Ecotoxicology and Environmental Safety 128 (2016) 109–117

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Ecotoxicology and Environmental Safety

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

Adsorption of methyl orange from aqueous solution by aminated

pumpkin seed powder: Kinetics, isotherms, and thermodynamic
studies
Munagapati Venkata Subbaiah, Dong-Su Kim n
Department of Environmental Science and Engineering, Ewha Womans University, 11-1 Daehyun-Dong, Seodaemun-Gu, Seoul 120-750, Korea

art ic l e i nf o a b s t r a c t

Article history: Present research discussed the utilization of aminated pumpkin seed powder (APSP) as an adsorbent for
Received 19 October 2015 methyl orange (MO) removal from aqueous solution. Batch sorption experiments were carried to eval-
Received in revised form uate the influence of pH, initial dye concentration, contact time, and temperature. The APSP was char-
1 February 2016
acterized by using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy
Accepted 2 February 2016
(SEM). The experimental equilibrium adsorption data were fitted using two two-parameter models
(Langmuir and Freundlich) and two three-parameter models (Sips and Toth). Langmuir and Sips iso-
Keywords: therms provided the best model for MO adsorption data. The maximum monolayer sorption capacity was
Adsorption found to be 200.3 mg/g based on the Langmuir isotherm model. The pseudo-first-order and pseudo-
Methyl orange
second-order model equations were used to analyze the kinetic data of the adsorption process and the
Kinetics
data was fitted well with the pseudo-second-order kinetic model (R2 40.97). The calculated thermo-
Isotherms
Thermodynamics dynamic parameters such as ΔG0, ΔH0 and ΔS0 from experimental data showed that the sorption of MO
onto APSP was feasible, spontaneous and endothermic in the temperature range 298–318 K. The FTIR
results revealed that amine and carboxyl functional groups present on the surface of APSP. The SEM
results show that APSP has an irregular and porous surface which is adequate morphology for dye ad-
sorption. Desorption experiments were carried to explore the feasibility of adsorbent regeneration and
the adsorbed MO from APSP was desorbed using 0.1 M NaOH with an efficiency of 93.5%. Findings of the
present study indicated that APSP can be successfully used for removal of MO from aqueous solution.
& 2016 Elsevier Inc. All rights reserved.

1. Introduction Over 7
105 tons and approximately 10,000 different types of

Water pollution due to the release of various toxic chemicals
from industrialization and urbanization is a global problem (Gupta
et al., 2004). Among the various notorious toxic chemicals, dyes,
organics and pharmaceuticals are of highly concerned (Gupta and
Nayak, 2012; Gupta et al., 1998, 2011a, 2011b, 2011c, 2012a, 2012b,
2005, 2015a, 2015b). However, industrial effluents released from
textile, paint, paper, varnishes, ink, plastics, pulp, cosmetics, tan-
nery, and plastic are one of the key causes of water pollution, since
these runoffs comprises highly colored substances. Their discharge
into the hydrosphere possesses a significant source of pollution
due to their visibility even at very low concentrations. This is due
to their recalcitrance nature, giving undesirable color to the water,
reducing sunlight penetration, resisting photochemical and bio-
logical attack, and their degradation products being toxic or even
mutagenic, and carcinogenic (Gupta et al., 2013a, 2013b).
n
Corresponding author.
E-mail address: dongsu@ewha.ac.kr (D.-S. Kim).
dyes and pigments are produced worldwide annually. It is esti-
mated that 10–15% of the dye is lost in the effluent during the
dyeing process (Gupta et al., 2011a, 2011b, 2011c). In general, dyes
are classified as anionic (direct, acid and reactive dyes), cationic
(basic dyes) and non-ionic (disperse dyes and vat dyes) (Zheng
et al., 2015). Among them, azo dyes (anionic) with the existence of
nitrogen-nitrogen double bonds, are considered to be the largest
and most versatile class of organic dyes (Netpradit et al., 2004;
Gao et al., 2013). But their degradation is difficult due to their
complicated aromatic structure and poor biodegradability (Fang
et al., 2010). Methyl orange (MO), a typical water-soluble anionic
azo dye, with IUPAC name of Sodium 4-[[4-(dimethyl amino)
phenyl] diazenyl] benzene sulfonate. MO is commonly present in
effluent discharges from textile, food, pharmaceutical, printing and
paper manufacturing industries (Cheah et al., 2013). Due to the
toxicity and persistence, these discharges can cause a serious
threat to physic-chemical properties of fresh water and to aquatic
life. Therefore, it is necessary to provide suitable technology for
the wastewater treatment.
The conventional methods for the removal of dyes from

http://dx.doi.org/10.1016/j.ecoenv.2016.02.016
0147-6513/& 2016 Elsevier Inc. All rights reserved.
110 M.V. Subbaiah, D.-S. Kim / Ecotoxicology and Environmental Safety 128 (2016) 109–117
wastewaters include coagulation and flocculation (Panswad and
Wongchaisuwan, 1986), oxidation or ozonation (Malik and Saha,
2003; Koch et al., 2002), membrane separation (Ciardelli et al.,
2000). However, most of these techniques suffer from high oper-
ating cost and sludge generation. Adsorption is one of the most
successful technique for color removal from wastewater among all
the techniques so far developed for dye removal (Ali and Gupta,
2007; Gupta et al., 2009). The major advantages of adsorption over
conventional treatment methods include; low cost, ease of op-
eration, high efficiency, minimization of chemical or biological
sludge, no additional nutrient requirement, regeneration of bio-
sorbent and possibility of sorbate recovery (Saleh et al., 2011;
Khani et al., 2010; Gupta et al., 2011a, 2011b, 2011c, 2012a, 2012b).
The agricultural and forestry products have a great potential to be
used as biosorbents. Some of the reported low cost biosorbents
include palm ash (Ahmad et al., 2007), de-oiled soya (Mittal et al.,
2005), broad bean peels (Hameed and EI-Khaiary, 2008), durian
peel (Hameed and Hakimi, 2008), rice husk (McKay et al., 1999),
almond shell (Senturk et al., 2010) and neem sawdust (Khattri and
Singh, 2000), etc. These types of biosorbents contain poly-
saccharides and proteins having various functional groups such as
carboxyl, hydroxyl, and phosphates (Bharathi and Ramesh, 2013;
Asgher, 2012). The biosorption of dye molecules by these materials
might be associated with these functional groups.
Pumpkin, a gourd-like squash of Cucurbitaceae’s family, is one
of the widely cultivated plant species for its fruit. The fruit of
pumpkin is one the most important vegetables in traditional
agricultural systems in the world. The fruit represents rich sources
of pectin-type dietary fiber, antioxidants (carotenoids), vitamins
(C, E, B6, K, thiamine, and riboflavin), and minerals (potassium,
phosphorus, magnesium, iron, zinc and selenium) (Celekli et al.,
2014). Pumpkin seeds have been valued as a special source of the
mineral zinc, and the World Health Organization recommends
their consumption as a good way of obtaining this nutrient.
Pumpkin seeds, pumpkin seed extracts, and pumpkin seed oil have
long been valued for their anti-microbial benefits, including their
anti-fungal and anti-viral properties. Thus, in the present study we
have chosen pumpkin seeds as biomass source for manufacturing
efficient adsorbent.
Although adsorbents have been regarded as promising mate-
rials for pollutant removal, raw adsorbents (without modification)
suffer from their low sorption efficiencies. In recent years, in-
creased interest has been focused on enhancing the sorption ca-
pacity of biomass by introducing various chemical functional
groups (Reddy et al., 2012; Sajab et al., 2013; Kumar et al., 2014).
As sorption mainly takes place on the biomass surface, enhancing/
activating the binding sites on the surface would be an effective
approach for improving the adsorption capacity. Considering the
aforesaid reasons in the present study we have chosen pumpkin
seeds a raw biomass sources and the surface of biomass was fur-
ther functionalized to enhance the sorption capacity.
The main objective of the present work is to investigate the
potential of APSP as an adsorbent material for the removal of MO
from aqueous solutions. The different parameters such as effect of
the pH, initial dye concentration, contact time, and temperature
that influences the sorption processes of MO onto APSP were
evaluated. The isotherm, kinetics as well as thermodynamic
parameters for the adsorption of MO onto the APSP were calcu-
lated. Characterization of adsorbent was carried using FTIR and
SEM analysis.
2. Materials and methods
2.1. Adsorbent preparation and chemical modification
Pumpkin seeds were used as the raw biomass for the pre-
paration of adsorbent, and the seeds were collected from a local
market in South Korea. The collected seeds were washed several
times with boiled water and finally with deionized water to re-
move any adhering dirt. It was then oven dried at 70 °C for 24 h to
a constant weight. The oven dried seeds were ground well to a fine
powder, sieved to 20–30 mesh fractions. This pumpkin seed
powder was named as PSP.
The aminated biomass was prepared by employing a reported
method (Brady and Duncan, 1994) of esterification. For the pre-
paration of aminated pumpkin seed powder (APSP), 5 g of the well
washed raw PSP was suspended in 100 mL of ethanolamine, and
20.8 mL of concentrated hydrochloric (HCl) acid was added to the
suspension. The reaction mixture was agitated on a rotary shaker
at 150 rpm for 6 h. This treatment was expected to result in the
increase of amine groups on the biomass by the ester link to the
carboxyl groups via the general equation:
HCl, room temp
Biomass − COOH + NH2 CH2 CH2 OH → Biomas
6h
s − COOCH2 CH2 NH2 + H2 O
The chemically treated suspension was then centrifuged and
sequentially washed with distilled water. The treated biomass was
dried at 60 °C inside a convection oven for 24 h. This treated bio-
mass was named as APSP. The resultant dried APSP was stored in a
desiccator, and subsequently used as an adsorbent in the sorption
experiments.
2.2. Chemicals and equipment
All chemicals used in this work were of analytical reagent grade
and used without purification. Double deionized water (Milli-Q
Millipore 18.2 MΩ cm  1 conductivity) was used for all dilutions.
MO dye [formula weight: C14H14N3NaO3S, molecular weight:
327.34, λmax: 464 nm] was purchased from Junsei Chemicals, Ja-
pan. Working standards were prepared by progressive dilution of
the stock MO solution. HCl, NaOH and buffer solutions (Dae Jung
Chemicals, Korea) were used to adjust the solution pH. A pH meter
(pH-240L, NEOMET, Korea) was used for pH measurements. The
pH meter was calibrated using standard buffer solutions of pH 4.0,
7.0 and 10.0. Infrared spectra of the PSP and APSP sample were
obtained using Fourier Transform Infrared Spectrometer (BIO-RAD,
FTS-135, USA). For IR spectral studies, 10 mg of sample was mixed
and ground with 100 mg of KBr and made into a pellet. The
background absorbance was measured by busing a pure KBr pellet.
The morphology of PSP and APSP was analyzed by Scanning
Electron Microscopy (JEOL, JSM-7600F, Japan). The samples were
first sputter-coated with homogeneous gold layer and then loaded
onto a copper substrate. The dye concentrations in the samples
were determined using UV/Vis spectrophotometer (Optizen Pop,
Korea) at maximum wavelengths of 464 nm.
2.3. Batch adsorption procedure
The adsorption of MO on the APSP was investigated as an effect
of pH, initial dye concentration, contact time, and temperature.
1000 mg/L of MO stock solution was prepared and was used fur-
ther to obtain a standard solution by appropriate dilution of stock
solution. In sorption experiments, 0.05 g of the sorbent was
brought into contact with 30 mL of MO solution in a 50 mL falcon
tube. The pH values of the solutions were adjusted using small
 M.V. Subbaiah, D.-S. Kim / Ecotoxicology and Environmental Safety 128 (2016) 109–117
volumes (1–2 drops) of 0.1 M HCl and 0.1 M NaOH solutions to
reach the desired pH. The total added volume to get the desired pH
was also considered for calculation of initial concentration. All
tubes were agitated in an electrical thermostatic reciprocating
shaker at 160 rpm. Sorption kinetic experiments were conducted
with an initial concentration of 300 mg/L at 298 K. Samples were
collected at various shaking time intervals until the concentration
of MO in the dilute phase became constant. Sorption isotherm
experiments were also carried out with different initial dye con-
centrations varying from 100 to 1000 mg/L at different tempera-
tures (298, 308 and 318 K) for 4 h. At the end of adsorption, 1 mL
sample was centrifuged at 3000 rpm for 10 min on a centrifuge.
The filtrate was diluted in polythene tubes before analysis. The
concentration of remaining MO in the adsorption medium was
determined by using a UV/Vis spectrophotometer. Each experi-
ment was repeated three times, and the mean values are used in
this study.
The MO uptake (q) was calculated from the difference between
the concentration of MO before and after sorption using the fol-
lowing equation:
Fig. 1. FTIR spectrum of (A) PSP, and (B) APSP.
111
CiVi − Cf Vf
q=
M (1)
where q is the uptake of MO (mg/g), Ci and Cf are the initial and
final MO concentrations in the solution (mg/L), Vi and Vf are the
initial and final (initial plus added HCl or NaOH solutions) solution
volumes, and M is the mass of sorbent (g) used in MO sorption.
2.4. Regeneration and reusability of adsorbent
The recovery and reusability of adsorbent material is an im-
portant parameter related to the application potential of adsorp-
tion technology. In this work consecutive batch adsorption and
desorption experiments were performed using the same biosor-
bent in order to test for its ability to be reutilized. For this purpose,
0.05 g of adsorbent was contacted with 30 mL MO solution
(300 mg/L) at pH 3.0. APSP saturated with MO was removed from
solution and transferred into 50 mL falcon tubes, to this 30 mL of
0.1–1 M NaOH solution was added and the tubes were shaken for
4 h. Then the mixer solution was centrifuged and the
112 M.V. Subbaiah, D.-S. Kim / Ecotoxicology and Environmental Safety 128 (2016) 109–117

concentration of the MO released into eluent solution was ana-

lyzed by using UV/Vis spectrophotometer. Adsorbent was washed
repeatedly with deionized water to remove any residual desorbing
solution. The sorbent was placed into dye solution for the suc-
ceeding adsorption cycle after drying to a constant weight. The
cycles were repeated five times using the same adsorbent. Deso-
rption efficiency was calculated by using the following equation:
Amount of MO desorbed
Desorption efficiency= × 100
Amount of MO adsorbed (2)

3. Results and discussion

3.1. Characterization of APSP

FTIR spectroscopy was used to identify the functional groups

that are responsible for adsorption and also for confirming the
successful modification of PSP. FTIR spectral data of PSP and APSP
was obtained in the range of 4000–400 cm  1 and the data was
shown in Fig. 1. A depicts the IR spectra of the PSP was shown in
Fig. 1A and the spectral analysis results were discussed as follows:
The band observed at around 2919 cm  1 was attributed to the C–
H stretching. The peak at 1732 cm  1 refers to the characteristics of
the C¼ O stretches of the carbonyls mainly those of ketones and
esters. The peak at 1445 cm  1 is due to C–H bending vibrations of
the alkyl group. The band at about 1326 cm  1 corresponds to the
C–N stretching. The peaks at 1162 cm  1 attributed to the
stretching vibrations of C–O group. Fig. 1B depicts the FTIR spec-
trum of the APSP. After modification, a new peak was observed at
3415 cm  1 (assigned to the N–H stretching vibration mode of the
amine functional groups) for APSP. Some shifts in wave numbers
from 2919 to 2925 cm  1, 1732 to 1746 cm  1, 1445 to 1465 cm  1,
1326 to 1365 cm  1 and 1162 to 1166 cm  1 were noticed in the
spectra of PSP and APSP. These significant changes in the wave
numbers of specific peaks suggested that amino and carboxyl
groups could be presented in the APSP. This observation is an
agreement with similar previously reported studies (Saleh et al., Fig. 2. SEM micrographs of (A) PSP, and (B) APSP.

2014; Saleh and Gupta, 2012; Mahmoodian et al., 2015; Gupta

et al., 2015a, 2015b; Saleh, 2015).
To evaluate the textual structure of adsorbent surface, SEM
micrographs of PSP and APSP were shown in Fig. 2. The surface
morphology of PSP was differed from that of APSP. From the sur-
face morphology of PSP it was observed that powder was an as-
semblage of fine particles, which did not have regular, fixed shape
and size. The particles were of various dimensions and all of them
contained a large number of steps and kinks on the external sur-
face, with broken edges. The size of the voids in the PSP was in-
creased after modification and some distortion of the shape could
be seen in the SEM of APSP.
3.2. Effect of pH
pH of the solution is one of the vital factor controlling the
adsorption capacity, pH of the solution influences not only the
surface charge of the adsorbent but also the solubility of dyes
(Reddy and Lee, 2013). Considering this in present study we have
studied effect of pH on MO removal and effect of initial solution
pH on MO removal was illustrated Fig. 3(A). From these results it
was observed that the amount of adsorption of solute decreases
from 126.1 to 4.9 mg/g as the pH increases from 3 to 11. The
maximum adsorption of MO on the APSP was observed at pH 3.0.
At this pH a considerable high electrostatic attraction exists be-
tween the positively charged surface of the adsorbent and anionic
dye, due to the ionization of functional groups (amines) of ad-
sorbent and anionic dye molecules. pKa of MO was 3.46, the MO
molecule exists as negatively charged species until pH 3.46 after-
wards MO exists as neutral and in high pH conditions as slightly
positive charged species. Therefore at studied pH 3.0 the ad-
sorbent surface has maximum positive charge and also the MO
molecule has maximum negative charge which will contribute to
the high adsorption capacity in an expected electrostatic way. As
the pH of the system increases, the number of positively ionized
charged amine functional groups decreases and negatively
charged sites increases on the adsorbent on the other hand ne-
gative charge on the dye molecule also decreases. The decrease of
MO adsorption can also be as at higher pH conditions repulsion
occurs due to the competition between the presence of the
abundant OH  ions in basic solution and MO anions. A negatively
charged site on the adsorbent surface does not favor the adsorp-
tion of anionic dyes due to the electrostatic repulsion (Arami et al.,
2005; Fouad and Omar el Farouk, 2015).
Adsorption mechanism may be as follow:
First MO is dissolved in an aqueous solution after which the
sulfonate groups of MO dye (R-SO3Na) become dissociated and
converted into anionic dye ions.
(i) R − SO3Na + H2O → R − SO−3 + Na+
Second the adsorption process is performed due to electrostatic
attractions between the adsorbent surface and the MO anions
(Reddy and Lee, 2013).
(ii) RNH+3 + RSO−3 → RNH+3 O3SR
Since the adsorbent shows high adsorption capacities at pH 3.0,
all the further studies were carried out at this pH. A similar type of
 M.V. Subbaiah, D.-S. Kim / Ecotoxicology and Environmental Safety 128 (2016) 109–117 113

140 3.5. Adsorption kinetics

(A)
120 In order to investigate the mechanism of the adsorption pro-
cess pseudo-first and second-order kinetic models were used to fit
100
the kinetic experimental data. The pseudo-first-order equation
80 assumes the adsorption is of one adsorbate molecule onto active
site on the adsorbent surface while in pseudo-second-order model
qe [mg/g]

60 one adsorbate molecule is adsorbed onto two active sites. The

non-linear form of the pseudo-first-order (Lagergren, 1898) and
40 pseudo-second-order (Ho and McKay, 1999) kinetic rate equations
are given as (Eqs. (3) and (4)):
20
Pseudo-first-order model
0 qt = q1(1 − exp( − k1t )) (3)

Pseudo-second-order model
2 4 6 8 10 12
q22k2t
Final pH qt =
1 + q2k2t (4)
140
(B)
where q1 and q2 are the amount of dye sorbed at equilibrium (mg/
120 g), qt is the amount of dye sorbed at time t (mg/g), k1 is the
pseudo-first-order equilibrium rate constant (1/min), and k2 is the
100 pseudo-second-order equilibrium rate constant (g/mg min).
The estimated kinetic parameters and coefficient of determi-
80 nation (R2) from the pseudo-first-order and pseudo-second-order
q [mg/g]

models are summarized in Table 1. The low R2 value and the dif-
60 ference between experimental qe and theoretical q1 indicate that
the pseudo-first-order model was not well suited to describe the
40 adsorption of MO by APSP. On the other hand, the R2 value (0.9741)
for the pseudo-second-order model was relatively higher than that
20 of the pseudo-first-order model. Moreover, the q2 value calculated
by the pseudo-second-order model was close to the experimental
0 qe value. Thus, these results suggest that the pseudo-second-order
0 50 100 150 200 250 300 350 model provided a good correlation for the adsorption of MO onto
Time [min] APSP.
Fig. 3. Effect of (A) pH, and (B) contact time on the adsorption of MO onto APSP.
3.6. Adsorption isotherms

behavior was also reported for the adsorption of the MO on dif- Adsorption isotherm is a functional expression that correlates
ferent adsorbents (Asuha et al., 2010; Tian et al., 2015). the amount of solute adsorbed per unit weight of the adsorbent
and the concentration of an adsorbate in bulk solution at a given
temperature under equilibrium conditions. It is important to es-
3.3. Effect of contact time tablish the most appropriate correlations for the batch equilibrium
data using empirical or theoretical equations as it plays a func-
As seen in Fig. 3(B), it is evident that time has significant in- tional role in predictive modeling procedures for analysis and
fluence on the adsorption of dye. It can be observed from the design of adsorption systems. The four most common isotherms
figure that adsorption of MO was quite rapid in the first 60 min, for describing solid-liquid sorption systems are the Langmuir,
then gradually increased with the prolongation of contact time. Freundlich (two-parameter isotherms), Sips and Toth (three-
After 110 min of contact time equilibrium was observed and with parameter isotherms). Therefore, the experimental data were fit-
further increase in contact time there is no additional enhance- ted to these equilibrium models.
ment in sorption capacity. Based on these results, 110 min was
taken as the equilibrium time in batch adsorption experiments. 3.6.1. Langmuir isotherm
Langmuir sorption model serves to estimate the maximum
uptake values where they cannot be reached in experiments.
3.4. Effect of temperature
Langmuir’s model does not take into account the variation in ad-
sorption energy, but it is the simplest description of the adsorption
The adsorption experiments were carried out at three different
temperatures (298, 308 and 313 K) with the different concentra- Table 1
tions to study the effect of temperature on the adsorption of MO Pseudo-first-order and pseudo-second-order model constants for the adsorption of
onto APSP. The adsorption capacity of APSP was increased from MO on APSP.
143.7 to 200.3 mg/g as the temperature was increased from 298 to
Sorbent qe (mg/ Pseudo-first-order Pseudo-second-order
313 K. The increase is due to increase in dye mobility that may g)
occur at high temperature between the adsorbent and the ad- q1 (mg/ k1 (L/ R2 q2 (mg/ k2 (g/mg R2
sorbate (Ahmad et al., 2014). Adsorption of MO onto APSP is an g) min) g) min)
endothermic process; the adsorption capacity increased with in-
APSP 114 108 0.155 0.8553 113 0.002 0.9741
crease in solution temperature.
114 M.V. Subbaiah, D.-S. Kim / Ecotoxicology and Environmental Safety 128 (2016) 109–117

process. It is based on the physical hypothesis that the maximum
biosorption capacity consists of a monolayer adsorption, that there
are no interactions between adsorbed molecules, and that the
adsorption energy is distributed homogeneously over the entire
coverage surface.
The Langmuir sorption isotherm has been successfully applied
to many pollutant sorption processes and has been the most
widely used to describe the sorption of a solute from a liquid so-
lution. A basic assumption of the Langmuir theory is that sorption
takes place at specific homogeneous sites on the surface of the
sorbent. It is then assumed that once a sorbate molecule occupies
a site, no further sorption can take place at that site. The rate of
sorption to the surface should be proportional to a driving force
and area. The driving force is the concentration in the solution,
and the area is the amount of bare surface. The Langmuir equation
is (Langmuir, 1918):
qmKLCe
qe =
1 + KLCe
where qe is metal concentration on sorbent (mg/g) at equilibrium,
Ce is the equilibrium metal concentration in solution (mg/L), qm is
monolayer adsorption capacity of sorbent (mg/g), and KL is the
Langmuir constant (L/mg) related with the sorption free energy.
The qmax value was increased from 143.7 to 200.3 mg/g (Table 2)
with an increase in the temperature from 298 to 318 K. This in-
crease in sorption capacity may be attributed to a rise in kinetic
energy of the sorbent particles due to the increase in temperature.
This rise in kinetic energy increases the frequency of collisions
between the adsorbent and the sorbate, resulting in enhanced
sorption on to the surface of the sorbent.
The 1/n values between 0 and 1 indicate that the adsorption of MO
onto APSP is favorable under the conditions studied.
3.6.3. Sips isotherm
Sips isotherm is a combination of the Langmuir and Freundlich
isotherm type models and expected to describe heterogeneous
surfaces much better. At low sorbate concentrations it effectively
reduces to the Freundlich isotherm and thus does not obey Henry’s
law. At high sorbate concentrations, it achieves a monolayer
sorption capacity characteristic of the Langmuir isotherm. The
model can be written as (Sips, 1948).
KSC fβS
q=
1 + aS C fβS (7)
where KS is the Sips model isotherm constant (L/g), aS the Sips model
constant (L/mg) and βS the Sips model exponent. The exponent va-
lues were close to unity meaning that MO sorption data obtained in
(5) this study is more of Langmuir form rather than that of Freundlich.
3.6.4. Toth isotherm
Toth isotherm, derived from potential theory, has proven useful
in describing sorption in heterogeneous systems such as phenolic
compounds on carbon. It assumes an asymmetrical quasi-Gaussian
energy distribution with a widened left-hand side, i.e., most sites
have sorption energy less than the mean value. It can be re-
presented as (Toth, 1971):
qmaxbT Cf
q=
[1 + (bT Cf )1/ nT ]nT (8)

3.6.2. Freundlich isotherm
Freundlich developed an empirical equation to describe the
adsorption process. The Freundlich isotherm was based on the
assumption that the adsorbent had a heterogeneous surface
composed from different classes of adsorption sites, with adsorp-
tion on each class of sites following the Langmuir isotherm.
Freundlich demonstrated that the ratio of the amount of solute
adsorbed onto a given mass of an adsorbent to the concentration
of the solute in the solution was not constant at different solution
concentrations. This isotherm does not predict any saturation of
the sorbent by the sorbate; thus infinite surface coverage is pre-
dicted mathematically, indicating multilayer sorption of the sur-
face. The Freundlich model (Freundlich, 1906) is:
qe = Kf Ce1/ n
(6)
where Kf (mg/g) is a constant relating the adsorption capacity and
1/n is an empirical parameter relating the adsorption intensity,
which varies with the heterogeneity of the material. The values of
Kf increased from 31.8 to 50.3 mg/g (Table 2) with an increase in
temperature of the solution from 298 to 318 K. As the Kf is a
measurement of adsorption capacity, the increase in the value
again confirms that the adsorption process of MO onto APSP is an
endothermic process. The 1/n values are found in the range of
0.23–0.22, when the temperature was altered from 298 to 318 K.
where bT is the Toth model constant and nT the Toth model ex-
ponent. It is obvious that for nT ¼ 1 this isotherm reduces to the
Langmuir sorption isotherm equation.
The correlation coefficients, R2 and the Chi-square (χ2) test
were also carried out to find the best fit among the adsorption
isotherm models that are used. The equation for evaluating the
best fit model is to be evolved as
⎛ (q − q )2 ⎞
χ2 = ∑ ⎜⎜ e e, m ⎟
⎟
⎝ qe, m ⎠
where qe,m equilibrium capacity obtained by calculating from a model
(mg/g) and qe experimental data of equilibrium capacity (mg/g).
The different isotherm parameters along with R2 and χ2 values
are given, respectively, in Table 2. High R2 values and low χ2 values
for the Langmuir isotherm model indicate that the adsorption of
MO onto APSP follows the Langmuir isotherm model. The ex-
cellent fit of the Langmuir isotherm to the experimental adsorp-
tion data confirms that the adsorption is monolayer; adsorption of
each molecule has equal activation energy and that sorbate-sor-
bate interaction is negligible. On the basis of correlation coeffi-
cients and chi-square test, the experimental data better described
by the Sips isotherm model followed by Toth. Besides, the Sips
constant confirms the fact that the isotherm is more approaching
the Langmuir than the Freundlich isotherms.

Table 2
Langmuir, Freundlich, Sips and Toth isotherm constants for the adsorption of MO on APSP.

T Langmuir Freundlich Sips Toth

qmax b R2 χ2 Kf n R2 χ2 KS aS βS R2 χ2 qmax bT nT R2 χ2

298 143.7 0.021 0.9934 4.2 31.8 4.385 0.9342 13.2 0.7147 0.0053 1.391 0.9992 1.58 132.9 0.015 0.637 0.9985 2.2
308 183.2 0.031 0.9955 4.5 46.3 4.659 0.9195 19.3 2.3200 0.0133 1.275 0.9996 1.51 172.9 0.023 0.705 0.9994 1.8
318 200.3 0.035 0.9987 2.7 50.3 4.559 0.9321 19.6 4.9265 0.0252 1.119 0.9996 1.73 194.7 0.031 0.856 0.9994 1.9
 M.V. Subbaiah, D.-S. Kim / Ecotoxicology and Environmental Safety 128 (2016) 109–117 115

Table 3 100
Comparison of adsorption capacity of APSP with different adsorbents. (A)
Biosorbent qmax pH References
80
Bottom ash 3.618 3.0 Mittal et al. (2007)

Desorption rate %
De-Oiled Soya 16.664 3.0 Mittal et al. (2007)
Banana peel 21.0 6.0-7.0 Annadurai et al. 60
(2002)
Orange peel 20.5 4 7.0 Annadurai et al.
(2002)
40
AC/ferrospinel composite 95.8 – Ai and Jiang (2010)
Modified sporopollenin 5.23 – Ayar et al. (2007)
Multiwalled Carbon nanotubes 52.86 2.3 Yao et al. (2011)
Hypercrosslinked polymeric 76.9 – Huang et al. (2008) 20
adsorbent
m-CS/Ƴ-Fe2O3/MWCNTs 66.09 – Zhu et al. (2010)
Activated clay 16.78 7.0 Ma et al. (2013) 0
Modified ultrafine coal powder 18.52 – Liu et al. (2009)
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Modified wheat straw 50.4 3.0 Su et al. (2014)
Modified HNTs 94.34 6.7 Liu et al. (2012) NaOH Concentration (M)
Acrylic acid grafted Ficus carica fiber 51.55 4.0 Gupta et al. (2013b)
Maghemite/chitosan nanocomposite 29.41 3.0 Jiang et al. (2012) 120
films (B)
Lapindo volcanic mud 333.3 3.0 Jalil et al. (2010) Adsorption
Magnetic chitosan beads 779 4.0 Obeid et al. (2013) 100 Desorption
Phragmites australis activated 217 3.0 Chen et al. (2010)

Adsorption/desorption %
carbon
APSP 200.3 3.0 This study 80

60
3.7. Comparison of APSP with other biosorbents

Adsorption capacities of various adsorbents towards MO as 40

reported in literature were presented in Table 3. A comparison
between this work and other reported data from the literature
shows that APSP is a better adsorbent for MO compared to other
adsorbents. Therefore, it could be safely concluded that the APSP
adsorbent has a considerable potential for the removal of MO from
an aqueous solution.
3.8. Thermodynamic studies
The determination of thermodynamics parameters has a great
importance to evaluate spontaneity and heat change for the ad-
sorption reactions (Tanyildizi, 2011). The free energy change (ΔG0)
of the adsorption reaction is given by the following equation.
ΔG 0 = − RT ln KL
3
where R is the universal gas constant (8.314
10 kJ/mol K), T is
an absolute temperature (K) and KL is the Langmuir constant at
temperature T.
The enthalpy (ΔH0) and entropy (ΔS0) change values were
estimated from the following equations:
ΔG 0 = ΔH 0 − T ΔS 0
ΔH 0 ΔS 0
ln KL = − + To reduce the adsorption processing cost and to open the
RT R (11)
The values of ΔG0 were calculated from Eq. (9). The values of
ΔH0 and ΔS0 can be calculated from the slope and the intercept of
the plot of ln KL versus 1/T, respectively (figure not shown). The
change of free energy for physisorption is generally between  20
and 0 kJ/mol, the physisorption together with chemisorption is at
the range of  20 to  80 kJ/mol and chemisorption is at a range of
80 to  400 kJ/mol (Baseri et al., 2012). Gibbs free energy change
(ΔGo) was also calculated to be  2.761,  4.473 and  5.201 kJ/
mol for 298, 308 and 318 K, respectively. The negative values of
overall free energy changes during the adsorption process indicate
the spontaneous nature of the adsorption process. The decrease in
20
0
1 2 3 4 5
Cycle number
Fig. 4. Desorption studies of MO: (A) desorption time, and (B) number of adsorp-
tion–desorption cycles.
values of ΔG0 with an increase in temperature showed an ad-
sorption process is more favorable at higher temperatures. The
entropy (ΔS0) value indicates whether a particular reaction pro-
ceeds faster or slower than another individual reaction (Hameed
(9) et al., 2007; Ozcan and Ozcan, 2004). The positive value of ΔS0
(0.123 kJ/mol K) resulted from the increased randomness due to
the adsorption of MO, which suggested good affinity of MO to-
wards the APSP and increased randomness at the solid-solution
interface during the fixation of MO on the active site of the APSP.
The positive value of ΔH0 (33.37 kJ/mol) for the process indicates
that the adsorption of APSP for MO was an endothermic process.
(10)
3.9. Desorption of MO and reuse of adsorbent
possibility of recovering the dyes extracted from the liquid phase,
it is desirable to regenerate the adsorbent material. Desorption
studies were performed with different NaOH concentrations and
the results are shown in Fig. 4(A). From the results of this study,
with the increasing of NaOH concentration, the desorption rate
decreased. The maximum percentage recovery of MO was 93.5%
with 0.1 M NaOH solution. In this study 0.1 M NaOH was used as a
regenerating agent. The regenerated adsorbent was reused for up
to five adsorption-desorption cycles and the results are illustrated
in Fig. 4(B). An efficiency of 93.5% recovery of MO was obtained
with 0.1 M NaOH in the first cycle and is therefore suitable for
regeneration of adsorbent. There is a gradual decrease in MO
116 M.V. Subbaiah, D.-S. Kim / Ecotoxicology and Environmental Safety 128 (2016) 109–117
adsorption with an increase in the number of cycles. After five
cycles, the adsorption capacity decreased from 77.1% to 65.3%
while the recovery of MO ions decreased from 93.5% in the first
cycle to 81.3% in the fifth cycle. There was slight decrease in both
the percentage of MO adsorbed and the percentage of MO des-
orbed from the first to fifth cycle. This small decrease may be due
to the MO bound to the APSP through electrostatic interactions are
not recoverable fully in subsequent cycles. The results showed that
the APSP could be used repeatedly in MO adsorption studies with
a small loss in the total adsorption capacity.
4. Conclusions
This study revealed that APSP was an effective adsorbent for
MO removal from aqueous solutions. The batch adsorption para-
meters such as pH of solution, initial dye concentration, contact
time, and temperature were effective on the adsorption process.
The equilibrium sorption phenomena were found to be well de-
scribed by both Langmuir and Sips isotherm models. The max-
imum monolayer adsorption capacity was found to increase from
143.7 to 200.3 mg/g with increase in temperature from 298 to
318 K. The Langmuir constants were used for calculating different
thermodynamic parameters such as ΔG0, ΔH0, and ΔS0. The ne-
gative values of ΔG0 indicate the spontaneity of the process,
whereas the positive values of ΔH0 and ΔS0 indicate the en-
dothermic nature and increase in randomness of the process, re-
spectively. The experimental results indicated that the adsorption
behavior was well represented by a pseudo-second-order kinetic
model. Five adsorption/desorption cycles were carried out with
0.1 M NaOH as the desorbing agent without any loss of adsorbent
or appreciable reduction in adsorption capacity. The results in-
dicated that APSP could be a potential alternative adsorbent for
the removal of MO from aqueous solution.
Acknowledgments
This research was supported by the R&D Program for Society of
the National Research Foundation (NRF) funded by the Ministry of
Science, ICT & Future Planning (Grant no.: NRF-
2013M3C8A3078596).
This study was supported by the R&D Center for Valuable Re-
cycling (Global-Top Environmental Technology Development Pro-
gram) funded by the Ministry of Environment (Project no.: GT-11-
C-01-070-0).
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