Applied Surface Science 218 (2003) 169–174

Effect of presence of ions on surface characteristics of

surfactant modified powdered activated carbon (PAC)
C. Akmil Başara,*, A. Karagunduzb, B. Keskinlerb, A. Cakicic
a
Department of Chemical Engineering, Faculty of Engineering, Inonu University, 44069 Malatya, Turkey
b
Department of Environmental Engineering, Gebze Institute of Technology, 41400 Çayırova, Kocaeli, Turkey
c
Department of Environmental Engineering, Atatürk University, 25240 Erzurum, Turkey
Received 10 April 2003; received in revised form 10 April 2003; accepted 10 April 2003

Abstract

Modification of surface characteristics of solids using surfactants has practical implications in industrial and environmental
applications. Extensive research has been conducted to explore the mechanism of surfactant sorption to different solid surfaces.
However, a clear understanding yet to be found especially for heterogeneous surfaces in which pores and structure show local
differences. The main objective of this study was to determine the effects of ions on the surface potential of surface modified
activated carbon. In order to achieve the objective, anionic and cationic surfactants were selected and adsorptions of these
surfactants to powdered activated carbon (PAC) were investigated. Then, zeta potential measurements were conducted for the
surface modified PAC and finally, the effects of mono- and di-valent anions and cations on the zeta potentials of PAC surface
were investigated. The results showed that even at very low cetyl trimethyl ammonium bromide (CTAB) concentrations charge
reversal was observed and substantial increase was observed in zeta potential. However, linearalkyl benzene sulfonate (LABS)
showed somewhat gradual decrease in zeta potential, reaching maximum when maximum sorption capacity was attained.
Presence of anions in addition to CTAB effected the change of zeta potential. Similar effects were also observed for LABS
modified PAC in the presence of mono- and di-valent cations. The change of zeta potential of with the valance of cations and
anions were linear.
# 2003 Elsevier Science B.V. All rights reserved.

Keywords: Powdered activated carbon (PAC); Surfactant; Adsorption; Zeta potential

1. Introduction processing [1], cement manufacturing [2], enhance-

Modification of surface characteristics of solids
using surfactants has practical implications in indus-
trial and environmental applications. Surfactants are
mainly used as additives to enhance certain properties
of surfaces in industrial applications such as coal
*
Corresponding author. Tel.: þ90-422-3410010;
fax: þ90-422-3410046.
E-mail address: cabasar@inonu.edu.tr (C. Akmil Başar).
ment of the adhesion of epoxy [3] and adsolubilization
of steroids in pharmaceutical industry [4]. Sorption of
surfactants to clays (organoclays) is used in water
purification [5], industrial wastewater treatment [6],
remediation of contaminated groundwater [7] and
heavy metal removal [8]. Chromate removal using a
cationic surfactant (HDTMA) modified zeolites was
investigated [9]. Modification of TiO2 surface with
surfactants to enhance the degradation of hydrophobic
organic matters has been recently investigated [10].

0169-4332/$ – see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0169-4332(03)00576-2
170 C. Akmil Başar et al. / Applied Surface Science 218 (2003) 169–174
Extensive research has been conducted to explore the
mechanism of surfactant sorption to different solid
surfaces. Monolayer, bilayer or hemimicelle formations
may occur in the surface depending on surface and
surfactant characteristics and surfactant concentration
[11,12]. However, a clear understanding yet to be found
especially for heterogeneous surfaces in which pores
and structure show local differences. Several character-
istics of solid surfaces may be affected as a result of
sorption of surfactants. First, the wettability of surfaces
may be affected. For example, a non-ionic surfactant
can adsorb to a non-polar surface trough hydrophobic
tail via van der Waals forces. As a result hydrophilic
head points toward bulk solution making the solid
surface more hydrophilic [13]. Second, the surface
charge reversal may be observed. For example, if a
cationic surfactant adsorbs to a negatively charged
surface through hydrophilic head, positively charged
surface first become non-ionic. Then, further increase in
sorption results hydrophobic tail interactions causing
bilayer formation in which positively charged heads
orients themselves toward the solution and surface
becomes positively charged.
Although extensive research conducted on the beha-
vior and the mechanisms of surfactant sorption to
different solid surfaces, changes in surface properties
was not thoroughly studied. In few research, zeta
potential measurements in addition to the sorption
experiments have been presented [13–15]. However,
the effect of the presence of anions and cations in
addition to surfactants on the change of surface char-
acteristics has not been addressed. The main objective
of this study is to determine the effects of ions on the
surface potential of surface modified activated carbon.
In order to attain the objective, anionic and cationic
surfactants were selected and adsorption of these sur-
factants to powdered activated carbon (PAC) was
investigated. Then, zeta potential measurements were
conducted for the surface modified PAC and finally, the
effects of mono- and di-valent anions and cations on
the zeta potentials of PAC surface were investigated.
2. Materials and methods
2.1. Materials
Powdered activated carbon was obtained from
Merck and used in the experiments as adsorbent.
The average grain size was determined to be 30 mm
using a particle size analyzer (Malvern). Cetyl tri-
methyl ammonium bromide, CTAB (C19H42NBr) was
selected as cationic surfactant. Ninety-eight percent
pure CTAB was obtained from Fluka and used as
received. As anionic surfactant, linearalkyl benzene
sulfonate, LABS (C13H27C6H4SO3H) was selected
and obtained from Fluka at 96% purity. LABS was
used as received without further purification. Analy-
tical grade Na2CrO44H2O, CuCl22H2O and NaCl
were obtained from Merck.
2.2. Measurement of zeta potential
Zeta potential measurements were performed using
0.1 g of PAC in 100 ml of water, CTAB and LABS
suspensions using a zeta meter þ3 at neutral pH
conditions. In the presence of metal ions (e.g. Cu2þ
and CrO4), measurements were done by maintaining
constant ion concentration as 1 mM, and varying
surfactant concentration from 0.1 to 2 mM.
2.3. Adsorption experiments
Sorption of CTAB and LABS to PAC was con-
ducted at varying concentrations above and below
CMCs using 100 ml glass flasks. Hundred milliliters
solution was added to each flask and equilibrated with
0.1 g of PAC for 120 min at 30 8C. Preliminary experi-
ments showed that sorption of both surfactants
reached equilibrium in less than 120 min. After equi-
librium reached, solid liquid mixture was separated
using filtration (Whatman filter paper #1). It was
determined that surfactant sorption to filter was insig-
nificant. Following filtration LABS and CTAB were
analyzed using UV (UV-160A SHIMADZU) and TOC
(Becham 915A), respectively.
3. Results and discussion
The sorption of CTAB to PAC and change in zeta
potentials with adsorption are presented in Figs. 1 and 2,
respectively. The results obtained from four different
sorption experiments showed that CTAB sorption to
PAC occurred in two steps. First, a rapid increase ob-
served in sorbed mass reaching to the first plateau at
around 0.05 mM of aqueous phase CTAB concentration.
 C. Akmil Başar et al. / Applied Surface Science 218 (2003) 169–174
Fig. 1. Sorption of CTAB to PAC.
Than at 0.15 mM, another rapid increase was observed
in the amount of sorbed CTAB and reached to the
maximum at 1 mM. Such isotherms (S-type) have
been commonly observed in the sorption of ionic
and non-ionic surfactants to solid materials [16].
Although there is not a universal agreement on how
the sorption occurs to the surfaces, it was speculated
that at low concentrations, cationic surfactants interact
with surface mainly due to the electrical attraction if
the surface has net negative charge. As surfactant
concentration increased, monomer interactions occur
on the surface resulting a small lag in the sorbed mass.
As a result of further increase of the surfactant con-
centration, aggregates (bilayer, hemimicelle, micelle
Fig. 2. Change in zeta potential with aqueous phase CTAB
concentration.
171
like structures) form on the surface [16]. If this was the
case in the experiments conducted in this study, zeta
potential would reach to zero at CTAB concentrations
between 0.05 and 0.15 mM. However as seen in Fig. 2,
zeta potential of PAC reached from 17.7 to 39 mV at
0.01 mM, causing a dramatic increase in surface
potential at very low CTAB concentrations. The
change in zeta potential between 0.01 and 1 mM (from
39 to 58 mV) was much less than that the initial
substantial change (from 18 to 39 mV). The results
suggested that the sorption of CTAB occurred via
hydrophobic forces to the hydrophobic PAC surface
at very low concentrations as oppose to electrical
interactions. Thus, positive head remains on the sur-
face or pointed towards the bulk solution. As the
concentration increased monomer interaction and
aggregation steps should follow. Similar conclusions
were reported in a recent study in which atomic force
microscopy results were presented. It was suggested
that at low concentrations, cationic surfactant mono-
mers lie flat to the surface similar to non-ionic sur-
factants [17]. It was also reported that CTAB sorption
to activated carbon surface was predominantly hydro-
phobic forces at the concentrations above 0.3 mg/l
(approximately 0.01 mM) [18].
In Fig. 3, the change in zeta potential as a function of
aqueous phase CTAB concentration is presented in the
presence and absence of CrO4. Addition of 1 mM of
CrO4 decreased the zeta potentials by about 20 mV at
all surfactant concentrations. This can be attributed to
the interactions of CrO4 with sorbed surfactant mono-
mers. Interaction of CrO4 with surfactant most likely
occurred via electrostatic attraction between CrO4 and
CTAþ of which positive head was pointed toward the
bulk solution. The change in zeta potential in the
presence of 0.1 mM initial CTAB concentration is
presented as a function of both CrO4 and NaCl in
Fig. 4. Single charged Cl caused less reduction in zeta
potential compared to the CrO4. As the valance of the
ions increased, diffuse layer shrank, resulting a smaller
change in zeta potential. It was observed that at the same
CTAB concentration (0.1 mM), the change in zeta
potential with the valance of ions was linear as seen
in Fig. 5. This result has an important implications,
however, it should be explored more in detail for a
definite conclusion.
LABS sorption to PAC is presented in Fig. 6. A
simple Langmuir type isotherm was observed in
172 C. Akmil Başar et al. / Applied Surface Science 218 (2003) 169–174

Fig. 3. The effect of CrO4 on the change of zeta potential with increasing initial CTAB concentration.

which maximum sorption reached approximately to
0.5 mM. The maximum sorbed LABS molecules
were approximately half of what observed for CTAB.
This is most likely the result of orientation of surfac-
tant molecules on PAC surface. Aggregation of CTAB
molecules on PAC surface caused more CTAB mole-
cules to be on PAC surface than LABS molecules.
LABS sorption occurred to PAC occurred via hydro-
phobic interaction between surfactant molecules and
PAC surface. As surfactant concentration increased a
compact monolayer occurred, reaching maximum
adsorption capacity.
The change in zeta potential of PAC as a function of
LABS concentration is presented in Fig. 7. As oppose
to CTAB, pronounced effect to zeta potential was
observed as concentrations of LABS increased, which
was consistent with the adsorption of LABS to PAC.
The zeta potential decreased from 17.7 to 44.6 at
2 mM of LABS at which maximum sorption occurred.
The effect of Cu2þ on the change of zeta potential is

Fig. 4. The effect of mono- and di-valent anions on zeta potential (1 g/l PAC þ 0:1 mM CTAB).
 C. Akmil Başar et al. / Applied Surface Science 218 (2003) 169–174 173

Fig. 5. The effect of valance of anions on zeta potential.

Fig. 8. The effect of Cu2þ on the change of zeta potential with
increasing initial CTAB concentration.

presented in Fig. 8. As surfactant concentration

increased, the effect of Cu2þ became more pro-
nounced. As LABS concentration increased more
surfactant molecules placed on the PAC surface point-
ing their negatively charged heads toward the bulk
solution. Therefore more Cu2þ would interact with
adsorbed LABS, resulting higher decrease in the zeta
potential of PAC with increasing surfactant concen-
tration. The effect of varying concentrations of NaCl
and Cu2þ at constant LABS concentration of 0.1 mM
is presented in Fig. 9. Increase in concentrations of
both NaCl and Cu2þ did not substantially alter the zeta
potential of PAC. However, similar to those observed
for cationic surfactant, the zeta potential was rela-
Fig. 6. Sorption of LABS to PAC.
tively less affected in the presence of NaCl solution

Fig. 7. Change in zeta potential with aqueous phase LABS Fig. 9. The effect of mono- and di-valent cations on zeta potential
concentration. (1 g/l PAC þ 0:1 mM LABS).
174 C. Akmil Başar et al. / Applied Surface Science 218 (2003) 169–174
Fig. 10. The effect of valance of cations on zeta potential.
than that of Cu2þ solution. The change in zeta poten-
tial with the valance of cations in the presence of
0.1 mM of initial LABS concentration is presented in
Fig. 10. Similar to those observed for CTAB, a linear
change was observed in zeta potential as the valance
increased.
4. Conclusions
Sorption of CTAB to PAC occurred via hydrophobic
interaction, resulting a dramatic increase in zeta
potential. It was concluded that even at low CTAB
concentrations charge reversal could be achieved.
Addition of anions decreased the zeta potentials of
CTAB adsorbed PAC. Decrease in zeta potential
changed linearly with the valance of anions. On the
contrary, change in zeta potential of PAC due to the
sorption of LABS was much more gradual with
increasing concentration. This was attributed to the
differences in sorption mechanisms of CTAB an
LABS to PAC surface. Similar to the case observed
for CTAB, cations effected zeta potential of surface
modified PAC and decrease in zeta potential was linear
with the valance of cations.
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