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Applied Surface Science 284 (2013) 8799

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Applied Surface Science


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Adsorption of surfactants on sand surface in enhanced oil recovery:


Isotherms, kinetics and thermodynamic studies
Achinta Bera, T. Kumar, Keka Ojha, Ajay Mandal
Department of Petroleum Engineering, Indian School of Mines, Dhanbad 826004, India

a r t i c l e

i n f o

Article history:
Received 15 May 2013
Received in revised form 5 July 2013
Accepted 7 July 2013
Available online 16 July 2013
Keywords:
Surfactant
Adsorption isotherm
Isotherm model
Adsorption kinetics
Thermodynamics of adsorption

a b s t r a c t
Adsorption of surfactants onto reservoir rock surface may result in the loss and reduction of their concentrations in surfactant ooding, which may render them less efcient or ineffective in practical applications
of enhanced oil recovery (EOR) techniques. Surfactant ooding for EOR received attraction due to its ability to increase the displacement efciency by lowering the interfacial tension between oil and water and
mobilizing the residual oil. This article highlights the adsorption of surfactants onto sand surface with
variation of different inuencing factors. It has been experimentally found that adsorption of cationic
surfactant on sand surface is more and less for anionic surfactant, while non-ionic surfactant shows intermediate behaviour. X-ray diffraction (XRD) study of clean sand particles has been made to determine the
main component present in the sand particles. The interaction between sand particles and surfactant has
been studied by Fourier Transform Infrared (FTIR) Spectroscopy of the sand particles before and after
aging with surfactant. Salinity plays an important role in adsorption of anionic surfactant. Batch experiments were also performed to understand the effects of pH and adsorbent dose on the sorption efciency.
The sand particles exhibited high adsorption efciency at low pH for anionic and nonionic surfactants.
But opposite trend was found for cationic surfactant. Adsorption data were analyzed by tting with Langmuir, Freundlich, Redlich-Peterson, and Sips isotherm models. Results show that the Langmuir isotherm
and pseudo-second order kinetics models suit the equilibrium and kinetics of adsorption on sand surface.
Thermodynamics feasibility of the adsorption process was also studied to verify the spontaneity of the
process.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Adsorption of surfactants on rock/clay/sediment solid matrix
may result in the loss and reduction of their concentrations, which
may render them less efcient or ineffective in practical applications of EOR techniques. Surfactants are also widely used in
various industrial processes for their favourable physicochemical
characteristics like detergency, foaming, emulsication, dispersion
and solubilization effects [14]. Due to extreme ability to reduce
oil-water interfacial tension (IFT), surfactants are very important
materials in chemical ooding for EOR methods. Adsorption of
surfactants from aqueous solutions in porous media is a fundamental issue in EOR from oil reservoirs because surfactant loss due
to adsorption on the reservoir rocks impairs the effectiveness of
the chemical solution injected to reduce the IFT of oil-water and
may turn into the process economically unfeasible [58]. Surfactant adsorption at solid/liquid interface has been studied for several

Corresponding author. Tel.: +91 326 2235485; fax: +91 326 2296632.
E-mail address: mandal ajay@hotmail.com (A. Mandal).
0169-4332/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2013.07.029

decades. A number of studies have been conducted on the adsorption of ionic and nonionic surfactants onto reservoir rocks [822].
The solid surfaces are either positively or negatively charged in
the aqueous medium by ionization/dissociation of surface groups or
by the adsorption of ions from solution onto a previously uncharged
surface. At low surfactant concentrations, the charge on the electrical double layer (proposed by Helmholtz in 1879, and modied
by Stern in 1924) of the solid surface largely determines the surfactant adsorption. The surfactant molecules are adsorbed on rock
surface or sediments as a single monomer and form monomeric
layer at low concentration of surfactant solution. As the surfactant concentration increases, the adsorbed surfactant monomers
tend to aggregate and form micelles [13,23]. This aggregate can
form one layer (ad micelles) or two layer (hemi micelles). The
onset of hydrophobic interaction between the adsorbed surfactant
molecules leads to a substantial increase in the adsorption levelling off at the critical micelle concentration (CMC) [24,25]. In order
to lower the adsorption, negatively charged surfactants are usually
considered as the main surfactant species of the slug and so anionic
surfactants are believed to be the most used type of chemicals in the
ooding of sandstone oil reservoirs [26]. The adsorption of surfactants from the solution is affected by its physicochemical properties

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A. Bera et al. / Applied Surface Science 284 (2013) 8799

Nomenclature
EOR enhanced oil recovery
XRD
X-ray diffraction
FTIR
Fourier Transform Infrared
IFT
interfacial tension
critical micelle concentration
CMC
SDS
sodium dodecylsulphate
CTAB
cetyltrimethylammonium bromide
design of experiments
DOE
COD
chemical oxygen demand
MSE
Mean Square Error
MINAPE Minimum absolute percentage error
MAXAPE Maximum absolute percentage error
Variables
C0
Initial concentrations of surfactants (mg/g)
Equilibrium aqueous concentration of surfactants
Ce
(mg/L)
V
Volume of the surfactant solution (L)
Weight of the sand particles (g)
m
Separation factor or equilibrium parameter
RL
KR
Redlich-Peterson isotherm constants (L/mg)
Sips isotherm constant [(L/mg)m s ]
KS
Exponential factor

Langmuir equilibrium constant (L/mg)


KL
KF
Freundlich adsorption constants related to sorption
capacity (mg/g)
t
Amount of surfactants adsorbed on sand particles at
time t (mg/g)
Rate constant of the pseudo-rst-order adsorption
k1
(min1 )
k2
Rate constant of the second-order equation
(g/mg/min)
Change in Gibbs energy (J/mol)
G
S
Change in entropy (J/mol)
H
Change in enthalpy (J/mol)
Amount of adsorbate adsorbed (mg/g)

 max
Maximum amount adsorbed (mg/g)
Sorption intensity
n
R
Redlich-Peterson isotherm constants [(L/mg) ]
Empirical constant in Sips isotherm
ms
T
Temperature (K)
R2
Regression coefcient
Universal Gas Constant (8.314 J/K/mol)
R
Kid
Rate
constant
of
intraparticular
diffusion
(mg/g/min)
Intercept
C

such as pH [2729], temperature [30,31], ionic strength [27,31],


adsorbent dose [32] and electrolyte concentration [27,30,33]. These
physicochemical properties of solutions can also inuence in the
dissolution behavior of minerals resulting signicant changes in
the precipitation behavior of the surfactants [34]. A slight variation
in one of the above factors or the other can result in a signicant
change in the adsorption characteristics of the system.
Adsorption is a unit operation in which dissolved constituents
are removed from the solvent by interphase transfer to the surface of an adsorbent particle. In chemical ooding, surfactants
are inevitably adsorbed on the surface of reservoir rock by the
rock/oil/brine interaction. Surfactant adsorption in porous media is
a typically complex phenomenon (e.g., mass transfer and reaction).
Adsorption in porous media is a phenomenon in which transport of surfactant molecules takes place from bulk phase onto the

interface at rock-uid boundary. This process can be explained as


the interface is energetically favoured by the surfactant molecules
compared to the bulk phase [35,36]. It has been shown that the
nature of the adsorption isotherm depends to a large extent on
the type of surfactant used, the morphological and mineralogical
characteristics of the rock, and the type of electrolytes present in
solution [37]. The adsorption of surfactants can be affected by the
surface charge on the rock surface and uid interfaces [3841]. Positively charged cationic surfactant is attracted to negatively charged
surfaces, while negatively charged anionic surfactant is attracted to
positively charged surfaces. The salinity and pH of brine strongly
affect the surface charge. When the effects of brine chemistry are
removed, silica tends to adsorb simple organic bases (cationic surfactant), while the carbonates tend to adsorb simple organic acids
(anionic surfactant). This occurs because silica normally has a negatively charged weak acidic surface in water near neutral pH, while
the carbonates have positively charged weak basic surfaces. Loss
of surfactants owing to their interactions with reservoir rocks and
uid is possibly the most important factor that can determine the
efciency of a micellar ooding process [42].
Studies of adsorption kinetics and equilibrium of different
surfactants are very practical tests in laboratory for study of surfactant adsorption onto rock surface. These phenomena depend
on the nature of the surfactants and also the solid-liquid interface
[36,4345]. Recently Ahmadi et al. [46] have studied the adsorption behavior of the Glycrihiza Glabra, a novel nonionic surfactant,
onto carbonate rock and Ahmadi and Shadizadeh [47] have investigated the effect of nanosilica on adsorption behavior of Zyziphus
Spina Christi onto rock surface. Ahmadi et al. [46] concluded that
adsorption isotherm follows the Langmuir model. On the other
hand when nanosilica is used the Linear, Langmuir, and Temkin
equilibrium adsorption models were not suitable for predicting the
surfactant adsorption, but the Freundlich equilibrium adsorption
was in good agreement between the experimental data. They also
studied the kinetics of the adsorption and showed that the process follows the second order kinetic model. Gogoi [48] reported
the effect of NaCl concentration and pH on the adsorption equilibrium of Na-lignosulfonate onto reservoir rocks. He demonstrated
that adsorption increases with increasing NaCl concentration but
decreases with increasing pH.
The net adsorption of surfactant in an EOR process strongly
depends on the presence of oil and the ow eld. When a surfactant slug is injected as displacing uid, it undergoes partitioning
into oil and water and lowers the interfacial tension between oil
and water thereby increasing the capillary number. As a result, the
trapped immobile oil becomes mobile. At the same time, an oilin-water emulsion is formed which blocks the larger pores leading
to an improvement in the effective mobility ratio. Otherwise the
injected surfactant solution ows through the highly permeable
zone bypassing the trapped oil in smaller pores. The injected surfactant continues to mobilize oil, until the surfactant is diluted or
otherwise lost due to adsorption on the rock surface. Consequently
the surfactant solutions with lower concentration could not be able
to lower the interfacial tension and mobilize oil. At that point, the
process degenerates into a water ood. Hence to design a surfactant
ooding for EOR, it is very important to have a complete knowledge
of adsorption of the specic surfactant on the reservoir rock under
the reservoir conditions.
In the present paper the adsorptions of three different surfactants namely anionic, cationic, and nonionic by clean sand particles
have been investigated with variation of different parameters i.e.,
salinity, pH, temperature, and adsorbent dose. Adsorption data
have been analysed by tting with Langmuir, Freundlich, RedlichPeterson, and Sips isotherm models. Kinetics of adsorption has also
been carried out with anionic surfactant. Thermodynamic feasibility of the adsorption process has also been studied to verify the

A. Bera et al. / Applied Surface Science 284 (2013) 8799

89

Fig. 1. Molecular structures of the surfactants used in the present study.

spontaneity of the process. Semi-quantitative analysis of clean sand


particles has been done by X-ray diffraction (XRD) study.
2. Experimental
2.1. Materials used
Three different categories of surfactants such as anionic, cationic
and nonionic were used to determine the adsorption isotherms
on the clean sand particles (6070 mesh size). Anionic surfactant,
Sodium dodecylsulphate (SDS) (with 98% purity) was purchased
from Fisher Scientic, India and cationic surfactant, Cetyltrimethylammonium bromide (CTAB) of 98% pure was procured from Merck,
India, both were used in the present study. Tergitol 15-S-7 (99.5%
pure) from sigma-Aldrich, Germany was used as nonionic surfactant. The molecular structures of the surfactant have been given in
Fig. 1. Sodium Chloride (NaCl) procured from Qualigens Fine Chemicals, India, was used for preparation of brine. Reverse osmosis
water from Millipore water system (Millipore SA, 67120 Molshein,
France) was used for preparation of solutions.
2.2. Design of experiments (DOE)
DOE refers to the process of planning, designing and analyzing the experiment so that valid and objective conclusions can
be drawn effectively and efciently. Three different surfactants
namely SDS (anionic), CTAB (cationic) and Tergitol 15-S-7 (nonionic) have been used for the adsorption studies at different salinity,
pH, temperature and adsorbent dose. Semi-quantitative analysis
of clean sand particles has been done by X-ray diffraction (XRD)
study to determine the main component present in the sand
particles. CMCs of the surfactants were determined by surface tension method. Adsorption data have been analysed by tting with
Langmuir, Freundlich, Redlich-Peterson, and Sips isotherm models.
Kinetics of adsorption has also been carried out with anionic surfactant. Effect of temperature on surfactant adsorption has been
investigated. Thermodynamic feasibility of the adsorption process
has also been investigated to verify the spontaneity of the process.

water for several times followed by settling and decanting. After


removing the dust particles the residual wet sand particles were
dried at 353 K for 18 h. The clean dried sand particles were used for
the experimental purposes.
2.3.2. XRD study of clean sand powder
The clean sands were ground to prepare powder sample. X-ray
diffractogram of prepared sample were recorded in a wide range
of Bragg angle 2 (10 2 90 ) using Bruker D8 advanced XRD
measuring instrument with Cu target radiation ( = 0.154056 nm).
The data were analysed with the help of the JCPDS les.
2.3.3. FTIR study
The apparatus used for measuring the FTIR spectra of the sand
particles before and after surfactant treatment in the range of
4504000 cm1 , was a PerkinElmer Spectrum version 10.03.07 FTIR
spectrometer. The instrument is operated by Spectrum two software supplied by PerkinElmer (USA). For the FTIR analysis, 4 mg of
dried sample was mixed with potassium bromide (KBr) (300 mg),
which was used as a reference standard sample. The mixture was
compressed by hydraulic pump to prepare pallet and the pallet was
placed in a desiccator to remove moisture content of the sample.
The dried sample then was used for experimental purpose.
2.3.4. Determination of critical micelle concentration (CMC)
Measurement of surface tension is very much useful supplementary test method for determination of CMC of surfactant. It is
particularly useful when only very small quantities of an experimental surfactant are available. In the present study surface tension
of the different concentrated surfactant solutions were measured
by a programmable tensiometer (Kruss GmbH, Germany, model:
K20 EasyDyne) under atmospheric pressure by the Du Noy ring
method. CMCs of the surfactants were determined from plot of
surface tension and surfactant concentration. The concentration at
the inexion point of the curve is termed as CMC. During the measurement, the experimental temperature was maintained at 298 K.
The platinum ring was thoroughly cleaned with acetone and amedried before each measurement. In all cases the standard deviation
did not exceed 0.1 mN/m.

2.3. Experimental procedures


2.3.1. Preparation of clean sand particles (adsorbent)
Sands which are used for making building were rst sieved to get
6070 mesh sized sand particles and washed with double distilled

2.3.5. Adsorption isotherms


A series of batch experiments were carried out to determine
the adsorption isotherms of different types of surfactants on the
adsorbent. 8 g of clean sand particles were added to a set of 50 ml

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A. Bera et al. / Applied Surface Science 284 (2013) 8799

surfactant solutions in a 100 ml glass vials and allowed to conduct the experiments by constant shaking at 303 K for 24 h on
a temperature controller horizontal shaker machine (Model No.
NovaShake BB03) at 120 rpm speed. After adsorption, the surfactant solutions were isolated by centrifugation with Remi centrifuge
instrument (Model No. Remi R-8 C). The equilibrium concentration
of the surfactant solutions were determined by Chemical Oxygen
Demand (COD) measurement of the solution. The amount of surfactant adsorbed on the adsorbent,  (mg/g), was calculated by a
mass balance relation (1):
 = (C0 Ce )

V
m

(1)

where, C0 and Ce are the initial and equilibrium concentrations


of surfactants (mg/g) respectively, V is the volume of the surfactant
solution (L), and m is the weight of the sand particles (g) (adsorbent)
used.
The effects of the pH, temperature, NaCl concentrations and
adsorbent dose on the adsorption capacity of the adsorbent to
the anionic surfactant, SDS were also investigated. To adjust the
required pH values of the solutions, HCl (0.1 N) and NaOH (0.1 N)
solutions were used. The thermodynamic study has been conducted
by change in temperature with above mentioned speed and procedure.
2.3.6. Adsorption kinetics and thermodynamics
8 g of clean sand particles were put into 50 ml of SDS solutions at
three different concentrations of 400 ppm, 800 ppm, and 1000 ppm
respectively. The adsorption kinetics experiments were carried out
at 303 K and the concentration of SDS in the solutions were determined at regular intervals until an equilibrium concentration was
achieved.
The effect of temperature (thermodynamic study) was carried
out by shaking 8 g of clean sand particles in 50 ml surfactant solution at different temperatures (303, 313, and 323 K) in temperature
controlled shaker. After 6 h, the sample was centrifuges and the
concentrations of the solutions were determined.
3. Results and discussion
3.1. Characterization of used sand particles and their interaction
with surfactant
3.1.1. XRD study
The sand particles have been characterized by XRD study. Fig. 2
shows the X-ray diffractogram of the powder sample. The single
headed peak indicates that there is no impurity in the sample and
only one phase is present. The characteristic peaks are obtained
at 21 , 27.74 , 28.57 , 47.23 , 60 and 76 , etc. The main peak
was obtained at 27.47 . JCPDS (le no. 861630) record indicates
the presence of silica in the pure sand. The other peaks show the
presence of quartz in low quantity.
3.1.2. FTIR study of sand particles
The main application of this technique is to detect the structure of chemical species and provide qualitative measurement,
based on the adsorption and molecular vibration peaks. The results
of the FTIR test for pure sand before and after treatment with
different surfactants are presented in Figs. 3(a)(d). The infrared
spectra of pure sand shows adsorption peaks at 776.33 cm1
and 1080.17 cm1 , in the region of stretching vibration for SiO symmetric and asymmetric bond vibration respectively. Again
absorption bands at 521.27 cm1 , 693.91 cm1 are related to the
bending vibration of Si-O group in asymmetric and symmetric
vibration. So it is clear that the used sand particles contain pure
silica as main composition. The sand sample also shows peaks at

Fig. 2. XRD study of the crushed sand particles used in the present work.

2851.85 cm1 and 2924.64 cm1 . These two peaks indicates the
symmetric and asymmetric CH2 stretching.
In Fig. 3(b) the results of the sample treated with SDS has
been shown. In general, SDS exhibits bands due to symmetric
and asymmetric stretching and deformation of methylene chain at
2851.85 cm1 and 2922 cm1 . The 2851.85 cm1 and 2920.73 cm1
bands overlapped with pure sand peaks. It is also seen that the sample treated with SDS, the stretching vibration of the S O bond is
observed at 1360.23 which is overlapped with different small peaks
of pure sand. The stretching vibration of alkyl C H bond is indicated
in SDS treated sand as a strong and sharp peak at 2920.73 cm1 ,
which shows that SDS is adsorbed on the sand surface.
Fig. 3(c) shows the results of the sample treated with CTAB. The
CH2 group to peak at 1637.18 cm1 for SDS treated sand shifted
to 1627.98 cm1 and therefore CTAB adsorption on sand particles
also takes place. The intense bands near 2850.52 and 2919.33 cm1
can be assigned to the C H stretching and deformation vibrations
of CTAB which are overlapped with spectra of pure sand. The shifting of methylene chain at 2850.52 cm1 and 2919.33 cm1 from
2852.1 cm1 is due to adsorption of CTAB on sand surface in solution phase.
In Fig. 3(d) FTIR spectra of Tergitol 15-S-7 treated sand is presented. In this case C H stretching vibration of surfactant shows at
2927.16 cm1 instead of 2920 cm1 . This is due to in solution Tergitol 15-S-7 with ethoxylated group gets adsorbed on sand surface
and absorption band is shifted. An additional band at 1888.05 cm1
is appeared due to adsorption of this ethoxylated nonionic surfactant.
In all cases after treatment with surfactants, bands at
3468.68 cm1 and 1637.18 cm1 , 3468.86 cm1 and 1627.98 cm1 ,
and 3469.04 cm1 and 1626.73 cm1 for SDS, CTAB, Tergitol 15-S-7
respectively originated from the stretching vibration of OH group
of interlayer water molecule during surfactant adsorption.
3.2. Critical micelle concentration and effectiveness of the
surfactants
It is well known that the surfactants reduce the surface tension of water by getting adsorbed on the liquidgas interface. The
critical micelle concentration (CMC), one of the main parameters
for surfactants, is the concentration at which surfactant solutions
begin to form micelles in large amount [49]. Surface tensions of
the above three surfactants (SDS, CTAB, and Tergitol 15-S-7) solutions at different concentrations were measured and plotted as a

A. Bera et al. / Applied Surface Science 284 (2013) 8799

91

Fig. 3. FTIR spectra of sand particles before and after surfactant treatment in brine (2 wt% NaCl): (a) pure sand; (b) treated with SDS; (c) treated with CTAB; (d) treated with
Tergitol 15-S-7.

function of concentration in Fig. 4. The concentration at the inexion point of the curve is critical micelle concentration. The lowest
surface tension value achieved by Tergitol 15-S-7 is 30 mN m1
which is signicantly lower than the surface tension value of water.
The CMCs of the surfactants are found to be 0.23 wt%, 0.0345 wt%,
and 0.0051 wt% for SDS, CTAB, and Tergitol 15-S-7 respectively.

3.3. Adsorption isotherms of surfactants on sand particles


The Langmuir adsorption isotherm and the Freundlich adsorption isotherm are two common isotherms used to describe the
equilibrium adsorption isotherm. Another two isotherms such as
Redlich-Peterson and Sips are considered here to describe the
experimental data and nd out the best tted model for adsorption
of surfactant on sand surface.
The Langmuir equation relates the amount of solid adsorbate
adsorbed,  , to the equilibrium liquid concentration at a xed temperature. The equation was developed by Irving Langmuir [50] in
1916 and is expressed in this nonlinear form as follows:
max KL Ce
 =
1 + KL Ce

parameter, and it is represented by the following equation [51,52]:

RL =

1
1 + KL C0

(3)

where, C0 (mg/L) expresses initial adsorbate concentration in aqueous solution. KL (L/mg) is the Langmuir constant. The RL parameter
gives important signs on the compatibility of adsorption for the
selected adsorbentadsorbate pair. There are four possibilities for
the RL value:

In the case 0 < RL < 1, adsorption is favorable.


In the case RL > 1, adsorption is unfavorable.
RL = 1 indicates linearity of adsorption.
In the case RL = 0, adsorption is irreversible.

The values of RL obtained in this study were between 0.0445


to 0.3507, indicating that the adsorption of surfactant onto sand
surface is favourable.
The Freundlich isotherm assumes that if the concentration of the
solute in the solution at equilibrium, Ce , is raised to the power 1/n,
C

(2)

where,  is the amount of adsorbate adsorbed (mg/g);  max is the


maximum amount adsorbed (mg/g); KL is the Langmuir equilibrium constant (L/mg); Ce is the equilibrium aqueous concentration
(mg/L). It is well-known that the Langmuir isotherm is applicable
for monolayer adsorption because of the homogeneous surface of
a nite number of identical sites. Another important parameter of
the Langmuir isotherm model is the term RL which is a nondimensional constant and called as separation factor or equilibrium

1/n

the amount of the solute adsorbed being  , the e is constant


at given temperature and the nonlinear form of the equation is
expressed as:
1/n

 = KF Ce

(4)

where, KF (mg/g) and n are the Freundlich adsorption constants


related to sorption capacity and sorption intensity, respectively.
Freundlich isotherm has been derived by assuming an exponentially decaying sorption site energy distribution. The Freundlich
isotherm assumes that the surfactant adsorption occurs on a heterogeneous surface by multilayer sorption.

92

A. Bera et al. / Applied Surface Science 284 (2013) 8799

Fig. 4. Plot of surface tension vs. surfactant concentration for nding the CMCs of the surfactants: (a) SDS, (b) CTAB and (c) Tergitol 15-S-12.

The Freundlich constant (1/n) is related to the adsorption intensity of the adsorbent. When, 0.1 < 1/n < 0.5, adsorption is favourable;
0.5 < 1/n 1, it is easy to adsorb; 1/n > 1, it is difculty to adsorb [53].
The Redlich-Peterson isotherm model is used as a compromise
between Langmuir and Freundlich isotherm models [54,55]. The
non-linearized form of Redlich-Peterson isotherm model can be
given as follows:
 =

KR Ce

(5)

1 + RCe

where, KR (L/mg) and R


are Redlich-Peterson isotherm
constants. is the exponent which lies between 0 and 1 and can
characterize the adsorption isotherm. If = 1, Eq. (5) reduces to the
Langmuir isotherm model, and if = 0, Eq. (5) reduces to the linear
isotherm model. The values of KR , R and can be obtained by
nonlinear regression method and are listed in Table 1.
The Sips isotherm model is obtained by introducing a power law
expression of the Freundlich isotherm into the Langmuir isotherm
[56]. The non-linearized form of Sips isotherm model can be given
as follows:
max KS Cems
1 + KS Cems

Table 1
Adsorption isotherm parameters of the surfactants.
Isotherm models

Parameters

Surfactants
SDS

[(L/mg) ]

 =

where,  max (mg/g) is the maximum monolayer surfactant adsorption capacity on sandstone. KS [(L/mg)m s ] is the Sips isotherm
constant representing the energy of adsorption. ms is the empirical constant. The values of KS ,  max and m can be obtained by

(6)

CTAB

Tergitol 15-S-7

Langmuir

 max (mg/g)
KL 102 (L/mg)
R2

0.771
2.122
0.975

0.867
1.851
0.968

0.816
2.152
0.958

Freundlich

KF (mg/g)
1/n
R2

0.225
0.177
0.957

0.302
0.149
0.812

0.256
0.171
0.908

Redlich-Peterson

KR 102 (L/mg)
R 102 (L/mg)

R2

2.626
6.244
0.914
0.936

4.524
8.826
0.851
0.797

3.162
7.246
0.827
0.889

Sips

 max (mg/g)
KS 102 (L/mg)m s
ms
R2

0.901
9.302
0.568
0.943

1.877
15.991
0.237
0.799

1.737
6.752
0.209
0.899

A. Bera et al. / Applied Surface Science 284 (2013) 8799

Fig. 5. Adsorption isotherms of different types of surfactants at 303 K.

nonlinear regression method and are given in Table 1. If the value


of KS approaches 0, the Sips isotherm will become a Freundlich
isotherm. While the value of ms = 1 or closer to 1, the Sips isotherm
equation reduces to the Langmuir equation; that is, adsorption
takes place on homogeneous surface [57].
Fig. 5 shows the adsorption of different types of surfactants
on sand surfaces at 303 K. To quantify the adsorption capacity of
the sand particles for surfactant adsorption, Langmuir Freundlich,
Redlich-Peterson, and Sips adsorption isotherm models have been
used. Fig. 6 depicts the different adsorption models for SDS surfactant. Curve ttings for Langmuir, Freundlich, Redlich-Peterson,
and Sips adsorption isotherm models for the other two surfactants
like CTAB and Tergitol 15-S-7 have been given in Figs. S1 and S2
(supplementary information) respectively. The calculated results
from the curves of Langmuir, Freundlich, Redlich-Peterson, and Sips
isotherm adsorption models for the surfactants have been summarized in Table 1. The values of regression coefcient (R2 ), mean
square error (MSE), minimum absolute percentage error (MINAPE),
and maximum absolute percentage error (MAXAPE) indicate that
the Langmuir model is well tted with the adsorption isotherm of
the surfactants on sand surface. The details of these values have
been given in supplementary information (Table S1).

93

The equilibrium amount of surfactant adsorbed on the sand


particles depends on their structures and nature of head groups.
It is clear from Fig. 5 that the amount of SDS adsorbed on the
adsorbent shows the lowest value compared to the others. The
equilibrium amount of CTAB and Tergitol 15-S-7 adsorbed on sand
particles are considerably higher than SDS. For all the surfactants, it was found that there is a sudden increase in adsorption
isotherm as concentration of the surfactant increases. The sudden increase in adsorption isotherm may be described in terms
of formation of surface aggregates, known as hemi micelles of
the surfactant molecules on the sand surface due to lateral interaction between hydrocarbon chains. This lateral attraction force
generates an additional driving force, which superimposes existing
electrostatic attraction causing a sharp increase in adsorption. In all
cases the increase of adsorption with concentration up to a certain
point and then no increase have been observed. In case of CTAB
when surfactant concentration reaches CMC, micelles starts to form
and exist in the bulk solution and act as chemical potential sink
for additional surfactant added to the system. As a result, surfactants cannot adsorb onto the surface and plateau of the adsorption
isotherm shown in Fig. 5 is characterized by little or no increases
in surfactant adsorption with increasing surfactant concentration.
With increase in SDS concentration strong repulsion takes place
between sand surface and surfactant molecules due to negative
head groups of SDS surfactant. Therefore before CMC no increase
in adsorption also takes place with increasing concentration of
surfactant. In case of Tergitol 15-S-7 after CMC small increase of
adsorption takes place due to weak hydrophobic and H-bond interaction.
The adsorption of an ionic surfactant at solidliquid interface is
strongly inuenced by the compositions of the sand which makes
the sand surface negatively charged therefore, weak interaction
takes place with anionic surfactant (SDS) having their negatively
charged head part. So the SDS adsorption capacity on sand particles is not signicantly high. However, CTAB is a cationic surfactant,
and the adsorption takes place mainly due to presence of some
charged components of sand particles such as silica which are negative in nature at neutral pH or in water. The high adsorption
capacity of CTAB on sand particles may be explained on the basis
of electrostatic interaction that exists between negatively charged
adsorbent and positively charged head group of surfactant. Adsorption of nonionic surfactant occurred on solid adsorbent due to weak
hydrophobic and hydrogen bond interactions between surfactants
and the adsorbent. Since no positive and negative charge can exist
on nonionic surfactants so the adsorption capacity of Tergitol 15S-7 is also low.
3.4. Effect of salt concentration on adsorption isotherm of SDS

Fig. 6. Different isotherm models t for adsorption of SDS surfactant on sand particles at 303 K.

Adsorption isotherms for SDS surfactant solution at different


salinities have been shown in Fig. 7. At the interface between surfactant and sand particles, there is always an unequal distribution
of electrical charges. This unequal charge distribution gives rise
to a potential across the interface and forms a so-called electrical
double layer [58]. With increase in NaCl concentration, the electrical double layer on the surface of adsorbent is compressed and
electrostatic repulsion between the adsorbed surfactant species
decreases, which results in the increase of adsorption capacity.
The surfactant adsorption capacity increases with the increase
in salinity of the system at a constant temperature of 303 K.
These facts imply that the adsorption of SDS on sand particle
adsorbent is favored at high salinity and therefore the adsorption
process is seen to be a chemical process with increasing salinity.
The curve ttings for Langmuir and Freundlich adsorption
isotherm models have been depicted in Figs. 8a and b respectively

94

A. Bera et al. / Applied Surface Science 284 (2013) 8799

Fig. 7. Adsorption isotherm of SDS surfactant on sand surface at different salinities


of brine at 303 K.

at 303 K. Table 2 shows the parameters obtained the two models used. In case of Langmuir model, the regression coefcients
(R2 ) for the linear equation ttings at different salinities are found
to be greater than 0.950 and at high salinity it is above 0.980
whereas the vales of R2 for the Freundlich isotherm model are
found to less than 0.950. Therefore, in presence of salt adsorption of surfactants on sand surface follow the Langmuir isotherm
model.

Fig. 9. The effect of the amount of sand on the adsorption process of the surfactants.

3.5. Effect of adsorbent dose on the extent of surfactants


adsorption
Adsorption of the surfactant on sand depends on its dose as
shown in Fig. 9. 1000 ppm concentration of different surfactants
(SDS, CTAB, and Tergitol 15-S-7) has been used for adsorption
study at 303 K. From Fig. 9 it has been found that adsorption
increases with adsorbent dose and then remains constant after
certain dose for each surfactant. As the amount of adsorbent

Fig. 8. Adsorption isotherms of SDS at different NaCl salt concentrations at 303 K: (a) Langmuir equation tting; (b) Freundlich equation tting.

Table 2
Adsorption isotherm parameters of SDS at different salinities.
Salinity (wt% NaCl)

0
2
4

Langmuir parameters

Freundlich parameters

 max (mg/g)

KL 10 (L/mg)

KF (mg/g)

1/n

R2

0.763
1.011
1.031

2.141
1.472
1.642

0.951
0.993
0.988

0.231
0.216
0.345

0.173
0.218
0.151

0.937
0.894
0.899

A. Bera et al. / Applied Surface Science 284 (2013) 8799

95

3.7. Adsorption kinetics


Adsorption is a physicochemical process that involves the mass
transfer of adsorbate from the liquid phase to the adsorbent surface.
A study of kinetics of adsorption is desirable as it provides information about the mechanism of adsorption, which is important to
evaluate efciency of the process. The experimental data of adsorption of surfactants on sand particles have been analysed by three
different models viz. Lagergren-rst-order equation, second-order
equation and intraparticle diffusion model.
3.7.1. Lagergren-rst-order kinetic equation
Lagergren-rst-order equation is very well known kinetic equation. It was rst proposed by Lagergren in 1988 to determine the
kinetic process of liquid-solid phase adsorption. The common form
of the equation is
dt
= k1 (e t )
dt
Fig. 10. The effect pH on the adsorption process of the surfactants.

On integration of this equation for the boundary condition t = 0


to t = t and  e = 0 to  e =  t , gives:
ln(e t ) = ln e k1 t

increases the adsorption sites also increase and the adsorption


process takes place easily with increase in order. After a certain
adsorbent dose there is no further adsorption because of gathering
of huge adsorption sites and produced particle interaction among
the sand particles in the system. Particle-particle interaction takes
place from high adsorbent concentration which leads to a decrease
in total surface area of the adsorbent and an increase in diffused
path length [59].

(7)

(8)

where,  e (mg/g) and  t (mg/g) are the amount of surfactants adsorbed on sand particles at equilibrium and at time t (min)
respectively. k1 (min1 ) is the rate constant of the pseudo-rstorder adsorption. The values of k1 can be calculated experimentally
from the slope of the linear plot of ln( e  t ) versus t.
In Fig. 11(a), adsorption kinetics of SDS surfactant on sand particle at different concentration at 303 K has been depicted. The
parameters are calculated from the model have been summarized
in Table 3.

3.6. Effect of pH on adsorption of surfactants


The pH of the aqueous solution is one of the important controlling parameters in the adsorption of surfactant on reservoir rocks.
Fig. 10 shows the effect of pH on the extent of adsorption of different surfactants (anionic, cationic and nonionic) on clean sand
surface. The sand particles exhibited high adsorption efciency at
low pH for anionic and nonionic surfactants. As pH increases the
adsorption decreases for anionic surfactant. The adsorption capacity at alkaline solution is lower due to the decrease of positively
charged sites on adsorbent and the competition between OH and
anionic surfactant for the adsorption site. A number of research
works has been reported regarding the effect of pH of solution
on adsorption of surfactants on rock surfaces [27,6063]. At low
pH, SDS adsorption capacity of sand is high due to acidic nature
of the solution which makes the sand surface more positive and
that is why the interaction of sand surface with anionic surfactant
SDS is high and hence adsorption capacity is high. In case of Tergitol 15-S-7 (nonionic), adsorption decreases up to neutral pH and
remains almost constant at alkaline pH region. This can be demonstrated that the presence of lone pair of electrons of the oxygen
atom of the ethylene oxide group of ethoxylated nonionic surfactant which is broadly attracted by the positively charged surfaces
of sand particles at pH values lower than 7. The lower adsorption of
the surfactant at alkaline region is due to hydrophobic interaction
only. As pH of the solution increases adsorption of CTAB surfactant
(cationic) also increases because positively charged head groups of
the cationic surfactant are strongly attracted at high pH with negatively charged sand surfaces. So from this study the adsorption of
the surfactants on rock surfaces can be reduced or alter by xing
the solution pH for nonionic and ionic surfactants which are very
important issue regarding the economic feasibility for surfactant
ooding.

3.7.2. Pseudo-second-order kinetic equation


The pseudo-second-order kinetic model equation is expressed
as follow:
dt
2
= k2 (e t )
dt

(9)

and rearranging the Eq. (9) gives


dt
(e t )

= k2 dt

(10)

where, k2 (g/mg/min) is the rate constant of the second-order


equation.
Now applying the boundary conditions t = 0 to t = t and  e = 0 to
 e =  t , the integrated linear form of Eq. (10) can be rearranged to
obtain Eq. (11).
1
t
t
=
+
t
e
k2 e2

(11)

The plot of t/ t versus t has been shown in Fig. 11(b). The values of equilibrium adsorption capacity  e and rate constant k2 ,
calculated from the intercept and the slope of the linear plot of
t/ t versus t, along with the value of regression coefcient R2 , MSE
values are listed in Table 3.
3.7.3. Intraparticle diffusion model
The intraparticle mass transfer diffusion model was proposed
by Weber and Morris [64]. For determination of rate constant and
reaction type, rst-order and second-order kinetic models are generally used. To understand the diffusion mechanism of adsorption
process it is very important to introduce intraparticle diffusion
model. In this model the fractional approach to the equilibrium

96

A. Bera et al. / Applied Surface Science 284 (2013) 8799

Fig. 11. The kinetics models for adsorption of SDS surfactant on sand particle at different concentrations at 303 K: (a) Lagergren-rst order kinetics; (b) pseudo second order
kinetics; (c) interparticle diffusion kinetics.
0.5

changes according to a function of (Dt/r 2 ) , where D is the diffusion coefcient within the solid adsorbent and r is the particle
radius.
The intraparticle diffusion rate constant can be determined from
the following equation [6568]:
t = Kid t 0.5 + C

(12)

where, Kid (mg/g/min) is the rate constant of intraparticular diffusion and C is the intercept. A plot of  t versus t0.5 should be
straight line with a slope Kid and intercept C when adsorption mechanism follows the intraparticle diffusion process. Ho [69] pointed
out that in case of intraparticle diffusion the  t versus t0.5 plot
must go through the origin and that is sole rate-limiting step. In
the present study, no plot passed through the origin. This indicates
that although intraparticle diffusion was involved in the adsorption
process, it was not sole rate-controlling step. This also conrms

that adsorption of surfactant on sand was a multi-step process;


involving adsorption on the external surface and diffusion into the
interior [70]. It can be demonstrated from Fig. 11(c) and Table 3
that other adsorption mechanisms along with diffusion contribute
in the interactions between the surfactant molecules and sand particles.
The high value of R2 and low value MSE obtained from the three
models suggest the applicability of the second-order kinetic model
to describe the adsorption kinetics data of surfactants onto sand
surface and the calculated  e values are in good agreement with
the experimental one.

3.8. Thermodynamic parameters of adsorption


Both enthalpy and entropy are the key factors to be considered
in any process design [71]. The feasibility of the adsorption process

Table 3
Kinetics parameters for the adsorption of surfactant on sand particles at different surfactant concentrations.
Kinetics model

Kinetics parameters

Surfactant concentration (ppm)


400

800
2

1000
2

Lagergren-rst-order

k1 (min )
 e (mg/g)
R2
MSE

1.249 10
0.4667
0.9657
2.6354

1.344 10
0.4409
0.9755
2.7661

2.03 102
0.4857
0.9471
1.9178

Pseudo-second-order

k2 (g/mg/min)
 e (mg/g)
R2
MSE

2.501 102
0.810
0.991
0.8343

3.230 102
0.875
0.994
0.6421

4.139 102
0.864
0.992
0.6678

Intraparticle diffusion

kid (mg/g/min)
C
R2
MSE

3.896 102
0.1313
0.988
1.2678

3.893 102
0.2319
0.981
1.1523

3.318 102
0.3197
0.990
1.1235

A. Bera et al. / Applied Surface Science 284 (2013) 8799

Fig. 12. Langmuir equation tting for adsorption isotherms of SDS at different temperatures.

is claried by the value of change in Gibbs energy, G (J/mol) and


it is estimated by applying thermodynamic equation [72,73]:
G = RT ln KL

(13)

where, R is the universal gas constant (8.314 J/K/mol), T is the temperature (K) and KL is the Langmuir constant at temperature T.
Again the feasibility and endothermic nature of the adsorption
process are determined by the entropy change, S (J/mol) and
enthalpy change, H (J/mol). The dependence of temperature on
adsorption of surfactant on sand particle was evaluated using vant
Hoff equation by calculating the values of H and S .
S
H

R
RT

(14)

G = H TS

(15)

ln KL =

The effect of temperature on adsorption of surfactant on sand


particle at different temperature has been depicted in Fig. 12. Temperature plays an important role on the adsorption of surfactant
onto sand particles. The variation of adsorption with temperature
has been explained with help of the thermodynamic parameters
such as change in standard Gibbs free energy, enthalpy and entropy.
The variation of Langmuir constant with temperature has been
shown in Fig. 13. The values of S and H were calculated from
the intercept and slope of plot between lnKL versus 1/T. The calculated values of all the thermodynamic parameters have been
reported in Table 4. The negative values of G indicate the spontaneous and feasibility nature of surfactant adsorption process. It may
also be noted that with increase in temperature from 303 to 333 K,
the negative values of the Gibbs free energy decrease. This suggests that with increase in temperature spontaneity and feasibility
of the process are decreased and resulting the weaker adsorptive
force. In general, the value of Gibbs free energy for physisorption
lies between 20 kJ/mol and 0 kJ/mol and that for chemisorptions
lies between 400 kJ/mol and 80 kJ/mol value [74]. The high
Table 4
Thermodynamic parameters for the adsorption of SDS on clean sand particles at
different temperatures.
Temperature (K)

KL (L/mol)

G (kJ/mol)

H (kJ/mol)

S (kJ/mol/K)

303
313
323

6.113
4.959
3.316

4.562
4.167
3.217

24.846

0.0667

97

Fig. 13. Relationship between Langmuir constant and temperature for SDS adsorption on sand surface.

adsorption of surfactant at low temperature attributed to the fact


that the adsorption interactions are exothermic in nature. The negative value of enthalpy change conrmed the exothermic nature
of the sorption process. Negative value of standard entropy change
conrmed that with increase in temperature the randomness of the
molecules at the solidsolution interface decreases during the xation of the surfactant molecules on the active site of sand surfaces.
Temperature signicantly inuences the adsorption of surfactant on reservoir rock surface. In the present study temperature
plays an important role. From Fig. 12, it is clear that with increase
in temperature adsorption capacity decreases. Two main impacts
of temperature are generally found. Firstly, when temperature
increases the rate of diffusion of the adsorbate across the external boundary layer and interior pores of the reservoir rocks is
decreased because of the solution viscosity declines as temperature increases. Secondly, temperature inuences the equilibrium
adsorption capacity of the sand particles depending on whether
the adsorption process is exothermic or endothermic.
Pressure can also play an important role on adsorption of gases
or liquids when physisorption has taken place onto solid surface.
The amount of adsorption will increase with increase in pressure.
The increased adsorption capacity is due to reduction in adsorbate
volume during adsorption with increase in pressure. It is important
to note that the effect of pressure on adsorption of gas is stronger
than liquid on solid surface.
4. Conclusions
The adsorption of the three types of surfactants namely anionic
(SDS), cationic (CTAB), and nonionic (Tergitol 15-S-7) onto clean
sand particles from aqueous solutions was systematically studied. Experimental investigations were carried out to examine the
adsorption equilibrium, isotherm, kinetic behaviors, and thermodynamics of adsorption of these surfactants. XRD study shows the
presence of silica in the pure sand which provides in active sites
for adsorption of different surfactants. FTIR of the sand particles
again indicates the presence of silica. After treatment of surfactant
spectral changes are found and adsorption is conrmed from the
result. According to the results obtained in the present study, as we
move from cationic to anionic via nonionic surfactant, adsorption
of surfactants on sand particles decreases. With increasing salinity of the solution adsorption of SDS increases on sand surface
due to low electrostatic repulsion between the adsorbed surfactant
species. With increase in the surfactant concentration, adsorption

98

A. Bera et al. / Applied Surface Science 284 (2013) 8799

on the surface of sand particles increases until the saturation point


reaches. The sand particles exhibited high adsorption efciency at
low pH for anionic and nonionic surfactants. But opposite trend
was found for cationic surfactant. Results also show that after a
certain adsorbent dose there is no further adsorption because of
gathering of huge adsorption sites and produced particle interaction among the sand particles in the system. Adsorption parameters
for the Langmuir, Freundlich, Redlich-Peterson, and Sips isotherms
were determined by using experimental data. Results show that the
Langmuir isotherm and pseudo-second order kinetics models suit
the equilibrium and kinetics of adsorption on sand surface respectively. With increasing temperature adsorption of SDS surfactant
decreases as the randomness of the molecules at the solid-solution
interface decreases during the xation of the surfactant molecules
on the active site of sand surfaces.
Acknowledgements
The authors gratefully acknowledge the nancial assistance provided by University Grant Commission [F. No. 37-203/2009(SR)],
New Delhi to the Department of Petroleum Engineering, Indian
School Of Mines, and Dhanbad, India. Thanks are also extended to
all individuals associated with the project.
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/
j.apsusc.2013.07.029.
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