Video Course : Nonferrous Extractive Metallurgy

Questions and Answers

Modules 1 and 2 ( Introduction , occurrence of metals, beneficiation etc.)
Discuss validity/invalidity of the following statements
1. Human civilization progressed through the following Ages : Chalcolithic,
Neolithic, Paleolithic, Bronze and Steel
Ans- Statement invalid because there is a mix up. Lithos means stone , Neo means
new and Paleo means old. The correct order is : Paleolithic Age ( Old Stone Age),
Neolithic Age ( Neo stone Age), Chalcolithic Age ( Chalcos means copper and hence,
the word refers to use of copper and stone), Bronze Age and Steel Age.
2. The ancient man knew of only a handful of metals
Ans: Statement valid. The metals known comprised Ag, Au, Cu, Hg, Pb, Sn, Fe and
perhaps As. Often alloys such as brass and bronze were thought of as metals. Zn was
isolated by Indians around the 5th century AD.
3. Indians are known to have produced copper first.
Ans- Statement invalid . Indians were the first to produce only Zn. Copper was first
produced in Egypt. All the pyramids were built using copper tools only.
4. All ores are mixtures of minerals
Ans- The statement is correct only with the exception of metals such as Au, Ag and Pt
group metals ( precious metals) which are present in some ores not as minerals or
compounds but in native or free state. Ag may be sometimes found as weakly stable
compound or mineral.
5. The earths crust ( which includes the oceans and the atmosphere) contains
many elements but only a few account for the bulk
Ans- This is true. 98% or more is accounted for by only a handful, namely, O2, Si, Al,
Fe, Ca, Na, K and Mg. Of these , the first two account for nearly 75%.
6. In the sea, the sea water is the only source of various metals
Ans- Statement is not complete. While it is true that all elements are present in sea
water, there are other sources of metals in the sea. These are : ocean floor nodules
and sea organisms i.e. animal and plant life. Elements are also added by volcanic
eruptions in sea bed.
7. Ocean floor nodules are called Nickel nodules
Ans No, although these nodules, often also called multimetal nodules, contain Ni, Co
and other valuable metals, by far the most abundant is Mn ( ~24%) . Hence the nodules
are often called manganese modules.

8. Primary metals refer to the more important metals and secondary metals refer
and secondary metals refer to metals of minor importance.
Ans Statement is invalid. Primary metals refer to all metals obtained though extraction
processes that process ores and minerals from land, sea water and sea modules.
When metals are obtained through processing of scrap then they are called secondary
metals.
9. The ore deposits for various metals in India are sufficient for indigenous
production of all important metals required by the country.
Ans- This statement is invalid. Metals whose deposits can be classified as adequate to
abundant include only the following Al, Be, Cr, Mn, Fe, Mg, Ti, Zr, Th and R.E.
Deposits of base metals are inadequate and ores of many others are very meagre.
10. A spiral used in beneficiation of minerals separates minerals based on
magnetic and electrical properties.
Ans: This statement is incorrect. A spiral exploits for minerals separation, properties
such as density, particle size and shape.

Module 3
General methods of reduction, Pyrometallurgy and Hydrometallurgy
A. Discuss the correctness of the following statements.
1. Not all metal compounds are equally stable and there are different criteria to
indicate relative stabilities.
Ans. The statement is correct. The relative stabilities can be expressed in terms of
electrode potential values, electronegativity values and free energies of formation of
compounds. Greater stability is indicated by higher electrode potential, lower
electronegatinity and more negative free energies of compounds.
2. The orders of stability and listing of various metals are identical in the use of
all the criteria applied.
Ans. This is not so and there are minor differences. Generally reactive metals occupy
higher positions and less reactive metals occupy lower positions, noble metals coming
at the bottom of every list.
3. Decomposition of a CaCO3 sample is about 9100C. This means that, during
heating, decomposition reaction starts at 9100C
Ans. This statement is invalid. Decomposition will start at lower temperatures but only
at 9100C the partial pressure of CO2 will reach the atmospheric pressure . Similarly, the
boiling point of water implies the temperature when vapour pressure of water will equal
to 1 atm. There will be water vapour even at room temperature but at lower
temperatures vapour pressure will be lower. At higher altitudes, where atmospheric
pressure is lower, the boiling will also be lower.
4. In Ellingham diagrams for oxides all lines showing free energies of formation
versus temperature are shown for per mole of the oxide.
Ans. The answer is not correct. The lines shown are always for one mole of oxygen for
forming corresponding metal oxide, CO or CO2. Metals have different valencies and
thus, while one mole of some oxide needs one half mole of oxygen (e.g. PbO, ZnO,
FeO) some other need two moles (e.g. SnO2, TiO2 ZrO2 etc) or other amounts. (For
Al2O3 and Fe2O3 it is 3/2). For one mole of C it can be one (as for CO2) or half (as for
CO). Lines indicate values per mole of oxygen so that one can easily and conveniently
calculate the free energy change when oxide of one metal is reduced by carbon to form
CO or CO2 or is reduced by another metal to form a more stable oxide. The required
values for change in free energy is obtained by deducting the free energy change
corresponding to reduction of the oxide by C (w.r.t. CO or CO2 as the case may) or the
second metal and the oxide being produced. In subtraction O2 is cancelled out and one
is left only with the chemical equation for carbon reduction or metallothermic reaction of
one oxide to produce the metal.
5. The lines in Ellingham diagrams that have positive slopes are nearly parallel
because each represents formation of a compound consuming one mole of
oxygen.

Ans. The statement is not correct fully. Moreover, it is not written correctly either. It is
true that lines showing free energy change, in the reaction for formation of a metal
oxide per mole of oxygen, have all positive slopes that are nearly equal so long as the
oxide and the metal are solid. If there is melting of any of the two then the slope
changes. For CO formation, the slope is negative and for CO2 formation the free energy
change line has zero slope, i.e. the line is horizontal.
The expression for standard free energy change is written as follows:
G0 = H0 - TS0
H0 and S0 values are almost independent of temperature and, therefore, variation is
G0 is because of the T term, essentially, S0 giving the slope and H0 the intercept.
For all lines S0 is constant (when there is no phase change) because it arises out of
disappearance of one mole of oxygen. When there is phase change there is greater
S0 and hence change is slope. There is no entropy change for formation of CO2
because one mole of O2 is consumed to produce one mole of CO2. However, there is
increase in entropy when we consider CO formation. Here one mole of O2 is consumed
to produce two moles of CO.
6. In theory all metal oxides can be reduced by carbon to produce the metal.
Ans. This statement is partially correct. For carbon reduction to be feasible the product
must be thermodynamically more stable. Since the stability of CO2 remains essentially
unchanged with temperature it can intersect lines for some metal oxides which are
stabler at lower temperatures but less stable than CO2 at some temperature where the
CO2 horizontal line intersects the metal oxide line sloped upwards (see Ellingham
diagrams) For very stable oxides this cannot happen for two reasons.

The temperature of intersection of CO2 line and metal oxide line is far too high.

Beyond around 7000C CO becomes more stable than CO2 and with increasing
temperature the ratio of partial pressure of CO to that of CO2 increases in C CO
CO2 system.

Since the CO line has negative slope it crosses all lines for metal oxides and
temperatures of intersections are not that high. Yet, for metals which produce very
stable oxides, carbon reduction is not recommended because at the high temperatures
of reduction the reactive metals also produce stable carbides which will contaminate the
metal.
7. The lines in predominance area diagram for metal sulphur oxygen
systems are easily obtained through thermodyramic calculations.
Ans. Yes, and that is how the lines that show for a fixed temperature, the relative
stabilities of various possible phases (M , MS, MSO4, MO etc.) are obtained for different
partial pressures of O2 and SO2.

As an example consider how one obtains the lines indicating equilibrium between Ni
and NiO and Ni and Ni3S2
Ni + O 2 = NiO
K = aNiO / aNi . p 0.5 = p -0.5
o2
o2
The value of K (Eq . const) can be obtained from thermo-dynamic data (G0 = - RT lnK)
and hence partial pressure of oxygen calculated. The line for Ni / NiO will be parallel to
the vertical line for partial pressure of SO2 in the area diagram (the horizontal axis
shows partial pressure for oxygen).
Ni can form Ni3S2 and we can consider NiO / Ni3S2 equilibrium for which the reaction is
Ni3S2(s) + 7/2 O2 = 3NiO + 2SO2
K = p2 / p7/2
so2 o2
= 7/4 log p + log K
log p
so2
o2
The slope in the log log plot will be 7/4 and its position can be fixed by the calculated
value of K.
8. Flash roasting gives accelared reaction compared to hearth roasting.
Ans. This statement is correct. In the former, sulphide particles are suspended mid-air
much longer and, therefore, more effectively oxidized.
B. Find, through calculation, answers to the following questions.
1. Can Fe reduce PbO at 10000C? The free energies of formation for FeO and
PbO are given, respectively, as 364 KJ and 184 KJ per mole of oxygen.

Ans.

2Fe + O2 = 2FeO
2Pb + O2 = 2PbO

Subtracting
Or

2Fe + 2PbO = 2FeO + 2Pb

Fe + PbO = FeO + Pb

The free energy change for the last reaction is [-364 + 184] / 2 i.e. -90 KJ / mol
Since the value is negative the reduction reaction is possible when all the species are in
their standard states.
1. The equilibrium constant for oxidation of a metal M to oxide MO is 5.76 x 10 at
1000 K. That for oxidation of CO to CO2 is 1.68 x 1010 at 1000 K. Will a gas
containing 15% CO2, 5% CO and 80% N2 oxide the metal at 1000 K?

Ans. The reaction is

M(s) + CO2 (g) = MO (g) + CO (g)
Eqm . Constants are for standard states only i.e. pure solids and gases under 1 atm.
The Eqm. Constant for the above reaction is obtained by considering the data given.
For metal oxidation
M(s) + O 2 (g) = MO (s)
5.76 x 107 = 1 / Po20.5 ...(a)
For CO oxidation
CO (g) + O 2 (g) = CO2 (g)
1.68 x 10

10

p
co2
p
. p0.5
co
o2

.(b)

Eqm. Constant for CO2 oxidation of M is obtained by dividing Eq . (a) with Eq (b)
p
/p
= 5.76 x 107 / 1.68 x 1010
co co2
= 3.43 x 10-3 at 1000 K
The eqm (p
/ p ) for oxidation of metal is, therefore, 1000 / 3.43 i.e. 291.5
co2 co
/ p ) ratio is 15/3 = 3
In the actual gas with 15% CO2 and 5% CO the (p
co2 co
Obviously, the metal will not be oxidized.

Module 4
Principles of metals refining and Electrometallurgy
A: Discuss the validity/invalidity of the following statements
1. A solute is to be transferred from Phase I to another Phase 2 that is in contact.
There is a choice between co-current flow and counter current flow. Over
extended duration of contact, transfer is more effective when the flows are
counter current
Ans This statement is correct. When Phase 2 with no solute comes in contact with
Phase 1 with the solute, as it happens in cocurrent flow. The initial driving force for
transfer of solute from Phase 1 to Phase 2 is high. But this driving force diminishes with
time quite rapidly. On the other hand, in counter current contacting Phase 2 with no
solute first encounters Phase 2 from which much of solute has been transferred
already. As Phase 2 advances in counter current flow with some enrichment in the
solute it encounters Phase 1 eicher in solute. That is, there is a steady driving force
maintained although and thus, over an extended duration solute transfer is more
effective.
Counter current flow is employed in solvent extraction and some slag cleaning
operation such as by counter current flow of slag and matte in continuous copper
smelting.
2. Both the electrolytic production of aluminium and its electrorefining are 3
layer processes.
Ans- No, the electrorefining process is a 3 layer process because there are 3 layers
pure molten Al cathode at the top , an AlF3, CaF2, cryolite electrolyte at the middle and
Al-Cu alloy cathode at the bottom. During electrolysis , there are essentially only 2
layers, molten aluminium at the bottom and then the electrolyte. On top is solid Al2O3
charge which is not considered a layer in the sense that it is not liquid.
3. The voltage requirement for electrorefining is generally much less than that
needed for electrowinning
Ans- This statement is correct. In electrorefining, metal is not produced by
decomposition of a salt, the electrolyte only providing a medium for transfer of metal
from an impure anode to a pure cathode. In theory, the required voltage is actually zero
because metal potential is the same at both electrodes. However , some voltage is
necessary to overcome resistance of the electrolyte and electronic resistances in the
circuit and the electrodes.
4. The vapour transport process may be schematically written as follows
Metal( Impure) + vapour 1
vapour 2 ( Temp T1)
Vapour 2 -


Vapour 1 + Metal (Pure) (Temp T2)
T2 is always higher than T1.
Ans This is not correct. For Ni ( forming Ni(CO4)) T2>T1. But for Al (forming AlCl3)
T2<T1

The sign of H0 for the reaction determines this.

5. In eletrolysis, it is desirable to have thick and wide electrodes and not thin
and deep ( long) electrodes.
Ans- This statement is correct. There is less voltage drop in the former case. The width
actually is immaterial and , therefore, by increasing the width one can increase more
electrode surface area and greater production.
6. An impure metal is thermodynamically more stable than the pure metal
Ans- This statement is correct. Assimilation of impurities increases the entropy of the
system ( configurational entropy) and decreases free energy. In fact, it becomes
increasingly difficult to achieve further purification when impurity level approaches zero,
specially so for reactive metals.
7. Zn reacts with acid solutions. Yet zinc metal can be obtained
electrolysis of acid solutions.

through

Ans This is correct. Normally Zn is placed higher in the e.m.f. series with hydrogen
electrode assigned zero potential. Being more electropositive, zinc will replace
hydrogen. During eletrolysis, however, passage of current causes activation
overpotential which pushes Zn/Zn2+ potential to below hydrogen electrode potential
making hydrogen more electropositive.
8. In ionic media there is completely random mixing of anions and cations in the
lattice positions.
Ans This statement is incorrect. In an ionic media, there are two interlocked sublattices, one for the anions and the other for the cations. Anions can be randomly
distributed only in the anion sublattice and cations in the cation sub-lattice.
9. Limiting current dencisty arises out of concentration overpotential which is
dictated by thermodynamics.
Ans- The first part of the sentence is correct but not the second part.
When current flows, cations are pushed to the cathode by a concentration gradient, the
cathode surface concentration of cations being lower than their bulk concentration . A
limit is reached when cation concentration at the surface falls to zero and no more
current can be passed unless electrode area is increased. This limiting current is thus
because of kinetic factors.
Of course, concentration overpotential becomes important only when the diffusion of
cations towards to cathode surface is slower than the ion discharge at the electrode
and , therefore, is rate controlling.
10. Fluidized bed electrolysis enhances the limiting current density during
electrolysis by almost one order of magnitude.
Ans- This statement is correct. A fluidized bed of metal particles makes available a
larger metal surface area for electro-deposition and hence limiting current can be
higher.

11. kinetics has no role in creating activation over potential at the cathode.
Ans- This statement is not correct. Activation over potential comes into play when the
rate of discharge of cations at the cathode surface is slower than the rate of diffusion of
cations from the bulk to the cathode surface. When the former becomes rate controlling
then there is accumulation of cations at the cathode surface and., therefore , a
deviation in the thermodynamic M/Mn+ electrode potential.
12. When a metal tends to dissolve in its molten salt during electrlysis then
addition of another salt generally decreases the solubility.
Ans- The statement is correct. Generally this happens more significantly when metal
valency is more than one. We can write the following equations for a divalent metal M
dissolving in, say, a halide MX2.
The dissolution is a 2 step process
Step 1 M(l)
M ( solution atomic/molecular dissolution)
Step 2 M(Solution) + MX2 = 2MX ( subhalide formation)
When a second salt, say NY, is added to MX2 then the activity of MX2 is decreased and
thus, both the above reactions are encouraged to shift equilibrium to the left.
B. Answer the following equations
1. A fused salt mixture contains equal number of moles of CaCl2 and NaCl. If an
equal number of moles of CdBr2 are added to the mixture then calculate
activities of these salts in the fused salt mixture.
Ans- Activity of any salt is given by the Temkin Model that takes into account ionic
fractions and probalibity of finding association of required number of cations and anions
making up to the salt . We remember that cation are randomly distributed only in the
cation sublattice whereas anions are randomly distributed only in the anion sublattice.
a
CaCl2

= X

2+

Ca

[X

]2

Cl

= [1/3] [ 3/5]2 = 3/25 = 0.12

a
NaCl
a

=X
.
Na+
=X

CdBr2

2+

Cd

=
Cl-

1 . 3
3
5

= 0.2

. [X ]2
Br-

= [1/3] [2/5]2 = 0.053

2. From the data given in Problem 1, can one calculate activities of CaBr2 NaBr
and CdCl2?

Ans- Yes one can. In the mixture, one only has ions and not what one added in the first
place. One can get activities of other salts, such as the ones mentioned here also using
the Temkin model.
Thus
a

=X
CdBr2

Ca2+

NaBr

=X
.
+
Na

. [X ]2 = [1/3] [2/5]2
BrX

= [1/3].[2/5] = 0.1355
-

Br

=X
. [X ]2
2+
Cd
ClCdCl2
= [1/3] [3/5]2 = 0.12

3. Consider a fused salt solution containing, in mole percent, the following

constituents: Al2O3 15, CaF2 - 5, NaF 2 and Cryolite (Na3AlF6) the rest.
Calculate the activity of Al2O3 the bath and comment on the value.
Ans- First assume that Al2O3 and Cryolite are dissociated as follows.
Al2O3 = 2Al3+ + 2O2Na3AlF6 = 3Na+ + AlF-6
CaF2 = Ca2+ + 2FNaF = Na+ + FThe bath will contain in moles, the following (we omit the charge signs)
Cations (+ ions) 30 Al, 5 Ca, (2 + 3 x 78) Na
i.e. 30Al, 5 Ca, 236 Na
Anions (- ions) - (3 x 15) O, 78 AlF6, (2 x 5 +2)F
i.e. 45 O, 78 AlF6, 12 F
a
Al2O3

= X2
Al

X3
O

=[
30
]2 . [
45
]3
[ 30+5+236 ]
[45+78+12 ]
= (0.110)2 . (0.333)3
= 0.012 x 0.037= 0.00044
= 4.4 x 10-4
This value appears very small indeed. Perhaps the dissociation of cryolite makes
available other ions so that this value becomes larger.

Module 5
Extraction of metals from oxides
A. Discuss validity/invalidity of the following statements
1. Fe-Si reduction of calcined dolomite ( Cao.MgO) is a solid solid reduction
reaction.
Ans- Not quite correct. Though both the reactants are solid and the initiation must be by
solid-solid reaction, soon a liquid Ca-Fe-Si alloy formed permeates the solid briquettes
and then this liquid reacts with calcined dolomite.
2. Al2O3 cannot be reduced by carbon to produce Al because the required
temperature for reduction is too high.
Ans- The C-CO line intersects Al-Al2O3 line in the Ellinghams digram at about 20000C.
That is beyond 20000C, CO becomes more stable than Al2O3 and therefore,
thermodynamically Al2O3 can be reduced by carbon beyond 20000 C. This temperature
can be achieved in an electric furnace. However, at such high temperatures aluminium
will also form stable carbide which will contaminate the metal.
The statement , therefore, is incorrect. However, In ALCAN process, one reduces Al2O3
by carbon in an electric furnace at about 20000C to produce an alloy containing 50
percent Al, 30 per cent Fe, 10 percent Si, 5 per cent Ti and 5 percent C. The impure Al
is purified by a vapour transport process.
3. The consumable carbon anode used in aluminium
decomposition voltage of Al2O3 in the electrolyte.

eletrolysis reduces the

Ans- This statement is correct. If the decomposition produced only Al at the cathode
and oxygen at the anode then the voltage required will be around 2:1. However when
the oxygen liberated reacts with carbon anode to produce CO and CO2 then
dissociation of Al2O3 is thermodynamically made easier and the required voltage is
nearly halved.
4. In an Al electrolytic cell of the Hall-Heroult process, Al2O3 concentration in
cryolite is controlled to be within limits to ensure proper heating of the bath.
Ans: The statement is incorrect and confusing. It is true that heating of the bath is
internal i.e. passage of the current provides heat because of ionic resistance of the
bath. The ionic resistance is essentially determined by inter-electrode and separation
and conductivity of the bath and variation in Al2O3 concentration has little role.
However, Al2O3 content is restricted for smooth operation because beyond a certain
value Al2O3 cannot dissolve in cryolite (at 10000 C the solubility is less than 15 per
cent). Again , below about 2 percent, Al2O3 , there is the Anode effect which stops
normal electrolysis, the anode surface being covered by fluorine bubbles. Normally
Al2O3 percentage is controlled within 5-8.
5. Some nonferrous metals are produced as ferro-alloys because they are often
used as such in the industry.

Ans- Yes this true but that is not the only reason. Alloys such as Fe-Mn, Fe-Cr, Fe-Ti
etc find application as such for alloying additions in steel, deoxidation etc. but there are
other reasons for ferroalloy production. In such alloys activities of Mn, Ti, Cr etc are
lower and therefore, it becomes thermodynamically easier to reduce the metal oxides.
At lower temperatures the formation of their carbides is also discourged.
6. A high carbon ferrochrome is melted in an electric furnace and oxygen is
injected into it. This oxygen will preferentially oxidize carbon and not
chromium.
Ans- This statement is true because, as per the Ellingham diagram CO becomes
thermodynamically more stable than Cr2O3 beyond about 13000C. In fact oxygen
injection is a standard method of decarbonization. By injection, the temperature is also
raised making carbon remove more effective kinetically.
7. During any electrolytic process Energy Efficiency can never be greater than
Current Efficiency.
Ans- That the answer is correct should be obvious. Current efficiency refers to the level
of utilization of current passed in the metal deposition reaction of interest. Loss of
current consumed in unwanted side reactions reduce Current Efficiency.
Energy Efficiency is also calculated with reference to the same desired reaction and
side reactions will lower this also. However, Energy Efficiency must always be lower
than the Current Efficiency because some of it must be lost as voltage losses in
overcoming the ionic resistance of the bath and electronic resistance in the circuit . The
energy consumed in overcoming the ionic resistance, however, is not always exactly a
loss, because the heating required for keeping a fused salt mixture molten is provided
by this.
The relationship between energy efficiency ( EE) and current efficiency ( CE) is as
follows:
E.E = VD . CE
VA
Where VD is decomposition voltage (theoretical) and VA is actual applied voltage.
B.Calculate the energy efficiency of an electrolytic process when 10 percent of
the current passed is wasted into unwanted side reactions and only 80 per cent
of the applied voltage of 6V is used in decomposition of the solute for metal
deposition.
Ans Energy Efficiency =[Theoretical energy / Actual Energy X100]
= VD . ITh x 100
VA . IAc
Where
VD = Decomposition voltage
ITh = Theoretical current as per Faradays Law
=

VD
VA
=

. Current efficiency
4.8 x 90
6

= 72 percent

VA = Actual voltate
IAc = Actual current passed.

Module 6
Extraction of metals from sulphides
A. Discuss the correctness of the following statements
1. During matte smelting of copper by multiple steps, there is no reduction step.
Ans: The steps or stages in traditional copper extraction process are : roasting of
sulphides ( copper pyrites), reverberatory smelting of roasted product to produce a
matte and then converting of matte to blister copper.
During roasting the aim is to oxidize iron sulphide of CuFeS2 ( or CuS. Fe2S3) to FeO
which can be easily slagged off later. To ensure that higher oxides are not formed some
FeS may be left behind.
During reverberating smelting all iron oxide is removed as slag and the product left is
essentially a mixture of copper and iron sulphides.
The oxidation process is continued in converting where iron sulphide is first oxidized
and slagged off to produce a white metal which is Cu2S. This is further subjected to
oxidation. When Cu2O formation proceeds sufficiently then Cu2S and Cu2O react to
produce Cu.
Thus all steps are oxidation steps and the statement made is true.
2. Blister Copper cannot be produced in Bessemer converters used in
steelmaking.
Ans : This is correct. Bessemer converter uses bottom blowing of air whereas in copper
converters oxygen is blown from the sides. This is so because during blowing copper
rich liquid is formed at the bottom. In the converter, heat is generated essentially by
exothermic oxidation of Cu2S. If air is blown from the bottom then some copper
produced will get oxidized to Cu2O. Moreover, the heat will be insufficient to keep the
metal molten and the tuyers will get clogged. Neither is desirable. In side blown
converter the metal produced collects below the level of air injection.
3. During electrorefining of impure copper anode, all undesirable impurities
are rejected as slimes that collect at the bottom of the anode.
Ans : The statement is not valid. The desired reaction is transfer of copper from the
impure anode to the pure cathode. Impurities which are more electropositive than
copper dissolve in the acid solution and these are metals like Fe, Co, Se etc. Those
that do not dissolve and collect as anode slime contain Pb, As, Te, Ni, S, Fe, Se, etc
and also precious metals Au, Ag, Pt etc and therefore the slime is not exactly
undesirable.Valuable by products are recovered from the slime.
4. Oxygen enrichment during copper smelting and converting consumes
more energy because of the energy requirement to produce oxygen in the
first place,

Ans This statement is not valid. It is true that oxygen production consumes energy but
this is more than offset by the enhanced intensity of reactions when there is oxygen
enrichment. Moreover, there is elimination of heat losses through nitrogen of air which
has no useful role in reactions.
5. When a single reactor is used in continuous copper production, then the
oxygen partial pressure within the reactor cannot be same all throughout.
Ans: This statement is valid. The stages of roasting, smelting and converting
accomplished in different regions of the reactor, require increasing partial pressures of
oxygen i.e. gradually enhanced oxygen potential. This is controlled by oxygen injection
in the converting zone, counter current flow of matte and slag and also outflow of exit
gases containing SO2.
6. In lead furnace, scrap iron is added to the charge ( lead oxide sinter, coke
and flux) to recover lead as Fe-Pb alloy.
Ans This is not correct. Iron and lead do not mix . Iron scrap is added to recover Pb
from any PbSiO3 going into slag. Fe reacts to form FeSiO3 and helps to recover Pb. Fe
also reacts directly with PbO and helps reduction reaction.
7. In the Imperial Smelting Process ( ISP) roasted zinc and lead sulphides, i.e.
sinters containing the metal oxides, are reduced by carbon in a type of
blast furnace. While lead is produced at the bottom, the zinc vapours
escaping with the exist gases are dissolved in molten lead to produce a
Pb-Zn alloy.
Ans- This statement is only partially correct. ISP does employ a blast furnace to
produce impure lead metal ( lead bullion as it is called) and the zinc vapours are
dissolved in a spray of molten zinc but then zinc recovery is not so simple.
The furnace gases exit at about 10000C containing about 6 percent Zn. The exit gases
are sprayed by liquid lead (containing about 2.15 percent Zn) at around 4500C.The
contacting increases lead temperature and zinc content increases to about 2.4% Zn,
the gases from the recovery system exiting at 4500C with 0.24% Zn. The lead streams
slightly enriched in Zn is cooled to 4500C to produce a Zn-layer which floats up and is
separated. The Zn content in Pb falls to 2.15 percent and this is pumped back to
contact incoming furnace gases afresh. It is a continuous process of zinc recovery
exploited difference in zinc solubility in lead at two different temperatures.
8. During electrolytic production zinc the aim is to first produces as purify it
to produce pure zinc.
Ans- This statement is not valid. Production of an impure metal in bulk and then
subsequent refining is a common procedure in pyrometallurgy such as in extraction
process for iron, copper and lead. In the case of zinc electrowinning it is necessary to
produce zinc from an acid solution free of all impurities because if impurities are
present then zinc electrolysis is not possible. During passage of current the
phenomenon of activation overpotential decreases Zn/Zn2+ potential to below H2 / H+
potential. If impurity ions are present then activation overpotential will be absent.
As a result of using highly purified leach liquor the Zinc produce is extremely pure
(99.99%), in fact the purify is far more than what is required for metals most important
application i.e. galvanizing.

Module 7
Extraction of metals from halides
Discuss the correctness of the flowing statements
1. All metal oxides can be chlorinated. This chlorination reaction requires
chlorine and carbon.
Ans : The statement is correct as far as only the first sentence is concerned.
Chlorination can be achieved by other chlorinating agents such as HCl and CCl4.
Oxides which are not very stable are easily chlorinated by chlorine only without any
presence of carbon and this is called direct chlorination . For reactive metal oxides such
as TiO2 one needs carbon to make indirect chlorination thermodynamically feasible.
One can look upon the reaction as combination of two steps: first , reduction of oxide to
metal by carbon and then second, chlorination of the metal to a chlortide.
2. A booster reaction helps metallothermic reduction of metal halides by
raising the temperature.
Ans: There is an element of truth in this statement but it is not the entire truth Booster
reactions are indeed exothermic and the heat generated does raise the temperature.
For example, consider calciothermic reduction of PuF4.
PuF4 + 2Ca = Pu + 2 CaF2
A booster reaction to provide heat is the flowing exothermic reaction
Ca + I2 = CaI2
This reaction has another important role. CaI2 dissolves CaF2 and thus reduces activity
of the fluoride. This drives the metallothermic reduction to the right. Enhanced
temperatures also helps to drive the reaction to the right and helps in cleaner
separation of the metal and the slag (i.e. the mixture of slats).
3. Uranium and Thorium are important in nuclear metallurgy because they are
fissionable elements.
Ans- This statement is not valid. Natural uranium contains three isotopes :
U238(99.28%), U235(0.70%) and U234(0.005%). Of these only U235 is fissionable.
However , U238 is a fertile isotype that can be converted by neutron irradiation to a
fissionable elemet Pu239. This man-made element is stable with a half life of 24,360
years. Thorium is not fissionable but the element Th232 can be converted to a
fissionable ( man made) isotype of uranium , U233.
4. Zirconium is called a reactor metal because nuclear energy is obtained by
its fission reaction
Ans : This statement is wrong. Zr is not a fissionable element and it does not, therefore,
produce energy. However, it makes an important contribution indirectly. The high
temperature strength and corrosion resistance of zirconium ( alloyed with minor
amounts of Cr, Fe, Ni, Sn or 2.5 per cent Nb) makes the metal ideally suited for use as
a cladding Material for the fissionable materials The charges are kept in Zr alloy tubes

and the group of such tubes is called a pile. Zr alloys do not absorb neutrons generated
by fission and allow their frere movement from one location in a pile to another.
The role of a moderator is to slow down very fast moving neutrons and minimize
escape of neutrons altogether by increasing the size and the mass of the fissle charge.
For a given mixture of fissle and nonfissible atoms, there is a proportion of neutrons is
so reducec that the condition for a nuclear reaction to take place is attained.
Zr alloys, which have a very low capacity for neutron absorbtion ( or low neutron
absorbtion (or low neutron absorption cross section) allows the pile to be kept as small
as possible.
5. BeO is reduced by carbon in presence of copper for easy refining
operation subsequently for production of pure Be.
Ans- The statement is totally wrong. Be-Cu alloys with 1.8-2.2 percent BeO and a slight
amount of other metals are heat treatable high strength alloys with high fluidity in the
molten state. Thus there is demand for such Be-Cu alloys in the industry for
manufacture of items such as springs, diaphragms and pump components. There are
Be-Cu alloys with other Be levels. Thus these alloys find direct use and no purification
is required for pure Be production. For pure Be, there are other routes.
Additionally, the presence of a large excess of Cu during carbon reduction of BeO
achieves two important objectives. When Be produced dissolves in copper , its activity
is greatly reduced, specially because Be concentration is very low. This makes the
reduction
reaction
thermodynamically
far
easier
and
feasible at lower temperatures and the possibility of formation of carbide of Be is also
eliminated.
6. The pentamolecular reaction at 10000C
Na(g) + TiCl4 (g) = Ti (s) + 4 NaCl (l)
is slow because it is a gas phase reaction.
Ans. It is correct to say that a gas phase reaction which implies bringing together at one
point 4 atoms of Na and one molecule of TiCl4 in the gas phase may be expected to be
slow. However, during the reaction subchlorides of TiCl4 are formed TiCl3, TiCl2, TiCl
etc.) which dissolve in reduction through Na(g) reacting with species in the liquid phase.
B. 10 mole percent of a salt MCl2 is being electrolyzed at 1000K in a fused
electrolyte contaings 90 mole percent NaCl. The decomposition voltage is Vl.
How will Vl change if the electrolyte is composed of 20 mole percent MCl2 and the
rest composed of equal mole percents of NaF and CaCl2. The metal M is neither
Na nor Ca.
Ans. Activity of MCl2 in the first electrolyte
al = X
. (X )2 = 10 .
2+
Cl10+90
M

12 = 0.1

Activity of MCl2 in the second electrolyte

a2 = X
. (X
)2
2+
M
Cl

20
. [2 x 20 + 2 x 40]2
20+40+40 [2x20+40+40x2]

= 0.15

Since a2/a1 is positive the decomposition voltage decreases in the second case. This
should be obvious, because it will be easier to decompose the solute if the activity is
higher.
To get a quantitative value we note the following. In calorie units
Faraday const, F = 23062 Cal/Volt . Equiv.
Gas const . , R = 1.98719 Cal / Deg . mole
2.303 . R
F

2.303 . 1.98719
23062

= 0.0001985
V1 V2 = 0.0001985 . 1000 . log 1.5
= 0.1985. 0.1761 / 2

= 0.017478 V

= 17mV