Journal of Environmental Chemical Engineering 5 (2017) 5921–5932

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Journal of Environmental Chemical Engineering

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Research Paper

Adsorption of methylene blue, crystal violet and congo red from binary and MARK
ternary systems with natural clay: Kinetic, isotherm, and thermodynamic
⁎
Safae Bentahar , Abdellah Dbik, Mohammed El Khomri, Noureddine El Messaoudi,
⁎
Abdellah Lacherai
Ibn Zohr University, Faculty of Science, Department of Chemistry, Laboratory of Applied Chemistry and Environment, BP 8106, 80000,Agadir, Morocco

A R T I C L E I N F O A B S T R A C T

Keywords: The adsorption of Methylene Blue (BM), Crystal Violet (CV) and Congo Red (CR) onto natural clay from Agadir
Clay region in the binary and ternary system was carried out. All the parameters influencing the adsorption of three
Adsorption dyes were studied namely effect of percentage, contact times (20–120 min), initial dye concentration
Isotherms (100–600 mg L−1), temperature (22–50 °C), and dye solution pH (2–12). The obtained results showed that the
Dye
adsorption of MB, CV, and CR is highly dependent on the initial dye concentration, the temperature, and the dye
Kinetic
Ternary system
solution pH. The kinetic study was performed by applying two kinetic models, the pseudo-first-order and the
pseudo second-order. According to the obtained results, the pseudo-second-order model is better described the
adsorption of dyes onto natural clay. The adsorption isotherms were studied such as Langmuir, Freundlich, the
obtained results indicate that the adsorption followed the Langmuir model with correlation coefficients which
are very close to 1. The maximum adsorption capacities for three dyes are 202.13 mg g−1 for MB (MB + CV),
289.59 mg g−1 for MB (MB + CR), 281.31 mg g−1 for MB (MB + CV + CR), 179.28 mg g−1 for CV (CV + MB),
289 mg g−1 for CV (CV + CR), 280.61 mg g−1 for CV (CV g MB + CR), 253.53 mg g−1 for CR (CR + MB),
240.06 mg g−1 for CR (CR + CV) and 264.54 mg g−1 for CR (CR + MB + CV). The thermodynamic study
showed that the adsorption of dyes in the binary and ternary system is spontaneous, physical and endothermic.

1. Introduction
The presence of dyes in textile effluents can pose a serious en-
vironmental menace when they are discharged into biosphere without
previous treatment or with an insufficient level of treatment [1–4].
Treatment will therefore be essential to remove these dyes which are
harmful to the environment [5–7]. Several techniques have been de-
veloped to remove dyes from wastewater such as coagulation/floccu-
lation [8,9], oxidation/ozonation [10], membrane separation [11,12],
photodegradation [13] et biological process [14], but most of these
conventional methods are beginning to prove insufficient for simple
and effective treatment, in addition they are very expensive [15]. It is
necessary to think about effective techniques and inexpensive. Ad-
sorption onto activated carbon has been recognized as one of the best
techniques for the treatment polluted water by organic and inorganic
materials, because the activated carbon has a high adsorption capacity
due to its large surface area [16,17], but activated carbon remains very
expensive and onerous [18]. Consequently, the treatment of water by
adsorption onto natural materials such as clays responds to this
constraint in an efficient and economical manner. Clays are now con-
sidered as interesting adsorbent materials, due to their low-cost, their
abundance in nature, their small size (less than 2 μm), their high spe-
cific surface area, high cation exchange capacity and high chemical
stability [19,20]. Consequently, these minerals are considered as nat-
ural wells to be facing to organic and inorganic pollutants.
Our main objective is to apply our support as an effective adsorbent
to treat textile effluents, which contains different types of dyes namely
cationic, anionic, and neutral. In this context, we have tested the ef-
fectiveness of our adsorbent which has several advantages such as its
availability and low cost because it requires no treatment, in the mix-
ture of dyes in a binary and ternary system. In our work, we chose three
dyes, Methylene Blue, Crystal Violet (cationic type), and Congo Red
(anionic type) as model dyes (Fig. 1), because of their harmful effects
on health and the environment. Methylene Blue is much used in textile,
printing, dyeing wood and strainers for medicinal surgery [21–23].
Crystal Violet dye is widely used in coloring paper, cotton and silk [24],
it is also employed in animal and veterinary medicine as a biological
stain [25]. Congo Red is employed as colorants in textiles, printing,

⁎
Corresponding author.
E-mail addresses: safae.bentahar@edu.uiz.ac.ma (S. Bentahar), abdellah.dbik@edu.uiz.ac.ma (A. Dbik), mohammed.elkhomri@edu.uiz.ac.ma (M.E. Khomri),
noureddine.elmessaoudi@edu.uiz.ac.ma (N.E. Messaoudi), a.lacherai@uiz.ac.ma (A. Lacherai).

https://doi.org/10.1016/j.jece.2017.11.003
Received 6 August 2017; Received in revised form 9 October 2017; Accepted 1 November 2017
2213-3437/ © 2017 Elsevier Ltd. All rights reserved.
S. Bentahar et al.
dyeing, paper, and plastic industries and also as the indicator of pH
[26–28]. This dye can cause cancer, vomiting, jaundice, skin irritation,
diarrhea in human beings [29–35]. For this reason, we have carried out
the adsorption of MB, CV, and CR onto the clay to evaluate the behavior
of these three dyes in binary and ternary mixtures. We studied all the
parameters influencing the adsorption of these dyes in the mixtures
such as the percentage effect, the contact time, the initial dye con-
centration, the temperature and the initial dye solution pH. The ad-
sorption isotherms, kinetic models and thermodynamic study were
performed to describe the mechanism involved in the adsorption pro-
cess.
2. Materials and methods
2.1. Materials
The natural clay was collected from Agadir region and was crushed
to obtain clay with a diameter less than 50 μm [36]. Methylene Blue
(MB) is a cationic dye, the molecular formula C16H18ClN3S·3H2O, a
molar mass of 373.90 g mol −1 and a maximum absorbance is equal
661 nm. Crystal Violet (CV) is a cationic dye, the chemical formula
C25H30ClN3, a molar mass 407.979 g mol−1, and a maximum absor-
bance is 589.5 nm. Congo Red (CR) is an anionic diazo dye, the che-
mical formula C32H22N6Na2O6S2, a molar mass 696.66 g mol−1 and a
maximum absorbance is 498 nm. These three dyes were purchased from
Sigma-Aldrich and used without purification.
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Journal of Environmental Chemical Engineering 5 (2017) 5921–5932
Fig. 1. Chemical structures of dyes used.
2.2. Characterization
According to our previous study [36,37], the results of the analyzes
are:
The X-ray diffractogram shows that the natural clay is characterized
by the presence of the dolomite phase which is the majority. This phase
is confirmed by the existence of intense peaks at 21.6°, 24.01°, 30.89°,
33,46°, 37.3°, 41.11°, 43.77°, 44.85°, 49 0.21°, 50.5°, 51.06°, 58.92° (in
2θ) which may be attributable to the Miller indices:(101) (012) (104)
(006) (110) (113) (021) (202) (024) (018) (116) (211), by comparison
with the standard JCPDS No. 36-0426 (corresponding to the dolomite).
In addition, this diffractogram also shows the existence of a minority
phase corresponding to silica, whose peaks 26.64°, 35.98°, 50.13°,
56.80° (in 2θ) attributable to the Miller indices (101) (110) (112) (103)
which is in accordance with standards JCPDS No. 33–1161(Fig. 2) [36].
The FTIR spectrum shows some characteristic bands of the silica in
the zone 1250–700 cm−1. Indeed, the bands appear at 1250 and
1000 cm −1 are due to the stretching mode of Si-O and Si-O-Si re-
spectively. Silica is also justified by an intense peak at 1099 cm−1 due
to Si-O-Si stretching vibration. In addition, the bands appear at 791 and
728 cm−1 and at 474 cm−1 are attributed to the Si-O stretching vi-
bration. It remains to be noted that the absorption spectra located at
3423 cm−1 (medium intensity) and 1638 cm−1 correspond to the hy-
droxyl group OH and the deformation of the H2O molecules respec-
tively (Fig. 2) [36].
SEM analysis shows that this sample is characterized by the pre-
sence of particles having different sizes and uniform morphology. The
S. Bentahar et al. Journal of Environmental Chemical Engineering 5 (2017) 5921–5932

Fig. 2. Characterization of natural clay, (a): the XRD patterns, (b): FTIR, and (c): SEM micrographs image [36,37].

shape of the sample is dispersed and characterized by grains whose size maxCV = 589.5 nm and λ maxCR = 498 nm) by UV–vis spectro-
is between 2 and 5 μm. These grains are characterized by the presence photometer (Techcomp UV2300). Dye concentrations were calculated
of different cavities and pores which are very important for adsorbing as follows:
dyes [37]. The local analysis carried out by EDXS is in relatively good For a binary mixture of components A and B, the optical densities d1
agreement with those of X-ray diffraction (Fig. 2) [37]. and d2 were measured at λ1 and λ2 [38]:
The specific surface area was determined by application of the BET
method which is equal to which is equal to 76.971 m2 g−1, and the pore CA =
kB2 d1 − kB1 d2
diameter was calculated by Dubinin Radushkevich equation amounts to kA1 kB2 − kA2 kB1 (1)
1.69 nm. In addition, the N2 adsorption/desorption isotherms of the
natural clay were of type IV according to the International Union of kA1 d2 − kA2 d1
CB =
Pure and kA1 kB2 − kA2 kB1 (2)
Applied Chemistry (IUPAC) [36].
For a ternary mixture of components A, B and C, the optical den-
sities d1, d2 and d3 were measured at λ1, λ2 and λ3 respectively [39,40]:
2.3. Batch studies
d1 X + d2 Y + d3 Z
Cei =
The adsorption of Methylene Blue (MB), Cristal Violet (CV) and k i1 X + k i 2 Y + k i 3 Z (3)
Congo Red (CR) onto local clay in binary (BM + CV), (BM + RC) and
(CV + RC), and ternary mixture (BM + CV + RC) was carried out in a Where i = A, B or C
batch system. The adsorption of three dyes was carried out in a ther- For i = A, X = kB3kC2–kB2kC3; Y = kB1kC3–kB3kC1; Z = kB2kC1–kB1kC2
mostatic bath, by adding 0.1 g of our support into flask containing
50 mL of the mixture of two dyes (BM + CV), (BM + RC) and (CV
+ RC) or three dyes (BM + CV + RC), by varying the concentration For i = B, X = kA2kC3–kA3kC2; Y = kA3kC1–kA1kC3; Z = kA1kC2–kA2kC1
from 100 to 600 mg L−1 at different temperatures 22, 30, 40 and 50° C
in the pH range 2–12 for a time varying from 20 to 120 min. After a
For i = C, X = kA2kB3–kA3kB2; Y = kA3kB1–kA1kB3; Z = kA1kB2–kA2kB1
suitable time, the dye solution was separated from the adsorbent by
centrifugation for 15 min at 4000 rpm. The concentration of MB, CV,
and CR in binary and ternary mixtures was determined by measuring The adsorbed amounts of MB, CV, and CR were calculated by this
the absorbance at maximum wavelengths (λ maxMB = 661 nm, λ equation:

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Fig. 3. Effect of percentage of dye on adsorption of MB, CV and CR in single (a), binary (b, c and d) and ternary system (e) systems onto natural clay (adsorbent dose = 2 gL−1, C0 (MB)
= C0 (CV) = C0 (CR) = 100 mg L−1, t = 60 min, T=22 °C, pH (MB + CV)=4.24, pH (MB + CR)=5.61, pH (CV + CR)=5.55, pH (MB+CV+ CR) = 5.5, pH (MB) = 3.48, pH (CV)
= 4.28 and pH (CR) = 6.51).

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S. Bentahar et al.
Fig. 4. Effect of contact time on adsorption of MB, CV and CR onto natural clay in binary and ternary mixture (C0 (MB) = (adsorbent dose = 2 g L−1, C0 (MB) = C0 (CV) = C0 (CR)
= 100 mgL−1, T = 22 °C, pH (MB + CV)=4.24, pH (MB + CR)=5.61, pH (CV + CR)=5.55, pH (MB+CV+ CR) = 5.5, pH (MB) = 3.48, pH (CV) = 4.28 and pH (CR) = 6.51).
(C0 − Ceq)
qe = *V
m (4)
where qe (mg g−1), C0 (mg L−1), Ce (mg L−1), V (L) et m (g) are the
adsorbed amount of dye on the absorbent, the initial dye concentration,
the concentration of dye at equilibrium, volume of dye solution used
and mass of absorbent respectively.
3. Results and discussion
3.1. Effect of composition dyes on adsorption
Effect of percentage on the adsorption of MB, CV and CR dye onto
natural clay in binary (CV + MB, CV + CR and MB + CR) and ternary
mixture (CV + MB + CR) comparing with the same dyes Taken in-
dividually has been investigated by varying the percentage of MB, CV
and CR in the binary and ternary mixture with the adsorbent dose, the
initial dye concentration and the contact time have been fixed at 2 g L
−1
, 100 mg L−1 and 60 min respectively, at the room temperature and
at the initial dye solution pH. The obtained results are illustrated in
Fig. 3. These results show that in the case of a single system MB
(qe = 98.06 mg g−1) and CV (qe = 82.13 mg g−1) are better adsorbed
than CR (qe = 23.52 mg g−1). Whereas in the binary (MB + CR) and
the ternary system (MB + CV + CR), the adsorbed amount of CR in-
creased from 32.62 to 49.79 mg g−1 and from 32.25 to 49.7 mg g−1
respectively with increase in the percentage of MB and CV in the
mixture of two dyes CR + MB and CR + CV respectively, and from
47.35 to 48.57 mg g −1 in the mixture of three dyes CV + MB + CR.
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Journal of Environmental Chemical Engineering 5 (2017) 5921–5932
This increase can be explained by the interactions of the CR with MB
and CV. In the case of mixing two cationic dyes, we observed that the
adsorbed amount of MB and CV is decreased comparing with MB and
CV in the single system, this is due to the competition between MB and
CV to occupy the reaction sites on the clay surface.
In general, the two cationic dyes MB and CV are much adsorbed on
our support in the single system contrary to CR (Fig. 3a). When MB and
CV are mixed, they come in competition with a slight favor for the
minority, which is normal since the latter in low concentration, is in
front of an important free support surface.
In the case of a binary system consisting of a cationic dye (MB or
CV) and an anionic dye (CR), we observed that adsorption is selective.
Thus adsorption saturation is achieved for the dye cationic (MB or CV)
for the different compositions, which leads to an increase in the ad-
sorbed amount of the dye anionic by decreasing its percentage. This can
be explained by the interactions between the CR molecules which are
accentuated by increasing the concentration of CR, by disadvantaging
its adsorption.
3.2. Effect of contact time on adsorption
Effect of the contact time on the adsorption of MB, CV and CR dye onto
clay in binary (MB + CV, CV + CR and CR + MB) and ternary mixture
(CV + MB + CR) has been studied by varying the contact time between 20
and 120 min with 2 g L−1 at initial dye concentration of 100 mg L−1, at
room temperature, at the initial dye solution pH and with percentages 50%
MB + 50% CV, 50% MB + 50% CR, 50% CV + 50% CR, 33% MB + 33%
CV + 34% CR (Fig. 4). As shown in Fig. 4, the adsorbed amount of all dyes
S. Bentahar et al.
Fig. 5. Effect of initial concentration on adsorption of MB, CV and CR onto natural clay in binary and ternary mixture (adsorbent dose = 2 g L−1, T = 22 °C, t = 60 min, pH (MB + CV)
=4.24, pH (MB + CR)=5.61, pH (CV + CR)=5.55, pH (MB + CV + CR) = 5.5, pH (MB) = 3.48, pH (CV) = 4.28 and pH (CR) = 6.51).
in a binary and ternary mixture increases rapidly with the contact time
between the adsorbate and the adsorbent in the first stage, then it has
slowed down in the second stage until equilibrium was reached
after 60 min with adsorbed amounts which are equal to
49.97 mg g−1, 49.98 mg g−1,49 0.64 mg g−1, 49.05 mg g−1,
49.43 mg g , 49.02 mg g , 45.2 mg g , 42,99 mg g−1, and
−1 −1 −1
48.22 mg g−1 respectively for MB (MB + CV), MB (MB + CR), MB (MB
+ CV + CR), CV (CV + MB), CV (CV + CR), CV (CV + MB + CR), CR
(CR + MB), CR (CR + CV) and CR (CR + MB + CV). The increase in the
amount adsorbed in the first stage is due to the availability of the reaction
sites on the clay surface [41,42]. After a lapse of some time, all the re-
action sites progressively become occupied by the dyes and consequently,
the surface of the clay has become saturated, which implies that the ad-
sorption becomes less efficient during this second stage [43,44].
3.3. Effect of initial dye concentration on adsorption
Effect of initial dye concentration on the adsorption of MB, CV and
CR dye onto natural clay in binary and ternary mixture was studied in
the concentration range 100–600 mg L−1, adsorbent dose 2 g L−1 at
22 °C and at initial dye solution pH for 60 min. The percentages used
are 50% MB + 50% CV, 50% MB + 50% CR, 50% CV + 50% CR, 33%
MB + 33% CV + 34% CR (Fig. 5). According to Fig. 5, we have found
the amount of dye adsorbed increased as the initial dye concentration
increased [45,46]. Indeed, at binary mixtures of MB (MB + CR) and CV
(CV + CR), we observed a strong increase in the adsorbed amount from
49 0.97 to 289.59 mg g−1 and from 49.81 to 282.25 mg g−1 for MB and
CV respectively with increasing initial dye concentration from 100 to
600 mg L−1. The same results were observed at ternary mixture of MB
(MB + CV + CR) and CV (MB + CV + CR). While in the case of
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Journal of Environmental Chemical Engineering 5 (2017) 5921–5932
mixing two cationic dyes MB (MB + CV) and CV (CV + MB), we no-
ticed that the adsorbed amount increased from 49.97 to 193.13 mgg−1
and from 49.96 to 171.77 mg g−1 for MB and CV respectively. How-
ever, these adsorbed quantities are lower than those in the binary
mixture MB (MB + CR), CV (CV + CR) and ternary MB (MB + CV
+ CR) and CV (MB + CV + CR). This probably is due to the compe-
tition between CV and MB to occupy the vacant surface sites. In the case
of binary system of CR (MB + CR) and CR (CV + CR), we also observed
that the adsorbed amount of CR increases from 45.2 to 213.88 mg g−1
and from 43.61 to 207. 59 mg g−1 for (MB + CR) and (CV + CR) re-
spectively, saturation is reached after 500 mg L−1. Whereas in the
mixture of three dyes CR + MB + CV we found a strong increase in the
adsorbed amounts of CR from 48.84 to 256.71 mg g−1 comparing with
the binary mixture of CR (MB + CR) and CR (CV + CR). This can be
explained by the strong interaction of CR with CV and MB in the ternary
mixture. The increase in the adsorbed amount of all dyes in binary and
ternary system with increased the concentration can be attributed to an
increase in motive force in the driving force to transfer dye molecules
between the aqueous and solid phases [47–49].
3.4. Effect of temperature on adsorption
The temperature effect on the adsorption of MB, CV and CR dye in
binary and ternary mixture was studied at different temperature 22, 30,
40 et 50 °C, with 2 g L −1, a constant initial dye concentration of
500 mg L−1 at initial dye solution pH for 60 min. The percentages used
are 50% MB + 50% CV, 50% MB + 50% CR, 50% CV + 50% CR, 33%
MB + 33% CV + 34% CR (Fig. 6). The obtained results indicate that
the temperature has a remarkable effect on the adsorption of MB and
CV in the mixture (CV + MB) and CR in the mixture of (CR + MB),
S. Bentahar et al.
Fig. 6. Effect of temperature on adsorption of MB, CV and CR onto natural clay in binary and ternary mixture (adsorbent dose = 2 g L−1, C0 (MB) = C0 (CV) = C0 (CR) = 500 mg L−1,
t = 60 min, pH (MB + CV)=4.24, pH (MB + CR)=5.61, pH (CV + CR)=5.55, pH (MB + CV + CR) = 5.5, pH (MB) = 3.48, pH (CV) = 4.28 and pH (CR) = 6.51).
Fig. 7. Effect of initial pH on adsorption of MB, CV and CR onto natural clay in binary and
ternary mixture (adsorbent dose = 2 g L−1, C0 (MB) = C0 (CV) = C0 (CR)
= 100 mg L−1, t = 60 min).
(CR + CV) and (CR + MB + CV). Indeed, the adsorbed amount in-
creased from 177.44 to 199.44 mg g−1, from 159.99 to 183.99 mg g−1,
from 206.05 to 225.52 mgg−1, from 203.44 to 224.83 mg g−1 and from
217.42 to 229.84 mg g−1 for MB (MB + CV), CV (MB + CV), CR (CR
+ MB), CR (CR + CV) and CR (CR + MB + CV) respectively. In the
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Journal of Environmental Chemical Engineering 5 (2017) 5921–5932
case of binary mixture of MB (MB + CR) and CV (CV + CR), and at the
ternary mixture MB (MB + CV + CR) and CV (MB + CV + CR), we
observed a slight increase in the adsorbed amount. The increase of
adsorbed amount with the rise in temperature [50] is due to the in-
crease of the mobility of the dye molecules with temperature which
ensures a better connection of the dye molecules with the active sites on
the surface of clay [32,51].
3.5. Effect of pH on adsorption
The effect of pH on the adsorption behavior of MB, CV and CR dye
in binary and ternary systems was studied with 2 gL−1 of the adsorbent
dose at the initial dye concentration of 100 mgL−1 at 22 °C for 60 min.
The pH of all binary and ternary mixtures was adjusted to values be-
tween 2 and 12. The percentages used are 50% MB + 50% CV, 50%
MB + 50% CR, 50% CV + 50% CR, 33% MB + 33% CV + 34% CR
(Fig. 7). The obtained results indicate that the adsorbed amount of MB
and CV increases with the rise in pH [50,52] in the case of binary
mixtures of MB (MB + CV), MB (MB + CR), CV (MB + CV) and CV
(CV + CR), and ternary mixtures of MB (MB + CV + CR) and CV (CV
+ MB + CR). The maximum adsorption occurs at pH 12 with an ad-
sorbed amount which is equal to 53.79 mgg−1 for MB (MB + CV),
56.19 mgg−1 for MB (MB + CR), 55.99 mgg−1 for MB (MB + CV
+ CR), 49.54 mgg−1 for CV (CV + MB), 54.61 mgg−1 for CV (CV
+ CR) and 54.19 mgg−1 for CV (CV + MB + CR). The increase in the
amount adsorbed at basic pH is due to the increase of negatively
charged sites on the surface of the clay and consequently the increase in
S. Bentahar et al. Journal of Environmental Chemical Engineering 5 (2017) 5921–5932

Fig. 8. (a) Pseudo- first-order model (b) Pseudo-second-order model for adsorption of MB, CV and CR onto natural clay in binary and ternary mixture.

Table 1
Characteristic parameters of kinetic models.

Pseudo first-order kinetic model Pseudo second-order kinetic model

qe (mg g−1) K1 R2 qe (mg g−1) K2 R2

MB (with CV) 0,062 0,005 0.152 50 4 1

MB (with CR) 0,277 0,065 0.844 50 0,571 1
MB (with CV + CR) 0,224 0,023 0.511 49,751 0,288 1
CV (with MB) 0,285 0,026 0.712 49,261 0,171 1
CV (with CR) 1532 0,029 0.515 49,504 1,0201 1
CV (with MB + CR) 0,982 0,052 0.805 49,261 0,082 1
CR (with MB) 14,35 0,0409 0.916 48,309 0,004 0.999
CR (with CV) 15,62 0,067 0.697 45,045 0,004 0.998
CR (with MB + CV) 13,17 0,057 0.722 49,751 0,006 0.999

Table 2 temperature with 2 gL−1, at initial dyes concentration of 100 mgL−1

isotherms parameters for the adsorption of MB, CV and CR in single system. and initial dye solution pH for 60 min. The percentages used are 50%
MB + 50% CV, 50% MB + 50% CR, 50% CV + 50% CR, 33% MB
dye Langmuir Freundlich
+ 33% CV + 34% CR (Fig. 8).
KL Qm R 2
KF nF R2 A linear form of the pseudo-first-order kinetic model is represented
by the following equation:
MB 0.01498 279.95 0.9787 32.8996 2.5483 0.9482
CV 0.01475 231.74 0.9774 26.313 2.7193 0.9662 K1
log (qe − qt ) = logqe − t
CR 0.05671 61.12 0.9921 17.3099 4.6042 0.8878 2.303 (5)
A linear form of the pseudo-second-order kinetic model is re-
electrostatic attractions between the negatively charged surface site on presented by the following equation:
the clay and positively charged cationic dye molecules (CV and MB) t 1 1
= + t
[18]. While at acid pH we observed a decrease in the adsorbed amounts qt K2 qe2 qe (6)
of MB and CV in binary and ternary mixtures, this can be explained by
−1 −1
the competition between H+ protons and positively charged dye CV Where qt (mg g ) and qe (mg g ) represent the amount of dye ad-
and MB to occupy the reaction sites [30,53]. In the case of binary sorbed at time t and equilibrium time, respectively, k1 and k2 are the
mixture of CR with MB and CR with CV, and ternary mixture of CR with rate constants for pseudo-first and pseudo-second-order kinetic rates
MB and CV, we observed that the best adsorption of CR occurs at acidic respectively.
pH. This results in the increase in a number of positively charged sites The obtained results are summarized in Table 1.
on the clay surface at acidic pH, and consequently the increase in The obtained results indicate that the pseudo-second-order kinetic
electrostatic attractions between positively charged sites and negatively model is better described the adsorption of the three dyes in all the
charged of CR [49]. binary and ternary mixtures onto natural clay with coefficients which
are close to or equal to 1 [39,50,56,57]. In addition, the theoretical
(qe,the) values calculated by the pseudo-second-order model are very
3.6. Adsorption kinetics in binary and ternary systems close to the experimental adsorption values (qe,exp) for all mixtures.

To understand the mechanism of adsorption of MB, CV and CR dye 3.7. Adsorption isotherms in binary and ternary systems
in binary and ternary mixtures, two kinetic models were used pseudo-
first-order [54] and pseudo-second-order kinetic models [55], at room The adsorption isotherms were used to describe the adsorption

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S. Bentahar et al.
Fig. 9. Equilibrium adsorption of MB, CV and CR in single, binary and ternary systems onto natural clay.
mechanism of MB, CV and CR dye onto natural clay in binary and
ternary mixture [58]. Three models including the Langmuir [59] and
Freundlich [60] models were studied by varying the concentration in a
range of 100–600 mg L−1, at different temperatures 22, 30, 40 and
50 °C, with 2 g L−1 at initial dye solution pH for 60 min at pH (MB
+ CV)=4.24, pH (MB + CR)=5.61, pH (CV + CR)=5.55, pH (MB
+ CV + CR) = 5.5, pH (MB) = 3.48, pH (CV) = 4.28 and pH (CR)
= 6.51). The percentages used are 50% MB + 50% CV, 50% MB
+ 50% CR, 50% CV + 50% CR, 33% MB + 33% CV + 34% CR.
The Langmuir isotherm is represented as:
qm KL Ce
qe =
1 + KL Ce
−1 −1 −1
Where Ce (mg L ), qe (mg g ), qmax (mg g ) and KL (L mg )
are the concentration of dyes at equilibrium, the amount adsorbed at
equilibrium, maximum adsorption capacity, and Langmuir constant
respectively.
The Freundlich isotherm is represented as:
1/ nf
qe = KF Ce
Where qe (mg g−1), Ce (mg L−1), 1/n and KF are the amount ad-
sorbed at equilibrium, the equilibrium dye concentration in solution,
the adsorption intensity and the Freundlich constant respectively.
The obtained results are listed in Table 2.
The non-linear Langmuir and Freundlich isotherm models for MB,
CV [36] and CR [37] dyes in the single system are shown in Fig. 9.
According to the obtained results, we found that the Langmuir corre-
lation coefficients are higher than those of Freundlich (the best fit was
Journal of Environmental Chemical Engineering 5 (2017) 5921–5932
obtained at 40° C), which implies that adsorption of MB, CV, and CR on
the natural clay in single system were well-fit to the Langmuir isotherm
model and does not follow the Freundlich isotherms. And therefore the
adsorption of three dyes occurs in monolayer coverage. In addition, the
maximum adsorption capacity calculated by the Langmuir isotherm is
much closer to the experimental value of adsorption.
According to Fig. 9, we noticed that the amount adsorbed increases
with increasing concentration from 100 to 600 mg g−1 at 40 °C:
For the binary mixture of MB and CV: the adsorbed amount in-
creased from 49.97 to 202.13 mg g−1 and from 49.98 to 179.28 mg g−1
for MB and CV respectively.
For the binary mixture of MB and CR: the adsorbed amount in-
(7)
creased from 49.78 to 289.59 mg g−1 and from 48.09 to 253.53 mg g−1
−1
for MB and CR respectively.
For the binary mixture of CV and CR: the adsorbed amount increases
from 49.85 to 289 mg g−1 and from 48.1 to 240.06 mg g−1 for CV and
CR respectively.
For the ternary mixture of MB, CV, and CR: the adsorbed amount
increased from 49.97 to 281.31 mg g−1, from 48.69 to 280.61 mg g−1
(8) and from 49.22 to 264.54 mg g−1 for MB, CV and CR respectively.
Interactions between the three dyes in the binary and ternary mix-
ture were evaluated by the ratio Qm.mix/QS [61,62] (Qmmix is the
maximum adsorption capacity in binary and ternary mixtures and QS is
the maximum adsorbed amount in the single system). If Qm.mix/QS < 1,
the presence of other dyes has an inhibitory effect on the adsorption, if
Qm.mix/QS = 1 there are no interactions between the dyes and if
Qm.mix/QS > 1 the presence of other dyes has a positive effect on the
adsorption. The maximum adsorption capacities of MB, CV and CR are
5929
S. Bentahar et al. Journal of Environmental Chemical Engineering 5 (2017) 5921–5932

Fig. 10. The comparison between the experimental and calculated qeq values for MB, CV and CR in binary and ternary mixtures.

Table 3
Thermodynamic parameters of adsorption.

Dye ΔH° (kJ mol−1) ΔS° (J mol−1 K−1) ΔG° (kJ mol−1)

295,15 K 303,15 K 313,15 K 323,15 K

MB (MB + CV) 14.422 116.579 −19.985 −20.918 −22.084 −23.25

MB (MB + CR) 91.833 431.225 −35.442 −38.892 −43.204 −47.516
MB (MB + CV + CR) 39.577 291.599 −46.488 −48.82 −51.736 −54.652
CV (CV + MB) 26.779 172.714 −24.197 −25.578 −27.306 −29.033
CV (CV + CR) 40.97 304.744 −48.975 −51.413 −54.46 −57.508
CV (CV+MB + CR) 33.721 262.146 −43.65 −45.747 −48.369 −50.99
CR (CR + MB) 49.301 257.786 −26.783 −28.846 −31.424 −34.002
CR (CR + CV) 38.861 225.621 −27.731 −29.536 −31.792 −34.048
CR (CR + MB + CV) 34.577 252.395 −39.917 −41.936 −44.46 −46.984

279.95 mg g−1, 231.74 mg g−1 [36] and 61.12 mg g−1 [37].In this qi, max K a, i Ceq, i
qeq, i = N
work, when mixed two cationic dye, the ratio Qm.mix/QS is less than 1, 1+ ∑j = 1 K a, j Ceq, j
(9)
which shows a great competition between the two dyes to occupy the
active sites (antagonism effect). Whereas in the case of mixing a ca- where qmax,i, and KL,i are physical parameters of single dyes.
tionic dye with an anionic dye or two cationic dye with an anionic dye, The comparison between the experimental equilibrium data and
the ratio Qm.mix/QS was greater than 1, this is due to the presence of calculated values (qeq,exp; qeq,calc) for binary and ternary mixtures are
strong interactions between the cationic and anionic dyes (synergism shown in Fig. 10. The analysis of the obtained results shows that the
effect). extended-Langmuir model represents the experimental adsorption data
The modified Langmuir model [63] has been applied to analyze of MB, CV, and CR in the binary and ternary mixture.
interference and competition phenomena between the MB, CV and CR
dyes in the binary and ternary mixture onto the natural clay. The 3.8. Adsorption thermodynamic
modified Langmuir isotherm model is given as:
The thermodynamic study was carried out to reveal the nature of

5930
S. Bentahar et al.
the adsorption of MB, CV and CR dye onto natural clay in binary and
ternary mixtures. The thermodynamic parameters, such as the Gibbs
energy change (ΔG °) (J mol−1), the enthalpy change (ΔH °) (J mol−1)
and the entropy change (ΔS °) (J.K−1 mol−1) were determined by these
equations [56]:
ΔG° = ΔH° − TΔS° (10)
ΔG° = RTlnKa (11)
Where Ka, T (K) et R(J.mol−1 K−1) are the thermodynamic equilibrium
constant without units, the absolute temperature and the universal gas
constant (8.314 J mol−1 K−1) respectively.
Liu [64] has demonstrated the relationship between the Langmuir
equilibrium constant KL and the thermodynamic equilibrium constant
Ka, can be represented by this equation:
KL
ka =
γe (1 mol L−1) (12)
where γe is the activity coefficient at the adsorption equilibrium. Ac-
cording to the Debye-Huckel, γe is a function of the ionic strength (Ie) of
the solute at adsorption equilibrium and the charge carried by solute (z)
(log γe = −Az 2Ie1/2 ).
According to Liu [64], for neutral adsorbates or adsorbates with
weak charges, eq 12 turns to:
ΔG° ≈ − RTln[KL (1 mol L−1)] = − RTlnKL (13)
The obtained results are illustrated in Table 3. According to these
results, we have found that the value of ΔG° at different temperatures
are negative for all three dyes in the binary and ternary mixtures, in-
dicating that adsorption of MB, CV, and CR onto natural clay in all
mixtures is spontaneous [39]. The values of ΔH ° are found to be po-
sitive for all the dyes, which confirm that the adsorption is endothermic
for the three dyes [65]. In addition, the magnitude of ΔH° may give an
idea about the type of sorption. The heat evolved during physical ad-
sorption is of the same order of magnitude as the heats of condensation,
i.e., 2.1–20.9 kJ mol−1, while the heats of chemisorption generally falls
into a range of 80–200 kJ mol−1 [66]. In this study the values of ΔH °
are between 14.422 and 91.833 kJ mol−1 which implies that the ad-
sorption of three dyes should be considered as between physical ad-
sorption and chemisorption [67]. Moreover, the positive values of ΔS °
show increased randomness at the solid/liquid interface during the
adsorption of the MB, CV and CR dyes onto natural clay [68–70].
4. Conclusion
In this manuscript, the removal of MB, CV, and CR onto natural clay
in binary and ternary mixtures were performed. The obtained results
show that the effect of concentration and temperature has a positive
effect on the adsorption of three dyes in the binary and ternary mixture,
we found that optimal contact time and temperature are 60 min and
40 °C respectively with adsorbent dosage 2 gL−1. Thus the adsorption is
better at basic pH for these mixtures MB (MB + CV), MB (MB + CR),
MB (MB + CV + CR), CV (CV + MB), CV (CV + CR) and CV (CV
+ MB + CR), and at acidic pH for CR (CR + MB), CR (CR + CV) and
CR (CR + MB + CV). The kinetic study shows that the pseudo-second-
order kinetic is better described the adsorption of MB, CV, and CR with
correlation coefficients which are close to 1. The adsorption isotherms
for single system is best fitted by Langmuir isotherm with R2 = 0.9787
for MB, R2 = 0.9774 for CV and R2 = 0.9921 for CR. The maximum
adsorption capacity of MB, CV and CR are 202.13 mg g−1 for MB (MB
+ CV), 289.59 mg g−1 for MB (MB + CR), 281.31 mg g−1 for MB
(MB + CV + CR), 179.28 mg g−1 for CV (CV + MB), 289 mg g−1 for
CV (CV + CR), 280.61 mg g−1 for CV (CV + MB + CR),
253.53 mg g−1 for CR (CR + MB), 240.06 mg g−1 for CR (CR + CV)
and 264.54 mg g−1 for CR (CR + MB + CV). The thermodynamic
study indicates that the adsorption is spontaneous, physical and
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Journal of Environmental Chemical Engineering 5 (2017) 5921–5932
endothermic. Based on the obtained results in this work, we can con-
clude that the natural clay from Agadir region can be considered as a
good material for the removal of MB, CV and CR dyes in binary and
ternary mixtures, due to their availability, their efficiency and also low
cost. All the results obtained are encouraging to use our support on an
industrial scale.
Conflict of interest
None declared.
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