MODULE 4_ELECTROMETALLURGY

Electrometallurgy implies processes which utilize electrical energy for electrolysis

and/or heating. Electrowinning refers to the process of metal extraction using
electrolysis.

Electrorefining – process of purification, also based on electrolysis. Some metals are

produced extensively and some others partially by electrowinning.

Extraction and refining of metals by electrometallurgy

Process Aq. medium Fused salt medium

Electrowinning Cu, Zn, Cd, Sb, Cu, Cr Al, Mg, Na, Be, R.E’s
Ga, Fe, Mn, Ag. Mo, Ta, V, Ti.
Electrorefining Cu, Ag, Au, Ni, Co, Pb, Al, Ti, Be, V, Cr, Mo
Sb, Bi, In, Hg, Sn

In electrowinning, the anode is an insoluble conductor while in electrorefining, it is

the impure metal itself. The electrolyte in either case is a solution with sufficiently
high electrical conductivity and solute concentration. The cathode may be pure metal
built up on a pure starting sheet or sometimes on a blank of another metal.

Recall Faraday’s laws:

1. The quantity of a material deposited at an electrode is directly proportional to the
quantity of electricity passed through the electrolyte.
2. The quantity of material deposited at an electrode is proportional to the equivalent
weight of the same. In other words, the same quantity of electricity will release the
same number of g, equivalent of a substance.
The electrical equivalent of a substance is defined as the number of grams of that
substance released by 1 coulumbs (C) of electricity, i.e., by a current of 1 Amp (A)
during its passage for a duration of 1 second.
Chemical equivalent weight is atomic weight divided by its valency. Thus the
chemical equivalent is proportional to the electrochemical equivalence. The
proportionality factor, called Faraday’s constant was first determined from
experimental results on electrodeposition of Ag.Ag has an atomic weight of 107.88
and valency of 1. One coulomb of electricity deposits, from aq solutions of Ag salts,
0.0011180 g of the metal on the cathode. The Faraday constant is thus obtained as
F = 107.88 g/g equiv/0.0011180g/C = 96,496 C/g equiv.
Mathematically, Faraday’s laws are expressed by the equation:
Nm = 1/zF
-1
where nm= rate of metal deposition, Mmols
z = number of electrons transferred per atom of M during deposition.
 Basic arrangement of electrolytic cell

An electrolyte is decomposed when a sufficiently high DC voltage is applied across

the electrodes. The positive ions move towards and then are discharged at the
negative electrode called the cathode. Similarly, the negative ions are discharged at
the positive electrode called the anode. The conduction of electricity through an
electrolyte should be entirely due to the movement of ions only. Faraday’s laws are
valid only if the conduction is satisfied. Any electrolyte should meet some additional
requirements. It should be chemically inert towards the electrodes, the container
material and the electrolysis products. It must also be stable at the temperatures of
operation.
The nature of electrolytic dissociation reactions depends on the ionic structure of
the media. Among non ag electrolytes , only molten salts are employed in
electrowinning and electrorefining. They exhibit a wide range of stable liquid
temperature.
Some compounds such as alkali chlorides readily dissociate in water to give rise to
ionic solutions.

This is commonly attributed to high dielectric constant of water. Water comprises of

associated molecules because of the polar nature of the molecules. In the state of
association, the asymmetric molecules clinging to each other through H bonds.

Question. Briefly explain the importance of water in the formation of ionic solutions
(for alkali chlorides).

Structural formula of water molecule

The H bonds are formed between slightly negatively charged O atom of one
molecule and slightly positively charged H atom of the other.
The nature of association of molecules in water results in liquid of high dielectric
constant which helps in the breakdown of the crystal lattice of ionic compounds. The
unlike charges in the compounds are no longer strongly bond because the attractive
force between the unlike charges is inversely proportional to the dielectric constant
of the medium between them.
In addition to its ability to break up ionic compounds, water also forms complex ions
with metal cations. Such complex ions are known as hydrated complexes.
 In the hydrated cu ions, the arrows representing coordinate covalent bonds formed
when each O atom donates a pair of electrons to the cupric ion to stabilize the
configuration. In general, most aq solutions of metal compounds contain metal ions
complexed with water molecules or with other reagents such as NH3, Cl-, CN-,OH
-
,P2O74-.
In ammoniacal solution for example, Ni forms a series of amines, designated as
Ni(NH3)x2+ where x varies from 1 to 6. If HCN is added to an aq solution of cupric
sulphate, the solvated cupric ionprogressively losses water molecules to finally form
a complex with Cl- only. The stepwise change, which results in the change of colour,
from blue to green may be represented as follows.
[Cu(H2O)3Cl]+ = [Cu(H2O)2Cl2]=[Cu(H2O)Cl3]- = [CuCl4]2-
Any study of electrolytic phenomena in aq solutions has to take into account the
existence and stability of these complex ions.
Recall that Faraday’s laws of electrolysis apply to all “perfect” electrolytes, i.e.,
electrolytes characterized by completely ionic conduction. In industrial practices, one
usually obtain less yields than what the law predicts. The effective utilization of
current is expressed as:
Current efficiency = actual amount of metal deposited / amount of the same metal
expected to be deposited according to Faraday’s laws X 100
Energy consumed = IV
Since current is directly related to output of metal, the energy consumption in
electrolytic production of metal can be minimized through either
1. maximization of the current efficiency
2. minimization of the voltage requirement, consistent with other requirements.
The total voltage requirement for an electrolytic cell may be expressed as a sum of
several terms:
V A = V D + V R + VO + V E
VA = Voltage across the cell
VD = thermodynamic voltage requirement for the overall cell reaction (decomposition
voltage)
VR = ohmic voltage drop due to resistance of the electrolyte
VO = sum of overpotential for cathode and anode (ηc and ηa)
VE = voltage drop due to electronic resistance in the dc (electrodes, contact points,
busbars, etc).
With the exception of Vo, all the factors in the r.h.s depend on the current density, i,
i.e., current per unit area of electrode surface. The higher the value of i, the higher the
values of VR, VO, and VC.
Decomposition voltage
The overall reaction is a summation of the reactions at two electrodes. Consider a
simple cell constituted by two strips of Cu immersed in CuSO4 solution. If one strip is
cathode and one anode.
(Cu)2+ + 2e- = Cu (at cathode)
Cu (at anode) = Cu2+ + 2e-
The electrons are transferred from anode to cathode through the external circuit.
The overall reaction is: Cu (at anode) = Cu (at cathode)
This is basically the transfer of Cu from one electrode to another with no overall
change in the electrolyte e.g., during electrorefining of Cu.
The thermo voltage requirement of the cell reaction VD is related to the free energy
change for the overall cell reaction:
ΔG = -zFVD
If reactants and products are at their standard states, then:
ΔG = ΔGo and VD = VDo
Take for instance the electrolysis of an aq solution of CdCl2

At anode, (2Cl-) = Cl2(g) + 2e Eao = -1.3695 V

At cathode, Cd = (Cd2+) + 2e- Eco = +0.402 V

For overall reaction we have

2+ -
(Cd ) + 2(Cl ) = Cd + Cl2(g)

i.e., CdCl2
o
VD = -1.3695 – 0.402 = - 1.7715 V
o
Again, ΔG = ΔG + RT ln Q

So,
o 2+ 2
ΔG = ΔG + RT ln [aCd].PCl2 / (aCd ).(aCl-) ………………….(2)

Combining (1) and (2); z = 2

o 2
VD = VA – RT/2F ln acd.PCl2/(acd2+).(aCl-)

If the metal deposited is pure and Cl gas evolves at 1 atm pressure, then aCd – PCl2 =
1

And hence,

VD = -1.7715 + RT/2F ln (aCd2+).(aCl-)2

Hence, VD is the thermodynamic decomposition voltage under non-standard

conditions, and hence is more general in nature than VDo. VD can be calculated if VDo
and activities of ions in aq solutions are known. VD can also be calculated from
standard single electrode potentials Eo.

Values of standard single electrode potentials, Eo, at 25oC and in solutions with
respect to standard H2 electrode (Reaction: M = Mz+ + 2e-)

Element/ion Eo, V Element/ion Eo, V Element/ion Eo, V

Li/Li+ +3.045 Cr/Cr2+ +0.860 Sb/Sb+ -0.100
K/K+ +2.925 Zn/Zn2+ +0.763 Bi/Bi3+ -0.200
Cs/Cs+ 2.923 Cr/Cr3+ 0.740 Cu/Cu2+ -0.337
Ca/Ca2+ +2.870 Fe/Fe2+ +0.440 Co/Co3+ -0.400
Na/Na+ +2.713 Cd/Cd2+ +0.402 Cu/Cu+ -0.520
Mg/Mg2+ +2.370 Co/Co2+ +0.300 Ag/Ag+ -0.800
Th/Th4+ +1.900 Ni/Ni2+ +0.250 Hg/Hg2+ -0.554
Be/Be2+ +1.650 Mo/Mo2+ +0.200 Pt/Pt2+ -0.987
U/U3+ +1.800 Sn/Sn2+ +0.140 Au/Au3+ -1.500
Al/Al3+ +1.660 Pb/Pb2+ +0.126 Au/Au+ -1.680
Zr/Zr4+ +1.530 Fe/Fe3+ +0.036
Mn/Mn2+ +1.190 H2/2H+ 0.000

Practice problems

(2) Magnesium is being produced by the electrolysis of MgCl2 dissolved in alkali

o
chlorides at 700 C. The chlorine gas liberated is at 1 atm. Calculate the change in
decomposition voltage when MgCl2 concentration is increased from 10 mole % to 50
mole %. Assume that MgCl2 ionizes completely and Temkin model of ionic melts is
valid.

Note: Temkin model of ionic melts

An ionized melt is a system of interlocked sublattices of anions and cations with

short range order extending over a distance of a few ionic diameters. Anions are
randomly distributed in the anion sublattice and cations are distributed in the cation
sublattice. If this distribution is truly random and the solution is ideal, then the
activity is given by the product of ionic fraction.

Thus for NaCl,

+ -
aNaCl = XNa . XCl
X = ionic fraction. XNa+ is that among the cations only
-
XCl is that among the anions only

XNa+ = moles of Na+ ions / moles of all cations

XCl- = moles of Cl- ions / moles of all anions

For a non-monovalent ions,

MnZn = (Xmn+)m (Xzm-1)n

Where m and n are respectively the valencies of species Z and M.

Problem

(1) Calculate activity in a 1:1 mole mixture of NaCl and CdBr2

(3) 100 metric tonnes of a copper concentrate averaging 21% Cu are to be

processed in 6 months (with 25 working days permonth and 8 working hours/day).
The concentrate is to be leached by H2SO4 and then the solution electrolyzed.
Estimate the minimum rating (voltage and current) of the power supply unit for 12
cells in series.

Hint: Eo(cathode) = - 0.337 V, Eo(anode) = +1.23 V

Ohmic Voltage Drop in Electrolytes

Consider two equal plane parallel electrodes. If the resistance of the electrolyte
between these electrodes is R, then the ohmic voltage drop (VR) is IR.

R is expressed as R = 1/x. l/A

x = specific conductance of electrolyte

l = distance of separation between the two electrodes

A = area of each electrode

Thus;

VR = I/A . l/x = λ l/x

Conductivity of electrolytes is sometimes expressed as equivalent conductance (λ)

λ = x . 1g equivalent of substance

The following tables show electrical conductivity of some electrolytes.

o 3
(A). Aqueous Solutions at 25 C and Solute Concentration of 1g.equiv/m
- -1 2
Solute Equiv. Conductance, ohm Solute Equiv. Conductance, ohm m
 1
m2
AgNO3 0.01091 KNO3 0.01204
CaCl2 0.01024 MgCl2 0.00971
Ca(OH)2 0.00506 NaCl 0.01067
KCl 0.0129

(B). Pure Fused Salts at Melting Point

Salt Equiv. Conductance, ohm-1m2 Salt Equiv. Conductance, ohm-1m2

LiCl 0.0166 AlCl3 1.5x10-10
NaCl 0.01335 KCl 0.01035
NaBr 0.0129 KBr 0.009
MgCl2 0.00288 CaCl2 0.00519

(C). Metal Oxide + Silica Melts at 1750oC

Metal Composition Conductivity, Conductivity at 1750oC, Ohm-

Range, Ohm-1m-1 x 10-2 1 -1
m x 10-2
MO/SiO2
Li 0.33 – 0.58 2.35 – 7.6 8.5
Na 0.19 – 0.34 0.95 – 2.8 5.6
K 0.2 – 0.35 0.66 – 1.9 4.2
Mg 0.39 – 0.55 0.33 – 0.98 2.9
Ca 0.25 – 0.60 0.25 – 1.0 5.3

Practice problems

(1). Given the following data:

λ of electrolyte = 20 ohm-1m-1

Inter-electrode separation = 0.04 m

Overvoltage at the electrodes = 0.5 V

Decomposition voltage = 1.23 V

-2
Current density = 165 Am

Voltage drop from cathode plate to bus bar = 0.05 V

Voltage drop from anode plate to bus bar = 0.10 V

Current efficiency (C.E) for metal decomposition = 85%

Equivalent weight of metal = 31.8

Calculate the kilowatt-hours used per Kg of metal deposited.

(2). The specific conductance of the electrolyte during aluminum electrolysis at
980oC is given by the following equation.

Log x = 0.4099 – 0.0101CAl2O3

where CAl2O3 is concentration of Al2O3 in the electrolyte (wt%).

Calculate the voltage drop due to the electrolyte resistance for some typical values
of CAl2O3 and inter-electrode separation. Show how the voltage drop increases with
Al2O3 concentration, current density and electrode separation.

Electrolysis in Aqueous Solutions

Arrangement of Electrodes in Electrolytic Cell: The rate of production is limited by

the surface area of the electrodes. Therefore, it is necessary to maximize the surface
area if the production is to be maximized. Since it is not convenient to use very large
electrodes, the surface area is increased by incorporating into the cell a large
number of electrodes of convenient size. For instance, in the electrowinning of
copper, a rectangular electrolytic tank may contain 20 – 40 cathodes and anodes,
the size of the tank being approximately 4 m x 1 m x 1 m. There are several possible
ways for the arrangement of the electrodes in the cells, i.e., the principal systems
being the Series Arrangement and the Parallel (multiple) Arrangement.

In the series arrangement, only the first and last electrodes of an electrolytic tank are
connected to the external electrodes. Between them are arranged the electrode
plates. The side of each plate facing the anode serve as a cathode and receives a
deposit. The side which faces the cathode end of the tank serves as the anode. Thus,
all the electrodes are bipolar except the first and last electrodes.

The Parallel (multiple) Arrangement

The more commonly employed parallel or multiple system as the electrodes

arranged in parallel in each tank but the tanks themselves are connected in series.
 Series system of electrodes

Parallel (multiple)system of electrodes

The current enters through a heavy conducting busbar to which the anodes are
connected. Similarly, cathodes are suspended from a cathode busbar. Proper
electrical insulations are provided to ensure that the current entering by the anode
busbar passes only to all the anodes in the tank and then, via the electrolyte, to the
cathodes, leaving the tank via the cathode busbar to enter the next tank. Here, the
same cathode busbar acts as the anode busbar. The current requirement is lower in
the series system but it requires higher voltages. There are also more technical
difficulties with the series system and less flexibility. The power requirement is same
in either case.

Practice Problem

An electrolytic refinery has a capacity of 200,000 t of copper annually (365 days)

when the current density is 200 Am-2 of the cathode surface. Each tank has 31
cathodes and 30 anodes in the parallel system and the cathodes measuring 0.75 m x
1.0 m are entirely immersed in the electrolyte. The average distance between anode
and cathode is 0.0135 m, and the voltage per tank is 0.24 V. the tanks are connected
in four separate circuits with one generator in each circuit. Calculate the following:

a) The number of tanks, if all were in regular operation with 90% current
efficiency.

b) The specific conductivity of the electrolyte assuming 50% of the voltage drop
is to overcome the electrolyte resistance.

c) The voltage and amperage to be supplied by each generator.

Electrolysis of Fused Salts

The emf series where Eo values are arranged with respect to the potential of the
standard hydrogen electrode as reference zero, indicates that metals placed above
hydrogen should not be normally amenable to electrowinning from aq solutions.
However, due to high overpotential of hydrogen evolution, some metals placed above
hydrogen and up to manganese can be successfully electrowon in aq solution.
metals above Mn in the emf series are too reactive to be produced from aq solutions.
These reactive metals can be produced by electrolysis only if non-aq media such as
fused salts are employed. Molten salt electrolysis has some distinct advantages,
some of which are:

1. Since molten salts do not contain water, reactive metals can be obtained.

2. High temperature electrolysis would be characterized by the general

advantages of pyro operations viz, higher production rate. If the metal is
produced in the molten state, then its easy collection is an added advantage.

3. Overpotentials on molten metals are often small enough to allow high current
densities and are therefore greater.

Disadvantages include:
1. The molten state of the electrolyte is maintained by electrolytic heating. Use
of electricity in heating may make molten salt electrolysis economically
unattractive if electrical energy is expensive.

2. At high temperatures, there is enhanced possibility of side reactions such as

those among the electrolysis products and the electrodes, dissolution of the
metal deposited at the cathode into the electrolyte. Such side reactions lower
current efficiency. Accordingly, the current efficiency during fused salt
electrolysis is normally between 70 and 80% where that for aq solution
electrolysis is generally better than 90%.

3. The anode material during molten salt electrolysis is generally graphite which
leads to the formation of CO and CO2. Leakage of CO is a possible hazard.
Also, reaction of metal with these gases can adversely affect its mechanical
properties. Provision of inert atom minimized this problem in some systems.

Loss of Current Efficiency During Electrolysis of Molten Salts

The various factors which cause current losses may be summarized as follows:

1. Mechanical losses of substances formed at the electrodes (handling losses).

These may be minimized through improved operational techniques.

2. Evaporation of the metal from the cathode. This is likely to happen if the
metal is produced at a temperature near its boiling point. For example, if
sodium (b.p 892 oC) is produced from molten NaCl (m.p 801 oC), the metal
may begin to vapourize. Vaporization loss will be minimal if the metal is
obtained from a lower melting fused salt mixture of, say, NaCl and KCl.

3. Reaction of electrolysis products with the electrolyte: This can be of two types,
viz, reaction leading to formation of lower compounds at the cathode and
reaction leading to the formation of higher compounds at the anode. For
example, during electrolysis of SnCl4, the Sn liberated in the initial periods
would continue to react to form SnCl2. The cathode current efficiency would
remain zero while the anode current efficiency may be 100%. The metal would
start depositing only after the SnCl4 has been converted into SnCl2 to the
maximum possible extent.

4. Dissolution of the metal in the electrolyte: A metal may dissolve in its own salt
causing loss of output and lowering of apparent current efficiency.

5. Recombination of electrolysis products: any recombination reaction leads to

lossof product at either electrode. Immediate and complete isolation of
electrolysis products is achieved through special designs of electrolytic cells.

6. Current losses due to presence of moisture: some molten salts may be

hygroscopic. It is often quite difficult to eliminate this water as it can be
 retained by the salt even above melting temperature. Moisture is better
removed through application of vacuum and purging of inert gas, Cl2, HCl acid
gas, etc, during heating of the solid salt. Some electrolytic processes aim at
producing chlorides in-situ in the cell. Thus Cl2 evolved at the anode is used to
chlorinate an oxide being fed into the cell continuously. Hot gases ensure
complete absence of moisture even though chlorides may be hygroscopic.

7. Other side reactions such as reaction of atmospheric oxygen also lead to

metal losses.

In general, lowering of operating temperature cuts down losses due to many of

the factors noted above, such as factors 2, 4 and 7. Lower operating temperature
can be achieved only if the melting point of the salt can be lowered. Such
lowering is possible by employing a mixture of salts rather than one salt alone.