Chemical Engineering Journal 180 (2012) 66–74

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Chemical Engineering Journal

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Factors affecting the carbon yield and adsorption capability of the mangosteen
peel activated carbon prepared by microwave assisted K2 CO3 activation
K.Y. Foo, B.H. Hameed ∗
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: This study presents the preparation of activated carbon from mangosteen peel via microwave assisted
Received 11 July 2011 K2 CO3 activation. The operational parameters including chemical impregnation ratio, microwave power
Received in revised form 28 October 2011 and irradiation time on the carbon yield and adsorption capability of the mangosteen peel derived acti-
Accepted 2 November 2011
vated carbon (MPAC) were investigated. The virgin characteristics of the prepared MPAC were examined
by pore structural analysis, Scanning Electron Microscopy, Fourier transform infrared spectroscopy, nitro-
Keywords:
gen adsorption isotherm, elemental analysis, surface acidity/basicity and zeta potential measurement.
Activated carbon
The adsorptive property of MPAC was tested using methylene blue as dye model compound. The best
Adsorption
Mangosteen peel
conditions resulted in MPAC with a maximum monolayer adsorption capacity of 379.63 mg/g and car-
Methylene blue bon yield of 80.95%, respectively. Equilibrium data were favorably described by Langmuir isotherm, while
Microwave adsorption kinetics was best fitted to the pseudo-second-order model. The findings support the feasibility
of mangosteen peel derived activated carbon as a promising and economic adsorbent.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction Although MPs have been reputed to have anti-inflammatory prop-

By nature, mangosteen (Garcinia mangostana), colloquially
known as “the queen of fruits”, is a tropical seasonal plant species
belonging to the members of family Clusiaceae and genus of
Garcinia. Mangosteen trees thrive well in a warm and humid
climate, ideally in the temperature range from 25 to 30 ◦ C, with
a height from 7 to 25 m. The fruit, capped by the prominent calyx
at the stem end and with 4–8 triangular, flat remnants of stigma
in a rosette at the apex, is round, dark to red-purple and smooth
externally. The inner arils are tangy, juicy, sweet and distinctly
acid in flavor [1].
Mangosteen fruit is primarily eaten fresh and available as food
complements in desserts, salads, fruit cocktail, jam, juice combina-
tions or can food processing industries [2]. Nevertheless, its wide
scale implementations by the food manufacturing industries are
deteriorated by the massive generation of peel and stem waste. For
each kg of mangosteen harvested, approximately 0.6 kg of man-
gosteen peels (MPs) can be obtained [3]. According to the statistical
data reported by the Ministry of Agricultural and Agro-Based Indus-
try Malaysia, the local production of mangosteen in 2010 was
projected at 29,520 MT/yr, translating to approximately 17,712 MT
of mangosteen peels as the by-products [4].
In the formal practice, some quantity of these residues is used
as boiler fuel, where major portion is discarded by open burning.
∗ Corresponding author. Tel.: +60 45996422; fax: +60 45941013.
E-mail address: chbassim@eng.usm.my (B.H. Hameed).
erties and traditional used as a remedy for chronic diarrhea, thrush,
urinary tract disorders, and applied externally as astringent lotions
on eczema, skin infections and wounds [5–7], there are relatively
limited studies in this field. Therefore, it is necessary to find a
rapid route towards upgrading of the available biomass from the
food processing plants. To the best of our knowledge, no study
has been reported on the preparation of activated carbon from MP
via microwave-induced activation. In this sense, the present work
is aimed at evaluating the viability of microwave irradiation for
preparation of activated carbon from MP via K2 CO3 activation.
Methylene blue, the most commonly used substance in the
dying process was chosen as the model adsorbate in this study,
due to its potential risk towards the environmental pollution and
ecosystems. The significant influences of chemical impregnation
ratio, microwave power and radiation time on the carbon yield
and adsorption capacity were investigated systematically. Textu-
ral, functional and surface chemistry of the prepared adsorbent
was performed. Moreover, the adsorption equilibrium, isotherms,
kinetics and thermodynamics were elucidated.
2. Materials and methods
2.1. Adsorbate
Methylene blue (CI: 52015; chemical formula: C16 H18 ClN3 S;
molecular weight: 319.86 g/mol, maximum wavelength: 668 nm),
a cationic pollutant difficult to be degraded in natural environment
was selected as the adsorbate in this study (Fig. 1). A standard stock

1385-8947/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.11.002
 K.Y. Foo, B.H. Hameed / Chemical Engineering Journal 180 (2012) 66–74
Fig. 1. Molecular structure of methylene blue dye.
solution of 1000 mg/L was prepared and suitably diluted to the
required initial concentrations. Deionized water supplied by USF
ELGA water treatment system was used to prepare all the reagents
and solutions.
2.2. Preparation of activated carbon
Mangosteen peel (MP), a by-product collected from the local
food processing factory, was the precursor used in the present
study. The raw precursor was washed exhaustively with deionized
water to remove adhering dirt from the surface. Dried MP was cut,
crushed, and screened to a particle size of 1–2 mm. The carboniza-
tion process was carried out by loading 500 g of dried precursor into
a modified muffle furnace, under N2 gas flow (150 cm3 /min) and
heated up to a carbonization temperature of 700 ◦ C, at the heating
rate of 10 ◦ C/min. The char produced was mixed with K2 CO3 pellets
with different impregnation ratio (IR), defined as:
wK2 CO3
IR =
wchar
where wK2 CO3 and wchar are the dry weight of K2 CO3 pellets (g) and
char (g).
Microwave heating was conducted in a 2.45 GHz commercial
microwave oven with suitable modifications. The oven has a power
controller to select different power levels and a timer for vari-
ous exposure times at a set microwave power level. The reaction
was performed in a reactor fixed in the chamber of microwave
oven. Nitrogen gas at a pre-set flow rate (300 cm3 /min) was used
to purge air in the reactor before the start of microwave heating
and it continued to flow during the activation stage. The resultant
activated carbon was washed with 0.1 M of hydrochloric acid and
rinsed repeatedly with hot and cold distilled water until the fil-
trate reached to neutral pH. The yield is defined as the weight of
activated carbon per weight of char utilized for activation.
2.3. Adsorption equilibrium studies
The batch adsorption experiments were undertaken in a set
of 250 mL Erlenmeyer flasks containing 0.20 g of adsorbent and
200 mL of dye solutions within the initial concentration range
of 50–500 mg/L. The mixture was agitated at 120 rpm and 30 ◦ C
until the equilibrium was reached. The concentration of methy-
lene blue (MB) dye solution was determined using a double beam
UV–Vis spectrophotometer (UV-1601 Shimadzu, Japan) at 668 nm.
MB uptake at equilibrium, qe (mg/g), was calculated by:
(Co − Ce )V
qe =
W
where C0 and Ce (mg/L) are the liquid-phase concentrations of dye
at initial and equilibrium, respectively. V (L) is the volume of the
solution, and W (g) is the mass of adsorbent used. The effect of
pH on dye removal was examined by varying the pH from 2 to
12, with initial dye concentration of 500 mg/L, MPAC dosage of
0.20 g/200 mL and adsorption temperature of 30 ◦ C. The initial pH
of the dye solution was adjusted by addition of 0.10 M solution of
HCl or NaOH.
67
2.4. Characterization of MPAC
The pore structural characteristics of MPAC prepared under
optimum preparation conditions were determined by nitrogen
adsorption at 77 K using an automatic Micromeritics ASAP-2020
volumetric adsorption analyzer. Prior to analysis, the sample was
degassed for 2 h under vacuum at 573 K. The sample was trans-
ferred to the analysis system where it was cooled in liquid nitrogen.
A 21-point analysis was carried out at 77 K to obtain the nitrogen
adsorption isotherm. The SBET was calculated by the BET equation,
micropore volume, micropore surface area and external surface
area were obtained using the t-plot method.
Chemical characterization of functional groups was detected by
Fourier transform infrared spectrometer (FTIR-100, Shimadzu) in
the scanning range of 4000–400 cm−1 . The surface morphology was
examined using a scanning electron microscope (Zeiss Supra 35 VP)
and elemental analysis was performed using an Elemental Analyzer
(Perkin-Elmer-2400).
2.5. Surface acidity/basicity and zeta potential measurement
(pHpzc )
The surface acidity was estimated by mixing 0.20 g of MPAC with
25 cm3 of 0.05 M NaOH solution in a closed flask, and agitated for
48 h at room temperature. The suspension was then decanted, and
the remaining NaOH was determined by titration with 0.05 M HCl
solution. The surface basicity was obtained by a similar procedure,
where 0.05 M HCl solution was contacted with 0.20 g of MPAC and
(1)
the titration solution was 0.05 M NaOH.
The determination of pHpzc was conducted by adjusting pH of
50 cm3 0.01 M NaCl solution to a value between 2 and 12. 0.15 g of
MPAC was added and the final pH was measured after 48 h under
agitation. The pHpzc is the point where pHinitial − pHfinal = 0.
3. Results and discussion
3.1. Preparation of MPAC
3.1.1. Effect of chemical impregnation ratio
Effect of chemical impregnation ratio (IR) on the carbon
yield and adsorption equilibrium of MB was investigated at the
microwave input power of 360 W and irradiation time of 4 min
(Fig. 2a). It can be observed that augmenting IR from 0.25 to 1.25
showed an enhancement of carbon yield from 76.03 to 88.10%.
Beyond the value, subsequent increase in IR illustrated a grad-
ual decrease in carbon yield. Similarly, increasing IR from 0.25 to
1.25 indicated an increase of adsorption uptake from 150.30 to
217.13 mg/g, and then it steadily decreased.
It was presumed that K2 CO3 activation involved the reduction
of K2 CO3 under inert condition to form K, K2 O, CO and CO2 . The
potassium compound formed during the activation step would dif-
fuse into the internal structure of char matrix, widens the existing
pores and creates new porosities, in according with the reactions
[8,9]:
K2 CO3 + 2C → 2K + 3CO (3)
(2) K2 CO3 → K2 O + CO2 (4)
K2 O + 2C → 2K + CO (5)
Therefore, by increasing the ratio of K2 CO3 /char, the activation
process would be strengthened. Correspondingly, the adsorption
uptake was further enhanced. Beyond the optimum value, the
excess of K2 CO3 and metallic potassium left in the carbon sur-
face caused blocking of the pores leading to a dramatic decrease
of accessible area. Additionally, the pores would be widened low-
ering the adsorption uptake and carbon yield. Therefore, the IR was
68 K.Y. Foo, B.H. Hameed / Chemical Engineering Journal 180 (2012) 66–74
Fig. 2. Effects of (a) chemical impregnation ratio (preparation conditions: microwave power = 360 W; radiation time = 4 min), (b) microwave power (preparation conditions:
chemical impregnation ratio = 1.25; radiation time = 4 min) and (c) radiation time (preparation conditions: chemical impregnation ratio = 1.25; microwave power = 600 W)
on the carbon yield and adsorption capacity.
proposed at 1.25 for effective activation at minimum consumption
of activating agent.
3.1.2. Effect of microwave power
Effect of microwave power on the adsorption uptake and car-
bon yield was evaluated at the IR of 1.25 and irradiation time of
4 min (Fig. 2b). Under low microwave power of 90 and 180 W, the
adsorption uptake and carbon yield remained almost unchanged,
indicating no continual reaction between the char and activating
agent. Enhancing microwave power from 180 to 600 W showed a
drastically increase in adsorption uptake, possibly ascribed to the
combined effect of internal and volumetric heating responsible for
the expansion of carbon structure and creation of high porosity and
larger surface area.
However, at high radiation power of 800 W, over gasification
might occur with detrimental impact to cause carbon burn and
destruction of the pore structures, thus the adsorption uptake
and yield were progressively decreased. Meanwhile, the weight
loss of carbon was found to be increased proportional to the
rising in microwave power level, mainly attributed to the degra-
dation reaction at higher thermal radiation which intensified rapid
volatilization, dehydration and decomposition.
3.1.3. Effect of radiation time
Microwave radiation time is another key factor affecting the
adsorption uptake and carbon yield. Effect of microwave radia-
tion time was conducted at the IR of 1.25 and microwave input
power of 600 W. From Fig. 2c, it is clearly revealed that prolonging
radiation time exhibited an enhancing of adsorption uptake from
151.81 mg/g to 298.32 mg/g. Obviously, prolonging time exposure
promotes an acceleration of energy, which in turn increases the
reaction rates, thus developed the porosity and rudimentary of the
pore structure.
A slight drop was observed at 6 min. The phenomenon implied
that temperature has risen dramatically as activation proceeded,
entailed the opening of the micropores and mesopores enlarg-
ing the average diameter. Besides, further heat treatment might
produce local hotspots, leading to the ablation and shrinkage
of the carbon internal channels reducing the accessibility of the
pore structure. Meanwhile, higher pyrolytic temperature promotes
C–K2 CO3 , C–K2 O and C–CO2 reactions facilitating elimination and
breaking of the C–O–C and C–C bonds thus decreased the carbon
yield [10].
3.2. Characterization of MPAC
The porous structure examination of the samples can be clearly
seen from the SEM photographs, depicted in Fig. 3. It can be clearly
seen that the surface texture of char is dense, compact, uneven,
undulating and covered by deposited tarry substances (Fig. 3a).
However, MPAC displays a well-pronounced porosity, with homo-
geneous pores distributed around the surface (Fig. 3b). Comparison
of the surface morphology verifies substantial changes occurred
due to microwave irradiation.
Nitrogen adsorption–desorption curve provides qualitative
information on the adsorption mechanism and porous structure
of the carbonaceous materials (Fig. 4). The isotherm resembles a
combination of type I and type II isotherms, in accordance with
the IUPAC classification [11]. This adsorption behavior exhibits a
combination of microporous–mesoporous structure. The surface
physical parameters obtained from the N2 adsorption isotherms
were summarized in Table 1. From the data, it is evident that the
BET surface area, Langmuir surface area and total pore volume of
 K.Y. Foo, B.H. Hameed / Chemical Engineering Journal 180 (2012) 66–74 69

Table 2
Elemental analysis of the MP derived char and MPAC.

Element Char (wt%) MPAC (wt%)

Carbon 62.66 78.45

Oxygen 28.83 16.62
Hydrogen 2.56 1.41
Nitrogen 5.79 3.37
Sulphur 0.16 0.15

MPAC were greatly improved, indicating pore development during

the activation stage. Meanwhile, the mesopores of MPAC accounts
about 45% of the total pore volume, with a well-developed porous
structure.
The chemical composition of char and MPAC was listed in
Table 2. The content of oxygen, hydrogen and nitrogen decreased
significantly after microwave treatment but the carbon level
indicated an opposite trend. This might be due to the removal
of volatiles compounds and elimination of oxygen containing
groups under microwave irradiation leaving a high purity carbon.
Whereas, the sulphur containing groups in the carbonized char
were thermally stable.
The FTIR spectrum (Fig. 5) of char indicates the peaks located
at 3436–3247, 2361, 2343, 2010, 1648, 1420, 1276, 1053, 934 and
806 cm−1 , identical to the presence of N–H, C C (alkynes), –COOH,
C N, in-plane O–H (hydroxyl), –CH2 (alkyl), C–O–C (ester, ether
and phenol), C–O (anhydrides), out-of-plane O–H and out-of-plane
C–H derivatives. Meanwhile, the surface chemistry of MPAC illus-
trated some shifts of adsorption bands, at 3436–3247, 2361, 2343,
1993, 1642, 1420, 1276 and 1053 cm−1 , corresponds to the N–H,
C C (alkynes), –COOH, C N, in-plane O–H (hydroxyl), –CH2 (alkyl),
C–O–C (ester, ether and phenol) and C–O (anhydrides) functional-
ities.
The surface acidity and basicity is an important criterion inter-
preting the surface chemistry of the carbon adsorbents [12]. MSAC
Fig. 3. SEM micrograph (500×) of the MP derived char (a) and MPAC (b). showed an acidic property, with a surface acidity of 2.63 mmol/g
and 1.08 mmol/g as surface basicity. From the result, it is well estab-
400 lished there were greater amounts of oxygen-containing groups
(mainly carboxylic, anhydrides, lactones and phenols) than oxygen-
Quantity Adsorbed (cm³/g STP)

free Lewis sites, carbonyls, pyrone and chromene type structures at

375 the edge of the carbon layers. The surface chemistry of MPAC was
further justified by determination of zero point of charge (pHZPC ),
the point at which the net charge of adsorbent is zero. In the present
350 work, the pHZPC was found to be 6.25.

325 3.3. Effects of initial concentration, contact time and solution pH

on the adsorption equilibrium

300 Generally, adsorption uptake capacity and dye removal effi-

0 0.2 0.4 0.6 0.8 1 ciency increased with prolonging the contact time. The curve
Relative Pressure (P/Po) adsorption uptake capacity, qt as a function of time, t in the ini-
tial concentration range of 50–500 mg/L was displayed in Fig. 6.
Fig. 4. Nitrogen adsorption–desorption curve of MPAC. Initially, the amount of dye adsorbed onto the carbon surface
increased rapidly, and with a lapse of time, the process slowed
Table 1 down and reached a plateau. The initial concentration provides an
Porosity structure of the MP derived char and MPAC. essential driving force to overcome the mass transfer resistance
Properties Char MPAC between the aqueous phase and the solid medium [13]. In the
present study, the adsorption equilibrium, qe increased from 50.49
BET surface area (m2 /g) 9.73 1098.75
Micropore surface area (m2 /g) 5.12 626.16 to 384.18 mg/g with an increase in initial concentration from 50 to
External surface area (m2 /g) 4.61 472.59 500 mg/L. Conversely, there was a reverse relationship between the
Langmuir surface area (m2 /g) 16.62 1662.52 equilibrium concentrations with the initial MB concentrations. The
Total pore volume (cm3 /g) 0.012 0.611 equilibrium concentration, Ce obtained at 50, 100, 150, 200, 300,
Micropore volume (cm3 /g) 0.002 0.334
Mesopore volume (cm3 /g) 0.010 0.277
400 and 500 mg/L was 0.12, 0.31, 1.22, 3.85, 34.11 and 120.34 mg/L,
Average pore size (Å) 28.56 22.25 respectively, indicating high percent removal of MB even at high
initial concentrations.
70 K.Y. Foo, B.H. Hameed / Chemical Engineering Journal 180 (2012) 66–74

22.0
Char

21.0

2010
20.0 2361
1648
2343 1276
19.0 806

1420 934
%T

18.0 3436
MPAC

3247
17.0
1053
1993
2361
16.0 2343 1642
1276

1420
15.0 3436
3247

1053
14.0
4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400
Wave number cm-1

Fig. 5. FTIR spectra of the MP derived char and MPAC.

Solution pH affects adsorption by regulating the adsorbents sur-
face charge as well as degree of ionization of adsorbates present
in the solution [14]. The adsorption behavior of MB over a broad
pH range of 2–12 was shown in Fig. 7. It was found that increas-
ing solution pH serves to increase the adsorption capacity, with
a significant enhancement as the pH increased from 6 to 8. This
can be attributed to the protonation of MB in the acidic medium,
and presence of excess H+ ions competing with dye cations for
the adsorption sites. At higher solution pH, MPAC may get nega-
tively charged and the formation of electric double layer changes
its polarity, consequently the dye uptake increases [15]. Effect of
pH can be described on the basis of zero point of charge (pHZPC ).
The experimental determination of pHZPC of MPAC was identified to
be 6.25. Activated carbon adsorbent will react as a positive surface
when solution pH < pHZPC , and as a negative surface when solution
pH > pHZPC . Therefore, for pH values above 6.25, the negative charge
density of MPAC increased which favors the adsorption of cationic
dye.
3.4. Adsorption isotherm
In the endeavor to explore novel adsorbents in accessing an
ideal adsorption system, it is important to establish the most
appropriate correlation for the equilibrium curves. The equation
parameters of these equilibrium models reveal the sorption mecha-
nism, surface properties and affinity of the carbonaceous adsorbent.
Due to the inherent bias resulting from linearization, alternative
isotherm parameter sets were determined by non-linear regression
[16].
For non-linear regression, a trial and error procedure, which
is applicable to computer operation, was developed to determine
the isotherm parameters by maximizing the respective coefficient
of determination between experimental data and the isotherms.
This provides a mathematically rigorous method for determining
isotherm parameters using the original form of isotherm equa-
tion. Thus, in this study the nonlinear Langmuir [17], Freundlich
[18], Temkin [19] and Dubinin–Radushkevich [20] isotherm models
were established to analyze the equilibrium data:
Q0 KL Ce
qe = (6)
1 + KL Ce
1/n
qe = KF Ce (7)
qe = B ln(ACe ) (8)
400

390
400
380

500 mg/L 370

300
qe (mg/g)

400 mg/L

300 mg/L
360
qt (mg/g)

200 200 mg/L 350

100 mg/L

50 mg/L
340
100
330

320
0 0 2 4 6 8 10 12 14
0 5 10 15 20 25 30 pH
Time (h)
Fig. 7. Effect of pH on the adsorption of MB onto MPAC (initial concentra-
Fig. 6. Adsorption equilibrium of the adsorption of MB onto MPAC at 30 ◦ C. tion = 500 mg/L; temperature = at 30 ◦ C).
 K.Y. Foo, B.H. Hameed / Chemical Engineering Journal 180 (2012) 66–74 71

Table 3
Isotherm parameters for the adsorption of MB onto MPAC at 30, 40 and 50 ◦ C.

Isotherms Temperature (◦ C) Constants

Qo (mg/g) KL (L/mg) R2

Langmuir 30 379.63 1.04 0.996

40 357.14 1.02 0.999
50 328.18 1.01 0.999

Isotherms Temperature (◦ C) Constants

n KF (mg/g) (L/mg)1/n R2

Freundlich 30 5.41 175.28 0.849

40 5.73 167.92 0.816
50 6.10 153.98 0.808

Isotherms Temperature (◦ C) Constants

A (L/g) B R2

Temkin 30 35.21 50.35 0.948

40 36.86 46.55 0.917
50 42.70 40.30 0.906

Isotherms Temperature (◦ C) Constants

qs (mg/g) E (J/mol) R2

Dubinin–Radushkevich 30 341.01 2124.30 0.902

40 331.66 1990.47 0.937
50 303.70 1965.70 0.942

qe = qs exp(−kad ε2 ) (9)
where Q0 (mg/g) and KL (L/g) are Langmuir constants related to
adsorption capacity and free energy of adsorption, respectively, and
KF (mg/g) (L/mg)1/n and 1/n are the Freundlich adsorption constant,
and a measure of the adsorption intensity. B = RT/b, where b, A, R
and T are the Temkin constant related to heat of sorption (J/mol),
equilibrium binding constant (L/g), gas constant (8.314 J/mol K) and
absolute temperature (K). Meanwhile, qs (mg/g) is denoted as the
theoretical isotherm saturation capacity, and Polanyi potential, ε
can be correlated as:
 1
 adsorption processes which in turn governs mass transfer and the
ε = RT ln 1 + (10)
Ce
The constant BDR gives the mean free energy, E (J/mol) of sorption
per molecule of the adsorbate when it is transferred to the surface
of solid from infinity in the solution, and can be computed by the
relationship:
 
1 ln
E=  (11)
2BDR
The detailed parameters of different forms of isotherm equations
at the temperatures 30, 40 and 50 ◦ C were listed in Table 3.
It was observed that the equilibrium data was getting valid
for Langmuir isotherm model, while Freundlich, Temkin and
Dubinin–Radushkevich isotherms do not much well represent
the experimental adsorption data. The applicability of Langmuir
isotherm model suggests that the adsorption takes place on homo-
geneous sites within the adsorption site; with each molecule
possess constant enthalpies and sorption activation energy. The
results also demonstrate no interaction and transmigration of dyes
in the plane of the neighboring surface.
A comparison of the adsorption capacity of MB with the
from the char surface widening the porosity in the original carbon
network. Moreover, microwave heating (internal and volumetric
heating) has assisted the penetration of activating agent within
the char matrix, which created a more orderly porous structure
by opening of previously inaccessible pores and formation of new
pores [32].
3.5. Adsorption kinetics
Adsorption kinetic describes the controlling mechanism of
equilibrium time [33]. The experimental data of MB adsorption
onto MPAC at different time intervals were examined with pseudo-
first-order and pseudo second-order models, using the plots of
ln(qe − qt ) against t and t/qt versus t, respectively. The first-order
rate expression of Lagergren [34] based on solid capacity is derived
in the form of:
 q  k1
e
= t (12)
qe − qt 2.303
where qe and qt (mg/g) are the amounts of adsorbate adsorbed
at equilibrium and at any time, t (h), respectively and k1 (1/h) is
the adsorption rate constant. Contrary to other model, pseudo-
second-order equation [35] predicts the behavior over the whole
time of adsorption, with chemisorption being the rate controlling
step given by:
1 1
= + k2 t (13)
(qe − qt ) qe
where k2 is the pseudo-second-order rate constant (g/mg min). The
corresponding results were shown in Table 5. The suitability of
the kinetic model to describe the adsorption process was further
validated by the normalized standard deviation, Äq (%) defined as:

literature [21–31], under optimum activation conditions was sum- 2

[(qexp − qcal )/qexp ]
marized in Table 4. It can be concluded that the adsorption capacity q = 100 (14)
of the activated carbon prepared in this work was comparative with n−1
the previous studies. The activation time due to present work is where n is the number of data points, qexp (mg/g) and qcal (mg/g) are
much shorter owing to the thermal efficiency of microwave heat- the experimental and calculated adsorption capacity, respectively.
ing system. This irradiation has promoted the release of volatiles Pseudo-second-order kinetic model yielded the best fit, with the
72 K.Y. Foo, B.H. Hameed / Chemical Engineering Journal 180 (2012) 66–74

Table 4
Comparison adsorption capacities of various activated carbons for MB.

Precursor Activation method Activating agent Activation time (min) Adsorption capacity (mg/g) Reference

Mangosteen peel Microwave heating K2 CO3 5 379.63 Present study

Coffee press cake Microwave heating – 6 0.14 [21]
Bamboo Microwave heating H3 PO4 10 286.10 [22]
Cotton stalk Microwave heating KOH 10 294.12 [23]
Spent catalysts of vinyl synthesis Microwave heating Steam 40 285.00 [24]
Pine wood powder Microwave heating ZnCl2 10 200.00 [25]
Posidonia oceanica (L.) dead leaves Conventional heating ZnCl2 120 285.70 [26]
Rice straw Conventional heating (NH4 )2 HPO4 120 129.50 [27]
Walnut shell Conventional heating ZnCl2 60 315.00 [28]
Durian peel Conventional heating CO2 60 284.00 [29]
Sludge Conventional heating Steam 40 263.16 [30]
Norit SA3 (Commercial grade powdered AC) – 91.00 [31]
Nuchar WWH (Commercial grade granular AC) – 21.50 [31]

lowest Äq values which ranged between 0.08 and 13.67% for initial 500
MB concentrations ranging from 50 to 500 mg/L. Besides, the cor-
kp1 kp2 kp3
relation coefficient values for the second-order kinetic model were 400 500 mg/L
almost equal to unity for all initial MB concentrations. This sug-
400 mg/L
gested that the overall rate of the adsorption process was controlled
300 300 mg/L
by chemisorption which involved valency forces through sharing

qt (mg/g)
200 mg/L
or exchange of electrons between the adsorbent and adsorbate.
100 mg/L
200
50 mg/L
3.6. Adsorption mechanism
100
To examine the practical applications of adsorption system, the
Weber and Morris intraparticle diffusion model [36], derived from
0
the Fick’s second diffusion law was applied to analyze the kinetic 0 1 2 3 4 5 6
data:
t0.5 (h0.5)
qt = kpi t 0.5 + Ci (15) (a)

3
where kpi (mg/g h0.5 )
is the diffusion rate constant and Ci gives an
idea about the thickness of the boundary layer. If intraparticle dif-
fusion occurs, then qt versus t0.5 will be linear, and intraparticle 2.5
diffusion is the sole rate limiting step if the plot passes through the
origin. 2 500 mg/L
Refer to the intraparticle diffusion plot as depicted in Fig. 8a, 400 mg/L
the first, sharper portion is attributed to the diffusion of adsorbate 300 mg/L
1.5
through solution to the external surface of adsorbent (external sur- 200 mg/L
face adsorption). The second portion describes the gradual layer 100 mg/L
Bt

adsorption stage, where intraparticle diffusion is rate limiting and 1

50 mg/L
the third portion is the final equilibrium stage where intraparti-
cle diffusion starts to slow down due to extremely low adsorbate 0.5
concentrations left in the solution. From Fig. 8a, it is revealed that
the third region did not exist for initial concentrations lower than 0
200 mg/L, as the equilibrium has been attained within the first 0 0.5 1 1.5 2 2.5 3 3.5 4
60 min. Moreover, the linear plots of the second and third region
Time (h)
did not pass through the origin, mainly ascribed to the deviation (b)
in mass transfer rate in the initial and final stages of adsorption,
which indicated that intraparticle diffusion was not the only rate Fig. 8. Plots of intraparticle diffusion (a) and Boyd (b) models for the adsorption of
limiting step [37]. The kinetic data were further analyzed using the MB onto MPAC at 30 ◦ C.

Boyd model [38] expressed as:

Bt = −0.4977 − ln(1 − F) (16)

Table 5
Kinetic models parameters for the adsorption of MB onto MPAC at different initial MB concentrations at 30 ◦ C.

C0 (mg/L) qe, exp (mg/g) Pseudo-first-order Pseudo-second-order

k1 (1/h) qe, calc (mg/g) R2 q (%) k2 (g/mg min) qe, calc (mg/g) R2 q (%)

50 50.49 3.308 63.16 0.955 25.08 0.095 55.05 0.999 9.03

100 101.33 1.400 49.40 0.857 51.25 0.096 101.79 0.999 0.54
200 204.23 1.580 73.00 0.799 64.26 0.096 200.95 1.000 1.60
300 278.51 0.936 180.78 0.844 35.09 0.020 278.72 1.000 0.08
400 366.86 0.838 255.67 0.896 30.31 0.010 343.86 0.999 6.27
500 384.18 0.672 271.67 0.862 29.28 0.011 331.66 0.997 13.67
 K.Y. Foo, B.H. Hameed / Chemical Engineering Journal 180 (2012) 66–74
Table 6
Thermodynamic parameters for the adsorption of MB onto MPAC.
H◦ (kJ/mol) S◦ (J/mol K) G◦ (kJ/mol)
303 K 313 K 323 K
−1.240 3.770 −0.097 −0.063 −0.021
which Bt is the mathematical function of F and F represents the
fraction of solute adsorbed at time, t (h), given by:
qt
F= (17)
qe
Pore diffusion is the rate-limiting step if the plot Bt versus t passes
through the origin. Conversely, the adsorption process is film dif-
fusion controlled. As illustrated from the curve as shown in Fig. 8b,
the linear curves did not pass through the origin, and the points
were scattered around the plots, thus ascertained that the adsorp-
tion of MB onto MPAC was governed by film diffusion controlled
mechanism.
3.7. Thermodynamic modeling
The concept of thermodynamic assumes that in an isolated sys-
tem where energy cannot be gained or lost, the entropy change
is the driving force. Thus, in the present study, thermodynamic
parameters, Gibbs free energy (G), enthalpy (H) and entropy
(S) change were determined using the equations [39,40] below:
S H
ln KL = − (18)
R RT
G = −RT ln KL (19)
where R (8.314 J/mol K) is the universal gas constant, T (K) is
the absolute solution temperature and KL (L/mg) is the Langmuir
isotherm constant. The values of H and S were estimated from
the slope and intercept of the van’t Hoff plot of ln KL versus 1/T. The
calculated values were presented in Table 6.
Positive S showed the affinity of MPAC for MB and increasing
randomness at the solid–solution interface with some structural
changes in the adsorbates and adsorbents during the adsorption
process. Negative G indicated the feasibility and spontaneous
nature of adsorption with high preference of MB onto MPAC while
negative value of H represents exothermic nature of the adsorp-
tion interaction. Increasing temperature leads to the decrease of
dye adsorption due to the enhancement of desorption step in the
sorption mechanism. This phenomenon might due to weakening
of adsorptive forces between the active sites of MPAC and the
dye species, and also between the adjacent dye molecules on the
adsorbed phase [41].
4. Conclusion
It appears that mangosteen peel may serve as a potential suit-
able biomass source for the manufacture of activated carbon with
a well-developed porous texture. This study has attempted a new
path for multi-purpose utilization of the biomass waste of mangos-
teen peel. MPAC prepared by microwave assisted K2 CO3 activation
attained maximum BET surface area as 1098.75 m2 /g, total pore vol-
ume as 0.611 cm3 /g and a high contribution of mesopores as 45% at
IR of 1.25, microwave power of 600 W and irradiation time of 5 min.
Equilibrium data could be favorably described by the Langmuir
isotherm and pseudo-second-order models.
Acknowledgements
The authors acknowledge the financial support provided by Uni-
versiti Sains Malaysia under the Research University (RU) Scheme
73
(Project No. 1001/PJKIMIA/814072) and RU-PRGS grant scheme
(Project 465 No. 8043030).
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