Corrosion Science, Vol. 40, No. 2/3, pp.

225-234, 1998
:(?1998 Elsevier Science Ltd. All rights reserved.
Printed in Great Britain.
001lb938x/98
$19.00+0.00

Pergamon

PII: SOOlO-938X(97)00122-4

A LEAD-ACID BATTERY ANALOGUE TO IN SITU ANODE

DEGRADATION
IN COPPER ELECTROMETALLURGY
G. CIFUENTES.

L. CIFUENTESb

and G. CRISOSTOMOb

Departamento
de Ingenieria Metalurgica,
Universidad
de Santiago, Av. B. OHiggins 3363, Santiago,
Departamento
de lngenieria de Minas, Universidad
de Chile, Tupper 2069, Santiago, Chile

Chile

Abstract-When
the applied current is interrupted
in a copper electrowinning
plant, lead anodes tend to corrode
once the plant is back in operation. This work aims to show, both from theoretical considerations
and experimental
evidence, that this phenomenon
may arise from the spontaneous
coupling of the oxidation of metallic lead to lead
(11) sulfate with the reduction of lead (IV) dioxide to lead (II) sulfate on the unenergized anodes. The process is
similar to the one that takes place in an idle lead-acid
battery. It is shown that, in the above conditions,
the
protective oxide layer on the anode takes between 5 and IO min to dissolve. Estimates are given for the rate of
lead (IV) dioxide dissolution
and lead sulfate formation
and conclusions
are drawn for plant practice. c 1998
Elsevier Science Ltd. All rights reserved
Ke~cords: anode
chemical kinetics,

corrosion,
copper
chronopotentiometry.

electrometallurgy,
electrowinning,
passivation,
cyclic voltammetry,
weight loss test.

lead-acid

battery.

electro-

INTRODUCTION
It is widely known that lead anodes used in copper electrowinning can corrode when the
current is switched on after an interruption. This phenomenon can be explained in terms
of the loss of anode passivity that takes place in the absence of an applied current. The
latter favours the integrity of the protective lead (IV) dioxide layer on the lead anode, i.e.,
during plant operation the anodes are anodically protected. This work presents the view
that, in the absence of an applied anodic overpotential, electrochemical reactions take place
spontaneously on the anode surface, leading to lead corrosion and dissolution of the lead
(IV) dioxide coating, as in an idle lead-acid battery. It is also shown that, in the absence of
the applied current, copper deposition takes place spontaneously on the lead anode.
THEORY
Electrochemical

reactions

in a lead-acid

battery

In a lead-acid battery, metallic lead and lead (IV) dioxide electrodes are immersed
in sulfuric acid. The lead dioxide electrode is obtained by depositing a porous lead (IV)
dioxide layer on a lead substrate. The reactions during operation are as follows..
At the anode, lead dissolves to give lead (II) ion which immediately reacts to form
lead (II) sulfate.
Manuscript

received

15 May 1997
225

Pb + SO, + PbSO,( s) + 2e
At the cathode, lead (IV) dioxide
form lead (II) sulfate.
PbO,+4H
The overall

reaction

reduces

+SO,

(1)

to Icad (II) ion which immediately

+2e

-+PbS0,(s)+2Hz0

reacts

to

(2)

is:
Pb+PbO~+2H~SO-+2PbSO,(s)+2H~O

(3)

During charging,
the rcversc reactions take place. When the device is not supplying
energy or charging,
both forward reactions
couple spontaneously
on the lead (IV)
dioxide electrode. which causes its transformation
to lead (II) sulfate. In this case, the
lead substrate is in contact with the electrolyte
through the lead (IV) dioxide pores.
Standard electrode potentials for all the relevant half-reactions
are given in Table I.

In copper electrowinning,
copper is deposited at the cathode while oxygen evolves
at the lead anode. The clectrolytc is 21solution of copper (II) sulfate in sulfuric acid. At
the operating
current (with densities higher than 2OOA mm). lead anodes are covered
with a passive layer of lead (IV) dioxide. the formation of which is favoured at potentials
higher than the equilibrium
potential
for the oxygen evolution
reaction.
Under these
conditions,
anode dissolution
is negligible and the anodic reaction is:
At theanode

2H,O-0,+4H.

+4e

(4)

When the cell current is switched oil, the oxide phase stays in direct contact with
concentrated
sulfuric acid and as the oxide film is porous. the metallic lead is also in
contact with acid and dissolves. Solid lead sulfate has been shown to form when lead is
immersed in concentrated
sulfuric acid. The situation
is similar to an idle lead&acid
battery. Reactions (I) and (2) couple spontaneously:
( I) takes place at the pores and (2)
at the oxide surface. Figure I pictures this process.
The formation
of solid lead (II) sulfate causes the break up of the protective film.
as lead sulfate molecules are larger than lead (IV) dioxide ones; their molar volume
ratio being sulfate: dioxide = 3.X: I. When the broken oxide film becomes detached from
the metal surface. a larger area of fresh metal is exposed. Then. lead corrosion continues
to take place. coupling with any available cathodic reaction, e.g. reaction (2) or the
reduction of oxygen gas dissolved in the electrolyte, which is reaction (4) in reverse.
Evans diagram of the reactions taking place on a lead
Figure 2 is a qualitative
electrode in the absence of an applied cell current. Under these conditions,
the electrode

Table I. Standard equtltbriutn

(I)
(2)
(4)
(9
(6)

PbSO,(\)+e
= Pb+SO,
PbO, $- 4H + SO, + 3
01+311 4-4~ : 2H,O
Cu $ 2e = <II
2H t 2e = H.

poknttala

I,r relevant

= Pb kSO,(s)+2H,O

half-reacttons
E =
E =
E =
F. =
E =

-0.36
1.6X5
I .2?V
0 .34 v
u.0 v

A lead-acid

battery

analogue

to in situ anode degradation

Substrate

in copper

227

electrometallurgy

Coating

Pb02/PbS0,

Anode
Fig. 1,

When no current is applied to the cell, both the lead substrate and the lead (IV) dioxide
coating react spontaneously
to form lead (11) sulfate.

-0.36

0.34

1.23

1.69

E
Fig. 2. Qualitative Evans diagram showing the main reactions for a lead annode in acidic copper
sulfate without an applied current. Standard equilibrium
potentials for the relevant reactions are
included as a reference. Notice that copper can deposit on lead.

exhibits a mixed potential.

Notice that, when no current
flows through
electrowinning
cell, the presence of cupric ions in solution allows the reaction
On Pb

Cu2+ + 2e- +Cu

a copper

(5)

(i.e. copper deposition

on the lead anode). This phenomenon
has been observed in plant
practice. In this case, copper deposition
couples with lead corrosion
in a cementationlike process. Other possible reactions are a hydrogen ion reduction to hydrogen gas
OnPb
and water decomposition

with oxygen

2H++2ee+H2
evolution

[reaction

(6)
(4)]. Reaction

(6) is very slow

on lead. In an Evans diagram,

the mixed potential
on the lead electrode
determined
by the intersection
of the curves representing
the sum of all anodic
rates and the sum of all cathodic reaction rates which are taking place.

The current density balance on the lead electrode.

place on the same surface area. is as follows

assuming

will be
reaction

that all reactions

take

4, li,so, + ~il.o (, = lLC,, PI~zo~/

+ IL, rr+l + 14 ,,1 ( LI/
Assuming that low concentration
reactants (oxygen, in this case) lead to diffusion
transfer) rate control. their rates will be given by Ficks law

(mass

where it = limiting current density. A m : I I= charge number; F = Faradays constant.

in the bulk
C equiv : D = diffusion coefficient, ms : C,, = reactant concentration
solution. mol m : and ;i = diffusion layer thickness. m.
This equation
assumes that no migration
effects are present. This is justified, as
corrosion takes place in the absence of an applied current.
High concentration
reactants
(lead. lead (IV) dioxide. cupric ion. vvatcr) favour
activation (charge transfer) rate control. so their reaction rates will be given by the highheld approximations
to the Butler ~Volmer equation

and

where the lirst equation

holds for an anodic reaction and the second one holds for a
cathodic reaction. The meaning of symbols is: i,, = exchange current density, A m :
x,,x, = charge transfer coefficients (anodic and cathodic); rl = overpotential,
V (in this
case 11= E,,,,,- 15,); T = temperature,
K; R = gas constant,
J mol- K ; f$,,,, = mixed
potential. V; and EC = equilibrium
potential.
V.
In order to quantify the lead corrosion
rate and the lead (IV) dioxide consumption
rate, a current balance is required. As a first approximation,
if only the main reactions
are taken into account, the current density balance is
/PI>IhXO,= lh,0, IW~,/
Substituting

where

the high held approximations

the subindex

refers

and solving

to the anodic

for E,,,,

reaction

[reaction

(I) above]

and

the

A lead-acid

battery

analogue

to in situ anode degradation

in copper electrometallurgy

229

subindex
C refers to the cathodic reaction [reaction (2) above]. The expression for the
mixed potential is given here for the sake of completeness.
As a second approximation to the lead (IV) dioxide consumption rate, it may be
assumed that the anodic reaction is balanced by both the lead (IV) dioxide and cupric
ion reduction reactions, so that the current density balance is
zPb,PbSO,

hb02,PbS04i

ku2+:Cui

Then, an estimate of the cupric ion reduction rate will give an improved value for the
lead (IV) dioxide consumption rate. If necessary, further approximations may be obtained
by taking into account the remaining reactions as given above.
EXPERIMENTAL
Potential-time

METHOD

curve

The experiments were carried out in a 180 gpl sulfuric acid and 40 gpl copper solution
at 40C. The anodes were made of a PbCa (0.02%)-Sn (0.5%) alloy. The working
electrode (anode) surface area was 0.86cm and a stainless steel coiled wire counterelectrode was used. Its surface area was over ten times greater than the working electrode
surface area. A silver/silver chloride reference electrode was used. The electrodes were
contained in a 500 ml cell. The electrolyte recirculated at a flowrate of 3 1 per minute by
means of a peristaltic pump.
A Model PSG 201 Tacussel potentiostat was used to carry out the following
procedure:
(1) A constant 200 A m-2 anodic current density was applied during two hours in order
to form a lead (IV) dioxide layer on the working electrode.
(2) Then the c.d. was abruptly interrupted and the electrode potential-time curve was
recorded (Fig. 3).
(3) Once the potential became stable, the electrode was removed and subject to
microscopic observation.
Cyclic voltammetry

In order to characterize the reactions taking place on lead, a cyclic voltammetry was
carried out in a three-electrode cell, using the potentiostat and electrolyte described in
the previous section. The working electrode was made of the already described lead
alloy, the counter electrode was made of platinum and the reference electrode was
saturated calomel (SCE). The electrolyte was 180 gpl sulfuric acid and the temperature
was 4OC. Sweep rate was 0.17 mV SK. The voltammetry is shown in Fig. 4.
Copper deposition

on the lead anode

In order to establish the rate of formation of a copper deposit on the lead anode
after the cell current is interrupted, the following experiment was carried out: a 25cm*
copper-free lead probe was subject to an anodic c.d. of 600Amp2 during 8.5 h in a
180 gpl sulfuric acid solution with addition of 40 gpl copper (II) sulfate. The increased
probe area-as
compared with the one used in the first experiment-was
due to the
need of obtaining a non-negligible amount of copper deposit. The increased current
density and anodizing time were chosen in order to obtain a good oxide layer on a

1000

2
>

800

E
u
600

400

200
__~~~~
0

~~ __

100

50

150

200

r (seconds)

Fig. 2.

Potential

chloride)

corresponds

agamst

tlmc

plot.

The ~nfexmn

to the transformation
hecamc qahle

oflsad

at about

point

at about

(IV) dioxide

1400mV

(agamst

into lead (II) sulfate.

400 mV after 300-600

SIIWI- Giver
The potential

s.

bigger probe. Then the current was interrupted

until the probe reached a stable potential
value. This happened
after 20min. The probe was withdrawn
from the solution and
carefully washed with warm distilled water. Then it was immersed in pure 18Ogpl sulfuric
acid and subject to an anodic c.d. of 50 A m in order to dissolve any copper deposit.
Before and after the test. the solution was analyzed for copper and lead via atomic
absorption.

Weight variation experiments

were carried out in order to establish and quantify the
spontaneous
corrosion of the lead anode during periods of current interruption.
Two experiments
were carried out. In both cases. a lead electrode of 14cm total
surface area was treated in a potassium
tartrate (2OOgpl), sodium hydroxide (1OOgpl)
and potassium iodide (SOgpl) solution in order to remove all surface oxides and sulfates.
washed in distilled water and weighed. Then. the lead anode was immersed in 18Ogpl
sulfuric acid at 40 C. together with two 304 stainless steel counterelectrodes
of the same
surface area placed at 2 cm distance on each side. A constant 250 Am 2 current density
was applied during
6.5 h with the lead electrode
connected
as anode. Then, the
experiments
followed a different path:

(1) Products
(2)

of reaction on the lead anode were removed according to the previously

described procedure and the lead anode was weighed.
The lead anode was left in solution. without an applied current, for 24 h in order to
ensure that all possible reactions ran to completion,
Then, all reaction products were
removed as before and the lead anode was weighed.

A lead-acid

battery

analogue

to in situ anode degradation

in copper

231

electrometallurgy

.
60

C
.

Fig. 4. Cyclic voltammetry.

It shows the main reactions taking place at various electrode potentials
(see text). The leftmost peak represents hydrogen evolution and the rightmost one, oxygen evolution.
At potential above 1500 mV the dominant species is lead (IV) dioxide.

Table 2.

Case I
Case 2

measurements

Initial weight

A. Time*

Rest time

Final weight

Difference

(g)

(h)

(h)

(g)

(mg)

1.8162
1.7503

6.5
6.5

24

1.7516
1.6814

-64.6
-68.9

*A. Time = anodizing

The results

Weight variation

time (at 250A mm ).

are given in Table

2.

EXPERIMENTAL

RESULTS

AND

DISCUSSION

Copper deposition on the lead anode

Microscopy
revealed the presence of deposited copper on the lead anode after its
removal
from the electrolyte.
This proves that reaction
(5) above does take place
spontaneously
after the current is interrupted.
The second experiment
showed that, after

131

<i.

c1suentes
(I

ill.

anodizing,
i.e. after the deposited copper was dissolved, it was present in the solution
at a concentration
of I .73 ppm in a 300ml beaker. This means that, in the experimental
conditions. copper deposits on the unenergized lead anode at an average rate of 2 x 1OPx g
cm~s~l
or 3x 10 mole cm s . No lead was detected in solution. This was to be
expected as any lead ions present tend to form lead (II) sulfate which precipitates.

The potentialMime
curve (Fig. 3) shows an inflexion point around 1400 mV (Ag/AgCl)
which corresponds
roughly to the transformation
of lead (IV) dioxide into lead (11)
sulfate, which points to the spontaneous
occurrence of this reaction.
The electrode potential became stable at around 400mV after 5 IOmin. This value
falls between the equilibrium
potentials
for reactions
(I) and (2) above. i.e. it may
represent a mixed potential for these reactions and other reactions in that range. as for
instance reaction (6) above.
From these results. it is clear that both the lead (IV) dioxide/lead
(11) sulfate and
the cupric ion/metallic
copper reactions take place spontaneously
after the current is
switched off. Both reactions are cathodic and. in order to occur, they need to couple
with an anodic reaction whose equilibrium
potential is less than the equilibrium
potential
for cupric ion/metallic
copper. In this system, the most likely reaction to play this role
is the oxidation of metallic lead to lead (11) sulfate.
Some time after the current is interrupted.
the anode becomes chemically unstable,
as the lead (IV) oxide. which protects the anode from corrosion, reacts to form lead (II)
sulfate.
The time required to achieve anode activation
(i.e.. loss of passivity) is between 5
and IOmin. This very brief period of time is likely to be due to the fact that the lead
(IV) dioxide layer is very thin (of the order of 50pm), i.e. the amount of oxide present
on the anode is low and disappears rapidly as a result of reaction (2).

Cyclic voltammetries
of lead in sulfuric acid solution
have been carried out and
The cyclic
discussed by several authors. so the possible reaction are well understood.
voltammetry
obtained in this work (Fig. 4) is similar to previously published ones and
shows known features: (a) formation
of lead (11) sulfate by oxidation
of metallic lead
to lead (11); (b) passivation
due to formation
of a lead (11) sulfate film: (c) formation of
lead (IV) dioxide by oxidation
of lead (11) to lead (IV). Oxygen gas evolution
takes
to metallic lead, of lead (II) sulfate and nonplace simultaneously:
(d) reduction.
stoichiometrical
lead oxy-sulfates formed during passivation.
The presence of sulfate and
non-stoichiometrical
oxy-sulfates is shown by the presence of three peaks in zone d. The
leftmost peak in this zone represents
hydrogen
gas evolution;
(e) reactivation,
i.e.
oxidation.
to lead (IV) dioxide. of the lead sulfates and non-stoichiometrical
oxysulfates which did not oxidize during the forward sweep. This behaviour
is typical of
semiconductor
materials such as non-stoichiometrical
oxy-sulfates;
and (f) reduction of
lead (IV) dioxide to lead (II) sulfate and non-stoichiometrical
oxy-sulfates.
The voltammetry
shows that the oxidation
of various species to lead (IV) dioxide
begins in the zone between the e and f peaks, that is, it takes place at potentials equal
or higher than 1500mV (SCE). This value is below the anode working potential, which

A lead-acid

battery

analogue

to in situ anode degradation

in copper

electrometallurgy

233

is about 2000mV (SCE). This shows that, at the anode working potential, the dominant
species is lead (IV) dioxide.
Weight variation

measurements

The following discussion refers to Table 2. In Case 1, the mass diference is -64.6mg.
It represents the lead mass which is lost during 6.5 h of normal operation at 250Am-.
In Case 2, the mass difference -68.9mg. It represents the lead mass which is lost
during normal operation plus the lead mass lost during the spontaneous transformation
of lead (IV) dioxide to lead (II) sulfate coupled with the oxidation of metallic lead to
lead (II) sulfate while the current is interrupted.
The difference between the two lead mass losses (4.3 mg or 0.3 1 mg cme2) represents
the lead mass lost during current interruption when the spontaneous process runs to
completion, i.e. all lead (IV) dioxide reacts to form lead (II) sulfate.
For an industrial cell which contains 71 anodes of 2 m2 total surface area each, the
lead mass lost during current interruption, if the interruption time is long enough for
all the lead (IV) dioxide to form lead (II) sulfate, is of the order of 440g per cell.
Reaction

rates

From the previous experiment, if a dissolution time of 10min is assumed, then the
average lead dissolution rate is 5.17 x 10p7g cm-*s- or 2.5 x lo-mol cm-* ss during
the period of lead (IV) dioxide to lead (II) sulfate conversion.
From the equations given to quantify the corrosion rate, it follows that the lead
mass loss must be balanced by the most likely cathodic reactions, i.e. reactions (2) and
(5). The copper deposition rate was calculated as 2 x lop8 g cmm2s- or 3 x 10~mole
cm -2ss, so it is less than the lead dissolution rate by a factor of about ten. It follows
that the lead dissolution reaction is mainly balanced by the lead (IV) dioxide reduction
to lead (II) sulfate. The reaction rate for the latter reaction is slightly less than
2.5 x 10-9mol cm-*ss. All mentioned reaction rates are average values.
Implications

,for plant practice

These results show that, in plant practice, a current interruption of less than 5min
may be acceptable and, in this case, anode damage after the current is switched on is
unlikely as a thin film of protective lead (IV) dioxide is still present. They also suggest
that an interruption which lasted more than 1Omin would be unequivocally damaging
to the anodes. As soon as the current is switched on, the anodes will dissolve until
passivation is achieved. This may lead to severe contamination of the copper cathode
with lead, causing financial loss.
Plant practice has also shown that, after current interruptions, anode performance
decreases, leading to an increased cell voltage. This suggests that lead (II) sulfate-which
would cover a fraction of the anode area after the sulfate-forming reactions have taken
place-has
a lower catalytic effect on oxygen gas evolution than lead (IV) dioxide.
Obviously, an increased cell voltage means increased energy costs, also causing financial
loss.
In order to preserve passivity, a protective (back up) anodic current should be
applied at all times to the lead anodes, including the periods during which the operation
is interrupted for cathode removal and cell clean up. Despite the fact that protective
c.d.s of less than 10 A rnp2 are often recommended in plant practice, unpublished results

from plant tests indicate that the c.d. required to preserve passivity during a longer
period of operation
interruption
(say. several hours) may be considerably
higher. Its
value for a specific plant depends on anode and electrolyte composition
and other plant
conditions.
so it should be determined
by experiment.
A higher protective current would. of course. demand the use of a more expensive
rectifier. The convenience
of installing it would depend on an economic study. For each
plant, the likelihood, duration and frequency of current interruptions
should be assessed.
The resulting financial losses should then be balanced against the cost of implementing
an improved anodic protection
system.

CONCLUSION
Both theoretical considerations
and experimental
evidence have been put forward to
show that lead anode corrosion~
which occurs after a current interruption
in copper
electrowinning
plants
arises from the spontaneous
coupling of the oxidation of metallic
lead to lead (11) sulfate with the reduction of lead (IV) dioxide to lead (II) sulfate on the
unenergized lead anode. which is immersed in an acidic copper sulfate electrolyte. Under
these conditions,
the protective lead (IV) dioxide layer on the anode takes between 5 and
10 min to dissolve. It follows that any current interruption
in a copper electrowinning
plant
which lasted longer than ten minutes would lead to anode corrosion, cathode contamination
and financial loss once the current is switched on.
The authors would like to thank the National
A~~X,7on~lec~l/c~~l~l~i?l
Research (CONICYT.

~ommittee

for Scientific and Technological

Chile) for the tinancial support given to this line of work vu FONDECYT

Project No.

19.50532.

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