Journal of Molecular Liquids 179 (2013) 133140

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Adsorption of hazardous dye Eosin Yellow from aqueous solution onto waste material
De-oiled Soya: Isotherm, kinetics and bulk removal
Alok Mittal , Damodar Jhare, Jyoti Mittal
Department of Chemistry, Maulana Azad National Institute of Technology, Bhopal 462 051 India

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

Article history: The main focus of this research is to develop a systematic method for the removal of a hazardous dye Eosin
Received 20 July 2012 Yellow from its aqueous solutions by adsorption process. Eosin Yellow is an anionic halogen containing dye
Received in revised form 27 November 2012 which belongs to Flouorescein class. During the batch studies it has been found that Eosin Yellow showed a
Accepted 27 November 2012
decrease in adsorption over De-oiled Soya with increasing pH, while increase in concentration, temperature,
Available online 20 December 2012
amount of adsorbent and sieve size increased the adsorption of the dye over De-oiled Soya. The ongoing
Keywords:
adsorption follows Langmuir, Freundlich, Tempkin and DR adsorption isotherm models. On the basis of
Eosin Yellow Langmuir constant values like Gibb's free energies at 30, 40 and 50 C have been found as 23.43, 25.15 and
De-oiled Soya 25.23 kJ mol 1 respectively, while enthalpy and entropy of the adsorption process were calculated as
Adsorption 3.598 kJ mol 1 and 66.277 JK 1 mol1, respectively. Kinetic studies reveal that pseudo second order kinetics
Isotherm is operative during the adsorption process and the rate constant for the process was close to 1109 sgMol1
Kinetic at all the temperatures. The treatment of kinetic data further reveals that the ongoing adsorption proceeds via
Column study lm diffusion process and adsorption of the dye is taking place mainly on the external surface of the De-oiled
Soya. The pre exponential constant (Do) and activation energy (Ea) have been found as 3.021014 and
32.85 kJ mol1 respectively. Under the column studies various parameters like fractional capacity of column,
mass ow rate, percentage saturation of column etc. have been evaluated and their values have been found as
0.9748, 0.044 mg/cm2/min and 98%, respectively. The recovery of the dye from the exhausted column was
made by eluting dilute NaOH solution and almost 94% of the dye recovery was achieved.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Eosin Yellow, is an anionic dye having IUPAC name, 2-(2,4,5,6-
Tetrabromo-6-oxido-3-oxido-3H xanthenes-9-yl) benzoate disodium
salt. It is highly water soluble and belongs to the uorescein class of
dye. Due to its ability of strong absorption by red blood cells and
red color, Eosine Yellow is widely used in gram staining of differenti-
ate bacterial species [1]. Edible usage of the dye has been banned by
the US authorities due to toxic effects [2].
The toxicological information of Eosin Yellow reveals that the dye
Eosine Yellow may cause severe skin and eye irritation. A physical
contact of the dye on the skin causes irritation with redness and
pain [3]. On ingestion, it poses several adverse effects particularly
on the vital organs like liver, kidney etc. [4]. A direct contact of
the dye with the eye can cause permanent injury to the cornea by
the destroying retinal ganglion cell, located near the inner surface of
the retina [5]. It also damages DNA in gastrointestinal organs of living
beings resulting thereby in several types of diseases in the human
body [6]. Inhalation of the dye reduces the pulmonary gas exchange
Corresponding author. Tel.: +91 9425025427; fax: +91 755 2670562.
E-mail address: aljymittal@gmail.com (A. Mittal).
capacity of the lungs [7]. Its metabolites are also highly toxic and car-
cinogenic in nature [8].
Keeping the toxicity of the Eosin Yellow in view, it was considered
worthwhile to develop an economic and fast method for its removal
from wastewater. From several decades various methods have evolved
in wastewater treatment such as electrochemical treatment [9], oxida-
tion [10], ozonation [11], photochemical treatment [12] and froth ota-
tion [13]. It is now well established that for the wastewater treatment,
adsorption has several advantages over other methods [14]. Moreover,
the ability of adsorption to remove toxic chemicals without producing
any toxic byproducts, thereby keeping quality of water undisturbed,
has also popularized the adsorption technique in comparison to electro-
chemical, biochemical or photochemical degradation processes. During
the past few years, the focus of the research is to utilize cheap materials
as potential adsorbents and the processes developed so far are based
on exploring such types of solid waste products, which can prove eco-
nomical and bring cost effectiveness [1550]. Therefore employing
adsorption process for the removal and recovery of the costly dye like
Eosin Yellow is advantageous and necessary, while the cost reduction
of the developed process can be done by selecting a suitable waste
material as adsorbent.
In the present paper attempts have been made to develop a fast
and economical method for the removal of Eosin Yellow using

0167-7322/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molliq.2012.11.032
134 A. Mittal et al. / Journal of Molecular Liquids 179 (2013) 133140
De-oiled Soya as adsorbent. De-oiled Soya is a waste material, which
has been processed out from the Soya Oil industries. It is obtained
as a bye product after extracting all possible nutrients of Soya
beans. It is a porous and dry aky material, with brownish white
color. Its use as animal feed is banned nowadays due to the formation
of anti-metabolites activities in their digestive systems [51,52]. India
is one of the major producers of the soya bean crop and captivatingly
many soyabean oil extraction mills are situated in our state.
2. Material & methods
The dye Eosin Yellow, also known as Eosin Y, Eosin Yellowish, Acid
Red 87, C.I. 45380, Bromoeosine, Bromouoresceic acid and D&C
Red No. 22, possesses molecular formula C20H6Br4Na2O5 (molecular
weight 691.88). It is procured from M/s Merck and used as obtained.
Double distilled water was used for the preparation of 1 10 3 M
stock solution of the dye and all further solutions were prepared by
diluting the stock with distilled water. Adsorbent De-oiled Soya was
a free gift from M/s Sanwaria Agro Oils Limited Bhopal, India. In
order to adjust the pH of the solution dilute HCl and NaOH were
used. All other chemicals used are of AR grade.
The microprocessor based pH meter model number HI 8424 (M/s
Henna Instruments, Italy) was used to measure the pH of the solu-
tions. The absorption studies were carried out using UV/Visible
spectrophotometer model number 117 (M/s Systronics, Ahmedabad,
India). To measure various physical properties of De-oiled Soya,
instruments like Mercury Porosimeter was used to determine poros-
ity of the material, specic gravity bottles were employed to nd out
density and Quantasorb Model QS-7 surface area analyzer was used
to measure surface area. To characterize De-oiled Soya, the IR spec-
trum was recorded on Infra-Red Spetrophotometer (HP FT-IR),
Scanning Electron Microscope experiments were performed on Philips
SEM 501 electron microscope, while X-ray measurements were carried
out on Philips X-ray Diffractophotometer employing Nickel Filtered
Cu--radiations.
3. Experimental
3.1. Material development
In order to enhance the adsorption ability of the De-oiled Soya the
procured material is rst subjected to the activation procedures. The
dry akes of De-oiled Soya were rstly groundd into very small gran-
ules, washed with double distilled water several times and then dried
in an oven. To oxidize all undesired organic impurities, the dried ma-
terial was then treated with hydrogen peroxide solution (30% w/v) at
room temperature for about 24 h. The material thus obtained was
further washed thoroughly several times by double distilled water
and to expel moisture, it was once again kept into an electric oven
at 100 C for about 1 h. The activated adsorbent thus formed was
then sieved to various mesh sizes such as 0.4250.150 mm (36 BSS
Mesh), 0.1500.088 mm (100 BSS Mesh) and 0.088 mm (170 BSS
Mesh) and nally stored separately in desiccators.
To determine the nature of De-oiled Soya, its weighted amount
was added in 25 mL of distill water of pH = 7.0 and stirred thorough-
ly. The solution was kept undisturbed for 24 h in a 100 mL airtight
measuring ask and then ltered to measure the pH. A decrease in
the value of pH of the solution conrmed the acidic nature of the
activated De-oiled Soya.
3.2. Adsorption studies
To carry out batch adsorption studies, in a 100 mL volumetric
ask, 25 mL of the dye solution was taken at a xed temperature
and activated De-oiled Soya of a suitable mesh size was then added
into it. The desired pH of the solution was now maintained by dilute
HCl and/or dilute NaOH and the mixture was given intermittent shak-
ing on a mechanical shaker. After about 24 h, when equilibrium is
thought to be established, the solution was ltered using Whattman
lter paper (No. 41) and the amount of dye uptake was monitored
spectrophotometrically at the absorbance maximum of Eosin Yellow,
viz. max 516 nm. It is important to note that under batch studies, the
effects of important parameters such as dye concentration, solution
pH, sieve size and amount of the adsorbent material, solution temper-
ature and contact time were observed.
3.3. Kinetic studies
In order to monitor the kinetics of the ongoing adsorption process,
in a series of 100 mL airtight volumetric asks, 25 mL of the dye solu-
tions was taken in each and a suitable amount of the adsorbent of
known mesh size was added into these. Flasks were taken in a
water bath and agitated periodically on a mechanical shaker. These
solutions were then ltered after a particular time interval and spec-
trophotometric analysis was carried out for the dye uptake.
3.4. Column studies
The bulk removal of the dye and its recovery was carried out
through adsorption and desorption, respectively using column opera-
tions. To prepare the column a long tubular glass column of 30 cm
length and 1 cm internal diameter was used. De-oiled Soya granules
were dipped in double distilled water and kept overnight. Over the
support of small amount of glass wool, slurry of De-oiled Soya was
carefully fed in the column. In order to avoid air entrapment, the out-
let of the column was kept open throughout the feeding. Once the
homogeneous bed of the adsorbent is formed in the glass column,
its outlet was closed. Now a dye solution of 1 10 4 M concentration
was percolated at a ow rate of 0.5 mL/min and expelled dye solu-
tions, each of 10 mL volume, were collected in test tubes to monitor
the dye concentration by UV/Visible spectrophotometer. The con-
tinuous adsorption of the dye over the adsorbent surface ultimately
exhausted the column bed and at this stage the feeding of the dye solu-
tion to the column was stopped. In order to retrieve the adsorbed mate-
rial from exhausted adsorbent, dilute NaOH was percolated through the
column bed and solution thus obtained was nally dried. When dye was
drained out almost completely, the adsorbent bed of the column was
properly washed with hot water and the column was made ready for
the next cycle of operation.
4. Result and discussion
4.1. Characterization of adsorbent
The characterization of the activated De-oiled Soya was carried
out by conventional chemical methods. It was found that the dry sam-
ple contains maximum prot percentage (about 48%), while proteins,
moisture, ber, SiO2, P, and Ca were present 29.0, 11.0, 6.0, 2.0, 0.7,
and 0.2%, respectively. Other physicochemical properties like, surface
area, density, porosity and loss of ignition of dry activated De-oiled
Soya were obtained as 728.6 cm 2g 1, 0.5614 gmL 1, 67% and
4.27%, respectively.
The Differential Thermogravimetry Analysis (DTA) curves of the ac-
tivated De-oiled Soya exhibit its good thermal stability and negligible
weight loss was accounted. SEM photographs ascertained that the par-
ticulates of activated De-oiled Soya are porous and almost spherical.
The Infra-Red spectrum of the activated De-oiled Soya gave sharp
absorption bands at 479, 779, 1113, and 3459 cm1, conrming there-
by the presence of gorthite [4(FeOOH)], Coesite [SiO2], Corundum
[2(-Al2O3)], and Laumonite [4(CaAl2Si4O124H2O)], respectively.
 A. Mittal et al. / Journal of Molecular Liquids 179 (2013) 133140 135

4.2. Preliminary adsorption studies 0.7

4.2.1. Effect of pH of solution 0.6

The effect of pH on the adsorption behavior of the dye was studied
at 30, 40 and 50 C by varying the pH of the dye solution from 3 to 12

Dye Uptake 105 (mol/g)

at a xed initial concentration of 1 10 4 M, 0.15 g amount and 100 0.5
BSS mesh size of the adsorbent. The percentage removal of the dye
with increasing pH at 30 C is plotted in Fig. 1. The graph clearly indi-
0.4
cates that the dye uptake decreases with increasing pH and maximum
uptake of the dye is achieved at low pH. Due to almost 50% dye
adsorption at pH 7.0, this pH was selected for all subsequent studies. 0.3

4.2.2. Effect of adsorbate concentration and temperature

The uptake of the dye adsorbed on De-oiled Soya was investigated
at initial concentration ranges from 1 10 5 to 10 10 5 M at a xed
pH (7.0) and at different temperatures 30, 40 and 50 C. The concen-
tration studies reveal that for the dye Eosin Yellow, with the increase
in concentration of the dye solution the extent of adsorption over
De-oiled Soya increases almost linearly (Fig. 2). It can also be
observed in Fig. 2 that with the rise in temperature of the solution
the amount of dye uptake increases, indicating thereby the endother-
mic nature of the ongoing adsorption.
4.2.3. Effect of amount of adsorbent
The batch adsorption study was performed to ascertain the effect
of variation of amount of adsorbent on the uptake of the dye.
Amounts ranging from 0.025 to 0.250 g of De-oiled Soya were
added separately in 100 mL volumetric asks having a dye solution
of 1 10 4 M concentration at pH 7.0 and temperatures 30, 40 and
50 C. It was observed that the adsorption of dye increases with
increase in the amount of adsorbent (Table 1). The most favorable
adsorption was observed between 0.100 and 0.200 g amounts of the
adsorbent. Subsequently, the adsorption studies were performed by
selecting 0.100 g of adsorbent at each temperature.
4.2.4. Effect of sieve size of adsorbent
The batch adsorption experiments were carried out using three
different particle sizes (36, 100 and 170 BSS mesh) at desired pH,
time, amount of adsorbent and temperature. It was observed that
the uptake of the dye increases with decreasing particle sizes and at
30 C, 2.52 10 6, 3.98 10 6 and 4.56 10 6 mol/g of the dye
was adsorbed over De-oiled Soya of sieve sizes 36, 100 and 170 BSS
80
DeOiled Soya
70
0.2
30 Degree C
0.1
40 Degree C
50 Degree C
0
0 2 4 6 8 10 12
Dye Concentration 105 (M)
Fig. 2. Effect of concentration for the Eosin Yellow (pH = 7.0)De-oiled Soya
(amount = 0.100 g & mesh size = 100 BSS) system at different temperatures.
mesh. This is mainly due to the increase in the surface area of the
adsorbent material with the decrease in its mesh size.
4.2.5. Effect of contact time
Contact time studies were helpful in understanding the trend of
dye adsorption over a period of time. The contact time studies were
carried out at 30, 40 and 50 C temperatures in 7 10 5 M dye con-
centration by taking xed amount (0.100 g) and mesh size (100
BSS) of the adsorbent. It was found that the equilibrium in adsorption
approaches after around 4 h (14400 s) of contact and extent of
adsorption of the dye increases with temperature, which further con-
rms the endothermic nature of the ongoing adsorption.
4.3. Kinetic studies
4.3.1. Adsorption rate constant study
To ascertain order of the Eosin YellowDe-oiled Soya adsorption the
data obtained during contact time studies were analyzed through vari-
ous kinetic models. The best t results were obtained in the Ho-Mckay
pseudo second order model (Eq. (1)) and it was established that the
ongoing adsorption follows a pseudo second order process.

1 1 t
60 1
qt k2 qe 2 qe

50
% Absorbed

Table 1
40 Effect of amount of De-oiled Soya (100 BSS mesh) on the adsorption of De-oiled Soya
(concentration 1 104 & pH = 7.0) at different temperatures.

30 Amount of De-oiled Soya (g) Amount of Eosin Yellow adsorbed 106

(g)

30 C 40 C 50 C
20
0.025 0.157 0.218 0.450
0.050 0.272 0.422 0.521
10 0.075 0.429 0.597 0.704
0.100 0.592 0.732 0.829
0.125 0.707 0.849 1.022
0
2 4 6 8 10 12 0.150 0.847 1.081 1.353
0.175 0.941 1.213 1.513
pH
0.200 1.040 1.284 1.615
0.225 1.149 1.498 1.709
Fig. 1. Effect of pH for the Eosin Yellow (concentration = 1 104 M)De-oiled Soya
0.250 1.259 1.539 1.752
(amount = 0.150 g & mesh size = 100 BSS) system.
136 A. Mittal et al. / Journal of Molecular Liquids 179 (2013) 133140

where qe and qt are adsorption capacities (Molg1) at equilibrium and
time t (Second), respectively, and k2 is the rate constant of the pseudo
second order rate expression (sgMol 1).
The kinetic measurements were carried out at 30, 40 and 50 C in
7 10 5 M dye concentration using 0.100 g of De-oiled Soya of 100
BSS Mesh at pH 7.0. The plot of t/qt against time gives straight lines
with regression coefcient values almost unity (Fig. 3), conrming
thereby pseudo second order kinetics of the ongoing process at all
the temperatures. At all the temperatures, the rate constants for the
process were found almost 1 10 9 sgMol 1.
4.3.2. Rate expression and treatment of data
It is a well known fact that adsorption processes proceed either via
particle diffusion mechanism or via lm diffusion mechanism. In the
reactions following particle diffusion mechanism, by and large trans-
portation of adsorbate takes place within the pores of the adsorbent
and a very small amount of adsorption occurs on the external surface
(external transport is more than internal transport). While in the lm
diffusion method, transport of adsorbate takes place largely to the
external surface of the adsorbent (external transport is less than
internal transport). Thus for an appropriate elucidation of experimen-
tal data, it is essential to identify the steps in the adsorption process.
In the present case, the kinetic data obtained by nite batch method
has been treated by ingenious mathematical treatment suggested
by Boyd et al. [53] and Reichenberg [54]. Following mathematical
expressions help in predicting particle diffusion or lm diffusion
mechanistic steps involved in the ongoing adsorption process:
   
6 X 2 2
F 1 1=n exp n Bt
2
1 T is the temperature and R is the universal gas constant.
where, F is the fractional attainment of equilibrium at time t and
is obtained by using Eq. (3) and n is the Freundlich constant of the
adsorbate.
Qt
F 3
Q
where, Qt and Q are amounts adsorbed after time t and after innite
time, respectively. The other parameter Bt is known as time constant
and obtained by following expression:
2 D
Bt  2 i 4
r0
where, Bt is time constant, Di is the effective diffusion coefcient of
adsorbate in the adsorbent phase and r0 is the radius of adsorbent
particles, assumed to be spherical.
Reichenberg's table [54] was used to evaluate Bt values, which is
analogous to the F values obtained in above case. The time and Bt
graphs at different concentrations are found non linear, indicating
thereby lm diffusion nature of the adsorption. This clearly conrms
that the extent of adsorption of the dye takes place largely on the
external surface of the adsorbent.
To determine energy of activation (Ea) and change in entropy of
activation (S #) of the ongoing adsorption processes, the following
well-known equations were employed:
 
E
Di Do exp a 5
RT
   
2 S
Do 2:72 d kT=h exp 6
R
In the equations given above Do is the pre-exponential constant, Di
is effective diffusion coefcient, S # is the entropy, d gives the aver-
age distance between two successive sites of the adsorbent, h is the
planks constant, k, Boltzmann constant, Ea, the energy of activation,
2
Table 2 presents values of effective diffusion coefcient (Di), pre ex-
ponential constant (Do), activation energy (Ea) and entropy of activa-
tion (S#) calculated at each temperature for the ongoing adsorption.
The decreasing values of effective diffusion coefcient (Di) with respect
to increase in the temperature clearly exhibit that the mobility of the
ions decreases due to increased retarding force acting upon adsorbate
particles. The negative values of S# obtained from the systems reveal
that there is no signicant alteration in the internal structure of the
De-oiled Soya during the adsorption of the Eosin Yellow.

4.4. Adsorption isotherm studies

3.551E+09 In order to successfully apply the adsorption technique for practi-

cal purposes, it is necessary to carry out adsorption isotherm studies
based on various adsorption isotherm models. These studies are help-
3.051E+09 ful in establishing the relationship between the amount of adsorption
of the dye (over a unit weight of the adsorbent) and the equilibrium
concentration of adsorbate in the reaction mixture. Thus Langmuir,
Freundlich, Tempkin and DR isothermal models are applied to the
t/qt (Sec.g/mol)

2.551E+09
experimental data obtained during the isothermal adsorption studies.

2.051E+09 4.4.1. Langmuir adsorption isotherm model

The well known linear form of Langmuir's adsorption isotherm equa-
tion (Eq. (7)) was applied for the Eosin YellowDe-oiled Soya system.
1.551E+09 1 1 1
7
qe Q o b Q o Ce

1.051E+09 R = 0.993 30 Degree C

R = 0.995 Table 2
40 Degree C
Values of effective diffusion coefcient (Di), pre exponential constant (Do), activation
R = 0.991 50 Degree C energy (Ea) and entropy of activation (S#) for the diffusion of Eosin Yellow adsorbing
551100000 over De-oiled Soya.
1500 3300 5100 6900 8700 10500 12300 14100 15900
Di 108 Do Ea -S#
Time (Sec)
1
30 C 40 C 50 C (kJ mol ) (JK1 mol1)
Fig. 3. Plot of time versus t/qt for Eosin Yellow (pH=7.0, concentration=7105 M)
1.3282 0.8243 0.5953 3.02 1014 32.85 539.217
De-oiled Soya (amount=0.100 g & mesh size=100 BSS) system at different temperatures.
 A. Mittal et al. / Journal of Molecular Liquids 179 (2013) 133140 137

50
R = 0.971
45 R = 0.985 -4.9

40
1/qe (g/mol) x 10000

35 -5.1

log qe
30

25 R = 0.992 -5.3

20

15 -5.5
30 Degree C
R = 0.975 30 Degree C
10 40 Degree C R = 0.981 40 Degree C
50 Degree C
5
R = 0.990 50 Degree C
-5.7
1.7 3.7 5.7 7.7 9.7 11.7 -5.1 -4.9 -4.7 -4.5 -4.3
1/Ce (M1) 10000 logCe
Fig. 4. Langmuir adsorption isotherm for Eosin Yellow (pH = 7.0)De-oiled Soya Fig. 5. Freundlich adsorption isotherm for Eosin Yellow (pH = 7.0)De-oiled Soya
(amount = 0.100 g & mesh size = 100 BSS) system at different temperatures. (amount = 0.100 g & mesh size = 100 bss) system at different temperatures.

where qe is the number of moles of solute adsorbed per unit weight at
concentration C (molg1), Ce is the equilibrium molar concentration
of the dye (molL1), Qo is the maximum adsorption capacity and b is
the energy of adsorption.
At all the temperatures, the 1/Ce versus 1/qe graphs give straight
lines with appreciable values of the regression coefcient (R 2) close
to unity, verifying the Langmuir adsorption model and ascertaining
that monolayer formation is taking place during the adsorption of
Eosin Yellow over the surface of De-oiled Soya (Fig. 4). On the basis
of gradient and interception of these straight lines, Langmuir constant
b and number of moles of the dye adsorbed per unit weight of the
adsorbent (Qo) have been evaluated and presented in Table 3.
4.4.2. Freundlich adsorption isotherm model
The following equation describing the Freundlich model for the
adsorption of solutes from a liquid to a solid surface was applied for
the present adsorption system:
where qe is the amount adsorbed (Mol.g 1), Ce is the equilibrium
concentration of the adsorbate (M), KF and n the Freundlich con-
stants, are related to adsorption capacity and adsorption intensity,
respectively. Straight lines with regression coefcients close to unity
were obtained in log Ce versus log qe, graph (Fig. 5) and values of
constants KF and n derived from the intercepts and slope of these
straight lines are presented in Table 3. The verication of the
Freundlich model conrms the homogeneous nature of adsorption
of Eosin Yellow over the surface of De-oiled Soya at each temperature.
4.4.3. Tempkin adsorption isotherm model
To evaluate heat of adsorption of adsorbate molecules with the ex-
tent of coverage over the surface of adsorbent particles, the adsorption
0.000014

logqe logKF 1=n logCe 8 R = 0.948

0.000012
Table 3
Various adsorption isotherm constants for Eosin Yellow (pH = 7.0) De-oiled Soya
(amount = 0.100 g & mesh size = 100 BSS) system at different temperatures. 0.00001
qe (mol/g)

Langmuir constants R = 0.934

Qo 105 (mol/g) b 103 (L/mol) R = 0.947
30 C 40 C 50 C 30 C 40 C 50 C 8E-06
1.42 1.10 12.16 10.98 15.79 12.16

Freundlich constants
n KF 6E-06
30 C 40 C 30 C 40 C 30 C 40 C
0.791 0.681 0.791 0.681 0.791 0.681
4E-06 30 Degree C
Tempkin constants
k1 105 (L/mol) k2 105 40 Degree C
30 C 40 C 30 C 40 C 30 C 40 C 50 Degree C
0.8 1.0 0.8 1.0 0.8 1.0 2E-06
-11.7 -11.2 -10.7 -10.2
DR constants
(mol2 J2) 109 Xm (mol/g) 10 3 ln Ce
30 C 40 C 30 C 40 C 30 C 40 C
Fig. 6. Tempkin adsorption isotherm for Eosin Yellow (pH = 7.0)De-oiled Soya
9.0 10.0 9.0 10.0 9.0 10.0
(amount = 0.100 g & mesh size = 100 bss) system at different temperatures.
138 A. Mittal et al. / Journal of Molecular Liquids 179 (2013) 133140

data was analyzed through linear form (Eq. (9)) of Tempkin isothermal Table 4
model. Thermodynamic parameters for Eosin Yellow (pH = 7.0) De-oiled Soya (amount=
0.100 g & mesh size = 100 BSS) system at different temperatures.

qe k1 lnk2 k1 lnCe 9 Go (kJmol1) H0 (kJ mol1) S0 (JK1 mol1)

30 C 40 C 50 C 3.598 66.277
1 23.43 25.15 25.23
where qe is the amount adsorbed at equilibrium in (Molg ), Ce is the
nal concentration at equilibrium (molL1), k1 is the Tempkin iso-
therm energy constant (Lmol1) related to the heat of adsorption
On the basis of values of , obtained from the DR isotherm graph,
and k2 is the Tempkin's isotherm constant.
values of mean sorption energy were calculated at each temperature.
At all the temperatures a plot of Ce versus qe gives straight lines
At all the temperatures the values have been found close to 7.47 kJ
(Fig. 6) and indicates the uniform distribution of binding energy
indicating thereby involvement of Chemisorption in the present
arising due to interaction of the absorbate molecule with adsorbent
adsorption process.
particles. The straight lines obtained from the graphs were also help-
ful in determining the values of Tempkin isotherm constants, which
4.4.5. Thermodynamic parameters
are presented in Table 3.
To monitor feasibility, favorability and spontaneity of the ongoing
adsorption process various thermodynamic parameters were eval-
4.4.4. DR adsorption isotherm model
uated with the help of data obtained from Langmuir adsorption isotherm
In order to identify nature of the ongoing adsorption process, fol-
graph. Following equations were used to calculate thermodynamic
lowing DR adsorption isotherm model was applied:
parameters like change in standard free energy (G0), change in en-
2 thalpy (H0) and change in entropy (S0):
lnCads lnXm 10
0
where Cads is the amount of the dye adsorbed per unit weight of the G R T ln b 13
adsorbent (mgg 1), Xm is the maximum sorption capacity provided
by the intercept (molg 1), (mol 2/J 2) is the activity coefcient 0 T2 T1 b
H R  ln 2 14
related to mean sorption energy, and (Eq. (11)) is Polanyi potential. T2 T1 b1
 
1
RTln 1 11 0 H0 G0
Ce S 15
T
where, R is universal gas constant and T is temperature in Kelvin.
The activity coefcient () and the adsorption capacities (ln Xm) where, b, b1 and b2 are the equilibrium constants at 30, 40 and 50 C,
were evaluated from the slopes and intercepts of the plot lnCads ver- respectively.
sus 2 (Fig. 7) at 30, 40 and 50 C and these results are depicted in Values of various thermodynamic parameters at different temper-
Table 3. The mean sorption energy (E) was calculated from the values atures are presented in Table 4. The spontaneous nature of the ongo-
of by following expression: ing adsorption process was ascertained by negative free energy G 0
values, while the positive value of change in enthalpy (H0) suggested
1 the endothermic nature of the process. The positive value of change in
E p 12 entropy S0 revealed the increased randomness during the adsorption
2
process and provided excellent afnity of De-oiled Soya towards the
Eosin Yellow molecule.
30 Degree C
-11.2 40 Degree C 10
50 Degree C
9

8
Collected Solution 105 (M)

-11.7
7
ln C ads

6
-12.2 R = 0.989 5

-12.7 3
R = 0.983
2
R = 0.979
1
-13.2
610000000 710000000 810000000 910000000 0
2 0 20 40 60 80 100 120 140
Eluted Volume (mL)
Fig. 7. DR adsorption isotherm for Eosin Yellow (pH = 7.0)De-oiled Soya (amount =
0.100 g & mesh size = 100 bss) system at different temperatures. Fig. 8. Breakthrough curve for Eosin YellowDe-oiled Soya column.
 A. Mittal et al. / Journal of Molecular Liquids 179 (2013) 133140 139

Table 5
Fixed bed adsorber calculations for the adsorption of Eosin Yellow in De-Oiled Soya column.

Co Cx Cb Vx Vb (Vx Vb) Fm D
(M) (M) (M) (mL) (mL) (mL) (mg/cm2/min) (cm)

10 105 1.37 105 9.19 105 90 20 70 0.0440 1.0

A dimensionless separation factor r, introduced by Weber and exhaustion of the adsorbent and breakthrough curve was recorded
Chakravorti [55] was also calculated to determine the feasibility and (Fig. 8). It is found that out of 8.30 mg of the dye taken in the original
favourability of the ongoing adsorption process, by using following solution, 3.07 mg was adsorbed over De-oiled Soya and remaining
equation: 5.23 mg was drained out. Different column parameters obtained
during the studies are presented in Tables 5 and 6. A percentage
1 saturation of 98% reveals a good afnity of Eosin Yellow towards the
r 16
1 bCo De-oiled Soya granules.

where, b is the Langmuir constant and Co is the initial concentration.

4.5.2. Column regeneration & dye recovery
The values of r were found as 0.47, 0.38 and 0.45 at 30, 40 and 50 C
Section 4.2.1 of this paper clearly exhibits that Eosin Yellow shows
respectively. Less than 1 values of 'r' at all the temperatures suggest
an extremely good adsorption towards De-oiled Soya in the acidic
highly favorable adsorption during the ongoing process.
medium, while in alkaline medium adsorption is feeble. Hence,
desorption of the dye from the exhausted adsorbent was achieved
4.5. Column studies
in basic medium and in order to retrieve the Eosin Yellow and regener-
ate the column, diluted NaOH was percolated through the exhausted
4.5.1. Dye adsorption
column maintaining a ow rate of 0.5 mL/min. The desorption curve
In order to develop a more practical approach, it is essential to
presented in Fig. 9 reveals that a large amount of the dye (about 75%)
carry out an operation involving bulk removal of the dye. Different
was removed by eluting initial 40 mL of NaOH and the remaining
workers [56,57] have suggested various types of models for this pur-
amount of dye was recovered in the next 90 mL of the NaOH. Thus a
pose. But if the rate to establish equilibrium of adsorbate con-
total 130 mL of NaOH was found sufcient to recover almost completely
centration between aqueous and adsorbed phase is known, then it
the dye from the column and 94.01% percentage recovery was achieved.
is always advisable to follow a straightforward approach by using
The adsorption efciency was determined by reloading the col-
xed bed adsorber using prescribed mathematical equations [57,58].
umn with dye solution of the same concentration and breakthrough
These equations are based on column studies and help in calculating
capacities were found as 87, 82, 74 and 65% during rst, second,
various column parameters like length of the primary adsorption
third and fourth cycles, respectively.
zone (), total time involved for the establishment of primary adsorp-
tion zone (tx), time for the primary adsorption zone to move down its
5. Conclusions
length (t), time for initial formation of primary adsorption zone (tf),
mass rate of ow of the adsorbent (Fm), fraction capacity of column
The entire studies conclude that the waste material De-oiled Soya
(f) and percent saturation of column at break point.
possess extremely high susceptibility for the batch and bulk removal
Vx of halogen containing hazardous dye Eosin Yellow at all tempera-
tx 17 tures. Results obtained clearly revel that De-oiled Soya is a cheap
Fm
and easily available waste material, which has excellent potential of
Vx Vb
t 18
Fm
0.7
t t V x V b
19
D t x t f t x t f 1 V b f V x V b
0.6
Amount of Dye Recovered (mg)

tf Ms
f 1 20
t Vx Vb Co
0.5
D f1
Percentage Saturation 21
D 0.4

where, Ms is the amount of adsorbed in the adsorption zone from

break point to exhaustion, Co is initial concentration of adsorbate 0.3
and D is the length of column.
In the present case the column operations were carried out as de- 0.2
scribed in the Experimental section of this paper. During the column
operations total about 120 mL of dye solution was percolated till
0.1

Table 6
Parameters for xed bed adsorber De-oiled Soya for Eosin Yellow adsorption. 0
tx t tf f Percentage saturation
0 50 100
(min) (min) (min) (cm) Collected Volume (mL)
2042.26 1588.42 40 0.9748 0.793 98.00
Fig. 9. Recovery of the dye Eosin Yellow from De-oiled Soya column.
140 A. Mittal et al. / Journal of Molecular Liquids 179 (2013) 133140
eradicating Eosin Yellow from wastewater than any other commercially
available material. The batch adsorption process is found dependent
upon pH of the solution, particle size of adsorbents, amount of adsor-
bent, concentration of solution, contact time and temperature. The
adsorption depicts a pseudo second order rate kinetic and the value
of rate constants at all the temperatures were found almost similar,
and equal to 1 109 sgMol1. Results of kinetic experiments indi-
cate that the ongoing adsorption process follows the lm diffusion
mechanism.
Well t straight lines were obtained in the linear forms of Freundlich,
Langmuir, Tempkin and DR adsorption isotherms and the adsorption
was found to follow the chemisorption process. Thermodynamic param-
eters like change in enthalpy, entropy and free energy, calculated
through Langmuir constants, reveal that the ongoing adsorption process
is spontaneous, feasible and endothermic in nature. Bulk removal of the
dye through column operations recommends that Eosin Yellow adsorbs
over the surface of De-oiled Soya column quite quickly with percentage
saturation of almost 98%. Being acidic dye the desorption of dye could
easily be made by NaOH solution and 94.01% of the dye could be safely
recovered from the rst desorption cycle.
Acknowledgment
One of the authors (DJ) is thankful to MANIT, Bhopal for providing
nancial assistance to carry out this research work.
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