Chemical Engineering Journal 184 (2012) 238247

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Chemical Engineering Journal
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Hexavalent chromium removal from aqueous medium by activated carbon
prepared from peanut shell: Adsorption kinetics, equilibrium and
thermodynamic studies
Z.A. AL-Othman, R. Ali

, Mu. Naushad

Department of Chemistry, College of Science, Building-5, King Saud University, Riyadh, Saudi Arabia
a r t i c l e i n f o
Article history:
Received 21 November 2011
Received in revised form9 January 2012
Accepted 9 January 2012
Keywords:
Activated carbon
Cr(VI) adsorption
Peanut shell
Isotherms model
Lagergren model
Thermodynamics
a b s t r a c t
Activated carbon was prepared from peanut shell by chemical activation with KOH. Unoxidized activated
carbon was prepared in nitrogen atmosphere which was then heated in air at a desired temperature
to get oxidized activated carbon. The prepared carbons were characterized for surface area and pore
volume and utilized for the removal of Cr(VI) from aqueous solution. The effects of pH, contact time,
initial concentration of adsorbate and temperature on adsorption of Cr(VI) were investigated. Adsorption
kinetics of Cr(VI) was analyzed by pseudo rst order, pseudo second order and intraparticle diffusion
kinetic models. Results showed that Cr(VI) adsorption on both oxidized and unoxidized samples followed
the rst and second order kinetics models most appropriately. Isotherm data were treated according to
Langmuir and Freundlich models. The results showed that both Langmuir and Freundlich models tted
the data reasonably but the Langmuir adsorption isotherm model tted better in the temperature range
studied. The adsorption capacity was found to increase with temperature, showed endothermic nature
of Cr(VI) adsorption. The thermodynamic parameters, such as Gibbs free energy change (G

), standard
enthalpy change (H

), standard entropy change (S

) were evaluated. The value of G

was found
negative for the adsorption of Cr(VI) which conrmed the feasibility and spontaneity of the adsorption
process.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Industrial progress has made life more comfortable and easy.
But at the same time the natural environment had suffered from
the unfavorable effects of pollution. Heavy metals are unpleasantly
affecting our ecosystemdue to their toxicological andphysiological
effects inenvironment. Thesemetals, if present beyondcertaincon-
centration can be a serious health hazard which can leads to many
disorders in normal functioning of human beings and animals [1].
The main reason for heavy metal pollution is due to metal-plating
facilities, battery manufacturing processes, mining and metallurgi-
cal engineering, dyeing operations, electroplating, nuclear power
plants, aerospace industries, the production of paints and pigments
and glass production industries [2]. The main heavy metals which
cause metal ion pollution are Th, Cd, Pb, Cr, As, Hg, Cu and Ni.
Unlike most organic pollutants, heavy metals are generally refrac-
tory and cannot be degraded or readily detoxied biologically [2].
Chromium is one of the most toxic pollutants which cause severe

Corresponding authors. Tel.: +966 560467434.

E-mail addresses: rahmat chemistpk@yahoo.com(R. Ali),
shad81@rediffmail.com(Mu. Naushad).
environmental and public health problems. When accumulated at
high levels, chromium can generate serious problems and when
concentration reaches 0.1mg/g body weight, it can ultimately
become lethal [3]. The most common forms of chromiumare Cr(0),
Cr(III), and Cr(VI). Hexavalent formis more toxic than trivalent and
requires more concern. Strong exposure to Cr(VI) causes cancer in
the digestive tract and lungs and may cause epigastric pain, nausea,
vomiting, severe diarrhea and hemorrhage [4]. In aqueous solu-
tion, Cr(VI) exists in the form viz. chromate CrO
4
2
, dichromate
Cr
2
O
7
2
and hydrogen chromate HCrO
4
2
. CrO
4
2
is predomi-
nant in basic solutions, H
2
CrO
4
is predominant at pH<1 while
HCrO
4
2
and Cr
2
O
7
2
are predominant at pH 26. The removal
of toxic metals from waste water has been achieved by several
processes such as ion exchange [5], sedimentation [6], electro-
chemical processes [7,8], cementation [9], biological operations
[10], coagulation/occulation [11], ltration and membrane pro-
cesses [12,13], chemical precipitation, adsorption [14] and solvent
extraction [15,16]. Most of these methods suffer from drawbacks
like high capital and operational cost and there are problems in
disposal of residual metal sludge [17]. In contrast, the adsorption
technique has become one of the most preferred methods for the
removal of heavy metals due to its high efciency and low cost.
Many agricultural wastes had directly been used as sorbents for
1385-8947/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2012.01.048
Z.A. AL-Othman et al. / Chemical Engineering Journal 184 (2012) 238247 239
heavy metal adsorption fromwastewater which included soybean
hull [18], olive cake [19], wheat straw[20], maize cob[21], rice husk
[22], barley straw[23], bagasse pith [24], coconut husk [25], cocoa
shells [26], tea leaves [27], orange peel and banana peel [28]. Acti-
vatedcarbons aremoreeffectiveintheremoval of heavymetals due
to some specic characteristics that enhance the use of activated
carbon for the removal of contaminants including heavy metals
fromwater supplies and wastewater [29]. Many studies have used
different type of activated carbon to remove Cr(VI) by adsorption.
Coconut shell activated carbon [30], wood and dust coal activated
carbons [31], hazelnut activated carbon [32], sawdust and used
tyre activated carbon [33] were used for Cr(VI) uptake. Commod-
ity crops such as peanuts generate considerable quantities of shells
each year which have little or no value. Peanut shells are low in
density and high in volume and are used in animal feed or burned
for energy. China ranks rst inpeanut productioninthe worldanda
potential of 4.5 million tons of peanut shells are produced annually
[34]. North Carolina currently ranks fourth in peanut production,
producing 95.2 thousand metric tons or 6.3% of the United States
production [35]. This represents a potential of 26 thousand met-
ric tons of peanut shells produced each year that have little value.
This leads to a need to convert these by-products to useful, value
added products, such as activated carbons. There have been several
reports that peanut shells convertedinto activatedcarbonandused
to absorb various metal ions and organic compounds [3639].
The present paper is concerned with the synthesis of acti-
vated carbons derived from peanut shells by chemical activation
with KOH and the removal of hexavalent chromiumfromaqueous
solution. The kinetics, isotherms and thermodynamics about the
sorption of Cr(VI) on the prepared samples were studied. The inu-
ence of several operating parameters, such as pH, contact time and
initial concentrations of adsorbate onthe adsorptioncapacity, were
also investigated.
2. Experimental
2.1. Materials and methods
All AR grade chemicals were used. K
2
Cr
2
O
7
, NaOH, HCl and
H
2
SO
4
were purchased from SigmaAldrich, Germany. A stock
solution of 1000mg/L of Cr(VI) was prepared from potassium
dichromate salt. The working solutions of desired concentrations
were prepared by appropriate dilution of the stock solutions. The
initial pH of the test solutions was adjusted to the desired value by
using dilute solutions of HCl and NaOH.
2.2. Equipments
pH measurement were made with a pH meter (model 744,
Metrohm) equippedwitha combinedglass-saturatedcalomel elec-
trode calibrated with buffer solutions of pH 4.0, 7.0 and 9.2. The
nitrogen adsorption isotherms were determined with a quan-
tachrome NOVA 2200e, surface area and pore size analyzer. The
carbonsamples weredriedinprogramcontroller NeberthermC-19,
model N 7/4 W Germany. Absorbance measurements were made
with a UVvisible spectrophotometer model UV-160A Shimadzu
Japan equipped with a 1cm path length quartz cell. Agitation of
the systemwas carried out on a thermostat-cum-shaking assembly
(model MSW 275).
2.3. Adsorbents development and characterization
The raw peanut shells for the production of activated carbons
were collected from local market in Riyadh (City in Saudi Ara-
bia). Peanut shells were rst washed with single distilled water
to remove dust, dried at 110

C for 24h and then crushed to the

desired particle size. The crushed peanut shells were mixed with
20% KOH solution in a ratio of 1:1 by mass and allowed to sock for
24h at roomtemperature. Carbonization of the impregnated mate-
rial was carried out in a horizontal tube furnace. Samples (25g)
were placed into the reactor and heated fromroomtemperature to
170

C (5

C) for 1h under nitrogen ow(owrate 100mL min

1
)
and then at 450

C (5

C) for 1h at the same owrate of nitrogen.

At the end of activation period, the samples were cooled down to
roomtemperature in nitrogen ow. Half of the amount of samples
obtained under the ow of nitrogen only, were oxidized by using
breathing grade air (ow rate 100mL min
1
) at 450

C for 1h and
then cooled. The products obtained, was rinsed with double dis-
tilled water (DDW) in a soxhlet extractor at 100

C until the pH of
the rinse water was neutral and nally dried at 110

C for 24h. The

prepared samples were cooled in desiccators and sieved to desired
particle size (170400 mesh). These activatedcarbonsamples were
classed as oxidized and unoxidized.
BET surface area, pore volumes, micropore surface area and
average pore diameter were determined by nitrogen adsorption
at 77K, using Quanta Chrome NOVA 2200e, surface area and
pore size analyzer. Before adsorption measurements, respective
samples were degassed at 150

C for 2h at a nal pressure of

133.3210
4
Pa. The BET surface area was calculated by the
Brunauer, Emmett, and Teller (BET) method using the adsorption
isotherms [40]. The cross-sectional area of nitrogen molecules was
taken 16.2

A
2
/mol. The total pore volume was determined by BJH
method[41] fromthe amount of nitrogenadsorbedat P/P
o
0.95. The
micropore volume, micropore surface area and average pore width
was determined by DubininRadushkevich (DR) equation [42]. The
mesopore volume was calculated by subtracting the micropore
volume from the total pore volume [43]. The microstructure of
the activated carbons prepared, was examined by SEM(JEOL-JSM-
5910, Japan). The elemental analysis of the prepared samples was
carried out by Energy Dispersive Spectrometer (EDS), Inca Oxford.
2.4. Adsorption procedure
The adsorption capability of the prepared activated carbons
toward Cr(VI) was investigated using their aqueous solutions. The
stock solution (1000mg/L) was diluted as required to obtain stan-
dardsolutions of concentrationranging from10to100mg/L. All the
adsorptionexperiments were performed by the batchtechnique by
using 400 mesh average particle size of carbons for all the adsorp-
tion studies. The carbon samples were dried for 24h at 110

C prior
to analysis.
The amount of Cr(VI) per unit weight of adsorbent, q
e
(mg/g)
was calculated by the following equation:
q
e
=
V(C
i
C
e
)
W 1000
(1)
where V is the volume of Cr(VI) solution in litre, C
i
and C
e
are the
initial and nal concentrations (mg/L) of Cr(VI) in solution, respec-
tively, and Wis the weight (g) of adsorbent.
2.5. Kinetic study
Pseudo-rst order, pseudo-second order and intraparticle dif-
fusion rate equations have been used for modeling the kinetics
of Cr(VI) adsorption. The batch technique was employed to study
the effect of contact time and adsorbate concentration for Cr(VI)
adsorption. For this purpose, a number of 100mL air tight asks
containing 40mL solution of desired concentrations of Cr(VI), were
agitatedina thermostat shaker at 200rpm. 0.1g of activatedcarbon
was added to each ask at the desired temperature. The solution
of the specied ask was separated from carbon at different time
interval and analyzed for the uptake of Cr(VI).
240 Z.A. AL-Othman et al. / Chemical Engineering Journal 184 (2012) 238247
Table 1
pH and elemental analysis of KOH treated oxidized and unoxidized carbons.
Parameters Oxidized Unoxidized
pH 9.68 8.96
PZC 9.12 8.37
C (weight %) 80.16 77.32
O (weight % 22.11 24.12
K (weight % 1.76 1.98
2.6. Batch equilibriumstudies
Batch adsorption studies were performed in a series of 100mL
conical, airtight Pyrex glass asks. Each ask was lled with
40mL solution of Cr(VI) of desired concentration and adjusted to
the desired pH and temperature. A known amount of activated
carbon was added to each ask and kept in isothermal shaker
(25

C) at 200rpmuntil equilibriumwas reached. Preliminary tests

showed that after 10h, Cr(VI) concentration remain unchanged.
The allowed contact time was 24h to reach the equilibrium. After
this period, the solution was ltered to remove the carbon particles
andanalyzedspectrophotometrically at the corresponding
max
for
the concentration of Cr(VI) remained in the solution.
The effect of pH on the adsorption of Cr(VI) over a pH range of
210 was investigated. Cr(VI) adsorption was also studied in con-
centration range of 10100mg/L at different temperatures (20

C,
30

C, 40

C) to elucidate the effect of temperature and adsorption

thermodynamic parameters. The amount of Cr(VI) adsorbed was
calculated by the above method (Eq. (1)).
2.7. Analysis of Cr(VI)
The analysis of Cr(VI) was carried out calorimetrically.
Absorbance values were obtained at the wavelength for maximum
absorbance (
max
=540nm) by making a purple-violet colored
complex of Cr(VI) with 1,5-diphenylcarbazide in the acidic condi-
tion which was converted into concentration data using calibration
relation pre-determined at the wavelength of interest [44].
3. Results and discussion
3.1. Characterization of prepared samples
Information about the physical properties of adsorbent such as
carbon content, pH and pore structure is essential procedure prior
to adsorption process. The various characteristics of activated car-
bon prepared frompeanut shells by chemical activation with KOH
and carbonization at 450

C under inert and air atmosphere are

listedinTables 1and2. As showninTable 1, the oxidizedcarbonhas
higher pH(9.68) and carbon (weight percent, 80.16) than the unox-
idizedcarbon(pH8.96 andcarbonweight percent, 77.32). Thus, the
oxidized carbon was more basic than unoxidized one. The specic
surface area (S
BET
) and micropore volume (V
DR
) of the prepared
carbon samples was evaluated by applying the Brunauer, Emmett
and Teller (BET) and DubininRadushkevich equations, respec-
tively. It can be observed fromTable 2 that the specic surface area
(S
BET
), micropore surface area (S
DR
), micropore volume (V
micro
)
Fig. 1. (a) Scanning electron micrograph of KOH treated oxidized carbon. (b) Scan-
ning electron micrograph of KOH treated unoxidized carbon.
and mesopore volume (V
meso
) of oxidized sample was greater than
the unoxidized sample which may be due to the air oxidation of
the impregnated material during carbonization that has facilitated
the evolution of volatile matter from the precursor material and
thereby enhanced the porosity in the carbon texture. It is also
clear fromTable 2 that both oxidized and unoxidized carbons were
mesoporous as the mesopore volume of oxidized carbon occupied
74% of the total pore volume while the unoxidized carbon occu-
pied 75% of the total pore volume. According to the International
Union of Pure and Applied Chemistry (IUPAC), the pore structures
of activated carbons are classied into three groups as microp-
ore (2nm), mesopore (250nm) and macropore (50nm). Both
type of activated carbons contained micropores and mesopores but
the mesopore volume was larger than the micropore volume. The
oxidationduringcarbonizationhadaconsiderableeffect onthetex-
tural properties of carbonsamples. The preparedsamples were also
characterized for their efciency for Cr(VI) adsorption and showed
Table 2
Physical properties of oxidized and unoxidized activated carbon samples.
Sample Surface area
(SBET), m
2
/g
Average pore
width (DR) ()
Micropore
volume (DR)
(cc/g)
Micropore
surface area
(DR) (m
2
/g)
Pore diameter
(BJH) ()
Surface area
(BJH) (m
2
/g)
Pore volume
(BJH) (cc/g)
Mesopore
volume (cc/g)
Properties
Oxidized 95.51 141.50 0.09 180.16 115.10 133.31 0.35 0.26
Unoxidized 88.85 142.84 0.08 179.34 114.27 129.89 0.33 0.25
Z.A. AL-Othman et al. / Chemical Engineering Journal 184 (2012) 238247 241
0
5
10
15
20
25
30
35
40
45
0 2 4 6 8 10 12
%

R
e
m
o
v
a
l
pHi
Oxidized
Un-oxidized
Fig. 2. Effect of pH on Cr(VI) adsorption for oxidized and unoxidized carbons at
25

C.
that the oxidized carbon had a higher adsorption capacity than the
unoxidized carbon.
3.2. SEMimages
Scanning electron micrographs (SEM) of the prepared carbon
samples, are shown in Fig. 1(a) and (b). It is clear from the SEM
gures that the external surfaces of both samples were rough and
contained pores of different size and shapes. The oxidized sample
surface had narrow elongated pores while the unoxidized sam-
ple had wide pores which showed that air oxidation resulted in
activated carbon with well developed porosity. The micrographs
showed that the cavities on the surfaces of the carbon samples
resulted from the evaporation of the KOH during carbonization,
leaving the space open that was previously occupied by KOH.
During impregnation, the molecules of the chemical impregnat-
ing agent diffused into the texture of the lignocellulosic material.
On carbonization at the desired temperature, the chemical impreg-
nating agent evaporated and made the remaining carbon texture
porous. The major elements present in both samples were car-
bon and oxygen with a small amount of potassium. Table 1 shows
that the percentage of carbon in oxidized sample was greater than
the unoxidized sample while the unoxidized sample had a higher
percentage of oxygen.
3.3. Effect of pH
Activated carbons are species with amphoteric character, thus
depend on the pHof the solution. Their surface might be positively
charged or negatively charged. The pore wall of activated carbon
contained a large number of surface functional groups. The pH
dependence of Cr(VI) adsorption can largely be related to the type
and ionic state of these functional groups and also on the adsorbate
chemistry in the solution. The solution pH is one of the important
parameter for the removal of heavy metals fromaqueous solution
because it affects the solubility of adsorbates, concentration of the
counter ions on the functional groups of the adsorbent and the
degree of ionization of the adsorbate during reaction [45]. Cr(VI)
removal was studied as a function of pH over a pH range of 210
on oxidized and unoxidized samples at the initial concentration of
50mg/L as shown in Fig. 2. It is clear fromFig. 2 that the prepared
activated carbons were more active in the acidic range and max-
imum adsorption occurred at pH 2.0. There was a sharp decrease
in the sorption capacity when pH was raised from 2.0 to 7.0 and
thereafter the effect became negligible. Cr(VI) may exist in three
different ionic forms (HCrO
4

, Cr
2
O
7
2
, CrO
4
2
) in aqueous solu-
tions andthe stability of these ions inaqueous systems is mainly pH
0
1
2
3
4
5
6
7
8
9
10
0 5 10 15 20 25 30 35 40 45 50
q
e

(
m
g
/
g
)
t (hrs)
30 mg/l
40 mg/l
50 mg/l
0
1
2
3
4
5
6
7
0 4 8 12 16 20 24 28 32 36 40 44 48
q
e

(
m
g
/
g
)
t (hrs)
30 mg/l
40 mg/l
50 mg/l
a
b
Fig. 3. Effect of time on Cr(VI) adsorption for (a) oxidized carbon, (b) unoxidized
carbon at 25

C.
dependent [46]. The percentage of Cr(VI) removal was higher in the
lower pHranges due to high electrostatic force of attraction. As the
number of H
+
ions increased with lowering the solution pH, which
neutralized the negative charge on adsorbent surface and thereby
increased the diffusion of chromate ions into the bulk of the adsor-
bent [50]. As reported by other workers that the dominant formof
Cr(VI) at pH up to 4.0 is HCrO
4

[46]. So, Cr(VI) was adsorbed on

the surface of activated carbon mostly in the formof HCrO
4

ions.
The decrease in the adsorption with increase in pH may be due to
the increased number of OH

ions in the bulk which retarded the

diffusion of chromate ions. The decrease in adsorption at higher pH
may be due to the competitiveness of the oxyanions of chromium.
Hence pH4.0 was taken as the optimal values for further studies of
Cr(VI) adsorption on oxidized and unoxidized carbons.
3.4. Effect of contact time and initial concentration
The amount of Cr(VI) adsorbed on oxidized and unoxidized car-
bons was studied as a function of shaking time at three different
initial concentrations (20, 30, 40mg/L) of Cr(VI) at 25

C, 0.1g of
adsorbent and desired pH. The results are given in Fig. 3(a) and (b),
respectively. It is evident fromthese gures that the adsorption of
Cr(VI) increased with increase in contact time from 10min to 7h,
thenbecame slowupto 20handthe saturationis almost reachedin
24h in case of both oxidized and unoxidized samples. The nature
and compactness of the adsorbent affected the equilibrium time.
The removal of Cr(VI) was found to be dependent on the initial
concentration. The amount of Cr(VI) adsorbed, q
e
(mg/g), increased
with increase in initial concentration. Further, the adsorption was
rapid in the early stages and then gradually decreased and became
almost constant after the equilibriumpoint. At lowconcentrations,
242 Z.A. AL-Othman et al. / Chemical Engineering Journal 184 (2012) 238247
the ratio of available surface to initial Cr(VI) concentration was
larger, so the removal became independent of initial concentra-
tions. However, in the case of higher concentrations, this ratio was
low. The percentage removal then depended upon the initial con-
centration. The curves also indicated that the adsorption led to
saturation, suggested the possible monolayer coverage of Cr(VI) on
the surface of adsorbent [51]. In the case of oxidized carbon, the
Cr(VI) removal was decreased from 46.63 to 41.56% as the Cr(VI)
concentration was increased from30 to 50mg/L and the amount of
Cr(VI) adsorbed increased from5.59 to 8.31mg/g. while in case of
unoxidized carbon, the Cr(VI) removal was decreased from 35.96
to 31.24% as the Cr(VI) concentration was increased from 30 to
50mg/L and the amount of Cr(VI) adsorbed increased from 4.31
to 6.25mg/g.
3.5. Kinetics of adsorption
Adsorption kinetics provides valuable information about the
reaction pathways and mechanism of the reactions. The kinet-
ics of Cr(VI) adsorption on oxidized and unoxidized carbons were
analyzed using pseudo rst-order [46], pseudo second-order [47]
andintraparticle diffusion[48,49] models. The conformity between
experimental data and the model predicted values was expressed
by the correlation coefcients (R
2
). A relatively high R
2
value indi-
cated that the model successfully describes the kinetics of Cr(VI)
adsorption.
3.5.1. The pseudo-rst order equation
The pseudo-rst order equation [46], is generally expressed as:
log(q
e
q
t
) = log q
e

k
1
t
2.303
(2)
where q
e
and q
t
are the amounts of Cr(VI) adsorbed (mg/g) at equi-
librium and at time t, respectively, and k
1
is the rate constant of
rst order adsorption (h
1
).
A straight lines were obtained by plotting log(q
e
q
t
) against t,
as shown in Fig. 4(a) and (b). The values of the rate constant k
1
and q
e
were obtained from the slopes and intercepts of the plots,
respectively (Table 3).
3.5.2. The pseudo second-order equation
The pseudo second-order adsorption kinetic rate equation is
expressed as [47]:
dq
t
dt
= k
2
(q
e
q
t
)
2
(3)
where q
e
and q
t
are the sorption capacity at equilibrium and time
t (mg/g), respectively, k
2
is the rate constant of the pseudo-second
order sorption (g/mgh). For the boundary conditions t =0 to t =t
and q
t
=0 to q
t
=q
t
, the integrated formof Eq. (3) will be as:
1
q
e
q
t
=
1
q
e
+k
2
t (4)
whichis the integratedrate lawfor a pseudosecond-order reaction.
Eq. (4) can be rearranged to obtain Eq. (5), which has a linear form:
t
q
t
=
1
k
2
q
2
e
+
t
q
e
(5)
The initial adsorption rate, h (mg/gh) is given as:
h = k
2
q
2
e
(6)
Furthermore, Eq. (5) can be written as:
t
q
t
=
1
h
+
t
q
e
(7)
-2.5
-2
-1.5
-1
-0.5
0
0.5
1
1.5
0 2 4 6 8 10 12 14 16 18
l
o
g

(
q
e

-
q
t
)
t (hrs)
30 mg/l
40 mg/l
50 mg/l
-2.5
-2
-1.5
-1
-0.5
0
0.5
1
1.5
0 2 4 6 8 10 12 14 16 18
l
o
g

(
q
e

-
q
t
)
t (hrs)
30 mg/l
40 mg/l
50 mg/l
-2
-1.5
-1
-0.5
0
0.5
1
0 2 4 6 8 10 12 14 16 18
l
o
g

(
q
e

-
q
t
)
t (hrs)
30 mg/l
40 mg/l
50 mg/l
a
b
Fig. 4. Lagergren rst order plot for Cr(VI) adsorption on (a) oxidized carbon, (b)
unoxidized.
0
0.5
1
1.5
2
2.5
3
3.5
4
0 2 4 6 8 10 12 14 16 18 20 22
t
/
q
t
t (hrs)
30 mg/l
40 mg/l
50 mg/l
0
0.5
1
1.5
2
2.5
3
3.5
4
0 2 4 6 8 10 12 14 16 18
t
/
q
t
t (hrs)
30 mg/l
40 mg/l
50 mg/l
a
b
Fig. 5. Pseudo secondorder kinetic plot for Cr(VI) adsorptionon(a) oxidizedcarbon,
(b) unoxidized carbon.
Z.A. AL-Othman et al. / Chemical Engineering Journal 184 (2012) 238247 243
Table 3
Kinetic constant parameters obtained for Cr(VI) adsorption on oxidize and unoxidized carbons.
Sample Pseudo-rst order Pseudo-second order Intraparticle diffusion model
C
i
(mg/l) k
1
(h
1
) R
2
k
2
(g/mgh) h (mg/gh) R
2
k
id
(mg/gh) C (mg/g) R
2
Oxidized
30 0.326 0.98 0.417 13.624 0.999 0.666 3.325 0.835
40 0.320 0.99 0.094 5.199 0.998 1.455 1.787 0.942
50 0.307 0.98 0.023 2.492 0.958 2.181 0.268 0.949
Unoxidized
30 0.215 0.96 0.875 16.313 0.999 0.372 2.985 0.859
40 0.229 0.98 0.331 9.88 0.998 0.756 2.673 0.931
50 0.219 0.98 0.127 5.279 0.993 1.263 1.567 0.957
The plots of t/q
t
versus t of Eq. (5) gave linear plots (Fig. 5(a) and
(b)). The values of q
e
and k
2
were determined fromthe slopes and
intercepts of the plots, respectively (Table 3).
3.5.3. The intraparticle diffusion model
The intraparticle diffusion model [49] is expressed as:
q
t
= k
id
t
1/2
+C (8)
where k
id
is the intraparticle diffusion rate constant (mg/gh
1/2
), C
is the intercept (mg/g).
The plot of q
t
versus t
1/2
gave straight line and the values of
k
id
were calculated from the slopes of the plots. Values of C gave
an idea about the thickness of boundary layer, i.e., the larger the
intercept, greater the contribution of the surface sorption in the
rate controlling step. The data for the adsorption of Cr(VI) on to
oxidized and unoxidized activated carbons applied to intraparticle
diffusion model is shown in Fig. 6(a) and (b) and the results are
given in Table 3.
0
1
2
3
4
5
6
7
8
9
10
4.5 4 3.5 3 2.5 2 1.5 1 0.5 0
q
t

(
m
g
/
g
)
t (h)
30 mg/l
40 mg/l
50 mg/l
0
1
2
3
4
5
6
7
4.5 4 3.5 3 2.5 2 1.5 1 0.5 0
q
t

(
m
g
/
g
)
t (h)
30 mg/l
40 mg/l
50 mg/l
a
b
Fig. 6. Intraparticle diffusion kinetic plot for Cr(VI) adsorption on (a) oxidized car-
bon, (b) unoxidized carbon.
Table 3 shows the values of the correlation coefcient (R
2
) of
pseudo-rst order, pseudo-secondorder andintraparticle diffusion
kinetic models. The results demonstrated that among these three
models, pseudo-rst order and pseudo-second order kinetic equa-
tions had high R
2
values. So, both theses kinetic models were taken
as the best t equations for the description of the mechanism of
sorption of Cr(VI) ions. Therefore, the sorption of Cr(VI) ions from
aqueous solution onto oxidized and unoxidized activated carbons
were found to follow both pseudo-rst order and pseudo-second
order kinetic equations.
3.6. Adsorption isotherms
The equilibriumisotherms for the adsorption of Cr(VI) onto oxi-
dized and unoxidized samples over a wide range of concentration
(10100mg/L), optimumpH of adsorption and different tempera-
tures are shown in Fig. 7(a) and (b), respectively. These isotherms
showed the relationship between the amounts of Cr(VI) adsorbed
0
2
4
6
8
10
12
14
0 10 20 30 40 50 60 70 80
q
e

(
m
g
/
g
)
Ce (mg/l)
20 C
30 C
40 C
0
2
4
6
8
10
12
0 10 20 30 40 50 60 70 80 90
q
e

(
m
g
/
g
)
Ce (mg/l)
20 C
30 C
40 C
a
b
Fig. 7. Isotherm study of Cr(VI) adsorption on (a) oxidized carbon, (b) unoxidized
carbon at different temperatures.
244 Z.A. AL-Othman et al. / Chemical Engineering Journal 184 (2012) 238247
(q
e
) and its equilibrium concentration (C
e
) in solution. It is also
clear from these gures that the adsorptivity of Cr(VI) increased
with increase in temperature. This suggested that Cr(VI) adsorp-
tion from aqueous solutions on oxidized and unoxidized carbon
was endothermic process. The increase in the adsorption capac-
ity may be due to the chemical interaction between adsorbate and
adsorbent, creation of some new adsorption sites or the increased
rate of intra particle diffusion of Cr(VI) ions into the pores of the
adsorbent at higher temperature [52,53].
To examine the relationship between sorbed (q
e
) and aque-
ous concentration (C
e
) at equilibrium, sorption isotherm models
are widely employed for tting the data, of which Langmuir and
Freundlich equations are most widely used. The Langmuir model
assumes that the uptake of adsorbate molecules occurs on a
homogenous surfacebymonolayer adsorptionwithout anyinterac-
tionbetweenadsorbedmolecules [54]. Freundlichmodel is suitable
for non-ideal adsorption on heterogeneous surfaces. The hetero-
geneity is caused by the presence of different functional groups on
the surface, and various adsorbentadsorbate interactions [54]. To
get the equilibrium data, initial Cr(VI) concentrations were varied
while the adsorbent mass for both samples were kept constant and
equilibriumtime 24h, were used for sorption experiments on both
oxidized and unoxidized samples.
To ensure equilibrium conditions, the linear form of the Lang-
muir equation was applied to the experimental data.
C
e
q
e
=
1
Q
o
b
+
C
e
Q
o
(9)
where q
e
was the quantity of Cr(VI) adsorbed per unit weight
of adsorbent (mg/g) at equilibrium, C
e
was the equilibrium con-
centration (mg/L) of Cr(VI) in solution. The constant Q
o
gives the
theoretical monolayer adsorption capacity (mg/g) and b is related
to the energy of adsorption (L/mg). Straight lines were obtained
by plotting C
e
/q
e
against C
e
as shown in Fig. 8(a) and (b) for oxi-
dized and unoxidized samples, respectively. The linear plot of
C
e
/q
e
against C
e
indicated the applicability of Langmuir adsorp-
tionisotherm. Consequently, suggestedtheformationof monolayer
coverage of the adsorbate onthe surface of the adsorbent. Langmuir
constants, Q
o
and b were calculated fromthe slopes and intercepts
of plots of C
e
/q
e
versus C
e
, respectively, and are given in Table 4
along with correlation coefcients (R
2
). It is clear fromTable 4 that
the b values were higher at higher temperatures, showedendother-
mic nature of Cr(VI) adsorption.
The essential characteristics of the Langmuir isotherm can
be expressed by a dimensionless equilibrium parameter, R
L,
also
knownas the separationfactor, dened by Weber and Chackravorti
[55].
R
L
=
1
1 +bC
i
(10)
where b is the Langmuir constant and C
i
is the lowest initial Cr(VI)
concentration (mg/L), R
L
values indicate the type of isotherm. The
average values of R
L
for each of the different initial concentration
and temperatures used, was between 0 and 1, which indicated the
favorable adsorption of Cr(VI) on both oxidized and unoxidized
samples.
The linear formof Freundlich isothermas expressed by Eq. (11),
was also applied to the adsorption data of Cr(VI)
lnq
e
= lnK
1
+
1
n
lnC
e
(11)
where K
1
(mg/g) and 1/n (g/l) are Freundlich adsorption constants,
indicatingtheadsorptioncapacityandadsorptionintensity, respec-
tively. Straight lines were obtained by plotting lnq
e
against lnC
e
as
shown by Fig. 9(a) and (b) for the adsorption on oxidized and unox-
idized carbon samples, respectively, which showed that adsorption
0
1
2
3
4
5
6
7
8
9
0 10 20 30 40 50 60 70 80
C
e
/
q
e

(
g
/
l
)
Ce (mg/l)
20 C
30 C
40 C
0
1
2
3
4
5
6
7
8
9
10
0 10 20 30 40 50 60 70 80 90
C
e
/
q
e

(
g
/
l
)
Ce (mg/l)
20 C
30 C
40 C
a
b
Fig. 8. Langmuir adsorption isotherms for Cr(VI) adsorption on (a) oxidized carbon,
(b) unoxidized at different temperatures.
0
0.5
1
1.5
2
2.5
3
1 1.5 2 2.5 3 3.5 4 4.5
l
n

q
e
ln Ce
20 C
30 C
40 C
0
0.5
1
1.5
2
2.5
3
1 1.5 2 2.5 3 3.5 4 4.5
l
n

q
e
ln Ce
20 C
30 C
40 C
a
b
Fig. 9. Freundlichadsorptionisotherms for Cr(VI) adsorptionon(a) oxidizedcarbon,
(b) unoxidized at different temperatures.
Z.A. AL-Othman et al. / Chemical Engineering Journal 184 (2012) 238247 245
Table 4
Langmuir and Freundlich isothermconstants for Cr(VI) adsorption on oxidized and unoxidized carbons.
Temperature (K) Oxidized carbon Unoxidized carbon
Langmuir constants Freundlich constants Langmuir constants Freundlich constants
Qo (mg/g) b (L/mg) R
2
1/n n K
1
R
2
Qo (mg/g) b (L/mg) R
2
1/n n K
1
R
2
293 16.26 0.023 0.93 0.64 1.56 0.70 0.98 13.68 0.02 0.98 0.65 1.54 0.57 0.98
303 13.48 0.049 0.96 0.55 1.82 1.13 0.91 13.28 0.03 0.99 0.62 1.61 0.68 0.97
313 13.89 0.062 0.96 0.51 1.96 1.46 0.91 14.31 0.04 0.96 0.57 1.75 1.05 0.94
of Cr(VI) obeyed Freundlich isotherm not very well. Values of
Freundlich constants and correlation coefcient (R
2
) are given in
Table 4. It is also evident from the correlation coefcient (R
2
) val-
ues that the Freundlich isotherm did not tted the experimental
data very well. The values of K
1
and n changed with the rise in
temperature. The value of n showed an indication of the favorabil-
ity of adsorption. Values of n larger than 1, showed the favorable
natureof adsorption[56,57]. Thevalueof nsuggestedthat Cr(VI) are
favorably adsorbed by the activated carbon prepared frompeanut
shells. The values of Q
o
(monolayer adsorption capacity), as calcu-
lated fromLangmuir adsorption isotherms for Cr(VI) was found to
be higher for oxidized carbon than unoxidized carbon which was
in agreement with the high surface area, high carbon content and
micropore volume of oxidized carbons.
3.7. Adsorption thermodynamics
The thermodynamic parameters such as H (enthalpy change)
andS (entropychange) were calculatedfromthe slopes andinter-
cepts of the plots of lnK
c
versus 1/T as shown in Fig. 10(a) and (b),
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
3.45 3.4 3.35 3.3 3.25 3.2 3.15
l
n


K
c
1/T (Kx10
-3
)
1/T (Kx10
-3
)
-3.9
-3.8
-3.7
-3.6
-3.5
-3.4
-3.3
-3.2
-3.1
3.45 3.4 3.35 3.3 3.25 3.2 3.15
l
n

K
c
a
b
Fig. 10. Plot of lnKc versus 1/T for Cr(VI) adsorption on (a) oxidized carbon, (b)
unoxidized carbon.
Table 5
Thermodynamic parameters for Cr(VI) adsorption on oxidized and unoxidized
carbons.
Adsorbent Thermodynamic parameters
T (K) G

Oxidized
293 28.38
0.04 0.10 303 29.39
313 30.32
Unoxidized
293 11.73
0.02 0.04 303 11.13
313 12.53
for adsorption on oxidized and unoxidized carbons, respectively,
by using the following relation.
ln K
c
=
H

RT
+
S

R
(12)
The G

(free energy change) was calculated from the following

relation:
G

= H

TS

(13)
where R (8.314J/mol K) is the gas constant, T (K), absolute tempera-
ture and K
c
(L/mg), standard thermodynamic equilibriumconstant
dened by q
e
/C
e
.
The values of H

, S

, and G

for Cr(VI) adsorption on oxi-

dized and unoxidized carbons are given in Table 5. It may be
observed from Table 5 that the values of H

was positive indi-

cated the endothermic process of adsorption and the values of S

were positive which showed that Cr(VI) adsorption caused disor-

derness in the system. The value of G

indicated the degree of

spontaneity of the adsorption process and a more negative value
showed an adsorption process which was favorable energetically.
The increase in G

with increasing temperature showed that the

adsorptionwas more favorable at hightemperature. Other workers
[58,59] have also been reported similar results for the adsorption
of Cr(VI). The value of G

was found negative in the adsorption of

Cr(VI) at all temperatures but more negative values were obtained
in case of oxidized carbon, which conrmed the feasibility of this
adsorbent and spontaneity of the adsorptionprocess. So, the capac-
ity of the oxidized carbon for the removal of Cr(VI) was higher than
unoxidized carbon.
4. Conclusion
Activated carbon was prepared from peanut shell by chemical
activation with KOH, characterized and utilized for the removal
of Cr(VI) from aqueous solutions in the concentration range of
10100mg/L. The oxidized carbon had high surface area and pore
volume and higher capacity for Cr(VI) adsorption than the unox-
idized carbon. Cr(VI) adsorption was found to be pH dependent.
Effective adsorption was occurred in the pH range of 24. The
kinetics of Cr(VI) followed both pseudo rst order and pseudo-
second order rate expressions. The removal of Cr(VI) was found to
be dependent on the initial concentration. The percentage removal
was decreased with increase in initial concentration. Isotherm
246 Z.A. AL-Othman et al. / Chemical Engineering Journal 184 (2012) 238247
data were treated according to Langmuir and Freundlich mod-
els but the Langmuir adsorption isotherm model tted well as
compared to Freundlich model in the temperature range stud-
ied. Cr(VI) adsorption on both oxidized and unoxidized samples
was found to be endothermic as adsorption capacity Q
o
and b
values were higher at higher temperatures. The values of Q
o
(mono-
layer adsorption capacity), as calculated fromLangmuir adsorption
isotherms for Cr(VI) was foundtobehigher for oxidizedcarbonthan
the unoxidized one which was in agreement with the high sur-
face area, high carbon content and micropore volume of oxidized
sample.
The value of G

was found negative in the adsorption of Cr(VI)

on both carbon samples but more negative values were obtained
in case of oxidized sample which conrmed the feasibility of these
adsorbent and spontaneity of the adsorption process. The positive
value of S

showed that Cr(VI) adsorption caused disorderness in

the system.
Acknowledgment
The authors extend their appreciation to the Deanship of Scien-
tic Research at King Saud University for funding the work through
the research group project no. RGP-VPP-043.
References
[1] S.A. Nabi, R. Bushra, Z.A. Al-Othman, Mu. Naushad, Synthesis, characteriza-
tion and analytical applications of a new composite cation exchange material
acetonitrile stannic(IV) selenite: adsorption behavior of toxic metal ions in
nonionic surfactant medium, Sep. Sci. Technol. 46 (2011) 847857.
[2] Z.A. Al-Othman, Mu. Naushad, Inamuddin, Organicinorganic type composite
cation exchanger poly-o-toluidine Zr(IV)tungstate: preparation, physicochem-
ical characterization and its analytical application in separation of heavy
metals, Chem. Eng. J. 172 (2011) 369375.
[3] F.C. Richard, A.C.M. Bourg, Aqueous geochemistry of chromium: a review,
Water Res. 25 (1991) 807816.
[4] K. Mohanty, M. Jha, B.C. Meikap, M.N. Biswas, Removal of chromium(VI) from
dilute aqueous solutions byactivatedcarbondevelopedfromTerminalia arjuna
nuts activated with zinc chloride, Chem. Eng. Sci. 60 (2005) 30493059.
[5] G. Tiravanti, D. Petruzzelli, R. Passino, Pretreatment of tannery wastewaters by
an ion exchange process for Cr(III) removal and recovery, Water Sci. Technol.
36 (1997) 197207.
[6] Z. Song, C.J. Williamsm, R.G.J. Edyvean, Sedimentation of tannery wastewater,
Water Res. 34 (2000) 21712176.
[7] H. Oda, Y. Nakagawa, Removal of ionic substances from dilute solution using
activated carbon electrodes, Carbon 41 (2003) 10371047.
[8] G.A. Vlyssides, C.J. Israelites, Detoxication of tannery waste liquors with an
electrolysis system, Environ. Pollut. 97 (1997) 147152.
[9] A. Filibeli, N. Buyukkamaci, H. Senol, Solidication of tannery wastes, Resour.
Conserv. Recy. 29 (2000) 251261.
[10] A. Kapoor, T. Viraraghavan, D.R. Cullimore, Removal of heavy metals using the
fungus Aspergillus niger, Bioresour. Technol. 70 (1999) 95104.
[11] Z. Song, C.J. Williams, R.G.J. Edyvean, Treatment of tannery wastewater by
chemical coagulation, Desalination 164 (2004) 249259.
[12] C. Fabianil, F. Rusciol, M. Spadonil, M. Pizzichini, Chromium(III) salts recovery
process fromtannery wastewaters, Desalination 108 (1996) 183191.
[13] A.I. Hafez, M.S. El-Manharawy, M.A. Khedr, ROmembrane removal of unreacted
chromiumfromspent tanning efuent. Apilot-scale study: part 2, Desalination
144 (2002) 237242.
[14] L.K. Wang, D.B. Dahm, R.E. Baier, Treatment of tannery efuents by surface
adsorption, J. Appl. Chem. Biotechnol. 25 (1975) 475490.
[15] C.S. Brooks, Metal Recovery from Industrial Waste, Lewis Publishers, Ins., MI,
USA, 1991, p. 27.
[16] G. Macchi, M. Pagano, M. Pettine, M. Santrori, G. Tiravanti, A bench study on
chromiumrecovery fromtannery sludge, Water Res. 25 (1991) 10101026.
[17] D.C. Sharma, C.F. Forster, A preliminary examination into the adsorption of
hexavalent chromium using low-cost adsorbents, Biores. Technol. 47 (1994)
257264.
[18] J.A. Laszlo, F.R. Dintzis, Crop residues as ion exchange materials. Treatment
of soybean hull and sugar beet ber (pulp) with epichlorohydrin to improve
cation-exchange capacity and physical stability, J. Appl. Polym. Sci. 52 (1994)
531538.
[19] S. Doyurum, A.C. Elik, Pb(II) and Cd(II) removal fromaqueous solutions by olive
cake, J. Hazard. Mater. 138 (2006) 2228.
[20] A. Kumar, N.N. Rao, S.N. Kaul, Alkali treated strawand insoluble strawxanthate
as lowcost adsorbents for heavy metal removal-preparation, characterization
and application, Bioresour. Technol. 71 (2000) 133142.
[21] A.A. Abia, J.C. Igwe, Sorption kinetics and intraparticulate diffusivities of Cd, Pb,
and Zn ions on maize cob, Afr. J. Biotechnol. 4 (2005) 509512.
[22] K.K. Wong, C.K. Lee, K.S. Low, M.J. Haron, Removal of Cu and Pb by tar-
taric acid modied rice husk fromaqueous solutions, Chemosphere 50 (2003)
2328.
[23] E. Pehlivan, T. Altun, S. Parlay, Utilization of barley straws as
biosorbents for Cu
2+
and Pb
2+
ions, J. Hazard. Mater. 164 (2009)
982986.
[24] K.A. Krishnan, T.S. Anirudhan, Removal of cadmium(II) fromaqueous solutions
by steam-activated sulphurised carbon prepared fromsugar cane bagasse pith:
kinetics and equilibriumstudies, Water SA 29 (2003) 147156.
[25] N.A.A. Babarinde, Adsorption of zinc (II) and cadmium(II) by coconut husk and
goat hair, J. Pure Appl. Sci. 5 (2002) 8185.
[26] N. Meunier, J. Laroulandie, J.F. Blais, R.D. Tyagi, Cocoa shells for heavy metal
removal fromacidic solutions, Bioresour. Technol. 90 (2003) 255263.
[27] T.W. Tee, R.M. Khan, Removal of lead, cadmium and zinc by waste tea leaves,
Environ. Technol. Lett. 9 (1988) 12231232.
[28] G. Annadurai, R.S. Juang, D.L. Lee, Adsorption of heavy metals fromwater using
banana and orange peels, Water Sci. Technol. 47 (2002) 185190.
[29] S. Valdimir, J.M. Danish, Characterization and metal sorptive properties of oxi-
dized active carbon, J. Colloid Interface Sci. 250 (2002) 213220.
[30] G.J. Alaerts, V. Jitjaturant, P. Kelderman, Use of coconut shell based activated
carbon for chromium(VI) removal, Water Sci. Technol. 21 (1989) 17011704.
[31] C. Selomulya, V. Meeyoo, R. Amal, Mechanisms of Cr(VI) removal from water
by various types of activated carbons, J. Chem. Technol. Biotechnol. 74 (1999)
111122.
[32] M. Kobya, Adsorptionkinetic andequilibriumstudies of Cr(VI) byhazelnut shell
activated carbon, Adsorpt. Sci. Technol. 22 (2004) 5164.
[33] N.K. Hamadi, X.D. Chen, M.M. Farid, M.G.Q. Lu, Adsorption kinetics for the
removal of chromium(VI) from aqueous solution by adsorbents derived from
used tyres and sawdust, Chem. Eng. J. 81 (2001) 95105.
[34] X.U. Tao, X.Q. Liu, Peanut shell activated carbon: characterization, surface mod-
ication and adsorption of Pb
2+
fromaqueous solution, Chin. J. Chem. Eng. 16
(2008) 401406.
[35] Agricultural Statistics, USDA, National Agricultural Statistics Service, US Gov-
ernment Printing Ofce, Washington, DC, 2003.
[36] C. Namasivayam, K. Periasamy, Bicarbonate-treated peanut hull carbon for
mercury (II) removal fromaqueous solution, Water Res. 27 (1993) 16631668.
[37] K. Periasamy, C. Namasivayam, Adsorption of Pb(II) by peanut hull carbon from
aqueous solution, Sep. Sci. Technol. 30 (1995) 22232237.
[38] K. Periasamy, C. Namasivayam, Removal of nickel plating industry wastewater
using an agriculture waste: peanut hulls, Waste Manag. 15 (1995) 6368.
[39] K. Periasamy, C. Namasivayam, Removal of Cu (II) by adsorption onto peanut
hull carbon fromwater and copper plating industry wastewater, Chemosphere
32 (1996) 769789.
[40] S.J. Gregg, K.S.W. Sing, Adsorption, Surface Area and Porosity, Academic Press,
NewYork, 1982.
[41] E.P. Barrett, L.C. Joyner, P.H. Halenda, The determination of pore volume
and area distribution in porous substances, J. Am. Chem. Soc. 73 (1951)
373380.
[42] M.M. Dubinin, Progress in Surface and Membrane, vol. 9, Academic Press, New
York, 1975.
[43] F.R. Reinoso, M. Molina-Sabio, M.T. Gonzalez, The use of steam and CO
2
as
activating agents in the preparation of activated carbons, Carbon 33 (1995)
1523.
[44] H. Demiral, I. Demiral, F. Tumsek, B. Karabacak oglu, Adsorption of
chromium(VI) from aqueous solution by activated carbon derived from olive
bagasse and applicability of different adsorption models, Chem. Eng. J. 144
(2008) 188196.
[45] A. Sharma, K.G. Bhattacharyya, Adsorption of chromium (VI) on Azadirachta
indica (neem) leaf powder, Adsorption 10 (2004) 327338.
[46] V.K. Singh, P.N. Tiwari, Removal and recovery of chromium(VI) fromindustrial
waste water, J. Chem. Technol. Biotechnol. 69 (1997) 376382.
[47] Y.S. HO, G. Mckay, D.A.J. Wase, C.F. Foster, Study of the sorption of divalent
metal ions on to peat, Adsorpt. Sci. Technol. 18 (2000) 639650.
[48] S.K. Srivastava, R. Tyagi, N. Pant, Adsorption of heavy metal ions on carbona-
ceous material developed from the waste slurry generated in local fertilizer
plants, Water Res. 23 (1989) 11611165.
[49] W.J. Weber, R.K. Chakravarthi, Pore and solid diffusion modules for xed bed
adsorbent, J. Am. Inst. Chem. Eng. 22 (1974) 228238.
[50] M. Rao, A.V. Parwate, A.G. Bhole, Removal of Cr
6+
and Ni
2+
fromaqueous solu-
tion using bagasse and y ash, Waste Manag. 22 (2002) 821830.
[51] C. Namasivayam, D. Sangeetha, Recycling of agricultural solid waste coir pith:
removal of anions, heavy metals, organics and dyes fromwater by adsorption
onto ZnCl
2
activated coir pith carbon, J. Hazard. Mater. 135 (2006) 449452.
[52] T. Karthikeyan, S. Rajgopal, L.R. Miranda, Chromium(VI) adsorption fromaque-
ous solution by Hevea brasilinesis sawdust activated carbon, J. Hazard. Mater.
124 (2005) 192199.
[53] C. Namasivayam, R.T. Yamuna, Adsorption of chromium (VI) by a low-cost
adsorbent: biogas residual slurry, Chemosphere 30 (1995) 561578.
[54] H. Deng, L. Yang, G. Tao, J. Dai, Preparation and characterization of activated
carbon from cotton stalk by microwave assisted chemical activation appli-
cation in methylene blue adsorption from aqueous solution, J. Hazard. Mater.
166 (2009) 15141521.
[55] T.W. Weber, R.K. Chackravorti, Pore and solid diffusion models for xed bed
adsorber, J. Am. Inst. Chem. Eng. 20 (1974) 228238.
Z.A. AL-Othman et al. / Chemical Engineering Journal 184 (2012) 238247 247
[56] N. Daneshvar, D. Salari, S. Aber, Chromium adsorption and Cr(VI) reduction
to trivalent chromiumin aqueous solutions by soya cake, J. Hazard. Mater. 94
(2002) 4961.
[57] P.K. Malik, Dye removal from wastewater using activated carbon developed
from sawdust: adsorption equilibrium and kinetics, J. Hazard. Mater. 113
(2004) 8188.
[58] J. Romero-Gonzalez, J.R. Peralta-Videa, E. Rodriguez, S.L. Ramirez, J.L. Gardea-
orresdey, Determination of thermodynamic parameters of Cr(VI) adsorption
from aqueous solution onto Agave lechuguilla biomass, J. Chem. Thermodyn.
37 (2005) 343347.
[59] E. Oguz, Adsorption characteristics and the kinetics of the Cr(VI) on the Thuja
oriantalis, Colloids Surf. 252 (2005) 121128.