Iron Oxides: Structure, Properties, Reactions, Occurrences and Uses'' Wiley-VCH ISBN 3527606440</ref> |
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==Preparation== |
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Pigment quality Fe<sub>3</sub>O<sub>4</sub>, so called synthetic magnetite, can be prepared using processes that utilise industrial wastes, scrap iron or solutions containing iron salts( e.g. those produced as by-products in industrial processes such as the acid treatment ([[pickling (metal)|pickling]]) of steel): |
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*Oxidation of Fe metal in the Laux process where [[nitrobenzene]] is reacted with iron metal using FeCl<sub>2</sub> as a catalyst to produce [[aniline]]<ref name = "Cornell"/> : |
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:C<sub>6</sub>H<sub>5</sub>NO<sub>2</sub> + 9Fe + 2H<sub>2</sub>O → C<sub>6</sub>H<sub>5</sub>NH<sub>2</sub> + Fe<sub>3</sub>O<sub>4</sub> |
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*Oxidation of Fe<sup>II</sup> 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.<ref name = "Cornell"/> |
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Reduction of Fe<sub>2</sub>O<sub>3</sub> with hydrogen<ref>US patent 2596954, 1947, Process for reduction of iron ore to magnetiteHeath T.D.</ref><ref> Kinetics of reduction of iron oxides by H2 Part I: Low temperature reduction of hematite, A. Pineau, N. Kanari, I. Gaballah, Thermochimica Acta, 447, 1, 1 (2006), 89-100 doi:10.1016/j.tca.2005.10.004</ref>: |
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:3Fe<sub>2</sub>O<sub>3</sub> + H<sub>2</sub> → 2Fe<sub>3</sub>O<sub>4</sub> +H<sub>2</sub>O |
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Reduction of Fe<sub>2</sub>O<sub>3</sub> with CO<ref>The effects of nucleation and growth on the reduction of Fe<sub>2</sub>O<sub>3</sub> to Fe<sub>3</sub>O<sub>4</sub> Hayes P. C., Grieveson P Metallurgical and Materials Transactions B (1981), 12, 2, 319-326,{{doi| 10.1007/BF02654465}}</ref>: |
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:3Fe<sub>2</sub>O<sub>3</sub> + CO → 2Fe<sub>3</sub>O<sub>4</sub> + CO<sub>2</sub> |
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Production of nano-particles can be performed chemically by taking for example mixtures of Fe<sup>II</sup> and Fe<sup>III</sup> salts and mixing them with alkali to precipitate colloidal Fe<sub>3</sub>O<sub>4</sub>. The reaction conditions are critical to the process and determine the particle size.<ref>Arthur T. Hubbard (2002) ''Encyclopedia of Surface and Colloid Science'' CRC Press, ISBN 0824707966</ref> |
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==Reactions== |
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Reduction of magnetite ore by [[carbon monoxide|CO]] in a [[blast furnace]] is used to produce iron as part of steel production process<ref name = "Greenwood"/>: |
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:Fe<sub>3</sub>O<sub>4</sub> + 4CO → 3Fe + 4CO<sub>2</sub> |
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Controlled oxidation of Fe<sub>3</sub>O<sub>4</sub> is used to produce brown pigment quality [[iron(III)oxide|γ-Fe<sub>2</sub>O<sub>3</sub>]] ([[maghemite]])<ref name = "Buxbaum">Gunter Buxbaum, Gerhard Pfaff (2005) ''Industrial Inorganic Pigments'' 3d edition Wiley-VCH ISBN 3527303634</ref>: |
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:2Fe<sub>3</sub>O<sub>4</sub> + ½ O<sub>2</sub> → 3(γ-Fe<sub>2</sub>O<sub>3</sub>) |
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More vigorous calcining, (roasting in air), gives red pigment quality [[iron(III) oxide|α-Fe<sub>2</sub>O<sub>3</sub>]] ([[hematite]])<ref name = "Buxbaum"/>: |
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:2Fe<sub>3</sub>O<sub>4</sub> + ½ O<sub>2</sub> → 3(α-Fe<sub>2</sub>O<sub>3</sub>) |
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==Structure== |
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Fe<sub>3</sub>O<sub>4</sub> has a cubic inverse [[spinel]] structure which consists of a cubic close packed array of oxide ions where all of the Fe<sup>2+</sup> ions occupy half of the octahedral sites and the Fe<sup>3+</sup> are split evenly across the remaining octahedral sites and the tetrahedral sites.<br /> |
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Both [[iron(II) oxide|FeO]] and [[iron(III) oxide|γ-Fe<sub>2</sub>O<sub>3</sub>]] 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.<ref name ="Greenwood"/> Fe3O4 samples can be non-stoichiometric.<ref name ="Greenwood"/><br /> |
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The [[ferrimagnetism ]]of Fe<sub>3</sub>O<sub>4</sub> arises because the electron spins of the Fe<sup>II</sup> and Fe<sup>III</sup> ions in the octahedral sites are coupled and the the spins of the Fe<sup>III</sup> 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.<ref name = "Greenwood"/> |
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==Properties== |
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Fe<sub>3</sub>O<sub>4</sub> is [[ferrimagnetic]] with a [[Curie point|Curie temperature]] of 858 K. There is a phase transition at 120K, the so-called '''Verwey transition'' where there is a discontinuity in the structure, conductivity and magnetic properties.<ref>Electronic Conduction of Magnetite (Fe<sub>3</sub>O<sub>4</sub>) and its Transition Point at Low Temperatures, Verwey E. J. W., nature 144, 327-328 (1939) {{doi|10.1038/144327b0}}</ref> This effect has been extensively investigated and whilst various explanations have been proposed, it does not appear to be fully understood.<ref>The Verwey transition - a topical review Walz F. J. Phys.:Condens. Matter (2002) 14, 285-340 {{doi|10.1088/0953-8984/14/12/203}}</ref><br /> |
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Fe<sub>3</sub>O<sub>4</sub> is a an electrical conductor with a conductivity is significantly higher (X 10<sup>6</sup>) than [[iron(III) oxide|Fe<sub>2</sub>O<sub>3</sub>]], and this is ascribed to electron exchange between the Fe<sup>II</sup> and Fe<sup>III</sup> centres.<ref name = "Greenwood"/> |
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==Uses== |
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Fe<sub>3</sub>O<sub>4</sub> is used as a black pigment and is known as '''C.I pigment black 11''' (C.I. No.77499).<ref name = "Buxbaum"/><br /> |
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Fe<sub>3</sub>O<sub>4</sub> is used as a catalyst in the [[Haber process]] and in the [[water gas shift reaction]].<ref name = "Lee">Sunggyu Lee (2006) Encyclopedia of Chemical Processing CRC Press ISBN 0824755634</ref> The latter uses an HTS (high temperature shift catalyst) of iron oxide stabilised by chromium oxide.<ref name = "Lee"/> This iron-chrome catalyst is reduced at reactor start up to generate Fe<sub>3</sub>O<sub>4</sub> from α-Fe<sub>2</sub>O<sub>3</sub> and Cr<sub>2</sub>O<sub>3</sub> to CrO<sub>3</sub>.<ref name = "Lee"/><br /> |
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Nano particles of Fe<sub>3</sub>O<sub>4</sub> are used as contrast agents in [[Magnetic resonance imaging|MRI scanning]] <ref>Synthesis of Iron Oxide Nanoparticles Used as MRI Contrast Agents: A Parametric Study, Babes L, Denizot B, Tanguy G, Le Jeune J.J., Jallet P. Journal of Colloid and Interface Science, 212,2, (1999), 474-482, {{doi|10.1006/jcis.1998.6053}}</ref> |
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==Biological Occurence== |
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Magnetite has been found as nano-crystals in bacteria (42-45 μm)<ref name = "Cornell"/> and in homing pigeon beak tissue<ref>Superparamagnetic Magnetite in the Upper Beak Tissue of Homing Pigeons Hanzlik M., Heunemann C., Holtkamp-Rötzler E., Winklhofer M., Petersen N., Fleissner G. BioMetals, (2000), 13, 4, 325-331 {doi|10.1023/A:1009214526685}}</ref> |
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==References== |
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{{reflist}} |
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[[Category:Oxides]] |
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[[Category:Iron compounds]] |
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[[Category:Iron oxide pigments]] |
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Revision as of 16:30, 21 April 2008
Template:Chembox new Iron(II,III) oxide is the chemical compound Fe3O4. It is found in nature as the mineral magnetite. It contains both Fe2+ and Fe3+ ions and is sometimes formulated as FeO.Fe2O3. It is encountered in the laboratory as a black powder. It exhibits permanent magnetism and is ferrimagnetic, but is sometimes incorrectly described as ferromagnetic.[1] Its most extensive use is as a black pigment which is synthesised rather than being extracted from the naturally occurring mineral as the particle size and shape can be varied by the method of production.[2]
Preparation
Pigment quality Fe3O4, so called synthetic magnetite, can be prepared using processes that utilise industrial wastes, scrap iron or solutions containing iron salts( e.g. those produced as by-products in industrial processes such as the acid treatment (pickling) of steel):
- Oxidation of Fe metal in the Laux process where nitrobenzene is reacted with iron metal using FeCl2 as a catalyst to produce aniline[2] :
- C6H5NO2 + 9Fe + 2H2O → 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.[2]
Reduction of Fe2O3 with hydrogen[3][4]:
- 3Fe2O3 + H2 → 2Fe3O4 +H2O
Reduction of Fe2O3 with CO[5]:
- 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.[6]
Reactions
Reduction of magnetite ore by CO in a blast furnace is used to produce iron as part of steel production process[1]:
- Fe3O4 + 4CO → 3Fe + 4CO2
Controlled oxidation of Fe3O4 is used to produce brown pigment quality γ-Fe2O3 (maghemite)[7]:
- 2Fe3O4 + ½ O2 → 3(γ-Fe2O3)
More vigorous calcining, (roasting in air), gives red pigment quality α-Fe2O3 (hematite)[7]:
- 2Fe3O4 + ½ O2 → 3(α-Fe2O3)
Structure
Fe3O4 has a cubic inverse spinel 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.[1] Fe3O4 samples can be non-stoichiometric.[1]
The ferrimagnetism of Fe3O4 arises because the electron spins of the FeII and FeIII ions in the octahedral sites are coupled and the 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.[1]
Properties
Fe3O4 is ferrimagnetic with a Curie temperature of 858 K. There is a phase transition at 120K, the so-called 'Verwey transition where there is a discontinuity in the structure, conductivity and magnetic properties.[8] This effect has been extensively investigated and whilst various explanations have been proposed, it does not appear to be fully understood.[9]
Fe3O4 is a an electrical conductor with a conductivity is significantly higher (X 106) than Fe2O3, and this is ascribed to electron exchange between the FeII and FeIII centres.[1]
Uses
Fe3O4 is used as a black pigment and is known as C.I pigment black 11 (C.I. No.77499).[7]
Fe3O4 is used as a catalyst in the Haber process and in the water gas shift reaction.[10] The latter uses an HTS (high temperature shift catalyst) of iron oxide stabilised by chromium oxide.[10] This iron-chrome catalyst is reduced at reactor start up to generate Fe3O4 from α-Fe2O3 and Cr2O3 to CrO3.[10]
Nano particles of Fe3O4 are used as contrast agents in MRI scanning [11]
Biological Occurence
Magnetite has been found as nano-crystals in bacteria (42-45 μm)[2] and in homing pigeon beak tissue[12]
References
- ^ a b c d e f Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
- ^ a b c d Rochelle M. Cornell, Udo Schwertmann 2007 The Iron Oxides: Structure, Properties, Reactions, Occurrences and Uses Wiley-VCH ISBN 3527606440
- ^ US patent 2596954, 1947, Process for reduction of iron ore to magnetiteHeath T.D.
- ^ Kinetics of reduction of iron oxides by H2 Part I: Low temperature reduction of hematite, A. Pineau, N. Kanari, I. Gaballah, Thermochimica Acta, 447, 1, 1 (2006), 89-100 doi:10.1016/j.tca.2005.10.004
- ^ The effects of nucleation and growth on the reduction of Fe2O3 to Fe3O4 Hayes P. C., Grieveson P Metallurgical and Materials Transactions B (1981), 12, 2, 319-326,doi:10.1007/BF02654465
- ^ Arthur T. Hubbard (2002) Encyclopedia of Surface and Colloid Science CRC Press, ISBN 0824707966
- ^ a b c Gunter Buxbaum, Gerhard Pfaff (2005) Industrial Inorganic Pigments 3d edition Wiley-VCH ISBN 3527303634
- ^ Electronic Conduction of Magnetite (Fe3O4) and its Transition Point at Low Temperatures, Verwey E. J. W., nature 144, 327-328 (1939) doi:10.1038/144327b0
- ^ The Verwey transition - a topical review Walz F. J. Phys.:Condens. Matter (2002) 14, 285-340 doi:10.1088/0953-8984/14/12/203
- ^ a b c Sunggyu Lee (2006) Encyclopedia of Chemical Processing CRC Press ISBN 0824755634
- ^ Synthesis of Iron Oxide Nanoparticles Used as MRI Contrast Agents: A Parametric Study, Babes L, Denizot B, Tanguy G, Le Jeune J.J., Jallet P. Journal of Colloid and Interface Science, 212,2, (1999), 474-482, doi:10.1006/jcis.1998.6053
- ^ Superparamagnetic Magnetite in the Upper Beak Tissue of Homing Pigeons Hanzlik M., Heunemann C., Holtkamp-Rötzler E., Winklhofer M., Petersen N., Fleissner G. BioMetals, (2000), 13, 4, 325-331 {doi|10.1023/A:1009214526685}}