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Sasol Technology (pty) Ltd, 33 Baker Street, Rosenbank, Johannesburg, South Africa.
1
ABSTRACT: The effect of impurities, smootheners and other factors on the current density in electrochemical reactions
was studied using a parallel plate model in a circular glass reactor heated by a thermostat-controlled water bath. A
reduction in current density of 50 mA/cm2 and 40 mA/cm2 was produced for an increase in volumes of thiourea and
EDTA of 300 and 100 ml respectively. An increase in distance between electrodes of 3 cm reduced the current density
from 34 to 12 mA/cm2 at 60 oC. An increase of 41oC produced an increase in current density of 66 mA/cm2 at 2 cm
distance between electrodes while an increase in electrode-active area of 20 cm2 produced a decrease in current density
of 56 mA/cm2 at 0.8 Amps. The presence of silver and bismuth removed the limiting current-density plateau more so at
higher concentrations (>0.06%; >1.48%). A 30 g/L increase in concentration of electrolyte produced an increase in
current density of 12 mA/cm2 at 0.25 volts and 26 mA/cm2 at 0.4 volts. The optimum operating current density was
found to be dependent on different levels of factors. Therefore the factors that affect the current density need to be
controlled if the electrochemical reactor is to be operated without problems of pitting, nodulation and passivation.
Keywords:Concentration;Optimum-current-density;Electrochemical-reactors; Impurities; Smootheners; Electrorefining;
Electrowinning; Electrochemical-engineering.
INTRODUCTION
The current density is the current per unit area of
electrode1. It is created by the distribution of charges
due to migration of electrons and ions in the anodecathode-reactor electrolyte where the metal transfer
takes place in electrodes of the first kind (Cu/CuSO4)2.
The current distribution on the electrode is not uniform
in most practical situations and so is the current
density due to a number of factors. The factors that
can affect the current density on the electrode include
the temperature, concentration of electrolyte (Cu2+),
distance between electrodes, electrode-active area,
presence of impurities and the use of strong
1290
anFh
In[Cu 2+ ] (1)
RT
(1 - a ) nFh
In[Cu 2+ ] . (2)
RT
Equipment
The experimental set up was as shown in Figure 1.
The Ammeter (A) was used to measure the current in
series with the variable resistor (rheostat) and the
electrochemical reactor but parallel to the voltmeter
(V). The rheostat was used to adjust the current flow
in the circuit. The voltmeter was used to measure the
overpotential (E) across the reactor. The reactor was
assembled using two electrodes; the cathode and
anode, placed in a circular-glass casing which was
heated by a thermostat-controlled water bath
(Ntengwe, 2008)15. The overpotential was used to
drive the current through the circuit and to distribute it
on the surfaces of electrodes thereby creating the
desired current density which was used to evaluate the
effect of the factors; temperature, concentration of
electrolyte, level of impurities in solution, electrodeactive area, level of smootheners and distance between
electrodes on the current density. Mercury in glass
thermometer and metre rule was used to counter check
the temperature controlled by the thermostat in the
water bath and measure electrode dimensions.
1291
1292
70
60
50
40
1cm
30
2cm
20
3cm
10
0
24
39
60
65
Temperature (*C)
Effect of concentration
The investigation of electrolyte concentration and
current density and resistance revealed two key
observations. The cell resistance increased with
decreased level of concentration and conversely the
resistance decreased with the increase in concentration
of electrolyte. The current density decreased with the
decrease in concentration and the opposite was also
true (Figure 4). The highest resistance was in 1 g/L at
25 and 20 for the 0.25 volts (R0.25V) and 0.4 volts
(R0.4V) respectively while the lowest was in 50 g/L
concentration of electrolyte. The highest concentration
in the study was 50 g/L while the lowest was 1 g/L of
copper sulphate. This translates to 19.9 g/L and 0.398
g/L of copper respectively. The highest concentration
of electrolyte produced the highest current densities of
40 mA/cm at 0.4 volts (j0.4V) and 20 mA/cm at 0.25
V (j0.2V) while the lowest concentration produced the
lowest current densities of 2 mA/cm at 0.4 Volts and 1
mA/cm) at 0.25 Volts. The concentrations above 15
g/L produced good deposits on the surface meaning
that optimum current densities were attained and these
would be the recommended levels of concentrations to
be used in electrorefining.
35
24*C
30
39*C
25
60*C
20
15
10
5
0
1
1293
50
40
30
20
10
0
0
10
20
30
40
50
60
R0.4V
j0.25V
R0.25V
90
80
I0.2A
70
60
I0.5A
I0.8A
50
40
30
20
10
0
10
12.5
17.5
22.5
30
1294
250
0.00%
200
0.05%
150
0.22%
0.50%
100
1.48%
50
3.10%
0
0
0.5
1.5
Overvoltage (Volts)
250
0g/L
200
.03g/L
150
.06g/L
100
.14g/L
.3g/L
50
.6g/L
0
0
0.5
1.5
Overvoltage (Volts)
1295
250
200
0.00%
150
0.03%
0.05%
100
0.11%
0.21%
50
0
0
0.5
1.5
Effect of thiourea
The results in Figure 9 show reduced values of
limiting-current density when the concentrations of
thiourea increase from 0 to 300 ppm. The thiourea
lowered the limiting current density from 80 to 40
mA/cm2 at 200 ppm and 80 to 20 mA/cm2 at 300 ppm
indicating a strong inhibition of the flow of current of
ions in the system. On the other hand, the levels of
thiourea from 40 ppm and below lowered the limiting
current density by 10 mA/cm2 at 0.5 volts, i.e., from 60
to 50 mA/cm2. The results revealed also that the
potential required to overcome resistance in the system
was 0.5 volts for all the cases of the concentrations of
250
0ppm
200
10ppm
150
20ppm
100
40ppm
50
200ppm
0
0
0.5
1.5
Overvoltage (Volts)
300ppm
1296
250
200
0ppm
150
4ppm
20ppm
100
40ppm
80ppm
50
0
0
0.5
1.5
Overvoltage (Volts)
250
5ml
200
10ml
150
20ml
100
40ml
100ml
50
150ml
0
0
Figure 11: Effect of K-glue, thiourea and NaCl on the current density
1297
250
1ml
200
5ml
10ml
150
20ml
100
40ml
50
100ml
150ml
0
0
0.5
1.5
2.5
Overvoltage (Volts)
Current (Amps)
Figure 12: Effect of G-Arabic, thiourea and NaCl on the current density
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
I1
I2
I3
I4
I5
I6
0
50
100
150
200
1298
250
200
5ml
10ml
150
20ml
100
40ml
50
150ml
100ml
0
0
0.5
1.5
Overvoltage (Volts)
Figure 14: Effect of EDTA, NaCl and B-glue on the current density
The inhibitors lower the current density particularly,
the limiting current density. The EDTA was found to
be a strong inhibitor when compared to B-glue, and
NaCl as smootheners. B-glue was found to have
similar characteristics to K-glue and therefore would
exhibit the same inhibition strength. The limiting
current densities decreased from 70 mA/cm2 for the 5
ml (0.377 g/L) to 20 mA/cm2 for the 100 and 150 ml
(3.64 and 4.29 g/L) volumes of EDTA indicating a
strong inhibition of current flow and hence a decrease
in current density was produced (Figure 14). The
results indicate therefore that the optimum operating
conditions for this system would a current density
below the limiting value, a voltage below 1 volt and a
concentration of EDTA above 0.714 g/L and below
4.29 g/L.
DISCUSSIONS
The presence of impurities; silver and bismuth in
electrolyte was found to inhibit the deposition of
copper on the cathode. This was vindicated by the
characteristic curves which turned into linear lines
without the limiting current density plateaus. Some
metals likely to produce a similar effect in
electrowinning and electrorefining of copper include
lead (Pb), iron (Fe), cobalt (Co) and zinc (Zn)14. A
study by Lonzano-Morales and Podlaha (2004)18
showed that low particles of aluminium oxide (Al2O3)
concentration (12.5 g/L) resulted in inhibited
deposition rate of copper while high particle
concentration (60 g/L) inhibited the deposition rate at
low over-potentials and accelerated it at high
overpotentials. In another study, the conductive
particulates of copper and graphite produced dense
nodulation at 50 oC while antimony and silver powders
caused pitting as well as nodulation15 since these
impurities are conducting and therefore interfere with
the current density. The non-conducting powders such
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REFERENCES
1. Lapedes D. N., McGraw-Hill dictionary of
Scientific and Technical Terms, 2nd Edition,
McGraw-Hill, New York, 1978.
2. Antropov L.I., Concentration polarisation, In:
Theoretical Electrochemistry, Mir Publishers,
Moscow, 1972.
3. Crow D.R., Principles and Applications of
Electrochemistry, 4th Edition, Blackie Academic
Professional, Glasgow, 1994, 132-140.
4. Subramanian V. R. and White R.E., A semianalytical method for predicting primary and
secondary current density distributions: linear
and non-linear boundary conditions, J. of
Electrochem. Soc., 2000, 147(5), 1636-1644.
5. Venkateswarlu P., Raj N.J., Rao D.S. and Subbaiah
T., Mass transfer conditions on a perforated
electrode support vibrating in an electrolytic cell,
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