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Development of novel cross-linked chitosan

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DOI: 10.1016/j.molliq.2017.09.006

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 Journal of Molecular Liquids 244 (2017) 211–218

Contents lists available at ScienceDirect

Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Development of novel cross-linked chitosan for the removal of anionic

Congo red dye
Abdul Zahir a, Zaheer Aslam a,⁎, Muhammad Shahzad Kamal b, Waqar Ahmad c,
Aamir Abbas a, Reyad Awwad Shawabkeh c
a
Department of Chemical Engineering, University of Engineering and Technology Lahore, 54890, Pakistan
b
Center for Integrative Petroleum Research, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
c
Department of Chemical Engineering, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia

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

Article history: The research results summarize the potential of novel cross-linked chitosan for the removal of Congo red dye
Received 24 July 2017 from an aqueous phase. Synthesized materials were characterized by FTIR, XRD, TGA, DSC and SEM. The effects
Received in revised form 31 August 2017 of several process conditions like effect of adsorbent dose, contact time, initial solution pH and temperature
Accepted 1 September 2017
were investigated. Equilibrium adsorption data was best fitted to Sips Isotherm model and maximum dye uptake
Available online 5 September 2017
was 1597 (mg/g) for diammonium tartrate modified chitosan (DMC) while 1447 (mg/g) for urea diammonium
Keywords:
tartrate modified chitosan (UDMC). The adsorption kinetic data was well followed by pseudo-second-order ki-
Chitosan netic model. The thermodynamic parameters (Gibbs energy, enthalpy and entropy) suggested the feasible and
Cross linking endothermic nature of Congo red adsorption over both adsorbents. The analyzed results indicated the promising
Congo red ability of novel cross-linked chitosan for the removal of Congo red from aqueous phase and it can be extended to
Adsorption use in the treatment of textile wastewater.
Waste water treatment © 2017 Elsevier B.V. All rights reserved.

1. Introduction
Besides the tremendous increase in the world's population, develop-
ment in industrialization as well as exorbitant use of chemicals led to
environmental pollution. Presence of waste (organic and inorganic) in
an environment because of human activities not only causes water pol-
lution but also have an acute and chronic health effects on human as
well as aquatic life. Hazardous affects associated with the presence of
textile dyes and pigments in the waste effluents pose threat to the envi-
ronment. Apart from an environmental threat, dyes also have adverse
effects on human health as they cause cancer, tumors, mutations and
heart diseases [1–4]. Among different chemical, physical and biological
methods, adsorption is considered as an economical and effective way
for wastewater decontamination. Several low cost adsorbents have
been investigated and reported for their ability to eradicate the dyes
from wastewater [5–9]. Special attention has been paid to polysaccha-
ride based adsorbents due to their easy availability and outstanding re-
moval capacities for wide range of dyes.
Chitin is the second highest naturally existing polysaccharide bio-
polymer which can be obtained from various natural resources i.e. the
skeleton of aquatic species such as crayfish, prawns, crab and shrimp
⁎ Corresponding author.
E-mail addresses: hmzaheer@uet.edu.pk (Z. Aslam), shahzadmalik@kfupm.edu.sa
(M.S. Kamal), rshawabk@kfupm.edu.sa (R.A. Shawabkeh).
[10]. This biopolymer has acquired much attention due to its prominent
and promising characteristics such as cationicity, biodegradability, non-
toxicity, high adsorption capacity, macromolecular structure, ease of
availability and low cost [11]. A linear polymer chitosan is synthesized
by the alkaline de-acetylation of chitin. De-acetylation of chitin involves
the conversion of acetyl groups of chitins into free amines groups by hy-
drolysis. This process of hydrolysis dictates the degree of de-acetylation
[12,13]. The presence of hydrophobic amino groups in the chitosan ren-
dered it insoluble at basic pH while the protonation of amino groups
makes it soluble in acidic pH. Chitosan in its various forms i.e. flakes,
beads, nanoparticles and powder has been reported for the treatment
of polluted water and showed high adsorption efficiencies. Benefits of
using chitosan over commercial activated carbon are its low cost, excel-
lent affinity for a number of contaminants due to presence of hydroxyl
and amino functional groups and high selectivity and reactivity towards
the pollutants [14,15].
Various studies have been put forward to remove pollutants from
wastewater streams [16]. Chitosan showed very high adsorption effi-
ciency up to 1000–1100 g/kg for reactive red in neutral solution [17].
100% deacetylated chitosan exhibited 30 μmol/g adsorption capacity
for methyl orange at pH 4 and dye uptake followed the pseudo second
order dynamics [18]. Dotto and Pinto investigated the adsorption be-
havior of food dyes i.e. acid blue 9 and yellow 3 on chitosan powder
and concluded that stirring rate and temperature effects the adsorption
rate whereas the adsorption of both occurred by chemisorption onto the

http://dx.doi.org/10.1016/j.molliq.2017.09.006
0167-7322/© 2017 Elsevier B.V. All rights reserved.
212 A. Zahir et al. / Journal of Molecular Liquids 244 (2017) 211–218
surface of adsorbent [19]. W.S. Ngah et.al compared the effect of differ-
ent cross-linkers on the removal efficiency of copper ions from aqueous
solution and found that the cross linking of chitosan with epichlorohy-
drin (ECH) gives the highest uptake capacity of copper ions among
other cross-linked chitosan forms [20]. Chiou, Kuo, and Li studied the re-
moval of a reactive dye i.e. Reactive Red 222 from aqueous solution via
adsorption using conventional cross-linker ECH based beads. The max-
imum uptake was 2252 mg/g at temperature 30 °C with a pH 3.0 [21].
Cross-linking agents when interact with the chitosan act as an intermo-
lecular bridge by making covalent bonds between different polymer
chains. Cross-linking reduce the segmental movement within the poly-
mer chains [22]. The most commonly used cross-linkers that create
intermolecular linkages are glutaraldehyde (GLA), epichlorohydrin
(ECH) and tripolyphosphate (TPP) [23–25]. The cross-linking of chito-
san turns it to stable compound that is resistive to dissolution in acidic
and basic solutions. Cross-linking can also affect the crystalline nature
of chitosan and enhances the adsorption characteristics. The adsorption
capacity of chitosan modified with conventional cross linkers is not ex-
ceptionally high and those cross-linkers are also hazardous as per OSHA
standards [10]. Keeping in mind the attraction of anionic dyes towards
amine based substrates; we intended to cross link chitosan with bifunc-
tional amine based material to enhance the adsorption capacity and
thermochemical properties of chitosan.
The present study addresses the synthesis and characterization of
chitosan cross-linked by Di-ammonium tartrate and urea/Di-ammoni-
um tartrate. Both modified forms were tested for their potential ability
to remove Congo red (CR) from aqueous phase. The influence of differ-
ent experimental conditions like equilibrium time, adsorbent dose, so-
lution pH and initial concentration of dye were studied. In addition,
the observed data were fitted using conventional isotherm models i.e.
Langmuir, Freundlich and Sips isotherm models. Moreover, the thermo-
dynamics and kinetics of Congo red adsorption were analyzed to under-
stand the mechanism of dye removal by modified chitosan.
2. Materials and method
2.1. Materials
Chitosan (degree of deacetylation N 85%, molecular weight of
218 kDa), glacial acetic acid (GR grade), methanol (GR grade), 33% v/v
ammonia solution, NaOH and Di-ammonium tartrate (DAT), were pur-
chased from Sigma Aldrich. The Condo red was purchased from BDH
Chemicals and urea (99.7% purity) was obtained from Fauji Fertilizer
Company Limited (FFC). All chemicals were utilized without any prior
purification.
2.2. Preparation of adsorbent
a) To synthesis DAT modified chitosan (DMC), 6 g of chitosan powder
was dissolved in 5% v/v of acetic acid solution. 2.25 g (37.5% of chito-
san) of Di-ammonium tartrate were added in chitosan solution. The
solution was placed on hot plate magnetic Stirrer (Wiggen hauser,
USA) at 100 °C and 200 rpm for 5 h. The solution was then poured
in 300 mL of methanol with 8% v/v ammonia solution to neutralize
the effect of acetic acid as well as to washout any soluble organic im-
purities from the fibrous material. The product was filtered and
washed with demineralized water several times to reduce the pH
of the material to 6–7. The adsorbent was stored in demineralized
water for further use. This adsorbent was named as Di-ammonium
tartrate cross-linked chitosan (abbreviated as “DMC”)
b) To synthesis urea/DAT modified chitosan (UDMC), 6 g of chitosan
powder was dissolved in 5% v/v of acetic acid solution. To this, calcu-
lated amount of urea and Di-ammonium tartrate were added in chi-
tosan solution such that the weight ratio of chitosan to DAT/urea
was 2:1. The solution was stirred on heating magnetic plate (Wiggen
hauser, USA) at 100 °C and 200 rpm for 5 h. The brownish viscous
solution was then poured in 300 mL of methanol with 8% v/v ammo-
nia solution to neutralize the effect of acetic acid as well as to wash-
out any soluble organic impurities from the fibrous material. The
product was filtered and washed with demineralized water several
times to reduce the pH of the material to 6–7. The adsorbent was
stored in demineralized water for further use. The prepared material
was named as urea-DAT cross-linked chitosan and abbreviated as
“UDMC”.
2.3. Material characterization
FTIR spectra were recorded by using JASCO-4100 from 400 cm−1 to
4000 cm−1 at the resolution of 4 cm−1. The samples were prepared by
mixing 1 mg of adsorbent with 100 mg of KBr powder and then mixture
was hydraulically pressed to 10 tons/m2 to obtain a thin disk. The disk
was then placed in an oven at 102 °C to prevent any interference with
water. Transmission mode was selected during analysis.
The XRD analysis was performed on PAN analytical Xpert Powder
Diffractometer with Cu-Xray generator. The material was grinded
and powdered well before analysis. It was operated at scanning speed
2°/min from 6° to 80° (2θ) with incident beam path of 240 mm.
Thermal gravimetric analysis (TGA) of raw and modified chitosan
were carried out on TA Instrument TGA SDT Q600. The samples were
heated over a temperature range of 30–600 °C at 10 °C/min heating
rate under N2 atmosphere.
Differential scanning calorimeter (DSC) analysis of adsorbent was
done by SHIMADZU DSC-60A. The samples were powdered and placed
in aluminum pan for the analysis. The test specimens were heated
over a temperature range of 30–200 °C at 10 °C/min heating rate
under N2 atmosphere.
Surface morphology of the raw and modified material was observed
by field emission scanning electron microscope (MIRA3, TESCAN-UK
Ltd.) at 5 kV accelerating voltage. The specimen was spread over a con-
ductive carbon tape and then gold coated by sputter coater (AGB7340,
Agar-UK Ltd.) at 0.06 mbar vacuum using Argon gas to have a uniform
thickness of sample during analysis.
Zero point of charge (ZPC) was performed by utilizing a batch equi-
librium technique to determine the pH value at zero point of charge.
0.1 M potassium nitrate solution having different initial pH (ranging
from 3 to 10) was prepared by adding either 0.1 M nitric acid or 0.1 M
sodium hydroxide. 0.2 g of adsorbent (0.2 g with 91% moisture content
in case of modified adsorbent) was mixed in 100 mL of 0.1 M potassium
nitrate solution with known initial pH. Each solution with different ini-
tial pH was put on an orbital shaker for 24 h at 150 rpm. After one day,
the flasks were removed from shaker and placed idly for half an hour to
settle the solid contents. Final pH was recoded. The pH was measured by
Hanna portable pH meter (HI-8314) and ΔpH and pHinitial were plotted
to determine the point of zero charge.
2.4. Batch adsorption studies
The adsorption of Congo red from aqueous solution was investigated
by batch adsorption experiments. The stock solution having 1000 ppm
concentration was prepared by dissolving appropriate amount of CR
dye and used it in batch experiments by making required dilution.
100 mL of adsorbate solution having 100 ppm initial concentration
was taken in a 250 mL Erlenmeyer flask at solution pH and room tem-
perature (30 °C). The various parameters studied include, (i) effect of
dose by varying the adsorbent dose from 0.05 g to 0.5 g (91% moisture
in modified chitosan); (ii) effect of contact time at different time inter-
vals ranging from 5 to 300 min (iii) effect of pH by changing the stock
solution pH from 3 to 10; (iv) effect of dye initial concentration at con-
stant dose (0.1 g), temperature (30 °C), time (8 h) and pH (6.5); (v) ef-
fect of temperature at constant dose (0.1 g), time (8 h), pH (6.5) and
initial concentration (100 mg/L). All the adsorption experiments were
 A. Zahir et al. / Journal of Molecular Liquids 244 (2017) 211–218 213

carried out at constant stirring rate of 150 rpm in an orbital shaker.

After the experimental runs, the suspensions were then filtered
through Whatman filter paper. No adsorption was observed either on
glassware or filter paper by running experiments without adsorbents.
Permeates were analyzed using OPTIMA SP-3000 UV-Vis Spectrometer
at λmax = 498 nm to determine dye concentrations. To calculate the
concentration of dye after each experiment, a calibration curve of
Congo red was first prepared by running known concentrations of dye
solution and recorded their absorbance. The calibration checks
were carried out in duplicate runs. Then, the maximum absorbance at
λmax = 498 nm was plotted against each dye concentration. The Cali-
bration graph was used as a reference to find out the unknown concen-
tration of dye solution after adsorption. The amount of the dye adsorbed
by the adsorbent was calculated using the following equation.


V C i −C fe
qe ¼ ð1Þ
w

where “qe” is the amount of dye at equilibrium (mg/g), “V” is the volume Fig. 1. FTIR spectrum of raw and modified chitosan samples.
of the dye solution (L) “Ci” is the initial concentration of dye (mg/L),
“Cfe” is the final concentration of dye at equilibrium after adsorption linking took place at both hydroxyl group and amino group of the chito-
and “w” is the dry weight of the adsorbent (g). san [28–31].

2.4.1. Dissolution test of raw and modified chitosan 3.2.2. XRD analysis
The dissolution test was performed by following the procedure de- XRD is a primary tool to extract information about crystallinity. Fig. 2
scribed by W.S. Wan Ngah [20]. The solubility of raw and modified shows the XRD pattern for raw and cross-linked chitosan. Two charac-
forms was tested by adding 0.1 g of each of the sample in 5% v/v acetic teristic peaks in the Fig. 2 at 2θ = 10° and 2θ = 21° exhibit the two crys-
acid solution, demineralized water and 0.1 M NaOH solution that were tals of different planes within chitosan i.e. Cr020 and Cr110 [32]. The
stirred for 24 h. crystalline index for the chitosan based adsorbent was determined by
using following expressions [33].
3. Results and discussions
I020 −I am
CrI020 ¼  100 ð2Þ
3.1. Solubility of modified chitosan I 020

It was found that DMC and UDMC was insoluble in acetic acid solu- I110 −I am
CrI110 ¼  100 ð3Þ
tion as well as in NaOH based alkaline solution as shown in Table S1. It is I 110
obvious that the hydrophobicity of the RC is due to the presence of pri-
mary amine groups in the backbone chain of the chitosan which makes where I020 represents the maximum intensity below 13°, I110 is
it insoluble in water but easily soluble in acetic acid and formic acid by the intensity at 21° and Iam is the intensity of amorphous diffraction at
forming hydrogel in water [26]. However, after cross-linking the molec- 2θ = 16°.
ular weight of the chitosan may be increased which hinders the forma- The crystal size of the adsorbent was determined by using Deby-
tion of hydrogel in acetic acid solution thus makes it pH stable [27]. Scherrer formula [34].

3.2. Characterization Kλ
D¼ ð4Þ
βcosθ
3.2.1. FTIR analysis
The FTIR spectra of RC and modified chitosan are shown in Fig. 1. For
RC the characteristic peaks at 3376.75 cm−1 represent the OH,
2879.2 cm−1 corresponds to the symmetric CH stretching due to the
presence of pyranose ring. The absorption peaks at 1656.55 cm−1 may
be due to deformational vibration of amide I (C_O stretching associated
with primary amines), 1598.12 cm− 1 ascribed the NH2 bending,
1425.14 cm− 1 is attributed to joint bend vibration of OH and CH,
1383.68 cm−1 due to vibrations of C\\H bonds corresponding to CH3
group, 1324.86 cm−1 shows the C\\N stretching, 1085.73 cm−1 is as-
cribed to C\\O stretching and 659.53 cm−1 is because of O\\H out of
plan bending. After cross-linking with DAT and urea/DAT, significant
changes have been observed in the spectrums as compared to raw ma-
terial as shown in Fig. 1. The small peak appears at 3855.97 in both DMC
and UDMC confirms the presence of primary amines within the
chitosan structure due to the addition of DAT. A new peak at
2347.91 cm−1, in both DMC and UDMC, is due to the C\\H bending in
diammonium tartrate. The amide I peak of RC, in DMC and UDMC, is
shifted at 1645.95 and 1650.77 cm−1, C\\O stretching is shifted to
1078.98 cm−1 with prominent change in intensity. Whereas, no peak
at 1598.12 cm− 1 is observed in DMC. This indicates that the cross- Fig. 2. XRD pattern of raw and modified chitosan samples.
214 A. Zahir et al. / Journal of Molecular Liquids 244 (2017) 211–218

where K is the Deby-Scherrer constant, λ is wavelength of the X-ray, β is

the full widh of half maximum and θ is the Braggs diffraction angle.
The relative percentage crystallinity is shown in the Fig. S1. Fig. 2 de-
picts that the incorporation of DAT and urea in to the chitosan backbone
decreases its crystallinity and induces the amorphicity in the raw chito-
san. This might be very promising property which enhances the adsorp-
tion capacity of Congo red after cross-linking with urea and DAT.
It can be observed from Fig. S1 that modification of chitosan with
urea/DAT enhanced the amorphous phase of the adsorbent up to 19%
at CrI020 and 17% at CrI110. Whereas, modification with DAT increased
the amorphous phase up to 23% at CrI020 and 28% at CrI110. Chitosan
structure is quite sensitive to multifunctional chemical agents such as
cross-linkers, additives and fillers due to the presence of hydroxyl and
primary amino groups in the back-bone chain. As the cross-linkers
were introduced, the hydrogen bonding within the linear polymer
chains became weaker or breaks apart causing formation of amorphous
structure [28,32]. Based on Deby-Scherrer calculation the average crys-
tal size of RC is found to be 39 Å for Cr020 and 44 Å for Cr110. The incor-
poration of DAT and Urea not only effect the percent crystallinity of the
chitosan but also effect the crystal structure of the chitosan. The average
crystal sizes for DMC adsorbent are 65 Å for Cr020 and 66 Å for Cr110
while for UDMC the average crystal sizes are 32 Å for Cr020 and 66 Å
for Cr110.

3.2.3. Thermal analysis

The Thermogravimetric analysis (TGA) of RC, DMC and UDMC are
presented in Fig. 3. In all the adsorbents, three distinct degradation
phases appear. The first degradation phase is same for all adsorbents
and is probably due to moisture loss. For RC, the maximum weight
loss is observed between 180 and 414 °C. However, for DMC and
UDMC the maximum weight loss lied between 228 and 465 °C and
171 and 401 °C, respectively. This shift in degradation temperature
from 180 to 228 °C may be due to the binding of polymer chains togeth-
er by the cross-linker along with the formation of hydrogen bonding
which restricted their segmental movement therefore more thermally
energy was required for their degradation. Based on initial, 20% and
50% degradation temperature of the RC, DMC and UDMC; DMC is
found to be thermally most stable adsorbent. The thermal stability of
chitosan has changed after modification. Based on 20% and 50% weight
loss temperatures, DMC shows highest thermal stability whereas,
UDMC shows least stability. RC exhibits better thermal stability as com-
pared to UDMC. This may due to more compact and strongly bonded
crystalline structure of RC. Moreover, DMC shows highest thermal sta-
bility when compared with both RC and UDMC. The highest thermal sta-
bility of DMC may be ascribed to hydrogen bonding due to
incorporation of DAT as a cross-linker [35,36].
The thermal stability of polymer can also be determined by mean of
glass transition temperature (Tg). The Differential Scanning Calorimeter
analysis was done to investigate the glass transition temperature (Tg) of
raw and cross-linked chitosan. The DSC plots for RC, DMC and UDMC are
shown in Fig. S2. Expansive exothermic peaks are observed for
each adsorbent sample corresponding to the crystallization of each of
the adsorbent [37,38]. The glass transition temperature for the RC is
95.8 °C, whereas, the glass transition temperature of DMC and UDMC
are 102 °C and 91.2 °C, respectively. The maximum thermal stability
showed by DMC may be due to presence of hydroxyl group in DAT
that creates hydrogen bonded linkages within the chains and make it
slightly more thermally stable than RC [39]. Both TGA and DSC analysis Fig. 3. Thermogravimetric analysis of (a) RC (b) DMC (c) UDMC.
have confirmed the highest thermal stability of the DMC among rest of
the adsorbents.

3.2.4. SEM analysis
Fig. S3 (a) shows the surface morphology of the adsorbent before
and after the adsorption of the Congo red on the adsorbent. The differ-
ence between the surface morphology of the three adsorbents can be
clearly observed in SEM micrographs. The surface of RC is quite smooth,
even and dense which indeed is consistent with the previous reported
studies [40–43]. However, the cross-linking induced surface roughness
as can be clearly seen in the micrographs. This surface roughness is
probably favorable for the adsorption of Congo red on the adsorbent.
Moreover, the surface roughness of the cross-linked adsorbent is
 A. Zahir et al. / Journal of Molecular Liquids 244 (2017) 211–218 215

decreased in Fig. S3 (b) which might be due to the adsorption of dye

molecules on the surface.

3.2.5. Point of zero charge

The charge density over the surface of adsorbent plays a vital role in
its adsorption capacity. The results of point of zero charge (where the
adsorbent surface has net neutral charge) for each raw and modified
chitosan forms are presented in the Fig. S4. The surface of the raw chito-
san becomes neutral at pHzpc is 6 for RC while the modifications to raw
chitosan change the pHzpc to ‘8’ for both DMC and UDMC. This shift in
pHzpc from 6 to 8 may be ascribed to the addition of diammonium tar-
trate as cross-linker which when reacted with the chitosan, reduced
the intensity of the negative charge in the chitosan structure therefore,
less positive ions were required to neutralize the surfaces of both DMC
and UDMC. Moreover, the solution pH N pHzpc there will be deficiency
of H+ ions resulting in negatively charged surface thus promotes
the adsorption of cationic species. Contrast to this when the solution
pH b pHzpc, H+ ions will reside on the adsorbent surface and produce
H+ rich surface and endorse the adsorption of anionic species [44].

3.3. Adsorption Fig. 4. Effect of pH on the adsorption of Congo red dye using raw and modified chitosan
(temperature 30 °C, dye conc. 100 mg/L, adsorbent amount 100 mg, contact time 8 h).

3.3.1. Effect of dose

Adsorbent dose is a crucial parameter in an adsorption process and it
appreciably affects the removal of dye. The adsorption capacity of the
modified adsorbent is far higher than that of raw chitosan as shown in
Fig. S5. Since the raw chitosan is more crystalline as compared to
cross-linked chitosan and provides limited access to the internal sorp-
tion sites for the dye adsorption thus exhibit low uptake capacity [45].
The difference in adsorption capacity of DMC and UDMC can be ex-
plained based on percentage crystallinity. Since the DMC is less crystal-
line as compared to raw and UDMC as confirmed by XRD analysis. This
reduction in crystallinity enhances the probability for an adsorbate to
interact with adsorbent due to loose inter-chain structure and bonding,
thus expose more active sites for adsorption which increased the ad-
sorption capacity of the DMC [46–48]. Fig. S5 also shows that the ad-
sorption capacity of Congo red decreases by increasing the adsorbent
dosage. As the amount of dose increases, the number of active sites to
adsorb dye molecules also increases, cause increase in adsorption effi-
ciency [49]. 0.1 g (0.1 g with 91.16% moisture for DMC and UDMC) of
dose was chosen qualitatively for the rest of the studies.
protonated amino groups. Certainly, the protons attacked the negatively
charged sulfonic ions to neutralize them, thus, reduces the uptake of dye
molecules by adsorption on the adsorbent surface [53,54].
The maximum values of equilibrium adsorption capacity ratio be-
tween acidic and basic medium reach 1.55, 2.0 and 1.54 for raw chitosan
(pH3/pH10), DAT cross-linked (pH4/pH10) and urea-DAT cross-linked
chitosan (pH5/pH10) respectively.
3.3.3. Thermodynamic parameters
Fig. S6(a) indicates that the adsorption of the CR is an endothermic
process for all adsorbents. The rise in adsorption capacity as the temper-
ature increases can probably be linked with higher kinetic energy of dye
ions which enhances the probability of collusions of adsorbate with the
solid adsorbent surface thus lead to higher removal.
Thermodynamic parameters namely enthalpy (ΔH°), entropy (ΔS°)
and Gibb's free energy (ΔG°) are calculated to study the nature and
spontaneity of an adsorption process. The pertinent mathematical ex-
pressions are given by following equations.

3.3.2. Effect of pH
The adsorption of Congo red strongly depends on the initial pH of ad-
sorbate solution [50]. Fig. 4 shows the effect of pH on uptake of Congo red
dye. The adsorption mechanism of the Congo red on the raw and modi-
fied chitosan can be elaborated based on electrostatic forces between dye
molecule and a protonated amino group of the adsorbent. In acidic solu-
tion, there will be excessive protons, required to protonate the amine
groups (\\NH2) within the chitosan backbone chain. Thus enhance the
electrostatic attractive forces between the negatively charged sulfonic
groups of Congo red dye molecules and the protonated sites of the chito-
san, resulting in high adsorption at low pH [14,51]. Similar trends for the
effect of pH have been reported by Chiou, M. S. [52]. The mechanism for
the decrease in adsorption capacity can be elucidated as follow
Ø−NH2 þ Hþ →Ø−NHþ
3 Table 1.
R−SO3 Na þ H2 O→R−SO−
3 þ Na
þ
R−SO− þ
3 þ H →R−SO3 H
Ø−NHþ
3 þ R−SO3 H→No adsorption
whereas, Ø is the pyranose ring with in the chitosan structure. At pH b 4
there were excessive protons (H+) those were in competition with
C AD
Kc ¼ ð5Þ
C SD
ΔG ° ¼ −RT ln K ð6Þ
ΔS ° ΔH °
ln K ¼ − ð7Þ
R RT
where Kc is the equilibrium constant defined as ratio of amount of dye
adsorbed on the surface of adsorbent (CAD) to the amount of dye in
the filtered solution (CSD). T is the absolute temperature and R is the uni-
versal gas constant. The term ΔH° can be obtained from the slope of the
linear plot (Fig. S6(b)) as lnKc vs 1/T (van't Hoff plot), whereas intercept
gives the value of ΔS°. The calculated results are summarized in the
The negative values of ΔG° reflect the feasibility and spontaneity of
an adsorption of Congo red on all adsorbents tested, whereby no energy
input is required from outside the system. Higher negative value of ΔG°
implies the greater driving force for adsorption at higher temperature.
The enthalpy value of adsorption (Δ H°) can be used to predict the
type of adsorption. The magnitudes of Δ H° in the range of 5 to
40 kJ/mol manifest the physical adsorption while higher energies (60
to 240 kJ/mol) reflect the chemisorption [55]. Moreover, the positive
value of ΔS° shows the affinity of an adsorbent surface for the adsorbate
216 A. Zahir et al. / Journal of Molecular Liquids 244 (2017) 211–218

Table 1 The kinetic parameters for these three models are presented in the
Calculated thermodynamics parameters for adsorption of Congo red on raw and modified Table S2. Intra-particle diffusion model Fig. S8(b) does not find to fit
chitosan.
the experimental data since the plot of intra-particle diffusion model
Sample T (°C) Kc R2 ΔG° (kJ/mol) ΔH° (kJ/mol) ΔS° (kJ/K mol) does not pass through the origin. This deviation from the origin may
RC 20 3.9 0.98 −3.07 59.9 0.22 be due to the variation of mass transfer rate between starting and end-
30 7.2 −5.22 ing stages of adsorption process therefore intra-particle diffusion model
40 15.7 −7.37 cannot be used to demonstrate the adsorption kinetics. Moreover, the
50 37.8 −9.52
equilibrium adsorption capacity (qe) calculated from the pseudo-first
DMC 20 2.9 0.99 −2.41 49.6 0.18
30 4.9 −4.19 order model is very less than that of experimental data. The experimen-
40 9.3 −5.97 tal data fits best for the pseudo-second order model based on the equi-
50 19.0 −7.74 librium adsorption capacity (qe) and correlation regression coefficient
UDMC 20 1.6 0.99 −0.99 41.1 0.14 R2 as can be seen from Fig. S8(a), therefore is found most suitable for de-
30 2.5 −2.43
40 4.3 −3.86
fining the adsorption kinetics.
50 7.6 −5.30
3.3.5. Equilibrium adsorption isotherms
Distribution of the dye molecules over the adsorbent surface and the
dye and this can also be linked with randomness at adsorbent/dye solu- interactive behavior between adsorbent and dye can be best explained
tion interface. The adsorbed solvent molecules displaced in favor of ad- using the equilibrium adsorption isotherm model. Adsorption isotherm
sorbate species and gain more translational entropy than is lost by the analysis is a primary tool to optimize the adsorption process and it also
adsorbate ions/molecules, thus allowing for the prevalence of random- calculates the adsorption capacity of an adsorbent, which is one of the
ness in the system. Both DMC and UDMC adsorbents showed lower important consideration while designing adsorption system. Several
value of ΔS° as compared to raw chitosan which could be linked with isotherm models have been proposed for this purpose. Langmuir iso-
strong bonding of Congo red in raw chitosan as compared to its modi- therm model assumes monolayer adsorption of dye on a homogeneous
fied forms. This is also supported by higher value of enthalpy of adsorp- adsorbent surface. It predicts that the adsorption of dye takes place on a
tion (ΔH°) in RC in comparison to DMC and UDMC. surface having finite and specific active sites for adsorption. The non-
linear form of the Langmuir isotherm model can be expressed as [58]
3.3.4. Adsorption kinetics
The optimum equilibrium time for the adsorption of Congo red can qm K L C e
qe ¼ ð11Þ
be evaluated by the change in uptake with change in time. Fig. S7 1 þ K LCe
shows the experimental results which depict that increase in time
causes an increase in adsorption. Since, the modified chitosan provides where Ce is the equilibrium concentration of Congo red (mg/L) in the fil-
more active sites for the adsorption of Congo red, therefore the equilib- trate solution, qe is the equilibrium adsorption capacity, KL is the Lang-
rium adsorption time observed for the raw chitosan was 80 min and muir constant (L/g) and qm is the maximum adsorption capacity of the
300 min for the modified chitosan. The maximum uptakes achieved adsorbent (mg/g). Freundlich isotherm model presupposes multilayer
were 88 mg/g, 976 mg/g and 805 mg/g for RC, DMC and UDMC, adsorption of an adsorbate onto a heterogeneous adsorbent surface
respectively. [56]. The non-linear expression for Freundlich isotherm can be written
Various kinetic models have been reported, those can be used to as
conclude the mechanism by which dye ions were adsorbed on the sur-
qe ¼ K F C e =n
1
face of an adsorbent. The Lagergren model (pseudo first order model) ð12Þ
can be represented in the following form
where KF is the Freundlich isotherm constant (mg1 − 1/n L1/n g−1) and n
ln ðqe −qt Þ ¼ lnqe −kL t ð8Þ is related to the adsorption intensity. Sips isotherm model is unique
model that contains both the properties of Langmuir as well as
where qt is the instantaneous uptake and the value of rate constant can Freundlich model and it can be expressed as
be found by plotting a graph between “t” vs ln(qe − qt). The slope and in-
tercept of the plot will be used to evaluate rate constant kL and equilib- qmax K eq C ne
qe ¼ ð13Þ
rium adsorption qe. 1 þ K eq C ne
Pseudo-second order kinetics can be described in the following form
as where n is the heterogeneity factor while Keq is the constant of equilib-
rium for Sips model (L/mg). Sips model reduces to the Langmuir model
t 1 t if n = 1 and predict homogeneous nature of adsorption [59,60].
¼ þ ð9Þ
qt k2 q2e qe The equilibrium saturation capacity of Congo red for each adsorbent
is presented in Fig. 5 where the experimental equilibrium data of CR
The rate constant k2 and the equilibrium adsorption can be found by was compared with theoretical equilibrium values obtained from Lang-
muir, Freundlich and Sip's isotherm models. It shows that the monolay-
the intercept and slope of the plot between t and qt [56]. The Weber and
t
er saturation or maximum adsorption increases manifold after cross-
Morris model, intra-particle diffusion model, has found great attention
linking of raw chitosan. The pertinent isotherm constants and regres-
to evaluate the kinetics of the adsorption process due to its intra-particle
sion coefficient (R2) were evaluated with nonlinear regression of iso-
diffusion which elaborate the rate of adsorption in solution systems.
therm models using Origin 9.1 software. The regression results of all
This model is represented as follow [57].
three isotherm models are summarized in the Table 2. Both isotherm
models (namely Langmuir and Sip's) proved to have better fit with
q ¼ kip t =2 þ C
1
ð10Þ Freundlich isotherm model with significantly higher correlation coeffi-
cients for raw and cross-linked chitosan. This reflects the homogeneous
where q (mg/g) is the amount of Congo red adsorbed at chitosan at time surface of adsorbents. Langmuir monolayer capacity (qmax) of both
t, kip (mg/g·min1/2) is intra-particle diffusion coefficient and C is the cross-linked adsorbents is significantly greater than raw material and
constant associated with the thickness of the boundary layer. Langmuir isotherm constant is lesser for DMC and UDMC than the raw
 A. Zahir et al. / Journal of Molecular Liquids 244 (2017) 211–218 217

Table 3
Maximum adsorption capacity of various adsorbent for the removal of Congo red from
water.

Adsorbent qmax(mg/g) Reference

Orange peel 163 [61]

Spent mushroom 147.1 [62]
Chitosan beads 93.7 [63]
N,O-carboxymethyl chitosan 330.6 [64]
CTAB modified chitosan beads 433.1 [65]
Treated sunflower stalks 155.2 [66]
Diammonium modified chitosan 1597.6 Present study
Urea-diammonium modified chitosan 1447.7 Present study

small there will be a small error in the calculated parameters, this

leads to more accurate and realistic results.
The values of chi-square (χ2) based on non-linear isotherm models
are shown in Table 2. The chi-square (χ2) values for Langmuir isotherm
model are quite larger for all adsorbents. Table 2 shows Freundlich Iso-
Fig. 5. Equilibrium isotherm models fitting for the adsorption of Congo red using raw and
therm model has very bad regression coefficient with very large chi-
modified chitosan. square (χ2) values. Very large value of chi-square depicts that the
Freundlich Isotherm model does not have physical explanation for the
adsorption mechanism.
chitosan. This indicates that the single surface reaction and constant ac- Maximum adsorption capacity of DMC and UDMC for removal of
tivation energy is the dominant adsorption mechanism. Processing the Congo red dye from water is compared with various other adsorbents
adsorption data with sip's model improved the correlation coefficient and presented in Table 3. It can be concluded that prepared DMC and
value for raw chitosan (R2 N 0.97) and regression coefficients of cross- UMDC have higher maximum adsorption capacity as compared to vari-
linked chitosan stays constant as shown in the Table 2. The heterogene- ous others and some chitosan based adsorbents reported in literature.
ity of the adsorption process could perceive from the value of heteroge-
neity factor. The raw chitosan has the highest value (n = 1.65) while the 4. Conclusion
DMC and UDMC ranked less with 1.09 and 1.13, respectively. To better
judge the applicability of isotherm model, chi-square test was also exe- This study explored that the chitosan cross linked with amine based
cuted on all isotherm models. The Chi-square test is the ratio of the sum material are highly effective and showed promising capability for the
of square of difference between experimental equilibrium adsorption removal of anionic dye. Various characterization techniques indicated
and equilibrium adsorption from model to the equilibrium adsorption improved thermochemical properties of chitosan after cross-linking.
from model. Mathematically it can be expressed as Adsorption capacities were highly dependent on several factors such
as adsorbent dose, time, temperature, pH and initial concentration of

2 dye. It was found that the adsorption capacity increases with increase
2 n qe −qe;m in temperature, time and initial concentration of dye, whereas de-
χ ¼ ∑i¼1 ð14Þ
qe;m creases with increase in adsorbent dose and solution pH. The adsorption
isotherm data, based on error analysis, revealed that Sips isotherm
model fitted best for the experimental adsorption data. Kinetic adsorp-
where qe the experimental equilibrium adsorption capacity (mg/g) is, tion data explored the pseudo-second order nature of dye adsorption on
qe , m is the adsorption equilibrium capacity obtained from the model the adsorbent. Moreover, thermodynamic study confirmed that the in-
(mg/g). If the difference between experimental data and model data is teraction between dye and adsorbent was chemical bonding. Thermo-
dynamic parameters i.e. enthalpy and entropy suggested the
endothermic and spontaneous nature of adsorption process.
Table 2
Equilibrium isotherm models data for the adsorption of Congo red using raw and modified
chitosan. Acknowledgements
Langmuir isotherm model
The authors would like to acknowledge the Department of Chemical
KL (L/g) qmax (mg/g) R2 χ2
Engineering, University of Engineering and Technology, Lahore for sup-
RC 0.54 114 0.95 11.5 port and facilities.
DMC 0.06 1623 0.98 77.1
UDMC 0.04 1482 0.95 26.7
Appendix A. Supplementary data
Freundlich isotherm model

Adsorbent KF (mg1 − 1/n

L1/n g−1) n R2 χ2 Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.molliq.2017.09.006.
RC 56.5 8.9 0.67 43.1
DMC 433.7 4.9 0.80 550
UDMC 367.4 4.7 0.77 580 References
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