International Journal of Biological Macromolecules 114 (2018) 1345–1353

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International Journal of Biological Macromolecules

journal homepage: http://www.elsevier.com/locate/ijbiomac

Adsorption removal of tartrazine by chitosan/polyaniline composite:

Kinetics and equilibrium studies
Sousna Sahnoun ⁎, Mokhtar Boutahala
Laboratoire de Génie des Procédés Chimiques (LGPC), Département de Génie des Procédés, Faculté de Technologie, Université Ferhat Abbas, Sétif-1‐ 19000, Algeria

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

Article history: The present work focused on the performance of chitosan/polyaniline (Cht-PANI) composite for removing
Received 11 August 2017 tartrazine dye from aqueous solutions. The adsorbent was characterized using SEM, XRD, FTIR, and TGA/DTA
Received in revised form 21 February 2018 techniques. The effects of pH, initial dye concentration, contact time, and temperature on azo dye removal
Accepted 22 February 2018
were studied. The kinetics and isotherm of tartrazine removal follow pseudo-second-order kinetics and the
Available online 24 February 2018
Freundlich isotherm, respectively. The Langmiur isotherm model exhibted a maximum adsorption capacity of
Keywords:
584.0 mg/g. The thermodynamic parameters were calculated and the negative values of ΔG° and positive value
Tartrazine of ΔH° indicate that the adsorption processes are spontaneous and endothermic in nature. In addition, the
Polyaniline resulting adsorbent reusability was demonstrated over four cycles, indicating that the Cht-PANI is a very prom-
Chitosan ising adsorbent for removal of toxic pollutants from aqueous solutions.
Composite © 2017 Elsevier B.V. All rights reserved.
Adsorption
Regeneration

1. Introduction Polyaniline (PANI) is one of the most interesting polymers because

Azo dyes are the most common group of synthetic colorants released
into the environment [1]. It has been estimated that about 8 × 105 t of
synthetic dyes are produced annually and a half of these is azo dyes
[2]. Many azo dyes and products of their degradation (e.g., aromatic
amines) are toxic and expose mutagenic and carcinogenic effects on liv-
ing organisms that raises serious environmental concerns [3]. Tartrazine
(TAR) was chosen as a representative of the sulfonated azo dyes which
are highly water soluble and most refractory to biodegradation [4]. It
was used at very low concentrations for drugs especially for the shells
of medicinal capsules, syrups, cosmetics and food additives [5]. How-
ever, it is very toxic when present in high concentrations, which cause
behavioral problems, such as asthma, migraines, eczema, thyroid can-
cer, lupus, hyperactivity and infertility for human beings [5]. Conse-
quently, the wastewater containing tartrazine with various
concentrations should be treated before discharge.
Various methods such as coagulation/flocculation, adsorption/
biosorption, ion exchange and chemical precipitation have been
employed for the removal of dyes from wastewater [1,6,7]. Adsorption
is one of the most effective methods for wastewater treatment. To
date, various adsorbents such as activated carbon, bentonite clay, fly
ash, mesoporous silica, magnetic nanoparticles, carbon nanotubes,
graphene, and graphene oxide, have been used for the adsorption of
dyes from aqueous solutions [7].
⁎ Corresponding author.
E-mail address: ssnsahnoun@yahoo.fr (S. Sahnoun).
of its easy preparation, inexpensive, high electrical conductivity, envi-
ronmental stability, and vast range of utilizations in plastic batteries, en-
ergy storage devices, sensors, light emitting diodes corrosion inhibition,
gas storage, anti-static food packaging materials and more recently for
adsorption removal of organic dyes and pollutants [8].The emeraldine
salt (ES) form of PANI appears to be polycationic and may provide a cat-
ionic site for adsorption of the anion, and the existence of the amino and
imine groups in the backbones may be in favor of the adsorption as well
[9], through electrostatic interaction or hydrogen bonding [10]. How-
ever, pure polyaniline particles are generally aggregated in solution
and lower the adsorption process and slow kinetics [11]. Chitosan
(Cht) is an eco-friendly biopolymer that is obtained from deacetylation
of chitin [12]. It is extracted from the main component of the exoskele-
ton of crustacean shells, such as shrimps and crabs. Chitosan is biode-
gradable, biocompatible, non-irritant and exhibits good film-forming
properties, high mechanical strength, and adhesion. It is relatively
cheap and has been widely used as an adsorbent for dyes, transition
metals, and organic species because the amino (\\NH2) and hydroxyl
(\\OH) groups on the chitosan chains can serve as coordination and re-
action sites [13]. Amino groups of chitosan can be cationized [14] and
available for adsorption of anionic dyes strongly by electrostatic attrac-
tion in the acidic media [14]. However, the disadvantage of this biopoly-
mer is readily soluble in dilute acidic solutions below at pH of 5.5 ± 0.5,
which limits its use as an adsorbent in removing dyes in acidic effluents
[13]. This results in suppression of specific binding sites, such as amino
(\\NH2) and hydroxyl (\\OH) sites and, therefore, a reduction of ad-
sorption capacity [13]. One method to overcome this disadvantage for

https://doi.org/10.1016/j.ijbiomac.2018.02.146
0141-8130/© 2017 Elsevier B.V. All rights reserved.
1346 S. Sahnoun, M. Boutahala / International Journal of Biological Macromolecules 114 (2018) 1345–1353
practical applications is to graft two or more conducting polymers into
the biopolymer chitosan. After grafting, the mechanical strength and
the resistance to acidic environment will be improved [15,16]. As a re-
sult, the active binding sites will be well exposed. Recently, researchers
have given considerable attention in synthesis of different conducting/
biopolymeric composite materials, according to their wide application
in environmental sciences [16]. These materials provided a stronger ad-
sorbent capacity for anion/oxyanions [16]. However, to our knowledge,
chitosan grafted with polyaniline (Cht-PANI) as a composite has never
been used as an adsorbent for the removal of tartrazine from aqueous
solution.
In this study, Chitosan/polyaniline material was synthesized by in
situ chemical polymerization method using ammonium peroxydisulfate
(APS) as an oxidant, and characterized by SEM, XRD, FTIR, and TGA tech-
niques. The composite capacity for the removal of tartrazine was stud-
ied and the effect of different parameters including pH of solution,
reaction time and initial concentration of the dye on the removal effi-
ciency was investigated in detail. Adsorption kinetics, adsorptions iso-
therms were also examined.
2. Experimental
2.1. Materials
Tartrazine (Acid Yellow 23, trisodium1-(4-sulfonatophenyl)-4-(4-
sulfonatophenylazo)-5-pyrazolone-3-carboxylate) is an anionic dye, also
known as the additive E102, with a molecular weight of 534.4 g·mol−1
and a molecular formula C16H9N4Na3O9S2, C.I. 19140, dye content ≥85%.
Its chemical structure is shown in Fig. 1. It was obtained from Sigma
Aldrich. Chitosan flakeswere used without further purification. Aniline
and ammonium persulfate ((NH4)2S2O8) required for polymerization
were obtained from GPR RECTAPUR.
2.2. Synthesis of polyaniline
The synthesis method described below is a modification of the pro-
cedure reported by Sun et al. [17]. The pure polyaniline was synthesized
by oxidative polymerization of aniline monomer using APS, as an oxi-
dant in hydrochloric acid solution. The mixture was magnetically stirred
for 4 h. Then, the greenish-black solid compound obtained was washed
with distilled water until no free Cl− ions were detected in the filtrate.
Finally, the PANI powder was dried at 60 °C.
2.3. Synthesis of the chitosan/polyaniline
Chitosan/polyaniline was synthesized by oxidative polymerization.
In detail, an amount of chitosan was dispersed in HCl solution. Then 1
mL aniline was added into the suspension. After stirring magnetically
for 15 min, a known amount of ammonium persulfate solution was
then added dropwise to the suspension within 4 h under mechanical
stirring. The sample was centrifuged and washed several times with dis-
tilled water until no free Cl− ions stop appearing in the filtrate and then
dried at 60 °C .
Fig. 1. Chemical structure of tartrazine.
2.4. Instrumental characterization
The morphological structure of the investigated samples was exam-
ined using scanning electron microscope (NEO SCOPE JEOL, JCM-5000).
X-ray diffraction (XRD) analyses of adsorbents were carried out with
a Rigaku Miniflex II diffractometer using CuKα radiation (1.5406 Ǻ) and
a graphite monochromator at room temperature, operated at 30 kV and
15 mA. Diffraction patterns were recorded between 5 and 90° (2θ)
using increments of 0.02° and a counting time of 2 s.
Fourier transform infrared spectroscopy (FTIR) analysis of the sam-
ples was carried out in KBr pellets in the range of 400–4000 cm−1
using Fourier Transform infrared (FTIR) 8400S Shimadzu having a stan-
dard mid-IR DTGS detector.
Thermal gravimetric analysis (TGA) of the materials was performed
on LABSYSevo de SETARAM instrument at a heating rate of 10 °C/min
from 25 °C to 900 °C in nitrogen gas.
The point of zero charge (pHpzc) value of Cht-PANI was determined
according to the method described by Nandi et al. [18]. Initial pH values
(pHi) of 10 cm3 H2O solution were adjusted in the pH range of 2–12
using HCl or NaOH. Then, 0.01 g of adsorbent was added to each sample.
The dispersions were stirred for 24 h at ambient temperature and the
final solution pHs (pHf) were noted. The point of zero charge was ob-
tained by plotting pHf versus pHi.
2.5. Dye adsorption experiments
The isotherm adsorption experiments were evaluated at different
initial concentration of TAR and at initial solution pH equal 7,2 (pH of
the solution). The effect of the initial solution pH on TAR adsorption
was studied by using 10 mL of the dye solution and 10 mg of the Cht-
PANI. The initial concentration of TAR dye solution was 400 mg/L, and
the pH of the solution was adjusted by adding few drops of HCl and
NaOH. To study the effect of contact time on the adsorptive removal of
TAR, batch experiments were conducted at 25 ± 1 °C and at pH of the
solution (pH = 7.2). For each experimental run, 10 mL of TAR solution
of initial concentration equal to 50, 100, 200 and 400 mg/l and
adsorbent dose equal to 10 mg was agitated on a rotary shaker at a
constant speed. The effect of temperature on the equilibrium
adsorption of TAR on the composite was studied at different tempera-
tures, i.e. 288 K, 298 K, and 318 K using a Thermostatic chamber. The
initial concentration of TAR was 400 mg/L and the composite
dosage was 10 mg at pH = 7.2. The supernatant liquid was centrifuged
out and the equilibrium concentration of TAR was determined using
UV–Vis spectra (Shimadzu UV-1700 UV/VIS spectrophotometer) at
426 nm. The removal (%) of tartrazine and the amounts adsorbed onto
the adsorbent at equilibrium qe (mg/g) and at any time qt (mg/g)
were calculated using Eqs. (1) and (2) :
C 0 −C e
Rð%Þ ¼  100 ð1Þ
C0


C 0 −C e;t  V
qe;t ¼ ð2Þ
m
where qe,t (mg/g) is the amount of adsorbed tartrazine at equilibrium
(qe) or at any time (qt); V the volume of solution (L), C0 (mg/L) is the
initial dye concentration; Ce,t is the tartrazine concentrations at equilib-
rium (Ce) or at any time (Ct) (mg/L) and m is the weight (g) of the ad-
sorbent used.
2.6. Desorption and regeneration of Cht-PANI composite
To make the adsorption procedure more environment-friendly and
economical, regeneration of adsorbent is very necessary aspect [19].
The low tartrazine adsorption quantity onto Cht–PANI at high pH
value implies that tartrazine loaded adsorbent can be desorbed in
 S. Sahnoun, M. Boutahala / International Journal of Biological Macromolecules 114 (2018) 1345–1353 1347

Fig. 2. SEM images of the (a) chitosane, (b) PANI and (c, d) Cht-PANI before and after adsorption of tartrazine, respectively.

alkaline medium. Desorption experiments of tartrazine from Cht-PANI
were performed using NaOH as desorbing agent and HCl solution as
the activation agent [20]. Repetitively, the regenerated adsorbents
were applied to treat the same concentration of tartrazine solution
(C0 = 200 mg/L). The percentage of desorption of TAR was calculated
according to Eq. (3) :
mdes
Rð%Þ ¼  100
mads
where mdes(mg) and mads(mg) are the amounts of desorbed and
adsorbed TAR, respectively.
2.7. Error analysis
The values of the kinetic and isotherm parameters were determined
by the regression analysis using ORIGIN program (version 8.5). The cor-
relation coefficients (R2) and residual root-mean-squared error (RMSE)
were used to analyse the data set and to confirm the best fit kinetics and
isotherm model for the adsorption. If data from the model are similar to
those obtained in experiments, R2 will be close to 1 and RMSE will be a
low value. The R2 and RMSE were evaluated using Eqs. (4) and (5).
3. Results and discussion
3.1. Characterization
The morphologies of Cht, PANI, and Cht-PANI before and after ad-
sorption were investigated by scanning electron microscopy (SEM).
The SEM images of the samples are shown in Fig. 2a–d. The SEM micro-
graph for pure Cht, Fig. 2a shows a smooth, opaque and homogeneous
ð3Þ surface with some wrinkles without pores [13]. Whereas the PANI in
Fig. 2b shows aggregated particles with no uniform size. The SEM
image of Cht-PANI composite (Fig. 2c) indicates that the particles are
in fiber like structure. After tartrazine adsorption, the same image (Fig.
2d) of Cht-PANI shows changes in adsorbent surface where particles
are stuck together and the pores are partially filled with tartrazine.
The difference in crystallinity between the Cht and Cht-PANI com-
posite were investigated by XRD (Fig. 3). For Cht, diffraction peaks are
observed at 2θ = 10.4° and 19.8°. The peaks at 2θ = 9.1°, 15.7°, 20.7°

 2
n
∑n¼1 qe;t: exp:n −qe;t:cal:n
2
R ¼ 1−  2 ð4Þ
n
∑n¼1 qe;t: exp:n −qe;t:cal:n

rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1  2
n
RMSE ¼ ∑ q −qe;t:cal:n ð5Þ
n−1 n¼1 e;t: exp:n

where qe, t. exp and qe, t. cal are the experimental adsorption capacity at
equilibrium (qe,exp) or at any time (qt,exp) and the calculated adsorption
capacity at equilibrium qe. cal or at any time qt. cal from the models,
respectively. Fig. 3. X-ray diffraction patterns of Cht, PANIand Cht-PANI.
1348 S. Sahnoun, M. Boutahala / International Journal of Biological Macromolecules 114 (2018) 1345–1353
Fig. 4. FTIR patterns of Cht, PANI and Cht-PANI.
and 25.3° are characteristic of PANI [16]. The peaks observed at 20.7°
and 25.3° for PANI can be ascribed to periodicity parallel and perpendic-
ular to the polymer chains, respectively [21]. However, the XRD pattern
of Cht-PANI shows distinct crystalline peaks with little shifts corre-
sponding together to the Cht and PANI, which further supported the
successful grafting of PANI on to the Cht backbone [16,22], in the
position of the peaks. It is clearly seen from XRD results that the com-
posite presents an amorphous nature with a small crystalline area
between 2θ = 15 and 30° [16]. The crystallinity of Cht has been de-
creased after grafting with PANI and this may be due to the intermolec-
ular interaction between the Cht and PANI, which is anticipated for the
removal of tatrazine.
Fig. 5. TGA/DTA curves of Cht, PANI and Cht-PANI.
The FTIR spectra of Cht, PANI, and Cht-PANI are shown in Fig. 4. FTIR
spectrum of Cht exhibits adsorption bands at 3446, 2924, 2870, 1649
and 1086 cm−1. The peak at 3446 cm−1 is due to overlapping of the
stretching bands of both primary amine [23] and –OH groups present
in chitosan. The peak located at 2870 cm−1 indicates the C–H stretching
vibration in CH and CH2 [23]. The peak occurs at 1649 cm−1 indicates a
stretching vibration peak of C=O in –NHCO– [24]. The spectrum of PANI
shows the presence of characteristic absorption bands at 1555 cm−1
(C=C stretching vibration of the quinoid ring), 1476 cm−1 (stretching
vibration of C=C of the benzenoid ring) and 1288 cm−1 (C–N stretching
vibration) [25]. The bands in the range of 3000–3500 cm−1 correspond
to secondary amine stretching (N–H) vibrations [26]. The FTIR spectrum
of Cht-PANI composite shows the following adsorption bands at 3442,
2936, 2853, 1643 and 1120 cm−1.With respect to Cht, many functional
groups shifted to different bands or disappeared. The bands at 3446,
1654 cm−1 shifted to a lower frequency band at 3442, 1643 cm−1. On
the contrary, the peak at 2870, 2924 cm−1 and the bands between
1200 and 1500 cm−1 were disappeared. These changes indicate that
an appreciable amount of O–H and N–H at Cht have been grafted with
PANI [27,28].
The TGA and DTA curves of PANI, Cht, and Cht-PANI are presented in
Fig. 5. The DTA curve for the PANI shows three weight losses at 105 °C,
286 °C and 520 °C corresponding on the TGA curves to three step de-
compositions. The first step of 9% ranging from room temperature to
approximately 140 °C corresponds to the loss of physisorbed and inter-
layer water. The second weight loss of 11% in the range of 140–355 °C
corresponds to the removal of dopant molecule and oligomer [21],
whereas the third mass loss of about 30% occurring beyond 355 °C is at-
tributed to the thermal decomposition and degradation of the PANI
chains [21]. The DTA curve of Cht displays two prominent endothermic
 S. Sahnoun, M. Boutahala / International Journal of Biological Macromolecules 114 (2018) 1345–1353 1349

Fig. 6. Adsorption isotherm for adsorption of tartrazine onto Cht, PANI and Cht-PANI (V = Fig. 7. Effect of initial pH on tartrazine removal from solution by Cht-PANI (C0 = 400 mg/L,
10 mL, m = 10 mg, pH = 7.2 and T = 25 ± 1 °C). V = 10 mL, m = 10 mg and T = 25 ± 1 °C).

peaks at 98 °C and 307 °C. The two weight loss stages, observed in the
TGA curve, coincide with the two endothermic peaks in the DTA pro-
files. The first weight loss (6%) between temperatures of 35 °C and
150 °C is ascribed to the removal of water from the adsorbent. The sec-
ond stage, starting at 220 °C up to 900 °C with 57% weight loss, is
assigned to the dehydration of the saccharide rings, depolymerization
and decomposition of the acetylated and deacetylated units of the ad-
sorbent and decomposition of Cht [29]. The Cht-PANI composite dis-
plays three major peaks during the DTA measurement. The first step
at 98 °C was related to the release of water molecules adsorbed in poly-
mer composite, which was consistent with the TGA result. A loss in TGA
curve around 200–250 °C, associated with the second peak at 225 °C,
was probably involved in the decomposition of the chitosan. The third
peak at 262 °C in the range of 250–900 °C was attributed to degradation
of polymer chain [30]. Comparing the TGA/DTA curves of three mate-
rials, it is clearly observed that the decomposition temperature of the
composite occurs at lower temperatures. This may be related to the in-
fluence of volatile substances of free chitosan and/or PANI, which accel-
erate the process of degradation of the composite [31].
3.2. Tartrazine adsorption studies
where Ce (mg/L) is the equilibrium concentration of TAR, qm (mg/g)
represents the maximum adsorption capacity, KL (L/mg) is the Lang-
muir constant related to the energy of adsorption and represents the af-
finity within adsorbent and adsorbate.
The essential feature of the Langmuir isotherm can be expressed in
terms of dimensionless separation factor (RL), which can be defined
via Eq. (7) [10]:
1
RL ¼ ð7Þ
1 þ K L C0
where C0 is the initial concentration (mg/L) of TAR. The value of RL indi-
cates the isotherm to be either favorable (0 b RL b 1), unfavorable (RL N
1), linear (RL = 1) or irreversible (RL = 0).
The Freundlich equation hypothesizes that the adsorption process
happens on heterogeneous surfaces in the multilayer pattern of varied
affinities. It is based on the fact that, the stronger binding sites are occu-
pied first and that the binding strength reduces as the degree of site oc-
cupation increases.
The nonlinear Freundlich equation is expressed as given by Eq. 8
[33]:

3.2.1. Adsorption isotherms

The adsorption isotherms describe the equilibrium adsorption pro-
cess at a constant temperature and pH. The variation of amount
adsorbed (qe) vs. concentration (Ce) is plotted in Fig. 6. The adsorption
isotherm data were fitted by the Freundlich and Langmuir models,
which are the most frequently used The Langmuir equation hypothe-
sizes that the adsorption process happens on a homogeneous surface
in the monolayer pattern, and the sorption energies are equivalent.
The non-linear Langmuir equation can be expressed as follows (Eq.
(6)) [32]:
qm K L C e
qe ¼
1 þ K LCe
1
=n
qe ¼ K F C e ð8Þ
where n is the Freundlich constant reflecting the intensity of the adsorp-
tion, KF ((mg/g) (L/mg)1/n) is a constant indicating the adsorption ca-
pacity of the adsorbent. A non-linear regression was used to
determine the best-fitting isotherm, and the applicability of the iso-
therm equations was judged by comparing the correlation coefficients,
R2 and RMSE. The calculated constants of the two isotherm equations,
along with R2 and RMSE values, are presented in Table 1.
The highest values of the R2 and low RMSE for both Langmuir and
Freundlich models showed that the adsorption isotherms of TAR by all
samples (Table 1, Fig. 6) were represented by the two models, but
ð6Þ
Freundlich model was better, indicating that the removal of TAR was

Table 1
Isotherm constants for the removal of tartrazine onto Cht, PANI and Cht-PANI.

qexp qm Langmuir Freundlich

2 2
KL ∗ 10 RL R RMSE KF 1/n R2 RMSE

Cht 46.4 51.5 0.009 0.965 0.926 4.50 5.30 0.328 0.936 4.20
PANI 434.5 425.9 0.272 0.188 0.782 87.24 337.5 0.035 0.783 87.12
Cht-PANI 617.8 584.0 0.231 0.214 0.877 89.01 323.5 0.094 0.882 87.16

qexp (mg/g), qm (mg/g), KL (L/mg), KF (mg/g (L/mg)1/n).

1350 S. Sahnoun, M. Boutahala / International Journal of Biological Macromolecules 114 (2018) 1345–1353
achieved on heterogeneous surface of all samples and the formation of a
multi-layer adsorption, which also supports the proposed physisorption
mechanism [34]. Moreover, the RL and 1/n values lie between 0 and 1,
indicating favorable conditions for the adsorption. The results obtained
are in good agreement with literature which reported that the
Freundlich model provided a better fit than the Langmuir model
[16,22,35,36]. As Cht-PANI is the best absorbent, only the effect of initial
pH of the solution, the kinetic and temperature of the Cht-PANI will be
further studied.
3.2.2. Effect of initial pH
Fig. 7 presents the amount of tartrazine adsorbed versus pH of the
solutions. The amount of tartrazine adsorbed was observed to increase
with increasing pH of dye solution when the pH values change from 2
to 7 from 393.9 mg/g to 397.8 mg/g and decrease from 397.8 mg/g to
188.1 mg/g when the pH increases from7 to 11. The effect of pH on
the TAR adsorption is related to the surface charge of the Cht-PANI
and adsorbate. The pKa values of different attractor groups representing
the tartrazine molecule (sulfonic acid group (\\SO− 3\ \), carboxylate
group (\\COO−\\) and azo group (\\N=N\\)) were 2.0, 5.0, and
10.86, respectively [37]. Thus, for pHsolution N pKa = 2, tartrazine mol-
ecules exist in an anionic form and for pHsolution b pKa = 2, tartrazine
molecules exist in a neutral form [38]. The pHpzc of Cht-PANI was found
to be 6.1 (Fig. 7, inset). At pH b pHpzc, the surface is positively charged
and favors the uptake of anionic tartrazine dye and at pH N pHpzc, the
surface is negatively charged. In the range of pH 2–7, protonation of ni-
trogen atoms of the composite occurred. Also, the predominant forms of
the dye at this pH are sulfonic acid group (\\SO−
3 ) and carboxylate
group (\\COO−) where the Cht-PANI would present more positively
charged sites. Therefore, adsorption occurs between the positively
charged surface and the anionic form of tartrazine. When the pH in-
creases, the number of negative sites increases and the surface becomes
negatively charged due to deprotonation of nitrogen atoms of the com-
posite and the competition adsorption of OH− on both imine and amine
functional groups. Hence, the repulsion of anionic tartrazine dye with
negative charges can be promoted. Similar trends were reported for
the removal of tartrazine using hen feathers [39] and biosorbent acti-
vated carbon of Lantana camera [40].
3.2.3. Effect of initial tartrazine concentration
The effect of initial concentration of TAR solution on the adsorption
by Cht-PANI was investigated. Batch experiments with different dye
concentrations were carried out at equilibrium time and the plot of ad-
sorption capacity (qe) and removal percentage (%) versus different TAR
concentrations are shown in Fig. 8. It was observed that the amount
adsorbed increased with increasing concentration from 25 mg/L to
Fig. 8. Effect of initial concentration on tartrazine removal onto Cht-PANI (pHi = 7.2, V =
10 mL, m = 10 mg and T = 25 ± 1 °C).
Fig. 9. Effect of contact time on the adsorption of tartrazine onto Cht-PANI (pH = 7.2, V =
10 mL, m = 10 mg and T = 25 ± 1 °C).
1600 mg/L of the solution, but the removal percentage decreased. It
was found that the removal efficiency of the TAR dye remains constant
(100%) for the initial dye concentration from 25 to 200 mg/L. The effi-
ciency decreased from 99.8 to 38.9% with an increase in TAR concentra-
tion from 400 to 1600 mg/L. We can say that the residual concentration
of dye molecules will be higher for higher initial dye concentrations. In
the case of lower concentrations, the proportion of initial number of dye
molecules to the available adsorption sites is low and subsequently, the
fractional adsorption becomes independent of initial concentration [12].
The similar effect is also observed in other research [41,42].
3.2.4. Effect of contact time
Fig. 9 shows the influence of contact time on the adsorption of
tartrazine onto Cht-PANI with different initial concentrations (50,100,
200 and 400 mg/L). The tartrazine dye was observed to rapidly achieve
equilibrium (120 min) at initial concentrations (50,100 and 200 mg/L).
However, at higher concentration (400 mg/L), tartrazine required lon-
ger contact time (1140 min) to reach equilibrium. The increase in equi-
librium time with increasing initial TAR concentration is due to the
increased competition for the active adsorption sites of the adsorbent
[18]. At a lower initial concentration of dye, excess adsorption sites are
vacant for dye molecules, but for a higher concentration, the proportion
of adsorbent sites decreases in contrast to available dye molecules and
all the binding sites easily get saturated due to the higher concentration
of dye molecules [43].
3.2.5. Kinetic studies
The kinetic data in this study were applied on pseudo-first-order and
pseudo-second-order models. The pseudo-first-order kinetic model is
an equation for the adsorption in a solid/liquid system based on the dif-
ference between equilibrium adsorption capacity, qe, and actual solid
phase concentration, qt, measured at a given time t. The linear form of
the pseudo-first-order equation is given by Eq. (9) [44]:
ln ðqe −qt Þ ¼ ln q−k1 t ð9Þ
where k1 (min−1) is the equilibrium rate constant of pseudo-first-order
equation. The rate constants are obtained from the straight line plots of
ln (qe − qt) vs. t. (Figure not shown) and the values are given in Table 2.
The pseudo-second-order model is based on the assumption of
chemisorption of the adsorbate on the adsorbent [45]. This model is
given by Eq. (10):
t 1 t
¼ þ ð10Þ
qt k2 q2e qe
 S. Sahnoun, M. Boutahala / International Journal of Biological Macromolecules 114 (2018) 1345–1353 1351

Table 2
Kinetic parameters for the adsorption of tartrazine onto Cht-PANI.

Models Parameters Initial concentration (mg/L)

50 100 200 400

Pseudo-first-order k1 ∗ 10+2 6.1 6.5 5.6 0.6

qcal 45.6 97.5 186.8 242.4
R2 0.987 0.995 0.992 0.885
RMSE 0.173 0.101 0.12 0.609
Pseudo-second-order k2 ∗ 10+3 5.0 2.6 1.2 0.08
qcal 50.4 102.1 202.0 408.2
R2 0.999 0.999 0.999 0.999
RMSE 0.079 0.033 0.018 0.027
Intraparticle diffusion Kid 0.6 1.3 2.6 8.0
C 34.5 70.9 137.2 160.7
R2 0.289 0.316 0.335 0.744
RMSE 9.94 18.62 37.10 58.49
qe,exp (mg/g) 50 100 200 397.5

qe,exp (mg/g), qcal (mg/g), k1 (L/min), k2 (g/mg·min), kid (mg·g−1 min−0.5).

where k2 (g /mg min) is the rate constant of pseudo-second-order ki-

netics. The linear plots of t/qt vs. t were used to obtain the rate parame-
ters given in Table 2. The pseudo-first-order and pseudo-second-order
kinetic parameters are determined taking into account the coefficient
R2 and RMSE function values. According to Table 2, the adsorption kinet-
ics of TAR onto Cht-PANI is better described by the pseudo-second-
order kinetic model values than the pseudo-first-order model at all ini-
tial concentrations because of the high R2 and low RMSE. In addition, the
qcal values estimated from the pseudo-second-order kinetic model were
also very close to the experimental values, qexp, for all the tested con-
centrations. This indicates that the TAR adsorption onto Cht-PANI is
controlled by a chemical process [46]. The adsorption rate constants cal-
culated based on the pseudo-second-order kinetics are 0.005, 0.0026,
0.0012 and 0.00008 g/mg·min at initial concentration of 50, 100, 200
and 400 mg/L, respectively, reflecting a slower adsorption process at a
high initial TAR concentration. This is probably due to the reduced ac-
cessibility to active sites of Cht-PANI adsorbent compared to the large
quantity of TAR adsorbate. This increases the electrostatic repulsion be-
tween the tartrazine molecules on the adsorbent obtained in the bulk
phase, which may also hinder the access of TAR molecules to Cht-
PANI, resulting in the slow adsorption rate. Several authors showed
the successful application of the pseudo-second-order model for the
representation of experimental kinetic data of pollutants adsorption
on various adsorbents [35,36,47].
3.2.6. Adsorption mechanism
Intraparticle diffusion is a transport process involving the movement
of species from the solution bulk to the solid phase. In a well-stirred
batch adsorption system, the intraparticle diffusion model is used to de-
scribe the adsorption process occurring on a porous adsorbent. A plot
that expresses the amount of the dye adsorbed, qt (mg/g) as a function
of the square root of the time, gives the rate constant by calculating the
plot slope. This model can be described via Eq. (11) [48]:
pffiffi
qt ¼ kid tþC
where, kid (mg·g−1 min−0.5) and C are diffusion coefficient and
intraparticle diffusion constant, respectively. C is directly proportional
to the thickness of the boundary layer.
According to this model, the plots (Fig. 10) are non-linear for the
whole range of the studied concentrations, indicating that intraparticle
diffusion is not the only rate-limiting step, but another process may also
be involved in the adsorption process. Two different sharp stages are
clearly observed in Fig. 10, for the concentration of 50, 100 and 200
mg/L and three stages for the high concentration (400 mg/g). The first
stage, including an adsorption period from 0 to 120 min (t1/2 b 7.0), de-
scribes the instant adsorption stage where TAR adsorption rate is high
because of a large surface area and a low competition between the
Fig. 10. Adsorption mechanism on the adsorption of tartrazine onto Cht-PANI.
tartrazine molecules. The second part, ranging from 120 to 1200 min
(7.0 b t1/2 b 35) for 50, 100 and 200 mg/L, is attributed to the low ad-
sorption stage caused by the low concentration gradients, producing
the equilibrium condition. The values of kid were determined from the
slopes of the linear plots and presented in Table 2.
3.2.7. Thermodynamic parameters
In order to better understand the nature and mechanism of the TAR
dye adsorption onto the Cht-PANI surface, adsorption data at different
temperatures were used to calculate thermodynamic parameters such
as the change in enthalpy (ΔH°), change in free Gibbs energy (ΔG°)
and change in entropy (ΔS°) Eqs. (12) and (13):
 
qe
ΔG ¼ −RT ln ð12Þ
Ce
 
qe ΔS ΔH
ln ¼ − ð13Þ
Ce R RT
where qe is the amount of TAR adsorbed per unit mass of samples (mg/
g), Ce is the equilibrium concentration (mg/L), R is the molar gas con-
stant (8.314 J/ mol K−1), and T is the absolute temperature (K). The
thermodynamic parameters were determined from the slopeand inter-
cept of Van't Hoff's plot of Ln (qe/Ce) versus 1/T (Figure not shown).The
values of all thermodynamic parameters are listed in Table 3. The de-
crease in the negative values of ΔG° with an increase in temperature
(288 K to 318 K) indicates that the adsorption becomes more favorable
at high temperature. The positive ΔH° values indicate that the adsorp-
tion is an endothermic process. Moreover, the positive ΔS° indicates
that the degrees of freedom increase at the solid-liquid interface during
adsorption of the dye onto Cht-PANI [43]. Generally, ΔH° value for
ð11Þ physisorption and chemisorption is between 2.1‐20.9 kJ/mol and
20.9–418.4 kJ/mol, respectively [16]. ΔH° values from Table 3 confirm
that the adsorption of TAR onto Cht-PANI is a physisorption in nature .
3.2.8. Suggested adsorption mechanism
The adsorption mechanism was investigated by SEM and FTIR anal-
ysis. According to the SEM image of the Cht-PANI after dye adsorption
(Fig. 2), the pores disappeared and the surface was smoothed and al-
tered slightly which further confirms the structural changes in the
Cht-PANI composite. In the FTIR spectrum of Cht-PANI after dye adsorp-
tion (Fig. 11), some modifications were verified in relation to the spec-
trum before adsorption. After the adsorption of TAR onto Cht-PANI,
many functional groups shifted to different bands. The bands at 3442,
1643 and 1120 shifted to lower frequencies at 3436, 1639 and 1102
1352 S. Sahnoun, M. Boutahala / International Journal of Biological Macromolecules 114 (2018) 1345–1353

Table 3 Table 4
Thermodynamic parameters for tartrazine adsorption on Cht-PANI. Comparison of the adsorption capacity of Cht-PANI with various adsorbents for tartrazine
removal.
T (K) ΔG° (kJ/mol) ΔH° (kJ/mol) ΔS° (J/mol K)
Adsorbents pH m T C0 qmax References
288 −10,9 11.6 78.2
(mg) (°C) (mg/l) (mg/g)
298 −11,6
318 −13,2 Bottom ash 2 100 50 5.3–53.4 12.6 [51]
Deoiled soya 2 50 50 5.3–53.4 24.6 [51]
Hen feather 2 10 50 5.3–53.4 74.82 [39]
polypyrrole coated tenorite / 1000 45 100–200 42.50 [43]
nanoparticle
Sawdust / / 45 1–15 4.71 [52]
Activated carbon of Lantana 2 200 50 25–200 90.9 [40]
Camara
Polyaniline nanolayer 2 500 25 50–200 2.47 [47]
composite
Cross-linked chitosan coated 2.5 10 47 20–300 294.1 [49]
bentonite
5 Ag/CNTs / 25 / / 84.04 [38]
Cht-PANI 7.2 10 25 10–1600 584.0 This study

Due to the electrostatic attraction between these two counter ions,

the adsorption process then proceeds,

−
R−NHþ þ 
3 þ D−SO3 →R−NH3 ⋯⋯ O3 S−D

This interaction mechanism was also verified in other research, which

Fig. 11. FTIR spectra of (a) Cht-PANI and (b) Cht-PANI after adsorption of tartrazine. used chitosan based materials as adsorbents [46,49].

3.2.9. Regeneration studies

cm–1, respectively, whereas the peak at 1305 cm–1 slightly shifted to a
high-frequency band at 1338 cm–1. These changes indicate that the pos-
sible interaction of surface sites with TAR ions. From the results men-
tioned above, it was observed that the Cht-PANI possessed great
adsorption capacity for the removal of TAR. The synthesis of the com-
posite Cht-PANI was done in acidic medium, so most amino groups of
chitosan are protonated and the PANI under acidic condition
(emeraldine salt ES form), it would be positively charged. The following
mechanism suggested the adsorption of TAR onto Cht-PANI may be:
Dye is first dissolved and the sulfonate groups of dye (D-SO3Na) are
dissociated and converted to anionic dye ions.
D−SO3 Na→D−SO−
3 þ Na
þ
Adsorption and desorption regeneration experiments were con-
ducted to reuse Cht-PANI composite. Generally, acidic or alkaline solu-
tions are used to regenerate the adsorbent. In this study, sodium
hydroxide (NaOH) solution was used to regenerate Cht-PANI compos-
ite. Four regeneration adsorptions capacities of Cht-PANI are shown in
Fig. 12 for the dye compound. It was observed that at the first, second,
three and four adsorption cycles, the adsorption capacities were 100%,
98.6%, 98.1% and 97.7%, respectively. The total adsorption capacity
slightly decreased after four-time regeneration. The small decrease in
each cycle may be attributed to the breakage of the polymer chains by
repeated acid/base treatment during the regeneration [50]. However,
the decrease was not too significant, demonstrating the high reusability
of the composite, and show an excellent regeneration property.

3.3. Comparison with other adsorbents

Also, the amino groups of Cht-PANI were protonated in the presence
of H+.
The Langmuir monolayer adsorption capacities were 51.5 mg/g,
425.9 mg/g, and 584.0 mg/g for Cht, PANI, and Cht-PANI, respectively.
R−NH2 þ H3 Oþ ⇆R−NHþ
3 þ H2 O The adsorption capacity of TAR in the present study was compared to
other adsorbents and reported in Table 4. It was observed that the
Cht-PANI exhibits much higher adsorption capacity for TAR as com-
pared to other reported adsorbents. For all the adsorbents named in
Table 4, the adsorption of TAR was studied at pH in the range of 2–4.5.
The acidification procedure would raise the salinity which is a new seri-
ous environmental problem. On the other hand, because of the high ad-
sorption of TAR in our experiments, Cht-PANI could be used for TAR
wastewater treatment directly without adding supplementary cost
and environmental issues.

4. Conclusion

A Cht-PANI composite was synthesized, characterized and examined

Fig. 12. Adsorption/desorption cycles of TAR onto Cht-PANI.
as adsorbant for tartrazine. Grafted with chitosan, PANI played an im-
portant role in modifying the morphology and decreasing the crystallin-
ity of chitosan. Therefore, the adsorption was favored due to amine and
imine groups in the composite. Freundlich isotherm model was found to
be better fitted with the experimental data than Langmuir isotherm
model. The maximum adsorption capacity of the composite was
 S. Sahnoun, M. Boutahala / International Journal of Biological Macromolecules 114 (2018) 1345–1353
measured to be 584.0 mg/g. The kinetic study indicated that the TAR ad-
sorption obeyed pseudo-second-order model. Thermodynamic studies
showed spontaneous and endothermic nature of the overall adsorption
process. These results show that Cht-PANI composite is a promising ma-
terial as an adsorbent for tartrazine removal from aqueous solutions
without an adjustment of pH of the dye wastewater.
Acknowledgements
The authors gratefully acknowledge the “Laboratoire de Chimie et
Physique Approche Multi-échelle des Milieux Complexes (LCPA2MC),
57500 Saint-Avold, France” for providing facilities for recoding ATG/
DTG and X-ray diffraction data. Special gratitude to Prof. Kahoul
Abdelkrim for his technical support.
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