Evaluating Additives and Impurities in

Zinc Electrowinning
J.A. Gonzalez-Dominguez and R.W. Lew

INTRODUCTION
The zinc electrowinning (EW) process is Most of the world's primary zinc is produced via a combined roast-Ieach-purifi-
very sensitive to the presence of impurities. cation-electrowinning process.! There is only one plant in the world in which the
There is only one EW plant in the world that roasting step has been totally replaced by pressure leaching. 2 In both cases, metallic
we know of that operates at moderate current zinc is produced by electrowinning (EW) in an acidic sulfate electrolyte. Depending on
efficiency and deposition times without us- the electrolysis conditions, several additives may be added to the electrolyte to
ing any additives. All the others must use counteract the detrimental effects caused by impurities. If the electrolyte is very pure
them continuously. Additives allow zinc E W and the electrolysis conditions not very demanding (e.g., short electrodeposition
to occur at high current efficiencies while cycles, reliable electrolyte feed) additives are not needed.
suppressing excessive acid mist formation. There is only one EW plant in the world known to the authors that works at moderate
The study of the electrochemical effects of current efficiency (CE) and deposition time without using any additives. 3 This is
additives in zinc E W is not straightforward. accomplished by using a very pure electrolyte and a good ventilation system. Because
This article presents a review of the experi- of difficulties associated with thorough impurity removal and adequate ventilation
mental techniques currently used at Cominco systems, most zinc plants use electrolyte additives. Usually, plant operators decide to
Research: Cyclic voltammetry, Hull cells, increase or decrease the amount of additives based on deposit quality. Undoubtedly,
laboratory and mini-cell electrowinning tech- the main parameter that regulates the usage of additives is CE. Correlations between
niques are all described and their relation- the concentration of additives and CE have been explained by several authors.4-/! Some
ship to the industrial operation is discussed. additives (e.g., glue) are used to counteract impurity effects while others are used as
"frothers" (e.g., metaparacresol, licorice) to prevent excessive acid mist formation.
Some plants have automated techniques for tracking daily CE, while others have to
rely on weekly CE measurements, which are often done manually. The less frequent
the CE measurement, the less accurate the additive regulation. Because of difficulties
associated with moderating the concentration of additives in the zinc EW process,
several "on-line" devices have been invented. Among these, the continuous electrolyte
analyzer9 and the quality meterJO are used in Canadian plants. Still, the need exists for
ACKNOWLEDGEMENTS evaluating the electrochemical properties of zinc electrolytes in the laboratory and
Electrochemical tests presented in this correlating them with plant performance.
article include contributions by Dilip While physical-chemical methods can be used to characterize ZnSO4- H 2SO4 electro-
Makwana and Chuck Macklon. The helpful lytes, they may not show the effect of minor impurities during electrowinning. Thus,
guidance of R.c. Kerby is gratefully ac- for example, additive-free electrolytes with similar densities, viscosities, and conduc-
knowledged. Thanks are also due to Cominco tivities may have different minor impurity concentrations (e.g., a few I1gfL of germa-
Ltd. for permission to publish this article. nium) that may cause significant changes in CEo The real value of physical-chemical
measurements is realized when they are combined with CE computations.
This article describes the electrochemical techniques used at Cominco Research to
evaluate zinc EW electrolytes at the laboratory scale. These techniques are simple, yet
they provide quantitative and physical evidence that can be correlated with plant
performance.
To study the zinc EW process under laboratory conditions, small-area electro-
chemical cells can be used. Many laboratory cells have been described ll-!3 and used
successfully to study additives and impurity effects. At Cominco Research, two
electrochemical setups are used: the "mini-cells" and the "lab cells." Experimental
results from these cells are complemented by Hull-cell and cyclic voltammetry data.
MINI·CELLS
CuWire
The mini-cell setup uses a small aluminum cathode (2.25 cm2 area) and a lead-silver
Epoxy Resin anode (3.20 cm2 area). Laboratory electrodes are manufactured using cellhouse mate-
Plastic Table I. Experimental Results Obtained Using the Mini-Cell EW Setup

Duration of
Electrolyte type Experiment (h) CE(%)
_Electrode Synthetic + 2.5 mg/l glue 2 94.0 101,112,102 13
17 94.0
Industrial + Organic Contamination 2 86.6 101 20
17.1 87.9
Industrial + Organic Removed
using Activated Charcoal 2 93.5 101,112,102 24
Figure 1. Detail of one of the electrodes used "Good" Industrial Electrolyte
in the mini-cell setup. No Organics Present 2 95.2 112,101,102 18

34 JOM • January 1995

rials. The electrolyte volume can be set at either 300 ml or 1.51. The larger the electrolyte
volume, the smaller the change in concentration during the EW test. Electrode spacing
and area can also be changed. As shown in Figure 1, electrodes are prepared using a >.
0
c
cold-mount epoxy resin (Buehler catalog number 20-8130-032) and a silver-rich .~
conductive cement Oohnson and Matthey, catalog number 12942). A copper wire is iE
w 94.5
used to complete the electrical connection. The electrolysis cell is a Pyrex beaker fitted c
with a lid in which spacers are drilled to maintain a fixed separation (2-4 cm) between ~ 94
:J
anode and cathode. u
In the zinc EW process there is significant gas evolution-oxygen at the anode and 93.5
hydrogen at the cathode. When required, electrolyte is mixed by continuously recir- 0 1 2 3 4 5 6
Glue Concentration (mg/l)
culating the electrolyte using a peristaltic pump. Recirculation rates are set to displace
one electrolyte volume per hour. With or without electrolyte recirculation, experimen- Figure 2. Changes in CE as a function of glue
tal results are very reproducible (within O.1percent CE) and sensitive to impurities. content. Mini-cell setup, typical synthetic zinc
A reference electrode is sometimes used to monitor changes in cathodic andlor electrolyte [Zn] = 55 g/I, [H2SOJ = 160 gIl.
anodic over-potential. A water bath is used to control the electrolyte temperature at
38±10c. Addition agents are added in batch quantities every 24 hours. A low-ripple,
highly stable power supply is used to deliver a constant flow of current to the cells.
Current efficiency is computed from the weight of the deposit and the number of
ampere-minutes obtained from the cali-
brated integrator. Electrodeposition
times can range between 2 and 72 h. A- min
Deposits can be analyzed using micros-
copy and x-ray techniques. The assem-
bly of the cells is straightforward. Up to
top view
+1 -
I power supply I
20 cells can be run in series. Cell volt- /\tv
ages, anodic and cathodic over-poten- shunt
tials, and electrolyte temperature can be
monitored continuously by using a com- recirculation
inlet
puterized data logger system. The un-
compensated ohmic drop is computed -.L ;--'-
using a current interruption technique. 14
•• •
neutral feed
The mini-cell setup has been very use- and organic ~ •
I·
cathode • • •
ful for preventing CE losses in the cell- additions
house. For example (see Table I), last ~V
year after a plant shutdown, the zinc
electrolyte ([Zn]- 55 gil, [HzSOJ-160
...
gil) stored in two storage tanks (total ~~

-
volume -7,500 m 3) was thought to be
contaminated with asphalt and organic I. anode
I.

()
recirculation
debris. To quickly assess whether these
+~ /
outlet
materials could adversely affect CE in
the cellhouse, the mini-cell technique
overflow
~"
was chosen. Two-hour and 17-hourmini-
cell experiments were carried out. For reservoir
comparison purposes, synthetic electro-
lyte was prepared from pure neutral
electrolyte and reagent-grade sulfuric Figure 3. Schematic of the lab cell setup.
acid. Crystallographic orientation of the
deposits was correlated with CE.15
Table I shows that CE values obtained with synthetic electrolyte are 94.0% and do
not change with electrolysis time. On the other hand, low current efficiencies were
obtained with the contaminated plant electrolyte. Moreover, preferred zinc orienta- High Current Density End SCDmin
tion [101] was seen in these deposits. After removing the detrimental organic present
in the plant electrolyte with activated charcoal, CE increased and the growth orienta-
tion was nonpreferential. Thus, itwas concluded that the electrolyte was contaminated
and unsuitable for electrowinning. This electrolyte was diverted to the leaching plant.
Electrolyte stored in the other two storage tanks was also screened with the mini-cell
setup and found acceptable for EW (CE 95.2%). This electrolyte was used during start-
up of the EW plant. Low Current Density
While the above case describes a practical application of the mini-cells, they have ,.-2,000..-----,;,.;..;..;;.;...;..,;..;...;;....;;+;....;,
also been used to perform quantitative analysis of the effect of additives and frothers E
in zinc EW. Most importantly, the effect of glue, the principal additive used in the zinc ~1,500
EW process, can be correlated to CE (see Figure 2). ~
~ 1,000
o
LAB CELLS c 500
~
The main difference between mini-cell and lab cells is the size of the electrodes. The 8 00------;-----:;-- 6
surface area of one lab-cell cathode is 107 cm2 • The volume of the lab cell is 1.5 1. This 8
gives the lab cell a cathode surface-area-to-cell-volume ratio almost 100 times greater Distance across the cathode, Li (cm)
than the mini-cell (143 cm2 II versus 1.5 cm2 /l). Thus, in the lab cells, bulk electrolyte Figure 4. Hull cell cathode. The positions at
composition changes can be significant. Zinc is deposited onto the cathode while H+ which SCDmin and SCDsmooth were obtained
and oxygen are generated at the anode. Manganese is also depleted from the solution are indicated.

1995 January • JOM 35

 400 r-------------,
Table II. Zinc EW Plant Electrolyte Hull Cell Measurements
350 Glue Conc.* Sb'3 Conc.* SCDsmoothT SCDrn;n'
Date (mgll) (mgll) (Aim') (Aim')
300
12 August o 0.00 175±9 151±22
'f 250 18 August o 0.00 172±0 172±0
~ 18 August o 0.Q2 280±0 280±0
~ 200 18 August 10 0.00 108±0 86±0
~
8
(f)
150 Sb,3(mg/l) 11- Added in excess of amounts already present in plant e1ectrolyte.

100 0-0.00
(H).01 as it forms manganese dioxide. To compensate for these changes, fresh electrolyte is
50 b.-0.03 constantly added and the cell overflow is collected in a reservoir. A steady-state bulk
V-0.05 electrolyte composition is eventually reached.
00...- -........- - - ' - - -........-----'
5 10 15 20
The lab cells (see Figure 3) are used to study electrochemical processes under
Glue Concentration (mg/l) continuous operating conditions over an extended period. These cells have been used
a to test electrolyte composition, and organic additives (such as deposit-leveling agents
and frothing agents). Because of the larger size of the electrodes used in the lab cells
400 r------------, compared to those used in the mini-cells, lab cells are less susceptible to small
350 variations in electrode composition, microstructure, and surface treatment. Thus, the
experimental results obtained with the lab cells provide further information on the
300
performance of anode and cathode materials, and electrode surface/conditioning
'f 250 treatments. Mass balances are always used to follow electrochemical phenomena at
;;C the interfaces and in the bulk electrolyte. Cell voltages, anodic and cathodic over-
-;;E 200 potentials, and electrolyte temperature are continuously recorded using a computer-
o
g 150 ized data logger system.
The operating conditions for the lab cells are as follows:
100 • One central anode and two opposing cathodes.
50 • Electrodes are fabricated from cellhouse materials. The cathodes are masked
along the edges and back with epoxy resin.
00 5 10 15 • The submerged anode dimensions are 6.S cm x 1 cm x 12.6 cm
Glue Concentration (mg/l) • The submerged cathode dimensions are 9.7 cm x 0.6 cm x 11 cm
b • Cathodic current is 440 A/m2.
Figure 5. Changes in (a) SCD,mooth and (b) • Cell temperature is maintained at 3S±1ac.
SCDm;n as a function of glue and Sb·3 concen- • Each deposition cycle can last from 2 hours to 72 hours.
trations. • Maximum number of lab cells that can be connected in series is 10. The main
constraints are the size of the power supply and the water bath.
HULL CELLS
20 The Hull cell is a small plating bath in which the cathode is positioned obliquely with
E respect to the anode. 16 Because of the changing distance between the anode and the
~ cathode, nonuniform potential and current fields are generated across the cell. Thus,
-800 -600 g
~
the current density in the cathode decreases as the anode-cathode distance increases.
: Polarization, LlE (mV) -20 .~ From primary current distribution, the product ofthe current density times the anode /
, - - 8E uncompensated o'" cathode distance should be constant:
-40~
. - - -- LlE true :;
<.)
-BO where Ii is the cathodic current density at point i (A/ m 2) and d iis the distance between
anode and cathode at position i, m.
Figure 6. Voltammogram showing the effect Changes in current density across the cathode for a 267 ml cell can be computed
of the uncompensated ohmic drop on polar- using the following equation:17
ization. Synthetic electrolyte [Zn]=55 gil, \ = Itotal[51 0-524 log L) O.Scm::; Li::; S.lcm (2)
[H 2S04] = 150 g/I, 35°C, area of aluminum
substrate 1 cm 2 • where Itotal is the total current applied to the Hull cell (A) and Li is the distance across
the cathode from the high current density end (cm).
The empirical correlation derived by Hull et al. (Equation 2) was modified 18 to
ABOUT THE AUTHORS describe Ii from the theoretical primary current distribution:

J.A. Gonzalez-Dominguez earned his Ph.D. Ii = Itotal[396-3SSlog L) O.Scm::; L::; S.lcm (3)
in metallurgy at the University of British Co- Although current density variations based on more sound theoretical derivations
lumbia in 1991. He is currently a senior re- are available l9- 22 the original equation derived by Hull et a1. is still used. This reflects
search metallurgist at Cominco Research and
an adjunct professor at the University of Brit- the highly empirical nature of the technique.
ish Columbia. Dr. Gonzalez-Dominguez is The Hull cell operates under galvanostatic conditions (I = Itotal)' The smaller Itotal' the
also a member of TMS. lower the cathodic current density range and vice versa. Tests are usually conducted
at Itotal =2 A, which provides a current density range of 60-1,100 A/ m 2(Equa tion 2). The
R.W. Lew earned his M.A.Sc. in metals and tests last 1-20 min. depending on the electrolyte to be studied. The appearance of the
materials engineering at the University of
British Columbia in 1994. He is currently a deposit (i.e., brightness, smoothness, pitting, dullness, peeling) are recorded and
research metallurgist at Cominco Ltd. compared to standard deposits obtained under controlled conditionsp-25 The thick-
ness of the deposit can be measured by x-ray fluorescence, sectioning the cathode, or
measuring the local current density with an ammeter.26 Scanning electron microscopy
For more information, contact J.A. Gonzalez-
Dominguez, Cominco Research, P.O. Box 2000,
can also be used to study changes in microstructure as a function of current density.27
Trail, British Columbia, Canada V1 R 454; e-mail: The main advantage of the Hull cell technique is its simplicity. Changes in deposit
[email protected]. morphology and appearance as a function ofthe concentration ofleveling reagents can

36 JOM • January 1995

be quickly learned. The technique can be used both by R&D and quality assurance. The
disadvantages of the technique are often mentioned in the literature: 28
References
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1. c.K. Gupta and T.K. Mukherjee, Hydrometallurgy ill Extrac-
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• Inability to provide high-speed solution agitation. 1990)
2. M.j. Collins et al.. "Starting Up the Sherritt Zinc Pressure
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• Small changes (e.g., 10 m!) in electrolyte volume lead to significant deviations in 3. F. Tamargo and Y Lefevre, "Concepts and Operation of
the New Conventional Cell House of Asturiana de Zinc at
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effects of Sb+ 3, Sb+s, Mn04 -, and glue in ZnS04 -containing electrolytes. 29 They related japan: MMI), 1985), pp. 219-234.
6. RM. Morrison et a1., "The Effect of Some Trace Metals
the presence of these impurities and addition agents to changes in the stabilizing Impurities on the Electrowinning of Zinc from Kidd Creek
current density (SCD) as a function of the acid content and the electrolyte temperature. Electrolyte," Hydrometallurgy. 29 (1992), pp, 413-430.
7. RC. Kerby and T.R Ingraham, "Effect of Impurities on the
The SCD is the minimum current density at which stable zinc deposits can be obtained. Current Efficiency of Zinc Electrodeposition," Research Re-
port R243 (Ottawa, Canada: Department of Energy, Mines
O'Keefe et al. suggested that the absolute current density values obtained in the Hull and Resources, (197]).
cell are not as meaningful as the relative changes in SCD. Further studies 30 proved that 8. J.D. Miller, "Solution Concentration and Purification,"
Rate Process Extr. Metall .• ed. H.Y. Sohn and M.E. Wadsworth
Hull cells can be used to study mass transfer effects, current efficiency, and crystallo- (New York: Plenum, 1979), pp. 197-244.
graphic orientation in ZnS04-containing electrolytes. 9. R.c. Kerby," ApplicationofPolarizationMeasurements to
the Control of Zinc Electrolyte Quality for Electrowinning,"
To overcome some of the disadvantages of the traditional Hull cell, novel cell Application of Polarization Measurements in the Control of Metal
designs have been proposed. 3 ] Among these, the rotating ring-cone setup is the most Deposition, ed. I.H. Warren (New York: Elsevier, 1984), Pl'.
84-132.
promising. Such electrode shape is designed to give segmented deposits from which 10. G. Houlachi et al., "An On-line Sensor for Monitoring the
microstructural differences can be studied and related to current efficiency and Quality of Zinc Sulfate Electrolyte," Modellil1g, Simulatiml
and Control of Hydrometallurgical Processes, ed. V.G. Papa-
throwing power. Another improvement is the measurement of the reflection of gelakis and G.P. Demopoulos, (Quebec City, Canada: CIM,
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11. A.R. Ault and G.c. Bratt, "Control of Manganese Level in
roughness. 32 an Electrolytic Zinc Plant Circuit by Anodic Deposition of
Oxide," Proc. Australas. Insl. Min. Metall .• 254 (1975), pp. 37-
Hull Cell Experimental Setup 45.
12. E.}. Frazer and I.e. Hamilton, "The Estimation of the
Coulombic Efficiency of Zinc Electrodeposition by Measure-
A 267 ml Hull cell was used at Itot .] = 2 A. Conditioned lead-silver (O.7S% Ag) anodes ment of Current Efficiencies at a Rotating Ring Disc Elec-
and aluminum cathodes were used (aluminum mill finished, series 3003 H-14, trode," ,. Appl. Eleetrochem .• 16 (1986), pp. 387-392.
13. R Wiart et a I., ,. Appl. Electrochem., 20(1990), pp. 381-389.
coupons size: 0.6 x 76 x 127 mm, from the Q- Panel Company, 26200 First St., Cleveland, 14. Instrumental Methods in Electrochemistry, Southhampton
Ohio). The total volume of electrolyte in the cell was fixed at 2S0 ml and Equation 2 was Electrochemistry Group (Chichester, Great Britain: Ellis
Horwood Ltd., 1985).
used to obtain the values of the SCD. The only convection source was due to H2 and 15. D.J. Mackinnon,} _M. Brannen, and P.L Fenn, "Character-
02 evolution. Tests were run at least in duplicate using freshly prepared electrolyte, at ization of Impurity Effects in Zinc Electrowinning from
Industrial Acid Sulfate Electrolyte," ,. Appl. Elcctroehem., 17
38±1°C. Purified neutral ZnS04 and reagent grade H 2S04 were used to prepare (1987), pp. 1129-1143.
synthetic electrolytes containing SS gil ZnS04 and 160 gil H 2S0 4 , To this solution, 16. "Directions for Hull Cell Plating Tests," McGean-Rohco
Inc., Data Sheet.
fixed amounts of reagent-grade K(SbO)C4HP6 . O.5HP, and South African pearl glue 17. A.F.5. Afshar, D.R Gabe. and B. Sewell, "Rotating Elec-
were added. trode Current Density Cells to Simulate High Speed Elec-
trodeposition," Tr. lnst. Met. Finish, 69 (J) (1991), pp. 37-44.
The SCD of zinc deposits was measured at two different locations along the cathode 18. j.B. Moller, "Plating Cells for Control of Plating Baths,"
(Figure 4). The first location shows the minimum point at which zinc deposits can be Metal Finishing, 86 (1982). pp. 65-68.
19. l. Kadija et aI., "Hydrodynamically Controlled Hull
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20. A.N. Koshev and N.r. Poddubnyi, "Effect of Electro-
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Current Distribution in the 1lull Cell," Tr. Inst. Met. Finish,52
Changes in SCDsrnooth and SCD rnin as a function of glue and Sb+ 3 additions are shown (2) (1974), pp. 71-72
22. N. IbI, "Current Distribution," Comprehensive Treatise of
in Figures Sa and Sb, respectively. As the glue concentration increases, the SCD Electrochemistry, vol. 4, ed. j.O. Yeager, B.E. Conway, and S.
decreases, indicating that zinc deposition has been favored by glue additions. Without Sarangapani, (New York: Plenum Press, 1983).
23. T. Rajagopaland K.5. Rajam, "A New Addition Agent for
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evolution. At Sb+ 3 levels of O.OS mg/I, glue additions cause a linear decline in the SCD. 24. H.V.K. Udupa, K.c. Marasimhan, and P.e. Gomathi,
"Codeposition of Lead-Copper from a Nitrate Bath," Plating
On the other hand, at Sb+ 3 levels lower than O.OS mg/I, glue additions larger than 10 and Surface Finishing (December 1975), pp. 1150-1154.
mg/l do not significantly affect the SCD (Le., SCD remains nearly constant at levels 25. T.V. Venkatesha, ). Balaahandra, and S.M. Mayanna.
"Acidic Zinc Sulfate." Metal Finishing, 83 (1979), pp 17-20.
higher than 10 mg/!). 26. }.B. Mohler, "Finishing Pointer-the Current Density
Meter," Metal Finishing. 87 (1983). pp. 53-54.
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and Operating Parameters in Zinc EW," J. App. Electrochem.,
Industrial electrolytes from the zinc EW plant have been characterized using the 21 (1991), pp. 785-792.
28. R. Terakado and H. Nagasaka," A New Alternative to the
Hull Cell technique (Table 11). SCDsrnooth value obtained on August 12 and August 18 Hull Cell," Metal fill/siting, 83 (1979), pp. 17-20.
29. A.Y. Hosny, T.j. O'Keefe, and W.j. james, "Hull Cell
is -170 A/m2 which is close to the values obtained with synthetic electrolytes Technique for Evaluating Zinc Sulfate Electrolytes," Min.
containing metaparacresol (a frotherused to suppress excessive acid mist formation 33 ). Ellg., 2 (2) (1989), pp. 415-423.
30. A.Y. Hosny et aI., "Effect of Gas Sparging on Mass
The plant electrolyte is very sensitive to glue and antimony additions: glue additions Transfer in Zinc Electrolytes," f. Appl. Elfctroehem., 22 (1992),
decrease the SCD while antimony increases it (e.g., see August 18 data). An interesting pp. 396-405.
31. P.Y. Lu, "The Lu Cell, A Hull Cell with a Rotating
characteristic of plant electrolytes is the proximity of the SCDsrnooth and SCD min values. Cathode," Plating alld Surface Finishing, 78 (1991), pp. 62-65.
32. M.G. Newman et a1., "Controlling Processes for the
CYCLIC VOL TAMMETRY Electrolytic Recovery of Metals," Canadian Patent Applica-
tion Number 2,003,913 (Mav 27,1991).
The electrochemical cell and experimental procedure have been described in Refer- 33. C.). Krauss and D.). beBiasio, "Mist Control with
MetaparacresoJ," Canadian Patent 978,137 (November 18,
ence 34, and a recent review of the technique and equipment is in Reference 3S. It is very 1975)
important to reduce and account for the uncompensated ohmic drop between the 34. D.j. Mackinnon, RM. Morrison, and j.M. Brannen, "The
Effects of Nickel and Cobalt and their Interaction with Anti-
reference and working electrodes. Figure 6 shows a typical voltammogram. There is mony on Zinc Electrowinning from Industrial Acid Sulfate
a significant difference between the "uncompensated" and "true" polarizations. With Electrolyte," f. Appl. Eleetrachem., 16 (1986), pp. 53-61.
35. }.A. Gonzalez-Dominguez, "A Review of Lead and Zinc
the availability of advanced electrochemical equipment, ohmic compensation is Electrodeposition Control by Polarization Techniques/' Min-
erals Engineeril1g, 7 (1) (1994), pp. 87-97.
straightforward. On the other hand, by using microelectrodes 36 the uncompensated 36. M. Fleischmann et al., Ultramicroelectrodes (Morganton,
ohmic drop is insignificant and can be neglected. NC: Datatech Systems Inc., 1987).

1995 January • JOM 37