Minerals Engineering 16 (2003) 529–535

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Electrical conductivity and density of CoSO4/H2SO4 solutions in

the range of modern cobalt electrowinning electrolytes
C. Kargl-Simard, J.H. Huang, A.M. Alfantazi *

Department of Metals and Materials Engineering, The University of British Columbia, 309-6350 Stores Road, UBC, Vancouver, BC, Canada V6T 1Z4
Received 20 December 2002; accepted 21 February 2003

Abstract
In order to optimize the current efficiency and power consumption of cobalt electrowinning, the electrical conductivity of the
electrolyte needs to be known. Electrical conductivity depends directly on various variables including the chemical composition and
acidity of the electrolyte. This study was carried out to determine the electrical conductivity and density of cobalt sulfate electrolyte
with varying levels of cobalt and sulfuric acid, measured at different temperatures. The experiment conditions selected in this study
simulated the range of modern industrial cobalt electrowinning electrolytes. From the experimental data, models were deduced,
correlating temperature, cobalt concentration and sulfuric acid concentration to the electrical conductivity and density of the cobalt
sulfate electrolyte. The models were developed using empirical formulas, which allowed for reasonable extrapolation, to produce a
tool to study the major trends of the electrical conductivity and density. From these models, suggestions could be made to enhance
the electrowinning process via increased current efficiency and decreased power consumption.
Ó 2003 Elsevier Science Ltd. All rights reserved.

Keywords: Electrowinning; Electrorefining; Hydrometallurgy; Modelling

1. Introduction hence cobalt is usually extracted in small quantities as a

Cobalt is a strategic and critical metal used in many
diverse industrial applications. Cathode cobalt is used
primarily to make superalloys for gas turbine engines,
but is also extensively used in chemicals, carbide and
diamond tools and magnets. In addition, cobalt finds
applications in medical implants, oil desulphurization,
ceramics and the computer industry, each requiring high
purity cathode cobalt which is 99.8% pure (Cobalt
News, 1997). It was stated that the production of refined
cobalt in 1997 amounted to 24.471 t from a product
mixture of metal and chemicals (Moskalyk and Alfant-
azi, 2000).
Various forms of cobalt metal, including briquettes,
cathode (electrolytic cobalt), fines, granules (shot), in-
got, powder, and rondelles, have been produced and
marketed. The most popular form is cathode cobalt
involving sulfate medium from a pressure leaching op-
eration (Honey et al., 1997). Cobalt is typically associ-
ated with heavy metals such as nickel, zinc and copper,
*
Corresponding author. Tel.: +1-604-822-8745; fax: +1-604-822-
3619.
E-mail address: alfantaz@interchange.ubc.ca (A.M. Alfantazi).
0892-6875/03/$ - see front matter Ó 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0892-6875(03)00059-1
byproduct from non-ferrous metal production. Most
cobalt production is associated with nickel production
from sulfide ores as well as laterites. Pressure leaching,
solvent extraction followed by the electrowinning of
nickel and cobalt, is the preferred route for nickel and
cobalt processing, replacing the reduction roasting and
electrorefining process route. This processing route al-
lows recovery rates of over 90% Co and Ni, much higher
than 50% for the reduction roasting route. Much higher
recovery rates of cobalt require novel technology in
cobalt electrowinning.
The main media for cobalt electrowinning are sulfate
or chloride solutions. In the electrowinning of cobalt
from a sulfate solution, cobalt is deposited on the
cathode coupled with oxygen evolution at the anode and
in chloride solutions, the deposition is coupled with
chlorine gas evolution at the anode.
In the electrowinning of cobalt from sulfate electro-
lytes, the following main reactions occur at the cathode:
Co2þ þ 2e ! Co E0 ¼ 0:277 V ð1Þ
þ  0
2H þ 2e ! H2 E ¼0V ð2Þ
The production of hydrogen gas occurs because cobalt is
less noble than the hydrogen ion, as can be seen from the
530 C. Kargl-Simard et al. / Minerals Engineering 16 (2003) 529–535
standard reduction potential of cobalt. The hydrogen
evolution, Eq. (2), is in competition with the cobalt
deposition (Eq. (1)), which is not desirable because it
represents a loss of current usage, and therefore it must
be kept to a minimum (Moskalyk and Alfantazi, 2000).
The main anodic reaction in sulfate electrolytes is
H2 O ! 12O2 þ 2Hþ þ 2e E0 ¼ 1:229 V
Thus, the overall reaction is
CoSO4 þ H2 O ! Co þ H2 SO4 þ 12O2
0
Etheoretical ¼ 1:506 V
The actual cell voltage consists of
Eactual ¼ Etheoretical þ Eohmic þ Eoverpotential þ Eresistance
Electrowinning processes are usually operated at a
current density of 200–400 A m2 , a voltage of 3–4 V,
pH 3–4 and a temperature of 50–60 °C. Typical current
efficiencies range between 96% and 99%. The electro-
deposition process can be greatly influenced by the
electrical conductivity of the electrolyte, but also by
other factors such as electrolyte composition, pH, tem-
perature, cell design, electrode materials and quality
control issues addressing the purity and morphology of
the deposit. A reduction in the ohmic drop during cobalt
and nickel electrowinning could substantially save op-
erational cost. Typically, the total energy use in the
electrowinning of cobalt is about 3–3.5 kWh/kg at a
current density of 200 A m2 . According to capacities of
main cobalt electrowinning operations in the world,
which were totaling about 25,000–30,000 t/year in 1999,
energy consumption for electrolytically refined cobalt in
the electrowinning stage was about 75–105 millions
kWh in one year. A 1% improvement in the total energy
requirement would save about one million kWh energy
in one year.
Review of literature indicates that there was very
limited information available on the electrical conduc-
tivity and density of cobalt electrolytes for cobalt elec-
trowinning from sulfate electrolytes. A number of
studies have been reported for other electrowinning
electrolytes such as copper (Price and Davenport, 1980),
zinc (Tozawa et al., 1993) and nickel (Wu et al., 2002).
Price et al. presented useful empirical relationships that
describe the change of the electrical conductivity via the
ratio between copper and acid concentration. Tozawa
et al. measured the electrical conductivity of zinc elec-
trowinning electrolytes as a function of sulfuric acid,
zinc and magnesium concentrations with a temperature
range between 25 and 60 °C. All of these studies devel-
oped relationships that related all of these variables to
the electrical conductivity of the electrolytes. The study
concluded that the specific conductivity could be cal-
culated by taking into account the second ionization
constant of sulfuric acid and the stability constants of
zinc sulfate and magnesium sulfate complexes at 25 °C.
This study is a follow up of Wu et al., which studied
the electrical conductivities and density of nickel sulfate
electrolytes. In Wu et al. (2002), the electrical conduc-
tivity and density of nickel sulfate electrolytes were
measured using the same procedures used in this study.
Wu et al. found that electrowinning of nickel sulfate
should be carried out under conditions of high electrical
ð3Þ
conductivity, which can be achieved at high tempera-
tures and high acid concentrations.
The main objective of this investigation was to mea-
sure the electrical conductivities and density of cobalt
ð4Þ sulfate electrolytes. The effects of cobalt concentration,
sulfuric acid concentration and temperature on the
electrical conductivities and density of the cobalt sulfate
ð5Þ
electrolytes were determined along with their corre-
sponding trends. Based on these experimental results,
empirical equations describing the measured values were
also presented using linear regression methods.
2. Experimental
The experiments for measuring both the density and
electrical conductivity were performed over the chemical
composition and temperature ranges shown in Table 1.
These ranges are typical of industrial cobalt electro-
winning conditions. The chemicals used to prepare the
electrolytes were of Fisher Scientific analytical reagent
grade cobalt sulfate (CoSO4  7H2 O) and sulfuric acid.
The water used was all double deionized. All concen-
trations were calculated in grams per liter of solution,
measured at room temperature (20 °C).
A Jenway 4320 conductivity meter was employed to
measure electrical conductivity. Prior to measurement,
conductivity cell was calibrated via 3-point calibration
using KCl standard solutions. The calibration procedure
was taken from the data of the Horiba Group (Horiba,
2002). For each test, a 20 ml test tube was used as a
sample holder. The conductivity cell eliminated poten-
tial mass transfer by covering the top of the tube.
Measurements were carried out over the temperature
range 20–70 °C, which was controlled by a Haake water
bath. Each experiment was repeated at least two times.
An average reading was then used as the final data.
Density measurements were conducted by using 25 ml
Fisher Scientific Gay-Lussac Specific Gravity Bottles.
The thermal expansion of the specific gravity bottles was
taken into considerations when measuring the absolute
Table 1
Typical ranges for electrolyte temperature, and cobalt and sulfuric acid
concentration based on cobalt electrowinning
Temperature 20–70 °C
Cobalt concentration 20–80 g/l
Sulfuric acid concentration 50–200 g/l
 C. Kargl-Simard et al. / Minerals Engineering 16 (2003) 529–535 531

density of the electrolytes. For each experiment, a spe- Table 2

cific gravity bottle full of solution and another bottle Specific electrical conductivity of CoSO4 –H2 SO4 electrolytes
with a thermometer were both placed inside the Haake Concentrations Specific conductivity (mS/cm)
water bath. Once the bottle with the thermometer Co (g/l) H2 SO4 (g/l) 20 °C 40 °C 60 °C 70 °C
reached the desired temperature, the bottle with solution 20 50 160 182 195 200
was taken out of the bath to be weighed. Measurements 20 100 230 268 286 298
were carried out over the temperature range 20–70 °C. 20 150 271 290 321 320
20 200 290 319 334 337
Each experiment was repeated at least two times. The
30 50 157 181 195 199
data was then averaged for creating empirical equations. 30 100 215 255 274 280
30 150 253 279 315 304
30 200 285 312 327 331
3. Results and discussion 40 50 154 179 192 195
40 100 204 245 260 270
40 150 244 268 302 290
3.1. Electrical conductivity 40 200 278 309 319 325
50 50 152 178 191 193
As shown in Eq. (5), the ohmic drop is an important 50 100 196 232 250 255
parameter in electrowinning, since it significantly con- 50 150 235 254 292 280
50 200 274 305 315 323
tributes to the total energy requirement. In cobalt and
60 50 148 174 189 189
nickel electrowinning, it can account for more than 15% 60 100 188 218 243 240
(Wu et al., 2002) or $2.9 million of the total energy re- 60 150 219 240 288 271
quirement calculated in Eq. (5). The ohmic drop in co- 60 200 267 304 315 320
balt and nickel electrowinning is considerably larger 70 50 145 170 185 187
70 100 179 208 236 228
than that of copper or zinc electrowinning, and there-
70 150 205 224 284 258
fore it is very important to consider this drop in cobalt 70 200 258 297 309 313
and nickel electrowinning. This is due to the conduc- 80 50 142 167 182 184
tivity of cobalt electrowinning electrolytes at 60 °C being 80 100 173 197 230 214
very similar to nickel at 0.12 S/cm (Wu et al., 2002), but 80 150 193 216 280 249
80 200 253 292 305 309
much lower than copper at 0.65 S/cm and zinc at 0.50
S/cm (Ettle, 1977).
The ohmic drop is proportional to the electrode
centration. Of note, the influence of temperature and the
gap, current density and is inversely proportional to
acid concentration on the specific electrical conductivity
the specific conductivity of the electrolyte as given by
is most significant at temperatures and the concentration
Eq. (6).
of the sulfuric acid below 40 °C and 150 g/l H2 SO4 re-
1 spectively, since both trends subsequently begin to level
Ohmic drop ðVÞ UE ¼ LI ð6Þ off. Despite of a lack of linearity and a complicated
k
dependency, the electrical conductivity can still be
where k is the specific conductivity of the electrolyte, L is
expressed by the following equation:
the electrode gap and I is the current density. In order to
 
decrease the ohmic drop, one has to increase the con- mS
ductivity, decrease the electrode gap or decrease the Conductivity ¼ 103:86  0:29464½Co

cm
current density. The latter two are difficult to change
due to restraints associated with cell design limitations þ 0:82661T þ 0:91000½H2 SO4

and production rate requirements, but an increase in ð7Þ

conductivity could be considered. As well known, higher
electrolyte conductivity could significantly reduce en-
ergy consumption because it could allow the electro-
winning to be performed at lower applied voltages.
The results of electrical conductivity measurement are
tabulated in Table 2 and in Figs. 1–3. Fig. 1 demon-
strates the linear effect of cobalt concentration on the
electrical conductivity. It was found that the conduc-
tivity decreases with an increase in cobalt concentration.
The effects of temperature (Fig. 2) and H2 SO4 concen-
tration (Fig. 3) on the electrical conductivity are not
linear. The electrical conductivity increases with an in-
crease in both electrolyte temperature and H2 SO4 con-
where [Co] and [H2 SO4 ] are concentrations of cobalt
and sulfuric acid (g/l) respectively, and T is the electro-
lyte temperature (°C). Eq. (7) shows that the conduc-
tivity of the electrolyte increases with the addition of
sulfuric acid and an increase in temperature, but de-
creases with increased cobalt concentration. From this
empirical equation, the variance between calculated data
and experimental data is within 3%, whereas for nickel
was 14% (Wu et al., 2002). The result is a surprisingly
accurate fit, but it is suggested that conductivities
be interpolated directly from the experimental data in
Table 3.
532 C. Kargl-Simard et al. / Minerals Engineering 16 (2003) 529–535

350

Specific Conductivity (mS/cm)

330
310
290
270
250
230
210
190
170
150
20 30 40 50 60 70 80
50 g/L H2SO4 + 60 C 100 g/L H2SO4 + 60 C 150 g/L H2SO4 + 60 C 200 g/L H2SO4 + 60 C

Cobalt Concentration (g/L)

Fig. 1. The effect of cobalt concentration on the specific conductivity at 60 °C.

330
Specific Conductivity (mS/cm)

320

310

300

290

280

270

260

250
20 25 30 35 40 45 50 55 60 65 70
60 g/L Co + 200 g/L H2SO4 70 g/L Co + 200 g/L H2SO4 80 g/L Co + 200 g/L H2SO4

Temperature ( oC)

Fig. 2. The effect of temperature on the specific conductivity with 100 g/l Co.

350
Specific Conductivity (mS/cm)

330
310
290
270
250
230
210
190
170
150
50 70 90 110 130 150 170 190
20 g/L Co + 60 C 40 g/L Co + 60 C 60 g/L Co + 60 C 80 g/L Co + 60 C

Sulfuric Acid Concentration (g/L)

Fig. 3. The effect of sulfuric acid concentration on the specific conductivity at 60 °C.
 C. Kargl-Simard et al. / Minerals Engineering 16 (2003) 529–535 533

Table 3 cobalt sulfate is linearly dependent on the cobalt con-

Absolute measured density of CoSO4 –H2 SO4 electrolytes centration and the temperature. The density of the
Concentrations Absolute density (g/cm3 ) electrolyte decreases with an increase in the electrolyte
Co (g/l) H2 SO4 20 °C 40 °C 60 °C 70 °C temperature. However, the influence of temperature on
(g/l) the density is very small, less then 0.001 g cm3 per de-
20 50 1.012 1.002 0.991 0.983 gree centigrade. Of note, the electrolyte density relates
20 100 1.036 1.026 1.015 1.007 closely to the cobalt concentration. The density in-
20 150 1.058 1.048 1.038 1.029
creases substantially when the concentration of cobalt is
20 200 1.112 1.102 1.091 1.083
30 50 1.048 1.038 1.026 1.019 increased. Fig. 6 clearly shows that the density increases
30 100 1.067 1.057 1.045 1.038 with the sulfuric acid concentration, however, the rela-
30 150 1.090 1.080 1.068 1.061 tion is not a linear relationship. The graph strays from
30 200 1.146 1.136 1.124 1.117 linearity above 150 (g/l) H2 SO4 . This phenomenon
40 50 1.085 1.075 1.066 1.056
though, still allows for linear extrapolation, and the
40 100 1.101 1.091 1.079 1.072
40 150 1.123 1.113 1.102 1.094 relationship among the electrolyte temperature, the co-
40 200 1.180 1.171 1.159 1.151 balt concentration, the sulfuric acid and the electrolyte
50 50 1.208 1.111 1.100 1.092 density can be described via the following empirical
50 100 1.135 1.125 1.113 1.106 equation:
50 150 1.164 1.154 1.143 1.135  g 
50 200 1.222 1.213 1.201 1.193 Density ¼ 0:919 þ 0:003600½Co

60 50 1.157 1.147 1.127 1.128 cm3

60 100 1.170 1.160 1.149 1.141  0:000572½T
þ 0:000648½H2 SO4

60 150 1.199 1.189 1.178 1.170

60 200 1.258 1.248 1.238 1.229 ð8Þ
70 50 1.934 1.835 1.171 1.644
where [Co] and [H2 SO4 ] are concentrations of cobalt
70 100 1.204 1.195 1.182 1.175
70 150 1.231 1.221 1.210 1.202 and sulfuric acid (g/l), respectively and T is the electro-
70 200 1.291 1.281 1.270 1.262 lyte temperature (°C). Density values calculated from
80 50 1.230 1.220 1.209 1.201 this equation are in excellent agreement with actual
80 100 1.240 1.230 1.219 1.211 data, with a variance of only 0.25%, meanwhile the Ni
80 150 1.269 1.259 1.248 1.240
results were within a variance of 1.62% (Wu et al., 2002).
80 200 1.330 1.320 1.309 1.301

3.2. Density 4. Conclusions

The density values measured are reported in Table 3 Electrical conductivities and densities of cobalt sul-
and in Figs. 4–6. Figs. 4 and 5 show the effect of cobalt fate electrolytes at different temperatures have been
concentration and temperature on the measured density. measured. All conditions are similar to those in indus-
From these two graphs, it can be seen that the density of trial electrowinning processes. The benefits of higher

1.400
Absolute Density (g/cm3)

1.300

1.200

1.100

1.000

0.900
0 10 20 30 40 50 60 70 80 90 100
50 g/L H2SO4 + 60 C 100 g/L H2SO4 + 60 C 150 g/L H2SO4 + 60 C 200 g/L H2SO4 + 60 C

Cobalt Concentration (g/L)

Fig. 4. The effect of cobalt concentration on the absolute density at 60 °C.

534 C. Kargl-Simard et al. / Minerals Engineering 16 (2003) 529–535

1.300

Absolute Density (g/cm3)

1.200

1.100

1.000
0 10 20 30 40 50 60 70 80
60 g/L Co + 100 g/L H2SO4 70 g/L Co + 200 g/L H2SO4 80 g/L Co + 200 g/L H2SO4
o
Temperature ( C)

Fig. 5. The effect of temperature on the absolute density with 100 g/l Co.

1.400
Absolute Density (g/cm3)

1.300

1.200

1.100

1.000

0.900

0.800

0.700
0 50 100 150 200 250
20 g/L Co + 60 C 40 g/L Co + 60 C 60 g/L Co + 60 C 80 g/L Co + 60 C

Sulfuric Acid Concentration (g/L)

Fig. 6. The effect of sulfuric acid concentration on the absolute density at 60 °C.

electrolyte conductivity are a decrease in the ohmic drop achieved at high operating temperatures and large acid
and a decrease in power consumption. The benefits of concentrations. However, there are other aspects of
this would be decreased operational costs. electrowinning that might not allow operation at these
The density of cobalt sulfate electrolyte increases with preferred conditions such as strict morphology control
cobalt and sulfuric acid concentration, but decreases or metal production rate.
with temperature. The measurement of the electrolyte
density provides data for engineering design and pro-
duction. Acknowledgements
These results can be combined into empirical rela-
tionships. For the electrical conductivity and the elec- Financial support for this work provided by the
trolyte density, the empirical relationships can be Natural Sciences and Engineering Research of Canada
respectively expressed as follows: (NSERC) and Integran Technologies Inc. is greatly ac-
 
mS knowledged. The authors would like to thank Rudder
Conductivity ¼ 103:86  0:29464½Co
Wu for assistance with some of the experiments.
cm
þ 0:82661T þ 0:91000½H2 SO4

 g 
Density ¼ 0:919 þ 0:003600½Co
 0:000572½T
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