Professional Documents
Culture Documents
2014
{1}
{2}
The units of q/nF are C/(mole e-/mol metal x C/mole e-) = mol metal. Charge
passed at constant current is q = It. Moles of metal = M/AW where M is the mass of
metal plated and AW is the atomic weight in g/mol. Then moles metal plated is,
nM = It/nF = M/AW
{3}
Rearranging gives,
M = It AW
nF
{4}
From Faradays law it is obvious that the lower n is, the less electricity that
will be required per unit mass of metal plated. Some metal ions have more than
one oxidation state. For typical copper electrowinning the cathodic half reaction is,
Cu+2 + 2e- = Cu
(1)
Alternative leaching processes have been developed that form cuprous complexes:
Copper sulfides
air, Cl-
CuCl2-aq
(2)
(3)
which would use half the electricity. (No such process is currently commercially
applied.)
(2) Current Efficiency
The simple formula above determines mass of metal plated for a given
current and time, or vice versa. If the only cathodic (reduction) process operative is
metal ion reduction to metal, then the formula gives an accurate indication of the
mass of metal for a given current and time. However, other reduction half reactions
may also occur simultaneously. These unwanted side reactions also consume
electricity (current) and result in a lowered efficiency of use of current for metal
plating. This leads to the idea of current efficiency. Current efficiency (CE) for
metal plating then (or any electrolytic process), is the ratio of actual mass of metal
plated to the theoretical mass based on Faradays law. It is usually given in %.
CE =
{5}
100M
It AW/nF
= 100nFM
It AW
{6}
Now M is actual mass of metal plated. For instance, calculate the current efficiency
for the following conditions: 100 g of copper was plated in a copper electrolysis
experiment using a constant current of 4 A for 23 hours. What was the current
efficiency?
{7}
{8}
{9}
{10}
where Werev and we'rev are the electrical work under reversible conditions.* In
electrowinning E is negative (G > 0; E < 0); the reaction as written is not
favourable so we'rev < 0. The units of w e'rev are J/mol. As per the engineering
convention, work done on a system is negative. The symbol W e'rev represents the
work in joules. The actual applied voltage is designated Eappl. The applied voltage
opposes the thermodynamic voltage and hence it is taken to be positive. For
practical rates we require Eappl > E . The current is forced to go in the opposite
direction to the natural tendency of the cell.)
CE = 100 nFM = 100 nFnM
It AW
q
{11}
* Reversible and irreversible processes are reviewed in the next section. For now suffice
it to say that if an opposing voltage equal to E , where E < 0, (an electrolysis) is applied,
then the thermodynamic tendency is just matched or just overcome and the reaction is
exceedingly slow, i.e. reversible.
{12}
{13}
EE = 100Werev =
We
= E CE
Eappl
{14}
{15}
This is not very high. Reasons for this will be explained later.
(4) Specific Energy Consumption
This is the actual energy requirement in units of energy per unit amount of
metal plated (e.g. J/mol). The derivation above employed the energy consumption,
i.e. Eappl q.
-We = 100Eappl nM nF
CE
{16}
Divide both sides by the moles of metal (n M here) to get the specific energy
consumption in J/mol (designated -we):
-we = 100 nFEappl
CE
{17}
A more conventional unit is kilowatt-hours per tonne of metal. A kWh is 1000 watts
for 1 hour = 1000 J/sec x 3600 sec = 3.6 x 10 6 J. To convert the energy
consumption number to kWh/t metal involves only unit conversions:
-we J
1 kWh
{18}
mol
3.6 x 106 J
AW g
{19}
{20}
{21}
nM =
{22}
q CE
100nF
where nM is the moles of metal produced. Only CE% (e.g. 91.7%) of the total
charge passed goes to plate metal. The charge at constant current is q = It.
nM = It CE
100nF
{23}
Metal is plated onto both sides of a cathode starter sheet (e.g. a steel sheet in
copper electrowinning). The total plating surface area for a number N cathodes is
AcN, where Ac is the surface area per cathode sheet. Taking j as the current density
in A/m2, the current being passed is j times the total plating area, i.e. I = jA cN.
nM = jAcNt CE
100nF
{24}
i.e. j (C/sec m2) x surface area (m2) x time (sec) = charge (C). Next, rearrange to
obtain:
nM = dnM = jAcN CE
t
dt
100nF
mol/sec
{25}
AcN is the total plating surface area. This may be obtained in two ways, either using
N to be the number of cathode starter sheets with A c being the area of both sides
combined, or with N being the number of plating surfaces and A c being the surface
area of just one side. Either way is equivalent. Regardless, the fact that metal is
plated on two sides is factored in. The area of the narrow sides is negligible and
little copper plates there since the electric field is rather diffuse at the sides anyway.
In practice, edge strips may be used to prevent plating there. This makes removal
of the plated metal sheets much easier.
To get plating rate in mass per unit time, multiply dn M/dt by appropriate
conversion factors. This depends on the metal being plated since it involves the
atomic weight. For tonnes per day:
dM = dnM mol x AW g x 10-6 t x 3600 sec x 24 h
dt
dt sec
mol
g
h
d
{26}
For copper,
dMCu = dnCu mol x 63.546 g x 10-6 t x 3600
dt
dt s
mol
g
{28}
= 0.11405 mol/sec
dMCu/dt = 0.11405 x 5.49037 = 0.6262 t Cu/day
Note: the cathode sheet has dimensions of 1 m x 1 m. The plating area on one
side is 1 m2. The plating area of the whole sheet is 2 m 2; we plate on both sides.
The calculation above allows estimation of copper production based on current and
current efficiency. This aids in design of an actual EW tankhouse. The number of
cells needed to achieve a desired production per year can be readily determined.
How many cells of 60 cathodes each would be needed to achieve 50,000 t/yr of
copper production under the conditions we have been using in the calculations
above?
0.6262 t Cu/day/cell x 365 days/y x S cells = 50,000 t/y
{29}
S = 218.8
We would need 219 cells. The total number of cathode sheets that must be
employed then is 219 x 60 = 13,140. If a fully plated copper cathode is 0.5 cm
thick on average and 1 m long on each side, and given that the density of copper is
8.92 g/cm3, the average weight of a cathode would be:
100 cm x 100 cm x 0.5 cm x 8.92 g/cm3 = 44.6 kg (0.0446 t)
{30}
This means that 1.1211 x 106 sheets of copper have to be handled per year, or
3071 per day. If the current density was increased the number of cells required
could be lower. Often cathode quality issues limit the current density.
How long would it take to plate a copper cathode to a thickness of 0.5 cm?
The metal production rate equation can be rearranged to obtain time. Since the
current is constant, dM/dt is constant as well, so the mass M plated over a specified
time t equals dM/dt:
MCu = jAcN CE x 63.546 g/sec
t
100 nF
{31}
t=
{32}
100 nF MCu
sec
jAcN CE x 63.546
where MCu in g. Now Ac is the area for a single sheet (on one side), i.e. 1 m 2 in this
case. N now is 1. (We are considering the time to grow a single cathode copper
sheet.) For MCu = 44.6 kg = 44,600 g as above, plated at 200 A/m 2 with 91.7% CE:
t=
{33}
= 8.55 days
Obviously the higher the current density, the shorter the plating time.
The five relationships above are summarized in the table below.
Table 1. Summary of the Faraday's Law relationships.
M = I t AW in g
Faradays law
nF
CE = 100nFM
Current efficiency
It AW
EE = E CE
Energy efficiency
Eappl
-we = 100 nFEappl in J/mol
Specific energy consumption
CE
Metal production rate
dnM = jAcN CE in mol/s
dt
100nF
change of state (e.g. 1 mol A aq 1 mol B aq, as above) is the sum of heat flow
minus work flow, (U = q - w; work done by the system is positive by definition and
heat exiting the system is negative.) Internal energy is a state function, i.e. it
depends only on the final and initial states, not how you get from one to the other.
Then, the less heat evolved for a given change, the more work that was extracted
from that change. For a real cell, operated under real conditions, the process is
necessarily irreversible and the heat flow is greater than in the reversible case, so
the work obtainable is less. The farther from reversibility (or the more irreversible
the process), the more the heat and the less the obtainable work. Extending the
idea that reversible processes run infinitely slowly, the faster the process is run, i.e.
the more rapidly the battery is discharged, the more irreversible the process, and
the more of the energy that is lost as heat.) The reversible case defines the limiting
possibility.
Some examples of irreversible processes include:
1. Flow of heat from a hot body to a cold one
2. Water flowing downhill
3. Hydrometallurgical leaching reactions
4. The conversion of chemical energy into electrical energy in galvanic cells.
5. An electrolysis.
Once the final equilibrium state is reached the capacity of the system to do
further work is exhausted. In example 1, the two bodies reach the same
temperature, and in example 4 the battery goes dead. Real processes involve finite
changes of state with finite energy changes. There is a driving force, or potential for
the process to occur. If the change is thermodynamically favourable then the
process is spontaneous and irreversible. (Recall that for a spontaneous process, G
< 0. The Gibbs free energy function expresses the requirement that spontaneous
processes must increase the net entropy of the system plus its surroundings.) If the
process is not favourable it is not spontaneous and does not naturally tend to occur.
The reverse (opposite) process is actually favoured and naturally does tend to
occur. The non-spontaneous process can be forced to occur by input of sufficient
energy, and when this is done the real process is also irreversible.
A Review of Some Relevant Thermodynamics
Next, a refresher on some aspects of the thermodynamics related to
electrochemical cells is needed. Enthalpy is the sum of internal energy + PV, where
P = pressure and V = volume.
H = U + PV
{34}
10
{36}
where T is the absolute temperature and dS is the entropy* change of the system
(this from the definition of entropy). Under reversible conditions, the system can do
its maximum possible work, and the heat flow is the minimum possible, i.e.
-dw = -dwrev = maximum work possible
{37}
G = H TS by definition
{38}
{39}
dG = dU + d(PV) TdS
{40}
{41}
{42}
Generally, the work is comprised of pressure-volume work and non-PV work, such
as electrical, gravitational etc. (the former is of interest here). The work term is,
-dwrev = -PdV dwrev
{43}
where dwrev is the non-PV work (electrical work here) under reversible conditions.
At constant pressure,
and,
{44}
G = -w'rev
{45}
since dP = 0 (constant pressure). (The cancelling of the PdV terms is what makes
the enthalpy function convenient.) Hence the maximum non-PV work (w rev) is equal
to -G (at fixed P, T), and this is obtainable only under reversible conditions. This is
a limiting case. Electrochemical cells commonly do operate under conditions of
constant temperature and pressure. However, real cells cannot operate under truly
reversible conditions. Sometimes real cells may come moderately close.
11
{46}
12
of the system is negative. Most chemistry texts follow the latter convention.) By
definition,
G = U + PV TS = H TS
{47}
{48}
Since U2 U1 = q - w
{49}
{50}
{51}
w is the total work, including work other than pressure-volume work (PV work; e.g.
expansion of a gas against some external pressure P). For an electrochemical cell
where electrical work is also possible (by means of electrons flowing through an
external circuit),
w = w + P(V2 V1)
{52}
where w represents the electrochemical work. Substituting this into the preceding
equation yields,
or
G2 G1 = q w T(S2 S1)
{53}
G = q w - TS
{54}
{55}
{56}
which is equal to the heat flow at constant pressure. For a change of state achieved
reversibly, at constant temperature and pressure, we would have the equation,
G = qrev wrev - TS
{57}
{58}
13
{59}
{60}
This is the flow of energy as heat in a cell operated reversibly and represents the
minimum possible heat loss (again for a cell where G < 0 which does electrical
work). Real cells, operated irreversibly will generate less work and more heat.
For an electrolytic cell (G > 0; not favourable), the minimum possible work
that we can input to force a reaction to go in the unfavourable direction is again
-w'rev (< 0). To make the reaction go at a practical rate, making the process
irreversible, the actual work input will be > -w'rev.
Definitions
The cell potential is also called the EMF (electromotive force). It is the
voltage of a cell under reversible conditions (no current is flowing, or, the current is
infinitely small). It represents the driving force for electron transfer. When E > 0
the cell reaction is spontaneous. When E < 0 the reaction as written is not
spontaneous, i.e. is not favoured. (Recall that G = -nFE.) In this discussion, in
order to distinguish charge from heat flow, the charge will be symbolized as q c.
Work (in joules) = voltage (V) x charge (C). The cell potential E and the reversible
electrical work wrev have the same sign (for the engineering convention, not the SI
convention) and are related as follows,
-G = nFE = wrev = qcE
{61}
E = 0 V
(4)
Zn+2 + 2e- = Zn
E = -0.76 V
(5)
There are two possibilities. The favourable reaction may occur, for which E > 0.
Alternatively the reaction can be forced to go in the opposite direction by applying a
14
suitably high opposing voltage. This is electrolysis. The favourable reaction involves
oxidation of Zn to Zn+2 and reduction of H+ to H2. In fact there is no thermodynamic
reason why the reaction should not spontaneously occur directly on the zinc
surface, as illustrated in Figure 3 below. However, the reduction of H + on very pure
Zn is very slow, whereas it is quite rapid on Pt. Because the reduction of H + on pure
Zn is so slow, the cell can be set up with Zn metal in direct contact with H +.
Otherwise two half cells with provision for ionic conduction would be used.
(a)
(b)
15
(6)
2H+ + 2e- = H2 E = 0 V
(7)
E = 0 - (-0.76) = 0.76 V
(8)
This is really equivalent to the situation in Figure 3 (b). Since the reduction of H + on
pure Zn is slow, all that is required for the reaction to proceed at a substantial rate
is a catalyst, which is the role of Pt.
G = -nFE = -2 mol e-/mol x 96485 C/mol e- x 0.76 V
= -1.47 x 105 VC/mol = -1.47 x 105 J/mol = -147 kJ/mol
{62}
H = q - w and w = 0
{63}
Since,
{64}
All the energy is dissipated as heat. Heat flows from the system (the cell) to the
surroundings, and so by convention is negative. The process is exothermic. (If you
have ever short-circuited a battery by connecting a wire across both ends, you
know this from experience; the wire can get red hot and the rate of discharge of
the cell can get dangerously fast.) Since there is no work being extracted, the
potential difference is zero (w = 0 = Eqc. Therefore E = 0). Note that the cell in
principle is capable of manifesting a voltage E, but when short-circuited this is not
realized. Cementation reactions and corrosion processes are examples of shortcircuited cells. Any redox reaction occurring directly between reagents without
running the electron transfer through an external circuit is a short-circuited cell. So
16
is a cell where a wire is connected across the poles. Other examples include
oxidative leaching processes of sulfides and combustion reactions.
2. Open-circuit cell. The half reactions are the same as in (1). However, if the
electrical connection between the two electrodes is broken, no current flows. A
voltmeter can be used to measure the potential difference. This may employ a very
large resistance inside the meter. Then the current flow is so small that the rate of
reaction also is extremely slow. This very nearly approaches the reversible case (a
process carried out infinitely slowly). (Alternatively, an opposing voltage can be
applied until the current is zero. The opposing voltage slows the reaction until a
point where the reaction stops. At this point the opposing voltage is equal to the
cell voltage. These devices, called potentiometers, are not much in use anymore.)
Under standard conditions (298 K, PH2 = 1 atm, unit activities of the ions) the
measured potential difference is 0.76 V. This indicates the thermodynamic potential
difference, or driving force for the reaction. If the conditions were non-standard the
potential difference would differ from E, as per the Nernst equation, and this
would indicate the driving force under those conditions. In principle, open circuit
cells can be used to measure thermodynamic potentials. In practice, it is often not
so easy for many reasons.
An open circuit cell is essentially a cell working reversibly; the rate of the
reactions is infinitely slow by virtue of the open circuit. The cell voltage equals the
thermodynamic potential. The cell can do its maximum possible work. For all
practical purposes, however, we can't extract work from such a cell in a finite time.
It's of no practical use as far as obtaining electrical work. It is of use for measuring
cell potentials. For practical work we use the cell galvanically or electrolytically.
3. Galvanic cell (battery). In this case the electrodes are connected to a moderately
high resistance device that uses electrical energy as work, such as a radio. The half
reactions are the same as in (1). The reaction is favourable. The current passes at a
fairly low, but, finite rate. This might be close to reversible conditions of operation,
though it is irreversible. Hence the heat loss must be somewhat greater than the
minimum reversible process heat loss, and the work obtained must be somewhat
less than it would be under truly reversible conditions. Since the same charge is
being passed as it would be under reversible conditions (2e - per Zn+2) and the
available work is less, the cell voltage (denoted V) must be lower:
(w = V qc) < (wrev = E qc)
{65}
Therefore V < E (E is the cell voltage under reversible conditions; the maximum
possible voltage). The greater the current, the faster the process and the greater
the extent of departure from reversibility. Then the heat loss is greater and the
work that can be extracted is lower. One way to rationalize this is that as the
current gets high, the process is getting closer to operating like a short-circuited
cell, where all the energy is dissipated as heat.
The thermodynamic potential for the reaction is given by the Nernst
equation:
17
{66}
Say PH2 is kept constant at 1 atm. As the reaction proceeds [Zn +2] increases, while
aH+ decreases. The ln term thus increases as the reaction proceeds and E drops.
Eventually equilibrium is reached and no further reaction occurs. Then E goes to
zero. E then is a measure of how far away from equilibrium the system is; how
great the driving force is for chemical reaction to occur.
The process will continue until chemical equilibrium is reached, at which point
G and E for the cell both go to zero. At equilibrium there is no more driving force
for the reaction to proceed; no further change occurs. At this point the battery is
dead. All real galvanic cells operate at less than the thermodynamic limit of
efficiency. However, if the cell is discharged slowly, the efficiency approaches that of
a reversibly operated cell. This is why fuel cells are naturally quite efficient. A fuel
cell is simply a galvanic cell in which the reactants are continuously replenished,
and the products are continuously removed.
The thermodynamics can be conveniently represented on a diagram as
shown below. Recall that H is a state function, meaning that for going from a
specified initial state (e.g. the left side of reaction 8 at a given temperature,
18
qrev is the minimum possible heat flow and w rev is the maximum possible work.
Galvanic cells operate at finite rates, are irreversible in the thermodynamic sense
and exhibit larger heat losses and lesser capabilities for work; q > qrev and w' <
w'rev. In addition, the faster the cell is operated (the greater the current) the more
irreversible it is and the greater the heat flow and the less the work. The quantity
q is the difference bewteen w'rev and w':
q = qrev + q
{67}
G = -w'rev = -nFE
{68}
{69}
q = G + w' + qrev
{70}
{71}
q = -w'rev + w'
{72}
-q = w'rev - w'
{73}
Then,
The heat loss is the sum of q rev + q (which is < 0). Thus the additional heat
loss arises from inefficiency in operating the cell, relative to the limiting, reversible
case. If the cell is short-circuited no work can be extracted and all the energy
output is lost as heat. This is the other limiting case.
Another possibility for a galvanic cell is when qrev > 0. This is depicted in the
alternative diagram below.
Figure 5. Alternative summary of thermodynamic effects for galvanic and shortcircuited cells. The sign of qrev is positive to account for heat into a system being
taken to be > 0, while work done by a system is > 0. Note that the net heat flow
depends on how much work is extracted from the cell. The net heat flow is
q = qrev + q. For a galvanic cell q < 0 always; some potential work is lost as heat.
19
(9)
H2 = 2H+ + 2e-
(10)
E = -0.76 V
(11)
This is NOT favourable and will not occur naturally. To overcome this, a voltage of
>0.76 V (under standard conditions) is applied externally to force the reaction to go
as written above, i.e. Eappl > 0.76 V. The flow of electrons is reversed and so are
the electrode reactions relative to the galvanic or short-circuited cases. The H 2/H+
reaction now becomes the anode and the Zn +2/Zn process becomes the cathode.
The reaction will reach equilibrium when the thermodynamic cell voltage reaches
Eappl. Then it will stop. The thermodynamic potential for the reaction is given by the
Nernst equation:
E = E - RTln aH+2
nF aZn+2PH2
{74}
Say PH2 is fixed at 1 atm. As the reaction proceeds aH+ increases and aZn+2
decreases. Hence the log term increases and consequently E decreases (becomes
a larger negative number) as the reaction proceeds. This will continue until E and
Eappl are equal. Then the thermodynamic cell potential is just balanced by the
applied potential and there is no net potential difference between the electrodes.
The reaction stops. To make the reaction proceed further still, one would have to
increase Eappl. Under conditions of fixed external potential, the reaction rate would
decrease as the thermodynamic cell voltage decreases (because the driving force,
which is the difference between Eappl and the thermodynamic E , decreases). In
practice, electrowinning is carried out under conditions of controlled current, rather
than controlled potential, as was explained in the section on Faraday's Law
relationships. As reactants are depleted, the applied voltage must increase to
maintain the constant current. In practice, electrowinning usually takes less than
50% of the desired metal ion from the solution. The barren electrolyte after EW is
recycled to increase the metal ion tenor. Considering that E changes by,
2.303RTlog(PH2 aZn+2) = 0.02958log(PH2 aZn+2)
2F
aH+2
aH+2
{75}
even a 50% change in concentrations has only a small effect on the cell voltage.
20
Now work is being done on the cell by the surroundings; an external voltage
is applied. Then w < 0, and the work done on the cell is given by,
w = -nFEappl
{76}
where Eappl is a positive number. The work done on the cell is directly proportional
to the applied voltage. The energy changes are summarized in the diagrams below.
H = q - w
{77}
Note that w' < 0, w < w rev and -w' > -w'rev. The minimum work required to drive
(a)
(b)
21
Figure 6. Summary of thermodynamic effects for an electrolytic cell. (a) q rev > 0.
Once -w' becomes large enough excess heat is dissipated to the surroundings. Note
that q is always < 0; excess applied energy is lost as heat. (b) q rev < 0. Additional
heat over and above qrev must be dissipated to the surroundings.
the reaction against its favourable direction (backwards) to effect electrolysis is
-w'rev. In practice more electrical work is required to obtain reasonable rates;
-w' > -w'rev. The net heat is the sum:
q = qrev + q = qrev -w'rev + w'
{78}
If qrev > 0, the sign of q depends on the magnitude of w', which in turn depends on
the magnitude of Eappl (Figure 6a). Once Eappl gets large enough there is a net
heat flow from the cell into the surroundings. Practical electrowinning usually uses
Eappl >> -E (the thermodynamic cell voltage) so that heat will be evolved. If
qrev < 0 the sign of q is always negative, as indicated in Figure 6b. Referring again
to the equation,
q = G + w + TS
{79}
Substituting in,
w = -nFEappl and w'rev = -nFE
{80}
then,
q = -nFE - nFEappl + qrev
{81}
{82}
<0
>0
When E = Eappl q = qrev, as we would expect; the applied voltage then just
matches E and the cell operates reversibly. As Eappl exceeds E then excess heat
begins to be evolved.
This discussion assumed an isothermal system. For an actual industrial cell
the electrolyte temperature will rise and reach some steady state (although it may
fluctuate with environmental conditions). There will be heat loss to the
surroundings, but also heating of the electrolyte. Depending on the metal being
electrowon, excess heat may need to be deliberately withdrawn by heat
exchangers. The temperature of the solution will depend on the heat generated,
loss to surroundings and the heat capacity of the solution.
Electrical work is supplied to the cell in order to overcome the cell's natural
thermodynamic tendency. Some of that supplied energy does work on the cell,
some of it ends up as heat. Some of the supplied work energy results in an increase
22
in chemical potential energy. This is the net effect of breaking bonds (e.g. H-H
bonds and Zn-O bonds in [Zn(H2O)6]+2, and forming new ones (e.g. Zn-Zn metalmetal bonds and H-O bonds in H 3O+) and, finally, changes in electrostatic
interactions in the solution due to changes in composition ([H +] increases; [Zn+2]
decreases). Electrostatic interactions involve charged ions (Zn +2, H3O+, SO42-) and
dipoles (such as partial charge separation in H-O-H, the oxygen being more
electronegative and developing a negative charge; the hydrogens having a positive
charge).
Rates of Electron Transfer and the Effects of an Applied Voltage
The rate of metal plating is directly proportional to the current through the
cell, since,
I = C/sec moles e-/sec moles Cu+2/sec reacted, etc.
{83}
In electrowinning we set the current and allow the voltage to adjust accordingly (as
governed by V = IR). Thus the higher the current, the higher the applied voltage
must be. When the applied voltage precisely matches the thermodynamic cell
voltage, Eappl = -E, the cell operates reversibly and the reaction is infinitely slow.
When Eappl > -E the reaction proceeds at a finite rate, and the greater the
difference the greater the rate.
Electrode polarity
For a spontaneous reaction electrons flow from (-) to (+); repelled from the
negative electrode and attracted to the positive one. Hence the cathode is positively
polarized and the anode is negative. This accords with the fact that the
thermodynamic cell voltage is positive,
E = Ecathode - Eanode > 0
{84}
23
M+2 + 2e- = M
(cathode)
(12)
(13)
(overall reaction)
(14)
(15)
E = 0.34 V
(16)
The oxidation half reaction is the reverse of the oxygen reduction half reaction, i.e.,
0.5O2 + 2e- + 2H+ = H2O
Then E = 0.34 - 1.23 V = -0.89 V
E = 1.23 V
(17)
{85}
24
half cell.) At this point a minute change in potential can reverse the direction of the
half reaction (again, consistent with reversible behaviour). For the upper branch the
oxidation occurs, e.g.
M s = Mn+ + ne-
(18)
For the lower branch the reduction half reaction occurs, e.g.
Mn+ + ne- = M s
(19)
It all depends on how the electrode is polarized (how the external potential is
applied). Consider the cathodic branch. As the potential is decreased M n+ is
reduced. At first a substantial increase in reduction current results from relatively
small decreases in applied voltage. Eventually a nearly linear region occurs, where
logI is virtually linear with applied potential. This is called the Tafel region. Its slope
is directly proportional to n, the number of electrons/mol of metal plated. (The form
of the curves is well understood from electrochemical theory, but that is beyond the
scope of this introduction.) The curve indicates that to obtain higher currents,
higher voltages, beyond the reversible value E, are needed.
The overpotential
This leads to the idea of the overpotential. Overpotential (or overvoltage) is
the additional potential needed beyond the thermodynamic potential E required to
make the half reaction go at the desired rate. It is given the symbol . As indicated
earlier, the value of n will have a direct effect on how big the overvoltage is. For a
given n value (2 for EW involving Cu+2, Ni+2, Co+2 or Zn+2), the shapes of the curves
are often quite similar (there are subtle differences). However, what really matters
is where the curves lie horizontally. This is illustrated in the figure below. The
reduction of Cu+2 on Cu is considerably faster than the reduction of Ni +2 onto Ni.
This appears as a shift of the Ni +2/Ni curve further to the left (to lower currents)
relative to Cu+2/Cu. As a result, at a given current Ni+2/Ni is greater than Cu+2/Cu. This
has implications for the energy consumption in electrowinning of the two metals. At
25
Loss of water molecules may occur in concert with electron transfer. Each of these
processes contributes to the overpotential; they all have an activation barrier, or
energy hurdle that must be overcome. Sometimes one of these steps can be a
major contributor to the overpotential.
26
(20)
E = -1.46 V
(21)
(22)
27
(anode)
(23)
(24)
Co+3 is a powerful oxidant and rapidly oxidizes water. It also lessens anode
corrosion and improves stability of the PbO2 layer. However, cobalt is expensive. It
is added at 100-200 mg/L, beyond which it has little beneficial effect.
Resistance losses
Conductors that carry electricity to the electrodes have an intrinsically low
resistance. However, these extend over the length of the tankhouse and overall the
resistance is enough to cause a moderate voltage drop. This is lost as heat.
Likewise, contact between anodes and the current distribution conductors (busbars)
and between cathode sheets and the busbars also has a resistance loss (contact
resistance). This is necessary since anodes and cathodes must be removed (anodes
in order to be replaced, cathodes for Cu metal harvesting). The other substantial
resistance in the circuit is the solution resistance. In solution the current is carried
by migration of ions. This allows for a complete circuit, without which there would
be no current. Cations move towards the cathode (negatively polarized) and anions
move toward the anode (positively polarized). Thus electrolyte conductivity is an
important technical consideration in EW.
Ions in solution are capable of conducting electricity. (This was one of the key
observations that lead scientists to conclude that some compounds were comprised
of discrete cations and anions.) A strong electrolyte is a salt that is soluble in water
28
and which fully dissociates into ions. Ions vary in their ability to conduct electricity
(per unit concentration). The hydrogen ion, H +, is by far the best conductor,
followed by OH-, then other cations. H+ is at least 3 times more conducting (per unit
concentration) than other cations*. Thus the presence of H 2SO4 in the electrolyte is
quite
beneficial.
Copper
EW
electrolytes
contain
on
the
* The reason is believed to be due to the "proton jump" mechanism. H + is present as H3O+.
An H+ in an H3O+ ion can "jump" to a neighbouring water molecule as shown below. This
allows it to move through solution much more rapidly than the diffusion or migration of
other ions. The same mechanism may be in effect for OH -, though it is somewhat less
effective, as indicated by its lower conductance.
order of 180 g/L H 2SO4. Much beyond this and corrosion of the steel starter sheets
and other parts of the plant becomes problematic.
EW is operated at constant current, so based on Ohm's law the voltage drops
due to resistance losses can be summed up:
VIR = IRi
{86}
The resistance of a resistor is a function of its geometry and its inherent resistivity
(the resistance of a standard geometry). The longer the distance through which the
electrons (or ions) must travel, the greater the total resistance; R L where L =
length. The greater the cross sectional area of the resistor, the more current it can
support (more pathways for electrons/ions to move through). Hence R 1/A where
A is the cross sectional area. Then,
R L/A
{87}
R = L/A
{88}
and
where = resistivity. This is illustrated in the figure below. Thus in EW large surface
area electrodes are used with a minimum practical spacing between cathodes and
anodes. Limitations on these features are discussed later. Clearly the lower the
resistivity the better. Thus a more concentrated solution of ions, and where feasible,
high concentrations of H+ are desirable. In electrowinning of divalent metal ions
from aqueous solution there is a complicating factor and that is ion pairing. This
essentially the formation of a complex, e.g.
M+2aq + SO42-aq = MSO4 aq
(25)
The extent to which this happens depends on the metal ion, temperature and pH;
recall that SO42- is also a weak base and may form HSO4- as well. A neutral ion pair
does not contribute significantly to the conductivity of the solution. Some example
29
30
{89}
The voltage drop across the resistance is V = IR. For a 300 A/m 2 current density,
0.000568 x 1.2 m2 plating area x 300 A/m2 = 0.204 V
{90}
{91}
-E ~ 0.9 V
Anodic overpotential (A) ~ 0.5 V (depends on current density)
Cathodic overpotential (C) ~ 0.1 V (depends on current density)
IRi ~ 0.5-0.6 V (depends on current); solution resistance ~0.3 V and
i
31
polarization curves start to approach infinite slope (tend toward vertical lines). As
metal ion is plated, the concentration drops near the surface, relative to the bulk
concentration. This creates a concentration gradient, which induces mass transport
of Mn+ towards the cathode. The greater the plating rate, the bigger the
concentration drop, i.e. the lower the concentration at the surface. This is illustrated
in the figure below. At some critical current density the concentration of metal ion
at the surface goes to zero. This is the diffusion limited current and represents the
maximum current that can be sustained under the given conditions. At this point
the polarization curve approaches infinite slope. Further increases in current cannot
be sustained by Mn+ reduction. Then the next available half reaction will begin to
occur. Reduction of H+ to H2 may then occur, for which E = -1.23 V. An increase in
the applied voltage then would also necessarily occur (at constant current). This
wastes electricity and would never be attempted in a normal electrowinning
situation. For copper EW the diffusion limited current density is about 500 A/m 2
[5].
Figure 11. Schematic illustration of concentration profiles for a metal ion being
plated at an electrode surface. Distance is measured from the cathode surface. The
dashed line represents the boundary layer thickness.
In practice significantly lower current densities are employed for conventional
EW. This is related to a practical limitation. At very high plating rates the copper
atoms deposited on the cathode surface do not have time to migrate to a suitable
crystallographic site. The net result is that large numbers of new crystals form on
the surface, rather than growing existing crystal faces. This makes for very crumbly
deposits that adhere very weakly to the cathode surface, making cathode
harvesting difficult and costly. Fine grained copper particles would spall off the
cathode and have to be collected, filtered and washed. At lower, but still too high
plating rates too many crystals are still forming; the deposit may be more
adherent, but it will be porous as crystals grow together rapidly and trap solution
between their faces. This will increase the sulfur (from electrolyte sulfate), oxygen
(from water, etc.), iron, etc. impurities content in the cathodes and make them offspec. Thus in conventional copper EW maximum current densities are about 350
A/m2 [6].
32
The 500 A/m2 limiting current density is for a solution without intentional
agitation. The vertical line in Figure 11 demarcates the point closest to the
electrode surface where the solution metal ion concentration is equal to the bulk
solution concentration. This is called the boundary layer. If the boundary layer is
made thinner by agitation then the concentration gradient steepens and higher
limiting (and practical) current densities are possible. However this requires energy.
A typical Cu EW tankhouse may have several hundred cells, each with as many as
60 cathodes and 61 anodes, closely spaced together. Agitation then becomes
difficult. However, if electrolyte is directed up between cathodes and anodes using a
header, this can impart some additional agitation allowing current densities to be at
the higher end of the practical range. The minimum thickness of the boundary layer
is about 0.01 mm, which requires intensive agitation [7] and is not achieved in EW.
There are two features in an EW cell that result in a measure of natural
agitation (actually convection) [5]. At the anode surface oxygen gas is evolved.
This gas pushes up solution as it rises. The bubbles accumulate at the surface
before rupture. Overall this displaces solution in an upward motion in the vicinity of
the anode. At the electrode surface Cu +2 is depleted, lowering the [Cu +2] and
decreasing the solution density. This causes solution to naturally rise near the
surface of the cathode. The net result is two counter-rotating loops, as shown in the
figure below, which also helps to thin the boundary layer near the cathode surface.
The boundary layer thickness achieved by this natural convection is about 0.1-0.2
mm [7]. Directing electrolyte up between electrodes using a header further thins
the boundary layer, though not to the limit of ~0.01 mm.
33
deposit. However, deposits are polycrystalline and surface roughness will eventually
develop. Then there are high and low spots on the surface.
Electric field lines tend to converge at points and diverge at depressions. This
leads to the situation shown in the diagram below. This makes the tips grow faster
and the depressions grow slower, further increasing surface roughness and
promoting growth of protrusions. Further, the high points are closer to the anode
and the depressions are further away, decreasing the IR voltage drop due to
solution resistance for the high points and increasing it for the depressions. Finally,
high points extend out into the boundary layer where the [M n+] is higher, making
electroplating easier. All totaled these effects can result in more rapidly growing
protrusions. As these extend further out from the surface their growth rate
increases. Then a polycrystalline agglomeration of copper called a dendrite will
extend out towards the anode, eventually making contact and causing a shortcircuit. At this point all the electrical energy in the cell is lost as heat. The current
follows the path of least resistance through the short circuit, rather than through
the solution to plate copper. This in part acts to limit how close cathodes and
anodes can be to each other.
34
protrusions being the most active sites, as indicated above, are most rapidly
oxidized, dissolving them. This effectively prevents growth of protrusions on the
cathode surface. Copper metal will plate on the lead electrode, briefly, but this will
again be completely oxidized off. The duration of the polarity switch is brief. This
may obviate the need for addition of leveling agents and associated costs, however,
it does cost electricity.
Copper Electrowinning Practice
Specifications
LME (London
specifications:
Metals
Exchange)
grade
copper
has
the
following
Pb < 5 ppm
S < 15 ppm
Other impurities <49 ppm
Cu >99.993%
A major source of sulfur impurity is sulfate from occluded electrolyte.
Cells and hardware
A diagram depicting a simplified cell is shown below in Figure 14. Cathodes
and anodes are connected in a parallel arrangement. Cathodes are interleaved
between pairs of anodes. A cell will have n cathodes and n +1 anodes. Then metal
may be plated onto both sides of every cathode, making the most of the available
plating surface area. A typical Cu EW cell will have up to 60 cathodes and 61
anodes. Cathode copper is often plated onto stainless steel blanks or starter sheets,
usually ~3 mm thick and 1 m X 1-1.2 m surface dimensions [6]. Stainless steel is
used to minimize corrosion. Sometimes copper starter sheets are used instead.
These are plated separately and are 0.5-1 mm thick. The starter sheets are
removed from a cathode substrate (such as titanium, to which copper adheres very
weakly) and placed into the main EW cells. A schematic illustration of a cell is
shown in Figure 15 below.
Cell dimensions are on the order of 6 m long x 1.4 m deep by 1.25 m wide
[9], with some variation. Long conductive bars called busbars conduct electricity to
the electrodes. Previously the electrolytic cells were made of concrete and had to be
lined to prevent corrosion. PVC was a common liner. Modern cells tend to be made
35
36
37
Iron enters the electrolyte from solvent extraction. In part this arises from
chemical absorption of Fe+3 by the hydroxyoxime extractants, and in part it comes
from entrainment of aqueous phase in the loaded organic. In a good plant the ratio
of Cu:Fe entering the electrolyte is 1000:1 on a mass basis. Iron up to a point has
some beneficial effects. It helps to promote a smooth copper deposit [14].
However, iron also lowers current efficiency. Ferric is reduced to ferrous at the
cathode and ferrous is oxidized back to ferric at the anode. Thus Fe +3/+2 cycles back
and forth and consumes current, lowering copper plating current efficiency. This is a
major source of current losses in copper EW. Up to about 3 g/L iron appears to
provide a good balance between promoting smooth Cu deposits and unduly
lowering current efficiency [8].
Chloride at 30-40 mg/L promotes smooth copper deposits [15]. Excess
chloride is harmful as it promotes corrosion of the steel cathode blanks.
Manganese may enter the electrolyte from solvent extraction by entrainment
of aqueous solution in the loaded organic if the PLS is high in manganese. This can
cause various problems in EW. Mn+2 can be oxidized at the anode to form MnO4-:
Mn+2 + 4H2O = MnO4- + 8H+ + 5e-
(26)
Permanganate is a powerful oxidant that can oxidize organic extractant and solvent.
It can also oxidize ferrous to ferric. In either process solid MnO 2 may form:
MnO4- + 3Fe+2 + 4H+ = MnO2 + 3Fe+3 + 2H2O (27)
Manganese dioxide is itself a strong oxidant. In addition the fine particles may foul
cathodes and cause crud formation in the stripping operation of SX [16].
Plant operations
Copper is usually plated to a thickness of about 5 mm (40-60 kg each) over
the course of 5-10 days. Much beyond this thickness and the mass becomes too
great and the cathode may dislodge from the steel sheet under its own weight. (It
is important that the copper not adhere too strongly to the cathode substrate,
otherwise it would be too difficult to remove.) Copper plated onto copper starter
sheets is plated to about 100 kg of mass. An average annual production rate is
50,000 tonnes per year. The largest plants produce about 100,000 t/y. Current
efficiency is typically 85% - 95% . Typical energy consumptions are 1900-2000
kWh/t Cu [6,9]. Figure 16 shows photographs of a modern EW tankhouse.
Either 1/3 or 1/2 of the cathodes are harvested from a cell at any given time.
(Hence the number of cathodes per cell must be evenly divisible by three or two.)
The rest remain in the cell so that it can keep operating [9] (called live stripping).
Cathodes are mechanically stripped from the steel sheets.
38
Cells are operated at 45-50C solution temperature [8]. This arises in part
from the electrical resistance heating directly from the EW process. The electrolyte
heated by the waste heat from electrolysis (solution resistance) is used to preheat
incoming electrolyte [10]. Good control of temperature is important for obtaining
smooth, dense deposits (fine-grained) [6,10]. It may be necessary to cool the lean
electrolyte returning to stripping to minimize organic degradation reactions [12].
Oxygen evolution at the anodes forms an acid mist when the gas breaks the
surface. This is corrosive and toxic and much effort goes into controlling it. It also is
a small loss of copper values. Control measures include polyethylene balls on top of
the surface to promote coalescence, surfactants that produce a foam layer and
prevent mist escaping and very good cross ventilation.
In many older plants electrolyte was introduced at one end of a cell and
exited from the other without any deliberate agitation. Sometimes poor quality
(rough) cathode deposits were formed. It was found that introducing the electrolyte
via a distribution manifold led to consistently better cathode quality with the added
39
(a)
(b)
Figure 16 [17]. (a) A copper electrowinning tankhouse. This example uses steel
starter sheets. Each parallel bank of electrodes is a cell. Openings along the right
wall are for fans for ventilation. Notice that the tankhouse accommodates two
parallel rows of cells. (b) An illustration of live stripping where a fraction of the
cathodes are removed and electrowinning continues in the cell.
40
advantage of allowing higher current densities (around 320 A/m 2 at the plant where
this was initiated) [5]. The manifold directs electrolyte flow upwards between the
electrodes from all across the bottom of the cell. This is illustrated in Figure 17
below. A typical good flow rate is 0.12 m 3/h/m2 of plating area (number of cathode
faces x area per face) [5,8]. The maximum is about 0.14 m 3/h/m2 [6] (too high
and PbO2 particles can stay suspended). If the electrolyte flow into the cells from
SX is too low to sustain this then additional recirculation pumps may be needed.
Roughly half of the worlds EW plants in 1999 had electrolyte inlet manifolds [13].
Strips or moldings or wax are placed on the edges of the cathodes to prevent
copper plating on the edges [5]. Plating on the edges would bind the cathodes on
each face together, making cathode stripping difficult. Uneven current distribution
at the edges produces dendritic growths and this copper is not readily recovered.
Spacers are also used to keep anodes and cathodes from coming into physical
contact. Another means of preventing contact is anode buttons [12]. These may be
made of PVC and attached to anodes at the corners and in the middle. Spacers on
various sorts keep a sufficient gap between anodes and cathodes so that exfoliating
PbO2 does not as readily come in contact with the cathodes [9].
41
As mentioned, in a good plant the Cu:Fe ratio entering the electrolyte from
SX is 1000:1, i.e. the concentration of iron in the electrolyte is 1/1000 that of the
copper, which is very good selectivity. If we take as an example 150 t/day copper
production (54,750 t/year) the iron entering the electrolyte is 0.15 t/day. If the iron
concentration that can be tolerated in the electrolyte is 2 kg/m 3 the bleed rate can
be calculated:
(0.15 t Fe/day x 1000 kg/t) / 2 kg Fe / m3 = 75 m3/day = 3.125 m3/hr
{92}
For instance, consider a 50,000 t/yr copper plant with Cu from SX = 10 g/L
(difference between rich electrolyte and lean electrolyte [Cu +2]). The electrolyte
flow rate then through EW is 571 m 3/hr. The bleed rate then represents only about
0.55% of the electrolyte. Obviously this should be kept to a minimum. The higher
the iron content that enters EW, the higher the bleed rate must be. Complete
removal from the electrolyte by bleeding is not feasible; then the whole electrolyte
would have to be treated. Then too a little iron has beneficial effects on cathode
quality.
The bleeding process necessarily removes cobalt from the electrolyte. Since
cobalt is quite expensive this adds a significant cost. Obviously, again, it is
important to keep the bleed stream flow to a minimum. This is best achieved by
having a very well operated SX plant to keep the Cu:Fe ratio high.
The bleed solution may be treated in a number of ways. It can be returned to
leaching or to solvent extraction loading. The acid concentration is quite high, so it
may have a mildly negative effect on extraction. Where iron, nitrate or chloride are
at high levels in the PLS, the loaded organic may have to be treated to lower the
impurities concentrations [8]. Then another stage is added in SX prior to stripping.
This is called scrubbing [18]. High copper and somewhat higher acid than in the
PLS can displace iron and with it Cl - or NO3-. Some of the bleed (diluted) can be
used for this purpose.
An ion exchange process for iron removal (ferric only) from EW electrolytes is
also available [19]. The resin selectively removes Fe+3. Once the resin capacity is
saturated the resin is stripped using a Cu +2/Cu+/H2SO4 solution; then the resin can
be reused. The great advantage is that no cobalt is lost from the electrolyte.
Plant configuration and electrolyte storage
Rich electrolyte from SX goes into an electrolyte storage tank. The flows to
and from this tank are shown in the figure below. It is common practice to split the
lean electrolyte flow between storage and return to SX [6]. This is necessary
because the change in copper concentration between rich and lean electrolytes may
be greater than the change in copper concentration between the inlet and outlet of
the cells. Note that electrolyte makes one pass through the cells and then is
returned to stripping as lean electrolyte.
42
{93}
(mass per unit time / mass per unit volume). The copper production rate from
equation {25} and equation {26} is:
dMCu = (j CE)(Ac N S) mol x 63.546 g x 10-3 kg x 3600 sec
dt
100nF
sec
mol
g
h
{94}
43
{95}
Figure 18. Schematic of flows between SX and EW and how electrolyte storage is
used. The [Cu+2]t is such that after EW the electrolyte [Cu +2] = lean electrolyte
[Cu+2]. Some of this returns to stripping, and some to the tank. This allows for
[Cu+2]stripping to be > [Cu+2]EW, and [Cu+2]R to be > [Cu+2]t into EW.
where Ac is the total plating area per sheet (both sides), S is the number of cells,
and values for j, CE, Ac, N and S are to be chosen. Similarly, the flow rate to the
cells, E, is given by the copper production rate divided by the change in copper
concentration across each cell:
E = 1.185499 x 10-5 (j CE)(Ac N S)
[Cu+2]tL
{96}
Ideally, the flow rate E should be such that the specific flow rate is
0.12-0.14 m3/h/m2 plating area. The total plating area is Ac N S. Then,
fs =
E
= 0.12 (or a similar value)
Ac N S
{97}
{98}
{99}
0.12
44
Take as an example j = 300 A/m2 and CE = 95%. Then for each cell,
[Cu+2]tL = 1.185499 x 10-5 x 300 x 95 = 2.816 kg/m3
{100}
0.12
If fs is smaller, then the concentration change will be larger (lower flow, longer
residence time for Cu+2 to be depleted). The mass balance for copper in Figure 18
is:
dMCu = As([Cu+2]R [Cu+2]L) = E([Cu+2]t [Cu+2]L)
{101}
dt
Hence, E = As [Cu+2]strip
{102}
[Cu ]tL
+2
= 2027.22 m3/h
{103}
E
Ac N fs
2027.22 m3/h
2 m2 x 60 x 0.12 m3/m2/h
= 140.8
{104}
There will be 141 cells in use. In a real tankhouse, there will be more cells in order
to allow for downtime, maintenance and cleaning. (Typically the tankhouse is split
in two, with a central cathode harvesting area. Then a tankhouse will have an even
number of cells.) The nominal copper production rate will be:
1.185499 x 10-5 x 300 x 95 x 2 x 60 x 141 kg/h
= 11433.2 kg/h = 50,078 t/y
{105}
{106}
45
The strip [Cu+2] is 15 g/L (as specified) and the [Cu+2] from the tank to the cells is
32.8 g/L.
Higher current efficiency, higher current density and higher cathode surface
area increase the copper plating rate in the cells. This necessitates a higher
circulation rate through the cells (E). The lower the copper concentration drop
across the cell, the higher the specific flow rate must be, and this too requires a
higher rate of flow of electrolyte to the cells. However, there is a limit to how high
the specific flow rate can be; too high and spalling PbO 2 particles from the anodes
may remain suspended in solution longer and contaminate the cathodes. Higher
flow rates also incur greater cost for pumping. Sometimes there are two electrolyte
storage tanks. Electrolyte clean-up processes may be conducted on solution flowing
from the first tank (e.g. column flotation to remove entrained organic) [16]. The
lean electrolyte should probably not have <30 g/L copper. A high concentration is
needed to allow for good quality copper plating at high current density.
Recent developments
Dimensionally stable anodes (DSA) have been in development for many
years. As mentioned previously, these are composed of a titanium substrate coated
with platinum-group metal oxides. They dramatically lower the oxygen evolution
overpotential, which in turn lowers the applied voltage, and results in cost savings
in energy utilization. Of course, the coatings are expensive. Nevertheless, the cost
savings in energy consumption appear to more than compensate for the cost. Thus,
there has been a move towards adopting DSA's into EW plants [20,21]. These
anodes do not required CoSO 4 addition either and labour and down time to clean
lead corrosion sludge out of cells is no longer necessary, both of which are cost
savings. Removing lead metal and compounds from the plant also improves worker
health and safety.
Current densities of up to 450 A/m2 are being employed in some modern
plants [21]. However, this will tend to produce rough, nodular deposits with
consequent increase in short circuits and loss of current and energy efficiency. What
is required is a decrease in the boundary layer thickness to steepen the Cu +2
concentration gradient and increase the limiting current density. (Recall that
practical current densities are roughly 2/3 of the limiting current density.) Thus air
sparging of the electrolyte in the cells is also practiced to improve mass transport of
Cu+2 to the cathode surfaces. Another problem is that traditional additives used to
promote smooth plating (guar derivatives) begin to break down more rapidly as
current density begins to exceed 300 A/m 2. This has necessitated development of
new, synthetic additives. Maintaining evenly spaced and parallel cathodes and
anodes is also increasingly important as current density increases.
There has been a move to add hoods or covers to copper EW cells [21].
These have been in use for many years in nickel EW plants where chlorine gas
evolution occurs at the anodes. The gas is much too toxic to allow it to escape into
the tankhouse and the atmosphere; it is also captured for use in leaching
operations. In copper EW hoods are starting to be used to prevent acid mist
46
accumulation in the tankhouse. This becomes all the more important at higher
current densities and with air sparging. It obviates the need for foaming agents to
reduce acid mist. Mists are directed to scrubbers. However, it also prevents manual
inspection of the cells to look for problems. New types of sensors (such as online
monitoring of cell temperatures and voltages) are needed to detect short circuits.
Electrowinning other Metals
Figure 19 shows potential/molal ion activity relationships. These E values are
essentially plots of E for the half reactions relative to the standard hydrogen
electrode (as per the Nernst equation) versus ion activity (on the molal scale). The
values at the right hand axis are E values for the various metal ion reductions
(where a = 1 m):
Mn+ + ne- M
(28)
{107}
Note again that orders of magnitude change are needed in ionic activities to effect
large changes in E. In electrowinning it is desirable to have high electrolyte
concentrations to maintain high energy efficiency (lower applied voltages). From
equation {107} as the metal ion concentration drops, E Mn+/M also decreases, and E
47
Figure 19. Potential-ionic activity relationships for several metal ions and H +/H2 on
Pt and O2/H2O on Pt at 25C.
becomes a bigger negative number (Eappl has to increase):
E = EMn+/M - EO2/H2O; EO2/H2O is near 1.23 V
{108}
* But, why then can aluminum be put in contact with water without noticeable effect?
Because of a very strong, adherent oxide coating that forms on the Al surface and protects
it from corrosion. This is another case of kinetic stabilization, making the thermodynamically
favourable process very slow. In a sufficiently acidic or basic solution, that oxide coating
gets broken down, and aluminum corrodes. The same considerations apply to titanium
48
(ETi+2/Ti = -1.6 V), which also forms a stable TiO 2 layer on its surface. This layer is stable in
an acidic and oxidizing environment, but degrades under reducing conditions.
Figure 20. Plots of log (exchange current density) for H + reduction vs. atomic
number. See text for explanation of exchange current. Data from [22].
intersection of the Tafel regions in Figure 21. The system just described is at
equilibrium, but equilibrium is a dynamic situation; reaction is still occurring, but
the forward and backward rates are identical. In essence, a higher J o means that
the overvoltage for the hydrogen evolution half reaction is smaller.*
Note the enormous range of current densities for the H +/H2 exchange current
density. They range from about 10 A/m 2 to 5 x 10-9 A/m2. This spans almost 12
orders of magnitude! Platinum has the highest exchange current density. It is a
very good catalyst for promoting hydrogen evolution. (This is why fuel cells have
used platinum electrodes; unfortunately it makes the technology very expensive.
Much research has gone into searching for alternative electrode materials that are
cheaper. Rhenium has a very similar Jo to Pt, but it is even more expensive.)
* There are correlations that provide something of an explanation for the variation in
exchange current densities. For instance, the exchange current densities can be at least
partially correlated with the strength of the metal-hydrogen bond. To make sense of this,
consider the nature of the H+ reduction process on a metal surface. H+ may adsorb onto the
surface, then accept an electron. This forms an adsorbed H atom. Two of these H atoms
49
must then combine to form H2 gas. If the metal-hydrogen bond is very weak, this inhibits
the electron transfer; a high-energy intermediate state (adsorbed H) involves a highly
endothermic reaction that is not very favourable. If the metal-hydrogen bond is fairly
strong, then the electron transfer is favourable. But if the metal-hydrogen bond is very
strong, then the formation of H2 is inhibited, and again this would slow the overall reaction.
Figure 21. Extrapolation of linear Tafel region lines to obtain the exchange current
density, Log Jo. The lines usually meet near E, the thermodynamic half reaction
potential. At this point the anodic and cathodic currents are identical. Both half
reactions proceed at this same rate so that there is no net change in composition.
Consider the example of the Zn +2/Zn couple. EZn+2/Zn is -0.76 V, which is well
below H+/H2. This is illustrated from the Eh-pH diagram in Figure 22. At all pH
where Zn+2 can predominate H2 evolution is the thermodynamically favoured
process. Beyond pH ~6.2 Zn+2 is no longer dominant, but rather solid ZnO is. But,
the rate of hydrogen evolution on pure Zn is very slow (J o = 3.2 x 10-7 A/m2) which
indicates a high overvoltage for H2 evolution. Thus it is practically feasible to
electrowin zinc metal from ZnSO 4 solution. The rate of Zn plating is much greater
and outruns the much more thermodynamically favourable, but much slower H +
reduction. Indeed, Zn EW is practiced from quite acidic solutions containing on the
order of 100 g/L H2SO4. (This helps with conductivity of the electrolyte and also is
important for the leaching process, which uses acid generated in EW.) This same
phenomenon allows Mn EW as well, albeit with at best about 60% current
efficiency, the rest going to make H2. And in this case high acidity cannot be
tolerated. The solution must have a relatively high pH, though not so high as to
precipitate an Mn(II) hydrolysis product, Mn(OH)2.
Purity of the electrolyte is a critical issue in Zn EW. Small amounts of Co +2,
Ni , etc. will readily deposit the parent metals on the zinc surface; E Ni+2/Ni and
+2
50
ECo+2/Co > EZn+2/Zn. Then regions of say Co metal form on the zinc surface. The rate
of H2 evolution on Co and Ni is quite high, so now hydrogen evolution has a site on
the Zn cathode surface where it can readily occur, thus opening up a kinetically
facile pathway for the thermodynamically favoured process. Then current efficiency
for zinc EW plummets and hydrogen gas is produced. Hence one of the biggest
concerns in zinc hydrometallurgy is electrolyte purification.
Figure 22. Partial Eh-pH diagrams for three M-H 2O systems. The H2 pressure is low
(0.01 atm), and in practice, it would be kept low to avoid the danger of explosion.
Metals in the Group VIII block of the periodic table exhibit especially high
rates of hydrogen evolution. The Ni, Pd and Pt column have the highest rates of any
group. For instance, ENi+2/Ni = -0.24 V and the rate of hydrogen evolution on Ni is
relatively high as well. So how can we electrowin Ni metal and those like it?
Consider again the Eh-pH diagram in Figure 22. The H +/H2 and Ni+2/Ni lines
intersect at pH 3. Below this pH H+ is easier to reduce to H2 than reduction of Ni+2
to Ni. Above this pH Ni+2 is the stronger oxidant; EhNi+2/Ni > EhH+/H2. This means that
Ni+2 can be electrowon above this pH. However, above pH 6.4 Ni(OH) 2 s precipitates
and this would foul the cathodes, introduce hydrogen and oxygen impurities into
the solid and passivate the electrode surface. Hence the pH must be kept at 3 < pH
< 6.4 (at these ionic activities, at least). In practice, the cathodes and anodes are
physically separated using porous cloth bags that surround either the cathodes or
the anodes. This is illustrated in Figure 23. Here bags surround the cathodes. Nickel
sulfate solution is pumped into the cathode bags (called the catholyte). This
maintains a small hydrostatic head in the bags, relative to the level in the anode
51
compartment (the anolyte solution). Hence solution flows from the cathode
chamber to the anode chamber. This prevents anolyte solution from coming into
contact with the cathodes. In the anode chamber acid is produced via oxygen
evolution (in sulfate medium):
SO42- + H2O = H2SO4 + 1/2O2 + 2e-
(29)
The increasing acid concentration is prevented from coming into contact with the
cathodes using the cloth bags. The anolyte is pumped out at the same rate that the
catholyte is pumped in. The anolyte is continuously neutralized with NaOH. Nickelenriched, neutralized catholyte is pumped back into the cathode bags. All this adds
considerable expense. The conductivity of the electrolyte is also lowered by having
to avoid H+ (which is the best ionic conductor) and use Na 2SO4 instead. This adds to
the energy costs. However, nickel is valuable enough that this can be tolerated.
Another variation on Ni EW is to use chloride medium. This has advantages in
leaching, though it is more corrosive. Then Cl 2 gas is formed at the anode. Now the
anode chambers must be enclosed and the Cl2 gas must be collected; it is highly
toxic and it is very useful in leaching. Again, it is imperative that powerfully
oxidizing Cl2 not come into contact with the cathodes, or EW will cease. Hence again
separate cathode and anode chambers are required.
52
E = 0.34 V
(30)
E = 0.34 V
(31)
The cathodes are negatively polarized and the anodes are positively polarized.
Clearly E for this process is 0 V. The activity of copper in the anodes is only
slightly less than one, and the copper concentration in the electrolyte is typically on
the order of 1 m. Hence the thermodynamic cell voltage in practice is actually quite
close to 0 V. However, there are other voltage drops that result in a cell voltage that
is somewhat less than 0 V. (The cell voltage is E cathode - Eanode < 0.) The following also
contribute to the required cell voltage:
53
The total cell voltage is typically 0.25-0.3 V. The greatest contributor to the
voltage is the electrical resistance of the electrolyte. Sulfuric acid concentrations are
kept high to keep the resistance of the electrolyte low. Since the solution resistance
of the electrolyte increases directly with the separation between anode and
cathode, a narrow anode-cathode spacing is desirable. (ER tankhouses also involve
very large numbers of cathodes and anodes, so minimizing the gap also is good for
lowering capital costs of the associated infrastructure.) However, cathodes need to
grow to a specified thickness (about 1.4-1.9 cm in electrorefining), starter sheets
(the substrates onto which the metal is plated) and anodes may not be perfectly
planar nor vertical and polycrystalline protrusions called dendrites can grow out
from the cathodes towards the anodes, causing short circuits and loss of metal
plating efficiency. For all these reasons the gap between cathodes and anodes in ER
is roughly at least 2.5 cm. Note that in ER as the cathode grows, the anode gets
thinner. The conductivity of typical ER electrolytes is 0.5-0.7 -1 cm-1. Typical
current densities are 190-260 A/m2 and cathodes typically are 1 m x 1 m. Given a
cathode-anode spacing of 2.7 cm, a current of 250 A and a conductivity of 0.7 -1
cm-1, the resistance of the electrolyte would be,
R = (1/0.7 -1 cm-1) x 2.7 cm x (1/104 cm2) = 0.000386
{109}
{110}
which is close to the lower end of the typical range of voltage drops due to solution
resistance listed previously.
Impurities
54
The table below lists the common impurities in anodes and the purer
cathodes. The main impurities are As, Bi, Ni, Pb, Sb, Se and Te. If an element has
an E that is less than ECu+2/Cu (0.34 V), then it can dissolve from the anode. (A
lower standard reduction potential means that the element is more easily oxidized.)
For an impurity metal in the anode,
Manode = Mn+aq + ne(32)
The reduction potential (for the reduction half reaction) is given by,
E = E - 2.303RT log aManode
nF
aMn+
{111}
The activity of metal impurity in the anode will be low. If the activity of the ion in
solution is also low, the reduction potential will be close to E.
Table 4. Impurities in copper before and after ER.
Impurities Anodes, % Cathodes, %
As
0-0.3
<0.0002
Bi
0-0.001
<0.0001
Fe
0.002-0.03
<0.002
Ni
0-0.5
<0.001
Pb
0-0.1
<0.0005
Sb
0-0.3
<0.0002
S
0.001-0.003 <0.001
Se
0-0.02
<0.0002
Te
0-0.001
<0.0001
Ag
trace-0.1
<0.001
Au
0-0.005
<0.00001
PGM*
trace
*PGM = platinum group metals (Rh, Ir, Ru, Os, Pd, Pt)
Iron, for example, has EFe+2/Fe = -0.41 V. It is much easier to oxidize than
copper. Now, however, since the reduction potential for Fe +2 + 2e- = Fe is
substantially lower than that for Cu+2 to Cu, copper will preferentially plate over
iron. (Fe+2 having a lower E than Cu+2 means that Cu+2 is a stronger oxidant; Fe+2
is harder to reduce.) On the other hand, elements with an E greater than that of
Cu+2 will not dissolve from the anode. Thus electrorefining is very selective. Only
species with reduction potentials similar to that of E Cu+2/Cu will dissolve from the
anode (at least by anodic oxidation) and plate at the cathode. Even then, kinetic
factors also would come into play. If a species has a substantial cathodic
overpotential for reduction, its tendency to reduce and co-plate with copper at the
cathode would be diminished.
A partial table of standard reduction potentials is reproduced below. The first
column indicates the principal species that would form in solution. Inspection of the
data indicates that mainly Fe, Ni, Pb, Sb, As and Bi should dissolve.
55
The other way that impurities can enter the cathodes is by occlusion (or
entrainment). Cathode surfaces are polycrystalline and not perfectly smooth.
Microscopic cavities form, which contain the electrolyte. These may grow over with
Table 5. Some standard reduction potentials relevant to Cu ER.
Oxidized
Half reaction
E V
form
Au+3
Au+3 + 3e- = Au
1.42
+
Ag
Ag+ + e- = Ag
0.80
+2
+2
Cu
Cu + 2e = Cu
0.34
BiO+
BiO+ + 2H+ + 3e- = Bi + H2O
0.32
HAsO2*
HAsO2 + 3H+ + 3e = As + 2H2O 0.25
SbO+
SbO+ + 2H+ + 3e- = Sb + H2O
0.21
+
+
H
2H + 2e = H2 (for reference)
0
Pb+2
Pb+2 + 2e- = Pb
-0.13
Ni+2
Ni+2 + 2e- = Ni
-0.23
Fe+2
Fe+2 + 2e- = Fe
-0.41
* Or perhaps H2AsO3.
copper metal and trap small amounts of electrolyte within the cathodes. Impurities
in the electrolyte, including copper sulfate and sulfuric acid are then occluded. This
is the principal origin of impurities in the cathodes. Notes on specific impurities
follow.
(a) Gold and platinum group metals do not dissolve from the anode. Their reduction
potentials are too high. These metals stay in the residues of the anodes. Anodes are
not completely dissolved. They are removed and replaced after about 85% reaction.
Precious metals may be a significant source of revenue.
(b) Silver does partially dissolve,
Aganode = Ag+ + e-
(33)
(34)
(35)
In fact, E for Ag+/Ag is 0.80 V. This is considerably higher than that for Cu +2/Cu
(0.34 V). This should preclude silver dissolving in the first place. But,
56
AgCl + e- = Ag + Cl-
E = 0.22 V
(36)
Since this is less than ECu +2/Cu, and chloride is present in the electrolyte,
conversion of anode silver to solid AgCl is favourable. Most of the AgCl reports with
the anode residues. Whatever does end up in the cathode results from occlusion of
suspended particles in the electrolyte. Silver may be present as a copper-silver solid
solution and as compounds with sulfur, selenium and tellurium, depending on
relative concentrations. These compounds are too stable to corrode. It is evident
then that mechanisms of dissolution may be complex.
(c) Sulfur, selenium and tellurium form stable copper compounds with many metals
(e.g. Ag2Se, Cu2Se, Ag2Te4, Cu2S etc.), which are not electrochemically oxidized.
These elements mainly report with the anode residues.
(d) Lead and tin (tin was not mentioned in the tables above) are readily corroded,
but form quite insoluble precipitates of PbSO 4 and a basic tin(II) sulfate. As a result
these elements do not dissolve to any significant degree in the electrolyte. Some
cathode contamination by occlusion occurs.
(e) Arsenic, bismuth, cobalt, iron and nickel are all less noble than copper (i.e. they
are more easily oxidized) and can enter the electrolyte as solution species (e.g.
HAsO2, BiO+, Co+2, Fe+2 and Ni+2, respectively; see table of reduction potentials on
previous page). Much of the antimony (~60%) and some of the arsenic (~25%)
end up staying in the anode residues, possibly as a result of forming stable
compounds with copper (e.g. arsenides) during anode casting. In principle the
impurities could plate at the cathode, but many have E < E H+/H2 (e.g. ECo+2/Co =
-0.28 V). The potential at the cathode is around E Cu+2/Cu = 0.34 V, i.e. the potential
for copper reduction is too oxidizing to allow less noble ions to reduce. (Besides,
even if they could plate, the strong acid of the electrolyte would redissolve them in
some instances.) This illustrates the beauty of electrorefining. The impurity metals
that are more easily corroded than copper (E < 0.34 V) cant electrochemically
plate at the cathode, while those that have E >0.34 V cant be corroded from the
anodes. The purification method is thermodynamically tuned to be very selective
for copper.
The case of bismuth is different. The E for BiO +/Bi is 0.32 V, which is quite
similar to E for Cu+2/Cu. The differences in the two potentials are quite small and
this might allow some Bi to be electrochemically deposited, in principle.
Nevertheless, all the corroded species build up in the electrolyte over time
and eventually would contaminate the cathodes by occlusion. This is the main
mechanism by which impurities enter the cathodes. Because of this they have to be
removed from the electrolyte. A bleed stream is taken from the electrolyte and
subjected to purification to remove the impurities from the circuit. Since the
impurities concentrations in the anodes are low, the bleed rates are also low (0.10.5 m3 of electrolyte per tonne of copper metal plated.)
Electrolyte purification
57
There are a number of methods available for purifying the bled electrolyte.
One method is to first plate copper electrochemically from the electrolyte. This is
done in three stages. These are called liberator cells. The first stage produces
quite high purity copper cathodes. This is essentially an electrowinning operation.
In the second stage an impure copper product is formed that can be recycled to the
furnace for generation of copper anodes. In the third stage most of the arsenic,
antimony and bismuth are removed as well. The copper product is highly
contaminated with these elements. The cathodes may be used for production of
arsenic or recycled to the smelter. (In the smelter these elements are partially
rejected as slags and dusts. This avoids build-up of these impurities in the process.)
The third stage in particular is quite energy inefficient due to the low concentrations
of ions in solution. In order to maintain high plating rates, high voltages are
required. This results in strongly reducing conditions at the cathode and some
arsine gas (AsH3) is also evolved. Arsine is extremely toxic and must be collected.
In arsenic-containing EW electrolytes there is also a danger of arsine generation.
After the third stage the solution contains mainly sulfuric acid, nickel, cobalt
and iron sulfates. Water is evaporated and the sulfate salts of the metals
precipitate. The precipitation is driven in part by the resulting high H 2SO4
concentration (source of high sulfate concentration). What is left is a high
concentration H2SO4 solution (1000 g/L or ~10 M). This is mostly recycled to
electrorefining to make up for lost acid.
An alternative to the first EW stage is to remove copper as CuSO 45H2O. This
is done by adding copper metal (shot) and reacting it with oxygen:
Cu + 1/2O2 + H2SO4 = CuSO4 + H2O
(37)
Evaporation and cooling of the solution precipitates much of the solution copper as
CuSO45H2O. The product contains a little iron and nickel as well. It may be sold.
Plating conditions
Organic additives are introduced to the electrolyte for a number of reasons.
One typical additive is bone glue, a mixture of natural proteins. It is added at
1-10 mg/L. It is added to minimize the growth of protrusions on the cathode
surface. Glue acts by adsorbing particularly on the tips of protrusions. This results
in an insulating layer that inhibits further deposition of metal. The adsorption of
glue to varying degrees on the cathode surfaces results in a slightly higher overall
resistance and a consequent voltage drop, as was noted previously. The same effect
can be attained by a technique called periodic current reversal (PCR). For a brief
interval, repeated regularly, the cell polarity is switched so that plating occurs
briefly on the anodes and corrosion of copper from the cathodes. The protrusions
are the most rapidly dissolved, while the indentations are the slowest to dissolve.
The result is that protrusions are prevented from growing. A side benefit is that
higher current densities can also be employed, resulting in greater overall plating
rates. Other additives are also added for various reasons. For instance, flocculants
58
may be added to promote flocculation and settling of fine precipitates and solids
derived from the anodes. This helps prevent impurity occlusion in the cathodes.
The electrolyte is heated by steam coils to 60-65C entering the circuit and
leaves at 55-60C. Some heating of the electrolyte occurs as a result of the solution
resistance. The electrolyte is circulated at a slow rate (~0.02 m 3/min). This ensures
that Cu+2 in solution is transported from anode to cathode. It also carries away
impurities and aids in distribution of additives to the solution.
A cathode substrate is needed for plating copper. These tend to be thin
sheets of copper metal (0.5-1 mm). They are plated onto titanium blanks. They are
plated for about 24 hours, after which they are mechanically removed from the
titanium substrates. Due to an adherent, conductive film on titanium, the copper
sheets are easily separated from the substrate. Titanium is expensive, but the
process is easier than previously practiced alternatives. Electrorefining cathodes are
plated for about 10-14 days, whereas the starter sheets are plated for one day, so
the number of titanium sheets needed is a small fraction of the total number of
cathodes being plated.
In principle, the higher the current density, the faster the copper cathode
production rate. However, much above 250 A/m 2 (or 300 A/m2 with PCR) anode
passivation occurs. The resistance of the anode greatly increases and copper
corrosions ceases. This has been attributed to rapid buildup of CuSO 4 in the
electrolyte at the anode surface and resultant precipitation of CuSO 4xH2O. This
would occur if the solubility of copper sulfate was exceeded. The precipitate is nonconductive and forms an insulating coating on the anodes. Passivation is prevented
by keeping the copper concentration in the electrolyte well below saturation
(typically around 40-45 g Cu+2/L), operating the cells at higher temperature
(~60C, which increases the solubility of copper sulfate), maintaining good
circulation and keeping the current density low enough. In addition, very high
current densities result in rough cathodes with more occlusion of electrolyte.
Efficiency and energy consumption
Current efficiency for ER is on the order of 90-96%. The main sources of loss
are stray currents to ground (1-3%), anode-cathode short circuits (1-3%) and
reoxidation of copper cathode (1%). Stray currents arise from fortuitous conduction
pathways, such as spilled electrolyte. Copper dendrites growing from cathode to
anode cause short circuits. These may be detected by infrared scanners. The
nodules are broken off to resume plating. The cathode is only weakly negatively
polarized (the thermodynamic cell voltage is almost zero). Hence oxygen in solution
can attack the copper in acidic solution and oxidize it. This occurs to a small extent.
Cu + 1/2O2 + H2SO4 = + H2O + CuSO4
(38)
Oxygen is not generated at the anode; copper metal corrosion is much more
favourable than water oxidation. However, oxygen is slightly soluble in the aqueous
59
solution and enters from the air. Oxygen may also oxidize ferrous to ferric to a
small extent, and ferric can corrode copper:
2Fe+3aq + Cu = 2Fe+2 + Cu+2
(39)
60
cells. For n anodes there are n+1 cathodes (opposite of electrowinning). After
10-14 days the cathodes are removed, then a new set of cathode starter sheets are
installed and the process continues. Each set of cathodes is removed and washed.
Cathodes are melted and cast into now very pure form. After two sets of cathodes
are recovered from one set of anodes the electrolyte is drained away. Spent anodes
are washed to remove residues and the cells are washed out to recover the
residues. These may be treated for precious metals recovery. The spent anodes are
then recycled to anode casting, which is done by melting the copper metal.
61
62
[3] Nguyen, T., Guresin, N., Nicol, M. and Atrens, A., Influence of cobalt ions on the
anodic oxidation of a lead alloy under conditions typical of copper electrowinning,
Journal of Applied Electrochemistry, 2008. 38, 215-224.
[4] Price, D.C. and Davenport, W.G., Densities, electrical conductivities and
viscosities of CuSO4/H2SO4 solutions in the range of modern electrorefining and
electrowinning electrolytes, Metallurgical Transactions B, 1980, 11B, 159-163.
[5] J.G. Jenkins and M.A. Eamon, Plant practices and innovations at Magma
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Meeting, P.L. Classens and G.B. Harris, eds., Montreal, Que., Canada, Oct. 21-24,
1990, pp. 41-56.
[6] J. Jenkins, W.G. Davenport, B. Kennedy and T. Robinson, Electrolytic copper
-leach, solvent extraction and electrowinning world operating data, Proceedings of
the Copper 99 Cobre 99 International Conference, S.K. Young, D.B. Dreisinger,
R.P. Hackl and D.G. Dixon, eds., Phoenix AZ, Oct. 10-13, 1999, Vol. 4, pp. 493-567.
[7] Hydrometallurgy: Theory and Practice Study Guide, Module 5, Kinetics of
Heterogeneous Reactions, University of Capetown, p. 19.
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http://www.cognis.com/NR/rdonlyres/97088921-AD31-461E-A1209C2B791ACD26/0/lixsolve.pdf
[9] W.G. Davenport, M. King, M. Schlesinger and A.K. Biswas, Extractive Metallurgy
of Copper, 4th edn., Pergamon, 2002.
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ed., Society for Mining, Metallurgy and Exploration, pp. 217-221.
[11] M.S. Prasad, V.P. Kenyen and D.N. Assar, Development of SX-EW process for
copper recovery-an overview, Mineral Processing and Extractive Metallurgy Review,
1992, vol. 8, pp. 95-118.
[12] N.T. Beukes and J. Badenhorst, Copper electrowinning: theoretical and
practical design, Hydrometallurgy Conference, South African Institute of Mining
and Metallurgy, Feb. 24-26, 2009, pp. 213-240.
[13] J.B. Hiskey, Principles and practical considerations of copper electrorefining
and electrowinning, in Copper Leaching, Solvent Extraction, and Electrowinning
Technology, G.V. Jergensen II, ed., Society for Mining, Metallurgy and Exploration,
pp. 169-186.
63
[14] G. Kordosky, S. Olafson and C. Hahn, Iron control strategies in copper solvent
extraction plants, the case for a wash stage, Randol Conference, 2000. Retrieved
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[15] G. Kordosky, M. Virnig and M. Mackenzie, Solvent extraction - reagents and
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64
Acid mist Gas bubbles breaking the surface of the electrolyte in the cells forms a
fine mist in the tankhouse.
Activity Effective concentration. Aqueous solutions are highly non-ideal, meaning
that there are strong interactions between solutes and water. This makes a solute
behave as if its concentration is either higher or lower than its analytical
concentration.
Anode The electrode where oxidation occurs (loss of electrons).
AW Atomic weight in g/mol.
Bleed A solution taken from a process stream, often to prevent excessive build-up
of impurities. In EW it is taken from the lean electrolyte to minimize build-up of
harmful impurities in electrowinning. See also bleeding.
Bleeding A term for the action of removing a fraction of a process solution stream.
Boundary layer The stagnant film in the vicinity of a solid in a solution (here an
electrode). The thickness of the boundary layer is determined in large part by the
extent of turbulence (agitation). The thinner it is, the higher the limiting current
density can be.
Cathode The electrode where reduction occurs (gain of electrons).
Conductance, conductivity
See resistance.
65
Electrowinning
its
n The number of moles of electrons passed for a half reaction or a cell reaction
per mole of reaction. A mole of reaction means that the molar quantities of
reactants form the molar quantities of products for a reaction as written. If the half
66
67
68