Revision Notes Copper Copper pyrite Copper

CuFeS2
glance Cuprite Malachite
Class - 12 Chemistry Cu 2S
Cu 2
Chapter 6 – Metallurgy Azurite
CuCO3  Cu(OH) 2
2CuCO3  Cu(OH) 2

1. INTRODUCTION:

Mineral is the natural compound of a metal and non-metal. Metals can be extracted Zinc Zinc blende or Sphalerite
ZnS
from minerals. A naturally existing solid material from which a valuable metal or Calamine ZnCO3
mineral can be commercially mined is called an ore. Ore is contaminated with
ZnO
impurities or undesired material known as gangue. All ores are minerals, but the Zincite
reverse is not true.

Some Important Ores of Metals

Lead Galena Anglesite
PbS
Metals Ores Composition PbSO 4
Cerussite
PbCO3
Aluminum Bauxite Al2 O3  2H 2
Corundum Al2 O3  H 2
Al2 O3 Magnesium Carnallite Magnesite
KCl.MgCl2 6H 2 O  K 2 MgCl4  6H 2O 
Dolomite
MgCO3
Iron Haematite Magnetite
Fe2 O3 MgCO3CaCO3
Siderite Iron pyrite Epsom salt (Epsomite)
Fe3O4 MgSO4 7H 2
FeCO3 K 2 Mg 2  SO4 3
FeS2
Fe2 O3 .3H 2
Tin Cassiterite (Tin Stone)
SnO2

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 Silver Silver glance (Argentite) separator is made up of a belt (made of leather or brass) that moves over two rollers,
Ag 2S one on each side. When the powdered ore is dumped on the belt at the other end, the
Pyrargyrite (Ruby Silver)
Ag 3SbS3 magnetic component of the ore is drawn to the magnetic roller and falls closer to it,
Chlorargyrite (Horn silver) AgCl while non-magnetic impurities fall away. For example, chromite ore is separated
Stefinite Ag 5SbS4 from non-magnetic siliceous material.
Ag 3 AsS3
Proustite 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
2. METALLURGY with water varies in gangue and ore. Generally, the gangue particles are wetted by
water and ore particles are wetted by oil.
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: 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
Crushing of the ore, Dressing or concentration of the ore, Isolation of the crude metal
property of other minerals present as impurities. Zinc blended and pyrites are present
from its ore, Purification of refining of the metal.
as impurities in galena. Potassium ethyl xanthate is used as a collector and NaCN
Crushing and Grinding and Na 2 CO3 is used as a depressant in the flotation process.

Jaw crushers first crushes the ore and then is grinded to a powder form (pulverization 2.2.4 Leaching of alumina from bauxite:
of the ore) in equipment like ball mills.
Bauxite, the primary source of aluminium, typically contains impurities such as SiO
Concentration 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
The removal of undesired material from ore is known as dressing or beneficiation of
leached out as sodium aluminate in this fashion leaving behind the impurities
ore.
present.
Hydraulic Washing
Al2O3  2NaOH  3H 2O  2Na Al  OH 4 
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 By passing carbon-dioxide gas through the solution, the aluminate is neutralized,
lighter particles of sand, clay, and other impurities are washed away, leaving the and hydrated Al2 O3 is precipitated. The solution is seeded with freshly prepared
heavier ore particles behind. samples of hydrated Al2 O3 at this point, causing Al  OH 3 to precipitate.

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

It's based on the magnetic characteristics of the ore's constituents. When the ore or 
Al2 O3 .xH 2 O   Al2 O3  xH 2 O
the contaminants connected with it are magnetic, this method is utilized. A magnetic

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 
The corresponding metal/ore is leached with a dilute solution of NaCN or KCN in 2PbS + 3O 2   2PbO  2SO 2
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 2ZnS + 3O 2   2ZnO  2SO 2
process is another name for it.
2CuFeS2  4O2  Cu 2S  2FeO  3SO2
Extraction of crude metal from concentrated ore
Self-reduction, auto-reduction, and air-reduction are among the terms used to
The concentrated ore must be transformed into a form that can be reduced. Before describe the direct reduction of sulphide ore into metal by heating it in air. The SO 2
reduction, the sulfide ore is usually transformed to oxide. Oxides are a lot easier to generated is used in the production of H 2SO 4 .
get rid of. As a result, the separation of metals from concentrated ore is divided into
two key phases, as shown below. Reduction of metal oxide to the metal

(I) Conversion to oxide; (ii) Conversion of oxide to metal. After that, the calcined or roasted ore is converted to a metallic form in one of two
ways.
Conversion to oxide:
Reduction by carbon (Smelting)
The process of converting ore to oxide is carried out in two ways depending on the
nature of ore. 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
Calcination: Calcination is the process of rapidly heating the mined ore in the
the blast furnace by heating them vigorously with coal or coke. Slag is a flammable
absence of air or with a limited supply of air. The following changes occur as a result
substance that forms during the reduction process. Slag is made up of two parts:
of the calcination process:
gangue and substance (for removing gangue) Fluxes are substances that are used to
(a) The carbonate ore decomposes to generate the metal's oxide. For example, remove gangue. Acidic fluxes: SiO2 , borax (remove basic impurity).
MgO,MgCO3 ,CaCO3 are basic fluxes (remove acidic impurity).

FeCO3   FeO  CO 2 
When the melting point of a compound is too high, Al powder is used as a reducing

CaCO3   CaO  CO 2  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-
(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 block oxide due to the presence of metal carbides. CaO  2C  CaC2  CO

(c) Organic stuff in the ore is ejected, causing the ore to become porous. Impurities Examples of some reaction are: CuO  CO  CO2  Cu , ZnO  CO  CO2  Zn ,
that are volatile are eliminated. PbO  C  CO  Pb


Roasting: It is a method of severely heating the concentrated ore (usually sulphide Acidic fluxes: SiO 2  CaCO3   CaSiO3  CO 2 
ore) below its melting point in an abundance of air. Once the roasting and exothermic 
Basic fluxes: SiO 2  MgCO3   MgSiO3  CO 2 
process has begun, no extra heat is required.

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Self reduction: Certain metal compounds are reduced to metal without the use of Between the graphite anode and the iron cathode, molten NaCl with a trace of CaCl2
additional reducing agents, such as ores of Cu,Pb and Hg. To produce oxide, their is electrolyzed. The numerous reactions that occur are as follows:
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 On fusion: NaCl  Na   Cl
procedure. or automatic lowering. Pb reduces through self-reduction. The reactions At cathode: Na   e  Na
are shown below.
At anode: 2Cl  Cl2  2e 
2PbS  3O2  2PbO  2SO2
(b) Hall-Heroult process (electrolytic reduction): Purified Al2 O3 is combined with
PbS  2PbO  3Pb  SO2
Na 3 AlF6 (cryolite) or CaF2 (fluorspar), lowering the melting point and increasing
Metal Displacement Method 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 ore is converted into a water soluble chemical in this technique. The compound's
The entire reaction can be summarised as follows:
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. 2Al 2 O3  3C   4Al  3CO 2 
(ii) Separation of silver by complex formation
Electrolysis of the molten mass takes place in an electrolytic cell with carbon
Silver and gold are extracted using a complicated forming procedure. In the presence electrodes. CO and CO 2 are produced when the oxygen liberated at the anode reacts
of air, powdered argentite is reacted with a dilute solution of sodium cyanide. The with the carbon of the anode. This method burns away around 0.5 kg of carbon anode
ore's silver dissolves in the cyanide solution, resulting in sodium argentocyanide.
for every kilogramme of aluminium produced. The electrolytic reactions are:
Ag 2S  4NaCN  2Na  Ag  CN 2   Na 2S
At cathode: Al3  3e  Al
When metallic zinc is introduced to the complex salt solution, it displaces silver from At anode: C  O 2  CO  2e 
the solution since it is a more electropositive element than silver.
2.4: Purification or refining of metals
2Na  Ag  CN 2   Zn  Na 2  Zn  CN 4   2Ag
Metals acquired through reduction methods still have some undesirable impurities
2.3.2.4: Electrolytic reduction and must be purified. Refining procedures differ greatly from metal to metal and
also rely on the intended application of the metal.
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 Liquation process:
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. 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,
(a) Manufacture of metallic sodium(Down’s process) 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 Vapour Phase Refining: This process involves converting the metal to its volatile
remove Pb from Zn  Hg alloy, which is produced by Parke's process and contains component, which is subsequently collected. It is then heated until it decomposes,
Pb as an impurity. yielding pure metal. In order to refine the vapour phase, the following two
prerequisites must be met.
Distillation process: This procedure is used to purify metals that are volatile but
contain non volatile contaminants, and vice versa. This procedure purifies (i) The metal should react with a reagent to generate a volatile chemical.
Cd,Zn and Hg.
(ii) The volatile chemical should decompose easily, allowing for easy recovery.
Zone refining method (Fractional Crystallization Method)
SOME IMPORTANT COMPOUNDS, MINERALS, MIXTURES & THE
This method is employed when extremely pure metals are required for a specific FORMULA
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 MgSO4 .7H2O CaCN 2
1. Epsom salt 21.
impure molten metal will deposit pure metal crystals as it cools, while the impurities Nitrolium
will stay in the residual molten metal.

Chromatographic methods: This method is based on the idea that different 2. Gypsum CaSO 4 .2H 2 O 22. CaH2
salt Hydrolith
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
3. Glauber’s Na 2SO4 .10H2O 23. Na 2CO3  K2CO3
adsorbent. At different levels on the column, different components are adsorbed. The
salt Fusion
adsorbed components are then eluted (removed) using a suitable solvent (eluant).
mixture
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. 4. Lime water Ca  OH 2 24. Gun KNO3  K 2CO3
The Hooper's cell, which has three liquid layers, has impure aluminum as the anode powder
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 5. Quick lime CaO 25. Pink  NH 4 2 SnCl6
Al. Al flows through solution as aluminium ion  Al3  at the anode (bottom layer),
salt

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 6. Washing Na 2CO3.10H2O 26. N2O
Soda Laughing
from the top. The recovered aluminium is 99.98 percent pure.
gas
At cathode: Al3  3e  Al
7. Crystal Na 2CO3.H2O 27 Red Pb3O4
At anode: Al  Al3  3e carbonate Lead

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 8. Soda ash Na 2 CO 3 28 Blue CuSO4 .5H2O 17.Hypo Na 2S2O3 .5H2O 37. Na 2SO 4 .Al 2  SO 4 3 .24H 2 O
vitriol Sodium
alum

9. Baking NaHCO3 29. Green FeSO4 .7H2O

Soda vitriol 18.Borax Na 2 B4 O7 .10H 2 O 38. Killed ZnCl2 .2H 2O
salt

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

19.Baryta Ba  OH 2 39.  NH 4 2 SO4 .Al2 SO4 3 .24H 2O
blue Chiense water Ammoniu
white m alum

11. Chile NaNO3 31. ZnO

20. Magnesia MgO 40. SnCl4 .5H2O
saltpetre Philosphe Oxymuria
r’s wool te

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

petre Potash
alum EXTRACTION OF SOME METALS:

(A) MAGNESIUM
13. Brine or NaCl 33. K 2SO 4 .Cr2  SO 4 3 .24H 2O
Table salt Chrome Electrolysis of fused oxide of fused anhydrous magnesium chloride is commonly
alum employed to remove it.

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

14. Potash ash K 2 CO3 34. Ferric Fe2  SO 4 3 .  NH 4 2 SO 4 .24H 2O
or pearl ash alum (magnesia).

MgCO3   MgO  CO 2 
15. Salt Cake K 2SO4 35. MnO2
Pyrolusite Magnesium can be extracted from magnesium oxide using electrolysis or thermal
reduction. The oxide is dissolved in a molten combination of magnesium, barium,
16.Carnallite KCl.MgCl2 .6H2O 36. Aqua conc.HNO3  conc.HCl and sodium fluorides. At 650 C, molten mixtures are electrolyzed employing carbon
Regia
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 involved in extracting aluminium from bauxite ore. (I) Bauxite ore purification, i.e.
elimination of ferric oxide and silica.
2MgO  Si  2Mg  SiO2
(a) Baeyer's process: This method is mostly used on bauxite ore that contains ferric
The reduction takes place in a vacuum at 2000 C. Magnesium vapours become oxide as a major contaminant.
condensed.
(b) Hall's process: This method is mostly used on bauxite ore that contains ferric
(ii) Anhydrous magnesium chloride electrolysis: Carnallite is a hydrated substance. oxide as a major contaminant.
It is heated in air first, then in a stream of HCl gas to render it anhydrous.
(c) Serpeck's process: This method is mostly used on bauxite ore that has silica as a
MgCl2 .6H2O  MgCl2  6H2O major contaminant.

MgO or sea water can also be used to make anhydrous magnesium chloride. Chlorine (C) EXTRACTION OF TIN
is sprayed upon a red-hot MgO and carbon combination.
Tin is obtained by extracting it from cassiterite ore. The ore is commonly found with
MgO  C  Cl2  MgCl2  CO siliceous debris, iron tungestates  FeWO4  and manganese  MnWO 4  .

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
(D) EXTRACTION OF LEAD

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Extraction: Galena ore is used to extract lead  PbS  . The extraction process consists 3Fe 2 O3 + CO 
300 - 400 C
 2Fe3O 4 + CO 2
o

of the following steps: (I) Ore concentration (ii) Reduction (iii) Purification
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
(E) EXTRACTION OF IRON carbon in the form of cementite, Fe3C, and when it is cooled slowly and steadily, it
The oxide ores of iron, particularly magnetite, haematite, and limonite, are used to becomes grey cast iron, which contains carbon in the form of graphite. Cast Iron,
extract the metal. The extraction process entails the phases outlined in the flow chart. 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.
S  O 2  SO 2 
Wrought iron: It is the cleanest type of commercial iron, with a carbon content of
As 2 S3  O 2  As 2 O3  SO 2  0.12 to 0.25 percent and impurities such as S,P,Mn and Si of 0.3 percent.

SnO2  C  Sn  CO (F) EXTRACTION OF COPPER

Extraction of Iron: 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 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
2As  3O2  2As2O3
0.15 to 0.35 percent. Steel has a fibrous structure due to its high Si concentration.
CuFeS2  O2  Cu 2 S  2FeS  SO5 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,
2FeS  3O2  2FeO  2SO4 whereas, FeS, causes steel to become brittle when heated.

FeO  SiO2  FeSiO3 Varieties of Steel: Steel comes in a variety of shapes and sizes, depending on the
quantity of carbon in it.
2FeS  3O2  2FeO  2SO2
1. Mild and quenched steels: Mild steel is a type of steel with a lower carbon content.
FeO  SiO2  FeSiO3 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.,
2Cu 2 S  3O2  2Cu 2O  2SO3
bright redness) and then quickly cooled by plunging in oil or water. And is referred
(G) EXTRACTION OF SILVER to as quenched steel, and the process is referred to as quenching or hardening.

In the lead ore galena, silver is also present in the form of Ag2S in the lead ore, galena 2. Hard Steel: This type of steel has a greater carbon content. It's like glass in terms
of hardness and brittleness.
 PbS . The extracted lead is known as argentiferous lead because it generally
contains silver. Prior to the usage of lead, silver is recovered. 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
Ag2 S  4NaCN 2NaAg(CN)2  Na 2 S
qualities such as hardness, tenacity, corrosion resistance, and coefficient of
4Na 2 S  5O2  2H2O  2Na 2SO4  4NaOH  2 S expansion. These materials are known as special steels or alloy steels, and they are
widely used in industry.
2NaAg(CN)2  Zn  2Ag  Na 2 Zn(CN)4
4. S and P -containing steel. When iron or steel contains too much S, it becomes
Black ppt. of Ag  KNO3 
fuse
 Compact mass brittle when hot (hot short), and when it contains too much P, it becomes brittle
when cold (cold short).

Steel manufacturing
STEEL:
The carbon content of steel is halfway between that of cast iron and that of wrought
Steel is an iron alloy (ferrite) with 0.25 to 2.5 percent carbon (cementite, Fe3C ) and iron, implying that steel can be made either by removing carbon from cast iron or by
traces of S,P,Mn and Si. As a result, the carbon content of steel lies somewhere adding carbon to wrought iron. As a result, steel is made from either cast iron or
between that of wrought iron and that of cast iron. Sulfur and Phosphorus are wrought iron. Following are the methods:
unwanted contaminants. Depending on the process of steel production, the

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(A) Bessemer’s process: This method is based on the fact that imperfections in cast convertor's mouth (Bessemer's condles). The burning of CO at the convertor's mouth
iron are totally oxidized in the presence of hot air blast, resulting in almost wrought ceases after all of the carbon in the cast iron has been oxidised to CO. The blowing
iron. This is then combined with a known amount of spiegeleisen, a Fe,Mn and C of O2 into the convertor comes to a halt at this point. The formation of slags should
alloy, to produce steel. 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
The inside of the converter is lined with silica (acidic lining) or lime /magnesia
manganese alloy formed has several functions. Some of them are:
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 (a) It functions as a deoxidizer, as Mn in the alloy lowers oxidized iron if any is
the process is known as Bessemer's acid process. When cast iron contains P as an present.
impurity, however, a CaO/MgO liner is utilised, and the technique is known as the
(B) The alloy provides the necessary amount of carbon, Mn, and Fe to produce steel
basic Bessemer's process. In practise, basic lining is created by combining CaO and
with the desired composition. It's worth noting that carbon is a necessary component
MgO with tar to bond them together. As will be seen in the following discussion, the
of all types of steel. Mn hardens steel and improves its tensile strength.
materials utilised to line the convertor  CaO, MgO,SiO 2  operate as flux.
The Siemens-Martin open-hearth process
Reactions involved in Bessemer’s process: (i) In the beginning, O2 oxidizes
P,Mn and Si (impurities) to their respective oxides. 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
Si  O2  SiO2 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
2Mn  O2  2MnO 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
MnO generated in this manner interacts with the Bessemer's converter SiO2 lining
lining is employed, and calcined dolomite lining is utilised if there is a lot of
(acidic lining) to make MnSiO3 slag, which is then removed. MnO (basic impurity)
phosphorus.
+ 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 Pig or cast iron, scraps, iron ore (haematite), and lime make up the charge. The
Ca 3  PO 4 2 and CaSiO 3 slags, which are then removed. P2O5 (acidic impurity) + CaO charge is heated on the furnace's hearth. The iron ore oxidizes the impurities.
(basic lining acting as a basic flux) Ca 3  PO 4 2 (slag) SiO2 (acidic impurity) + CaO CaO  SiO2  CaSiO3
(basic lining acting as a basic flux) CaSiO3 (acidic impurity) + CaO (basic lining
MnO  SiO2  MnSiO3
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 2Fe2O3  3Si  4Fe  3SiO2
which are employed to line the convertor, are clearly seen in this discussion.
10Fe2O3  12P  20Fe  3P4O10
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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Steel samples are drawn and checked for carbon content on a regular basis. Finally, 5O2  P4  P4O10
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 The oxidized products formed are removed as slag.
complete. The procedure is more time consuming than the Bessemer process. In MnO  SiO2  MnSiO3
comparison to Bessemer's process, the open-hearth process provides the following
advantages. CaO  SiO2  CaSiO3

(i) Because the heating is done externally, the temperature can be adjusted. FeO  SiO2  FeSiO3

(ii) Because it is a slower process, it can be better regulated. Composition and quality Because it is lighter, this slag floats over the metallic component. The furnace is
can be carefully managed. carefully tilted and the slag is poured out of it once the oxidation and production of
slag is complete.
(iii) This method loses only 4% of the iron that Bessemer's process loses, whereas
Bessemer's process loses roughly 15%. (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
The duplex method
furnace. Any FeO present in the steel is reduced to Fe with the addition of coke.
Now-a-days Steel is manufactured in massive quantities using the duplex process.
FeO  C  Fe  CO
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 By processing FeS with CaO, sulfur present as FeS is converted to CaS. The FeO
of C in this process. The molten pig iron is then transported to an open-hearth generated is immediately converted to Fe, , as before, and the CaS is deposited in the
furnace with a basic lining to remove the remaining phosphorus and carbon before slag. When the steel has been desulphurized (that is, the sulfur has been removed),
being completed as usual. Tata Iron and Steel Works manufactures steel using the it is put into moulds.
Duplex process.
Alloy steels, tool steels, stainless steels, and special quality steels are all made using
The electric procedure this procedure. The following are the key benefits of the procedure:
Steel is prepared in an arc furnace (also known as Heroult's furnace) in this method. (i) A reduction in capital expenditure and an increase in productivity.
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 (ii) One batch can be treated in 45 minutes.
reactions occur throughout this process:
(iii) Lower operating costs and higher steel quality.
(a) Oxidation and slag formation. The charge melts at the temperature of the electric
The process is carried out in a magnesite-lined converter, which varies from the
arc, and a violent reaction begins. P,C,Mn and Si are oxidized to SiO2 MnO CO and
Bessemer converter in that it does not have a perforated bottom and instead has a
P4O10 respectively, in this reaction, and CaCO3 is decomposed. solid bottom. Through a copper lance, pure air is blown from the top.
CO2  C  2CO Properties of Steel:

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1. Mechanical characteristics. Steel combines the advantages of cast and wrought CuSO4  2NaCl  CuCl2  2Na 2SO4
iron by being both hard and elastic, and it can be forged and welded as long as the
carbon content isn't too high. CuCl2  2Ag2S  Cu 2Cl2  S

2. Heat Action: Heat Treatment of Steel Steel has a unique property that separates it Cu 2Cl2  Ag2S  Cu 2S  2AgCl
from other industrial forms of iron: its hardness and flexibility may be altered
2AgCl  2Hg 
through adequate heat treatment. Consider the following example:
Ag  Hg  Ag  Hg  
distillation
 Ag  Hg
(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 Desilverization of Lead: When a lead-silver alloy has a low silver content (such as
as annealing. argentiferous lead of galena), Parke's technique affects lead desilverisation. It
(b) Hardening or quenching. Mild steel becomes as hard and brittle as glass when depends on the fact that:
heated to a high temperature (i.e., bright redness) and then quickly cooled by (i) When zinc is added to a melted silver-lead alloy, zinc removes silver from the
immersing it in oil or water. This is referred to as quenching. alloy and forms an alloy with silver rather than lead.
(c) Tempering. By heating quenched steel to different temperatures for different (ii) When zinc is added to a melted silver-lead alloy, zinc removes silver from the
lengths of time, it can lose its brittleness. The method. Tempering is the term used alloy and forms an alloy with silver rather than lead.
to describe the process of bringing steel to a desired hardness and flexibility.
(iii) When zinc is added to a melted silver-layers.
3. Steel surface treatment. The following procedure is used to treat the steel's surface:
Pattinson's Method: It all comes down to the fact that a lead-silver alloy with less
(a) Hardening of the case. Case hardening is the process of applying a thin layer of than 1.8 percent silver melts at a lower temperature than pure lead. When this sort
hardened steel to the surface of mild steel. This is accomplished by first burning the of alloy is melted and allowed to cool, lead separates first, and by repeating the
mild steel with charcoal before submerging it in oil. process, the silver content increases. Cupellation is used to complete the
b) Nitriding. Nitriding is the process of applying a hard coating of iron nitride on the recuperation process.
surface of steel. Steel is heated to 500  600 C in a dry ammonia environment for 3– Lead Process: This procedure is based on the fact that when silver ores are melted
4 days, resulting in a hard covering of iron nitride on the surface. down with lead, a lead-silver alloy is created, which is then oxidised to remove the
Some Special Process for Silver: 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.
Amalgamation Process: The powdered mineral comprising H2O and NaCl is mixed
with mercury and magistral (burnt pyrites-sulphates and copper and iron oxides). 3. Thermodynamic Principles of Metallurgy
The combination is kept in the refrigerator for many days. The amalgam form of The fundamental concepts of thermodynamics are extremely useful in determining
silver is created. Silver is collected through washing, drying, and subsequent which element will be the best reducing agent for a specific oxide during a
distillation.

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metallurgical operation. It can also estimate the ideal temperature for the decrease to 2xM  O2  2Mx O
take place smoothly.
In the above reaction, the value of S decreases and, thus, the value of S is
Gibb's Helmholtz free energy change  G  is given by the equation for any reaction negative.
or process.
(i) The slope of the metal oxide formation curves is positive because  G  becomes
G  H  T S less negative or increases as temperature rises.
where H represents the enthalpy change, S represents the entropy change, and T (ii) Except when there is a change in phase  s  l , l  g  each curve is a straight line.
represents the absolute temperature at which the change occurs. For the reaction to
An increase in the slope on the +ve side indicates the temperature at which such a
be spontaneous, the value of  G  must be negative. The Gibbs free energy is also
change occurs. The melting of zinc, for example, is shown by a rapid increase in the
related to the equilibrium constant K of the temperature. positive slope at temperature 692 K, in the Zn  ZnO curve.
G   RT ln K
(iii) At high temperatures,  G  turns positive in less reactive metals such as silver
In the equation, a negative  G  implies a positive K. This is only possible if the and mercury. Both silver oxide  Ag 2 O  and mercury oxide  HgO  are unstable and
reaction progresses to the products. The following are some of the inferences that breakdown at high temperatures.
can be drawn:

2Ag 2 O   4Ag  O 2
A. The reaction is more spontaneous when the negative value of free energy change

 G  is greater. 2HgO   2Hg  O 2

B. If two reactions are combined in a system with a net  G  of negative, the overall (iv) As S grows,  G  drops in the CO curve. The declining trend demonstrates
reaction will occur, i.e., a reaction with a positive  G  can be made to occur by this.

coupling it with another reaction with a significant negative  G  so that the net (v) Any metal oxide with a lower  G  value is more stable than one with a higher
 G  of both reactions is negative. Ellingham diagrams make it simple to understand  G  value. This means the metal oxide at the top of the diagram can be reduced by
such coupling reactions. the metal involved in the production of the oxide at the bottom. Cr2 O3 can be reduced
Ellingham diagram: An Ellingham diagram is a set of graphs that show how the by Al metal, whereas, Al2 O3 cannot be reduced by Cr.
standard free energy of the formation of oxides of various elements varies with
As a result, the relative proclivity of certain metals to serve as reducing agents is
temperature, i.e.,  G  versus T. Plots that are similar can also be found. Sulfides
determined.
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 Ca  Mg  Al  Cr  Zn  Fe  Ni
feasible.
3.1 Reducing Nature of Carbon
The metal oxide is formed by,

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In pyrometallurgical activities, carbon in the form of coke, charcoal, or carbon temperatures, carbon may reduce any metal oxide and then be oxidized to CO.
monoxide is utilized as a reducing agent. Smelting is the word for a reduction process However, at high concentrations, the reduction of carbon is not possible in all the
used in metal extraction. The following three reactions are possible when carbon is cases due to following reasons:
used as a reducing agent:
(a) It has a hefty price tag.
C  O2  CO2
(b) At high temperatures, some metals react with carbon to generate carbides.
2C  O 2  2CO
(c) Maintaining a high temperature poses numerous practical challenges.
2CO  O2  2CO2
(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.

There is almost little change in entropy in the first reaction (creation of CO 2 ), i.e. Fe2O3  3CO  2Fe  3CO2
S  0, and hence  G  remains virtually constant as temperature rises, i.e.,  G  is
(B) The Ellingham diagram of the theory of ZnO reduction demonstrates that the
temperature independent. The entropy of the second process (the production of CO curves involving the synthesis of ZnO and carbon monoxide cross at about 1270 K.
) increases ( S is positive), therefore  G  becomes more negative as the Above 1180 K, the value of  G  for the formation of ZnO increases dramatically.
temperature rises. However, in the third reaction, entropy decreases ( S is negative), This is owing to the fact that at this temperature, zinc begins to boil.  G  of the
and so  G  gets less negative as temperature rises.
following equation above 1270 K.
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

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