ELECTROWINNING AND

ELECTROREFINING OF
COPPER

A COURSE PRESENTED TO AMIRA P705A SPONSORS

April 2008

M J Nicol
Murdoch University

ELECTROWINNING AND
ELECTROREFINING OF
COPPER
1

Introduction

Redox Equilibria

2.1

Electrochemical Potentials

2.2

Single Electrode Potentials

2.3

Non Standard Electrode Potentials

Electrochemical Kinetics10

3.1

Faradays Laws

3.2

Reactions at electrodes10

3.3

Potential Dependence of Electrode Kinetics 11

3.4

Characteristics of the Butler-Volmer (BV) Equation 13

Mass Transport to Electrodes

16

4.1

Mass Transport Processes

16

4.2

Diffusion Layer Model 16

4.3

Mass Transport Correlations

4.4

Influence of Mass Transport on Electrochemical Kinetics 21

4.5

Mass Transport of Ions 21

Mass Transfer at Vertical Electrodes

5.1

Natural Convection

5.2

Application to Copper Deposition

5.3

Effect of Gas Evolution 26

Electrocrystallization 29

6.1

Influence of Kinetics on Deposit Morphology 30

6.2

Application to Metal Deposits

32

Current distribution in a cell

35

7.1

Types of Current Distribution

35

7.2

Primary Current Distribution

36

7.3

Secondary Current Distribution 37

7.4

Tertiary Current Distribution

7.5

Current Distribution in 3-Dimensional Electrodes

Energy consumption

Materials for cells and electrodes

9.1

Anodes and cathodes 45

10

Cell design

11

Tankhouse current distribution 48

12

Copper electrorefining 54

12.1

Cathodes and starter sheets

10

19

24

24
26

40

43

47

54
2

44

42

12.2

Electrolytes

55

12.3

Current density

55

12.4

Anode passivation

56

12.5

Deportment of anode impurities 56

13

Electrowinning of copper57

13.1

Competing Reactions 58

13.2

Quality of Copper Cathodes

13.3

Additives in copper deposition 63

13.4

Anodes for Electrowinning

65

14

Electrowinning in Novel Cells

66

14.1

Packed or Fluidized Bed Cells

66

14.2

Forced Flow Cells

68

15

Appendix

70

15.1

Class Problems - EW Course

15.2

Workshop Problems - EW Course

Workshop Problem 1

75

Workshop Problem 2

76

59

70

75

ELECTROWINNING AND
ELECTROREFINING OF
COPPER
1

Introduction

his course examines the use of electrical power to reduce copper ions in solution
to metal on a cathode from which the metal is subsequently removed. The power
can also be used to oxidize copper metal to copper ions. The following sections
will deal with both the general theoretical aspects of the electrodeposition of metals in
general with a focus on copper and also on the more practical conditions under which
copper is recovered.
Electrowinning is the recovery onto a cathode of a metal which will contain a range of
impurities which are codeposited from the impure feed solution. The feed solution may be
directly from a leach operation or may be partly or wholly purified prior to electrowinning such
as in the SX/EW process. Electrorefining involves the electrodissolution of an impure anode
(often from pyrometallurgical processes or preliminary electrowinning) into a solution from
which it is electrodeposited as a highly purified metal onto a cathode which is often made from
the pure metal. The crude anodes contain material which either dissolves and accumulates in
the solution, or is insoluble and falls to the bottom of the cell as anode slime. The build-up of
impurities in solution is controlled by removing part of the electrolyte (a bleed) and removing
the unwanted metals by precipitation, or other means. The anode slimes are generally treated to
recover valuable metals such as Ag, Au, Te, PGMs).
For many of the base metals, minimization of the energy cost in electrowinning or refining
processes is an important consideration.
For every metal, the specifications are dictated by the major commodity metal exchanges, such
as that in London (LME). For LME Grade A and Comex Grade 1 copper cathodes the
specifications are given in Table 1.1
Table 1.1 Chemical specifications for copper cathode
Element
Se
Te
Bi
Sb
As
Pb
S
Sn
Ni
Fe
Ag

LME Grade A
2
2
2
4
5
5
15
5
10
10
25
4

Comex Grade 1
2
2
1
4
5
5
15
5
10
10
25

Clearly, the high purity of the copper required for commodity sales is difficult to produce
except under tightly controlled conditions and many other methods of metal production
(notably pyrometallurgy) cannot produce a suitably pure product. The copper produced by
smelters is typically around 99.8% Cu, the remainder being comprised of a range of elements,
including iron, arsenic, silver, gold and PGM.

Redox Equilibria

This section is largely revision of the most important concepts and applications of
electrochemical potentials as they apply to the reactions taking part during the electrowinning
of copper, with the emphasis on reactions at electrodes.
2.1

Electrochemical Potentials

The reaction
2H2O + 2CuSO4 (aq) = Cu + O2(g) + SO42-(aq) +4H+(aq)
occurs in the cell during the electrowinning of copper .
It can (theoretically and practically) be separated into two half reactions
2H2O = O2(g) + 4H+(aq) + 4e
Cu2+ + 2e = Cu
Consider a cell composed of these two half-reactions as shown in Fig. 2.1.

V
e

Reduction
Cu Cathode

Oxidation
Pb
Anode

Zn2+

Cu2+

Figure 2.1 An electrochemical cell

2.2

Single Electrode Potentials

In the case of the above cell, a voltage (or potential difference) of 0.89V would be measured by
the voltmeter if the solutions contained copper and hydrogen ions of concentrations equivalent

to unit activity and is saturated with oxygen at one bar pressure. The copper electrode would be
negative with respect to the lead electrode.
The cell voltage can be considered to be composed of a difference between the potential of the
copper electrode and that of the lead/oxygen electrode,
i.e. E = V = EO2 - ECu
It is only possible to measure the potential difference (or voltage) between two
electrodes.
A scale of relative potentials can be devised if all potentials are measured relative to one
electrode. For various reasons this standard reference electrode has been chosen as the
Standard Hydrogen Electrode (SHE)
2H+ + 2e = H2
for which , at unit activity H+ and unit fugacity H2, E0 = 0.0V.
Thus for any redox couple,
Ox + ne = Red

or

Mn+ + ne = M
the electrode potential(E) is the potential difference of a cell composed of this couple and a
SHE.
i.e. E = E - E0H
For the above reaction the cell voltage(under standard conditions) given by
E = EO2o - ECuo = 1.229 0.340 = 0.889V
The following table gives a selection of the Eo values for some couples of importance in the
electrowinning and refining of copper.
Table 2.1 Some relevant standard reduction potentials.
Half reaction

E0 , volts

Mn2+ + 2e = Mn
Fe2+ + 2e = Fe
PbSO4 + 2e = Pb + SO42Co2+ + 2e = Co
Ni2+ + 2e = Ni
Pb2+ + 2e = Pb
2H+ + 2e = H2
AgCl + e = Ag + ClCu2+ + 2e = Cu
Fe3+ + e = Fe2+
Ag+ + e = Ag
O2 + 4H+ + 4e = 2H2O
MnO2 + 4H+ + 2e = Mn2+ + 2H2O
Cl2 + 2e = 2ClMn3+ + e = Mn2+
MnO4- + 8H+ + 5e = Mn2+ + 4H2O
PbO2 + SO42- + 4H+ + 2e = PbSO4 + 2H2O

-1.18
-0.44
-0.35
-0.28
-0.26
-0.13
0
0.222
0.34
0.77
0.80
1.23
1.33
1.36
1.49
1.51
1.70

Preferred
Reduction or
Cathodic Reaction

Preferred
Oxidation or
Anodic Reaction
(Reverse)

The equilibrium potentials for the reduction of the more important metal ions are compared in
Figure 2.2. Thus, the only metal which will be co-deposited with copper is silver because its
potential is more positive than that for the reduction of copper ions. From a thermodynamic
point of view, we would not expect lead, iron or nickel to codeposit with copper.

Order of Reducibility

0.8
0.6
0.4
0.2

E ,V

0
-0.2

Ag

Cu

Pb

Ni

Co

Fe

Cd

Cr

Zn

Mn

-0.4
-0.6
-0.8
-1
-1.2

Figure 2.2 Standard reduction potentials for metal ions.

2.3

Non Standard Electrode Potentials

Most reactions are carried out under conditions in which the activities of the species taking part
are not unity and one must be able to quantitatively account for deviations from the standard
states. The well-known Nernst equation can be applied to calculate the equilibrium potential
under any conditions. For a general half-reaction
Ox + ne = Red
E = E0 - RT/nF. ln{ ared / aox }
The formation of complexes between a metal ion and a ligand can have a significant effect on
the value of the standard reduction potential for couples involving the metal ion. Fortunately in
the case of acidic metal sulfate solutions, this is not a major effect.
For example, for the reduction of copper ions
Cu2+ + 2e = Cu

E0 = 0.34V

and the presence of complexing ligands such as SO42- can change this potential. The effect of
complexation can be viewed as a reduction in the activity of the free Cu2+ ion which will make
it more difficult for it to be reduced to metallic copper i.e. one will require a more negative
potential.
This effect can be quantitatively accounted for if the stability constants for the formation of the
complexes are known.
Thus , for the relatively weak outer-sphere sulfate complex,
7

Cu2+ + SO42- = CuSO4(a)

K1 = 5

from which
[Cu2+] = [CuSO4]/ [SO42-].K1
= [Cu]T/(1+K1.[SO42-]) where [Cu]T is the total copper concentration.
and one can calculate [Cu2+] after substitution of [SO42-]. However, this calculation is more
complex because of the simultaneous equilibria involving the sulfate and bisulfate ions in acid
solutions. One can make use of thermodynamic software packages to derive species
distribution diagrams such as that shown in Figure 2.3 from which one can estimate the
free cupric ion concentration under various conditions of acidity.
Note that the free cupric ion concentration increases as the acidity increases as a result of the
fact that the free sulfate ion concentration decreases due to protonation to HSO4- as the acid
concentration increases. Thus, although the acivity of copper ions in solution decreases with
increasing concentration, addition of protons can increase the activity of the cupric ion.
M

0.7
Cu(+2a)

0.6

0.5

0.4

0.3
CuSO4(a)

0.2

0.1

SO4(-2a)

0.0
0.0

0.5

1.0

1.5

2.0

2.5

H(+a)
M

Figure 2.3 Effect of acid concentration on the species distribution in a

sulfate solution containing 40 g/l (0.63M) copper at 40oC.
Thus, at 40oC, [Cu2+] = 0.61M and substitution in the Nernst equation gives
ECu = E0Cu - RT/2F. ln {1/[Cu2+]} = 0.340 0.006 = 0.334V.
i.e. the effect is very small in this case and can effectively be ignored.
The thermodynamics of such systems can be conveniently summarized in EH/pH diagrams,
with the one for the copper system in uncomplexing media shown in Figure 2.4.
Lower dotted line: 2H+ + 2e = H2
Upper dotted line: O2 + 4H+ + 4e = 2H2O

1.5

EH

Cu

2+

CuO

0.5
Cu2O

-0.5

Cu

-1
0

10

12

14

pH

Figure 2.4 EH/pH diagram for the copper water system at 298K (0.1M
activity of aqueous ions)
The areas of stability of the various species can now be identified on the diagram. Thus, the
Cu2+ ion is only stable at a concentration equivalent to unit activity in the grey area in the lefthand side of the diagram.
Several general features of these diagrams should be pointed out:

The oxidation state of the metal (or other central species) increases as one moves
vertically in the diagram.
Thus, at pH 8 a vertical movement starts with Cu(0), moves through Cu(1) and into
the Cu(II) area of stability.

The extent of hydrolysis increases from left to right.

In the above case, the extent of hydrolysis increases from Cu2+ to Cu(OH)2 (or CuO)
as we move from left to right at potentials above about 0.5V.

Soluble species are generally present on the left and sometimes (for amphoteric metals)
on the right of the diagram.

The area of stability of water is between the two dotted lines. The consequence of this
is that species with an area of stability below the lower line will be unstable in aqueous
solutions reducing water to hydrogen gas.
Thus, because the line separating Cu2+ from Cu(s) is above the lower line, the reaction
Cu(s) + 2H+ = Cu2+ + H2(g)
is not thermodynamically favourable at pH values below about 4 and, in fact, the
reverse reaction is possible, i.e. we can use hydrogen to reduce copper ions.

Similarly, species with an area of stability which lies above the upper line will oxidize
water to oxygen .

It should be pointed out that although these diagrams are invaluable in assessing and predicting
what processes are possible from a thermodynamic point of view, any practical application of
9

a possible reaction will necessarily require that the rate of the reaction is such that it can be
made to occur in the time available for processing.
Thus, reference to the copper-water diagram above shows that it should be
possible to electrodeposit copper from aqueous solutions. This follows from the
fact that the line for the reduction of copper ions lies above the lower line i.e. the
preferred reaction at the cathode in an electrowinning cell will be
Cu2+ + 2e = Cu
and not the reaction

2H+ + 2e = H2

which requires a more negative potential.

You should be able to define the conditions required to produce Cu2O by reduction of
cupric ions.

Electrochemical Kinetics

These reactions involve the transfer of electrical charge (generally electrons) across interfaces
between phases. Thus, in addition to the influence of reactant concentrations on the rate of
such reactions, the electrochemical potential difference between the phases (or the
concentration of electrons, if you like) also has a profound effect on the rate.
3.1

Faradays Laws

The rate of production of copper at a cathode is determined by Faradays law

m = Mit/nF (= 0.448 Mi g for t = 1 day and n=2)
where
m - mass of metal deposited (g)
i - applied current (A)
t - time (s)
n -no. of electrons/mole of metal (e.g. 2 for Cu since the solution comprises Cu2+ ions )
M - atomic mass of the metal g/mole (63.5 for Cu)
F is the Faraday (96487 coulomb/equivalent)
is the current efficiency i.e. fraction of the current resulting in metal production.
3.2

Reactions at electrodes

Consider the simple cell shown below which consists of two copper electrodes in a solution or
electrolyte of aqueous copper sulphate . A reference electrode has been added to the cell close
to one of the copper electrodes. This enables us to measure the potential of the copper
electrode as a function of the current passed (which can be varied by changing the voltage,V,
applied by the power supply).
Note that the reference electrode could be another copper electrode or any suitable reference
such as a Ag/AgCl electrode. Assume that it is the former.

10

V
+

Power
Supply

e(I)
Cu

Ec
Cu

Cu2+

Figure 3.1 An electrochemical cell

For the current I=0, Ec= Ea = Ee (equilibrium potential) = 0 .
As current is allowed to flow in the direction indicated, Ec will decrease and Ea will increase.
The overpotential () as defined by
= E - Ee
will increase at the anode and decrease at the cathode.
Sign Conventions:
By above definition and that of E, cathodic overpotentials are negative and anodic
overpotentials positive. Similarly, anodic currents are positive and cathodic currents negative
Rate of reaction at the cathode v = No of mol of Cu deposited/ unit time.
= I/2F (by Faradays law)
As the process is heterogenous, the current density (i = I/A, where I is the current and A the
active electrode area) is normally used.
3.3

Potential Dependence of Electrode Kinetics

For a chemical reaction, the rate v is related to the free energy of activation (G#) by
v = kT/h. a. exp(-G#/RT)
where k and h are constants and a is the product of the activities or concentrations of the
reactants taking part in the rate-determining step.
For an electrode process, we have seen that G =-nFE and it is reasonable, therefore, to
expect the rate to be some exponential function of the potential.
Thus, for the above cell, we can draw a schematic current-potential curve for the reactions
which occur as we change the potential. As we increase the voltage applied to the cell with the
flow in the direction indicated, the right hand electrode will become an anode and copper will
be dissolved at a rate proportional to the magnitude of the current. If we reverse the polarity
and increase the current in the opposite direction, the right hand electrode will become a
11

cathode on which copper will deposit. If we measure the potential of the electrode (relative to a
copper zinc reference electrode) at each of the currents applied we can plot the current as a
function of the potential as shown in Fig 3.2. (Remembering the sign conventions).
ia
Cu = Cu2+ + 2e

Cu2+ + 2e = Cu
Figure 3.2. Schematic current-potential curve for the Cu2+/Cu couple
The above current-potential relationship is, in fact, a composite of two exponential curves as
shown in Fig. 3.3. Note that the net current is zero at the equilibrium potential, Ee and that we
have changed our reference electrode to, for example, a standard hydrogen electrode so that,
for unit activity of copper ions, Ee is 0.34V.
ia
Cu = Cu2+ + 2e

io

Ee

ic

E, V vs NHE

Cu2+ + 2e = Cu

Figure 3.3 Schematic current potential curves for electrochemical reactions.

12

Thus, the overall curve (black) is the algebraic sum of the currents due to the anodic (red) and
cathodic (blue) reactions. At equilibrium (i=0), the rates of both reactions are equal but
opposite and the current due to each reaction at equilibrium is known as the exchange

current density (io).

These curves can be described quantitatively as follows

For the cathodic reaction,
Cu2+ + 2e = Cu
ic = -nFkc [Cu2+] exp( -c FE /RT)
where kc is a heterogeneous rate constant and c (see below) a parameter known as the cathodic
transfer coefficient. E is the potential with respect to any reference electrode. Note the negative
exponent because the cathodic current will decrease with increasing potential and also the
negative sign for the current.
Similarly, for the anodic reaction,
ia = nFka exp( a FE /RT)
Note that in this case, [Cu] = 1 (solid )
At any potential, the net observed current i = ia + ic
At the equilibrium potential, Ee , i = 0 and ia = -ic
i.e. nFka exp(a FEe/RT) = nFkc[Cu2+] exp(-c FEe/RT)
= i0 (Exchange current density)
Thus, remembering that = E - Ee one can write the current/potential relationship as follows,
i = i0 [ exp{ aF(E-Ee)/RT} - exp{ -cF(E-Ee)/RT}]
= i0 [ exp( a F/RT) - exp(- c F/RT)]
This is the well known Butler-Volmer equation.
Note that the exchange current density is a function of the concentrations of the reactants and
in this case varies with [Cu2+]1/ .
3.4

Characteristics of the Butler-Volmer (BV) Equation

For >0, the first exponential term in the BV equation is greater than unity while the second is
less than one - the net current density is positive(anodic). For <0 the reverse applies. At the
equilibrium potential (=0) the rates of both processes are equal (i0).
A plot of the BV equation is shown in Figure 3.4, together with dotted line plots of the
separate anodic and cathodic terms.
There are two limiting conditions under which the equation can be simplified,
Low-field Region
For <50mV, there is an approximately linear region, which can be derived from the
approximation exp(x) 1+x for x<<1.
13

Under these conditions,

i = i0 [1+ (1-)F/RT -1 - (-F/RT)] = i0 F/RT
This enables one to obtain i0 using the so-called linear polarization technique which is very
common in corrosion science.
Butler- Volmer Equation
2

i o = 1 A/m , beta(anodic)= 0.4

6
4
2
0
-100

-50

-2

50
100
Overpotential, m V

-4
-6
Current
Density,
A/m 2

-8
-10
-12

Figure 3.4 Calculated current- potential relationship

High-field Region
At large overpotentials, the cathodic contribution to the anodic reaction can be neglected and
ia = i0 exp[ (1-)F/RT]
or
ln ia = ln i0 + (1-)F/RT
which is the form of the empirical Tafel equation for an anodic process,
a = a + b.log10 ia with a = -b.log10io
i.e.

a = b.log10 (ia /io)

The so-called Tafel Slope b = 2.303RT/(1-)F and is normally given in mV/decade current.
Note that
i) the Tafel equation is written in terms of logs to the base 10.
ii) the exchange current density can be obtained by extrapolation of the Tafel line to the
equilibrium potential ( = 0)
iii) for a cathodic reaction, the corresponding Tafel equation is
14

c = b.log10 (io /ic)

Typical schematic Tafel plots are shown in Figure 3.5. Note the common intercept on the
ordinate of the anodic and cathodic extrapolations. From these plots, the parameters c , a
and i0 can be obtained.

Tafel Plot of Butler-Volmer Equation

1.2
1
0.8

log10(i)

0.6
0.4
0.2
0
-150

-100

-50

-0.2

50

100
150
200
Overpotential, mV

-0.4
-0.6

Figure 3.5 Calculated Tafel plots using the data from Fig. 3.4
Most electrochemical processes of importance in electrowinning occur in the high-field region.
Table 3.1 gives the electrochemical kinetic parameters for some common reactions
encountered in the electrowinning of copper. Note that the exchange current density (the
electrochemical equivalent of rate constant) for a particular reaction is dependent on the nature
of the electrode and also the nature of and concentrations of the electroactive species.
Table 3.1 Electrochemical Parameters for Some Reactions at 25oC
Reaction

E0
V

Electrode

Solution

Tafel
slope, mV
120

i0
A m-2
1.10-5

2H+ + 2e = H2

Cu

1M H+

Ni2+ + 2e = Ni

Ni

-0.26

1M NiSO4

120

2.10-5

Cu2+ + 2e = Cu

Cu

0.34

1M CuSO4

40

0.2

Ag+ + e = Ag

Ag

0.80

0.1M Ag+

60

1.104

2H2O = O2 + 4H+ + 4e

Pt

1.23

1M H2SO4

120

1.10-4

-PbO2

1.23

120

1.10-6

Pt

0.77

0.1M Fe2+,3+

120

4.103

Fe3+ + e = Fe2+

15

Calculate the overpotentials at the cathode and anode for a

Cu electrowinning cell operating at 300 A/m2 with unit
activity copper ions and protons. Use the data in Table 3.1.
What will the actual potentials (relative to SHE) of the
cathode and anode and the overall cell voltage be under
these conditions?

Mass Transport to Electrodes

The overall rate determining step in the deposition or dissolution of a metal may not be the
electrochemical reaction but the rate at which material can be transported to or from the
electrode surface. Under these conditions, we say that the rate of the reaction is mass-transport
controlled.
4.1

Mass Transport Processes

Transport of species to and from electrodes can be accomplished by

1) Convection
Hydrodynamic transport can be induced by
Stirring
Pumping
Air Sparging
Gas Evolution
Density Gradients
Thermal Gradients
Convection is generally the most effective means of enhancing mass transport and will be dealt
with in more detail at a later stage.
2) Diffusion
A concentration gradient acts as the driving force for diffusion from regions of high to low
concentration.
3) Migration
The contribution of migration(movement of ions under the influence of the electrical field) to
the overall transport process is of importance only in processes such as mass transport to
electrodes or in ion exchange materials or membranes. In theory, this can be calculated as we
shall see later. In many processes, this is a rather small contribution (particularly in acidic
solutions) and is therefore often neglected.
4.2

Diffusion Layer Model

In this section, we will introduce a simple but very effective method for describing mass
transport to or from an electrode surface. It uses the concept of a stationary liquid film adjacent
16

to the surface. Mass transport through this film is considered to occur solely by diffusion (and
possibly by migration in an electrical field in the case of electrochemical reactions). Beyond the
film (or diffusion layer), mass transport is enhanced by means of convection involving relative
movement of the surface/liquid interface by stirring or other convective processes.
Thus, Fig. 4.1 schematically depicts this model in which the concentration of a reacting species
such as Cu2+ ions is plotted as a function of distance from the electrode surface. The diffusion
layer of thickness is shown by the vertical line. It is assumed that the concentration is
maintained by convection at its bulk value beyond the diffusion layer.

Cb

Chemical

Co

Diffusion
Distance, x

Figure 4.1 Diffusion layer model for mass transport.

There are two limiting cases for the rate of the reaction at the surface,
i)

The rate is controlled by the rate of the electrochemical chemical reaction. In this
case, mass transport of the reacting species to the surface is very much faster than
the rate of the reaction at the surface. Under these conditions, the concentration of
the reactant at the surface will be essentially the same as its concentration in the
bulk of the solution i.e. its concentration at the surface is not perturbed by the fact
that there is an electrochemical reaction. Under these conditions, Co Cb and the
concentration profile is as shown by the dotted blue line.

ii)

The rate of the reaction is controlled by mass transport of the reactant to the
surface. In this case, the electrochemical reaction is very much faster than that of
mass transport. Under these conditions, the reactant is consumed by electrode
reaction as soon as it arrives at the surface. Under these conditions, Co 0 and the
concentration profile is shown by the solid black line.

For a process involving diffusion, the flux (j) at the surface (or rate at which the reacting
species arrives per unit area of surface) is given by Ficks First Law of Diffusion,
j = D (C/x)x=0
i.e. the rate of diffusion is proportional to the concentration gradient with D being the
diffusion coefficient.

17

In the above case, the concentration gradient at the surface is approximated by that over the
diffusion layer as shown by the dotted red line. Thus,
j = D(Cb - C0 )/
The maximum flux that can be supported under these conditions will be achieved for C0 = 0,
jL = Cb D/ = Cb . kL
where kL = D/ is often used and is known as the mass transfer coefficient..
The table below lists some typical values of the diffusion coefficients of common species in
aqueous solution.
Table 4.1 Some Diffusion Coefficients
Infinite Dilution at 25oC for ions
Species
Diffusion Coefficient
m2 s-1 x 109
H+
9.31
OH
5.26
Cl
2.03
2SO4
1.06
+
Na
1.33
2+
2+
2+
Cu , Ni , Zn
0.72
2+
Fe
0.71
3+
Fe
0.60
O2(aq)
2.10
O2(g)
23000
Note that most metal ions have diffusivities close to 5 x 10-6 cm2 s-1 while the proton and the
hydroxide ion have unusually high values for the same reason that their conductivities are high.
The effect of concentration on the diffusion coefficients is not as pronounced as in the case of
the conductivity and is therefore often ignored.
The thickness of the diffusion layer (and, of course the mass transfer coefficient) is strongly
dependent on the effectiveness of the convective processes in the bulk of the aqueous phase.
Some typical values are shown in Table 4.2.
Table 4.2 Some Approximate Diffusion Layer Thicknesses
Surface

(mm)

kL ( m s-1 )

Freely suspended 100m particle of density 4g/cm3

Suspended gas bubble
Plane surface with longitudinal flow (25cm s-1)
Rotating cylinder (100 cm s-1 )
Natural convection on vertical electrode

0.01
0.02
0.1
0.04
0.1 0.2

50 x10-6
25 x 10-6
5 x 10-6
12.5 x 10-6
5-10 x 10-6

*Assumes D = 5 x 10-10 m2 s-1

18

4.3

Mass Transport Correlations

We have seen that it is possible to estimate the rate of mass transport of a species to a surface if
we know the relevant mass transfer coefficient. Unfortunately, as we could expect, the
coefficient will depend strongly on the geometry and flow conditions close to the surface.
Thus, unlike diffusion coefficients, tables of mass transfer coefficients do not exist. A number
of useful semi-empirical correlations have been established which enable one to calculate the
Sherwood Number, Sh (the dimensionless surface concentration gradient averaged over the
mass transfer surface) for various surface geometries and operating conditions. These
correlations use several so-called dimensionless numbers which are given in Table 4.3.
Table 4.3 Some Dimensionless Groups
Number(or Group)

Physical significance

Form

Sherwood number (Sh)

Mass transfer/Diffusion

kL.l/D

Schmidt number (Sc)

Momentum diffusion/Mass diff.

/D or /.D

Reynolds number (Re)

Inertial forces/Viscous forces

l.U/

Grashof number (Gr)

Buoyancy forces/Viscous forces

l3g/(.2)

Peclet number (Pe)

Flow/Diffusion velocity

U.l/D

The symbols and their dimensions are :

D diffusion coefficient (L2/t)
kL mass transfer coefficient (L/t)
U fluid velocity (L/t)
/ fractional density change

g acceleration due to gravity (L/t2)

l characteristic length (L)
kinematic viscosity (L2/t)
viscosity (M/L.t)

It should be remembered that the exact definition of each of these dimensionless groups
implies a specific physical system. Thus, for example, the characteristic length l in the
Sherwood number will be the height from the bottom of a planar electrode for mass transfer
by natural convection but will be the diameter of a spherical particle which is dissolving.
Many of these correlations have the same general form. They involve the Sherwood number
which contains the mass transfer coefficient. In the case of diffusion, the Sherwood number
varies with the Schmidt number. The variation of the Sherwood number with flow is more
complex because of the different physical origins of flow i.e. forced convection due to
pumping or other means and natural convection due to density or thermal gradients. The
former involves the Reynolds number while the latter is described by the Grashof number.
i)

Natural Convection

Sh = 0,67 ( Sc. Gr)0,25 for 104 < Sc. Gr < 1013 (Laminar)
Sh = 0,31 ( Sc. Gr)0,28 for 1013 < Sc. Gr < 1015 (Turbulent)
Sh = kL.B/D
Gr = g(o - s) B3 /( o 2)
where o and s are bulk and surface solution densities.
Sc = /( D)
where = solution viscosity and = kinematic viscosity (/).
19

ii)

Gas Evolving Surfaces

Sh = 0,93 Re0,5 Sc0,49

where Re = Vg .d./A. and Vg is the volumetric gas evolution rate.
d is the bubble break-off diameter ( 40m for H2 in alkaline solutions and O2 in acid solutions
and 60m for H2 in acid and O2 in alkaline solutions.)
In many cases, this can be simplified to
kL = m ign
where m=5-10. 10-6 A-1 m3.s-1 for H2 evolution and iH in Am-2
iii)

Forced Convection
L

For laminar flow as shown between two large planar surfaces (height>>gap)
Sh = 1,85 { Re. Sc. de/L}1/3
Sh = kL . de /D where de =2S
Re = U. de /
B

and, for surfaces of finite height,

Sh = 1,47{ Re. Sc. de/L}1/3 {2/(1+)}1/3
where = S/B

Flow

For fully-developed turbulent flow,

Sh = 0,023 Re0,8 Sc1/3
iv)

Particulate Beds

For a packed bed of spheres with Re < 0,1,

Sh = 1,09/ . ( Re. Sc )1/3
For a packed bed of spheres with Re > 0,1,
Sh = 1,44 Re0,58 Sc1/3
For a fluidized bed (< 25% expansion),
Sh = (1-)1/2. Re1/2 Sc1/3 /
where, Re = U d / and Sc = /(.D) and U = superficial fluid velocity,
= bed voidage and d = particle diameter
vi)

Spinning Disk

Sh = 0.62 Re1/2. Sc1/3

where Sh = kd/D, Re = d2/ , Sc = /D, d is the diameter of the disk and is the
angular velocity of the disk.
This relationship is the well known Levich equation for mass transport to a rotating disk, an
important characteristic of which is the local mass transfer coefficient is independent of the
position on the disk.
20

4.4

Influence of Mass Transport on Electrochemical Kinetics

The current- potential curves discussed above were derived and depicted on the assumption
that the rates of the reactions at the electrodes are controlled by the rates of the electrochemical
processes. Thus, for example, the cathodic curve for the reduction of Cu2+ ions shown in Fig.
3.3, shows that the current increases exponentially with decreasing potential. However, the
concentration of Cu2+ ions at the electrode surface will decrease due to reduction and at a
sufficiently high overpotential, this concentration will decrease to effectively zero. Further
increases in the overpotential cannot increase the rate of reduction which has now become
controlled by mass transport and the curve will take on the shape as shown below in Fig. 4.3.
The maximum current that can be passed is known as the limiting current density.

il
Cu2+ + 2e = Cu
ic

Figure 4.2 Current-potential curve for a cathodic reaction involving mass

transport.
The maximum current that can be passed is known as the limiting current density. The
equation for the current-potential curve including mass transport in terms of the limiting
current density iL, can be shown to be of the following form for a cathodic reaction with a high
exchange current density,
= -(RT/nF). ln{(iL i)/i} where = E E1/2 and E1/2 is the half-wave potential
4.5

Mass Transport of Ions

In addition to convection and diffusion, the mass transport of ions in aqueous solutions can be
influenced by the presence of an electrical field and it is necessary to briefly review these
additional modes of transport.
a) Conductivity
Consider two electrodes of cross-sectional area A placed a distance l apart in a solution of an
electrolyte as shown,

21

l
A

l
As in the case of any electrical conductor, the resistance and its reciprocal, the conductance or
conductivity, is given by
Resistance :

R = l /A

Conductivity :

=1/

where = resistivity in ohm.m

(ohm-1 m-1 or S m-1 where S is the Siemen)

Unlike metallic conductors, the conductivity of electrolytes is concentration dependent, and

therefore we define,
Molar Conductivity

= /c

( S m2 mol-1)

Generally decreases with increasing concentration and, approximately,

= 0 - Ac1/2
where 0 is Limiting Molar Conductivity at infinite dilution and A is a constant for a
particular metal ion. These values can be found in tables.
Transport Number

tj = Ij / Ii

where Ij is the current carried by species i and Ii is the total current carried by all ions i.
This enables one to calculate contributions of single ions to the overall conductivity and
tj = cj j / (ci i)
where j is the molar conductivity of species i. The summation is carried out over all ions.
The conductivity of any salt can be calculated from a combination of cation and anion values
= (cj 0j)
for dilute solutions.
As shown in Table 4.4 there are published values of the conductivity of typical electrolytes as a
function of composition and temperature. There are also empirical equations such as
Resistivity(ohm m) ={3200 + 7.3[Cu] + 4.5[Fe] + 1.3[As] + 9.6[Ni] - 5.6[H2SO4] 14.6T}/105

22

Table 4.4 Specific Conductivity ( ) of Copper Electrolytes

[Cu]
g/L
30
30
30
30
35
35
35
35
40
40
40
40
35
35
35
35
35
35
35
35

[Acid]
g/L
150
160
170
180
150
160
170
180
150
160
170
180
150
160
170
180
150
160
170
180

Temp
deg C
45
45
45
45
45
45
45
45
45
45
45
45
40
40
40
40
50
50
50
50

Resistivity
ohm m
0.0192
0.0187
0.0181
0.0175
0.0196
0.0190
0.0185
0.0179
0.0200
0.0194
0.0188
0.0183
0.0203
0.0198
0.0192
0.0186
0.0189
0.0183
0.0177
0.0172

Conductivity
1/(ohm m)
52.0
53.6
55.2
57.0
51.1
52.6
54.2
55.9
50.1
51.6
53.1
54.7
49.2
50.6
52.1
53.7
53.0
54.7
56.4
58.2

In the electrowinning of copper, anodes and cathodes of

dimensions about 1m x 1m are used and the anode-cathode
separation is 2cm. Calculate the resistance between the
electrodes and the voltage drop due to the electrolyte at a
current density of 300 A m-2 for an electrolyte containing
40gpl Cu as sulfate and 170 gpl H2SO4 at 45oC .

b) Combined Diffusion and Migration

The total flux/unit area of an ionic species to the electrode surface is given by the sum of that
due to diffusion and migration,
J = D(C/x)x=0 + t.i/nF
where t is the transference number of the ion in question.
The limiting current density is therefore given by
iL = nFDCb / (1-t)
For example, in a 1 mol/dm3 solution of CuSO4
tCu = 53.6/(53.6 + 80) = 0.40
Thus, the limiting current will be some 1.67 times that for diffusion alone.

23

On the other hand, a typical copper electrorefining solution also contains about 1.7 mol/ dm3
H2SO4 , and in this case tCu = 0.19 and the limiting current will be only some 1.23 times that
for diffusion alone. Why is acid added if this is detrimental to mass transport of Cu2+ ions to
the cathode?

Mass Transfer at Vertical Electrodes

In industrial cells with vertical electrodes of length up to 2 m and narrow cathode-anode gaps,
mass transport to the cathode is an important quantity as it limits the current density which can
be applied. Thus, most processes operate at current densities of 1/3 to 1/2 of the limiting
current density. The flow of electrolyte due to circulation of the electrolyte in the gap between
the electrodes is generally relatively low with values of 1 to 10 cm/min being used. Mass
transport to the cathode is also important as it can determine the rate at which impurities can
be co-deposited with the copper.
5.1

Natural Convection

In the absence of gas evolution at the cathode (such as in the electrowinning of copper),
natural or free-convective flow is generally the most effective means whereby the electroactive
ions are transported from the bulk of the electrolyte to the surface of the cathode. Natural
convection is caused by density or temperature differences in the electrolyte which results in a
concentration gradient from the cathode. For a vertical cathode, the electrolyte is partially
depleted of relevant metal ion at the cathode surface. This results in a lower density of the
electrolyte in the vicinity of the cathode which, in turn, induces a vertical flow of electrolyte
close to the cathode as shown in Figure 5.1.

Velocity, mm/s

Obviously, in a refining cell in which a metal is being dissolved at the anode, the electrolyte
becomes denser close to the anode surface and the flow generated by natural convection is in
the opposite direction, i.e. downwards. In combination with the upward flow at the cathode,
this sets up a circulating flow between the electrodes which can be quite effective in enhancing
mass transport as shown in Figure 5.1.

Velocity Profiles at Half-Height

30
25
20
15
10
5
0
-5
-10

Refining
Winning

10

15

20

25

30

Distance from Cathode, mm

Figure 5.1 Variation of flow as a function of distance from cathode in

copper refining and winning cells.

24

For constant concentration in the bulk and at the electrode surface, i.e. constant current
density, the following correlation has been found to describe mass transport due to natural
convection induced by density differences,
Sh = C.(Sc.Gr)1/4
where C is a constant and the Sherwood number Sh = kL.L/D, the Schmidt number
Sc = /D and the Grashof number Gr = {g(o - e)L3} / (o2) = g{(Co Ce)L3} / 2
and kL is the mass transfer coefficient, L the length of the electrode, D the diffusion coefficient
of the electroactive species, the kinematic viscosity of the electrolyte and o,e the density of
the electrolyte in the bulk and at the cathode surface respectively.
is the so-called densification factor which relates the density of an electrolyte to the
concentration.
For most electrolytes, Sc>103 and C = 0.67
i) For a simple binary electrolyte such as copper sulfate, the above can be rearranged to give an
expression for the average mass transfer coefficient over the electrode,
kL = 1.19 {(Co Ce)}1/4 D1/4 -1/4 L-1/4 m/s
Note that mass transport is a relatively weak function of all the relevant parameters and that the
average value decreases as the length of the electrode increases. The difference Co Ce is
obviously related to the current density at the electrode.
In the case of a mixture of electrolytes, such as CuSO4 and H2SO4, the situation is somewhat
more complicated because of the presence of the acid. Thus, as we have previously seen, in
solutions typical of copper refining or winning, most of the electrical current is carried by the
protons in the electrolyte, i.e. the transference number tH ~ 1 and tCu ~ 0. Thus, protons
migrate to the cathode but are not reduced (in the case of copper deposition) and they
therefore accumulate in the vicinity of the cathode. At steady-state, the rate of migration to the
electrode is balanced by a diffusion flux in the opposite direction. This increase in acidity at the
cathode is shown is shown in Figure 5.2.
C

H+
Cu2

Distance from
Cathode

Figure 5.2 Concentration profiles near the cathode in a refining cell

25

This increase in acidity affects the density of the electrolyte at the cathode surface and therefore
the density gradient. It tends to reduce the density gradient and thereby also the mass transport
of copper ions to the cathode.
Under these conditions, the calculation of the mass transfer coefficient is more complex and
only the final result will be shown, expressed as the limiting current density, i.e for Ce = 0,
il = 114835 z (1-tCu)-1 DCu3/4 Co5/4 (/L)1/4 A/m2
where z is the no of electrons involved and = Cu - H.{tH/(1 tCu)}. (DCu/DH)3/4
where Cu is the value of the densification factor for CuSO4 and H the value for H2SO4.
5.2

Application to Copper Deposition

The above can be used to estimate the limiting current density during electrowinning or
refining of copper from an electrolyte containing 40 g/l of copper and 150 g/l sulfuric acid in
cells containing vertical electrodes of height 1m at 60oC . The electrolyte is normally circulated
through the cells at such a slow flow rate that the influence of the forced flow on mass
transport to the cathode can be neglected with the major component in mass transport being
natural convection.
The relevant values of the required parameters are
DCu = 1.2 x 10-9 m2/s, DH = 4.3 x 10-9 m2/s at 60oC
= 6.4 x 10-7 m2/s
tH = 0.6, tCu = 0.07
Cu = 1.5 x 10-4 m3/mol for 630 mol/m3 of CuSO4
H = 5.2 x 10-5 m3/mol for 1530 mol/m3 of H2SO4
from which, = 1.37 x 10-4 m3/mol
and il = 830 A/m2
Operating plants generally use current densities between 250 and 350 A/m2 which is in the
range of about 1/3 to 1/2 of the limiting current density.
In the absence of the supporting electrolyte, i.e. the acid in this case, one can calculate the
limiting current density using the above equation with = Cu and tCu = 0.4 to give
il = 1000 A/m2
Thus, although the use of acid in the electrolyte to increase the conductivity is
desirable, it has a negative impact on the mass transport of copper ions to the cathode
surface.
5.3

Effect of Gas Evolution

Mass transfer to the cathode can be considerably enhanced as a result of the flow
generated by the rising oxygen bubbles from the anode. This effect is even more
pronounced in the case of hydrogen evolution at the cathode which is applicable in zinc
and some extent nickel but not copper electrowinning. This effect is shown schematically
in Figure 5.3 and the consequences are that

26

i)
ii)
iii)

Mass Transfer Coeff, cm/s

mass transfer at the anode is greater than that at the cathode. This has
consequences for the speciation of, for example, iron in the electrolyte as we
shall see later.
Mass transport is greater towards the top of both anode and cathode.
On the other hand, the increased volume of gas in the electrolyte towards the
top of the inter-electrode gap results in an increased resistivity of the
electrolyte and a lower current density on the upper surfaces of the electrodes.
This hold up as a percentage of the inter-electrode volume is shown in Figure
5.3 for increasing current densities and its effect on the current distribution in
Figure 5.4.

3.0E-04
2.5E-04
2.0E-04
1.5E-04
1.0E-04
200

11
10
9
8
7
Mass Transfer 6
5
Gas Holdup
4
250
300
350
400
Current density, A/m2

Figure 5.3 Effect of gas evolution at the anode on mass transport

1.3

300A/m2
500A/m2

i/im

1.2
1.1
1
0.9
0.8
0

0.2
0.4
0.6
0.8
Fraction of Height from Bottom

Figure 5.4 Effect of gas hold-up on the current distribution in a typical Cu

electrowinning cell. The ratio i/im is that of the local current density to the
mean value for the overall cathode.
The results of recent CFD (Computational Fluid Dynamic) simulation of a typical copper EW
cell are shown in Figure 5.5. The strong vertical movement of electrolyte close to the anode
27

and the very much weaker flow at the cathode is apparent. It is not clear from the diagram, but
the flow is upward at the cathode in the lower section and downward in the upper section.
Also apparent is greater extent of oxygen gas holdup in the upper section of the cell although
the absolute maximum value of about 3-4% is considerably less than those shown in Figure
5.3. This difference could be attributed to the assumptions made for bubble size in the
simulations.

Fig. 5.5. CFD simulation of

flow and oxygen gas
holdup in a cross section of
a copper EW cell anode is
on right

One of the most effective methods of increasing mass transport in cells is to sparge air
between the anode and cathode and the results of testwork aimed at quantifying the effect on
the mass transport coefficient at the cathode using a tracer of silver ions that are deposited at
the limiting current during the deposition of copper are shown in Figure 5.6.

28

Agitation by Air Sparging

3.5
3
103kL, cm/s

Distance from bottom, cm

Diffusion Layer

100
90
80
70
60
50
40
30
20
10
0

Air, 5 l/min
No air

2.5
2
1.5
1
Natural convection

0.5
0

0.1
0.2
Diff Layer Thickness, mm

0.1

0.3

1
Air Flow, l min-1 dm-2

10

Figure 5.6 Effect of air sparging on mass transport at the cathode during the
electrowinning of copper.

Calculate the current density due to the mass-transport

controlled reduction of ferric ions (5.6 g/L) on the top and
bottom half of a copper cathode assuming that the mean
thickness of the diffusion layer is 0.17mm on the top half and
0.25mm on the bottom half. Assume that the diffusion
coefficient for ferric ions in the electrolyte is 1 x 10-9 m/s.

Electrocrystallization

The purity and properties such as electrical conductivity of metal deposits depend on their
crystallographic structure, texture and surface morphology. These properties will depend on a
number of operating parameters during the electrocrystallization process such as the current
density (or, more importantly, the current as a fraction of the limiting current), metal ion
concentration, pH, temperature, agitation, nature of the anions and cations present and the
presence of additives such as smoothing agents.
The cathodic deposition of a hydrated metal ion M(H2O)n2+ onto a metal electrode M occurs in
several steps
i) Charge transfer to the hydrated metal ion in the double layer with the formation of a neutral
or partially charged ad-atom or ad-ion which may still be partially hydrated.
ii) Migration of the ad-atom by surface diffusion to a growth site (such as an edge or kink) at
which further cordination to metal atoms in the lattice occurs.
iii) Growth of the crystal lattice by successive transfer and diffusion steps.
This sequence of steps, any one of which may be rate-determining, is shown schematically
below in Figure 6.1.

29

The essential difference between an aqueous metal ion and a metal ion in a lattice is that the coordination sphere of the former is composed of water molecules while that of the latter is
composed of other metal ions i.e. metal - H2O bonds have to be broken and replaced by metal
- metal bonds. As could be expected, the rate of this process is influenced by a number of
factors such as the nature and concentration of the metal ion and the anions present, the
presence of inhibitors and the nature of the substrate. In the case of electrocrystallization, an
important additional parameter is the potential difference between the solution and the
substrate.
Aqueous
Aq
ion
eo

i)

AAd-ion/atom

(ii)

(iii)

Figure 6.1 Steps in the electrocrystallisation process

6.1

Influence of Kinetics on Deposit Morphology

i) Charge Transfer
The exchange current density of metal-metal ion electrodes varies between wide limits
depending on the nature of the metal ion and its state in solution. For simple ions, the
following table gives some idea of the range of reversibility. Replacement of water molecules by
other molecules or anions in the metal co-ordination sphere can either accelerate or inhibit
charge transfer e.g. chloride tends to increase the i0 for the deposition of the iron-group
30

metals while cyanide can prevent deposition completely. These effects are complex
combinations of thermodynamic and kinetic factors.
Table 6.1 Classification of Metal Deposition Reactions
10 - 10-3
Lead(II)
Tin(II)
Mercury(II)
Cadmium(II)
Silver(I)
Gold(I)

i0 ( A cm2)
10-3 - 10-8
Copper(II)
Zinc(II)
Manganese(II)

10-8 - 10-15
Iron(II)
Cobalt(II)
Nickel(II)
Chromium(II)
Platinum(II)

ii) Crystallization
The formation and morphology of electro-deposits is dependent on several factors the most
important of which is the relative rates of nucleation and growth. In crystallization in general,
the rate of nucleation is a strong function of the degree of supersaturation of the solution. In
the case of electrocrystallization, the degree of supersaturation is determined in addition by the
overpotential which therefore determines the nature of the deposit as follows:
Unlike other crystallization processes, the additional variable of the overpotential determines
the nature of the deposit as follows:
Rate of Nucleation Conc of Ad-atoms Overpotential
SEM micrographs of copper nuclei formed on a platinum surface are shown on Figure 6.2. In
this case, the overpotential for nucleation on a foreign surface exceeds that for growth of the
nuclei and therefore the density of nuclei is not great. This has obvious implications in regard
to the adhesion of metal deposits to foreign substrates.
A high nucleation rate will create a large number of small crystallites i.e. a fine-grained smooth
deposit. This is generally observed and, in the extreme, powders are formed as the current
density approaches its limiting value.

Figure 6.2 Nucleation of copper on stainless steel

31

The use of complexed metal ions, such as Ag(CN)2- also tends to promote the formation of
dense fine-grained deposits. Furthermore, growth can be inhibited by the addition of various
levelling or brightening agents which absorb preferentially on the crystal defects which are the
growth sites. Higher periodic current densities produced in superimposed pulsed or A.C
current also act to promote nucleation and produce finer deposits at the same mean current
density.
iii) Lateral versus Outward Growth
Outward growth of a perfect crystal requires nucleation of new 2-dimensional layer. On the
other hand, lateral growth can occur at edge and kink sites and is generally preferred. Few
crystals are perfect and the presence of defects such as screw dislocations enables lateral growth
to be translated into an outward growth.
As we have seen, the electrical field is concentrated at a tip of a growing crystal and results in
increased deposition in this region. Metals with high exchange current densities, i.e. large
changes in rate for small changes in overpotential, will be most susceptible to this
phenomenon.
The metals in the Periodic Table can be roughly sub-divided into various groups depending on
the thermodynamic and kinetic characteristics of metal deposition as shown in Table 6.1. The
most important properties of the two outermost groups can be summarized as shown in Table
6.2. The normal (or soft) metals generally have low melting points and are not highly stressed
when deposited. The opposite is true of the inert (or hard) metals as shown by the data in
Table 6.3. Note the high stress associated with the iron-group metals, particularly Co and Cr.
Table 6.2 Characteristics of Metal Deposition Reactions

6.2

Characteristic

Normal

Inert

Reversibility

High

Low

Overpotential

Low

High

Grain Size

Large

Small

Current Efficiency

High(~100%)

Low(30-80%)

H2 evolution rate

Slow

Fast

Stress

Low

High

Hardness

Soft

Hard

Application to Metal Deposits

The physical and , to a lesser extent, the chemical properties of cathodes are determined by a
number of factors, on of the most important of which is the current density. The effect of
current density on the morphology is shown in a general case in Figure 6.3. As the current
density (or more accurately the ratio i/iL) increases, the mean size of the crystallites making up
the deposit decreases with well formed large crystals giving way eventually to very fine crystals
or powdery deposits. This is expected in terms of the effect of overpotential on the relative
rates of nucleation and growth.

32

i/iL

Fine powders
with hyroxides

2H+ + 2e = H2
1.0

Course powders
Increasing rate of

Nodules, dendrites

nucleation

M2+ + 2e = M

Polycrystalline
Bunched layers, ridges
Spirals, blocks

-E

Figure 6.3 Effect of current density on the nature of deposits.

Other factors also contribute to the size of the crystallites and the morphology as shown
qualitatively in Figure 6.4.

Increasing
Metal ion Conc.

Current Density

Temperature

Mass Transfer

Smoothing Agents

Figure 6.4 Effects of various parameters on the size of crystallites

The maximum current density that can be applied in industrial operations is normally about 3040% of the limiting current density. In the case of base metal electrowinning, a rule-of-thumb
is that that the ratio
Current density (A/m2)/Metal concentration (g/L) in spent < 10
Thus, for a cell concentration of 40 g/L Cu, the maximum current density should be about 400
A/m2.
The simplified Winand diagram (Figure 6.5) shows "stability domains" for the main types of
electrodeposits according to a system proposed by Winand. The main types identified are
i) the field-oriented isolated type (FI) that consists of dendrites, whiskers and powders,
33

ii) the basis-oriented reproduction (BR) type typified by a dense deposit with large
diameter crystals oriented parallel to the substrate and a high surface roughness,
iii) the field-oriented texture (FT) type that consists of columnar crystals with increased
density and a low surface roughness,
iv) the unoriented dispersion (UD) type that consists of randomly oriented small crystals
with a low surface roughness.
This diagram follows from observations that the inhibition intensity and/or increased
deposition rate lead to changes from one type to another, with FI and BR at lower inhibition
and FT and UD at high inhibition.

Figure 6.5 The Simplified Winand Diagram

In the context of this diagram, an inhibitor is any species that can adsorb on the metal surface
thereby reducing the rate of electron transfer and thus nucleation and/or the rate of growth of
the crystallites. In some cases, adsorption is specific to particular crystal faces leading to
preferential growth in one crystal orientation. The vertical axis can also be viewed as decreasing
exchange current density. Thus, for example, deposition of Ag from uncomplexed solutions
such as nitrate has a very high io and could be described by a horizontal line near the top of the
diagram(whiskers) whereas deposition from cyanide solutions involves a low io (due to
inhibition by strongly adsorbed cyanide) and could be described by a line near the bottom of
the diagram (smooth microcrystalline).
Thus, in the case of copper, sulfate is a weak inhibitor and io is reasonably high so that deposits
obtained from pure sulfate solutions are of BR or FT types and eventually become the
undesirable FI type. Organic additives are added to increase the inhibition intensity and, in
electrowinning/refining plants, the desired FT/UD type can be produced. Winand has pointed
out limitations in the diagram, particularly in relation to organic inhibitors.
34

Current distribution in a cell

he distribution of current in electrochemical cells affects the distribution of the extent of

reaction ( or product)

To individual cells and electrodes in a multi- cell, multi-electrode operation.

To various macroscopic areas on individual electrodes.

To various microscopic areas on the surface of individual electrodes.

In general, the current density distribution over electrode surfaces is not uniform and can
depend on a number of factors such as size and geometry of the cell, current density,
conductivity of the solution, kinetics of the electrode reactions and mass transport to the
electrode.
7.1

Types of Current Distribution

There are three different types of current distribution which can be distinguished as
summarized in Table 7.1.
Table 7.1 Types of Current Distribution
Type of current
Assumptions
distribution
Primary
absence of overvoltages
Secondary

Tertiary

Parameters
geometry of cell and electrodes

activation overvoltage without

concentration variation near
electrode
activation and concentration
overvoltages

geometry
activation overvoltage
conductivity of electrolyte/ electrodes
geometry
activation
conductivity

Consider the simple so-called Haring and Blum cell below consisting of two cathodes at
distances Lf and Ln from a central anode.

Figure 7.1 Haring Blum Cell

If the same voltage is applied across each electrode pair, then the currents flowing through the
cells will be
in = V/Rn and if = V/Rf
where Rf and Rn are the total resistances of the electrode pairs.
35

The total resistance (Rf ) to current flow at e.g. the far electrode pair,
Rf = Rc + Rs + Rp
where Rc is due to contacts, bus-bars etc
Rs is the resistance of the solution (anode to cathode)
Rp is the sum of the polarization resistances at each electrode
NB Rp is the sum of the reciprocals of the slopes of the current/potential curves for cathode
and anode of the far electrode pair.
It should also be noted that in the above simple case, the current distribution is uniform
over the surface of each cathode. This follows from the obvious observation that the
potential gradient (E/x) is zero in all directions except that normal to the plane of the
cathodes. The potential (Ex) at any point in the electrolyte at a distance x from one of the
cathodes is simply given by
Ex = Ec + x(Ea - Ec )/d
where Ea and Ec are the anode and cathode potentials and d is the distance between them.
This relationship is the solution (for a 1-dimensional case) of the more general Laplace
equation
2E / x2 + 2E / y2 + 2E / z2 = 0
with boundary conditions E = Ec at x = 0 and E = Ea at x = d.
Another reactor which has a uniform current
- +
distribution is the so-called concentric cylinder cell
which is typical of, for example the EMEW cell.
Even without mathematical examination of this
system, it is evident that the current distribution is
uniform and that the equipotential surface will be
cylindrical as shown.
Unfortunately, very few other types of geometry give uniform current distribution and the
full Laplace equation has to be solved with the relevant boundary conditions.
7.2

Primary Current Distribution

Where the electrode reactions have no overpotential, the only contribution to the total
resistance, R, of an electrode pair is the resistance of the solution, therefore

and the current density distribution in the system is controlled by the geometry of the
electrodes with those areas less readily accessible having a lower current density. This is the
primary current distribution and is a simple first approximation.
Quite often the labour involved in establishing a primary current distribution is not
worthwhile because, as we shall see, it is seldom valid in real systems. Thus, for the
relatively simple parallel plate reactor in which the electrodes do not fully occupy the
cross- sectional area of the reactor, as shown, it can be shown that the ratio of the local

36

current density(i) at a point x from the edge of one electrode to the average current
density (iav) is given by the rather complicated expression
i/iav =

. cosh / k (m ).(tanh 2 )
(sinh 2 sinh 2 (2x L). / l )

1/ 2

where = IIL/2h and k(m) is the complete elliptical integral. The primary current
distribution for various values of L/h and the Wagner number(Wa) (see below) are shown
in Figure 7.2. Note that for Wa 0, the interelectrode spacing is very large.

h
L

i/iAv

2.8
2.6
2.4
2.2
2
1.8
1.6
1.4
1.2
1
0.8
0.6
-0.5

L/h=1, Wa=0
L/h=50, Wa=0
L/h=50, Wa=10

0
x/L

0.5

Figure 7.2 Effect of edges on primary current distribution

Apart from the infinite current densities predicted at x=0 and x = L, the current density is
reasonably uniform over a substantial part of the electrode. The large current densities at
the edges can at least be partly eliminated in real parallel plate cells by the use of edge
strips of a non-conducting material. Another interesting case which will be discussed in
more detail at a later stage is that of a three-dimensional particulate electrode such as a
packed - or fluidized-bed. In terms of the primary current distribution only, the bed can
be treated as a homogeneous combination of a zero- resistance conducting solid phase in
an electrolyte whose resistivity is considerably higher (by a factor 1/ where is the
voidage of the bed) than that of bulk electrolyte. In this case, the primary current
distribution is simply a linear function of the depth into the bed.
7.3

Secondary Current Distribution

It has been shown that the primary current distribution predicts a ratio of 5 for the metal
distribution in the simple Haring and Blum cell for Lf=5Ln. Actual experiments with an
electrolyte typical of copper electrowinning practice reveal that the current density ratio is
37

less than 5 it is about 3.5. The question arises: what has made the current distribution
more uniform than dictated by geometry alone? The answer is not difficult to see. It will
be recalled that an electrochemical cell consists of three components viz.: the two
electrode/electrolyte interfaces and the electrolyte and that each of these regions offer
resistance to the flow of current. The primary current distribution takes only the
electrolyte resistance into account. To take into account the resistance associated with the
electrode/electrolyte interfaces, one has to derive it from the current/potential
relationships, i.e. the Butler-Volmer equation. In theory, this can then be combined into
an overall model by way of the Laplace equation. However, as indicated previously, the
solution to these equations is difficult even for relatively simple geometries.
It is instructive, however, to derive the relevant relationships for the Haring and Blum cell
under two limiting conditions.
(i) For electrode processes which operate close to equilibrium where the so-called lowfield approximation to the Butler-Volmer equation is valid, i.e.
i = nFi0 / RT
i - current density (A/m2)
n - number of electrons
F - Faraday's constant (96500 C mol-1)
i0 - exchange current density (A/m2)
- overpotential (V)
This can be rearranged to

/i = RT/nFio = Rp

giving the polarisation or charge-transfer resistance, Rp (ohm m2)

Thus, the above equation for the HB cell becomes
Lf
in
= 1 + 1 / Wf
=
=
L
if Rp + Rn
1 + 1 / Wn
Rp + n

Rp + Rf

Rp +

where is the specific conductivity of the solution (S m-1) and

Rp =

RT
F

1
1
+

na io ,a nc io ,c

is the polarisation or charge-transfer resistance, Rp (ohm m2 ) of the cell. It is the sum of the
resistances of the electrode reactions at the anode and the cathode. Note that it is the reciprocal
of the slope of the current/potential curve (/i = RT/nFio = Rp)
The second form is obtained by making the substitution Lf/ = Rf which is the resistance
between two parallel electrodes of 1m2 area and Lf m apart and is the specific conductivity of
the solution (S m-1)
Note that the ratio Rp/Rf =Wf is a dimensionless quantity called the Wagner Number.
Since all quantities are positive, in / if < Lf / Ln and therefore the current distribution is more
uniform than in the previous case. Also, for Rp >> Lf , in / if 1 i.e. electrode reactions with
low exchange current densities (io) and/or solutions with high conductivity favour more uniform current
distribution. It should also be noted that, in this case of low overpotential, the current
38

distribution is independent of the current density. The effect of the exchange current density is
shown by the curves in Figure 7.3. Thus, by complexing the copper ions with, for example,
cyanide, the exchange current density is reduced by several orders of magnitude resulting in a
very even current distribution in a cell designed to exaggerate the difference between point A
and point B on the cathode. The same effect albeit at a reduced effect is observed on addition
of a smoothing agent such as gelatine which adsorbs on the surface and lowers the exchange
current density for deposition. Thus, the excvhange current density for reduction of copper
ions is about 5x lower in the presence of 3ppm gelatine. This property is called throwing
power by the electroplating industry.

Figure 7.3 Effect of exchange current density on current distribution.

(ii) For electrode processes which operate far from equilibrium where the high-field
approximation to the Butler-Volmer equation is valid, it will be recalled that, in this case,
the current density increases exponentially with increasing overpotential and the value of
the change-transfer resistance, i.e. the slope of the potential/current curve is not constant
but decreases with increasing current density. Thus, although the addition of the chargetransfer resistance will improve the current distribution over that based on the primary
effect, the inverse dependence of the change-transfer resistance on the current density
results in decreasing uniformity of deposition with increasing current density.
Thus for a Haring and Blum cell operating within the region where Tafel's law applies, it can be
shown that
b ln

in
if

in Lf
=

if Ln
Lnif

Lf
i
Wf ln n
Ln
if

where b = ba + bc is the sum of the Tafel slopes for the anode and cathode reactions (based
on natural logs!), and W = b/(Lnif), is a modified Wagner number.
The effects of unequal cathode-anode spacing can be seen in the so-called Hull cell
arrangement shown in Figure 7.4. This would be typically expected with a non-vertical cathode
39

with a higher (than average) current density on the one side of the blank and a lower current on
the other at the same depth. The equalizing effect of operating in the high field region is
apparent.
Primary
Secondary

i/iav

x=0

d
x=d

x/d

Figure 7.4 Current distribution in a Hull Cell

It is worth emphasizing that the primary current distribution (dotted line) predicts a less
uniform distribution than that which takes into account the secondary current distribution
(calculated assuming the high-field approximation).
7.4

Tertiary Current Distribution

Previously it has been shown that, as the overpotential increases at an electrode, the
current density increases until, in the limit, it reaches a plateau value determined by the
rate of mass-transport of the electroactive species to the electrode. In principle, therefore,
such a situation in a Haring and Blum cell would result in equal current densities at both
cathodes, i.e. under mass-transport controlled conditions, the current distribution is
uniform. Another way of looking at this is to note that the slope of the current/potential
curve tends to zero under these conditions, i.e. Rp . The various regions of such a
curve are shown in Figure 7.5
i
Mass transport

1/Rp
High Field
Low Field

Figure 7.5 Overall current/potential curve for cathodic reduction

Note that the value of the polarization or charge-transfer resistance(Rp) is the reciprocal
of the slopes of the lines as drawn.
40

A tertiary level of current distribution is also associated with the microdistribution of current
due to imperfections on the surface of the electrode. Consider a microscopic cross-section of
an electrode surface....

iR

Figure 7.6 Schematic of tertiary current distribution

Three factors tend to influence the current distribution in the vicinity of the surface protrusion.
a) The current density is higher at a point or edge than on a plane - as depicted by the field
lines.
b) The increased iR drop between the plane and the protrusion will enhance reaction on the
latter.
c) The rate of diffusion to the tip is greater than that to the plane due to the shorter diffusion
path and, even under mass-transport conditions, reaction will be faster at the tip.
These observations explain why metal deposits tend to become rougher with time of
deposition and, in extreme cases such as silver deposition from nitrate solutions (very high i0)
dendrites can be seen to grow visibly. The opposite effect is put to good use in electropolishing
which preferentially removes the protrusions by anodic dissolution.
Combining all of these models and observations leads to the conclusions that the current
distribution is more uniform...

the greater the slope of the polarisation curve (i.e. a high polarisation resistance)

the larger the conductivity of the solution

the smaller the distance between anode and cathode

Applying this to industrial situations...

the current distribution depends on the composition of the electrolyte and adding
supporting electrolyte (increasing the solution conductivity) or of additives which inhibit
the desired reaction (increasing the polarisation resistance) lead to a more uniform current
density

many industrial processes operate under activation control and the Tafel approximation
applies, under this condition the higher the mean current density the less uniform the
current density

since all three current distributions are dependent upon the geometry of the system, scaleup from laboratory to industrial (or even pilot) scale needs to account for the changes in
current distribution due to larger electrodes and different cell designs

41

7.5

Current Distribution in 3-Dimensional Electrodes

Within the general category of three dimensional electrodes we can include those which
are genuinely porous such as a sintered or pasted electrode (e.g. a lead-acid battery
electrode) and those which are composed of discrete particles with no mechanical
adhesions. These may be in the form of a packed bed or the particles may be fluidized by
flow of the electrolyte. There are various configurations of current and electrolyte flow
possible and we shall consider only the case depicted below, viz. parallel flow of solution
and current with the current feeder to the three-dimensional cathode and the anode
arranged as shown in Figure 7.5.
+

s
m

packed

fluidized

heff

flow

Figure 7.5 Potential distribution in a 3-dimensional cell.

As already mentioned, the ohmic drop in the electrolyte within the interstices of the bed
will result in a current distribution which decreases with penetration of the bed (i.e. as x
increases). Another way of looking at this is to note that the potential of the solution s
will decrease with x as shown. If the bed material is highly conductive (e.g. metallic or
graphite), the potential of the metal phase ( m ) is constant. The difference s - m is the
overpotential and it can be seen that, at some value of x = heff , it will be zero.
Thus the bed will be active for a depth of heff only. If s - m is great enough to
produce mass-transport controlled reaction over part of the bed, then the current (and
metal) distribution will take the form shown below
i
or
metal
mass
trans

heff

Theoretical models for such a system have been developed which, as will by now be
appreciated, are exceedingly complex. Experimental investigations of the scale-up of the
height of the bed have confirmed the existence of the so-called effective bed height and a
semi-empirical but useful relationship is
heff = 0.4 ( /i)
42

where is the specific conductivity of the solution phase (ohm-1 cm-1 ) and (/i)
is the slope of the polarisation curve measured at a bed height h < heff . Notice that this
relationship can be written as Weff = 1/0.4 = 2.5 where Weff is the effective Wagner
number.
This restriction on the effective height of the bed can be relaxed somewhat if the bed is
fluidized. In this case, m is not constant but also decreases as shown in the figure, i.e.
the resistance of the solid phase is no longer very much smaller than that of the solution
phase. Under these conditions the difference s - m decreases less rapidly with distance
x and the effective bed height therefore increases. To-date there are no satisfactory
theoretical treatments of this system

Energy consumption

This is often the most significant operating cost in the recovery of metals by electrolytic
processes.
To examine the energy efficiency of such processes, it is useful to breakdown the total cell
current and voltage into their individual components as follows:

Voltage Components
Equilibrium Cell Voltage (Ee(anode) - Ee(cathode))
Cathodic overpotential
Anodic Overpotential
Ohmic potential drop in electrolyte
Ohmic potential drop in cell hardware
Voltage loss in power supply

Ve
c
a
Vs
Vh
Vp

Current Components
Stoichiometric current
Current in-efficiency due to side-reactions
Current in-efficiency due to shorts
Stray currents in tankhouse

nF
CIe
CIs
SC

The energy components can be obtained from the product of the corresponding voltage and
current components. If the current (or, more accurately, the charge/mol of metal deposited) is
plotted against the voltage as shown in Figure 8.1, the resulting areas of the rectangles are
proportional to the components of the total energy requirement as shown below for the
electrowinning of copper,

43

F/mol
stray current, (SC)
CIe + CIs

Va + V c

Vh
+
VP

Vs

Figure 8.1 Components in the overall energy consumption.

Thus for the electrowinning of copper,
Thermodynamic Energy Requirement = (1.23 0.34)V . 2 . 96500/63.5
= 2690 Ws/g
= 0.75 kWh/kg
Actual Energy Requirement = 1.97 kWh/kg
( Cell voltage of 2.1V and 90% current efficiency.)
i.e. energy efficiency is about 30%.

The electrowinning of copper is carried out at a current

density of 300 A/m2 with a cell voltage of 2.1V at a current
efficiency of 90%. It was found that the current efficiency
increased to 94% if the current density was increased to 350
A/m2 but the cell voltage increased to 2.4V. You are asked to
assess with justification which option requires the least
electrical energy/unit of copper produced.

Materials for cells and electrodes

he materials involved in the construction and operation of an electrolytic cell are obviously
of critical importance. Clearly, materials which corrode or are otherwise incompatible with
the electrolyte cannot be used as they would require frequent replacement. However,

44

electrorefining relies on the corrosion and dissolution of an impure anode for subsequent
plating onto a pure cathode. Any material used in an electrochemical cell should have a range
of properties depending upon it function within the cell.
9.1

Anodes and cathodes

Table 9.1 shows which materials are used as anodes and cathodes for a range of industrial
electrolytic processes, it is worth noting that sometimes the metal can be recovered
electrolytically using oxidation (e.g. to MnO2) rather than the more common reduction to
metal.
Table 9.1 Materials for anodes and cathodes
Metal

Electrowin blank

Starter sheet

Anode

()-electrode for starter sheet

Cu (win)

none, stainless

Cu (stainless, Ti)

Pb Ca - Sn

Cu (refine)

stainless

Cu (stainless, Ti)

impure Cu

Zn

Al

none

Pb-0.5%Ag(Ca)

Co

stainless

none

Pb - 0.5% Sb

Ni

none

Ni (Ti)

Pb - Sb

Mn

stainless, Ti

none

Pb

MnO2

graphite, titanium

none

stainless (cathode)

none

stainless

Au (rolled)

impure Au

Au (win from CN- steel wool

-

Au (refine from Cl none

In general, the materials used for anodes and cathodes are chemically resistant to the solution,
except in the case of electrorefining where the anode is made of impure metal which is
deliberately dissolved. In cases where the anode does not dissolve, it is important to minimise
the overpotential of the reaction occurring at the anode (typically oxygen evolution)to reduce
the cell voltage and minimise power. The choice of electrode material in this circumstance
depends on the composition of the solution due to the dependence of oxygen evolution
overpotential on pH, electrolytes present etc. Lead is used in most systems involving sulfate
electrolytes as it is chemically inert and other elements are alloyed with the lead to strengthen
the anode and reduce the rate of corrosion.
A number of the processes use starter sheets, these are simply thin sheets of the metal to be
won. The sheets are made on inert electrodes in a separate plating bath and after they achieve
the desired thickness (around 3mm) are stripped. Most modern copper tankhouses now make
use of so-called permanent cathode technology in which copper is plated onto stainless steel
sheets or blanks from which it is stripped as shown in Figure 9.1.

45

Fig. 9.1 Stainless steel cathode blank and automatic stripping of copper
cathodes
The starter sheets are typically larger than the anodes to minimize edge effects on the cathode
and plastic edge strips are fitted to the vertical edges and sometimes to the bottom of the blank.
In the case of the blank shown in Figure 9.1, a thin section of wax is applied to the bottom of
the blank to prevent copper deposition around the bottom of the sheet and to facilitate
stripping which is generally carried out using mechanical stripping machines.
The stainless steel used is generally 316L which has a reasonably good corrosion resistance,
particularly to pitting corrosion in the presence of chloride ions which is added to the
electrolyte as a grain refining agent. The stainless steel plate is bonded to a solid copper or
copper-plated steel hangar bar.
The complexity of a tankhouse flowsheet can be assessed by the schematic of a copper refinery
shown in Figure 9.2.

46

BLISTER
COPPER

ANODE FURNACE

WASHING

ANODE
CASTING

STARTER
SHEET
MACHINE

SPACING

SHEET
STRIPPING

ANODE SCRAP

BLANKS

STRIPPER
SECTION

TANKHOUSE

LIBERATOR
CELLS

CATHODE
WASHING

ELECTROLYTE
TREATMENT

ACID
PLANT

REFINED
CATHODES
TO MELTING

STEAM

NiSO4

RECTIFIER

SLIME
TREATMENT

PRECIOUS
METALS
Se and Te

Figure 9.2 Flowsheet of a typical copper electro-refinery

10

Cell design

he basic design of cells hasn't really changed much since the first application of electricity
to metal recovery and still consists of what is little more than a rectangular box. Depth is
larger than width as it is simpler to increase the cell height than width to give a larger
working area. The greater depth is also required to avoid electrical short circuiting due to the
build-up of anode slime at the bottom, a small clearance results in more frequent cleaning of
the cells and loss of production. The length of the cell is dictated by the number of anode /
cathode pairs to be accommodated and their spacing. The trend is to decrease the
interelectrode spacing thus giving more pairs in a fixed cell length, this necessitates the
installation of higher current capacity systems to maintain the required current density. A larger
electrode area also requires a larger volume of pregnant solution to be pumped through each
cell to maintain efficiency. Even distribution of fresh solution is also important to ensure that
the solution is not depleted of metal in some parts of the cell. For this reason, the solution is
not usually completely depleted of metal but retains a moderate concentration by only plating
part of the content on each pass through the cell.

The electrolyte level is maintained by adjustable weirs at either end of the cell, this system
allows for differences in the heights of the cell and selective removal of the spent solution from
one end or the other. The electrolyte can be fed at one end or via distribution pipes (typically a
complex plumbing system) which evenly feeds the cell with fresh solution.
Most large plants use overhead cranes to install and remove the electrode pairs. The picture
shows a crane picking up pre-spaced electrodes for installation in a cell.

47

Figure 10.1 Typical modern cell

construction and cathode handling
equipment

The cells themselves are typically made from reinforced concrete with a chemically resistant
lining, such as lead, welded PVC, epoxy resin, rubber, neoprene, silica-loaded-asphalt or, more
recently, a sprayed polymer layer.

11

Tankhouse current distribution

An image of a typical copper tankhouse is shown in Figure 11.1. A large number of cells can be
seen on both sides of the walkway with each consisting of a large number of anodes and
cathodes.

Figure 11.1 Typical copper electrowinning tankhouse

48

As the cost of providing DC power and the size and cost of the distribution system (bus-bars)
is determined largely by the magnitude of the current, modern tankhouses have adopted the
procedure of operating the electrodes in each cell (22-60 cathodes and anodes) in parallel but
the cells in series as shown schematically in Figure 11.2 which also shows the electrolyte
distribution to the cells.

PLS manifold

Anodes
Cathodes

Spent manifold

Figure 11.2 Current and electrolyte distribution

A typical electrical contact arrangement in which cathodes of a cell are connected to the anodes
of the adjacent cell by the use of a triangular contact bar is shown in Figure 11.3
In this arrangement, the anodes of one cell are connected to the cathodes of the next and so
on. Thus, for N cells in series,
Total Voltage Vt = N x Vc
where Vc is the voltage/cell.

49

Figure 11.3 Typical arrangement of contacts between adjacent cells

If It is the total current requirement i.e. if all the electrodes were operated in parallel across the
power supply (Vt=Vc) , and Ic is the current requirement with N cells in series, then
Ic = It /N
i.e. the same total power W = Vc .It = Vt .Ic but at a reduced current which reduces the cost of
the power supply and the size and cost of the bus-bars.
Short circuiting of current between electrodes that are touching is a loss of current efficiency.
Sometimes this is the result of improper positioning of the electrodes in the cell, warped
anodes and / or starter sheets, or nodular or dendritic growth on the cathodes. Various
techniques such as the use of hand-held gaussmeters, infra-red sensors mounted on the
overhead cranes and, more recently, continuous individual cell voltage measurements can be
used to detect poorly operating cells and electrodes.
A well designed and operated tankhouse will have a minimum number of electrodes whose
current density is not close to the cell-house average. Figure 11.3 shows the distribution of
currents to cathodes in 4 cells in a modern copper plant during normal operation.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

Current, A
>700
650-700
600-650
550-600
500-550
<500

Figure 11.3 Distribution of current to

cathodes in a copper tankhouse

50

Recent modelling of the current distribution within cells using network analysis is yielding
interesting and potentially important results as shown in Figure 11.4 for 5 cells each
containing 5 cathodes. Note the higher current (5% higher than the mean) flowing
through the end cathode face due to the fact that the end anodes have only one active
face.
Relative Current Distibution for
Centre-fed Low Resistance Busbars at 300 A/sqm
10

Cell 1
D ir (%)

Cell 2

Cell 3

Cell 4

Cell 5

Figure 11.4 Simulated current distribution to cathodes in 5 adjacent cells.

Note the higher current density on the end cathodes.
The current distribution to cathodes (and anodes) within a cell can be significantly
increased during periods when cathodes are removed for stripping. Current practice is to
minimize both the overall effect on current density and the time during which the
remaining cathodes are exposed to higher current densities. Thus, the effect is shown in
Figure 11.5 for the case in which one third of the cathodes are removed for stripping.
Normal
Electrowinning
Operation
3rd
Row
320 A/m2

2nd
Row
320 A/m2

1st
Row
320 A/m2

Stripping

3rd
Row
480 A/m2

2nd
Row
480 A/m2

1st
Row
0 A/m2

Cathode
Anode

Figure 11.5 Effect of cathode stripping on current distribution in a cell.

51

Simulated current distributions in adjacent cells when half of the 10 cathodes in cell 3 are
removed are shown in Figure 11.6. Note that, because of the finite resistance of the busbars, major changes in the current distribution in one cell can have noticeable effects on
the adjacent cells in a tankhouse using the conventional Walker system.
Relative Change in Distibution on each Cathode Surface at 100 A/sqm
when Half the Cathodes are Removed from Cell 3
1.5
1.0

Cell 1

Cell 2

Cell 3

Cell 4

Cell 5

D i r (%)
0.5
0

0.5
1.0

1.5

Fig. 11.6. Simulated current distribution in adjacent cells (10 cathodes in

each) when one half of the cathodes are removed from cell 3.
A relatively recent development has been the introduction of the so-called double-contact
or equalizing bar system which allows for all cathodes and/or anodes in a cell to be in
contact with each other on both sides of the cell. It consists of a second triangular or
circular bar on which all cathodes (or anodes) rest on the opposite side from the main
busbar in each cell as shown in cross section in Figure 11.7. This system should result in a
more uniform distribution of current in that each electrode has two points of contact with
a busbar. Some results presented by the manufacturer of such systems is shown in Table
10.1 which also demonstrates that, as could be expected, the variation in current
distribution to cathodes in a cell increases as the plating cycle increases due to uneven
plating, partial shorts, bending of the cathodes and possible poor contacts.

Fig 11.7 Outukumpu Double

Contact System

52

Table 10.1 Effect of equalizing bar on current distribution.

Without Equalizing Bar
Plating time
Number of cells measured
Average current - measurement time, A/cathode, A
Standard deviation of the measurements, A

1-Day
10
507
70

4-Days
2
515
93

5-Days
2
488
93

6-Days
16
539
101

With Equalizing Bar

Plating time
Number of cells measured
Average current - measurement time, A/cathode, A
Standard deviation of the measurements, A

1-Day
10
513
74

4-Days
2
474
64

5-Days
2
471
62

6-Days
16
506
57

A photograph of an actual cell with such a system is shown in Figure 11.8. Note that the
two anodes as indicated on the left are not actually making contact with the equalizing bar
due to a small widening of the gap between adjacent cells (by about 15mm) which is
sufficient to prevent contact of the anodes with the equalizing bar.

Figure 11.8. Typical operating double contact system.

Note also the plastic balls on the surface of the electrolyte to minimize the generation of
acid mist in the tankhouse.

53

12

Copper electrorefining

In the electrorefining of copper, anodes of impure copper are suspended in an electrolyte

solution, adjacent to cathodes of pure copper. Electrical current is passed between the anodes
and cathodes, through the electrolyte, in such a way as to cause copper to dissolve from the
anodes and deposit onto the cathodes. The impurities in the anodes either do not dissolve, or
do not deposit onto the cathodes, therefore the copper deposited onto the cathodes is purer
than that of the anodes.
The reactions at the cathodes and anodes, caused by the passage of electricity, are
electrochemical in nature. The major reactions are:
At the anode: Cu = Cu2+ + 2eAt the cathode: Cu2+ + 2e- = Cu
The design of copper electro-refining plants depends on the nature of the above two reactions.
In particular, the magnitude of electrical current per unit area of electrode (anode/cathode),
and the voltage required to produce the desired current, are important factors in the capital
cost of the plant (plant size) and the operating costs (energy consumption per unit mass of
copper refined). The higher the current per unit area of electrode (i.e. current density), the
fewer the anodes and cathodes required for a given production rate, but the higher the voltage
(i.e. energy cost) required to produce the desired production rate. Of course, the current
density is also limited by purely technical factors.
In practice, not all the current passing through the system goes into the desired reactions,
therefore the mass of copper actually electro-refined (deposited onto the cathodes) is less than
the mass predicted by Faradays Laws. The portion of the total current not reacting to produce
the desired metal (in this case copper) is consumed by side reactions, for example the oxidation
of Fe2+ to Fe3+ at the anode and the reduction of Fe3+ to Fe2+ at the cathode.
12.1

Cathodes and starter sheets

The use of stainless steel cathode sheets instead of copper starter sheets is known as the Isa
process. The full copper deposit is plated onto the stainless-.steel sheets over five to nine days.
This system gives fewer short circuits, improved current efficiency and product quality, as well
as enhanced plant capacity and easier refinery management. Obviously, in this system the
copper must be removed from the stainless-steel cathode sheets and this is done by automated
machinery. This system is rapidly becoming accepted refinery practice.
The cathodes used in copper electrorefining are either copper starter sheets or stainless-steel
sheets. Starter sheets are made by electrodepositing copper onto titanium or stainless-steel
sheets (blanks). Once deposited, the copper starter sheets are stripped from the blanks, then
trimmed and flattened by machine. They are often embossed to improve their rigidity. Copper
suspension loops are fitted, and the starter sheets are hung from crossbars for insertion into the
electrorefining cells. Although the starter sheets are flattened before insertion into the
electrorefining cells, copper plating tends to cause them to warp, especially during the first few
days in the cell. Some operations remove and press or straighten the cathodes after one to two
days of electrorefining. Electrode warpage in commercial copper electrorefining causes shortcircuits which decrease current efficiency and product quality.

54

12.2

Electrolytes

Copper electrorefining electrolytes can vary significantly in impurity concentrations, depending

on the composition of the incoming anodes, which depends in turn on the source of the
smelter feed. Some features, however, are relatively standard, viz:
Copper concentration

40-45 g dm-3

Nickel concentration

10-20 g dm-3

Acid concentration

150-200 g dm-3

Inlet temperature

60-65 oC

Exit temperature

55-60 oC

The electrolyte composition is a compromise between high concentrations with higher

electrical conductivity which gives lower electrical power consumption, and avoiding
concentrations high enough to result in anode passivation. Also, excessively high electrolyte
concentrations give higher than desirable electrolyte viscosity, which results in increased solids
in suspension and therefore reduced copper product quality via increased incorporation of
impurity solids in the copper deposits. To limit the concentration of suspended solids, the
electrolyte is filtered and its suspended solid content is measured routinely. A bleed of
electrolyte is continuously removed to control the concentration of copper and other
impurities (mainly nickel and arsenic). The bleed stream is stripped of copper in liberator cells,
then subjected to evaporation prior to the crystallization of nickel sulphate and the recycle of
the remaining sulphuric acid. Other methods are known and practiced for removal of
impurities such as arsenic, antimony, and bismuth.
12.3

Current density

It is desirable, in copper electrorefining, to have the same current flowing between all anodes
and cathodes. Uniform electrode spacing, vertical hanging of anodes and cathodes, flat
cathodes, good electrolyte composition and avoidance of passivation are all aimed at this
requirement for uniform current distribution. Differing current density in a tankhouse can
cause poor product copper quality (high local convection and slime contents), decreased
current efficiency (i.e. higher energy consumption), local passivation and short circuits.
Most refineries operate at current densities between 200 and 250 A m-2. Some refineries may be
able to achieve current densities over 300 A m-2, provided they take special precautions to
avoid anode passivation and to improve electrolyte quality and to enhance electrolyte mixing.
However, there is always some hydrogen evolution even with careful control of the electrical
input to the cell, the evolution of gas not only reduces current efficiency but also causes an acid
mist above the cells. This acid mist is primarily sulphuric acid and is obviously hazardous to
health and needs to be minimised (some plants do not allow personnel to walk across the cells
without breathing apparatus), this can be partly achieved by using beads which float on the
electrolyte.
55

12.4

Anode passivation

Passivation (significant decline of the current to a particular anode) is thought to occur as a

result of the build-up of adherent, non-porous layers on the anode surface, that essentially
block the mass transport of cupric ions from the anode surface into the electrolyte. The
formation of these layers is influenced by current density, electrolyte temperature and anode
and electrolyte compositions. The most common form of anode passivation is the
precipitation of copper sulphate crystals and/or cuprous oxide on the anode surface. Copper
sulphate is precipitated when its solubility product in the electrolyte is exceeded due to limited
mass transport of cupric ions through the anode slime layer.
Thick and tenacious slimes layers, and high concentrations of sulphates (either as copper or
nickel sulphates or as free sulphuric acid) in the electrolyte stimulate this form of passivation.
Cuprous oxide (Cu2O) can be formed during anode casting with high levels of oxygen in the
copper or during electrolysis via the formation and hydrolysis of cuprous ions.
De-passivation may occur only as a result of current interruption for a period of time, increased
mixing effectiveness, current reversal for a short time, increased electrolyte temperature or
decreased electrolyte concentrations.
12.5

Deportment of anode impurities

Table 12.1 shows where the various impurities in the anodes end up after dissolution of the
copper. The most valuable impurities report to the slimes (any PGM present also report to the
slimes) which are processed to recover these metals. The elements which go into solution can
be electrowon onto the cathode or, if not actually reduced, entrained (or captured) during the
copper electrowinning and incorporated into the cathode. These impurities must be carefully
controlled to ensure that the copper meets the required specification (usually LME Grade A
where the requirement is As <5.0ppm and Sb <4.0ppm).
Table 12.1 Deportment of impurities in Cu refining
Impurity

Slimes, %

Electrolyte, %

Au

99

Ag

98

Se(Te)

98

Pb

98

Sb

60

40

As

25

75

Ni

5-40

95-60

Fe

99

56

13

Electrowinning of copper

Many of the considerations in refining apply equally well to the electrowinning of copper which
does not suffer from the drawbacks of anode passivation but has additional problems
associated with the corrosion of the lead anodes and the resulting contamination of the
cathodes. A shematic of one anode/cathode pair in an electrowinning cell is shown in Figure
13.1.
Anode of next cell

Cathode of next cell

Stainless steel
cathode

Lead alloy
anode

Copper
metal

Oxygen
H2O = 0.5O2 + 2H+ + 2e-

Cu2+ + 2e- = Cu0

Figure 13.1 Electrowinning reactions

The following table summarizes the important differences between the two operations.
Table 13.1 Typical operating parameters

Current Density, A m
Current Efficiency, %

Refining
210
97

Winning
220
90

Cell Voltage Components

Cathode Overpotential, mV
Anode Overpotential, mV
Ohmic drop in Electrolyte, mV
Ohmic drop in Hardware, mV
Reversible Voltage, V
Average Cell voltage, V
Electrical (DC) Power, kWh/kg

80
30
100
70
0
280
0.25

80
1200
100
70
900
2350
2.3

-2

The major development in the electrowinning (and refining to a lesser extent) of copper during
the past decade has been the introduction of the permanent cathode processes (ISA and Kidd).
The advantages claimed for these processes include one-step cathode production, reduced
materials handling, a better quality product and smaller tankhouse (due to closer cathode
57

spacing). The following table compares conventional practice using copper starter sheets with
permanent cathode blanks.
Table 13.2 Comparison of Cathodes
Conventional
10
87
97
35
86
170
0.41
69
26
0.36
1.35

No of Starter Cells
No of Commercial Cells
Total no of Cells
Production (t/d)
Current Efficiency (%)
Current Density (A/m2)
Power (kWh/kg)
Cobalt Conc (mg/l)
EW Labour
t/d of Cu/cell
t/d of Cu/person
13.1

Permanent
93
55
90
230
0.37
97
11
0.59
5.0

Competing Reactions

The cathode current efficiency during the electrowinning of copper is generally about 90% i.e.
about 10% of the current is consumed in the reduction of other species at the cathode. The
main contributor to this is the reduction of ferric ions produced by oxidation of iron in the
electrolyte at the anode. To a lesser extent, dissolved oxygen is also reduced at the cathode and,
even in the absence of iron in the electrolyte, the current efficiency would not exceed about 9596%. Current potential curves for the cathodic processes are shown in Figure 13.2.
Cu = Cu2+ + 2e

ia

iO2

iFe
iCu

E
3+

Fe

+ e = Fe2+

O2 + 4H+ + 4e
= 2H2O

iTotal = iCu + iFe + iO2

CE = iCu/iTotal

ic

Cu2+ + 2e = Cu

Figure 13.2 Schematic current-potential curves for the cathodic reactions in

electrowinning
58

Current efficiency (%)

Some results of the effect of iron on the current efficiency at a total current density of 280
A/m2 are shown in Figure 13.3.
100%
95%
90%
85%
80%
75%
70%
65%
60%
55%
50%
0

10

12

Iron concentration (g/L)

Figure 13.3
efficiency

Effect of iron concentration in the electrolyte on current

The ferric ions and the dissolved oxygen are reduced at their mass transport controlled rates at
the potential of the cathode. The current due to these reactions can therefore be estimated if
the mass transport coefficient is known.
13.2

Quality of Copper Cathodes

The goal of copper electrowinning is the consistent and economic production of cathodes that
are
Uniformly thick and smooth
Chemically pure
Readily stripped, handled and processed
In order to achieve this in practice, it is important to
(i)

maintain the proper electrolyte chemistry and composition, control the

electrochemical parameters (flow, mixing, temperature, current density and anode
performance), provide optimum engineering and design for physical and
mechanical conditions (alignment, cleanliness, current distribution, etc).

(ii)

establish reasonably steady state conditions and minimize system non-uniformity

(various process differences, particularly localized, are a major driving force for
uneven growth). Identify and control impurities and additives, as well as their
concentrations, that dominate the deposition process.

(iii)

recognize the potentially significant effects that the anode chemistry,

electrochemistry and electrocrystallization can have on cathode growth.

The optimum conditions that lead to a good quality cathode are generally considered to
be the following

59

(i)

The copper concentration in the spent electrolyte should be above about 35

g/L. The temperature of the electrolyte should be maintained at 45 2 oC.
An acid concentration of 150 190 g/L should also be maintained in the
electrolyte.

(ii)

From 1.0 to 2.0 g/L of iron in the electrolyte has been claimed to have a
positive effect on copper quality. The level of chloride should be maintained
at 10 to 25 ppm. At higher concentrations, chloride can have a significant
detrimental effect on the growth of the copper deposit. Above about 50 ppm,
chloride can cause pitting of the stainless steel cathodes.

(iii)

A low current density is conducive to the production of good quality copper

cathodes. The typical range of current density used in operations is 240 to 280
A/m2. However, some plants are now operating at over 300 A/m2. At this
current density, the operating envelope of all other parameters is very
restricted and their influence and impact becomes more critical. The
distribution of the current can also affect the cathode quality. This is
extremely important at higher current densities. Poor housekeeping is
normally the problem with shorts and poor dirty electrode contacts leading to
uneven current distribution.

(iv)

In electrowinning the most important contribution to mass transport is from

the oxygen bubbles that are evolved at the anode. This agitation is not evenly
distributed, with the bottom one third of the cell receiving considerably less
agitation than the top two-thirds. This problem has been overcome by the
installation of electrolyte distributors which allow the distribution of
electrolyte from ring main systems in the bottoms of the cells. The electrolyte
in flow is thereby used to agitate the critical lower area. Flowrates of 0.10 to
0.15 m3/hr/m2 of cathode are commonly used. The flow rate is generally
selected to give a maximum drop of 3 to 5 g/L in copper concentration from
feed to discharge of the cell.

(v)

The presence of suspended solids, especially those that are electronic

conductors such as PbO2 from the anodes can have a significant effect on
cathode quality. Their presence is normally associated with the formation of
rough nodular copper deposits as shown in Figure 13.4.

(a)

(b)

Figure 13.4 Nodular copper deposit (a) without additives and (b) with guar

60

The main impurities that are of importance in determining the quality of copper cathodes are
lead, sulfur and oxygen. There are several methods whereby such impurities can be
incorporated into the cathodes. The most important of these are
Co-reduction of impurity metal not applicable to almost all metal ions in solution
Occlusion of electrolyte - this is the main source of sulfur and oxygen. As shown in Figure
13.5 this is largely due to the morphology of the deposit which becomes less dense and more
porous as the current density increases. Nodular growth can also contribute to occlusion of
electrolyte.
Sulfur Incorporation

S, ppm

30
25
20
15
10
5
0
0

0.2

0.4

0.6

0.8

i/iL

Figure 13.5 Effect of current density on sulfur impurity in cathode copper.

Occlusion of suspended solids this is the main source of lead contamination.
Examples of the incorporation of suspended lead particles from anode corrosion are shown in
Figure 13.6 in which the small white spots are PbO2 particles.

Figure 13.6 Fractured surface of copper cathode showing particulate lead

dioxide
Tankhouse practice requires that the anodes be periodically removed and the anode scale
removed to minimize the spalling of the material into the electrolyte. This is shown by the data
in Figure 13.7 which shows the periodic increase in lead in the cathodes prior to each cleaning
cycle. Note the periodic variation in the iron and manganese content of the electrolyte.

61

120
100
Pb & Mn (ppm)

1.4

Cathode Pb (ppm)
Electrolyte Fe (g/L)
Electrolyte Mn (ppm)

1.2

Anodes cleaned

80

0.8

60

0.6

40

0.4

20

0.2

Fe (g/L)

140

Figure 13.7 Effect of anode cleaning on the lead content of cathodes

It is interesting to note that recent work has shown that the highest concentrations of lead (and
sulfur) in the cathodes produced with synthetic PbO2 suspended in the electrolyte occur close
to the surface as shown by the SIMS (Secondary Ion Mass Spectroscopy) results in Figure 13.8.
These observations are consistent with the data shown in Figure 13.9 which shows that, in
similar experiments, the amount of lead incorporated decreases with the thickness of the
deposit. Note the order-of-magnitude decrease in lead contamination in the presence of a
smoothing agent such as galactosol.
1 g/L of PbO2 in the
absence of Galactosol

10000

1000
800
Pb / counts

Pb / counts

8000

1 g/L of PbO2 in the presence

of galactosol (3.5 mg/L)

6000
4000
2000

600
400
200

-5

10 15 20 25 30
Depth / microns

35

-5

40

10 15 20 25 30
Depth / microns

35

40

2000

1g/L PbO2 in the absence and

presence of galactosol (3.5 mg/L)

S content/ counts

1600
1200
800
400

absence
0

presence
0

10

20

30

40

50

Depth / microns

Figure 13.8 SIMS depth profiles of lead and sulfur in copper cathodes which
also show the effect of the addition of a smoothing agent.
62

Figure 13.9. Effect of deposition time (cathode thickness) on the extent of

particulate lead (PbO2) contamination in copper cathodes in the absence of a
smoothing agent.
13.3

Additives in copper deposition

A number of additives are used in both the electrorefining and winning of copper.
Organics such as guar gum, galactosol, and chloride are used at low concentrations in the
electrolyte (less than 30 ppm) to give smooth compact deposits, via grain refining and levelling
action. (micro current distribution). The levelling nature of reagents such as glue is thought to
be due to adsorbed molecule deposition on points of high current density and mass transfer
thereby reducing the rate of deposition at these points. This is shown by the photographs in
Figure 13.4.
In copper electrowinning and refining, chloride ions are added to the electrolyte in order to
reduce the grain size of the copper crystals (moving from a BR to FT type of deposit in the
Winand diagram in Figure 5.4). The concentration is controlled in the range 10-50mg/L. It
appears that chloride is crucial in minimizing the contamination of the cathodes by lead as
shown by the data in Figure 13.10 which was obtained from small scale cathodes produced in
the presence of suspended PbO2.
4500
Concentration of Pb / ppm

4000

3925

3500
3000
2500
2000
1500
1000
500

26

24

22

25 ppm

45 ppm

55 ppm

0 ppm

Amount of chloride ion concentration

Figure 13.10. Effect of chloride ions on the contamination of copper

cathodes with particulate lead.
63

Chloride concentrations in excess of about 40-50ppm are not desirable due the enhanced
pitting corrosion of the stainless steel blanks used as permanent cathodes.
Glue or guar (galactosol) is also added as a smoothing agent. These natural product
polysaccharides have a high molecular mass and a large number of carboxyl, hydroxyl and
amine groups which give these molecules a high solubility in aqueous solutions and allow
interaction with the surface of the metal, particularly in regions of high field strength such as
nodules. Because they are added in small amounts (concentrations below 5mg/L) selective
adsorption occurs in areas of high mass transfer such as the growing tips of nodules and the
rate of deposition of copper in these areas is reduced with a resultant smoothing action.
However, these additives are subject to acid hydrolysis to produce smaller molecules that are
not as effective and therefore continual addition to the electrolyte is necessary. It is important
not to add too much guar as the selectivity for adsorption on the nodular growths will be lost..
It has become standard practice to allow the ferric ion concentration in the electrolyte to build
up to about 3 g/L in many SX/EW plants. As shown in Section 13.1, ferric ions are reduced at
the mass transport limited rate at the cathode, Because of the higher rate of mass transport to
the tips of nodules, the current due to the reduction of ferric ions will be higher at these points
and therefore the current due to the deposition of copper will be less thus reducing the rate of
growth of the nodule.
Organic surfactants are foaming agents employed to suppress the generation of acid mist
above the electrolyte in cells. Acid mist is an aerosol of acidic spent electrolyte derived from the
bursting of oxygen bubbles evolved at the anode. These bubbles are effectively trapped inside a
foam layer on the surface which allows time for the solution to drain from the surface of the
bubbles before they burst. The health and safety aspects of acid mist generation has become a
significant issue in modern electrowinning tankhouses and the use of these reagents can assist
in minimizing the effect. An alternative more recent method is the provision of hoods on the
cells which are attached to a scrubbing system that reduces the acid mist problem to negligible
proportions as shown in Figure 13.11.

Figure 13.11 Copper tankhouse with hooded cells to eliminate acid mist.
In the electrowinning of copper, cobalt ions are added to the electrolyte in concentrations
between about 50 and 100 mg/L. The role of cobalt is to reduce the rate of corrosion of the
64

anodes (see below) which, in turn, reduces the extent of contamination of the copper cathodes
by lead.
13.4

Anodes for Electrowinning

The most widely used anodes in the electrowinning of copper are alloys containing lead
and small amounts of calcium and tin. In sulfuric acid electrolytes the lead anode surface
is initially covered with non-conducting layer of PbSO4. Owing to the high oxygen
overvoltage on the anode surface, PbSO4 then transforms to a conducting PbO2 surface
which inhibits further corrosion of the underlying metal. The lead dioxide PbO2 exists in
two forms: rhombic () and tetragonal (); in which the -PbO2 forms adherent deposits
composed of large and closely packed crystals whereas, the -PbO2 deposits are
considerably less adherent and composed of poorly bonded, fine, needle-shaped crystals
It appears that initially the lead surface is passivated by a continuous lead sulphate layer.
A thin film of -PbO2 is formed on top of the sulphate layer. Further polarisation allows
oxygen to diffuse through the layer of -PbO2, leading to the formation of -PbO2 under
the -PbO2 layer.
Pb + SO 42 PbSO 4 + 2e

Eo = -0.36V

PbSO 4 + 2H 2 O - PbO 2 + H 2 SO 4 + 2H + + 2e

Eo = 1.69V

Cobalt ions are added to the electrolyte (see above) in order to reduce the rate of
corrosion of the anodes. Moreover, the addition of cobalt reduces the oxygen
overvoltage on the lead anodes as shown by the data in Figure 13.12. The mechanism of
the action of cobalt is not known with any certainty.
2.3

0 ppm
5 ppm
50 ppm
100 ppm
500 ppm

2.25

Potential (V)

2.2
2.15
2.1
2.05
2
1.95
1.9
0

500

1000

1500

2000

2500

3000

3500

4000

Time (sec)

Figure 13.12 Effect of cobalt ions on the potential of Pb-Ca-Sn anode at

300 A/m2

65

On the other hand, the presence of other metal ions such as iron and, particularly
manganese, can have a detrimental effect on the rate of corrosion of the anodes as shown
by the data in Table 13.3.
Table 13.3 Effects of metal ions on the corrosion of Pb-Ca-Sn anodes
Co
(ppm)

Mn
(ppm)

Fe
(g/L)
1
2
5
10

50
200
350
500
50
100
150
300

Corrosion rate
(g/kAh)
3.77
6.44
6.64
5.47
4.62
3.24
3.04
2.71
2.69
11.45
10.27
10.22
9.68

Current efficiency
(%)
95.7
93.1
89.2
81.0
71.0
97.2
95.5
97.3
96.6
95.9
95.2
97.0
97.3

The effect of low concentrations of manganese ions on the corrosion of the anodes is
significant in the light of much evidence from operating plants that lead contamination in
the cathodes increases when the manganese concentration increases above about 50 ppm.
Another important consequence of manganese ions in the electrolyte is the formation of
Mn(VII) and Mn(III) ions at the anode both of which are powerful oxidants which can
result in degradation of the organic solvents in a SX/EW operation. In this regard, low
concentrations of manganese can be more detrimental than higher concentrations due to
reactions such as
MnO4- + 4Mn2+ + 8H+ = 5Mn3+ + 4H2O
2MnO4- + 3Mn2+ + 2H2O = 5MnO2(s) + 4H+
which will occur at higher Mn2+ concentrations.

14

Electrowinning in Novel Cells

14.1

Packed or Fluidized Bed Cells

Consider a batch electrowinning cell, with a volume of V and a cathode area of A. Assume that
the cell is filled with a solution of copper of initial concentration C0 .
The maximum rate of deposition of copper i.e. of depletion of copper from the solution, will
be given by the mass-transport controlled rate of deposition.
Under these conditions,
-dC/dt = k.A.C/V
where k = Mass transfer coefficient (cm/s)
Integrating,
66

C = C0 exp( -k.A.t/V)
Assume that the following conditions apply
C/C0 = 0.1 i.e. 90% recovery
A = 2 m2, V = 10 m3 , k = 1.10-3 cm/s (a best case)
Substitution in the above gives,
0.1= exp( - 10-3.2.104.t/10.106)
or, t = 320 h
i.e. a cell of this type (with A/V=0.2m-1) is not suited to this application because its cathode
area/volume ratio or space/time yield is too low.
In order to increase the specific cathode surface area, the cathode is constructed using a porous
material such as graphite wool or granules (iron or steel wool or a number of steel mesh sheets
stacked together in the case of gold recovery from CIP eluates) packed into a perforated plastic
frame or mesh containing a current feeder as shown.

Figure 14.1 Packed bed cell typically used in the electrowinning of gold
Solution flows through each cathode compartment in a direction parallel to the flow of current.
Perforated metal plate or mesh is used as the anode material. The thickness of the cathode bed
is limited by the potential drop which occurs as one moves away from the anode into the bed
as shown. The thickness of the active mass-transport controlled region is determined by the
porosity of the bed, the conductivity of the solution and the current density used. This
thickness is generally of the order of 5cm.

Figure 14.2 Potential distribution

in a packed bed cell.

67

The deposition of a metal onto a packed bed electrode at a rate controlled by mass transport is
given by
C = Co exp (-L/) = Co (1-E)
where Co is the inlet concentration
C is the outlet concentration
L is the thickness of the bed in the direction of solution flow
is the characteristic length of the cell
E is the single-pass extraction of the cell
is an experimentally determined parameter which is characteristic of a particular bed and
which varies with the flow-rate ( =kU0.5, where U is the linear flow-rate)
For electrowinning of a batch of eluate( volume V) by recirculation at a volumetric flow-rate Uv
from a well-mixed tank as shown in Figure 14.3.
Figure 14.3 Recycle operation
of a packed bed cell

the following equation describes the decay of the metal concentration with time,
Ct = CI exp{-Uv(1-exp(-L/).t/V} = CI exp(-Uv.E.t/V)
where CI is the initial concentration and Ct the concentration after time t.
Thus, by determining , one can calculate the total cathode thickness(L) required to achieve a
particular recovery in a given time at a given flow-rate. Note that the product Uv.t appears in
the exponential term i.e. increasing flow-rate will decrease the time for electrowinning. This
decrease is not inversely proportional to the flow-rate however, because increases with the
square root of the flow-rate.
14.2

Forced Flow Cells

The other method for improving the space-time yield of electrolytic cells is to increase the rate
of mass transfer of the metal ions to the cathode surface which will enable a higher current
density to be achieved, thereby potentially increasing the space-time yield of the cell and also
permitting the use of more dilute electrolytes. This can be achieved by various methods, the
most common of which is increased flow of the electrolyte. Typical of this approach is the socalled EMEW cell shown in Figure 14.4. These cells have found some application in the
recovery of relatively small amounts of valuable metals, such as silver, from dilute solutions.
They are also being considered for copper removal from bleed streams in copper tankhouses.

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Figure 14.4 EMEW cell

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15
15.1

Appendix
Class Problems - EW Course

The solubility of lead (atomic mass 207) in normal Cu EW

electrolytes is about 10mg/l at 40oC. Calculate the potential of the
Pb2+/Pb couple under these conditions.
Would you expect lead to co-deposit with copper under normal EW
conditions? Why?

70

Calculate the overpotentials at the cathode and anode for a

Cu electrowinning cell operating at 300 A/m2 with unit
activity copper ions and protons. Use the data in Table 3.1.
What will the actual potentials (relative to SHE) of the
cathode and anode and the overall cell voltage be under
these conditions?

71

In the electrowinning of copper, anodes and cathodes of

dimensions about 1m x 1m are used and the anode-cathode
separation is 2cm. Calculate the resistance between the
electrodes and the voltage drop due to the electrolyte at a current
density of 300 A m-2 for an electrolyte containing 40gpl Cu as
sulfate and 170 gpl H2SO4 at 45oC .

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Calculate the current density due to the mass-transport controlled

reduction of ferric ions (5.6 g/L) on the top and bottom half of a
copper cathode assuming that the mean thickness of the diffusion
layer is 0.17mm on the top half and 0.25mm on the bottom half.
Assume that the diffusion coefficient for ferric ions in the
electrolyte is 1 x 10-9 m/s.

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The electrowinning of copper is carried out at a current density of

300 A/m2 with a cell voltage of 2.1V at a current efficiency of 90%. It
was found that the current efficiency increased to 94% if the current
density was increased to 350 A/m2 but the cell voltage increased to
2.4V. You are asked to assess with justification which option
requires the least electrical energy/unit of copper produced.

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15.2

Workshop Problems - EW Course

Workshop Problem 1
Mass Transport
The cathode current efficiency during the electrowinning of copper is generally
about 90% i.e. about 10% of the current is consumed in the reduction of other
species at the cathode. The main contributor to this is the reduction of ferric
ions produced by oxidation of iron in the electrolyte at the anode. To a lesser
extent, dissolved oxygen is also reduced at the cathode and, even in the
absence of iron in the electrolyte, the current efficiency would not exceed
about 95-96%
This workshop will show how we can estimate the current efficiency for the EW of
copper in the presence of increasing amounts of iron and also the effect of
current density on the current efficiency.
Data

Mass Transfer Coeff, cm/s

The spreadsheet on the supplied USB disk (EW Workshop 1.xls) can be used
as a template for the calculations. The following figure provides data for the effect
of the anode current density on the mass transport coefficient for reduction of
copper on the cathode of a typical EW cell operated at 40oC. The increased
mass transport at higher current densities is due to the increasing volume of
oxygen generated at the anode.

6.E-04
5.E-04
4.E-04
3.E-04
2.E-04
200

250
300
350
Current density, A/m2

400

Assume that the electrolyte is saturated with dissolved oxygen (7.5 x 10-4 M) at 1
Bar at 40oC.
Activities:
1. Enter the necessary data into the blank yellow cells in the spreadsheet. You
will need to estimate the mass transfer coefficients for ferric ions and dissolved
oxygen. (See your notes for the Table of diffusion coefficients).
2. Calculate the current due to the reduction of ferric ions at an initial
concentration of 2g/l and also due to the reduction of oxygen at the cathode
75

assuming that each reaction is mass transport controlled for a total anode current
density of 300 A/m2. Calculate the current efficiency.
3. Repeat (2) for ferric ion concentrations of 4, 6, 8 and 10 g/l. Plot the CE as a
function of the concentration of ferric ions.
4. Repeat (2) for current densities of 300 and 400 A/m2 at a ferric ion
concentration of 4g/l. Plot the CE as a function of current density.
5. The actual measured effect of ferric ions on the CE is normally greater by a
factor of up to two times than that calculated. Suggest possible reasons for this
difference.
5. If the feed solution to the cells contains equal concentrations of ferric and
ferrous ions, how would you expect the ratio of ferric to ferrous to change in the
spent electrolyte?

Workshop Problem 2
Current Distribution in Cells
The uniform distribution of current to all cathodes in a EW cell is important in
order to produce cathodes of uniform thickness and quality and also to
minimize the frequency of shorts to cathodes operating at higher than the
average current density. This problem will explore the effects of an unequal
distribution to the two faces of a cathode which has not been correctly aligned
in the cell with the result that one face is closer and the other further from the
corresponding anodes.
The spreadsheet (EW Workshop 2.xls) can be used as a template for the
calculations. The actual data required is available in relevant sections of the
notes. You will be assuming that the electrolyte in the cell contains 40 g/l copper
sulfate and 150 g/l sulfuric acid and that the cell operates with a cathode current
density of 300 A/m2 and that the cathode consists of a 1m2 blank.
Activities:
1. Obtain the necessary data from the course notes and enter into the blank
yellow cells in the spreadsheet.
2. Calculate the current to each side of the cathode assuming that the cathodeanode spacing on the one side is 50% greater than that on the opposite face. Do
this initially assuming that the primary current distribution is only applicable.
3. Repeat (2) on the basis of the secondary current distribution assuming that
both anode and cathode reactions are operating in the high-field i.e. Tafel
regions of the current-potential relationships.
4. Repeat (3) with 100 and 200g/l acid.
5. You can then plot the ratio of the current densities as a function of the mean of
the current densities.
6. What conclusions can you draw about the optimum conditions for minimizing
the effects of improper cathode blank location?

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