Chemical Engineering Journal 170 (2011) 82–89

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Chemical Engineering Journal

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Equilibrium and kinetic studies of methyl orange adsorption on multiwalled

carbon nanotubes
Yunjin Yao ∗ , Bing He, Feifei Xu, Xiaofeng Chen
School of Chemical Engineering, Hefei University of Technology, Hefei 230009, China

a r t i c l e i n f o a b s t r a c t

Article history: The adsorption of methyl orange onto multiwalled carbon nanotubes (MWCNTs) from aqueous solu-
Received 29 October 2010 tions was studied, in which the influence of contact time, dosage, temperature, pH, and methyl orange
Received in revised form 5 March 2011 concentration in the solution were investigated. The equilibrium adsorption data were analyzed using
Accepted 8 March 2011
three common adsorption models: Langmuir, Freundlich and Temkin. The results revealed that Lang-
muir isotherm fit the experimental results well. Kinetic analyses were conducted using pseudo-first
Keywords:
and second-order models and the intra-particle diffusion model. The regression results showed that the
Adsorption
adsorption kinetics was more accurately represented by pseudo-second-order model. Values of activation
Carbon nanotube
Methyl orange
parameters such as Standard free energy changes (G0 ), standard enthalpy change (H0 ), and standard
Thermodynamics entropy change (S0 ) were calculated using adsorption equilibrium constants obtained from the Lang-
muir isotherm at different temperatures. All G0 values were negative; the (H0 ) values and (S0 )
values of MWCNTs were 19.39 kJ/mol and 0.1015 kJ/mol K, respectively, indicating that the adsorption
was feasible, spontaneous and endothermic process in nature.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction proposed for various applications such as hydrogen storage devices,

The colored materials and dyes constitute the focus of
many environmental concerns because of their non-biodegradable
and polluting nature. There exist several physicochemical pro-
cesses/methods for removal and/or recovery of colored materials
and dyes from effluents, and the adsorption is one of the most
effective [1]. Because the adsorbent is one of the key factors, deter-
mining the effectiveness of any adsorption processes, the scope of
many studies have been constructed based on investigation of alter-
native adsorbents which suitable to particular operations. Taking
the adsorption of dyes and colored materials, the usability of var-
ious natural and synthetic adsorbents have been studied, such as
banana peel [2], orange peel [2], calcined layered double hydroxides
[3], hypercrosslinked polymeric adsorbent [4], pinecone derived
activated carbon [5]. Usually, the effectiveness of any adsorption
process largely depends on the physicochemical properties of the
adsorbent used. Thus, the regenerability, availability and opera-
tional costs coming out are becoming of prime importance aspects
in adsorption processes.
Since the discovery by Iijima in 1991 [6], carbon nanotubes
(CNTs) have attracted great attention in multidisciplinary areas due
to their unique hollow tube structure and their many outstanding
mechanical, electronic and optical properties [7]. CNTs have been
∗ Corresponding author. Tel.: +86 551 2901458; fax: +81 551 2901453.
E-mail address: yaoyunjin@gmail.com (Y. Yao).
sensors and so on [8]. In comparison with classical adsorbents such
as activated carbon and clay, CNTs is more attractive because of
its favorable physicochemical stability, high selectivity, and struc-
tural diversity. Extensive experiments have been conducted on the
adsorption of inorganic or organic contaminants on CNTs such as
Zn2+ [9], Cd2+ [10], Pb2+ [11], Cu2+ [12], Cr6+ [13], fluoride [14] and
dioxin [15]. Therefore, CNTs might be ideal sorbents for the removal
of dyes from water. Earlier studies have obtained only equilibrium
adsorption data and few works have measured the kinetics and
thermodynamic parameters of adsorption on CNTs. Few investi-
gations focused on the adsorption of organic pollutants on CNTs
and simultaneously determined the kinetics equilibrium and ther-
modynamic parameters. Hence, this study elucidates the kinetics
equilibrium and thermodynamics of the adsorption of dyes onto
CNTs.
In this study Methyl orange (MO) with large and complicated
structures was selected as model pollutant to examine adsorp-
tion kinetics and thermodynamics of pollutant onto multiwalled
carbon nanotubes (MWCNTs) under different experimental con-
ditions, such as the effect of MO concentration, temperature,
pH, and contact time on the adsorption process. Kinetics and
thermodynamics studies have been performed and the results
have been analyzed by applying conventional theoretical meth-
ods. Thermodynamic parameters, such as G0 , H0 and S0 , were
calculated. This information may be useful for further research
and practical applications of the adsorbent in dyeing wastewater
treatment.

1385-8947/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.03.031
 Y. Yao et al. / Chemical Engineering Journal 170 (2011) 82–89 83

2. Materials and methods

2.1. Materials

MWCNTs were produced by chemical vapor deposition using

the carbon from acetylene cracking; iron nanoparticles embedded
in mesoporous silica, prepared by mixing iron nitrate solution and
tetraethoxysilane in a sol–gel process, were employed as the cat-
alyst. The method of synthesis had been described before [16].
The raw product contains the aerogel support, catalyst particles,
and a few amorphous carbons (mostly as a coating on the catalyst
nanoparticles) as impurities. The as-grown MWCNTs were puri-
fied using a two-step purification procedure involving acid washing
and oxidation in diluted air. The morphology of adsorbents was
analyzed by a transmission electron microscope (TEM, JEM-1200
EX/S, JEOL, Tokyo, Japan). The BET surface area was determined
from adsorption isotherms using a Micromeritics ASAP 2020 Sur-
face Area Analyzer. The BET surface area, average pore diameter,
and pore volume was 160 m2 /g, 20 nm, and 0.67 cm3 /g, respec-
tively. The structure information of adsorbents was evaluated by
a Raman spectrometer (Model Nanofinder 30 R., Tokyo Instrument
Inc., Tokyo, Japan).
MO (C14 H14 N3 O3 SNa, molecular weight 327.33) was obtained
from Shanghai Reagents Co. and used without further purification.
All of the reagents were analytical reagent grade. A stock solu-
tion of 1000 mg/L was prepared by dissolving accurately weighed
amounts of MO in separate doses of 1000 mL distilled water. The
desirable experimental concentrations of solutions were prepared
by diluting the stock solution with distilled water when necessary.
Fig. 1. TEM images of MWCNTs.
2.2. Batch equilibrium studies

To study the effect of parameters such as adsorbent dose, con-
tact time, initial concentration, solution pH, and temperature for
the removal of adsorbate on MWCNTs, batch experiments were
performed using 100 mL glass bottles with addition of purified
MWCNTs and fixed initial concentrations of dyes solution. The glass
bottles were sealed and placed within a temperature control box
to maintain water temperature. The effect of pH on MO adsorption
was studied by varying the pH from 1.0 to 10.0. The concentration
of MO solution used for this study was 20 mg/L and the adsorbent
dose was 0.015 g. The pH of the samples was adjusted by adding
2 M HCl or 0.5 M NaOH to each 200 mL of the prepared solution.
The pH of solutions was measured with a pH meter. To observe the
effect of adsorbent dose on dyes adsorption, different amounts of
adsorbent (varying from 0.01 to 0.08 g) were respectively added
into initial concentration of 20 mg/L MO solution at 298 K at pH 7.0
until the equilibrium time was reached. In the experiments on the
effect of temperature, the temperature was held at four different
temperatures (273, 298, 318and 333 K) with different concentra-
tions, where all other variables such as activated carbon dose, and
contact time while the solution pH was original without any adjust-
ment. At the end of the equilibrium period, the suspensions were
separated for later analysis of the dye concentration. The amount
of MO adsorption at equilibrium qe (mg/g) was calculated from the
following equation:
V (C0 − Ce )
qe =
W end of MWCNTs as indicated by circles.
where C0 and Ce (mg/L) are the liquid phase concentrations of dye at
initial and equilibrium, respectively, V (L) the volume of the solu-
tion and W (g) is the mass of adsorbent used. The concentration
of MO after and before adsorption was determined using a spec-
trophotometer at max = 460 nm.
The procedures of kinetic experiments were identical with those
of equilibrium tests. The effect of contact time on the amount of
dye adsorbed was investigated at different initial concentrations
(20 mg/L, 30 mg/L and 40 mg/L) at 298 K.In this case, the solution
pH was kept natural without any pH adjustment.
The amounts of dye adsorbed on MWCNTs at any time, time (t),
were calculated from the concentrations in solutions before and
after adsorption. At any times, the amount of MO adsorbed (mg/g)
(qt ) onto MWCNTs was calculated from the mass balance equation
as follows:
V (C0 − Ct )
qt = (2)
W
where qt is the amount of adsorbed dye on MWCNTs at any time
(mg/g); C0 and Ct are the initial and liquid-phase concentrations
of MO at any time (mg/L), respectively; V (L) is the volume of MO
solution, and W (g) is the mass of MWCNTs sample used.[17,18]
3. Results and discussion
3.1. Characterizations of MWCNTs
Fig. 1 exhibits the TEM images of MWCNTs. It is seen that the
MWNTs were 15–25 nm outer diameter and 4–5 nm inner diame-
ter. The isolated MWCNTs of different size and direction are usually
curved and form an aggregated structure due to inter-molecular
force. Both ends of MWCNTs were opened as indicated by arrows
(1) and only a small amount of metal catalysts was remained in the
The Raman spectra of MWCNTs presented in Fig. 2 are com-
posed of two characteristic peaks. The peak near 1350 cm−1 is the
D band which is related to disordered sp2 -hybidized carbon atoms
of nanotubes containing vacancies, or other symmetry-breaking
defects. The peak near 1580 cm−1 is the G band, which is related
to graphite E2g symmetry of the interlayer mode reflecting struc-
tural integrity of sp2 -hybridized carbon atoms of the nanotubes.
84 Y. Yao et al. / Chemical Engineering Journal 170 (2011) 82–89
Fig. 2. Raman spectra of MWCNTs.
Fig. 3. Effect of pH on the adsorption of MO by MWCNTs (experimental conditions:
initial dye concentration: 20 mg L−1 , adsorbent dose: 15 mg/50 mL, temperature:
298 K, contact time: 2 h).
Hence, the extent of carbon-containing defects of adsorbents can
be evaluated by intensity ratio of D band to G band (ID /IG ). The ID /IG
ratio of employed MWCNTs (0.96) is higher than those of commer-
cially available MWCNTs (0.68) documented in the literature [19].
This indicated that the employed MWCNTs possess more carbon-
containing defects than the commercially available MWCNTs.
3.2. Adsorption experiment studies
3.2.1. Effect of solution initial pH on dye uptake
MO has two chemical structures, whose chromophores are
anthraquinone or azo bond depending on the pH of the solution,
as can be expressed as [20]:
The pH of the system exerts profound influence on the
adsorptive uptake of adsorbate molecule presumably due to its
influence on the surface properties of the adsorbent and ion-
ization/dissociation of the adsorbate molecule. Fig. 3 shows the
variations in the removal of dye at various solution initial pH.
Fig. 4. Effect of adsorbent dose on the adsorption of MO by MWCNTs (experimental
conditions: initial dye concentration: 20 mg L−1 , temperature: 298 K, contact time:
2 h).
It is evident that the maximum removal of MO is observed at
pH 2.3.With increase in pH from 4 to 10, adsorption capaci-
ties decreases from 30.4 mg/g to 24.8 mg/g. This may attribute
to the electrostatic interaction between anionic dyes and par-
tially negative charged CMWNTs surface due to the presence of
oxygen containing functional groups [21–23]. Increase of the pH
value (basic condition) led to increase of the number of nega-
tively charged sites and the number of positively charged sites
decreases. The lowest adsorption occurred at pH 10.0 and the great-
est adsorption occurred at pH ∼2.0. Moreover, the decreasing in
the adsorption of MO with increasing of pH value is also due to
the competition between anionic dye and excess OH− ions in the
solution.
3.2.2. Effect of adsorbent dose on dye adsorption
The adsorbent dose is an important parameter in adsorption
studies because it determines the capacity of adsorbent for a given
initial concentration of dye solution. Fig. 4 presents the effect of
MWCNTs dosage on the adsorption of MO. The amount adsorbed
increased with the dose of MWCNTs; however, the adsorption
capacity dropped as the MWCNTs dosage increased. Increasing the
MWCNTs dose increases the probability of the MWCNTs entangle-
ment in the solution, causing adsorption in the interlayer space
and a decrease in the aggregation of dye at the external sur-
face. Accordingly, the adsorption capacity declined as the MWCNTs
dosage increased. Moreover, the high MWCNTs dosage may influ-
ence the physical characteristics of the solid–liquid suspensions,
such as by increasing the viscosity and inhibiting the diffusion of
dye molecules to the surface of the MWCNTs. Since the concentra-
tions of MO were fixed, the adsorption capacity decreased as the
MWCNTs dosage increased. The increase with MWCNTs dosage of
the amount of dye adsorbed was caused by the availability of more
surface area of the MWCNTs [16,24]. Bhattacharyya and Sharma
[25], who utilized Neem leaf powder to adsorb dyes, suggested
that the amount adsorbed (mg/g) decreased as the amount of the
adsorbent increased; similar results were also obtained for algae
cell walls by Marungrueng and Pavasant [26] and for cross-linked
chitosan beads by Chiou et al. [27].
 Y. Yao et al. / Chemical Engineering Journal 170 (2011) 82–89
Fig. 5. Effect of contact time on the adsorption of MO by MWCNTs (experimental
conditions: temperature: 298 K, adsorbent dose: 15 mg/50 mL).
3.2.3. Effect of contact time and initial concentration
Equilibrium time is one of the most important parameters in
the design of economical wastewater treatment systems [20]. To
investigate the kinetics of adsorption, three different initial con-
centrations of MO were chosen, 20 mg/L, 30 mg/L and 40 mg/L.
Fig. 5 shows plots of adsorption capacity (qt ) of MO onto MWC-
NTs versus contact time for different initial MO concentrations.
As seen in Fig. 5, qt value increased evidently from 29 mg g−1 to
41.9 mg/g with the increase in initial concentration from 20 mg/L
to 40 mg/L. The initial concentration played an important role in
the adsorption capacity of MO on MWCNTs adsorbent. The result
that adsorption capacity of MO increased with the increasing of
initial MO concentration might be attributed to an increase in the
driving force of concentration gradient with the increase in the
initial concentration [28]. The adsorption is initially (contact time
<45 min) rapid, and then slows, perhaps because a large number of
vacant surface sites were available for adsorption during the initial
stage, and then, the remaining vacant surface sites were difficult to
occupy because of the repulsive forces between the dye molecules
on the MWCNTs and the bulk phase [29]. In addition, the curves
are single, smooth and continuous towards saturation, indicating
the formation of monolayer coverage of dye molecules on MWCNTs
surface.
3.2.4. Effect of temperature on adsorption capacity of MWCNTs
Temperature is an important parameter for the adsorption pro-
cess and batch adsorption studies were carried out at three different
temperatures over a range of initial dye concentrations. Fig. 6 shows
the effect of the temperature on the adsorption in terms of adsorp-
tion isotherms. As seen from Fig. 6, equilibrium uptake increased
with the increasing of equilibrium MO concentrations at the range
of experimental concentration. This is a result of the increase in the
driving force from the concentration gradient. In the same condi-
tions, if the concentration of MO in solution was bigger, the active
sites of MWCNTs were surrounded by much more MO ions, and
the process of adsorption would carry out sufficient. Therefore, the
values of qe increased with the increase of equilibrium MO concen-
trations. Interestingly, it is observed that the adsorption capacity
increased with increase in temperature, indicating the endother-
mic nature of the adsorption reaction of MO onto MWCNTs. The
reason may be that the physical bonding between dye molecules
and the active sites of the adsorbent weakened as temperature
increased, whereas, the solubility of dyes increased thus enhancing
the interaction forces between the solute and the solvent.
85
Fig. 6. Effect of temperature on adsorption of MO by MWCNTs (experimental con-
ditions: initial dye concentration: 20 mg L−1 , adsorbent dose: 15 mg/50mL, contact
time: 2 h).
3.3. Evaluation of adsorption kinetics
Adsorption is a physicochemical process that involves mass
transfer of a solute from liquid phase to the adsorbent surface. Three
of the most widely used kinetic models, i.e. Lagergren-first-order
equation, pseudo-second-order equation and intra-particle diffu-
sion model were used to research the adsorption kinetic behavior
of MO onto MWCNTs. The best-fit model was selected based on the
linear regression correlation coefficient values (R2 ).
Lagergren-first-order kinetic model might be represented by Eq.
(3) [30]
k1 t
ln(qe − qt ) = ln(qe ) − (3)
2.303
where qe and qt are the amounts of MO adsorbed (mg/g) at equi-
librium and time t (min), respectively; k1 is the rate constant of
Lagergren-first-order kinetic model (min−1 ). Values of k1 can be
calculated from the plots of ln (qe − qt ) versus t for Eq. (3).
A linear form of pseudo-second-order kinetic model was
expressed by Eq. (4) [24]
t 1 t
= + (4)
q k2 qe 2 qe
where k2 is the rate constant (g mg−1 min−1 ) of pseudo-second-
order kinetic model for adsorption. The slope and intercept of the
linear plots of t/qt against t yield the values of 1/qe and 1/k2 q2e for
Eq. (4).
Since neither the pseudo first-order nor the second-order model
can identify the diffusion mechanism, an intra-particle mass trans-
fer diffusion model proposed by Weber and Morris can be written
as follows [31]:
qt = ki t 1/2 + C (5)
where C (mg/g) is the intercept and ki is the intra-particle diffu-
sionrate constant (mg (g min)−1 ), which can be calculated from the
slope of the linear plots of qt versus t1/2 .
Different kinetic parameters of MO adsorption onto MWC-
NTs for different MO initial concentrations are shown in Table 1.
Plots of Lagergren-first-order and pseudo-second-order kinetic
models are shown in Fig. 7a and b for the effect of initial MO
concentrations. All the experimental data showed better compli-
ance with pseudo-second-order kinetic model in terms of higher
correlation coefficient values (R2 > 0.995). It could be found that
pseudo-second-order kinetic model was more valid to describe
86 Y. Yao et al. / Chemical Engineering Journal 170 (2011) 82–89

Table 1 a
Coefficients of pseudo-first and second-order adsorption kinetic models and intra-
particle diffusion model.

Model Parameters Initial dye concentrations (mg/L)

20 30 40

Pseudo-first-order model k1 (min−1 ) 0.05229 0.06054 0.05564

R2 0.9699 0.9528 0.9502
Pseudo-second-order model K2 (min−1 ) 0.00457 0.00422 0.00231
2
R 0.9980 0.9985 0.9958
Intraparticle diffusion model ki (mg/g min0.5 ) 0.8909 1.029 1.479
C (mg/g) 17.92 19.84 23.80
R2 0.9824 0.9138 0.9540

the adsorption behavior of MO onto MWCNTs. Similar phenomena

have been observed for MO adsorption on activated carbon derived
from phragmites australis [32], hypercrosslinked polymeric adsor-
bent [4], Coal Powder [33].
The removal of MO by adsorption on MWCNTs was found to be
rapid at the initial period and then to become slow and stagnate b
with the increase in contact time. The removal of MO by adsorp-
tion on surface of MWCNTs was due to MO as MO+ cationic form.
Typically, various mechanisms control the adsorption kinetics; the
most limiting were the diffusion mechanisms, including external
diffusion, boundary layer diffusion and intra-particle diffusion [34].
Hence, the intra-particle diffusion model was utilized to determine
the rate-limiting step of the adsorption process. If the regression of
qt versus t1/2 was linear and passes through the origin, then intra-
particle diffusion was the sole rate-limiting step. The regression
was linear, but the plot did not pass through the origin (Fig. 7c),
suggesting that adsorption involved intra-particle diffusion, but
that was not the only rate-controlling step. The values of C were
helpful in determining the boundary thickness: a larger C value
corresponded to a greater boundary layer diffusion effect [35]. The
C values (17.92–23.80 mg/g) increased with the initial concentra-
tions (20–40 mg/L) (Table 1). The results of this study demonstrated
increasing the initial concentrations promoted the boundary layer
diffusion effect. c

3.4. Adsorption isotherms

Equilibrium data, commonly known as adsorption isotherms,

describe how the adsorbate interacts with adsorbents, and give
a comprehensive understanding of the nature of interaction. It is
important to optimize the design of an adsorption system. Sev-
eral isotherm equations have been developed and employed for
such analysis and the three important isotherms, the Langmuir,
Freundlich and Temkin isotherms are applied in this study.
The Langmuir isotherm [36] is represented by the following lin-
ear equation:

Ce 1 1
= + Ce (6)
qe q0 KL q0

where Ce (mg/L) is the equilibrium concentration, qe (mg/g) the

amount of adsorbate adsorbed per unit mass of adsorbate, and q0
and KL are the Langmuir constants related to adsorption capac-
ity and rate of adsorption, respectively. When Ce /qe was plotted
against Ce , straight line with slope 1/q0 was obtained (Fig. 8a), indi-
cating that the adsorption of MO on MWCNTs follows the Langmuir
isotherm. The Langmuir constants KL and q0 were calculated from
this isotherm and their values are listed in Table. 2. Furthermore,
the effect of the isotherm shape is considered with a view to predict
whether an adsorption system is favorable or unfavorable.
The essential features of Langmuir adsorption isotherm can be
expressed in terms of a dimensionless constant called separation
Fig. 7. Regressions of kinetic plots different initial concentrations: (a) pseudo-first-
order model, (b) pseudo-second-order model and (c) intra-particle diffusion model.
factor or equilibrium parameter (RL ), which is defined by the fol-
lowing relationship [37]:
1
RL = (7)
1 + KL C0
where KL is the Langmuir constant and C0 (mg/L) is the highest dye
concentration. The value of RL indicates the type of the isotherm to
be either unfavorable (RL > 1), linear (RL = 1), favorable (0 < RL < 1) or
 Y. Yao et al. / Chemical Engineering Journal 170 (2011) 82–89 87

a Table 2
Isotherm parameters for removal of MO by MWCNTs at different temperatures.

Isotherms Parameters Temperatures (K)

273 298 318 333

Langmuir qo (mg/g) 50.25 51.74 52.43 52.86

KL (L/mg) 0.1172 0.2380 0.4697 0.5605
R2 0.9915 0.9903 0.9914 0.9952
RL 0.2214 0.1229 0.06627 0.05613
Freundlich KF (mg/g (L/mg)1/n ) 8.767 17.58 24.37 28.30
n 2.959 3.020 4.529 5.246
R2 0.9872 0.9756 0.8895 0.9281
Temkin B 12.04 10.90 8.541 7.156
Kt 1.110 3.131 12.78 47.27
R2 0.98412 0.9668 0.92589 0.9007

where qe is the amount adsorbed at equilibrium (mg/g) and Ce is

the equilibrium concentration of the MO. KF and n are Freundlich
constants, n giving an indication of how favorable the adsorp-
b
tion process and KF (mg/g (L/mg)1/n ) is the adsorption capacity of
the adsorbent. It is generally stated that values of n in the range
2–10 represent good, 1–2 moderately difficult, and less than 1 poor
adsorption characteristics. The studied materials are good adsor-
bents for MO (n > 2). The slope 1/n ranging between 0 and 1 is a
measure of adsorption intensity or surface heterogeneity, becom-
ing more heterogeneous as its value gets closer to 0 [38]. The plot
of ln qe versus ln Ce (Fig. 8b) gives straight lines with slope 1/n.
Fig. 8b shows that the adsorption of MO also follows the Freundlich
isotherm. Accordingly, Freundlich constants (KF and n) were calcu-
lated and listed in Table 2.
The linear form of Temkin isotherm is expressed as [39]:

qe = B ln Kt + B ln Ce (9)

The adsorption data were analyzed according to Eq. (9). A plot of

c corresponding to the maximum binding energy and constant B is
Fig. 8. (a) Langmuir, (b) Freundlich and (c) Temkin isotherms for MO dye adsorption
onto MWCNTs at different temperatures.
qe versus ln Ce (Fig. 8c) enables the determination of the isotherm
constants Kt and B. Kt is the equilibrium binding constant (L/mg)
related to the heat of adsorption. The values of the parameters are
given in Table 2.
From Table 2, the Langmuir isotherm model yielded the best fit
with the highest R2 value (0.99) at all temperatures compared to
the other two models. The values of KL were 0.1172, 0.2380, 0.4697,
and 0.5605 L/mg at 273, 298, 313 and 333 K, respectively, revealing
that the adsorption of MO on MWCNTs increased with tempera-
ture. The results implied that the affinity of the binding sites for
MO increased with the temperature. All three models suggest that
increasing temperature increased adsorption capacity, revealing
that the adsorption is endothermic. The following section presents
the detailed thermodynamic parameters.
As also seen in Table 2, the adsorption capacities of MWCNTs for
MO are varied in the range of 42.29–78.07 mg/g. Previously some
researchers investigated several adsorbents for the removal of MO
from aqueous solutions. By comparison of the results obtained in
this study with those in the previously reported works (Table 3) on
adsorption capacities of various adsorbent and activated carbon in

Table 3
Previously reported adsorption capacities of various adsorbents for MO [5].
irreversible (RL = 0). As shown in Table 2, the calculated values of
Adsorbent q0 (mg/g) Reference
RL were found between 0 and 1. This implies that the adsorption of
Banana peel 21 [2]
the investigated dye on both modified silica samples from aqueous
Orange peel 20.5 [2]
solutions is favorable under the conditions used in this study. Calcined layered double hydroxides 200 [3]
The linear form of the Freundlich equation is Hypercrosslinked polymeric adsorbent 70.9 [4]
Diaminoethanesporopollenin biopolymer 4.7 [1]
1 Pinecone derived activated carbon 404.4 [5]
ln qe = ln KF + ln Ce (8) Carbon nanotubes 35.4–64.7 This study
n
88 Y. Yao et al. / Chemical Engineering Journal 170 (2011) 82–89
Fig. 9. Van’t Hoff plot for the adsorption of MO dye on MWCNTs.
aqueous solution for MO, It is clear that MWCNTs used in this work
had a relatively suitable adsorption.
3.5. Thermodynamic analyses
To estimate the effect of temperature on the adsorption of MO
onto MWCNTs, the free energy change (G0 ), enthalpy change
(H0 ), and entropy change (S0 ) were determined. The Langmuir
isotherm was used to calculate thermodynamic parameters using
the following equations:
S 0 H 0
ln (KL ) = − (10)
R RT
G = H − TS (11)
where KL is the Langmuir equilibrium constant (L/mol); R is the
gas constant (8.314 J/mol K) and T is the temperature (K). Consid-
ering the relationship between G0 and KL , H0 and S0 were
determined from the slope and intercept of the Van’t Hoff plots of
ln (KL ) versus 1/T (Fig. 9). Table 4 presented the thermodynamic
parameters at various temperatures. The negative values confirm
the feasibility of the process and the spontaneous nature of the
adsorption. The values of G0 , were found to decrease −27.62 to
−33.71 kJ/mol using the equilibrium constant, KL . The decrease in
the negative value of G0 with an increase in temperature indi-
cates that the adsorption process of MO on MWCNTs becomes more
favorable at higher temperatures. The values of H0 and S0 calcu-
lated from the plot of ln (KL ) versus 1/T were given as 19.39 kJ/mol
and 0.1015 kJ/mol K, respectively. Kara et al. [40] suggested that
the H0 of physisorption is smaller than 40 kJ/mol. Based on H0 ,
this study suggested that the adsorption of MO onto MWCNTs was
a physisorption process. The value of H0 was positive, indicating
that the adsorption reaction was endothermic. The positive value
of S0 reflects the affinity of MWCNTs for MO and suggests some
structural changes in dye and MWCNTs.
Table 4
Values of thermodynamic parameters (kJ/mol) for the adsorption of dyes onto
MWCNTs.
T (K) G0 (kJ/mol) H0 (kJ/mol) S0 (kJ/mol K)
273 −27.62 19.39 0.1015
298 −30.15
318 −32.19
333 −33.71
4. Conclusion
The adsorption of methyl orange onto MWCNTs from aqueous
solutions was systematically investigated under various conditions.
Adsorption parameters for the Langmuir, Freundlich and Temkin
isotherms were determined and the equilibrium data were best
described by the Langmuir isotherm model. The adsorption kinet-
ics can be successfully fitted to pseudo-second-order kinetic model.
The results of the intra-particle diffusion model suggested that
intra-particle diffusion was not the only rate-controlling step. Ther-
modynamic analyses indicated that the adsorption of MO direct
dyes onto MWCNTs was endothermic and spontaneous; addi-
tionally, the adsorption of direct dyes onto MWCNTs was via a
physisorption process.
Acknowledgments
The authors thank College Student FOAK Nature Experiment
Plan Project Council for financially supporting this research under
Contract No. 2009CXSY128 and 2010CXSY65.
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