Oxides and Hydroxides
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1 Descriptive Mineralogy Oxides and Hydroxides Classification of the Minerals Non-Silicates Native Elements Halides Sulfides Oxides Hydroxides Carbonates Sulfates Phosphates Silicates Orthosilicates Sorosilicates Cyclosilicates Chain Silicates Layer Silicates Tektosilicates Hemioxides Cuprite (Cu 2 O) Ice (H 2 O) Monoxides Periclase (MgO) Wüstite (FeO) Manganosite (MnO) Lime (CaO) Zincite (ZnO) Bromellite (BeO) Tenorite (CuO) Simple Oxides Sesquioxides Corundum (Al 2 O 3 ) Hematite (Fe 2 O 3 ) Bixbyite (Mn 2 O 3 ) Dioxides Rutile (TiO 2 ) Anatase (TiO 2 ) Brookite (TiO 2 ) Cassiterite(SnO 2 ) Pyrolusite(MnO 2 ) Simple Oxides Hemi-Oxides (M2O) Ice (H2O) Hexagonal Cuprite (Cu2O) Why not Na2O? Na radius too large Na has no covalent orbitals available Hemi-Oxides (M2O) Na 2 O occurs as a mineral A. True B. False 1
2 Cuprite Cu 2 O Occurrence: Low Temp Hydrothermal (Supergene) Use: Minor ore of Cu Cuprite Cu 2 O Occurrence: Low Temp Hydrothermal (Supergene) Strongly covalent O SP 3 Cu SP Use: Minor ore of Cu Ice H 2 O Ice H 2 O Crystal System Hexagonal Point Group 6/mmm Space Group P6 3 /mmc Optical Uniaxial Color Colorless Luster Vitreous Hardness 1.5 Density 0.95 Ice H 2 O snow morphology Ice H 2 O High Pressure Phase Diagram 2
3 Ice H 2 O What s Wrong Here? Monoxides (MO) Rocksalt oxides Periclase MgO - Wüstite FeO Manganosite MnO Lime CaO Bunsenite NiO Zincite oxides: Zincite ZnO, Bromellite BeO Other monoxides: TenoriteCuO, Montroydite HgO Rocksalt Oxides MgO -FeO -MnO -CaO Crystal System Point Group Space Group Optical Cubic 4/m-32/m Fm3m Isotropic Periclase - Wüstite MgO - FeO Periclase MgO Lower mantle phase Mg 2 SiO 4 = MgSiO 3 + MgO Ringwoodite = Perovskite + periclase 3
4 Zincite Group ZnO Zincite, BeO Bromellite Crystal System Hexagonal Point Group 6mm Space Group P6 3 mc Optical Uniaxial Extreme Piezoelectric Uses: Transducers Other Monoxides CuO Tenorite HgO Montroydite Oxidized hydrothermal deposits Covalent Bonding Irregular coordination Sesquioxides (M2O3) Corundum Group Corundum Al2O3 Hematite Fe2O3 Karelianite V2O3 and Eskolaite Cr2O3 Other Sesquioxides Bixbyite Mn2O3 Corundum Al 2 O 3 Crystal System Trigonal Point Group -32/m Space Group R-3c Optical Uniaxial Color Colorless Luster Vitreous Hardness 9 Density 4.02 Corundum Al 2 O 3 Corundum Al 2 O 3 4
5 Hematite Fe 2 O 3 Hematite Fe 2 O 3 Crystal System Trigonal Point Group -32/m Space Group R-3c Optical Nearly opaque Color Red/Metallic Luster Earthy/metallic Hardness 6 Density 5.26 Bixbyite Mn 2 O 3 Crystal System Cubic Point Group 4/m-32/m Space Group Ia3 Optical Nearly opaque Color Red/Metallic Luster Earthy/metallic Hardness 6 Density 4.95 Dioxides Rutile Group Rutile TiO2; Anatase; Brookite Cassiterite SnO2 Pyrolusite MnO2 Stishovite SiO2 Uraninite (UO2) and Thorianite (ThO2) Baddeleyite ZrO2 Rutile TiO 2 Pyrolusite MnO 2 Cassiterite SnO 2 Stishovite SiO 2 Rutile TiO 2 Crystal System Tetragonal Point Group 4/mmm Space Group P4 2 /mnm Optical Nearly opaque Color Red Luster Adamantine Hardness 6 Density
6 Anatase and Brookite TiO 2 Cassiterite SnO 2 Uraninite UO 2 Crystal System Cubic Point Group 4/m-32/m Space Group Fm-3m Optical Nearly opaque Color Black Luster Submetallic Hardness 5.5 Density 7-9 Occurrence Lo T Hyd Roll-front Use: Major Ore of U Uraninite UO 2 The Major ore of U U4+ or U6+? Same structure as fluorite U 6+ is soluble U 4+ is insoluble U is mobilized by oxidation; immobilized by reduction Roll-front deposits. Natural reactors Simple Oxides Complex Oxides Two or more different cations Spinel Group: M2TO4 Ilmenite Group : FeTiO3 Pseudobrookite Group : A2BO5 Perovskite Group : CaTiO3 High Pressure silicate analogues 6
7 Spinel Group Spinel MgAl2O4 Hercynite FeAl2O4 Chromite FeCr2O4 Magnesiochromite MgCr2O4 Magnetite Fe 2+ Fe 3+ 2O4 Magnesioferrite MgFe2O4 Gahnite ZnAl2O4 Ulvospinel TiFe2O4 Ringwoodite Mg2SiO4 Space Group Fd3m Edge sharing octahedra Cell edge ~8.5Å Two octahedra per Tetrahedron MgAl 2 O 4 (Normal) or Al (MgAl) O 4 (Inverse) Spinel Structure Ringwoodite (spinel) γ-(mgfe) 2 SiO 4 Ilmenite Group Ilmenite FeTiO 3 Dark blue color km ~5% Earth Geikielite MgTiO 3 Akimotoite MgSiO 3 Ilmenite Structure FeTiO 3 Corundum Structure Space Group R-3 Alternating layers of Fe and Ti Octahedra Face-sharing Octahedra Dense Pseudobrookite Group Pseudobrookite Fe 2+ Ti2O5 Ferro-pseudobrookite TiFe 3+ 2O5 Armalcolite (Mg,Fe 2+ )Ti2O5 7
8 Pseudobrookite Structure Accessory Oxides Space Group Bbmm M1 dark M2 lighter Open Structure Accessory Oxides Perovskite Perovskite CaTiO 3 MgSiO 3 (Lower mantle phase) Perovskite Structure Pseudo-cubic Orthorhombic Space Group Pbnm Hydroxides Brucite Mg(OH) 2 Gibbsite Al(OH) 3 Boehmite and Diaspore AlO(OH) Bauxite (Mixed Al hydroxides) Goethite FeO(OH) (+Lepidochrosite) Limonite Fe(OH) 3 8
9 Gibbsite Al(OH) 3 Di-octahedral Brucite Mg(OH) 2 Tri-octahedral Two out of three possible octahedral sites occupied Tri-valent cations All three possible octahedral sites occupied Divalent cations 9
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