Metallurgy

CHEMICA Chemistry Classes _________By DheerendraShrivastva (DS Sir)
Metallurgy
(Principles of Isolation of Metals)
Definition:
Isolation of metals from ores in large scale in conveniently and economical way is called metallurgy.
Minerals:
These are substances present in earth crust in which metals are present.
 Silicates & aluminates are two most abundant substances present in earth crust but to isolate metal from
these become uneconomical therefore these substances are not used to extract metals.
 % abundance in the earth crust
Non-metals Oxygen
Metals  Si > Al > Fe > Na > K > Mg > H
Ores: Naturally occurring substances from which metals can be conveniently& economically extracted.
Therefore, all ores are minerals but all minerals are not ores.
Eg. : Clay [Al2(Si2O5) (OH)4] x. H2O
Bauxite Al2O3·2H2O [Used for extraction of aluminium]
Since Bauxite is more rich in Aluminium so extraction of Aluminium is carried out by Bauxite are
Types of Ores: Combined Ores and Native Ores:
Combined Ores:
1. Oxide Ores:
Fe2O3 Haematite
Fe3O4 Magnetite
SnO2 Tin Stone/Cassiterite
Cu2O Cuprite
2. Sulphide Ores:
Pbs Galena
Ag2S Argentite
Cu2S Copper Glance
CuFeS2 Copper Pyrite
FeS2 Iron Pyrite
3. Halide Ores:
NaCl
KCl· MgCl2· 6H2OCarnelite
4. Ores Containing Oxo Anions:

CO32–,NO3–,SO42–,PO42–
a) Carbonate Ores:
CaCO3· MgCO3 Dolomite
MgCO3 Magnetite
CHEMICA Chemistry Classes _____________________________________By DheerendraShrivastva (DS Sir) (Ex. Resonance & Bansal Faculty)
G-31,44,43 Bagherwal Four Season Building, Opp. City Mall Kota, 70141-64482 | 95889-81610 Page 1
FeCO3 Siderite
b) Nitrate Ores:
KNO3 Indian Salt Peter
NaNO3 Chile Salt Peter
c) Sulphite Ores:
MgSO4 · 7H2O Epsam Salt
CaSO4·2H2O Gypsom
d) Phosphorite:
Ca3 (PO4)2
Native Ores:
 These ores exist in pure metallic state.
 Inert metals exists as native ores e.g. Pt, Au, Ag, Hg, etc.
 These can exist as lumbs of pure metals which is called nuggets.
Gaunge or Matrix:
Impurities in form of soil, stone & silicates that are present in ores. These rocky and early impurities are called
Gaunge or Matrix.
Acidic Impurities (Acidic Oxides)  SiO2, P4O10
Basic Impurities (Basic Oxies)  FeO, MnO, TiO2, CaO, MgO
Flux: An additional substance added during metallurgy in the smelting step.(reduction of metal) to remove
impurities is called flux.
Acidic Flux: SiO2, P4O10
Acidic Flux + Basic Impurity  Slag ()
SiO2 + CaO  CaSiO3 ()
SiO2 + FeO  FeSiO3 ()
SiO2 + PbO  PbSiO3 ()
Basic Flux: CaO, MgO

Basic Flux + Acidic Impurities  Slag ()
CaO + SiO2  CaSiO3 ()
6CaO + P4O10  2Ca3(PO4)3
Natural Flux: NaCl, CaF2, Na3AlF6 (Fluorspar and Cryollite)

Natural Flux are used to decrease melting point of electrolyte and also increase the electric conductance
of electrolyte.
Eg. CaF2 + Na3AlF6  decreased the M.P. of Al2O3 from 2050°C to 900°C
Slag () :
This is highly fusible (low M.P.) substance. It will exist in liquid state in the metallurgy. Being lighter it
will floats on the surface of molten metal and prevent oxidation of metal by air. After removal of slag
we will get molten metal.
CaSiO3  Cement Industry
Ca3 (PO4)2  Fertilize Industry
Refractories:
Refractories are these substances which are having high M.P.& B.P. these are also insulator of heat.
Eg. MgO, CaO, SiO2
Types of Metallurgy
1. Pyrometallurgy: It is carried out in presence of heat by using some suitable reducing agents. It is
carried out by two methods.
(a) Self Reduction Method : It is used for sulphite ores containing less electro positive metals.
PbS, Cu2S, HgS
(b) Carbon Reduction: Carbon (coke) is used to reduce oxide of metal in presence of heat.
Eg. Fe,(Fe2O3) Cu(Cu2O), Zn(ZnO), Mn, Sn
It is based on concept of thermodynamics.
2. Hydrometallurgy:It is carried out in aqueous medium at room temperature and pressure. It is based on
metal displacement
Zn + 2 [Ag(CN)2]–  [Zn (CN)4]2– + 2 Ag (s)
It is used for low grade ores.
3. Electrometallurgy: In this type of metallurgy metals are extracted by passing electricity in molten
state. It I based on principle of electrolysis.
Ex. Electrolysis Al2O3, MgCl2, NaCl
  
Al Mg Na
Note: Electrolysis is not carried out in aqueous medium because at cathode H2O is reduced with respect to
metal.
2H2O + 2e  Cathode
 H2 + 2 OH–
General Metallurgical Process
A. Crushing and Grinding: Before the concentration of ore these are crushed into small size particles.
When ores are obtained in powdered form it is called pulverization of ore.
B. Concentration of Ores:
Physical Method Chemical Method

1. Gravity Separation 4. Leaching
2. Magnetic Separation
3. Froth Floatation
1. Gravity Separation:
It is based on principle of different density of ores &impurities. In this ores particles are washed into
stream of water. Heavy ore particles settle on the wilfley table which lighter impurities are washed with
water.
2. Magnetic Separation:
It is used when either ore particles or impurities are magnetic in nature.
E.g.
1. Tin Stone / Casseterite(SnO2) is concentrated by magnetic separation.
Tin stone is found to be associated with a paramagnetic impurities of Wulframite of Fe2+
andMn2+
SnO2(Diamagnetic) is Repelled by external magnetic field.
And due to Magnetic nature wulframite of Fe2+& Mn2+ are removed.
Wulframite of Fe2+
FeWO4  Fe2+ + WO42-
6
3d 5d0 Paramagnetic
2+ 2-
MnWO4  Mn + WO4
3d5 5d0 Paramagnetic
2. Chromite Ore [ FeCr2O4]
II III 4
Fe6 Cr2 O4 (Paramagnetic) have impurity of Sn O2 (Diamagnetic) concentrated by magnetic
3d 3d3
separation.
3. Haematiteore:[ Fe2O3]
Fe2O3(Paramagnetic) have impurity of SiO2(Diamagnetic) concentrated by Magnetic Separation.
3. Froth Floatation Process:
A slurry is prepared by powdered ore + pine oil + sodium ethyl anthate + water + cresol and air is
passed to develop froth.
This is based on the principle that ore and impurity show different degree of wet abilityw.r.t. pine oil
and water.
Here ore particles preferentially wetted by pine oil while impurity particles preferentially wetted by
water.
S
Å
S=C=S + O—R S–C–O–H
H H
HS – C – OH [Xanthic Acid]
NaOH or KOH
S
+
Na S – C – O – R [Sodium Xanthate]
S
Lyophobic PartR – O – C – S–  Lyophillic Part
 Metal which have high polarizing power are best concentrated.

 The process is mainly used for concentrating sulphideores.
 When air is passed into the slurry, froth is developed. Here lyophilic part want to stay in water
while lyophobic part want to stay in air. Therefore best location for them is water air interface.
 SulphideOre particle get attached with sulphur atom of Xanthate by adsorption. As froath moves
up these particles get collected at froth liquid.
Frothers: These will decrease surface tension of water and facilitates the formation of froth.
E.g. Pine Oil, Camphor Oil.
Collector: These will combined with sulphide ore and decrease the wetting ability of ore particle with
water and make than water repellent. Pine Oil with sodium ethyl Xanthate is called collector.
Stablizers:It will increase the stability of an air bubble so that air bubble can carry out sulphide particle
to the froth level. These will increase stability of froth. E.g. Amines, Cresol.
Depressants:
These will decrease the wetting ability of impurities with pine oil by forming a water soluble
compound. Depressants are different for different impurities.
Eg. During the concentration of PbS (Galena) have impurity of ZnS which can be depressed by using
NaCN or KCN
ZnS + 4NaCN  [Zn (CN)4]2– + 4Na+ + S2- Soluble
Activators: These substances increase the wetting ability of Ore particles with pine Oil. Eg. ZnS can
be activated by Using CuSO4. Since ZnS have poor polarizing power and CuSO4 have moderate
Polarizing power.
ZnS
Zn + CuSO4  Water repellent .
Absorbtion
4. Leaching:
It is a chemical method in which ore particles are dissolved in a reagent (which can react with ore)
impurities ore unreactive.
It is used mainly for low grade ore.
Example-1
Step-I Ag (Native Ore) +NaCN / KCN  [Ag (CN)2]–+ Na+
4Ag(s) + 8 NaCN + 2H2O + O2  4[Ag (CN)2]–+ 4NaOH
Step-II 2[Ag(CN)2]–+ Zn  [Zn(CN)4]2– + 2 Ag(s)
Conversion of Ore to Oxide

I. Calcinations: It is the process in which ore are heating in absence of air below melting point of metal
ore.
 Impurities like S, As, Sb are vapourised by forming their vapours.
 Moisture present in the ore can be removed.
Al2O3·2H2O  Al2O3 + 2H2O (g) 
2Fe2O3·3H2O  2Fe2O3 + 3H2O (g) 
Ore containing oxoanions are calcined to form their oxides.
ZnCO3ZnO+ CO2 (g) 
MgCO3CaCO3MgO +CaO+ CO2
FeCO3FeO + CO2
During calcinations ore become porous due to removal of gasses. This become lighter and rate
of reduction increased due to increase surface area this calcined ore.
II. Roasting:
In roasting ore is heated in presence of air below the melting point.
 It is used mainly for sulphide ores.
2PbS + 3O2 PbO + SO2
2ZnS + 3O2 ZnO + SO2
2HgS + 3 O2 HgO + SO2
 Below 750°C temperature sulphates are also formed.
1 T 750C
SO2 + O2   SO3
2
PbO + SO3  PbSO4
PbS + 2O2  PbSO4
ZnS + 2O2  ZnSO4
 Lower oxidation state oxides are converted into higher oxidation state oxides.
4FeO + O2 2Fe2O3
 Moisture present in are can be removed.
 Elemental impurities like S, As &Sb are removed by forming their oxides.Some volatile
impurities are also removed.
S + O2  SO2
3
2AS + O2 AS2O3
2
3
2Sb + O2 Sb2O3
2
 Ores become porous.
Q. Which of the following ores can be calcined?
(A) ZnS (B) Fe2O3 (C) ZnCO3 (D) Al2O3·2H2O
Q. Which of the following ores can be roasted?
(A) ZnS (B) Fe2O3 (C) ZnCO3 (D) Al2O3·2H2O
(1) Smelting (Melting + Reduction):
The metallurgical process in which metal is isolated from the impurities(Which are physically mixed
or chemically associated with ore)by reduction & melting is called smelting process.
Heat (Blast + Furnance)
Ore (Oxides) + Reducing Agent + Flux  Molten Metal + Slag
Selection of Reduction Process (Reducing Agents)

Ellingum Diagram (Thermodynamics of Metallurgical Process)
1. In this diagram Gf( formation of oxides) is plotted w.r.t. temperature.
M(s) + O2 (g)  MO2 (s) ; Gf (oxide)<0 ; S < 0
2. If Gf is positive for any oxide then at any temperature then oxide already decomposes.
If on increasing temperature G become positive. At this temperature reaction
(M(s) + O2(g)  MO2(s); Gf< 0) goes in backward direction and oxides will decompose to give
metal.Example: HgO, Ag2O. (G>0)
 1 2XM  s   O 2  g   2M X O  s 
Ag2O   2Ag + O2
2
 1 (G=0)
HgO   Hg(l) + O2
2 Positive slope
 G = H – TS 
Gf
Y = c + mx
Slop = – S (G<0)


3. Ellingam diagram can explain only thermodynamics aspect of metallurgical process. It cannot explain
kinetics of the metallurgical process.
4. While plotingGf of oxide with temperature H &S assumed to be independent of temperature.
5. Reducing agents like carbon(s) or carbon monoxide (CO) oxidize itself and reduces the metal oxide.
i.e.
Oxide
Oxide + C(s)  Metal CO2 or Oxide + CO(g)  M(S) + CO2 (g)
Red
Phase Transformation:
(1) M(s) + O2 (g) 
 MO2 (s); S1
(2) M() + O2 (g) 
 MO2 (s); S2
(3) M(g) + O2 (g) 
 MO2 (s); S3
|S3 | > | S2| > |S1 |
Gf
Temperature
T1 T2
(M.P.) (B.P.)
Selection of Reducing Agent:
M(s) + O2(g)  MO2 (s) ; Gf [oxide] < 0
Let us take carbon as a reducing agent
4
C(s) + O2(g)  CO2 (g) (s) ; Gf [CO2(g)] < 0
Metallurgical Process:
(i) MO2 (s)  M(s) + O2 (g); Gf (oxide) > 0
(ii) C(s) + O2 (g)  CO2(g); Gf [CO2 (g)] < 0
MO2 (s) + C(s)  M(s) + CO2 (g);
Grxn = Gf [Oxide] +Gf[CO2(g)]
(+) (–)
A metal oxide line present below the oxide line of any metal can reduce the oxide present above it. If
the difference is large reduction is easier.
C(s) v/s CO(g) As reducing Agents:
(1) C(s) + O2 (s)  CO2 (g) ; S = 0 i.e. slope constant
1
C(s) + O2 (g)  CO (g) ; S > 0 i.e. slope negative
2
1
CO (g) + O2 CO2 (g) ; S < 0 i.e. slope positive
2
( g)
CO
2
) 
( g
O 2
+ 1/2
(g)
CO C(s)+ O2 (g)  CO2 (g)
Gf0
C(s
)+ 1
/2 O
(g)

2
CO
(g)
710°C T
Slope = –S
i.e. below 710°C CO is in better reducing agent but at higher temperature above 710°C carbon is a good
reducing agent.
Q. Why sulphide ores are roasted before the reduction.
OR
Why sulphide are not directly reduced by carbon.

Ans. (i) ZnS + C(s)   Zn(s) + CS2 (); G1 = H1 – TS1
S1>0 G1< 0
3
(ii) ZnS + O2 ZnO(s) + SO2 (g)
2
ZnO + C(s)  Zn(s) + CO (g) G2 = H2 – TS2
S2>0 G1< 0
But S2>S1 So, G2 is more negative than G1
Another reason is the side product in first case is liquid while in second case is gas.
1. Carbon Reduction: Because of low cost & wide available of carbon, it is mainly used in metallurgical
process.Coprate
(a) Direct Carbon Reduction
Fe2O3 + 3C  2Fe() + 3CO
FeO + C  Fe() + CO
Actual Process
Fe2O3  Fe3O4FeO Fe
3Fe2O3 + C  2Fe3O4 + CO
Fe3O4 + C  2FeO + CO
FeO + C  Fe + CO
Tin Stone
SnO2 + C  Sn+ CO2
(b) Indirect Carbon Reduction
Calcination
ZnCO3  ZnO + CO2
ZnO + C  Zn + CO
(c) In the case of sulphide ore
3
PbS + O2PbO + SO2
2
PbO + C  Pb + CO
2. Reduction by CO:
Fe2O3 + 3CO  3CO2 + 2Fe
C(s) + CO2 (s)  2CO(s)
In lower temperature region CO is a better reducing agent.
3. Self Reduction:
It is used mainly for sulphide ores containing less electropositive metal.
Eg. PbS, HgS, CuS
In self reduction sulphide ores are converted into oxide during roasting. Then formed oxides will
combine with remaining sulphides to give metal.
3
I. PbS + O2 PbO+ SO2
2
(Sulphide) (Oxide)
PbS + 2 PbO  3Pb +SO2
3
HgS + O2 HgO + SO2
2
2HgO + HgS  3Hg + SO2
In lower temperature self reductiontake place by forming sulphate
750ºC
II. PbS + 2O2   PbSO4
PbS + PbSO4  2Pb + 2SO2
4. Reduction ByAluminium (Alumino Thermite Process):

Aluminium metal is used as reducing agent for those oxides in which there is substantially high
covalent character is present & having high melting point.
Eg. Mn2O3, Mn3O4, Cr2O3, Fe2O3
It is based on the fact that Aluminium have greater affinity to compare with oxygen. The reaction
between them is highly exothermic.
Process:
Covalent oxides [Cr2O3, Mn3O4] and aluminium powder is taken a crucible. This process is triggered
(initiated) by igniting mixture of Mg ribbon + BaO2 + KClO3
3
Mg + BaO2+ KClO3  MgO + BaO + KCl + O2 + Heat
2
Cr2O3 + 2Al Al2O3 + 2Cr + Heat
3Mn3O4 + 8Al 4Al2O3 + 9Mn + Heat
Fe2O3 + 2Al Al2O3 + 2Fe () + Heat
 It is highly exothermic process because of the formation of Al2O3 (high lattice energy)
 Heat liberated in the process is sufficient to sustain complete process if heat source later is out
off.
 This process is used if the temperature needed for carbon to reduce an oxide is too high for
economical or practical purposes.
Thermite Welding:
5. Reduction By other metal:
High electropositive metal can displace less electropositive metal in aqueous medium
2[Ag (CN)2]– + Zn   [Zn (CN)4]2– + 2Ag
Krall Process
TiCl4 + 2Mg   2MgCl2 + Ti
IMI Process
TiCl4 + 2Na 
(Imperial Mining Industry)
 4NaCl + Ti
Na & Mg are good reducing agent & their halides are water soluble.
6. Electrolytic Reduction:
Isolation of high electropositive metal like Al, Na, Mg etc. is carried out by electrolytic reduction in
molten state only.
Electrolysis of Aqueous NaCl:
Cathode:
(i) Na+ + e–   Na(s); ° = – 2.7V
(ii) 2H2O + 2e–   2OH + H2 ; ° = –0.83V
(iii) 2H2+ + 2e–   H2; ° = 0
Electrolysis of Molten NaCl:
Cathode:
(i) Na+ + e–   Na(s);
+3 –
(ii) Al + 3e   Al(s);
7. ByHeating Oxides:
300C 1
Ag2O(s)   2Ag° + O2 [Ag+/Ag = 0.8 V]
2
1
HgO(s)Hg() + O2
2
The oxides of less electropositivee element have more positive SRP value formed less stable oxides.
These oxides on heating decomposed to gives metal.
8. Reduction By Hydrogen:
Cu2+ + H2  Cu + 2H+
MoO3 + 3H2  Mo + 3H2O
MoO3 + 3H2  Co + 3H2O
Now a days this technique is not in use because at high temperature hydrogen gas may get exploded.
Extraction of Aluminium From Bauxite Ore
Bauxite Ore: Al2O3·xH2O
Al2O3·2H2O, Al2O3·3H2O, Al(OH)3, AlO·OH
Step-I Concentration of Ore:

Bauxite Ore
Red Bauxite White Bauxite

(Al2O3 ·xH2O) (Al2 O3 . xH2 O)
Main Impurity - Fe2 O3  Red Main Imp. - SiO2  White
Minor Impurity SiO2 , TiO2
Minor Impurity  Fe2O3, TiO2
Bayer’s Process Hall Method Serpeck’s Process
Bayer’s Process:
Powdered Ore + Conc. NaOH
Note:
 All oxide of d-block reacts by first forming their hydroxides.
 Oxides of most of d-block elements are basic in nature.
 Al2O3 + 3H2O 2Al (OH)3

Al  OH 3 + NaOH Na[Al(OH)4] 
2H2O
 NaAlO2
W.Ppt Sodium metal alluminate
 SiO 2  2NaOH 
 Na 2SiO3  H 2 O
Acidic oxide Sillicate
Filtrate:
Acidified by CO2
Na[Al(OH)4 ] + Silicates Al(OH)3
& dil. HCl Re-precipated (w.ppt)
dry calcination
Al2O3 (pure)
electrolyte reduction
Al
Note: Conc. HCl is not used because Al(OH)3 reacts to form AlCl3.
Hall Method:
Al2O3 + Na2CO3  2NaAlO2 (soluble) + CO2

Fe2O3 +Na2CO3 2NaFeO2 + CO2
SiO2 +Na2CO3 Na2SiO3 (soluble) + CO2
Small extend
CaCO3 CaO + CO2
CaO + SiO2CaSiO3
Filtrate  Same as Bayer’s Process:
Serpeck’s Process:
Heated upto 1800 K
Powdered Ore
With Coke & N2 Gas
AlN Si  + CO 
+
Fe2O 3 + TiO 2
Al2O3 + 3C + N2AlN + 3CO (g) 

SiO2 + 2C(g)  Si(g) + 2CO (g) 
AN + 3H2 O A(OH)3 + NH3
A /N
3+ 3-
H /OH
+ –
NaOH
Filtrate Residue
Na[A(OH)4] Fe2O3 + TiO 2
Acidified
A(OH)3 (Reprecipated)
Calcination
A2O 3
Electrolytic reduction
A
Extraction of metal Aluminium from Pure Allumina

Ref. J.DLee
Aluminium is usually extracted by the Hall-Heroult process. Al2O3 is melted with cryolite Na3[AlF6],
and electrolysed in a graphite lined steel tank, which serves as the cathode. The anode are also made of
graphite. The cell runs continuously, and at intervals molten aluminium (M.P. 660°C) is drained from
the bottom of the cell and more bauxite is added. Some cryolite is mined as a mineral in Greenland, but
this is insufficient to meet the demand for it, and most is made synthetically.
Al(OH)3 + 3NaOH + 6HF  Na3 [AlF6] + 6H2O
Cryolite improves the electrical conductivity of the cell as Al2O3 is a poor conductor. In addition, the
cryolite serves as an added impurity and CaF2 and AlF3 may also be added. (A typical electrolyte
mixture is 85% Na3[AlF6], 5% CaF2, 5% AlF3 and 5% Al2O3.) Various products are formed at the
anodes, including O2, CO2, F2 and carbon compounds of fluorine. These erode the anodes, which must
be replaced periodically. The traces of fluorine formed cause serious corrosion. Large amounts of
Li2CO3 are now used as an alternative impurity, because this reduces corrosion. Energy consumption is
very high, and the process is only economic where there is a source of cheap electricity, usually
hydroelectric power.
Electrolyte Reaction / Hall Heroult Method:
Electrolyte Mixture:
Na3 [AlF6] + Al2O3 + CaF2 + AlF3
85% 5% 5% 5%
 Al2O3 is melted into the cryolite [Na2AlF6] and electrolyzed in a graphite lined steel containers,
steel contains weeks as cathode while anode is also made by graphite rod.
 Na3AlF6 reduced the melting point of Al2O3 from 250°C to 950°, electrolytic mixture also
increases the electrical conduction of the process.
Electrolytic Reduction:
Cathode : Al3+ + 3e– Al × 2
1
Anode : O2–  O2 + e– × 3
2
Cell Reaction:
3
2Al3+ + 3O2– 2Al + O2 (g)
2
3
Al2O3  2 Al (l) + O2 (g)
2
n=6
G = – nFE0cell
nd
II Methode:
[F–] > [O2–]
Na3 (AlF6) 3NaF + AlF3
AlF3 Al3++ 3F–
3
Anode: Al2O3 + 6F–2AlF3+ O2+ 6e–
2
AlF3 Al3++ 3F–
Cathode: Al3++ 3e– Al (l)
Step-III Refining of Aluminium (Purification) Hopper Process
Pure A() Layer III (Cathode)
Na3 [AF6] + CaF2 Layer II (Electrolyte)

Feld spar
Impure A() Layer I (Anode)
Electrolytic Refining
Extraction of Silver (Marc. ArtharCynaidation Process)

Hydrometallurgy:
Step-I Combined Ore:
Ag2S + 4NaCN +2O2  2Na [Ag(CN)2] + Na2SO4
Argentite Leaching Soluble
Agent
If O2 is not passed then it is reversible in nature.
Native Ore
Ag++ 2 CN–[Ag(CN)2]–
1
1
2Ag + 4NaCN + O2+ H2O  2 Na[Ag(CN) 2 ] + 2NaOH
2
Here, O2 is used as oxidizing agent for Ag.
Step-II
II
2[Ag(CN)2]–  [Zn(CN) 4 ]2 + 2Ag 
Extraction of Silver From Silver Coin:
Ag AgNO3
dissolved dil. HO AgCl NaCN
+ +
Cu in dil. HNO3 Cu(NO 3) 2 w.ppt KCN
Cross
–
[Ag(CN) 2]
Silver Coin
Zn
2
Ag + [Zn (CN)4 ]
Purification:
Ag Reacted with
dil. H2 SO4 Ag Cuppellation
Zn Ag + [Zn(CN)4 ]
Zn is dissolved as Zn Pb +
1
O  PbO
ZnSO4 2 2
Pb
Amalgamation Electrolytic
Process Refining
Ag-Hg 1. Impure Ag Anode
2. Pure Ag Cathode
Electrolyte
AgNO3 + HNO3
Ag Hg
Ag 99.99% Pure
Extraction of Gold:
It has two forms vein gold or placer gold.
Concentration Process : (Panning Process)
Density of Gold : 1.93 gm/cm3
Density of silicon : 2.5 gm/cm3
It is based on principle of gravity separation.
Cyanidation Process:
Step-I
1
2Au + 4NaCN +H2O + O2  2Na [Au(CN)2] + 2NaOH
2
Native Ore Leaching Soluble
Agent
Step-II
Zn + 2 [Au(CN)2]–  [Zn(CN)4]– + 2 Au 
Purification:
Au dil. H2 SO4 Au Au Heated with Borax and
Zn dissolve Cuppellation formed Cu(BO2 )2 Au
Ag, Cu Ag, Cu Ag
as ZnSO4 1 is extracted Ag
Pb + O2  PbO by with water
Pb, Zn Pb 2 Pb
Conc. H2 SO4
Au
Ag dissolve
Amalganation Electrolytic
Au-Hg Refining
99.99% Pure Au
Anode : Impure Au
Ag Hg
Cathode : Pure Au
Electrode : HAuCl4 + AuCl3
Extraction of Copper:
Ore:
Cu2O : Cuprite (Carbon Reduction)
CuFeS2 : Copper Pyrite (Chalcopyrite) (Self Reduction)
Cu(OH)2·CuCO3 : Malachite Ore (Hydromettalurgy) (Low Grade Ore)
1. By Pyrometallurgy:
Oxide line of copper is present almost at the top of ellingam diagram, therefore it is easily reduced by
carbon and carbon monoxide. This method of extraction is used only for low grade ore.
Cu2O + C2Cu + CO
Cuprite
Cu2O + CO  2Cu + CO2
2. Extraction of copper from sulphide Ore /From CuFeS2,
By Self Reduction Method:
Step-I: Concentration of Ore: Froath floatation process
Step-II:Roasting
Concentrated ore is heated in presence of hot air & impurity is removed by farming oxide
Si +O2 SiO2 
3
2As + O2As2O3
2
3
2Sb + O2Sb2O3
2
Main Reaction
2CuFeS2+ O2 Cu2S + 2FeS + SO2
Side Reaction
3
Cu2S + O2  Cu2O + SO2
2
FeS+ O2 FeO + SO2
III Smelting: Roasted ore is heated by hot blast of air in presence of SiO2
FeO+ SiO2FeSiO3 (l)
Impurity Flux Slag
Basic acidic
Here of the formed Cu2O in charge react with FeS and converted into Cu2S.
FeS +Cu2O Cu2S + FeO
The mixture FeS (less) and Cu2S (More) is Copper Mattie. It is obtained in molten state after removal of
slag.
IV. Extraction of Copper From Copper Mattie (Bessemerisation):
Molten copper Mattie and silica is take into the Bassemer Convertor. In which it is heated by hot blast
of air.
3
FeS+ O2 FeO+ SO2
FeO
2
FeO +SiO2  FeSiO3 () Slag
Upto this stage after removal

moval of slag almost all FeO is removed. And molten mixture is completely free
from of FeO.
Now, a part Cu2S is oxidized into Cu2O which will combined with remaining part of Cu2S and give
metal by self reduction.
Cu2S + O2Cu2O+ + SO2
Cu2S + 2Cu2O 6Cu Cu() + SO2
During the coolingling of molten copper, SO2 (g) expelled out which formed blistered in copper. Therefore
it is called blister copper, contains 98% pure copper wi
with
th impurities Au, Pt, Ag, Fe, Co,
Co Ni, Zn.
Purification:
Anode : Impure Cupper rod
Cathode : Pure rod of copper
Electrolyte : H2SO4 + CuSO4
Anode Mud : Pt, Au, Ag
Electrolyte Solution : Fe, CO, Ni, Zn (Soluble sulphate)
3. Hyrometallurgy:
Dissolve the ore in suitable reagent in which impuri
impurity in insoluble.
Step-I
Cu(OH)2·CuCO3 + 2H2SO4  2CuSO4 + 3H2O + CO2
Malachito Ore
Step-II
CuSO4 + H2  Cu + H2SO4
CuSO4 + Zn  Cu + ZnSO4
CuSO4 + Fe  Cu + FeSO4
Extraction of Lead from Galena (PbS)
Carbon reduction method is used for low grade ore.
Self reduction method is used for high grade ore.
1. Carbon Reduction Method:
(i) Froath Floation

Ore PbS Process Roughting
Concentrated PbO + PbSO4 + PbS
Impurity ZnS (ii) NaCN is used Ore 1
Pb + 2 O2  PbO
as depressant
for ZnS
Self
Pb ( ) + CaSiO3 ( ) Reduction
heated with
Coke + CaO
Pb ( ) + CaSiO3 ( )
(Slag)
Reaction : (Roasting)
3
PbS + O2 PbO + SO2
2
PbS + 2O2  PbSO4
Smelting (Reduction + Melting)
In presence of Coke and CO
PbSO4 + 4C PbS+ 4CO
3
PbS+ O2PbO+ SO2
2
PbO +C Pb() + CO
PbO+ CO Pb() + CO2
PbS+ 2PbO  2Pb() + 2SO2
PbSO4 + PbS  2Pb + 2SO2
CaO+ SO2CaSO3 ()
Self Reduction:
3
(i) PbS+ O2PbO+ SO2
2
2PbO + PbS  2Pb() + SO2
(ii) PbS +2O2 PbSO4
PbSO4 + PbS  2Pb() + 2SO2
Note: Calcium oxide (CaO) is added to this mixture during smelting to avoid formation of
PbSiO3 (slag)
3
PbS+ O2PbO+ SO2
2
PbO +SiO2 PbSiO4
(Impurity) (Slag)
CaO+ SiO2 CaSiO3 (Slag)
CaO+ PbSiO3 CaSiO3 + PbO
Refining Process:
1. Parke’s Process: Removal of Ag from Pb.
2. Electrolytic Refining : (Betts Process)
Anode : Impure Pb
Cathode : Pure Pb
Electrolyte : PbSiF6 + H2SiF6
Extraction of Zinc from ZnS [Zinc Blende]

Ore:
1. Zinc Blende (ZnS)
2. Calamine (ZnCO3)
3. Zincite (ZnO)
Most suitable ore for extraction of Zn is Zns. It is also called as black jack due to presence of impurity
PbS. Which is black in colour.
Step-I: Concentration: Froath Floatation Process.

Step-II:Roasting:
850C
ZnS +3O2   ZnO + SO2 (g) [Collected to from H2SO4 ]
850C
ZnS +2O2   ZnSO4
850C
ZnSO4   ZnO+ SO2 (g) 
0Zn 2 / Zn  0.76V
ZnS +2ZnO  3Zn + SO2
Zn is a high electropositive element and does not participate in selt reduction.
Step-III:
Smelting (Excess Carbon + High Temperature)
ZnSO4 + 4C  ZnS + 4CO
3
ZnS + O2 ZnO+ SO2
2
ZnO +C(g)  Zn(g) + CO
ZnO+ CO(g)  Zn(g) + CO2 (g)
Gf
–100
–200
–300
–400
–500
–600
–700
–800
–900
900°C 1200°C
Q. Why Zn is not extracted from ZnO by carbon monoxide.[from NCERT]
Ans. The gaseous mixture of Zn and CO2 was simply removed from the furnace and cooled, then some
reoxidation of Zn would occur. Thus the zinc powder obtained would contain large amounts of ZnO.
ZnO + CO ↔ Zn + CO2 [Reversible reaction]
Modern smelters minimize the reoxidation in two ways:
(a) by having excess carbon, so the CO2 formed is converted to CO.
(b) by shock cooling the gases leaving the smelter so they do not have time to attain equilibrium.
This rapid cooling is achieved by spraying the hot gas with droplets of molten lead. This gives
99% pure Zn. Any cadmium present can be separated by distillation.
Alternatively ZnS is heated in air at a lower temperature, yielding ZnO and ZnSO4. These are dissolved
in H2SO4 solution is electrolysed to give pure Zn. The electrolytic process is expensive and is not used
in the UK.
IInd Method:( expensive method)

Roast at dissolve
ZnS low temp. ZnO in H SO ZnSO4
2 4
(solution) Electrolysed
Zn
Purification:
Cd (g)
Zn B.P.= 908°C
Heated up
Cd B.P.= 765°C Zn (g)
to 800°C
Fe Zn
B.P.> 1500°C
Pb Heated
Pb > 920°C
Fe
Pb
Fe
Electrolytic Refining:
Anode : Impure Zn
Electrolyte : ZnSO4 + H2SO4
Cathode : Al metal
Zn + H2SO4  ZnSO4 + H2
Extraction of Magnesium (Mg)
Ore: Carnalite Ore  KC· MgCl2 · 6H2O
Dolomite  CaCO3 · MgCO3
Magnessite  MaCO3
A Extraction of Carnalite Ore:
Step-I To obtained MgCl2 · 6H2O Crystals
KC (Separated)
less soluble
dissolve in
KC·MgC2 ·6H2 O Solution evapourated
water and then
recrystallision
MgC2 (Soluble) due to high

hydration of
Add water and MgC2
then heat &
recrystallision
MgC2 MgC2 ·6H2 O

(Saturated solution) (Crystals)
NaCl is hydrated in atmosphere the to impurity at MgCl2·6H2O & CaCl2 · 6H2O.
Step-II:To obtained Dry MgCl2
dry HCl
MgCl2 ·6H2O 
Vapours
 MgCl2
(unhydrous)
Direct heating of MgCl2·6H2o hydrolysed it in MgO & HCl.

Heat
MgCl2 ·6H2O   MgCl2 ·H2O + 5H2O

MgO + 2HCl
Note :
Dry HCl gas in passed instead of direct heating to avoid formation of MgO which becomes very
difficult to extract Mg from MgO by electrolytic reduction.
Heat
MgCl2 ·6H2O   MgO + 2HCl
SrCl2 · 6H2O  SrCl2 + 6H2O
CaCl2 · 6H2O  CaCl2 + 6H2O
Step-III:
Electrolytic Reduction of Molten MgCl2
Electrolytic Mixture : MgCl2 + NaCl
4 Part 1 Part
Here NaCl work as Neutral flux, decrease the malting point &increased the conductance.
B.: Extraction from Magnasite (MgCO3)


MgCO3   MgO + CO2 (g) 
MgO + C + Cl2 
heat
 MgCl2+ CO
electrolysis
MgCl 2  Mg
( Molten )
Step-I Reaction with Ca(OH)2

MgCl2 + Ca(OH)2 Mg(OH)2 + CaCl2
dry HCl gas electrolysis
Mg(OH)2+ dil. HCl  MgCl2·6H2O    MgCl2   Mg
(unhydrous)
Extraction of Iron
Ore:
Fe2O3 Hammettite
Fe3O4 Magnatite
Fe2CO3  Siderite
FeS2  Iron Pyrite (Fool’s gold)
Fe2O3·6H2O  Limonite Ore
Iron is not extracted from iron pyrite because iron obtained from this have high sulphur content due to
which brittleness of iron increases.
Metallurgical Process:
Fe2O3
+
Fe3O4 1. Gravity Separation
2. Magnetic Separation Concentrated Roasting &
+
FeCO3
(Concentrated Ore) Ore Calcination
+
Fe2 O33H2 O
Roasting & Calcination:

Impurities are oxidized by forming their oxides
S + O2  SO2 
3
2AS + O2  AS2O3 
2
3
2Sb + O2  Sb2O3 
2

# Fe2O3 ·3H2O   Fe2O3 + 3H2O (g)  (Moisture removed)

FeCO3   FeO + CO2 (g) (Decomposed)
Fe3O4 
 FeO + Fe2O3 (Decomposed)
2FeO + 2O2   2Fe2O3
Q. Why Iron ore is roasted from reduction?
Ans. To convert FeO into Fe2O3& avoid formation of slag.
FeO  SiO 2 
 FeSiO 3
(Basic Oxide) Acidic Impurity (Slag )
1
2FeO + O2 
 Fe2O3
2
Fe2O3  More acidic than FeO& not combined with SiO2.
Smelting:
Roasted Ore /Calcinedore : Coke Powder : Lime Stone = 8:2:1

[500k – 900k] [Reduction Zone]
Reduction is carried by CO.
Fe2O3 Fe3O4FeO  Fe
3Fe3O3 + CO  2Fe3O4 + CO2
Fe3O4 + CO  3FeO + CO2
FeO + CO  Fe + CO2
900k – 1500k (Heat absorption Zone)

CaCO3  CaO + CO2
CaO + SiO2  CaSiO3()
Basic Flux Main Acidic Slag
Impurity
C(s) + CO2 (g)  2CO (g)

(Endothermic Process)
FeO + C(g) Fe() + CO (g)
1500K – 2000 K (Zone of Fusion)
FeO + C(g)  Fe() + CO (g)
CaO + SiO2CaSiO3 ()
SiO2 + C(g)  Si + CO2(g)
MnO2 + C(g) Mn + CO2 (g)
Ca3(PO4)2 present in lime stone is reduced to phosphorus by coke.

Ca3(PO4)2`+ 3SiO2 3CaSiO3+ P2O5
2P2O5 + 10C(s)  P4 + 10CO(g)
In the lower part of blast furnace after removed of slag will get molten iron having impurity of carbon,
Mn, Si, S & P. This iron is containing 4.5% carbon is called cost iron or pig iron.
Type of Iron:
1. Cast Iron:It is most impure form of iron having 4-5% carbon with impurity of Mn, S, P & Ni.
Cast iron have high load bearing capacity but it is brittle in nature.
2. Wrought Iron: It is most purest form of iron. It is having only 0.5% impurity content. It is having
only 0.15% of carbon.
Wrought Iron is obtained from cast iron by Puddling Process (oxidative refining).
3. Steel : it is having carbon content on 0.15 to 1.5% with impurity of Mn, Cr, Ni , P and N.
Elements Properties
1. Cr, Ni It imparts stainless property to steel by forming impression
free oxide layer of Ni & Cr.
2. Mn Mn makes steel very hard & increase tensile strength.
Railway track have 13% Mn.
3. Carbon It will increase hardness and bearing capacity.
4. Nitrogen above 0.01% It will increase brittleness of steel.
This kind of steel is difficult to weld.
L-D Process:
Out of all steel manufacturing process L-D process is most suitable process because in this process pure
oxygen is used for oxidation. In all other process air is used for oxidation. Air is having nitrogen which
can form nitride. Nitrogen and nitride made steel brittle & difficult to weld.
Heat Treatment of Steel:

1. Annealing: In this hard steel is heated upto redness (800°C) and then slowly cooled to room
temperature. It will increase softness of steel.
2. Owenching or Hardening: In this steel is heated up redness (800°C) & then suddenly. It cooled by
emerging it in to water or oil. This will increase hardness and brittleness of steel.
3. Tempering: In this steel is heated below the redness level upto 200°-300°C, then it is slowly cooled to
room temperature. It will decrease brittleness but hardness remain same.
4. Nitriding: Steel containing 1% Al is heated in presence of NH3. It will produce hard coating of Iron and
aluminium nitride on surface of steel. This kind of steel is used in drill machine.
5. Case Hardening: In this steel is heated upto redness in presence of hydrocarbon or K4[Fe(CN)6]. Then
it is cooled by using NaCN solution. Surface of steel become very hard due to formation of Iron
carbide. This kind of steel become very hard and used in formation of cutting tools.
Common method of
Metal Occurrence Remarks
extraction
Electrolysis ofAl2O3 For the extraction, a
1. Bauxite, Al2O3.x H2O
Aluminium dissolved inmolten good source of
2. Cryolite, Na3AlF6
Na3AlF6 electricity is required
Reduction of Temperature
1. Haematite, Fe2O3
Iron theoxide with COand approaching 2170 K
2. Magnetite, Fe3O4
coke in Blastfurnace is required.
It is self reduction in a
specially designed
1. Copper pyrites, CuFeS2
converter. The
2. Copper glance, Cu2S Roasting reduction takes place
Copper 3. Malachite, ofSulphidepartially easily. Sulphuric acid
CuCO3.Cu(OH)2 andreduction leaching is also used
4. Cuprite,Cu2O
in hydrometallurgy
from low grade ores.
1. Zinc blende or
The metal may be
Sphalerite, ZnS Roasting followedby
Zinc purified by fractional
2. Calamine, ZnCO3 reduction withcoke distillation.
3. Zincite, ZnO
PURIFICATION PROCESS
1. Polling Process: This method is used when impure metal have impurity of its own oxide.
Eg. Impure Tin have impurity of SnO2 and blister copper have impurity of Cu2O.
 In this method impure metal is stirred with green wood poles. Green wood produces
hydrocarbon it will reduce metal oxide.
Green Wood + Heat  CH4
4Cu2O + 4CH4  8Cu (l) + CO2 + 2 H2O
 It is used for Cu & Sn.
 Other oxidisable impurity are removed by hot blast of air.
2. Liquation Process / Method:

It is used when there is a different in melting point of metal & impurity and best used when metal have
low melting point than impurities.
 By this method lead is removed from Zn-Ag all
 This method is used for Sn, Zn,Bi, Hg and Pb.
3. Distillation Process:
 It is used when there is difference in boiling point of metal & impurity.
 Here metal & impurity have different degree of volatility.
 In this method impure metal is heated in a restort and formed volatile substance is collected in a
receiver where we can condensed the vapour. In this way we can separate metal from impurity.
 This method is used mainly for Zn, Cd & Hg.
4. Zone Refining Method:

 This method is based on the basis of fractional crystallization.
 It is based on the principle of fractional crystallization that impure molten on gradual cooling
will deposite particles of pure metal first.
 By this method semiconductors can be developed & metal obtained in ultrapure state.
5. Vapour Phase Refining:

In this method, the metal is converted into its volatile compound and collected elsewhere. It is then
decomposed to give pure metal. So, to apply this method the two requirements are:
(i) the metal should form a volatile compound with an available reagent,
(ii) the volatile compound should be easily decomposable, so that the recovery is easy.
Following examples will illustrate this technique.

Mond Process for Refining Nickel:In this process, nickel is heated in a stream of carbon monoxide
forming a volatile complex, nickel tetracarbonyl:
330350K
Ni + 4CO   Ni(CO)4
The carbonyl is subjected to higher temperature so that it isdecomposed giving the pure metal:
450770K
Ni(CO)4   Ni + 4CO
van Arkel Method for Refining Zirconium or Titanium: This method isvery useful for removing all
the oxygen and nitrogen present in theform of impurity in certain metals like Zr and Ti. The crude metal
isheated in an evacuated vessel with iodine. The metal iodide beingmore covalent, volatilises:
Zr + 2I2 → ZrI4
The metal iodide is decomposed on a tungsten filament, electricallyheated to about 1800K. The pure
metal is thus deposited on thefilament.
ZrI4 → Zr + 2I2
 Zr, Ti& B Hf are purified by this method.
6. Electrolytic Refining:
 It is used mainly for Cu, Zn, Pb, Sn, Al, Ag, Au
 Requirement
(i) Impure metal Rod Anode
(ii) Pure metal Rod  Cathode
(iii) Electrolytic Solution
(iv) Current Sources (dc)
Electrolysis of CuSO4 Using Cu – Electrodes:
Anode: (Oxidation)
(i) 2H2O  O2 + 4H+ + 4e–; ESOP = – 1.26V
(ii) Cu  Cu2+ + 4e– ; ESOP = – 0.34V
As Esop of (ii) is more , it is feasible.
Cathode:
(i) Cu2+ + e–  Cu(s); ESRP = + 0.34V
– –
(ii) 2H2O + 2e  H2 + 2OH ; ESRP = – 0.83V
2+
 Cu from impure rod through solution goes to pure metal rod & pure metal rod is taken out.
 At Anode compartment inert metal are found which are neither oxidized nor soluble in sulphate
solution.
Metal Electrolyte
Cu CuSO4 + H2SO4
Ni Ni(NO3)2 + HNO3
Pb PbSiF6 + H2SiF6
Zn ZnSO4 + H2SO4
Ag AgNO3 + HNO3
Au AuCl3 + HAuCl4
Al Na3AlF6 + CaF2
 Purify upto 99.99% can be obtained by this method.
7. Amalgamation Process:
 In this process metals forms amalgam with-Hg except Fe, Ni and Pt.
 Ag and Au are refined by this method.
heat 750C
Ag + Hg   Ag·Hg  
impure Amalgum
Impurities + Hg  No rvn.
8. Cupellation (Oxidative Refining):
In this method impure metal is heated in a cupel made of cement or bone ash and a blast of hot air over
the molten mass. By this method Pb is removed from silver because Pb have more affinity with oxygen
to form its oxide. Here impurity (Pb) is removed in turn of oxide.
1
Pb + O2  PbO
2
9. Chromatography Method:
This method is used when substance is present in very small or minute amount. This method is based on
the principle that different substance is absorbed at different absorbent.
10. Parke’s Process (Desilverisation of Lead):

By this method silver is removed from lead.
In this zinc is used as solvent. Impure metal is heated in presence of excess zinc. Lead is very less
soluble in zinc but silver have 300 times more solubility than lead in zinc. Silver form Zn-Ag alloy
with Zn and floats on upper part of Pb. Which can be skinned off to get pure Pb free from Ag.

Metallurgy

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CHEMICA Chemistry Classes _________By DheerendraShrivastva (DS Sir)

4. Ores Containing Oxo Anions:

Basic Flux: CaO, MgO

Natural Flux: NaCl, CaF2, Na3AlF6 (Fluorspar and Cryollite)

General Metallurgical Process

Physical Method Chemical Method

 Metal which have high polarizing power are best concentrated.

Conversion of Ore to Oxide

Selection of Reduction Process (Reducing Agents)

|S3 | > | S2| > |S1 |

PbS + 2 PbO  3Pb +SO2

4. Reduction ByAluminium (Alumino Thermite Process):

Step-I Concentration of Ore:

Red Bauxite White Bauxite

Bayer’s Process Hall Method Serpeck’s Process

 Al2O3 + 3H2O 2Al (OH)3

Al2O3 + Na2CO3  2NaAlO2 (soluble) + CO2

Al2O3 + 3C + N2AlN + 3CO (g) 

Extraction of metal Aluminium from Pure Allumina

Pure A() Layer III (Cathode)

Na3 [AF6] + CaF2 Layer II (Electrolyte)

Impure A() Layer I (Anode)

Extraction of Silver (Marc. ArtharCynaidation Process)

Upto this stage after removal

1. Carbon Reduction Method:

(i) Froath Floation

Extraction of Zinc from ZnS [Zinc Blende]

Step-I: Concentration: Froath Floatation Process.

IInd Method:( expensive method)

MgC2 (Soluble) due to high

MgC2 MgC2 ·6H2 O

Direct heating of MgCl2·6H2o hydrolysed it in MgO & HCl.

B.: Extraction from Magnasite (MgCO3)

Step-I Reaction with Ca(OH)2

Roasting & Calcination:

Roasted Ore /Calcinedore : Coke Powder : Lime Stone = 8:2:1

900k – 1500k (Heat absorption Zone)

C(s) + CO2 (g)  2CO (g)

Ca3(PO4)2 present in lime stone is reduced to phosphorus by coke.

Heat Treatment of Steel:

2. Liquation Process / Method:

4. Zone Refining Method:

5. Vapour Phase Refining:

Following examples will illustrate this technique.

 Zr, Ti& B Hf are purified by this method.

10. Parke’s Process (Desilverisation of Lead):

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