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1) Elemental Form e.g. Ag, Au, Pt – noble metals. 2) Aluminosilicates and Silicates Metal + Al, Si, O e.g. Beryl = Be3Al2Si6O18 Hard to extract metals. 3) Nonsilicate Minerals Oxides – Al2O3, TiO2, Fe2O3 Sulfides – PbS, ZnS, CuFeS2 Carbonates – CaCO3
the process of obtaining a metal from its ores
1) Preliminary treatment to concentrate ore: Floatation. Hindered settling Magnetic separation 2) Further purification and reduction to obtain the metal in its elementary state: Hydrometallurgy – leaching. Pyrometallurgy – roasting, smelting. Electrometallurgy. 3) Final purification and refining of the metal.
2 .Hydrometallurgy Metal is refined from ore using aqueous reactions Example: Dissolve Au by forming complex ion with CN− 4Au(s) + 8CN−(aq) + O2(g) + 2H2O(l) → 4[Au(CN)4]−(aq) + 4OH−(aq) Kf[Au(CN)4]− = 2x1038 Pure gold is then obtained by reduction: 2Au(CN)4−(aq) + 3Zn(s) → 3Zn2+(aq) + 8CN-(aq) + 2Au(s) Similar process for silver (dissolves as [Ag(CN)2]−) SILVER Found as pure metal (Ag) or sulfide (Ag2S) [Ag(CN)2]− Kf = 1 x 1021 4Ag + 8CN−(aq) + O2 + 2H2O → 4[Ag(CN)2](aq) + 4OH−(aq) Ag2S + 4CN−(aq) → 2[Ag(CN)2]−(aq) + S2−(aq) Practice problem: Use Kf. with E0 and Ksp values (from tables) to calculate Keq for these reactions.
3 . thin sheets of pure Cu are the cathodes. • The metallic impurities do not plate out on the cathode. • Acidic copper sulfate is used as the electrolyte. • The voltage across the electrodes is designed to produce copper at the cathode. • Metal ions are collected in the sludge at the bottom of the cell.COPPER Copper containing ore (CuFeS2) is stirred with aqueous H2SO4 + O2 2CuFeS2(s)+2H+(aq)+SO42−(aq) + 4O2(g) → 2Cu2+(aq) + 2SO42-(aq) + Fe2O3(s) + 3S(s) + H2O \ / 2CuSO4(aq) ↓ Electrolyzed to Cu Electrometallurgy Electrorefining of Copper • Slabs of impure Cu are used as anodes.
primary ore for Al impurities: SiO2 Fe2O3 Bayer Process • Bayer process: bauxite (~ 50 % Al2O3 ) is concentrated to produce aluminum oxide. SiO2 do not dissolve • Lower the pH so that Al(OH)3(s) precipitates Takes advantage of the amphoteric nature of Al oxide. P Al2O3 dissolves [Al(H2O)2(OH)4]− hydrated metal complex • Filter out solids Fe2O3. 4 . • Dissolve bauxite in strong base (NaOH) at high T.xH2O. • Bauxite: Al2O3.Electrometallurgy Hydrometallurgy of Aluminum • Aluminum is the second most useful metal.
• Hall: use purified Al2O3 in molten cryolite (Na3AlF6. Electrometallurgy of Al The Hall Process Anode: C(s) + 2O2-(l) → CO2(g) + 4eCathode: Al3+(l) + 3e. melting point 1012°C).→ Al(l) 5 . Problem: Al2O3 melts at 2000°C and it is impractical to perform electrolysis on the molten salt.Electrometallurgy of Aluminum Hall process is used to obtain aluminum metal. Anode: C(s) + 2O2−(l) → CO2(g) + 4e− Cathode: 3e− + Al3+(l) → Al(l) • The graphite rods are consumed in the reaction.
CaCl2 is used to lower the melting point of NaCl from 804°C to 600°C. Less active metals are often reduced HgS(s) + O2(g) → Hg(l) + SO2(g) 6 . At the cathode (iron): 2Na+(aq) + 2e− → 2Na(l) At the anode (carbon): 2Cl-(aq) → Cl2(g) + 2e− All metals in Groups I and II are obtained by molten salt electrolysis Pyrometallurgy • Pyrometallurgy: using high temperatures to obtain the free metal. Converts carbonates and sulfides to oxides: 2 ZnS(s)+ 3O2(g) →2ZnO(s) + SO2(g) 3. Calcination is heating of ore to eliminate a volatile product: PbCO3(s) → PbO(s) + CO2(g) Roasting is oxidation of the ore: 1. Burns off organic matter. 2.Electrometallurgy of Sodium Sodium is produced by electrolysis of molten NaCl.
Pyrometallurgy The Pyrometallurgy of Iron • sources of iron: hematite Fe2O3 and magnetite Fe3O4. • Iron Ore: Iron oxides and SiO2 • Add limestone and coke Coke is coal that has been heated to drive off the volatile components. Blast Furnace 7 .
Pyrometallurgy of Fe • Reactions 2C(s) + O2(g) → 2CO(g) + heat heat + C(s) + H2O(g) → CO(g) + H2(g) Fe3O4(s) + 4CO(g) → 3Fe(l) + 4CO2(g) Fe3O4(s) + 4H2(g) → 3Fe(l) + 4H2O(g) Coke: 1) heats furnace 2) reduces iron Why is limestone (CaCO3) added? Pyrometallurgy of Fe • At high T CaCO3 → CaO + CO2 CaO Metal + nonmetal → oxide oxide basic acidic + SiO2 → CaSiO3(l) slag Limestone (CaCO3) removes SiO2 (and other) impurities slag floats on Fe(l). protects it from oxidation by O2 Slag: cement cinder block building materials 8 .
• Metals are crystals in which every atom has 8 or 12 neighbors. lightweight and strong. Co5Sm – permanent magnets in headsets. • There are not enough electrons for the metal atoms to make electron pair bonds to each neighbor. Alloys: Mixtures of metals . good conductors of heat and electricity.Metals and Alloys Physical Properties of Metals • Important physical properties of pure metals: malleable. Cr3Pt – razor blades.g. Nb3Sn – superconductors 9 .often have improved physical properties ALLOYS 1) Homogeneous (solution) alloys: Mixed at the atomic level . 3) Intermetallic alloys – compounds of two different metals having definite proportions: e. Fe3C).one solid phase 2) Heterogeneous alloy: Non-homogeneous solid (e. Au3Bi. ductile. Ni3Al – jet engines. pearlite steel has two phases: almost pure Fe and cementite.g.
Interstitial alloy – when a non-metal is present in the “holes” in a metal crystal lattice. – Interstitial atoms are smaller – The alloy is much stronger than the pure metal (increased bonding between nonmetal and metal). – metals must have similar atomic radii. – Example steel (contains up to 3 % carbon). – metals must have similar bonding characteristics. 10 .Homogeneous (solution) alloys substitutional interstitial Cr in Fe C in low-carbon steel SOLUTION ALLOYS Two kinds: Substitutional alloy – when one metal substitutes for another in the structure.
45%) annealed Al 4 x 103 pure (99.45%) cold drawn Al 24 x 103 Al alloy . etc. Non-directional bonding. you go to work for Boeing. you can triple cargo load (to 150 tons). yield stress. large number of nearest neighbor atoms → metallic structures readily tolerate “mistakes” vacancy (missing atom) point defect Not important dislocation (extra plane of atoms) line defect Very important 11 . “perfect” single crystal Al as a yield stress of ca. Material Tensile Yield Stress (psi) pure (99.Mechanical Properties of Metals and Alloys Hypothetical situation: Upon graduation. Your job – select a high-strength Al alloy for jet airplanes. Airplane: 500 tons } 50 tons cargo 150 tons plane structure 300 tons fuel If you can triple the alloy strength. 106 psi! Defects in Metallic Crystals Defects are responsible for important mechanical properties of metals: malleability.precipitated. hardened 50 x 103 big improvement But.
e. jet turbine blade Impossible for large items (airplane wings.g. bridges…) 2. girders.g.moves dislocations to grain boundaries planar defect (stronger under stress) “Cold working” or “drawing” of a metal increases strength and brittleness (e. horseshoes) 12 . iron beams. How? 1. Use annealed single crystals (expensive) Some specialty applications – e... airplane wings Need to minimize movement of dislocations. knife blades.Dislocations Move Under Stress shear force Key point: Moving a dislocation breaks/makes a line of metal-metal bonds (easy) Shearing a perfect crystal means we have to break a plane of bonds (requires much more force) Hardening of Alloys Structural alloys . knives.g. Work hardening .
Metal Crystal Structures Body-centered cubic (bcc) 8 nearest neighbors Not close packed Close packed (hexagonal or cubic) hcp ccp 13 . dislocations move (metal becomes more malleable) 3. Alloying – homogeneous or heterogeneous Impurity atoms or phases “pin” dislocations.) Work Hardening and Annealing have opposite effects Annealing: crystal grains grow.Hardening of Alloys (contd.
“speed bumps” Cu (fcc) Zn (hcp) CuZn alloy (brass) Amorphous (Glassy) Alloys Metals are typically polycrystalline Amorphous alloys have superior mechanical properties because dislocations cannot move. etc. etc.Malleability of Metals and Alloys Some metals are soft and ductile (Au. Al. Ag.its.12-coordinate . Cu.edu/%7Evitreloy/development. Cr.8-coordinate . http://www.hard close packed (fcc and hcp) . Two types: body centered cubic (bcc) . W.htm 14 .) Others are hard (Fe.caltech.) Why? Crystal structure is important.soft Close-packed planes slip easily Non-close packed .
iron is close packed (fcc) . Stainless Steel: 73% Fe. iron has bcc structure .6-1.6% C – tough used in girders and rails.soft Can be worked into various shapes when hot Steelmaking: Carbon steel contains ~ 1% C by weight (dissolves well in fcc iron but not in bcc) Slow cooling (tempering): fcc Fe/1%C → mixture of bcc Fe and Fe3C (pearlite) Fe3C (cementite) grains stop movement of dislocation in high carbon steel .very hard material STEELS Steel: Fe (pig iron) + small amounts of C Mild Steel: <0.2% C – malleable and ductile used in cables. 18% Cr. tools.2-0. 1% C.Iron and Steels Below 900oC. nails.5% C – very tough used in knives. and springs. and chains. 8% Ni. 15 . High Carbon Steel: 0.“hard as nails” Above 900oC. Medium Steel: 0.
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