Microporous and Mesoporous Materials 83 (2005) 51–59

www.elsevier.com/locate/micromeso

Electrokinetic properties of kaolinite in mono- and

multivalent electrolyte solutions
Mahir Alkan *, Özkan Demirbasß, Mehmet Doğan
Department of Chemistry, Faculty of Science and Literature, Balikesir University, 10100 Balikesir, Turkey

Received 23 November 2004; received in revised form 22 March 2005; accepted 22 March 2005
Available online 23 May 2005

Abstract

Zeta potential, known as the electrical potential at the shear plane, f, is one of the important electrokinetic properties of clay
minerals. For many applications, the sign and the magnitude of the f potential is necessary to be known. For clay soils, it is usually
negative. In this study, the electrokinetic properties of kaolinite have been investigated using the microelectrophoresis technique as a
function of solid–liquid ratio, pH and type and concentration of electrolyte. The electrokinetic properties of kaolinite suspensions
have been determined in aqueous solutions of mono-, di-, and trivalent salts such as NaCl, KCl, LiCl, NaNO3, NaCH3COO, MgCl2,
CaCl2, BaCl2, Na2CO3, Na2SO4, AlCl3, FeCl3, Na3PO4 and divalent heavy metal salts such as CoCl2, CuCl2 and Pb(NO3)2. Fur-
thermore, systematic zeta potential experiments have been performed to determine the isoelectric point (iep) and potential determin-
ing ions (pdi). From the experimental results, (i) the zeta potential of kaolinite is not significantly affected by the solid concentration;
(ii) pH strongly altered the zeta potential of kaolinite; (iii) kaolinite has an isoelectric point at about pH 2.35; (iv) monovalent cat-
ions and anions, and di- and trivalent anions were indifferent electrolytes for kaolinite whereas MgCl2, CaCl2, BaCl2, CoCl2, CuCl2,
Pb(NO3)2, AlCl3 and FeCl3 changed the interface charge from negative to positive.

2005 Elsevier Inc. All rights reserved.

Keywords: Zeta potential; Kaolinite; Potential determining ion; Electrolyte concentration; Electrical double layer

1. Introduction six main structural groups of layer silicate minerals: (i)

The term clay mineral is applied to a specific group of
layer-type aluminosilicate minerals, which contain struc-
tural hydroxyl groups and belong to the general class of
phylosilicates. Clay minerals are hydrous aluminosili-
cates, with magnesium and iron substituting for alumi-
num in varying degrees and with exchangeable alkali
and alkaline earth elements as potentially essential con-
stituents. According to Brown and co-workers, there are
*
Corresponding author. Tel.: +90 266 249 10 11; fax: +90 266 249 10
12.
E-mail addresses: malkan@balikesir.edu.tr (M. Alkan), ozkan@
balikesir.edu.tr (Ö. Demirbasß), mdogan@balikesir.edu.tr, mdogan
7979@yahoo.com (M. Doğan).
kaolinite—serpentine, (ii) pyrophyllite—talc, (iii) mica,
(iv) smectite—vermiculite, (v) polygorskite—sepiolite,
and (vi) the chlorite group [1].
Kaolinite is a 1:1 dioctahedral aluminosilicate that
has two different basal cleavages faces [2]. One basal face
consists of a tetrahedral siloxane surface very inert –Si–
O–Si– links. The other basal surface consists of an octa-
hedral, gibbsite (Al(OH)3) sheet. Both of these surfaces
are theoretically electrically neutral. At the edges of a
1:1 layer, the structure is disrupted and broken bonds
occur that are accommodated as OH groups. These
edges are estimated to occupy approximately 10% of
the whole kaolinite surface [3,4]. The computer-gener-
ated model of the kaolinite lattice has been given in
Fig. 1, which adopted with some modifications from
Ref. [5]. The kaolinite surface has a complex chemistry

1387-1811/$ - see front matter
2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2005.03.011
52 M. Alkan et al. / Microporous and Mesoporous Materials 83 (2005) 51–59
Fig. 1. Computer generated model of the kaolinite lattice.
due to the existence of these different sites on the basal
faces and edges. Kaolinite is a mineral that has a wide
variety of applications in industry, particularly as a pa-
per filler and a coating pigments [6]. It is used as an ex-
tender in water based paints and ink, as a functional
additive in polymers and is a major component of
ceramics [6]. Kaolinite is an inexpensive additive that
can improve the properties of the material in which it
dispersed provided that a stable dispersion is formed.
The surface interactions that occur at the interface
when this material is incorporated into aqueous disper-
sions or polymer systems are poorly understood. For
example, the development of surface charge in aqueous
systems and, consequently, the electrical double layer
properties of the surface as a function of pH, electrolyte
type and concentration have not been critically
examined.
The study of the electrochemical properties of the
clay/water interface is important to understand a large
number of properties of clay-rich porous media and col-
loid suspension of clays [7]. Otherwise, electrokinetic
properties such as the isoelectric point (iep) and poten-
tial determining ions (pdi) of fine particles in an aqueous
solution play a significant role in understanding the
adsorption mechanism of inorganic and organic species
at the solid/solution interface [8]. The principal reason
for determining the f-potential was to obtain on indica-
tion of the magnitude of the potential at the beginning
of the diffuse double layer around the particle. This
can then be used to estimate the effect of the particle
charge on such things as aggregation behaviour, flow,
sedimentation, and filtration [9]. In this manner, some
researchers have investigated electrokinetic properties
of clay minerals. Fernandez-Nieves and Ias Nieves have
investigated the electrokinetic characterization and col-
loid stability of different TiO2/water interfaces under
the presence of NaCl, NaNO3, Na2SO4 and CaCl2 elec-
trolytes and found that the medium pH and the valence
of the ions have proven to be of great influence in elec-
trokinetic behaviour of their suspension [10]. Ersoy and
Çelik have been studied the electrokinetic properties of
clinoptilolite and found that excluding the trivalent
Al+3 cation, monovalent and divalent cations are not
able to reverse the surface sign of clinoptilolite [8]. Xu
and co-workers studied the surface charge properties
and dispersion stability of aqueous silica suspension. Al-
kan et al. investigated the electrokinetic properties of
sepiolite in various electrolyte solutions [11]. Doğan
et al. studied the electrokinetic properties of perlite
[12]. However, many researchers have investigated elec-
trokinetic properties of some other minerals. Some of
these are TiO2 [13], boron minerals [14], calcite [15],
hydroxyapatite [16,17].
Knowledge of the surface properties of kaolinite is
essential to optimizing the above-mentioned applica-
tions. Therefore, a detailed characterization of its elec-
trokinetic properties is of primary interest from both
fundamental and applied research perspectives. The
aim of this study is to examine the electrochemical
properties of a well-ordered pure kaolinite in various
electrolyte solutions and to better understanding of its
electrical properties.
2. Materials and methods
2.1. Materials
The kaolinite sample was obtained from Güzelyurt
(Aksaray, Turkey). pH measurements were made using
a pH meter (Orion 920A). X-ray measurements were
performed using a Philips X-ray diffractometer employ-
ing nickel-filtered CuKa radiation. X-ray diffraction
pattern of kaolinite was given in Fig. 2. The chemical
constituent of kaolinite was analysed by XRF and
given in Table 1. All inorganic chemicals used in
this study were from Merck and Fluka. The cation
exchange capacity (CEC) of kaolinite was determined
as 13 meq 100 g
1 by ammonium acetate method, and
the density as 2.18 g ml
1 using a picnometer [18].
 M. Alkan et al. / Microporous and Mesoporous Materials 83 (2005) 51–59 53

Fig. 2. XRD pattern of kaolinite.

Table 1 The zeta potential measurements were carried out as

Chemical composition of kaolinite a function of the solid to liquid ratio, pH, and type and
Constituent Percentage present (%) concentration of electrolyte. A sample of 0.3 g kaolinite
SiO2 53.00 in 100 ml distilled water containing desired electrolyte
Al2O3 26.71 was added to a thermostatic shaker bath and rinsed
Na2O 0.62 for 24 h at 20 ± 2 C. The samples were allowed to stand
K2O 1.39
CaO 0.57
for 5 min to let larger particles settle. An aliquot taken
Fe2O3 0.37 from the supernatant was used to measure the zeta po-
MgO 0.28 tential. The average of 15 measurements was taken to
LoI 17.20 represent the measured potential. The applied voltage
LoI: loss of ignition. during the measurements was generally varied in the
range of 50–150 mV.

2.2. Purification of kaolinite

Kaolinite sample was treated before using in the
experiments as follows [19]: The suspension containing
kaolinite 10 g l
1 was mechanically stirred for 24 h,
and after waiting for about 2 min the supernatant sus-
pension was filtered through filter paper (U = 125 mm).
The solid sample was dried at 105 C for 24 h, ground
then sieved by 75 lm sieve. The particles under 75 lm
were used in further experiments.
2.3. Zeta potential measurements
The zeta potential of kaolinite suspensions was mea-
sured using a Zeta Meter 3.0 (Zeta Meter Inc.) equipped
with a microprocessor unit (schematically shown in Fig.
3). The unit automatically calculates the electrophoretic
mobility of the particles and converts it to the zeta po-
tential using the Smoluchowski equation. The Smolu-
chowskiÕs equation, the most elementary expression for
zeta potential gives a direct relation between zeta poten-
tial and electrophoretic mobility,
4pV t
f¼  EM
Dt
where EM is electrophoretic mobility at actual tempera-
ture, Vt is viscosity of the suspending liquid, Dt is dielec-
tric constant, p is constant and f is zeta potential [20].
3. Results and discussion
3.1. Electrical double layer and zeta potential
The electrical double layer model is used to visualize
the ionic environment in the vicinity of a charged solid
and explains how electrical repulsive forces occur. The
fact that a solid surface in water or solution has an elec-
trical charge has occurred in terms of the potential
determining ions. The ions that are chemisorbed on
the solid surface establish the surface charge and are
termed as potential determining ions. The opposite sign
ions with the solid surface accumulate near the solid sur-
face and equilibrate the surface electrical charge. These
ions, which accumulate at the solid–liquid interface,
are known as counterions. Counterions are adsorbed
by Coulombic or electrostatic attraction at the solid sur-
face bearing the potential determining ions. If the coun-
terions are adsorbed by electrostatic attraction alone,
their source in solution is called as indifferent ion. If
the counterions posses a special affinity for the solid sur-
face but are not chemisorbed, they are known as specif-
ð1Þ ically adsorbed ions. Specifically adsorbed ions adsorb
strongly at the surface because of such phenomena as
covalent bond forming and solvation effect.
The plane through the center of charge of the counte-
rions adjacent to the surface is called the Stern plane.
54 M. Alkan et al. / Microporous and Mesoporous Materials 83 (2005) 51–59

2
9
Clay Particles
OX OX
88

77
1/8 1/4 Full Scale
Scale Scale
Division Division Division
55 6

1. Keypad 2. DC Power Supply 6. Platinum Cathode Electrode

3. Lamp and Focused Light Beam 7. Microscope Module
4. Electrophoresis Cell 8. CCD Camera 9. Monitor
5. Molybdenum Anode Electrode
3

Fig. 3. General arrangement of Zeta-Meter 3.0+ Unit.

This layer of counterions is known as the Stern layer.
Adjacent to the Stern layer is the diffuse layer of counte-
rions. When there is motion of the solution relative to
solid surface, shear occurs at a plane close to the bound-
ary between the Stern and diffuse layers. The Stern layer
is considered to be rigidly attached to the solid, while the
diffuse layer is not. The electrical potential at shear plane
is related to the mobility of the solid and is called the
zeta potential. The points at which surface charge and
zeta potential became zero are called as zero point of
charge (pzc) and isoelectrical point, respectively. Fig. 4
has shown the structure of the electrical double layer
for kaolinite [21].
3.2. Effect of solid concentration
The solid concentration in solution is a major param-
eter governing the surface charge generation. This
means that the ionic species produced at the solid–liquid
interface increase with increase in solid concentration
and that using inadequate solid concentrations can lead
to errors in the interpretation of zeta potential measure-
ments. The variation of the zeta potential with solid con-
centration of kaolinite suspensions has been shown in
Fig. 5. As seen in this figure, there is no significant effect
of the solid concentration on the zeta potential of kaol-
inite suspensions. Therefore, in the subsequent zeta
potentials measurements the solid-to-liquid ratio was
kept constant as 3 g l
1.
3.3. pH profile of kaolinite
The pH profiles of kaolinite in a 0.3 wt.% suspension
have been given in Fig. 6 as a function of time at an ini-
tial pH of natural, acidic and basic media. When kaoli-
nite is added to distilled water of pH 6.78, the
suspension pH rises and then remains almost constant
upon reaching the equilibrium pH of 8.33 after 24 h.
The reason for the rapid rise in pH at first is ascribed
to the rapid adsorption of H+ ions in water onto the
negatively charged kaolinite surface as a pdi in the elec-
trical double layer (EDL) in order to provide electroneu-
trality. In addition, the H+ ions in solution undergo
exchange with some of the cations in the kaolinite lattice
leading to the consumption of H+ ions in suspension.
When the initial pH is adjusted to 4, after kaolinite addi-
tion, the suspension pH rises till it reaches around equi-
librium pH 7.88 after 24 h. The reason for rise in pH are
the same as above, but when the initial pH is adjusted to
10, pH comes down and reaches at its equilibrium pH
8.84 at 24 h. The decrease of the suspension pH can be
attributed to the adsorption of OH
ions onto the posi-
tive sites or the adsorption of H+ ions onto the negative
sites on the kaolinite surfaces like in broken bonds (see
Fig. 7).
3.4. Effect of pH
Fig. 8 illustrates the effect of pH on zeta potential of
kaolinite. As shown in this figure, kaolinite has an iep at
about pH 2.35 and exhibits negative zeta potential value
at over pH 2.35. In the literature the iep of kaolinite var-
ies considerably depending on the source of the sample
and the procedure used for cleaning the surface prior
to study [22]. Kitchener correctly points out that there
is no one procedure for cleaning the surface of kaolinite
and the surface properties depend critically on its prehis-
tory [23]. Braggs et al. found the iep of kaolinite as pH 3
[22]. The increase of the suspension pH results in an
increase in the negative charge of kaolinite. This can
 M. Alkan et al. / Microporous and Mesoporous Materials 83 (2005) 51–59 55

CH3COO-
Ca2+
CO32- Cl-
PO43-
SO42-
Cu(OH)+ Co(OH)+
-
K+ +
NO3 Pb(OH)
Pb2+
Ba2+ H+ Co2+
Al 3+
Fe3+ Fe3+ Al3+
Li+ 2+ 2+
Cu2+ KAOLINITE Mg
Fe(OH)
CH3COO- Al(OH)2+ Cl-
2+ H+ Counter ions
Al Ba
3+
3+ 2+
PO43-
Fe Al3+ Pb Co2+ Fe3+
Ca2+ 2+
Cu
Mg2+ Cu(OH)+ Al(OH)2+
Li+ 2+
Ba
SO42-
Cl- Na+
+
Li

Shear Plane
Stern Plane
Diffuse Layer

Surface Ψ0
Potential

(-) ζ1

Potential
ζ2 Distance
ζ3
(+)

IHP
OHP 1/κ3
1/κ2
Stern Layer
1/κ
1

Fig. 4. A schematic illustration of the structure of EDL of kaolinite (not to scale).

-20 10

9
Zeta potential (mV)

-25 8
pH

-30
6
Initial pH Equilibrium pH
: 5.00 6.78
5 : 6.78 (in water) 7.90
-35 : 9.00 8.03
0.1 0.2 0.3 0.4 0.5 0.6 0.7 4
Solid concentration (g 100 mL-1) 0 180 360 540 720 900 1080 1260 1440
time (min)
Fig. 5. The variation of zeta potential with solid concentration of
kaolinite in water. Fig. 6. The variation of pH with time (min) of kaolinite suspensions.

be ascribed to either the adsorption of OH
ions onto tion of surface hydroxyl groups. In addition, the reac-
the positive charge centers of kaolinite or the deprotona- tion of OH
with dissolved cations to form metal
56 M. Alkan et al. / Microporous and Mesoporous Materials 83 (2005) 51–59

O Si+ SiOH
OH- O
O
Si Si Si+ SiOH

(Hydroxyl or silanol groups)

O O

Si -
O H+ OH
Si Si
O O -
O OH
-
O (Silanediol groups)
Si Si
-
O
O- OH
O H+
- Si
Si O OH
-
O OH
(Silanetriol groups)

Fig. 7. Broken bonds and surface charge development in silicates.

hydroxides may result in a decrease in the pH. The de- ½MOHþ

2  ¼ ½
MO  ð4Þ
crease of the suspension pH results in a decrease of
The iep also indicates that there is no charge at the
the negative potential owing to the H+ adsorption on
surface, that is, the total positive charges are equal to
the negative charge centers. At around pH 2.35, the zeta
the total negative charges (Eq. (4)). The fact that there
potential is about 0 mV. Most silicate or clay minerals
has an iep of kaolinite shows the reaction responsible
have the iep of pH 2–4 [24]. The experimental data in
for the surface charge of the solid is mainly the reaction
this study are described assuming that the kaolinite sur-
in Eq. (2) below iep and in Eq. (3) above iep, respec-
face behaves as an amphoteric oxide, where the electrical
tively. As seen in Fig. 8, at low pH values the suspen-
double layer properties are due to different surface sites
sions are positively charged, whilst at higher pH values
on the basal planes and edges. Kaolinite has a perma-
the suspensions are negatively charged. Fig. 8 shows
nent negative charge on the basal planes of it, due to iso-
that the iep is approximately pH 2.35. In this case, Eq.
morphic substitutions rather than to gel coatings [22].
(4) is valid. The charge on the broken edges of kaolinite
The electrical charge at the oxide surface/aqueous phase
particles as a function of the pH has been given in Eq.
to protonation/deprotonation of the surface hydroxyl
(5).
can be ascribed as [9,12]
OH OH OH
AMOH þ Hþ
MOHþ
2 ð2Þ Si Si Si
OH +1/2 OH +1/2 O -1/2
AMOH þ OH

AMO
þ H2 O ð3Þ Al Al Al ð5Þ
and at iep, OH 2+1/2 OH -1/2 OH -1/2

pH<pHiep edge iep pH>pHiep

Equilibrium pH
10

3.5. Indifferent and potential determining ions (pdi)

0
0 1 2 3 4 5 6 7
Zeta potential (mV)

-10
Indifferent ions such as, the simple alkali metal ions
and the NO
3 ion are attracted to a charged surface by
-20 simple electrostatic forces [9]. The pdi are those ions that
establish or change the surface charge of a solid [24].
-30 Since potential determining ions control the surface
reactions, it is an important parameter for identifying
-40 the adsorption mechanisms [25]. For silicate type miner-
als potential determining ions are generally H+ and
-50 OH
ions [24]. Because OH
can be considered as an
Fig. 8. The variation of zeta potential with equilibrium pH of kaolinite equivalent of a lattice constituent ion (oxygen), H+
suspensions. may replace the metallic cation [26]. Thus, the potential
 M. Alkan et al. / Microporous and Mesoporous Materials 83 (2005) 51–59 57

determining ions for kaolinite are most likely H+ and
OH
ions. Wierer and Dobias showed that H+ and
OH
ions were potential determining ions for kaolinite
in aqueous solutions [4]. The iep of kaolinite was ob-
tained by measuring the zeta potential as a function of
pH (Fig. 8). The increase of the suspension pH results
in an increase in the negative charge of kaolinite. This
can be ascribed to either the adsorption of OH
ions
onto the positive charge centers of kaolinite or the
deprotonation of surface hydroxyl groups as seen in
Eqs. (2)–(4). The decrease of the suspension pH results
in a decrease of the negative potential owing to the H+
adsorption on the negative charge centers and kaolinite
has iep at about pH 2.35.
3.6. The effect of various electrolytes on zeta potential
3.6.1. The effect of monovalent electrolytes
Fig. 9a and b presents the zeta potential of kaolinite
in the presence of various electrolytes of monovalent
such as NaCl, KCl, LiCl, NaNO3 and NaCH3COO.
Fig. 9a and b shows that for both cations and anions
the surface is, at first, negatively charged, and then,
for cations, the negativity decreases, as the concentra-
0 of the EDL and consequently causes a reduction in the
LiCl : (a)
-10 NaCl :
KCl :
Zeta potential (mV)
tion of electrolyte is higher than about 1 · 10
2 M.
These results are in a good agreement with other litera-
tures [12,21,27]. The reduction in the zeta potential of
kaolinite in the presence of monovalent ions (Li+,
Na+, K+, Cl
, NO


3 and CH3COO ) can be explained
in the following manner: the monovalent counter ions
are known as indifferent electrolytes [9] excluding the
ion exchange mechanism, they cannot adsorb specifi-
cally onto kaolinite, and are not capable of causing a
charge reversal. Because of the coulombic attraction
they only accumulate as counter ions in the electrical
double layer (EDL). Consequently, they compress the
EDL and change the magnitude of the zeta potential
of kaolinite (see Fig. 4). However, they can lower the
surface potential by charge neutralization and in turn
compress the thickness of the EDL with a reduction in
the zeta potential. But this is realized differently for
mono- and multivalent cations in accord with the for-
mula of
1 3
¼ ð6Þ
j ZC 1=2
where j1 is the thickness of the diffuse layer (Å), Z de-
notes the valency and C represents the ion concentration
(mol l
1) [28]. This formula indicates that for the same
valence the concentration contributes to the thickness
zeta potential.
3.6.2. The effect of divalent electrolytes

-20
Figs. 10a, b and 11 present the zeta potential of kaol-
-30
inite in the presence of various divalent electrolytes, i.e.,
CaCl2, MgCl2, BaCl2, Na2CO3, Na2SO4, and heavy
-40 metal salts, i.e., CoCl2, CuCl2 and Pb(NO3)2. Fig. 10a
shows the effect of divalent cations, i.e., Ca2+, Mg2+
-50 and Ba2+ on the zeta potential of kaolinite; Fig. 10b
the effect of divalent anions, i.e., CO2
2

3 and SO4 ; and
-60 Fig. 11 the effect of divalent heavy metal ions, i.e.,
-5 -4 -3 -2 -1
Co2+, Cu2+ and Pb2+. As the concentration of divalent
log[C] cations and heavy metal ions increase in the solution,
0 the zeta potential of kaolinite decreases (becomes less
NaCH3COO : (b) negative) but when the concentration of divalent anions
-10 NaNO3 : in the solution increases, the zeta potential increases
NaCl :
(more negative) (see Fig. 10b). Note that at low divalent
Zeta potential (mV)

-20 cation and heavy metal ion concentrations (10
4 and

10
5 M), kaolinite has a negative zeta potential; how-
-30 ever, as the concentration of Ca2+ and Mg2+ ions are in-
creased (10
1 M), zeta potential of kaolinite approaches
-40
to zero. On the other hand, the zeta potential of kaoli-
-50
nite with increasing BaCl2 concentration has changed
from negative to positive (Fig. 10a).
-60 The zeta potential of kaolinite with heavy metal ions
-5 -4 -3 -2 -1 also shows similar trends. As the concentration of ions
log[C] increases, the zeta potential and the suspension pH de-
Fig. 9. The variation of zeta potential with electrolyte concentration of crease, and the zeta potential becomes less negative.
kaolinite: (a) monovalent cations and (b) anions. But the zeta potential of kaolinite becomes positive
58 M. Alkan et al. / Microporous and Mesoporous Materials 83 (2005) 51–59

20
(a) SO -
BaCl2 :
+
10 CaCl2
MgCl2
:
: 2SOH + Ms2+ M2+ + 2Hs ð7Þ
0 NaCl :
SO -
Zeta potential (mV)

-10

s þ H2 OSO AMOH þ 2Hs

þ þ
-20
SOH þ M2þ ð8Þ

-30 The reason for decreasing of solution pH with

increasing concentrations of di- or trivalent cations
-40
and heavy metal ions can be explained by reactions (7)
-50 and (8).
-60
-5 -4 -3 -2 -1 3.6.3. The effect of trivalent electrolytes
log[C] Fig. 12 presents the zeta potential of kaolinite in the
0
presence of various trivalent electrolytes, i.e., AlCl3,
NaCl : FeCl3 and Na3PO4. Addition of AlCl3 and FeCl3 re-
(b)
Na2SO4 :
-10 duces steadily the zeta potentials of kaolinite in the con-
Na2CO3 :
-20 centration range of 1 · 10
5–1 · 10
1 M but Na3PO4
Zeta potential (mV)

has not any significant effect on the zeta potential of

-30
the kaolinite. This has shown that PO3
4 trivalent anion
-40 is an indifferent ion for kaolinite such as mono or diva-
-50 lent anions. The zeta potential of kaolinite becomes po-
sitive when the concentration is higher than 1 · 10
3 M
-60
for AlCl3 and 1 · 10
4 M for FeCl3 salts. This may be
-70 explained on the basis of the specific adsorption of
Al3+ and Fe3+ counterions in the inner Helmhotz plane
-80
-5 -4 -3 -2 -1 (IHP) of the Stern layer as shown in Fig. 4. The pH
log[C] range of kaolinite suspensions is 6.11–3.78 for AlCl3
and 5.85–2.21 for FeCl3 in the above concentration
Fig. 10. The variation of zeta potential with electrolyte concentration
range. In this state, Al3+ and Fe3+ ions are in the non-
of kaolinite: (a) divalent cations and (b) anions.
hydroxyl form, and can form hydroxyl complexes such
þ þ
as AlðOHÞ2 , Al(OH)2+, Al(OH)3, FeðOHÞ2 , Fe(OH)2+,
Fe(OH)3 [8]. The specifically adsorbed ions are those
25
ions, which adsorb on the particles because of some spe-
10
cific, nonelectrostatic affinity [8]. However, ‘‘specific
adsorption’’ is defined as the attraction of these ions
Zeta potential (mV)

-5 to the adsorbent surface by chemical forces in addition

to electrostatic forces [9].
-20

-35
95
PbNO3 : FeCl3 :
CuCl2 : AlCl3 :
-50 75
CoCl2 : NaCl :
NaCl : Na3PO4 :
55
-65
Zeta potential (mV)

-5 -4 -3 -2 -1
35
log[C]
15
Fig. 11. The variation of zeta potential with the heavy metal ion
concentration of kaolinite. -5

-25
when the concentrations of heavy metal ions are higher
than 1 · 10
2 M at pH 5.58 for Cu2+ solution, pH 5.54 -45

for Pb2+ solution and pH 6.30 for Co2+ solution. -65

-5 -4 -3 -2 -1
According to the following reactions given by James
et al. who suggested that surface charge may be a result log[C]
of some combination of following reactions [29], in the Fig. 12. The variation of zeta potential with trivalent electrolyte
case of M = Mg: concentration of kaolinite.
 M. Alkan et al. / Microporous and Mesoporous Materials 83 (2005) 51–59
Again, according to Eq. (6) for the same cation con-
centration, the valence of electrolyte contributes signifi-
cantly to the thickness of the EDL.
4. Conclusions
• Kaolinite suspensions exhibit a buffer pH at around
pH 7 ± 1.
• The zeta potential of kaolinite samples is not signifi-
cantly affected by solid concentration.
• The potential determining ions for kaolinite as simi-
lar to other silicates and clay minerals are H+ and
OH
ions.
• The kaolinite surface in water has a net negative sur-
face charge at natural pH and the iep of kaolinite is at
about pH 2.35.
• The monovalent salts such as NaCl, KCl, LiCl,
NaNO3, NaCH3COO and multivalent salts such as
Na2CO3, Na2SO4, and Na3PO4 are indifferent elec-
trolytes for kaolinite.
• Multivalent cations exert a greater influence on the
zeta potential of kaolinite than those of monovalent
cations.
• A model has been proposed to illustrate the accom-
modation of mono- and multivalent ions in the
EDL.
Acknowledgements
The authors thank the Balikesir University Research
Center of Applied Science (BURCAS) for the zeta po-
tential measurements and the support from Balikesir
University Research Foundation (Project No: 2004/17)
is gratefully acknowledged.
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