Metallurgy ,2nd Part

C9 ,4th Sem

Dr Sukla Chakladar

Associate Professor,RNKWC,Midnapopre

Electrolytic reduction
For more reactive metals like Na,Mg ,Al etc cannot be reduce by carbon reduction
process. So they can be reduced by electrolysis and these metals are not obtained
by electrolysis from aqueous solution of their salt. So in these cases electrolytes are
molten salts.

Some e.gs
Metal Electrolyte Reaction at the electrodes
Na NaOH (Castner’s Process) At Cathode Na++e Na
At anode 4OH-
2H2O+O2+4e
NaCl(Down’s Process) Na++e Na(at Cathode)
-
2Cl Cl2+2e(at Anode)
2+
Mg Molten MgO Mg +2e Mg(Cathode)
O2- 1/2O2+e(Anode)
MgCl2 Mg2++2e Mg(Cathode)
2Cl- Cl2+2e(Anode)
Al Alumina(Al2O3,Na3 AlF6+CaF2) Al2O3 2Al3++3O2-
Al3++3e Al(Cathode)
2-
3O 3/2O2+3e-
(Anode)

Hydrometallurgy
Hydrometallurgy involves extraction of metal from ore by preparing an aqueous
solution of a salt of the metal and recovering the metal from the solution. The
operations usually involved are leaching, or dissolution of the metal or
metal compound in water, commonly with additional agents; separation of the
waste and purification of the leach solution; and the precipitation of the metal or
one of its pure compounds from the leach solution by chemical or electrolytic
means.

It involves extraction of less electropositive or less reactive metals like gold and
silver. Powdered ore is first dissolved in a suitable reagent by complex formation
e.g.

Ag2S+4NaCN 2Na[Ag(CN)2]+Na2S

4Au+8NaCN+2H2O+O2 4Na[Au(CN)2]+4NaOH

Now a strong electropositive metal added to above salt solution from which metal
is obtained.

2Na[Ag(CN)2]+Zn Na2[Zn(CN)4] +2Ag

2Na[Au(CN)2]+Zn Na2[Zn(CN)4] +2Au

Hydrometallurgy is based on the principle that a more electropositive metal

displaces a less electropositive metal from its salt.

Electrolytic Kroll Process

Titanium cannot be extracted by reduction with C since it forms TiC with carbon
instead of free metal.
TiO2(s)+3C(s) TiC(s)+2CO(g)
Prior to the Kroll process, titanium was separated from its ores by the chloride
process, where a feedstock of refined rutile or ilmenite is reduced with petroleum-
derived coke in a fluidized bed reactor at 1000 °C. The product is then treated
with chlorine gas, producing TiCl4 and other volatile chlorides, which are then
separated by continuous fractional distillation.
The Kroll process is a pyrometallurgical industrial process used to produce
metallic titanium. It was invented in 1940 by William J.Kroll.
TiO2 is reacted with C and Chlorine to produce TiCl4 which is liquid at normal
condition and can be purified by distillation.
TiO2+2Cl2(g)+2C(s) TiCl4(l)+2CO(g)
Gaseous TiCl4 is reduced by liquid magnesium at 800–850 °C in a stainless
steel retort to ensure complete reduction.
TiCl4(g)+2Mg(l) Ti(s)+2MgCl2(l)
Reaction is carried out in Ar atmosphere to prevent the violent reaction of Mg with
air..After the reaction is over molten MgCl2 is tapped off. Ti sponge contains upto
30% of impurities (mainly MgCl2). Heating at high temperature removes MgCl2
from Ti sponge. Mg is recovered from MgCl2 by electrolysis.
MgCl2 Mg(l)+Cl2(g)
The chlorine is recycled.
Titanium is about six times as expensive as stainless steel.
In the Hunter process, which is not commercial, the TiCl4 from the chloride
process is reduced to the metal by sodium.
TiCl4(l)+4Na(l) Ti(s)+4NaCl(l)
Parting Process
Parting, in metallurgy is the separation of gold and silver by chemical or
electrochemical means. Gold and silver are often extracted together from the same
ores or recovered as by-products from the extraction of other metal ores and are
chemically similar and therefore hard to separate.
A solid mixture of the two, known as bullion, or doré, can be parted by boiling
in nitric acid. The silver is dissolved as silver nitrate, leaving a residue of gold that
is filtered off and washed; silver is precipitated out of solution by the addition of
ferrous sulfate. This is the traditional method used in assaying the content of gold
and silver samples.
Most gold and silver are parted electrolytically after being recovered in the slimes
left over from copper refining or as a metallic by-product of lead or zinc smelting.
The bullion is cast into anodes, which are placed into an electrolytic cell and
subjected to an electric current. Silver dissolves in the electrolyte and then deposits
onto the cathodes. Gold and trace amounts of silver are recovered in the slimes and
are parted either electrolytically or by boiling in sulfuric acid and potassium nitrate
to dissolve the silver.

For some years now a new acidless separation process based on the vacuum
distillation method, is being used; it is a physical method, which does not use any
chemical and therefore it is considered the greenest of the gold parting processes.
 Vapour Phase refining
In this refining process of purifying metal:

 The impure metal is heated with a specific reagent that produces a suitable
volatile compound as the product.
 Volatile compound is heated strongly, which undergoes decomposition
producing pure metal

So the two requirements are:

a) Metal should form a volatile compound with suitable reagent.

b) The volatile compound should be easily decomposable so that the recovery of

metal is easy.

Two tmethods of vapour phase refining are:- 1.Mond’s process 2.van Arkel-de
Boer process

1.Van Arkel de Boer Process: This method is very useful for removing all the
oxygen and nitrogen present in the form of impurity in certain metals like Zr
and Ti.

 Used in the refining of Zr and Ti.

 Impure Zr/Ti is heated in an evacuated vessel with iodine
 Volatile ZrCl4/TiCl4is obtained as product.
 Volatile compound is heated strongly over a tungsten filament to give
pure metal(Zr/Ti).The pure metal is thus deposited on the filament.

5970C 18000C

Zr(s)+2I2(g) ZrI4(g) Zr(s)+2I2(g)

Impure zirconium zirconium tetraiodide Pure zirconium

2500C 14270C

Ti(s)+2I2(g) TiI4(g) Ti(s)+2I2(g)

Impure Titanium Titanium tetraiodide Pure titanium

2. Mond’s Process

 Used for refining of Nickel

 Impure nickel is heated with a stream of CO gas.
 A volatile nickel tetracarbonyl, Ni(CO)4 is produced.
 Impurities are left behind.
 Volatile Ni(CO)4 is heated strongly which decomposes to produce pure
nickel.
57-770C 177-1970C
Ni (s)+4CO(g) Ni(CO)4 (g) Ni (s)+4CO(g)
Impure Nickel Nickel tetracarbonyl Pure Nickel

Zone Refining
Definition: This is a technique for the purification of an impure metal in which a
molten region travels through the material to be refined, picks up impurities at its
advancing edge, and then allows the purified part to recrystallize at its opposite
edge.
Zone refining is a very useful method to get metals with very high purity such as
silicon and germanium, gallium and tellurium. It is also referred to as zone
melting, floating zone process, and traveling melting zone.
Zone refining was discovered by scientist W.G.Pfann and is based in the principle
that the impurities have higher solubility in the molten metal as compared to that of
solid metal. The difference in the solubility of impurities makes it possible to
segregate the impurities in the metals to be refined.
During the process of Zone Refining:
 A circular mobile heater is placed around the impure metal rod which is
moved along the rod from one end to the other.
 As the heater shifts from one zone of the metal rod to another, the impurities
also shift to the zone with molten metal.
 Finally the impurities get concentrated at one end of the metal rod which is
later removed.
Zone refining procedure: The metal rod is placed in a tubular zone refiner. In the
Zone Refiner an inert gas atmosphere is maintained. A circular mobile heater is
placed around the rod. This heater moves along the rod from one end to the other.
At the time, the heater melts a particular zone or a portion of metal rod along with
its impurities. As the heater moves along the rod the molten metal of the previous
zone solidifies again. During solidification of the metal impurities of the zone
move to newly heated zone or the zone that is in contact with the heater. In another
words, as the heater shifts from one zone of the metal rod to another, the impurities
also shift to the zone of molten metal. By the time the heater reaches to the other
end of the impure metal rod, the impurities get concentrated there. The end of the
metal rod with concentrated impurities is then removed and discarded. The same
process is repeated again and again till highly purified metal is obtained.