Beruflich Dokumente
Kultur Dokumente
Received 11 January 2005; received in revised form 31 May 2005; accepted 1 June 2005
Abstract
The adsorption of Acid Blue 193 (AB193) onto benzyltrimethylammonium (BTMA)-bentonite was investigated in aqueous solution in
a batch system with respect to contact time, pH and temperature. The surface modification of BTMA-bentonite was examined using the
FTIR technique. The pseudo-first-order, pseudo-second-order kinetic models and the intraparticle diffusion model were used to describe the
kinetic data and the rate constants were evaluated. The experimental data fitted very well the pseudo-second-order kinetic model and also
followed the intraparticle diffusion model up to 60 min, whereas diffusion is not only the rate controlling step. The Langmuir, Freundlich
and DubininRadushkevich (DR) adsorption models were applied to describe the equilibrium isotherms and the isotherm constants were
also determined. The Langmuir, Freundlich and DR models agree with experimental data well. The change of free energy, enthalpy and
entropy of adsorption were also evaluated for the adsorption of AB193 onto BTMA-bentonite. The results show that BTMA-bentonite could
be employed as low-cost material for the removal of acid dyes from effluents.
2005 Elsevier B.V. All rights reserved.
0927-7757/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2005.06.001
74 A.S. Ozcan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 266 (2005) 7381
3.3. Effect of pH
further increase in the adsorption and it is thus fixed as the where q1 and qt are the amounts of the dye adsorbed at equi-
equilibrium contact time. librium and at time t (mg g1 ) and k1 is the pseudo-first-order
The equilibrium adsorption capacity of AB193 onto rate constant (min1 ), applied to the adsorption of AB193.
BTMA-bentonite was also affected by temperature and Values of k1 calculated from the slope of the plots of 1/qt
decreased with increasing temperature from 20 to 40 C versus 1/t are shown in Table 2 (figure not shown). It was
which indicates that the adsorption of AB193 onto BTMA- found that the correlation coefficients for the pseudo-first-
modified adsorbent surface was favored at lower temperatures order model are lower than the pseudo-second-order model.
and it is controlled by an exothermic process. This is partly This indicates that the adsorption of AB193 onto BTMA-
due to a weakening of the attractive forces [28,29] between bentonite does not follow pseudo-first-order kinetics.
AB193 and BTMA-bentonite. Based on the above results, it The pseudo-second-order kinetic model [30] is expressed
implies that physical adsorption mechanism may play a vital as:
role in this system. Before and after equilibrium time, the
adsorption capacity shows different trends at various temper-
t 1 1
atures. In general, below the equilibrium time, an increase = + t, (2)
in the temperature leads to an increase in dye adsorption qt k2 q 2
2 q 2
rate, which shows a kinetically controlling process. After the
equilibrium attained, the uptake decreases with increasing
temperature indicating that the adsorption of AB193 onto where q2 is the maximum adsorption capacity (mg g1 )
BTMA-bentonite from aqueous solution is controlled by an for the pseudo-second-order adsorption and k2 is the equi-
exothermic process. librium rate constant of pseudo-second-order adsorption
(g mg1 min1 ). Values of k2 and q2 were calculated from
the plot of t/qt against t (Fig. 5). All of kinetic data of AB193
under different conditions were calculated from plots and
3.5. Kinetics of adsorption
are given in Table 2. The correlation coefficients for the
second-order kinetic plots at all the studied concentrations
The kinetics of adsorption is one of the most important
were generally above 0.999 (Table 2) and the calculated q2
characteristics in defining the efficiency of adsorption. Vari-
values also agree with experimental q2 values. These results
ous kinetic models have been proposed by different research
imply that the adsorption system studied obeys to the second-
groups where the adsorption has been treated as a pseudo-
order-kinetic model, a similar phenomenon which we have
first-order [30], a pseudo-second-order [30] and intraparticle
observed in the adsorption of acid dyes by acid-activated ben-
diffusion [31]. The pseudo-first-order kinetic model equation
tonite [14] and sepiolite [10].
is:
The pseudo-first-order and pseudo-second-order kinetic
models cannot identify the diffusion mechanism and the
1 k1 1 kinetic results were then analyzed by using the intraparti-
= + , (1)
qt q1 t q1 cle diffusion model. The intraparticle diffusion equation [31]
Table 2
Kinetic parameters for the adsorption of AB193 at various temperatures
t ( C) Co (mg dm3 ) k1 (min1 ) q1 (mg g1 ) r12 k2 (104 ) q2 (mg g1 ) r22 kp (mg g1 min1/2 ) C (mg g1 ) rp2
(g mg1 min1 )
20 100 2.024 257.7 0.936 12.85 260.7 0.999 7.681 195.72 0.945
150 3.425 353.6 0.960 8.702 352.6 0.999 16.23 222.51 0.948
175 3.170 394.2 0.915 7.090 398.3 0.999 16.74 257.45 0.914
200 3.540 438.6 0.955 6.829 437.4 0.999 20.28 273.57 0.921
225 3.300 488.5 0.926 6.334 478.5 0.992 21.51 316.99 0.826
250 3.003 515.5 0.918 5.911 518.9 0.999 19.09 355.49 0.819
30 100 2.573 237.6 0.990 16.22 237.6 0.999 7.965 171.81 0.869
150 2.585 330.7 0.895 10.18 333.6 0.999 10.69 240.52 0.779
175 1.751 364.4 0.804 8.837 377.6 0.999 7.987 294.52 0.795
200 3.016 422.8 0.924 7.500 423.3 0.999 15.54 292.29 0.777
225 2.631 469.3 0.860 6.986 473.4 0.999 14.84 342.30 0.722
250 2.997 495.1 0.977 6.905 494.5 0.999 19.21 336.21 0.923
40 100 1.724 211.6 0.666 17.32 216.3 0.999 5.714 165.73 0.751
150 2.678 316.9 0.961 11.82 316.7 0.999 11.10 225.55 0.836
175 2.643 360.9 0.882 9.551 363.0 0.999 12.33 258.20 0.793
200 4.922 435.5 0.856 8.339 415.1 0.999 21.72 250.91 0.686
225 2.803 460.4 0.964 8.326 458.8 0.999 17.40 318.90 0.884
250 3.002 487.1 0.938 7.229 485.8 0.999 20.08 324.82 0.899
78 A.S. Ozcan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 266 (2005) 7381
Fig. 6. Langmuir plots for the adsorption of AB193 onto BTMA-bentonite Fig. 8. DubininRadushkevich plots for the adsorption of AB193 onto
at various temperatures. BTMA-bentonite at various temperatures.
Table 3
Adsorption isotherm constants for the adsorption of AB193 onto BTMA-bentonite
t ( C) Langmuir Freundlich DubininRadushkevich (DR)
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