Beruflich Dokumente
Kultur Dokumente
DOI 10.1007/s10800-007-9474-2
ORIGINAL PAPER
Received: 27 July 2007 / Revised: 16 December 2007 / Accepted: 19 December 2007 / Published online: 15 January 2008
Springer Science+Business Media B.V. 2008
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570 J Appl Electrochem (2008) 38:569–577
oxidation rate in the presence of cobalt ions in sulphuric commercial Pb–Ca–Sn alloy was 1.4%Sn, 0.080%Ca,
acid at high current densities. This research indicated that 0.020%Al and balance Pb. Unless stated otherwise, the
the surface film controls the oxidation rate of the lead alloy. electrode was rotated at 500 rpm. Immediately before each
In the presence of a moderate cobalt ion concentration, in experiment, the electrode was polished using 1200-grit paper
steady state there remain the three layers: (i) PbSO4, (ii) a- and thoroughly rinsed with acetone and distilled water.
PbO2 and (iii) b-PbO2 in contact with the solution. The
presence of cobalt ions improves the imperviousness of the
a-PbO2 in hindering the oxidation of metallic lead to 2.3 Oxygen evolution on lead dioxide
a-PbO2 and also in hindering the oxidation of PbSO4 to
b-PbO2. In summary, the a-PbO2 layer is the key to the The PbO2 deposits were prepared on a substrate of plati-
oxidation rate of the lead alloy. num (Pt) or vitreous carbon. Prior to the deposition, each
This paper extends previous [13, 15] to address the fol- substrate was gently roughened with sand paper to increase
lowing issues: (i) the manner in which the steady state the adhesion of the PbO2 deposit; polarised in a 10%
surface film changes with oxidation time, (ii) the influence of sodium hydroxide solution for 30 min with a 1 mA anodic
cobalt ions on the formation of the initial lead sulphate film, current in the electrochemical cell to remove any particles
(iii) film formation at constant potential and (iv) the potential on the surface; immersed in a 10% nitric acid solution for
of the oxygen evolution reaction on lead dioxide in relation 10 min and thoroughly washed with distilled water.
to the oxygen evolution potential on lead anodes. The aim is The deposits of b-PbO2 and a-PbO2 were produced by
to more fully understand the mechanism by which cobalt anodic electrodeposition as described by Narasimham and
ions decrease the oxidation of the lead alloy under steady Udupa [12] and Devilliers et al. [4] in a water-jacketed cell
state conditions typical of copper electrowinning. on either vitreous carbon or Pt, 2.95 mm or 2 mm in
diameter, with an exposed surface area of 6.83 9 10-6 m2
and 3.14 9 10-6 m2 respectively. A stainless steel plate
2 Experimental was used as the cathode. All chemicals were AR reagents.
The crystallographic form of the PbO2 deposit was char-
2.1 Electrochemical cell acterised by X-ray diffraction (XRD).
Pure b-PbO2 was electrodeposited from an electrolyte
The water-jacketed glass three-electrode electrochemical containing 350 g L-1 lead nitrate (Pb(NO3)2) and 30 g L-1
cell had a volume of 200 mL. The electric motor for the copper nitrate (Cu(NO3)2) at a current density of 300 A m-2
rotating working electrode was mounted directly above the at 65 C for 5 min. The copper ions prevented the depo-
cell. A Luggin capillary was fitted in the bottom of the cell sition of dendritic lead on the cathode, which would
via a threaded port. A platinum wire was used as the decrease the efficiency of PbO2 deposition on the anode.
counter electrode. Unless otherwise stated, the electrolyte Copper, being more electropositive than lead, deposits
was a 170 g L-1 H2SO4 solution. The cobalt ions were preferentially on the cathode.
added to the solution in the form of cobalt sulphate, Pure a-PbO2 was deposited from 140 g L-1 NaOH and
CoSO4 7H2O. All solutions were prepared with AR grade 50 g L-1 PbO with a current density of 10 A m-2 for 2 h
chemicals and distilled water. A Hg|HgSO4|saturated at 30 C.
K2SO4 reference electrode was used to avoid chloride Each PbO2 electrode was removed from the plating
contamination. The potentials are reported with respect to solution, carefully rinsed in distilled water, introduced into
the standard hydrogen electrode (SHE). The potential of the 170 g L-1 H2SO4 solution containing the required
the working electrode was controlled by a PAR 362 cobalt concentration and oxidised for a specified time at a
scanning potentiostat. The potential and current from the rotation rate of 500 rpm and at a constant current density of
potentiostat were logged by a computer using a data 285 A m-2. The PbO2 electrodes were examined using
acquisition system operated by Lab VIEW 7 software. All scanning electron microscopy (SEM) and X-ray diffraction
measurements were made at room temperature. (XRD) before and after oxidation.
The working electrode was a rotating disc in the shape of a 3.1 Anodic oxidation of lead anode at constant current
cylinder attached to a stainless steel disc using conductive
silver-loaded epoxy and embedded in epoxy resin (Araldite A typical cyclic voltammogram is presented in Fig. 1. This
LC 191, Hardener LC 26). The composition of the was measured after the Pb–Ca–Sn alloy had been oxidised
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J Appl Electrochem (2008) 38:569–577 571
1200 2.3
A
Current Density /A m-2
800 B 2.25
400 2.2
0 ppm
Po tentn tia l /V
0
D 2.15
-1.5 -1 -0.5 0 0.5 1 1.5 2 2.5
2.1
-400
E C 2.05 50 ppm
F -800 100 ppm
2
-1200 500 ppm
Potential vs SHE /V 1.95
1.9
Fig. 1 Typical cyclic voltammogram, at room temperature and at
0 0.2 0.4 0.6 0.8 1
500 rpm, of a rotating Pb–Ca–Sn alloy electrode after 24 h oxidation
Time /h
at 285 A m-2 in 170 g L-1 H2SO4. The potential was swept at
10 mV s-1 in a negative direction from the potential at *2.1 V.
Fig. 2 The influence of the cobalt ion concentration on the potential
Subsequently the positive scan was measured
of the Pb–Ca–Sn alloy during oxidation at 285 A m-2. The potential
approached steady state during the first hour as plotted. There was no
substantial change during the remainder of the 24 h period of
oxidation (not plotted)
for 24 h at 285 A m-2 in 170 g L-1 H2SO4 and PbO, PbO2
and PbSO4 had formed on the surface during this oxidation. cobalt ion concentration. The steady state potential
The voltammogram was measured at a scan rate of decreased approximately 197 mV in the presence of
10 mV s-1, a scan rate not untypical for such research. The 500 ppm Co2+. The progressive decrease in potential with
potential during the oxidation was *2.1 V. During the increasing [Co2+] indicates a progressive facilitation of
negative scan from this potential, reduction of PbO2 to oxygen evolution.
PbSO4 occurs at about 1.55 V (peak C), followed by a The extent of oxidation of the Pb–Ca–Sn alloy, expres-
small anodic peak D at about 1.45 V, the reduction of PbO sed as the amount of PbO2 and total Pb oxidised, derived
to Pb at about -0.4 V (peak E), PbSO4 to Pb at -0.45 V from the voltammograms measured after 24 h oxidation for
(peak F) and the evolution of hydrogen at more negative the experiments shown in Fig. 2 are summarised in Fig. 3.
potentials. The small peak D is generally interpreted as These results are in agreement with [15]. Both the amount
being due to the oxidation of metallic lead to lead sulphate of PbO2 and the total oxidation rate decreased with
or oxide [3, 16] in cracks produced in the PbO2 film during increasing cobalt ion concentration. The largest decrease
reduction to lead sulphate. On the positive scan from occurred for small cobalt ion concentrations, concentrations
negative potentials, the oxidation of Pb to PbSO4 occurs at less than 20 ppm.
approximately -0.3 V. Figure 4 shows that the oxidation rate decreased steadily
The quantity of Pb oxidised to PbO2 during the anodic from the values measured after 1 h oxidation until steady
oxidation can be evaluated by integrating the charge under state had been reached by 24 h of oxidation. The values
peak C whilst the total amount of Pb oxidised can be measured in this work after 1 h oxidation were consistent
obtained from the area under peaks E and F. This method
4
of evaluation of the oxidation rate assumes that all the
oxidation products remain on the electrode surface during
oxidation. After each experiment the solution was carefully
Oxidation Rate /g(kAh)-1
3
examined and there was no evidence of spalling of oxi-
dation products. The oxidation rate is presented in terms of
the total mass of Pb oxidised in terms of the equation 2
MIt
W¼ ð1Þ
nF
1 Total Pb
where W = weight of the electro-active species/g,
M = molecular mass of lead, I = current/A, t = time/s and
PbO2
F = Faraday = 96480 C mol-1. The oxidation rate is 0
conventionally expressed in units of g Pb (kAh)-1. 0 100 200 300 400 500 600
Figure 2 shows the potential of the Pb–Ca–Sn alloy Cobalt Concentration /ppm
during oxidisation at a constant current density of
Fig. 3 The influence of cobalt ion concentration on the oxidation rate
285 A m-2. In agreement with [15], the steady state (expressed as total Pb) and the amount of PbO2 (expressed as Pb) of
potential of the Pb–Ca–Sn alloy decreased with increasing the Pb–Ca–Sn alloy oxidised for 24 h at 285 A m-2
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572 J Appl Electrochem (2008) 38:569–577
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J Appl Electrochem (2008) 38:569–577 573
500 200
(a) 500 ppm 180
0 160
0 ppm
-0.7 -0.2 0.3 0.8 1.3 1.8 140
100 ppm 10 ppm
120
-500 50 ppm
50 ppm 100
100 ppm
80
-1000
60
0 ppm 40
-1500 20
0
-2000 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1 2.2
Potential vs SHE /V Potential vs SHE /V
100 Fig. 8 Anodic scan of the voltammogram for the freshly polished
(b)
Pb–Ca–Sn alloy at scan rate 5 mV s-1 in 170 g L-1 H2SO4 solution
50 with the stated cobalt concentrations
Current Density /A m-2
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574 J Appl Electrochem (2008) 38:569–577
0 ppm
0
90
0 0.5 1 1.5 2 2.5 3 3.5
80 Time /h
Current Density /A m-2
70
Fig. 10 Influence of cobalt ion concentration on the current/time
60 curves for the Pb–Ca–Sn alloy oxidized at constant potential at (a)
50 1.85 V, (b) 1.9 V and (c) 1.95 V
40
30 oxygen evolution increased by ten fold compared to that at
20 1.85 V. At V = 1.95 V, the effect of cobalt on oxygen
10 evolution was even more pronounced with a current den-
0 sity of about 60 A m-2 with just 50 ppm Co2+. These
0 0.5 1 1.5 2 2.5 3 3.5 results showed that the evolution of oxygen was enhanced
Time /h at potentials above 1.9 V.
Figure 11 presents plots of the steady state current
Fig. 9 Typical current-time transient for the Pb–Ca–Sn alloy during
oxidisation at 1.9 V in 170 g L-1 H2SO4 containing 1000 ppm Co2+ versus potential (from Fig. 10) for the Pb–Ca–Sn alloy
at room temperature and 500 rpm oxidised at constant potential. Comparison with Fig. 8
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J Appl Electrochem (2008) 38:569–577 575
50 ppm 1.6
120 100 ppm
1.4
Potential vs SHE /V
100 500 ppm
1000 ppm 1.2
80
1
60
0.8
40 0.6
20 0.4
0 0.2 100 ppm 0 ppm
1.8 1.85 1.9 1.95 2 2.05
-20 0 500 ppm
Potential vs SHE /V
-0.2
0 10 20 30 40 50
Fig. 11 Plots of steady state current (from Fig. 10) for the Pb–Ca–Sn
Time /min
alloy oxidized at constant potential
1.6
indicates that the peaks B1 and B2 are absent in the steady
1.4
Potential vs SHE /V
state. This again indicates that the formation of the lead
1.2
dioxide surface film is a transient phenomenon.
1
0.8
0.6
3.4 Potential decay transients 0.4
0 ppm
0.2
100 ppm
The formation of lead compounds was examined by means 0
500 ppm
of potential decay transients for the lead alloy oxidised at -0.2
1.85, 1.9 and 1.95 V, Fig. 12. The potential remained for 0 10 20 30 40 50
Time /min
some time period at a potential plateau corresponding to
the presence of lead dioxide, then decreased rapidly to the 1.95 V
(c) 2
PbSO4 potential. The times at the plateau are presented in
Table 2; assuming that the form of the lead dioxide is the
same in all cases and that its ease of reduction is the same, 1.5
Potential vs SHE /V
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576 J Appl Electrochem (2008) 38:569–577
Table 2 The times at the plateau corresponding to lead dioxide Co2+ ions alter the catalytic properties of the active cen-
Cobalt concentration/ Duration of potential
tres involved in the oxygen evolution reaction. Thus the
ppm of lead alloy at influence of the cobalt ions in solution is quite subtle. It is
lead dioxide plateau/min an indirect influence, in that the influence is to change the
surface film, from a thick porous film to a thin compact
1.85 V 1.90 V 1.95 V
film. Moreover, the catalytic properties are enhanced, so
0 4.3 2.0 4.8
that the oxygen evolution reaction is facilitated. The film
100 2.9 1.8 1.8
on the lead surface is more compact and more protective.
500 4.3 3.2 0.4
The film is also more catalytic in facilitating the oxygen
evolution reaction. This second film property (catalytic) is
2.3 useful commercially (decreases costs) however it appears
not to be directly related to the increased oxidation
2.25
resistance, because, [15] showed that the lead oxidation
2.2 was not related to potential.
Potential vs SHE /V
2.15
2.1 0 ppm
2.05 4 Conclusions
50 ppm
2 100 ppm • In the presence of cobalt ions in the electrolyte, the
potential of the lead alloy decreased, as did the amount
1.95 500 ppm of surface corrosion product.
1.9 • The oxidation rate in the presence of cobalt ions
0 200 400 600 800
decreases significantly with increasing oxidation time
Time /s
to a steady state value, indicating that the protective-
Fig. 13 Effect of cobalt ion concentration on the potential of b-PbO2 ness of the surface film is dynamic, the film is
continuously forming and dissolving.
• The surface film in the absence of cobalt ions was thick
respectively. The implication is that the potential of the and porous, whereas the film was thin and compact
Pb–Ca–Sn alloy is determined by the b-PbO2 on its surface when formed in the presence of cobalt ions.
as determined in [15]. • The present study indicates, consistent with the surface
Subsequently the potentials were measured for a-PbO2 film model, that the formation of a continuous
and b-PbO2 electrodeposited on Pt. The potential, in PbSO4 + a-PbO2 film on the surface of the lead alloy
170 g L-1 H2SO4 at 285 A m-2 at a cobalt ion concen- in the presence of cobalt ions hinders further oxidation
tration of 100 ppm, of a-PbO2 and b-PbO2 was essentially of the metal. The protectiveness of the film is dynamic;
the same. The potential of b-PbO2 remained essentially the film is continuously forming and dissolving.
unchanged and essentially equal to that presented in Fig. 2. • The presence of cobalt in the solution decreases the
The potential of a-PbO2 had a slight increase and reached amount of PbSO4 formed on the alloy surface.
almost 2.0 V after 24 h. • The lead dioxides a-PbO2 and b-PbO2 form in the
Figure 13 showed that the steady state potential for potential region above about 1.55 V.
oxygen evolution on b-PbO2 in 170 g L-1 H2SO4 at • Potential decay transients after oxidation at constant
285 A m-2 was decreased in the presence of cobalt ions, potential indicated that the influence of cobalt ions on
and moreover the steady state potential of b-PbO2 was the lead dioxide occurred for potentials of 1.95 V and
essentially the same as the potential of the Pb–Ca–Sn above.
alloy measured in Fig. 2 and in [15]. The steady state • Measurement of the potential of the oxygen evolution
potential for oxygen evolution of a-PbO2 in 170 g L-1 reaction on a-PbO2 and b-PbO2 in 170 g L-1 H2SO4
H2SO4 at 285 A m-2 was initially essentially the same as with and without cobalt ions in the solution indicated
that of b-PbO2. The implication is that the potential of the that the potential of the Pb–Ca–Sn alloy is determined
Pb–Ca–Sn alloy is determined by the a-PbO2 and/or b- by the a-PbO2 and/or b-PbO2 on its surface and that the
PbO2 on its surface and that the lead dioxide catalyses the lead dioxide catalyses the oxygen evolution reaction.
oxygen evolution reaction when the lead dioxide surface
layer is formed in the present of cobalt ions. This is Acknowledgements The AJ Parker CRC and The University of
consistent with the suggestion by Cachet et al. [2] that Queensland are thanked for research support.
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J Appl Electrochem (2008) 38:569–577 577
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