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Adsorptive Removal of Malachite Green Dye Using Durian Seed-Based

Activated Carbon

Article  in  Water Air and Soil Pollution · January 2014

DOI: 10.1007/s11270-014-2057-z

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Water Air Soil Pollut (2014) 225:2057
DOI 10.1007/s11270-014-2057-z

Adsorptive Removal of Malachite Green Dye Using Durian

Seed-Based Activated Carbon
Mohd Azmier Ahmad & Norhidayah Ahmad &
Olugbenga Solomon Bello

Received: 1 March 2014 / Accepted: 2 July 2014 / Published online: 19 July 2014
# Springer International Publishing Switzerland 2014

Abstract Chemically prepared activated carbon de- parameters such as ΔG, ΔH, and ΔS were also calculated
rived from durian seed (DSAC) was used as adsorbent for the adsorption process. The process was found to be
to adsorb Malachite green (MG) dye. The prepared spontaneous and endothermic in nature. This work pro-
DSAC was characterized using Brunauer–Emmet–Tell- vided an attractive adsorbent for the removal of MG dye
er (BET), Fourier transform infrared (FTIR), scanning from wastewaters.
electron microscope (SEM), and proximate analysis,
respectively. Batch adsorption studies were carried out Keywords Durian seeds . Malachite green dye .
for the removal of MG dye from aqueous solutions by Adsorption . Spontaneous
varying operational parameters like contact time, initial
MG dye concentration, solution temperature, and initial
solution pH. Maximum dye removal of 97 % was ob-
1 Introduction
tained at pH 8. Experimental data were analyzed by
eight model equations—Langmuir, Freundlich, Temkin,
Dyeing is a fundamental operation during textile pro-
Dubinin–Radushkevich, Radke–Prausnitz, Sips, Vieth–
cessing. There are various types of dyes that are com-
Sladek, and Brouers–Sotolongo isotherms—and it was
monly used such as basic dye, reactive dye, and acid
found that the Freundlich isotherm model fitted the
dye. Basic dyes such as Malachite green (MG) and
adsorption data the most. Adsorption rate constants
methylene blue (MB) have chromophores with positive
were determined using pseudo-first-order and pseudo-
ion and amino group in their molecule which are water
second-order rate equations, Elovich, intraparticle diffu-
soluble. It has favorable characteristics of high brilliance
sion, and Avrami kinetic model. The results clearly
and intensity of colors; it is highly visible even in very
showed that the adsorption of MG dye onto DSAC
low concentrations. It is used for dyeing silk, cotton,
followed the pseudo-second-order model, and the mech-
nylon, coir, and wool (Ahmad and Alrozi 2011). Ac-
anism of adsorption was controlled both by film diffu-
cording to Nethaji et al. (2010), about 10,000 different
sion and intraparticle diffusion. Thermodynamic
dyes weighing approximately 0.7 million tons/year were
produced annually worldwide with 10–15 % of these
M. A. Ahmad : N. Ahmad : O. S. Bello
dyes released into the effluent during the dyeing pro-
School of Chemical Engineering, Universiti Sains Malaysia,
Engineering Campus, 14300 Nibong Tebal, Penang, Malaysia cess. These large amounts of spent dye baths resulted
from inefficiency of the dyeing process. The discharge
O. S. Bello (*) of these compounds into water causes several ecological
Department of Pure and Applied Chemistry, Ladoke Akintola
and environmental problems owing to their toxic, non-
University of Technology,
P.M.B 4000, Ogbomoso, Oyo State, Nigeria biodegradable, and potentially carcinogenic nature
e-mail: [email protected] (Baskaralingam et al. 2006). Such colored effluents
2057, Page 2 of 18 Water Air Soil Pollut (2014) 225:2057

consume dissolved oxygen from the stream and prevent durian seed was placed in a vertical tubular reactor.
reoxygenation in receiving water. The complex molec- Nitrogen gas was purged into the reactor to create inert
ular structure of dyes makes them resistant to biological condition. The flow rate of nitrogen gas and the heating
or even chemical degradation. This also renders the rate were held at 150 cm3/min and 10 °C/min, respec-
treatment methods insufficient and costly (Koprivanac tively. The temperature was ramped from room temper-
and Kusic 2008). Several adsorbents have been used to ature to 700 °C and held for 1 h. Then the reactor was
remove Malachite green dye from solutions, and some cooled down to room temperature. The char produced
of them include the following: potato peel (Guechi and was stored in an air-tight container for further treatment.
Hamdaoui 2011) of potato (Solanum tuberosum), plant The char produced was then impregnated. The impreg-
wastes (Gupta et al. 2011), fruit waste (Parimaladevi and nation ratio (IR) was calculated using
Venkateswaran, 2011), cashew nut bark Alfa Universal wKOH
(Parthasarathy et al. 2011), Annona squamosa seed IR ¼ ð1Þ
wchar
(Santhi et al. 2011), and Limonia acidissima (wood
where wKOH wKOH is the dry weight (g) of potassium
apple) shell (Sartape et al. 2013). In a quest for a better
hydroxide pellet and wchar is the dry weight (g) of char.
and efficient adsorbent for MG dye, modified durian
The char and KOH powder (depending on the IR) were
seed was selected.
mixed together with deionized water in a 250-mL bea-
Durian (Durio zibethinus Murray) is the most popu-
ker. The mixture was stirred thoroughly until it dried in
lar seasonal fruit in Southeast Asia, particularly Malay-
an oven overnight at 105 °C for dehydrating purpose.
sia, Indonesia, Thailand, and the Philippines, and be-
The KOH-impregnated char was placed inside the ver-
longs to the family Bombacaceae (Booncherm &
tical tubular reactor for activation process. The system
Siriphanich, 1991). A significant percentage of the
was purged under nitrogen flow of 150 cm3/min. The
planted durian fruit crop is wasted each year. Only one
temperature was ramped from ambient temperature to
third of durian fruit is edible, whereas the seeds (20–
the activation temperature at a heating rate of 10 °C/min.
25 %) and the shells are usually discarded. The wasted
Once the desired activation temperature was reached,
durian seed represents a significant potential for the
the gas flow was switched to carbon dioxide at a flow
development of value-added products. To the best of
rate of 150 cm3/min to complete the activation process.
our knowledge, no report has been documented on the
Then, the reactor was cooled to room temperature under
removal of Malachite green dye using durian seed;
nitrogen flow. The sample was washed with 0.1 M HCl.
hence, this study investigates the preparation of durian
It was further washed with deionized water several times
seed-based activated carbon using physicochemical ac-
until the pH of the washing solution reached 6.5–7. The
tivation, characterization of the prepared adsorbent, and
pH was measured using a pH meter (Model Delta 320,
study of various adsorption parameters as follows: initial
Mettler Toledo, China). Filter paper and filter funnel
dye concentration, contact time, temperature, solution
were used in the washing process. The washed sample
pH, adsorption isotherms, and kinetic and thermody-
was kept in an oven at 105 °C for 12 h. The dried sample
namic studies of the adsorption of MG dye onto durian
which was the activated carbon derived from durian
peels.
seed (DSAC) was stored in air-tight containers for fur-
ther characterization and adsorption studies. The DSAC
yield was calculated using the equation:
2 Materials and Methods
wc
Yield ð%Þ ¼  100 ð2Þ
2.1 Activated Carbon Preparation w0
where wc and w0 are the dry weight of DSAC (g) and the
Durian fruits (DS) were purchased from a local market dry weight of precursor (g), respectively.
in Parit Buntar area, Perak, Malaysia. The fruit was
dehusked (the rind was cut open), by cutting along the 2.2 Adsorbate Used
suture on the back of the lobules. Durian seeds were
removed, cleaned, and rinsed thoroughly with distilled MG was used as adsorbate to determine the adsorption
water. It was then dried to constant weight and stored in performance of the prepared activated carbon. The prop-
an air-tight container for further use. Ten grams of erties of MG dye used are listed in Table 1.
Water Air Soil Pollut (2014) 225:2057 Page 3 of 18, 2057

Table 1 Properties of
malachite green (Santhi Properties
et al. 2010a)
Chemical name 4-[(4-Dimethylaminophenyl)-phenyl-methyl]-N,N-dimethyl-aniline
Common name Malachite green hydrochloride
Generic name Basic green 4
CAS number 123333-61-9
Color index number 42000
Ionization Basic
Maximum wavelength 618 nm
Empirical formula C23H26N2O·HCl
Molecular weight 382.93 g/mol
Chemical structure

2.3 Batch Equilibrium Studies point was reached. Samples are withdrawn at intervals
to determine the residual concentration of the dye at
The effects of initial dye concentration, contact time, 618 nm wavelength using a UV–visible
solution temperature, and solution pH on the adsorption spectrophotometer.
uptake of MG dye on DSAC were studied. Sample
solutions were withdrawn at intervals to determine the 2.5 Effect of Solution Temperature
residual concentration by using a UV–visible spectro-
photometer at the maximum wavelength of 618 nm. The The effect of solution temperature on the adsorption
amount of dye adsorbed at equilibrium, qe (mg/g) was process was carried out by varying the adsorption tem-
calculated as: perature at 30, 45, and 60 °C by adjusting the tempera-
ðC o −C e ÞV ture controller of the water bath shaker, while other
qe ¼ ð3Þ operating parameters such as adsorbent dosage (0.1 g)
W
and rotation speed (120 rpm) were kept constant.
where Co and Ce (mg/L) are the liquid-phase concentra-
tions of initial adsorbate and equilibrium, respectively. V
is the volume of the solution (dm3) and W is the mass (g) 2.6 Effect of Solution pH
of DSAC used.
Solution pH was studied by varying the initial pH of
2.4 Effect of Initial Adsorbate Concentration solution from 2 to 12. The pH was adjusted by 0.1 M
and Contact Time NaOH or 0.1 M HCl and measured by using a pH meter.
The adsorbent dosage, rotation speed, solution temper-
One hundred milliliters of MG dye solution with known ature, and initial dye concentration were fixed at 0.1 g,
initial concentration was placed in a series of 250 mL 120 rpm, 30 °C, and 100 mg/L respectively.
Erlenmeyer flasks. The amount of adsorbent that was
added into each flask was fixed at 0.1 g. The flasks were 2.7 Adsorption Isotherm Studies
placed in an isothermal water bath shaker (Model
Protech, Malaysia) at a constant temperature of 30 °C, This was carried out by fitting the equilibrium data to the
with rotation speed of 120 rpm, until an equilibrium Langmuir (Langmuir, 1918), Freundlich (Freundlich,
2057, Page 4 of 18 Water Air Soil Pollut (2014) 225:2057

1906), Temkin (Temkin and Pyzhev, 1940), Dubinin– capacity values. A lower value of Δqt indicates a good fit
Radushkevich (Dubinin and Radushkevich, 1947), Sips between the experimental and calculated data.
(Sips, 1948), Vieth–Sladek (Vieth and Sladek, 1965),
Brouers–Sotolongo (Brouers et al. 2005), and Radke– 2.9 Adsorption Thermodynamics
Prausnitz (Radke and Prausnitz, 1972) isotherms. The
applicability and suitability of the isotherm equation to The experimental data obtained from batch adsorption
the equilibrium data were compared by judging the studies performed earlier were analyzed by using the
values of the correlation coefficients, R2 and Δqe. Linear thermodynamic equations as expressed by Eqs. 6:
regression was carried out by using Microsoft Excel
ΔG ¼ −RTlnK L ð6Þ
spreadsheet with Solver add-in to determine the iso-
therm parameters.
ΔS ΔH
LnK ¼ − ð6aÞ
R RT
2.8 Batch Kinetic Studies ΔG was calculated using Eq. 6. The values of ΔH
and ΔS can be obtained, respectively, from the slope
This procedure is similar to that of batch equilibrium and intercept of Van’t Hoff plot of lnKL versus 1 / T.
studies. The difference is that the adsorbent–adsorbate Values of KL may be calculated from the relation lnqe /
solution was taken at preset time intervals and the con- Ce at different solution temperatures of 30, 45, and
centration of the solution was measured. The amount of 60 °C, respectively. Arrhenius equation has been ap-
adsorption at time t, qt (mg/g), was calculated using plied to evaluate the activation energy of adsorption
Eq. 4: representing the minimum energy that reactants must
have for the reaction to proceed, as shown by the fol-
ðC o −C t ÞV
qt ¼ ð4Þ lowing relationship:
W
Ea
where Co and Ct (mg/L) are the liquid-phase concentra- lnk 2 ¼ lnA− ð6bÞ
RT
tions of adsorbate at initial and at any time t, respective-
where k2 is the rate constant obtained from the pseudo-
ly. V is the volume of the solution and W is the mass of
second-order kinetic model (g/mg h), Ea is the Arrhenius
adsorbent used. The adsorption kinetics of the dye on
activation energy of adsorption (kJ/mol), A is the Arrhe-
adsorbent was investigated using the pseudo-first-order
nius factor, R is the universal gas constant (8.314 J/
model (Lagergren 1898), pseudo-second-order model
mol K), and T is the absolute temperature. When ln k2
(Ho and McKay, 1999), Avrami model (Avrami,
is plotted against 1 / T, a straight line with slope of−Ea /
1940), and Elovich model (Aharoni and Ungarish
R is obtained.
1976), respectively.
2.10 Adsorption Mechanism
2.8.1 Validity of the Kinetic Model
The adsorption mechanisms of MG dye on the adsor-
The applicability and fitting of the isotherm equation to
bent were investigated using intraparticle diffusion and
the kinetic data was compared by judging from the R2
Boyd models represented by Eqs. 7 and 8, respectively.
values and the normalized standard deviation Δqt (%)
The applicability and fitting of the model throws more
calculated from Eq. 5. The normalized standard devia-
light into the mechanism of MG dye adsorption onto the
tion, Δqt (%), was used to verify the kinetic models used
DSAC prepared.
to describe the adsorption process. It is defined as:
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
h . iffi2 2.10.1 Intraparticle Diffusion Model
100 Σ nT qexp −qcal qexp
Δqt ð%Þ ¼ ð5Þ The intraparticle diffusion model (Weber and Morris,
n−1
1962) is expressed as shown in Eq. 7
where n is the number of data points, and qexp and qcal 1
(mg/g) are the experimental and calculated adsorption qt ¼ k pi t 2 þ C i ð7Þ
Water Air Soil Pollut (2014) 225:2057 Page 5 of 18, 2057

where Ci is the intercept and kpi (mg/g h1/2) is the Table 2 Surface area and pore characteristics of the samples
intraparticle diffusion rate constant, which can be eval- Sample BET Mesopore Total pore Average
uated from the slope of the linear plot of qt versus t1/2. surface surface area volume pore
The qt is the amount of solute adsorb per unit weight of area (m2/g) (m2/g) (cm3/g) diameter
adsorbent per time (mg/g), and t1/2 is the half adsorption (nm)
time (g/h mg). The intercept of the plot reflects the DS 9.44 – – –
boundary layer effect. The larger the intercept, the great-
DS char 197.80 106.36 0.198 3.27
er the contribution of the surface sorption in the rate-
DSAC 980.62 516.28 0.528 3.40
controlling step. If the regression of qt versus t1/2 is
linear and passes through the origin, then intraparticle DS durian seed, – not available
diffusion is the sole rate-limiting step. If the linear plots
at each concentration did not pass through the origin, it adsorption. A similar result was obtained in the removal
indicates that the intraparticle diffusion was not only a of MG dye using Cocos nucifera shell-based activated
rate-controlling step (Wu et al. 2005). carbon (Bello and Ahmad, 2012).
The surface area of DSAC prepared was comparable
2.10.2 Boyd Model with other AC obtained from literature. The physio-
chemical activation process had contributed to the high
In order to identify the slowest step in the adsorption surface area and total pore volume of the prepared
process, Boyd kinetic equation (Boyd et al. 1947) was DSAC. The DSAC expansion porosity is associated
applied, and it is expressed as: with gasification reaction (Basta et al. 2009). The diffu-
sion of carbon-KOH and CO2 molecules into the pores
6 Bt
F ¼ 1− e ð8Þ promotes reactions which developed more pores in the
π2
DSAC. The KOH melts and its oxide component reacts
with carbon dioxide, which assists in the enhancement
qt
F¼ ð8aÞ of the surface area of the samples. This result was in
qe agreement with the findings of Ahmad and Alrozi
where qt is the amount of the adsorbate adsorbed at time (2011), who reported the BET surface area, total pore
t (mg/g), F is the fraction of adsorbate adsorbed at time t, volume, and average pore diameter of the rambutan
and Bt is the mathematical function of F. Equation 8 can peel-based AC as 908.35 m2 /g, 0.52 cm 3 /g, and
be rearranged by taking the natural logarithm to obtain 2.63 nm, respectively, thus confirming that the combi-
the following equation: nation of both chemical and physical activating agents
of KOH and CO2 promotes the formation of mesopores
Bt ¼ −0:4977 − lnð1 − F Þ ð8bÞ and enhances the surface area of DSAC.

3.1.2 Proximate Analysis

3 Results and Discussions
The precursors were found to be rich in moisture and
3.1 Characterization of the Prepared Adsorbent volatile matter. However, the moisture and volatile con-
tent were found to decrease significantly from precursor
3.1.1 Surface Area and Pore Characteristics to activated carbon. During carbonization and activation
processes, organic substances become unstable as a
The Brunauer–Emmett–Teller (BET) surface area, result of the heat causing the molecules to break their
mesopore surface area, total pore volume, and average bonds and linkages. During the activation step, the
pore diameter of DSAC are shown in Table 2. The volatile matter is released as gas, and liquid products
surface area of DSAC was 980.62 m2/g with a high pore evaporate off leaving the material with a high carbon
volume of 0.528 cm3/g. The average pore diameter is content (Ahmad and Alrozi, 2010). Proximate analysis
3.40 nm. According to IUPAC classification (IUPAC clearly indicates that the physiochemical activation has
et al. 1972), DSAC belongs to the mesopore region successfully increased the fixed carbon content and
which has significant mesopores suitable for MG dye decreased the volatile matter (Table 3).
2057, Page 6 of 18 Water Air Soil Pollut (2014) 225:2057

Table 3 Proximate analysis of the precursor, char, and activated impregnation and heating stage. The medium peaks
samples
around 1,014 and 867–590 cm−1 found on the spectra
Sample Proximate analysis (%) were due to the presence of C–O groups stretching in
ester, ether, or phenol group and C–H out-of-plane
Moisture Volatile matter Fixed carbon Ash bending in benzene derivatives, respectively. A sim-
ilar result was obtained in the preparation of activated
DS 8.94 69.70 17.26 4.10
carbon from cherry stones by chemical activation
DS char 5.14 29.65 61.39 3.82
with ZnCl2 (Olivares et al. 2006).
DSAC 3.10 22.41 70.89 3.60

3.1.4 Surface Morphology

3.1.3 Surface Chemistry
The surface morphologies of DS and DSAC are shown
Table 4 shows the assignment of absorption bands for in Fig. 2. The surface structures of both precursors were
the Fourier transform infrared (FTIR) spectrum of rough and uneven. Different imaging magnifications
DSAC (Fig. 1). The spectrum of the samples shows between DS and DSAC were due to the modification
the presence of several functional groups. These spectra using an activating agent. A significant pore structure
revealed either a reduction, disappearance, or broaden- exists with a series of rough cavities distributed over the
ing of the peaks after the process of impregnation. surface of DSAC. This was due to the breakdown of
The long bandwidth around 3,601–3,861 cm−1 in- lignocellulose at high temperature followed by evapo-
dicated that the main functional groups found on DS ration of volatile compounds leaving samples with well-
were O–H stretching vibration of hydroxyl functional developed pores. During the activation process, the C-
groups including hydrogen bonding. Other major KOH reaction rate was increased, thus resulting in car-
peaks detected at bandwidths of 2,399–2,102, bon “burn off,” thereby developing good pores on the
1,732–1,901, 1,635, and 1,361 cm−1 were respective- sample. The C-KOH reaction also increased the porosity
ly attributed to C≡C stretching of the alkyne group; of DSAC as well as created new pores due to loss of
vibration of carboxylic C=O stretching of lactones, volatile components, carbon in the form of CO, and CO2
ketones, and carboxylic anhydrides; C=C of aromat- (Auta and Hameed, 2011). The physiochemical treat-
ic ring; and C–H stretching in alkanes or alkyl group. ment was able to produce porous adsorbent thus increas-
The disappearance of ether and phenol in the DSAC ing the surface area. Kilic et al. (2011) found out that
samples shows that these functional groups are ther- KOH assists in widening the porosity of tobacco residue
mally unstable. DS exhibits peaks at band position AC. The tobacco residue was found to have very little
1,635 cm −1, which was assigned to the aromatic porosity, whereas the surface structure of TRAC was
group but disappeared in DS char and DSAC. The full with cavities. Physiochemical activation produces a
aromatic group disappeared due to oxidative degra- porous adsorbent resulting in increased uptake in the
dation of aromatic rings during chemical adsorption of MG dye.

Table 4 FTIR spectrum band assignment for DS, DS char, and DSAC

Assignment Band position (cm−1)

DS DS char DSAC

O–H stretching of hydroxyl group 3,861–3,738 3,857–3,614 3,861–3,610

C≡C stretching of alkyne group 2,287–2,102 2,399–2,295 2,337
C=O stretching of lactones, ketones, and carboxylic anhydrides 1,901 1,739 1,732
C=C of aromatic ring 1,635 – –
C–H stretching in alkanes or alkyl group 1,361 – –
C–O groups stretching in ester, ether, or phenol group 1,014 – –
–C≡C–H–C–H bend in functional group 867–767 597 590
Water Air Soil Pollut (2014) 225:2057 Page 7 of 18, 2057

(a)

(b)

(c)

Fig. 1 FTIR spectra: a DS, b DS char, and c DSAC

2057, Page 8 of 18 Water Air Soil Pollut (2014) 225:2057

(a) (b)

Fig. 2 SEM micrographs of a DS (×2,000) and b DSAC (×2,000)

3.2 Batch Equilibrium Studies There was an initial sharp increase of MG dye adsorp-
tion uptake (qt) due to the large number of available
3.2.1 Effect of Contact Time and Initial Concentration active sites. The gradual slower adsorption at the end is
of Adsorbate probably due to the saturation of active sites and a
decrease in dye concentration (Li et al. 2009; Khattri
Figure 3 shows the MG dye adsorption uptake with and Singh, 2009). The remaining surface sites are diffi-
respect to time at various initial dye concentrations cult to be occupied. This was due to the repulsion
(25–500 mg/L) by DSAC at three different temperatures between the solute molecules and bulk phases of DSAC.
of 30, 45, and 60 °C, respectively. The percentage of Similar results were obtained in the adsorption of MG
MG dye removal with respect to time is shown in Fig. 4. dye on neem sawdust (Khattri and Singh, 2009) and
At 30 °C, the amount of MG dye adsorbed as well as the banana stalk-activated carbon (Bello et al. 2011a, b).
percentage of dye removal increased with the increase in The contact time needed for dye solutions with initial
initial dye concentration. As the initial dye concentra- concentrations of 25–200 mg/L to reach equilibrium
tion increased from 25 to 500 mg/L, the adsorption was around 6 h. However, for dye solutions of higher
uptake at equilibrium for MG dye was found to increase initial concentrations (400–500 mg/L), equilibrium
from 22.0 to 332.08 mg/g. This was due to the increase times of 20–24 h were required. This is due to the fact
in mass transfer driving force with increase in initial dye that the initial dye molecules have to first encounter the
concentration. The initial dye concentration provides a boundary layer effect and then have to diffuse into the
driving force to overcome mass transfer resistance of boundary layer film onto the adsorbent surface. Finally,
dyes between the aqueous and solid phases. The adsorp- it has to diffuse into the activated carbon and adsorbed
tion curves were smooth and continuous profiles leading onto the binding surface (Santhi et al. 2010a, b). There-
to equilibrium (Djeribi and Hamdaoui, 2008). When an fore, a dye solution with higher initial concentrations
equilibrium condition was reached, the dye molecule in would take relatively longer contact time to achieve
the solution is in a state of equilibrium with the molecule equilibrium due to the higher amount of adsorbate mol-
adsorbed by the DSAC. The higher MG dye concentra- ecules. The larger surface area and the total pore volume
tion provides a strong driving force of the gradient; of DSAC relatively highly enhanced the adsorption
hence, an enhanced adsorption capacity was observed process. A similar result was obtained in the adsorption
(Mahmoud et al. 2012). Similar trends were observed at of MB dye using periwinkle shells (Bello et al. 2008).
higher temperatures as shown in Fig. 3b, c.
The MG dye adsorption uptake curves have three 3.2.2 Effect of Solution Temperature
parts. In the first 6 h, about 50 % of MG dye adsorption
occurred at temperatures of 30, 45, and 60 °C, respec- Figure 5 shows the MG dye adsorption capacity against
tively. In the second part (6 h<t<22 h), the slopes the solution temperature for DSAC at 30 °C. As tem-
became gentle resulting in an additional 20 % adsorp- perature increased from 30 to 60 °C, the amount of MG
tion. In the third part (t>22 h), the dye adsorption uptake dye adsorbed increased from 332.08 to 370.94 mg/g.
(qt) was steady and the adsorption reached equilibrium. The adsorption capacity (qe), increased with increase in
Water Air Soil Pollut (2014) 225:2057 Page 9 of 18, 2057

Fig. 3 Plot of MG dye

adsorption uptake against a
adsorption time at various initial
concentrations at a 30, b 45, and c
60 °C on DSAC

temperature indicating that the adsorption was an endo- Ahmad and Alrozi (2011) and rice straw by Basta
thermic process. As the solution temperature increased, et al. (2009).
dye mobility increased to undergo interaction with the
active site at the DSAC’s surface (Mahmoodi et al. 3.2.3 Effect of Initial pH
2011). In addition, the rate of dye molecule diffusion
across the external boundary layer and in the internal The pH point of zero charge of DSAC was found to
pores of the AC particle increased (Dogan et al. 2009). occur at pH 3.2, implying that DSAC surface has a
The diffusion rate of adsorbate molecules across the positive charge in solution up to pH 3.2 and a negative
external boundary layer and in the internal pores of the charge above this pH (Nowicki et al. 2010) (figure not
adsorbent increased as the viscosity of the solution shown). The contents of oxygen-containing function-
decreased at high temperature. In addition, different al groups with various acidic groups which were
temperatures tend to change the equilibrium capacity determined using the Boehm titration (Boehm,
of the adsorbent for a particular adsorbate (Alkan et al. 2002) are as follows: carboxyl (0.1432 meq g−1), lac-
2008). Adsorption capacity by DSAC was high because tonic (0.4315 meq g−1), phenolic (0.2214 meq g−1),
of the larger surface area and total pore volume of total acidic group (0.7961 meq g−1), and total amount
DSAC. A similar trend was reported for adsorption of of the basic groups (0.3546 meq g−1). The acidic
basic dye on AC prepared from rambutan peel by group content is much higher than the basic group
2057, Page 10 of 18 Water Air Soil Pollut (2014) 225:2057

Fig. 4 MG dye percentage

removal against adsorption time a
at various initial concentrations at
a 30, b 45, and c 60 °C on DSAC

content. This is consistent with a value of pHpzc 3.2, of excess H+ ions competing with the cationic groups
showing the dominance of acidic groups. The effect on the MG dye for adsorption sites. As the solution
of initial pH on MG dye removal onto DSAC is pH increases, the surface charge density decreased
shown in Fig. 6. The maximum MG dye removal and the electrostatic repulsion between the positively
was recorded at pH 8 to be 97 %. At this pH, more charged dye and the surface of the DSAC was
OH − ions accumulate on the adsorbent surface lowered, thus resulting in high MG dye removal. A
resulting in the interaction between the negatively similar result was obtained in the removal of Mala-
charge adsorbent surface and cationic MG dye mole- chite green from an aqueous solution by activated
cule, thus an enhanced MG dye removal. However, at carbon prepared from the epicarp of Ricinus
low pH, low MG dye uptake was due to the presence communis (Santhi et al. 2010a, b).

Fig. 5 MG dye adsorption

capacity against the solution
temperature for DSAC at different
temperatures
Water Air Soil Pollut (2014) 225:2057 Page 11 of 18, 2057

Fig. 6 Effect of initial pH on MG

removal on DSAC

Fig. 7 Plots of a Langmuir, b Freundlich, c Temkin, d Dubinin–Radushkevich, e Radke–Prausnitz, f Sips, g Vieth–Sladek, and h Brouers–
Sotolongo isotherms for MG dye adsorption on DSAC
2057, Page 12 of 18 Water Air Soil Pollut (2014) 225:2057

Table 5 Isotherm parameters for the adsorption of MG dye onto DSAC at 30 °C

DSAC-MG

Langmuir Freundlich Temkin Dubinin– Sips Vieth–Sladek Brouers– Radke–

Radushkevich Sotolongo Prausnitz
Qm 476.19 1/nF 0.679 B 77.716 bDR 0.0035 Qm 480.20 Kvs 0.4856 Qm 532.30 KRP 0.0083
−3
KL 0.0118 KF 0.3727 A 0.2542 E 5.3430 Ks 0.0116 Qm 445.60 kBS 9.9×10 Qm 516.52
R2 0.9467 R2 0.9995 R2 0.9061 qs 11.95 ms 1.1106 βvs 9.20×10−3 α 0.907 mRP 0.974
RL 0.1449 R2 0.8194 R2 0.892 R2 0.985 R2 0.982 R2 0.970
Δqe 3.215 Δqe 0.544 Δqe 5.481 Δqe 2.154 Δqe 8.174 Δqe 6.221 Δqe 5.841 Δqe 4.987

3.3 Adsorption Isotherm Studies fit the experimental equilibrium data. Figure 7 shows the
plots of the linearized equation isotherm parameters for
The adsorption isotherm signifies the amount of mole- MG dye removal at temperature 30 °C. Similar plots
cules distributed between the liquid phase and the solid were obtained for the adsorption systems at 45 and
phase when the adsorption process reaches equilibrium 60 °C, respectively (figure not shown). Table 5 shows
state. Langmuir, Freundlich, Temkin, Dubinin– the values of maximum monolayer coverage (Qm), cor-
Radushkevich, Sips, Vieth–Sladek, Brouers–Sotolongo, relation coefficient (R2), normalized standard deviation
and Radke–Prausnitz isotherm models were chosen to (Δqe), and other parameters as calculated from isotherms

Table 6 Comparison of adsorption capacities of MG dye using various adsorbents

Adsorbent Capacity qo (mg/g) Conditions References

pH Temp (K)

Carbon prepared from Borassus bark 20.70 6 303 Arivoli et al. (2009)
Caulerpa racemosa var. cylindracea (marine alga) 25.67 6 318 Bekci et al. (2009)
Saccharomyces cerevisiae 17.00 5 308 Godbole and Sawant (2006)
Potato peel 32.39 4 298 Guechi and Hamdaoui (2011)
Leaves of Solanum tuberosum 33.3 7 303 Gupta et al. (2011)
Unsaturated polyester Ce (IV) phosphate 1.01 8 300 Khan et al. (2010)
Neem sawdust 4.35 7.2 303 Khattri and Singh (2009)
Rubber wood sawdust 36.45 – 305 Kumar and Sivanesan (2007)
Commercial activated carbon 8.27 7 303 Mall et al. (2005)
Waste fruit residues 37.03 5–8 300 Parimaladevi and Venkateswaran (2011)
Dried cashew nut bark carbon 20.09 6.60 – Parthasarathy et al. (2011)
Tamarind fruit shell 1.95 5 303 Saha et al. (2010)
Epicarp of Ricinus communis-activated carbon 27.78 – – Santhi et al. (2010a)
Annona squamosa seed-activated carbon 25.91 6 300 Santhi et al. (2010a)
Annona squamosa seed 25.91 6 300 Santhi et al. (2011)
Cellulose powder 2.42 7.2 298 Sekhar et al. (2009)
Kapok hull-activated carbon 30.16 6.7 300 Syed (2011)
Chlorella-based biomass 18.4 7 298 Tsai and Chen (2010)
Carbon prepared from Arundo donax root 8.69 5–7 303 Zhang et al. (2008)
Wood apple shell 34.56 7.5 299 Sartape et al. (2013)
DSAC 476.19 8.0 298 This work
Water Air Soil Pollut (2014) 225:2057 Page 13 of 18, 2057

at temperature 30 °C. Freundlich isotherm fitted well The fundamental feature of the Langmuir isotherm is
with the data (R2 >0.99) for MG dye adsorption onto expressed in terms separation factor (RL). RL indicates
DSAC. The maximum adsorption capacity (Qm) values isotherm to be either unfavorable (RL >1), linear (RL =
obtained from isotherm were in range of 445.6– 1), favorable (0<RL <1), or irreversible (RL =0). The RL
532.3 mg/g for DSAC-MG (Table 5). Freundlich iso- for DSAC onto MG dye ranged between 0 and 1, which
therm shows the lowest Δqe values in addition to the indicates that the adsorption was favorable at the con-
highest R2 value. centration range studied. The RL values decreased as the
From the experimental data, the Freundlich iso- initial concentration dye concentration increased which
therm model indicated the heterogeneous nature of indicates that the sorption process was favorable at high
DSAC surface, in which the energy term in the Lang- initial dye concentration. Table 6 compares the various
muir equation varies as a function of the surface adsorption capacities of different adsorbents with the
coverage (Wang et al. 2010). A higher value of KF one obtained in the present study. DSAC gave a higher
indicates an adsorbent having a higher capacity for value of qo above other adsorbents used in the removal
adsorption (Tunç et al. 2009). Table 5 shows the of MG dye.
calculated values of KF suggesting a high adsorptive
capacity for MG dye uptake. The 1/n value for 3.4 Batch Kinetic Studies
Freundlich was 0.679 for DSAC, indicating that the
physical process was favorable for MG dye adsorp- The adsorption equilibrium studies are important in
tion on DSAC. The 1/n value was below 1, indicating determining the effectiveness of adsorption. Four dif-
that the adsorbate was favorable on the adsorbent ferent kinetic models were used to predict the adsorp-
(Tunç et al. 2009). tion process: pseudo-first-order, pseudo-second-

(a) (b)

(c) (d)

Fig. 8 Linearized plots of a pseudo-first-order, b pseudo-second-order, c Avrami, and d Elovich kinetic model for MG adsorption on
DSAC-MG at 30 °C
2057, Page 14 of 18 Water Air Soil Pollut (2014) 225:2057

Table 7 Kinetic model constant values for DSAC-MG adsorption at 30 °C

Model Kinetic parameters Initial MG dye concentration (mg/L)

25 50 100 200 400 500

Pseudo-first-order qeexp (mg/g) 21.26 41.63 78.43 144.50 270.17 313.46

k1 (min−1) 0.507 0.353 0.308 0.312 0.283 0.303
qecal (mg/g) 17.15 34.66 66.50 127.58 239.80 284.05
R2 0.956 0.958 0.94 0.961 0.961 0.968
Δqt (%) 20.195 22.508 13.921 15.822 27.281 10.921
Pseudo-second-order qecal (mg/g) 18.05 29.76 52.35 97.08 172.41 212.76
k2 (min−1) 0.162 0.096 0.052 0.022 0.012 0.008
h (mg/g min) 52.91 84.74 142.85 204.08 357.14 357.14
R2 0.982 0.984 0.989 0.981 0.994 0.988
Δqt (%) 4.876 2.739 9.435 7.895 8.843 7.354
Elovich αEl (mg/g min) 13.50 3.89 1.51 0.61 0.280 0.213
βEl (g mg−1) 3.224 6.560 12.74 24.33 46.27 54.85
R2 0.966 0.963 0.972 0.967 0.969 0.980
Δqt (%) 24.482 16.142 16.449 21.796 18.442 20.982
Avrami nAV 0.585 0.523 0.540 0.568 0.588 0.646
kAV (min−1) 75.52 124.43 155.6 180.62 198.22 192.41
R2 0.976 0.956 0.970 0.982 0.982 0.987
Δqt (%) 14.283 27.871 33.683 30.561 27.580 29.792

order, Elovich, and Avrami models. As shown by concentrations, the competition for the surface active
plots in Fig. 8, the pseudo-second-order kinetic sites was high, and consequently, lower sorption rates
models fit well with data when compared to other were obtained. However, Elovich desorption con-
kinetic models. The experimental data in Table 7 stant, βEl, increases as the initial dye concentration
showed that the MG dye adsorption parameters gave increases, and this is related to the extent of surface
good agreement with the pseudo-second-order kinetic coverage and activation energy for the chemisorption
model with R2 value close to unity and low values of process. On the other hand, the Elovich constant, αEl,
Δq t , and this reaction is significant in the rate- decreased with increase in initial dye concentration.
controlling step. The rate coefficient, k2, of pseudo- This indicates that the adsorption process involves
second-order was found to decrease with increase in more than one mechanism. The findings were in
initial dye concentration. It indicates that as the initial agreement with several studies on the adsorption of
concentration increases, the electrostatic interaction MG dye onto Arundo donax root (Zhang et al. 2008),
decreased on the site, thus lowering the dyes’ affinity maize cob (Sonawane and Shrivastava, 2009), flower
toward the adsorbent (Chu, 2002). In addition, this biomass (Nethaji et al. 2010), rambutan peel (Ahmad
behavior was due to the lower competition for the and Alrozi, 2011), and ginger waste (Ahmad and
sorption sites at lower concentration. At higher Kumar, 2010) respectively.

Table 8 Thermodynamic param-

eters for MG dye adsorption onto Activated carbon ΔH (kJ/mol) ΔS (J/mol K) Ea (kJ/mol) −ΔG (kJ/mol)
DSAC at different temperatures
303 K 318 K 333 K

DSAC-MG 10.64 12.56 5.05 11.43 11.42 11.51

Water Air Soil Pollut (2014) 225:2057 Page 15 of 18, 2057

Table 9 Intraparticle diffusion model constant for adsorption of MG dye onto DSAC at 30 °C

Activated carbon MG initial concentration (mg/L) 25 mg/L 50 mg/L 100 mg/L 200 mg/L 400 mg/L 500 mg/L

DSAC Kp1 (mg/g h1/2) 25.2896 46.1531 70.7080 110.5409 171.7696 200.5876
Kp2 (mg/g h1/2) 1.577 4.1183 6.5271 11.2141 26.1921 28.9647
Kp3 (mg/g h1/2) 0.0001 0.0004 0.0004 0.0004 0.0004 0.0004
C1 1.0564 1.8288 2.4792 4.4507 6.7326 3.9944
C2 10.2004 14.6260 25.3041 41.8429 73.9450 88.6514
C3 21.2570 41.6356 78.4290 144.4972 270.1659 313.464
(R1)2 0.8565 0.8676 0.9093 0.8773 0.8992 0.9710
(R2)2 0.8383 0.9530 0.9697 0.9323 0.9627 0.9233
(R3)2 0.9643 1.0000 0.9231 0.9999 0.9643 0.9998

Fig. 9 Plots of intraparticle

diffusion model for MG
adsorption on DSAC at 30 °C

3.5 Thermodynamic Studies between −20 and 0 kJ/mol which confirmed the
physisorption nature of the adsorption process (Tan,
Thermodynamic adsorption parameters such as 2008).
change in enthalpy (ΔH), entropy (ΔS), Gibbs free Another characteristic of the physical adsorption
energy (ΔG), and activation energy (Ea) for the ad- mechanism is low activation energy (5–40 kJ/mol),
sorption of MG dye onto DSAC are listed in Table 8. while higher activation energy (40–800 kJ/mol) sug-
From the table, the ΔH value obtained is positive gests a chemisorption mechanism (Hameed et al.
indicating that the process is endothermic in nature. 2007). Ea value in Table 8 was between 5 and 40 kJ/
This was due to the decrease in the viscosity of the mol, indicating that the adsorption of MG dye onto
solution at higher temperature (Wang et al. 2005). ΔH
for physisorption is generally less than 80 kJ/mol,
whereas for chemisorption, it falls within the range
80–420 kJ/mol (Tan, 2008). Values obtained for ΔH
are less than 80 kJ/mol, indicating that the adsorption
process follows the physisorption mechanism. The
positive values of ΔS indicate that the degrees of
freedom increased at the solid–liquid interface during
dye adsorption onto adsorbent. The negative values
of ΔG indicate the spontaneous nature of the adsorp-
tion processes at the range of the temperature studied.
The magnitude of ΔG values obtained in this study is Fig. 10 Boyd plots for adsorption of MG dye onto DSAC
2057, Page 16 of 18 Water Air Soil Pollut (2014) 225:2057

DSAC follows a physisorption process. mass transfer (film diffusion) where the particle diffu-
sion was the limiting step. The first stage of adsorption
3.6 Adsorption Mechanism is attributed to the diffusion in the macropore and the
second stage to micropore diffusion (Ahmad et al.
3.6.1 The Intraparticle Diffusion Model 2009). A similar observation was obtained in the ad-
sorption of MG dye onto treated ginger waste (Ahmad
The kinetic mechanisms were further analyzed by using and Kumar 2010).
the intraparticle diffusion model. The first, sharper re-
gion within the first 15 min was termed rapid adsorption
due to the strong electrostatic attraction between the dye 4 Conclusion
and the external surface of the adsorbent. The second
region, the gradual adsorption stage, indicates the The adsorption process of DSAC in the removal of MG
intraparticle diffusion of dye molecules through the dye was very effective at pH 8 resulting in 97 % removal
pores of the adsorbent which is the rate-controlling step efficiency. Adsorption isotherm data fitted the
(Ahmad et al. 2009). The third region was the final Freundlich model the most. The dimensionless separa-
equilibrium stage when intraparticle diffusion starts to tion factor of Langmuir isotherm, RL, lies between 0 and
slow down due to the very low adsorbate concentration 1. The Freundlich constant (1/n) is less than 1, indicating
in the solution (Wang et al. 2010). It can be seen that the that the adsorption process is favorable. The kinetics of
linear lines of the second and third stages did not inter- adsorption followed the pseudo-second-order rate equa-
cept through the origin. It shows that intraparticle diffu- tion. Both intraparticle diffusion and boundary layer
sion was not only a rate-limiting mechanism in the diffusion govern the mechanism of the adsorption pro-
adsorption process. Table 9 shows the intraparticle mod- cess. The negative value of ΔG revealed the spontaneity
el constant for adsorption of MG dye onto DSAC. The of the process, while the positive value of ΔH indicated
kp values and intercept C values for all initial concen- that the process is endothermic. The positive value of ΔS
tration were found to increase from the first stage of showed the increased randomness of the adsorbate mol-
adsorption toward the third stage. Increase in dye con- ecules on the solid surfaces than in the solution. The
centration results in an increase in the driving force, prepared adsorbent can be effectively used in the remov-
thereby increasing the dye diffusion rate. The constant, al of MG dye from industrial effluents.
C, was found to increase with increase in initial dye
concentration, indicating the boundary layer effect Acknowledgments The financial support in the form of grants
(Wang et al. 2010) (Fig. 9). from USM; the 3 months USM-TWAS Visiting Researcher Fel-
lowship, FR number: 3240268492 awarded to the corresponding
author; and the accumulated leave granted to Dr. O.S Bello by his
3.6.2 Boyd Model
home institution to utilize the fellowship is thankfully recognized.

The Boyd model which is a linearity test of Bt versus

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