Applied Surface Science 284 (2013) 87–99

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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 a b s t r a c t

Article history: Adsorption of surfactants onto reservoir rock surface may result in the loss and reduction of their concen-
Received 15 May 2013 trations in surfactant flooding, which may render them less efficient or ineffective in practical applications
Received in revised form 5 July 2013 of enhanced oil recovery (EOR) techniques. Surfactant flooding for EOR received attraction due to its abil-
Accepted 7 July 2013
ity to increase the displacement efficiency by lowering the interfacial tension between oil and water and
Available online 16 July 2013
mobilizing the residual oil. This article highlights the adsorption of surfactants onto sand surface with
variation of different influencing factors. It has been experimentally found that adsorption of cationic
Keywords:
surfactant on sand surface is more and less for anionic surfactant, while non-ionic surfactant shows inter-
Surfactant
Adsorption isotherm
mediate behaviour. X-ray diffraction (XRD) study of clean sand particles has been made to determine the
Isotherm model main component present in the sand particles. The interaction between sand particles and surfactant has
Adsorption kinetics been studied by Fourier Transform Infrared (FTIR) Spectroscopy of the sand particles before and after
Thermodynamics of adsorption aging with surfactant. Salinity plays an important role in adsorption of anionic surfactant. Batch experi-
ments were also performed to understand the effects of pH and adsorbent dose on the sorption efficiency.
The sand particles exhibited high adsorption efficiency at low pH for anionic and nonionic surfactants.
But opposite trend was found for cationic surfactant. Adsorption data were analyzed by fitting with Lang-
muir, 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 decades. A number of studies have been conducted on the adsorp-

Adsorption of surfactants on rock/clay/sediment solid matrix
may result in the loss and reduction of their concentrations, which
may render them less efficient or ineffective in practical appli-
cations of EOR techniques. Surfactants are also widely used in
various industrial processes for their favourable physicochemical
characteristics like detergency, foaming, emulsification, dispersion
and solubilization effects [1–4]. Due to extreme ability to reduce
oil-water interfacial tension (IFT), surfactants are very important
materials in chemical flooding for EOR methods. Adsorption of
surfactants from aqueous solutions in porous media is a funda-
mental 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 [5–8]. Surfac-
tant 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).
tion of ionic and nonionic surfactants onto reservoir rocks [8–22].
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 elec-
trical double layer (proposed by Helmholtz in 1879, and modified
by Stern in 1924) of the solid surface largely determines the sur-
factant 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 surfac-
tant 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 level-
ling 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
flooding of sandstone oil reservoirs [26]. The adsorption of surfac-
tants from the solution is affected by its physicochemical properties

0169-4332/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2013.07.029
88 A. Bera et al. / Applied Surface Science 284 (2013) 87–99

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

Nomenclature the interface is energetically favoured by the surfactant molecules
compared to the bulk phase [35,36]. It has been shown that the
EOR enhanced oil recovery
nature of the adsorption isotherm depends to a large extent on
XRD X-ray diffraction
the type of surfactant used, the morphological and mineralogical
FTIR Fourier Transform Infrared
characteristics of the rock, and the type of electrolytes present in
IFT interfacial tension
solution [37]. The adsorption of surfactants can be affected by the
CMC critical micelle concentration
surface charge on the rock surface and fluid interfaces [38–41]. Pos-
SDS sodium dodecylsulphate
itively charged cationic surfactant is attracted to negatively charged
CTAB cetyltrimethylammonium bromide
surfaces, while negatively charged anionic surfactant is attracted to
DOE design of experiments
positively charged surfaces. The salinity and pH of brine strongly
COD chemical oxygen demand
affect the surface charge. When the effects of brine chemistry are
MSE Mean Square Error
removed, silica tends to adsorb simple organic bases (cationic sur-
MINAPE Minimum absolute percentage error
factant), while the carbonates tend to adsorb simple organic acids
MAXAPE Maximum absolute percentage error
(anionic surfactant). This occurs because silica normally has a neg-
atively charged weak acidic surface in water near neutral pH, while
Variables
the carbonates have positively charged weak basic surfaces. Loss
C0 Initial concentrations of surfactants (mg/g)
of surfactants owing to their interactions with reservoir rocks and
Ce Equilibrium aqueous concentration of surfactants
fluid is possibly the most important factor that can determine the
(mg/L)
efficiency of a micellar flooding process [42].
V Volume of the surfactant solution (L)
Studies of adsorption kinetics and equilibrium of different
m Weight of the sand particles (g)
surfactants are very practical tests in laboratory for study of sur-
RL Separation factor or equilibrium parameter
factant adsorption onto rock surface. These phenomena depend
KR Redlich-Peterson isotherm constants (L/mg)
on the nature of the surfactants and also the solid-liquid interface
KS Sips isotherm constant [(L/mg)m s ]
[36,43–45]. Recently Ahmadi et al. [46] have studied the adsorp-
ˇ Exponential factor
tion behavior of the Glycrihiza Glabra, a novel nonionic surfactant,
KL Langmuir equilibrium constant (L/mg)
onto carbonate rock and Ahmadi and Shadizadeh [47] have inves-
KF Freundlich adsorption constants related to sorption
tigated the effect of nanosilica on adsorption behavior of Zyziphus
capacity (mg/g)
Spina Christi onto rock surface. Ahmadi et al. [46] concluded that
t Amount of surfactants adsorbed on sand particles at
adsorption isotherm follows the Langmuir model. On the other
time t (mg/g)
hand when nanosilica is used the Linear, Langmuir, and Temkin
k1 Rate constant of the pseudo-first-order adsorption
equilibrium adsorption models were not suitable for predicting the
(min−1 )
surfactant adsorption, but the Freundlich equilibrium adsorption
k2 Rate constant of the second-order equation
was in good agreement between the experimental data. They also
(g/mg/min)
studied the kinetics of the adsorption and showed that the pro-
G◦ Change in Gibbs energy (J/mol)
cess follows the second order kinetic model. Gogoi [48] reported
S◦ Change in entropy (J/mol)
the effect of NaCl concentration and pH on the adsorption equilib-
H◦ Change in enthalpy (J/mol)
rium of Na-lignosulfonate onto reservoir rocks. He demonstrated
 Amount of adsorbate adsorbed (mg/g)
that adsorption increases with increasing NaCl concentration but
 max Maximum amount adsorbed (mg/g)
decreases with increasing pH.
n Sorption intensity
The net adsorption of surfactant in an EOR process strongly
˛R Redlich-Peterson isotherm constants [(L/mg)ˇ ]
depends on the presence of oil and the flow field. When a surfac-
ms Empirical constant in Sips isotherm
tant slug is injected as displacing fluid, it undergoes partitioning
T Temperature (K)
into oil and water and lowers the interfacial tension between oil
R2 Regression coefficient
and water thereby increasing the capillary number. As a result, the
R Universal Gas Constant (8.314 J/K/mol)
trapped immobile oil becomes mobile. At the same time, an oil-
Kid Rate constant of intraparticular diffusion
in-water emulsion is formed which blocks the larger pores leading
(mg/g/min)
to an improvement in the effective mobility ratio. Otherwise the
C Intercept
injected surfactant solution flows through the highly permeable
zone bypassing the trapped oil in smaller pores. The injected sur-
factant continues to mobilize oil, until the surfactant is diluted or
such as pH [27–29], temperature [30,31], ionic strength [27,31], otherwise lost due to adsorption on the rock surface. Consequently
adsorbent dose [32] and electrolyte concentration [27,30,33]. These the surfactant solutions with lower concentration could not be able
physicochemical properties of solutions can also influence in the to lower the interfacial tension and mobilize oil. At that point, the
dissolution behavior of minerals resulting significant changes in process degenerates into a water flood. Hence to design a surfactant
the precipitation behavior of the surfactants [34]. A slight variation flooding for EOR, it is very important to have a complete knowledge
in one of the above factors or the other can result in a significant of adsorption of the specific surfactant on the reservoir rock under
change in the adsorption characteristics of the system. the reservoir conditions.
Adsorption is a unit operation in which dissolved constituents In the present paper the adsorptions of three different surfac-
are removed from the solvent by interphase transfer to the sur- tants namely anionic, cationic, and nonionic by clean sand particles
face of an adsorbent particle. In chemical flooding, surfactants have been investigated with variation of different parameters i.e.,
are inevitably adsorbed on the surface of reservoir rock by the salinity, pH, temperature, and adsorbent dose. Adsorption data
rock/oil/brine interaction. Surfactant adsorption in porous media is have been analysed by fitting with Langmuir, Freundlich, Redlich-
a typically complex phenomenon (e.g., mass transfer and reaction). Peterson, and Sips isotherm models. Kinetics of adsorption has also
Adsorption in porous media is a phenomenon in which trans- been carried out with anionic surfactant. Thermodynamic feasibil-
port of surfactant molecules takes place from bulk phase onto the ity of the adsorption process has also been studied to verify the
 A. Bera et al. / Applied Surface Science 284 (2013) 87–99
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 (60–70 mesh size). Anionic surfactant,
Sodium dodecylsulphate (SDS) (with 98% purity) was purchased
from Fisher Scientific, India and cationic surfactant, Cetyltrimethy-
lammonium 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 surfac-
tant. The molecular structures of the surfactant have been given in
Fig. 1. Sodium Chloride (NaCl) procured from Qualigens Fine Chem-
icals, 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 analyz-
ing the experiment so that valid and objective conclusions can
be drawn effectively and efficiently. Three different surfactants
namely SDS (anionic), CTAB (cationic) and Tergitol 15-S-7 (non-
ionic) 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 ten-
sion method. Adsorption data have been analysed by fitting with
Langmuir, Freundlich, Redlich-Peterson, and Sips isotherm models.
Kinetics of adsorption has also been carried out with anionic sur-
factant. 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.
2.3. Experimental procedures
2.3.1. Preparation of clean sand particles (adsorbent)
Sands which are used for making building were first sieved to get
60–70 mesh sized sand particles and washed with double distilled
89
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 files.
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
450–4000 cm−1 , was a PerkinElmer Spectrum version 10.03.07 FTIR
spectrometer. The instrument is operated by Spectrum two soft-
ware 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 supple-
mentary test method for determination of CMC of surfactant. It is
particularly useful when only very small quantities of an experi-
mental 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 Noüy ring
method. CMCs of the surfactants were determined from plot of
surface tension and surfactant concentration. The concentration at
the inflexion point of the curve is termed as CMC. During the mea-
surement, the experimental temperature was maintained at 298 K.
The platinum ring was thoroughly cleaned with acetone and flame-
dried before each measurement. In all cases the standard deviation
did not exceed ±0.1 mN/m.
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
90 A. Bera et al. / Applied Surface Science 284 (2013) 87–99
surfactant solutions in a 100 ml glass vials and allowed to con-
duct 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 surfac-
tant 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 sur-
factant adsorbed on the adsorbent,  (mg/g), was calculated by a
mass balance relation (1):
V
 = (C0 − Ce )
m
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 proce-
dure.
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 deter-
mined 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 solu-
tion 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 (file 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 struc-
ture 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 cm−1
and 1080.17 cm−1 , in the region of stretching vibration for Si-
O symmetric and asymmetric bond vibration respectively. Again
absorption bands at 521.27 cm−1 , 693.91 cm−1 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
(1)
Fig. 2. XRD study of the crushed sand particles used in the present work.
2851.85 cm−1 and 2924.64 cm−1 . 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 cm−1 and 2922 cm−1 . The 2851.85 cm−1 and 2920.73 cm−1
bands overlapped with pure sand peaks. It is also seen that the sam-
ple 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 cm−1 ,
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 cm−1 for SDS treated sand shifted
to 1627.98 cm−1 and therefore CTAB adsorption on sand particles
also takes place. The intense bands near 2850.52 and 2919.33 cm−1
can be assigned to the C H stretching and deformation vibrations
of CTAB which are overlapped with spectra of pure sand. The shif-
ting of methylene chain at 2850.52 cm−1 and 2919.33 cm−1 from
2852.1 cm−1 is due to adsorption of CTAB on sand surface in solu-
tion phase.
In Fig. 3(d) FTIR spectra of Tergitol 15-S-7 treated sand is pre-
sented. In this case C H stretching vibration of surfactant shows at
2927.16 cm−1 instead of 2920 cm−1 . This is due to in solution Ter-
gitol 15-S-7 with ethoxylated group gets adsorbed on sand surface
and absorption band is shifted. An additional band at 1888.05 cm−1
is appeared due to adsorption of this ethoxylated nonionic surfac-
tant.
In all cases after treatment with surfactants, bands at
3468.68 cm−1 and 1637.18 cm−1 , 3468.86 cm−1 and 1627.98 cm−1 ,
and 3469.04 cm−1 and 1626.73 cm−1 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 ten-
sion of water by getting adsorbed on the liquid–gas 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) solu-
tions at different concentrations were measured and plotted as a
 A. Bera et al. / Applied Surface Science 284 (2013) 87–99
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 inflex-
ion point of the curve is critical micelle concentration. The lowest
surface tension value achieved by Tergitol 15-S-7 is 30 mN m−1
which is significantly 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 adsorp-
tion 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 find out the best fitted 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 fixed tem-
perature. 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
where,  is the amount of adsorbate adsorbed (mg/g);  max is the
maximum amount adsorbed (mg/g); KL is the Langmuir equilib-
rium 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 finite number of identical sites. Another important parameter of
the Langmuir isotherm model is the term “RL ” which is a nondi-
mensional constant and called as separation factor or equilibrium
91
parameter, and it is represented by the following equation [51,52]:
1
RL = (3)
1 + KL C0
where, C0 (mg/L) expresses initial adsorbate concentration in aque-
ous solution. KL (L/mg) is the Langmuir constant. The RL parameter
gives important signs on the compatibility of adsorption for the
selected adsorbent–adsorbate 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,
1/n
C
the amount of the solute adsorbed being  , the e is constant
(2) 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 exponen-
tially decaying sorption site energy distribution. The Freundlich
isotherm assumes that the surfactant adsorption occurs on a het-
erogeneous surface by multilayer sorption.
92 A. Bera et al. / Applied Surface Science 284 (2013) 87–99

Fig. 4. Plot of surface tension vs. surfactant concentration for finding 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 inten- where,  max (mg/g) is the maximum monolayer surfactant adsorp-
sity of the adsorbent. When, 0.1 < 1/n < 0.5, adsorption is favourable; tion capacity on sandstone. KS [(L/mg)m s ] is the Sips isotherm
0.5 < 1/n ≤ 1, it is easy to adsorb; 1/n > 1, it is difficulty to adsorb [53]. constant representing the energy of adsorption. ms is the empir-
The Redlich-Peterson isotherm model is used as a compromise ical constant. The values of KS ,  max and m can be obtained by
between Langmuir and Freundlich isotherm models [54,55]. The
non-linearized form of Redlich-Peterson isotherm model can be
Table 1
given as follows:
Adsorption isotherm parameters of the surfactants.
KR Ce
 = ␤
(5) Isotherm models Parameters Surfactants
1 + ˛RCe SDS CTAB Tergitol 15-S-7

where, KR (L/mg) and ˛R [(L/mg)ˇ ]

are Redlich-Peterson isotherm Langmuir  max (mg/g) 0.771 0.867 0.816
constants. ˇ is the exponent which lies between 0 and 1 and can KL × 102 (L/mg) 2.122 1.851 2.152
R2 0.975 0.968 0.958
characterize the adsorption isotherm. If ˇ = 1, Eq. (5) reduces to the
Langmuir isotherm model, and if ˇ = 0, Eq. (5) reduces to the linear Freundlich KF (mg/g) 0.225 0.302 0.256
isotherm model. The values of KR , ˛R and ˇ can be obtained by 1/n 0.177 0.149 0.171
R2 0.957 0.812 0.908
nonlinear regression method and are listed in Table 1.
The Sips isotherm model is obtained by introducing a power law Redlich-Peterson KR × 102 (L/mg) 2.626 4.524 3.162
˛R × 102 (L/mg)ˇ 6.244 8.826 7.246
expression of the Freundlich isotherm into the Langmuir isotherm
ˇ 0.914 0.851 0.827
[56]. The non-linearized form of Sips isotherm model can be given R2 0.936 0.797 0.889
as follows:
Sips  max (mg/g) 0.901 1.877 1.737
max KS Cems KS × 102 (L/mg)m s 9.302 15.991 6.752
 = (6)
1 + KS Cems ms 0.568 0.237 0.209
R2 0.943 0.799 0.899
 A. Bera et al. / Applied Surface Science 284 (2013) 87–99
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 sur-
factant. Curve fittings 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 sum-
marized in Table 1. The values of regression coefficient (R2 ), mean
square error (MSE), minimum absolute percentage error (MINAPE),
and maximum absolute percentage error (MAXAPE) indicate that
the Langmuir model is well fitted with the adsorption isotherm of
the surfactants on sand surface. The details of these values have
been given in supplementary information (Table S1).
Fig. 6. Different isotherm models fit for adsorption of SDS surfactant on sand parti-
cles at 303 K.
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 surfac-
tants, it was found that there is a sudden increase in adsorption
isotherm as concentration of the surfactant increases. The sud-
den 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 inter-
action 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, surfac-
tants 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 inter-
action.
The adsorption of an ionic surfactant at solid–liquid interface is
strongly influenced 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 parti-
cles is not significantly 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 neg-
ative 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. Adsorp-
tion 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 15-
S-7 is also low.
3.4. Effect of salt concentration on adsorption isotherm of SDS
Adsorption isotherms for SDS surfactant solution at different
salinities have been shown in Fig. 7. At the interface between sur-
factant 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 elec-
trical 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 salin-
ity.
The curve fittings 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) 87–99

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

Fig. 9. The effect of the amount of sand on the adsorption process of the surfactants.
of brine at 303 K.

3.5. Effect of adsorbent dose on the extent of surfactants

at 303 K. Table 2 shows the parameters obtained the two mod-
els used. In case of Langmuir model, the regression coefficients
(R2 ) for the linear equation fittings 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 adsorp-
tion of surfactants on sand surface follow the Langmuir isotherm
model.
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 fitting; (b) Freundlich equation fitting.

Table 2
Adsorption isotherm parameters of SDS at different salinities.

Salinity (wt% NaCl) Langmuir parameters Freundlich parameters

 max (mg/g) KL × 10 (L/mg)

2
R2
KF (mg/g) 1/n R2

0 0.763 2.141 0.951 0.231 0.173 0.937

2 1.011 1.472 0.993 0.216 0.218 0.894
4 1.031 1.642 0.988 0.345 0.151 0.899
 A. Bera et al. / Applied Surface Science 284 (2013) 87–99 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 infor-
mation about the mechanism of adsorption, which is important to
evaluate efficiency of the process. The experimental data of adsorp-
tion of surfactants on sand particles have been analysed by three
different models viz. Lagergren-first-order equation, second-order
equation and intraparticle diffusion model.

3.7.1. Lagergren-first-order kinetic equation

Lagergren-first-order equation is very well known kinetic equa-
tion. It was first 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 ) (7)
dt
On integration of this equation for the boundary condition t = 0
Fig. 10. The effect pH on the adsorption process of the surfactants.
to t = t and  e = 0 to  e =  t , gives:

ln(e − t ) = ln e − k1 t (8)
increases the adsorption sites also increase and the adsorption
process takes place easily with increase in order. After a certain where,  e (mg/g) and  t (mg/g) are the amount of surfac-
adsorbent dose there is no further adsorption because of gathering tants adsorbed on sand particles at equilibrium and at time t (min)
of huge adsorption sites and produced particle interaction among respectively. k1 (min−1 ) is the rate constant of the pseudo-first-
the sand particles in the system. Particle-particle interaction takes order adsorption. The values of k1 can be calculated experimentally
place from high adsorbent concentration which leads to a decrease from the slope of the linear plot of ln( e −  t ) versus t.
in total surface area of the adsorbent and an increase in diffused In Fig. 11(a), adsorption kinetics of SDS surfactant on sand par-
path length [59]. ticle 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
3.7.2. Pseudo-second-order kinetic equation
The pH of the aqueous solution is one of the important control- The pseudo-second-order kinetic model equation is expressed
ling parameters in the adsorption of surfactant on reservoir rocks. as follow:
Fig. 10 shows the effect of pH on the extent of adsorption of dif-
ferent surfactants (anionic, cationic and nonionic) on clean sand dt 2
= k2 (e − t ) (9)
surface. The sand particles exhibited high adsorption efficiency at dt
low pH for anionic and nonionic surfactants. As pH increases the and rearranging the Eq. (9) gives
adsorption decreases for anionic surfactant. The adsorption capac-
ity at alkaline solution is lower due to the decrease of positively dt
2
= k2 dt (10)
charged sites on adsorbent and the competition between OH− and (e − t )
anionic surfactant for the adsorption site. A number of research
where, k2 (g/mg/min) is the rate constant of the second-order
works has been reported regarding the effect of pH of solution
equation.
on adsorption of surfactants on rock surfaces [27,60–63]. At low
Now applying the boundary conditions t = 0 to t = t and  e = 0 to
pH, SDS adsorption capacity of sand is high due to acidic nature
 e =  t , the integrated linear form of Eq. (10) can be rearranged to
of the solution which makes the sand surface more positive and
obtain Eq. (11).
that is why the interaction of sand surface with anionic surfactant
SDS is high and hence adsorption capacity is high. In case of Ter- t 1 t
gitol 15-S-7 (nonionic), adsorption decreases up to neutral pH and = + (11)
t k2 e2 e
remains almost constant at alkaline pH region. This can be demon-
strated that the presence of lone pair of electrons of the oxygen The plot of t/ t versus t has been shown in Fig. 11(b). The val-
atom of the ethylene oxide group of ethoxylated nonionic surfac- ues of equilibrium adsorption capacity  e and rate constant k2 ,
tant which is broadly attracted by the positively charged surfaces calculated from the intercept and the slope of the linear plot of
of sand particles at pH values lower than 7. The lower adsorption of t/ t versus t, along with the value of regression coefficient R2 , MSE
the surfactant at alkaline region is due to hydrophobic interaction values are listed in Table 3.
only. As pH of the solution increases adsorption of CTAB surfactant
(cationic) also increases because positively charged head groups of 3.7.3. Intraparticle diffusion model
the cationic surfactant are strongly attracted at high pH with neg- The intraparticle mass transfer diffusion model was proposed
atively charged sand surfaces. So from this study the adsorption of by Weber and Morris [64]. For determination of rate constant and
the surfactants on rock surfaces can be reduced or alter by fixing reaction type, first-order and second-order kinetic models are gen-
the solution pH for nonionic and ionic surfactants which are very erally used. To understand the diffusion mechanism of adsorption
important issue regarding the economic feasibility for surfactant process it is very important to introduce intraparticle diffusion
flooding. model. In this model the fractional approach to the equilibrium
96 A. Bera et al. / Applied Surface Science 284 (2013) 87–99

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

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

changes according to a function of (Dt/r 2 ) , where D is the dif-
fusion coefficient within the solid adsorbent and r is the particle
radius.
The intraparticle diffusion rate constant can be determined from
the following equation [65–68]:
t = Kid t 0.5 + C
where, Kid (mg/g/min) is the rate constant of intraparticular dif-
fusion 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 mech-
anism 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 confirms
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 par-
ticles.
(12) 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 1000

−1 −2 −2
Lagergren-first-order k1 (min ) 1.249 × 10 1.344 × 10 2.03 × 10−2
 e (mg/g) 0.4667 0.4409 0.4857
R2 0.9657 0.9755 0.9471
MSE 2.6354 2.7661 1.9178

Pseudo-second-order k2 (g/mg/min) 2.501 × 10−2 3.230 × 10−2 4.139 × 10−2

 e (mg/g) 0.810 0.875 0.864
R2 0.991 0.994 0.992
MSE 0.8343 0.6421 0.6678

Intraparticle diffusion kid (mg/g/min) 3.896 × 10−2 3.893 × 10−2 3.318 × 10−2
C 0.1313 0.2319 0.3197
R2 0.988 0.981 0.990
MSE 1.2678 1.1523 1.1235
 A. Bera et al. / Applied Surface Science 284 (2013) 87–99
Fig. 12. Langmuir equation fitting for adsorption isotherms of SDS at different tem-
peratures.
is clarified 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 tem-
perature (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 van’t
Hoff equation by calculating the values of H◦ and S◦ .
S ◦ H ◦
ln KL = − (14)
R RT
G◦ = H ◦ − TS ◦ (15)
The effect of temperature on adsorption of surfactant on sand
particle at different temperature has been depicted in Fig. 12. Tem-
perature 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 cal-
culated values of all the thermodynamic parameters have been
reported in Table 4. The negative values of G◦ indicate the sponta-
neous 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 sug-
gests 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 6.113 −4.562
313 4.959 −4.167 −24.846 −0.0667
323 3.316 −3.217
97
Fig. 13. Relationship between Langmuir constant and temperature for SDS adsorp-
tion on sand surface.
adsorption of surfactant at low temperature attributed to the fact
that the adsorption interactions are exothermic in nature. The neg-
ative value of enthalpy change confirmed the exothermic nature
of the sorption process. Negative value of standard entropy change
confirmed that with increase in temperature the randomness of the
molecules at the solid–solution interface decreases during the fix-
ation of the surfactant molecules on the active site of sand surfaces.
Temperature significantly influences the adsorption of surfac-
tant 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 exter-
nal boundary layer and interior pores of the reservoir rocks is
decreased because of the solution viscosity declines as tempera-
ture increases. Secondly, temperature influences 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 stud-
ied. Experimental investigations were carried out to examine the
adsorption equilibrium, isotherm, kinetic behaviors, and thermo-
dynamics 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 confirmed 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 salin-
ity 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) 87–99
on the surface of sand particles increases until the saturation point
reaches. The sand particles exhibited high adsorption efficiency 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 interac-
tion 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 respec-
tively. With increasing temperature adsorption of SDS surfactant
decreases as the randomness of the molecules at the solid-solution
interface decreases during the fixation of the surfactant molecules
on the active site of sand surfaces.
Acknowledgements
The authors gratefully acknowledge the financial assistance pro-
vided 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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