Int. J. Miner. Process.

72 (2003) 151 – 162

www.elsevier.com/locate/ijminpro

Electrochemical potential controlling flotation

R. Woods *
School of Science, Griffith University, Nathan Campus, Nathan, Queensland 4111, Australia
Received 18 June 2002; received in revised form 20 June 2003; accepted 30 June 2003

Abstract

The development of the understanding of flotation systems based on electrochemical concepts and techniques is reviewed.
An improvement in devising flotation strategies has been achieved through the consideration of electrochemical potential as one
of the parameters to be monitored and controlled in the laboratory. The progress that has been made in applying potential
measurements in flotation plants is also examined.
D 2003 Elsevier B.V. All rights reserved.

Keywords: electrochemistry; monitoring potential; potential control; self-induced flotation

1. Electrochemistry of flotation first studies of the interaction of flotation collectors

It is now more than four decades since Nixon
proposed an electrochemical mechanism to explain
the interaction of thiol flotation collectors with sulfide
mineral surfaces and provide a means of reconciling
the different theories that had previously been reso-
lutely advanced (Woods, 1996). The electrochemical
approach considers a surface species to be formed by
an anodic oxidation reaction involving the collector
occurring simultaneously with a cathodic process
which is usually the reduction of oxygen. Thus,
adsorption of the collector, the key chemical step in
the flotation process, is amenable to investigation
using electrochemical techniques and the component
anodic and cathodic processes can be studied sepa-
rately at sulfide mineral electrodes.
Doug Fuerstenau was a pioneer in the study of
sulfide flotation systems under potential control. The
* Tel.: +61-7-38757550; fax: +61-7-38756572.
E-mail address: ronwoods@sct.gu.edu.au (R. Woods).
with sulfide mineral electrodes were made by Woods
(1971) (galena/ethyl xanthate), Kowal and Pomianow-
ski (1973) (chalcocite/ethyl xanthate), and Chander
and Fuerstenau (1974) (chalcocite/diethyldithiophos-
phate). Electrochemical techniques were applied by a
number of authors to the investigation of sulfide
flotation systems, particularly during the late 1970s
and the 1980s (Woods, 1996). These studies have
identified potential regions in which (i) the thiol
chemisorbs, (ii) a thiol compound is formed with a
metal component of the mineral, and (iii) the dithio-
late is produced. Chemisorption is generally the
thermodynamically favoured process and occurs at
potentials below the reversible value for the formation
of the metal thiolate. The potential dependence of
equilibrium chemisorption coverage for a number of
mineral/collector systems has been found to obey the
Frumkin adsorption isotherm (Woods, 1996). This
isotherm is a phenomenological equation based on
macroscopic considerations and has been shown to
apply to a range of systems in which species are

0301-7516/$ - see front matter D 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0301-7516(03)00095-4
152 R. Woods / Int. J. Miner. Process. 72 (2003) 151–162

chemisorbed on solid surfaces from the gas phase or
from solution. The Frumkin isotherm has been
explained in terms of molecular-model theories in
which the free energy of adsorption varies with
coverage, through either heterogeneity of surface sites
or interactions between adsorbed molecules. Chemi-
sorption offers the most effective utilization of the
collector because a monolayer forms before the nu-
cleation and growth of the bulk phase. Metal thiolate
phases usually develop on the chemisorbed monolay-
er. Dithiolates may form in addition to the metal
thiolate, the dominant bulk reaction depending on
which of the two redox potentials is the most negative.
By using particle bed electrodes, or controlling the
potential of mineral pulps through the addition of
redox reagents, the potential dependence of flotation
recovery has been determined for a number of sulfide
mineral/thiol collector systems. The potential depen-
dence of flotation for three sulfide mineral/thiol col-
lector systems is compared to the corresponding
adsorption isotherms in Fig. 1.
Clearly, if there is a difference in the potential at
which different minerals float with a particular col-
lector, then control of the potential should allow
flotation separation. For example, Chander and Fuer-
stenau (1983) showed that chalcocite could be sep-
arated from molybdenite through appropriate choice
of the potential of flotation. The early work on the
potential dependence of flotation led researchers to
assume that it would be possible to develop separa-
tion strategies from differences in recovery/potential
relationships established experimentally for individ-
ual minerals. Progress in this endeavour became
constrained, however, by the finding (Guy and
Trahar, 1985; Gebhardt et al., 1985; Gebhardt and
Richardson, 1987) that the behaviour of mixtures
could not be predicted accurately from single mineral
studies. The behaviour of simple mixtures compared
with those of the individual minerals is shown in
Figs. 2 and 3.
Fig. 2 shows the results reported by Guy and
Trahar (1985) for mixtures of galena and chalcopyrite

Fig. 1. Comparison of potential dependence of flotation recovery with the corresponding adsorption isotherm for (A) galena/ethyl xanthate, (B)
chalcocite/ethyl xanthate, and (C) chalcocite diethyldithiophosphate (from Woods, 1996).
 R. Woods / Int. J. Miner. Process. 72 (2003) 151–162
Fig. 2. Floatabilities under reducing and oxidizing conditions for
chalcopyrite (Cp) and galena (Gn) from quartz (Q) and from
chalcopyrite, galena, quartz mixtures with ethyl xanthate as
collector (from Guy and Trahar, 1985).
Fig. 3. Floatabilities with ethyl xanthate as collector of chalcocite (Co) and pyrite (Py) alone and from mixtures of the two minerals which were
prereduced at 0.36 V or preoxidized at open circuit (0.2 V) prior to flotation (from Gebhardt and Richardson, 1987).
153
with ethyl xanthate as collector compared with those
for the individual minerals. These authors noted that,
from single mineral studies, it should be possible to
float chalcopyrite from galena at oxidizing potentials,
while the converse flotation separation of galena from
chalcopyrite should be possible at low potentials. As
Fig. 2 shows, chalcopyrite was found to float effec-
tively at the oxidizing potential of 0.45 V whereas
galena recovery is small and conversely, galena to
float efficiently at the reducing potential of 0.15 V
whereas chalcopyrite recovery is small. However, it
can be seen that the minerals interact with each other
when they are present together in such a manner that
the inherent differences between their recoveries are
diminished. Thus, at 0.45 V, chalcopyrite recovery is
reduced by a factor of f 4 when galena is present
while galena recovery is approximately doubled in the
presence of chalcopyrite. At the reducing potential of
0.15 V, galena flotation is diminished by f 40%
whereas chalcopyrite recovery is enhanced by a factor
of f 5 when the minerals are present together.
The influence of each mineral on the flotation
response of the other was explained (Guy and Trahar,
1985) by a modification in the flotation response of
galena (towards that of chalcopyrite) by incorporation
of copper ions derived by oxidation of chalcopyrite
and a modification in the response of chalcopyrite
154 R. Woods / Int. J. Miner. Process. 72 (2003) 151–162
(towards that of galena) by replacement of iron in
chalcopyrite by lead ions from galena.
A similar loss in selectivity in a pyrite –chalcocite
mixture was reported by Gebhardt and Richardson
(1987) and this is illustrated in Fig. 3. This figure
shows that, with single minerals, chalcocite floats
efficiently with ethyl xanthate at potentials above
0.15 V, while pyrite does not begin to float until
f 0.05 V. This indicates that there should be a
potential window of f 0.2 V in which chalcocite
could be readily floated away from pyrite. But the
difference between the potential dependence of flota-
tion of the two sulfide minerals is diminished consid-
erably in the mixture, ease of separation depending on
mode of pretreatment. Thus, Fig. 3 shows that the
presence of pyrite significantly depresses chalcocite
while chalcocite activates pyrite when the minerals are
present in a mixture.
It is clear from these studies that flotation recovery
of sulfide minerals from mixtures is still a function of
potential, even though it is not readily predictable
from single mineral studies.
Electrochemical techniques have provided valuable
information on the kinetics and mechanisms of pro-
cesses occurring at the solid/solution interface, but
electrochemical characterizations lacks the molecular
specificity required to give unequivocal identification
of species formed at electrode surfaces. For this
reason, a number of in situ and ex situ spectroscopies
have been applied to augment electrochemical
approaches and provide information on the elemental
and molecular composition, the atomic geometry, and
the electronic structure of the interface. Spectroelec-
trochemical studies of mineral flotation have been
reviewed recently by Buckley et al. (2002).
The importance in flotation of the effects of gal-
vanic interaction between sulfide minerals and grind-
ing media was highlighted by Iwasaki et al. (e.g.,
Adam et al., 1984; Pozzo and Iwasaki, 1989). These
authors demonstrated in laboratory studies the electro-
chemical nature of such interaction, which adversely
affects the floatability of sulfide minerals. Later studies
at Virginia Polytechnic Institute and State University
have sought to minimize wear and corrosion of grind-
ing media in ball mills through cathodic protection.
Pazhianur et al. (1997) employed impressed current to
cathodically protect grinding media and reported that
this procedure reduced wear by 30 –60%.
2. Self-induced flotation
A few sulfide minerals are naturally floatable as
a result of preferential cleavage along planes of
sulfur atoms that have all chemical bonds satisfied.
Other sulfides have been found to float under oxi-
dizing but not reducing conditions. As with collec-
tor-induced flotation, the process responsible for
rendering the mineral floatable is electrochemical in
nature. In the self-induced flotation case, the anodic
reaction is oxidation of the surface to a sulfur
species.
Fig. 4 shows a comparison of the potential depen-
dence of floatability of chalcopyrite at pH 11 as
determined by Heyes and Trahar (1977), Luttrell
and Yoon (1984), and Gardner and Woods (1979),
with the anodic current on a voltammogram at this pH
reported by Gardner and Woods (solid line). It can be
seen that there is a good correlation between the
potential of onset of flotation and the commencement
of the anodic current.
The electrochemical mechanism of self-induced
flotation is further supported by the observation
(Woods, 1991) that the potential of onset of flotation
correlates with the reversible potentials for sulfide
mineral oxidation. The open circles in Fig. 5A show
the potential for 50% recovery reported by Healy
and Trahar (1989) plotted against the standard
potentials of the reactions forming S0 plus M(OH)2
for the binary sulfides and S0 plus Fe(OH)2 plus
Fig. 4. Anodic current and flotation response of chalcopyrite in the
absence of collectors (from Woods, 1996).
 R. Woods / Int. J. Miner. Process. 72 (2003) 151–162
Fig. 5. Potential of onset of flotation compared with standard and
reversible values (from Woods, 1991).
copper or nickel sulfide for the ternary sulfides.
The solid line is drawn at a 45j slope that cor-
responds to an exact correlation between the two
parameters.
The standard potential refers to each component in
its standard state and hence to pH 0, since H+ ions are
released in the oxidation reaction. The dashed line in
Fig. 5A corresponds to the reversible potentials at a
pH value of 8.5, which is close to that corresponding
to the flotation measurements. It can be seen that a
good correlation exists with the observed flotation
edges.
The important reaction could be the formation of
the M2 + ion rather than M(OH)2. The flotation
potentials of Healy and Trahar are plotted in Fig. 5B
(open circles) against the standard potentials of the
MS/M2 +, S0 couples, again assuming that only iron is
removed from the ternary sulfides. It is apparent that a
good correlation exists for this reaction as well as for
the formation of the metal hydroxides. The standard
potential relates to 10 5 mol dm 3 M2 + for each
mineral (dashed line), which is a realistic value for
flotation systems.
155
3. Practical application of self-induced flotation
The self-induced flotation of a range of sulfide
minerals has been well established in laboratory
studies. However, this phenomenon has yet to be
applied effectively in practice. Two problems are
encountered that are difficult to overcome.
Firstly, the self-induced flotation of related miner-
als of the same metal can be quite different. For
example, chalcopyrite can float most effectively in
the absence of collectors whereas chalcocite displays
negligible floatability in similar environments. These
minerals occur together in many copper ores and
hence the different responses of these related minerals
raise serious problems.
Secondly, self-induced flotation is sensitive to
inhibition from metal hydroxides (Senior and Trahar,
1991; Grano et al., 1997). The development of metal
hydroxides will depend on the grinding media and
will vary with ore type and water source. The inhibi-
tion by metal oxides can readily be avoided under
laboratory conditions but is difficult to control on the
industrial scale. The effect of hydroxides can be
reduced or eliminated by complexing the depressant
ions but this is unlikely to be economically favourable
with respect to the addition of collectors. The addition
of collectors, even at low levels, can counter the effect
of hydroxides and establish efficient flotation. It is
often difficult to ascertain to what extent this amounts
to collector-induced flotation or to countering the
inhibition by hydroxides of self-induced flotation
(Senior and Trahar, 1991).
Attempts were made by Control International to
exploit the phenomenon commercially in Arizona
copper mines in the late 1980s (Arbiter and Gebhardt,
1992). Flotation recoveries in the complete absence of
collector failed to match that achieved in conventional
practice. The conclusions reached in these studies are
best expressed in the words of Arbiter and Gebhardt
(1992) when they reviewed the work carried out by
Arbiter and Vargas in the southwest US copper mines,
‘‘In view of the low collector requirements and cost
for the copper ores tested, the present practicality of
collectorless flotation on an industrial scale is ques-
tionable. Based on cost of collector alone, it would not
appear practical that one could achieve sufficient
control of the electrochemical environment at similar
cost. However, if one can offset, by better control of
156 R. Woods / Int. J. Miner. Process. 72 (2003) 151–162
the electrochemical conditions, the extensive use of
lime as a modifier for flotation and corrosion control
and achieve similar or improved metallurgy, then it
may be practical to pursue this goal. Other costs
associated with controlling the system environment
need to be considered, including those for replacing or
purifying system water, or using complexants to
nullify ionic depressant effects, and the probable costs
of additional equipment for these purposes. The
combination of control of the electrochemical envi-
ronment with judicious use of reagents may offer the
best approach to optimizing metal recovery at mini-
mal costs’’.
Although it has not proved possible to date to
exploit flotation without collectors, it should be point-
ed out that self-induced flotation can occur whenever
the potential is in the region of surface oxidation.
Thus, self-induced flotation acts as a complication in
collector-induced flotation.
An interesting approach to inhibiting the collector-
less flotation of pyrite in coal flotation was adopted by
Yoon et al. (1996). It was shown that pyrite rejection
can be improved by galvanic coupling the pulp with
active metals such as zinc, manganese, and alumini-
um. These metals act as sacrificial anodes and main-
tain the potential of the pulp below the region in
which superficial oxidation of pyrite occurs to form a
hydrophobic surface layer.
4. Monitoring potential in developing flotation
strategies
Electrochemical studies of sulfide flotation systems
have clearly shown that flotation recovery is a func-
tion of the potential across the mineral/solution inter-
face. The possibility of using measurements of
potential, commonly known as the Eh, to monitor or
control flotation has been considered by many groups
throughout the world since the pioneering measure-
ments of Eh in Australian flotation plants made by
Jones and Woodcock (1971). For example, Ralston
(1991) reviewed ‘‘Eh and its consequences in sulphide
mineral flotation’’ more than a decade ago and point-
ed out that ‘‘Eh is a very useful diagnostic parameter,
whether it is used in the plant or the laboratory’’. Now,
most laboratories apply potential measurement to
derive optimum flotation strategies for operation in
the plant. As pointed out by Hintikka and Leppinen
(1995) ‘‘monitoring of potential with noble metal
electrodes is now almost routinely carried out in
laboratory testwork and full-scale processes’’. Early
examples of the application of potential measurements
in developing flotation strategies are those of Johnson
(1988) at Mt. Isa Mines in Queensland.
The aim in laboratory studies is to establish the
same Eh at the commencement of flotation as occurs
in the plant. The scale-up factor from laboratory to
plant mill, together with aeration during cyclone
classification, is such that the Eh profile in the process
will differ between the laboratory and the plant
situation. One approach to simulating the plant was
adopted by Arbiter and Vargas (private communica-
tion), who found that grinding in a mill charged with
80 – 85% stainless steel and 15 – 20% mild steel
resulted in flotation behaviour in the laboratory anal-
ogous to that in the plant.
4.1. Outokumpu Oy
Outokumpu Oy promotional literature, ‘Turning
theory into profit’, states that, in flow sheet develop-
ment, special attention is paid to electrochemical
measurements and that ‘‘Eh data, in conjunction with
other metallurgical information, can lead to significant
improvements in existing processing strategies’’.
Rounala et al. (1997) reported laboratory investi-
gations on the influence of grinding media and flota-
tion gas composition on flotation efficiency of sulfide
ores. Studies on Outokumpu ores have also been
made by VTT Chemical Technology laboratories
(Hintikka and Leppinen, 1995) in which the flotation
gas composition was varied for potential-controlled
flotation. Following grinding, air was used in the
flotation cell until the potential of noble metal and
mineral electrode probes inserted in the pulp reached a
selected value and then a mixture of nitrogen and air
was used to maintain the potential of a mineral
electrode to within 2 –5 mV of this value throughout
the flotation stage.
Fig. 6 shows the results obtained for a complex
copper –zinc –lead ore using a chalcopyrite electrode
to monitor potential. It can be seen that the optimum
potential for separation of the chalcopyrite from the
other two sulfides is f 0 V. The authors reported that
‘‘the selectivity in the flotation process was signifi-
 R. Woods / Int. J. Miner. Process. 72 (2003) 151–162
Fig. 6. Effect of potential on the recovery of elements from a
complex Cu – Zn – Pb ore. Potassium amyl xanthate 150 g/t, SO2
400 g/t, pH 11.5, flotation time 10 min (from Hintikka and
Leppinen, 1995).
cantly improved under conditions of controlled po-
tential compared to open potential conditions’’.
4.2. Original potential flotation
The Central South University of Technology in
Changsha, China has utilized electrochemical studies
Fig. 7. Effects of pulp pH and Eop on lead – zinc – iron sulfide minerals flotation (from Guohua et al., 2000).
157
in the laboratory to develop their Original Potential
Flotation (OPF) technology. This group studied the
electrochemistry of galena flotation and, from these
studies, advanced a modified, conventional flotation
procedure for the treatment of lead – zinc ores using
different collectors from those in previous practice
and floating at different pH.
This group reported (Guohua et al., 2000) that the
OPF technology has been applied successfully in
galena flotation of complex lead –zinc –iron sulfide
minerals in China. The flotation flow sheet is
simpler than that used previously due to the lead
flotation rate being accelerated. For example, in the
Nanjing lead – zinc mine of Jiangshu Province, the
number of flotation machines needed was decreased
to one half without cutting down the production
capacity. Other ores investigated were from the
Fankou and Lechang lead – zinc mines of Guang-
dong Province and the Beishan lead – zinc mine of
Guangxi Province. The main minerals present in the
four ores were galena, sphalerite and pyrite, but their
content and the degree of oxidation, were different.
The most effective collector identified in OPF stud-
ies was diethyldithiocarbamate and this compound
was applied at a dosage below 70 g/t, and lime was
158 R. Woods / Int. J. Miner. Process. 72 (2003) 151–162

used to modify pH and Eop. Their test results are

given in Fig. 7.
Although the ores were obtained from different
mines, the relationship between pH and Eop was found
to be the same. Thus, they were able to translate their
findings to the plant situation by simply monitoring
pH. It can be seen from Fig. 7 that, at pH >12.5, the
Eop is < 0.17 V and, under these conditions, the
recovery of galena is the optimum and the content
of sphalerite and pyrite in the lead rougher concentrate
is least.
The improvements achieved by the adoption of the
OPF flotation strategy, compared to that using the
previous approach, are reported to be substantial as Fig. 8. Grade vs. recovery curve for lead indicating the effect of
can be seen from Table 1 (Guohua et al., 2000). changes in the pulp potential from the value occurring in the
plant and of amyl xanthate additions (from Uribe-Salas et al.,
2000b).
4.3. SIPSA Peñoles, Mexico

Uribe-Salas et al. (2000a,b) recently reported that had been adopted for industrial operation and good
significant metallurgical improvement was achieved results were obtained.
in the flotation of galena and chalcopyrite from a fine-
grain, complex pyritic ore as a result of adjusting the
pulp potential to around 0.3 V by the addition of 5. Potential monitoring and control of flotation
hydrogen peroxide. The collector used in this study
was a mixture of Aeroflot 404 (sec-butyl dithiophos- 5.1. Copper – molybdenum flotation
phate and mercaptobenzothiazole), Aerophine 3418A
(diisobutyl dithiophosphinate), and amyl xanthate. The use of nitrogen to replace air in the flotation
Noble metal electrodes were used to monitor the pulp stage of plants in which molybdenite is separated from
potential. Fig. 8 shows the improvement achieved by copper sulfides was introduced in the mid-1980s in
changing the pulp potential from the value reached in North and South American to minimize oxidation of
the plant under the prevailing conditions. the NaHS used to depress copper sulfides. At the same
The authors reported that a potential control sys- time, sulfide additions were monitored and controlled
tem, equivalent to the one described in their paper, by the use of noble metal electrodes inserted in the
pulp. Aravena (1987) reported that NaHS consump-
tion was reduced by 48% with the introduction of
nitrogen at the Chuquicamata mine in Chile and a
Table 1 further saving of 21% achieved when depressant
Flotation performance before and after adoption of the OPF
flotation strategy (Guohua et al., 2000)
additions were controlled by electrode measurements.
Mine Flotation Lead concentrate Zinc concentrate
technology
5.2. Controlled potential sulfidization
Grade Recovery Grade Recovery
Fankou OPF 62.61 85.40 55.11 95.51 Jones and Woodcock (1978) proposed that sulfid-
traditional 58.02 82.40 53.03 92.27 ization of oxidized lead and copper ores should be
Lechang OPF 57.20 82.35 51.05 91.65
traditional 56.47 80.11 50.70 87.02
carried out under potential control to improve perfor-
Beishan OPF 58.28 75.19 54.91 92.86 mance. Controlling the potential during sulfidization
traditional 55.05 70.01 54.67 88.87 ensures that the oxide component of the ore is
Nanjing OPF 55.45 90.06 53.62 91.52 sufficiently converted to sulfide for it to float while
traditional 51.57 86.17 51.49 87.00 the sulfide ions remaining in solution are insufficient
 R. Woods / Int. J. Miner. Process. 72 (2003) 151–162
to depress subsequent flotation. In both controlled
potential sulfidization (CPS) and copper/moly separa-
tion, the electrode responds to solution species, al-
though the solution species are responsible for control
of the potential of the mineral/solution interface.
Woodcock and Jones suggested that silver sulfide
ion selective electrodes be applied but this proved
inappropriate in plant practice and were replaced by
noble metal electrodes (Jones, 1991).
The improvement in performance resulting from
the use of CPS compared with that obtained with
‘slug’ addition of NaHS is shown in Fig. 9. In
Australasia, CPS, marketed through AMDEL labora-
tories, is being, or has been, applied at the Bodding-
ton, Cadia, Horseshoe, Mineral Hill, North Parkes, Ok
Tedi, Red Dome, Selwyn, and Telfer mines for the
treatment of copper/gold ores containing reactive
sulfides or mixed oxides and sulfides (Jones, 1991;
Woodcock and Hamilton, 1993; Woodcock, private
communication).
Mekhanobr in St Petersburg, Russia has also mar-
keted a CPS system (Mashevsky, private communica-
Fig. 9. Comparison of ‘slug’ vs. CPS sodium sulfide additions for
flotation of a mixed oxide – sulfide copper ore (from Ashton, 1984).
159
tion) and it has been applied in mines in Europe and
Asia for the separation of molybdenite from copper
sulfides and the flotation of oxidized lead –zinc and
copper ores.
Herrera-Urbina et al. (1999) have also concluded
that the xanthate flotation of sulfidized, mixed oxide –
sulfide ores may be controlled by monitoring pulp
potential.
Outokumpu recently suggested (Heimala and Jou-
nela, 2000) that djurleite (Cu1.96S) electrodes should
be used for CPS flotation of oxidized copper and
cobalt ores with the potential controlled between
600 and 300 mV vs. SCE, the optimum value
depending on mineral composition. It was found that
effective mixing of NaHS additions was important in
achieving good grades and recoveries.
5.3. Sulfide mineral flotation
More challenging for the flotation engineer than
controlling sulfide additions is the monitoring and
control of the potential of the mineral/solution inter-
face across the full range of flotation situations in
order to enhance performance and maintain it at a high
level. A number of groups throughout the world have
researched the concept of controlling flotation plants
through continuous measurement of potential in the
pulp.
The questions to be answered before a control
system can be made effective are:
 how should the potential be measured, and
 how should the potential be adjusted.
As pointed out above, noble metal electrodes are
appropriate for determining potential in systems in
which a dominant redox couple determines the
potential, such as in monitoring NaHS additions.
Such electrodes can also be used in conventional
flotation pulps for monitoring pulp potential; for
example, Hecker et al. (1999) applied platinum
electrodes for potential monitoring in the El Teniente
Colon concentrator’s SAG line feeding the copper
flotation rougher circuit. However, potential mea-
sured by a noble metal electrode in a conventional
pulp may not be that corresponding to a mineral/
solution interface of interest. Rand and Woods
(1984) demonstrated that a platinum or gold elec-
160 R. Woods / Int. J. Miner. Process. 72 (2003) 151–162
trode could express a potential close to that of a
galena electrode inserted into the same pulp due to
continued collision between the noble metal surface
and galena particles. However, this does not apply to
complex ores because different sulfide minerals in a
pulp can be at different potentials (Rounala et al.,
1997). Also, noble metal electrodes do not corre-
spond to sulfide mineral potentials in dilute pulps,
such as in the flotation of platinum group metal ores
(Buswell et al., 2002).
It would appear that the most appropriate method
of determining the potential of each sulfide mineral in
the flotation of complex ores is to use electrodes
composed of the individual minerals being floated
or depressed. However, the surface of the mineral
electrodes will continuously react with the collector
and other constituents of the pulp and hence will not
continue to respond in the same manner as the freshly
ground mineral particles of the same composition in
the flotation pulp. Outokumpu has addressed this
problem (Rounala et al., 1997) by regenerating sulfide
mineral electrodes ‘‘by electricity or ultrasound as
well as by mechanical cleaning’’. It is difficult to
know to what extent these treatments alleviate the
problem, or if better techniques are required to main-
tain the activity of sulfide mineral electrodes and
ensure that the potential expressed is the same as that
of the particular mineral in the flotation pulp being
monitored.
Adjustment of potential can be achieved by mod-
ifying the conditioning time or by changing the
composition of the pulp or flotation gas. It is interest-
ing to note that Newmont Technologies has developed
a process, N2TecR, for the flotation of refractory gold
ores that employs nitrogen as the carrier gas. This
process is being employed at the Lone Tree mine and
at the Tonkin Springs gold project (Symmons et al.,
1999). Presumably, the use of nitrogen inhibits the
oxidation of auriferous sulfide mineral fines. Measur-
ing pulp potential would appear to be a useful method
of monitoring such a process.
In most cases, the pulp chemistry that gives good
flotation recovery has been established by conven-
tional methods, and only small changes in potential
are required to maintain flotation efficiency at the
optimum level. A recent paper (Panayatov et al.,
2000) described technology for direct potential con-
trol using electrodes inserted in the pulp but regulating
pulp chemistry offers a simpler and more economic
approach.
5.3.1. Control International
Control International adopted an electrochemical
monitoring procedure for sulfide flotation plants (E-
CON) that was claimed to establish the relationship
between ore mineralogy and electrochemical varia-
bles. It was reported (Suttill, 1990; Herbst et al., 1994)
that application in a ‘‘major lead –zinc plant’’ resulted
in a reduction in overall processing costs as a result
of improved metallurgical performance and lower
reagent consumption. In particular, flotation could
be accomplished at much lower pH values than those
that were used in plant practice. Control International
promoted E-CON as a control method, in particular,
to regulate conditions in grinding that influence
subsequent flotation. No details of the electrodes
were announced in the Company’s promotional docu-
mentation but it is likely that a noble metal electrode
was employed. Apparently, the announcement in
1990 of this control system being available on the
market was premature and the Company did not
proceed with its development.
5.3.2. Outokumpu Oy
Outokumpu Oy in Finland has progressed further
than any other Company in the application of poten-
tial measurement for flotation control and has intro-
duced its OK-PCF potential monitoring system in a
number of its flotation plants. The system has been in
operation at the Hitura nickel mine since 1984, at the
Vammala nickel and Vihanti Cu/Zn/Pb mines since
1988 and was installed at the Pyhasalmi Cu/Pb/Zn/
FeS2 mine in the early 1990s. At Hitura, the replace-
ment of pH control by potential control resulted in an
improvement in nickel recovery by up to 2% depend-
ing on ore type (Rounala et al., 1997). At Vihanti, it is
claimed that lime and collector consumption has been
decreased to one third of the values experienced prior
to the installation of the OK-PCF system. It is claimed
that profitability has increased by 10 – 20% since
potentials have been monitored.
Outokumpu use electrodes composed of synthetic
or natural sulfide minerals, usually of the composition
being floated. For each valuable mineral, it is claimed
(Rounala et al., 1997) that there may be one or more
combinations of variables for the most economic
 R. Woods / Int. J. Miner. Process. 72 (2003) 151–162
processing, and this requires integration of on-stream
X-ray analysis, electrochemical potential measure-
ments, and collector concentrations. Despite a number
of years of experience in the application of electrode
measurements in flotation plants, Outokumpu has yet
to market a potential monitoring or control system.
6. Concluding remarks
Considerable advances have been made in under-
standing sulfide mineral flotation from an electro-
chemical viewpoint. This review seeks to highlight
how this knowledge has been used to identify and
solve problems in flotation plants and to develop
improved flotation strategies. The use of Eh measure-
ments to achieve more effective flotation in laboratory
and plant studies is now common practice. Continu-
ous monitoring of electrode potential is well estab-
lished practice in flotation plants in situations where
the potential is determined by a strong redox couple,
such as in chalcopyrite –molybdenite separation or the
sulfide activation of oxidized ores. The ultimate aim
of controlling potential in sulfide flotation plants in
the usual situation in which the potential is determined
by a balance between two or more electrochemical
processes has, however, proved elusive. It would be
incorrect to conclude that this means of potential is
not a realizable control parameter in such situations.
Maintaining electrode probes so that they respond
appropriately in these plants is difficult to achieve,
and the choice of materials for electrode probes and
methods to activate or regenerate surfaces have, most
likely, yet to be optimized. Clearly, this is an area for
further research.
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