Journal of Chemical Engineering of Japan, Vol. 52, No. 8, pp.

671–679, 2019 Research Paper

Modeling of CO2-Activated Adsorption on Chitosan Hydrogel

for Dye Removal in Aqueous Solution
Huy Q. Le and Yusuke Shimoyama
Department of Chemical Science and Engineering, School of Materials and Chemical Technology,
Tokyo Institute of Technology, S1-33, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550, Japan

Keywords: CO2-Activated Adsorption, Dye Removal, Chitosan, Kinetic Modelling, Isotherm Modelling

This work focuses on adsorption kinetics and isotherm modelling in CO2-activated chitosan. Removal efficiency and
adsorption capacity were measured for three anionic dyes: Brilliant Blue FCF (BBF), Congo Red (CR), Orange II (O-II) and
one cationic dye: Crystal Violet (CV). While the highest removal efficiencies of BBF, O-II and CR were 97%, 91% and 48%, it
was found that very low adsorption capacity occurred in the case of CV due to the repulsion between the cationic groups
of CV and that of CO2-activated chitosan. In terms of adsorption kinetics, pseudo-first-order and pseudo-second-order
models were applied. The adsorption in the CO2-activated system was found to follow the pseudo-first-order model. The
activation of adsorption by CO2 was found to lead to a higher adsorption rate constant and a higher adsorption capac-
ity due to the protonation of chitosan’s amino groups. Interestingly, as the temperature of the CO2-activated system in-
creased, the pseudo-first-order model predicted a decrease in adsorption rate constant, k1. This is thought to be a result
of lower CO2 dissolution into the aqueous solution, which leads to a slower protonation process of chitosan’s adsorption
sites. The chemical structure of the dye species affects the adsorption kinetics in the CO2-activated system. There are four
charged functional groups on the CR molecule and three on the BBF molecule, which allow faster alignment onto ad-
sorption sites compared with O-II molecules with only one charged group. In terms of adsorption isotherm, BBF adsorp-
tion was found to follow the Langmuir model in the CO2-activated system.

1898 is considered the earliest adsorption kinetics model

Introduction
Dye is a major industrial product with nearly one million
tons produced annually (Lalnunhlimi and Krishnaswamy,
2016). Along with the huge production rate, the treatment
of dye in wastewater has become a challenge for researchers
around the world due to their harmful effects human health
(Wan Ngah et al., 2011). In recent years, the adsorption using
chitosan hydrogel has proved to be one of the most attrac-
tive methods for dye removal in aqueous solutions. This is
because chitosan is the second most naturally occurring
bio-polymer after cellulose, low in toxicity and can be eas-
ily extracted from the shells of crustacean animals (Kumar
et al., 2009). Chitosan is reported to be extremely effective
towards the anionic dye removal because of the high adsorp-
tion capacity at low pH conditions (Chiou and Li, 2003;
Chiou et al., 2004; Huang et al., 2017). There are also many
studies on chitosan modification by cross-linking (Wan Ngah
and Fatinathan, 2006, 2008, 2010), impregnation (Chatterjee
et al., 2009, 2010) or polymer blending (Jin and Bai, 2002).
As part of those studies on dye adsorption using chitosan,
modelling plays an important role. A modelling investiga-
tion usually includes both kinetics and isotherm model-
ling on the adsorption. In terms of adsorption kinetics,
the pseudo-first-order model, introduced by Lagergren in
Received on December 7, 2018; accepted on February 2, 2019
DOI: 10.1252/jcej.18we342
Correspondence concerning this article should be addressed to Y. Shi-
moyama (E-mail address: yshimo@chemeng.titech.ac.jp).
(Ho, 2004). It suggests that the rate of change of an ad-
sorbate is directly proportional to the amount of adsorp-
tion sites on the surface of the adsorbent. Meanwhile, the
pseudo-second-order model was developed by Ho’s group
to describe the adsorption of divalent metal ions onto peat,
which takes into account the chemical bonding between
the adsorbate and the adsorbent (Ho and McKay, 1999).
A number of studies have interpreted pseudo-first-order
model as an indicator of physisorption, and pseudo-second-
order model as an indicator of chemisorption (Stephen
Inbaraj et al., 2006; Crini, 2008). Weber–Morris proposed
the intra-particle diffusion model based on the assumption
that the rate-determining step of an adsorption process is
not the chemical interaction, but rather the diffusion within
the solid adsorbent particles (Weber and Morris, 1965).
Zeldovich et al. developed the Elovich kinetic model, but
this model has been more common for the chemisorption
of gases onto heterogeneous solids rather than adsorption
in aqueous solutions (Low, 1960). In terms of adsorption
isotherm, the Langmuir model, which assumes a monolayer
coverage on the adsorbent surface, can be used to predict a
maximum adsorption capacity (Langmuir, 1916). Another
popular isotherm model is the Freundlich model, which
assumes multilayer coverage and a heterogeneous adsor-
bent surface (Freundlich and Heller, 1939). The Freundlich
model is an entirely empirical model, thus providing little
physical meaning compared with Langmuir model.
Recently, our group has introduced a CO2-activated sys-
tem as a new dye adsorption technique (Le et al., 2018).

Vol. 52  No.©8 2019 

Copyright 2019The Society of Chemical Engineers, Japan 671
Carbon dioxide was found to be capable of activating chito-
san’s adsorption strength for anionic dyes by protonation of
NH2 groups into NH+3 . Furthermore, chitosan’s stability in
acidic conditions could also be enhanced by the formation
of carbamate cross-link with CO2. This synergistic effect of
a CO2-activated system proves that it could be applied as an
effective, environmentally–friendly and simple adsorption
technique without using conventional acidic compounds or
cross-linkers. However, a CO2-activated system is a unique
adsorption process, where adsorption behavior can be af-
fected by CO2 in multiple ways: CO2 dissolution, chitosan
protonation, chitosan cross-linking with CO2 and adsorp-
tion. As adsorption in the CO2-activated system is more
complicated than a conventional system, it is interesting
to model the adsorption kinetics and isotherms to know
the specific CO2-activated adsorption. Therefore, in this
study, pseudo-first-order and pseudo-second-order kinetics
models, Langmuir and Freundlich isotherm models, were
utilized for modelling the adsorption of the dyes on chito-
san hydrogel at various operating conditions. The effects of
CO2 activation are studied by comparison with that in pure
water. The effects of dye species were discussed thoroughly
for the three anionic dyes: Brilliant Blue FCF, Congo Red,
Orange II and the one cationic dye, Crystal Violet based on
the dye’s chemical structure.
1. Experimental
1.1 Materials
Chitosan, acetic acid (CH3COOH), sodium hydroxide
(NaOH), hydrochloric acid (HCl), Brilliant Blue FCF (BBF),
Congo Red (CR), Orange II and Crystal Violet (CV) were all
purchased from Wako Pure Chemical Industries, Ltd. The
purities of acetic acid, NaOH, HCl, and BBF were higher
than 99.9, 97.0, 35.0 to 37.0 and 85.0% by mass, respectively.
The structures of the dyes are given in Figure A1 (Appen-
dix). Chitosan had a degree of de-acetylation of more than
80%. Ultrapure water was produced by a Direct-Q UV3
Water Purification System (EMD Millipore Co.), the resis-
tivity was 18.2 MΩ cm.
1.2 Fabrication of chitosan hydrogel
Chitosan was firstly dissolved into 2.0 wt% acetic acid
aqueous solution with the chitosan composition 2.5 wt% in
the solution. The viscous chitosan aqueous solution was vig-
orously stirred for 5 h, sealed and left overnight to remove
any air remaining in the solution. After stirring, the chitosan
solution was dropped from a syringe (Terumo SS-10SZ) into
the coagulation mixture, 10.0 wt% NaOH aqueous solution.
Then, the chitosan hydrogel formed was left overnight be-
fore being washed extensively by ultrapure water. Chitosan
hydrogels were spherical in shape with an average diameter
of 4.1 mm and were stored in ultrapure water.
1.3 Dye adsorption on CO2-activated chitosan
The Chitosan hydrogels fabricated in Section 1.2 were
activated by CO2 bubbling in the aqueous solution and used
672
for the dye adsorptions of Brilliant Blue FCF (BBF), Congo
Red (CR), Orange II and Crystal Violet (CV). First of all, a
known amount of the dye powder was firstly dissolved into
ultrapure water for preparation of the aqueous solution.
Carbon dioxide from a gas cylinder was installed into the
adsorption vessel. The flow rate of CO2 was controlled by a
gas flow controller (Kofloc RK-1200) as 200 mL min−1. The
temperature of the adsorption system was kept in a water
thermostatic bath (Yamato Thermo-Mate BF 200). The chi-
tosan was loaded of 1.0 g into the dye aqueous solution at
200 mL volume. The initial pH of the dye aqueous solution
before the adsorption was 3.9 due to the dissolution of CO2.
The pH of the solution was measured by a Eutech pH meter
PC2700.
The adsorption on the CO2-activated chitosan is evalu-
ated by the removal efficiency E and the adsorption capacity
of dye Qe defined as follows.
C0 − C e
E= ×100 (1)
C0
C0 − C e
Qe = ×V (2)
Wc
C0 and Ce in mg L−1 are the initial and equilibrium concen-
trations of the dye in aqueous solution, respectively. V is the
volume of the aqueous solution in L and Wc is the weight of
the dried chitosan hydrogel in g. The dye concentration in
the aqueous solution during the adsorption experiment was
measured by a UV-VIS spectrometer (JASCO V730). The
absorbances at the wavelengths 629, 484 and 590 nm were
used for the determination of the concentration of BBF,
Orange II and CV, respectively. In the case of CR, as the dye
color changes in the low pH solution which leads to λmax
shift, the peak area of absorbance at the wavenumbers 418 to
578 nm was used for the determination of the concentration.
1.4 Modeling of adsorption kinetics
The pseudo-first-order model is expressed in the form of
the following rate expression.
dQ t
= k1(Qe − Qt ) (3)
dt
Qt = Qe (1 − e − k1t ) (4)
Herein, t is time in min, Qt is the adsorption capacity at time
t in mg g−1, k1 is the adsorption rate constant in min−1 and
Qe is equilibrium adsorption capacity in mg g−1.
In the traditional linear regression method, Eq. (4) can be
used as follows: given a value of Qe which can be determined
experimentally, plotting ln (Qe−Qt) vs. t would give a value
for the adsorption rate constant k1. However, as pointed
out in various studies, the conventional linear regression
method might not be appropriate in predicting the best-
fitted model as well as kinetic parameters (Ho, 2006; Kumar
and Sivanesan, 2006; Lin and Wang, 2009; Moussout et al.,
2018). As a result, kinetics modelling was conducted by
a non-linear regression method. The method utilizes Mi-
crosoft Excel Solver’s function, which is described in detail
below.
Journal of Chemical Engineering of Japan
 The pseudo-second-order model is expressed in the form
of the following equations.
dQ t
= k2 (Qe − Qt )2 (5)
dt
Qe2k2t
Qt = (6)
1+Qek2t
Herein, t is time in min, Qt is the adsorption capac-
ity at time t in mg g−1, k2 is the adsorption rate constant in
g mg−1 min−1 and Qe is the equilibrium adsorption capacity
in mg g−1.
Similar to a pseudo-first-order model, it has been pointed
out in various studies that the conventional linear regression
method might not be appropriate as the best-fitted model
(Ho, 2006; Kumar and Sivanesan, 2006; Lin and Wang, 2009;
Moussout et al., 2018). Therefore, a non-linear regression
method was used using Eq. (6).
Microsoft Excel’s Solver function was applied for the
calculation of the best-fitted set of predicted adsorption ca-
pacity data t fitted to the data. First of all, a set of simulated
time-dependent adsorption capacity, Qsim, was calculated
by inputting random values of Qe and k into Eq. (4) for the
pseudo-first-order model and into Eq. (6) for the pseu-
do-second-order model, respectively. Next, the differences
between the simulated and the experimental adsorption
capacity, defined as Squared Deviation, SD, is calculated as
follows.
SD =  (Q exp − Qsim )2 (7)
Herein, Qexp is the experimental adsorption capacity data.
The total difference between experimental and simulated re-
sults is defined as the summation of SD. In the Solver’s func-
tion, a command was inserted to find the corresponding Qe
and k value so that the summation of SD is a minimum.
1.5 Modeling of adsorption isotherms
The Langmuir model, which assumes monolayer coverage
on a homogenous surface, has the following equation.
Qmax K LCe
Qe = (8)
1+ K LCe
Ce 1 C
= + e (9)
Qe Qmax K L Qmax
Herein, Qe is the equilibrium adsorption capacity in mg g−1,
Qmax is the maximum adsorption capacity in mg g−1, KL is
the Langmuir constant in L mg−1, and Ce is the equilibrium
concentration of the adsorbate in mg L−1. By using Eq. (9), a
plot of Ce/Qe vs. Ce would give the values of KL and Qmax.
The Freundlich model, which assumes multilayer cover-
age on a heterogenous surface, has the following empirical
equation.
Qe = K FC1/e n (10)
1
ln Qe = ln K F + ln Ce (11)
n
Herein, Qe is the equilibrium adsorption capacity in mg g−1,
KF is the Freundlich constant related to adsorption capac-
ity in L g−1, n is the constant related to adsorption energy
Vol. 52  No. 8  2019
and Ce is the equilibrium concentration of the adsorbate in
mg L−1. By using Eq. (11), a plot of ln Qe vs. ln Ce would give
the values of KF and n.
2. Results and Discussion
2.1 Adsorption on chitosan hydrogel
Figure 1 shows the removal efficiencies of the four dyes
on CO2-activated chitosan. The removal efficiencies of BBF,
O-II and CR reached 97%, 91% and 48%, respectively. In
our previous work (Le et al., 2018), it was found that the
electrostatic repulsion between –NH+3 groups on CR mol-
ecules and –NH+3 groups on CO2-activated chitosan leads
to a lower adsorption capacity of CR compared with BBF.
In this work, it can be seen that for O-II, a dye species that
does not have any cationic groups, the removal efficiency
is higher than CR. The removal efficiency of O-II is only
slightly lower than that of BBF, which is due to having a
smaller number of sulfonic groups (SO3−). On other hand, it
can be seen that CV cannot be adsorbed on CO2-activated
chitosan. This is because CV molecule carries a positive
charge on the nitrogen atom, which can have a repulsive
interaction with protonated –NH+3 groups on CO2-activated
chitosan molecules. The adsorption mechanism for different
dye species is shown in Figure 2.
Furthermore, it can be seen that the time taken to reach
the adsorption equilibrium for CR is 180 min, which is
shorter than that of BBF (300 min) and O-II (360 min). This
is because CR has a higher number of charged functional
groups on its molecule (two sulfonic groups and two amino
groups) than BBF (three sulfonic groups) and O-II (one sul-
fonic group). The effects of this on adsorption kinetics will
be discussed in Section 2.2.
2.2 Kinetics modelling
Figures 3 and 4 show the pseudo-first-order and -second-
order fittings for BBF adsorption on chitosan in pure water
and CO2-activated chitosan, respectively. The modelling pa-
rameters are summarized in Table 1. It can be seen that
the adsorption in both conditions follow pseudo-first-order
Fig. 1 Dye removal efficiency by adsorption on CO2-activated chito-
san at 55°C, C0 =20 mg L−1. ●: Brilliant blue FCF, ■: Congo
Red, ▲: Crystal Violet, ◆: Orange II
673

Fig. 2 Dye adsorption mechanism on CO2-activated chitosan
Fig. 3 Pseudo-first-order and Pseudo-second-order fitting of BBF
adsorption on chitosan in pure water; T=45°C; C0 =5 mg L−1;
●: experimental data; ——: Pseudo first order; – – –: Pseudo-
second-order
Fig. 4 Pseudo-first-order and Pseudo-second-order fitting of BBF
adsorption on CO2-activated chitosan; T=45°C; C0 =5 mg L−1;
●: experimental data; ——: Pseudo first order; – – –: Pseudo-
second-order
model. Conventionally, the pseudo-first-order model is a
representation of physical interaction between the adsorbate
and the adsorbent, with the adsorption rate changing pro-
674
Table 1 Adsorption kinetic parameters for BBF on chitosan in pure
water and CO2-activated chitosan at 45°C; C0 =5 mg L−1
Pure water
Model SD k Qe [mg g−1]
Eq. (4) 3.91 0.0353 min−1 14.5
Eq. (6) 4.38 2.90×10−3 g mg−1 min−1 16.4
CO2-activated system
Model SD k Qe [mg g−1]
Eq. (4) 8.96 0.0562 min−1 26.8
Eq. (6) 22.51 3.26×10−3 g mg−1 min−1 29.0
portionally with the amount of available adsorption sites.
Meanwhile, the pseudo-second-order model was developed
based on the assumption that: apart from the direct interac-
tion between adsorbent and adsorbate, the adsorbate mol-
ecules also undergo a chemical reaction on the adsorbent’s
surface (Ho and McKay, 1999).
In our case, the adsorption sites on CO2-activated chi-
tosan can be the protonated amino group –NH+3 . At the
same time, the aqueous solution is at low pH under the
effects of CO2 activation. Therefore, the dominant species
in the bulk aqueous solution is H+ ions, which cannot be
present on the adsorbent’s surface due to electrostatic re-
pulsion with the positive –NH+3 . As a result, that is direct
access to the adsorption sites for the sulfonic groups of dye
molecules. This leads to a physical electrostatic attraction
between oppositely-charged species without any chemical
reaction, as suggested by the modelling results. Further-
more, CO2 activation does not only improve adsorption
capacity, but also adsorption kinetics. The carbon dioxide-
activated system has a first-order adsorption rate constant,
k1 of 0.0562 min−1, which is higher than that of pure water,
0.0353 min−1. This is thought to be the result of –NH+3
groups on CO2-activated chitosan, which leads to a rapid
adsorption behavior.
Figures 5 and 6 give the pseudo-first-order and -second-
order fittings for BBF adsorption on CO2-activated chitosan
with C0 =5 mg L−1 at 55 and 65°C, respectively. The model-
ling parameters for the temperature range of 45 to 65°C are
shown in Table 2. It can be seen that the pseudo-first-order
model shows consistently high accuracy at all temperatures
from 45 to 65°C. Interestingly, the pseudo-first-order mod-
elling results show that as temperature increases from 45 to
65°C, k1 would decrease from 0.0562 to 0.0173 min−1. This
counter-intuitive behavior is opposite to usual cases. The
CO2-activated adsorption system consists of the following
steps.
Step 1 (CO2 dissolution):
CO2 (g) → CO2 (aq)
Step 2 (Proton formation):
CO2 (aq)+ H2O → HCO3− + H+
Step 3: Chitosan protonation and formation of carbamate
cross-linking
Journal of Chemical Engineering of Japan
Fig. 5 Pseudo-first-order and Pseudo-second-order fitting of BBF Fig. 7 Pseudo-first-order and Pseudo-second-order fitting of BBF ad-
adsorption on CO2-activated chitosan; T=55°C; C0 =5 mg L−1; sorption on CO2-activated chitosan; T=45°C; C0 =20 mg L−1;
■: experimental data; ——: Pseudo first order; – – –: Pseudo- ●: experimental data; ——: Pseudo first order; – – –: Pseudo-
second-order second-order

Fig. 6 Pseudo-first-order and Pseudo-second-order fitting of BBF Fig. 8 Pseudo-first-order and Pseudo-second-order fitting of BBF ad-
adsorption on CO2-activated chitosan; T=65°C; C0 =5 mg L−1; sorption on CO2-activated chitosan; T=55°C; C0 =20 mg L−1;
▲: experimental data; ——: Pseudo first order; – – –: Pseudo- ■: experimental data; ——: Pseudo first order; – – –: Pseudo-
second-order second-order

Table 2 Pseudo-first-order and pseudo-second-order kinetic param-

eters of BBF adsorption on CO2-activated chitosan at various
temperatures; C0 =5 mg L−1

T=45°C

Model SD k Qe [mg g−1]

Eq. (4) 8.96 0.0562 min−1 26.8

Eq. (6) 22.51 3.26×10−3 g mg−1 min−1 29.0

T=55°C

Model SD k Qe [mg g−1]

Eq. (4) 2.03 0.0366 min−1 30.5

Eq. (6) 9.94 1.20×10−3 g mg−1 min−1 35.9
Fig. 9 Pseudo-first-order and Pseudo-second-order fitting of BBF ad-
T=65°C sorption on CO2-activated chitosan; T=65°C; C0 =20 mg L−1;
Model SD k Qe [mg g−1] ▲: experimental data; ——: Pseudo first order; – – –: Pseudo-
second-order
Eq. (4) 0.47 0.0173 min−1 31.3
Eq. (6) 3.72 0.44×10−3 g mg−1 min−1 39.4
Dye-SO2− + Chi-NH+3 → Dye-SO3−  NH+3 -Chi
Chi-NH2 + H+ → Chi-NH+3
In our previous work (Le et al., 2018), it was found that
2Chi-NH2 + CO2 → Chi-NH-COO−  NH3+ -Chi since carbamate cross-link formation, is exothermic, an in-
Step 4: Adsorption crease in temperature would not favor cross-link formation

Vol. 52  No. 8  2019 675

Table 3 Pseudo-first-order and pseudo-second-order kinetic param-
eters of BBF adsorption on CO2-activated chitosan at various
temperatures; C0 =20 mg L−1

T=45°C

Model SD k Qe [mg g−1]

Eq. (4) 597.15 0.0181 min−1 140.7

Eq. (6) 1436.36 1.26×10−4 g mg−1 min−1 166.2

T=55°C

Model SD k Qe [mg g−1]

Eq. (4) 107.19 0.0144 min−1 136.4

Eq. (6) 553.24 1.01×10−4 g mg−1 min−1 162.5

T=65°C Fig. 10 Pseudo-first-order and Pseudo-second-order fitting of CR ad-

sorption on CO2-activated chitosan; T=55°C; C0 =20 mg L−1;
Model SD k Qe [mg g−1] ■: experimental data; ——: Pseudo first order; – – –: Pseudo-
second-order
Eq. (4) 43.40 0.0148 min−1 131.2
Eq. (6) 191.20 1.27×10−4 g mg−1 min−1 150.2

Table 4 Adsorption kinetic parameters of Congo Red and Orange II

on CO2-activated chitosan at 55°C; C0 =20 mg L−1

Congo Red

Model SD k Qe [mg g−1]

Eq. (4) 2.82 0.0149 min−1 77.9

Eq. (6) 17.92 1.94×10−4 g mg−1 min−1 92.5

Orange II

Model SD k Qe [mg g−1]

Eq. (4) 21.64 0.0150 min−1 117.8

Eq. (6) 110.27 1.29×10−4 g mg−1 min−1 139.0
and thus lead to more chitosan protonation in Step 3. How-
ever in overall, an increase in temperature would lead to
less CO2 dissolution in Step 1 (Carroll et al., 1991; Diamond
and Akinfiev, 2003; Duan and Sun, 2003; Peng et al., 2013).
Therefore, less protons formed in Step 2. This leads to a
slower chitosan protonate rate, which results in decreasing k
values as given in Table 2. The protonation state of the CO2-
activated system is indicated by the initial pH values of BBF
aqueous solution at various temperatures, as given in Table
A1 (Appendix).
Figures 7–9 show the pseudo-first-order and -second-
order fittings for BBF adsorption on CO2-activated chito-
san with C0 =20 mg L−1 at 45, 55 and 65°C, respectively.
The modelling parameters are summarized in Table 3. It
can be seen that even at higher initial BBF concentration,
the adsorption still follows the pseudo-first-order model.
Furthermore, comparing the results between Tables 2 and
3, it can also be seen that increasing the initial concentra-
tion decreases k1 values. This is because at high initial BBF
concentrations, there is more competition between sulfonic
groups for adsorption sites, which leads to a slower adsorp-
tion process.
The results of adsorption kinetics on CO2-activated chito-
san for CR and O-II dyes are given in Figures 10 and 11, re-
Fig. 11 Pseudo-first-order and Pseudo-second-order fitting of
O-II adsorption on CO2-activated chitosan; T=55°C;
C0 =20 mg L−1; ■: experimental data; ——: Pseudo first
order; – – –: Pseudo-second-order
spectively. The kinetic parameters are summarized in Table
4. It can be seen that adsorption of CR and O-II on CO2-
activated chitosan also follow the pseudo-first-order model.
Comparing with the kinetic parameters of BBF at the same
operating conditions in Table 3 (T=55°C, C0 =20 mg L−1),
it can be seen that the value of k1 for all three dye species are
approximately the same: 0.0144 min−1 for BBF, 0.0149 min−1
for CR and 0.0150 min−1 for O-II. This can be explained
by the combination of both mass transfer effects and the
dye’s chemical structure. First of all, in terms of size, BBF
molecules are the biggest (MBBF =793 g mol−1). Congo Red
molecules are slightly smaller with MCR =697 mg mol−1,
while O-II molecules have a significantly smaller size with
MO-II =350 g mol−1. As a result, if only mass transfer is con-
sidered, O-II molecules could be adsorbed more rapidly
than BBF and CR molecules. However, BBF and CR mol-
ecules have a higher number of charged functional groups
than O-II molecules. On each CR molecule, there is a total
of the four charged groups: two SO3− groups and two amino
groups which can be protonated into –NH+3 . On each BBF
molecule, there are the three SO3− groups. Orange II mol-
ecules have only one SO3− group. As a result, there is a faster

676 Journal of Chemical Engineering of Japan

 Fig. 13 Langmuir and Freundlich model fitting of BBF adsorption on
chitosan in pure water; T=25°C; ●: experimental data; ——:
Fig. 12 Effects of the dye’s chemical structure on adsorption kinetics Langmuir plot; – – –: Freundlich plot

alignment of BBF and CR molecules onto adsorption sites

and this cancels out the effects of mass transfer. This leads
to approximately the same value of k1 for all dye species.
The effect of the number of charged functional groups on
adsorption kinetics is illustrated in Figure 12. Furthermore,
it is important to note that the value of k1 is not related to
the removal efficiency. As explained previously, the removal
efficiency of CR is much lower than BBF and O-II due to
the presence of the amino groups on CR molecules, which
can have a repulsive interaction with the adsorption sites on
chitosan. The time taken to reach adsorption equilibrium
for CR is significantly shorter than BBF and O-II due to
two reasons. First of all, with the four charged groups, CR Fig. 14 Langmuir and Freundlich model fitting of BBF adsorption
dye molecules have the fastest alignment onto adsorption on CO2-activated chitosan; T=55°C; ●: experimental data;
sites. Secondly, the repulsive amino groups on CR molecules ——: Langmuir plot; – – –: Freundlich plot
prevent adsorption, whereby it takes a much shorter time
to reach the equilibrium state compared with BBF and O-II Table 5 Langmuir and Freundlich parameters for BBF adsorption on
case. chitosan in pure water at 25°C and in CO2-activated system
at 55°C
2.3 Isotherm modelling Pure water at 25°C
Modelling results of adsorption isotherms for BBF on
Langmuir Freundlich
CO2-activated chitosan are shown in Figures 13 and 14.
Langmuir and Freundlich isotherm models were used for R2
0.9980 R2
0.8799
fitting in pure water at 25°C and in the CO2-activated sys- KL [L mg−1] 0.061 KF [L g−1] 22.4
tem at 55°C, respectively. Qmax [mg g−1] 94.3 n 4.55
In our previous work (Le et al., 2018), the high tem- CO2-activated system at 55°C
perature in the CO2-activated system is required for the ac-
Langmuir Freundlich
tivation of carbamate formation, which enhances chitosan’s
2 2
stability and prevents dissolution. The numerical values of R 0.9907 R 0.8303
the fitted parameters are listed in Table 5. It can be seen KL [L mg−1] 0.095 KF [L g−1] 89.1
Qmax [mg g−1] 1862.2 n 2.04
that adsorption of both conditions follows the Langmuir
model, which indicates a homogenous adsorbent surface
and monolayer adsorption. The maximum adsorption ca-
Conclusion
pacity, Qmax, in the CO2-activated system, is 1862.2 mg g−1,
which is much higher than that in pure water (94.3 mg g−1). In this study, we evaluated the kinetics and isotherm
This value is also significantly higher than BBF maximum models for dye adsorption on CO2-activated chitosan. Ad-
adsorption capacity previously reported on clay (6.2 to sorption was found to follow a pseudo-first-order model.
14.2 mg g−1, Hernández-Hernández et al., 2013), bottom ash Compared with pure water, CO2 activation was found to
(6.9 mg g−1, Gupta et al., 2006) or de-oiled soya (18.2 mg g−1, improve not only adsorption capacity, but also the first-
Gupta et al., 2006). order adsorption rate constant, k1, which is a result of –NH+3

Vol. 52  No. 8  2019 677

groups. An interesting phenomenon was found when an in-
crease in temperature of CO2-activated adsorption leads to a
decrease in adsorption rate constant. This unusual tendency
is due to the effects of temperature on CO2 dissolution: as
temperature increases, less CO2 dissolves into the aqueous
solution. This leads to less protons available, which results
in a slower rate of chitosan protonation and thus a slower
adsorption rate constant. The dye chemical structure was
found to strongly affect the adsorption kinetics. At the same
operating condition, the adsorption rate constant of Congo
Red, Brilliant Blue and Orange II were found to be approxi-
mately the same. A large number of the protonated chemical
group on the dye molecules leads to faster alignment onto
adsorption sites. In terms of isotherm modelling, BBF ad-
sorption in both pure water and CO2-activated system was
found to follow the Langmuir model. Furthermore, BBF ad-
sorption on CO2-activated chitosan is found to have a high
value of Qmax of 1862.2 mg g−1.
Appendix
Fig. A1 Chemical structure of dyes
678
Table A1 The initial pH of BBF aqueous solution (5 mg L−1) in CO2-
activated system at various temperatures
Temperature [°C] Initial pH
25 3.92
45 3.94
55 3.95
65 3.99
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