Manganese(II,III) oxide

Manganese(II,III) oxide is the manganese oxide with the chemical compound with formula Mn₃O₄. Manganese is present in two oxidation states, +2 and +3, and the formula is sometimes written as MnO·Mn₂O₃. Mn₃O₄ is found in nature as the mineral hausmannite.

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Manganese(II,III) oxide
Names

IUPAC name manganese(II) dimanganese(III) oxide
Other names Manganese tetroxide Manganese oxide Manganomanganic oxide Trimanganese tetraoxide Trimanganese tetroxide^[1]
Identifiers
CAS Number	1317-35-7^Y
3D model (JSmol)	Interactive image
ChemSpider	34986713
ECHA InfoCard	100.013.879
EC Number	215-266-5
PubChem CID	90479253
RTECS number	OP0895000
UNII	70N6PQL9JS^Y
CompTox Dashboard (EPA)	DTXSID9051660
InChI InChI=1S/3Mn.4O Key: GVNFAUMGUISVJW-UHFFFAOYSA-N
SMILES [Mn]=O.O=[Mn]O[Mn]=O
Properties
Chemical formula	Mn₃O₄ MnO·Mn₂O₃
Molar mass	228.812 g/mol
Appearance	brownish-black powder^[1]
Density	4.86 g/cm³
Melting point	1,567 °C (2,853 °F; 1,840 K)
Boiling point	2,847 °C (5,157 °F; 3,120 K)
Solubility in water	insoluble
Solubility	soluble in HCl
Magnetic susceptibility (χ)	+12,400·10⁻⁶ cm³/mol
Structure
Crystal structure	Spinel (tetragonal), tI28
Space group	I4₁/amd, No. 141
Hazards
GHS labelling:
Pictograms	‹ The template below (GHS exclamation mark) is being considered for merging with GHS pictogram. See templates for discussion to help reach a consensus. › ‹ The template below (GHS health hazard) is being considered for merging with GHS pictogram. See templates for discussion to help reach a consensus. ›
Signal word	Warning
Hazard statements	H315, H319, H335, H361
Precautionary statements	P203, P261, P264, P264+P265, P271, P280, P302+P352, P304+P340, P305+P351+P338, P318, P319, P321, P332+P317, P337+P317, P362+P364, P403+P233, P405, P501
NIOSH (US health exposure limits):
PEL (Permissible)	C 5 mg/m³^[1]
REL (Recommended)	None established^[1]
IDLH (Immediate danger)	N.D.^[1]
Thermochemistry
Std molar entropy (S^⦵₂₉₈)	149 J·mol⁻¹·K⁻¹^[2]
Std enthalpy of formation (Δ_fH^⦵₂₉₈)	−1387 kJ·mol⁻¹^[2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Y verify (what is ^YN ?) Infobox references

Preparation

Mn₃O₄ formed when any manganese oxide is heated in air above 1000 °C.^[3] Considerable research has centred on producing nanocrystalline Mn₃O₄ and various syntheses that involve oxidation of Mn^II or reduction of Mn^VI.^[4]^[5]^[6]

Reactions

Mn₃O₄ has been found to act as a catalyst for a range of reactions e.g. the oxidation of methane and carbon monoxide;^[7]^[8] the decomposition of NO,^[9] the reduction of nitrobenzene^[10] and the catalytic combustion of organic compounds.^[11]

Structure

Mn₃O₄ has the spinel structure, where the oxide ions are cubic close packed and the Mn^II occupy tetrahedral sites and the Mn^III octahedral sites.^[3] The structure is distorted due to the Jahn–Teller effect.^[3] At room temperature Mn₃O₄ is paramagnetic, below 41-43 K, it is ferrimagnetic^[12] although this has been reported as reducing in nanocrystalline samples to around 39 K.^[13]

Uses

Mn₃O₄ is sometimes used as a starting material in the production of soft ferrites e.g. manganese zinc ferrite,^[14] and lithium manganese oxide, used in lithium batteries.^[15]

Manganese tetroxide can also be used as a weighting agent while drilling reservoir sections in oil and gas wells.^{[citation needed]}

References

[1]
NIOSH Pocket Guide to Chemical Hazards. "#0381". National Institute for Occupational Safety and Health (NIOSH).
[2]
Zumdahl, Steven S. (2009). Chemical Principles 6th Ed. Houghton Mifflin Company. p. A22. ISBN 978-0-618-94690-7.
[3]
Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. doi:10.1016/C2009-0-30414-6. ISBN 978-0-08-037941-8.
[4]
Hausmannite Mn₃O₄ nanorods: synthesis, characterization and magnetic properties Jin Du et al. Nanotechnology, (2006),17 4923-4928, doi:10.1088/0957-4484/17/19/024
[5]
One-step synthesis of Mn₃O₄ nanoparticles: Structural and magnetic study Vázquez-Olmos A., Redón R, Rodríguez-Gattorno G., Mata-Zamora M.E., Morales-Leal F, Fernández-Osorio A.L, Saniger J.M. Journal of Colloid and Interface Science, 291, 1, (2005), 175-180 doi:10.1016/j.jcis.2005.05.005
[6]
Use of Carbonaceous Polysaccharide Microspheres as Templates for Fabricating Metal Oxide Hollow Spheres Xiaoming Sun, Junfeng Liu, Yadong Li, Chemistry - A European Journal,(2005), 12, 7, 2039 – 2047, doi:10.1002/chem.200500660
[7]
The reduction and oxidation behaviour of manganese oxides Stobhe E.R, de Boer A.D., Geus J.W., Catalysis Today. (1999), 47, 161–167. doi:10.1016/S0920-5861(98)00296-X
[8]
An in situ XRD investigation of singly and doubly promoted manganese oxide methane coupling catalysts.Moggridge G.D, Rayment T, Lambert R.M. Journal of Catalysis, (1992), 134, 242–252, doi:10.1016/0021-9517(92)90225-7
[9]
NO Decomposition over Mn₂O₃ and Mn₃O₄. Yamashita T, Vannice A., Journal of Catalysis (1996),163, 158–168, doi:10.1006/jcat.1996.0315
[10]
Selective reduction of nitrobenzene to nitrosobenzene over different kinds of trimanganese tetroxide catalysts.Wang W.M., Yang Y.N., Zhang J.Y., Applied Catalysis A. (1995), 133, 1, 81–93 doi:10.1016/0926-860X(95)00186-7
[11]
Catalytic combustion of C3 hydrocarbons and oxygenates over Mn₃O₄. Baldi M, Finocchio E, Milella F, Busca G., Applied Catalysis B. (1998), 16, 1, 43–51, doi:10.1016/S0926-3373(97)00061-1
[12]
Magnetic Structure of Mn₃O₄ by Neutron Diffraction Boucher B., Buhl R., Perrin M., J. Appl. Phys. 42, 1615 (1971); doi:10.1063/1.1660364
[13]
Synthesis of superparamagnetic Mn₃O₄ nanocrystallites by ultrasonic irradiation I.K. Gopalakrishnan, N. Bagkar, R. Ganguly and S.K. Kulshreshtha Journal of Crystal Growth 280, 3-4, (2005), 436-441, doi:10.1016/j.jcrysgro.2005.03.060
[14]
Method of making manganese-zinc ferrite U.S Patent number: 4093688 (1978) Arthur Withop, Roger Emil Travagli
[15]
Process for preparing lithium manganese oxides, U.S Patent number: 6706443,(2004), Horst Krampitz, Gerhard Wohner

Manganese(II,III) oxide

Preparation

Reactions

Structure

Uses

References

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