ELECTROREFINING AND ELECTROWINNING OF COPPER

1. Aim of the experiment

The main scopes of this experimental study are
a- to describe major electrolytic processes and to measure anode and cathode
polarizations, cell potentials, specific energy consumptions, and etc; as well as to
examine the diversities of these two electrolytic processes in terms of obtained
measurements.
b- to investigate the effects of organic additives on the quality of deposited surface via
copper electrorefining

2. Technical background
Electrolysis is the electrochemical reactions in which electrons transfer between the
electrolyte-electrode interfaces by applying an external electromotor force (emf) toward the
electrodes inserted into electrolyte [1-4].
An electrochemical cell basically composes of electrodes (anode and cathode), electrolyte,
direct current (DC) power supply and connectors. In an electrochemical system, an electrode
connected to the positive terminal acts as an anode, where a cathode electrode is polarized
negatively. Therefore, the electrons are passing from anode to cathode on the outside of
electrolyte, while the electron steam is flowing in the opposite direction inside of the
electrolyte from cathode to anode. As given in Figure 2.1., once current is applied to the
system, the positive ions, cations, (Mez+) move toward the cathode, as the negative ones,
anions (Xn-) flow to the anode.
_ _
ze ze

O2 Me
_
ze
_ z+
ze H2O Me aq

+
Haq

Metal Oxide
aloksit (Anode)
(Anot) Electrolyte
Elektrolit Metal
Metal(Cathode)
(Katot)
Figure 2.1. Schematic illustration of electrode reactions in copper electrowinning [2]

The cathode reactions in both electrowinning and electrorefining processes are the same (see
Eq. 1), whereas anode reactions are completely different. In electrorefining, the dissolved
metal ions from an anode deposit on a cathode. However in electrowinning, an insoluble
anode is utilized; namely lead alloys, precious metal coated titanium (DSA), platinum,
graphite and etc; hence the anode reaction is the oxidation of anions from electrolyte solution.
The anodic reaction generally is the oxidation of water in aqueous system and consequently
the oxygen evolution is observed on the surface of anode (Eq. 2).
When a certain amount of current is applied to the electrolytic system, positive ions- cations
(Mez+) are reduced on the cathode according to Eq. 1; only if the cations on the surface of
cathode are polarized as their standard potentials (E°) [3].
Mez+ + ze- → Me0 (1)
During electrolysis, the accumulated electrons on the anode -in case of insoluble one- will
increase the polarization of anode, and once it reaches to the oxidation potential of water, the
oxygen evolution will occur on the surface of anode (Eq 2.).
2H2O → O2 + 4H+ + 4e- (2)
Releasing electrons in accordance with the anodic reactions pass through the cathode via first
class conductors (metals, alloys, etc), and hence anodic and cathodic reactions take place
correspondingly. The quantity of chemical substances reacting on the electrodes can be
theoretically calculated based on the passing current through the cell according to Faraday’s
Law (Eq.3). The current efficiency [% efficiency] is determined by dividing the
electrodeposited mass of metals on the cathode to the calculated theoretical amount (Eq.4).
AIt
MT  (3)
nF
MT = the mass of electrodeposited metal [g]
A = the molar mass of the deposited metal [g]
I = the total passing current through the system [A]
t = the electrolysis time [s]
n = the valency of electrodeposited metal [1/mol]
F = Faraday’s constant [96485.3383 A.s/mol]

MP
[%efficien cy]  100 (4)
MT
[% efficiency] = The current efficiency
MP = the practical quantity of electrodeposited metal [g]

When an electrode is the part of an electrochemical cell through which current is passing, its
potential will be different from the equilibrium potential. If the equilibrium potential of the
electrode with the absence of external current is E° and the potential of the same electrode as
a result of external current flowing is E(I), the difference between these two potential can be
defined as a overpotential, η (Eq. V). [2-4].

η  E(I)  E O (5)
η = Overpoterntial [V]
E° = Equilibrium potential of the electrode [V]
E(I) = Potential of the electrode under the external current flowing [V]
The overpotential η is required to overcome hindrance of the overall electrode reaction,
composing of the sequence of partial reactions. There are four possible partial reactions and
hence four types of rate control steps; namely, charge transfer, diffusion, chemical reaction
and crystallization (Eq. 6). The overpotential requires more energy than thermodynamically
expected to drive a reaction. In practice, this means that the addition potential to the standard
potential of the reduced metal should be supply to the system, and this potential should be
also bigger than all overpotential voltages [4].
ηT  ηCT  ηD  ηR  ηC (6)
η T= Total overpotential η CT= charge transfer overpotential
η D= diffusion overpotential η R= reaction overpotential
η C= crystallization overpotential
In electrowinning process when the electrolysis is initiated, the metal ion concentration begins
to change. Therefore, the extremely thin layer (Nernst Diffusion Layer, δN) occurs in the
vicinity of the cathode due to the accumulation of reducing ions as illustrating in Figure 2.2.
The ion concentration in this thin layer is always lower than rest of the electrolyte bulk
because of continuing reduction of ions on the surface of cathode. This concentration gradient
taking place between the Nernst layer and the rest electrolyte causes a voltage difference and
hence called as a cathode polarization. The similar phenomenon also occurs in the anode
side of the electrolyte. Accordingly, the total of both cathode and anode polarization is named
as a concentration polarization.
Nernst
diffusion
layer, δN Nernst Approach
Concentration

Actual
Concentration
Gradient

Distance from cathode [x]

Figure 2.2. Variation of ion concentration (cX) formed in the electrode/electrolyte interface as
a function of applied current density, non-steady-state electrolysis [9].

The mass transfer at the electrode/electrolyte interface occurs in mutual directions based on
three mechanisms;
a) Ion migration through the electric field formed between electrodes, migration
b) Ion diffusion at the electrode/electrolyte interface, diffusion
c) Relative motion forming or formed between electrodes, convection
Ion convection is the refrained motion of spheres in the homogenous environment due to the
friction forces. The effect of convection (hydrodynamic motion) is negligible at the interface
of electrode/electrolyte; for this reason, diffusion is only the control mechanism of mass and
charge transfer at the vicinity of the electrode surface. The concentration of ions closed to the
cathode surface continuously decreases according to Eq.7 (Fig. 2.2) [9].
Mez+ + ze- → Me0 (7)
Faraday Law is no longer valid for the quantity estimation of reduced metal ions at high
current densities due to this concentration gradient, and consequently the desired amount of
current will not be able to pass through the system. In other words, the system reaches its own
limited value, limiting current density (iLim) (see Figure 2.3).
Electrochemical cell potential (EC) is simply the sum of the equilibrium potential difference
between the anode and cathode (EA° +EK°) and the total loss of potential (due to
misconnections as well as all sources of resistance in the system, especially the resistance of
electrolyte and hence calculated according to the Ohm’s Law (IXR)) plus the entire total
overpotential ( η T) (Eq.8).
Ec =EA° +EK°+ IXR + η T (8)
EC = Cell Potential [V]
EA° = equilibrium potential of anode
EK° = equilibrium potential of cathode
R = electrolyte resistance [Ω]
I = Applied current [A]
η T = total overpotential [V]
The value of cell potential is related to the applied current by reason of the total overpotential
and the IxR drops. For this reason the specific energy consumption, WS is then given by Eq
9. The specific energy consumption, WS, is the most important energetic parameter in metal
electrowinning and electrorefining technologies [1-6].

E C xIxt
WS  (9)
MP
WS = specific energy consumption [Wh/kg]
EC = Cell potential [V]
t = Duration of electrolysis [h]
MP = the practical quantity of electrodeposited metal [kg]
I= applied current [A]

Electrochemical techniques can be categorized into three separate classes based on the
production and/or recovery of metals from their aqueous solutions [6-8]:
1. Electrorefining; the purification of metals noble than hydrogen
2. Electrowinning; the recovery of metals; including manganese and noble than
manganese in EMF series
3. Electrodialysis; regeneration from spent/waste solutions, partial salt disposal, the
separation of degradation products and components, etc
Electrorefining has been becoming a much more significant process to supply the increasing
demands of pure metals. Electrowining is still the essential process or a part of sequence
process for the recovery of basic metals and the production of powder metals. In addition, the
increasing conscience of environmental protection and the recovery of metal ions in many
branches of industry as well as the obligation of regeneration from spent/waste solutions are
the other reasons of the wide usage of electrowining processes. Table 2.1 summarizes general
operating conditions for the recovery of some metals from their aqueous solutions by utilizing
electrowinning techniques [6,7].

Table 2.1. Common operating conditions for the recovery of some metals from their sulphate
solutions via electrowining technique [6,7]
Metal Electrolyte T [oC] Eteo [V] EC [V] I [A/m2] [%] WS [kWh/kg]
Cu Sulphate+H2O 40 0.89 1.9-2.3 170 85-90 1.9-2.4
Co Sulphate+H2O 60 1.52 3.5-4 160 80-90 3.7
Cd Sulphate+H2O 35 1.66 2.8 100 90 1.5
Zn Sulphate+H2O 35 2.00 3.1-3.9 400-1000 90-94 3.1-3.9
Mn Sulphate+H2O 35 2.41 6.0 400-600 65-70 9

2.1. Electrowinning of Copper

Oxide ores of copper generally are treated in a hydrometallurgical way in which copper
electrowining is the critical step process. Particularly, the progresses done in the solvent
extraction and ion exchange resin technologies provide very significant developments and
improvements in the application of electrowining technique. For instance, in very earlier
application of copper electrowining, the common applied current density was 100A/m2, but,
now the applied values of current density have been increased up to 280A/m2 in a standard
operation. Moreover, in some cases the current density value has been raised as much as 600
A/cm2 with the usage of jumbo electrolyte and under extreme convection appliance. The
typical variation of potential with respect to current density in an electrowinning process is
given in Figure 2.3.

140
Current Density [A/m2]

120

100

80

the plateau of limiting current density

60

40

20

0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160

Potential [V]

Figure 2.3. Typical variation of potential versus current density in electrowining process [1]

Considerably slow exchanges of masses and the obligation of huge quantity of material
transportation during the treatment of oxide copper ores, namely leaching and solvent
extraction, make hydrometallurgical copper production way very energy intensive and costly.
However, still this copper production technique is inevitable and provides 15 % copper
demand (≈1.25x106 ton) in all over the world.
The anode and cathode reactions taking place during copper electrowining are as following:
Cu2+ + 2e- Cu0 E0 = - 0.34 V (10)
2H2O  O2 + 4H+ + 4e- E0 = 1.229-0.0591pH (11)
The total reaction is:
Cu2+ + SO42- + H2O  Cu0 + 1/2 O2 + 2H+ + SO42- E0 = +0.89-0.0591pH (12)
The thermodynamically required energy to drive reactions in copper electrowining is 0.89 V;
however in practice the required potential value reaches up to 2 to 2.4 V at the current density
of 200 A/m2. The distribution of cell potential value can be given as

Necessary cell potential of the reaction, Eq. 12  0.89 V

Oxygen overpotential  0.5 – 0.9 V
Total cathodic overpotentials  0.05 V
IxR drops occurring at 200 A/m2  0.5 V

2.2. Electrorefining of Copper

The earliest application of copper electrorefining was initiated with the discovery of power
unit, dynamo and was patented by Elkington (USA) in 1883. However, the first copper
electrorefining plant was built by Balbach in 1918. The main purposes of copper
electrorefining are to eliminate impurities in order to increase conductivity and to recover
precious metals and semimetals (Se, Te) which almost cover all cost of electrorefining
process. The approximate composition of copper anode is given in Table 2.2.

Table 2.2. The approximate composition of copper anode [6]

Metal composition of copper anode [%] Metal composition of copper anode [%]
Cu 99.0-99.5 Sb 0.05 - 0.1
Pb 0.08 - 0.13 As 0.05 - 0.2
Ni 0.1 - 0.4 Se <0.002 - 0.25
Ag 0.02 - 0.3 Te <0.005 - 0.01
Bi 0.005 - 0.013 O 0.2 - 0.35

When current is applied to the electrorefining cell, the following sequence of events take
place in the CuSO4-H2SO4-H2O based electrolyte:
a) Anode begins to dissolve as Cu2+ ions into the electrolyte by reason of anodic
oxidation and electrons move from anode metal to cathode metal
Cu° = Cu2+ + 2e- E= 0.34 V (13)
b) Electrons from the surface of anode pass through cathode metal by following the
external circuit
c) Cu2+ ions in the electrolyte immigrate to the surface of cathode
 d) The reached Cu2+ ions on the surface of cathode again react with electrons coming
from the external cycle to reduce into the metallic form.
Cu2+ + 2e- = Cu° E°= -0.34 V (10)
The thermodynamically required energy to drive reactions in a-d steps should be zero;
however, in practice, overpotential is needed to apply into the system to overcome the kinetic
obstacles of anodic and cathodic reactions. The common cell potential value for the copper
electrorefining system working at 200 A/m2 is around 200-350 mV by taking IxR drops and
all potential voltage losses into the account. The typical variation of potential with respect to
current density in electrorefining process is given in Figure 2.4.

120
Current Density [A/m2]

100

80

60

the plateau of limiting current density

40

20

0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170

Potential [V]

Figure 2.4. Typical variation of potential versus current density in electrorefining process [1]
In the electrorefining system consisting of CuSO4-H2SO4-H2O based electrolyte, the
behaviors of elements inside of anode can be classified as four main groups according to their
electrochemical properties:
1- Elements more basic than copper ; Fe, Sn, Zn, Ni, Cd
2- Metals with the closed standard potential to copper; As, Sb, Bi
3- Metals noble than copper; Au, Ag ve Pt group metals
4- Elements producing unsolvable components; Se, Te, Sn, Pb
The classical working conditions of copper electrorefining are given in Table 2.3.
Table 2.3. Classical copper electrorefining conditions [5].
Electrolyte concentration 35-40g/l Cu2+ , 140-220 g/l free H2SO4
Electrolyte cyclization 18-20 l/min
Current Density 150-250 A/m2
Temperature 50-650C
colloids (gelatin, thiourea, etc) ~3-6g/t cathode Cu
Cell potential 0.2-0.35 V

The typical weight of copper anodes is 150-300 kg. Copper anodes will be kept into the bath
until 85% of them dissolved; meanwhile, when the cathodes’ masses reach to 50 to 150 kg,
they will be withdrawn from the bath. The typical cathode formation duration is around 7 to
14 days and accordingly one anode stays into the electrolyte approximately 21 to 28 days. The
purity of cathode copper is minimum 99.9 % and the working average current efficiency is
around 90-95 % plus that the specific energy consumption is very low with the value of 0.2 -
0.25 kWh/kg Cu [5].

2.3. Inhibitor (Surface activators)

Inhibitors are the matters not participating into the ultimate reactions but adsorbing on the
surface of electrodes to decrease the rate of electrochemical reactions and to increase the
overpentantials at a constant current. In principle, all components of electrolyte such as
anions, cations, dissolvent dipoles and etc. behave like an inhibitor due to the blocking effects
of electrode surface. Simple salts of anions and cations are considered as a weak inhibitor in
the electrochemical reactions because of less blocking influences of the electrode surfaces
even at high concentrations. On the other hand, inorganic and/or organic substances are the
strong inhibitors even at low concentrations due to their good adsorption abilities on the
surfaces [5,10,11].
Inhibitors (surface activators) can be classified in two groups, namely primary and secondary
inhibitors:
1. Primary inhibitors: surface active substances added into the bath such as thio-
components, colloidal substances, gelatin, etc.
2. Secondary inhibitors: reaction products such as metal hydroxides formed after
hydrolysis
Inhibitors never completely cover the surface. They partially coat the active sides of the
surface like edges and tips. The addition of inhibitors in copper electrorefining to have
smooth surface is
 50 g/t copper Thioharnstoff
 100 g/ t copper gum arabic, <200 A/m2
 200 g / t copper gum arabic >200 A/m2
Over addition of inhibitors, such as thiourea and gum arabic causes modular and stripe
surface formation of cathode, respectively. The addition of thiourea leads the growth of
<100> direction; whereas the addition of gum arabic is the reason of <110> directional
growth in copper electrorefining [5].
Thiourea and gum arabic are added continuously into the copper electrorefining bath to keep
the content at 0.1 g/dm3.

3. Materials and instruments

 Digital DC power supply  reference electrodes (Calomel and/or
electrolytic copper)
 Voltmeter
 Different Electrolytes containing Cu2+
 Heater – stirrer
ions ve free H2SO4
 Scales
 Inhibitors such as thiourea and gum arabic
 Beakers
 PbSb, blister copper, stainless
steel cathodes
4. Experimental procedure
The schematic depiction of experimental setup is given in Figure 2.5.
8
7
8 8 8 8

3 6 6 3
8

5 3 4 2 5 4 3 2

1 1

1: Electrolytic
1: ElektrolizCells
hücresi 5: Cathode
5: Katot 9:
9 DC Power
: Güç supply
kaynağı
2: Anot
2: Anode 6: Kapak
6: Cap 10: Voltmetre
3: Referens elektrodu 7: Şönt
3: Reference electrodes
4: Karıştırıcı
7: Shunt
8: Voltmetre
4: Stirrer 8: Voltmeter

Figure 4.5. Schematic drawing of two connected electrolytic cells

1) Three types of electrolyte are going to be used in the serial connected electrolytic
cells.
Cell I : 50 g/l Cu2+, 150 g/l H2SO4 (Copper electrorefining)
Cell II : 50 g/l Cu2+, 150 g/l H2SO4, 20 ppm Cl-, 30 g/tCu gum arabic ve
100 g/tCu thiourea (Copper electrorefining)
Cell III : 50 g/l Cu2+, 150 g/l H2SO4 (Copper electrowinning)
2) Pour electrolytes into the cells and then add the mixture of the inhibitors into the
2ndcell.
3) Choose anode and cathode materials. Before initiating electrolysis, measure the weight
of electrodes.
4) Put selected electrodes into corresponding cells, then after connect cables accordingly.
5) Luggin probes and reference electrode should be place into system properly with the
maximum distance of 1 mm from the surfaces of anode and cathode in order to
measure half cell polarizations.
6) After measuring anode and cathode initial polarizations, the experiments can be
started.
7) The temperature of cells, cell potentials, anode and cathode polarizations should be
measured periodically (every 10-15min.) during the experiment.
8) When the experiment is completed, measure the weight of electrodes again.
5. Requested Questions
1. Plot the variation of polarizations and cell potentials as a function of time and explain
them.
2. Calculate the values of current efficiencies and specific energy consumptions for all
three electrolytic cells.
3. Mark on our working conditions on the potential –current density curves.
4. Why lead is using as an anode material in copper electrowinning process even it is a
basic metal, explain it in detail with relevant reactions.
5. As an engineer, you notice that the value of cell potential is sharply increasing in
your responsible cells of copper electrorefining. What are the reasons of this
problem? How do you approach this issue? List your possible solutions.

6. References
[1] Bor F.Y., 1989 Ekstraktif Metalurji Prensipleri, Kısım II, İTÜ, Gümüşsuyu.
[2] Timur S., 1996 Einfluss von Co, Rh, und Palladium auf die Sauerstoffdepolisation
an Electrochemisch Beschichteten Bleianoden, PhD. thesis, TU Bergakademie
Freiberg.
[3] Duman İ., Ekstraktif Metalurji Prensipleri II Ders Notları.
[4] Paunovic M., Schlesinger M., 1998, Fundamental of Electrochemical Deposition,
John Wiley & Sons, Inc., New York.
[5] Hein K., 1977 Grundlagen der Metallelektrolyse in Wassrigen Systemen,
Habilitation, TU Bergakaademie Freiberg.
[6] Graf, Hartinger, Lohmayer, Schwering, 1994, Abwassertechnik in der Produktion,
WEKA Fachverlag, Augsburg.
[7] Hartinger L., 1990, Handbuch der Abwasser-und Recyclingtecknik, Carl Hanser
Verlag, Münih.
[8] Pawlek F., 1983 Metalhüttenkunde, Walter de Gruyter, Berlin, Newyork.
[9] Orhan G., 2001. Galvanoteknik Endüstrisi Atık Çözeltilerinin Yüksek
Konveksiyonlu Elektroliz Hücrelerinde Demetalizasyonu, Doktora Tezi, İTÜ Fen
Bilimleri Enstitüsü.
[10] Hein K, Morgenstern G, 1981, Die Elektrolytische Kupperrafination,
Bergakaademie Freiberg, Section Metallurgie und Werkstofftechnik.
[11] Winnacker-Küchler, 1980, Chemische Technologie, Band 4, 4 Auflage, Carl
Hanser Verlag München