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Experimental and Theoretical Study of a New Plant

Derived Surfactant Adsorption on Quartz Surface:
Kinetic and Isotherm Methods
a b
Mohammad Ali Ahmadi & Seyed Shadizadeh
a
Department of Petroleum Engineering , Ahwaz Faculty of Petroleum Engineering,
Petroleum University of Technology (PUT) , Ahwaz , Iran
b
Faculty of Petroleum Engineering Department , Petroleum University of Technology ,
Abadan , Iran
Published online: 17 Oct 2014.

To cite this article: Mohammad Ali Ahmadi & Seyed Shadizadeh (2015) Experimental and Theoretical Study of a New
Plant Derived Surfactant Adsorption on Quartz Surface: Kinetic and Isotherm Methods, Journal of Dispersion Science and
Technology, 36:3, 441-452, DOI: 10.1080/01932691.2013.860035

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 Journal of Dispersion Science and Technology, 36:441–452, 2015
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print=1532-2351 online
DOI: 10.1080/01932691.2013.860035

Experimental and Theoretical Study of a New Plant

Derived Surfactant Adsorption on Quartz Surface:
Kinetic and Isotherm Methods
Mohammad Ali Ahmadi1 and Seyed Shadizadeh2
1
Department of Petroleum Engineering, Ahwaz Faculty of Petroleum Engineering, Petroleum
University of Technology (PUT), Ahwaz, Iran
2
Faculty of Petroleum Engineering Department, Petroleum University of Technology, Abadan, Iran

GRAPHICAL ABSTRACT
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Nowadays, the use of surfactants through petroleum reservoirs to raise oil production in the
subset of enhanced oil recovery (EOR) schemes has received much attention from scholars.
Throughout their use, surfactants’ adsorption onto the porous media surfaces is a crucial aspect
of chemical EOR: The robustness and efficiency of the surfactant solution in regard to interfacial
tension reduction between the oil and water phases and the wettability alteration of the reservoir
rock surfaces toward more water is highly depend on the surfactant content of the aqueous
solution while adsorption onto the rock surface reduced surfactant content through the referred
solution. In light of this, in the current research, huge efforts have been made to monitor the
adsorption behavior of the new plant-based surfactant as a proven EOR agent onto quartz rock
samples in terms of adsorption isotherm and kinetic models which plays a crucial role in designing
chemical stimulation through petroleum sandstone reservoirs. In addition, the adsorption fates of
surfactant onto reservoir rock versus surfactant cost are major concerns of feasibility of chemical
flooding through the porous medium. To achieve the main goal of the current study, batch adsorp-
tion approaches were utilized. Adsorption of the mentioned natural surfactant onto quartz
samples was recorded versus time to describe the adsorption kinetic behavior experimentally,
while the obtained kinetic results compared with four robust kinetic approaches. To achieve
the adsorption outcomes, the Freundlich approach was found to be superior to other isotherm
models in estimating the adsorption density of the new surfactant onto quartz surface. Moreover,
pseudo-second-order model outputs followed the actual adsorption data with a high level of
precision and integrity thanks to the value of correlation coefficient (R2).
Keywords Adsorption equilibrium, conductivity, isotherm, kinetics, natural surfactant,
quartz surface

Received 7 October 2013; accepted 24 October 2013.

Address correspondence to Mohammad Ali Ahmadi, Department of Petroleum Engineering, Ahwaz Faculty of Petroleum
Engineering, Petroleum University of Technology (PUT), P.O. Box 63431, Ahwaz, Iran. E-mail: ahmadi6776@yahoo.com
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/ldis.

441
 442 M. A. AHMADI AND S. SHADIZADEH
1. INTRODUCTION
Adsorption of surface active agents onto reservoir rock
solid surface may yield the fate onto rock face and
reduction of their concentrations through aqueous solu-
tions, which may render them less well run or ineffectual
in feasible implications of enhanced oil recovery (EOR)
approaches. Surfactants are also widely utilized through
different industrial applications for their favorable physico-
chemical attributes like as detergency, foaming, emulsifi-
cation, dispersion, and solubilization effects.[1–4] Owing to
an extreme faculty of surfactant to reduce interfacial tension
(IFT) between oil and water phases, surfactants’ materials
have significant effects through the application of chemical
flooding for EOR schemes. Feasibility of the surfactant flood-
ing is highly dependent on surfactant cost, environmental
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effects, and amount of surfactant adsorption from aqueous
solutions onto porous media. Adsorption loss is an underly-
ing problem in EOR projects by means of surfactant flooding
from petroleum reservoirs because surfactant loss dedicated
to adsorption on the reservoir rocks impairs the robustness
and performance of the injected chemical solution in lowering
the IFT of oil–water and may change into the method econ-
omically inapplicable.[5–8] Due to these crucial facts, adsorp-
tion of surfactants onto rock and surfactant solution
interface has been investigated over many years. Much
research has been carried out on the adsorption of ionic
and nonionic surfactants onto reservoir rocks.[8,9–21]
Knowledge regarding the adsorption process of surfactant
onto rock porous media has been dedicated to the equilibrium
isotherm and kinetics of the process while equilibrium
adsorption data has been detailed for the final condition of
an adsorption mechanism and kinetic data provides a good
view about the rate of changes through the adsorption pro-
cess. Through our current study, equilibrium adsorption
and the associated kinetics of newly proposed raw surfactant
onto quartz rock surface is investigated. Recall that there is
little to no information about the adsorption process of the
suggested natural surfactant onto quartz porous media in
literature surveys. As previously noted in Ahmadi and Shadi-
zadeh[20,22–23] the robust advantages of the extracted biode-
gradable surfactant are a very low cost, availability in
Middle East and Africa, and environmentally friendly charac-
teristics contrasted with other commercial and industrial sur-
factants utilized through petroleum upstream. The depletion
solution approach was examined to determine the adsorption
trend of the extracted natural surfactant from leaves of Zyzi-
phus spina-choursisti (ZSC). Through the above-
mentioned approach, the conductivity method was used to
determine surfactant concentration in aqueous solutions. It
is worth bearing in mind that adsorption kinetics were
experimentally carried out at atmospheric conditions, record-
ing the concentration changes of the above-mentioned raw
surfactant as a function of adsorption time. To determine
adsorption behavior for both isotherm and kinetic aspects,
the obtained data was evaluated with four generally used iso-
therms and kinetic approaches and the required model para-
meters were determined for each type.
2. MATERIALS AND METHODS
2.1. Surfactant
As reported in previous research, the concentration of
saponins in ZSC is high while the plant is a tree commonly
found in Jordan, Iran, Iraq, and Egypt.[24] (Saponin is a
biosurfactant is derived from the leaves of ZSC.) It is worth
mentioning that the utilized leaves of ZSC were collected
from south of Iran and the saponin produced by the spray
dryer method. The total derived powder contains saponin
and flavonoids, while the powder has light brown color
and is soluble in water and alcohol. Properties of the novel
surfactant are summarized in Table 1.[20–23]
2.2. Adsorbent
Crushed quartz purchased from Mojalali Company
(Iran) with 99.9% purification. The powdered or crushed
rock was prepared by crushing the corresponding solid
core with a maximum size determined by passing the
crushed quartz through a standard Number 50-70 sieve.
2.3. Preparation of Surfactant Solution
The stock solution of proposed natural surfactant with
concentrations of between 1000 mg=L and 80000 mg=L
were prepared by dissolving 0.10–8 g of the surfactant in
100 mL double distilled water in a container. These solu-
tions were then diluted to get standard solutions containing
1000, 5000, 10000, 15000, 20000, 40000, 50000, 60000,
70000, and 80000 mg=L of the derived natural and biode-
gradable surfactant.[20–23]
TABLE 1
Properties of derived raw surfactant from leaves
of Zyziphus spina-christi[20–23]
Product Total extract powder of Zyziphus
spina-christi
Used part Leaves
Preparation Spray dryer
Description Fine powder
Color Brown
Solubility in cold Soluble
water
Solubility in Soluble
alcohol
pH value 5.9–6.0
(10% solution)
Applications Medicine Enhanced oil recovery (EOR)
 A NEW PLANT DERIVED SURFACTANT ADSORPTION ON QUARTZ SURFACE
2.3.1. CMC Measurement
Owing to previous research, the robust approach for
determining critical micelle concentration (CMC) of the
extracted raw surfactant from leaves of ZSC was done by
the conductivity method, which uses the conductivity curve
of surfactant solutions versus corresponding surfactant con-
centration. Through the conductivity plot, the turning point
represents the CMC of the implemented surfactant. The
procedure of CMC measurement by using the conductivity
technique has been demonstrated previously by Ahmadi and
Shadizadeh.[20–23] The outcomes of the above experiments
are shown in Figure 1, which illustrates the conductivity of
aqueous solution versus relevant surfactant concentration.
2.4. Adsorption Experiment
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The depletion solution approach was utilized by
implementing an accurately weighted amount of suggested
natural surfactant to obtain equilibrium conditions with
crushed quartz solutions of different initial surfactant
concentrations lying in the span of 1000–80000 ppm. Fixed
weights of crushed quartz rock samples (8 g) were added to
a 40 mL solution of the mentioned raw surfactant while the
containers were shaken under a controlled set room
temperature. Owing to the described procedure, the gained
adsorption density versus equilibrium surfactant concen-
tration is shown in Figure 2.
It is worth bearing in mind that conductivity of surfac-
tant solution was utilized for determining surfactant
concentration before and after adsorption onto quartz rock
surfaces. After that, by putting the determined surfactant
concentration before and after adsorption process into
the following equation, the adsorption of the tested surfac-
tant concentration was determined[19–21,23]:
mtot:solution
ðC o  C Þ
q¼
103
msandstone
in which
[20–23]
FIG. 1. Conductivity versus surfactant concentration.
443
FIG. 2. Adsorption density versus equilibrium surfactant concentration.
q ¼ loss of surfactant on quartz surface, mg=g-rock;
mtot.solution ¼ total mass of solution in original bulk
solution, g;
Co ¼ concentration of surfactant throughout initial sol-
ution prior to equilibration with quartz
C ¼ concentration of surfactant throughout aqueous sol-
ution following equilibration with quartz, ppm; and
Mquartz ¼ total mass of crushed quartz, g.
3. ADSORPTION MODELS
This section demonstrates the four adsorption isotherms:
Langmuir, Freundlich, Temkin, and linear approaches;
restrictions and advantages of each adsorption model are
also discussed.
½1 3.1. Langmuir Isotherm
The Langmuir isotherm evolved was dedicated to the
main assumption that the adsorption takes place at specific
homogeneous sites in the adsorbent like as quartz sur-
face.[25,26] Moreover, when a location is engaged by a
solute-like surfactant, no further adsorption can occur at
that location while the rate of adsorption process to the
surface is corresponding to a driving force and adsorption
area.[25,26] Keep in mind that the driving force is referred to
the concentration in the surfactant solution, and the area is
referred to the amount of nude quartz surface. The Lang-
muir equation corresponding to the solid-phase surfactant
concentration qe to the equilibrium surfactant concen-
tration at a desired controlled temperature. The Langmuir
approach can be formulated as following equation which
evolved by Irving Langmuir (1916)[19–21,23,25,26]:
qo Kad Ce
qe ¼ : ½2
. 1 þ Kad Ce
 444 M. A. AHMADI AND S. SHADIZADEH

Thus, to determine Langmuir parameters such as qo and

Kad, a graph of 1=qe against 1=Ce should plotted and the
slop of fitted straight line denotes the (1=qe(Kad) and
intercept 1=qo. The examination of the surfactant adsorp-
tion data with the Langmuir approach is demonstrated
through Figure 3.

3.2. Freundlich Isotherm

The main assumption through evolving the Freundlich
adsorption isotherm in 1906 is that the adsorbent (rock
surface in this study) has a heterogeneous surface consist-
ing of various types of adsorption spots. Freundlich
illustrated that the ratio of the amount of adsorbed solute
(surfactant) onto a given mass of a rock samples to the con-
centration of the solute through the aqueous solution is not
FIG. 4. Freundlich isotherm model.
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unchanged by varying the surfactant concentration. Fitting

of experimental adsorption data certified that the multi-
layer nature of adsorption process onto the surface.[26,27]
The Freundlich adsorption isotherm presumes that the
value of Ce1=n=qe keeps consistent at a desired temperature
if the concentration of the surfactant through the aqueous
solution at equilibrium condition, Ce, is raised to the power
of 1=n, the value of the adsorbed surfactant onto rock face
denotes by qe. The Freundlich adsorption isotherm is for-
mulated as[19–21,23,26,27]:
qe ¼ Kf Ce1=n ; ½3
where 1=n and Kf represent the Freundlich constants.
Figure 4 demonstrates the evaluation of the obtained
experimental with the Freundlich approach.
3.3. Temkin Isotherm
Dedicated to several experimental investigations, Temkin
showed that the heat of adsorption would be lower in most
cases with an increase in scoop. The following represen-
tation is the linear form of Temkin isotherm[19–21,23,26,28,29]:
qe ¼ BlnKt þ BlnCe ; ½4
where B and Kt represent the Temkin constant and equilib-
rium binding constant, respectively. This approach consid-
ers indirect surfactant–quartz rock faces interactions on
adsorption isotherms. To calculate the addressed para-
meters of the Temkin approach a graph of qe versus ln(Ce)
should plotted and the isotherm constants B and Kt deter-
mined from the slope and intercept of the fitted straight line
through referred plot.[19–21,23] Analysis of the gained adsorp-
tion data of the mentioned raw surfactant with the Temkin
approach is demonstrated in Figure 5.
3.4. Linear Isotherm
If it is assumed that the adsorption isotherm for the sur-
factant is linear, the chromatographic approach turns into

FIG. 3. Langmuir adsorption model. FIG. 5. Temkin isotherm model.

 A NEW PLANT DERIVED SURFACTANT ADSORPTION ON QUARTZ SURFACE 445

investigation was conducted at room temperature (25 C) by

recording the rate of changes of the surfactant as a function
of time as illustrated through Figure 7.

4.1. Pseudo-First-order Rate Equation

Pseudo-first-order rate approach was firstly evolved
by Lagergren (1898) to determine the kinetic process of
liquid-solid phase adsorption of oxalic acid and malonic
acid onto charcoal. The main characteristic of this
approach is the Pseudo-first-order approach corresponding
to the adsorption rate on the basis of the adsorption
capacity. The pseudo-first-order equation in terms of
differential form is illustrated as follows[19–21,23,29–32]:

dqt
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FIG. 6. Linear isotherm model. ¼ K1 ðqe  qt Þ; ½6

dt

where qe and qt (mg=g) stand for the adsorption capacities

at equilibrium and time t (min), correspondingly. k1 (min 
straightforward form, which is illustrated by the Henry
1) denotes the pseudo-first-order rate constant for the
equation[19–21,23,26,30n:
kinetics approach. Dedicated to integrating Equation (6)
with the boundary conditions of qt ¼ 0 at t ¼ 0 and qt ¼ qt
qe ¼ KH Ce ½5 at t ¼ t, following formulation was developed:

where qe denotes the amount adsorbed surfactant

lnðqe  qt Þ ¼ lnðK1 qe Þ  K1 t: ½7
onto rock faces, Ce stands for the equilibrium surfactant
concentration, and KH represents a constant in units
of L=m2.
4.2. Pseudo-Second-order Kinetics Model
The linear behavior of the adsorption isotherm is limited
The differential expression of the pseudo-second-order
the specific surfactant concentration, which mostly lies on
approach is formulated as[29–32]:
the low concentration range, while at greater surfactant
concentrations, the adsorption isotherm closes to nonlinear
trend.[19–21,23] Evaluation of the adsorption data from the dqt
¼ K2 ðqe  qt Þ2 ½8
current study with the linear isotherm model is depicted dt
through Figure 6.

4. ADSORPTION KINETICS
As noted previously, another crucial aspect of the
adsorption process is kinetic evaluation of the adsorption
system, which depends on the system condition and surfac-
tant–quartz surface interaction for the current study. Raw
surfactant concentration change rate indicates the settle
time spend for finalizing the adsorption process and can
be elaborated from kinetics analysis implementing various
kinetics approaches. Owing to this fact, huge efforts
have been put forth to evolve a general formulation to rep-
resent the kinetic behavior of adsorption on solid surfaces
for the liquid–solid adsorption system. In the current
investigation, pseudo-first-order and pseudo-second-order
kinetics, intradiffusion, and Elovich models[29–32] were
implemented to determine the rate of adsorption of the
extracted raw surfactant from leaves of ZSC onto quartz FIG. 7. Adsorption of surfactant versus time for different surfactant
rock surfaces. As mentioned earlier, the adsorption kinetics concentrations.
 446 M. A. AHMADI AND S. SHADIZADEH

To gain linear form of the pseudo-second-order

approach, integrating of Equation (8) should be performed
and rearranged. The obtained linear form of the approach
developed as Equation (9), which is generally implemented
for solid–liquid adsorption systems.[29–32]

t 1 t
¼ þ ; ½9
qt K2 q2e qe

where K2 represents the pseudo-second-order adsorption

rate constant (g=mg min); and other model parameters
such as qe and qt are same as in pseudo-first-order kinetics
approach. If kinetic adsorption data follow the linear form
of pseudo-second-order approach, the estimated equilib-
rium adsorption amount qe,cal and K2 could be determined
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from the slope and intercept of the linear plot. It should be

noted that the pseudo-second-order approach is mostly
demonstrated to forecast the kinetic trend through the
entire range of the adsorption process.[29–32] The initial
adsorption rate (h) and half-adsorption time (t1=2) can be
determined by implementing Equations (10) and (11),
respectively.[19–21,23,29–32]

h ¼ K2 q2e ½10

t1=2 ¼ 1=Kqe ½11

It should be stressed here that the above-mentioned

pseudo-second-order rate approach has been actually imple-
FIG. 8. Intraparticle diffusion plot for surfactant adsorption
mented to the adsorption of metal ions, dyes, herbicides, onto quartz rock with different surfactant concentrations (a) wt%
oils, and organic materials from aqueous solutions.[33–36] [0.1,0.5,1.0,1.5,2.0]; (b) wt% [4.0, 5.0, 6.0, 7.0, 8.0].

4.3. Intraparticle Diffusion Model

In order to determine the diffusion mechanism in the
adsorption of the surfactant onto quartz rock sam-
ples[26,29–32] throughout the current study, intraparticle dif-
fusion approach (Equation (12)) was used to indicate the
diffusion mechanism and to determine the intraparticle dif-
fusion rate constant (Ki) by fitting straight line through
plot of qt versus t1=2. In the plot, the slope of linear line
represents the intraparticle diffusion rate constant (Ki).
The evolved equation of the intraparticle diffusion
approach is expressed as follows[19–21,23]:
1=2
qt ¼ K i
t : ½12
The evaluated gained results with the Intraparticle dif-
fusion approach are depicted through Figure 8, which
demonstrates rate of surfactant adsorption versus adsorp-
tion time squared. Obeying obtained adsorption data with
the intraparticle diffusion approach demonstrates that the
nature of adsorption of the natural derived surfactant on
the quartz surface follows multilinearity behavior.
4.4. Elovich’s Equation
Zeldowitsch (1934) evolved the kinetic expression of
chemisorptions process and implemented the developed
approach to demonstrate the adsorption rate of carbon
monoxide on manganese dioxide that declines exponen-
tially with a raise in the amount of adsorbed gas.[26,30–32]
The developed model is called Elovich equation as below
formula[19–21,23,26]:
dqt
¼ aebqt ; ½13
dt
where qt (mg=g) stands for the adsorption capacity at
desired time t, a (mg=g.min) represents the initial adsorp-
tion rate, and b (mg=g.min) denotes the adsorption
constant through adsorption experiment. It should be
mentioned here that the Elovich approach is widespread
performed to determine the kinetics of chemi-sorption of
gases onto solid heterogeneous systems.[26] If assumed that
the ba t> > 1, Equation (14) is evolved by implementing
 A NEW PLANT DERIVED SURFACTANT ADSORPTION ON QUARTZ SURFACE
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FIG. 9. Elovich model plot for surfactant adsorption onto quartz sur-
face with different surfactant concentrations (a) wt% [0.1,0.5,1.0,1.5,2.0];
(b) wt% [4.0, 5.0, 6.0, 7.0, 8.0].
the boundary conditions of q ¼ 0 at t ¼ 0 and q ¼ qt at t ¼ t
to result the following correlation[19–21,23,26]:
1 lnðabÞ lnðtÞ
¼ þ qt :
qt b b
Therefore, by fitting the linear form of the above
equation and adsorption data through a plot of qt versus
ln (t), the constants of the Elovich approach a and b can
be determined from the slope and intercept of the fitted
linear line as demonstrated in Figure 9.
5. RESULTS AND DISCUSSION
Adsorption equilibrium and kinetics of aqueous
solutions of raw derived surfactant from ZSC leaves onto
the quartz rock surface is explicated here through this section.
5.1. Important Parameters in Adsorption Process
Main parameters affecting extracted natural surfactant
adsorption onto quartz porous media are considered
through the current study to carry out the interaction
447
mechanism of a liquid phase and a solid phase in a specific
case explicated in this research work.
Figure 2 demonstrates the effects of initial raw surfac-
tant concentration on the amount of adsorption. As clear
be seen from Figure 2, raising the surfactant concentration
in the aqueous solution results increasing the adsorption
capacity of the mentioned surfactant onto quartz rock
faces. The increase in the concentration gradient between
the bulk and the surface of the crushed quartz rocks with
the increase in initial surfactant concentration through
aqueous solution is the main reason for this. It is worth
mentioning that, the adsorption density of the extracted
natural surfactant onto quartz rock samples is very lower
than that reported by Ahmadi and Shadizadeh[20–21,23]
for carbonate rock samples. This is due to to the negative
charges of the quartz surface, which prevents adsorption
of the surfactant by means of electrostatic repulsion forces
between hydroxyl groups of surfactant and negative
charges of rock faces.
With the aim of determining the rate of the surfactant
adsorption, the effect of contact time on robustness of
the extracted raw surfactant adsorption on quartz rock sur-
face is carried out. The implemented surfactant concentra-
tions to gain the referred goal lie on the ranges of 0.1 to
8.0 wt% while rate of the mentioned surfactant adsorption
onto quartz samples as a function of adsorption time is
determined as depicted in Figure 7. As is clearly demon-
strated in Figure 7, the initial surfactant concentrations
the maximum adsorption rates are gained almost in the 4
days for lower bound of surfactant concentrations and 6
days for higher surfactant concentration than 6 wt%. The
rate of adsorption is greater in the onset points due to a lar-
ger surface area of the quartz rock samples, which is access-
ible for surfactant molecules. The rate of adsorption
declines in final phases conceivably due to the slow pore
diffusion of the surfactant molecules into the bulk surfaces
of the quartz rock samples.
½14
5.2. Equilibrium Adsorption Models
Keep in mind that the investigation of surfactant
adsorption equilibrium plays an important role for feasi-
bility study in both technical and economical aspects of
the surfactant flooding through petroleum porous media,
which indicates the maximum amount adsorbed surfactant
per unit area or mass of the rock samples and provides an
adsorption isotherm of the study. The adsorption isotherm
is defined as a graph of the amount of adsorbed surfactant
per unit mass or unit area of the quartz rock by changing
the surfactant concentration through aqueous solution
against corresponding equilibrium surfactant concen-
tration at the surfactant–rock interface.
The gained experimental adsorption data were fitted
with the four adsorption approaches discussed in this
article. Experimental isotherm approaches were conducted
 448 M. A. AHMADI AND S. SHADIZADEH

TABLE 2
Parameters determined for different adsorption models used in this study
Isotherm Correlation Parameters

Langmuir 1=qe ¼ 0.671=Ce þ 0.5051 R2 qo Kad

0.9676
Freundlich qe ¼ 0.7181(Ce)0.7141 R2 1=n Kf
0.9815 0.7141 0.7181
Temkin qe ¼ 0.6359ln (Ce) þ 1.126 R2 Kt B
0.8827 5.875 0.6359
Linear qe ¼ 0.3544Ce þ 0.377 R2 KH C
0.9561 0.3544 0.377

at an equilibrium time for different concentration of raw as a well-known empirical equation followed very well the
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surfactant. Figures 3–6 show the obtained adsorption data
of the derived raw surfactant from leaves of ZSC onto the
quartz surface with the four isotherm models discussed
herein, while calculated parameters and correlation
coefficient of each isotherm approach are summarized in
Table 2.
As previously noted, the Langmuir constants qo and Kad
correspond to the adsorption capacity and the energy of
adsorption, correspondingly. Table 2 presents the calcu-
lated Langmuir constants Kad and qo values. Following
the experimental adsorption isotherm data, the Freundlich
approach certified that the quartz rock surface is hetero-
geneous.[26–27,29] As demonstrated earlier, by fitting the
experimental adsorption isotherm with the Frendlich equa-
tion, the required parameters can be determined and are
reported in Table 2 as are the calculated values of the
model parameters for Temkin and linear approaches.
Owing to the correlation coefficient (R2) values for the
adsorption isotherm approaches, it is inferred that nearly
all the referred approaches can forecast the equilibrium
adsorption trend of the proposed natural surfactant on
quartz surface, whereas the Freundlich isotherm approach
experimental data for the quartz surface.
5.3. Adsorption Kinetics Models
As demonstrated in Figure 7, the gained experimental
kinetics data of adsorption process indicate that the
adsorption of the surfactant was very quick at the onset
and then decreased until the equilibrium condition was
reached. As earlier discussed, the adsorption kinetic models
were connected with the surfactant adsorption rate.
Choosing an appropriate kinetic approach plays a vital role
to forecast surfactant loss rate and designing of surfactant-
based EOR process through petroleum reservoirs. As noted
in Section 4, the employed kinetic models are: pseudo-first-
order equation, pseudo-second-order equation, intraparti-
cle diffusion, and the Elovich equation, which were utilized
to determine the elite approach for extracted raw surfactant
adsorption onto quartz surface. Details of the calculated
parameters of each adsorption kinetic approaches are sum-
marized in Tables 3–6.
The fitting of the experimental kinetic adsorption data
with pseudo-first-order model is shown in Figure 10. In
addition the determined kinetic model parameters are

TABLE 3
Kinetics rate of surfactant with different concentrations on the absorbent based on the pseudo first-order
reaction
Surfactant concentration, wt% Correlation Correlation coefficient (R2)

0.5 ln(qe-qt) ¼ 0.074t  1.1379 R2 ¼ 1

2
1.0 ln(qe-qt) ¼ 0.0263t  0.4892 R ¼ 0.9953
1.5 ln(qe-qt) ¼ 0.0448t  1.7843 R2 ¼ 0.9851
2.0 ln(qe-qt) ¼ 0.0331t þ 0.5036 R2 ¼ 0.9015
4.0 ln(qe-qt) ¼ 0.014t þ 0.4322 R2 ¼ 0.9794
5.0 ln(qe-qt) ¼ 0.0181t þ 0.5107 R2 ¼ 0.9514
6.0 ln(qe-qt) ¼ 0.0306t þ 0.5529 R2 ¼ 0.9221
7.0 ln(qe-qt) ¼ 0.0156t þ 0.6947 R2 ¼ 0.8922
8.0 ln(qe-qt) ¼ 0.0215t þ 1.0687 R2 ¼ 0.8858
 A NEW PLANT DERIVED SURFACTANT ADSORPTION ON QUARTZ SURFACE 449

TABLE 4
Correlations for kinetics rate of surfactant with different concentrations on the absorbent based on
the pseudo second-order reaction
Surfactant concentration, wt% Correlation Correlation coefficient (R2)

0.1 t=qt ¼ 16.237t R2 ¼ 1

2
0.5 t=qt ¼ 3.0972t þ 4.1597 R ¼ 0.9997
1.0 t=qt ¼ 1.4998t þ 17.005 R2 ¼ 0.9905
1.5 t=qt ¼ 0.8587t þ 11.47 R2 ¼ 0.9868
2.0 t=qt ¼ 0.6628t þ 12.155 R2 ¼ 0.9803
4.0 t=qt ¼ 0.5126t þ 19.051 R2 ¼ 0.957
5.0 t=qt ¼ 0.4695t þ 9.2111 R2 ¼ 0.9843
6.0 t=qt ¼ 0.4164t þ 2.8491 R2 ¼ 0.9981
7.0 t=qt ¼ 0.3573t þ 6.8513 R2 ¼ 0.9833
8.0 t=qt ¼ 0.3185t þ 7.8057 R2 ¼ 0.9783
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TABLE 5
Correlations obtained for the kinetics rate of surfactant with different concentrations on the
absorbent based on the intraparticle-diffusion model
Surfactant concentration, wt% Correlation Correlation coefficient (R2)

0.1 q ¼ 0.0028(t0.5) þ 0.0278 R2 ¼ 0.5039

0.5 q ¼ 0.0159(t0.5) þ 0.1269 R2 ¼ 0.5979
1.0 q ¼ 0.0385(t0.5) þ 0.1415 R2 ¼ 0.7923
1.5 q ¼ 0.068(t0.5) þ 0.2239 R2 ¼ 0.8017
2.0 q ¼ 0.0897(t0.5) þ 0.2244 R2 ¼ 0.8396
4.0 q ¼ 0.114(t0.5) þ 0.1107 R2 ¼ 0.9593
5.0 q ¼ 0.1227(t0.5) þ 0.3337 R2 ¼ 0.8938
6.0 q ¼ 0.1302(t0.5) þ 0.686 R2 ¼ 0.7508
7.0 q ¼ 0.1593(t0.5) þ 0.4687 R2 ¼ 0.8873
8.0 q ¼ 0.182(t0.5) þ 0.3893 R2 ¼ 0.9248

TABLE 6
correlations for kinetics rate of surfactant with different concentrations on the absorbent based on
the Elovich model
Surfactant concentration, wt% Correlation Correlation coefficient (R2)

0.1 q ¼ 0.0106 ln(t) þ 0.0109 R2 ¼ 0.8052

0.5 q ¼ 0.0574 ln(t) þ 0.0417 R2 ¼ 0.8805
1.0 q ¼ 0.1243 ln(t) – 0.0028 R2 ¼ 0.9361
1.5 q ¼ 0.2169 ln(t) – 0.0202 R2 ¼ 0.9263
2.0 q ¼ 0.2791 ln(t) – 0.0679 R2 ¼ 0.9236
4.0 q ¼ 0.3323 ln(t) – 0.165 R2 ¼ 0.9257
5.0 q ¼ 0.3792 ln(t) – 0.0546 R2 ¼ 0.9692
6.0 q ¼ 0.4368 ln(t) þ 0.1269 R2 ¼ 0.9599
7.0 q ¼ 0.4944 ln(t) – 0.0446 R2 ¼ 0.9707
8.0 q ¼ 0.5514 ln(t) – 0.1394 R2 ¼ 0.9637
 450 M. A. AHMADI AND S. SHADIZADEH
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FIG. 10. Pseudo-first-order plot for surfactant adsorption onto
quartz surface with different surfactant concentrations (a) wt%
[0.5,1.0,1.5,2.0], (b) wt% [4.0, 5.0, 6.0, 7.0, 8.0].
reported in Table 3. The obtained experimental data
utilizing pseudo-second-order approach are illustrated in
Figure 11, and the calculated parameters of pseudo-second-
order method are demonstrated in Table 4. As can be seen
from both Figure 11 and Table 4, the pseudo-second-order
approach provides a very brilliant agreement between the
all of the experimental data and corresponding kinetic
model outcomes. Due to the calculated adsorption capaci-
ties by the pseudo-second-order method are very close to
those of real adsorption measurements, and the deviations
are less than 8%. Equation (12) was used to determine the
possibility of intraparticle transport in the current work.
If q versus t1=2 follows the linear line, then intraparticle
diffusion happens, and the other side of the intraparticle
diffusion was the sole mechanism controlling the surfactant
adsorption process onto rock surface then the linear plot
will pass through the origin.[19–21,23,26,27,29] The evaluation
of intraparticle diffusion approach for adsorption process
of the extracted natural surfactant from leaves of ZSC is
FIG. 11. Pseudo-second-order plot for surfactant adsorption onto
quartz surface with different surfactant concentrations (a) wt%
[0.1,0.5,1.0,1.5,2.0], (b) wt% [4.0, 5.0, 6.0, 7.0, 8.0].
depicted through Figure 8. The determined parameters
from the experimental kinetics data of this new plant-based
surfactant onto quartz surface dedicated to intraparticle
diffusion kinetic approach is illustrated in Table 5. By the
determined values of R2, it can be inferred that the intrapar-
ticle diffusion approach is not a suitable adsorption kinetic
model for the introduced raw surfactant in the current
study because the correlation coefficients for the evaluated
actual adsorption data were found very low and unaccept-
able (R2 < < 1).
Figure 9 demonstrates the fitting of the adsorption kin-
etic data and Elovich equation. Through this approach, a
linear relationship was determined between amount of
adsorbed raw surfactant, qt, and ln(t) over the whole
adsorption process time with unacceptable value of corre-
lation coefficients (R2 < < 1) for all the fitted lines as illu-
strated in Figure 9 and Table 6. Table 6 demonstrates the
parameters of the Elovich kinetic adsorption approach.
Figure 9 and Table 6 depict a weak relationship between
the gained adsorption data and the outcomes forecasted
 A NEW PLANT DERIVED SURFACTANT ADSORPTION ON QUARTZ SURFACE 451

by the Elovich approach as determined by Equation (13). Ce equilibrium concentration (mg=L)

As can be seen from the Figure 9, the Elovich approach Co surfactant concentration in initial solution
cannot explain the kinetics of adsorption of suggested before equilibrium (ppm)
natural surfactant onto quartz rock faces. Thus, a suitable h initial kinetics rate (mg=g)
kinetics reaction approach is needed to spell out the Kf Freundlich constant
kinetics of the derived raw surfactant onto quartz rock Kt equilibrium binding constant correspond-
surface. ing to the maximum binding energy
(L=mg)
KH constant in linear model (L=m2)
6. CONCLUSIONS K1 Pseudo-first-order rate constant
The adsorption of plant-based surfactant extracted from K2 Pseudo-second-order adsorption rate con-
leaves of ZSC onto quartz surface from aqueous solutions stant (g=mg min)
was scientifically investigated. Experimental studies were Mquartz total mass of crushed quartz (g)
conducted to diagnose the adsorption equilibrium and mtot.solution total mass of solution in original bulk sol-
kinetics behaviors of the natural surfactant onto quartz ution (g)
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rock faces. Owing to the obtained adsorption results, the n Freundlich constant
following conclusions can be drawn: q adsorption capacity (mg=g-rock)
1. Adsorption variables for the Freundlich, Langmuir, qe equilibrium adsorption (mg=g-rock)
Temkin, and linear approaches were determined by fitting qo adsorption capacity in Langmuir model
the approaches with measured adsorption data. Owing to (mg=g-rock)
the correlation coefficient of the outcomes of the studied R universal gas constant (J=mol.K)
models for both isotherm and kinetic approaches, results T Temperature (K)
were best demonstrated by the Freundlich model and t time (hours)
pseudo-second-order approach, respectively. t1=2 half-adsorption time (hours)
2. The Freundlich equilibrium adsorption exhibited a bril- Greek Letters
liant agreement between the obtained measured adsorp- a initial adsorption rate for Elovich model
tion data of the surfactant onto quartz particles and (mg=g.min)
Freundlich outcomes with R2 ¼ 0.9815. Furthermore, b adsorption constant for Elovich model
the pseudo-second-order kinetics approach provided (mg=g.min)
acceptable forecasts of the kinetics of surfactant adsorp- C surfactant adsorption on rock surface
tion on the quartz rock samples (R2 ¼ 0.98583). (mg=g-rock)
3. In light of the the obtained adsorption data with Freun- Subscripts
dlich isotherm model, the adsorption of the derived ad adsorption
natural surfactant onto quartz rock samples has hetero- e equilibrium
geneous and multilayer behavior. f Freundlich
4. The main mechanism proposed by the current study due o maximum capacity of adsorption
to the structure of the rock phase and surfactant is hydro-
gen bonding between hydrogen and the oxygen of the sil-
ica groups. Extracted saponin has many hydroxyl
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