Arabian Journal of Chemistry (2018) 11, 615–623

King Saud University

Arabian Journal of Chemistry

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ORIGINAL ARTICLE

Adsorption thermodynamics of cationic dyes

(methylene blue and crystal violet) to a natural clay
mineral from aqueous solution between 293.15 and
323.15 K
Omer Sakin Omer a,b, Mohammed Ali Hussein b, Belal H.M. Hussein a,c,
Arbi Mgaidi a,d,*

a
Chemistry Department, Faculty of Sciences and Arts, Al Ula Branch, Taibah University, Saudi Arabia
b
Department of Industrial and Applied Chemistry, Faculty of Pure and Applied Science, International University of Africa, Sudan
c
Department of Chemistry, Faculty of Science, Suez Canal University, Ismailia, Egypt
d
University Tunis El Manar, Faculty of Sciences, Chemistry Department, Tunisia

Received 23 August 2017; accepted 26 October 2017

Available online 4 November 2017

KEYWORDS Abstract Wastewater from dyestuff production is one of the main water pollutants. Several meth-
Adsorption; ods have been applied for the remediation of contaminated water. Currently, adsorption using a
Cationic dyes; cheap, abundant, and environmental-friendly adsorbent such as natural clay is the simplest and
Illitic clay; most useful method. This study aimed to determine the enthalpies of adsorption of the organic
Temperature effect; cationic dyes, methylene blue (MB) and crystal violet (CV), from polluted water onto a natural clay
Enthalpies of adsorption mineral. Early on, we performed mineralogical and textural analyses of a clay sample using various
techniques, namely X-ray diffraction, scanning electron microscopy/energy dispersive X-ray spec-
troscopy, Brunauer-Emmett-Teller analysis, Fourier-transform infrared spectroscopy, and differen-
tial scanning calorimetry, before and after adsorption. The experimental results showed that this
adsorbent is a mesoporous and non-swelling clay with illite and kaolinite as the major components.
The effects of various parameters such as contact time, pH, and temperature were examined. The
experimental data were analyzed using the linear forms of the Langmuir and Freundlich isotherm
models and showed a good fit with the Langmuir equation for MB adsorption. Thermodynamic
parameters such as the changes in Gibbs free energy, enthalpy, and entropy were determined from

* Corresponding author at: Chemistry Department, Faculty of Sciences and Arts, Al Ula Branch, Taibah University, Saudi Arabia.
E-mail addresses: omsakin@gmail.com (O. Sakin Omer), moalhu01@gmail.com (M.A. Hussein), Belalhussein102@yahoo.com (B.H.M.
Hussein), amgaidi@taibahu.edu.sa (A. Mgaidi).
Peer review under responsibility of King Saud University.

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This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
616 O. Sakin Omer et al.

batch experiments. Results revealed that the adsorption of MB onto illitic clay was endothermic,
while that of CV was an exothermic and spontaneous process.
Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an open access article
under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction Fourier transform infrared (FTIR) spectroscopy, and differen-

More than 1000 types of dyes are commercially available and
widely employed in the pharmaceutical, food, cosmetics, plas-
tics, photography, paper, and textile industries. The textile
dyeing industry consumes large volumes of clean water, which
places it in the forefront of the polluters (Abidi et al., 2015).
Currently, more than 7
105 tons of dyestuffs are produced
annually and a significant fraction is discharged directly in
aqueous effluents. The presence of colored effluents in an
aquatic ecosystem reduces the penetration of sunlight to ben-
thic organisms, thus hindering the process of photosynthesis.
Dyes can be classified into three types according to their
nuclear structures: anionic dyes (acidic and reactive), nonionic
dyes (disperse), and cationic dyes (basic) (Robinson et al.,
2001). Organic cationic dyes like methylene blue (MB) and
crystal violet (CV) are considered more toxic than anionic ones
(Gao et al., 2016). In general, those dyes adsorb on clay in
amounts higher than the cation exchange capacity (CEC max-
imum number of cations adsorbed on the clay). Previous stud-
ies (Rytwo and Ruiz-Hitzky, 2003) have concluded that clay-
dye interactions at the adsorbent surface are endothermic
while dye-dye interactions are exothermic. The enthalpy of
adsorption may be derived from adsorption experiments at dif-
ferent temperatures or measured directly by using the
microcalorimetric technique. For MB-mineral clay-aqueous
solution and CV-mineral clay-aqueous solution systems, ther-
modynamic data, i.e. DG, DH, and DS, evaluated using these
two methods, are divergent and sometimes contradictory with
respect to the nature of the adsorption phenomena of the dyes
onto the clay mineral surface (see Table 1). Accurate determi-
nation of these parameters is useful for the design of adsorp-
tion unit operations and for successful implementation of
adsorption technology. In general, adsorption is a less
energy-intensive unit operation (Gopinathan et al., 2017),
and it is well known that |DG| range between 0 and 20 kJ/mol
for physical processes and that |DG| is 20 kJ/mol for chemi-
cal reactions. Numerous factors can affect the enthalpy of
adsorption of a cationic dye onto natural clay such as the
structure of the adsorbent, the extent of hydration, and their
negatively charged layers. Clay minerals that have been tested,
adsorbed organic cationic dyes with maximum adsorption
capacities between 10 and 370 mg/g, but increasing the temper-
ature produced a swelling effect. This effect facilitates the dif-
fusion of dyes into the internal structure of the clay. On the
other hand, the adsorption of MB onto natural clay has been
reported to be an athermal process (Hajjaji and Alami, 2009)
and less influenced by increases in temperature (Elmoubarki
et al., 2015). The main objective of this study was to investigate
the effect of temperature on the adsorptions of cationic dyes
MB and CV onto a natural clay mineral. For this purpose,
mineralogical and textural analyses of a clay sample were per-
formed using X-ray diffraction (XRD), scanning electron
microscopy (SEM), Brunauer-Emmett-Teller (BET) analysis,
tial scanning calorimetry (DSC), and some operating experi-
mental factors such as contact time, pH, and adsorbent dose
were studied using a batch-contact-time method.
2. Experimental
2.1. Materials
Methylene blue (C.I.52015, chemical formula C16H18ClN3S,
mol. wt. = 319.86, kmax = 664 nm) and crystal violet (C.I.
42555, chemical formula C25H30N3Cl, mol. wt. = 407.99, sol-
ubility in water = 16 g/L at 25 °C, kmax = 590 nm) were pur-
chased from Sigma Aldrich. All chemicals were used as
received. The structures of the dyes are given in Fig. 1. Raw
clay sample was purchased from AlMarwani for Spices Com-
pany, Saudi Arabia. A certain amount of the clay was sus-
pended in a 1 M NaCl solution at a 5% clay-to-solution
ratio, and the suspension was agitated for 12 h using a
mechanical stirrer. The suspended solid was separated from
the solution by centrifugation for 10 min at 4000 rpm using a
Hettich EBA 20 centrifuge, dried in an oven for 72 h at 60
°C, ground, and sieved to obtain a fine texture.
2.2. Characterization of adsorbent
The clay was characterized using a powder X-ray diffractome-
ter (Phillips Xpert-pro) between 2h values of 5° and 60° using
Cu Ka radiation. The microstructure of the adsorbent was
examined using a JEOL JED2200 series apparatus coupled
with an energy dispersive X-ray detector. The specific surface
areas and pore size distribution were estimated through N2
physisorption at 77 K by applying the BET equation on a
Micromeritics ASAP2000 apparatus. The sample was degassed
at 373 K for 1 h prior to BET measurements. FTIR spectra in
the 4000–400 cm1 region were obtained for the samples
before and after adsorption using a Thermo Scientific spec-
trometer with a deuterated triglycine sulfate (DTGS) detector
and a KBr splitter. The KBr pressed disc technique (1 mg of
sample and 200 mg of KBr) was used. Spectra were manipu-
lated using the OMNIC software package (Thermo Instru-
ments Corp.). Finally, raw sample and two samples after dye
adsorption were also examined using DSC under an air atmo-
sphere using a Shimadzu DSC-60 detector. The heating rate
was 2 °C/min.
2.3. Batch equilibrium studies
Batch equilibrium investigations were carried out using a set of
Erlenmeyer flasks (50 mL) with 25 mL of dye solutions at dif-
ferent temperatures (20 °C, 30 °C, 40 °C, and 50 °C). Initially,
batch experiments were performed at 30 °C to study the effects
of contact time, pH, and adsorbent dose. The optimal condi-
 Adsorption thermodynamics of cationic dyes (methylene blue and crystal violet) to a natural clay mineral
Table 1 Reported DG°, DH°, and DS° values from literature.
Dye Clay mineral used Nature DG° kJ/mol DH° kJ/mol DS° J/(molK) T range °C Ref.
Methylene Montmorillonite Endo +3.9 Cal.a Rytwo and Ruiz-Hitzky (2003)
blue(MB) (Na,Ca)0.3(Al,Mg)2Si4O10(OH)2nH2O
Kaolinite Endo 0.27 to 1.72 +14.11 +48.13 25–55 Gopinathan et al. (2017)
Al2Si2O5(OH)4
Montmorillonite Endo 6.70 to 19.0 +145.0 +492 35–60 Almeida et al. (2009)
Bentonite Endo 17.0 to 19.4 +9.21 +92.2 10–35 Hong et al. (2009)
(Al,Mg)8(Si4O10)4(OH)812H2O
Smectite No effect 15–35 Hajjaji and Alami (2009)
(Na,Ca)0.3(Al,Mg)2Si4O10(OH)2nH2O
Sepiolite Endo – +56.28 – 30–60 Özdemir et al. (2006)
Mg4Si6O15(OH)26H2O
Illite associated with chlorite Exo +0.318 to + 1.42 7.5 27.4 10–50 Elmoubarki et al. (2015)
(K,H3O)(Al,Mg,Fe)2(Si,Al)4O10[(OH)2,(H2O)]/
(Fe,Mg,Al)6(Si,Al)4O10(OH)8
Illite/kaolinite Exo 2.3 to 0.75 13.6 40.3 10–50 Elmoubarki et al. (2015)
(K,H3O)(Al,Mg,Fe)2(Si,Al)4O10[(OH)2,(H2O)]
Montmorillonite associated with nontronite Exo 20–40 7.99 20–60 Gürses et al. (2006)
Ky(Fe3+,2  xAlx)(Si4yAly)O10(OH)2nH2O Endo 40–60 (isosteric enthalpy)
Crystal violet Montmorillonite Exo 13.5 Cal.a Rytwo and Ruiz-Hitzky (2003)
Kaolinite Exo 4.11 to 4.48 0.235 +13.14 22–50 Nandi et al. (2008)
Pyrophyllite Endo 10.1 to 12.2 +9.28 +66.37 20–50 Miyah et al. (2016)
Al2(Si4O10)(OH)2
Bentonite Exo 4.41 to 0.64 83.81 260.0 22–36 Eren and Afsin (2008)
Montmorillonite Exo 3.63 to 2.06 18.97 52.38 20–50 Kumar et al. (2016)
Sepiolite Exo 1.3 to 0.46 18.79 60.0 22–36 Eren and Afsin (2007)
Mixed clay (kaolinite + pyrophyllite) Exo 19.5 to 18.0 25.59 9.77 30–50 Monash and Pugazhenthi (2009)
a
Cal.: Determined directly using calorimetric measurements.

617
618
3C H + CH3
N S N -
Cl
CH3 CH3
Fig. 1 Structures of (a) methylene blue and (b) crystal violet.
tions were a pH of 7.0, contact time of 180 min, and adsorbent
dose of 0.5 g per liter of dye solution for MB, while for CV, the
optimal pH and contact time were 7.5 and 180 min, respec-
tively. The flasks were placed in a shaker and the solutions
were shaken until equilibrium time, at which the flasks were
removed from the shaker and the solutions were centrifuged
at 4000 rpm for 20 min. The supernatant was analyzed using
an ultraviolet–visible (UV–Vis) spectrophotometer at k =
664 nm for MB and k = 590 nm for CV.
2.4. Calculation
The amount of dye adsorbed by the clay in each time interval,
t, was calculated according to the following mass balance
equation:
V
qe ¼ ðC0  Ce Þ
ð1Þ
m Fig. 4 shows the FTIR spectra of the adsorbent samples before
where qe is the amount of dye adsorbed per unit weight of clay
(mg/g), C0 and Ce are the initial and equilibrium dye concen-
trations (mg/L), respectively, V is the volume of the solution
(L), and m is the dry weight of the clay (g).
3. Results and discussion
3.1. Characterization of the adsorbent
XRD patterns of clay samples (washed and unwashed sam-
ples) are shown in Fig. 2. The two samples show the character-
Fig. 2 Results of XRD analyses of the clay mineral samples
used.
O. Sakin Omer et al.
istic (0 0 1), (0 0 2), and (0 0 3) peaks of illite and kaolinite,
which indicates that illite and kaolinite are the dominant clay
minerals with a small amount of quartz.
Morphological characterization of the adsorbent using a
field emission scanning electron microscope revealed an irreg-
ular texture and porous cavities on the surface (see Fig. 3).
The specific surface area (SBET), average pore size by BET,
and total pore volume of the clay obtained from N2
adsorption-desorption isotherms at 77 K were 128 m2/g, 75.6
Å, and 0.320 cm3/g, respectively. Investigation of the pore size
distribution using Barrett-Joyner-Halenda (BJH) analysis
showed that the pore size distribution was in the mesopore
range (5–50 nm) with a significant contribution from pores
40 nm in diameter. Our results are in agreement with those
published for an illitic clay sample (Ghorbel-Abid et al., 2010).
FTIR analysis was conducted to evaluate the roles of func-
tional groups on the clay surface in the adsorption process.
and after dye adsorption. A broad band at 1024 cm1 is char-
acteristic of SiAO stretching vibrations. The peaks for the OH
stretching of hydroxide groups coordinated to Al3+ ions are
located at 3697 and 3614 cm1while the peak for the OH
deformation of water is located at 1630 cm1. New bands were
observed at 1340, 1370, and 1595 cm1 after the dyes were
adsorbed. These bands could be assigned to ACANA,
AC‚NA, and AC‚CA stretching in polyheterocycles. These
bands could be used as evidence for the adsorption of the dyes
on clay.
In the DSC curves (see Fig. 5), there is an endothermic peak
at around 90 °C for the clay before adsorption, which can be
assigned to the loss of adsorbed water. After adsorption, we
observed two exothermic peaks at around 260 °C for MB
and 370 °C for CV. For CV, our observation is in agreement
with previous work (Eren and Afsin, 2008). The exothermic
oxidation of the dye under an air atmosphere is the principal
thermal reaction in this temperature range.
3.2. Effects of contact time and pH
The effect of contact time on the adsorptions of MB and CV at
30 °C is illustrated in Fig. 6. It appears that a rapid initial
uptake occurs and equilibrium is reached in less than 50 min.
For both MB and CV, the adsorption is very rapid in the
first 5 min and then becomes slower until equilibrium is
reached. The rapid initial increase in the amount of adsorbed
dye may be due to an increase in the number of vacant sites
available at the beginning. The adsorption behaviors of MB
Adsorption thermodynamics of cationic dyes (methylene blue and crystal violet) to a natural clay mineral
Fig. 3 SEM images of clay sample.
Fig. 4 FTIR spectra: raw clay, clay after CV adsorption, and
clay after MB adsorption.
Fig. 5 DSC curves: raw clay, clay after CV adsorption, and clay
after MB adsorption.
and CV on the clay were studied over a wide pH range of 3–12.
Fig. 7 shows the effect of initial pH on the removal of MB and
CV by clay. A reduction in the amount adsorbed was observed
for both dyes as the pH decreased. The lower adsorptions of
MB and CV at acidic pH values are probably due to the pres-
ence of excess H+ ions competing with the dye cations for the
adsorption sites. At a higher pH (pH > 7), the clay surface will
619
Fig. 6 Effect of contact time on the adsorptions of MB and CV
by a clay mineral (adsorbent dose = 1 g/L, T = 30 °C, pH = 7.5
for CV and pH = 7 for MB).
be more negatively charged, facilitating association between
the cationic dyes and the adsorbent surface.
3.3. Effects of initial concentration and temperature on
adsorption
The effect of the initial concentration of the dye solution on
the adsorptions of MB and CV onto clay is illustrated in
Fig. 8. It was observed that the adsorption of MB decreased
as the concentration of the dye solution increased from 90 to
300 mg/L. It was also noted that the adsorption of MB was
not favored at high temperatures (see Fig. 8a). In contrast,
the adsorption of CV increased with increasing dye concentra-
tion and is favored at high temperatures (see Fig. 8b).
The difference between these isotherms is probably due to
the different adsorption mechanisms of the two monovalent
organic cationic dyes (Rytwo et al., 1995). Those studies con-
cluded that the interactions between CV molecules and natural
clay differ in certain aspects from those between MB and clay
due to the amount of charged complexes formed between two
dye molecules (monomer, dimmer or trimer). The aggregation
of MB molecules in solution also reduces its adsorption on the
clay. But, at low temperature, there is competition between
MB molecules and water molecules in the inter-lamellar spaces
620 O. Sakin Omer et al.

Fig. 7 Effect of solution pH on the adsorptions of MB and CV by a clay mineral (adsorbent dose = 1 g/L, time = 120 min, T = 30 °C).

(a) Methylene Blue (b) Crystal Violet

Fig. 8 Effects of initial concentration and temperature on the adsorption of the dyes onto illitic clay.

of clay and it is well known that the adsorption of water mole-
cules on a solid is higher at lower adsorption temperature.
The experimental data were analyzed using the Langmuir
and Freundlich isotherm models. The linear forms of these
equations are as follows:
Ce 1 1
¼
Ce þ
qe qmax kL
qmax
1 Kumar et al., 2016; Auta and Hameed, 2012). The calculated
Lnðqe Þ ¼
LnðCe Þ þ LnðkF Þ
n
where qmax, kL,n, and kF are the constants for the Langmuir
and Freundlich models.
Fig. 9 shows the Langmuir and Freundlich plots for the
adsorptions of MB and CV onto illitic clay at 20 °C, 30 °C,
40 °C, and 50 °C. This figure shows that the Langmuir
approach accommodated the equilibrium data well, with a
high correlation coefficient (R2), as shown in Table 2. A similar
result was obtained in a previous investigation (Al-Futaisi
et al., 2007). The authors found that the Langmuir model
described the equilibrium adsorption data well for MB adsorp-
tion and the Freundlich model was effective for CV adsorption
onto palygorskite.
The results in Table 2 also show that an increase in temper-
ature resulted in a decrease in the maximum adsorption of
MB. At 50 °C, the Langmuir monolayer capacity, qmax, is
62.5 mg/g. This result is in agreement with previous results
(Özdemir et al., 2006; Elmoubarki et al., 2015). For CV
adsorption, qmax appears to be temperature independent.
ð2Þ The parameters kL, n, and kF are also on the same orders of
magnitude as those reported in literature (Gao et al., 2016;
ð3Þ Langmuir constant (kL) and Freundlich constant (n) can be
interpreted as the free energy of adsorption and the adsorption
intensity, respectively. High kF values reflect a high adsorption
capacity of the adsorbent.
Thermodynamic studies are an essential component of
proposing adsorption mechanisms (e.g., chemical and physi-
cal). To calculate the thermodynamic parameters, we used
the following equation:
DG ¼ RT ln K ð4Þ
where R is the constant of perfect gas (R = 8.314 J/mol. K), T
is the absolute temperature of solution (K), K° is the standard
equilibrium constant, which is a dimensionless parameter
(without units).
Adsorption thermodynamics of cationic dyes (methylene blue and crystal violet) to a natural clay mineral 621

Fig. 9 Langmuir and Freundlich plots of the adsorptions of MB and CV onto illitic clay at 20 °C, 30 °C, 40 °C, and 50 °C: (a) Langmuir
plot for MB adsorption; (b) Langmuir plot for CV adsorption; (c) Freundlich plot for MB adsorption; and (d) Freundlich plot for CV
adsorption.

Table 2 Fitted isotherm parameters and their goodness of fit to the adsorption data.
Dye Parameter qmax (mg/g) KL (L/mg) kF (mg11/ng1L1/n) n R2 Langmuir R2 Freundlich
Methylene blue T = 293.15 K 100.0 0.0649 494.2 5.7 0.99 0.88
T = 303.15 K 76.9 0.0425 1075.9 3.1 0.98 0.93
T = 313.15 K 71.4 0.0375 1314.1 2.7 0.98 0.95
T = 323.15 K 62.5 0.0320 2024.5 2.1 0.97 0.97
Crystal violet T = 293.15 K 330.0 0.0492 150.3 3.95 0.98 0.98
T = 303.15 K 330.0 0.0612 214.2 5.12 0.99 0.96
T = 313.15 K 330.0 0.0857 1314.1 5.88 0.99 0.96
T = 323.15 K 330.0 0.0789 2024.5 6.06 0.98 0.96
622 O. Sakin Omer et al.

Table 3 Thermodynamic constants for the adsorption of cationic dyes on illite + kaolinite clay at various temperatures (time = 3 h,
pH = 7–7.5, and adsorbent dose = 0.5 g/L).
Dye T (K) DG (kJ/mol) DH (kJ/mol) DS (J/(molK))
Methylene blue 293.15 +6.75 +6.5 (+3.9) a
23.0
303.15 +6.98
313.15 +7.2
323.15 +7.44
Crystal violet 293.15 8.31 9.8 (13.5)a +28.5
303.15 8.63
313.15 8.90
323.15 9.25
a
Values are from Rytwo and Ruiz-Hitzky (2003).

The relationship between DG°, DH° and DS° is given by:
   adsorption of MB to illitic-kaolinite natural clay is better mod-
DG ¼ DH  TDS ð5Þ
Substituting Eq. (4) into Eq. (5), we obtained the well-known
vant’Hoff equation:
DH 1 DS
ln K ¼
þ ð6Þ
R T R
K° is related to the Langmuir constant kd(qe/Ce) which is
dimensional with common units (L/mg) and can be calculated
as follows (Sakin et al., 2017; Tran et al., 2017):
q mechanism for both monovalent cationic dyes adsorption onto
K ¼ e
MAdsorbate
C0 ð7Þ
ce
where qe is the amount of dye adsorbed per unit mass of the
clay, Ce is the equilibrium dye concentration (mg/L), M is
the molecular weight of the adsorbed species, and C° is the
concentration of the solution in the chosen standard state
(C° = 1 mol/L).
The values of the thermodynamic parameters determined in
this study are summarized in Table 3. The enthalpy of adsorp-
tion of MB, +6.5 kJ/mol, indicates that the process is
endothermic and is on the same order of magnitude as those
reported in the past (Rytwo and Ruiz-Hitzky, 2003;
Gopinathan et al., 2017; Hong et al., 2009). The negative val-
ues of DS° for MB adsorption suggest a decrease in random-
ness at the solid/solution interface, whereas the positive
value of DS° as a result of CV adsorption corresponds to an
increased degree of freedom in the system and indicates high
affinity of the adsorbent for CV molecules. The negative value
of DH°, 9.8 kJ/mol, indicates an exothermic adsorption pro-
cess for CV. From this table, we noted that the values of DG°
are between 9.25 and +7.44 kJ/mol, which indicate that the
adsorptions of MB and CV are physical in nature.
No comparative study has been reported scarcely up to
now. In this table we reported for comparison the enthalpies
of adsorption of methylene blue and crystal violet to mont-
mortillonite determined using calorimetric measurements
(values in parentheses from Rytwo and Ruiz-Hitzky (2003).
We note that our values are in the order of magnitude of those
published data.
4. Conclusion
In the present study, the effect of temperature on the removal
of methylene blue and crystal violet from synthetic wastewater
is studied using a natural clay mineral as an adsorbent. The
eled by Langmuir model. On the other hand, the adsorption
equilibrium of CV is predicted by Freundlich approach. The
results also show that the enthalpy of adsorption of MB is
slightly positive (DH° = +6.5 kJ/mol) signifying that the pro-
cess is endothermic. However, the enthalpy of adsorption of
CV is negative (DH° = 9.8 kJ/mol) which is in accordance
with an exothermic process. These results are in line with the
reported values on the direct determination of enthalpies of
adsorption using calorimetry. Physisorption is the prevailing
natural clay.
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