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Procedia Environmental Sciences 4 (2011) 266280

Urban Environmental Pollution 2010

Removal of Chromium (VI) from wastewater using chemically

activated Syzygium jambolanum nut carbon by batch studies
Muthukumaran K*, Sophie Beulah
* Department of Chemistry, Thanthai Periyar Govt. Institute of Technology, Vellore 632 002, Tamilnadu, India.

Department of Chemistry, Govt. College of Engineering, Tirunelveli 627 007, Tamilnadu, India.

Received date September 30, 2010; revised date January 30, 2011; accepted date January 30, 2011

Abstract

The chemically activated carbon prepared from Syzygium jambolanum nut, an agricultural waste, after activation with
ammonium persulphate in the presence of sulphuric acid and then subjected to thermal activation by dolomite process, was
successfully used to remove chromium (VI) from wastewater in batch studies by adsorption process. Effects of pH, carbon dose
and equilibration time were determined. Desorption of Cr (VI) was done with 1 M NaOH and 10 % H2O2 mixture followed by 2
M HCl. Adsorption followed Freundlich, Langmuir and Temkin isotherms but was conformed to Freundlich adsorption isotherm
predominantly. Kinetic studies indicated that the removal process followed pseudo second order predominantly rather than
pseudo first order and reversible first order reaction. Removal of Cr (VI) followed the film diffusion process. Negative G0
values indicated the feasibility and the spontaneous nature of the adsorption process. The performance of Chemically Activated
High Temperature Syzygium jambolanum nut Carbon (CHSJC) was compared with a Commercial Activated Carbon (CAC).

Key words: Chromium (VI); Syzygium jambolanum nut carbon; (NH4)2S2O8; Chemical Activation; CAC; Batch studies;
Desorption; Isotherms; Kinetics; G0 values.

1. Introduction

Chromium and its compounds are widely used in industries. Chromium is encountered in the environment in the
oxidation states of Cr (III) and Cr (VI) [1]. Cr (III) is more stable and less toxic whereas Cr (VI) is highly toxic and
soluble in water. Hexavalent chromium is present in the effluents from electroplating, paint, pigment, cement,
mining, dyeing, fertiliser and photography industries [2]. At high concentrations, all compounds of chromium are
toxic. Ingestion of chromium may cause epigastric pain, nausea, vomiting and severe diarrhea. The tolerance limit
for Cr (VI) for discharge into drinking water is 0.05 mg/L according to USEPA [3]. Hexavalent chromium is
carcinogenic in nature [4]. Hence it is highly imperative to treat the wastewater containing Cr (VI) before its
discharge.

* Corresponding author. Tel.: +91-9489302842;

E-mail address: bamikumar@yahoo.co.in.

1878-0296 2011 Published by Elsevier Open access under CC BY-NC-ND license.

doi:10.1016/j.proenv.2011.03.032
 Muthukumaran K and Sophie Beulah / Procedia Environmental Sciences 4 (2011) 266280 267

A variety of approaches have been in use for the treatment of chromium containing wastes which include ion
exchange, electro dialysis, reverse osmosis, precipitation etc. However, these techniques lead to incomplete
removal, cause problems in the disposal of sludge and are also expensive. Alternate method using adsorbents has
been studied widely during the last three decades [5]. Activated carbons prepared from a variety of agricultural
wastes have been studied extensively for the removal of Chromium (VI) from wastewater [2].
Low cost activated carbon derived from a wide variety of agricultural waste like coconut shell [5], almond husk
[6], tamarind nut [7], pongamia leaf powder [8] etc, has been reported for the removal of traces of toxic inorganic
ions from wastewater. Among the agricultural wastes, Syzygium jambolanum nut is a potential agricultural waste. S.
jambolanum tree is an evergreen tropical tree. It also grows easily in sub-tropical climates and it grows largely all
over India. It is commonly called java plum, jambul, jamun, jaman, black plum, Indian blackberry, jambol, jambolan
etc. The berry has a single nut which is used for the treatment of diabetic and blood pressure. Even though it is used
for medicinal purposes, a large amount of nuts remain as a waste. The abundance of the nut is high, which prompted
the studies on the use of S. jambolanum nut for the removal of toxic Chromium (VI) from wastewater after
activation.
The aim of this paper is to prepare a Chemically Activated Carbon from Syzygium jambolanum nut carbon and to
evaluate its effectiveness for the removal of Cr(VI) from wastewater by Batch Studies and also to compare its
removal capacity with a Commercial Activated Carbon.

2. Materials and Methods

2.1. Preparation of Chemically Activated High Temperature Syzygium jambolanum nut Carbon (CHSJC)

S. jambolanum nut was treated with H2SO4 (1:1.5 weight ratio) in the presence of oxidising chemical (NH4)2S2O8
(0.1 part). The chemically activated material was left in an air oven maintained at 140 160 0C for 24 hours. The
material was repeatedly washed with distilled water followed by 2 % NaHCO3 solution to remove the free acid and
finally left immersed in 2 % NaHCO3 solution overnight. After separating the material, it was washed with distilled
water, and dried at 105 5 0C. The dried material was subjected to thermal activation in CO2 atmosphere by
sandwiching the material between powdered CaCO3 beds in a closed container at 800 850 0C for 30 minutes by
modified dolomite process [9]. The material was washed thoroughly with water and then soaked in 10 % HCl to
remove CaO as well as undecomposed CaCO3. After separating the material, it was washed with distilled water, and
dried at 105 5 0C. The carbon was referred to as Chemically Activated Syzygium jambolanum nut Carbon
(CHSJC). Commercial activated carbon (CAC) of M/s LOBA chemicals was used for comparison purposes. Both
the carbons were ground and sieved to separate 20 50 mesh ASTM particles.

2.2. Evaluation of carbon characteristics

The important characteristics of carbons such as bulk density, moisture content, ash, matter soluble in water,
matter soluble in acid, pH, decolourisation property, phenol number, ion exchange capacity, surface area and iron
content were analysed for both the carbons as per Indian Standards [10]. From the results, the bulk density of
CHSJC was 0.63 g/ml which was higher than that of CAC whose bulk density was 0.51 g/ml. The surface area of
CHSJC was 660 m2/g which was higher than that of CAC (629 m2/g). Hence CHSJC was expected to be a better
adsorbent than CAC for the removal of Cr(VI).

2.3. Batch Studies

Batch studies were carried out by using mechanical shaker. In order to find out the optimum pH for maximum Cr
(VI) removal, experiments were carried out using 0.5 g of the carbons under study and 100 mL of 10 mg of Cr
(VI)/L solutions adjusted to cover the pH range 1.0 to 6.0. The solutions were equilibrated for 24 hours in a
mechanical shaker. They were then filtered and analysed for Cr (VI) content by using UV-Visible
Spectrophotometer (PGI 1901) at 540 nm by standard methods [11].
Other parameters such as effect of carbon dose at optimum pH and effect of equilibration time under optimum
pH and carbon dosage were also established by the above method. Desorption experiments were conducted with 1
268 Muthukumaran K and Sophie Beulah / Procedia Environmental Sciences 4 (2011) 266280

M NaOH and H2O2 in various ranges of 2 % to 20 % to desorb Cr (VI) from the carbons followed by equilibration
with 100 mL of 2 M HCl for 24 hours to recover remaining Cr (VI) as Cr (III). Adsorption isotherm studies were
carried out with different initial concentrations of Cr (VI) and fixed doses of carbon. Kinetic studies were also
carried out at different time intervals and fixed Cr (VI) concentration, carbon doses and pH.

3. Results and Discussion

3.1. Effect of pH

From Figure 1, it is clear that quantitative removal of Cr (VI) occurred in the pH range 1.5 - 4.5. Maximum
removal took place at pH 2.0 for both the carbons. For further studies, the pH was chosen as 2.0. The removal of Cr
(VI) by adsorption is highly dependent on the pH of the solution. The dominant form of Cr (VI) at pH 2.0 is HCrO4 -
. In highly acidic media, the adsorbent surface might be highly protonated and favour the uptake of Cr (VI) in the
anionic form HCrO4-. Maximum adsorption at pH 2.0 indicates that it is the HCrO4- form of Cr (VI) which is
adsorbed preferentially on the adsorbents [12].

120

100

80
% Cr(VI) removal

Carbon dose= 0.5 g/100 mL, Equil. Time= 24 hrs,

60 Cr(VI)= 100 mL of 10 mg/L

40

CHSJC
20
CAC

0
0 1 2 3 4 5 6
pH

Figure.1 Effect of pH on Cr (VI) removal. CHSJC Chemically Activated Syzygium jambolanum nut Carbon;
CAC Commercially Activated Carbon.

A pure carbon surface is considered to be non-polar, but in actual practice some carbon-oxygen complexes such
as CXO, COX and CXO2 are usually present which render the surface slightly polar [13] and it may be noted that
satisfactory methods are not available to determine the polar character of the surface quantitatively [14]. CHSJC was
prepared upon treatment with sulphuric acid and ammonium persulphate and washed with sodium bicarbonate, dried
and then heated to 800 oC in CO2 atmosphere. Activation of carbons at high temperature makes the surface charge
positive [15]. CAC is also a high temperature carbon since it was found to remove Cr (VI) as HCrO4-. At high
temperatures, groups such as CXONa+, CXONa22+, CxOH22+, CxOH+, etc. are assumed to be present on the surface of
carbon. HCrO4- ion seems to be adsorbed on the surface groups as follows:

CxOH+ + HCrO4- CxOH HCrO4 (1)

CXONa+ + HCrO4- CXONa HCrO4 (2)
 Muthukumaran K and Sophie Beulah / Procedia Environmental Sciences 4 (2011) 266280 269

Since quantitative removal of Cr (VI) occurred in the pH range 1.5 - 4.5 and maximum removal took place at pH
2.0 for all the carbons, it is probably assumed that more groups such as CXONa+, CXONa22+, CxOH22+, CxOH+ are
available at pH of 2.0 which is responsible for the maximum adsorption of HCrO4- .

3.2. Effect of carbon dose

From Figure 2, it could be seen that for maximum Cr (VI) removal, the solution should be equilibrated with at
least 0.1 g of CHSJC and 0.3 g of CAC. So it could be inferred that CHSJC was thrice as effective as CAC when
the pH of the 100 mL of 10mg/L of Cr(VI) solutions were kept as 2.0.

120

100
% Cr(VI) remo va

80
pH = 2, Equ il. Time= 24 H rs ,
60 Cr(VI)=100 mL o f 10 mg /L

40
CHSJC
20 CA C

0
0 0.1 0.2 0.3 0.4 0.5 0.6
Carbon dose in mg

Figure 2 Effect of carbon dose on Cr (VI) removal. CHSJC Chemically Activated Syzygium jambolanum nut
Carbon; CAC Commercially Activated Carbon

3.3. Effect of equilibration time

The results are shown in Figure 3, from which it is clear that 4 hours of equilibration was sufficient for CHSJC
for maximum removal of Cr (VI) and for CAC 6 hours was needed for maximum removal. So the optimum time
needed for removal of Cr (VI) by CHSJC was 1.5 times lesser than that of CAC when the pH was kept 2.0 with
optimum doses.

3.4. Desorption

It was observed that 10 % H2O2 with 1 M NaOH was sufficient for maximum removal of 85% Cr (VI) by CHSJC
and 80.5% Cr (VI) by CAC. A maximum of 10 % Cr (III) could be desorbed by 2 M hydrochloric acid from both
the carbons. Cr (III) was analysed by oxidising it to Cr (VI) using KMnO4 and NaN3 and determined
spectrophotometrically by diphenyl carbazide method [11].

3.5. Adsorption isotherms

The Freundlich, Langmuir and Temkin isotherm models are the simplest and the most frequently applied
270 Muthukumaran K and Sophie Beulah / Procedia Environmental Sciences 4 (2011) 266280

isotherm models to explain the sorption process of various metal ions on activated carbons.
The Freundlich equation is written in the logarithmic form as [16]:

120

100
% Cr(VI) remo val

80

pH = 2, CHSJC= 0.1 g /100 mL, CAC= 0.3 g /100 mL,

60 Cr(VI)= 100 mL o f 10mg /L

40
CHSJC

20 CA C

0
0 1 2 3 4 5 6
Time i n Hours

Figure 3 Effect of equilibration time on Cr (VI) removal. CHSJC Chemically Activated Syzygium
jambolanum nut Carbon; CAC Commercially Activated carbon

pH = 2, Equ il.time= 24 hrs, CHSJC= 0.1g/ 100 mL,

1.8
CA C= 0.3 g /100 mL, Cr(VI )=100 mL o f 20-100 mg /L
1.6

1.4
log x/ m

1.2

0.8 CHSJC
CA C
0.6

0.4
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
l og Ce

Figure 4. Freundlich adsorption isotherms on Cr (VI) removal. CHSJC Chemically Activated Syzygium
jambolanum nut Carbon; CAC Commercilly Activated carbon
 Muthukumaran K and Sophie Beulah / Procedia Environmental Sciences 4 (2011) 266280 271

log x/m = log k + 1/n log Ce (3)

where x = amount of solute adsorbed in mg/L
m = the weight of the adsorbent in g/L
Ce = equilibrium concentration of the solute in mg/L
k,1/n = constants characteristics of the system and are the measures of adsorption capacity in
mg/g and intensity of adsorption in L/mg.
The plot of log x/m against log Ce is shown in Figure 4. Plots of log x/m Vs log Ce were linear for CHSJC and
CAC. The straight line nature of the plots indicated that the process followed was of Freundlich adsorption type.
Values of k and n were calculated from the intercepts and slopes and are shown in Table 1. Values of 1/n (slope)
and regression co-efficient (R2) values are also given in Table 1.

Table 1. k, n and R2 values of Freundlich adsorption isotherm for Cr (VI) on different carbons
Carbon 1/n (L/mg) n (mg/L) k (mg/g) R2
CHSJC 0.2761 3.6219 39.8107 0.9717
CAC 0.4000 2.5000 3.8019 0.9928

Identical slope values (1/n) indicated that similar type of adsorption reactions occurred on the surface of the
carbon [17]. From Table 1, it could be seen that the carbons gave nearly identical slope values which suggested that
similar type of adsorption reactions of Chromium (VI) had occurred on the surface of the carbons studied. Steep
slopes of 1/n close to 1 indicated good adsorption potential of the adsorbent or intensity of adsorption at equilibrium
concentration [18]. From Table 1, it could be inferred that as the values of 1/n are near to unity, the two sorbents had
good adsorption potential or intensity of adsorption at equilibrium concentration. The values of 1 < n < 10 showed
favourable adsorption of adsorbate on the carbons [19]. Since in this case, 1 < n < 10, it was evident that favourable
adsorption of Cr (VI) occurred on CHSJC and CAC.
High values of k (greater than 1) from Freundlich isotherm suggested that the adsorption capacity of carbons
were significant [19]. For both the carbons, k value was greater than 1 which implied significant adsorption capacity
of the carbons. Since the k value of CHSJC was higher than that of CAC, it could be inferred that the adsorption
capacity of CHSJC was more than that CAC. Regression co-efficient (R2) values close to unity indicated the
applicability of the Freundlich isotherm and the monolayer coverage of adsorbed species on the carbon surface [20].
The observed linear relationships were statistically significant as evidenced from the regression co-efficient (R2)
values close to unity which indicated the applicability of the Freundlich isotherm and the monolayer coverage of
chromium species on the carbon surfaces. The Langmuir adsorption isotherm equation is expressed as [21]:

Ce /qe = 1/Qob + Ce/Qo (4)

where Ce = equilibrium concentration in mg/L
qe = the amount adsorbed at equilibrium in mg/g
Qo and b = Langmuir constants related to adsorption capacity in mg/g and
energy of adsorption in L/mg

The linear plots of Ce/ qe Vs Ce showed that the adsorption obeys Langmuir model for CHSJC and CAC and is
shown in Figure 5. It suggested the formation of monolayer coverage of the adsorbate on the surface of the
adsorbent in the concentration range studied [22]. The data of Langmuir adsorption isotherm is given in Table 2.

Table 2. Qo, b and R2 values of Langmuir adsorption isotherm

Carbon Qo (mg/g) b (L/mg) R2
CHSJC 100 0.0588 0.9424
CAC 27.2 0.0459 0.9689
272 Muthukumaran K and Sophie Beulah / Procedia Environmental Sciences 4 (2011) 266280

2.8

pH = 2, Equ il.T ime= 24 h rs , CHSJC= 0.1g /100 mL,

2.4
CA C= 0.3g/100 mL, Cr(VI)= 100 mL o f 20-100mg /L

2
CH SJC
1.6
CA C
C e/ qe

1.2

0.8

0.4

0
0 5 10 15 20 25 30 35 40 45
Ce

Figure 5. Langmuir adsorption isotherms on Cr (VI) removal. CHSJC Chemically Activated Syzygium
jambolanum nut Carbon; CAC Commercially Activated Carbon

The monolayer adsorption capacity Qo value of CHSJC indicated that it was a better adsorbent for Cr (VI) than
CAC. Analysis of the energy of adsorption or surface energy (b) showed that CHSJC had more surface energy than
and CAC. The regression co-efficient (R2) values close to unity indicated the applicability of the Langmuir isotherm
and the monolayer coverage of adsorbate on the carbon surface [20]. From the Table 3, it could be seen that the
regression co-efficient (R2) values were close to unity. So it could be inferred that Langmuir isotherm is also
applicable and that monolayer coverage of Cr (VI) took place on CHSJC and CAC.
The essential characteristics of Langmuir isotherm could be expressed in terms of dimensionless constant
separation factor or equilibrium parameter RL [23]. RL= 1 / 1 +bC0 where b is Langmuir constant and C0 is the initial
concentration of Cr (VI). Separation factor shows the nature of adsorption process, and its value indicates that the
sorption process could be favourable, linear, unfavourable, irreversible when 0<RL<1, RL = 1, RL>1, RL = 0
respectively. The values of RL are shown in Table 3.

Table 3. Equilibrium parameter RL values for CHSJC and CAC

CHSJC CAC
0.4596 0.5213
0.2983 0.3526
0.2208 0.2664

The Temkin equation has generally been applied in the following linearised form [24]:

qe= at +2.3bt log Ce (5)

where qe = the amount adsorbed at equilibrium in mg/g
Ce = equilibrium concentration in mg/L
at and bt = Temkin isotherm constants related to adsorption capacity in mg/g and intensity of
adsorption in L/mg respectively

The linear plots of qe Vs log Ce showed that the adsorption process followed Temkin isotherm model for CHSJC
 Muthukumaran K and Sophie Beulah / Procedia Environmental Sciences 4 (2011) 266280 273

and CAC and is shown in Figure 6 and the data of Temkin isotherm is given in Table 4.

70

pH= 2, Equ il. Time= 24 h rs , CHSJC=0.1g /100 mL,

60
CAC= 0.3 g /100 mL, Cr(VI)= 100 mL of 20-100 mg /L

50

40
CHSJC
qe

CAC
30

20

10

0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
log Ce

Figure 6. Temkin adsorption isotherms for Cr (VI) removal. CHSJC Chemically Activated Syzygium
jambolanum nut Carbon; CAC Commercially Activated carbon

Table 4. at, bt and R2 values of Temkin adsorption isotherm

Carbon at (mg/g) bt (L/mg) R2
CHSJC 13.5700 12.7643 0.9009
CAC 2.3445 3.8948 0.9359

The adsorption capacity at value of CHSJC indicated that it was a better adsorbent for Cr (VI) than CAC as the
value for CHSJC was higher than CAC. Analysis of the intensity of adsorption bt showed that the intensity of
adsorption was more on CHSJC than on CAC. The regression co-efficient (R2) values of the carbons close to unity
indicated the applicability of the Temkin isotherm.
On comparing the regression co-efficient (R2) values of Freundlich, Langmuir and Temkin adsorption isotherms,
it was found that the R2 values of Freundlich adsorption isotherm were closer to one than that of Langmuir and
Temkin adsorption isotherms for both the carbons. So adsorption fitted the Freundlich adsorption isotherm better
when compared to Langmuir adsorption isotherm and Temkin adsorption isotherm. Adsorption conformed to
Freundlich adsorption isotherm model based on the formation of monolayer on the surface of the adsorbent.

3.6. Kinetic studies

The reversible first order rate equation is written in the form [25]:

ln (1 Ut) = -kt (6)

where ut = x/Xe and k is the overall rate constant ut can be calculated using the expression (7)
274 Muthukumaran K and Sophie Beulah / Procedia Environmental Sciences 4 (2011) 266280

CA(o) CA(t ) x
=
CA(o) CA(e) Xe

where ut is called fractional attainment of equilibrium

CA(o) = initial concentration of metal ion
CA(t) = the concentration of metal ion present at any time (t)
CA(e) = the concentration of metal ion present at equilibrium condition
By knowing the values of k and kc, it is possible to calculate k1 and k2 using the expression (8)

k1 1
k = k1 + k 2 = k1 + = k1 1 +
kc kc
The straight line plot of log (1-ut) vs t as shown in Figure 7 indicated that the adsorption of Cr (VI) on CHSJC
and CAC followed reversible first order kinetics.

0
0 60 120 180 240 300 360
-0.5
pH= 2, CHSJC= 0.1 g/100 mL, CAC=0.3 g /100 mL,
Cr(VI)= 100 ml o f 10 mg /L
-1

-1.5
lo g(1-Ut)

-2

-2.5
CHSJC
-3 CAC

-3.5
Time(min)

Figure 7. Reversible first order kinetics for Cr (VI) removal. CHSJC Chemically Activated Syzygium
jambolanum nut Carbon; CAC Commercially Activated Carbon

The straight line portions of the curves were used for obtaining the slope values, which give the overall rate
constants (k) of the process. The forward k1 and backward k2 rate constants were calculated using equation (8).
These data are furnished alongwith R2 values in Table 5 for CHSJC and CAC.
From Table 5, it is evident that the forward rate constant was much higher than the backward rate constant
suggesting that the rate of adsorption was clearly dominant in both the cases [26]. The applicability of reversible
first order rate equation was also confirmed by their regression co-efficient R2 values which were near to unity.
 Muthukumaran K and Sophie Beulah / Procedia Environmental Sciences 4 (2011) 266280 275

Table 5. Rate constants for the adsorption of Cr (VI)

Sorbent k = k1 + k2 (min-1) k1 (min-1) k2 (min-1) R2
CHSJC 0.007 0.006993 0.000007 0.9476
CAC 0.0035 0.0034965 0.0000035 0.9604

The linearised form of the pseudo first order rate equation of Lagergren is given as [27]:

ln(qe-qt) = ln qe k1t (9)

where qe = the amount of metal ions adsorbed at equilibrium (mg/g)
qt = the amount of metal ions adsorbed at time t (mg/g)
t = time (min)
k1 = pseudo first order equilibrium rate constant (1/min)

A plot of log(qe-qt) versus t as shown in Figure 8 gave a straight line with slope of k1 and an intercept of log qe .
It confirmed the applicability of pseudo first order rate equation. The data of pseudo first order kinetic constants are
furnished alongwith R2 values in Table 6. The applicability of pseudo first order rate equation was also confirmed by
their regression co-efficient (R2) values which were closer to unity.

0. 3

0
0 60 120 180 240 300 360
- 0. 3

- 0. 6
C HSJC
log(qe-qt)

- 0. 9
CA C
- 1. 2

- 1. 5 p H= 2, C HS JC= 0.1g /100 mL,

C A C= 0.3 g/100 mL, Cr( VI)= 100 mL o f 10 mg/ L
- 1. 8

- 2. 1

- 2. 4
T ime (mi n)

Figure 8. Pseudo first order kinetics for Cr (VI) removal. CHSJC Chemically Activated Syzygium
jambolanum nut Carbon; CAC Commercially Activated Carbon

Table 6. Pseudo first order kinetic constants for the adsorption of Cr (VI)

qe(exp) qe(theo) k1
Carbon P R2
mg/g (mg/g) (1/min)

CHSJC 9.99 2.2162 0.0164 77.8 0.9377

CAC 3.33 0.7065 0.0081 78.8 0.9661

276 Muthukumaran K and Sophie Beulah / Procedia Environmental Sciences 4 (2011) 266280

The pseudo-second-order model rate equation may be expressed as (10) [28]:

t 1 t
= 2
+
qt K 2q e qe

where qe = the amount of metal ions adsorbed at equilibrium (mg/g)

qt = the amount of metal ions adsorbed at time t (mg/g)
t = time (min)
k2 = pseudo second order adsorption rate constant (g/mg/min)

A plot of (t/qt) versus t also produced a straight line with a slope of 1/qe and an intercept of 1/k2qe2. It indicated
the applicability of pseudo second order model (Figure 9). The kinetic data for pseudo second order are furnished in
Table 7. The rate of the pseudo second order equation may be dependent on the amount of solute sorbed on the
surface of the adsorbent at any time and the amount sorbed at equilibrium [29]. The data of pseudo second order
kinetic constants along with R2 values are furnished in Table 7. The applicability of pseudo second order rate
equation was also confirmed by their regression co-efficient (R2) values which were closer to unity.

120

pH = 2, C HSJC = 0.1g/ 100 m L, C A C= 0.3 g/100 mL,

100 Cr( VI)= 100 mL o f 10 mg /L

80
CH SJC
CA C
t/qt

60

40

20

0
0 60 120 180 240 300 360
Time ( min)

Figure 9. Pseudo second order kinetics for Cr (VI) removal. CHSJC Chemically Activated Syzygium
jambolanum nut Carbon; CAC Commercilly Activated Carbon

Table 7. Pseudo second order kinetic constants for the adsorption of Cr (VI)
k2
Carbon qe(exp) mg/g qe (theo) (mg/g) P R2
(g/mg/min)
CHSJC 9.99 10.1215 0.0191 1.3163 0.9999
CAC 3.33 3.3580 0.0324 0.8408 0.9996

In order to compare the quantitative applicability of kinetic models in fitting to the data, the percent relative
deviation (P), given by the following equation (11) was calculated [30].
 Muthukumaran K and Sophie Beulah / Procedia Environmental Sciences 4 (2011) 266280 277

100 q e(exp) q e(theo)

P =
N q e(exp)

where qe(exp) is the experimental value of qe at any value of Ce, qe(theo), the corresponding theoretical value of qe
and N is the number of observations. It is found that the lower the value of percentage deviation (P), the better is the
fit. It is generally accepted that when P value is less than 5, the fit is considered to be excellent [31]. The results
have been analysed using equations (9) and (10). The experimental data fitted well in both the equations. The values
of qe(theo) calculated from these models were compared with experimental values qe(exp) as shown in Tables 6 and 7. It
was found that the values of qe(theo) calculated from the pseudo-first-order kinetic model differed appreciably from
the experimental values qe(exp). The percent relative deviation (P) was also very high.
On the other hand, values of qe(theo), were found to be very close to qe(exp) when pseudo second order rate equation
was applied. The percent relative deviation (P) was well below 5. The P values could not be found out for reversible
first order kinetics. The values of regression co-efficient (R2) were closer to one for pseudo second order kinetics
when compared with that of pseudo first order and reversible first order kinetics. The results indicated that the
adsorption of Cr (VI) on CHSJC, HSJC and CAC was governed by pseudo second order kinetics predominantly.

3.7. Diffusion co-efficient

For the adsorption of metal ions on a carbon surface, for film diffusion to be rate determining step, the value of
the film diffusion co-efficient (Df) should be in the range 10-610-8 cm2/sec. If pore diffusion were to be the rate
determining, the pore diffusion co-efficient (Dp) should be in the range 10-1110-13 cm2/sec [25]. Assuming spherical
geometry for the sorbents [32], the overall rate constants of the process can be correlated to the pore diffusion co-
efficient in accordance with the expression (12).
r0 2
t1/2 = 0.03
Dp
or
2
r0
D p = 0.03
t1/2

Expression for film diffusion co-efficient is (13)

r0 C
Df = 0.23
t1/2 C

where ro = radius of the sorbent (cm)

Dp = pore diffusion coefficient (cm2/sec)
Df = film diffusion coefficient (cm2/sec)
C /C = equilibrium loading of the adsorbent
= film thickness (cm)
t = time for half change (sec)

Table 8. Diffusion coefficient for the removal of Cr (VI)

Film diffusion Pore diffusion
Sorbent
co-efficient (cm2/sec) co-efficient (cm2/sec)
CHSJC 4.0036 10-7 1.5028 10-7
-7
CAC 2.0018 10 7.5142 10-8
Concentration of Chromium (VI) = 10 mg/L
278 Muthukumaran K and Sophie Beulah / Procedia Environmental Sciences 4 (2011) 266280

It is evident from Table 8 that the removal of Cr (VI) followed the film diffusion process since the co-efficient
values are in the range 10-610-8 cm2/sec.

3.8. Calculation of G0

The thermodynamic parameter, the Gibbs free energy G0 is the fundamental criterion of spontaneity. Reactions
occur spontaneously at a given temperature if G0 is negative quantity. The free energy of adsorption was obtained
from the Langmuir isotherm equation as follows [33]:

G0 = -2.303 RT logK (14)

where G0 = free energy change (KJ/mol)
K = equilibrium constant
R = universal gas constant (8.314 J mol-1k-1)
T = absolute temperature (K)

The Gibbs free energy of adsorption can be related with the equilibrium constant K corresponding to the
reciprocal of the Langmuir constant b.
G0 values were calculated for CHSJC and CAC respectively using the equilibrium constant values of the
adsorption process. It was found that the values of G0 were -7.0217 KJ/mole and -7.635 KJ/mole respectively. The
negative values indicated the feasibility of the process and the spontaneous nature of the adsorption process [32].

4. Conclusion

Batch studies on removal of Chromium (VI) by CHSJC showed that maximum removal occurred at pH of 2.0 as
HCrO4-. The optimum carbon dose needed was only 0.1 g and the optimum time needed was only 4 hours for
quantitative removal of Chromium (VI) in the batch mode. Chromium (VI) could be recovered up to 85.1 % using 1
M NaOH and 10 % H2O2. The remaining chromium was desorbed as Cr (III) using 2 M HCl up to 10 %. Though
adsorption conformed to Freundlich, Langmuir and Temkin adsorption isotherms, the Freundlich adsorption
isotherm model fitted well for Cr (VI) adsorption. Kinetic studies showed that adsorption process was governed by
pseudo second order kinetics predominantly than reversible first order and pseudo first order. Kinetic studies also
indicated that the removal of Cr (VI) also followed film diffusion process. Go values calculated showed that the
adsorption was spontaneous. Performance of CHSJC was compared with a commercial activated carbon (CAC) and
it was found that CHSJC was superior to CAC for the removal of Cr (VI) from wastewater. The method of
preparation of chemically activated high temperature S. jambolanum nut carbon is viable and could be used as a
promising tool to remediate Chromium (VI) from wastewater.

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