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Starting Materials for Solid State Chemistry Prof. Dr. Thomas Jüstel Research Group TOM, Department of Chemical Engineering (Steinfurt) Münster University of Applied Sciences Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 1 Lithium Li Li: [He]2s1 Chemical composition LiAl[SiO3]2 Atomic number Rel. atomic mass Melting point Boiling point Density 3 6.941 g/mol 181 °C 1342 °C 0.53 g/cm3 Starting materials Li LiClO4 Li2C2O4 Li2CO3 LiF LiNO3 Li2O Li2O2 Li3PO4 Li2SO4 Properties relevant for solid state chemistry hard to handle, prone to oxidation explosive decomposes to Li2O, CO, and CO2 decomposes to Li2O and CO2 water insoluble, fluxing water soluble, may take up some water take up of H2O and CO2 instable water insoluble water soluble, may take up some water Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s Mineral name Spodumene FH Münster Sheet Nr. 2 Beryllium Be Be: [He]2s2 Chemical composition Be3Al2Si6O18 Atomic number Rel. atomic mass Melting point Boiling point Density 4 9.012 g/mol 1287 °C 2469 °C 1.85 g/cm3 Starting materials Be Be(acac)3 Be(NO3)2 BeCl2 BeCO3 BeO BeSO4 Properties relevant for solid state chemistry very toxic, prone to oxidation very toxic water soluble, decomposes to Be4O(NO3)6 hygroscopic decomposes to BeO and CO2 take up of H2O and CO2 water soluble Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s Mineral name Beryll FH Münster Sheet Nr. 3 Boron B B: [He]2s22p1 Chemical composition Na2[B4O6(OH)2] · 3 H2O Atomic number Rel. atomic mass Melting point Boiling point Density 5 10.811 g/mol 2076 °C 3927 °C 2.35 g/cm3 Starting materials α-B BBr3 BCl3 BF3 BF3O(C2H5)2 B2O3 Problem areas in solid state chemistry low reactivity hygroscopic hygroscopic gas, high reactivity reacts violently with H2O take up of H2O and CO2 Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s Mineral name Karnit FH Münster Sheet Nr. 4 Carbon C C: [He]2s22p2 Chemical composition C(sp3) Atomic number Rel. atomic mass Melting point Boiling point Density 6 12.0107 g/mol 3550 °C (d) 4800 °C (d) 3.51 g/cm3 (d) Starting materials Activated C Amorphous C Graphite Problem areas in solid state chemistry reaction with strong oxidants flameable in air inreactive Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s Mineral name Diamond (d) FH Münster Sheet Nr. 5 Nitrogen N N: [He]2s22p3 Chemical composition Si3N4 Atomic number Rel. atomic mass Melting point Boiling point Density 7 14.007 g/mol -210 °C -196 °C 1.12 g/dm3 Starting materials N2 LiN3 NaN3 NH3 NH4NO2 Problem areas in solid state chemistry low reactivity instable, decompses to Li and N2 instable, decompses to Na and N2 decomposes to N2 and H2 explosive Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s Mineral name Silicon nitride FH Münster Sheet Nr. 6 Oxygen O O: [He]2s22p4 Chemical composition ß-PbO2 Atomic number Rel. atomic mass Melting point Boiling point Density 8 15.999 g/mol -218 °C -183 °C 1.33 g/dm3 Starting materials O2 Li2O2 Na2O2 KO2 Problem areas in solid state chemistry low reactivity reacts with CO2 to Li2CO3 and O2 reacts with CO2 to Na2CO3 and O2 decomposes in water to KOH and O2 Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s Mineral name Plattnerite FH Münster Sheet Nr. 7 Fluorine F O: [He]2s22p5 Chemical composition CaF2 Atomic number Rel. atomic mass Melting point Boiling point Density 9 18.998 g/mol -220 °C -188 °C 1.58 g/cm3 Starting materials F2 CF4 LiF MnF4 NaF NaHF2 NH4F KF Problem areas in solid state chemistry low reactivity decomposes at high temp. to CF2 and F2 somewhat hygroscopic decomposes at high temp. to MnF2 and F2 somewhat hygroscopic decomposes at high temp. to NaF and HF decomposes at high temp. to NH3 and HF somewhat hygroscopic Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s Mineral name Fluorite FH Münster Sheet Nr. 8 Sodium Na Na: [Ne]3s1 Chemical composition Na[AlSi3O8] Mineral name Albit Atomic number Rel. Atomic mass Melting point Boiling point Density 11 22.989769 g/mol 97.72 °C 890.0 °C 0.968 g/cm3 Starting materials Na NaCl Na2CO3 NaH Problem areas in solid state chemistry reacts violently with H2O, flameble water soluble soluble in H2O sensitive to moisture, intolerante with alcohol, acids and oxygen air sensitive, incompatible with strong acids oxidant, water soluble, may take up some water decay in H2O incompatible with Tin, Lead and Zinc NaI NaNO3 Na2O Na2SiO3 Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 9 Magnesium Mg Mg: [Ne]3s2 Chemical composition CaMg[CO3]2 Mineral name Dolomit Atomic number Rel. atomic mass Melting point Boiling point Density 12 24.305 g/mol 650 °C 1110 °C 1.738 g/cm3 Starting materials Mg Problem areas in solid state chemistry reacts violently with H2O, avoidable conditions are high temperatures and open flames rather soluble in water, decomposes to MgO at 540 °C hygroscopic instable oxidant, water soluble, may take up some water insoluble in H2O, air sensitive hygroscopic MgCO3 MgCl2 .6H2O MgI2 Mg(NO3)2 .6H2O MgO MgSO4.7H2O Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 10 Aluminium Al Al: [Ne]3s22p1 Chemical composition γ-Al(OH)3, γ/α-AlO(OH) Mineral name Bauxite Atomic number Rel. atomic mass Melting point Boiling point Density 13 26.9815385 g/mol 660.32 °C 2470 °C 2.70 g/cm3 Starting materials Al AlCl3 Problem areas in solid state chemistry oxidizes to Al2O3 soluble in H2O, incompatibility with alcohol and strong oxidizers soluble in H2O caustic, sensitive to hydrolysis water insoluble, irreconcilability with strong acids and bases with bases convicted to aluminates, unsoluble in neutral water, incompatibility with strong acids irritant, soluble in water AlF3 AlN Al2O3 Al(OH)3 Al2(SO4)3 Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 11 Silicon Si Si: [Ne]3s22p3 Chemical composition (Ba,Ca,Na,K,NH4)(Al,B,Si)4O8 Atomic number Rel. atomic mass Melting point Boiling point Density 14 28.085 1414 °C 3265 °C 2.329 g/cm3 Starting materials Si SiCl4 Problem areas in solid state chemistry low reactivity low boiling point, highly reaction with water, irreconcilability with strong acids and bases low reactivity low reactivity decay in water decay in water decay in water Si3N4 SiO2 Si(OCH3)4 (TMOS) Si(OC2H5)4 (TEOS) Si(OC3H7)4 (TPOS) Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s Mineral name Feldspar FH Münster Sheet Nr. 12 Potassium K K: [Ar]4s1 Chemical composition KCl Mineral name Sylvin Atomic number Rel. atomic mass Melting point Boiling point Density 19 39.0983 g/mol 63.38 °C 774 °C 0.856 g/cm3 Starting materials K KCl K2CO3 K2SO4 KNO3 KOH Problem areas in solid state chemistry reacts violently with H2O soluble in H2O, hygroscopic soluble in H2O soluble in H2O oxidant exothermic reaction with H2O, reacts violently with metals and halogens soluble in H2O strong oxidiser, decomposes to KCl and O2 upon heating KSCN KClO4 Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 13 Calcium Ca Ca: [Ar]4s2 Chemical composition CaCO3 Mineral name Calcit Atomic number Rel. atomic mass Melting point Boiling point Density 20 40.078 g/mol 842 °C 1484 °C 1.55 g/cm3 Starting materials Ca CaCO3 CaCl2 .6H2O CaF2 Ca(NO3)2·4H2O CaO CaSO4.2H2O Problem areas in solid state chemistry intense reaction with water, prone to oxidation insoluble in water, decomposes to CaO at 900 °C soluble in water prone to defect formation oxidant reacts with water to Ca(OH)2, picks up CO2 hygroscopic, little soluble in water Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 14 Scandium Sc Sc: [Ar]3d14s2 Chemical composition (Sc,Y)2Si2O7 Atomic number Rel. atomic mass Melting point Boiling point Density 21 44.955908 g/mol 1541 °C 2730 °C 2.985 g/cm3 Starting materials Sc Sc2O3 Sc(NO3)3 ·H2O Sc2(SO4)3·5H2O ScCl3 Sc2(C2O4)3·xH2O ScF3 Problem areas in solid state chemistry flammeable low reactivity oxidant soluble in water hygroscopic toxic Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s Mineral name Thortveitit FH Münster Sheet Nr. 15 Titanium Ti Ti: [Ar]3d24s2 Chemical composition FeTiO3 Mineral name Ilmenit Atomic number Rel. atomic mass Melting point Boiling point Density 22 47.867 g/mol 1668 °C 3260 °C 4.50 g/cm3 Starting materials Ti TiO2 (anatase) TiBr4 Ti(OCH2CH2CH2CH3)4 TiCl2 Problem areas in solid state chemistry insoluble in water low reactivity reacts violently with water flammable, irritand (Titanium(IV)-butoxide) spontaneously combustable, heavy reaction with water, to handle under inter gas flammable, avoid the contact with air, high reactivity TiCl3 Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 16 Vanadium V V: [Ar]3d34s2 Atomic number 23 Rel. atomic mass 50.9415 g/mol Melting point 1910 °C Boiling point 3407 °C Density 6.11 g/cm3 Chemical composition Pb5(VO4)3Cl Mineral name Vanadinite Source: Didier Descouens Starting materials Problem areas in solid state chemistry V oxdises slowly to green vanadium oxide KVO3 water soluble, decomposes to V2O5 NH4VO3 water soluble, decomposes to V2O5 V2O5 water soluble, incompatible with strong acids VCl3 hydrolysis in water Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 17 Chromium Cr Cr: [Ar]3d44s2 Chemical composition FeCr2O4 Mineral name Chromite Atomic number Rel. atomic mass Melting point Boiling point Density 24 51.9961 g/mol 1907 °C 2482 °C 7.14 g/cm3 Starting materials Cr CrO3 (Chrom(VI)-oxide) Cr2O3 (Chrome(III)-oxide) Problem areas in solid state chemistry oxdises slowly to green chromium oxide water soluble, toxic, instable, irritant unsoluble in water and diluted acids, melting point 2435 °C Cr2(SO4)3·H2O CrCl3·6H2O Cr(NO3)3·9 H2O corrosive corrosive oxidising material, not compliable to reducing agents, inaccurate composition Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 18 Manganese Mn Mn: [Ar]3d54s2 Chemical composition Mineral name γ-MnO(OH)2 Manganite Atomic number Rel. atomic mass Melting point Boiling point Density 25 54.938044 g/mol 1246 °C 2100 °C 7.43 g/cm3 Starting materials Mn MnO2 MnO Mn2O3 Mn3O4 MnCl2·4H2O MnCO3 Mn(ClO4)·xH2O Problem areas in solid state chemistry oxdises slowly to green manganese oxide decomposes chlorides and reducing agents irritant soluble in water, not compliable to alkaline materials decomposes in acids strong oxidiser, explosive Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 19 Iron Fe Fe: [Ar]3d64s2 Chemical composition Fe3O4 Mineral name Magnetite Atomic number Rel. atomic mass Melting point Boiling point Density 26 55.845 g/mol 1538 °C 2862 °C 7.874 g/cm3 Starting materials Fe FeO Fe2O3 Fe3O4 FeF3 FeCl3 FeCl2 Problem areas in solid state chemistry flammable, insoluble in water non-stochiometric intolerance with strong acids and peroxides intolerance with strong acids and peroxides intolerance with strong bases, corrosive intolerance with alkali metals and strong oxidants air-sensitive, intolerance with strong oxidants and sodium/potassium Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 20 Cobalt Co Chemical composition CoAsS Co: [Ar]3d74s2 Mineral name Cobaltite Atomic number 27 Rel. atomic mass 58.933194 g/mol Melting point 1495 °C Boiling point 2900 °C Density 8.9 g/cm3 Starting materials Problem areas in solid state chemistry Co flammable, reacts facilitated with acids (hydrogen created) CoO low solubility in water, toxic, intolerance with strong oxidants Co3O4 low solubility in water, toxic, intolerance with reducting agents CoF3 corrosive, intolerance with org. materials and red. Agents Co(NO3)2 soluble in water, oxidising Co(CH3COO)2 soluble in water, toxic Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 21 Nickel Ni Ni: [Ar]3d84s2 Chemical composition (Ni,Fe)9S8 Mineral name Pentlandite Atomic number Rel. Atomic mass Melting point Boiling point Density 28 58.6934 g/mol 1455 °C 2730 °C 8.908 g/cm3 Starting materials Ni Problem areas in solid state chemistry toxic, intolerance with oxygen, hydrogen, acids, fluor, org. solvents and aluminium toxic, soluble in water, intolerance with peroxides toxic, unsoluble in water, intolerance with strong acids toxic, intolerance with strong acids toxic, intolarance with org. materials, metal powder strong reducting agents NiCl2 NiO Ni(OH)2 Ni(NO3)2·6H2O NiBr2 Starting Materials Prof. Dr. Thomas Jüstel toxic, intolerance with strong acids and oxidising agents T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 22 Copper Cu Cu: [Ar]3d104s1 Chemical composition Cu(OH)2.CuCO3 Mineral name Malachite Atomic number Rel. Atomic mass Melting point Boiling point Density 29 63.546 g/mol 1455 °C 2730 °C 8.92 g/cm3 Starting materials Cu Cu2O CuO CuCl2 Cu(OH)2 Cu(NO3)2·6H2O CuSO4 CuSO4·5H2O Problem areas in solid state chemistry soft metal, difficult to mill toxic, instable in water toxic, unsoluble in water toxic, soluble in water toxic, intolerance with strong acids toxic, decomposes to CuO upon heating emetic, decomposes to CuO and SO3 above 340 °C decomposes to CuSO4·3H2O at 95 °C & to CuSO4·H2O at 116 °C Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 23 Zinc Zn Zn: [Ar]3d104s2 Chemical composition ZnS Mineral name Sphalerite Atomic number Rel. Atomic mass Melting point Boiling point Density 30 65.38 g/mol 420 °C 907 °C 7.14 g/cm3 Starting materials Zn ZnO Zn(OH)2 ZnS Zn(NO3)2 ZnSO4 ZnSO4·7H2O Problem areas in solid state chemistry prone to oxidation dissolves in strong acids and bases dissolves in strong bases decomposes in strong acids decomposes to ZnO upon heating decomposes to ZnO, O2, and SO3 above 680 °C decomposes to ZnSO4·6H2O at 39 °C, to CuSO4·H2O at 70 °C, and then to ZnSO4at 240 °C Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 24 Gallium Ga Ga: [Ar]3d104s24p1 Chemical composition Ga(OH)3 Atomic number Rel. Atomic mass Melting point Boiling point Density 31 69.723 g/mol 30 °C 2204 °C 5.91 g/cm3 Starting materials Ga Ga2O3 Ga(OH)3 GaF3 GaCl3 Ga(NO3)3 Ga2(SO4)3 Problem areas in solid state chemistry prone to oxidation dissolves in strong acids and bases decomposes to GaO(OH) at 170 °C insoluble in water, sublimes at 800 °C reacts heavily with water decomposes to Ga2O3 at 110 °C decomposes to Ga2O3 and SO3 Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s Mineral name Soehngeite FH Münster Sheet Nr. 25 Germanium Ge Ge: [Ar]3d104s24p2 Chemical composition Cu26Fe4Ge4S3 Mineral name Germanite Atomic number Rel. Atomic mass Melting point Boiling point Density 32 72.64 g/mol 938 °C 2820 °C 5.32 g/cm3 Starting materials Ge GeO2 GeF4 GeCl4 K2GeF6 Bi4Ge3O12 Problem areas in solid state chemistry prone to oxidation dissolves in strong bases gaseous compound colourless liquid, reacts heavily with water soluble in hot water insoluble, very stable oxide, shows strong scintillation Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 26 Rubidium Rb Rb: [Kr]5s1 Chemical composition RbCl Mineral name by-component in Carnallite Atomic number Rel. atomic mass Melting point Boiling point Density 38 85.468 g/mol 39 °C 688 °C 1.53 g/cm3 Starting materials Rb RbCl Rb2CO3 Rb2SO4 RbNO3 RbOH Problem areas in solid state chemistry reacts violently with H2O soluble in H2O, hygroscopic soluble in H2O soluble in H2O oxidant, soluble in H2O exothermic reaction with H2O, reacts violently with metals and halogens strong oxidiser, decomposes to RbCl and O2 upon heating RbClO4 Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 27 Strontium Sr Sr: [Kr]5s2 Chemical composition SrCO3 Mineral name Strontianit Atomic number Rel. atomic mass Melting point Boiling point Density 38 87.62 g/mol 777 °C 1412 °C 2.63 g/cm3 Starting materials Sr SrCO3 SrCl2·6H2O SrF2 Sr(NO3)2·4H2O SrO SrSO4 Problem areas in solid state chemistry intense reaction with water, prone to oxidation insoluble in water, decomposes to SrO at 1270 °C soluble in water prone to defect formation oxidant, may pick up some water Reacts with water to Sr(OH)2, picks up CO2, melts at 2430 °C insoluble in water, decomposes to Starting Materials Prof. Dr. Thomas Jüstel T OM Tai l or ed Opt i cal Mat er i al s FH Münster Sheet Nr. 28