M.A. Mohamed et al / Chemistry Journal (2012), Vol. 02, Issue 03, pp.

95-105 ISSN 2049-954X

Research Paper

Adsorption Studies on the Removal of Hexavalent

Chromium-Contaminated Wastewater using Activated
Carbon and Bentonite
Salah Abdel Waneesa, Abdel Monem M. Ahmedb, Mohamed S. Adamc and Mamdouh A. Mohamed*a
a
Chemistry Department, Faculty of Science, Zagazig University,44519, Sharkia, Egypt
b
Chemistry Department, Faculty of Science, Alexandria University, Alexandria, Egypt
c
Chemistry Department, Faculty of Science, Sohag University, Sohag, Egypt
Tel.: +2093 2303929; fax: +2093 2303929
*E-Mail: mamsahar2020@yahoo.com

Abstract
In this study, the adsorption potential of activated carbon and bentonite for removal of Cr(VI) ions from wastewater has
been investigated. The study involves batch type experiments to investigate the effects of initial concentration, adsorbent
dose, agitation speed, contact time, temperature and pH of solution on adsorption process and the evaluation of optimum
conditions. The adsorption process has fit pseudo-second order kinetic models. Langmuir and Freundlich adsorption
isotherm models were applied to analyze adsorption data, and both were found to be applicable to this adsorption process.
Thermodynamic parameters, e.g., ∆G◦, ∆S◦ and ∆H◦ of the on-going adsorption process have also been calculated and found
the sorption process as endothermic. Finally, it can be seen that bentonite was found to be more effective for the removal of
Cr(VI) than activated carbon, under the same experimental conditions.

Keywords: Wastewater, Chromium, Activated Carbon, Bentonite, Removal

1. Introduction
The pollution of heavy metal ions in the environment is a
critical problem because of their toxicity and other adverse
effects on the receiving waters and /or soils. They must be
removed from wastewater before discharging them into
water bodies. Water pollution by chromium is due to both,
natural sources and manmade activities. Chromium is
found in rocks, animals, plants, soils and in volcanic dusts
and gases. Various industrial processes which involve the
use of Cr(VI), such as steel production, electroplating,
leather tanning, nuclear power plants, textile industries,
wood preservation, anodizing of aluminum, water-cooling
and chromate preparation. Discharge of wastes containing
chromium occurs into environment, with its varied
concentration between 5 and 220 mg/L. Such discharge
ultimately contaminates soil and water (Okuda et al, 1975;
Ouki & Neufeld, 1997 and Altundogan, 2005). Chromite
world mine production was estimated at a gross mass of
13x106 metric tons in 2002 (Papp, 2003).
In nature chromium exists in two most stable oxidation
states, i.e., trivalent and hexavalent forms in aqueous
systems. Although, at trace level, the trivalent form is
considered as an essential nutrient (Alloway, 1995 and
Rojas et al, 2005) whereas hexavalent form of chromium is
toxic, carcinogenic and mutagenic in nature (Norseth,
1981; USDHHS, 1991; Cieslak-Golonka, 1995; Myers et
al, 2000; Zhitkovich et al, 2002 and Dupont & Guillon,
2003). Kowalski (1994) revealed that the hexavalent form
is about 500 times more toxic than trivalent form.
Furthermore, Cr(VI) is highly mobile in soil and aquatic
system, and also is a strong oxidant capable of being
adsorbed by skin (Singh, & Singh, 2002). Considering its

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 M.A. Mohamed et al / Chemistry Journal (2012), Vol. 02, Issue 03, pp. 95-105
toxicity and carcinogenic nature, the maximum levels
permitted for trivalent chromium in wastewater is 5 mg/L
and for hexavalent chromium as 0.05 mg/L (BIS, 1991 and
Acar & Malkoc, 2004).
The most common methods of Cr(VI) ions removal from
aqueous system are chemical precipitation, ion exchange,
membrane processes, electrodialysis and adsorption
(Patterson, 1977; George, 1985; Tiravanti et al, 1997 and
Dahbi et al, 1999). Hexavalent chromium usually exists in
wastewater as oxyanions such as chromate CrO4-2 and
dichromate Cr2O7-2 and does not precipitate easily using
conventional precipitation methods. Ion exchange, reverse
osmosis and elctrodialysis are efficient for Cr(VI) ions
removal but the cost is relatively high (George, 1985).
Furthermore, chromium removal techniques such as co-
precipitation, membrane techniques and solvent extraction
are challenged by the removal of lower concentrations of
metals from solution (Valix et al, 2006). On the other
hand, adsorption has been proved to be one of the
respective methods, which is simple, selective and
economical process for the removal of heavy metal ions
from aqueous solution.
In this work two different adsorbents (activated carbon and
bentonite) were used for the removal of hexavalent
chromium (Cr+6) from wastewater. Bentonite is considered
by many authors as main candidate in the decontamination
and treatment of detrimental metal ions, because of its
large specific surface area and high adsorption capacity
(Tsai et al, 2001; Lin & Juang, 2002 and Al-Qunaibit et al,
2005).
The objectives of the present study are: 1) to study the
effect of contact time of Cr+6 metal ions adsorption on
activated carbon and bentonite; 2) to investigate the
influence of pH on the adsorption of Cr+6; 3) to study the
adsorption of Cr+6 at different temperatures and to
calculate the adsorption thermodynamic parameters (i.e.,
∆H°, ∆S° and ∆G°); 4) to find the effect of adsorbent dose
and initial concentration on the adsorption of Cr+6; 5) to
describe the experimental data of adsorption isotherms
through Langmuir and Freundlich models; 6) to investigate
the adsorption properties of Cr+6 and to discuss its
adsorption mechanism.
2. Materials and Methods
2.1. Materials and Reagents
All chemicals used in present work were either of
analytical reagent (AR) or laboratory reagent (LR) grade.
K2Cr2O7 (99%) and H2SO4 (98% w/w) supplied by BDH
chemicals Ltd. Distilled water was used in all preparations.
Potassium dichromate (K2Cr2O7) and deionized water were
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ISSN 2049-954X
used to prepare synthetic chromium containing
wastewater. Powder Activated Carbon (PAC) was
produced by ADWIC whereas bentonite by Alexandria
Company for Refractories.
2.2 Adsorbents Analysis
The surface area and particle size analyses for the two
adsorbents i.e. PAC and Bentonite, were checked and
recorded (Table 1). Elemental analysis for bentonite was
evaluated using x-ray fluorescence (Philips PW 1390) as
shown in (Table 2).
2.3. Apparatus and Instrumentation
Magnetic hot plate stirrer was used to stir the heavy metal
ions solutions with adsorbents (activated carbon or
bentonite). A known volume of heavy metal ions solution
of a known initial ions concentration was mixed and stirred
with a specific amount of adsorbent for certain period of
time at fixed temperature and agitation rate. The pH values
of the solutions were measured by digital pH meter (Model
µ pH system-361, India). The metal ion concentration was
measured using atomic-absorption spectrophotometer,
AAS, (Model, AA55; Varian Inc., USA).
2.4. Experimental Procedures
Potassium dichromate (K2Cr2O7) and redistilled water
were used to prepare a stock solution of 1000 ppm
Cr(VI) concentration, which was further diluted
for the preparation of test solutions. Several solutions
with different initial concentrations of potassium
dichromate (50, 100, 200, 300 and 400 ppm)
were prepared. The required pH was adjusted by
drop wise addition of 0.1N H2SO4, depending on the
acidity of the sample. All experiments were
carried out at 25 oC by adding different amounts of
adsorbents (0.1, 0.3, 0.5, 0.7 and 1.0 g) to different
concentrations of 250 ml of heavy metal ions solution. The
agitation rate for all experiments was 200 rpm and the
residence time was (0, 15, 30, 45, 60, 75, 90 and 120
minutes).
1 ml of sample was taken from reaction
solution and diluted to 10 ml by redistilled
water, adsorbents were then separated from the solution
by using filter paper (Watman No. 40) and the
residual Cr+6 ions concentration in the solution was then
determined by atomic-absorption spectrophotometer
(AAS).
The effects of several parameters, such as contact time,
initial concentration, adsorbent dose, pH and temperature
on the adsorption of Cr(VI) ions onto activated carbon and
bentonite were studied.
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Table 1. Surface Area and Particle Size Analysis of Activated Carbon and Bentonite

Adsorbents Analysis Activated Carbon Bentonite

Surface Area (BET) Nova 2000 Quantachrome 931.9 m2/g 119.8 m2/g (dry)
Size (Micrometer) Wt. % Size (Micrometer) Wt. %
32-16 2.75 > 63 1
16-8 55.89 63-32 1
8-4 16.03 32-16 2
Particle size (XRD) Philips PW 1730
4-2 21.14 16-8 3
<2 4.19 8-4 2
4-2 4
<2 87

2.5. Data Analysis removal was 73% for activated carbon and 77% for
bentonite after 120 min. It is clear that, at the beginning %
The uptake of Cr(VI) ions was calculated from the Mass removal increased rapidly in few minutes, by increasing
Balance, define as the amount of solute adsorbed onto contact time, % removal increased lightly and slowly till
the solid. It equals the amount of solute removed from reach maximum value and this can be explained on the
the solution. Mathematically, it can be expressed by basis that as initially a large number of vacant surface sites
Equation 1: are available for adsorption of metal ions but with passage
of time the surface sites become exhausted (Zhan et al,
qe = (Ci Ce)/S…………………………………………...1 2000). These results indicate that the activated carbon and
bentonite have a very strong capacity for adsorption of
Where: Cr(VI) ions in solutions.
qe: The heavy metal ions concentration adsorbed by an adsorbent at
Table 2. Elemental Analysis for Bentonite was Evaluated Using X-
equilibrium (mg of metal ions/g of adsorbent)
Ray Fluorescence (Philips PW 1390)
Ci: The initial concentration of metal ions in the solution (mg/L)
Ce: The equilibrium concentration or final concentration of metal ions
in the solution (mg/L)
S: The dosage concentration.
Oxides (wt.%) Bentonite
SiO2 (%) 55.89
Dosage concentration, S, is expressed by Equation 2:
Al2O3 (%) 16.03
S = m/V………………………………………………...2 Fe2O3 (%) 4.19
CaO (%) 3.25
Where:
MgO (%) 2.75
V is the initial volume of metal ions solution used (L) and m is the K2O (%) 0.49
weight of dried used adsorbent (g)
Na2O (%) 0.34
The percentage of adsorption (%) is calculated using TiO2 (%) 0.15
Equation 3:
P2O5 (%) 0.086
% adsorption = [(Ci Ce)/Ci ] x 100………………..……3 SO3 (%) 0.23
LOI (%) 17.2
3. Results and Discussion
3.2. Effect of Adsorbent Dose
3.1. Effect of Contact Time
The percentage adsorption of Cr+6 ions onto activated
The effect of contact time on Cr(VI) adsorption on both carbon and bentonite was studied at different adsorbent
activated carbon and bentonite was investigated to study doses (0.4, 1.2, 2.0, 2.8 and 4.0 g/L), keeping pH (2.0),
the rate of Cr(VI) ions removal (Figure 1). It is easily seen temperature (25 oC), contact time (120 minutes) and initial
from Figure 1 that the percentage removal of Cr(VI) metal Cr+6 ions concentration of (400 mg/L) constant (Figure 2).
ions increased with increasing the contact time. The % The results showed that with increase in adsorbent dose,

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 M.A. Mohamed et al / Chemistry Journal (2012), Vol. 02, Issue 03, pp. 95-105 ISSN 2049-954X

the percentage adsorption of Cr+6 was increased. The percentage removal of Cr+6 was studied by varying
Maximum removal was observed with adsorbent dose of 4 Cr+6 concentrations from 50 to 300 mg/L with 4 g/L
mg/L for both activated carbon and bentonite. Increasing adsorbent dose of activated carbon and bentonite with the
the percentage of adsorption with adsorbent dose may be same standard conditions as illustrated in Figure 4.
due to the increase in adsorbent surface area and
availability of more adsorption sites (Namasivayam et al, activated carbon
1998 and Garg et al, 2007). Unit adsorption was, however, 600 bentonite
decreased with increasing in adsorbent dose (Figure 3).
500
This is may be due to overlapping of adsorption sites as a

Amount adsorbed (mg/g)

result of overcrowding of adsorbent particles (Garg et al, 400
2007).
300

80
200
70
100
60
+6

0
% Removal of Cr

50
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
40 Adsorbent dose (g/L)

30
Figure 3. The Effect of Variant Activated Carbon or Bentonite
20 Adsorbent Dosage (0.4, 1.2, 2.0, 2.8, and 4.0 g/L) on the
Quantity Adsorbed for 400 mg/L Cr+6 Ions from
10 activated carbon Wastewater at Contact Time: 2 Hours; Temperature:
bentonite 25 oC; Agitation Speed: 200 rpm
0
0 20 40 60 80 100 120
t, min 90
activated carbon
+6
bentonite
Figure 1. Effect of Contact Time on Cr Ions Removal 80
(Conditions; Adsorbate Initial Concentration: 400
mg/L; pH: 2.0; Adsorbents Dose: 4 g/L; Agitation
Speed: 200 rpm; Temperature: 25 oC)
+6
% Removal of Cr

70

78
60
76

74
50
72
+6
% Removal of Cr

70
40
68 50 100 150 200 250 300
initial conc. (m g/L)
66

64
Figure 4. The Effect of Initial Concentration (Namely 50, 100, 200
62 activated carbon and 300 mg/L) on Removal of Cr+6 Ions (Conditions:
bentonite Adsorbents Dose: 4 g/L; Agitation Speed: 200 rpm;
60
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 Temperature: 25 oC)
A dsorbent dose (g/L )
The results represented in Figure 4, showed that the
percentage Cr+6 ions adsorption was decreased with
Figure 2. The Effect of Variant Activated Carbon or Bentonite increasing in initial concentration. But the actual amount
Adsorbent Dosage (0.4, 1.2, 2.0, 2.8, and 4.0 g/L) on the
Removal of 400 mg/L Cr+6 Ions from Wastewater at
of Cr+6 ions adsorbed per unit mass of the adsorbent was
Contact Time: 2 Hour; Temperature: 25 oC; Agitation increased with increasing in Cr+6 ions concentration in the
Speed: 200 rpm test solution as illustrated in Figure 5. At low
concentration the ratio of surface active sites to the total
3.3. Effect of Initial Chromium (VI) Ions Concentration metal ions in the solution is high and hence all metal ions
interact with the adsorbent and are removed quickly from
The initial heavy metal ions concentration is an important the solution. However, the amount of metal ions adsorbed
parameter in adsorption since a certain amount of per unit weight of adsorbent, q , is higher at high
adsorbent can adsorb a certain amount of heavy metal ions. concentration. According to these results, the initial Cr+6

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 M.A. Mohamed et al / Chemistry Journal (2012), Vol. 02, Issue 03, pp. 95-105
ions concentration plays an important role in the
adsorption capacities. Higher concentrations of metal ions
were used to study the maximum adsorption capacity of
adsorbent (Mohanty et al, 2006 and Karthikeyan et al,
2005).
activated carbon
50 bentonite
40
amount absorbed (mg/g)
30
20
10
50 100 150 200
initial conc. (m g/L)
Figure 5. The Effect Of Initial Concentration (Namely 50, 100, 200
and 300 mg/L) on Quantity Adsorbed of Cr+6 Ions
(Conditions: Adsorbents Dose: 4 g/L; Agitation Speed:
200 rpm; Temperature: 25 oC)
3.4. Effect of pH on the Uptake of Cr+6
The pH of the solution is an important variable which
controls the adsorption of the metal ions at the solid-water
interface. Hence, the influence of pH on the adsorption of
Cr+6 ions onto activated carbon and bentonite was
examined in the pH range of 1-4. These results were
represented in Figure 6, which showed that the adsorption
capacities of Cr+6 ions onto both adsorbents increased
significantly, with decreasing pH value and the maximum
removals of Cr+6 ions by both adsorbents for contact time
(120 min) were carried out at pH (2.0). The improved
removal of Cr(VI) at low pH is probably due to reduction
of hexavalent chromium to trivalent chromium ions (Anon,
1995), Equation 4 .
Cr2O72 + 14H+ + 6e1 → 2Cr+3 + 7H2O………………..4
Also at low pH, there is presence of a large number of H+
ions, which in turn neutralize the negatively charged
adsorbent surface, thereby reducing hindrance to the
diffusion of dichromate ions (Sharma, & Forster, 1994).
3.5. Effect of Temperature
Figure 7 indicates the effect of temperature on the removal
efficiency of Cr+6 ions from wastewater using activated
carbon and bentonite. Four different temperatures were
considered in this study (25, 30, 35 and 40o C). The figure
showed that the removal efficiency increased by increasing
the temperature, where the maximum adsorption (76%
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ISSN 2049-954X
approx.) is achieved at 40 oC in case of activated carbon.
The adsorption pro Cess does not usually operate at high
temperature (more than 40 oC) and this may be due to the
damage of active binding sites and because of high
operational cost, so experiments were performed at the
temperature range (25-40 oC). Furthermore, in the case of
activated carbon, the enhancement in adsorption capacity
may be due to the chemical interaction between adsorbates
and adsorbent, creation of some new adsorption sites or
increased the rate of intraparticle diffusion of Cr(VI) ions
into the pores of the adsorbent at higher temperatures (40
o
C). Also, it is mentioned that, the metal cations become
more faster with increasing temperature. While, in the
adsorption of Cr(IV) onto bentonite at 40 oC, probably the
available binding sites have been saturated and the
adsorbent no longer can bind further ions as the number of
sites available on the adsorbent is constant.
250 300
74 activated carbon
bentonite
72
70
+6
68
% Removal of Cr
66
64
62
60
58
1.0 1.5 2.0 2.5 3.0 3.5 4.0
pH
Figure 6. Effect of pH for the Adsorption of Cr(VI) Ions onto
Activated Carbon and Bentonite at 25 oC
The augmentation of the removal efficiency by stepping up
the temperature are due to: Firstly, the higher temperatures
activate the metal ions for enhancing adsorption at the
coordinating sites of the adsorbent, and the metal cations
became more faster (Babel & Kurniawan, 2003 and
Inglezakis et al, 2004). Secondly, acceleration of some
originally slow step(s) and creation of some new activation
sites on the adsorbent surface (Domenico & Schwartz,
1990). Herein, the phenomenon can be observed in both
adsorbents, but activated carbon is affected much higher
than in case bentonite Figure 7.
6. Adsorption Kinetics
Adsorption kinetics describe the solute uptake rate which
intern control the residence time and hence the size of
adsorption equipment. The experimental results for the
adsorption of Cr+6 ions onto activated carbon and bentonite
showed rapid initial adsorption rate followed by a slower
rate. Initially, the adsorption sites are open and the metal
ions interact easily with the sites and hence a higher rate of
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 M.A. Mohamed et al / Chemistry Journal (2012), Vol. 02, Issue 03, pp. 95-105
adsorption is observed. Further, the driving force for
adsorption (the concentration difference between the bulk
solution and the solid-liquid interface) is higher initially
and this leads to a higher adsorption rate. However, after
the initial period, slow adsorption may be due to slower
diffusion of solute into the interior of the adsorbent.
Several adsorption kinetics models have been developed to
understand the adsorption kinetics and rate limiting step
(Lagergren, 1898; Ho & Mckay, 1999; Uzun & Guzel,
2000 and Ricordel, 2001).
76
74
+6
% Removal of Cr
72
70
68
66
24 26 28 30 32 34
T e m p e ra tu re (°C )
Figure 7. The Effect Of Temperature Between 25 and 40o C for the
Removal of Cr+6 Ions from Wastewater (Conditions:
Adsorbate Initial Concentration: 400 mg/L; pH: 2.0;
Adsorbents Dose: 4 g/L; Agitation Speed: 200 rpm;
Contact Time: 2 Hours)
The following models have been widely used (Lagergren,
1898 and Ho & Mckay, 1999) Largergren pseudo-first
order model can be expressed by Equations 5 and 6:
dq/dt = k1(qe - q)………………………………………..5
ln(qe - q) = lnqe - k1t……………………………………6
Equations 7 and 8 give the pseudo-second order model as:
dq/dt = k2(qe - q)2………………………………………7
t/q = t/qe + 1/k2qe2……………………………………...8
Where:
q and qe are the amount of Cr+6 metal adsorbed per unit weight of
adsorbent (mg/g) at time t, and at equilibrium, respectively, and k1
and k2 are the adsorption rate constants. The initial adsorption rate
(h) is equal to k1qe and k2qe2 (mgg-1min-1) for first and second order
models, respectively
The applicability of the above two models can be
examined by each linear plot of ln(qe-q) vs. t, and (t/q) vs.
t, respectively and are represented in Figures 8 (a,c) and 8
(b,d) respectively. To quantify the applicability of each
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ISSN 2049-954X
model, the correlation coefficient, R2, was calculated from
these plots. The linearity of these plots indicates the
applicability of the two models. However, the correlation,
R2, showed that the pseudo-second order model, fits better
the experimental data (R2>0.990) than the pseudo-first
order model (R2 in the range of 0.888-0.964).
The kinetic parameters calculated are shown in Table 3. It
has been found that the equilibrium sorption capacities
determined using second-order model were in agreement
with the experimentally determined equilibrium sorption
capacities. Also, the rate constant decreased with the
solution concentration increasing.
In general, the adsorption reaction is known to proceed
through the following three steps:
1) Transfer of adsorbate from bulk solution to adsorbent
surface, which is usually mentioned as diffusion
2) Migration of adsorbate into pores
a c tiv a te d c a rb o n
b e n to n ite
36 38 40 42 3) Interaction of adsorbate with available sites on the
interior surface of pores.
3.7. Adsorption Isotherms
Several models have been used in the literature to describe
the experimental data of adsorption isotherm. The
Langmuir and Freundlich models are the most frequently
employed to describe equilibrium (Zeldowitsch, 1934).
The Langmuir isotherm is based on the theoretical
principle that only a single adsorption layer exists on an
adsorbent and it represents the equilibrium distribution of
metal ions between the solid and liquid phases. The basic
assumption of the Langmuir adsorption process is the
formation of a monolayer of adsorbate on the outer surface
of the adsorbent and after that no further adsorption takes
place. The Langmuir-type isotherm remains to be the most
widely used for practical application. The Langmuir
isotherm for pure component adsorption can be obtained
from Equation 9:
Ce/qe = 1/(qmaxb) + (1/qmax) Ce………………………....9
Where:
qmax is the Maximum Metal Ions uptake per unit mass of adsorbent
(mg/g), which is related to the adsorption capacity and b is Langmuir
Constant (L/mol) which is exponentially proportional to the heat of
adsorption and related to the adsorption intensity.
Therefore, a plot of Ce/qe versus Ce gives a straight line of
the slop 1/qmax and intercept 1/(qmax b) as in Figure 9.
Zeldowitsch (1934) assumed an exponentially decaying
function of site density with respect to heat of adsorption
and obtained the classical empirical isotherm, Equation 10:
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lnqe = lnKf + 1/n lnCe………………………………...10
This is known as Freundlich isotherm. The Freundlich
adsorption isotherm is an indicator of the extent of
heterogeneity of the adsorbent surface, where the
Freundlich constants Kf and n, which respectively
indicating the adsorption capacity and the adsorption
intensity, were calculated from the intercept and slope of
the plot of lnqe versus lnCe as shown in Figure 10.
This Freundlich type of behavior is indicative of surface
heterogeneity of the adsorbents, i.e the adsorptive
sites (surface of activated carbon and bentonite) are
made up of small heterogeneous adsorption patches that
are homogeneous in themselves. The activation of
adsorption sites takes place, leading to increased
adsorption probably through the surface exchange
mechanism.

Table 3. The Adsorption Kinetics Model Rate Constants for Adsorption of Cr+6 Ions onto Activated Carbon and Bentonite at Various
Concentrations and Constant Temperature 25 oC

Lagergren First-Order Pseudo-Second-Order

Conc. qe exp.
Adsorbent
(mg/L) (mg/g) K1 q1 k2 q2
R2 R2
(min-1) (mg/g) (gmg-1min-1) (mg/g)
50 10.5 2.7x10-2 6.95 0.9276 9.7x10-3 10.7 0.9954
Activated
100 17.25 2.6x10-2 15 0.9840 1.9x10-3 20.4 0.9934
Carbon
200 29.25 2.3x10-2 27.7 0.9371 7.2x10-4 36.9 0.9597
50 10 2.8x10-2 5.6 0.8851 1.1x10-2 10.5 0.9968
Bentonite 100 18 2.7x10-2 13.2 0.9585 3.0x10-3 18.9 0.9934
200 31.75 2.5x10-2 24.5 0.9642 1.4x10-3 35.7 0.9912

3.5 (a) 50 ppm

100 ppm
10 50 ppm (b )
3.0 100 ppm
200 ppm 9
200 ppm
2.5 8

2.0 7
ln(qe-q)

6
1.5
t/q

5
1.0
4
0.5
3
0.0 2

-0.5 1

0 20 40 60 80 100 10 20 30 40 50 60 70 80 90 100 110 120 130

t, min t, m in
14
3.5 (c) 50 ppm 50 pp m (d )
100 ppm 12 100 p pm
3.0
200 ppm 200 p pm
2.5
10
2.0
8
1.5
ln(qe-q)

t/q

1.0 6

0.5
4
0.0

-0.5 2

-1.0 0
0 20 40 60 80 100 0 20 40 60 80 100 120
t, m in t, m in

Figure 8. Pseudo-First Order Kinetic Plots for the Adsorption of Cr+6 Ions onto: a) Activated Carbon and c) Bentonite; Pseudo-Second Order
Kinetic Plots for the Adsorption of Cr+6 Ions on: b) Activated Carbon and d) Bentonite. (Conditions: Concentrations: 50, 100 and
200 ppm; pH: 2.0; Adsorbents Dose: 4 g/L; Agitation Speed: 200 rpm; Temperature: 25 oC)

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 M.A. Mohamed et al / Chemistry Journal (2012), Vol. 02, Issue 03, pp. 95-105 ISSN 2049-954X

3.0 the bentonite is more powerful adsorbent than

activated carbon. These results indicate that both
2
2.5 R = 0.9658 adsorbents have a very strong adsorption capacity towards
Cr+6 ions.
2.0

3.8. Thermodynamic Parameters

Ce/qe

1.5
2
R = 0.9686 Thermodynamic parameters such as free energy (∆G°),
1.0 enthalpy (∆H°) and entropy (∆S°) changes of adsorption
can be evaluated from the following Equations 11 and 12:
activated carbon
0.5
bentonite

0 10 20 30 40 50 60 70 80 90
Kc = CAe/Ce…………………………………………...11
C e (m g/L)
∆G° = - RT lnKc……………………………………....12
Figure 9. Langmuir Adsorption Isotherm for Cr+6 Ions Adsorption Where:
by Activated Carbon and Bentonite at Constant
Temperature 25 oC and Contact Time 2 hours Kc is the equilibrium constant and CAe and Ce (both in mg/L) are the
equilibrium concentrations for solute on the sorbent and in the
From the calculated results of Langmuir and Freundlich solution, respectively
isotherm constants, given in Table 4, it can be shown that
the Freundlich model yields a much better fit than the The Kc values are used in Equations 11 and 12 to
Langmuir model, when the R2 values are compared in determine the ∆G°, ∆H° and ∆S°, the Kc may be expressed
Table 4. This suggests that the boundary layer thickness is in terms of the ∆H° (kj mol-1) and ∆S° (kj mol-1K-1) as a
increased. The Freundlich constant Kf indicates the function of temperature, Equation 13:
sorption capacity of the sorbent. From Table 4, the values
of Kf are 1.84 and 1.58 for activated carbon and bentonite, lnKc = - ∆H°/RT + ∆S°/R……..………………………13
respectively.
Thermodynamic parameters such as free energy of
sorption (∆G°), the heat of sorption (∆H°) and standard
1.6
2
R = 0.9956
entropy (∆S°) changes during the sorption process
1.5 were calculated using Equations 11 and 12, temperature
range of 25-40 oC , initial concentration 50 mg/L
1.4
of Cr+6 ions and dose 4 g/L for activated carbon
1.3
and bentonite. (∆H°) and (∆S°) were obtained from
ln qe

the slope and intercept of a plot of lnKc versus 1/T

1.2 (Figure 11). The values of these parameters were recorded
in Table 5.
1.1
2
R = 0.9953
activated carbon
1.0 1.6
bentonite activated carbon
bentonite
0.8 1.0 1.2 1.4 1.6 1.8 2.0
1.4
ln C e
1.2

+6
Figure 10. Freundlich Adsorption Isotherm for Cr ions
1.0
Adsorption by Activated Carbon and Bentonite at
lnKC

o
Constant Temperature 25 C and Contact Time 2 hours
0.8

Furthermore, the values of n are 2.26 and 1.78 0.6

for activated carbon and bentonite, respectively. It
is noted that the values of n are bigger than 1, 0.4

reflecting the favorable adsorption. On the other 0.00316 0 .003 18 0.00320 0.00322 0.00324 0.00326 0.00 328 0.00330 0 .003 32 0.00334 0 .003 36 0.00338
hand, the qmax and the adsorption intensity 1/T (K )
-1

values of bentonite are higher than activated carbon.

The calculated b values indicate the interaction
Figure 11. A Plot of lnKC Versus 1/T for Cr+6 Ions Adsorption onto
forces between bentonite surface and Cr+6 ions are stronger Activated Carbon and Bentonite for 50 mg/L Initial
than in case of activated carbon, this means that Concentration at Constant Adsorbents Dose: 4 g/L

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 M.A. Mohamed et al / Chemistry Journal (2012), Vol. 02, Issue 03, pp. 95-105 ISSN 2049-954X

Table 4. Langmuir and Freundlich Isotherm Constants for the Adsorption of Cr+6 Ions onto Activated Carbon and Bentonite at Constant
Temperature 25 oC

Langmuir Isotherm Constants Freundlich Isotherm Constants

Adsorbent
2
qmax (mg/g) b (L/mol) R Kf (mg/g) n R2
Activated Carbon 38.17 0.0252 0.9686 1.8446 2.26 0.9953
Bentonite 48.83 0.0377 0.9658 1.5826 1.78 0.9995

Table 5. Thermodynamic Parameters for the Adsorption of Cr(VI) ions onto Activated Carbon and Bentonite

∆G° (kj mol-1)

Adsorbent ∆H° (kj mol-1) ∆S° (kj mol-1K-1)
25o C 30o C 35o C 40o C
Activated Carbon 51.45 0.1776 - 1.24 - 2.12 - 3.00 - 3.89
Bentonite 36.72 0.1268 - 1.06 - 1.70 - 2.33 - 2.71

The negative values of ∆G° indicate the spontaneous nature
of the process and more negative value with increase of
temperature showed that an increased in temperature
favours the sorption process. The positive values of ∆H°
indicated that the sorption process was endothermic in
nature and the positive values of ∆S° showed the increased
randomness at solid/solution interfaces during the
adsorption of metal ions onto both adsorbents and also
reflected the affinity of activated carbon and bentonite
toward Cr+6 ions under consideration. It is also suggested
that the positive values of entropy indicated some
structural changes in the adsorbate and adsorbent
(Altundogan et al, 2000; Ajmal et al, 2003 and Fuhrman et
al, 2004).
the sorption was feasible, spontaneous and endothermic in
nature. The positive value of the entropy change,
suggested the increased randomness.
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