South African Journal of Chemical Engineering 35 (2021) 33–43

Contents lists available at ScienceDirect

South African Journal of Chemical Engineering

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

Editorial

Adsorption of brilliant green dye from aqueous solution onto chemically

modified areca nut husk
Kamal Sukla Baidya a, *, Upendra Kumar a
a
Department of Civil Engineering, National Institute of Technology, Silchar, Assam, India

A R T I C L E I N F O A B S T R A C T

Keywords: Areca nut husk, an inexpensive, easily available agricultural by-product modified with sodium hydroxide has
Agro-waste been applied to remove Brilliant green (BG) dye from aqueous solution. Surface characteristics and the elemental
Areca nut husk composition of areca nut husks were examined using Scanning electron microscope (SEM) and Energy dispersive
Biomaterial
X-ray (EDX). The chemical treatment changes the surface morphology of the areca nut husk. The alkali treatment
Chemically modified adsorbent
removes natural wax, resins and lignin from husks and thus it added extra active surface area and pores for better
Brilliant green dye
Adsorption isotherm adsorption. The Fourier-transform infrared (FTIR) spectroscopy indicated that the presence of functional groups
(-OH), (-C=O), (-C=C), (-COOH). Experiments were performed in batch adsorption procedure. The optimum
removal of 97% BG dye was obtained at pH 7.0, adsorbent dosage 10 g/L, initial concentration 100 mg/L,
agitation speed 200 rpm and temperature 298 K. Adsorption data fit better to Langmuir model in comparison
with Freundlich, Temkin and Dubinin-Radushkevich isotherm model. The maximum adsorption capacity of
18.21 mg/g was obtained. Kinetic date followed pseudo-second-order rate kinetic better than pseudo-first-order
model. The thermodynamic parameters ΔH0 = 12.522 kJ/mol and ΔS0 = 0.044 J/mol indicate endothermic and
spontaneous adsorption process. Taking considerations of all experimental results and model analysis, it is
concluded that sodium hydroxide treated areca nut husk is a good, low cost and effective biosorbent for the
removal of BG dye from aqueous solution.

1. Introduction
Water pollution due to human technological advances and the rapid
development of industries is becoming a major environmental concern
(Saleh and Gupta, 2014; R. Saravanan et al., 2013). Wastewater from
industries contaminating water bodies with toxic pollutants at concen­
trations well above the limits set by the World Health Organization
(WHO) (Gupta et al., 2015; Chowdhury et al., 2011). Synthetic dyes are
extensively used and over 100,000 different synthetic dyes are presently
available in the market. The total yearly production of these dyes is
nearly 7 × 105 – 1 × 106 tons and nearly 10–15% of wasted dyes reach
the ecosystem through wastewater from textile, plastic, cosmetics,
printing, paper, leather, rubber, pesticide, food, petroleum, solvent and
other industries (Gupta et al., 2011; Gupta and Suhas, 2009). Dumping
of wastewater from industries to the environment can contaminate
freshwater resources, thus, pose hazardous effects on the ecosystem and
human beings (R. Saravanan et al., 2013; R. Saravanan et al., 2014).
Dyes increase the risk of skin cancer, skin problems like allergy, skin
irritation and skin sensitization, if dyes are exposed to skin or orally
ingested. Dyes are toxic, carcinogenic and leads to mutagenic problem
(Gupta et al., 2016; Akar et al., 2009).
Dyes can be easily recognized and visible in wastewater even at a
very low concentration of 1 mg/L (Rehman et al., 2019). They interfere
with the transmission of light, absorbed and reflect sunlight entering
into the water. As a result, it affects the photosynthesis process of
aquatic life and can hinder the growth of bacteria. Hence, dye bearing
wastewater is highly objectionable and requires treatment before
effluent discharge to any stream, river or ocean. Researchers are also
developing new technologies for effective and efficient dye removal
from wastewater. Synthetic dyes have complex aromatic structures and
they are ineffective upon exposure to light, heat, microbial attacks or
chemicals like oxidizing agents (Nekouei et al., 2015; Ghaedi et al.,
2015; Bharathi and Ramesh, 2013). Based on the structure and prop­
erties, dyes may be categorized as cationic (basic dye), anionic (direct,
reactive, acid dyes) and non-ionic (dispersive dyes). Cationic dyes are
generally brighter in colour and more toxic than anionic dyes (Etim
et al., 2016).
At present, a variety of technologies are available for removal of dyes

* Correspondent author.
E-mail address: kamalsuklabaidya@gmail.com (K. Sukla Baidya).

https://doi.org/10.1016/j.sajce.2020.11.001
Received 29 July 2020; Received in revised form 28 October 2020; Accepted 2 November 2020
Available online 10 November 2020
1026-9185/© 2020 The Authors. Published by Elsevier B.V. on behalf of Institution of Chemical Engineers. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
K. Sukla Baidya and U. Kumar South African Journal of Chemical Engineering 35 (2021) 33–43

Table No. 1 often regarded as worthless and either burnt inefficient or wasted. The
Various dye removal methods and their advantages and disadvantages. areca nut husk can be used as an adsorbent, but the adsorption capacity
Technology/ Advantages Disadvantages of this type of agricultural by-products is very low. To improve their
Methods adsorption capacity they require activation through a physical or
Physical treatment chemical process. In this case, chemical activation was done using so­
Coagulation/ Simple, economically feasible Need further filtration, high dium hydroxide (NaOH) treatment to improve the adsorption capacity.
flocculation sludge production Alkali removes maximum waxes, natural fat and part of lignin from the
Membrane Removes all types of dyes, high Expensive, incapable of surface of areca nut husk. Thus, it improves the roughness on the surface
filtration quality effluent treating large volumes
Ion exchange Effective, no regeneration loss Not effective for all types of
and activates functional groups (Yusriah et al., 2012; Ranganagowda
of adsorbent dyes et al., 2019; Basker et al., 2014; Binoj et al., 2016).
Adsorption Most effective adsorbent, Very expensive, The present study was intended to examine and explore the removal
simple design, sludge free regeneration loss potential of Brilliant Green (BG) dye using chemically treated areca nut
operation and high adsorption
husk. The BG dye are commonly used in the dyeing of silk, wool, cotton,
capacity
Oxidation Rapid and effective process High energy cost, chemicals paper, leather and other dye based industries. The effects of adsorption
required parameters like pH, adsorption dose, initial concentration, contact time,
Chemical treatment temperature and agitation speed have been investigated. The equilib­
Fenton reagent Effective process and cheap Sludge generation and rium isotherm model with error functions, kinetic rate models, ther­
technique reagent disposal problem
Ozonisation No sludge is produced High operational cost and
modynamic parameters and activation energy were also evaluated,
short half-life (20 min) presented and discussed.
Photo-catalytic Economically feasible, low Formation of toxic by-
methods operational cost products 2. Experimental methods
Biological treatment
Aerobic Removes azo dyes, low Very slow process, possible
degradation operational cost growth of microorganisms 2.1. Preparation of adsorbent
Anaerobic By products can be used as Need further treatment,
degradation energy sources yield methane and hydrogen Areca nut husk was obtained from nearby areas of Silchar, Assam,
sulfide gas
India and primarily cleaned with tap water to eliminate any dust or dirt.
Ref. (Dawood and Sen, 2012; Crini et al., 2007). The husks were sliced into pieces between particle sizes 300 - 500 µm.
Husks were cleaned with distilled water to avoid dust, debris or any
such as, chemical coagulation/flocculation (Wang et al., 2007), unwanted foreign particles. Distilled water cleaned husks were dried
membrane-filtration (T.A. Saleh and Gupta, 2012), reverse osmosis over 24 h in an oven at 363 K and after drying, samples were kept in a
(Avlonitis et al., 2008), ion exchange (V.K. Gupta et al., 2012), oxidation sealed bottle.
process (R. Saravanan et al., 2014), adsorption process (Bansal and The chemical modification was done by mixing and agitating
Goyal, 2005), Fenton process (Behnajady et al., 2007), ozonation (Wu distilled washed areca nut husk with 0.1 M NaOH solution for 2 h, fol­
et al., 2008), electro-chemical process (Ali, 2018), photo-catalytic (R. lowed by 24 h soaking in the same solution. This samples were contin­
Saravanan et al., 2013) electro-coagulation (Ali et al., 2012) and bio­ uously washed with distilled water to neutralise the pH of the husks and
logical degradation. The advantages and disadvantages of these methods then dried at 363 K for 6 h. These dried chemically modified husks were
are listed in Table No. 1. However, each removal methods have disad­ kept in a sealed container for further experiments (Kumar and Kumar,
vantages. Amongst all treatment process adsorption seems to be the 2015; N. Laskar and Kumar, 2017).
most promising removal technique. It is due to its simple design,
sludge-free operation and high efficiency in dye removal. More often 2.2. Stock solution
activated carbon widely used as adsorbent due to its chemically active
nature, high specific surface area, well developed large mesopores and BG dye also known as basic green 1 or Zelyonka, a cationic dye
microporous structure, as well as strong adsorption ability (Burakov having chemical formula C27H33N2.HO4S, colour index number 42,040,
et al., 2018; Gupta and Saleh, 2013). But it is costly and difficult to λmax is 625 nm and molecular weight 482.63 g/mol. 1 g of commercial
regenerate while being exhausted. Therefore, researchers are mainly grade BG dye (MERCK, purity ≥ 90%) was diluted in 1 litre of distilled
focusing on the utilization of cheap and easily available agro-waste water to get the stock solution of a concentration of 1000 mg/L. The
materials for the efficient alternative adsorbent. Many researchers desired pH was obtained after mixing the required quantity of sodium
have already successfully investigated the dye removal process using hydroxide (0.1 M) and hydrochloric acid (0.1 M) solution in dye solution
agricultural by-products such as pine cones, groundnut shell, coir pith, using a digital pH metre (pH-80, HM digital).
sawdust, coconut, orange peel, rice husk and bamboo (V.K. Gupta et al.,
2014; Dawood and Sen, 2012; Kannan and Sundaram, 2001; Namasi­
vayam et al., 2001; Ferrero, 2007; Annadurai et al., 2002; Kumar and 2.3. Characterization of adsorbent
Kumar, 2015; N. Laskar and Kumar, 2017).
The areca nut husk is a by-product of areca palm fruit. Areca nut is The surface structure and morphology of the areca nut husk samples
the fruit of the areca palm tree (Areca catechu). It is generally grown were analysed using Scanning electron microscope namely Field emis­
along with the coastal areas of South-East Asian countries, some parts of sion gun scanning electron microscope (FEG-SEM) model name JEOL
Africa. In India, areca nut is an important commercial crop and domi­ JSM-7600F. The analysis was done with high energy secondary elec­
nate the world by producing nearly 53% of the world’s production. The trons, magnification (1000x) and an acceleration voltage of 10 kV,
husk is the outer part of areca fruit. Fibre is enclosed in the middle layer samples were covered with a fine layer of gold before scanning.
of husk and it can be obtained via dehusking or by manual stripping. The Energy dispersive X-ray analysis (EDX) is also done with SEM, it was
husk consisted of cellulose, hemicellulose, lignin and pectin. Cellulose done to understand the fundamental composition present on the surface
could be used as an adsorbent due to its good mechanical properties, of the areca nut husk.
non-toxic and easy disposability after use (Suhas et al., 2016). The husk The Fourier transform infrared (FTIR) spectrometer HYPERION
is nearly 15 – 30% of the raw areca nut and roughly 224 tons of areca nut 3000, Germany was used to detect functional groups existing in the
husk produced every year in India. This huge quantity of areca nut husk areca nut husk before and after dye adsorption, the spectra were in the
scale of 4000 - 450 cm− 1 and having a spectral resolution of 0.2 cm− 1.

34
K. Sukla Baidya and U. Kumar South African Journal of Chemical Engineering 35 (2021) 33–43

Table No. 2
List of different models in its linear form used in this study.
Model/Equation Equation Parameters

1. Langmuir isotherm 1 1 1 qe: amount of dye adsorbed at

= +
model qe q m b Ce equillibrium (mg/g)
1 Ce: equilibrium concentration of
qm dye (mg/L)
Separation factor 1 C0: initial concentration of dye
RL =
1 + b C0 (mg/L)
qm: maximum adsorption
capacity (mg/g)
2. Freundlich isotherm b: Langmuir constant (L/mg)
lnqe = lnKF +
model KF: Freundlich constant related to
( )
1 adsorption capacity (mg/g)
lnCe
n
3. Temkin isotherm qe = BT lnKT + n: adsorption intensity constant
model BT lnCe
4. Dubriin- lnqe = lnqs − β ε2 KT: Temkin adsorption potential
Radushkevich (L/g)
(
isotherm model BT: Temkin constant
ε = RTln 1 +
)
1
,
E Ce
1 qs: theoretical saturation capacity
E =
(2β)1/2 (mg/g)
β: D-R isotherm constant (mol2/
kJ2)
5. Pseudo-first-order log(qe − qt ) = ε: polanyi potential (J/mol)
k1 E: mean sorption energy (kJ/
logqe − t
2.303 mol)
R: universal gas constant
T: temperature (K)
6. Pseudo-second-order t 1 t qt: amount of dye adsorbed at
= +
qt k2 q2e qe time t (mg/g)
k1: pseudo-first-order rate
constant
7. Intra-particle qt = Kid t0.5 + Ci k2: pseudo-second-order rate
diffusion constant
Kid: intra-particle rate constant
(mg/g.min1/2)
8. Boyd diffusion ln (1 − F) = − Ci: thickness of the boundary
(Kfd t) layer
Kfd: coefficient of mass transfer in
the film diffusion (cm/min)
9. Arrhenius equation Ea A: proportionality constant
lnK = lnA −
RT Ea: activation energy (kJ/mol)
( )
10. Clausius-Clapeyron ΔHx K: rate constant
lnCe = +C
equation RT ΔHx: isosteric heat of adsorption
(kJ/mol)

2.4. Batch adsorption experiments

Batch adsorption experiments were performed with 100 mL of BG

dye solution in a 250 mL conical flasks at room temperature. The dye
solutions were put into a rotary shaker after mixing a fixed amount of
adsorbent and agitated for 120 min. The influence of various adsorption
parameters such as adsorbent dose (1–12 g/L), pH (3–9), specified
contact time (5–120 min), initial dye concentration (50, 100, 200 mg/
L), agitation speed (125–250 rpm) and temperature (298, 308, 318 K)
were investigated during this study. The remaining amount of dye pre­ Fig. 1. SEM image (x 1000) of (a) Distilled washed areca nut husk (b) Sodium
sent in solution was quantified with UV/VIS spectrophotometer hydroxide treated areca nut husk (c) BG dye adsorbed areca nut husk.
(Chemito-3501/0706) at λmax of 625 nm. The amount of dye adsorbed at
equilibrium (qe) and the percentage removal of dye was evaluated using
the adsorbent mass (g). Similarly we also calculate the amount of dye
relationship (1) and (2) (T.A. Saleh and Gupta, 2012; Saravanan et al.,
adsorbed at any instant of time (qt). All experiments were done thrice
2016):
and the averaged values were considered.
V
qe = (Co − Ce ) (1)
m
2.5. Adsorption isotherm
(Co − Ce )
% Removal = 100 (2)
Co The isotherm study offers vital information regarding the funda­
Where Ce and C0 are the equilibrium and initial concentrations of BG mental behaviour and the mechanism of the adsorption process. The
dye (mg/L), respectively, V is the volume of BG dye solution (L) and m is isotherm studies were done by varying the adsorbent dosage from 1 to
12 g/L keeping the other parameters at an optimal level. It helps to

35
K. Sukla Baidya and U. Kumar
Fig. 2. FTIR of sodium hydroxide treated and BG dye adsorbed areca nut husk.
describe the correlation between adsorbate and adsorbent. When
adsorption reaches an equilibrium state, the distribution of adsorbate
between the solid and fluid phase can also be understood. The study of
equilibrium data for various models helps to optimize the process and
the usage of adsorbent in adsorption. In this present work Langmuir,
Temkin, Freundlich, and Dubinin-Radushkevich (D-R) isotherm models
have been utilized to study the equilibrium data. The linear form of these
four isotherm models are shown Table No. 2 which were plotted to
obtain the isotherm constants (Laskar and Kumar, 2018).
The Langmuir isotherm model is the most popular isotherm, pre­
sumes a monolayer formation of dye adsorbate around the adsorbent
homogeneous surface. The adsorbent surface contains a fixed number of
adsorption sites. The equilibrium state is attained when all the adsorp­
tion sites are occupied by the adsorbate. Langmuir isotherm can be
represented with the aid of separation factor RL, it indicates either the
adsorption process unfavourable (RL > 1), linear (RL = 1), favourable (0
< RL < 1), or irreversible (RL = 0) (V.K. Gupta et al., 2012). Another
popular isotherm model is the Freundlich isotherm model. It presumes a
multilayer adsorbate formation on the non-homogeneous surface with
differentiated adsorption heat sharing (Ali et al., 2019). The Temkin
isotherm model considered adsorbate-adsorbent interaction on the
heterogeneous surface and the adsorption binding energy is uniformly
distributed up to maximum binding energy. With an increase in
coverage of the adsorbent, the adsorption heat of the adsorbate mole­
cules declines linearly (Abd El-Latifa and Ibrahim, 2010). The D-R
Isotherm is an empirical adsorption model developed to measure the
effects of porous structure on the adsorption and apparent free energy. It
is more useful than Langmuir model because it did not assume limited
active sites nor homogeneous adsorbent surface. The nature of adsorp­
tion can be identified through this model, whether chemical or physical
adsorption (Lafi et al., 2014).
2.6. Adsorption kinetics
Kinetic analysis of any chemical activity is inescapable and impor­
tant in the design of a fast and effective adsorption model. The dye
adsorption rate kinetics is helpful to define the rate at which it moves
towards equilibrium state and helps to understand the adsorption
mechanism. In this analysis, pseudo-first-order and pseudo-second-
order kinetics were investigated and shown in Eqs. 5 & 6, Table No. 2.
36
South African Journal of Chemical Engineering 35 (2021) 33–43
Experiments were conducted with initial concentrations of 50, 100, 200
mg/L and at temperatures of 298, 308, 318 K to explore the adsorption
mechanism of BG dye onto chemically treated areca nut husk.
3. Results & discussion
3.1. Characterization of areca nut husk
The SEM investigation has been accomplished to investigate the
surface quality and morphology of areca nut husk. Fig.1.(a, b, c) displays
SEM representations of distilled water washed areca nut husk, sodium
hydroxide treated areca nut husk and BG dye adsorbed areca nut husk,
respectively. The micrographs reveal that the surface of the areca nut
husk is comprised of the rough and uneven pore with cavities of various
dimensions. This type of heterogeneous structure offers a greater surface
area for dye adsorption. After treatment with alkali, the surface rough­
ness of areca nut husk improved considerably. These include more
widening of surface pores with extra new cavities and partial cracking.
During the chemical treatment process, the wax, natural oil, some
amount of lignin and several foreign substances found in areca nut husk
get removed and the exterior becomes more porous with larger cavities.
However, after the adsorption of the dye, the surface morphology
changes. The pores and cavities get disappeared as it was taken by the
dye and the adsorbent surface become smooth with prominently swollen
on the pores. The improvement in smoothness and reduction in the
heterogeneity of the adsorbent surface indicates that the BG dye get
adsorbed onto the surface and functional groups exist onto the surface of
the adsorbent.
The EDX analysis of areca nut husk after chemical modification
reveal that the areca nut husk consists of mainly carbon (48.31) wt.%,
oxygen (51.62) wt.% and chlorine (0.07) wt.%. The percentage of car­
bon element increased by 4.2 wt.% after dye adsorption. So, it is obvious
that dye gets adsorbed onto the exterior of the chemically treated areca
nut husk.
The FTIR spectra of the sodium hydroxide treated and BG dye
adsorbed areca nut husk are shown in Fig. 2. It shows several peaks at a
different wavelength, indicating the various functional groups present in
areca nut husk. The spectra displayed a strong wide band at 3430 cm− 1
signifies the hydroxyl (- OH) group (Ahmaruzzaman and Gupta, 2011;
R. Saravanan et al., 2013). The peak at 2920 cm− 1 was due to (- C–H)
K. Sukla Baidya and U. Kumar
Fig. 3. Effect of adsorbent dose.
Fig. 4. Effect of pH.
stretching from the alkyl (- CH2) group and peak at 1741 cm− 1 repre­
sents the (- C=O) stretching from the carboxyl (- COOH) group (Devaraj
et al., 2016; Priya et al., 2014). The characteristic groups indicated by a
band at 1633 cm− 1 links to (- C=O) stretching vibration of carbonyl
group (Saleh and Gupta, 2011), 1463 cm− 1 relates to the (- C–O)
stretching vibration of carboxylate (- C–OH) group (R. Saravanan et al.,
2013). The peak at 1037 cm− 1 is due to the (- C–O-C) stretching and
769 cm− 1 relates to the β(1→4)-glycosidic group (Ciolacu et al., 2011).
The presence of (- OH) and (- C–H) groups indicate the presence of
cellulose and lignin, also the (- C=O) groups indicate the presence of
hemicellulose in the areca nut husk.
3.2. Batch adsorption studies
3.2.1. Effects of adsorbent dose
The optimal dose of the adsorbent is crucial in adsorption studies to
find the effectiveness and adsorption capacity with a minimum dose of
an adsorbent from the economical point of view. Tests were performed
with varying adsorbent doses in the scale of (1–12) g/L while the initial
dye concentration = 100 mg/L, pH = 7, agitation speed = 200 rpm and
temperature 298 K, respectively. Fig. 3 shows that the percentage of
removal improves with a rise in doses up to 10 g/L, beyond which very
little improvement has been observed. So the optimum dose was
considered as 10 g/L.
As the doses increase more adsorbent surface area and active sites are
available resulting in increase in dye removal. On another side, the
adsorption capacity reduces as the dosage increases, due to decrease in
adsorbate to adsorbent ratio. The superficial sorption onto the adsorbent
surface is very fast, that means at lower concentration the adsorption
37
South African Journal of Chemical Engineering 35 (2021) 33–43
Fig. 5. Effect of initial concentration.
reduces. However, at high concentration, the volume of dye adsorbed by
a unit mass of areca nut husk increases due to concentration gradient
(N. Laskar and Kumar, 2017).
3.2.2. Effects of pH
The pH experiment is believed to be one of the highly relevant
parameter in adsorption. The adsorption capacity was greatly influenced
by the surface load and ionization degree of the adsorbate functional
groups. The influence of pH on BG dye was performed in the range of pH
3 to 9 for the adsorbent dose = 10 g/L, temperature = 298 K, initial dye
concentration = 100 mg/L and agitation speed = 200 rpm as shown in
Fig. 4. The dye removal enhances with the increase in pH and thereafter
it became constant at pH 7 and further it tense to precipitate. Thus op­
timum pH was considered as pH 7. The removal percentage increase
from 72.33 to 91.64 to as the pH changes from acidic to neutral. Reason
for this behaviour is that BG dye is a cationic dye that stays as positively
charged in solution. At a low pH, extra H+ ions struggle with dye mol­
ecules (positively charged) for adsorption sites, resulting in lowering of
removal. As the solution pH increases, more adsorption sites (negatively
charged) become available. These adsorbent sites form an electrostatic
attraction with dye molecules, thus the removal percentage increases
indicating that the chemical reaction between dye molecules and
negatively charged ions, affects the adsorption process (Guo et al., 2014;
Crini et al., 2007).
3.2.3. Effects of contact time and initial concentration
Influence of contact time is necessary for the design of any batch
experiment. From the experimental results, it is found that more than
80% of dye was adsorbed during the first 30 min. It gradually slowed
and reached a state of equilibrium in 120 min. Initially, the adsorption
rate was fast as outer surface of the sorbent were having huge number of
available sites for adsorption. Gradually dye molecules penetrate the
adsorbent’s inner pores and the adsorption rate decreased gradually
(Mohammadi et al., 2011).
In adsorption studies, the initial concentration is a critical parameter
and directly influences the rate of adsorption. Fig. 5 shows the impact on
dye adsorption using chemically treated areca nut husk with initial
concentration of 50, 100 and 200 mg/L at pH =7, adsorbent dose = 10
g/L, temperature = 298 K and agitation speed was 200 rpm, respec­
tively. The dye removal rate decreases as the concentration of BG dye
raised from 50 to 200 mg/L, on the other hand, the adsorption capacity
enhanced from 10.66 to 40.98 mg/g. This is because the adsorbents have
a finite number of active binding sites. After certain concentration all
such active sites were filled with dye molecules and the adsorbents
became saturated. But with a higher concentration gradient the amount
of dye molecules increased. Resulting in a greater driving force between
K. Sukla Baidya and U. Kumar South African Journal of Chemical Engineering 35 (2021) 33–43

Fig. 8. Different isotherm models.

Fig. 6. Effect of temperature.

Table No. 3
Isotherm parameters for adsorption of BG dye onto sodium hydroxide treated
areca nut husk.
Isotherm model Parameters Values

Langmuir q max (mg/g) 18.21

b (L/mg) 0.330
R2 0.989
RL 0.523
Freundlich KF (mg/g) 7.26
n 3.722
R2 0.955
Temkin KT (L/mg) 4.828
BT 3.582
R2 0.974
Dubriin-Radushkevich qs (mg/g) 16.152
β (mol2/kJ2) 1 × 10− 6

E (kJ/mol) 0.707
R2 0.907

Fig. 7. Effect of agitation speed.

the liquid phase and the solid phase, which helps to counteract all the
mass transition resistance of dye molecules (Mehmood et al., 2015).
3.2.4. Effects of temperature
The influence of temperature on BG dye adsorption by chemically
treated husk was examined at temperatures of 298, 308 and 318 K at pH
= 7, adsorbent dose =10 g/L, agitation speed = 200 rpm and initial dye
concentration = 100 mg/L, respectively. Fig. 6 shows the effect of
temperature on the adsorption of BG dye using chemically treated husk.
The result revealed that temperature significantly influences the dye
uptake. As the temperature rises the removal rate also increases, sug­
gesting the adsorption process is temperature favoured. Temperature
improves the availability of active adsorption sites and increases
porosity in the adsorbents pore volume. The rise in temperature further
reduces the viscosity of the solution resulting in increased diffusion of
the adsorbate through the exterior and into the inner pores of the
adsorbent. Similarly, the kinetic energy of the dye molecules increases
and the removal rate improves. The uptake of BG dye increases due to
temperature rise, thereby indicating that the adsorption mechanism to
be endothermic in nature (B.K. Nandi et al., 2009).
3.2.5. Effects of agitation speed
Another significant parameter in the adsorption studies is the level of
agitation. It influences the external boundary layer formation by
distributing the dye molecules in the solution. The influence of rpm was
tested at 125, 150, 175, 200, 225, and 250 rpm, at pH = 7, adsorbent
dose =10 g/L, temperature =298 K and initial dye concentration = 100
mg/L, respectively as shown in the Fig. 7. It is found that with an
increase in agitation speed there is an elevated percentage of removal
rate and maximum removal was achieved at 200 rpm and beyond that
the removal lightly decreases. It is due to agitation speed beyond 200
rpm generates excess centripetal force. As a result, the adsorbed dye
molecules feel a repulsive force between them and if this force is greater
than binding force, desorption starts. Hence the optimum agitation
speed is considered as 200 rpm (Kumar and Acharya, 2011; Kumar and
Bandopadhyay, 2006).
3.3. Adsorption isotherm
The adsorption isotherm investigation was conducted using four
different models as stated in the earlier. The isotherm graph is shown in
Fig. 8 and results were listed in Table No. 3. Equilibrium data best suited
for the Langmuir isotherm with a qmax value of 18.21 mg/g. The value of
RL was 0.523, indicating the process was favourable. According to the
result, Freundlich constant (KF), Langmuir constant (b), Temkin con­
stant (BT) and qs for D-R isotherm model increases with an increase in
temperature, implies that the adsorption favourable at higher temper­
ature and endothermic type. Also, the magnitude of Freundlich isotherm
constant n is 3.722 (2 < n < 10) indicate the adsorption is favourable
and physical. Similarly, the value of E from the D-R isotherm model was
found as 0.0707 kJ/mol (E < 8 kJ/mol). Hence, it can be categorized as a
physical adsorption mechanism (Asfaram et al., 2015).
3.4. Adsorption kinetics studies
The outcomes of kinetics studies were reported in Table No. 4 for
various initial concentration and for different temperatures. The

38
K. Sukla Baidya and U. Kumar South African Journal of Chemical Engineering 35 (2021) 33–43

Table No. 4
Adsorption kinetic parameters of BG dye onto sodium hydroxide treated areca nut husk at different initial concentration and different temperature.
Adsorbent Pseudo- 1st order model Pseudo- 2nd order model
Co (mg/L) qe, Exp (mg/g) qe, Cal (mg/g) k1 R2 qe, Cal (mg/g) k2 R2

50 4.832 1.613 0.037 0.792 4.919 0.071 0.999

100 9.622 5.453 0.041 0.930 10.152 0.015 0.999
200 18.314 10.812 0.041 0.942 19.380 0.007 0.999
Temperature (K) qe,Exp qe,Cal k1 R2 qe,Cal k2 R2
298 4.832 1.613 0.037 0.792 4.919 0.071 0.999
308 4.847 1.537 0.0396 0.812 4.929 0.081 0.999
318 4.853 1.466 0.0386 0.802 4.929 0.088 0.999

3.5. Mass transfer parameter

Fig. 9. Test plot for the intra-particle diffusion model.
findings reveal that the pseudo-second-order model is better fitted to
experimental data with R2 = 0.999. A plot between ln (qe – qt) vs t and t/
qe vs t have been employed to find the values of rate kinetics from the
intercept and slope of the graph. Also, the difference between qe cal and
qe exp is very small for the pseudo-second-order model, thereby
strengthening the validity of this model. With a temperature rise, the
value of the pseudo-second-order rate constant k2 increases, confirming
the endothermic process (Burakova et al., 2019).
The removal of BG dye onto chemically treated areca nut husk was
rapid in the initial stage and gradually slows down with time. In the
solid-fluid sorption process, the transmission of adsorbate occurs either
by film diffusion or intra-particle diffusion. The sorption process in­
volves several steps. Initially, the adsorbate molecules migrate to the
exterior of the adsorbent from the bulk solution. Then, molecules diffuse
into the boundary layer of the adsorbent, and molecules are adsorbed
successively at active sites. Finally, molecules move through the
adsorbent micropores to the inner portions. The slowest of those steps
will control the adsorption rate or rate-limiting step.
To check the rate-limiting step, two types of models have been
employed. Weber and Morris defined intra-particle diffusion model
which was employed to check the rate-limiting step as shown in as Eqs. 7
in Table No. 2. The intra-particle diffusion of the BG dye onto sodium
hydroxide treated areca nut husk was analysed by a plot between qt vs t1/
2
as shown in Fig. 9. It is witnessed that the graph is not linear for the
period, but it is separated in two-part due to a multistage adsorption
process. The first part represents the film diffusion when the dye mol­
ecules moved to the exterior of the adsorbent and its rate is very fast.
Successively, in next step dye molecules get into pores of the areca nut
husk by intra-particle diffusion. Between these two lines, the first one
goes along the origin, then in the second section, there has been a change
in the time of the intercept. This implies that the width of the boundary
layer grows with the period. Furthermore, there was no zero intercept so
it could be understood that the intra-particle diffusion is included in
adsorption and both the diffusion acts concurrently (Rashidi Nodeh
et al., 2016).
The film diffusion is also very significant to check whether the film
diffusion is a rate-limiting step. So, liquid film diffusion model as

Fig. 10. Test plot for the Boyd diffusion model.

39
K. Sukla Baidya and U. Kumar South African Journal of Chemical Engineering 35 (2021) 33–43

Table No. 5 Table No. 7

Thermodynamic parameters of BG dye adsorption onto sodium hydroxide Values of different error functions used for equilibrium isotherm analysis.
treated areca nut husk. Isotherm model SSE SAE HYBRID ARE MPSD
T (K) ∆G0 (kJ/mol) ∆H0 (kJ/mol) ∆S0 (kJ/mol.K) R2
Langmuir 0.037 0.193 − 0.250 − 0.200 0.707
293 0.671 12.522 0.044 0.986 Freundlich 0.327 0.572 − 0.741 − 0.593 2.097
308 1.024 Temkin 0.296 0.544 − 0.705 − 0.564 1.994
318 1.555 D-R model 2.080 1.442 − 1.870 − 1.496 5.288

that the adsorbate require to become adsorbed on the adsorbent surface

Table No. 6 is called as the activation energy. The magnitude of pseudo-second-
Different error functions used for equilibrium isotherm analysis.
order rate constant k2 was considered for calculating activation energy
Error function Formula at various temperature using Arrhenius empirical equation [83] as
The sum of the squares of the errors SSE =
∑n
− qe,exp )2i shown in Eqs. 10 at Table No. 2. The values have been established from
i=1 (qe,calc
(SSE)
∑n
the plot between ln k2 vs 1/T. The activation energy (Ea) was calculated
The sum of the absolute errors(SAE) SAE = − qe,meas |i
i=1 |qe,calc as 89.28 kJ/mol, which is greater than 83.70 kJ/mol indicated physical
[ ]
The hybrid fractional error function 100 ∑n (qe,meas − qe,calc ) adsorption (Theivarasu and Chandra, 2013).
(HYBRID) HYBRID =
n− p i=1 qe,meas
i
The average relative error (ARE) 100 ∑n (qe,meas − qe,calc )
ARE = | |i 3.8. Error analysis
n i=1 qe,meas
Marquardt’s percent standard
deviation (MPSD) MPSD =
In this research, five different error functions of non-linear regression
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
[ ] basin were used to figure out the most effective isotherm model to
√ 1 ∑n (qe,meas − qe,calc ) 2
√
100√ describe the experimental data. These error functions are listed in
n− p i=1 qe,meas
i
Table No 6. Where qe,meas is the experimental value, qe,calc is the calcu­
lated value, n is the number of data in the experiment and p is the
proposed by Boyd was employed and describe in Eqs. 8 of Table No. 2. number of parameters. The sum of the square of the errors (SSE) is most
The film diffusion was analysed by a plot between ln (1 - F) vs t and commonly used error function but it has a major drawback. The chal­
shown in Fig. 10. It can be seen in the figures that the linear plots for lenge of using SSE is that at higher concentration the isotherm param­
adsorption process pass through the point which is very close to the eters showing a better fit. This is because the magnitude of the errors and
origin suggesting that the film diffusion was more predominant over hence the square of the errors will increase as concentration increases.
pore diffusion. (V.S. Mane et al., 2007). The sum of the absolute errors (SAE) function is
similar to the SSE, isotherm parameters determined using this function
3.6. Thermodynamics studies provide better fit as the magnitude of the errors increases, biasing the fit
to the high concentration data (Dahri et al., 2015). The average relative
The thermodynamic study of any adsorption process provides in­ error (ARE) function attempts to minimize the fractional error distri­
formation about the energy changes and shows whether process is bution across the entire concentration range (N. Gupta et al., 2012). The
spontaneous or not. Thermodynamics of the adsorption process were hybrid fractional error function (HYBRID) was developed in order to
examined at 3 different temperatures (T) of 298, 308 and 318 K. Ther­ improve the fit of the SSE method at low concentration. The error
modynamic factors such as Gibb’s free energy change (ΔG0), the change function is divided by the measured value (V.S. Mane et al., 2007).
in enthalpy (ΔH0) and the change in entropy (ΔS0) were evaluated using Marquardt’s percent standard deviation (MPSD) error function was
the Van’t Hoff equation as shown in Eqs. (Mittal et al., 2010) previously very much used by researchers. It is similar to a geometric
mean error distribution that has been modified to allow for the number
ΔG0 = − RT ln K of degrees of freedom in the system (Gimbert et al., 2008).
The values of the error functions were listed in Table No. 7. After
ΔG0 = ΔH 0 − T ΔS0 analysing the results of the error functions, it is found that Langmuir
Where K is the equilibrium constant and K = Ca /Ce. Here, Ca is the isotherm model fits better compare to other isotherm models for the BG
equilibrium dye concentration on the adsorbent (mg/L) and Ce is the dye adsorption using sodium hydroxide treated areca nut husk. How­
equilibrium dye concentration in solution (mg/L). The thermodynamic ever, all the error functions provide a reasonably wide selection and the
results were tabulated in Table No. 5. There was an endothermic reac­ distribution does not give excessive bias in experimental data.
tion suggested by the positive value of ΔH0. Similarly, the positive value
of ΔS0 proposes improved randomness in the solid-liquid interface 3.9. Adsorption mechanism
throughout the adsorption process. With all the variations in tempera­
ture, ΔG0 showed negative values, indicating the viability and sponta­ The FTIR spectra show several peaks for various functional groups,
neous nature of BG dye adsorption onto chemically treated areca nut amongst them two major peaks at peak 3430 cm− 1 indicating (-O-H)
husk. As the temperature raises the value of ΔG0 also increases, indi­ stretching of hydroxyl group and at peak 1741 cm− 1 showing (-C=O)
cated the process supports higher temperature. From literature, it is stretching of carboxyl group. The presence of such group signifies the
found that when the value of enthalpy change is in the range of 80–400 presence of cellulose, lignin and hemicellulose. These functional groups
kJ/mol then it implies chemical adsorption and if the range is 20–40 kJ/ are mainly responsible for the adsorption of BG dye from aqueous so­
mol then it proposes physical adsorption. In this case, the value of lution. In this case, BG is a cationic dye and pH tests confirms that the
enthalpy change is 12.522 kJ/mol. Therefore, the nature of adsorption adsorption process supports higher pH. Therefore, the adsorption
of BG dye onto treated husk is physical adsorption (Sivarajasekar and mainly possible due to intermolecular H-bonding between O atom pre­
Baskar, 2014). sent in areca nut husk and the H atom of BG dye or vice versa.
The mechanism of adsorption can be understood from the steps
3.7. Activation energy which involve in mass transfer parameters. It can be seen that initial 30
min the adsorption rate was fast and it reaches at the equilibrium state
The adsorbent surface has an energy wall and the minimal energy after 120 min. So, it was for sure film diffusion is more predominant and

40
K. Sukla Baidya and U. Kumar South African Journal of Chemical Engineering 35 (2021) 33–43

Table No. 8 The negative values of thermodynamic factors ΔG0 and positive value of
List of alternative low-cost adsorbents and their maximum adsorption capacity. ΔH0 recommended that the sorption process was spontaneous and
Adsorbents for BG dye Maximum adsorption Reference endothermic in nature. This is reinforced by the enhanced adsorption
adsorption capacity qmax (mg/g) potential with rising temperature. The equilibrium data were best fit in
Bagasse fly ash 133.33 (V.S. Mane et al., the Langmuir isotherm model. Isotherm study describes the process as
2007) homogeneous and monolayer surface bindings. It also indicate the
Ashoka leaf powder 125.00 (N. Gupta et al., adsorption is favourable and physical. The maximum monolayer
2012) adsorption capacity was calculated as 18.21 mg/g. Adsorption kinetics
Red clay 125 (Rehman et al.,
2013)
was well described by the pseudo-second-order rate kinetics model and
Pinus roxburghii leaves 71.42 (Rehman et al., film diffusion mechanism. Considering the above results, the chemically
2019) modified areca nut husk can be used as an efficient and low-cost sub­
Kaolin 65.42 (B.K. Nandi et al., stitute material to remove BG dye from aqueous solution.
2009)
Saw dust 58.47 (Mane and Babu,
2011)
Bambusa Tulda fibre 41.67 (Laskar and Declaration of Competing Interest
Kumar, 2018)
Areca nut husk 18.21 This study The authors declare that they have no known competing financial
Luffa cylindrical sponge 18.20 (Segun Esan et al.,
interests or personal relationships that could have appeared to influence
2014)
Tannin gel 8.55 (Akter et al., 2016) the work reported in this paper. The authors declare the following
Saklikent mud 1.18 (Kismir and financial interests/personal relationships which may be considered as
Aroguz, 2011) potential competing interests:
Solanum tuberosum peels 1.173 (Rehman et al.,
2015)
Psidium guajava leaves 1.075 (Rehman et al., References
2015)
Cempedak durian 0.203 (Dahri et al., 2015) Saleh, T.A., Gupta, V.K., 2014. Processing methods, characteristics and adsorption
behaviour of tire derived carbons: a review. Adv Colloid Interface Sci 211, 93–101.
https://doi.org/10.1016/j.cis.2014.06.006.
Saravanan, R., Karthikeyan, S., Gupta, V.K., Sekaran, G., Narayanan, V., Stephen, A.,
both diffusions are acting in the series.
2013a. Enhanced photocatalytic activity of ZnO/CuO nanocomposite for the
The uptake of BG dye increases at higher temperature indicating that degradation of textile dye on visible light illumination. Materials Science and
the adsorption mechanism to be endothermic in nature. Endothermic Engineering: C 33 (1), 91–98. https://doi.org/10.1016/j.msec.2012.08.011.
reaction was also confirmed by positive value of ΔH0. The value of Gupta, V.K., Nayak, A., Agarwal, S., 2015. Bioadsorbents for remediation of heavy
metals: current status and their future prospects. Environmental Engineering
enthalpy change 12.522 kJ/mol and E = 0.0707 kJ/mol as obtained Research 20, 1–18. https://doi.org/10.4491/eer.2015.018.
from the D-R isotherm model indicated physical adsorption. Chowdhury, S., Mishra, R., Saha, P., Kushwaha, P., 2011. Adsorption thermodynamics,
kinetics and isosteric heat of adsorption of malachite green onto chemically modified
rice husk. Desalination 265, 159–168. https://doi.org/10.1016/j.desal.2010.07.047.
3.10. Comparison of the adsorption capacity of areca nut husk with other Gupta, V.K., Jain, R., Nayak, A., Agarwal, S., Shrivastava, M., 2011. Removal of the
hazardous dye—Tartrazine by photodegradation on titanium dioxide surface.
adsorbents
Materials Science and Engineering: C 31 (5), 1062–1067. https://doi.org/10.1016/j.
msec.2011.03.006.
A comparison of adsorption capacity of chemically modified areca Gupta, V.K., Suhas, 2009. Application of low-cost adsorbents for dye removal – A review.
J. Environ. Manage. 90, 2313–2342. https://doi.org/10.1016/j.
nut husk with other alternative bio waste adsorbents is represented in
jenvman.2008.11.017.
Table No. 8. The maximum adsorption capacity of sodium hydroxide Saravanan, R., Thirumal, E., Gupta, V.K., Narayanan, V., Stephen, A., 2013b. The
treated areca nut husk calculated from Langmuir isotherm was found to photocatalytic activity of ZnO prepared by simple thermal decomposition method at
be 18.21 mg/g. Comparing the adsorption capacity of areca nut husk various temperatures. J Mol Liq 177, 394–401. https://doi.org/10.1016/j.
molliq.2012.10.018.
with other adsorbents, it is clear that chemically treated areca nut husk Saravanan, R., Gupta, V.K., Mosquera, E., Gracia, F., 2014a. Preparation and
has a considerably high adsorption capacity and can be used to remove characterization of V2O5/ZnO nanocomposite system for photocatalytic application.
BG dyes from wastewater. J Mol Liq 198, 409–412. https://doi.org/10.1016/j.molliq.2014.07.030.
Gupta, V.K., Suhas, I.Tyagi, Agarwal, S., Singh, R., Chaudhary, M., Harit, A.,
From the literature survey it is found that removal of BG dye using Kushwaha, S., 2016. Column operation studies for the removal of dyes and phenols
chemically modified areca nut husk has not been reported by any using a low cost adsorbent. Global J. Environ. Sci. Manage. 2, 1–10. https://doi.org/
researcher. This is the first report where sodium hydroxide treated areca 10.7508/gjesm.2016.01.001.
Akar, S.T., Özcan, A.S., Akar, T., Özcan, A., Kaynak, Z., 2009. Biosorption of a reactive
nut husk used as an adsorbent in batch adsorption procedure which textile dye from aqueous solutions utilizing an agro-waste. Desalination 249,
established the novelty of the research work. 757–761. https://doi.org/10.1016/j.desal.2008.09.012.
Rehman, R., Muhammad, S.J., Arshad, M., 2019. Brilliant Green and Acid Orange 74
Dyes Removal from Water by Pinus roxburghii Leaves in Naturally Benign Way: an
4. Conclusion Application of Green Chemistry. J Chem 3, 1–10. https://doi.org/10.1155/2019/
3573704.
Sodium hydroxide (0.1 M) treated areca nut husk has been success­ Nekouei, F., Nekouei, S., Tyagi, I., Gupta, V.K., 2015. Kinetic, thermodynamic and
isotherm studies for acid blue 129 removal from liquids using copper oxide
fully utilized as an efficient and reliable adsorbent to remove BG dye nanoparticle-modified activated carbon as a novel adsorbent. J Mol Liq 201,
from aqueous solution. Morphological investigation revealed that 124–133. https://doi.org/10.1016/j.molliq.2014.09.027.
chemical treatment created more porous and rough surface which Ghaedi, M., Hajjati, S., Mahmudi, Z., Tyagi, I., Agarwal, S., Maity, A., Gupta, V.K., 2015.
Modeling of competitive ultrasonic assisted removal of the dyes – Methylene blue
enhanced the removal of BG dye. The two major peaks at peak of FTIR and Safranin-O using Fe3O4 nanoparticles. Chemical Engineering Journal 268,
spectra at 3430 cm− 1 indicating (-O–H) stretching of hydroxyl group 28–37. https://doi.org/10.1016/j.cej.2014.12.090.
and at peak 1741 cm− 1 showing (-C =O) stretching of carboxyl group are Bharathi, K.S., Ramesh, S.T., 2013. Removal of dyes using agricultural waste as low-cost
adsorbents: a review. Appl Water Sci 3, 773–790. https://doi.org/10.1007/s13201-
mainly responsible for removal of BG dye. The adsorption rate increases
013-0117-y.
with increase in the contact duration, temperature and initial concen­ Etim, U.J., Umoren, S.A., Eduok, U.M., 2016. Coconut coir dust as a low cost adsorbent
tration. The adsorption process was strongly pH dependant and opti­ for the removal of cationic dye from aqueous solution. J. Saudi Chemical Society 20,
mum parameters for adsorption were at pH 7, adsorbent dosage 10 g/L, 67–76. https://doi.org/10.1016/j.jscs.2012.09.014.
Wang, J.P., Chen, Y.Z., Ge, X.W., Yu, H.Q., 2007. Optimization of
agitation speed 200 rpm, contact duration 120 min, initial concentration coagulation–flocculation process for a paper-recycling wastewater treatment using
100 mg/L and temperature 298 K that resulted in 97% BG dye removal. response surface methodology. Colloids and Surfaces A: Physicochemical and

41
K. Sukla Baidya and U. Kumar
Engineering Aspects 302, 204–210. https://doi.org/10.1016/j.
colsurfa.2007.02.023.
Saleh, T.A., Gupta, V.K., 2012a. Synthesis and characterization of alumina nano-particles
polyamide membrane with enhanced flux rejection performance. Sep Purif Technol
89, 245–251. https://doi.org/10.1016/j.seppur.2012.01.039.
Avlonitis, S.A., Poulios, I., Sotiriou, D., Pappas, M., Moutesidis, K., 2008. Simulated
cotton dye effluents treatment and reuse by nanofiltration. Desalination 221,
259–267. https://doi.org/10.1016/j.desal.2007.01.082.
Gupta, V.K., Ali, I., Saleh, T.A., Siddiqui, M.N., Agarwal, S., 2012a. Chromium removal
from water by activated carbon developed from waste rubber tires. Environmental
Science and Pollution Research 20, 1261–1268. https://doi.org/10.1007/s11356-
012-0950-9.
Saravanan, R., Gupta, V.K., Narayanan, V., Stephen, A., 2014b. Visible light degradation
of textile effluent using novel catalyst ZnO/γ-Mn2O3. J. Taiwan Institute of
Chemical Engineers 45, 1910–1917. https://doi.org/10.1016/j.jtice.2013.12.021.
Bansal, R.C., Goyal, M., 2005. Activated Carbon Adsorption. CRC press, New York.
https://doi.org/10.1201/9781420028812.
Behnajady, M.A., Modirshahla, N., Ghanbary, F., 2007. A kinetic model for the
decolorization of C.I. Acid Yellow 23 by Fenton process. J. Hazard. Mater. 148,
98–102. https://doi.org/10.1016/j.jhazmat.2007.02.003.
Wu, J., Doan, H., Upreti, S., 2008. Decolorization of aqueous textile reactive dye by
ozone. Chemical Engineering J. 142, 156–160. https://doi.org/10.1016/j.
cej.2007.11.019.
Ali, I., 2018. Microwave assisted economic synthesis of multi walled carbon nanotubes
for arsenic species removal in water: batch and column operations. J Mol Liq 271,
677–685. https://doi.org/10.1016/j.molliq.2018.09.021.
Saravanan, R., Joicy, S., Gupta, V.K., Narayanan, V., Stephen, A., 2013c. Visible light
induced degradation of methylene blue using CeO2/V2O5 and CeO2/CuO catalysts.
Materials Science and Engineering: C 33 (8), 4725–4731. https://doi.org/10.1016/j.
msec.2013.07.034.
Ali, Imran, Gupta, Vinod K., Khan, Tabrez A., Asim, Mohd, 2012. Removal of Arsenate
from Aqueous Solution by Electro-Coagulation Method Using Al-Fe Electrodes. Int. J.
Electrochem. Sci. 7, 1898–1907.
Burakov, A.E., Galunin, E.V., Burakova, I.V., Kucherova, A.E., Agarwal, S., Tkachev, A.
G., Gupta, V.K., 2018. Adsorption of heavy metals on conventional and
nanostructured materials for wastewater treatment purposes: a review. Ecotoxicol.
Environ. Saf. 148, 702–712. https://doi.org/10.1016/j.ecoenv.2017.11.034.
Gupta, V.K., Saleh, T.A., 2013. Sorption of pollutants by porous carbon, carbon
nanotubes and fullerene- An overview. Environmental Science and Pollution
Research 20, 2828–2843. https://doi.org/10.1007/s11356-013-1524-1.
Gupta, V.K., Nayak, A., Agarwal, S., Tyagi, I., 2014a. Potential of activated carbon from
waste rubber tire for the adsorption of phenolics: effect of pre-treatment conditions.
J Colloid Interface Sci 417, 420–430. https://doi.org/10.1016/j.jcis.2013.11.067.
Dawood, S., Sen, T.K., 2012. Removal of anionic dye Congo red from aqueous solution by
raw pine and acid-treated pine cone powder as adsorbent: equilibrium,
thermodynamic, kinetics, mechanism and process design. Water Res. 46,
1933–1946. https://doi.org/10.1016/j.watres.2012.01.009.
Kannan, N., Sundaram, M.M., 2001. Kinetics and mechanism of removal of methylene
blue by adsorption on various carbons—A comparative study. Dyes and Pigments 51,
25–40. https://doi.org/10.1016/s0143-7208(01)00056-0.
Namasivayam, C., Kumar, M.D., Selvi, K., Begum, R.A., Vanathi, T., Yamuna, R., 2001.
Waste coir pith—A potential biomass for the treatment of dyeing wastewaters.
Biomass and Bioenergy 21, 477–483. https://doi.org/10.1016/s0961-9534(01)
00052-6.
Ferrero, F., 2007. Dye removal by low cost adsorbents: hazelnut shells in comparison
with wood sawdust. J. Hazard. Mater. 142, 144–152. https://doi.org/10.1016/j.
jhazmat.2006.07.072.
Annadurai, G., Juang, R., Lee, D., 2002. Use of cellulose-based wastes for adsorption of
dyes from aqueous solutions. J. Hazard. Mater. 92, 263–274. https://doi.org/
10.1016/s0304-3894(02)00017-1.
Kumar, B., Kumar, U., 2015. Adsorption of malachite green in aqueous solution onto
sodium carbonate treated rice husk. Korean J. Chemical Engineering 32, 1655–1666.
https://doi.org/10.1007/s11814-014-0351-5.
Laskar, N., Kumar, U., 2017a. Adsorption of Crystal Violet from Wastewater by Modified
Bambusa Tulda. KSCE J. Civil Engineering 22, 2755–2763. https://doi.org/10.1007/
s12205-017-0473-5.
Suhas, V.K.Gupta, Carrott, P.J.M., Singh, R., Chaudhary, M., Kushwaha, S., 2016.
Cellulose: a review as natural, modified and activated carbon adsorbent. Bioresour.
Technol. 216, 1066–1076. https://doi.org/10.1016/j.biortech.2016.05.106.
Yusriah, L., Sapuan, S.M., Zainudin, E.S., Mariatti, M., 2012. Exploring the Potential of
Betel Nut Husk Fiber as Reinforcement in Polymer Composites: effect of Fiber
Maturity. Procedia Chem 4, 87–94. https://doi.org/10.1016/j.proche.2012.06.013.
Ranganagowda, R.P.G., Kamath, S.S., Bennehalli, B., 2019. Extraction and
Characterization of Cellulose from Natural Areca Fiber. Material Science Research
India 16, 86–93. https://doi.org/10.13005/msri/160112.
Basker, A., Shabudeen, P.S.S., Daniel, S., Kumar, P.V., 2014. Adsorptive removal of
malachite green from aqueous solution using areca husk carbon. Rasayan J. Chem. 7,
1–15.
Binoj, J.S., Raj, R.E., Sreenivasan, V.S., Thusnavis, G.R., 2016. Morphological, Physical,
Mechanical, Chemical and Thermal Characterization of Sustainable Indian Areca
Fruit Husk Fibers (Areca Catechu L.) as Potential Alternate for Hazardous Synthetic
Fibers. J Bionic Eng 13, 156–165. https://doi.org/10.1016/s1672-6529(14)60170-
0.
Saleh, T.A., Gupta, V.K., 2012b. Photo-catalyzed degradation of hazardous dye methyl
orange by use of a composite catalyst consisting of multi-walled carbon nanotubes
42
South African Journal of Chemical Engineering 35 (2021) 33–43
and titanium dioxide. J Colloid Interface Sci 371, 101–106. https://doi.org/
10.1016/j.jcis.2011.12.038.
Saravanan, R., Sacari, E., Gracia, F., Khan, M.M., Mosquera, E., Gupta, V.K., 2016.
Conducting PANI stimulated ZnO system for visible light photocatalytic degradation
of coloured dyes. J Mol Liq 221, 1029–1033. https://doi.org/10.1016/j.
molliq.2016.06.074.
N. Laskar, U. Kumar, Removal of Brilliant Green dye from water by modified Bambusa
Tulda: adsorption isotherm, kinetics and thermodynamics study. Int J.
Environmental Science and Technology (2018). doi:10.1007/s13762-018-1760-5.
Gupta, V.K., Ali, I., Saleh, T.A., Siddiqui, M.N., Agarwal, S., 2012b. Chromium removal
from water by activated carbon developed from waste rubber tires. Environmental
Science and Pollution Research 20, 1261–1268. https://doi.org/10.1007/s11356-
012-0950-9.
Ali, I., Burakov, A.E., Melezhik, A.V., Babkin, A.V., Burakova, I.V., Neskomornaya, M.E.
A., Kuznetsov, D.V., 2019. Removal of Copper(II) and Zinc(II) Ions in Water on a
Newly Synthesized Polyhydroquinone/Graphene Nanocomposite Material: kinetics,
Thermodynamics and Mechanism. ChemistrySelect 4, 12708–12718. https://doi.
org/10.1002/slct.201902657.
Abd El-Latifa, M.M., Ibrahim, A.M., 2010. Removal of reactive dye from aqueous
solutions by adsorption onto activated carbons prepared from oak sawdust.
Desalination Water Treat 20, 102–113. https://doi.org/10.5004/dwt.2010.1215.
Lafi, R., ben Fradj, A., Hafiane, A., Hameed, B.H., 2014. Coffee waste as potential
adsorbent for the removal of basic dyes from aqueous solution. Korean Journal of
Chemical Engineering 31, 2198–2206. https://doi.org/10.1007/s11814-014-0171-
7.
Ahmaruzzaman, M., Gupta, V.K., 2011. Rice Husk and Its Ash as Low-Cost Adsorbents in
Water and Wastewater Treatment. Ind Eng Chem Res 50, 13589–13613. https://doi.
org/10.1021/ie201477c.
Saravanan, R., Gupta, V.K., Narayanan, V., Stephen, A., 2013d. Comparative study on
photocatalytic activity of ZnO prepared by different methods. J Mol Liq 181,
133–141. https://doi.org/10.1016/j.molliq.2013.02.023.
Devaraj, M., Saravanan, R., Deivasigamani, R., Gupta, V.K., Gracia, F., Jayadevan, S.,
2016. Fabrication of novel shape Cu and Cu/Cu2O nanoparticles modified electrode
for the determination of dopamine and paracetamol. J Mol Liq 221, 930–941.
https://doi.org/10.1016/j.molliq.2016.06.028.
Priya, B., Gupta, V.K., Pathania, D., Singha, A.S., 2014. Synthesis, characterization and
antibacterial activity of biodegradable starch/PVA composite films reinforced with
cellulosic fibre. Carbohydr Polym 109, 171–179. https://doi.org/10.1016/j.
carbpol.2014.03.044.
Saleh, T.A., Gupta, V.K., 2011. Functionalization of tungsten oxide into MWCNT and its
application for sunlight-induced degradation of rhodamine B. J Colloid Interface Sci
362, 337–344. https://doi.org/10.1016/j.jcis.2011.06.081.
Saravanan, R., Karthikeyan, S., Gupta, V.K., Sekaran, G., Narayanan, V., Stephen, A.,
2013e. Enhanced photocatalytic activity of ZnO/CuO nanocomposite for the
degradation of textile dye on visible light illumination. Materials Science and
Engineering: C 33 (1), 91–98. https://doi.org/10.1016/j.msec.2012.08.011.
Ciolacu, D.E., Ciolacu, F., Popa, V.I., 2011. Amorphous cellulose – structure and
characterization. Cellulose Chem. Technol. 45, 13–21.
Laskar, N., Kumar, U., 2017b. SEM, FTIR and EDAX Studies for the Removal of Safranin
Dye from Water Bodies using Modified Biomaterial - Bambusa Tulda. IOP Conference
Series: Materials Science and Engineering 225, 012105. https://doi.org/10.1088/
1757-899x/225/1/012105.
Guo, J.-.Z., Li, B., Liu, L., Lv, K., 2014. Removal of methylene blue from aqueous
solutions by chemically modified bamboo. Chemosphere 111, 225–231. https://doi.
org/10.1016/j.chemosphere.2014.03.118.
Crini, G., Peindy, H., Gimbert, F., Robert, C., 2007. Removal of C.I. Basic Green 4
(Malachite Green) from aqueous solutions by adsorption using cyclodextrin-based
adsorbent: kinetic and equilibrium studies. Sep Purif Technol 53, 97–110. https://
doi.org/10.1016/j.seppur.2006.06.018.
Mohammadi, N., Khani, H., Gupta, V.K., Amereh, E., Agarwal, S., 2011. Adsorption
process of methyl orange dye onto mesoporous carbon material–kinetic and
thermodynamic studies. J Colloid Interface Sci 362, 457–462. https://doi.org/
10.1016/j.jcis.2011.06.067.
Mehmood, A., Bano, S., Fahim, A., Parveen, R., Khurshid, S., 2015. Efficient removal of
crystal violet and eosin B from aqueous solution using Syzygium cumini leaves: a
comparative study of acidic and basic dyes on a single adsorbent. Korean Journal of
Chemical Engineering 32, 882–895. https://doi.org/10.1007/s11814-014-0308-8.
Nandi, B.K., Goswami, A., Purkait, M.K., 2009a. Adsorption characteristics of brilliant
green dye on kaolin. J. Hazard. Mater. 161, 387–395. https://doi.org/10.1016/j.
jhazmat.2008.03.110.
Kumar, U., Acharya, J., 2011. Thermodynamics of the Sorption of Pb (II) from Aqueous
Solution on NCRH. International Journal of Chemical Engineering and Applications
2, 416–420.
Kumar, U., Bandopadhyay, M., 2006. Sorption of cadmium from aqueous solution using
pretreated rice husk. Bioresour. Technol. 97, 104–109. https://doi.org/10.1016/j.
biortech.2005.02.027.
Asfaram, A., Ghaedi, M., Agarwal, S., Tyagi, I., Gupta, V.K., 2015. Removal of basic dye
Auramine-O by ZnS:cu nanoparticles loaded on activated carbon: optimization of
parameters using response surface methodology with central composite design. RSC
Adv 5, 18438–18450. https://doi.org/10.1039/c4ra15637d.
Burakova, Ali, I., Galunin, E., Burakov, A., Mkrtchyan, E., Melezhik, A., Grachev, V.,
2019. High-Speed and high-capacity removal of methyl orange and malachite green
in water using newly developed mesoporous carbon: kinetic and Isotherm Studies.
ACS Omega 4 (21), 19293–19306. https://doi.org/10.1021/acsomega.9b02669.
Rashidi Nodeh, H., Wan Ibrahim, W.A., Ali, I., Sanagi, M.M., 2016. Development of
magnetic graphene oxide adsorbent for the removal and preconcentration of As(III)
K. Sukla Baidya and U. Kumar
and As(V) species from environmental water samples. Environmental Science and
Pollution Research 23, 9759–9773. https://doi.org/10.1007/s11356-016-6137-z.
Mittal, A., Mittal, J., Malviya, A., Gupta, V.K., 2010. Removal and recovery of
Chrysoidine Y from aqueous solutions by waste materials. J Colloid Interface Sci
344, 497–507. https://doi.org/10.1016/j.jcis.2010.01.007.
N. Sivarajasekar, R. Baskar, Adsorption of Basic Magenta II onto H2SO4 activated
immature Gossypium hirsutum seeds: kinetics, isotherms, mass transfer,
thermodynamics and process design. Arabian J. Chemistry (2014). doi:10.1016/j.
arabjc.2014.10.040.
Theivarasu, C., Chandra, S., 2013. Adsorption performance of activated carbon prepared
from elephant (Elephas maximus) dung for the removal of Reactive Yellow 15 from
aqueous solution. Desalination Water Treat 51, 7639–7654. https://doi.org/
10.1080/19443994.2013.781966.
Mane, V.S., Deo Mall, I., Chandra Srivastava, V., 2007a. Kinetic and equilibrium
isotherm studies for the adsorptive removal of Brilliant Green dye from aqueous
solution by rice husk ash. J. Environ. Manage. 84, 390–400. https://doi.org/
10.1016/j.jenvman.2006.06.024.
Dahri, M.K., Lim, L.B.L., Mei, C.C., 2015. Cempedak durian as a potential biosorbent for
the removal of Brilliant Green dye from aqueous solution: equilibrium,
thermodynamics and kinetics studies. Environ Monit Assess 187. https://doi.org/
10.1007/s10661-015-4768-z.
Gupta, N., Kushwaha, A.K., Chattopadhyaya, M.C., 2012c. Adsorption studies of cationic
dyes onto Ashoka (Saraca asoca) leaf powder. J. Taiwan Institute of Chemical
Engineers 43, 604–613. https://doi.org/10.1016/j.jtice.2012.01.008.
Mane, V.S., Mall, I.D., Srivastava, V.C., 2007b. Use of bagasse fly ash as an adsorbent for
the removal of brilliant green dye from aqueous solution. Dyes and Pigments 73,
269–278. https://doi.org/10.1016/j.dyepig.2005.12.006.
43
South African Journal of Chemical Engineering 35 (2021) 33–43
Gimbert, F., Morin-Crini, N., Renault, F., Badot, P.M., Crini, G., 2008. Adsorption
isotherm models for dye removal by cationized starch-based material in a single
component system: error analysis. J. Hazard. Mater. 157, 34–46. https://doi.org/
10.1016/j.jhazmat.2007.12.072.
Nandi, B.K., Goswami, A., Purkait, M.K., 2009b. Adsorption characteristics of brilliant
green dye on kaolin. J. Hazard. Mater. 161, 387–395. https://doi.org/10.1016/j.
jhazmat.2008.03.110.
Segun Esan, O., Nurudeen Abiola, O., Owoyomi, O., Olumuyiwa Aboluwoye, C.,
Olubunmi Osundiya, M., 2014. Adsorption of Brilliant Green onto Luffa Cylindrical
Sponge: equilibrium, Kinetics, and Thermodynamic Studies. ISRN Physical
Chemistry 1–12. https://doi.org/10.1155/2014/743532.
Kismir, Y., Aroguz, A.Z., 2011. Adsorption characteristics of the hazardous dye Brilliant
Green on Saklıkent mud. Chemical Engineering J 172, 199–206. https://doi.org/
10.1016/j.cej.2011.05.090.
Rehman, R., Mahmud, T., Irum, M., 2015. Brilliant Green Dye Elimination from Water
Using Psidium guajava Leaves and Solanum tuberosum Peels as Adsorbents in
Environmentally Benign Way. J Chem 1–8. https://doi.org/10.1155/2015/126036.
Akter, N., Hossain, M.A., Hassan, M.J., Amin, M.K., Elias, M., Rahman, M.M., Hasnat, M.
A., 2016. Amine modified tannin gel for adsorptive removal of Brilliant Green dye.
Journal of Environmental Chemical Engineering 4, 1231–1241. https://doi.org/
10.1016/j.jece.2016.01.013.
Rehman, M.S.U., Munir, M., Ashfaq, M., Rashid, N., Nazar, M.F., Danish, M., Han, J.I.,
2013. Adsorption of Brilliant Green dye from aqueous solution onto red clay.
Chemical Engineering Journal 228, 54–62. https://doi.org/10.1016/j.
cej.2013.04.094.
Mane, V.S., Babu, P.V.V., 2011. Studies on the adsorption of Brilliant Green dye from
aqueous solution onto low-cost NaOH treated saw dust. Desalination 273, 321–329.
https://doi.org/10.1016/j.desal.2011.01.049.