Results in Surfaces and Interfaces 3 (2021) 100011

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Results in Surfaces and Interfaces

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Batch adsorption of indigo carmine on activated carbon prepared from

sawdust: A comparative study and optimization of operating conditions
using Response Surface Methodology
Sayan Bhowmik a ,∗, Vijoyeta Chakraborty b , Papita Das a
a
Department of Chemical Engineering, Faculty of Engineering and Technology, Jadavpur University, India
b
School of Water Resources Engineering, Faculty of Interdisciplinary Studies, Law & Management, Jadavpur University, India

ARTICLE INFO ABSTRACT

Keywords: Raw sawdust was used to prepare two chemically activated carbon — one after treating with Ortho-phosphoric
Sawdust acid and another using sodium hydroxide. The adsorbents thus prepared were used to study indigo carmine
Activated carbon removal under batch mode. The adsorbents were thus characterized and compared using the results. The
Adsorption
isotherm models were employed to test the adsorption isotherm data. The Langmuir model showed the best
Comparative study
fit among the models for both of the adsorbents. The pseudo-second-order model characterized the kinetic
Indigo carmine
Response Surface Methodology optimization
behaviour for both of the adsorbents. The thermodynamic results implied that the process was exothermic.
The activated carbon prepared after activation with Orthophosphoric acid gave better removal than the one
activated with Sodium Hydroxide; hence a Fourier Transform Infrared (FT-IR) spectroscopy was performed.
Further, a Response Surface Methodology Optimization of the operating conditions was done using it as the
adsorbent.

1. Introduction chemical techniques. These methods require high power in electricity

Dyes are substances with colouring capacity used to impart colour to
materials in various industries like leather, textile, food, pharmaceuti-
cal, cosmetics, paper, printing, and photography. All of these industries
use water as one of the utilities in the manufacturing and the finishing
processes. Most of the conventional treatment processes are unable
to remove the dye satisfactorily (Rodríguez Couto, 2009). The erratic
rainfall and adverse climatic conditions have contributed to water
scarcity in the recent past. Thus, water conservation and remediation of
water pollution become imperative to meet the ever-increasing demand
for water.
The dyes are noticeable even if their concentration is low and
causes great visual displeasure along with other toxicological or car-
cinogenic effects (Hunger, 2003). Indigo Carmine (I.C.) is used as a food
colouring (Singh et al., 2017) and extensively in the textile industry.
Colour has a specific tolerance limit of 5 Hazen units (desirable) with
a maximum limit of 15 Hazen units for drinking water (BIS, 2012).
There are various available methods of removing dye, categorized into
the chemical, physical and biological mode. Enzymes are utilized in the
biological process, which is cheap and safe, but the enzymatic cells’
growth rates often disrupt accurate results (Katheresan et al., 2018).
Oxidative procedures, photochemical and photocatalytic degradation,
ozone treatment, and other reactive procedures constitute removal’s
and often require high precision expensive equipment (Rafatullah et al.,
2010).
Principles involving mass transfer operations like adsorption, floc-
culation, coagulation, filtration — ultra or membrane, reverse osmosis
and ion exchange constitute the physical processes used to simplify
application and high efficiency (Katheresan et al., 2018). Membrane
filtration, ion exchange and reverse osmosis are expensive methods of
separation. Adsorption, a cost-effective, efficient and straightforward
method, is used extensively to eliminate dyes. This necessitates the
finding of efficient, cost-effective and environment-friendly adsorbents
which can be easily separated and regenerated after use.
Carbonaceous material like bio-char prepared by thermal treatment
of biomass or biowaste in the absence of oxygen may be used ef-
fectively as an adsorbent. A wide range of biomass is available for
bio-char preparation — agricultural and domestic wastes, wastes from
paper and pulp industries, timber by-products and wastes and cattle
wastes (Tang et al., 2018). Activated carbon (A.C.) is a porous material
with a large surface area used to expel dyes or heavy metals from the
solution. Commercially prepared activated carbon has high adsorbing
capacities, but there has been a constant search for low-cost economical
adsorbents to match their commercial counterparts’ performance.

∗ Corresponding author.
E-mail address: sayanb1997@gmail.com (S. Bhowmik).

https://doi.org/10.1016/j.rsurfi.2021.100011
Received 9 July 2020; Received in revised form 19 February 2021; Accepted 27 March 2021

2666-8459/© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
S. Bhowmik, V. Chakraborty and P. Das
Sugarcane bagasse was used as an agricultural waste to prepare
adsorbents. The waste was treated to various carbonization tempera-
tures with varied intervals to find the optimum temperature and the
activation time. The study was then carried out with the prepared A.C.
from sugarcane bagasse, and satisfactory results were obtained from
the experiments (Hazzaa and Hussein, 2015). Studies indicated that
rice husk could be used for the preparation of A.C. as well (Ahiduz-
zaman and Sadrul Islam, 2016). It is locally available as paddy is the
predominant crop produced in West Bengal, which is grown year long,
making the state one of India’s largest paddy producers (Bureau of Ap-
plied Economics and Statistics Department of Statistics and Programme
Implementation Government of West Bengal, 2016). This process might
always not be economical as a substantial amount of rice husk is used
as a raw material to produce fuel and fertilizers (Bodie et al., 2019).
A.C. prepared from sawdust also indicated a potential to eliminate
dyes from effluent or sewerage. Steam activation mechanisms were
studied, and its performance as an adsorbent was observed using Acid
Yellow 36 dye. The results indicated that A.C. prepared from sawdust
has substantial removal capacity, but it indicated an optimum pH of
3 or below, which might cause a release of acidic waters as effluents
against the prevalent environmental norms (Malik, 2003). Hence, the
scope of further research is to find wherein the operating conditions
could be made more efficient. Thus, sawdust was chosen as the primary
carbonaceous raw material to prepare A.C. Not much work has been
reported on I.C. removal in the recent literature, although it is a
common textile dye and is also used for medical diagnosis. Various
removal methods have been studied, and it was indicated that adsorp-
tion, with the help of A.C., was an efficient mode of removal (Khadhri
et al., 2019). Two types of adsorbents were prepared from sawdust,
and a comparative study was performed on I.C. removal efficiency
of the adsorbents and their characterizations. Isotherm fitting study,
thermodynamics and kinetics of the process was examined as well.
Finally, a Response Surface Methodology (R.S.M.) Optimization was
carried out to find out the optimum operating regimes. The Central
Composite Design (C.C.D.) of R.S.M. was used to predict the inter
parameter interactions in a quadratic model of relevant parameters.
It employs regression and correlation analysis to evaluate the depen-
dent variable considering several independent variables’ effects. R.S.M.
analysis was carried out on batch experiments using A.C. prepared
from sawdust (Chakraborty et al., 2019). It essentially included design-
ing experiments and performing them, evaluating the coefficients in
the employed mathematical model and checking for model adequacy.
The validation of predicted response and inter parameter interaction
variables is accomplished by performing Analysis of Variance test
(ANOVA) (Chakraborty et al., 2018).
2. Methods and materials
2.1. Materials
Raw sawdust was gathered from a carpentry shop at Jadavpur,
Kolkata, India, which produced sawdust as waste material. The sawdust
was sieved through a 72 mesh sieve and washed thoroughly. The saw-
dust was dried to 105 ◦ C in a hot air oven. The sawdust thus obtained
was divided into two parts — one was treated with NaOH solution
of specific strength, and the other was treated with H3 PO4 solution
of particular strength. The two parts were used for thermal activa-
tion subsequently. Analytic grade Sodium Hydroxide pellets, Potassium
Nitrate, fuming Hydrochloric acid (37%), and Ortho-Phosphoric acid
(85%) were purchased from Merck, India. The Indigo Carmine dye was
purchased from Loba Chemie.
2
Results in Surfaces and Interfaces 3 (2021) 100011
2.2. Preparation of activated carbon
The first part of the dried sawdust was treated with 1 N NaOH solu-
tion. Then it was repeatedly cleaned with distilled water to neutralize
the pH. The resulting sawdust dried again in the hot air oven at 378 K
until completely dry. The dried sawdust was then kept in silica crucible
and activated in a muffle furnace at 973 K.
The second part of the dried sawdust was treated with 10% (w/w)
H3 PO4 solution, and the procedure mentioned above for washing and
drying was followed. Thus, the resulting sawdust was activated for 2 h
at 973 K in a muffle furnace and labelled as SDP. The A.C.s obtained
from these were used for separate batch adsorption studies.
2.3. Preparation of indigo carmine (I. C.) dye solution and standard curve
Indigo carmine stock solution was prepared by dissolving required
of I.C. in distilled water. These solutions were then used for batch mode
adsorption studies. The pH was adjusted using dilute acid (0.1 N HCl)
or diluted alkali (0.1 N NaOH) solutions.
The resulting solutions were analysed using UV–visible spectropho-
tometer (Perkin Elmer, Lambda 365.) at 𝜆max = 610.25 nm. The ab-
sorbance was plotted against dye concentration to obtain the standard
curve.
2.4. Determination of point of zero charge pH𝑝𝑧𝑐
The methodology used to determine the pHpzc of the A.C.s is similar
to the ones mentioned in the literature (Sinha et al., 2012b; Gokulaku-
mar and Narayanaswamy, 2008). The salt addition method was used
in this study wherein 50 mL of 0.01 M KNO3 solution was poured in
11 separate conical, flat bottom flasks. The pH was regulated using the
diluted acid (0.1 N HCl) or alkali (0.1 N NaOH), and solutions of pH
ranging from 2–12 were prepared. Then, 50 mg of A.C. was added to
the flasks, and they were left for 24 h in an orbital incubator shaker
until equilibrium at 308 K. The final pH of the solutions were noted.
The point at which the 𝛥pH line crossed the 𝑥-axis (initial pH) gave the
value of pHpzc for that A.C. The same procedure was followed for both
the A.C.s.
2.5. Batch adsorption studies
The effects of pH (2–10), adsorbent dose (1–10 g L−1 ), time of
contact (0–180 min), initial concentration of dye (10–50 mg L−1 ) and
temperature (298–313 K) on the adsorption of I.C. was studied. For the
batch studies, the desired amount of activated carbon was contacted
with 50 mL of I.C. solutions in flat bottom conical flasks. These were
then agitated in an orbital incubator, and the solutions were examined
at desired intervals and centrifuged. The remaining I.C. content in the
supernatant was investigated at 𝜆max = 610.25 nm using a UV–Vis
spectrophotometer (Perkin Elmer, Lambda 365). The amount of I.C.
absorbed is given by:
(𝐶0 − 𝐶𝑒 )𝑉
𝑞𝑒 = (1)
𝑚
where 𝑞e (mg g−1 ) is the amount of I.C. adsorbed on the A.C., 𝐶0
(mg L−1 ) is the initial I.C. concentration, 𝐶e (mg L−1 ) is the I.C.
concentration at an instant of time t (min), V (L) is the solution volume,
and m (g) is the mass of A.C. used.
S. Bhowmik, V. Chakraborty and P. Das
Table 1
Range and levels of independent parameters for RSM optimization.
Parameters Unit Notation −1 Level +1 Level −𝛼
pH A 2.5 6 1.31
Time min B 90 180 59.32
Dosage g/L C 2 5 0.98
Fig. 1. FT-IR spectra of A.C. (SDP).
2.6. Response surface methodology optimization — Experimental design
The effect of the parameters on each other cannot be established
with batch mode adsorption studies. Therefore, the optimum condi-
tions as predicted by the batch mode studies might not be the actual
optimum conditions. Factors like pH, contact time and dosage were
identified as the significant parameters from the batch experiments, and
a standard CCD of RSM design was used to find the response function
(Removal efficiency in percentage) considering the effects of each of
these parameters along with their mutual effects on each other (Sinha
et al., 2012b). The selected parameters and their experimental ranges
are provided in Table 1.
The RSM experiment chart was generated using the software Design
Expert Version 7.1.6 (Stat-Ease, USA). 20 experiments were conducted
in total according to the chart, and the same software analysed the
results. The model developed was tested for adequacy, and the ANOVA
was used to test the significance of the regression coefficients.
3. Results and discussion
3.1. Characterization of the adsorbents
A Fourier Transform Infrared Spectroscopy (FT-IR) analysis of SDP
was done, as shown in Fig. 1. The peak at 2925 cm−1 indicated C–
H stretching of the –CH2 groups. This might be an indication that
aliphatic CH groups are present (Gokulakumar and Narayanaswamy,
2008). The peak at 2856 cm−1 indicated –CH2 stretching of the aliphatic
groups present (Banerjee and Chattopadhyaya, 2017). The appearance
of a peak at 1542 cm−1 confirmed the presence of aromatic C=C bonds.
The peak at 1002 cm−1 can be attributed to the C–O stretching (Postai
et al., 2016).
3.2. Batch adsorption optimization study
3.2.1. Effect of pH
The results implied that the amount of I.C. adsorbed at the equi-
librium decreases with increasing pH of the solution (Fig. 2). It was
seen that SDP had a higher adsorption capacity than SDNa and thus
performed better as an adsorbent. The maximum removal of dye was
Results in Surfaces and Interfaces 3 (2021) 100011
+𝛼
7.19
210.68
6.02
Fig. 2. pH and I.C. adsorption.
Fig. 3. pHpzc determination of the A.C.s.
detected at pH = 2, where the A.C. (SDP) had a 𝑞e = 3.92 mg g−1,
which was better performing than A.C. (SDNa), whose capacity was
𝑞e = 3.2 mg g−1 . The surface furnishes negative charges above the
pHpzc (Harrache et al., 2019), which decreases the adsorption capacity
as I.C. is an anionic dye that causes electrostatic repulsion in that zone.
Below the pHpzc, the surface of the A.C.s is positively charged, which
enhances I.C. adsorption with the aid of electrostatic attraction. The
pHpzc results are shown in subsequent figures (Fig. 3). The A.C.(SDP)
had a pHpzc = 5.84, whereas the A.C. (SDNa) had a pHpzc = 3.22. This
indicates that the solution’s pH need not be adjusted for a higher degree
in SDP, whereas adjustment to a greater acidic pH is required for SDNa
for better capacity and performance of the adsorbents (Khadhri et al.,
2019).
3.2.2. Effect of contact time
The adsorption showed an increase as the contact time was in-
creased and reached a maximum value at 150 min with not much
change after 120 min. This indicated that equilibrium was reached
at 150 min. Thus once equilibrium has been attained, there is not
much removal on further treatment. Thus, it can be inferred that
initially, the rate of adsorption was higher as all the pores were vacant
for adsorption. The adsorbents’ surface became saturated as the time
increased and could remove no further I.C. from the solution (Harrache
et al., 2019). A force of repulsion among the dye molecules in the
A.C. surface and the dye solution at equilibrium is the cause (Banerjee
and Chattopadhyaya, 2017). It is seen from the plot (Fig. 4) that SDP
performs better as the adsorption characteristics of SDP is better than
SDNa, and the difference increases further with time.
3
S. Bhowmik, V. Chakraborty and P. Das
Fig. 4. Time of contact and I.C. adsorption.
Fig. 5. Dose of adsorbent and I.C. adsorption.
3.2.3. Effect of dose of adsorbent
The mass of the adsorbent taken was varied. It was seen (Fig. 5) that
the capacity of adsorption decreases with increase in dose. The removal
of I.C. increases on increasing the amount of adsorbent. Despite the
increase in the removal, the capacity of the adsorbent decreases. 1
g L−1 gave best results for both SDP and SDNa. In principle, adding
more adsorbent should have increased the number of active sites and
pores (Dada et al., 2017b). However, in reality, it is observed that
excess adsorbent dose leads to more inter-particle interactions like
conglomeration leading to an eventual reduction of surface available
for adsorption and thus leading to saturation of available adsorption
sites (Oladoja and Akinlabi, 2009). A small amount of adsorbent dosage
leads to better contact between the adsorption surface and dye sur-
face (Bhattacharyya and Sharma, 2004). 1.38 mg g−1 for SDP and 0.9
mg g−1 for SDNa were found as the best results.
3.2.4. Effect of initial dye concentration
The adsorption changed from 2.31 mg g−1 to 9.39 mg g−1 for SDP
and from 1.4 mg g−1 to 6.74 mg g−1 in the case of SDNa (Fig. 6).
Adsorption is a mass transfer operation, and a rise in concentration
gradient increases adsorption. Thus, the rise in adsorption capacity is
justified as the concentration gradient between the dye solution and the
adsorbent surface is minimum for 10 mg L−1 and maximum for 50 mg
L−1 (Harrache et al., 2019). Removal is 25.34% and 15.44% at 10 mg
L−1 for SDP and SDNa respectively and 20.39% and 14.64% at 50 mg
L−1 for SDP and SDNa. 1 g L−1 adsorbent dose was used for analysis in
both the cases as maximum 𝑞e was observed at 1 g L−1 dosage.
3.3. Adsorption isotherm
Adsorption isotherm was studied for both of the adsorbents to
identify the appropriate model of equilibrium. Four models, namely:
4
Results in Surfaces and Interfaces 3 (2021) 100011
Fig. 6. Initial concentration of dye and I.C. adsorption.
Langmuir, Freundlich, Henry and Temkin, were compared to find the
best fit. The equations are provided in Table 2. In the Freundlich model,
𝐾F represents the constant related to adsorption capacity, and 1/n
gives a measure of the heterogeneity of the surface (Ojediran et al.,
2020). Linear behaviour of the adsorption process is assumed in the
Henry isotherm model. The model consists of only a single parameter.
The model predicts adsorption capacities till a specific value which is
generally lesser than the saturation value (Ahmadi and Shadizadeh,
2013; Ayawei et al., 2017). Reduction in the heat of adsorption with
linear coverage is assumed in the Temkin Isotherm model. This is
attributed to the inter-particle interactions. The binding energies are
uniformly distributed in such adsorption processes (Dada et al., 2017a,
2020b). The Langmuir isotherm model assumes monolayer coverage
with no interaction between the molecules which are adsorbed. It also
assumes adsorption on finite localized sites of the adsorbent (Kapoor
and Yang, 1989; Dada et al., 2020a). The results are given in Ta-
ble 3. The Langmuir model fits best with the maximum regression
coefficient = 0.9995 (SDP), 0.9985 (SDNa). The average relative error
(ARE) observed for this model was 1.69% and 2.06% for SDP and
SDNa, respectively. The Langmuir isotherm fit suggests that the A.C.s
formed had monolayer adsorption at localized sites with little interac-
tion between the adsorbed molecules. The favorability of the adsorption
process was determined by the non-dimensional separation factor, 𝑅L,
given by the following equation:
1
𝑅𝐿 = (2)
1 + 𝐾𝐿 𝐶0
𝑅L is the separation factor, 𝐾L is the Langmuir constant, and 𝐶0 is
the initial dye concentration.
For the 𝐶0 range (10–50 mg L−1 ) used in the study, 𝑅L lies be-
tween 0.67–0.91 for SDP and 0.87–0.97 for SDNa, indicating that I.C.
adsorption was favoured on both the adsorbents (Chakraborty et al.,
2019).
3.4. Adsorption kinetics
The adsorption kinetics of the process reveals the rate of the adsorp-
tion process. The data obtained were subjected to model fitting by the
following equations:
( ) ( )
ln 𝑞𝑒 − 𝑞𝑡 = ln 𝑞𝑒 − 𝑘1 𝑡 (3)
𝑡 1 𝑡
= + (4)
𝑞𝑡 𝑘2 𝑞𝑒 2 𝑞𝑒
Eq. (3) is the pseudo-first-order kinetic model, and Eq. (4) is the
pseudo-second-order kinetic model. The summary of the results is
provided in Table 4. The regression coefficients were 0.9938 and
0.9911 for SDP and SDNa, respectively. The regression coefficients
S. Bhowmik, V. Chakraborty and P. Das Results in Surfaces and Interfaces 3 (2021) 100011

Table 2
Isotherm models used.
Model Governing equation Parameters
𝑞𝑒 𝐾𝐿 𝐶𝑒
Langmuir isotherm 𝑞0
= 1+𝐾𝐿 𝐶𝑒
𝐾L = Langmuir’s constant (L/mg), 𝑞0 =
maximum monolayer coverage (mg/g),
𝑞e = equilibrium adsorption (mg/g), 𝐶e
= equilibrium dye concentration (mg/L)
1∕𝑛
Freundlich isotherm 𝑞𝑒 = 𝐾𝐹 𝐶𝑒 𝐾F is the indicator of adsorption
capacity, and 1/𝑛 is the indicator of
adsorption intensity.
Henry isotherm 𝑞𝑒 = 𝐾𝐻 𝐶𝑒 𝐾H constant of Henry isotherm.
Temkin isotherm 𝑞𝑒 = 𝐵 ln 𝐾𝑇 + 𝐵 ln 𝐶𝑒 B is the Temkin constant and 𝐾T
represents the binding constant.

Table 3 Table 5
Isotherm model fit results and coefficients. Adsorption mechanism models.
Isotherm model Parameters 𝑅2 ARE (%) SDP
Parameters for SDP Model Parameters 𝑅2
Langmuir 𝐾L = 0.01, 𝑞0 = 34.97 0.9995 1.69 Weber Morris model 𝑘p = 0.1456, 𝑐 = 0.1093 0.9905
Freundlich 𝐾F = 0.39, 𝑛 = 1.12 0.9801 6.42 Boyd kinetic model 𝑐 = −0.4945 0.9925
Linear 𝐾H = 0.276 0.9469 8.39
SDNa
Temkin 𝐾T = 0.24, 𝐵 = 4.15 0.9804 6.68
Rate kinetics model Parameters 𝑅2
Parameters for SDNa
Weber Morris model 𝑘p = 0.0968, 𝑐 = −0.0748 0.9901
Langmuir 𝐾L = 0.003, 𝑞0 = 55.87 0.9985 2.06
Boyd kinetic model 𝑐 = −0.5222 0.9976
Freundlich 𝐾F = 0.23, 𝑛 = 1.08 0.9798 23.82
Linear 𝐾H = 0.1833 0.9657 6.48
Temkin 𝐾T = 0.19, 𝐵 = 3.09 0.9777 6.19 Table 6
Thermodynamic parameters.

Table 4 Temperature (K) K (mL g−1 ) 𝛥G0 (kJ mol −1

) 𝛥H0 (kJ mol −1
) 𝛥S0 (kJ mol −1
)
Rate kinetics model fit results and coefficients. Thermodynamic parameters for SDP
Rate kinetics model Parameters 𝑅2 ARE (%) 𝜒2 298 239.03 −13.57
Rate kinetics model fitting parameters for SDP 303 202.08 −13.37
−62.31 −0.16
308 138.02 −12.62
Pseudo first order 𝑘1 = 0.0241, 𝑞e = 1.88 0.9941 10.38 0.0117
313 99.64 −11.97
Pseudo second order 𝑘2 = 0.011, 𝑞e = 2.216 0.9938 4.24 0.00299
Thermodynamic parameters for SDNa
Rate kinetics model fitting parameters for SDNa
298 145.07 −12.33
Pseudo first order 𝑘1 = 0.0184, 𝑞e = 1.116 0.9976 4.79 0.00205
303 91.77 −11.38
Pseudo second order 𝑘2 = 0.00889, 𝑞e = 1.558 0.9941 3.38 0.000878 −53.75 −0.14
308 71.14 −10.92
313 50.22 −10.19

were observed to be lesser than the pseudo-first-order model. However,

the statistical parameters — average relative error (ARE) and the 𝜒 2
yielded lower values for the pseudo-second-order model, suggesting it
to be the more probable model (Dada et al., 2016). It has been found in
most of the studies that dye adsorption is mostly a pseudo-second-order
kinetic step; therefore, the results obtained are in accordance (Olakunle
et al., 2018; Dada et al., 2020a; Bello et al., 2020).
3.5. Mechanism of adsorption
Weber and Morris intraparticle diffusion model and Boyd Kinetic
model were fitted to the experimental data to ascertain the mechanism
of adsorption.
3.5.2. Boyd kinetic model
The following equation gives the model:
𝑞
𝐵𝑡 = −0.4977 − ln(1 − 𝑡 ) (6)
𝑞𝑒
𝑞t is the adsorption capacity at the time, t, and 𝑞e is the equilibrium
adsorption capacity. The 𝐵t values were plotted against time. A linear
plot passing through the origin indicates that the particle diffusion is
the rate-determining step. A linear plot with an intercept indicates that
the process is governed by external mass transfer (Singh et al., 2015).
The results are presented in Table 5. The plots for both SDP and SDNa
are linear but have an intercept indicating that the adsorption process
is governed by external film diffusion.

3.6. Thermodynamic parameters

3.5.1. Weber Morris intraparticle diffusion
The following equation gives the model:
The thermodynamic parameters are given by the following equa-
𝑞𝑡 = 𝑘𝑝 𝑡1∕2 + 𝑐 (5) tions (Jaman et al., 2009):
𝑞
𝑘p is the intra-particle diffusion rate constant, and c is the intercept 𝐾𝑐 = 𝑒 (7)
𝐶𝑒
in the above equation. Large intercept indicates a process dominated
by surface adsorption, whereas a linear line passing through the origin
indicates a process dominated by intra-particle diffusion (Sharma and 𝛥𝐺0 = −𝑅𝑇 ln 𝐾𝑐 (8)
Verma, 2021). The results are reported in Table 5. The presence of an
intercept in both SDP and SDNa indicates that adsorption is dominated
𝛥𝑆 0 𝛥𝐻 0
by surface adsorption. ln 𝐾𝑐 = − (9)
𝑅 𝑅𝑇

5
S. Bhowmik, V. Chakraborty and P. Das Results in Surfaces and Interfaces 3 (2021) 100011

Table 7
Comparison of specific adsorbents in I.C. removal.
Adsorbent Maximum monolayer Reference
capacity (mg/g)
Abrasive spherical materials made of rice husk ash 0.3–0.4 Arenas et al. (2017)
Brazil Nuts 1.09 de Oliveira Brito et al. (2010)
Coal Fly Ash 1.48 De Carvalho et al. (2011)
Zeolites synthesized from coal fly ash 1.23 De Carvalho et al. (2011)
Chitin 5.78 Prado et al. (2004)
Silk 18.38 Ahmed et al. (2017)
Orthophosphoric acid-treated activated carbon 34.97 This work
NaOH treated activated carbon 55.87 This work

Fig. 8. Response of contact time and pH on removal efficiency of I.C.

Fig. 7. Predicted vs Actual values of removal efficiency.

where 𝐾c is the distribution coefficient, 𝑞e is the amount of dye ad-

sorbed per unit mass of the A.C.s, 𝐶e is the equilibrium concentration
of dye in the solution, 𝛥G0 is Gibb’s free energy, 𝛥S0 is the entropy
change, 𝛥H0 is the enthalpy change, 𝑇 is the absolute temperature, and
𝑅 is the universal gas constant.
The results have been summarized in Table 6. The Gibbs free energy
change was found to be negative at all temperatures indicating the
adsorption process’s spontaneous nature. The 𝛥H0 was found to be
−62.30 kJ mol−1 and −53.75 kJ mol−1 for SDP and SDNa, respectively,
indicating that the adsorption process involved was exothermic. The
𝛥S0 was found to be −0.16 kJ mol−1 and −0.14 kJ mol−1 for SDP
and SDNa, respectively. This shows that the randomness decreases
at the surface, and at a higher temperature, the adsorption capacity
decreases (Saha et al., 2017).

3.7. RSM optimization

Fig. 9. Response of Dose and pH on removal efficiency of I.C.
The performance of SDP was better as indicated by the batch
experiments, and hence an RSM optimization was done for SDP only.
The results obtained from the adsorption experiments according to CCD The final equation in terms of actual parameters was given as:
model matrix were used for analysis. The model obtained from the
software is:
Removal efficiency (%) = 65.07 − 21.79 pH + 0.094 Time
Removal efficiency (%) = 66.73 − 11.73A + 6.93B + 14.91C
+ 0.78AB + 4.25AC + 0.038BC + 2.91A2 + 16.06 Dose + 0.009 pH ∗ Time + 1.62 pH ∗ Dose
2
+ 0.12B − 4.21C 2 + 0.0006 Time ∗ Dose + 0.95 pH2 + 0.00006 Time2 − 1.87 Dose2

6
S. Bhowmik, V. Chakraborty and P. Das
Fig. 10. Response of Dose and Time on removal efficiency of I.C.
The values given by the model were plotted versus the experimen-
tal results (Fig. 7). The ANOVA results suggested that the quadratic
model was significant. This was inferred from Fisher’s F-value (55.67)
and probability value (𝑃 < 0.0001) (Sinha et al., 2012a). A high 𝑅2
(0.9804) implied the statistical significance of the regression model.
The Adj. 𝑅2 was 0.9628, and the predicted 𝑅2 value was 0.8514, which
was in reasonable agreement with the Adj. 𝑅2 . A signal to noise ratio
of 27.357 (>4) indicated an adequate signal. A coefficient of variance
of 5.31 % was found. Hence, the ANOVA analysis indicated the model’s
appropriateness for dye removal using SDP within the experimental
range.
The contour plots were used to study inter parameter interactions.
The red colour indicates a higher percentage of removal. The fading of
the red colour into yellow and green indicates a lower percentage of
removal. The response of time of contact and pH on removal efficiency
is shown in Fig. 8. The efficiency increased with a reduction in pH and
a rise in contact time. The plot in Fig. 9 depicted the combined response
of dose and pH on Removal Efficiency. A rise in removal efficiency with
a rise in the dose and a reduction in pH. The response of dose and time
of contact on removal efficiency was studied from Fig. 10.
The optimum conditions thus found from the model was:
i. pH = 2.5
ii. Time = 180 min
iii. Dose = 5 g L−1
The removal efficiency, which was obtained at these conditions, was
94.12% by the model. The experimental value obtained at these condi-
tions was 93.11% which is significantly close (Relative error of 1.08%)
to the predicted value.
4. Conclusion
Removal of I.C. from the water was studied. Two adsorbents were
used — Phosphoric acid-treated thermally activated charcoal and
NaOH treated thermally activated charcoal. Both the adsorbents were
prepared from the same raw material, sawdust and activated at 700
◦ C. The adsorbent prepared after treating with Phosphoric acid showed
better removal capacity and efficiency as suggested by the batch ex-
periments. Adsorption capacity as high as 9.39 mg g−1 was observed
using SDP, and 6.74 mg g−1 was obtained using SDNa. The adsorption
isotherm study indicated that the Langmuir adsorption isotherm best
7
Results in Surfaces and Interfaces 3 (2021) 100011
represented the adsorption process. A comparison of specific adsor-
bents’ monolayer capacity in I.C. removal has been shown in Table 7.
The rate kinetics study suggested that the process followed pseudo-
second-order kinetics. RSM optimization and FT-IR characterization
were conducted only for SDP as it performed better as an adsorbent.
93.11% removal was obtained at optimized conditions of pH = 2, 180
min and 5 g L−1 dose. Not much work has been reported on anionic
dye removal like I.C. using low-cost adsorbents like activated charcoal
obtained from biowastes. This work demonstrates and compares the
efficiency of two adsorbents prepared from biowaste in removing an
anionic dye (I.C.) from water. Thus this study effectively shows that
low-cost adsorbents from waste like sawdust can be prepared to remove
dye from water effectively.
CRediT authorship contribution statement
Sayan Bhowmik: Conducted the major work, Analysed the results
and was the major grant or in arranging the manuscript. Vijoyeta
Chakraborty: Assisted in the experimentation, Analysis of results.
Papita Das: The complete work was performed under the guidance.
Availability of data and materials
The data used in the study’s course shall be accessible by the authors
at a reasonable request.
Acknowledgements
The authors acknowledge the SERB (DST), Government of India for
the monetary assistance and the Department of Chemical Engineering,
Jadavpur University, India, for the laboratory where the work was
performed. All the authors have read the final manuscript and have
approved it.
Funding
The authors extend their gratitude to the Science and Engineering
Research Board (SERB), Department of Science and Technology (DST),
Government of India for the financial assistance.
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