Kroll Process

Originally Wilhelm Kroll produced Ti by reducing TiCl4 with Ca in an electric furnace. Later
Mg was used, and now-a-days in some places Na is used instead. Ti-extraction from the oxide
ore possess difficulties because of high melting temperature of the metal and its reactivity with
air, O2, N2 and hydrogen. The oxide in not amenable to reduction with C as it forms carbide.
Hence the oxide is heated with C and Cl2 gas at 900o C to convert it to TiCl4 in the first step. It is
distilled off (b. p. 137o C) to separate it from FeCl3 and other impurities.

TiO2 + 2C + 2Cl2 TiCl4 + 2CO

o o
TiCl4 + 2Mg 1000 - 1150 C Ti + 2MgCl2

The MgCl2 formed can be removed by leaching with water, or better with dil. HCl as this also
dissolves any excess Mg. Alternatively, the MgCl2 is removed by vaccum distillation. This
leaves a sponge of Ti rather than a solid block. The Ti is converted to the massive form by
melting in an electric arc in a high vaccum or an atmosphere of Ar. In another process TiCl4 is
reduced by Na in an atmosphere of Ar, and NaCl is leached out with water. The Ti obtained is in
the form of small granules. These can be fabricated in to metal parts using “powder forming”
techniques and sintering in an inert atmosphere. Zr and Hf are also produced in a similar mannar.

Ti-extraction from the oxide ores posses difficulties because of high melting temperature
of the metal and its reactivity with air, O2, N2 and H2. The oxide is also not amenable to
reduction with C as it forms carbide. Hence the oxide is heated with C and Cl 2 gas at 900o C to
convert it to TiCl4 in the first step. It is distills off to separate it from FeCl3 and other impurities.

Van Arkel-de Boer Method

Small amounts of very pure metal can be produced by this process. Impure Ti or Zr are heated in
an evacuated vessel with I2, TiI4 or ZrI4 is formed and volatilizes (thus separating it from any
impurities). At atmospheric pressure TiI4 melts at 150o C and boils at 377o C; ZrI4 melts at 499o
C and boils at 600o C. Under reduced pressure, however, the boiling points and lower. The
gaseous MI4 is decomposed on an electrically heated white hot tungsten filament. As more metal
is decomposed on the filament it conducts electricity better. Hence, more electric current must be
passed to keep it white hot.
Zone Refining

Metals of high purity can be obtained by this method by removing an impurity which shows
differences in solubility in the liquid and solid states of the metals.

A circular heater is fitted around a rod of impure metal and is slowly moved along the length of
the rod. At the heated zone the rod melts and as the heater moves forward pure metal crystallizes
while impurities pass on to the adjacent molten part. In this way the impurities are ‘swept’ into
one end of the rod which is cut off. Several such successive operations are needed to get the
metal in a state of high purity. Ge, Si, and Ga used in semiconductors are refined in this manner.

Partition method

This is the basis of the classical Parke’s process for removing Ag & Au from Pb. Molten Zn and
Pb are nearly immiscible, while Ag and Au are very much more soluble in Zn than in Pb (Ca,
300 times in case of Ag at 800o C).

So when Zn is added (ca, 1%) to molten Pb having Ag or Au most of the Ag or Au passes into
the Zn and the resulting alloys have melting points much higher than that of Pb and hence
solidify and floats on the surface of the molten Pb. This is remove as much Ag and /or Au from
the Pb as possible (reduction to ca. 0.0004% of Ag or Au in Pb can be achieved). From the Zn-
Ag / Au alloy Zn is removed by distillation after mixing with a little charcoal powder to prevent
ZnO formation.

Mond’s Process

By this method the Ni ions are converted to volatile Ni(CO)4 which was decomposed at 200o C
for metallic Ni.

NiO + H2 Ni + H2O

Ni + 4CO Ni(CO)4

Ni & Cu can also be separated by this process. The Cu-Ni-Fe matte is roasted to form mixed
oxides. These are then heated to 350o C in a current of water gas (CO + H2). The Fe2O3 is not
appreciably reduced at this temperature, while oxides of Ni & Cu are reduced to metallic state by
H2 of the water-gas which is thereby enriched in CO. The metallic mixture is then passed at 50-
60o C down a tower provided with shelves, and the enriched CO is passed up the tower. Ni
combines with CO to form the volatile Ni(CO)4. The vapour of Ni(CO)4 is then made to pass
through a tower packed with Ni-pellets; Ni(CO)4 → Ni + 4CO. The CO is returned to back to the
volatilizing tower. The metal thus obtained is quite pure and contains ca. 99.95% Ni. The
residual matte contains all the precious metals Ag, Au, Pt etc. originally present in the ore.
Electrolytic Reduction process

In the usual Hall and Heroult process for extraction of Al, a solution of 5-6% by weight of Al2O3
(obtained from bauxite ore by suitable purification) in fused cryolite (Na3AlF6) with ca. 6-10%
by weight of fluorspar (CaF2) added to lower the melting point and some AlF3 to bring the
NaF:AlF3 ratio (w/w) to ca. 1.4 which improves efficiency, is electrolysed using carbon
electrodes (anode and cathode) when Al is deposited at the cathode and O2 liberated at the anode.

3O2- 3/2O2 + 6e-; 2Al3+ + 6e- 2Al

F2 is not liberated at the anode as it reacts with Al2O3;

2Al2O3 + 6F2 4AlF3 + 3O2

Similarly, extraction of highly electropositive metals like Na, Ca, etc. is carried out be
electrolysis of their fused halides (mixed with some halides to lower the melting point; CaCl2 is
added to NaCl to lower the melting point from 800o C to ca. 500o C):

At anode: Cl- Cl. + e-

Cl. + Cl. Cl2 (g)

+ -
At cathode: Na + e Na

The Na metal cannot be produced in the aqueous medium as it is very violently attacked
by water. There is no stable chemical reducing agent which can reduce Na+ to Na. Electrolytic
reduction overcomes these two problems and easily converts sodium chloride to metallic sodium.
The electrolysis of NaCl(aq) does not produce Na(s) because of the following electrode
reaction.

Na+ + e- Na (s)

It has a highly negative E0 (-2.71 V). In addition, the sodium formed reacts with H2O. The
overall reaction is

2NaCl(aq) + 2H2O(l) Cl2(g) + H2(g) + 2NaOH(aq)

Cl2 is an important bi-product of this process.

Hydrometallurgy is the treatment of bringing the metal into solution by the action of suitable
chemical reagents, e.g., sodium cyanide solution or chlorine in the presence of water. This is
followed by recovery of the metal by electrolysis or by the use of suitable precipitating agents.
For example, poor ores of silver are suspended in a dilute solution of sodium cyanide and air is
blown through it. The silver present goes into as the argentocyanide complex from which the
metal is precipitated by adding zinc tunnings.

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

Or,

AgCl + 2NaCN Na[Ag(CN)2] + NaCl

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

This method involves the process at room temperature, is not only economic but also
ecofriendly. Low grade ores may also be used in this process.

Extraction of gold involves the use of hydrometallurgical principles in which inert gold
(cf. Au+ + e- Au, E0 = +1.7 V) becomes quite active in the presence of
- -
CN- (cf. Au(CN)2 + e Au + 2CN-, E0 = -0.60 V) and aerial oxygen can oxidise the
elemental gold to bring it into solution in presence of KCN. At the next step Au(CN)2‒ complex
2+ -
is reduced to elemental gold by Zn-powder (cf. Zn + 2e Zn, E0 = -0.76 V;

Zn(CN)42- + 2e- Zn + 4CN-, E0 = -1.39 V) ).

Low grade sulphide ores (e.g., Fe & Cu) may be kept exposed to air in moist condition
and on standing these are oxidized to sulphates. Then the heaps are leached with water to extract
the soluble sulphates.

Now the hydrometallurgy process uses the microorganism (e.g., bacteria, algae) to extract
the metals from their ores which are often of low economic grade.

Acidophilic bacteria like Thiobacillus ferrooxidians can oxidise insoluble copper sulphide by O2
or by Fe(III) produced from Fe(II) by bacteria. Thus the net reaction is:

CuS + 2O2 CuSO4

Iron pyrites is also oxidise as follows:

Or, Fe
2+
Fe3+ + e; 2S2- + 3O2 + 2H2O 2SO42- + 4H+ + 4e