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Abstract
The adsorption behavior of methylene blue (MB) on four fuller’s earth (FE) samples of varying compositions was investigated using a
spectrophotometric technique to obtain information on the color removal. The distribution coefficient (KD ) increased with an increase in the
initial concentration (C0 ) of the dye, attained a maximum value, and decreased again at higher initial concentrations. Dye solutions became
colorless for a C0 value corresponding to maximum KD . A progressively increased flocculation behavior in the clay suspensions was observed
and the maximum value of KD corresponds to optimum flocculation of the clay. The KD values were found to decrease exponentially after of
the solution again became colored while the amount adsorbed increased with an increase in the initial concentration of MB. Only adsorption
data obtained for this region could be defined by adsorption isotherm equations. The shifts of the C0 values corresponding to KD max toward
higher concentrations were correlated with the composition of FE samples by using XRF, XRD patterns, and SEM images. The influence of
temperature on MB adsorption was also studied and thermodynamic parameters were calculated.
2003 Elsevier Science (USA). All rights reserved.
Keywords: Fuller’s earth; Dye adsorption; Methylene blue; Adsorption isotherm; Distribution coefficient
area calculations because it was recently shown that the gen- in the range of (5 × 10−5 )–(2 × 10−2 ) M. Except for
erally accepted adsorption geometry is questionable and the the largest concentrations generally no dilution of the su-
MB molecules adsorb a tilted arrangement [6,8]. Visible pernatant was required prior to spectrophotometric mea-
MB spectra in dilute solution show a band associated with surements. Absorbances were determined a wavelength of
monomeric MB at 665 nm with a shoulder at 605 nm. The 665 nm, which corresponds to the maximum absorption peak
observed red shift of the MB monomer band in clay suspen- of MB monomers in water, or at the maximum of the red-
sions arises from the interaction of dye molecules in the in- shifted monomer peak.
ternal domains of tactoids. MB in aqueous clay suspensions Kinetic experiments were made to compare adsorption
shows metachromatic behavior even at lower concentrations rates of MB on FE and on commercial activated carbon
with respect to the aqueous dye solution. The decrease in the (CAC). Beakers containing 5 cm3 of MB solution of 3.25 ×
monomer band and the appearance of bands at lower wave- 10−3 mol dm−3 were immersed in a thermostatic shaker
lengths are attributed to formation of dimers and higher ag- controlled at 298 K. Adsorbents were added to the beakers
gregates on the external surface [2,4–8]. and the timing was started. The suspensions were shaken as a
The aim of this study is to produce a satisfactory effluent function of time from 1 min to 4 h. At various time intervals,
for discharge into receiving waters or for reuse as a water samples were taken and MB concentration was measured,
supply from highly concentrated MB solutions by using FE after centrifugation as already described.
samples with different compositions. The adsorption data The distribution coefficient for adsorption KD (cm3 g−1 )
have also been correlated to the ratio of clay minerals in was derived using the formula
FE samples and have been used to determine the adsorption
capacity for MB of the adsorbents. C0 − C V
KD = , (1)
C0 m
where C0 and C are the initial and final concentration of the
2. Experimental dye solution (mol dm−3 ), respectively, m (g) is the weight of
adsorbent, and V (cm3 ) is the volume of the aqueous phase.
Four FE samples from different deposits in the Mihal-
liccik region were used for batch experiments. FE samples
were kindly provided by Professor M. Yeniyol from the Ge-
ology Department of Istanbul University and Y. Bilge from 3. Results and discussion
Bensan A.S. X-ray diffraction (XRD) paterns of the four FE
samples revealed that they were composed mainly of Ca- 3.1. MB adsorption isotherms
montmorillonite, loughlinite, and analcime [1]. The chemi-
cal composition of the FE samples was analyzed by X-ray As an example of the adsorption isotherms of FE samples,
fluorescence spectrometry (XRF). Analyses of the FE sam- Fig. 1 depicts the amounts of MB adsorbed by FE-2 against
ples are given in Table 1. The surface morphology of the raw the equilibrium concentrations for various temperatures.
material and the product obtained after MB treatment of FE Three regions can be distinguished on the isotherm curves.
were examined by scanning electron microscopy (SEM). In the first region (I), an S-shaped isotherm which corre-
Adsorption of MB was performed by using a batch sponds to a slow increase, followed by a fast growth, and a
method. The clay samples were crushed and sieved through region growing to a plateau is observed at very low dye load-
a 200-µm sieve. A liquid–solid ratio V /m of 100 cm3 g−1 ing, except for the lowest temperature. After that, the curves
was chosen. Thus 0.05 g of clay was put into contact with show a behavior in which at lower equilibrium concentra-
5 cm3 of dye solution in a polypropylene beaker of 25 cm3 tions the adsorption is higher than at higher equilibrium con-
for 4 h (i.e., a time period long enough to reach equilib- centrations in the second region. However, the amount of
rium) at a given temperature in a thermostatic shaker/water adsorbed dye increases depending on the initial concentra-
bath and left overnight. Later, the clay suspensions were tion for all cases. The adsorption of MB on FE leads to
centrifuged at 4000 rpm for 30 min and the equilibrium changes in the absorption spectra of the dye. As may be
MB concentration was determined by using a Perkin Elmer seen from visible spectra for the first region in Fig. 2 the
UV–vis. spectrophotometer model 554 with silica cells of maximum wavelength of the monomer peak is observed at
length 1 cm. The initial MB concentrations were changed 675 nm. This represents a red shift by about 10 nm with
Table 1
Chemical analyses (wt%) of the FE samples used in this study
Clay SiO2 Al2 O3 MgO CaO Na2 O Fe2 O3 TiO2 MnO K2 O P 2 O5
FE-1 51.09 10.09 10.57 4.38 3.83 4.19 0.42 0.06 2.45 0.01
FE-2 51.70 9.51 11.06 4.10 4.85 3.95 0.38 0.06 2.00 0.01
FE-3 52.42 7.73 12.55 1.90 6.60 3.14 0.29 0.05 1.64 0.01
FE-4 50.23 6.29 13.61 1.84 6.81 2.25 0.22 0.04 1.07 0.00
34 G. Atun et al. / Journal of Colloid and Interface Science 261 (2003) 32–39
Table 2
max
Isotherm parameters of MB adsorption on FE samples and parameters for KD
Clay sample T Freundlich parameters Langmuir parameters max
Parameters for KD
n k × 104 r qm × 104 K × 10−4 r C0 × 103 qcs × 104
(K) (mol g−1 ) (M) (mol g−1 )
FE-1 290 0.116 2.94 0.982 1.50 3.77 0.999 0.85 0.84
298 0.093 5.20 0.992 3.15 6.17 0.999 1.50 1.49
318 0.083 6.95 0.951 4.25 3.13 0.999 2.00 1.90
333 0.080 9.15 0.948 4.48 14.00 0.999 2.35 2.30
FE-2 290 0.079 3.09 0.961 1.78 16.27 0.999 0.90 0.98
298 0.068 5.89 0.962 3.47 20.48 0.999 2.00 2.00
318 0.050 8.13 0.958 5.65 21.53 0.999 3.60 3.50
333 0.061 9.42 0.994 6.11 36.58 0.999 3.80 3.79
FE-3 290 0.059 3.55 0.950 2.95 22.19 0.999 2.50 2.50
298 0.057 6.62 0.911 4.15 36.58 0.999 3.25 3.22
318 0.051 7.84 0.986 5.79 29.65 0.999 3.63 3.62
333 0.060 9.33 0.995 6.00 56.81 0.999 3.80 3.79
FE-4 290 0.058 5.15 0.967 3.96 38.08 0.991 3.00 2.99
298 0.061 8.51 0.977 6.02 45.59 0.999 3.35 3.30
318 0.069 9.12 0.977 6.23 56.24 0.999 3.70 3.69
333 0.065 10.47 0.999 6.34 79.02 0.995 3.80 3.79
36 G. Atun et al. / Journal of Colloid and Interface Science 261 (2003) 32–39
temperature increases from 290 to 333 K. However, smaller forming small tactoids of larger spacing. So, the adsorbent
changes were observed for higher temperatures. A series of possesses a higher surface area and a more porous nature.
experiments were conducted with water without MB at 298, As a result of these phenomena, the adsorption capacities qcs
318, and 333 K to study the transformation of clay in hot at CS, the maximum adsorption capacities qm , and the equi-
water. librium constants K increased with increasing temperature
A comparison of SEM images and XRD patterns of raw (Table 2).
The change of free energy of adsorption can be calculated
material and hot-water-treated FE showed that peak inten-
from equilibrium adsorption constants:
sities of XRD patterns increased with increasing tempera-
ture and SEM images showed that clay layers are separated, G0 = −RT ln K. (4)
38 G. Atun et al. / Journal of Colloid and Interface Science 261 (2003) 32–39
References