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1
International Journal of Chemical and Environmental Engineering
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
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
19
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)
30 313 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
20
Removal of Zn(II) Ions from Aqueous Solution by New Adsorbent: Calligonum comosum
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)
and intra-particle diffusion. The process is spontaneous in [7 L. Norton, K. Baskaran, T. Mckenzie, "Biosorption of zinc from
aqueous solutions using biosolids" Adv. Environ. Res., vol. 8, pp.
nature and the degree of spontaneity increases as the
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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