Advances in Colloid and Interface Science 114–115 (2005) 9 – 26

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Zeta potentials in the flotation of oxide and silicate minerals

D.W. Fuerstenaua,T, Pradipb
a
Department of Materials Science and Engineering, University of Califonia, Berkeley, CA 94720, United States
b
Tata Research Development and Design Centre 54B, Hadapsar Industrial Estate Pune 411 013, India
Available online 23 March 2005

Abstract

Adsorption of collectors and modifying reagents in the flotation of oxide and silicate minerals is controlled by the electrical double layer
at the mineral–water interface. In systems where the collector is physically adsorbed, flotation with anionic or cationic collectors depends on
the mineral surface being charged oppositely. Adjusting the pH of the system can enhance or prevent the flotation of a mineral. Thus, the
point of zero charge (PZC) of the mineral is the most important property of a mineral in such systems. The length of the hydrocarbon chain of
the collector is important because of chain–chain association enhances the adsorption once the surfactant ions aggregate to form hemimicelles
at the surface. Strongly chemisorbing collectors are able to induce flotation even when collector and the mineral surface are charged similarly,
but raising the pH sufficiently above the PZC can repel chemisorbing collectors from the mineral surface. Zeta potentials can be used to
delineate interfacial phenomena in these various systems.
D 2005 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2. The electrical double layer and electrokinetic potentials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.1. Electrical double layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.2. Electrokinetic potentials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.3. Effect of electrolytes on the zeta potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3. Application of electrokinetics in flotation systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.1. Determination of PZC’s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.2. Relationship of flotation response to the PZC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.3. Role of the hydrocarbon chain in surfactant adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.4. Effect of pH and surface potential on oxide flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.5. Flotation depression with inorganic ions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.6. Flotation activation with inorganic ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.7. Collector uptake by physisorption or chemisorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.8. Chemisorption and physisorption in oxide flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.9. The adsorption of dodecylammonium acetate on talc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

T Corresponding author. Fax: +1 510 643 5792.

E-mail address: dwfuerst@berkeley.edu (D.W. Fuerstenau).

0001-8686/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.cis.2004.08.006
10 D.W. Fuerstenau, Pradip / Advances in Colloid and Interface Science 114–115 (2005) 9–26

1. Introduction

Although useful for determining the efficacy of reagents

for making flotation separations, conducting flotation experi-
ments under carefully controlled physical–chemical condi-
tions simply cannot be carried out with standard laboratory
test machines. So one of the earliest research tools used for
fundamental investigation of surface chemical phenomena in
flotation was the determination of factors that affect contact
angles, a technique used with great success by Sutherland and
Wark [1]. Since most flotation separations are based on the
selective adsorption of collectors (organic surfactants) at
mineral/water interfaces, direct measurement of the amount
of the reagent adsorbed permits a physical–chemical analysis
of adsorption phenomena in relation to wettability. Gaudin
[2] and his co-workers determined adsorption isotherms of a
number of collectors on a variety of minerals, leading the way
in this important approach to flotation chemistry. A signifi-
cant step forward in delineating the physical chemistry of
flotation systems was bringing the concepts of the electrical
double layer and electrokinetic potentials into widespread use
in the interpretation of flotation phenomena [3–5]. Real
progress in correlating flotation response with the physical
chemistry of the system was not made until the modified Fig. 1. Correlation among adsorption density, contact angles, flotation
Hallimond tube was designed and a controlled experimental response and zeta potentials of quartz as a function of pH with 4
105M
procedure devised [1,6]. Earlier, vacuum flotation experi- dodecylammonium acetate solutions (after Ref. [8]).
mental methods delineated the limits of flotation, that is float/
no-float conditions, but these could provide no information by electrical double layer interactions. Flocculation–
about anything in between [7]. Fig. 1 shows the first dispersion phenomena are of crucial importance not only
correlation of the flotation of quartz with surface chemical to flotation but also to such other unit operations as
and electrical double layer phenomena when using dodecy- comminution, gravity separation, thickening, filtration
lammonium acetate (DAA) as collector [8]. This figure and tailings management.
illustrates how measurements that reflect conditions at the ! The sign and magnitude of the surface charge controls
solid/liquid interface (adsorption density and zeta potential) the adsorption of physically adsorbing flotation agents.
can be correlated directly with surface phenomena that reflect ! A high surface charge can inhibit the chemisorption of
complex conditions at solid/liquid/gas interfaces (contact chemically adsorbing collectors.
angle and flotation behavior). That the zeta potential becomes ! Slime coatings are controlled by electrical double layer
more negative with increasing pH in the acidic region is due and hydrodynamic phenomena.
to the effect of pH on the surface potential of quartz, as will be ! The double layer on air bubbles has a significant effect
discussed subsequently. on the flotation of naturally floating mineral systems.
Significant progress has been made during the past several ! Flotation kinetics relates directly to the effect of double
decades in delineating the physical chemistry of flotation layers on the rate of film thinning during bubble–particle
systems through utilization of a number of experimental contact
techniques, such as those used in obtaining the results ! Fine particle/air bubble/oil droplet interactions are
presented in Fig. 1. This review, in particular is concerned dominated by surface charge effects.
with electrical double layer phenomena in mineral separation
systems and primarily with the application of electrokinetic Electrical double layer parameters can be evaluated by a
studies for delineation of the relevant double layer effects in number of different experimental methods, depending on
the flotation of oxide and silicate minerals. the properties of the material being investigated. These
The electrical double layer at interfaces plays a broad role methods include the measurement of surface charge by
in many mineral processing operations and is of primary titration or other techniques, direct determination of the
importance in flotation. Some of the surface-physico-chemical capacitance of the double layer, electrocapillarity effects,
effects encountered in these systems include the following: and measurement of electrokinetic potentials which result
from relative tangential motion when at least one of the
! The flocculation and dispersion (and as a consequence phases is a liquid. Electrokinetic potentials, though difficult
also the rheology) of mineral suspensions is controlled to interpret precisely, are relatively simple to measure and
 D.W. Fuerstenau, Pradip / Advances in Colloid and Interface Science 114–115 (2005) 9–26
do yield valuable information on adsorption effects and on
potentials between interacting phases. Therefore, these
methods have become both popular and useful in the study
of basic phenomena in mineral processing. The purpose of
this paper is to review briefly the nature of electrokinetic
potentials and the use of electrokinetic information in
understanding flotation behavior. For the sake of brevity,
this paper emphasizes the fundamental aspects of electro-
kinetic phenomena and their interpretation in relation to the
behavior of flotation separation systems only rather than
details of experimental measurement techniques. The read-
ers are also referred to several excellent review papers and
recent monographs on the topic [9–17].
2. The electrical double layer and electrokinetic potentials
2.1. Electrical double layer
The immersion of a solid into an aqueous solution
produces a region of electrical inhomogeneity at the solid–
solution interface. An excess (+ or ) charge apparently
fixed at the solid surface is exactly balanced by a diffuse
region of equal but opposite charge (termed counter ions)
and is called the electrical double layer.
Since adsorption of collectors at mineral–water inter-
faces is controlled in many cases by the electrical double
layer, we must be concerned with factors responsible for the
surface charge on the solid and with the behavior of ions
that adsorb as counter ions to maintain electroneutrality.
Fig. 2 is a schematic representation of a simple model of the
electrical double layer at a mineral/water interface, showing
the charge on the solid surface and the diffuse layer of
counter ions extending out into the aqueous phase. This
Fig. 2. Schematic representation of the electrical double layer and potential
drop through the double layer at a mineral/water interface. The planes b and
d represent the inner and outer Stern planes.
11
figure also shows the drop in potential across the double
layer. The closest distance of approach of hydrated counter
ions to the surface, d, is called the Stern plane. The total
double layer potential, or surface potential, is w 0 and that at
the Stern plane is w d . From the Stern plane out into the bulk
of the solution, the potential drops exponentially to zero.
The electrokinetic or zeta potential is usually taken as an
approximation of w d . In the case of ions that interact with
surface sites, either chemically or by some other strong
specific adsorption forces, the adsorbed ions may lie closer
to the surface at a plane b. These two planes are now
known as the outer (d) and inner (b) Stern planes,
respectively, but in earlier literature they were referred to
as the outer and inner Helmholtz planes. As a first
approximation, one often simply refers to adsorption in
the Stern plane and assumes for simplicity that d and b
coincide. In the case of large organic ions, plane b could lie
outside plane d.
Several different parameters that quantify the electrical
double layer are useful in interpreting flotation behavior,
particularly the selective adsorption of collectors. This
includes such factors as the magnitude of the surface
charge, the point of zero charge of the mineral, interfacial
potentials, thickness of the electrical double layer, specific
adsorption of collectors, and ion exchange phenomena.
The surface charge in systems of importance to mineral
processing may arise from a number of different sources.
For example, the surface charge on an oil droplet may result
from the adsorption of long-chained surfactant ions at the
oil/water interface. In the case of layer-silicate minerals
(such as clays and micas), because of substitution of A13+
for Si4+ in the silica tetrahedra and Mg2+ for A13+ in the
octahedral layer of the crystal lattice, the surfaces of these
crystal faces carry a constant negative charge that is
independent of solution conditions. In the case of salt-type
minerals such as barite (barium sulfate), fluorite (calcium
fluoride), argentite (silver sulfide), iodyrite (silver iodide),
etc., the surface charge arises from the preference of one of
the lattice ions for the solid relative to the aqueous phase.
Equilibrium is attained when the electrochemical potential
of these ions is constant throughout the system. Those
particular ions which are free to pass between both phases
and therefore establish the electrical double layer are called
potential-determining ions.
For oxide minerals, hydrogen and hydroxyl ions have
long been considered to be potential-determining [18], but
today there still remains a difference in opinion as to how
pH controls the surface charge on oxides. Since oxide
minerals form hydroxylated surfaces when in contact with
water vapor, a hydroxylated surface should also be expected
when the solid is in equilibrium with an aqueous solution.
Adsorption/dissociation of H+ from the surface hydroxyls
can account for the surface charge on the oxide.
MOHðsurf Þ ¼ MO þ
ðsurf Þ þ Haq ;
þ þ
MOHðsurf Þ þ Haq ¼ MOH2ðsurf Þ ð1Þ
12 D.W. Fuerstenau, Pradip / Advances in Colloid and Interface Science 114–115 (2005) 9–26
If M +z and A z are the potential-determining ions of
valence z for a given mineral, then the surface charge (r 0) is
simply given by
r0 ¼ zF ðCM þz  CAz Þ ð2Þ
where F is the Faraday constant and the adsorption density
(C M +z C A z ) mole per cm2 can be measured by titration of a
suspension of the mineral in water [20].
With regard to flotation behavior, the single most
important parameter that describes the electrical double
layer of a mineral in water is the point of zero surface charge
(PZC). The PZC is expressed as the condition in the aqueous
solution at which r 0 is zero and this is determined by a
particular value of the activity of the potential-determining
(PD) ion (a +M +z (pzc)) for the PD cation). Assuming that
potential differences due to dipoles, etc., remain constant, the
surface potential is considered to be zero at the PZC. The
value of the surface potential at any activity of potential-
determining electrolyte, a M mz is given by
RT aþ þz
w0 ¼ ln þ M ð3Þ
zF aM þZ ð pzcÞ
where R is the gas constant and T the absolute temperature.
In the case of oxides, the relation for the change of w 0 with
the activity of potential-determining electrolyte (pH) is more
complicated because the activity of species at the surface may
not be unity as in the case of the normal reversible electrode.
Because of this [12,17,10–22], the change in w 0 with pH can
be less than the Nernstian slope of 59 mV. However, some
studies show that oxide electrodes do follow Nernstian
behavior. As a first approximation, the potential of an oxide
surface can be considered to vary with pH as
RT h i h i
w0 ¼ 2:3 pH pzc  pH ¼ 0:059 pH pzc  pH volts:
F The concentration of indifferent ions in the outer Stern plane
ð4Þ
The importance of the PZC is that the sign of the surface
charge has a major effect on the adsorption of all other ions
(and particularly those ions charged oppositely to the
surface) because those ions function as the counter ions to
maintain electroneutrality. In contrast to the situation in
which the potential-determining ions are special for each
system, any ions present in solution can function as the
counter ions. As has been well established [10], the counter
ions occur in a diffuse layer that extends from the surface
out into the bulk solution. For a symmetrical electrolyte
consisting of ions of valence z (z +=z =z) at a concentration
C, the bthicknessQ of the diffuse double layer, is 1/j where j
is given by
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2z2 F 2 C
j¼ ð5Þ
ee0 RT
where e is the dielectric constant of the liquid and e 0 is the
permittivity of a vacuum. As the ionic strength of the
solution is increased, the thickness of the double layer
decreases. For 1-1 valent electrolytes, 1/j is 100 nm in 105
M, 10 nm in 103 M, and 1 nm in 10l M solutions, for
example.
If there is only adsorption in the outer Stern plane, then
the surface charge, r 0, is oppositely equal to the diffuse
layer charge, r d. The charge in the diffuse double layer r d
given by the Gouy–Chapman relation [10] as modified by
Stern for a symmetrical electrolyte is:
rd ¼  r0 ¼ ½ 8ee0 RT C 1=2 sinh ð zFwd =2RT Þ ð7Þ
where w d is the potential in the outer Stern plane. Further, if
w d does not change appreciably, this equation shows that
the adsorption density of counter ions should vary as the
square root of the concentration of added electrolyte, as
deBruyn [23] found for the adsorption of dodecylammo-
nium acetate on quartz at low concentrations without ionic
strength control.
If counter ions are adsorbed only by electrostatic
attraction, they are called indifferent electrolytes. The
Boltzmann factor gives the probability of finding an ion i
of charge z i e at a particular point with potential w, so that
the distribution of ions in a potential field is given by
 
zi Fw
Ci ¼ Ci0 exp  ð8Þ
RT
where C i is the concentration of i at the point where the
potential is w, C i0 is the concentration of i at the point
where the potential is zero (out in the bulk solution), and z i
is the valence of i (including sign).
As presented here, concentrations are given in terms of
moles and not numbers of ions, so Eq. (8) is written in terms
of the Faraday constant and not the Boltzmann constant.
(d) would be that given by Eq. (8) at the potential w d . On
the other hand, some ions exhibit surface activity in addition
to electrostatic attraction and adsorb strongly in the Stern
plane because of such phenomena as covalent bond
formation, hydrophobic bonding, hydrogen bonding, sol-
vation effects, etc. The term specific adsorption is used for
such situations. Because of their surface activity, the charge
of such surface-active counter ions adsorbed in the inner
Stern plane (b) can exceed the surface charge. In such cases,
r0 þ rb þ rd ¼ 0: ð9Þ
For some purposes, the inner and outer Stern planes can
be considered simply to coincide, since much of the
interpretation of collector adsorption mechanisms will be
done in terms of electrokinetic potentials, as will be
discussed shortly. For adsorption densities with less than
about 30% coverage, Grahame [24] derived a Boltzmann-
type relation, now generally called the Stern–Grahame
equation, which will be expressed here in terms of
 D.W. Fuerstenau, Pradip / Advances in Colloid and Interface Science 114–115 (2005) 9–26
adsorption free energies and adsorption densities, rather than
in terms of charge and potentials as done by Grahame:
 
Cd ¼ 2rCexp  DG0ads =RT ð10Þ
where C d is the adsorption density in mol/cm2, r is the
effective radius of the adsorbed ion, here C is the bulk
concentration in mol/cm3, and DG 0ads the standard free
energy of adsorption. If ions are adsorbed only because of
electrostatic interactions, then the standard free energy of
adsorption is given by
DG0ads ¼ DG0elec ¼ zFwd : ð11Þ
When an ion exhibits surface activity, such as a flotation
collector, then the standard free energy of adsorption has
additional terms
DG0ads ¼ zFwd þ DG0spec ð12Þ
where DG 0ads represents the specific interaction terms. There
can be various contributions to the specific adsorption free
energy:
DG0spec ¼ DG0chem þ DG0h þ DG0hpb þ DG0solv
þ DG0hpb T þ N ð13Þ
where the individual terms represent changes in the standard
free energy due to chemical bonding, hydrogen bonding,
hydrophobic bonding, and solvation effects, respectively.
The term DG 0T
hpb represents the specific adsorption phenom-
ena through surfactant chain interaction with a hydrophobic
solid, such as talc or graphite. Depending on the mecha-
nisms involved in the interaction of the collector with the
mineral surface, the contributions to the change in adsorp-
tion free energy can be essentially zero or have a finite
value.
The structure of the diffuse part of the double layer
depends upon the composition of the bulk solution and any
change in the composition of the bulk solution can cause ion
exchange within the double layer [10]. If two different kinds
of counter ions, a and b are present, then
Ca =Cb ¼ K ðCa =Cb Þ ð14Þ
where C a and C b are the adsorption densities in the double
layer, C a and C b are their respective bulk concentrations,
and K is a constant. For indifferent counter ions such as K+
and Na+, K has a value close to unity [10]. However, ions
having a strong affinity for the surface will tend to
concentrate in the double layer over simple indifferent
electrolytes. Where appreciable adsorption occurs in the
Stern layer, the competition for sites would include specific
adsorption phenomena:
"   0  #
DG0ads b DGads a
Ca ra Ca
¼ exp  ð15Þ
Cb rb Cb RT RT
13
with the radius of the two kinds of ions having to be taken
into account if they differ in size. If the competing ion a is
an ion that adsorbs only electrostatically (such as Na+ on
quartz), and b is an ion that has specific affinity to the
surface (such as a flotation collector), then the exponential
term would simply be exp[(DG 0spec)b /RT]. In ion exchange,
divalent ions dominate over monovalent ions because of the
valence effect in the Boltzmann relation (Eq. (12)).
2.2. Electrokinetic potentials
Electrokinetic phenomena, which involve the interrela-
tion between mechanical and electrical effects at a moving
interface, have found widespread use in colloid and surface
chemistry. The electrical potential involved is that at the
slipping plane, that is the plane at which the relative motion
takes place. This potential is commonly referred to as the
zeta potential, f. The problem is what potential does f
represent in the double layer. Across the diffuse layer, the
potential decays with distance according to the equation:
wðxÞ ¼ wd expð  jxÞ ð16Þ
where x represents the distance from the outer Stern plane to
the slipping plane. Thus, the closer the slipping plane is to
the Stern plane, the closer will w (x) [the zeta potential in this
case] approximate w d . In applying electrokinetic results, the
assumption that w (x) iw y is very useful. This approximation
seems permissible because the potential difference between
the Stern plane and the slipping plane is small compared to
the total potential difference across the double layer. In the
case of micelles, Stigter [25] showed that the slipping plane
might occur within 0.1 nm of the polar heads of the ions
constituting the micelle. Lyklema and Overbeek [26] have
suggested a gradual transition between the mobile and
immobile parts of the double layer in such systems.
However, it is of interest to note that the electrokinetic
potential has been found to be independent of Reynolds
number, over a wide range from laminar to turbulent flow
conditions [27]. Smith [12,28,29] has presented an interest-
ing approach to confirm the validity of the w x iw y
assumption in actual colloidal systems, It turns out that
the assumption that the slipping plane and the Stern plane
coincide is not only valid but extremely useful in dealing
with the electrical double layer theory of adsorption.
There are four well-known types of electrokinetic
phenomena, from which zeta potentials can be determined
[10,14]. Electro-osmosis is the process whereby the
application of an electric field causes flow of liquid.
Electrophoresis is the process by which the application of
a field causes suspended particles to move through a liquid.
Streaming potential is the process in which the application
of a pressure gradient causes a liquid to flow through a bed
of particles or a capillary, generating an electric current
which leads to an electric field. Sedimentation potential (the
Dorn effect) is the process by which particles are moved
14 D.W. Fuerstenau, Pradip / Advances in Colloid and Interface Science 114–115 (2005) 9–26
under the influence of gravity or centrifugal force, thereby
generating an electric field. Both electrophoresis and
streaming potential methods have been widely used for
investigation of mineral/aqueous solution systems of interest
to flotation. Sedimentation potentials have been used for the
study of air bubbles. These methods have complications.
When determining streaming potentials with beds of mineral
particles, the overlapping of double layers, surface con-
ductance and varying pore diameters can cause the
calculated zeta potentials to be too low at low solution
concentrations. Electrophoresis techniques have been
widely used for flotation chemistry studies, but the mineral
must be finely ground for these measurements and the
suspensions must have low solids content. Evaluation of the
zeta potential from electrophoretic mobilities can be
complicated, depending on particle diameter and double
layer thickness [14]. In general, the size of particles used in
flotation chemistry studies is sufficiently large that the
simple Smoluchowski equation can be used to convert
electrophoretic mobilities (l E) to zeta potentials (f) and is
given here since some of the results in this review have been
presented in terms of mobilities:
ee0 f
lE ¼ ð17Þ
g
where g is the viscosity of the solution. With aqueous
solutions at 25 C, f (volts)=13 l E. The readers are referred
to several excellent reviews for more details about electro-
kinetics [10,14,17,32–35].
More recently for measurements with relatively concen-
trated suspensions, instruments based on the electro-
acoustophoretic effect are available [36–40]. Even though
the theory of electro-acoustic effects in concentrated
colloidal suspensions is still not fully worked out, this
technique offers certain distinct advantages over conven-
tional electrokinetic techniques since colloids containing
particles of sizes ranging from a few nanometers to several
microns can be analyzed and samples having a wide range
of solid-to-liquid ratios can be conveniently used without
dilution. Electro-acoustophoretic techniques thus provide a
means to directly measure the zeta potential (or at least
relative surface charge characteristics) of the actual pulps
during flotation and flocculation processes. However, for
relating behavior to solution chemistry, the concentration of
electrolytes in solution must also be determined (because of
the very high surface area of solids in the system).
2.3. Effect of electrolytes on the zeta potential
Electrokinetic measurements can provide very useful
information on adsorption phenomena since changes in the
zeta potential reflect directly adsorption in the Stern plane.
Since the zeta potential is the potential at the slipping plane
when liquid is forced to move relative to the solid, only ions
in the diffuse layer outside the slipping plane are those that
are involved in the electrokinetic process. All sorts of charge
compositions on the surface and in the inner and outer Stern
planes can give the same zeta potential, depending on
surface potential, ionic strength, and specific adsorption
[18]. Thus, to understand the significance of the zeta
potential at some single condition, determination of the
change in zeta potentials as solution conditions are varied is
generally required. From these changes, modes of adsorp-
tion of various kinds of ions can be ascertained if one makes
the useful assumption that the slipping plane and the Stern
plane coincide.
Table 1 summarizes how the different types of electro-
lytes can affect various double layer parameters. How
various types of electrolytes may affect the zeta potential
can be illustrated with potential–distance curves of the
electrical double layer. Fig. 3a, b, c illustrate schematically
the effects of adding potential-determining (PD) electrolytes
(salts containing either the PD cation or anion), indifferent
electrolytes and surface-active electrolytes respectively. Fig.
3a and c show that the addition of two kinds of electrolytes
can reverse the sign of f, one being the potential-
determining ions and the other specifically adsorbed ions.
The solution conditions where f is zero is termed the
isoelectric point (IEP) or the point of zeta potential reversal
(PZR). The addition of a PD ion can bring f to zero because
the surface is uncharged. This IEP is also the point of zero
charge, PZC. Fig. 3c shows that a specifically adsorbed
counter ion can also reverse the zeta potential. This is
because contributions to the specific adsorption free energy
in addition to electrostatic interactions lead to increased
adsorption in the Stern plane such that r d Nr 0. Here the
IEP or PZR is not the PZC.
Usually the results of electrokinetic studies are presented
in terms of f-vs-log C curves. As can be ascertained from
Fig. 3 and Table 1, the addition of a positively charged PD
ion causes f to increase and then decrease because the
double layer is compressed as the ionic strength is increased.
The addition of a PD anion leads to the reversal of f when
the surface potential is reversed. As indicated in Fig. 3b, the
lower the ionic strength, the more f approaches w 0. So when
the zeta potential is determined as a function of pPD, zeta
potentials are reduced but still cross at the PZC. If
Table 1
The effect of adding potential-determining ions, indifferent electrolytes and
surface-active electrolytes to a suspension of a material with a reversible
electrochemical double layer on double layer parameters: surface potential
(w 0) double layer thickness (l/j), surface charge (r 0), and zeta potential (f)
Parameter Potential-determining Indifferent Surface-active
electrolytes electrolytes electrolytes
w0 Increases or Remains Remains constantT
decreases constant
1/j Reduced Reduced Reduced
r0 Increases or Increases Increases
decreases
f Increases, decreases, Only tends Can reverse sign
or reverses sign to zero
T Assuming any shift in PZC to be very small.
 D.W. Fuerstenau, Pradip / Advances in Colloid and Interface Science 114–115 (2005) 9–26 15

utilization of electrokinetic techniques for distinguishing

between physical and chemical adsorption of flotation
collectors and for delineating conditions under which
various kinds of specific adsorption phenomena might
occur. Often small changes in adsorption are reflected in
pronounced changes in electrokinetic potentials. In the
following paragraphs, we illustrate the utility of electro-
kinetic studies in flotation systems with the help of a few
selected examples.

3.1. Determination of PZC’s

As already stated, an isoelectric point determined by

electrokinetic measurements may or may not correspond to
the point of zero charge of the material. A careful set of
experiments must be carried out to ascertain if an IEP is a
PZC. The true PZC is the condition where the surface is
uncharged. Fig. 4 (top) presents the results of titrating
alumina with acid/base solutions to determine the adsorption
density (surface charge) of H+ and OH on alumina [14,41].
Only at pH 9.1 is the net adsorption of these ions nil, clearly
showing that only at pH 9.1 is the surface uncharged and,
thus, pH 9.1 is the PZC of alumina. Fig. 4 (bottom) shows
the electrophoretic mobility of the same alumina as a
Fig. 3. Schematic representation of the effect of the addition of various
function of pH in solutions of 0.001 M of several indifferent
types of electrolytes on the surface potential, the zeta potential and
thickness of the electrical double layer: (a) the addition of potential-
determining electrolytes, (b) indifferent electrolytes, and (c) specifically
adsorbed electrolytes.

electrokinetic measurements are made as a function of the

concentration of an indifferent electrolyte (such as NaCl
with quartz), f only decreases towards zero with increasing
electrolyte addition. However, effects due to overlapping
double layers reduce the apparent value of the electrokinetic
potential at low ionic strengths when streaming potential or
electro-osmotic methods are used with beds of particles
[14,30] so that f can appear to increase until roughly
millimolar concentrations are reached. If counter ions have a
constant specific adsorption potential, typically f-vs-log C
curves are straight lines that reverse the zeta potential
(similar to those observed upon the addition of the PD
electrolyte but the slope is generally lower). If the
specifically adsorbing electrolyte is a surfactant that forms
hemimicelles or is a multivalent cation that hydrolyzes, the
f-vs-log C curves follow those for indifferent electrolytes
and then deviate sharply when hemimicelles form or cations
hydrolyze. From simple double layer theory, it is possible to
model f-vs-log C curves [30,31].

3. Application of electrokinetics in flotation systems

Fig. 4. Determination of the point of zero charge (PZC) of alumina by acid–
Electrokinetic measurements can be used to delineate base titration of suspensions with KCl as indifferent electrolytes (upper
interfacial phenomena where electrical double layer effects plots) and measurement of the electrophoretic mobility of alumina with
are of relevance to flotation. Of particular importance is the three different indifferent electrolytes (after Refs. [18,41]).
16 D.W. Fuerstenau, Pradip / Advances in Colloid and Interface Science 114–115 (2005) 9–26
electrolytes. All curves exhibit an IEP or PZR at pH 9.1,
indicating that the IEP is the PZC. In using electrokinetics to
determine the PZC, one must decide which electrolyte is
potential-determining and then choose another salt as the
indifferent electrolyte. The curves given in Fig. 4 show that
the surface charge increases with increasing ionic strength,
in accordance with Eq. (7). On the other hand, as salt is
added to the system, the double layer is compressed (Fig.
3b) and the zeta potential decreases in absolute magnitude.
Fig. 4 also shows that when the surface is negatively
charged, all of the salts have a similar effect on f, since the
counter ions are K+ in each case, whereas the different
electrolytes have a small effect on f below the PZC because
of differences in ionic size and polarizability of perchlorate,
nitrate and chloride anions.
Conducting electrokinetic measurements as a function of
PD ion activity at several ionic strengths yields curves that
all cross at a point and this IEP should be the PZC (as can be
seen by the plots given in Fig. 5 for corundum). Electro-
kinetic measurements provide a very convenient and widely
used tool for determining the PZC of a mineral.
As will be discussed in the next section, for systems
involving the physisorption of ionic surfactants as the
Fig. 5. The dependence of the flotation of corundum (alumina) on surface
charge. Plots of the zeta potential as a function of pH at different
concentrations of NaCl show the PZC of corundum. Lower curves are the
flotation recovery of corundum in 4
105 M sodium dodecylsulfonate,
sodium dodecylsulfate, and dodecylammonium chloride (after Refs.
[4,44,45]).
flotation collector, flotation separations depend on differ-
ences in the PZCs of the minerals. Typical values of the PZC
for some of the oxide minerals are the following [9]: quartz
[SiO2] pH 2, cassiterite [SnO2] pH 4.5, zirconia [ZrO2] pH 4,
rutile [TiO2] pH 5.6, natural hematite [Fe2O3] pH 4.8–6.7,
synthetic hematite pH 8.6, corundum [Al2O3] pH 9.1,
magnesia [MgO] pH 12. The PZCs of silicate minerals are
affected by crystal chemistry and selective leaching of metal
cations or silica from the surface. Typical values of the PZC
of some silicate minerals are the following [42]: kyanite
[Al2SiO5] pH 7.8, zircon [ZrSiO4] pH 5.8, olivine [(Mg,Fe)2
SiO4] pH 4.1, almandine [Fe3Al2(SiO4)3] pH 5.8, beryl
[Be3Al2(Si6O18)] pH 3.4, spodumene [LiAl(SiO3] pH 2.6,
rhodonite [MnSiO3] pH 2.8, talc [Mg6(Si8O20)(OH)4] pH
3.6, muscovite [K2Al4(Al2Si6O20)(OH,F)4] pH 1, and
orthoclase [K(AlSi3O8] pH 1.8.
3.2. Relationship of flotation response to the PZC
Over the period 1953–1956, Fuerstenau began to evolve
the flotation concept that flotation collectors which physi-
cally adsorb must function as counter ions in the electrical
double layer, that is, that oxide mineral flotation with an
anionic collector is appreciable only at pHs below the PZC
and with a cation collector on at pHs above the PZC [43].
These concepts, which have been termed the electrostatic
model of flotation collection, are summarized in the
paragraphs that follow. As part of his doctoral thesis, Modi
[44] determined the PZC of corundum and conducted
modified Hallimond tube flotation experiments with a
variety of physisorbed collectors as a function of concen-
tration and pH. Fig. 5 presents the results of the very first
experiments on these concepts which were conducted as
part of Modi’s thesis [43,44], but were not published until
1960 [4]. The upper part of Fig. 5 presents the zeta potential
of corundum (synthetic sapphire) determined by streaming
potential measurements as a function of pH at various
additions of sodium chloride as indifferent electrolyte [45].
All the curves intersect and cross at zero zeta potential at
about pH 9, which is the PZC of this material. Flotation
experiments were conducted at a solution concentration of
4
105 M with three different high-purity collectors:
dodecylammonium chloride, sodium dodecylsulfate, and
sodium dodecylsulfonate. The lower part of Fig. 5 shows
clearly that corundum responds to the anionic collectors at
pHs below the PZC where corundum is positively charged,
and to the cationic collector at higher pHs where corundum
is negatively charged. The pKa of dodecylamine is 10.4, and
at pH 10.4 the DAC in solution will be 50% aminium ions
and 50% amine molecules. Under these conditions, flotation
is maximal due to coadsorption of aminium ions and amine
molecules. As the pH is raised to about 12, flotation drops
sharply and ceases at pH 12.6. Under these conditions, there
are insufficient aminium ions to bind the collector to the
surface. This upper pH limit for flotation with dodecylami-
nium collectors is virtually universal.
 D.W. Fuerstenau, Pradip / Advances in Colloid and Interface Science 114–115 (2005) 9–26 17

Subsequently, Iwasaki and Cooke and several co-workers

carried out similar detailed research on the flotation of a
wide range of iron ore minerals with high-purity reagents
and presented and interpreted their results in this same
manner [46,47]. The flotation response of oxide and silicate
minerals to these types of collectors is characteristically
similar to that presented in Fig. 5. Fig. 6 is a composite
showing the flotation response of four different oxides
whose PZCs range from pH 2–9 with dodecylammonium
chloride and sodium dodecylsulfate as collector (data from
[44,46,48]). Here the results are plotted relative to the PZC
of each mineral. Since the flotation time differed with each
investigation (15 s in the case of corundum and 5 min in the
case of goethite), the plots do not fall on top of each other,
but the four different oxide minerals clearly behave quite
similarly. The flotation of all the minerals with the 12-
carbon amine ceases above pH 12, but by presenting the
data relative to the PZC, this does not appear in the plots
except for corundum. Cases [49] conducted a thorough
investigation of the flotation behavior of a series of well-
characterized silicate minerals also using dodecylammo-
nium chloride and sodium dodecylsulfate as the collector.
Fig. 7 summarizes his results for the flotation response of
kyanite (disthene), zircon, garnet, beryl, augite and biotite
with these two collectors, with flotation recovery being
plotted relative to the PZC of each mineral. Presenting the
flotation results in this manner shows whether the collectors Fig. 7. The flotation response of a number of silicate minerals relative to the
interact only by physical forces or whether there are any pH of their PZC in the presence of 104 M dodecylammonium chloride and
additional forces interacting between the collector and the sodium dodecylsulfate as collectors [49]).
mineral surface (Eq. (13)). As can be seen from the plots
given in Fig. 7, only garnet appears to have any extra this suite seem to be governed quite well by electrostatic
affinity (although not strong) for both anionic and cationic interactions with the surface. Because the PZC of biotite,
collectors. The flotation behavior of the other minerals in and also augite, is very low, only limited flotation with
anionic collectors was observed with these minerals.

3.3. Role of the hydrocarbon chain in surfactant adsorption

The hydrocarbon chain of the surfactant contributes to

Fig. 6. The flotation response of a number of oxide minerals with 104 M
dodecylammonium chloride and 104 M sodium dodecylsulfate as
collectors as a function of pH relative to the pH of their PZC (after Refs.
[44,46,48]).
enhanced adsorption due to the chain–chain interactions in
the Stern plane, as first suggested in 1953 [39]. This can
quantitatively be represented as two terms in the free energy
of adsorption, namely DG 0elec and DG 0hpb. The adsorption of
surfactant ions at low concentration occurs as individual
counter ions, but once the adsorbed ions reach a certain
critical concentration at the solid–liquid interface they begin
to associate into two-dimensional patches of ions at the
surface in much the same way as they associate by self-
assembly into three-dimensional micelles in bulk solution.
The forces responsible for this association at the surface will
be the same as those operating in the bulk during micelle
formation, except that the Coulombic attraction for the
surface adsorption sites will aid the association. Because
the head groups are oriented towards the solid surface before
the zeta potential reverses sign, the patches of associated ions
at the water–solid interface have been termed bhemimicellesQ
[3,18]. The bulk critical concentration at which the associ-
18 D.W. Fuerstenau, Pradip / Advances in Colloid and Interface Science 114–115 (2005) 9–26

ation is observed is referred to as the hemimicelle (HMC)
concentration. The HMC is not constant, but will depend on
the potential-determining ion activity in solution. In the case
of alkylammonium ions on quartz at neutral pH, the hemi-
micelle concentration is about 0.01 of the bulk critical micelle
concentration (the CMC), but a simple calculation shows that
the concentration of adsorbed ions within the Stern layer
approximates the CMC [50,51].
To help visualize these concepts, a simple schematic
drawing is given in Fig. 8 for an anionic surfactant or
collector adsorbing on a positively charged mineral surface.
Fig. 8a represents the case for low adsorption densities
where the surfactant ions adsorb individually, both in the
diffuse layer and in the Stern layer. Flotation would be
limited under these conditions. Fig. 8b illustrates the
association of adsorbed surfactant ions into hemimicelles
in the Stern layer. As drawn, the system is at its IEP or PZR,
where the double layer can simply be considered to be a
bimolecular condenser (without a diffuse layer). Flotation
should be optimal under these conditions since the
surfactant head groups are oriented towards the solid and
the zeta potential is zero. Further surfactant adsorption
causes the zeta potential to be reversed because the charge in
the Stern layer exceeds the surface charge, and a triple layer
builds up with the head groups of some of the surfactant
ions now being oriented towards the water. Flotation will
tend to decrease under these conditions.
Since the length of the hydrocarbon chain of a surfactant
is important in adsorption processes, the number of carbon
atoms in the chain should directly relate to adsorption
behavior. By conducting a series of streaming potential
measurements on quartz with alkylammonium acetates
having alkyl chains ranging from 8 to 18 methylene groups,
Fuerstenau [50] clearly showed that hemimicelle formation
indeed depends on hydrocarbon chain length. In these
electrokinetic studies, octylammonium acetate behaved
identically to ammonium acetate. Studies of micelle
formation have shown that the cohesive free energy for
the formation of micelles is 1.0 to 1.1 RT (about 25
kJ) per mole of CH2 groups [51]. If the cohesive free energy
per mole of CH2 group in the hydrocarbon chain is / and
the number of carbon atoms in the alkyl chain is N, then for
hemimicelle formation (if N is about 8 or greater)
DG0hpb ¼ N /: ð18Þ
If all other specific adsorption effects are negligible, then
above the hemimicelle concentration the adsorption density
of surfactant ions in the Stern layer is given by
   
 DG0ads  zFwd  N /
Cd ¼ 2rCexp ¼ 2rCexp ð19Þ
RT RT
This equation shows that the amount of surfactant adsorbed
in the Stern plane should depend strongly on the hydro-
carbon chain length, once the hemimicelle concentration is
exceeded. This has been demonstrated for the adsorption of
alkylammonium ions on quartz [51] and alkyl sulfonate ions
on alumina [52].
Somasundaran conducted a detailed systematic study of
the effect of the chain length of aminium collectors on the
flotation of quartz and in the course of that research also
measured the effect of chain length on the zeta potential
of quartz. Fig. 9 presents the results of measurements of
the zeta potential of quartz at neutral pH as a function of
the concentration of alkylammonium acetates (without
ionic strength control) ranging from 10 to 18 carbon
atoms [51]. As expected, the zeta potential of quartz with
the various surfactants approximates that with ammonium
acetate until hemimicelle formation sets in. Earlier
measurements showed that octylammonium acetate
behaves almost identically to ammonium acetate, indicat-
ing that the hydrocarbon chain must exceed, say, 8 carbon
atoms to be sufficiently hydrophobic for hemimicelle
formation to occur [50]. Increasing the length of the
hydrocarbon chain causes a systematic decrease in the
hemimicelle concentration.

Fig. 8. Schematic representation of the aqueous adsorption of an anionic surfactant (collector) on a positively charged mineral. (a) Adsorption as individual
counter ions at low concentrations. (b) Aggregation of adsorbed surfactant ions into hemimicelles at higher adsorption densities with the charged head groups
oriented towards the solid surface and at the PZR in this case. (c) At adsorption densities where the charge in the Stern plane exceeds that of the surface, a triple
layer forms with surfactant ions being adsorbed in reverse orientation due to electrostatic repulsion.
 D.W. Fuerstenau, Pradip / Advances in Colloid and Interface Science 114–115 (2005) 9–26
Fig. 9. The zeta potential of quartz as a function of the chain length of
alkylammonium acetates at neutral pH. The upper curves give a plot of the
cationic surfactant concentration at which the zeta potential is zero as a
function of the number of carbon atoms in the hydrocarbon chain, the
concentration at which Hallimond tube flotation increases sharply (termed
the flotation parameter), and the flotation edge or critical flotation
concentration obtained from vacuum flotation experiments (after Refs.
[51,54,55]).
When the zeta potential is reduced to zero after
association of the alkyl chains, it follows from Eq. (19) that
lnC0 ¼ N ð/=RT Þ þ lnðCd Þ0  ln2r ð20Þ
where C=C 0 at w d =0. If the ratio of the adsorption density
at w d =0 to the factor 2r is relatively independent of chain
length, then the logarithm of the concentration of surfactant
Fig. 10. Flotation response of quartz at pH 6–7 as a function of the concentration of alkylammonium acetates of different hydrocarbon chain lengths (after Ref.
[55]).
19
ions at w d =0 should be a linear function of the alkyl chain
length with a slope equal to //2.3RT. Fig. 8 (top) includes
such a plot for alkylammonium ions on quartz, and from this
plot / is calculated to be 1RT (about 0.6 kcal/mol of
CH2 groups) in agreement with values obtained from
solubility and micelle data [51].
For rapid flotation to occur, the collector must be adsorbed
in the Stern plane and in sufficient quantity for the mineral to
be hydrophobic. Rapid flotation takes place once hemi-
micelles form. The one system in which chain length and
flotation response has been investigated in detail is the
flotation of quartz with high-purity alkylammonium acetates.
Vacuum flotation experiments were conducted by deBruyn
[53] and also by Somasundaran [54]. Vacuum flotation
experiments have been conducted to determine incipient
flotation conditions with collector concentration and pH
being the two variables. Often the resulting plots have been
termed critical flotation curves. The term flotation edge has
been used to designate the conditions for incipient flotation.
The results obtained by Somasundaran and by deBruyn both
show that incipient flotation exhibits a chain-length effect,
probably assisted by transfer of surfactant adsorbed on the
bubble to the mineral surface. In Fig. 9 (top) the results of
Somasundaran’s measurements of the aminium concentration
for incipient flotation of quartz (the flotation edge) at pH 6.5
is also plotted as a function of the number of carbon atoms in
the collector chain. These experiments again show a system-
atic chain-length effect. With all of the alkylaminium
collectors, deBruyn and Somasundaran found that flotation
ceases slightly above pH 12, where the collector has
hydrolyzed to amine molecules, and below about pH 2.5–
3.5 near the PZC of quartz.
Detailed Hallimond tube flotation experiments were
carried out for quartz with a full range of high-purity
alkylammonium acetate collectors, from 18 down to 4 carbon
atoms [55]. These flotation results, which are presented in
Fig. 10, show that the concentration of collector needed for
flotation decreases systematically as the chain length of the
aminium salt is increased. Flotation is even possible with
20 D.W. Fuerstenau, Pradip / Advances in Colloid and Interface Science 114–115 (2005) 9–26

butylammonium acetate, but at a collector concentration of

about 1 M. Here again, the collector adsorbed on the bubble
must also be assisting adsorption since chain–chain inter-
action phenomena would be negligible. Of interest is that
with a strongly chemisorbing collector, such as ethyl
xanthate, sulfide minerals respond to flotation at a residual
collector concentration of about 1 ppm in solution. The quartz
flotation results were analyzed in a manner analogous to that
for the effect of aminium ion concentration on the PZR, using
an equation similar to Eq. (20), except in terms of the
hemimicelle concentration which was obtained by extrap-
olation of the flotation recovery curve and was termed the
flotation parameter [55]. In Fig. 9, this flotation parameter
(essentially the HMC) is plotted as a function of the number
of carbon atoms in the aminium collector, and a straight line
similar to that for the PZR is obtained, again giving a value
for / as 1RT.
Somasundaran and Fuerstenau [56] conducted the first
experiments on the adsorption of sodium dodecylsulfonate on
alumina with controlled ionic strength, using sodium chloride
as the supporting electrolyte. With ionic strength fixed, they
observed a distinct three-stage isotherm when the results are
plotted logarithmically (sometimes called an SF isotherm). At
low concentrations, surfactant ions are adsorbed individually
by exchange with chloride counter ions; but when the
hemimicelle concentration is reached, the slope of the Fig. 11. Effect of the concentration of sodium dodecylsulfate on the
isotherm increases markedly due to chain–chain interaction; flotation recovery of corundum at various pH values. The upper curves
and when the zeta potential is reversed, the slope of the present the zeta potential of corundum as a function of the concentration of
isotherm decreases again (due to reversal of f). Later work sodium dodecylsulfate. In addition, the effect of sodium chloride on the zeta
potential of corundum is also shown, to illustrate the difference between an
showed that these isotherms exhibit a fourth region as the
indifferent electrolyte and a surfactant forming hemimicelles (after Refs.
CMC is approached. This review will not discuss details of [4,57]).
adsorption isotherms, but the contact angle exhibited abrupt
changes at the boundaries of the three regions.
mineral being floated. At pH 9.3 there is limited flotation,
3.4. Effect of pH and surface potential on oxide flotation which was also observed in the curves given in Fig. 5. This is
because there are still a certain number of positive sites on the
Modi and Fuerstenau [4,57] investigated how pH controls surface at pHs above the PZC. When pH 11 is reached, the
the effect of sodium dodecylsulfate on the zeta potential and surface is so negatively charged that there is no flotation of
flotation response of corundum, and their results are corundum with dodecylsulfate as collector. Comparison of
presented in Fig. 11. For the alumina/dodecylsulfate system, the upper and lower parts of Fig. 11 shows that flotation
decreasing the pH from 6.5 to 4.0 increases the surface increases sharply as the hemimicelle concentration is reached
potential and surface charge, leading to increased adsorption and flotation is about 100% when the IEP or PZR is reached.
of counter ions. For a physisorbing surfactant, such as sodium
dodecylsulfate, the hemimicelle concentration is reduced 3.5. Flotation depression with inorganic ions
nearly 10 fold, as can be seen by the sharp change in the
slopes of the f-log C curves for SDS given in the upper part of With physisorbed collectors that float insoluble oxides
Fig. 11. It is at these points where the SDS plots deviate from and silicates, reducing and reversing the surface charge by
the plots for sodium chloride. At pH 11 where the corundum changing the pH depresses flotation, as exemplified by
is negatively charged, the counter ions are sodium ions and raising the pH when floating corundum with SDS (Fig. 10).
the dodecylsulfate ions do not take part in the adsorption Since physisorbed surfactants act as flotation collectors by
processes. Because of hemimicelle formation occurring at a adsorption as counter ions in the double layer, the addition
lower concentration as the pH is lowered, flotation of of any salt should compete with the surfactant ions as
corundum also occurs at a lower reagent concentration, as counter ions and at sufficiently high concentration depress
can be seen by the plots given in the lower part of Fig. 11. flotation. This might be important in the industrial flotation
Clearly, reduction in reagent consumption can be achieved if of nonmetallic minerals using seawater. To illustrate this
selectivity is maintained at higher surface potential for the phenomenon, Fig. 12 presents plots of the effect of sodium
 D.W. Fuerstenau, Pradip / Advances in Colloid and Interface Science 114–115 (2005) 9–26
Fig. 12. Depression of the flotation of corundum using sodium dodecyl
sulfate as collector at pH 6 by the addition of sodium chloride and sodium
sulfate. Included in this figure is the effect of the two inorganic salts on the
zeta potential of corundum (after Refs. [4,45,57]).
sulfate and sodium chloride on the zeta potential of
corundum and also their effect on corundum flotation with
4
105 M SDS at pH 6 [4,45,57]. Sulfate ions exhibit
specific adsorption on corundum, as evidenced by the
reversal in the zeta potential at 3
104 M Na2SO4. The
plots given in Fig. 12 show excellent correlation of the
effect of the two inorganic salts on the zeta potential of
corundum (in the absence of SDS) and in depressing
flotation. This figure shows that both Cl and SO42 inhibit
the flotation of positively charged alumina but with the
effect of SO42 being nearly 500 times that of Cl.
The greater effect of sulfate over chloride ions in
depressing alumina flotation results from the valence effect
and the specific adsorption potential of SO42 on alumina.
This can be interpreted in accordance with Eq. (15). The
concentration of SDS used in these experiments was
4
105 M, and hemimicelles had formed at the surface,
with the adsorption free energy being 5.6RT under these
conditions [57]. From conditions leading to the PZR of
corundum with sodium sulfate, the specific adsorption free
energy of divalent sulfate ions is about 6.9RT. The ionic
radii are 0.18 nm for chloride ions and 0.29 nm for both
sulfate ions and the head group of dodecylsulfate ions. For
these calculations, we will consider conditions that reduced
flotation recovery to 50%. Fig. 12 shows that 5.6
103 M
NaCl is required to do this when the collector concentration
is 4
105 M, or 140 times as much. Assuming that half the
dodecylsulfate ions in the Stern plane are replaced by
chloride ions, Eq. (15) estimates that the required ratio of
chloride to dodecylsulfate is 170. To carry out the
calculation for depression with divalent sulfate ions, we
have to take into account that one divalent sulfate ion will
displace two dodecylsulfate ions in the Stern plane and
bring the zeta potential into the calculation. Doing so shows
that the concentration of divalent sulfate ions necessary to
reduce the recovery to 50% is one-fourth that of the SDS in
solution, or 0.9
105 M compared to the 1.3
105 M
observed. Given that a rigorous calculation would require
21
potentials at different planes and knowledge of hydration
phenomena, these estimates starting with electrokinetic
results are interestingly close.
3.6. Flotation activation with inorganic ions
We have just seen the effects of sodium sulfate in
inhibiting the flotation of positively charged alumina with
an anionic collector. Fig. 13 illustrates how the same
inorganic salt can promote flotation. At pH 6, alumina does
not respond to flotation with dodecylammonium chloride as
collector since the organic cations do not adsorb on a
positively charge solid. On the other hand, by adding
sufficient SO42 to the system, the net charge in the Stern
layer and the surface is reversed, and the solid can now
adsorb organic cations [4]. In flotation terminology, sulfate
ions are said to function as an activator; they serve as a link
between the surface and similarly charged collector ions. In
such systems the electrical double layer is in reality a triple
layer.
Opposite to the case of activation of corundum with
sulfate ions shown in Fig. 13, industrial activation of oxides
generally involves the linkage of an anionic collector to a
negatively charged mineral through the addition of strongly
adsorbing metal cations. Since hydrolyzed metal cations are
extremely surface-active, they will function best as activa-
tors at the incipient hydrolysis pH. Fig. 14 shows the results
of such an investigation of quartz flotation carried out by
M.C. Fuerstenau and Palmer [58] using 104 M sulfonate as
collector and various metal cations at 104 M as activator.
As the pH is increased, activation occurs sharply when the
activating cation begins to hydrolyze in solution. Hydroxy-
lated metal ions are extremely surface active and readily
adsorb on all sorts of adsorbents. In Fig. 14, only the initial
flotation edge is shown for clarity in making the plots.
However, flotation ceases at about pH 3.8 with Fe(III), at
pH. 4.5 with Al(III), and at pH 11.7 with Mg(II), which are
the pH values at which those metal hydroxides precipitate.
Since the PZC of quartz occurs at about pH 2, quartz
Fig. 13. The activation of positively charged corundum at pH 6 with sodium
sulfate for flotation with dodecylammonium chloride (after Ref. [4]).
22 D.W. Fuerstenau, Pradip / Advances in Colloid and Interface Science 114–115 (2005) 9–26
Fig. 14. The activation of quartz with 104 M metal cations and 104 M
sulfonate collector as a function of pH. The minimum flotation edges are
plotted for clarity, but maximal flotation occurs only where the data points
are shown (after Ref. [63]).
responds to flotation with a sulfonate or a soap only after
extensive adsorption of the activating metal cation in the
Stern layer. In the case of complex silicates, autoactivation
can occur by metal ions derived from the crystal lattice by
their dissolution and readsorption as a flotation activator.
3.7. Collector uptake by physisorption or chemisorption
If counter ions are adsorbed only through such forces as
electrostatic attraction and hydrophobic bonding (van der
Waals interaction between the hydrocarbon chains), the
process is termed physical adsorption or physisorption. If
the surfactant forms covalent bonds with metal atoms in the
surface, then the process is called chemisorption. As already
discussed, examples of physical adsorption in mineral/water
systems include alkylammonium ions on quartz and other
oxide minerals and alkyl sulfates and sulfonates on alumina.
Examples of chemisorption of surfactants are the, oleate/
hematite, hydroxamate/hematite, hydroxamate/MnO2 and
oleate/fluorite systems. Infrared spectroscopic studies have
helped confirm the existence of calcium oleate, ferric oleate,
ferric hydroxamate and Mn-hydroxamate species on the
surface, indicating chemisorption by covalent bond linkages
[59–62].
The nature of the plot of zeta potential as a function of
the potential-determining (PD) ion activity can be used to
distinguish whether the adsorption occurs by physical or
chemical interactions. Plotting f-vs-pPD for systems at
constant concentration of an indifferent electrolyte with and
without added surfactant yields visible evidence of various
adsorption mechanisms. Fig. 15 is a schematic illustration
showing the effect of various interactions on the zeta
potential of a solid. The solid line in this figure is typical for
that of an indifferent electrolyte on a hydrophilic material,
with the reversal of zeta potential at point A being the PZC.
At point A, the surface charge is zero and ideally there is no
double layer. Nearly all minerals encountered in mineral
processing are hydrophilic in the absence of a collector,
except for graphite, molybdenite and talc which are
naturally hydrophobic because of their crystal structure.
If a physisorbing anionic surfactant is added to the
system (such as alkyl sulfates on alumina) with the
concentration of indifferent salt being the same, a curve
similar to the dashed one in Fig. 15 is obtained. Starting at
high pPD, the curves coincide because there is no specific
adsorption of the anionic surfactant on the negatively
charged mineral. As the pPD is decreased, point A is
reached, and this still is the PZC of the solid. As the pPD is
decreased further and the solid becomes positively charged,
the negatively charged surfactant ions begin to adsorb.
When the pDP is lowered to the region around point D, the
adsorption density of the surfactant ions reaches the
hemimicelle concentration and chain–chain association
leads to an increasing specific adsorption potential such
that at point C the zeta potential is reversed. Point C is an
IEP (or PZR) and not the PZC. Even though the surface
itself is becoming more highly positively charged, the
increased adsorption of negatively charged surfactant ions
increases the specific adsorption potential because of
increased chain–chain interaction. At point C the double
layer is a molecular condenser consisting of a surface charge
and a molecular layer of surfactant anions. In the case of a
hydrophobic material, such as talc, the f-vs-pPD curve will
have the appearance of the curve with open circles in Fig.
15, where the reversal of f occurs at point BV, somewhat
lower than point A. This is again an IEP that is not the PZC
but reflects specific adsorption due to the hydrophobic chain
of the surfactant displacing water molecules from the
Fig. 15. Schematic illustration of the effect of potential-determining ions
(pH for oxides) on the zeta potential in the presence of an indifferent
electrolyte, a physisorbing anionic surfactant on a hydrophilic mineral, a
physisorbing collector on a hydrophobic mineral, and a chemisorbing
anionic collector.
 D.W. Fuerstenau, Pradip / Advances in Colloid and Interface Science 114–115 (2005) 9–26 23

hydrophobic surface. In this case, the curves come together and the double layer can be considered to be a molecular
0 0
again at point EV where the mineral surface is sufficiently condenser with DG ads =DG spec . Under these conditions, the
negatively charged to overcome the specific adsorption Stern–Grahame relation can be expressed as
potential due to hydrophobic interactions with the surface.  
For surfactants that chemisorb at the surface of a mineral, w0 Km ¼ 2rC0 zFexp  DG0spec =RT ð21Þ
bonding to the surface can be very strong and, for an anionic
collector, only when the surface becomes sufficiently
where K m is the capacitance of the molecular condenser, r is
negatively charged by raising the pPD will adsorption
the effective radius of the ionic head of the adsorbed ion,
cease. This occurs at point EW where the two curves come
and C 0 is the concentration in mole per cm3 at the IEP. For a
together again. At this point chemical contribution to the
given activity of potential-determining ions, w o is obtained
free energy of adsorption is counter balanced by electro-
from Eq. (3) (or other form of the Nernst equation modified
static repulsion. Where the two curves join again generally
for oxides). If K m is assumed constant (for example, 15 AF/
marks the upper limit for flotation by a chemisorbing
cm2), then DG 0spec can be estimated. With this method,
collector. Also, again point BW is an IEP and not the PZC.
Fuerstenau and Modi [57] calculated DG 0spec to be 9RT at
Detailed experiments were conducted by Han et al. [63]
the PZR for dodecylsulfonate ions on corundum at pH 6.5
where the electrophoretic mobilities of synthetic hematite
(Fig. 9). Its value would be zero at the HMC and at the
we measured for various concentrations of sodium dodecyl
break in the zeta potential curve above the HMC, which
sulfate, potassium octylhydroxamate, and oleic acid in
appears to represent monolayer coverage in streaming
aqueous solutions containing 0.002 M NaCl as a function
potential experiments, extrapolation indicates that DG 0spec
of pH. In Fig. 16, their results for 2
104 M hydroxamate
is 13RT at this point.
and dodecylsulfate are plotted together with results for
At Point E in Fig. 15, specific adsorption in the Stern
1
104 M oleic acid. The oleate chain must enter into the
plane must be nil and the specific adsorption potential is just
adsorption process also because the curve remains in the
counter balanced by the electrostatic contribution, that is,
negative region (and even becomes slightly more negative)
DG 0elec=DG 0spec. In the case of chemisorption, this relation
as the pH is lowered.
permits estimation of DG 0chem.
At any IEP, the free energy of adsorption can be
Specific interactions during the adsorption of a surfactant
calculated or estimated. For the sake of simplicity, assume
on a mineral surface result in a shift of isoelectric point
that the inner and outer Stern planes coincide and that
(IEP). Pradip [64] has shown that this shift in IEP,
specific adsorption occurs in the plane d. The adsorption
DpH=(pPZRPZCp) is related through the following
density in the Stern layer is given by Eq. (10). At any IEP or
0 equations derived on the basis of electrical double layer theory:
PZR (such as point B in Fig. 13), f=w d =0, so that DG ads

Fig. 16. The electrophoretic mobility of hematite as a function of pH in
solutions containing 2
103 M NaCl, 2
104 M sodium dodecylsulfate
and potassium octylhydroxamate, and 1
104 M sodium oleate. All
solutions with the three different surfactants also contained 2
103 M
NaCl as supporting electrolyte for ionic strength control (after Ref. [63]).
DpH ¼ 1:040C0 exp  DG0spec =RT ð22Þ
where C0 is the equilibrium molar concentration of surfactant
at the IEP (or PZR) and DG 0spec is the specific free energy of
interaction in kcal/mol or RT units. The validity of this
relationship is illustrated in Fig. 17 for the chemisorption of
octylhydroxamate for two oxide minerals. The calculated
values are comparable to those computed from the corre-
sponding adsorption isotherms [64].
3.8. Chemisorption and physisorption in oxide flotation
The flotation response of manganese dioxide with
sodium dodecylsulfonate [62], potassium octylhydroxamate
[62] and sodium oleate [65], are given in Fig. 18 (top, center
and bottom). These plots illustrate the complicated nature of
physical and chemical adsorption in flotation processing.
The PZC of this manganese dioxide (high-purity g-MnO2)
occurs at pH 5.6 [62]. The results given in Fig. 18 (top)
indicate that the flotation of manganese dioxide with anionic
sulfonate behaves as expected for a physisorbing collector.
Flotation only occurs below about pH 6, where the surface
carries a positive charge and hence adsorbs the anionic
sulfonate collector as a counter ion in the double layer. The
24 D.W. Fuerstenau, Pradip / Advances in Colloid and Interface Science 114–115 (2005) 9–26

containing the same amount of indifferent electrolyte but

also a constant concentration of surfactant (such as oleate),
the shift in the zeta potential is a measure of the specific

Fig. 17. Shift in the isoelectric point (IEP) through specific adsorption of a
surfactant (hydroxamate) on hematite and pyrolusite and the calculated shift
expected from electrical double layer theory (after Ref. [64]).

results presented in Fig. 18 (center) show the flotation

response with potassium octylhydroxamate, a chelating
agent that strongly coordinates with manganese ions at the
mineral surface, as substantiated by infrared spectroscopy.
In this chemisorbing system, flotation takes place at pHs
where the solid surface is highly negatively charged. The
maximum in flotability occurs at about pH 9, similar to the
case for hematite, which is approximately the pKa of
hydroxamic acid. As the pH is increased above this value,
flotation decreases, ceasing by about pH 11, because of
strong repulsion of the hydroxamate anions by the
negatively charged surface. Hydroxamic acid molecules
must be the chemisorbing species.
The flotation of manganese dioxide with oleate collector
is particularly complicated, with two flotation peaks being
present in this system, as can be seen in Fig. 16 (bottom). The
peak at about pH 8 is typical for the chemisorption of oleate
on many minerals. Ananthapadmanabhan et al. [66] have
suggested that the acid–soap dimer, which is at a maximum
under these conditions, is extremely surface-active. Adsorp-
tion at these alkaline pHs occurs under conditions where the
solid is negatively charged, and strong chemical bonding
must be responsible for the observed mineral–collector
interaction. Infrared spectroscopy showed the presence of
ferric–carboxylate bonds when oleate is adsorbed on
hematite [59]. In the vicinity of pH 5.5, there is little
flotation of manganese dioxide. However, as the pH is
lowered further, a second flotation maximum appears. This
must now be due to physical adsorption that involves a
positively charged surface adsorbing oleate anions. Since the
pKa of oleate is about 4.7, the actual collecting species must
be oleate ions together with oleic acid molecules. At pHs less
than 3 or so, most of the oleate has been transformed to oleic
acid, which is not the reactive species, and flotation ceases
(similar to the action of amines at high pH).
Fig. 18. The effect of pH on the flotation of manganese dioxide (PZC=pH
Fuerstenau and Shibata [67] pointed out that if f-vs-pH 5.6) with various additions of three different collectors: sodium dodecylsul-
curves are measured at constant concentration of indifferent fonate, potassium octylhydroxamate and sodium oleate (after Refs.
electrolyte (such as sodium chloride) and also with solutions [62,65]).
 D.W. Fuerstenau, Pradip / Advances in Colloid and Interface Science 114–115 (2005) 9–26
adsorption free energy and that this correlates quite well
with flotation response under the same conditions.
3.9. The adsorption of dodecylammonium acetate on talc
Because of the natural flotability of talc, specific
adsorption phenomena on talc differs from that on oxides
and other silicate minerals. Talc belongs to the family of
silicate minerals that are comprised of three repeating
binfiniteQ sandwich-like layers: a layer of octahedrally
coordinated magnesium–hydroxyl ions between two layers
of tetrahedrally coordinated silicon–oxygen ions. Since each
three-layer sheet is electrically neutral, the crystal is held
together by weak van der Waals forces acting across
adjoining sheets, and the crystals readily cleave along these
sheets, forming faces that are uncharged and nonpolar in
water. On the other hand, the edges of talc particles are
formed by breaking ionic/covalent bonds and therefore
exhibit a high pH-dependent electrical charge in water and
are highly polar. Because the faces are hydrophobic and the
edges hydrophilic, the flotation behavior of talc can be
rather complex.
Some insight into the behavior of talc/aminium systems
can be gained from the measurement of zeta potentials. The
plots given in Fig. 19 present the f-potential of talc as a
function of pH with concentrations of dodecylammonium
acetate ranging from 0 to 0.001 M in 0.002 M potassium
Fig. 19. The effect of pH on the zeta potential of talc in the presence of
various additions of dodecylammonium acetate with 2
103 M potassium
nitrate as supporting electrolyte, illustrating specific adsorption through
hydrophobic bonding with a hydrophobic mineral surface (after Ref. [67]).
25
nitrate as supporting electrolyte [67]. These results without
surfactant indicate that the condition for zero net surface
charge (the isoelectric point) of talc occurs at pH 2.5.
Because a talc particle has a highly anisotropic surface, the
net charge on the particles must be controlled to a large
extent by adsorption/dissociation reactions of H+ and OH
ions with broken Si–Mg–O bonds at the crystal edges. As
can be seen, f becomes only slightly more positive over all
pHs with aminium additions up to 105 M. It is over this
same range that flotation increases to a plateau. It appears
that at low amine concentrations, the most significant
adsorption of the organic cations takes place on the charged
edges. At higher amine concentrations, there is a sharp
change in the adsorption mechanism, as can be seen from
the jump in the f-vs-pH curve for 5
105 M surfactant. The
pronounced shift of the curves towards more positive zeta
potentials probably results from the hydrophobic surface
contribution to the adsorption free energy. Here adsorption
must take place by the hydrocarbon chains displacing water
molecules from the hydrophobic surface. Because the face
of a soft talc crystal will have steps on it, these small edge
effects must also contribute to adsorption on the faces. At
higher DAA concentrations at acidic pHs, the major
contribution to the adsorption free energy must result from
hydrophobic interactions of surfactant chains with the
hydrophobic surface since the zeta potential is highly
0
reversed (the DGhpb* term in Eq. (13)). The sharp increase
in f at pH 10 in millimolar surfactant solutions results from
coadsorption of aminium ions and amine molecules in
hemimicelles. Above pH 12, adsorption of aminium ions
cease and the zeta potential drops sharply to the same
negative value observed without collector.
4. Summary
The electrical double layer has a dominant role in
collector adsorption and flotation of oxide and silicate
minerals. Measurements of zeta potentials provides a
straight-forward way of ascertaining adsorption mechanisms
and conditions in such systems. Cationic collectors adsorb
when the surface charge on the mineral is negative, and
vice-versa for anionic collectors. Separations are based on
differences in the points of zero charge (PZCs) of minerals
in an ore. For physically adsorbing collectors, surfactant
ions can aggregate in the Stern plane, forming hemimicelles
through hydrocarbon chain association. For rapid flotation
rates, collector adsorption in the Stern plane must be
pronounced. Collector adsorption can be enhanced by
increasing the surface potential by adding potential-deter-
mining ions (through pH regulation in the case of oxides),
increasing the chain length of the collector, and adding
neutral organic molecules. Flotation can be depressed by
adding inorganic salts that compete with the collector.
Minerals will respond to flotation with anionic chemisorb-
ing collectors even when the mineral surface is highly
26 D.W. Fuerstenau, Pradip / Advances in Colloid and Interface Science 114–115 (2005) 9–26
negatively charged, that is above the PZC. However,
electrostatic effects are important even in chemisorbing
surfactant systems since strongly opposing electrostatic
interaction can overcome chemisorption, thereby preventing
collection. Whether flotation collectors are physisorbed or
chemisorbed, they have distinct effects on the zeta potential
of the mineral, and these effects can be used to evaluate
specific adsorption free energies.
Acknowledgements
Pradip wishes to acknowledge support from the Depart-
ment of Science and Technology, India, under an Indo–U.S.
STI program during the preparation of this paper.
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