Revision Notes

Class - 12 Chemistry

Chapter 6 – Metallurgy

1. INTRODUCTION:

Mineral is the natural compound of a metal and non-metal. Metals can be extracted
from minerals. A naturally existing solid material from which a valuable metal or
mineral can be commercially mined is called an ore. Ore is contaminated with
impurities or undesired material known as gangue. All ores are minerals, but the
reverse is not true.

Some Important Ores of Metals

Metals Ores Composition

Aluminum Bauxite Al2 O3  2H 2

Corundum Al2 O3  H 2
Al2 O3

Iron Haematite Magnetite

Fe2 O3
Siderite Iron pyrite
Fe3O4
FeCO3
FeS2
Fe2 O3 .3H 2

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Copper Copper pyrite Copper
CuFeS2
glance Cuprite Malachite
Cu 2S
Cu 2
Azurite
CuCO3  Cu(OH) 2
2CuCO3  Cu(OH) 2

Zinc Zinc blende or Sphalerite

ZnS
Calamine ZnCO3
ZnO
Zincite

Lead Galena Anglesite

PbS
PbSO 4
Cerussite
PbCO3

Magnesium Carnallite Magnesite

KCl.MgCl2 6H 2 O  K 2 MgCl4  6H 2O 
Dolomite
MgCO3
MgCO3CaCO3
Epsom salt (Epsomite)
MgSO4 7H 2
K 2 Mg 2  SO4 3

Tin Cassiterite (Tin Stone)

SnO2

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Silver Silver glance (Argentite)
Ag 2S
Pyrargyrite (Ruby Silver)
Ag 3SbS3
Chlorargyrite (Horn silver) AgCl
Stefinite Ag 5SbS4
Ag 3 AsS3
Proustite

2. METALLURGY

The process used for the extraction of metal from its ore is known as metallurgy.
The isolation and extraction of metal can be done in the following 4 steps:

Crushing of the ore, Dressing or concentration of the ore, Isolation of the crude metal
from its ore, Purification of refining of the metal.

Crushing and Grinding

Jaw crushers first crushes the ore and then is grinded to a powder form (pulverization
of the ore) in equipment like ball mills.

Concentration

The removal of undesired material from ore is known as dressing or beneficiation of

ore.

Hydraulic Washing

It is based on the density differences between the gangue and or particles. The ore is
agitated with water or washed with an upward stream of running water, and the
lighter particles of sand, clay, and other impurities are washed away, leaving the
heavier ore particles behind.

Electromagnetic Separation

It's based on the magnetic characteristics of the ore's constituents. When the ore or
the contaminants connected with it are magnetic, this method is utilized. A magnetic

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separator is made up of a belt (made of leather or brass) that moves over two rollers,
one on each side. When the powdered ore is dumped on the belt at the other end, the
magnetic component of the ore is drawn to the magnetic roller and falls closer to it,
while non-magnetic impurities fall away. For example, chromite ore is separated
from non-magnetic siliceous material.

Froth Floatation Process:

Low grade sulfide ores such as galena, copper iron pyrite, zinc blend are usually
concentrated from this method. It is based on the fact that the degree of wet ability
with water varies in gangue and ore. Generally, the gangue particles are wetted by
water and ore particles are wetted by oil.

When a mineral has impurities such as other minerals. The presence of these
substances helps to separate the impurities by activating or depressing the flotation
property of other minerals present as impurities. Zinc blended and pyrites are present
as impurities in galena. Potassium ethyl xanthate is used as a collector and NaCN
and Na 2 CO3 is used as a depressant in the flotation process.

2.2.4 Leaching of alumina from bauxite:

Bauxite, the primary source of aluminium, typically contains impurities such as SiO
iron oxides, and titanium oxide. The powdered ore is digested with a concentrated
solution of NaOH at 473  523 K and 35  36 bar pressure to concentrate it. Al2 O3 is
leached out as sodium aluminate in this fashion leaving behind the impurities
present.

Al2O3  2NaOH  3H 2O  2Na Al  OH 4 

By passing carbon-dioxide gas through the solution, the aluminate is neutralized,

and hydrated Al2 O3 is precipitated. The solution is seeded with freshly prepared
samples of hydrated Al2 O3 at this point, causing Al  OH 3 to precipitate.

2Na  Al  OH 4   CO 2  Al 2O3 .xH 2O  2NaHCO 3


Al2 O3 .xH 2 O   Al2 O3  xH 2 O

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The corresponding metal/ore is leached with a dilute solution of NaCN or KCN in
the presence of air in the metallurgy of silver and gold, and the metal is recovered
subsequently by displacement with zinc scrap. The Mac-Arthur Forrest Cyanide
process is another name for it.

Extraction of crude metal from concentrated ore

The concentrated ore must be transformed into a form that can be reduced. Before
reduction, the sulfide ore is usually transformed to oxide. Oxides are a lot easier to
get rid of. As a result, the separation of metals from concentrated ore is divided into
two key phases, as shown below.

(I) Conversion to oxide; (ii) Conversion of oxide to metal.

Conversion to oxide:

The process of converting ore to oxide is carried out in two ways depending on the
nature of ore.

Calcination: Calcination is the process of rapidly heating the mined ore in the
absence of air or with a limited supply of air. The following changes occur as a result
of the calcination process:

(a) The carbonate ore decomposes to generate the metal's oxide. For example,

FeCO3   FeO  CO 2 


CaCO3   CaO  CO 2 

(b) Water of crystallization in the hydrated oxide ore is lost as moisture, for example

2Fe 2 O3 .3H 2 O   2Fe 2 O3  3H 2O

(c) Organic stuff in the ore is ejected, causing the ore to become porous. Impurities
that are volatile are eliminated.

Roasting: It is a method of severely heating the concentrated ore (usually sulphide

ore) below its melting point in an abundance of air. Once the roasting and exothermic
process has begun, no extra heat is required.

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
2PbS + 3O 2   2PbO  2SO 2


2ZnS + 3O 2   2ZnO  2SO 2

2CuFeS2  4O2  Cu 2S  2FeO  3SO2

Self-reduction, auto-reduction, and air-reduction are among the terms used to

describe the direct reduction of sulphide ore into metal by heating it in air. The SO 2
generated is used in the production of H 2SO 4 .

Reduction of metal oxide to the metal

After that, the calcined or roasted ore is converted to a metallic form in one of two
ways.

Reduction by carbon (Smelting)

Smelting is the process of reducing an oxide with carbon at a high temperature. The
oxides of less electropositive metals such as Pb,Zn,Fe,Cu and others are reduced in
the blast furnace by heating them vigorously with coal or coke. Slag is a flammable
substance that forms during the reduction process. Slag is made up of two parts:
gangue and substance (for removing gangue) Fluxes are substances that are used to
remove gangue. Acidic fluxes: SiO2 , borax (remove basic impurity).
MgO,MgCO3 ,CaCO3 are basic fluxes (remove acidic impurity).

When the melting point of a compound is too high, Al powder is used as a reducing
agent, and the result is thermite, which is referred to as the Gold-Schmidt Alumino
Thermite method. Coke isn’t helpful for s-block oxide and Al2 O3 isn’t helpful for d-
block oxide due to the presence of metal carbides. CaO  2C  CaC2  CO

Examples of some reaction are: CuO  CO  CO2  Cu , ZnO  CO  CO2  Zn ,

PbO  C  CO  Pb


Acidic fluxes: SiO 2  CaCO3   CaSiO3  CO 2 


Basic fluxes: SiO 2  MgCO3   MgSiO3  CO 2 

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Self reduction: Certain metal compounds are reduced to metal without the use of
additional reducing agents, such as ores of Cu,Pb and Hg. To produce oxide, their
sulfide ores are partially roasted. The residual sulfide ore now reduces this oxide to
metal at high temperatures in the absence of air. Self-reduction is the term for this
procedure. or automatic lowering. Pb reduces through self-reduction. The reactions
are shown below.

2PbS  3O2  2PbO  2SO2

PbS  2PbO  3Pb  SO2

Metal Displacement Method

The ore is converted into a water soluble chemical in this technique. The compound's
aqueous solution is reacted with a more electropositive metal, which causes the
metal to be displaced from the solution. For example, (i) Zairvogel process of silver.
(ii) Separation of silver by complex formation

Silver and gold are extracted using a complicated forming procedure. In the presence
of air, powdered argentite is reacted with a dilute solution of sodium cyanide. The
ore's silver dissolves in the cyanide solution, resulting in sodium argentocyanide.

Ag 2S  4NaCN  2Na  Ag  CN 2   Na 2S

When metallic zinc is introduced to the complex salt solution, it displaces silver from
the solution since it is a more electropositive element than silver.

2Na  Ag  CN 2   Zn  Na 2  Zn  CN 4   2Ag

[Link]: Electrolytic reduction

This method is typically used to extract highly electropositive metals. Electrolysis is

performed in large cells with the addition of a small amount of another suitable
electrolyte that: (a) lowers the melting point of the main electrolyte (b) improves its
conductivity (c) reduces corrosion problems. For example, Na,Mg,K,Al,Ca.

(a) Manufacture of metallic sodium(Down’s process)

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Between the graphite anode and the iron cathode, molten NaCl with a trace of CaCl2
is electrolyzed. The numerous reactions that occur are as follows:

On fusion: NaCl  Na   Cl

At cathode: Na   e  Na

At anode: 2Cl  Cl2  2e 

(b) Hall-Heroult process (electrolytic reduction): Purified Al2 O3 is combined with

Na 3 AlF6 (cryolite) or CaF2 (fluorspar), lowering the melting point and increasing
conductivity. Electrolysis is employed to dissolve the fused matrix. The cathode is
steel, and the anode is graphite. The graphite anode is important for metal reduction.
The entire reaction can be summarised as follows:

2Al 2 O3  3C   4Al  3CO 2 

Electrolysis of the molten mass takes place in an electrolytic cell with carbon
electrodes. CO and CO 2 are produced when the oxygen liberated at the anode reacts
with the carbon of the anode. This method burns away around 0.5 kg of carbon anode
for every kilogramme of aluminium produced. The electrolytic reactions are:

At cathode: Al3  3e  Al

At anode: C  O 2  CO  2e 

2.4: Purification or refining of metals

Metals acquired through reduction methods still have some undesirable impurities
and must be purified. Refining procedures differ greatly from metal to metal and
also rely on the intended application of the metal.

Liquation process:

This procedure is used to purify a metal that is readily fusible in itself but not with
the impurities existing in it, i.e. the impurities are infusible. To put it another way,
the melting point of the pure metal should be lower than the melting point of each

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of the metal's impurities. his procedure is used to purify Sn and Zn, as well as to
remove Pb from Zn  Hg alloy, which is produced by Parke's process and contains
Pb as an impurity.

Distillation process: This procedure is used to purify metals that are volatile but
contain non volatile contaminants, and vice versa. This procedure purifies
Cd,Zn and Hg.

Zone refining method (Fractional Crystallization Method)

This method is employed when extremely pure metals are required for a specific
application. Pure Si and Ge, for example, are utilized in semiconductors and are thus
purified via this approach. The zone refining method works on the idea that an
impure molten metal will deposit pure metal crystals as it cools, while the impurities
will stay in the residual molten metal.

Chromatographic methods: This method is based on the idea that different

components of a mixture are adsorbed on an adsorbent in distinct ways. The
combination is poured into a liquid or gaseous media and passed through the
adsorbent. At different levels on the column, different components are adsorbed. The
adsorbed components are then eluted (removed) using a suitable solvent (eluant).

Electrolytic Refining: Electrolytic refining is used to refine some metals, such as

Cu,Ni and Al. The Hoope's technique is an electrolytic aluminium refining method.
The Hooper's cell, which has three liquid layers, has impure aluminum as the anode
and pure aluminum as the cathode. The bottom layer is molten impure Al, the middle
layer is a fused salt layer containing aluminium fluoride, and the top layer is a pure
Al. Al flows through solution as aluminium ion  Al3  at the anode (bottom layer),
and these ions are converted to pure metal at the cathode (top layer). When the cell
is turned on, molten metal is added to the bottom and pure aluminium is extracted
from the top. The recovered aluminium is 99.98 percent pure.

At cathode: Al3  3e  Al

At anode: Al  Al3  3e

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Vapour Phase Refining: This process involves converting the metal to its volatile
component, which is subsequently collected. It is then heated until it decomposes,
yielding pure metal. In order to refine the vapour phase, the following two
prerequisites must be met.

(i) The metal should react with a reagent to generate a volatile chemical.

(ii) The volatile chemical should decompose easily, allowing for easy recovery.

SOME IMPORTANT COMPOUNDS, MINERALS, MIXTURES & THE

FORMULA

MgSO4 .7H2O CaCN 2

1. Epsom salt 21.
Nitrolium

2. Gypsum CaSO 4 .2H 2 O 22. CaH2

salt Hydrolith

3. Glauber’s Na 2SO4 .10H2O 23. Na 2CO3  K2CO3

salt Fusion
mixture

4. Lime water Ca  OH 2 24. Gun KNO3  K 2CO3

powder

5. Quick lime CaO 25. Pink  NH 4 2 SnCl6

salt

6. Washing Na 2CO3.10H2O 26. N2O

Soda Laughing
gas

7. Crystal Na 2CO3.H2O 27 Red Pb3O4

carbonate Lead

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8. Soda ash Na 2 CO 3 28 Blue CuSO4 .5H2O
vitriol

9. Baking NaHCO3 29. Green FeSO4 .7H2O

Soda vitriol

10. Turnbull’s Fe3  Fe  CN 6  2 30. ZnO

blue Chiense
white

11. Chile NaNO3 31. ZnO

saltpetre Philosphe
r’s wool

12. Indian salt KNO3 32. K 2SO 4 .Al 2  SO 4 3 .24H 2O

petre Potash
alum

13. Brine or NaCl 33. K 2SO 4 .Cr2  SO 4 3 .24H 2O

Table salt Chrome
alum

14. Potash ash K 2 CO3 34. Ferric Fe2  SO 4 3 .  NH 4 2 SO 4 .24H 2O

or pearl ash alum

15. Salt Cake K 2SO4 35. MnO2

Pyrolusite

[Link] KCl.MgCl2 .6H2O 36. Aqua conc.HNO3  [Link]

Regia

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[Link] Na 2S2O3 .5H2O 37. Na 2SO 4 .Al 2  SO 4 3 .24H 2 O
Sodium
alum

[Link] Na 2 B4 O7 .10H 2 O 38. Killed ZnCl2 .2H 2O

salt

[Link] Ba  OH 2 39.  NH 4 2 SO4 .Al2 SO4 3 .24H 2O

water Ammoniu
m alum

20. Magnesia MgO 40. SnCl4 .5H2O

Oxymuria
te

EXTRACTION OF SOME METALS:

(A) MAGNESIUM

Electrolysis of fused oxide of fused anhydrous magnesium chloride is commonly

employed to remove it.

(i) From magnesite: Magnesite  MgCO3  is calcined to produce magnesium oxide

(magnesia).

MgCO3   MgO  CO 2 

Magnesium can be extracted from magnesium oxide using electrolysis or thermal

reduction. The oxide is dissolved in a molten combination of magnesium, barium,
and sodium fluorides. At 650 C, molten mixtures are electrolyzed employing carbon
rods as anodes suspended in the molten mass and cast iron rods as cathodes.
Magnesium is obtained in a molten state through electrolysis. Reducing agents such
as carbon, silicon, aluminium, or calcium carbide can be used to thermally reduce
magnesium oxide.

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MgO  C  Mg  CO

2MgO  Si  2Mg  SiO2

The reduction takes place in a vacuum at 2000 C. Magnesium vapours become

condensed.

(ii) Anhydrous magnesium chloride electrolysis: Carnallite is a hydrated substance.

It is heated in air first, then in a stream of HCl gas to render it anhydrous.

MgCl2 .6H2O  MgCl2  6H2O

MgO or sea water can also be used to make anhydrous magnesium chloride. Chlorine
is sprayed upon a red-hot MgO and carbon combination.

MgO  C  Cl2  MgCl2  CO

Because the water of crystallization reacts chemically with magnesium chloride to

form magnesium oxychloride and finally magnesium oxide, it cannot be dehydrated
by heating.
 
MgCl2 .6H 2O   MgCl 2 .2H 2O   Mg 2OCl  MgO  Mg

Magnesium compounds can be found in seawater. When magnesium hydroxide

precipitates, it is treated with calcium hydroxide. It's dissolved in a weak HCl
solution. When the hydrated magnesium chloride crystallises, the solution becomes
more concentrated. As previously said, it is dehydrated.

Seawater  Ca  OH 2  Mg  OH 2

Mg  OH 2  2HCl  MgCl 2 .6H 2O

(B) EXTRACTION OF ALUMINUM

Extraction: Bauxite ore, which is commonly contaminated with ferric oxide and
silica, is used to extract aluminium. The removal of ferric oxide and silica from
bauxite ore is required before it can be electrolyzed. The following three steps are

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involved in extracting aluminium from bauxite ore. (I) Bauxite ore purification, i.e.
elimination of ferric oxide and silica.

(a) Baeyer's process: This method is mostly used on bauxite ore that contains ferric
oxide as a major contaminant.

(b) Hall's process: This method is mostly used on bauxite ore that contains ferric
oxide as a major contaminant.

(c) Serpeck's process: This method is mostly used on bauxite ore that has silica as a
major contaminant.

(C) EXTRACTION OF TIN

Tin is obtained by extracting it from cassiterite ore. The ore is commonly found with
siliceous debris, iron tungestates  FeWO4  and manganese  MnWO 4  .

(D) EXTRACTION OF LEAD

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Extraction: Galena ore is used to extract lead  PbS  . The extraction process consists
of the following steps: (I) Ore concentration (ii) Reduction (iii) Purification

(E) EXTRACTION OF IRON

The oxide ores of iron, particularly magnetite, haematite, and limonite, are used to
extract the metal. The extraction process entails the phases outlined in the flow chart.

S  O 2  SO 2 

As 2 S3  O 2  As 2 O3  SO 2 

SnO2  C  Sn  CO

Extraction of Iron:

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3Fe 2 O3 + CO   2Fe3O 4 + CO 2
o
300 - 400 C

Fe3O 4 + CO   3FeO + CO 2

o
500 - 600 C

FeO + CO   Fe + CO 2
o
700 C

1000 C
CaCO3  CaO  CO 2

CaO  SiO2  CaSiO3 (Slag)

P4O10  10C  4P  10CO

SiO2  2C  Si  2CO

MnO2  2C  Mn  2CO


SiO 2  CO 
1200 C
 Si  2CO

MnO2  2C  Mn  2CO

P4O10  10C  4P  10CO

C  O2  CO2CO2  C  2CO

When molten pig iron is cooled quickly, it becomes white cast iron, which contains
carbon in the form of cementite, Fe3C, and when it is cooled slowly and steadily, it
becomes grey cast iron, which contains carbon in the form of graphite. Cast Iron,
sometimes known as pig iron, is the least pure form of commercial iron, with a
carbon content of 2.5 to 4.5 percent and traces of impurities such as S,P,Mn and Si.

Wrought iron: It is the cleanest type of commercial iron, with a carbon content of
0.12 to 0.25 percent and impurities such as S,P,Mn and Si of 0.3 percent.

(F) EXTRACTION OF COPPER

Copper is mostly derived from copper pyrites  CUFeS2  . The extraction process is
broken down into the steps outlined in the flow chart.

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S  O2  SO2

2As  3O2  2As2O3

CuFeS2  O2  Cu 2 S  2FeS  SO5

2FeS  3O2  2FeO  2SO4

FeO  SiO2  FeSiO3

2FeS  3O2  2FeO  2SO2

FeO  SiO2  FeSiO3

2Cu 2 S  3O2  2Cu 2O  2SO3

(G) EXTRACTION OF SILVER

In the lead ore galena, silver is also present in the form of Ag2S in the lead ore, galena
 PbS . The extracted lead is known as argentiferous lead because it generally
contains silver. Prior to the usage of lead, silver is recovered.

Ag2 S  4NaCN 2NaAg(CN)2  Na 2 S

4Na 2 S  5O2  2H2O  2Na 2SO4  4NaOH  2 S

2NaAg(CN)2  Zn  2Ag  Na 2 Zn(CN)4

Black ppt. of Ag  KNO3 

fuse
 Compact mass

STEEL:

Steel is an iron alloy (ferrite) with 0.25 to 2.5 percent carbon (cementite, Fe3C ) and
traces of S,P,Mn and Si. As a result, the carbon content of steel lies somewhere
between that of wrought iron and that of cast iron. Sulfur and Phosphorus are
unwanted contaminants. Depending on the process of steel production, the

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percentage of Sulfur and Phosphorus is usually less than 0.05 percent. Si is found in
the form of iron silicide, FeSi, which is soluble in ferrite and has a concentration of
0.15 to 0.35 percent. Steel has a fibrous structure due to its high Si concentration.
Mn is added to steel throughout the manufacturing process to act as a deoxidizer and
to counteract the detrimental effects of sulphur by creating MnS, which is inert,
whereas, FeS, causes steel to become brittle when heated.

Varieties of Steel: Steel comes in a variety of shapes and sizes, depending on the
quantity of carbon in it.

1. Mild and quenched steels: Mild steel is a type of steel with a lower carbon content.
It combines the qualities of wrought iron with steel's flexibility and toughness. Mild
steel becomes as hard and brittle as glass when heated to a high temperature (i.e.,
bright redness) and then quickly cooled by plunging in oil or water. And is referred
to as quenched steel, and the process is referred to as quenching or hardening.

2. Hard Steel: This type of steel has a greater carbon content. It's like glass in terms
of hardness and brittleness.

3. Alloy Steels or Special Steels: Small amounts of nickel, cobalt, chromium,

tungsten, molybdenum, manganese, and silicon are added to steel to give it unique
qualities such as hardness, tenacity, corrosion resistance, and coefficient of
expansion. These materials are known as special steels or alloy steels, and they are
widely used in industry.

4. S and P -containing steel. When iron or steel contains too much S, it becomes
brittle when hot (hot short), and when it contains too much P, it becomes brittle
when cold (cold short).

Steel manufacturing

The carbon content of steel is halfway between that of cast iron and that of wrought
iron, implying that steel can be made either by removing carbon from cast iron or by
adding carbon to wrought iron. As a result, steel is made from either cast iron or
wrought iron. Following are the methods:

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(A) Bessemer’s process: This method is based on the fact that imperfections in cast
iron are totally oxidized in the presence of hot air blast, resulting in almost wrought
iron. This is then combined with a known amount of spiegeleisen, a Fe,Mn and C
alloy, to produce steel.

The inside of the converter is lined with silica (acidic lining) or lime /magnesia
depending on the type of the impurities contained in the cast iron (basic lining). If
the cast iron contains impurities such as S,C,Mn and Si , silica lining is utilised, and
the process is known as Bessemer's acid process. When cast iron contains P as an
impurity, however, a CaO/MgO liner is utilised, and the technique is known as the
basic Bessemer's process. In practise, basic lining is created by combining CaO and
MgO with tar to bond them together. As will be seen in the following discussion, the
materials utilised to line the convertor  CaO, MgO,SiO 2  operate as flux.

Reactions involved in Bessemer’s process: (i) In the beginning, O2 oxidizes

P,Mn and Si (impurities) to their respective oxides.

Si  O2  SiO2

2Mn  O2  2MnO

MnO generated in this manner interacts with the Bessemer's converter SiO2 lining
(acidic lining) to make MnSiO3 slag, which is then removed. MnO (basic impurity)
+ SiO2 (acidic lining, which acts as an acidic flux) = MnSiO3 (slag). P2O5 and SiO2
created react with the Bessemer's convertor's CaO liner (basic lining) to form
Ca 3  PO 4 2 and CaSiO 3 slags, which are then removed. P2O5 (acidic impurity) + CaO
(basic lining acting as a basic flux) Ca 3  PO 4 2 (slag) SiO2 (acidic impurity) + CaO
(basic lining acting as a basic flux) CaSiO3 (acidic impurity) + CaO (basic lining
acting as a basic flux) CaSiO3 (slag). Basic slag, which is a mixture of the three slags
MnSiO 3 Ca 3  PO 4 2 and CaSiO 3 is used as a fertilizer. The fluxes SiO2 CaO and MgO
which are employed to line the convertor, are clearly seen in this discussion.

1. The blast of air later oxidizes C and S to CO and SO 2 respectively. SO 2 escapes

from the convertor's mouth, while CO burns with a blue flame at the Bessmer

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convertor's mouth (Bessemer's condles). The burning of CO at the convertor's mouth
ceases after all of the carbon in the cast iron has been oxidised to CO. The blowing
of O2 into the convertor comes to a halt at this point. The formation of slags should
be mentioned here. Manganese steel is formed after the removal of impurities, and
then a tiny amount of spiegeleisen alloy is mixed to the molten cast iron. The
manganese alloy formed has several functions. Some of them are:

(a) It functions as a deoxidizer, as Mn in the alloy lowers oxidized iron if any is

present.

(B) The alloy provides the necessary amount of carbon, Mn, and Fe to produce steel
with the desired composition. It's worth noting that carbon is a necessary component
of all types of steel. Mn hardens steel and improves its tensile strength.

The Siemens-Martin open-hearth process

This is the current method, and the furnace employed is known as an open-hearth
furnace. This furnace is also known as a regenerative furnace since it operates on the
regenerative principle of heat economy. Steel is made from cast iron via this
technique. An open hearth is used in an open-hearth furnace. Depending on the
nature of impurities present in pig or cast iron, the hearth is lined with silica or
calcined dolomite. If the impurities are manganese, silicon, or other metals, silica
lining is employed, and calcined dolomite lining is utilised if there is a lot of
phosphorus.

Pig or cast iron, scraps, iron ore (haematite), and lime make up the charge. The
charge is heated on the furnace's hearth. The iron ore oxidizes the impurities.

CaO  SiO2  CaSiO3

MnO  SiO2  MnSiO3

2Fe2O3  3Si  4Fe  3SiO2

10Fe2O3  12P  20Fe  3P4O10

Class 12: Chemistry [Link] 20

Steel samples are drawn and checked for carbon content on a regular basis. Finally,
spiegleisen (an iron-manganese-carbon alloy) is added to the molten mass to produce
the desired steel. The entire procedure takes approximately 8 to 10 hours to
complete. The procedure is more time consuming than the Bessemer process. In
comparison to Bessemer's process, the open-hearth process provides the following
advantages.

(i) Because the heating is done externally, the temperature can be adjusted.

(ii) Because it is a slower process, it can be better regulated. Composition and quality
can be carefully managed.

(iii) This method loses only 4% of the iron that Bessemer's process loses, whereas
Bessemer's process loses roughly 15%.

The duplex method

Now-a-days Steel is manufactured in massive quantities using the duplex process.

This method is a hybrid of Bessemer's and the open-hearth method. The molten pig
iron is first processed in an acid Bessemer's converter to remove Si,Mn and a portion
of C in this process. The molten pig iron is then transported to an open-hearth
furnace with a basic lining to remove the remaining phosphorus and carbon before
being completed as usual. Tata Iron and Steel Works manufactures steel using the
Duplex process.

The electric procedure

Steel is prepared in an arc furnace (also known as Heroult's furnace) in this method.
This crucible-shaped furnace is made out of a steel shell that is lined on the interior
with dolomite magnesite and topped with heat-resistant bricks. The following
reactions occur throughout this process:

(a) Oxidation and slag formation. The charge melts at the temperature of the electric
arc, and a violent reaction begins. P,C,Mn and Si are oxidized to SiO2 MnO CO and
P4O10 respectively, in this reaction, and CaCO3 is decomposed.

CO2  C  2CO

Class 12: Chemistry [Link] 21

5O2  P4  P4O10

The oxidized products formed are removed as slag.

MnO  SiO2  MnSiO3

CaO  SiO2  CaSiO3

FeO  SiO2  FeSiO3

Because it is lighter, this slag floats over the metallic component. The furnace is
carefully tilted and the slag is poured out of it once the oxidation and production of
slag is complete.

(b) Desulfurization and deoxidation. Following the removal of the slag from the
furnace, a charge of lime, sand, fluorspar, coke, and ferro-silicon is added to the
furnace. Any FeO present in the steel is reduced to Fe with the addition of coke.

FeO  C  Fe  CO

By processing FeS with CaO, sulfur present as FeS is converted to CaS. The FeO
generated is immediately converted to Fe, , as before, and the CaS is deposited in the
slag. When the steel has been desulphurized (that is, the sulfur has been removed),
it is put into moulds.

Alloy steels, tool steels, stainless steels, and special quality steels are all made using
this procedure. The following are the key benefits of the procedure:

(i) A reduction in capital expenditure and an increase in productivity.

(ii) One batch can be treated in 45 minutes.

(iii) Lower operating costs and higher steel quality.

The process is carried out in a magnesite-lined converter, which varies from the
Bessemer converter in that it does not have a perforated bottom and instead has a
solid bottom. Through a copper lance, pure air is blown from the top.

Properties of Steel:

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1. Mechanical characteristics. Steel combines the advantages of cast and wrought
iron by being both hard and elastic, and it can be forged and welded as long as the
carbon content isn't too high.

2. Heat Action: Heat Treatment of Steel Steel has a unique property that separates it
from other industrial forms of iron: its hardness and flexibility may be altered
through adequate heat treatment. Consider the following example:

(a) Annealing- When hard steel is heated to a bright red colour and then allowed to
cool slowly, its hardness is greatly reduced and it becomes soft. This is referred to
as annealing.

(b) Hardening or quenching. Mild steel becomes as hard and brittle as glass when
heated to a high temperature (i.e., bright redness) and then quickly cooled by
immersing it in oil or water. This is referred to as quenching.

(c) Tempering. By heating quenched steel to different temperatures for different

lengths of time, it can lose its brittleness. The method. Tempering is the term used
to describe the process of bringing steel to a desired hardness and flexibility.

3. Steel surface treatment. The following procedure is used to treat the steel's surface:

(a) Hardening of the case. Case hardening is the process of applying a thin layer of
hardened steel to the surface of mild steel. This is accomplished by first burning the
mild steel with charcoal before submerging it in oil.

b) Nitriding. Nitriding is the process of applying a hard coating of iron nitride on the
surface of steel. Steel is heated to 500  600 C in a dry ammonia environment for 3–
4 days, resulting in a hard covering of iron nitride on the surface.

Some Special Process for Silver:

Amalgamation Process: The powdered mineral comprising H2O and NaCl is mixed
with mercury and magistral (burnt pyrites-sulphates and copper and iron oxides).
The combination is kept in the refrigerator for many days. The amalgam form of
silver is created. Silver is collected through washing, drying, and subsequent
distillation.

Class 12: Chemistry [Link] 23

CuSO4  2NaCl  CuCl2  2Na 2SO4

CuCl2  2Ag2S  Cu 2Cl2  S

Cu 2Cl2  Ag2S  Cu 2S  2AgCl

2AgCl  2Hg 

Ag  Hg  Ag  Hg  
distillation
 Ag  Hg

Desilverization of Lead: When a lead-silver alloy has a low silver content (such as
argentiferous lead of galena), Parke's technique affects lead desilverisation. It
depends on the fact that:

(i) When zinc is added to a melted silver-lead alloy, zinc removes silver from the
alloy and forms an alloy with silver rather than lead.

(ii) When zinc is added to a melted silver-lead alloy, zinc removes silver from the
alloy and forms an alloy with silver rather than lead.

(iii) When zinc is added to a melted silver-layers.

Pattinson's Method: It all comes down to the fact that a lead-silver alloy with less
than 1.8 percent silver melts at a lower temperature than pure lead. When this sort
of alloy is melted and allowed to cool, lead separates first, and by repeating the
process, the silver content increases. Cupellation is used to complete the
recuperation process.

Lead Process: This procedure is based on the fact that when silver ores are melted
down with lead, a lead-silver alloy is created, which is then oxidised to remove the
lead. Cupellation technique is used to make a silver-rich Pb  Ag alloy. Parke's or
Pattinson's technique is used to make a Pb  Ag alloy that is low in silver.

3. Thermodynamic Principles of Metallurgy

The fundamental concepts of thermodynamics are extremely useful in determining

which element will be the best reducing agent for a specific oxide during a

Class 12: Chemistry [Link] 24

metallurgical operation. It can also estimate the ideal temperature for the decrease to
take place smoothly.

Gibb's Helmholtz free energy change  G  is given by the equation for any reaction
or process.

G  H  T S

where H represents the enthalpy change, S represents the entropy change, and T
represents the absolute temperature at which the change occurs. For the reaction to
be spontaneous, the value of  G  must be negative. The Gibbs free energy is also
related to the equilibrium constant K of the temperature.

G   RT ln K

In the equation, a negative  G  implies a positive K. This is only possible if the

reaction progresses to the products. The following are some of the inferences that
can be drawn:

A. The reaction is more spontaneous when the negative value of free energy change
 G  is greater.

B. If two reactions are combined in a system with a net  G  of negative, the overall
reaction will occur, i.e., a reaction with a positive  G  can be made to occur by
coupling it with another reaction with a significant negative  G  so that the net
 G  of both reactions is negative. Ellingham diagrams make it simple to understand
such coupling reactions.

Ellingham diagram: An Ellingham diagram is a set of graphs that show how the
standard free energy of the formation of oxides of various elements varies with
temperature, i.e.,  G  versus T. Plots that are similar can also be found. Sulfides
and halides should be plotted. H.J.T. Ellingham was the first to plot these. These
diagrams assist us in determining whether or not thermal reduction of an ore is
feasible.

The metal oxide is formed by,

Class 12: Chemistry [Link] 25

2xM  O2  2Mx O

In the above reaction, the value of S decreases and, thus, the value of S is
negative.

(i) The slope of the metal oxide formation curves is positive because  G  becomes
less negative or increases as temperature rises.

(ii) Except when there is a change in phase  s  l , l  g  each curve is a straight line.
An increase in the slope on the +ve side indicates the temperature at which such a
change occurs. The melting of zinc, for example, is shown by a rapid increase in the
positive slope at temperature 692 K, in the Zn  ZnO curve.

(iii) At high temperatures,  G  turns positive in less reactive metals such as silver
and mercury. Both silver oxide  Ag 2 O  and mercury oxide  HgO  are unstable and
breakdown at high temperatures.

2Ag 2 O   4Ag  O 2


2HgO   2Hg  O 2

(iv) As S grows,  G  drops in the CO curve. The declining trend demonstrates

this.

(v) Any metal oxide with a lower  G  value is more stable than one with a higher
 G  value. This means the metal oxide at the top of the diagram can be reduced by
the metal involved in the production of the oxide at the bottom. Cr2 O3 can be reduced
by Al metal, whereas, Al2 O3 cannot be reduced by Cr.

As a result, the relative proclivity of certain metals to serve as reducing agents is

determined.

Ca  Mg  Al  Cr  Zn  Fe  Ni

3.1 Reducing Nature of Carbon

Class 12: Chemistry [Link] 26

In pyrometallurgical activities, carbon in the form of coke, charcoal, or carbon
monoxide is utilized as a reducing agent. Smelting is the word for a reduction process
used in metal extraction. The following three reactions are possible when carbon is
used as a reducing agent:

C  O2  CO2

2C  O 2  2CO

2CO  O2  2CO2

There is almost little change in entropy in the first reaction (creation of CO 2 ), i.e.
S  0, and hence  G  remains virtually constant as temperature rises, i.e.,  G  is
temperature independent. The entropy of the second process (the production of CO
) increases ( S is positive), therefore  G  becomes more negative as the
temperature rises. However, in the third reaction, entropy decreases ( S is negative),
and so  G  gets less negative as temperature rises.

The intersection of the three curves was discovered at 983 K. It means that the
reaction (ii) is best suited above this temperature. It indicates that at extremely high

Class 12: Chemistry [Link] 27

temperatures, carbon may reduce any metal oxide and then be oxidized to CO.
However, at high concentrations, the reduction of carbon is not possible in all the
cases due to following reasons:

(a) It has a hefty price tag.

(b) At high temperatures, some metals react with carbon to generate carbides.

(c) Maintaining a high temperature poses numerous practical challenges.

(A) Theory of Haematite Reduction

Three curves are depicted in the Ellingham diagram: formation of ferric oxide from
iron, formation of carbon from carbon, and formation of CO 2 from carbon. The curve
intersects each other at 1073 K. The value of  G  for the formation of FeO is less
negative than oxygen above 1073 K. Above, 1073 K carbon coke can reduce ferric
oxide. The  G  for the reaction is negative.

Fe2O3  3C  2Fe  3CO

 G  for CO formation from carbon is less negative below 1073 K than  G  for
Fe 2 O3 formation. Alternatively, the reduction of Fe 2 O3 with carbon will be positive,
indicating that no reduction is feasible. However, the  G  of CO 2 formation from
CO is more negative than  G  of Fe 2 O3 formation, as seen in the diagram. This
suggests that CO can reduce Fe 2 O3 below 1073 K i.e., Fe 2 O3 can be lowered by CO.

Fe2O3  3CO  2Fe  3CO2

(B) The Ellingham diagram of the theory of ZnO reduction demonstrates that the
curves involving the synthesis of ZnO and carbon monoxide cross at about 1270 K.
Above 1180 K, the value of  G  for the formation of ZnO increases dramatically.
This is owing to the fact that at this temperature, zinc begins to boil.  G  of the
following equation above 1270 K.

Class 12: Chemistry [Link] 28