Extraction of Metals

-the chemistry behind

http://www.chem.iitb.ac.in/~rmv/ch102/extraction.pdf

Oxygen Silicon Aluminum Iron Calcium Sodium Potassium Magnesium Titanium Hydrogen Phosphorus Carbon Manganese Sulfur Barium Chlorine Chromium Fluorine Zirconium Nickel

46.71 27.69 8.07 5.05 3.65 2.75 2.58 2.08 0.62 0.14 0.13 0.094 0.09 0.052 0.05 0.045 0.035 0.029 0.025 0.019

1774 1824 1825 ancient 1808 1807 1807 1755 1791 1776 1669 ancient 1774 ancient 1808 1774 1797 1886 1789 1751

92 % 99.5 %

All other elements = 0.03 %

99.97 %

Need for efficient separation techniques

Methods of Separation / Extraction 1. Mechanical separation 2. Thermal decomposition 3. Displacement of one element by other 4. High temperature chemical reduction 5. Electrolytic reduction

Mechanical separation Free elemental form unreactive elements Coinage & Pt metals Gold; 19.3 g/cm-3, separated by panning

Thermal decomposition
Unstable compounds Ag2O 2Ag + O2 Constituent elements

Marsh test: As, Sb salt + Zn/H2SO4 As/SbH3 Silver mirror of the metal Decomposition of NaN3 to Na and N2 Mond process; production of nickel van Arkel process

Displacement of one element by other

In principle, any element may be displaced by another element which has more negative Eo in electrochemical series. Cu2+ + Fe
-0.44

Fe2+ + Cu
+0.16

Cl2 + 2Br+1.36

2Cl- + Br2

+1.09

High temperature chemical reduction

1. Many metals are found as their oxides 2. Oxide Ores: Directly reduced (smelted) to the metal. General reducing agents: C , Al, Si, H2. Carbon is the most widely used reducing agent (can form carbide) 3. Sulfide Ores: First roasted to convert them to oxide and then reduced to the metal (for thermodynamic reasons oxides rather than sulfides used) (SELF REDUCTION) 4. Other metals as reducing agents
(all points will be elaborated)

Electrolytic reduction
1. 2. Electron the strongest known reducing agent. Highly electropositive metals, e.g. alkaline earth metals are produced this way (Electrolytic reduction of their fused halides) 3. Ionic materials (salts) are electrolyzed reduction at cathode 4. Excellent method, gives pure metal, but expensive

Methods of Separation / Extraction 1. Mechanical separation 2. Thermal decomposition 3. Displacement of one element by other 4. High temperature chemical reduction 5. Electrolytic reduction

High-T chemical reduction Thermodynamic considerations .

1. 2. Used to identify which reactions are spontaneous under the prevailing conditions. To choose most economical reducing agent and reaction condition Criterion for spontaneity Go = RT ln K Negative Go corresponds to K > 1; favorable reaction Kinetics is not important as reductions are done at high. temp & fast

High-T chemical reduction Thermodynamic considerations .

Go = Ho - TS For the formation of metal oxide, 2M(s) + O2(g) 2MO(s) S is negative; because oxygen gas is used up. If temperature is raised, TS becomes more negative Thus the free energy change (Go) increases with an increase in temperature

Go = Ho - TS

The free energy changes that occur when one gram molecule of a common reactant (O2) is used, is plotted against temperature. This graph is called Ellingham Diagram

Properties of Ellingham diagram

All metal oxide curves slop upwards If materials melt / vaporize, the slope changes When the curve crosses Go = 0, decomposition of oxide begins (Ag, Au, Hg) Electropositive metal curves are at the bottom of the diagram Any metal will reduce the oxide of other metal which is above in Ellingham diagram (the Go will become more negative by an amount equal to the difference between the two graphs at a particular temperature)

Carbon as the reducing agent

Go = Go(C,CO) - Go(M,MO)

CO(g) + O2(g)

CO2(g)

(S ve)

710 oC

C + O2(g)

CO2(g)

(S constant)

C + O2(g)

CO(g)

(S +ve )

When C CO line is below M MO line, When C CO2 line is below M MO line,

C reduces the MO and produces CO. C reduces the MO and produces CO2.

When CO CO2 line is below M MO line, CO reduces the MO and produces CO2.

The three curves intersect at 710 oC Below 710 oC, CO is better reducing agent. Above 710 oC, carbon is better reducing agent.

Using ED, find out what is the lowest temp. at which ZnO can be reduced to Zn by carbon. What is the overall reaction?

What is the minimum temp. required for the reduction of MgO by carbon?

Thermit Process Sacrificial Method

Cr2O3 Go (kJmol-1)
-600 -800 -1000 -1200

Al2O3

Temperature (oC) 4/3 Al + O2 4/3 Cr + O2 2/3 Al2O3 2/3 Cr2O3 4/3 Cr + 2/3 Al2O3 H = -266 Kcal/mol H = -180 Kcal/mol H = -86 Kcal/mol

4/3 Al + 2/3 Cr2O3

G H (since S is similar)

Thermit Process Details

4/3 Al + 2/3 Cr2O3 4/3 Cr + 2/3 Al2O3 H = -86 Kcal/mol G is negative at all temperatures. S is very small since there are no gaseous products Hence, G is approximately same at different temperatures However Al reduction requires higher temperature to trigger off. Kinetic factor: Activation energy Priming the reaction with Mg-ribbon and barium peroxide / a KNO3+S+Al pellet is necessary. The reduction is usually exothermic. Once initiated, the whole mass gets reduced spontaneously. Alloy formation with Al can take place in some cases.

H2 -Poor reducing agent

H2O Go (kJmol-1) H2 MO

Temperature (oC)
2H2(g) + O2(g) 2H2O; entropy decreases points upwards and runs parallel to many MO curves. Up above in the diagram Metal hydride formation Dissolved (interstitial) hydrogen poor properties

Reduction of Metal Sulfides

Many metals, which are chemically soft, occur as sulfide ores. e.g. Cu, Hg, Zn, Fe, etc. Carbon is not a good reducing agent to for sulfide ores. MS + C CS2 has no slope in ED. First roasted to MO and then reduced to metal 2MS + 3O2 2MO + 2SO2 C Self reduction: CuS [CuS + CuO] Cu + SO2

H2 is also a poor reducing agent for metal sulfides.

Ellingham diagram Metal Sulfides

Hgs -40 - 80 - 120 SO2 - 160 - 200 - 240 0 1000 oC 2000 oC Cas H 2S CS2 Zns Fes MnS Go( KCal/ mole S2(g) )

Ellingham diagram Metal Halides

CCl4 SnCl4 TiCl4 CF4 ZrCL4 MgCl2 -40 NaCl HF NaF MgCl2 UF4 CaF2 -100
Gfo

HCl

NbF5 CaCl2

300oC 500oC

1500oC

2500oC

Purification of Elements
Special attention to metals
1.

Fusion, distillation, crystallization.

Fusion removed adsorbed gases (SO2, O2, etc.) Distillation of volatile metals to remove impurities Fractional distillation of OsO4 and RuO4 from other Pt-metals in the presence of oxidising agents. Fractional Crystallization of Pt/Ir as (NH4)2MCl6

2.

Oxidative refining
When impurities have more affinity to oxygen than the metal. Pig iron contains C, Si, P, and Mn, which can be purified by blowing air through the molten metal in Bessimer Convertor. CO, SiO2, P4O10, MnO formed combine with added CaO to give slag - Ca3(PO4)2, MnSiO3

3.

Thermal Decomposition
Carbonyl (Mond process) for purification of Fe, Ni, etc. Van Arkel de Boers filament growth method (ZrI4, BI3, etc.) Decomposition of Hydrides (AsH3, SbH3 etc.)

Purification of Elements
Special attention to metals

4. Electrolytic refining 5. Zone refining 6. Chromatographic methods 7.Solvent Extractions 8. Ion-Exchange Methods