Arabian Journal for Science and Engineering

https://doi.org/10.1007/s13369-019-03993-6

RESEARCH ARTICLE - CHEMICAL ENGINEERING

Removal of Congo Red from Aqueous Solution Using ‘Perna viridis’:

Kinetic Study and Modeling Using Artificial Neural Network
Adarsh Ajith Naik1 · Vishnuprasad Selvaraj1 · Haribabu Krishnan1

Received: 11 September 2018 / Accepted: 24 June 2019

© King Fahd University of Petroleum & Minerals 2019

Abstract
In this work, the removal of Congo red dye from its aqueous solution by a low-cost adsorbent obtained from Perna viridis sea
shell, an aquacultural solid waste, was studied. Maximum removal of 98% of the dye was obtained with adsorbent dosage
22 g L−1 , pH of 5.5, contact time of 30 min and temperature of 308.5 K. Various adsorption reaction models were investigated
and found that the pseudo-second-order model best described the reaction kinetics. Further, the mechanism of adsorption
was studied using the intra-particle diffusion model, and it was confirmed that the intra-particle diffusion and boundary layer
diffusion were the rate-controlling factors. Artificial neural network model was developed for the prediction of the percentage
removal of the dye from its aqueous solution, and the prediction was in agreement with the experimental results obtained. It
was inferred that the adsorbent prepared from P. viridis having high thermal stability (600 °C), a surface area of 13.746 m2
g−1 and mean pore diameter 7.0625 nm should be an excellent alternative for the conventional adsorbent used for the removal
of the carcinogenic dye such as Congo red from its aqueous solution at any operating condition.

Keywords Adsorption · Congo red · Perna viridis · Kinetics · Error analysis · ANN

Abbreviations statistics reveal that the average consumption of available

fresh water by agriculture, industry and household sector is
AC Activated carbon 70%, 19% and 11%, respectively [1]. Out of these divisions,
ANN Artificial neural network the industrial sector paves the path for pollution of most of the
BET Brunauer–Emmett–Teller water bodies leading to a crisis for high-quality water, for the
CR Congo red coming generation. Industries like leather, textile, paper and
EDS Energy-dispersive X-ray spectroscopy pulp are on the top list for using these potentially toxic dyes
FTIR Fourier transform infrared spectroscopy in their process. Reports suggest that around 7 × 105 ton of
PVSS Perna viridis sea shell dye is produced yearly, and around 10,000 commercial dyes
SEM Scanning electron microscopy are available in the market worldwide [2]. Owing to this, it
TGA Thermo-gravimetric analysis is clear that synthetic dyes are the potential pollutant present
in wastewater and release of untreated effluent causes the
destruction of nature.
1 Introduction Congo red is one of the examples of azo dyes which is
highly toxic and carcinogenic in nature. Features like non-
The Earth is covered with two-thirds of water, and still, one biodegradability, high solubility in aqueous solution and the
of the major problems that are faced by humankind today is ease of dying fabrics lead to the extensive use of CR dye
the unavailability of pure and good-quality drinking water. among the textile industry. Studies have put forward that the
The demand for potable water is increasing alarmingly, and exposure of workers in contact with CR dye causes bladder
cancer and usage of hair coloring agents causes breast cancer
B Vishnuprasad Selvaraj [3]. Its harmful nature is not limited to the above mentioned,
vishnuprasad215@gmail.com but it also causes irritation to skin and eye, causes a blood
clot and is mutagenic in nature [4].
1 Department of Chemical Engineering, National Institute of
Technology Calicut, Kozhikode, Kerala 673601, India

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The conventional wastewater treatment method is not Table 1 Physicochemical properties of CR dye
practicable for the removal of CR because of its non- CAS no. 573-58-0
biodegradable nature [5]. Alternative methods like adsorp- CA index name 1-Naphthalenesulfonic acid,
tion [6, 7], coagulation and flocculation [8], membrane 3,30-[(1,10-biphenyl)-4,40-
separation [9, 10], ozonation [11–13], biosorption [3, 14], diylbis(2,1-diazenediyl)]bis[4
sonochemical and electrochemical [15] are being employed amino-, sodium salt (1:2)]
to remove CR. Economic feasibility limits the industries Molecular formula C32 H22 N6 Na2 O6 S2
present in developing countries in using these advanced sep- Molecular weight 696.66 g mol−1
aration methods. In such a scenario, adsorption has been Physical form Brownish-red powder
identified as a practical method for treatment of these dye- Molecular surface area 577.6 Å2
containing effluents. Adsorption is a surface phenomenon, Solubility Soluble in water, ethanol; very
where the adsorbate adheres to the surface of the adsorbent; slightly soluble in acetone;
practically insoluble in ether,
hence, the selection of the adsorbent is very crucial. In the
xylene
past few years, various types of adsorbent have been reported
Melting point > 360 °C
for the removal of CR which are developed from waste mate-
pH range 3.0–5.0
rials such as cocoa pod husk [16], mango leaf [17], orange
Color Blue (pH 3.0) to red (pH 5.0)
peel [18], apricot stone [19] and stem of pineapple plant
Maximum absorption 497 nm
[20]. Development of low-cost and eco-friendly adsorbent wavelength
has always been the area of interest for researchers, and it
Synonyms Cotton red, direct red 28, CI
was identified that the Perna viridis shells which are an aqua- 22120
culture waste could be converted into a value-added product.
From the extensive literature survey that was carried out, it
was found that only a handful of works had been done using 2.2 Preparation of Adsorbate (CR) Solution
these shells as an adsorbent.
In this work, Perna viridis shells were used to prepare a Congo red of commercial quality, supplied by Indokem Ltd,
low-cost adsorbent for the efficient removal of CR dye from India, was used as an adsorbate in this study. The character-
aqueous solution. The prepared adsorbent was characterized istics of the Congo red dye and its molecular structure are
using scanning electron microscope (SEM), Brunauer–Em- given in Table 1 and in Fig. 1, respectively. A working solu-
mett–Teller (BET), energy-dispersive X-ray spectroscopy tion 100 ppm of the adsorbate was prepared by dissolving
(EDS), and Fourier transform infrared spectroscopy (FTIR). the precisely weighed amount of dye (100 mg) in distilled
Various parameters which influence the adsorption of CR water (1 L).
dye on PVSS like particle size, time of contact, temperature,
adsorbent dosage, pH, etc., were investigated. The adsorption
reaction models and adsorption mechanism models for the 2.3 Pretreatment and Activation of Adsorbent
adsorption of CR dye onto PVSS were studied. The degree of
correlation between the models was analyzed using several Acid wash was performed on the powdered adsorbent by
error functions which include the function like SSE, RMSE, mixing with 0.1 N HCl and heating it to a temperature of
etc., and statistical functions like Chi-square test and t test 50–60 °C for a period of 10 min and then was filtered and
were reported. A comparison between the ANN model pre- dried overnight in the oven. The activation of the of the PVSS
diction and experimental was also done. was done by heating the adsorbent in a 10 wt% ZnCl2 solution
for 2.5 h at 70 °C. The activated adsorbent was allowed to
cool to room temperature which was then filtered, washed
2 Materials and Method with deionized water and kept for drying in the oven for
8 h.
2.1 Adsorbent Collection and Preparation
2.4 Adsorbent Characterization
Asian green mussel shell Perna viridis was collected from the
local fish market located at Calicut, Kerala, India. Double- The surface structure and morphology were studied using a
distilled water was used to clean the shells that were allowed scanning electron microscopy (Regulus SU 6600, FE-SEM,
to dry in the oven at a temperature of 383 K for 12 h. The Hitachi High Technologies, Japan). Thermo-gravimetric
cleaned shells were then crushed using roll mill and the fine- analysis (TGA) (STA 7200, Thermal Analysis System,
ground using a hammer mill to obtain the desired adsorbent Hitachi High Technologies, Japan) of the adsorbent mate-
size of the range. rial was carried out to study its thermal stability. The

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Arabian Journal for Science and Engineering
Fig. 1 Chemical structure of Congo red dye
Brunauer–Emmett–Teller (Belsorp HP, Microtrac Belcorp,
Japan) was done to determine the surface area of the adsor-
bent. Identification of the functional groups present on the
surface of the adsorbent was done using Fourier trans-
form infrared spectroscopy (Cary 630 FTIR, Spectrometer,
Thermo Fisher Scientific, USA). The elemental composition
was determined by energy-dispersive X-ray spectroscopy
(Regulus SU 6600, FE-SEM, Hitachi High Technologies,
Japan).
2.5 Experiments
Adsorptions were carried out in a batch reactor of the working
volume of 50 mL in 250-mL glass-stoppered Erlenmeyer
flask. Experiments were carried by varying parameters
like adsorbent size (425–180 µm), adsorbent dosage
(2–26 g L−1 ), pH (2.0–8.0), agitation speed (100–200 rpm),
time (5–60 min) and temperature (308–333 K). The
residual dye concentration was evaluated by absorbance
measurement using double-beam UV–VIS spectropho-
tometer (Lambda 1050 UV/Vis/NIR Spectrophotometer,
Perkin Elmer, USA) at a wavelength of 497 nm. The
amount of dye adsorbed per unit mass of adsorbent
at any time t (qt ) expressed as mg g−1 was given by
Eq. (1):
(Ci − Ct ) × V
qt  (1)
m
where Ci is the initial dye concentration (mg L−1 ), Ct is the
concentration of the dye after t time (mg L−1 ), V the total
volume of dye solution (L), and m is the mass of the adsorbent
taken (g).
The percentage removal (%) of dye by the adsorbent was
given by Eq. (2)
Ci − Ct
Removal (%)  × 100 (2)
Ci
3 Theory
3.1 Adsorption Models
The information about the chemical kinetics, mechanism of
mass transfer, and steps involved in the diffusion of the CR
dye to the adsorbent could be understood by carrying out
modeling of the process [21]. Various mathematical mod-
els have been developed to study the adsorption process,
and they are broadly classified as adsorption reaction model
and adsorption diffusion model. Models like pseudo-first
order, pseudo-second order, Elovich kinetic model and frac-
tional power model describe the chemical reaction kinetics
of the adsorption process, whereas the intra-particle diffu-
sion model comes under adsorption diffusion model which
gives us an insight into the various steps taking place during
adsorption [22]. In this work, both the models were consid-
ered to study the kinetics and the mechanism of adsorption
in the removal of CR dye from an aqueous solution.
3.1.1 Pseudo-First-Order Model
The general expression of the pseudo-first-order model is as
follows [22]:
dqt
 k1 (qe − qt ) (3)
t
The linearized form is obtained by integrating Eq. (3)
between the limits at t  0, qt  0 to t  t,qt  qt as
given below:
log(qe − qt )  logqe −
k1
t (4)
2.303
where the amount of CR dye adsorbed by the adsorbent at
equilibrium is given by qe and qt represents the amount of CR
dye adsorbed at any time ‘t’ by the adsorbent, both expressed
as mg of CR dye adsorbed/g of the seashell. The plot of
the graph between log(qe − qt ) and t yields the pseudo-first-
order rate constant k1 (min−1 ) and the equilibrium adsorption
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capacity qe from the slope and intercept of the straight-line Linearization of Eq. (9) yields:
graph, respectively.
ln(qt )  ϑ ln(t) + ln(k) (10)
3.1.2 Pseudo-Second-Order Model
where k and ϑ are constants and value of ϑ < 1 if the kinetic
Second-order rate constant can be obtained from the model data fit well for the fractional power model [28].
described below [22, 23].
dqt 3.1.5 Intra-Particle Diffusion Model
 k2 (qe − qt )2 (5)
dt
Weber and Morriss developed an empirical to explain the
The linearized form is obtained by integrating Eq. (5) adsorption mechanism between the amount of dye adsorbed
within the limits t  0 to t  t and qt  0 to qt  qt as and time, which was reported as Eq. (11) [29]:
given below:
t 1 t qt  ki t 0.5 + I (11)
 2
+ (6)
qt k 2 qe qe
In the empirical equation, k i (mg g−1 min−0.5 ) is the
where k 2 (g mg−1 min−1 ) is the second-order rate constant intra-particle rate diffusion constant and I (mg g−1 ) gives
for the adsorption of the CR dye by the adsorbent and qe the information about the boundary layer thickness. The plot
and qt represent the concentration of the CR dye adsorbed at of the concentration of dye adsorbed versus the time exhibits
equilibrium and at any time ‘t,’ respectively. The plot of t/qt multilinear graph which is interpreted as two or more steps
versus t yields the rate constant for the model. The y-intercept influencing the rate of adsorption of the dye [30].
of the plot gives information about the initial adsorption rate
h  k2 qe2 (mg g−1 min−1 ). 3.2 Error Analysis

3.1.3 Elovich Kinetic Model Error analysis is done to estimate the deviation of experimen-
tal data points from that of theoretically predicted in which
In recent time, this model is being used to describe the adsorp- the error might arise due to the linearization of the nonlinear
tion process of removal of pollutants [22] and it holds well regression kinetic models. Here, we are trying to find out the
for chemisorption process [24], which is formulated as [25]: best fit for the proposed kinetic model by using four different
error functions.
dqt
 αe(−βqt ) (7)
dt
3.2.1 The Sum of the Squares of the Errors (SSE)
On integrating Eq. (7) on the assumption αβt  t and
boundary conditions t  0, qt  0 and t  t, qt  qt , we SSE is the error functions widely used to determine the devi-
get ation of the experimental data from that of the theoretical
[31], given by the formula:
ln(αβ) ln(t)
qt  + (8)
β β 
N
 2
SSE  qcal − qex p (12)
where the initial adsorption rate is given by α (mg g−1 min−1 ) i1
and β (g mg−1 ) is the desorption constant, tells us about
the activation energy and degree of surface coverage by the where qcal and qexp are the theoretically calculated and exper-
adsorbate. The plot of qt versus ln(t) yields a linear relation- imental values of adoption capacity (mg g−1 ).
ship from which the slope 1/β indicating the availability of
site for adsorption and ln(αβ)/β indicating the initial adsorp- 3.2.2 Average Relative Error Deviation (ARED)
tion quantity could be calculated [26].
This gives an idea about the fractional error distribution
3.1.4 Fractional Power Model among the calculated and experimental data given by [32]:

N  
The model is described as [27]: 100  qcal − qexp 
ARED    (13)
N  qexp 
qt  kt ϑ (9) i1

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3.2.3 The Sum of Absolute Error (SAE)

It provides us with information about the better fit of the

kinetic model [31]:


N
 
SAE  qcal − qexp  (14)
i1

3.2.4 Root Mean Square Error (RMSE)


 2
qcal − qexp
RMSE  (15)
N

3.2.5 Statistical Functions

Fig. 2 SEM image of adsorbent before activation
Two statistical tests are being done in this study to evalu-
ate among the kinetic models, the best fit model. The tests
are Student’s t test and Chi-square test, and if the p value is
greater than the alpha value, then we accept the null hypoth-
esis Ho : No difference in calculated and experimental data
values, else the null hypothesis is rejected.

3.3 Artificial Neural Network (ANN) Structure

Artificial neural network utilizes a mathematical technique

to identify the link between the input given to the system and
the corresponding output generated by it. It could be either
linear or nonlinear depending on the complexity of the sys-
tem. ANN has now been identified as a potential tool to model
complex process in the field of water resource management,
dye adsorption, heavy metal removal, etc., [33] which uti-
lizes a set of experimental data to model the process rather
than the traditional method. The architecture of the ANN
comprises three levels: an input layer, a hidden layer, and the
output layer. Each layer consists of neurons which resemble
the biological neurons and consist of two parts, a summing
part and weighted parameter [34].
In this study, a 3-layer feedforward backpropagation ANN
had been developed with contact time (min), adsorbent
dosage (g L−1 ), temperature (K), agitation speed (rpm) and
pH as the input data to the network to predict the percentage
removal of the dye by the adsorbent. Tansigmoid function
and liner function have been utilized as the activating func-
tions in the hidden layer and the output layer, respectively.
The Levenberg–Marquardt (LM) algorithm had been used to
train the network, and the gradient descent method (GDM)
was used as the learning function while training the model.
The inputs were normalized to values between 0 and 1, and
the numbers of neurons in the hidden layer were optimized
by varying them between 2 and 14 and analyzing the mean
square error (MSE) and the determination coefficient (R2 ) of
the neural network.
Fig. 3 SEM image of adsorbent after activation
4 Results and Discussion
4.1 Adsorbent Characterization
From the SEM images in Fig. 2, we could see a sheet-like
layer structure with low porosity and distorted surface distri-
bution of the pores in the raw adsorbent [35]. After activation,
it has resulted in the opening up of pores on the surface of
the adsorbent to yield more micropores of spherical shape as
in Fig. 3.
The TGA curves presented in Fig. 4 show a 2% loss
in weight, indicating the removal of un-bounded moisture
present on the surface of the adsorbent in the temperature
range of 90–100 °C. With further increase in temperature
up till 600 °C, a loss of 8% was observed which would
be attributed to the loss of volatile in inorganic impurities
present in it, and above 600 °C, the material slowly starts to
decompose [35]. The FTIR spectra of the adsorbent material
before and after adsorption of dye are shown in Fig. 5. The

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Fig. 4 TGA of adsorbent after activation
Fig. 5 FTIR of adsorbent a before adsorption of dye b after adsorption
of dye
peaks at 3500 cm−1 and 2922.2 cm−1 show the presence
of O–H stretching of the alcoholic and carboxylic groups
respectively. It was also noticed that the intensity of the peaks
reduced substantially after the adsorption process because of
the loading of the dye onto the adsorbent. The peaks rang-
ing from 1400 to 3400 cm−1 indicate the various stretching
and bending of carboxylic group and amide groups [36]. The
strong band at 1472.3 cm−1 indicates the C–O stretching
of CaCO3 [37]. The bands at 715.6 and 864.7 cm−1 were
attributed to various in-plane and out-plane bending vibration
of the CO3 2− ion [38]. From the spectrum, it could be con-
cluded that the hydroxyls, carboxylic, amides and carbonyls
are the groups responsible for the adsorption of CR dye.
The BET analysis of the adsorbent was performed, and
Fig. 6 shows the adsorption–desorption curve for the same.
The obtained BET results are given in Table 2. A total sur-
face area and mean pore diameter of 13.746 m2 g−1 and
7.0625 nm, respectively, were obtained.
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Fig. 6 Adsorption desorption curve of adsorbent
Table 2 BET analysis of adsorbent
1 Total surface area, as 13.746 m2 g−1
2 Total pore volume 0.024271 cm3 g−1
3 Mean pore diameter 7.0625 nm
The EDS curve of the adsorbent material is shown in
Fig. 7. A weight percent of 30.22% for calcium, 43.52%
for oxygen, 8.74% for carbon and the presence of other ele-
ments like zinc and chlorine were confirmed from the EDS
analysis of the adsorbent.
4.2 Effect of Particle Size
The size of the adsorbent material is a controlling param-
eter in adsorption [39], which plays a crucial role in the
amount of dye that is adsorbed by it. In this work, three
different size ranges of particles of PVSS were considered:
> 425 µm, 425–180 µm and < 180 µm. The result obtained
is as shown in Fig. 8. It could be seen that as the particle
size increases, the percentage removal of the CR dye from
the solution decreases. A percentage removal of 97.77 was
obtained for the particles of size range < 180 µm because
as the particle size is reduced, the specific surface area and
availability of active pore site for the dye to get adsorbed
increase [40] and hence this size fraction of PVSS particles
was selected for the further batch experiments.
4.3 Effect of Adsorbent Dose
It could be seen from the plot (Fig. 9) for percentage removal
versus adsorbent dosage that as the amount of adsorbent
increases, the percentage removal of the CR dye increases,
which is acknowledged to the increase in the number of
active adsorption sites available for the CR dye to adsorb
Arabian Journal for Science and Engineering
Fig. 7 EDS analysis of
adsorbent
Fig. 8 Effect of particle size on adsorption of CR dye by PVSS (exper-
imental condition: amount of adsorbent: 0.02 g mL−1 , agitation speed:
100 rpm, contact time: 0.5 h. pH: 5.5, initial concentration: 100 ppm,
temperature: 308.5 K)
[41, 42]. However, as we increase the dosage, it is seen that
the process attains equilibrium at an adsorbent dosage of
22 g L−1 . This could be owing to the unavailability of active
sites for the uptake of the dye. From Fig. 9, it is observed
that the adsorption capacity decreases with increases in the
dose of adsorbent material which is consistent with the result
reported previously [38, 40] and hence 22 g L−1 is taken
as the optimized dose of PVSS required for the maximum
removal of CR dye at specified experimental conditions.
4.4 Effect of pH
Various properties like surface charge, the stability of the
adsorbent and the chemistry of the adsorption are greatly
influenced by the pH of the initial solution [5]. CR dye is a
dipolar molecule with a cationic and anionic form at acidic
and basic pH, respectively. The study of pH on the effect
of the adsorption on the PVSS was done, and the result is
shown in Fig. 10. From the plot, it is seen that the adsorption
Fig. 9 Effect of adsorbent dosage on adsorption of CR dye by PVSS
(experimental condition: agitation speed: 100 rpm, contact time: 0.5 h,
pH: 5.5, initial concentration: 100 ppm, temperature: 308.5 K)
of CR dye by PVSS increases from pH 2–6 after which it
decreases. A similar trend has been reported by Mittal et al.
[43] in adsorption of CR dye. The highest uptake of CR dye
by PVSS was obtained for a pH range of 5.5–6, which might
be due to the strong inter-ionic attraction between the cationic
form of the CR dye molecule and the strong electronegative
functional groups like carboxylic, alcoholic and carbonyl.
The tendency of the dye to replace the H+ ion on the surface
of the adsorbent would be more at acidic pH rather than basic
because at higher pH the repulsion between the anionic CR
form and the negatively charged surface of PVSS is more.
Hence, the greater rate of mass transfer is achieved at lower
pH [44]. An optimized pH of 5.5 has been considered for
further studies in this work.
4.5 Effect of Agitation Speed
The speed with which the CR dye PVSS mixture is agi-
tated has an essential role in the rate of mass transfer of the
process. An optimum agitation speed is required because if
the speed is too low, then there would be no proper mixing
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Fig. 10 Effect of pH on adsorption of CR dye by PVSS (experimental
condition: agitation speed: 100 rpm, adsorbent dose: 22 g L−1 , contact
time: 0.5 h, initial concentration: 100 ppm, temperature: 308.5 K)
Fig. 11 Effect of contact time on adsorption of CR dye by PVSS (exper-
imental condition: agitation speed: 125 rpm, pH: 5.5, adsorbent dose:
22 g L−1 , initial concentration: 100 ppm, temperature: 308.5 K)
and hence low removal of dye or if the speed is too high,
then the appropriate contact time between them would not
be attained and hence again low percentage removal. In this
study, optimum agitation speed of 125 rpm, which yields
removal of 98.33%, has been identified and the same has
been used for further study.
4.6 Effect of Contact Time
The uptake of CR dye is initially rapid up till 25 min after
which the process slowly comes to equilibrium as shown in
Fig. 11. This could be due to the saturation of the active
sites with CR dye present on the surface of PVSS. Under
the performed experimental condition, the attainment of the
equilibrium stage reveals the adsorbents maximum adsorp-
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Fig. 12 Effect of temperature on adsorption of CR dye by PVSS (exper-
imental condition: agitation speed: 125 rpm, pH: 5.5, adsorbent dose:
22 g L−1 , initial concentration: 100 ppm, contact time: 0.5 h)
tion capacity. The single, smooth and continuous curve
indicates the possibility of monolayer adsorption of the CR
dye [45]. In this study, the equilibrium stage is attained after
30 min of operation.
4.7 Effect of Temperature
The temperature of operation of the process plays a major role
in governing the rate of adsorption by altering the equilibrium
adsorption capacity of the adsorbent. The study of the adsorp-
tion process was evaluated at three different temperatures,
and the results are as shown in Fig. 12. It could be observed
that as the temperature rises, the percentage removal of the
CR dye is reduced. This reduction could be attributed due to
the increase in solubility of the dye in the solvent hence form-
ing a stronger bond between them rather than the physically
formed bond between adsorbent and dye. Also, an increase
in temperature increases the kinetic energy of the molecules
and hence chances for the breaking of inter-molecular bond-
ing between the CR dye and PVSS are more and previous
studies have presented similar results [24, 40].
4.8 Adsorption Reaction Model
The study of the kinetics of the adsorption process is very
essential to understand the mechanism and the rate of adsorp-
tion of the process. As mentioned earlier, the optimized
conditions of the parameters were used to evaluate the kinet-
ics of adsorption of CR dye onto PVSS. Correlations of the
experimental data were done using the linearized forms of the
different kinetic models, and consolidated results are tabu-
lated in Table 3. A comparative plot is shown between the
Arabian Journal for Science and Engineering

Table 3 Kinetic model parameters for adsorption of CR dye by PVSS

Models Model parameters

Pseudo-first order qe,cal (mg g−1 ) 0.609

qe,expt (mg g−1 ) 4.520
k 1 (min−1 ) 0.117
R2 (%) 85.04
Pseudo-second order qe,cal (mg g−1 ) 4.608
qe,expt (mg g−1 ) 4.520
k2 (g mg−1 min−1 ) 0.382
R2 (%) 99.97
Intra-particle diffusion k i (mg g−1 min−1/2 ) 0.078
I (mg g−1 ) 4.086
R2 (%) 93.12
Elovich kinetic α (mg g−1 min−1 ) 6.693
Fig. 14 Pseudo-second-order kinetics for adsorption of CR dye on
β (g mg−1 ) 7.246 PVSS
R2 (%) 86.82
Fractional power k 4.043
υ 0.031
R2 (%) 87.71

Fig. 15 Intra-particle diffusion model for adsorption of CR dye on PVSS

crassipes [39], removal of CR from wastewater [43] and

Fig. 13 Comparison between experimental and calculated adsorption
capacity of CR dye onto PVSS as a function of time
calculated adsorption capacity for the different kinetic mod-
els and the experimentally obtained in Fig. 13.
The evaluation of the pseudo-second-order model was
done by plotting t/q(t) versus time and is shown in Fig. 14.
It was observed that the R2 value obtained is 99.97 which
was higher when compared to the R2 of pseudo-first order.
A good agreement could be seen with the values of exper-
imentally obtained and calculated equilibrium adsorption
capacity. This indicates that the rate of the adsorption is
mainly controlled by the chemical process, and so it could be
successfully explained by the pseudo-second-order kinetic
model. Reports on adsorption of CR dye usingEichhornia
adsorption of CR dye using guava leaf-based AC [4] had
shown analogous kind of results. Other kinetic models like
Elovich kinetic model and fractional power model were
evaluated, and model parameters were calculated and are
presented in Table 3. Low R2 values were obtained for both
the models, which conclude that the pseudo-second-order
kinetic model best explains the rate of adsorption of CR dye
by PVSS.
4.9 Adsorption Diffusion Model
The adsorption mechanism and the rate-controlling step
could be predicted from the Weber–Morris plot shown in
Fig. 15. The model parameters were k i , and I was determined
from the plot and is listed in Table 3. From the graph, it could
be seen that the plot exhibits multilinearity and doesn’t pass

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Table 4 Error estimation for adsorption of CR dye on PVSS using error it was seen that from the kinetic model fitting correlation,
functions the Elovich kinetic model and fractional power model have
Model SSE SAE RMSE ARED R2 values of 86.82 and 87.71, respectively, which are way
less than the R2 obtained for pseudo-second order, and hence
Pseudo-first order 92.176 23.515 3.920 89.006
these two models do not fit the data well. So it is evident that
Pseudo-second order 0.034 0.323 0.075 1.242
the pseudo-second-order model best explains the adsorption
Elovich kinetic 0.006 0.176 0.033 0.670 kinetics. From the statistical test done, a high probability
Fractional power 0.006 0.188 0.033 0.715 value of 0.96 and 0.99 is observed for the pseudo-second-
Intra-particle diffusion 0.003 0.132 0.024 0.501 order model which supports the above conclusion.

Table 5 Error estimation for adsorption of CR dye on PVSS using the

statistical tool 5 Artificial Neural Network Model
Model t test Chi-square test
The modeling was carried out with the help of MATLAB,
Pseudo-first order 9.93689 × 10−14 1.98246 × 10−42 and the ANN architecture utilized here is shown in Fig. 16.
Pseudo-second order 0.965327900 0.999999697 The total input data were divided into training data (70%),
Elovich kinetic 0.987539188 0.999999996 validation data (15%) and testing data (15%) for developing
Fractional power 0.890182862 0.999999996 the neural network. The training was carried by varying the
Intra-particle diffusion 0.937862122 0.999999999 number of neurons in the hidden layer with a training goal of
error of the order 10−5 and a total of 1000 epochs, where the
upgradation of the weights was after each epoch. An MSE
through the origin (I  0), which indicates that the process of 4 × 10−6 error was obtained for 10 neurons in the hidden
is not only intra-particle diffusion rate-controlled but also layer at 11th epoch out of total 17 epochs as depicted in
boundary layer diffusion-controlled [43, 46]. The three steps Fig. 17. The R-value for the training, validation, testing and
are involved in adsorption according to this model: initially for the overall model from Fig. 18 is as follows 1, 0.998,
the boundary layer diffusion which represents the external 0.994 and 0.998, indicating the ANN model developed here
adsorption of the CR dye to the PVSS followed by the inter- is best suited for the process. The model was simulated with
particle diffusion and finally the attaining of the equilibrium test data, and a comparison between the actual percentage
stage [38]. Hence, it could be concluded that the intra-particle removal of the dye and the predicted percentage removal
diffusion model is the best to explain the diffusion mecha- by ANN was plotted and is as shown in Fig. 19. The plot
nism. indicates that the training of the network was successful and
can predict the percentage removal with at most accuracy.
4.10 Error Analysis

In this study, different error functions like SSE, ARED, SAE,

etc., are utilized to find out the best fitting model and the
results are tabulated in Table 4. The statistical prediction
using statistical tools is given in Table 5. It is observed that
error obtained for the pseudo-second-order for SSE is 0.034,
SAE is 0.323, and RMSE and ARED are 0.075 and 1.242,
respectively, which are slightly larger than the same obtained
for Elovich kinetic and Fractional kinetic models. However,
6 Conclusion
In this study, the adsorption ability of the PVSS to remove
CR dye from its aqueous solution was done. Characteri-
zation of the prepared adsorbent was done using Fourier
transformed infrared spectroscopy (FTIR), scanning electron
microscope (SEM), Brunauer–Emmett–Teller (BET), etc.

Fig. 16 ANN architecture

123
Arabian Journal for Science and Engineering

Fig. 19 Comparison plot between ANN predicted and experimental

result
Fig. 17 Validation performance plot of ANN

Various parameters like adsorbent size, adsorbent dosage, contact time of 30 min and a temperature of 308.5 K were
pH, contact time, agitation speed, temperature which control required for a maximum removal of 98% of CR dye. The
the adsorption were studied, and it was found that an opti- maximum adsorption capacity of 4.52 mg g−1 was obtained.
mal dosage of 22 g L−1 , pH of 5.5, agitation speed 125 rpm, Further to these, the adsorption reaction models were inves-

Fig. 18 Regression values for

training, validation, testing, and
the overall model

123

tigated and it was seen that the pseudo-second-order best fits
the process with an R2 value of 0.99. The adsorption diffu-
sion model studies reveal that the adsorption is controlled by
both intra-particle diffusion and boundary layer diffusion.
The various errors estimated and statistical test evaluated
support the above conclusion that the pseudo-second-order
and intra-particle diffusion model best explain the kinetics
and mechanism of the adsorption of CR dye onto PVSS,
respectively. ANN modeling was carried out, and the pre-
dicted values were in conformity with the experimental data.
Finally, the low cost and the availability of the PVSS make
them a potential candidate for adsorption of CR dye.
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