Minerals Engineering 85 (2016) 130137

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

The use of zeta potential to investigate the interaction of oleate on

hematite
Keith Quast
Ian Wark Research Institute, University of South Australia, Mawson Lakes, SA 5095, Australia

a r t i c l e

i n f o

Article history:
Received 29 June 2015
Revised 27 September 2015
Accepted 6 November 2015
Available online 14 November 2015
Keywords:
Zeta potential
Oleate
Hematite
Isoelectric point
Effect of silica

a b s t r a c t
The aim of this paper was to investigate how the use of zeta potential measurements on the hematite
oleate system as a function of pH could provide additional information on this system. From the literature
survey it was found that the presence of oleate causes a reduction in both the zeta potential and isoelectric point of hematite compared to their values in the absence of oleate. There have been a number of
suggested mechanisms including the adsorption of soluble oleate solution species and precipitation of
oleate salts and/or oleate colloids or micelles, depending on the pH and the concentration of oleate in
solution. These phenomena were investigated using two hematite samples containing differing amounts
of silica. The results for oleate addition to the hematite sample containing the lower amount of silica followed the anticipated trends indicating lower values of zeta potential and isoelectric point with increasing oleate addition. The situation for the hematite sample containing the higher amount of silica, even
though it only contained 2.5% silica, was more complex. Although the increased addition of silica reduced
the values of the zeta potential, there appeared to be a major influence of the silica driving the values of
the zeta potential below those of the oleate at acid values of pH. It was proposed that this was due to a
combination of the presence of silica and oleate, suggesting that the mechanism was the physical adsorption or heterocoagulation of colloidal hematite on fine silica followed by the adsorption of oleate species
onto the hematite. An attempt was made to correct the equilibrium oleate concentration to account for
the adsorption of oleate onto the surface of the hematite, but this was only significant at the very low
addition rate of the oleate.
2015 Published by Elsevier Ltd.

1. Introduction
The author has investigated and published a number of articles
on the surface chemistry and flotation of hematite over many years
(Quast, 1999, 2000, 2005, 2006, 2010, 2012, 2015a,b; Quast and
Quast, 2010). Most of these articles involved the measurement of
the interfacial chemistry characteristics of the hematite surface
and laboratory flotation tests conducted on these hematite samples as a function of pH. It is the purpose of this paper to investigate how the use of zeta potential measurements on hematite as
a function of pH in the presence of oleate can provide additional
information on the interaction of oleate species with the hematite
surface as a function of pH. This can be seen as complementing the
detailed analysis of the hematiteoleate system at pH 7 previously
published by the author (Quast, 2010). At pH 7, the interaction of
oleate with hematite was confirmed as chemisorption, with the
orientation of the adsorbed oleate species progressing from horizontal to two-point to vertical as the addition of oleate was
E-mail address: Keith.Quast@unisa.edu.au
http://dx.doi.org/10.1016/j.mineng.2015.11.007
0892-6875/ 2015 Published by Elsevier Ltd.

increased. It is the purpose of this paper to report details of an

experimental study involving the effects of oleate addition on
two samples of naturally occurring hematite containing different
levels of impurities.
2. Literature survey
2.1. Surface chemistry of the oleate/aqueous system
A reference located in searching electronic databases by
Swaroop (1970) provided information concerning measurements
of zeta potential of aqueous solutions of sodium oleate, oleic acid
and a 1:1 mixture of the two species at pH 4.5. This was close to
the accepted value of the pKa of fatty acids, as used in the construction of solution equilibria diagrams referred to later. Under these
conditions, the concentration of undissociated oleic acid should
dominate over oleate ions. Swaroops numerical data was plotted
by the current author in Fig. 1. The obvious difference between
Swaroops data and that of all other data obtained is that all the
values of zeta potential are positive. I have plotted the solubility

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K. Quast / Minerals Engineering 85 (2016) 130137

40

Zeta Potential (mV)

30
NaOl/water
HOl/water
NaOl/HOl/water 1:1

20

cmc of sodium oleate

Zimmels and Lin (1974)
10
Oleic acid
Solubility edge

Oleate species soluble

Oleate species insoluble

0

-8

-7

-6

-5

-4

-3

-2

-1

log (Concentration)
Fig. 1. Zeta potential as a function of log (concentration) (molar) of oleate species at pH 4.5 and 35 C (data of Swaroop, 1970).

transition between soluble and insoluble species from Swaroop,

plus the generally accepted values of the aqueous solubility of oleic
acid and the critical micelle concentration from Zimmels and Lin
(1974). Although the values of whatever species are being measured in Fig. 1 are often reduced with increasing addition of
reagents, the values still remain positive. Positive oleate species
have been identified by Laskowski and his co-workers (see later),
but at pH values lower than 4.5. Swaroop (1970) reported that
the sodium oleate is present as micelles, even though the additions
are below the accepted value of the cmc. The oleic acid is assumed
to be present as an emulsion. There are major changes in the zeta
potentials of oleic acid and sodium oleate at approximately 10
6
and 10
5 molar respectively, a finding also reported by other
authors (see later). The peaks in the zeta potential/pH curve were
accompanied by visual changes in the brightness of the field of
view.
Drzymala (1985) calculated the surface charge on oleic acid
droplets as a function of pH which showed a high value of surface
charges, from approximately
200 lC/cm2 at pH 5 to
700 lC/
cm2 at pH 8. These values were seen as unrealistic since the theoretical maximum surface charge should only be 128 lC/cm2 based
on the cross-sectional area of the carboxyl group of the oleic acid
molecule. The experimental titration curves for the oleic acid could
better be explained by the formation of spherical aggregates of 0.2
0.3 lm in diameter consisting of fine oleic acid droplets similar in
size to micelles, the formation of mesospheres of similar size containing both oleic acid and oleate ions, the formation of acid soap
(HOlNaOl) at intermediate values of pH and the presence of
micelles in addition to oleic acid droplets and simple oleate species. These characteristics emphasise the complexity of the oleic
acid-aqueous system as a function of pH. The equilibrium diagram
for the aqueous oleic acid system has been reported and discussed
by many authors (e.g. Somasundaran and Ananthapadmanabhan,
1979; Ananthapadmanabhan et al., 1979; Kulkarni and
Somasundaran, 1980; Yap et al., 1981; Ananthapadmanabhan
and Somasundaran, 1981; Pugh and Stenius, 1985; Pugh, 1986;
Morgan et al., 1986; Jung et al., 1987; Antti and Forssberg, 1989)
and a graph based on the data reported by Jung et al. (1987) is presented in Fig. 2. This shows the increasing value of the pH of the
limit of solubility of oleate as the concentration of added oleate
is increased. It also highlights a major area in the acid pH region
where oleic acid is present as insoluble phases, variously described
as oleic acid droplets, emulsions, insoluble films etc.

Drzymala (1987) used the experimental zeta potential data of

Lekki to estimate the changes in the surface potential of oleic acid
in NaCl solutions. These data are plotted in Fig. 3. Drzymala (1987)
assumed that the measured values of zeta potential represented
the values in the diffuse layer of the oleic acid-aqueous interface.
These data showed that the values of the zeta potential linearly
progressed from
37 mV to
100 mV as the pH was increased
from 3 to 7 in 10
3 M NaCl. Surface potentials were calculated to
change from 0 (extrapolated) to approximately
230 mV as the
pH was raised from 2 to 7. The intrinsic ionisation constant was
estimated as 4.4.
Vurdela and Laskowski (1987) measured the isoelectric points
of a number of fatty acids, including sodium oleate using microelectrophoresis. The values of the isoelectric points were all around
3, in agreement with the hypothesis of Jung et al. (1987).
Laskowski (1988) reported the electrophoretic mobility characteristics for oleic acid as a function of pH. The isoelectric point for
oleic acid was measured as 2.5. This meant that chemisorption of
oleate occurs in alkaline solutions while the precipitation of oleic
acid on the mineral surface was responsible for its physical adsorption in an acidic environment. In addition, the isoelectric point of
microbubbles in aqueous solutions of sodium oleate was also
around pH 3 (Laskowski et al., 1989).
Laskowski (1993) described how the changes in the zeta potential and isoelectric points of minerals in the presence of fatty acids
can be explained by the presence of colloidal species in solution.
These colloidal precipitates have isoelectric points around 23,
and apparently coagulate/precipitate onto solid particles and bubbles and determine the zeta potentialpH relationship for the mineral particles and bubbles generated in such solutions. Laskowski
suggested that the interpretation of the electrokinetic measurements carried out in aqueous solutions of weak electrolyte surfactants may lead to erroneous conclusions if the presence of such
colloidal species is ignored. He cited cases for hematite (Akhtar
and Lai, 1975) and values of the effects of sodium salts on the zeta
potentials of siderite. When the isoelectric data of Akhtar and Lai
(1975) for the hematiteoleate system were superimposed onto a
domain diagram for the oleic acidwater system, the dramatic
change in isoelectric point of the hematite corresponded very well
to the change from oleic acid being in the colloidal suspension to
that of oleate ions being present in true solution.
Kaibara et al. (1997) used turbidity and light scattering techniques to suggest a very complex series of oleate complexes

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K. Quast / Minerals Engineering 85 (2016) 130137

-3
2

10

cmc

12

-4

log [species]

-5
Liquid Oleic Acid
Region

Oleate ion

-6
Oleate dimer

-7

Acid-soap complex

-8
Soluble Oleic acid

-9

pH
Fig. 2. Equilibrium diagram showing soluble oleate species for the oleatewater system using the data reported by Jung et al. (1987).

0
2

Zeta Potential (mV)

-20

-40

-60

-80

-100

pH
Fig. 3. Zeta potential for oleic acid on 0.001 M NaCl (data of Lekki reported by Drzymala, 1987).

formed in the pH region 511. Although no measurements of zeta

potential were made, various stoichiometric complexes and
micelles with different ratios of oleate ion and oleic acid were
proposed.
Sadowski (2000) measured the zeta potentialpH characteristics for various oleate salts. They all returned isoelectric points
around 3.1, similar to the values reported by Vurdela and
Laskowski (1987) and Laskowski (1988, 1993). At pH 8, the zeta
potential of ferric oleate was approximately
30 mV, but for
sodium oleate it was closer to
80 mV. The curves for calcium
and barium oleates were similar to those for the sodium oleate.
The negative surface charges on the precipitated fatty acid soaps
were due to the heterocoagulation of precipitated soap particles
with the oleate ions.
An Electron Spin Resonance (ESR) study on the titration of
sodium oleate solutions with HCl gave information concerning
the types of structures likely to be obtained (Fukuda et al., 2001).
From ESR, turbidity and microviscosity studies a complex picture
of different types of oleic acid/oleate aggregates was postulated
including micelles, lamellar bilayers and vesicles, with the presence of vesicles and non-lamellar aggregates coexisting throughout the entire pH range.

2.2. Oleate interactions with hematite

Peck et al. (1966) used infrared spectroscopy to study the
adsorption of oleate collector on three varieties of hematite (compact red, specular and synthetic). Potentiometric titration and oleate flotation tests were conducted on these three samples of
hematite, together with a detailed infrared study of oleate adsorption. Each mineral was found to react with either oleic acid or a
solution of sodium oleate to form a mineral cation-collector anion
chemisorbed layer at the solidliquid interface. Physical adsorption of oleic acid produced a characteristic carbonyl band at a different frequency to the chemisorbed oleate. The chemisorption
reaction displaced surface hydroxyls and was found to be pH
dependent. Maximum chemisorption of oleate appeared to coincide with the zero point of charge of each hematite sample. Infrared absorbance was correlated with the flotation behaviour of the
mineral.
Han et al. (1973) studied the adsorption of oleic acid on the surface of hematite using microelectrophoresis measurements. At an
addition of 1  10
4 molar, oleic acid caused the zeta potential
for hematite to remain negative between pH values of 6 and 9.
The charge reversal and the elimination of the isoelectric point

K. Quast / Minerals Engineering 85 (2016) 130137

for hematite indicated chemisorption as the dominant mechanism

for the interaction of oleate on the surface of the hematite.
Akhtar and Lai (1975) measured the changes in the isoelectric
point of naturally occurring hematite using microelectrophoresis.
They aged their 2% hematite suspensions for 24 h prior to contact
with the sodium oleate. The isoelectric point of the unreacted
hematite surface was at 7.85 0.05. The isoelectric point of the
hematite surface remained above 7 for oleate solutions less than
10
6 molar, but reduced to 5 at an oleate concentration of 10
5 molar. At an oleate concentration of 10
4 molar, the isoelectric
point of the hematite was approximately 2.3. This was seen as evidence of chemisorption of oleate occurring on the surface of the
hematite. The authors postulated that the variation of the isoelectric point of hematite in the presence of oleate occurs by
chemisorption of undissociated oleic acid on negative hematite
surface sites and oleate ions on neutral hematite surface sites.
The chemisorption of oleate ions on positive hematite surface sites
probably occurs but should not affect the value of the isoelectric
point of the hematite. Ananthapadmanabhan and Somasundaran
(1981) however ascribe the major change in isoelectric point at
10
5 molar to the precipitation of ferric oleate rather than
chemisorption of oleate onto the surface of the hematite.
Yap et al. (1981) studied the adsorption of sodium oleate onto
synthetic hematite using microelectrophoresis testing on suspensions containing 0.004% solids. The isoelectric point of the hematite
in the absence of oleate was 8.2, but the presence of only 10
6 molar sodium oleate caused the disappearance of any positive values of zeta potential. At higher additions of sodium oleate
(>10
5 molar), the values of zeta potential of the coated hematite
surface remained strongly negative and relatively independent of
pH over the pH range 510. Chemisorption was concluded as the
mechanism of oleate adsorption onto the hematite surface; however physical adsorption was postulated to also occur at higher
coverages and lower values of pH.
Bibawy and Yousef (1982) reported that the zeta potential of
hematite in the presence of sodium oleate reduced from approximately
25 mV to close to
100 mV at around and above the
cmc of the sodium oleate. These high negative zeta potentials at
values above the cmc were interpreted as due to the orientation
of a second layer of oleate adsorbed with its negatively charged
polar group towards the liquid phase.
Sadowski and Smith (1985) reported how increasing the concentration of sodium oleate on hematite caused the zeta potential
of the hematite to go progressively more negative with increasing
addition between 5  10
6 and 5  10
4 molar oleate at pH 8.
A previous study on the flotation of hematite using oleate published by the author (Quast, 1999) showed that the use of increasing additions of oleate gave higher hematite recoveries at
increasing values of pH. One of the contributing factors to this
observation was postulated to be due to the precipitation of oleate
onto the hematite surface causing increased hematite hydrophobicity which tended to follow the solubility limit of the oleate with
increasing oleate addition (see Fig. 2).
Gong et al. (1991) used DRIFT (Diffuse reflectance infrared Fourier transform) spectroscopy to study the adsorption of oleate on
hematite. Their spectra suggested that chemisorption of oleate
took place under all conditions between pH 6.0 and 9.8. Oleic acid
monomer appeared at relatively high oleate concentrations on the
hematite surface at pH 8.0, which corresponded to the pH at which
the maximum adsorption of all oleate species occurred. The oleic
acid monomer probably adsorbed via hydrogen bonding as well
as hydrocarbon chain association. Sadowski (2000), however,
showed that sodium oleate adsorption on hematite increased in
the order of pH 2.5 > pH 7.5 > pH 10.5. Recent published work by

133

Joseph-Soly et al. (2015) showed that oleate flotation of hematite

is enhanced under conditions where ferric oleate is the stable
phase.
Pattanaik et al. (2000) measured the effect of making various
additions of sodium oleate on the electrophoretic mobility-pH
characteristics of a natural hematite sample. Increasing the addition of sodium oleate caused the isoelectric point of the hematite
to decrease, and the value of mobility to decrease. At high sodium
oleate additions (10
3 molar), the measured electrophoretic mobility was lower than that measured for ferric oleate precipitate. The
mechanism of interaction was reported as both chemical interaction with the surface groups plus lateral hydrophobichydrophobic
interactions of non-polar segments of the surfactant.
Shibata and Fuerstenau (2003) investigated the interaction
between synthetic hematite and oleic acid by measuring the
changes in the electrophoretic mobility of the hematite as a function of pH at various oleic acid additions. The isoelectric point of
the synthetic hematite occurred at 8.3, but was reduced by the
addition of oleic acid even as low as 10
6 molar when it was measured at 6. Increasing the addition of oleic acid caused the zeta
potentialpH characteristics to approach those of oleic acid droplets, which gave an isoelectric point less than 3. The high negative
charge on the surface was due to the adsorption of oleate anion,
with the charge reducing to zero with decreasing pH caused by
the decrease in oleate ion concentration. The fact that significant
adsorption of oleic acid occurred at pH values 12 units above
the isoelectric point indicated that the adsorption of oleate was
not purely physical but quite likely a combination of chemical
and physical adsorption.
An excellent depiction of the effects of potential determining
ions on the zeta potential of oxide minerals is given in their
Fig. 15 by Fuerstenau and Pradip (2005). They show the zeta
potential characteristics of a typical oxide mineral in the presence of an indifferent electrolyte, a physisorbed surfactant on a
hydrophilic surface, a physisorbed surfactant on a hydrophobic
surface and a chemisorbed surfactant. The isoelectric point corresponds to the pH value where the zeta potential of the mineral is
zero using an indifferent electrolyte. For the case of a physisorbing anionic surfactant, the zeta potential curves above the isoelectric point are identical, but below the isoelectric point, the
zeta potential is reduced due to electrostatic attraction between
the positive surface and the anion. Lowering the pH further could
cause hemi-micelle formation and chainchain association leading to a significant reduction in the observed zeta potential. In
an extreme case the double layer is a molecular condenser consisting of a surface charge and a molecular layer of surfactant
ions, where the zeta potential can be negative, causing a point
of zeta reversal. For the adsorption of a surfactant on a
hydrophobic mineral surface the zeta potential will be reduced
below the isoelectric point due to displacement of water molecules from the hydrophobic surface. For a chemisorbed surfactant, bonding onto the surface can be very strong and for an
anionic collector, only when the surface becomes sufficiently
negatively charged by increasing surfactant addition will the
adsorption cease. The example given was the adsorption of dodecylsulphate, hydroxamate and oleate onto the hematite surface,
as reported by Han et al. (1973).
Although this paper primarily addresses the technique of zeta
potential in the investigation of the interaction of oleate with the
surface of hematite, other complementary techniques (e.g. FTIR)
also contribute to our understanding of the mechanisms. The use
of these techniques, together with zeta potential, to better understand the interaction of oleate with non-sulphide minerals, is the
subject of a manuscript in preparation by the author.

K. Quast / Minerals Engineering 85 (2016) 130137

3. Materials and reagents

Two samples of high grade iron ores from the Middleback Range
area in South Australia were investigated in this study. These samples were received as lump ore from Onesteel (now Arrium Mining), Whyalla. These samples were crushed and pulverised in a
ring mill prior to testing and analysis. Iron assays were determined
using the method of Kolthoff et al. (1969) which involved digestion
using stannous chloride and hydrochloric acid followed by titration
with potassium permanganate solution. The amount of acid insolubles (primarily silica) was determined gravimetrically on the residue remaining by filtration using ashless filter paper after the acid
digestion, burning off the paper and weighing the residue. Physical
and chemical characteristics of the two pulverised hematite samples are given in Table 1. The % hematite values for Iron Knob
and Iron Prince are 99.3% and 97.1% respectively.
The pulverised sample of Iron Knob ore showed a specular lustre and was a deep purple to black colour compared to the redbrown pulverised Iron Prince sample.
Specific Gravity (S.G.) was measured by displacement of nitrogen in a Quantachrome Stereopycnometer and the surface areas
of the pulverised samples were measured using a Fisher SubSieve Sizer Model 95 as per ASTM B330-88 (1988).
The sample of sodium oleate used was technical grade supplied
by BDH and contained a mixture of saturated and unsaturated fatty
acids (Quast, 1999). Glass distilled water with a conductivity of less
than 0.2 mS/m was used throughout the test work.
4. Experimental procedure
Zeta potential data was measured on suspensions of 1 g of
hematite in 80 mL of distilled water, with the pH adjusted using
dilute solutions of either hydrochloric acid or sodium hydroxide.
When solutions of various concentrations of sodium oleate were
used, these solutions were adjusted to pre-determined values of
pH and contacted with the hematite sample for 1 h. The slurries
were then centrifuged for 30 s at 2000 rpm. Substituting the centrifugal force acting in the Stokes Law equation for free settling
reveals that the largest hematite particle remaining in suspension
after centrifuging was 1.5 lm. The supernatant liquid containing
virtually all sub-micron particles was transferred to the flat cell
of a Rank Bros. Microelectrophoresis Apparatus Mark II.
Particles were timed in moving a distance of 50 lm under a
known potential gradient which was chosen to give timings
between 5 and 10 s. At least 10 separate particles were timed, followed by another 10 after the electrode polarity had been reversed.
The average of the 20 timings was used in the calculation of mobility. Zeta potentials were calculated from mobility data using the
rationalised Smoluchowski equation which is applicable for this
system. Under normal operating conditions, zeta potential (f) in
mV is given by Eq. (1).

f 14:38l

flat cell of the microelectrophoresis apparatus without centrifugation. Particles were timed in moving a distance of 50 lm as before
and the mobilities converted to zeta potential using Eq. (1) for
comparison with the values obtained for the hematite particles.
5. Results
The plots for the effects of oleate additions on the zeta potentialpH characteristics for the two samples of hematite are given
in Figs. 4 and 5. The effect of the addition of oleate on the isoelectric point of Iron Knob hematite is given in Fig. 6. For details of the
solubility limits, see Section 6.
6. Discussion
From the literature review (Section 2) one would expect the
measured zeta potential of the hematite samples to be reduced
in the presence of oleate, with a corresponding reduction of the
isoelectric point of the mineral. This is indeed the case for the Iron
Knob hematite sample (Figs. 4 and 6). In fact, in Fig. 4 the zeta
potentialpH curve for the Iron Knob hematite in contact with 10
3
molar sodium oleate lies very close to the curve for the oleate
species in the absence of the hematite. These facts are in good
agreement with other published data (see Section 2). In fact, the
zeta potentialpH curve for sodium oleate in the absence of hematite shown in Figs. 4 and 5 is similar to that for oleic acid droplets
reported by Shibata and Fuerstenau (2003). On the basis of the reasoning above we could postulate that the negatively charged oleate
species are physically adsorbing on the positive sites below the

40

0 oleate
10 -5 M oleate
10 -4 M oleate
10 -3 M oleate
20

NaOl

0
2

Zeta potential (mV)

134

10

12

-20

SL

-40

where l is the mobility in lm cm (s)
1 (V)
1.

Suspensions of 1 g of sodium oleate in 80 mL of distilled water
set to specific values of pH were also prepared after carefully
crushing the powder using an agate mortar and pestle. These were
allowed to equilibrate for 1 h, then sampled and injected into the

Table 1
Physical and chemical characteristics of pulverised hematite samples.
Sample

Colour

% Fe

% SiO2

S.G.

Surface area (m2/g)

Iron Knob
Iron Prince

Black
Red-brown

69.5
68.0

0.3
2.5

5.36
5.02

0.136
0.135

-60
SL

-80

-100

pH
Fig. 4. Effect of oleate on the zeta potential of Iron Knob hematite showing oleate
solubility limits (SL).

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K. Quast / Minerals Engineering 85 (2016) 130137

40

20

3.5
0
4

10

12

-20
SL

SL

-40

Isoelectric point

Zeta Potential (mV)

SL

2.5

-60

0 oleate
-80

10 -5 M oleate
10 -4 M oleate
10 -3 M oleate
2

NaOl

-5

-100

pH
Fig. 5. Effect of oleate on the zeta potential of Iron Prince hematite ore showing
oleate solubility limits (SL).

isoelectric point of the Iron Knob hematite and chemisorbing on

the negative sites above the isoelectric point of the Iron Knob
hematite. The other fact to be considered is the fact that at acid
to neutral pH values, the main oleate moiety will be undissociated
oleic acid. The reduction in the isoelectric point of the Iron Knob is
linear with the log of the oleate addition (Fig. 6), consistent with
other published data.
The data shown in Fig. 5 for the Iron Prince hematite in contact
with oleate do not conform to all these findings. While it is true
that the addition of oleate causes the zeta potential of the Iron
Prince to become more negative with increasing addition, the
curves appear to be displaced about 3 pH units to the left. This is
due to the increased amount of silica present in the Iron Prince
hematite compared to the Iron Knob sample (see Table 1). The Iron
Prince hematite sample had a much greater amount of silica (2.5%
vs 0.3%) compared to the Iron Knob sample. The zeta potentialpH
curve for the Iron Prince hematite is very similar to that reported
by Yin et al. (2011) for their naturally occurring hematite sample
containing 2.19% silica. Esumi et al. (1988) reported that the presence of as little as 0.1 mg of silica in 30 mL of slurry of synthetic
hematite caused the iep to shift from 7.9 to 3.1, coincident with
that for silica. Carlson and Kawatra (2013) reported that the values
of zeta potential of hematite containing 3.6% silica along with other
minerals in a plant stream were independent of pH and maintained
a value of approximately
40 mV over the pH range 310. Kumari
et al. (2010) reported an iep for iron ore slimes containing 2.64%
silica at 5.1, however their sample also contained 4.56% Al2O3,
which may have influenced the measured value of the iep.

-4

-3

log [oleate addition]

Fig. 6. Effect of oleate on the isoelectric point of Iron Knob hematite.

Esumi et al. (1988) explained the measured values of low zeta

potential by postulating a dispersionflocculationredispersion
mechanism. At pH values well above the iep of the hematite (i.e.
pH 10), both hematite and silica have negative zeta potentials, so
all the particles remain dispersed. As the pH is lowered to the iep
of the hematite (approximately pH 7) silica starts to coagulate or
flocculate on the surface of the hematite since there is no longer
any repulsion. Lowering the pH even further caused the hematite
to attract the silica particles by electrostatic attraction between
positive (hematite) and negative (silica) charges on the particles.
At this point, hematite is coated with silica and redisperses as if
the particles were all larger silica particles.
It is well known that the presence of fine silica in hematite
causes the zeta potential of the hematite surface to mimic that of
silica (Kulkarni and Somasundaran, 1976), and is this one of the
effects that we are seeing here? These authors (Kulkarni and Somasundaran) showed that the measured isoelectric point of a heterogeneous mineral surface is between the values of the two
components. Remembering that the slurries containing the mineral particles were centrifuged prior to injecting into the flat cell
of the microelectrophoresis apparatus means that the particles
being measured are predominantly very fine in size. The silica
component of the Middleback Range ores is very fine (Quast,
2012), hence would be exerting an influence on the measured values of zeta potential. (From the theory of Esumi et al. (1988), at
lower pH values, all the hematite particles could be coated with silica, hence they could be behaving as negatively charged silica particles). The negative silica surfaces at low values of pH could
possibly be partially coated with ultrafine positive hematite colloids, which in turn could have some form of adsorbed oleate on

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K. Quast / Minerals Engineering 85 (2016) 130137

their surfaces leading to a very complicated solid system. It is proposed that this is one of the reasons for the different zeta potential
behaviour shown by the Iron Prince hematite compared to the Iron
Knob sample shown in Fig. 4. It would also explain why the zeta
potentialpH characteristics for the Iron Prince hematite are below
those of the sodium oleate colloids in the lower pH region where
the silica would be exerting its influence on the measured zeta
potential since the isoelectric points of various samples of silica
are often very low (<2) as reported by Kosmulski (2001).
The adsorption of the BDH sodium oleate onto a sample of Iron
Prince hematite has been previously investigated by the author
(Quast, 2010). The actual amount of adsorbed oleate onto the surfaces of hematite was determined directly using differential thermal analysis. This was then converted to monolayer coverages
knowing the surface area of the hematite and the molecular areas
of oleate under three different attachment orientations: horizontal,
two-point and vertical. Correcting this data for the surface areas of
the two hematite samples used in this study gives the following
values of mg oleate/g hematite for monolayer coverages under
the different attachment orientations: horizontal 0.059, twopoint 0.126 and vertical 0.258. In all the tests, 1 g of hematite
was used in 80 mL of water. For a solution concentration of 10
5
molar oleate, there would be 224 lg oleate available initially.
Assuming monolayer coverage under horizontal oleate attachment, 59 lg of oleate is adsorbed, leaving 165 lg of oleate in solution. This corresponds to an equilibrium concentration of 206 lg/L
or 7.4  10
7 molar. For a monolayer by vertical attachment,
258 lg oleate can be adsorbed, which is more than the available
amount of oleate added. From Fig. 2, complete monolayer coverage
by horizontal attachment could shift the solubility limit down to
approximately 5.5. This value corresponds to a minimum in zeta
potential for Iron Prince hematite in the initial oleate solution concentration of 10
5 molar in Fig. 5. This minimum under similar
conditions was not observed in Fig. 4 for the higher purity hematite
sample. Care must be taken in this analysis since Morgan et al.
(1987) have reported that precipitation and complexation reactions contribute significantly to oleate extraction in the hematiteoleate system.
According to Fig. 2 (Jung et al., 1987), a precipitate appears in
this solution at any pH value lower than 8.0. This can be seen from
the soluble oleic acid curve that reaches a constant concentration
of 10
7.6 molar (2.5  10
8 molar) at pH 8. As pH decreases below
8 additional amounts of oleic acid start precipitating, and as a
result a significant concentration of precipitate is present even at
pH 7.5 in equilibrium with a soluble species concentration of 10
6
molar, or basically right in the middle of the diagram. This curve
would show as a nearly vertical line originating at pH 8, going
above the solubility limit and quickly levelling off at lower pH
values approaching a total concentration of 10
4 molar (see Pugh
and Stenius, 1985 and Laskowski, 1993). The precipitate is therefore the only significant species in this solution at pH values lower
than 5, and even at pH 7 the precipitate is still the dominant form.
When higher initial additions of sodium oleate were used (10
4
and 10
3 molar), there will always be residual insoluble oleate present after conditioning for 1 h, hence the difference between initial
and equilibrium oleate concentrations will not be as great as in the
10
5 molar case described above. For example, at an addition of
10
4 molar oleate, there will be 2.24 mg of oleate available, with
the worst case (monolayer coverage by vertical orientation) of
0.258 mg being adsorbed still leaving an 8.8  10
5 molar oleate
solution at equilibrium. This reduces the pH of the solubility limit
from approximately 9 to 8.7. This is predicated on the equilibrium
between soluble oleate ions and insoluble oleic acid. For additions
of 10
3 molar oleate, the effect of adsorption on equilibrium oleate
concentration is insignificant, assuming only monolayer attachment. This concentration is below the value of the critical micelle

concentration (cmc) of the oleate reported by Jung et al. (1987),

but is above the concentration where oleate hemi-micelles are
believed to form (typically at 1% of the cmc (Quast, 2010)). It also
assumes no multilayer adsorption of oleate onto hematite. Pugh
and Stenius (1985) suggested that multilayers of oleate could form
on the minerals that they investigated (apatite, calcite and fluorite)
and this has also been suggested by Jung et al. (1987) on high surface area synthetic goethite.
7. Conclusions
As a result of a literature survey concerning the use of primarily
zeta potential measurements in investigating the solution species
associated with the use of oleic acid as a flotation agent for hematite, it has been concluded that adsorption of this reagent can occur
by either or both physical and chemical mechanisms depending on
the solution chemistry. These mechanisms are also supported by
previously published infrared data. These adsorption phenomena
are accompanied by the reduction in the zeta potential of the substrate and lowering of its isoelectric point. This was indeed the case
for the interaction of sodium oleate with the Iron Knob hematite
sample, where the zeta potential of the hematite in contact with
the oleate approached the values of the oleate species in the
absence of hematite across the pH range. In the case of the Iron
Prince hematite ore, the presence of more silica in this sample presented a complex system, where the effects of the inherent fine silica dominated over those of the adsorbed oleate in the acid pH
region where undissociated oleate will dominate over oleate ions.
It was postulated that the fine silica in the sample could acquire a
partial hematite surface by heterocoagulation, followed by the
adsorption of oleate on this surface, causing the observed effects
on zeta potential as a function of the pH of the system. An attempt
was made to correct the equilibrium oleate concentration to
account for the adsorption of oleate onto the surface of the hematite, but this would be only significant at the very low addition rate
of the oleate. It also depends on the equilibrium between soluble
and insoluble oleate species in the system.
Acknowledgement
The author is grateful to Onesteel (now Arrium Mining) for providing the hematite samples investigated in this study.
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