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Abstract
MCM-22 was employed as an effective adsorbent for removal of basic dyes including methylene blue, crystal violet, and rhodamine B from
aqueous solution. The adsorption kinetics and isotherms were investigated. The adsorption capacity of MCM-22 for three dyes follows an order of
MB > CV ∼ RB. Kinetic studies indicate that the adsorption follows the pseudo second-order kinetics and the adsorption is a two-step diffusion
process with film diffusion dominating the process. The adsorption isotherm can be well fitted by both the Langmuir and the Freundlich models.
Thermodynamic calculations suggest that the adsorption of basic dyes on MCM-22 is an endothermic reaction.
2005 Elsevier Inc. All rights reserved.
Fig. 1. Chemical structure of basic dyes. Fig. 2. Adsorption of basic dyes on MCM-22 at 30 ◦ C.
S. Wang et al. / Journal of Colloid and Interface Science 295 (2006) 71–78 73
Fig. 3. Adsorption isotherm of MB on MCM-22 at different temperatures. (a) Freundlich model, (b) Langmuir model.
Fig. 4. Adsorption isotherm of CV on MCM-22 at different temperatures. (a) Freundlich model, (b) Langmuir model.
1.1 × 10−4 mol/g. The difference in adsorption for three dyes is adsorption capacity, and KL is the constant related to the free
probably ascribed to the varying molecular size. As seen from energy of adsorption.
Fig. 1, MB is quite smaller than CV and RB, so that MB easily The Freundlich isotherm is an empirical equation employed
enters the inner pores of MCM-22. Vinod and Anirudhan [18] to describe heterogeneous systems. The Freundlich equation is
investigated the adsorption of three basic dyes, MB, CV, and
1/n
RB, on the humic acid (HA)-immobilized pillared clay (PILC) Qe = KCe , (3)
and found the adsorption follows the order of MB > CV > RB.
where K and n are Freundlich adsorption isotherm constants,
Graham et al. [19] studied methylene blue and crystal violet ad-
indicative of the extent of the adsorption and the degree of
sorption on activated carbon and reported similar results.
nonlinearity between solution concentration and adsorption, re-
spectively.
3.2. Adsorption isotherms
Figs. 3–5 present adsorption isotherms of three dyes on
The equilibrium adsorption isotherm is of importance in the MCM-22 at different temperatures and the fitted curves for
design of adsorption systems. Several isotherm equations are Langmuir and Freundlich models. The parameters obtained
available and two important isotherms are selected in this study, from the isotherms are given in Table 1. As seen the adsorp-
the Langmuir and Freundlich isotherms. tion isotherms at different temperatures for the same dye are
The Langmuir isotherm is based on an assumption that the very close and can be fitted very well using two isotherm mod-
adsorption occurs at specific homogeneous sites within the ad- els (evidenced from the correlation coefficients, >0.990). From
sorbent. The equation is Table 1, it is also seen that the obtained adsorption capacities
from the Langmuir isotherm show slightly higher adsorption
Q0 KL Ce for CV than RB on MCM-22.
Qe = , (2)
(1 + KL Ce ) The increase in dye adsorption with increasing temperature
where Qe is the adsorbed amount of the dye, Ce is the equilib- might also be due to the enhanced rate of external and intra-
rium concentration of the dye in solution, Q0 is the monolayer particle diffusion of the adsorbate, as diffusion is a dominant
74 S. Wang et al. / Journal of Colloid and Interface Science 295 (2006) 71–78
Fig. 5. Adsorption isotherm of RB on MCM-22 at different temperatures. (a) Freundlich model, (b) Langmuir model.
Table 1
Parameters of adsorption isotherms of basic dyes on MCM-22 at different temperatures
Temperature (◦ C) Dye Langmuir model Freundlich model
Q0 (mol/g) KL (dm3 /mol) R2 K [mol/g (L/mol)1/n ] 1/n R2
30 MB 1.73 × 10−4 4.03 × 107 0.999 3.11 × 10−4 0.0486 0.997
40 1.79 × 10−4 2.63 × 107 0.985 4.06 × 10−4 0.0673 0.996
50 1.76 × 10−4 3.53 × 107 0.999 2.86 × 10−4 0.0407 0.998
30 CV 1.20 × 10−4 8.97 × 106 0.994 2.06 × 10−4 0.0473 0.990
40 1.20 × 10−4 6.12 × 106 0.995 2.22 × 10−4 0.0543 0.991
50 1.26 × 10−4 8.70 × 106 0.995 2.27 × 10−4 0.0512 0.992
30 RB 1.05 × 10−4 8.89 × 106 0.989 3.10 × 10−4 0.0891 0.996
40 1.13 × 10−4 4.07 × 106 0.994 3.10 × 10−4 0.0891 0.996
50 1.11 × 10−4 7.87 × 106 0.999 3.35 × 10−4 0.0919 0.997
Table 2 Table 3
Comparison of adsorption capacity of various adsorbents Thermodynamic parameters for the adsorption of basic dyes on MCM-22
Dyes Adsorbent Adsorption capacity Reference Dye G0 (kJ/mol) H 0 (kJ/mol) S 0 (J/mol K)
(mol/g) 30◦ 40◦ 50◦
MB AC from coal 1.38 × 10−3 [21] MB −44.1 −44.5 −46.7 5.40 159.3
MB AC-aluminosilicate 3.66 × 10−4 [22] CV −40.3 −40.7 −43.0 1.24 133.9
MB AC from bamboo 4.48 × 10−4 [23] RB −40.3 −39.6 −42.6 4.96 142.3
MB AC from coconut shell 8.70 × 10−4 [23]
MB AC from coconut shell 5.24 × 10−5 [20]
MB AC from coconut husk 2.68 × 10−4 [19] MB, CV, and RB. MCM-22 shows a higher adsorption capacity
MB Natural zeolite 4.50 × 10−5 [9] than natural zeolite and comparable capacity to activated car-
CV AC from coconut husk 1.67 × 10−4 [19] bon.
CV AC from saw dust 8.37 × 10−4 [24]
Thermodynamic parameters, i.e., free energy (G0 ), en-
CV Humid acid-modified pillared clay 1.19 × 10−3 [18]
RB Humid acid-modified pillared clay 8.62 × 10−4 [18] thalpy (H 0 ), and entropy (S 0 ) changes, were also calculated
RB AC from rice husk (0.7–1.0) × 10−3 [25] based on the adsorption isotherms using Eqs. (4)–(6) [20] and
RB Activated charcoal 2.09 × 10−4 [26] are given in Table 3.
RB AC from fertilizer 1.67 × 10−4 [26]
1.80 × 10−4 G0 = −RT ln K1 , (4)
MB MCM-22 [This work]
CV MCM-22 1.20 × 10−4 [This work] T2 T 1 K2
1.10 × 10−4
H 0 = −R ln , (5)
RB MCM-22 [This work] T 2 − T1 K1
H 0 − G0
S 0 = , (6)
process in the adsorption with an endothermic nature, which T
will be discussed in Section 3.3. where K1 and K2 are the Langmuir constants at T1 = 30 and
Table 2 compares the adsorption capacity of MCM-22 with T2 = 50 ◦ C.
activated carbons and other adsorbents reported before. As seen As seen G0 for all cases is negative, which indicates
activated carbon generally has a high adsorption capacity for the feasibility and spontaneous nature of basic dye adsorption
S. Wang et al. / Journal of Colloid and Interface Science 295 (2006) 71–78 75
Table 4
Parameters of kinetic models of basic dye adsorption on MCM-22
Dye Pseudo-first-order model Pseudo-second-order model Diffusion
k1 (h−1 ) qe (mol/g) R2 k2 (g/mol h) qe (mol/g) R2 kd R2
MB 0.5038 1.52 × 10−4 0.854 1247.7 1.70 × 10−4 0.999 3.55 × 10−6 0.964
CV 0.4910 1.01 × 10−4 0.844 2555.1 1.12 × 10−4 0.999 2.42 × 10−6 0.938
RB 0.4449 1.04 × 10−4 0.858 2717.8 1.10 × 10−4 0.999 2.16 × 10−6 0.919
Table 5
Parameters of kinetic models of basic dye adsorption on MCM-22
Temperature (◦ C) Dye Pseudo-second-order model
k2 (g/mol h) qe (mol/g) R2
30 MB 1247.7 1.70 × 10−4 0.999
40 1278.8 1.63 × 10−4 0.999
50 1461.8 1.74 × 10−4 0.999
30 CV 2555.1 1.12 × 10−4 0.999
40 2223.9 1.13 × 10−4 0.998
50 2558.9 1.17 × 10−4 0.998
30 RB 2717.8 1.10 × 10−4 0.999
40 6157.65 1.08 × 10−4 0.999
50 4056.0 1.09 × 10−4 0.999
4. Conclusion
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