July 2010, Volume 1, No.

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International Journal of Chemical and Environmental Engineering

Removal of Zn(II) Ions from Aqueous Solution by

New Adsorbent: Calligonum comosum
M. A. ACKACHA
Department of Chemistry, Faculty of Science, Sebha University, Libya
*Corresponding Author email:ackacha57@yahoo.com

Abstract
In order to remove toxic Zn(II) ions from aqueous solutions, A new adsorbent material: Calligonum comosum was used.
The adsorption process was studied using batch experiments. The very important parameters affecting the adsorption
process such as initial pH of adsorbate, contact time and contact temperature were studied. Kinetic models such as
pseudo first-order, pseudo second-order and intra-particle diffusion were applied, in order to study the mechanism of the
adsorption. Thermodynamic parameters such as Gibbs free energy ( ∆ G0), standard enthalpy ( ∆ H0) and entropy change
( ∆ S0) were investigated. The Langmuir isotherm model fits well the experimental data when compared with Freundlich
isotherm model. The maximum adsorption capacities of Calligonum comosum stems were found to be 26.15, 30.51,
34.86, 37.04 mg/g at 293, 303, 313, 323 K, respectively. The present study revealed that Calligonum comosum stems
could be used as an efficient new adsorbent for the removal of Zn(II) ions from polluted water

1. Introduction contact temperature. The Langmuir and Frundlich

The discharge of toxic heavy metals into the water
environment is still large due to the increase of industrial
activates [1]. The heavy metals are not biodegradable,
therefore accumulate in living organisms and cause
various diseases such as anemia and renal damage [2,3].
Zinc is one of toxic heavy metals widely used in
electroplating industries and also considered as enzyme
activator in humans [4]. The maximum permissible level
of zinc in wastewater according to WHO standards is 5.0
mg/l [5]. Different methods may be used to eliminate
heavy metal ions from wastewaters include extraction,
chemical oxidation and reduction, filtration, ion exchange
and precipitation [6]. There are various disadvantages of
these methods such as operating cost and high energy
consumption. Among the mentioned methods, adsorption
is classified as economical and efficient method for the
removal of heavy metals from wastewater environment
[7]. The advantages of this method include high
adsorption
capacity, low cost and possible to reuse. Different natural
adsorbents such as agriculture wastes were used to
eliminate the concentration of Zn(II) ions in aqueous
solutions [8,9].
The present work describes the batch adsorption of
Zn(II) ions onto the surface of Calligonum comosum
stems. Optimum adsorption conditions were determined
as a function of initial pH of adsorbate, contact time and
isotherm model were used to describe the equilibrium
isotherms. The adsorption mechanism of Zn(II) ions onto
the surface of Calligonum comosum stems also evaluated
in terms of kinetics and thermodynamics.
2. Materials and Methods
2.1. Biomass preparation
Calligonum comosum stems were received from Zalaf
area in the south of Libya, washed with tab water then
double distilled water and heated in oven at 90oC for 1 h.
The dried sample was grounded and sieved (<125µm).
The prepared sample was stored in plastic container till
use.
2.2. Reagents and equipments
The stock solutions of Zn(II) ions (1000 mg/l) were
prepared in double distill water using zinc acetate [10 ].
All working solutions were prepared by diluting the stock
solution with double distill water. Disodium-EDTA
standard solution (0.0005 mol/l) was prepared [10].
A pH meter, model 3505, Jenway Felsted, Dunmow,
Essex C.46 SLB, United Kingdom was employed for the
measurements of pH values in the aqueous solutions. The
batch technique were carried out by mechanical shaker of
501 model from Stuart Scientific, United Kingdom.
2.3. Batch technique
 Removal of Zn(II) Ions from Aqueous Solution by New Adsorbent: Calligonum comosum

A volume of 50 ml of Zn(II) solutions was placed in The values of qe and K1 were calculated respectively
a 100 ml bottle. The pH of the solution was controlled from the intercept and slop of the plots of log(qe - qt)
using HCI and NaOH solutions. A 0.05 g of Calligonum versus t (Figure not shown).
comosum stems was added to the solutions. The flask The pseudo second order equation was expressed, as in
content was mixed at a constant speed of 400 rpm in a t 1 1
shaking water bath at desirable temperature. The mixture = 2 + t (3)
was filtered. The concentration of filtrate was determined qt K 2 qe qe
by titration with Disodium-EDTA using xylenol orange as Where K2 is the pseudo second order constant
indicator [10]. The plots of t/qt versus t (Figure not shown) were
The amount of metal ions adsorbed qe (mg/g) was used to calculate the values of qe and K2 using the slop
determined using the initial concentrations Co (mg/g), and intercept of these plots, respectively. The values of
concentrations of adsorbate at equilibrium Ce (mg/g), different parameters of pseudo first and second order
volumes of metal ions V (l) and the weight of adsorbent equations are presented in Table 3 and Figure 4,
material W (g) according to the following expression: respectively. It is very clear from Table 3 that qea and qeb
(Co − Ce ) × V values are different, suggesting that the adsorption
qe = (1) process is not a pseudo first order reaction. On the other
W
hand (Table 4), the correlation coefficient (R2) of the
pseudo second-order model are nearly equal 1 and the qea
3. Results and discussion
agree very well with qeb values. These results suggest that,
3.1 Effect of initial pH the adsorption of Zn(II) onto the surface of Calligonum
pH is one of the important parameters controlling the comosum stems follows the pseudo second order kinetic
removal of heavy metals from wastewater [11]. Table 1 model.
shows the effect of initial pH on adsorption process. The Table.1 Effect of initial pH
study was conducted at initial Zn(II) ion concentration of Initial pH qe (mg/g)
89.3 mg/l, contact time of 2 h and contact temperature of 2.5 1.6
303 k under varying initial pH range (2.5-6.5). The 3 4.2
optimum value of initial pH was 6.5. At low pH the H+ 3.5 8.8
ions are increased. This gives the surface of Calligonum 4 13.1
comosum stems a positive character, which leads the 4.5 16.3
repulsion of the positively charged Zn(II) ions from this 5 19.6
surface and reduce the adsorption capacity. At higher pH 5.5 25.5
values, the -OH groups on the surface are ionized,
6 26.8
therefore negatively charged oxygen (-O-) are produced
6.5 29.1
which enhances the cation exchange capacity.
3.2. Effect of contact time Table.2 Effect of contact time
Table 2 shows the effect of contact time on the Contact time 29.8 89.3 148.9 208.5
adsorption capacity at different initial concentrations of (minutes) mg/l mg/l mg/l mg/l
Zn (II), pH of 6.5 and temperature of 303 K. The qe qe qe qe
equilibrium state tacks place within 80 minutes. (mg/g) (mg/g) (mg/g
(mg/g) )
3.3. Adsorption kinetic model
Three kinetic models were used to test the 0 0 0 0 0
experimental data. These models are lagergren pseudo 10 13.07 16.02 21.57 27.45
first order equation [12], pseudo second order equation 20 14.38 17.97 22.88 28.11
[13] and intraparticle diffusion [14]. 40 14.71 18.63 22.88 28.76
The form of lagergren pseudo first-order equation, as in 60 15.04 19.28 24.19 30.07
K1 80 16.33 23.20 28.11 32.56
log( qe - qt ) = log qe - t (2) 100 16.34 23.23 28.23 32.65
2.303 120 16.34 23.24 28.35 32.68
Where qt is the amount of adsorbed Zn(II) ions at
time t and k1 is the lagergren pseudo first-order constant,
min-1.
a
experimental qe and b theoretical qe
a
experimental qe and b theoretical qe

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 Removal of Zn(II) Ions from Aqueous Solution by New Adsorbent: Calligonum comosum

The intra-particle mass transfer diffusion model where qmax (mg/g) and b (l/mg) are the Langmuir
according to Weber and Morris expressed, as in constants related to the maximum adsorption capacity and
1
qt = k p t 2
+C (4) Ce
energy of adsorption, respectively. The plots of
Where kp is the intra-particle diffusion coefficient and C qe
gives an idea about the thickness of the boundary layer. Table 4 Pseudo second order parameters at different
If the rate-limiting step is intra-particle diffusion, a initial concentration
plot of the adsorption capacity at any time against the Pseudo second order
square root of the contact time should yield a straight line. R2 q eb q ea K2
The Weber and Morris plots of qt versus t½ (Figure not 0.9999 15.43 16.34 0.0378 29.8
shown) have the same features: initial curved portion
represents the bulk diffusion stage, the linear portion
0.9998 20.00 23.21 0.0200 89.3
represents the intra-particle diffusion and the plateau
portion represents the final equilibrium stage. The values
0.9985 24.57 28.11 0.0236 148.9
of Kp and C which presented in Table 5 are calculated
respectively from the slop and intercept of the linear 0.9990 30.58 32.69 0.0201 208.5
portion (Figure 1).
versus Ce as presented in Figure 3, proved that the
adsorption process obeyed a Langmuir isotherm model
29.8 mg/l due to high R2 values and also due to the similarity
40
89.3 mg/l between qmaxa and qmaxb values. qmaxb and energy of
qe (mg/g)

30 148.9 mg/l adsorption, b were determined respectively from the slop

20 208.5 mg/l and intercept of the plots. The Langmuir constant, KL will
10 be used later for calculating the Gibbs free energy of the
0 adsorption process. KL was determined, as in
4 6 8 10
t½ (min)½ =
K L q max × b (6)

Table 5 Rate parameters of Intra-Particle diffusion

Fig 1. The linear portion of intra-particle diffusion.
and correlation coefficient at different initial
concentrations
Table 3 Pseudo first order parameters at different Co KP
C R2
initial concentrations (mg/l) (mg/g. min½)
Pseudo first order 29.8 0.475 11.794 0.9003
K1 q ea q eb R2
29.8 0.0164 16.34 3.27 0.8551 89.3 1.030 12.712 0.8417

89.3 0.0108 23.21 7.26 0.8791 148.9 0.936 18.187 0.7664

148.9 0.0088 28.11 6.84 0.8621 208.5 0.819 24.398 0.8677

208.5 0.0134 32.69 6.09 0.9576

3.4. Adsorption isotherm 293 k
The adsorption isotherm (Figur 2) provides a 40 303 k
relationship between the amounts of Calligonum
qe (mg/g)

30 313 k
comosum stems and the Zn(II) ions solution when both 20 323 k
phases are at equilibrium. Three adsorption isotherm 10
models were used in this work include Langmuir [15] 0
and Freundlich [16]. The Langmuir isotherm model
0 100 200 300
suppose that the observed maximum adsorption in a
saturated monolayer onto the homogeneous surfaces of a Ce (mg/l)
dsorbent, as in
Ce 1 1 Fig. 2. Equilibrium adsorption isotherm of Zn(II)
= + Ce (5) onto Calligonum comosum stems at different
q e q max .b q max
temperatures

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 Removal of Zn(II) Ions from Aqueous Solution by New Adsorbent: Calligonum comosum

10 293 K Table. 7 Freundlich isotherm parameters at different

9
8
303 K temperatures
7 T Freundlich isotherm
Ce / qe (g/l)

6
313 K (K)
5 KF n R2
4
3
323 K 293 22.68 4.02 0.9904
2
1
303 24.48 3.94 0.9856
0 313 27.44 4.05 0.9943
0 50 100 150 200 250 300
323 32.28 4.28 0.9897
Ce (mg/l)

3.5. Thermodynamic parameters

Fig. 3. Langmuir adsorption isotherm of Zn(II) onto
Calligonum comosum stems at different temperatures
The Freundlich isotherm described the adsorption
onto heterogeneous surfaces. The Freundlich equation
was applied in the present work, as in
1
log qe = log K F + loqCe
n
where KF and n are the Freundlich constantsand they
are determined from the plots of log ce versus log qe
(Figure 4). The correlation coefficient values were high
proving the obeyed of adsorption process to Freundlich
model.
The Langmuir and Freundlich isotherm parameters are
presented in Table 6 and Table 7, respectively.
The thermodynamic parameters of the adsorption, i.e.
the Gibbs free energy ∆ G0, standard enthalpy ∆ H0 and
entropy change ∆ S0 were calculated , as in
∆ G0 = -RTln KL (8)
∆ G0 = ∆ H0 - T ∆ S0 (9)
(7) Where R is universal gas constant (8.314 j/mol k)
The values of ΔH0 and ΔS0 were calculated
respectively from the slop and intercept of the plots of T
versus ΔG0 (Figure not shown). The obtained
thermodynamic parameters are presented in Table 8. The
negative values of ΔG0 proved that the process is
spontaneous and the degree of spontaneity increases with
increasing temperature. The positive value of ∆Ho
indicating that the adsorption process is endothermic in
nature. The positive value of ∆So suggest the increasing
randomness during the adsorption process. Finally the
adsorption is likely to occur spontaneously at normal and
high temperatures due to ∆Ho and ∆So > 0.

Table .8. Thermodynamic parameters at different

temperatures
Temperature, ∆Go ∆Ho ∆So (kJ/mol.
K (kJ/mol.
(kJ/mol. K)
K)
K)
Fig. 4. Freundlish for adsorption of Zn(II) at different 293 -2.88
temperatures 303 -2.91 7.03 0.034
Table. 6 Langmuir isotherm parameters at different 313 -3.29
temperatures 323 -3.87
T Langmuir isotherm
(K) qmaxa qmaxb b KL
R2
(mg/g) (mg/g) (l/mg) (l/g) 4.Conclusion
293 103.41 107.53 0.030 3.26 0.9929 The adsorption of zinc ions onto Calligonum
303 116.90 121.95 0.026 3.17 0.9832 comosum stem was pH dependent and reaches the
313 128.14 131.58 0.027 3.54 0.9833 equilibrium at 40 minutes.The results are fitted well on
323 141.62 140.85 0.030 4.22 0.9788 Langmuir isotherm model more than Freundlich isotherm
a
experimental qmax and b theoretical qmax model. The adsorption isotherm was endothermic in
a
experimental qmax and b theoretical qmax nature which confirmed by the obtained positive value of
∆ H0. The process is psedo second order reaction. The
mechanism of adsorption was carried out by adsorption
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 Removal of Zn(II) Ions from Aqueous Solution by New Adsorbent: Calligonum comosum

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629-635, 2004.
temperature increase. The maximum adsorption capacities
of Calligonum comosum stems were found to be 26.15, [8] N. T. Abdel-Ghani, G. A. Elchaghaly, "Influence of operating
conditions on the removal of Cu, Zn, Cd and Pb ions from
30.51, 34.86, 37.04 mg/g at 293, 303, 313, 323 K, wastewater by adsorption" Int. J. Environ. Sci. Tech., vol. 4(4), pp.
respectively. 451-456, 2007.
[9] C. Igwe, A. Augustin, "Equilibrium sorption isotherm studies of
ACKNOWLEDGEMENT Cd(II), Pb(II) and Zn(II) ions detoxification from waste using
The author wish to thank Prof. Hamdy Mahmud unmodified and EDTA-modified maize husk" Electronic Journal
Esmail for his assistant of this work. of biotechnology, vol. 10(4), pp. 536-547, 2007.
[10] A. I. Vogel, A Text-book of Quantative Inorganic Analysis, 3rd ed.,
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