Journal of Colloid and Interface Science 337 (2009) 345–354

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Journal of Colloid and Interface Science

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Adsorption studies on the removal of coloring agent phenol red

from wastewater using waste materials as adsorbents
Alok Mittal a, Dipika Kaur a, Arti Malviya a, Jyoti Mittal a, V.K. Gupta b,c,*
a
Department of Applied Chemistry, Maulana Azad National Institute of Technology, Bhopal 462 007, India
b
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247 777, India
c
Department of Chemistry, College of Science, P.O. Box 5057, King Fahad University of Petroleum and Mines, Dhahran 31261, Saudi Arabia

a r t i c l e i n f o a b s t r a c t

Article history: Bottom ash, a waste of thermal power plants, and deoiled soya, an agricultural waste material, were
Received 3 April 2009 employed for successful removal and recovery of hazardous phenol red dye from wastewaters. The
Accepted 12 May 2009 adsorption characteristics and operational parameters were determined by monitoring different param-
Available online 19 May 2009
eters such as effect of pH, effect of concentration of the dye, amount of adsorbents, contact time, and tem-
perature. The equilibrium data were analyzed on the basis of various adsorption isotherm models,
Keywords: namely Langmuir, Freundlich, Tempkin, and Dubinin–Radushkevich. The highest monolayer adsorption
Adsorption
capacity has been obtained for the phenol red-bottom ash system (2.6  105 mol/g) at 50 °C. Different
Bottom ash
Deoiled soya
thermodynamic parameters such as free energy, enthalpy, and entropy have been calculated and it
Phenol red was concluded that with the increase in temperature adsorption increases, indicating the endothermic
Dye nature of the process for both adsorbent materials. Kinetic parameters were derived from pseudo-first-
order and pseudo-second-order kinetics. Differentiation between particle and film diffusion mechanisms
operative in the present study has been carried out. The column regeneration characteristic has been also
investigated and recovery percentage greater than 90% was obtained for both adsorbents by utilizing
acidic eluent.
Ó 2009 Elsevier Inc. All rights reserved.

1. Introduction ity of color removal, concerned industries are required to treat the
dye-bearing effluents before dumping them into the water bodies.
Due to rapid industrial development, pollution of water bodies Thus the scientific community shoulders the responsibility of
by industries is an issue of major concern. It is estimated that a contributing in the waste treatment by developing effective dye-
huge amount of dyes (nearly 20%) of global production is removal techniques.
discharged by textile industries due to incomplete exhaustion of The conventional physicochemical and biological methods such
coloring material and washing operations [1]. The effluents gener- as oxidation and filtration [4–6] are not efficient enough to be uti-
ated by these industries are highly visible even at very low concen- lized for large streams due to their less cost effectiveness and dif-
trations. The disposal of such materials into water bodies not only ficult operational conditions [7]. Among the various available
destructs the esthetic nature but also interferes with the penetra- water treatment techniques adsorption is the most reliable and
tion of sunlight, thus affecting the food web existing in water eco- efficient technique for decoloration, in which the recovery and
systems [2]. The majority of the dyes dumped into the water recycling of the adsorbent materials can be achieved along with
bodies by industries are toxic and even carcinogenic to both ani- the distinct advantages of nonproduction of any toxic sludge and
mals and humans. The problem becomes graver due to the fact that cost effectiveness. This has encouraged the development of adsor-
the complex aromatic structures of the dyes render them ineffec- bents that are abundantly available and economical. Nowadays
tive in the presence of heat, light, microbes, and even oxidizing numerous low cost adsorbents are available including products
agents and degradation of the dyes becomes difficult [3]. Hence of agricultural origin such as wood dust, sugarcane, fruit peel [8],
these pose a serious threat to human health and water quality, wheat straw, and apple pomance [9]. Certain other low cost adsor-
thereby becoming a matter of vital concern. Keeping the essential- bent materials of industrial origin such as activated slag [10] and
bagasse fly ash [11] have also been employed in the recent past.
However, still there arises a great need to explore new low cost
* Corresponding author. Address: Department of Chemistry, Indian Institute of
adsorbent materials with high adsorption capacity.
Technology Roorkee, 22/2 Niti Nagar, IIT, Roorkee 247 777, India. Fax: +91 1332
273560. The present research deals with the applicability of adsorption
E-mail address: [email protected] (V.K. Gupta). techniques in the removal of the dye phenol red from wastewaters.

0021-9797/$ - see front matter Ó 2009 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2009.05.016
346 A. Mittal et al. / Journal of Colloid and Interface Science 337 (2009) 345–354

Phenol red is a highly water-soluble textile dye belonging to the ics, Ahmedabad, India). Philips SEM 501 electron microscope was
class of triphenylmethane dyes. It exists as a red crystal and is sta- employed to obtain scanning electron microscopy while a Philips
ble in air with solubility of 0.77 g/L in water [12]. At 20 °C the pKa X-ray diffractophotometer was used for X-ray measurements.
value has been found to be 8.00. It is frequently used as a reagent Quantasorb Model QS-7 surface analyzer was used to calculate
dye for measuring the pH of water in a range from 6.8 to 8.2. It the surface of the adsorbent particles. The pore properties and spe-
changes color from yellow to purple as the pH goes from 6.7 to cific gravity of the adsorbents were determined by employing a
8.2. It is thus widely employed as a pH indicator in cell biology lab- mercury porosimeter and specific gravity bottles, respectively.
oratories and for water testing applications.
Toxicity data reveal that phenol red inhibits the growth of renal 2.2. Material development
epithelial cells [13]. Direct or indirect contact with the dye leads to
irritation to the eyes, respiratory system, and skin [14]. Phenol red Both adsorbent materials, bottom ash and deoiled soya, were
dye is toxic to muscle fibers [15] and its mutagenic effects are also first washed with distilled water and dried. Then the oxidation of
reported [16]. Thus keeping the toxic effects of the dye in view organic impurities was achieved by dipping the materials in
attempts have been made to develop an efficient and cost effective H2O2 solution for about 24 h followed by washing with double dis-
technique for the removal of dye from wastewaters by employing tilled water. The moisture content of the materials was then
two waste materials, namely bottom ash and deoiled soya. Both removed by heating at 100 °C for about 1 h in an oven. Deoiled
adsorbent materials are easily and abundantly available. Bottom soya was then sieved using various mesh sizes, viz. 36, 100, and
ash is obtained from coal-fired stations, whose disposal is always 170 BSS mesh, while bottom ash was further heated at 500 °C for
a problem for the industrialists and environmentalists. Deoiled 15 min for activation followed by the sieving process. The adsor-
soya is a by-product obtained after complete processing of soya- bents were finally stored in a desiccator.
bean. Its use as animal feed is banned nowadays due to formation
of antimetabolites which block enzymatic activities in living sys- 2.3. Adsorption studies
tems [17]. In the past few years, our laboratory has developed
these materials as efficient adsorbents or removal of various dyes Adsorption characteristics were determined with the help of
from wastewaters [18–24]. primary analysis. To study the effect of important parameters such
as effect of concentration, amount of adsorbent, and pH, batch
2. Experimental studies were performed by taking 25 ml of dye solutions in 100-
ml volumetric flasks at 30, 40, and 50 °C. A suitable mesh size
2.1. Materials and methods was chosen for both adsorbent materials (particle size 100 BSS
mesh for bottom ash and 36 BSS mesh for deoiled soya) and was
0
Phenol red, 4 -(3 H-2,1-benzoxathiol-3-ylidene) bis-phenol, S,S- added into each flask with intermittent shaking. After 24 h these
dioxide, having molecular formula C19H14O5S and molecular solutions were filtered with Whatman filter paper (No. 41) and
weight 354.38 was obtained from M/s Merck. A commonly known the amount of the dye adsorbed was analyzed at kmax 435 nm.
synonym for phenol red is phenol sulfonephthalein. The extended The adsorbent dose, concentration, etc. were altered and variation
conjugation system of the alternate double and single bond in the in the amount of dye taken up was analyzed for both adsorbents.
dye structure gives it an intense color. Some general physicochem-
ical properties of phenol red are presented in Table 1. Dye stock 2.4. Kinetic studies
solution was prepared in doubly distilled water. All solutions were
prepared by diluting the stock with distilled water. Suitable amount of the adsorbents were added to 25 ml of the
O dye solutions taken in an air-tight 100-ml volumetric flasks and
shaking was done periodically. In each case 0.10 g of either acti-
vated bottom ash or activated deoiled soya was taken and studies
were performed at different temperatures (30, 40, and 50 °C).
These solutions were then filtered after a particular time interval
and spectrophotometric analysis was carried out for the amount
C OH of dye uptake.

2.5. Column studies

SO 3H
Bottom ash and deoiled soya, the adsorbent materials in the Column studies were carried out by using two separate glass col-
present research work, were obtained from thermal power station umns of 30 cm length and 1 cm internal diameter, for filling known
(TPS) of M/s Bharat Heavy Electrical Limited (B.H.E.L.), Bhopal amounts of bottom ash and deoiled soya, supported on glass wool. To
(India) and Sanwaria Agro Oils Ltd. Bhopal, respectively. A micro- avoid air entrapment, adsorbents were fed into the columns in the
processor-based pH meter Model HI 8424 (M/s Henna Instruments, form of slurry. Dye solution of 10  105 M concentration of phenol
Italy) was used for pH measurements. The absorption studies were red was then percolated through the columns at a flow rate of 0.5 ml/
carried out using UV–Vis spectrophotometer Model 117 (Systron- min. After complete adsorption the adsorbed dye was eluted using
acidic water (HCl solution of pH 2), maintaining the flow rate as
0.5 ml/min, for both adsorbent materials. The columns were washed
Table 1 with distilled water after complete elution.
Physicochemical properties of phenol red.

Parameters Values 3. Results and discussion

Class Triphenylmethane dye
Molecular formula C19H14O5S 3.1. Characterization of the adsorbents
Molecular weight 354.38
Solubility Soluble in water (0.77 g/L)
The details of the constituents of the adsorbent materials as per
Absorption maxima 435 nm
chemical analysis are provided in Table 2. Electron microscopy and
 A. Mittal et al. / Journal of Colloid and Interface Science 337 (2009) 345–354 347

Table 2 Table 3
Chemical constituents of the adsorbents. Effect of amount of adsorbents on the adsorption of phenol red (dye concentra-
tion = 10  105 M and pH 7.0).
Bottom ash Deoiled soya
Amount of Amount Amount of Amount
Constituents Percentage by weight Constituents Percentage by weight
bottom ash (g) adsorbed  105 (g) deoiled soya (g) adsorbed  105 (g)
Moisture 15.0 Moisture 11.0
30 °C 40 °C 50 °C 30 °C 40 °C 50 °C
SiO2 45.4 SiO2 6.0
Al2O3 10.3 Fiber 7.0 0.1 43.5 46.6 49.3 0.1 15.9 28.4 43.3
Fe2O3 9.7 Ca 0.2 0.15 44.4 47.5 49.9 0.15 17.6 30.9 44.9
CaO 15.3 P 0.7 0.2 45.1 48.1 50.6 0.2 19.0 32.2 46.0
MgO 3.1 Profat 48.0 0.25 45.9 48.3 50.7 0.25 19.7 33.8 46.8
0.3 46.6 48.8 51.1 0.3 22.1 35.3 47.6

infrared spectroscopy were helpful in providing the absorptive

nature and analyzing the two adsorbents. SEM photographs ascer- The decrease in the extent of adsorption with increase in pH
tained that the particulates of bottom ash and deoiled soya are value initially is due to the increased protonation by neutralization
almost spherical in shape. Bottom ash gave a sharp absorption of negative charges at the surface of the adsorbents. For further
band in the region of 3700–3500 cm1. Laumonite [4(CaAl2Si4 studies pH 7 was chosen, as this would give an idea of adsorption
O124H2O)], amber, mulite [2Al2O32SiO2)], azurite [Cu3(CO3)2 capacity in neutral conditions.
(OH)2], bavenite [4Ca4(BeAl)4Si9OOH)29(OH)2], and kaolinite
[2(Al2Si2O5(OH)4)] in bottom ash are indicated by bands at 3467, 3.2.2. Effect of amount of adsorbents
2930, 2676, 1502, 1097, and 790 cm1, whereas gorthite In order to study the variation in adsorption on the basis of the
[4(FeOOH)], coesite [SiO2], corundum [2(a-Al2O3)], and laumonite amount of the adsorbent materials, various amounts ranging from
[4(CaAl2Si4O124H2O)], for deoiled soya, were indicated by the 0.1 to 0.3 g for bottom ash and deoiled soya were taken in 100-ml
bands obtained at 479, 779, 1113, and 3459 cm1, respectively. volumetric flasks having a dye solution of 10  105 M concentra-
As per DTA curves bottom ash was found to show negligible weight tion and pH 7. The study was performed at three different temper-
loss even at high temperatures and was also observed to be ther- atures (30, 40, and 50 °C). With increase in amount of adsorbent
mally stable. The X-ray spectrum of the adsorbents showed the adsorption was found to increase (Table 3). Such a trend is mainly
presence of gypsum (CaSO42H2O, beverite [Pb(Cu,Fe,Al)3(SO4)2 attributed to the fact that with increase in the amount of the adsor-
(OH)6], alumina (Al2O3), kaolinite [2(Al2Si2O5(OH)4)], and borax bent the adsorptive surface area increases which provides a greater
(Na2B4O710H2O). For deoiled soya, the XRD spectrum does not number of active sites for adsorption [25]. It is interesting to note
give any major peak(s), which could be due to lack of inorganic that the amount adsorbed also increased with elevation in temper-
substances in the activated deoiled soya. ature from 30 to 50 °C.

3.2. Adsorption studies 3.2.3. Effect of particle sizes

Adsorption is further influenced by particle sizes. Three differ-
3.2.1. Effect of pH ent particle sizes, viz. 36, 100, and 170 BSS mesh, were selected
pH is one of the most influencing factors for dye adsorption as it for batch adsorption studies for both adsorbents. The amount
directly affects the dissociative and adsorptive ability of the dye on adsorbed increased with the increase in mesh size, which was
the adsorbent surface. For phenol red dye the pH range was chosen found to be substantial for mesh size 170 BSS mesh, because the
as 2–9 for both adsorbents, viz. bottom ash and deoiled soya. The increased surface area of the adsorbent materials is due to smaller
pH of the test solutions was adjusted by using HCl and NaOH solu- sizes (Table 4). This facilitates the accessibility of the adsorbent
tions. As evident from Fig. 1, with the increase in pH adsorption pores for diffusion of the dye, resulting in increased adsorption.
was found to decrease till pH 5, but further increase in the pH value The above result is further supported by the rate constant and
(till pH 9) increases the amount adsorbed by both adsorbents. half-life values obtained in each case.

3.2.4. Effect of concentration

30 A concentration range of 1  105 to 10  105 M was selected
De-Oiled Soya and fixed amounts of the adsorbents were added to these solu-
Bottom Ash tions. It was found that with the increase in concentration of the
25
dye adsorption increases at all temperatures (30, 40, and 50 °C)
Amount Adsorbed × 10 (g)
-5

for both bottom ash and deoiled soya (Figs. 2 and 3). The figures
20
also reveal that higher temperatures support a greater extent of
adsorption. Greater temperature provides greater mobility to the
15

10 Table 4
Effect of sieve sizes of different adsorbents on the rate of adsorption of phenol red
over bottom ash and deoiled soya (concentration = 10  105 M, pH 7.0, tempera-
5 ture = 30 °C, adsorbent dose = 0.1 g bottom ash and 0.1 g deoiled soya).

Mesh Bottom ash Deoiled soya

0 size
1
0 2 4 6 8 10 Amount k (h ) t1/2 (h) Amount k (h1) t1/2 (h)
pH adsorbed adsorbed
 105 (g)  105 (g)
Fig. 1. Effect of pH on the uptake of phenol red by bottom ash and deoiled soya at
36 39.8 0.02 27.8 15.9 0.01 83.8
30 °C (bottom ash: concentration = 10  105 M, adsorbent dose = 0.05 g, particle
100 46.9 0.03 22.0 23.0 0.01 55.2
size = 100 BSS mesh) (deoiled soya: concentration = 10  105 M, adsorbent
170 54.0 0.04 17.7 28.3 0.02 43.1
dose = 0.05 g, particle size = 36 BSS mesh).
348 A. Mittal et al. / Journal of Colloid and Interface Science 337 (2009) 345–354

60 26
Amount Adsorbed × 10 (gm)

50 24

Amount Adsorbed × 10 (g)

-5

-5
40
22

30
20
20
18
30 Degree C
10
40 Degree C
16 30 Degree C
50 Degree C
0 40 Degree C
0 2 4 6 8 10 12
-5 50 Degree C
Concentration × 10 (M) 14
0 100 200 300 400
Fig. 2. Effect of concentration on the removal of phenol red by bottom ash at Time (minutes)
different temperatures (adsorbent dose = 0.1 g, particle size = 100 BSS mesh, pH
7.0). Fig. 4. Effect of contact time on the uptake of phenol red by bottom ash at different
temperatures and at a concentration of 10  105 M (adsorbent dose = 0.1 g,
particle size = 100 BSS mesh, pH 7.0).

45

40 24
Amount Adsorbed × 10 (gm)

35 22
Amount Adsorbed × 10 (gm)
-5

30
20
-5

25
18
20
16
15
14
10 30 Degree C
5 40 Degree C 12
50 Degree C
0 10 30 Degree C
0 2 4 6 8 10 12 40 Degree C
-5 50 Degree C
Concentration × 10 (M) 8
0 100 200 300 400
Fig. 3. Effect of concentration on the removal of phenol red by deoiled soya at Time (minutes)
different temperatures (adsorbent dose = 0.1 g, particle size = 36 BSS mesh, pH 7.0).
Fig. 5. Effect of contact time on the uptake of phenol red by deoiled soya at
different temperatures and at a concentration of 10  105 M (adsorbent
dose = 0.1 g, particle size = 36 BSS mesh, pH 7.0).
ionized dye molecules, thereby leading to greater adsorption.
However, on increasing the concentration of the dye solution satu-
ration of the adsorbent sites occurs which does not allow further deals mainly with four different kinds of isotherms, namely Lang-
adsorption of the dye molecules at all temperatures [26]. muir, Freundlich, Tempkin, and D–R isotherms.

3.2.5. Effect of contact time 3.3.1. Langmuir isotherm

Contact time studies are helpful in understanding the amount of The Langmuir isotherm assumes that the surface of any adsor-
dye adsorbed at various time intervals by a fixed amount of the bent material contains a number of active sites where the adsor-
adsorbent (0.10 g for bottom ash and deoiled soya) at various tem- bate attaches itself. This attachment can either be physical or
peratures 30, 40, and 50 °C. Figs. 4 and 5 clearly indicate that with chemical. When the attachment is via Van der Waal interactions
increase in the time of contact and temperature, adsorption it is known as physisorption and when via covalent bond it is
increases. The increase in adsorption with temperature indicates known as chemisorption. It says that there is not much interaction
the endothermic nature of adsorption. After almost 4 h of contact, between the adsorbate molecules and once a saturation value has
the percentage adsorption was 27.5% and 24.0% over bottom ash been reached no further adsorption would take place [28–31].
and deoiled soya, respectively. After this time no further increase
1 1 1
in the adsorption is observed due to aggregation of the dye mole- ¼ þ ð1Þ
qe Q o bQ o C e
cules at the adsorption sites on the adsorbents and increased diffu-
sion path length [27]. The half-life value in both cases was where qe is the amount of phenol red adsorbed (mol/g), Ce is the
calculated and was found to be 8.61 and 9.63 h, respectively. equilibrium molar concentration of the dye (mol/L), Qo is the max-
imum adsorption capacity (mol/g), and b is the energy of adsorption
3.3. Adsorption isotherms (L/mol).
A linear plot obtained for Langmuir isotherm is shown in Figs. 6
The adsorption of phenol red dye onto both adsorbents was and 7. This isotherm holds good for the phenol red-bottom ash sys-
studied at all three temperatures, viz. 30, 40, and 50 °C. The paper tem and phenol red-deoiled soya system, which is indicated by the
 A. Mittal et al. / Journal of Colloid and Interface Science 337 (2009) 345–354 349

450000 -4.6
R2 = 0.985 R2 = 0.9495
400000 R2 = 0.955
-4.8
350000
R2 = 0.9943 -5
1/qe (gm mol )
-1

300000 R2 = 0.9471

-5.2
250000

log qe
200000 -5.4
R2 = 0.9969
150000
-5.6
100000 30 Degree C
30 Degree C -5.8 40 Degree C
50000 40 Degree C
50 Degree C 50 Degree C
-6
0 -6 -5.5 -5 -4.5 -4
0 50000 100000 150000 200000 250000 300000
log Ce
-1
1/Ce (M )
Fig. 8. Freundlich adsorption isotherms for the phenol red-bottom ash system
Fig. 6. Langmuir adsorption isotherms for the phenol red-bottom ash system (adsorbent dose = 0.1 g, particle size = 100 BSS mesh, pH 7.0).
(adsorbent dose = 0.1 g, particle size = 100 BSS mesh, pH 7.0).
1
r¼ ð2Þ
1 þ bC o
630000
where b denotes the Langmuir constant and Co the initial concentra-
R2 = 0.9352 tion [32]. At all temperatures r values have been found less than
540000
unity (0.74, 0.71, and 0.68 for bottom ash and 0.33, 0.27, and 0.22
for deoiled soya) at 30, 40, and 50 °C, respectively, indicating there-
450000
R2 = 0.9432 by favorable processes for both adsorbents.
1/qe (gm mol )
-1

360000 3.3.2. Freundlich isotherm

The Freundlich model [33,34] is given by the relation
270000
R2 = 0.9872 1
log qe ¼ log K F þ log C e ; ð3Þ
180000
n
where qe is the amount adsorbed (mol/g), Ce is the equilibrium con-
30 Degree C
90000 centration of the adsorbate (mol/L). KF and n, the Freundlich con-
40 Degree C
stants, are related to adsorption capacity and adsorption intensity,
50 Degree C
0 respectively. The model is based on the assumption that adsorption
0 50000 100000 150000 occurs on a heterogeneous adsorption surface having unequally
1/Ce (M )
-1 available sites with different energies of adsorption. Figs. 8 and 9
depict the plots obtained for the Freundlich isotherm for the two
Fig. 7. Langmuir adsorption isotherms for the phenol red-deoiled soya system adsorbents along with their R2 values. The Freundlich constants
(adsorbent dose = 0.1 g, particle size = 36 BSS mesh, pH 7.0). for both adsorbents were calculated and are presented in Table 5.

3.3.3. Tempkin isotherm

linear plots obtained for 1/qe against 1/Ce, at each temperature.
The Tempkin isotherm assumes that the heat of adsorption of
Various Langmuir constants have been calculated at 30, 40, and
all the molecules increase linearly with coverage [35]. The linear
50 °C and depicted in Table 5.
form of this isotherm can be given by
The essential feature of the Langmuir isotherm can be
expressed by means of dimensionless constant separation factor,
which is calculated using -4.7
R2 = 0.9601
-4.9 R2 = 0.9665
Table 5 -5.1
Freundlich and Langmuir constants for removal of phenol red (bottom ash: adsorbent
R2 = 0.9623
dose = 0.1 g, particle size = 100 mesh, pH 7.0; deoiled soya: adsorbent dose = 0.1 g, -5.3
particle size = 36 mesh, pH 7.0).
log qe

-5.5
Adsorbent Freundlich constants
-5.7
n KF
30 °C 40 °C 50 °C 30 °C 40 °C 50 °C -5.9
30 Degree C
Bottom ash 1.5 1.5 1.5 0.01 0.01 0.02 -6.1 40 Degree C
Deoiled soya 1.1 1.2 1.4 0.06 0.04 0.01
50 Degree C
Langmuir constants -6.3
-6 -5.5 -5 -4.5 -4 -3.5
Qo  105 (mol/g) b  104 (L/mol) log Ce
Bottom ash 2.1 2.4 2.6 3.4 3.9 4.6
Deoiled soya 1.5 1.6 1.7 1.9 2.6 3.5 Fig. 9. Freundlich adsorption isotherms for the phenol red-deoiled soya system
(adsorbent dose = 0.1 g, particle size = 36 BSS mesh, pH 7.0).
350 A. Mittal et al. / Journal of Colloid and Interface Science 337 (2009) 345–354

0.00002 Table 7
Tempkin and D–R constants for phenol red-deoiled soya system.

Temperature (°C) Deoiled soya

0.000015 Tempkin constant D–R constants
k2 b (mol2/J2) Xm (lmol/g) E (kJ/mol)
5
30 2.7  10 7  109 5.8 8.5
0.00001
qe (mol g )

2.7  105 6  109

-1

40 5.1 9.1
50 2.7  105 4  109 4.6 11.2

0.000005

ln C ads ¼ ln X m  be2 ; ð5Þ

R2 = 0.9951
0 30 Degree C
where Cads is the amount of the dye adsorbed per unit weight of the
R2 = 0.9954 40 Degree C
adsorbent in mg/g, Xm is the maximum sorption capacity provided
R2 = 0.9894 50 Degree C by the intercept in lmol/g, b (mol2/J2) is obtained from the slope
-0.000005
of the straight-line plot of ln Cads versus e2 (Figs. 12 and 13), and
-13 .5 -12 .5 -11 .5 -10 .5 -9 .5
ln C e
e, the Polanyi potential, can be calculated as
e ¼ RT lnð1 þ 1=C e Þ; ð6Þ
Fig. 10. Tempkin isotherms for the phenol red-bottom ash system at different
temperatures. where R is the universal gas constant in kJ/(mol K) and T is the tem-
perature in Kelvin.

qe ¼ k1 ln k2 þ k1 ln C e : ð4Þ
qe is the amount adsorbed at equilibrium in mol/gm, k1 is the Temp-
kin isotherm energy constant in L/mol, and k2 is the Tempkin 3
R2 = 0.9558 30 Degree C
isotherm constant. The slopes and intercepts obtained from the 2.5 R2 = 0.9651 40 Degree C
graphical plot (Figs. 10 and 11) were used to calculate the Tempkin
2 R2 = 0.963 50 Degree C
constants (Tables 6 and 7).
1.5
3.3.4. Dubinin–Radushkevich isotherm 1
The linear form of the Dubinin–Radushkevich isotherm [36] can
0.5
be given as
ln Cads

-0.5
0.000014
-1
0.000012
-1.5
0.00001 -2
0.000008
6E+08 7E+08 8E+08 9E+08 1E+09 1.1E+0 1.2E+0 1.3E+0
9 9 9
qe (mol g )

0.000006 ε2
-1

0.000004 Fig. 12. D–R isotherms for the phenol red-bottom ash system at different
temperatures.
0.000002

0
R2 = 0.9288 30 Degree C 2.5
-0.000002 30 Degree C
R2 = 0.9654
R2 = 0.943 40 Degree C 2
-0.000004 2
R = 0.9649 40 Degree C
R2 = 0.9786 50 Degree C 1.5 2 50 Degree C
R = 0.9756
-0.000006
-13 -12.5 -12 -11.5 -11 -10.5 -10 -9.5 1
ln C e
0.5
ln Cads

Fig. 11. Tempkin isotherms for the phenol red-deoiled soya system at different 0
temperatures.
-0.5

-1
Table 6 -1.5
Tempkin and D–R constants for phenol red bottom ash system.
-2
Temperature (°C) Bottom ash
-2.5
Tempkin constant D-R constants 5E+08 6E+08 7E+08 8E+08 9E+08 1E+09 1.1E+0 1.2E+0
k2 b (mol2/J2) Xm (lmol/g) E (kJ/mol) 9 9
30 1.6  105 6  109 4.6 10.0 ε2
40 1.6  105 6  109 4.7 11.1
50 1.6  105 4  109 4.8 11.1 Fig. 13. D–R isotherms for the phenol red-deoiled soya system at different
temperatures.
 A. Mittal et al. / Journal of Colloid and Interface Science 337 (2009) 345–354 351

Table 8 -4
Thermodynamic parameters for the uptake of phenol red (bottom ash: adsorbent R2 = 0.9141 30 Degree C
dose = 0.1 g, particle size = 100 mesh, pH 7.0; deoiled soya: adsorbent dose = 0.1 g, R2 = 0.9407 40 Degree C
-4.2
particle size = 36 mesh, pH 7.0).
R2 = 0.9123 50 Degree C
Adsorbent DG° 104 (J/mol) DH° (J/mol) DS° (J/K/mol) -4.4
30 °C 40 °C 50 °C

log (qe-qt)
-4.6
Bottom ash 2.6 2.7 2.9 190.9 88.6
Deoiled soya 2.5 2.6 2.8 373.1 85.9
-4.8

E, the mean sorption energy, is calculated using the following

-5
relation (Tables 6 and 7)

E ¼ ð2KÞ1=2 : ð7Þ -5.2

The values of E for both phenol red-bottom ash and phenol red- -5.4
deoiled soya system are found to be in the range 8–11 kJ/mol. Thus, 0 50 100 150 200
the calculated values of E suggest that chemisorption is responsible Time (minutes)
for the adsorption process for both systems at all the temperatures
[37]. Fig. 15. Plot of log(qe  qt) versus time for the phenol red-deoiled soya system at
different temperatures.

3.4. Calculation of thermodynamic parameters

Gibb’s free energy (DG°), change in entropy (DS°), and change in 180
enthalpy (DH°), etc. have been calculated from the following rela- 160
tions [38,39]:
140
DG ¼ RT ln b; ð8Þ
    120
T2T 1 b2
t/qt (min g/ mg)

DH ¼ R  ln ; ð9Þ
T2  T1 b1 100
 
DH  DG
D S ¼ ; ð10Þ 80
T
where R is a universal gas constant, b, b1, and b2 are the Langmuir 60
constants at 30, 40, and 50 °C, respectively, obtained from slopes 40
and intercepts of Langmuir isotherms. R2 = 0.995 30 Degree C

An increase in randomness is indicated by positive values of 20 R2 = 0.9984 40 Degree C

entropy change whereas the endothermic nature of the process is R2 = 0.999 50 Degree C
0
indicated by positive values of enthalpy. The feasibility of the pro- 0 100 200 300 400
cess on the other hand is shown by negative values of free energy Time (minutes)
(Table 8).
Fig. 16. Plot of time versus t/qt for the phenol red-bottom ash system at different
3.5. Rate constant study temperatures.

Pseudo-first-order and second-order rate equations were

kad
applied to phenol red-bottom ash system and phenol red-deoiled logðqe  qt Þ ¼ log qe   t; ð11Þ
2:303
soya system [40,41]. The equations given below summarize the
t 1 t
Lagergrens pseudo-first-order rate equation and pseudo-second- ¼ þ : ð12Þ
qt k2 q2e qe
order equation, respectively:
In the above equation qe and qt denote the amounts adsorbed at
-3.6 R2 = 0.9205 30 Degree C equilibrium and at any time t in grams, respectively, and k is a con-
R2 = 0.9659 40 Degree C stant. In the case of pseudo-first-order a graph was plotted
R2 = 0.993 50 Degree C between log (qe  qt) versus time (Figs. 14 and 15), the slope of
which gives the value of kad, whereas in the case of pseudo-sec-
-4.1
ond-order a graph was plotted between t/qt versus time and in
both cases straight-line graphs were obtained (Figs. 16 and 17).
log (qe-qt)

The R2 values are indicative of the fact that the ongoing reaction
-4.6
proceeds via a pseudo-second-order mechanism rather than pseu-
do-first-order mechanism.

-5.1 3.6. Rate expression and treatment of the data

For proper interpretation of the kinetic data, it is vital to identify

-5.6 the adsorption process steps, which govern the overall removal
0 50 100 150 200 250
adsorption rate. The mathematical treatment recommended by
Time (minutes)
Boyd et al. [42] was employed to differentiate between particle dif-
Fig. 14. Plot of log(qe  qt) versus time for the phenol red-bottom ash system at fusion and film diffusion. Film diffusion occurs when the transport
different temperatures. of adsorbate to the surface of the adsorbent takes place (external
352 A. Mittal et al. / Journal of Colloid and Interface Science 337 (2009) 345–354

250 3.5

3
200
2.5
t/qt (min g/mg)

150 2

Bt
1.5

100
1
R2 = 0.8834 30 Degree C
0.5 R2 = 0.921 40 Degree C
50 R2 = 0.9954 30 Degree C R2 = 0.9056 50 Degree C
R2 = 0.9981 40 Degree C 0
50 Degree C 0 50 100 150 200
R2 = 0.9971
0 Time (minutes)
0 100 200 300 400
Time (minutes) Fig. 19. Plot of time versus Bt for the phenol red-deoiled soya system at different
temperatures.
Fig. 17. Plot of time versus t/qt for the phenol red-deoiled soya system at different
temperatures.

transport > internal transport) and particle diffusion when trans- Table 9
port of the adsorbate within the pores of the adsorbent takes place Values of effective diffusion coefficient (Di), preexponential constant (Do), activation
(external transport < internal transport). energy (Ea), and entropy of activation (DS#) for the diffusion of phenol red adsorbing
over bottom ash and deoiled soya.
The fractional attainment F of equilibrium at time t was calcu-
lated as follows: Adsorbent Di Do Ea DS#
(J/mol) (J/K/mol)
Qt 30 °C 40 °C 50 °C
F¼ : ð13Þ
Q1 8 8
Bottom ash 5.1  10 5.7  10 8.0  108 6  105 17862.2 284.6
Here Qt and Q1 are amounts adsorbed after time t and after infinite Deoiled soya 3.5  107 4.3  107 6.1  107 3  103 22819.5 252.1

time, respectively.
The F values were used to retrieve the Bt values from the
Reichenberg’s table and a distinction between film diffusion and In the equations given above Do is the preexponential constant,
particle diffusion adsorption rate was made with the help of Bt DS# is the entropy, d gives the average distance between two
graphs obtained [43]. It is seen that the present adsorption process successive sites of the adsorbent, h is Planks constant, k, Boltzmann
proceeds via particle diffusion at 30, 40, and 50 °C for phenol red- constant, Ea, the energy of activation, T, the temperature, and R is
bottom ash system (Fig. 18) and at 50 °C for phenol red-deoiled soya the universal gas constant. Table 9 shows the value obtained from
system whereas it proceeds via film diffusion at 30 and 40 °C for phe- these equations.
nol red-deoiled soya system (Fig. 19). For both adsorbent materials
the values of effective diffusion coefficient Di were calculated with 3.7. Column studies
the help of slopes of time versus Bt graphs at 30, 40, and 50 °C.
  Fixed-bed column studies were applied in order to observe the
Ea
Di ¼ Do exp  ; ð14Þ adsorptive tendency of the two adsorbent materials [44]. The
RT
! adsorption process in fixed-bed columns appears to have a distinct
DS# 2 advantage over batch-type operations due to the fact that in batch-
Do ¼ ð2:72 d kT=hÞ exp : ð15Þ
R type operations the effectiveness of the adsorbent material for
removing solute from solution decreases as the adsorption pro-
ceeds, whereas in column operations the adsorbent is continuously
4.5 in contact with solution of fixed concentration. As a result the
4 exhaustion capacity of the column is relatively greater than that
of batch capacity [45].
3.5 R2 = 0.9079

3 R2 = 0.9773 3.7.1. Column adsorption

R2 = 0.9269
Inlet flow rates, concentration, bed height, etc. were some of the
2.5
factors playing a major role in column studies. A solution of con-
Bt

2 centration 10  105 M of the dye was passed through the columns

at the rate of 0.5 ml/min. The predicted breakthrough curves of
1.5
eluted volume against concentration of eluted dye were sketched
1 30 Degree C for the adsorption of dye over bottom ash and deoiled soya
0.5 40 Degree C columns and are depicted in Fig. 20. It is found that bottom ash
50 Degree C (0.25 g) adsorbs 0.84 mg of the dye from 6.02 mg of the dye pres-
0 ent in the solution whereas on the other hand deoiled soya
0 50 100 150 200 250 300
(0.25 mg) adsorbs 0.74 mg of the dye out of 2.83 mg of it in the
Time (minutes)
solution.
Fig. 18. Plot of time versus Bt for the phenol red-bottom ash system at different The equations below were used to calculate different parame-
temperatures. ters describing breakthrough curves:
 A. Mittal et al. / Journal of Colloid and Interface Science 337 (2009) 345–354 353

12 8
Bottom Ash
7 De-Oiled Soya
10
Concentration × 10 (M)

Concentration × 10 (M)
6
-5

-5
5

6
4

4 3

2
2
Bottom Ash
De- Oiled Soya 1
0
0 50 100 150 200 0
0 50 100 150 200
Volume (ml)
Volume (ml)
Fig. 20. Breakthrough curve for the phenol red-bottom ash and phenol red-deoiled
soya columns. Fig. 21. Desorption of phenol red from bottom ash and deoiled soya columns.

Vx 3.7.2. Column regeneration and dye recovery

tx ¼ ; ð16Þ Acidic water (pH 2) was used for the eluting of columns of both
Fm
Vx  Vb adsorbents. The flow rate in both cases was maintained at 0.5 ml/
td ¼ ; ð17Þ min. The curves for desorption obtained for the two adsorbents are
Fm
shown in Fig. 21. Complete desorption of the dye was achieved by
d td td ðV x  V b Þ
¼ ¼ ¼ ; ð18Þ using 140 ml of acidic water in both cases. In the case of bottom
D t x  t f t x þ t d ðf  1Þ V b þ f ðV x  V b Þ
ash and deoiled soya the percentage recovery of the dye was
tf Ms 91.4% and 98.2%, respectively.
f ¼1 ¼ ; ð19Þ
t d ðV x  V b ÞC o Out of the 8.42  104 g of the dye adsorbed 84% of the dye was
D þ dðf  1Þ removed in the case of bottom ash whereas out of 7.42  104 g of
percentage saturation ¼  100: ð20Þ
D the dye adsorbed 92% is removed in the case of deoiled soya, for
the first 70 ml. The rest of the 70 ml of the eluent was sufficient
Here, d length of the primary adsorption zone, tx, is the total
to remove almost all of the adsorbed dye from both columns.
time involved for the establishment of primary adsorption zone,
After the desorption process both columns were washed with hot
td, time for the primary adsorption zone to move down its length,
water at a flow rate of 0.5 ml/min. The columns were loaded with the
tf, time for initial formation of primary adsorption zone, Fm, mass
dye solution of known concentration and then desorption was car-
rate of flow of the adsorbent, and f fractional capacity of the col-
ried out several times to obtain the breakthrough capacities of the
umn. Tables 10 and 11 portray the values calculated for all these
columns. The breakthrough capacities during the first, second, third,
parameters. The mass flow rate calculated in case of both adsor-
and fourth cycles were found to be 72, 50, 44, and 48 mg/g for bottom
bent materials is found to be 2.25  105 mg/cm2/min for bottom
ash column and 70, 63, 55, and 40 mg/g for the deoiled soya column.
ash and 2.25  102 mg/cm2/min for deoiled soya. The total time
involved for the establishment of primary adsorption zone (tx)
and the time for the primary adsorption zone to move down its 4. Conclusions
length (td) were found to be 5.75  106 and 4.87  106 min for bot-
tom ash and 2.6  103 and 2.2  103 min for deoiled soya, respec- The foregoing experiments reveal that bottom ash and deoiled
tively. A greater set of values for tx and td is obtained for the phenol soya prove to be efficient adsorbents for the removal of phenol
red-bottom ash system than the phenol red-deoiled soya system. red dye from wastewaters. These adsorbent materials are cheap
and easily available with high potential of adsorbing the dye from
wastewaters than the commercially available materials. Maximum
monolayer capacity was observed at higher temperatures for both
Table 10
Fixed-bed adsorber calculations. adsorbents. The negative values of DG° indicate the spontaneity
whereas the positive values of DH° and DS° indicate the endother-
Adsorbent Co Cx Cb Vx Vb (Vx  Vb) Fm D
mic nature and increase in randomness of the process taking place,
(M) (M) (M) (ml) (ml) (ml) (mg/cm2/ (cm)
min) respectively. The activation energies for the phenol red-bottom ash
and phenol red-deoiled soya system were found to be 1.78 and
Bottom 10  105 9.7  105 1.1  105 130 20 110 2.2  105 0.5
ash 2.28 K J/mol, respectively. The process was concluded to proceed
Deoiled 10  10 5
9.5  10 5
1.2  105
60 10 50 2.2  10 2
0.5 by a pseudo-second-order mechanism. The percentage recovery
soya greater than 90% for both adsorbents proved their effectiveness.
Hence from the above discussion the fact has been established that
bottom ash and deoiled soya can be used effectively as adsorbents
for the removal and recovery of phenol red from wastewaters.
Table 11
Parameters for fixed-bed adsorber.
Acknowledgments
Adsorbent tx (min) td (min) tf (min) f d (cm) Percentage
saturation
Authors Dipika Kaur and Arti Malviya are thankful to MHRD,
Bottom ash 5.7  106 4.8  106 40 1.0 0.4 99.1
New Delhi, for providing fellowship under Technical Education
Deoiled soya 2.6  103 2.2  103 20 1.0 0.4 99.1
Quality Improvement Program (TEQIP) of Govt. of India.
354 A. Mittal et al. / Journal of Colloid and Interface Science 337 (2009) 345–354

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