UNIT : 12 GENERAL PRINCIPLES AND

PROCESSES OF ISOLATION OF METALS

Important Points
Occurrence of elements: Highly electropositive metals of S-block occur in nature in combined state with
several anions. The lesser electropositive metal like chloride, silicate, carbonate (p & s block) occur as sulphides;
while noble metals like Au, Pt, Ag are dative that is free state.
Abundance:

Ten abundant elements in Earth’s crust:

Mineral: The chemicalcompounds ormetalcompounds which occur naturally in earth’s crust are known
as minerals.
Ores: The minerals from which metal can be extracted economically are known as ores.
It can be concluded that “all minerals are not ores but all ores are minerals”.
Principal Ores of some metals:
Metal Ore Composition
Al Bauxite Al2O3.2H2O
Corundum Al2O3
Diaspora Al2O3.H2O
Cryolite Na3AlF6
China Clay Al2O3.2SiO2.2H2O
Mica K2O.3Al2O3.6SiO2
Feldspar KAlSi3O8
Cu Malachite CuCO3.Cu(OH)2
Azurite 2CuCO3.Cu(OH)2
Copper pyrites CuFeS2
Copper Glance Cu2S
Fe Iron Pyrites FeS2
Haematite Fe2O3
Magnetite Fe3O4
Limonite Fe2O3.3H2O
Siderite FeCO3
Zn Zinc Blend /Sphalerite ZnS
Calamine ZnCO3
Zincite ZnO

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Different methods of concentration of ores:
1) Gravity separation: Principle used: difference in specific gravity.
2) Magnetic separation: Principle used: difference in magnetic properties.
3) Froth Flotation: Principle used: differential wetting properties.
I. Substances used: Frothing agent & collecting agent like pine oil and Sodium Ethyl Xanthate
respectively.
II. Froth Stabilizers: Cresols and Aniline.
III. Depressant: Used to prevent certain type of particles from forming the froth.
4) Leaching: The ore is treated with chemical to make it soluble. It is also used in concentration of
noble metals like Gold, Silver, which occur in Free State.
Different methods of reduction
Chemical reduction:
Using Carbon: Carbon is useful as a reducing agent because it is very cheap and can be used for
reduction of several metal oxides. The ore is mixed with coke with flux and heated to high temperature.
This is called smelting or pyrometallurgy.
Using more reactive metals: For extraction of lesser electropositive metal, Al powder can be used.
The process is known Aluminothermite or Thermite.
Oxides of Cr, Mn are reduced by Aluminum.
Auto reduction: Reducing agent is not required. Cu2S + Cu2O ® 4Cu +SO2
Electrolytic reduction: Highly electropositive metals like Na, Mg, Ca etc cannot be reduced using
carbon, carbon monoxide or metal. Therefore these elements are extracted electrolyitcally using fused
salts of the metal. It is mainly used for S-block elements and Al.
Different methods used in refining
The removal of impurities from metals after extraction is known as refining. The refining technique
depends upon the nature of impurity and metal and the use to which the metal is put.
Refining techniques can be classified into 2 types:
(1) Physical (2) Chemical.
Physical:

Method Principle or property Process Metals purified

Liquation Difference in fusibility of metal Heated on a sloping hearth. Impurities Bi, Sn, Pb, Hg.
impurities. remain behind and metal flows down.
Distillation Used for volatile metal. Metal is heated and vapor of pure metal are Zn, Cd,Hg
Difference in volatile character. condensed in a receiver.
Zone Difference in solubility of The circular heater is fitted round a rod of Very high purity
refining impurity in molten and solid impure metal and is slowly moved down the viz Ge, Ga
state. rod.

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Thermodynamic principles of metallurgy:

The basic concepts of thermodynamics are useful in selection of reducing agent for a particular oxide.

Free energy of changes during reduction process are important. For a reaction to be spontaneous free
energy changes must be negative. Any compound with lower value of standard free energy of
formation is more stable. They are converted to oxide prior to reduction.

DG = DH - TDS DG= Change in free energy

T= Temperature in Kalvin
DS= Enthalpy change
DG 0 = -RTlnK
= -2.303 RT log10 K K= equation constant
R= Universal gas constant
If K value is high, it indicted [P] >> [R] & DG 0 becomes more negative
Eg. 2Mg(s) + O 2(g) 2MgO (s)- DG 1000’c = -941KJ/mole

2C (s) + 2CO (g) DG 1000’c = -439 KJ/mole

MgO + C ® Mg + CO

DG = SG p - SG r

= -439 + 941

= +502
Since DG is +ve carbon cannot be used as reducing agent

2Zn + O 2 ® 2ZnO DG 1100’c = -360 KJ mol-1

2C + O 2 ® 2CO DG 1100’c = -460 KJ mole-1

SG = SG p - SG r

= -460 – (- 360)

= -100 KJ mol-1
Reduction is possible.

Electrochemical Principle

Electrode potential DG 0 = - nFE0

This concept is useful in electrolytic reduction. If E0cell is positive the DG 0 is negative. Therefore
reaction is spontaneous.

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Types of iron preparation Impurities &Properties Uses

Pig iron Obtained from blast 4%C &S ,P Manufacture of cast

furnace iron

Cast iron Blowing hot air in 3%C Gutter pipes, Lamp

mixture of pig posts, casting of
iron,iron scrap Hard & brittle articles like stoves
&coke etc. It does not rust.

Wrought iron Heating cast iron in Purest form of iron.It is Anchors, chains nails
reverberatory extremely tough with high etc
furnace lined with melting point &malleable.
hematite, limestone
is added as flux to
remove S,P,Si
(impurities)

Fe2O3 +C(cast
iron)à2Fe +CO

Metal from is
passed furnace is
passed through the
rollers to remove
impurities

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Þ Manufacture of Zn Continued
ORE

Crushing

Forth flotation if Zn blend Concentration

Rosting, Calcination ZnS + 3O 2 ® 2 ZnO + 2SO 2

D
ZnCO3(s ) ¾
¾® ZnO(s ) + CO 2 ( g )
Reduction

Chemical with Carbon Leaching

ZnO(s) + C(s) ¾¾
Δ
® Zn (s) + CO (g) ZnO + H 2SO 4 ¾¾®
ÏÜع
ZnSO 4 + H 2 O
Heated ZnOwith coal ZnSO4 impurities like Cd, Fe, Sb & As
in cylindrical retortØ (i) Zn Dust (ii) Filter
Zn vapours are cooled and Cdppq ZnSO4 + Soluble Salt of Fe, Sb, AS
Collected (i) Ca(OH)2
(ii) Filter
Impure Zn or spelter Soluble ZnSO4 Pot of hydroxides of Fe, Sb, As

Purification Pure ZnSO4

Electrolysis

Liquidation Distillation Electrolytic Pure Zn 99.9%

refining

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 M.C.Q.
1) The most abundant metal in the earth crust
a) Al b) Fe c) Ca d) Na
2) The impurities associated are
a) Flux b) Gangue c) Slag d) Ore
3) An ore after concentration was found to have basic impurities. The flux which can be used is
a) CaCO3 b) SiO2 c) FeO d) Ca(OH)2
4) Choose the correct statement
a) All ore are mineral b) All mineral are ores
c) Minerals are not ores d) a & b
5) A metal oxide is reduced with a metal, M1 of pd 3 & Gp13. The process is known as ____ & the metal
is
a) Pyrometallurgy &Mg b) Thermite & Ga c) Liquation & Al d) Thermite & Al
6) Diaspore & Corundum are ores of ______ & ______
a) Al & Fe b) Fe & Al c) Al & Al d) Si & Al
7) Choose the correct option
a) Siderite à FeCO3 b) Limonite à Fe2O3 c) Calamine à ZnCO3 d) a & c
8) The salt which is most unlikely to occur as mineral is
a) Bromide b) Sulphate c) Oxide d) Sulphides
9) During concentration of ore by froth flotation, the ore particles float on surface because:
a) Ores are insoluble b) Sulphides ores are lighter
c) The surface is not wetted by H2O d) Difference in densities
10) An ore contains Pbs with impurity Zns. NaCN is added in the froth flotation process ZnS does not form
the froth because
a) NaCN forms a complex of ZnS on surface of ZnS b) ZnS is not wetted by pine oil
c) ZnS is wetted by H2O d) NaCN reacts with ZnS ionic compound
11) The method used for concentration of magnetic ore is
a) Gravity separation b) Froth floatation c) Magnetic separation d) Leaching
12) During froth flotation process the student observed that the froth was disappear after formation. The
student added-----_______to the container to overcome the difficulty
a) Pine oil b) Cresol c) Benzene d) NaCN
13) Silver ore is related with NaCN(aq) to
a) Reduce silver b) Extract pure silver
c) Refine silver d) To remove the impurities

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14) The principle involved in leaching is
a) Difference in volatility b) Difference in density
c) Difference in solubility d) Soluble complex formation
15) Heating of ore in presence of O2 below its melting point is known as
a) Roasting b) Calcinations c) Smelting d) b & c
16) During electrolysis graphite is used as an electrode & not diamond because
a) Graphite is cheaper b) Graphite is soft
c) Graphite posses free electron while diamond doesn’t d) Graphite is non reactive
17) Group 1 & 2 elements are extracted by
a) Thermite process b) Electrolytic method c) Bessomerisation d) Cupellation
18) Hydrometallurgy is used in extraction of
a) Sodium b) Manganese c) Iron d) Silver
19) Several metals are commercially produced by reduction of oxides by carbon. The oxides which can be
reduced with carbon are
a) ZnO & Fe2O3 b) CaO & Cr2O3 c) BaO & U3O8 d) SiO2 & Al2O3
20) Blister copper is
a) Pure copper b) Ore of Cu c) Alloy of Cu d) Impure copper
21) In Hall Heroult’s process cryolite is added to alumina to
a) Increase the conductivity b) Lower the melting point
c) Increase the mobility of iron d) All of above
22) During extraction of metal charcoal powder is sprinkled on top of molten metal. This is useful in preventing
a) Oxidation of metal b) Formation of alloy c) Reduction d) a & b
23) zone refining is used to obtain ———— metal
a) Pure Cu b) Zirconium c) Ultrapure Si d) Nickel
24) Strongly
D
Metal + _______ à Volatile compound ¾¾¾¾
Strongly
® Pure Metal

This method is known as

a) Liquation b) VanArkel c) Zone refining d) Distillation
25) ______ metal is purified by Mond’s process
a) Zr b) Ti c) Ge d) Ni
26) The slag obtained during manufacture of Cu is
a) CaSiO3 b) FeSiO3 c) CuSiO3 d) FeO

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27) The principle used in zone refining
a) Fractional distillation b) Adsorption
c) Fractional crystallisation d) Chromatographic separation
28) In the reaction 2MO(s) + C(s) à M(s) + CO2(g) the entropy of the reaction will
a) Decreases b) Increases
c) Remain constant d) May increases or decreases
29) In electrolytic refining of copper, anode mud contains
a) Earthly impurities b) Zn & Mn c) Noble metal d) Oxides of Cu
30) Zn is extracted from ZnS. The reducing agent used is _________ & method of refining is ______
a) Coke & Electrolysis b) Mg & Liquation
c) Coke & Zone refining d) Coke & fractional distillation
(31 To 40 are match the following sets.)
31) Set 1 Set 2
1) Al p) Haematite
2) Fe q) Nuggets
3) Zn r) Sphalerite
4) Ag s) Feldspar
t) Limonite
a) 1-p, 2-t, 3-r, 4-q b) 1-s, 2-p & t, 3-r, 4-q
c) 1-s, 2-r & t, 3-p, 4-q d) 1-p, 2-t, 3-r, 4-s
32) Set 1 Set 2
1) Pi g iron p) Hard & brittle
2) Cast iron q) Prepared from cast Fe
3) Wrought iron r) Prepared by methyl pig iron
s) Malleable
t) Fe + 4% C
a) 1-t, 2-p & r, 3-q & s b) 1-t, 2-r , 3- s
c) 1-p, 2-r & t, 3-q & s d) 1-p, 2-s & r, 3-t & q
33) Set 1 Set 2
1) Cr2O3 + Al p) electrolysis
2) Zinc q) Bayer’s process
3) M2O3 + NaOHà r) Thermite
D
Soluble ¾¾ ® M2O3 s) Hall Heroult

a) 1-r, 2-p, 3- s b) 1-r, 2-s, 3- p c) 1-s, 2-p, 3-q d) 1-r, 2-p, 3-q

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34) Set 1 Set 2
1) Chromatography p) Chemical process
2) Poling q) Difference in solubility
3) Liquation r) Difference in meltingpoint
4) Zone refining s) Low boiling point metal
t) Adsorption
a) 1-r, 2-p, 3-s, 4-q b) 1-q, 2-r, 3-p, 4-s c) 1-t, 2-p, 3-s, 4-q d) 1-p, 2-p, 3-s, 4-q
35) Set 1 Set 2
1) Earthly impurities p) Froth flotation
2) Sulphide ores q) Magnetic separation
3) Bauxide r) Gravity separation
4) Magnetite s) Leaching
a) 1-p, 2-r, 3-s, 4-q b) 1-r, 2-p, 3-s, 4-q c) 1-q, 2-r, 3-p, 4-s d) 1-s, 2-p, 3-r, 4-q
36) Given below are the different temperature reactions & products during extraction of iron in blast furnace
1) 5000-8000 K p) Pig iron
2) 12700 q) Molten slag
3) 21700 r) C + O2 à 2CO
4) 2170 s) 3Fe2 O3 +COà 2Fe3O4 +CO 2
5) > 2170 0
t) CaO + SiO2 à CaSiO3
a) 1-s,2 q,3r,4-p b) 1-s,t ; 2-r,3-q ,4-p
c) 1-r,s ;2-t,3-p,4-q d) 1-s,2-r,3-q,4-ps
37) Set 1 Set 2
1) Bauxite p) Bayers
2) Zinc blend q) Blast Furnace
3) Copper pyrites r) Hall- heroult
4) Haematite s) Bessemerisation
t) Fire Clay cylindrical retort
a) 1-r & p, 2-t, 3-s, 4-q b) 1-p, 2-t, 3-s, 4-q c) 1-r, 2-s, 3-s, 4-q d) 1-r, 2-t, 3-s, 4-q
38) Set 1 Set 2
1) Zn p) Auto mobiles
2) Wrought iron q) Galvanising
3) Steel r) Bell Meta
4) Copper s) Muntz Metal
t) Anchors
a) 1-s, 2-r, 3-t, 4-q b) 1-q & r, 2-t, 3-p, 4-r & s
c) 1-q, 2-s, 3-p, 4-r d) 1-q, 2-t, 3-p, 4-r & s

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39) Set 1 Set 2
1) Electrolysis p) Wide range of temperature
2) Zone refining q) Adsorption
3) Blast furnace r) Electrode potential
4) Liquation s) Noble gas atmosphere
t) Low meltingpoint
a) 1-r, 2-t, 3-p, 4-t b) 1-r, 2-s, 3-p, 4-t c) 1-r, 2-s & t, 3-p, 4-q d) 1-t, 2-s, 3-p, 4-r
40) Set 1 Set 2
1) Non spontaneous p) DG= 0
2) spontaneous q) K < 1
3) Equilibrium r) DG decreases
s) K > 1
t)
a) 1-q, 2-r & s, 3-p & t b) 1-q, 2-r & s, 3-p c) 1-t, 2-r & s, 3-p d) 1-q, 2-r, 3-p
Questions 41 to 51 are assertion reason type
a) Statement 1 is correct, statement 2 is the correct reason for statement 1
b) Statement 1 is correct, statement 2 is correct but does not give reason of for statement 2
c) Statement 1 is correct, statement 2 is false
d) Statement 1 is false, statement 2 is correct
41) Statement 1) Magnesium is mainly extracted by electrolysis of molten electrolyte and not by
chemicalmethods.
Statement 2) The DiH of Mg is very low & hence it is very difficult to reduce Mg2+(aq)àMg(s)
42) Statement 1) Cu is obtained by ____ . Then by pdt CO2 obtained
Statement 2) The by-product obtained is SO2& is used in manufacture of sulphuric acid.
43) Statement 1) In Bayer’s process the ore is heated with Conc. Ca(OH)2.
Statement 2) The ore used in Bayer’s process is atmospheric & is soluble in NaOH therefore ore
is concentrated.
44) Statement 1) Froth flotation is used for concentration of sulphide ores.
Statement 2) Cresol is used as a depressant in froth flotation.
45) Statement 1) Metal oxide can be easily reduced with carbon
D
Statement 2) Metal oxide + C ¾¾ ® Melted + CO DG = -x KJ

46) Statement 1) DG = -nFE0 is applicable to metallurgy

Statement 2) If cell potential is negative electrolytic reduction of metal ions is possible

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47) Statement 1) Ultra pure silicon is manufactured by vapour phase refining
Statement 2) Vapour phase refining gives ultra pure metals
48) Statement 1) Ni is converted to Ni(CO)4 in Mond process
Statement 2) Ni(CO)4 is volatiles & the compound can be easily disposable
49) Statement 1) Mercury is purified by distillation
Statement 2) Mercury has low melting point
True / false questions (50-58)
50)
1) Ag & Au are manufacture by hydrometallurgy
2) Fe can be extracted by electrolytic method
3) Mg is extracted from aq MgCl2 by passing electric current
4) Zn is extracted from Zinc blend by using coal or anthracite coal
a) TFFT b) TFTT c) FFFT d) FFTT
51) The metals which can be extracted using carbon/coke
1) Magnesium
2) Iron
3) Potassium
4) Zinc
a) FTTF b) TTFF c) TTFT d) FTFT
52)
1) DG0 = -nFE0
2) The above equation is the principle used in electrolytic reduction for manufacture of metals
D
3) 2Cu2S(s) + 3O2(g) ¾¾ ® 2Cu2O(s) + 2SO2(g) DS is positive in this reaction

4) DG = DH – TDS if free energy change is negative the reaction is spontaneous

a) TFFT b) TTFT c) TTTT d) TFTF
53)
1) Kaolinite is an ore of Al
2) Sphalerite is an ore of sulphide of Cu
3) Malachite is an oxide ore of copper
4) sphalerite is iron carbonate
a) TFTT b) TTFT c) TFFT d) TFFF

279
54)
1) Ore is heated strongly during calcinations to remove all volatile impurities
2) Ore is heated with oxygen during roasting to convert sulphide to oxide
3) Cryolite is added to bauxite in Hall Heroult’s process to increase solubility of bauxite in ____
4) After leaching of bauxite, it is directly used as an electrolyte
a) TTFF b) TTFT c) TTTF d) TFFT
55)
1. The reduction reaction by accepting electrons is known as electro nation
2. In extraction of Gold and silver by process of leaching K > 1
3. If DH = -1369 KJ/ mol-1, DS= +26 J/mol-1 T = 400K for the reaction
A + B à C the reaction is non spontaneous
a) TTT b) TTF c) TFT d) TFF
56)
1. Chewing of cathode occurs in Hall Heroult’s process
2. When water is added after digesting boxide, CO2 is bobbled to nutrelise the solution
3. HCl can not be replaced in (2) because AlCl3 is formed which is highly soluble
a) FTF b) TTF c) FFF d) FTT
57)
1. Al is used in preparation of parts of airplane and manufacture of alloy alnico.
2. Copper is used in preparation of tubes of boilers, delta metal and muntz metal.
3. Copper and aluminum are used in alloys – Duralumin, Aluminum bronze.
4. Cu & Zn are used in manufacture of German Silver.
a) TFTF b) TTFT c) TFFT d) TFTT
58)
1. Wet metallurgical process is used for pyrites ores of lower grade.
2. 2Cl- +2H2Oà2OH- +H2 +Cl2 The cell potential is -2.186V.This reaction will take place in forward
direction.
3. Pure Zn metal is called spleter.
4. The abundance of Al is highest .Its place is third & is about 8.3% by weight.
a) TFFT b) TTTT c) FTFT d) FFFT

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 Linked Comprehension type:
59) Cassiterite ( SnO 2) and ore of Tin contains FeWO4 & MnWO 4 as impurities as well as small
amounts of sulfur. SnO2 is melted with cold, Lime stone and sand in a reveberatory furnace.
The impure Tin Sn is purified by liquation
I. The ore is concentrated by
A) Froth flotation B) Magnetic separation
C) Leaching D) a & b
II. The impurities of sulfur can be removed by
A) Treatment with NaOH B) Treatment with HCl
C) Roasting D) Calcinations
III. If limestone and sand are added during smelting the nature of impurities are
A) Acidic and basic B) Amphotric C) Acidic D) Basic
(a) i-B, ii-C, iii-C, iv-B (b) i-C, ii-D, iii-D, iv-A
(c) i-A, ii-C, iii-B, iv-C (d) i-A, ii-C, iii-A, iv-B
55) DG 0f for CuS, CaS, SO2, CS 2 & CuO are -49, -1230, -300.4, +63.6 & - 127.2 KJ/ mol-1
respectively.
i. The most stable and unstable compounds are
A) SO2 & CaS B) CaS & CS 2 C) CuS & SO2 D) CaS & SO2
ii. CuS & CaS are reduced with Carbon to give Cu or Ca and CS2. The reaction which will
be spontaneous is
A) Reduction of CuS because DG is positive
B) Reduction of CaS because DG is negative
C) Both are spontaneous because DG is positive
D) Both are non spontaneous because DG is positive
iii. The DG 0 for the reaction 2CuS + 3O2 à 2CuO + 2SO 2 is ________ & the reaction
is _________
A) – 756.8KJ & Spontaneous B) +756.8KJ & non- Spontaneous
C) -378.4KJ & Spontaneous D) +378.4 KJ & non-Spontaneous
(a) i-B, ii-D, iii-A (b) i-D, ii-C, iii-B (c) i-B, ii-D, iii-C (d) i-C, ii-B, iii-D

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 ANSWER KEY
1 A 16 C 31 B 46 C
2 B 17 B 32 A 47 D
3 B 18 D 33 D 48 A
4 A 19 A 34 C 49 A
5 D 20 D 35 B 50 A
6 C 21 B 36 D 51 D
7 D 22 A 37 A 52 B
8 B 23 C 38 D 53 C
9 C 24 B 39 B 54 A
10 A 25 D 40 B 55 B
11 C 26 B 41 A 56 D
12 b 27 C 42 D 57 B
13 D 28 B 43 D 58 A
14 D 29 C 44 C 59 D
15 A 30 D 45 A 60 A

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