ELECT-E8174 Sustainable Electronics (5 cr)

Homework 3, 18.10.2019

Topics: Dimensioning an electrochemical reactor, calculation of energy consumption

Calculate following four examples and answer the additional questions. Upload your answers in
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Copper is produced electrolytically using either electrolytic refining (ER) or electrowinning

(EW). In electrolytic refining the impure copper anode (98-99% Cu) is dissolved and pure
copper is deposited on the cathode (99.996% Cu). In electrowinning the anode is insoluble and
the anode reaction gas evolution. The cathodes are again pure copper. Energy consumption in
electrolysis depends on the cell voltage and current efficiency. The electrolysis cell voltage is
composed of the difference between anode and cathode equilibrium potentials, anodic and
cathodic polarization, solution resistance and voltage losses in the busbars and connections.

Questions:

1. A copper electrorefining tankhouse operates at current density 300 A/m2 and the average
cell voltage between the anode and the cathode is 350 mV. Calculate the copper refining
energy consumption in kWh/kg when copper deposition current efficiency is 96%. What
is the share of this electrical energy from the total embodied energy? Total embodied
energy can be found for example in CES Edupack.

2. In copper refining tankhouse the cathode plates are made of stainless steel, and copper is
deposited on them and removed mechanically after the plate has sufficient thickness.
Using the current density 300 A/m2 and efficiency 96%, what is the cathode weight when
it is stripped after 7-day deposit period? Cathode surface area is 1 m2.

3. A copper electrowinning plant operates using current density 300 A/m2. The cell voltage
is now 2.2 V, because the anode reaction is oxygen evolution instead of dissolution of
copper. Calculate the energy consumption in kWh/kg of deposited copper when cathodic
current efficiency is 96%. What is the share of this electrical energy from the total
embodied energy?

4. A copper electrorefining cell contains 36 cathodes and 37 anodes. From one anode batch
three cathode crops are deposited. Electrolysis operates at cathode current density
290 A/m2. The average weight of the anodes is 350 kg, and scrap from one anode has
average weight 52 kg. The average weight of the cathode is 50 kg and one cathode plate
deposits two copper cathodes. The anode dimensions are 0.95 m x 0.95 m and cathode
dimensions 1.05 m x 1 m. The cathode deposition period is six days. Calculate the anodic
and cathodic current efficiencies.
Electrowinning, electrorefining and electroplating involve the exchange of electrons between a
solid electrode and ions or molecules dissolved in solution. The underlying physical and
chemical laws are the same for most metals and applications. The rate of the reaction involved
depends on the electrode potential, the electrode area and the rate of mass transport of the
electroactive species to the electrode surface. The main differences are in the construction of the
cells, their geometry, construction materials, and operating practice.

Figure 1 shows the principle of electrolysis processes. The electrolysis cell consists of two
electrodes (anode and cathode) and an electrolyte. In an electrolysis cell such as in
electrowinning or refining, the negative electrode is the cathode and the positive electrode is the
anode. The electrodes are electrically conductive materials that are in connection with the
electrolyte, and the electrochemical reactions take place on the boundary between electrode and
electrolyte. When the two electrodes are placed in a solution containing metal ions and an
electric current is passed between them, the metal can be deposited on the cathode. The
electrolyte next to the anode is the anolyte and that next to the cathode is the catholyte. The
properties of anolyte and catholyte differ from those of the bulk electrolyte.

In the electrorefining, impure metal is dissolved from the anode and pure metal is deposited on
the cathode. Electrorefining is a successful method because metallic impurities that are more
noble than the metal to be refined do not dissolve into the electrolyte. These impurities include
often precious metals, silver, gold and the platinum group metals, which are recovered by
treatment of the sludge that falls to the bottom of the cell. Since impurities that do enter the
electrolyte are less noble than the material to be refined, they do not deposit on the cathode.
Some metals accumulate in the electrolyte and they are extracted in a separate stage. Electrolyte,
current density, and additives are chosen to produce a dense, compact deposit.

Electrowinning is done from purified solutions. The anodes are insoluble metal or oxide. In the
electrowinning of most metals, oxygen is evolved from decomposition of water at the anode.
Electrowinning of some metals is done from chloride solutions with evolution of chlorine gas as
anode reaction. The metal to be recovered is deposited on the cathode as in the electrorefining
process.

Electrorefining Electrowinning
+ - + -
Deposited cathode
Permanent anode
Purified cathode
Metal dissolution

Metal deposition

Metal deposition
Impure anode

Gas evolution

Electrolyte Electrolyte

Figure 1. The principle of electrolysis processes.

Electrolyte in Electrolyte out

Main electrolyte flow

Figure 2. Copper electrorefining cell with multiple anodes and cathodes.

The background of electrolysis processes is the Faraday’s law that connects the amount of
electricity and mass of reacted material. The quantity of electricity in coulombs equals the
number of electrons involved in the reaction multiplied by the Faraday’s constant (F). The value
of Faraday’s constant is 96,485 coulombs, that is the quantity of electricity of a mole of electrons
(6.023·1023 electrons). The quantity of electrical current in coulombs that passes through a
conductor is proportional to both the current and the length of time it flows. Thus amperes
multiplied by time gives coulombs, or q = I·(t2 - t1) assuming that the current is constant during
the time interval between t1 and t2. Assuming a constant current and a 100% current efficiency,
this expression can be written as Faraday’s law (1)

I × Dt
Dm = ×M
z×F (1)

where
Dm is mass, g
I is current, A
Dt is time, s
M is atomic weight of depositing metal, g/mol
z is valency of the metal (number of electrons)
F is Faraday's constant, 96485 C/mol.
The current efficiency is the yield based on the electrical charge passed during electrolysis. If the
current efficiency is less than 100%, the equation (1) is modified as (2)
I × Dt × M
Dm = ×h (2)
z×F
where h is current efficiency, %

A value of current efficiency less than 100% indicates usually that by-products are formed.
Another possibility is that reverse reaction happens, e.g. dissolution of deposited metal. In metal
recovery from acidic solutions, the hydrogen evolution reaction is a common side-reaction that
lowers the current efficiency. The current efficiency can also vary with the current density.
Current efficiency is a widely used measure of tankhouse proficiency in producing metal, but it
does not provide a direct measure of metal quality.

The cell voltage depends on the thermodynamic equilibrium potentials of the anode and cathode
reactions, kinetic overvoltages, and ohmic resistances caused by the cell hardware. The cell
voltage can be calculated using equation (3)

Ecell =Ecathode - Eanode - S(h ) - i × Rcell (3)

In equation (3) Ecathode and Eanode are the equilibrium potentials of the electrode reactions, Σ(η) is
the sum of all polarization effects on the electrodes and i×Rcell is the ohmic loss due to the cell
construction. As the electrolysis systems are consuming energy, the cell voltage sign is negative.

The energy costs are related closely to the cell voltage. The energy consumption can be
estimated by specific energy consumption w, equation (4)

z × F × Ecell
w (J/g) = (4)
h×M

where Ecell is the cell voltage (V). The specific energy consumption for a particular metal and
process is calculated using the electrochemical equivalent of the metal, voltage needed to drive
the process and current efficiency. The common way to express energy consumption is to use
kWh/kg by dividing the right-hand side of equation (4) by 3600. To lower the specific energy
consumption it is necessary to lower the cell voltage and/or increase the current efficiency.