Journal of Industrial and Engineering Chemistry 20 (2014) 564571

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Journal of Industrial and Engineering Chemistry

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Competitive adsorption of Direct Yellow 12 and Reactive Orange 12 on

ZnS:Mn nanoparticles loaded on activated carbon as novel adsorbent
Shaaker Hajati a,*, Mehrorang Ghaedi b,**, Farahnaz Karimi b, Behnaz Barazesh b,
Reza Sahraei c, Ali Daneshfar c
a
Department of Physics, Yasouj University, Yasouj 75918-74831, Iran
b
Chemistry Department, Yasouj University, Yasouj 75918-74831, Iran
c
Chemistry Department, Ilam University, Ilam, Iran

A R T I C L E I N F O A B S T R A C T

Article history: A novel adsorbent (ZnS:Mn nanoparticles loaded on activated carbon) was made. The competitive
Received 2 October 2012 adsorption of Direct Yellow 12 (DY12) and Reactive Orange 12 (RO12) dyes in binary mixture onto this
Accepted 14 May 2013 adsorbent was studied. DY12 and RO12 with severe spectra overlapping were chosen and analyzed
Available online 20 May 2013
simultaneously with high accuracy by rst order derivative spectrophotometric method in binary
solutions. The effect of multi-solute systems on the adsorption capacity was investigated. Because of the
Keywords: specic characteristics of ZnS:Mn-NP-AC was found to be efcient for the removal of the dyes studied.
Adsorption
The adsorption capacities were investigated and described by the mono- and multi-component
Binary mixture
Direct Yellow 12
Langmuir and Freundlich isotherm models for both single and binary dye solutions. The isotherm
Reactive Orange 12 constants for DY12 and RO12 were calculated. For single solution of DY12 and RO12 dyes, the adsorption
Derivative spectrophotometry capacities of the applied adsorbent were found to be 90.05 mg/g and 94.52 mg/g, respectively.
ZnS:Mn nanoparticle loaded activated Equilibrium uptake amounts of DY12 and RO12 in binary solution onto the applied adsorbent were
carbon found to be considerably decreasing with increasing the concentrations of the other dye. A better
agreement between the adsorption equilibrium data and mono-component Langmuir isotherm model
was found. However, at concentrations within moderate ranges, the extended Freundlich isotherm
model satisfactorily predicted multi-component adsorption equilibrium data. An endothermic and a
spontaneous nature for the adsorption of the dyes studied were shown from thermodynamic
parameters.
2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

1. Introduction dyes because they tend to pass through the conventional

Large quantities of dangerous dyes, pigments and metals [1]
originated from dye manufacturing, textile as well as pulp and
paper industries are emitted into wastewaters. This makes
difculties to treat water contamination, because the color tends
to persist even after the conventional removal processes [2]. The
dye contaminations in water tend to prevent light penetration and
therefore, affect photosynthesis considerably. There are many
structural varieties, such as acidic, basic, disperse, azo, diazo,
anthraquinone based and metal complex dyes [3]. The difculties
in conventional wastewater treatment methods for removal of
color from different efuents are major problem [4,5]. In particular,
it is most severe for the removal of water-soluble reactive and acid
* Corresponding author. Tel.: +98 7412223048; fax: +98 7412223048.
** Corresponding author.
E-mail addresses: Hajati@mail.yu.ac.ir (S. Hajati), m_ghaedi@mail.yu.ac.ir
(M. Ghaedi).
treatment systems. Therefore, efcient treatment methods are
necessary to apply.
Various physical, chemical, and biological methods, including
adsorption, biosorption, coagulation, precipitation, membrane
ltration, solvent extraction, and chemical oxidation have been
widely applied for the treatment of dye-containing wastewater [6].
Here, we apply the adsorption method by using zinc:manga-
nese sulde nanoparticles loaded on activated carbon (ZnS:Mn-
NP-AC) for the removal of Direct Yellow12 (DY12) and Reactive
Orange 12 (RO12) dyes in binary solutions. The reason of using
ZnS:Mn-NP-AC is the specic characteristics of nanoparticles. It is
well known that the nanoparticles are of interest because of their
physicochemical properties such as ordered structure, high aspect
ratio, ultra-light weight, high mechanical strength, high electrical
and thermal conductivity, metallic or semi-metallic behavior and
high surface area. There exists much information on the adsorption
of single component dyes by various adsorbents [7].
However, many industrial efuents are mixture of several dyes,
and data availability on the adsorption of multi-component dye is

1226-086X/$ see front matter 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2013.05.015
 S. Hajati et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 564571
limited. Therefore, our study is of importance because of using: (a)
nanoparticles as adsorbent and (b) binary solutions. In addition to
the study of the competitive adsorption of DY12 and RO12 onto
ZnS:Mn-NP-AC, various mono- and multi-component isotherm
models were applied to the experimental data to determine
ZnS:Mn-NP-AC adsorption capacity which is of both technological
and fundamental importance.
Moreover, overlapping between the spectra of the components
necessitates an analytical technique for the simultaneous analysis
of the dyes mixture. Therefore, several studies have been done for
resolving the overlapping spectra of binary solutions by using
derivative spectrophotometry [8,9]. For instance, Turabik [9]
studied the simultaneous analysis of Basic Red 46 and Basic
Yellow 28 for which the overlap may not be critical and severe. To
investigate the applicability and accuracy of the method for binary
solutions with most severe overlapping, we successfully render the
simultaneous analysis of the mixture of DY12 and RO12 dyes with
severe overlapping.
2. Experimental
2.1. Instrumentation and method
The pH measurements were done using pH/Ion meter model-
686. Absorption studies were carried out using Jasco UV-Visible
spectrophotometer model V-570. A 1 cm quartz cell containing the
dyes was mounted in the spectrophotometer and the spectra were
recorded at a scan speed of 1000 nm/min and a xed slit width of
2 nm. For the analysis of the individual dyes, the absorbance
spectra of single solutions were used. Concentrations of DY12 and
RO12 were determined at 392 and 418 nm, respectively. For the
study of the binary solutions, the rst order derivatives of the
spectra of the mixtures were used.
Inductively coupled plasma atomic emission spectroscopy
(ICPAES; Varian Vista-Pro) was employed to determine the
elemental content of the ZnS:Mn nanoparticles. Absorption
measurements were carried out on a Perkin Elmer Lambda 25
spectrophotometer using a quartz cell with an optical path of 1 cm.
X-ray diffraction (XRD) pattern was recorded by an automated
Philips XPert X-ray diffractometer with Cu Ka radiation (40 kV
and 30 mA) for 2u values over 20608. The shape and surface
morphology of the ZnS:Mn nanoparticles were investigated by
eld emission scanning electron microscope (FE-SEM, Hitachi
S4160) under an acceleration voltage of 15 kV. For FE-SEM, it is
necessary to coat the ZnS:Mn nanoparticles by gold, which was
carried out by an Auto Fine Coater (JFC-1300, JEOL).
2.2. Material
2.2.1. Preparation of dye solutions
All chemicals, with analytical grade purity available, were
purchased from Merck, Darmstadt, Germany. DY12 (see Fig. S1a in
the Supplementary Data) and RO12 (see Fig. S1b in the
Supplementary Data) were used as received without any further
purication; while these colors were stable within the pH range
studied. The stock solutions of both dyes (50 mg/L) and respective
diluted working solution were prepared daily by weighting and
dissolving required amount of each dye in volumetric ask. The
mixture solution for simultaneous competitive dye removal was
prepared by the addition of appropriate increment of their stock
solution. In all solutions, the pH was adjusted by the addition of
HCl and/or NaOH.
2.2.2. Preparation of ZnS:Mn nanoparticles
ZnS:Mn nanoparticles were synthesized based on the reaction
of the mixture of zinc acetate [Zn(CH3COO)22H2O] and manganese
565
acetate [Mn(CH3COO)22H2O] with thioacetamide (CH3CSNH2) in
aqueous media. In a typical synthesis, 1 mmol of
Zn(CH3COO)22H2O) and 4 mmol of Mn(CH3COO)22H2O were
dissolved in 50 mL double distilled water. Subsequently, 10 mL of a
0.5 mol/L tri-sodium citrate was added into the solution under
stirring and the pH was adjusted to 6.0 by adding a 1 mol/L NaOH
solution. In the next step, 30 mL of a 0.5 mol/L CH3CSNH2 solution
was added. Finally, double distilled water was added to the
solution to make the volume close to 100 mL and pH was adjusted
to 6.0. The resulting mixture was heated to 50 8C and the citrate-
stabilized ZnS:Mn nanoparticles started to grow slowly. After
about 30 min, the solution turned to milky white, which indicated
the initial formation of ZnS:Mn nanoparticles. The mixture was
maintained at 50 8C for 6 h and the color of the reaction solution
became milky white mixed with light pink.
In the next step, 500 mL of the freshly prepared ZnS:Mn
nanoparticles suspension was mixed with 10 g of the activated
carbon in a 1000 mL Erlenmeyer ask under magnetic stirring for
up to 10 h, resulting in the deposition of the ZnS:Mn nanoparticles
on the activated carbon. The carbon-supported ZnS:Mn nanopar-
ticles were then ltered and extensively washed with double
distilled water. Undiluted supernant solutions were analyzed for
the ZnS:Mn nanoparticles using UVvis spectrophotometry. The
carbon-supported ZnS:Mn nanoparticles were generally dried at
110 8C in an oven for 10 h. A mortar was used to homogeneously
grind the carbon-supported ZnS:Mn nanoparticles powder. The
carbon-supported ZnS:Mn nanoparticles were stored in air at room
temperature and were found to have a shelf life of at least one year.
2.3. Batch adsorption studies
All experiments were carried out using 0.003 and 0.015 g of
ZnS:Mn nanoparticles loaded activated carbon in 50 mL beakers in
an IKA magnetic stirrer operating at 200 rpm to elucidate the
optimum conditions (pH, contact time and initial dye concentra-
tion). Working temperature was chosen over a range of 283.15
333.15 K. The DY12 and RO12 adsorption capacities of adsorbent
were determined at certain time intervals (150 min) at tempera-
tures in the range of 283.15333.15 K. The effect of pH on
adsorption was studied by adjusting pH of 15 mg/L sample
solution in the range of 17 in single dye solution. For single
dye solution, the concentrations were determined by measuring
the absorbance at lmax for DY12 and at lmax for RO12. The amount
of each dye was analyzed via its corresponding calibration curve at
the corresponding lmax. In binary solutions, the rst order
derivatives of the absorbance spectra were used to obtain the
optimal wavelength for each dye at which the impact of the other
component was minimized. The optimal wavelengths were found
to be 392 nm and 418 nm for DY12 and RO12, respectively. The
amounts of DY12 or RO12 adsorbed at equilibrium, qe (mg/g) were
calculated as:
vC 0  C e
qe (1)
w
where C0 is the initial dye concentration (mg/L) in the solution; Ce
is the residual dye concentration (mg/L) at equilibrium; v is the
volume (L) of the solution; and w is the weight (g) of the adsorbent
used.
3. Results and discussion
3.1. Characterization of adsorbent
The amount of Mn in the ZnS:Mn nanoparticles was determined
by ICP-AES measurements. The obtained Mn/Zn atomic percent
ratio in the Mn doped ZnS nanoparticles was 2%. Absorption
566 S. Hajati et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 564571
Fig. 1. Evolution of absorption spectra of the ZnS:Mn nanocrystals taken at 1 h
intervals following the initiation of the reaction for the rst 6 h.
spectra measurements were extended to much longer times than
the 6 h shown in Fig. 1. The ZnS:Mn nanoparticles suspension
shows a well-resolved absorption maximum of the rst electronic
transition indicating a sufciently narrow size distribution of the
ZnS:Mn nanoparticles, which shifts to shorter wavelengths with
decreasing size of the nanoparticles as a consequence of quantum
connement. As Fig. 1 exhibits, the citrate-stabilized ZnS:Mn
nanoparticles have absorption edges in the range of 308320 nm
(4.013.87 eV) and show no further change for periods longer than
5 h. From the absorption spectra, energy band gap of ZnS
nanoparticles was obtained using the following relation [10]:
2
ahy AEg  hy
where Eg represents the energy band gap of the nanoparticles and A
is a characteristic constant. A typical graph of (ahn)2 versus energy
(hn) for ZnS:Mn nanoparticles is plotted. By using extrapolation the
linear portion of the respective curve to (ahn)2 = 0, the energy band
gap was determined. The straight-line characteristic of the curve
indicated that the ZnS:Mn nanoparticles have direct band gap in
the range of 3.874.01 eV, while the bulk material has a band gap
of 3.67 eV.
Fig. 2 shows the XRD pattern taken from the powdered ZnS:Mn
nanoparticles synthesized at 50 8C. The indicators on the abscissa
of Fig. 2 show the standard XRD pattern for ZnS (Joint Committee
for Powder Diffraction Standards, JCPDS card No. 05-0566). The
three broad peaks observed in the diffractogram at around 28.568,
47.438 and 56.258 reveal a cubic lattice structure of ZnS (b-ZnS
phase). These peaks can be assigned to the planes (1 1 1), (2 2 0)
and (3 1 1), respectively, of the cubic phase [11]. In addition, we did
not observe any diffracted peaks due to MnS in the XRD pattern
Fig. 3. FESEM images of (a) the activated carbon and (b) the ZnS:Mn nanoparticles deposited on activated carbon.
Fig. 2. X-ray diffraction (XRD) pattern of the citrate-caped ZnS:Mn nanoparticles.
because of very low concentration of the Mn in the nanoparticles as
can be seen from the ICP measurements. On the basis of the full
width at half-maximum of (1 1 1) peak and applying the Debeye
Scherrer equation [12], the average nanoparticles size in the
ZnS:Mn nanoparticles was estimated to be about 35 nm.
The FESEM images of the activated carbon surface and the
ZnS:Mn nanoparticles deposited on activated carbon are shown in
Fig. 3(a) and (b). It can be seen that the surface morphology of the
activated carbon is homogeneous and relatively smooth. Fig. 3(b)
shows the detailed morphologies of the ZnS:Mn nanoparticles
deposited on the activated carbon which are highly disperse in the
surface without any aggregation are approximately uniform in size
distribution. The size of each ZnS:Mn nanoparticles is in the range
of 3045 nm. The particle size measured directly from this FE-SEM
(2) image agrees with that determined by the XRD analysis.
3.2. The analysis of the single solutions and simultaneous analysis of
the binary solutions
After the preparation of the single solutions containing 15 mg/L
of DY12 or RO12, the absorbance spectrum corresponding to each
dye was acquired over the wavelength range of 300800 nm
(Fig. 4) and then it was analyzed. It is seen that the wavelengths at
which the absorbance is maximum for DY12 and RO12, are 392 nm
and 418 nm, respectively. The absorbance spectra taken from
mixture of DY12 and RO12 show severe overlapping. This overlap
indicates that the spectra of individual dyes interfere and show
that the absorbance spectra of binary solution cannot give a good
estimation of concentrations. Therefore, to simultaneously analyze
DY12 and RO12 in their mixture, the absorbance spectra were
differentiated. A plot of the differentiated spectra of DY12 and
RO12 in single and binary solution was illustrated in Fig. 5 which
indicates the possibility of the determination of DY12 dye at
 S. Hajati et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 564571 567

418 nm while RO12 is present. At this wavelength, there exists no

contribution of RO12 in the differentiated spectra of the binary
solutions. In a similar way, RO12 is quantied at 392 nm while
DY12 is present. At this wavelength there exists no contribution of
DY12 in the differentiated spectra of the binary solutions (Fig. 5).
Therefore, by using the values of the differentiated spectra of the
binary solutions at 418 nm and 390 nm, calibration curves
corresponding to DY12 and RO12 were made, respectively.
The concentrations were measured theoretically (Ct) and
experimentally (Cm) and then recoveries (%), errors (%) and average
percentage errors (%) between them were determined using
Eqs. (2)(4), respectively.

Cm
Recovery %  100 (3)
Ct

Cm  Ct
Error %  100 (4)
Ct
PN
i1 jC m C t =C t j
e %  100 (5)
N
where N is the number of measurements. Fig. 5. First order derivative spectra of DY12 and RO12 in single and binary solutions
(initial dye concentration of 15 mg/L).
To investigate the accuracy of the differentiation technique for
the quantication of the concentration of each dye in the mixture,
the recovery studies were done. To this end, the mixtures of DY12
and RO12 with different concentrations of each component were
prepared. Then the absorbance spectra of the binary solutions were
taken and differentiated. The differentiated spectra were shown in
Figs. 58. As mentioned above, by making the calibration curves
using the values of the differentiated spectra at a given wavelength
corresponding to each dye, the concentration of any of the DY12
and RO12 dyes is easily quantied (see Table S1). The recovery
studies proved the accuracy of the simultaneous determination of
DY12 and RO12 in binary solution using the differentiation
method. Note that the method was successfully applied with high
accuracy for an extreme case with severe spectra overlapping.

3.3. The adsorption of DY 12 and RO 12 inuenced by initial pH

It was investigated to what extent the adsorption of DY12 and

RO12 onto ZnS:Mn-NP-AC is inuenced by the initial values of pH
within the range 1.07.0 (see Fig. 9). The correlation between the
pH and the dye adsorption onto ZnS:Mn-NP-AC is seen from Fig. 9.
Fig. 6. First order derivative spectra of DY12 and RO12 in binary solutions in the
The optimized pH was found to be 2. This dependency is because of range of 115 mg/L of each two dyes concentration.
two reasons; rst is because of non-columbic interactions between
an adsorbed anion and a neutralized site and, second is because of

Fig. 7. First order derivative spectra of DY12 and RO12 in binary solutions at 1 mg/L
Fig. 4. Zero order absorption spectra of DY12 and RO12 in single and binary of constant DY12 concentrations and in the range of 215 mg/L of RO12
solutions (initial dye concentration of 15 mg/L). concentrations.
568 S. Hajati et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 564571
Fig. 8. First order derivative spectra of DY12 and RO12 in binary solutions at 1 mg/L
of constant RO12 concentrations and in the range of 215 mg/L of DY12
concentrations.
ion exchange via releasing exchangeable proton in interlayer and
basal plane surfaces. The working pH was chosen to be 6.0
(approximately equal to the pH of natural aqueous dye solutions)
at which the maximum adsorption occurred. The effect of the pH
value on the zeta potential of the nanoparticle is illustrated in Fig.
10. In the studied pH range, the adsorbent showed the positive zeta
potential that indicates the positive charge of the surfaces of the
adsorbent in the pH range. The surface of the material is neutral
when pH = pHzpc. The surface is negatively charged at pH values
greater than pHzpc, and is positively charged at pH values lower
than pHpzc [13].
3.4. The correlation between the adsorption of dyes and the initial dye
concentration in binary mixtures
To investigate the extent to which the adsorption of dyes onto
ZnS:Mn-NP-AC is inuenced by the initial concentration of each
dye in binary solution, various dyes concentrations were used and
a comparison with single solution systems was done. The initial
Fig. 9. Effect of pH on the removal of DY12 and RO12 by (ZnS:Mn-NP-AC) at room
temperature, contact time of 40 min, adsorbent dosage of 0.01 g in 50 mL and dye
concentration of 15 mg/L for each dye.
concentration of DY12 was changed over the range 120 mg/L
while the initial concentration of RO12 was chosen to be 0, 1, 5, 10,
15 and 20 mg/L for each experiment at pH 2.0 and temperature
30 8C. In another experimental setup, the initial concentration of
RO12 was changed while the concentration of DY12 was kept
constant during the experiments. The amounts of individual and
total adsorbed dye were calculated at equilibrium from qeq,i (mg/g)
and qeq,total (mg/g) where qeq,total = qeq,DY12 + qeq,RO12. The results of
the study were shown in Table S2 for DY12 adsorption and in Table
S3 for RO12 adsorption in single and binary solution, respectively.
A comparison showed lower yields for the individual adsorption of
DY 12 and RO12 in binary solution than those in single solution. For
example, the yields of the adsorption for 10 mg/L of RO12 were
found to be 98.85% when DY12 was not present. While the yields of
the adsorption for RO12 were found to be 97.85, 95.87, 92 and
84.89% when 1, 5, 10 and 20 mg/L of DY12 were present,
respectively. At higher concentrations of the dyes, the adsorption
sites would be saturated and therefore it would give a lower yield
for the adsorption. On the other hand, at higher initial concentra-
tion, an important driving force would overcome all mass transfer
resistances of dye between the aqueous and solid phases and
therefore it would give high uptake values [14,15]. In the binary
solution of DY12 and RO12, each dye struggle to reach and occupy
the adsorption sites available on the surface, particularly when
they have high concentration (see Figs. S2 and S3 in the
Supplementary Data). In an additional study, for the adsorption
of DY12 and RO12 on ZnS:Mn-NP-AC in single component solution,
the experimental and modeled isotherm were compared. It
showed a good agreement with Freundlich model (see Figs. S4
and S5 in the Supplementary Data). See the text below for more
discussion on the models.
3.5. Inuence of contact time
Equilibrium time is of economical importance for a system of
wastewater treatment. To verify the required adsorption equilib-
rium time, we studied the adsorption of individual dyes onto
ZnS:Mn-NP-AC (at 15 mg/L for both dyes) as a function of contact
time. 0.01 mg/L of the adsorbent at 50 mL was used and the
working pH was chosen to be 2. Fig. S6 in the Supplementary Data
shows an increasing behavior of the adsorption efciency versus
contact time. As seen, the efciency approaches to a saturation
limit.
3.6. Inuence of adsorbent dosage
The adsorbent dosage estimates the capacity of adsorbent for a
given initial concentration of dye solution which in turn shows the
level of being cost-effective. Therefore, it is of high importance. The
plot of dosage over the range of 0.0030.015 g versus the
adsorption of RO12 and DY12 is shown in Fig. S7 in the
Supplementary Data. This study was done for 50 mL of 15 mg/L
for both dyes at pH 2 after 40 min contact time. The same trend as
contact time was seen. In other words, an increase in the removal
percentage of each dye against the adsorbent dosage was seen.
There was also seen a saturation limit for the removal percentage
at a critical dosage. Note that the greater the adsorbent dosage, the
more surface area and adsorption sites would be available and
therefore, the more adsorption would be obtained.
3.7. The inuence of temperature on the adsorption of dyes
To study the extent to which the temperature inuences the
DY12 or RO12 adsorption onto ZnS:Mn-NP-AC, the temperature of
the solution with a constant initial concentration of 15 mg/L for
both dyes was varied (see Fig. S8 in the Supplementary Data). The
 S. Hajati et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 564571
capacities of ZnS:Mn-NP-AC for equilibrium adsorption and
consequently the dyes removal percentage were increased against
the increase in temperature. This means that to gain a better dye
removal by ZnS:Mn-NP-AC, it is needed to use higher tempera-
tures. The fact that the more adsorption occurs at higher
temperature shows that large dye ions are more mobile at higher
temperature [16,17].
3.8. Adsorption equilibrium study
To carry out the removal of DY12 and RO12, initial dye
concentrations were varied over the range 18.5 mg/L, at
optimized conditions. Two conventional models of Freundlich
and Langmuir were applied and compared to experimental
equilibrium data [18]. For binary solution, a good agreement
between the data and Freundlich was found, while discrepancy
was seen with Langmuir (see Figs. S9 and S10 in the Supplemen-
tary Data). The Langmuir equation for homogenous surface with a
nite number of indistinguishable sites with insignicant interac-
tion is expressed in the following linear form.
Ce 1 Ce
qe K L Q m Q m
The values of Qm and KL (calculated based on slope and intercept)
and the correlation coefcient for Langmuir isotherm [19] are
shown in Table S4.
The following linear form expresses the Freundlich isotherm
model
1 process for the DY12 and RO12 adsorption onto ZnS:Mn-NP-AC.
log qe logK F log C e
n Involvement of interactivity and competition makes it complex
The intercept and slope of linear plot of log (qe) versus log (Ce) give
the values of KF and 1/n, respectively. As seen, for all dyes studied,
the high correlation coefcient of the Freundlich model shows its
applicability for the interpretation of experimental equilibrium
data [20,21]. In the past decades, the study of multi-component
equilibrium has being developed during several steps. However, no
attempt on competitive adsorption was done and a few of them
studied the selectivity of adsorption processes. To model the
experimental data, common extended isotherms can be used,
some of which are the extended Langmuir and Freundlich model,
the interaction factor, the P-factor, and the Jain and Snoeyink
modied extended Langmuir model. Among the mentioned
models, only the extended Freundlich and the P-factor were used.
The extended Freundlich can describe multi-component adsorp-
tion. The expression of the solute uptake per unit weight, qi in
binary system [22] is
nK i =ni 1=ni C i
qi h i1n DF j
K i =ni 1=ni C i K j =n j 1=n j C j
where
K i =ni 1=ni C i K j =n j 1=n j C j
DF j ni  n j h i2n
K i =ni 1=ni C i K j =n j 1=n j C j
h i
 ln K i =ni 1=ni C i K j =n j 1=n j C j ;
and
ni K i =ni 1=ni C i n j K j =n j 1=n j C j
n dqt
K i =ni 1=ni C i K j =n j 1=n j C j
569
The parameters Ki and ni are obtained from single adsorption
isotherm systems using the Freundlich equation,
q KC 1=n (9)
The correlative method of P-factor has been developed [20] and
used for dye-adsorbent systems. This simple method is based on
introducing a lumped capacities factor Pi.
 
K L;i =aL;i single solute
Pi (10)
K L;i =aL;i multi solute
where K L;i =aL;i single solute and K L;i =aL;i multi solute are the sorbent
monolayer capacity for component i in single- and multi-solute
system, respectively.
A Langmuir isotherm is assumed in this model. Consequently,
for each component i, the following equation can be used for multi-
component isotherm.
0
KL;i C e;i;multi
qe;i;multi h i (11)
P i 1 a0L;i C e;i;multi
(6) To obtain a best t model for the single-component data, the P-
factor model was used to make a good prediction for the
performance of multi-component system and also to make a good
correlation with the experimental data (see Table S5). The
Freundlich isotherm constant and its respective correlation
coefcients 1/nF and KF constants, which are determined from the
slope and intercept of respective line, are shown in Table S5. The
values of nF were found to be higher than unity indicating a physical
(7)
to predict the multi-component equilibrium data [22,23]. None-
theless, efforts have been made for the prediction of multi-
component data (based on single component data) and for the
correlation of them [23]. An investigation on the competitive
adsorption of DY12 and RO12 onto ZnS:Mn-NP-AC in binary
solution was done. The working condition was set at room
temperature and pH 2.0. The extended Freundlich isotherm and
the P-factor were applied. From modied models for the DY12 and
RO12 adsorption, the competitive Langmuir and Freundlich
isotherm constants were evaluated, see Table S5. A good t was
found between the P-factor as well as the extended Freundlich
isotherm models and the data for the adsorption of mixture of
DY12 and RO12 onto ZnS:Mn-NP-AC. Using the determined
constants, the qe values were obtained from the applied models.
A comprehensive comparison of the values of qe which were
determined experimentally and theoretically, for DY12 and RO12
for isotherm data is shown in Figs. S11 and S12 in the
Supplementary Data.
(8)
3.9. Kinetic study
A number of steps were used to study adsorption dynamics
controlling sorption process such as chemical reaction, diffusion
control and mass transfer. The useful kinetic parameters for the
calculation of adsorption rate provide key information for
designing and modeling the adsorption processes. Hence, pseu-
do-rst-order [24] and pseudo-second-order [25] kinetic models
were applied for DY12 and RO12 adsorption onto ZnS:Mn-NP-AC.
The correlation coefcients, R2, show the level of consistency
between the experimental and calculated values. The higher R2
value and the value closer to one show the better applicability of
the model. The Lagergren equation is described by
k1 qe  qt : (12)
dt
570 S. Hajati et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 564571
Integrating Eq. (4) over interval 0t for t and 0qt for q, gives:
 
qe k1
log (13)
qe  qt 2:303t
The rearrangement of Eq. (13) gives the following linear form:
k1
logqe  qt logqe  (14)
2:303t
The variation of log (qe  qt) versus t is linear. The slope of the plot
of this variation gives k1 and the intercept of it gives qe. When the
intercept is different than qe, the reaction is unlikely to be rst-
order regardless of the value of correlation coefcient [24]. The
variation in rate should be proportional to the rst power of
concentration for stringent surface adsorption. Nevertheless, pore
diffusion could make a limitation on the adsorption process and
therefore, it will avoid having a linear relationship between the
initial concentration of solute and the adsorption rate.
The relatively low R2 values for most adsorption data (Table S6)
show that the DY12 and RO12 adsorptions onto ZnS:Mn-NP-AC do
not follow rst-order reaction.
In general, the following pseudo-second order model may
explain the kinetic of adsorption [26],
dqt
k2 qe  qt 2 (15)
dt
Integrating this equation over interval 0t for t and over 0qt for q,
after a little algebra gives:
t 1 1 enthalpy change (DH0), and entropy change (DS0), can be obtained
(16)
qt k2 q2e qe t
The initial sorption rates were calculated by using the second-
order rate constants, based on the following equation
h k2 q2e (17)
As mentioned above, the plots of log (qe  qt) versus t does not
t well to the entire sorption data, while the linear variation of t/qt
versus t for full range of initial dye concentrations studied, proves
that the pseudo-second-order equation is applicable (see Figs. S13
and S14 in the Supplementary Data). The value of intercept of the
plot of t/qt versus t was used to determine the value of k2, and its
slope was used to determine qe. The values of R2 and qe represented
in Table S6, show that the pseudo-second-order kinetic model
satisfactorily applies for the adsorption of RO12 and DY12 for the
entire sorption period.
Another alternative method for kinetic evaluation of an
adsorption process is intra-particle diffusion [27,6]. In this
process, RO-12 and DY12 are probably transported from its
aqueous solution to the adsorbents by intra-particle diffusion.
Therefore, this model should be used to study the rate-limiting
step for RO-12 and DY12 adsorption onto ZnS:Mn-NP-AC. The
intra-particle diffusion is commonly expressed by the following
equation:
qt K dif t 1=2 C: (18)
The values of Kdif and C were calculated, respectively, from the
slope and intercept of qt versus t1/2 and were reported in Table S6
and Fig. S7 [28]. The values of qt were found to give two lines part
with values of t1/2 and the rate constant Kdif, directly evaluated
from the slope of the second regression line.
If the intra-particle diffusion is the sole rate-limiting step
[29,30], it is essential for the qt versus t1/2 plot to pass through the
origin. This means that if the value of C was equal to zero, it would
indicate that the intra-particle diffusion model may be the
controlling factor in determining the kinetics of the process [31].
The R2 values given in Table S6 is far from unity which indicates
that this model is not applicable, and it may reject that the rate-
limiting step is the intra-particle diffusion process, but the intra-
particle diffusion model may be the controlling factor in
determining the kinetics of the process.
4. Thermodynamic study
Here, thermodynamic parameters were used to verify the
nature of the adsorption. The thermodynamic constants, free
energy change, enthalpy change and entropy change were
determined to assess the thermodynamic viability and the
spontaneous nature of the process. To this end, the following
equations were used to calculate the thermodynamic
constants:
DG0 RT ln K e (19)
where DG0 is the free energy change (kJ mol1), R is the universal
gas constant (8.314 J mol1 K1), Ke is the thermodynamic
equilibrium constant and T is the absolute temperature (K). The
values of Ke are obtained from the variation of ln qe/Ce versus qe at
various temperatures and extrapolating to zero [25,26]. In Table
S7, the list of the thermodynamic parameters is represented. The
spontaneous nature and applicability of the adsorption process are
proven from the negative DG0 values. A decrease in the values of
DG0 is observed against increasing the temperature from 283.15 K
to 333.15 K, which in turn, proves the physical nature of the
adsorption process. The values of other parameters such as
from the slope and intercept of Vant Hoff plot of ln K0 versus 1/T,
respectively (see Fig. S11 and Table. S7 in the Supplementary Data).
DS0 DH 0
ln K 0  (20)
R RT
Exothermic nature of the adsorption process is proven from the
negative values of DH0, while the negative values of DS0 show the
decrease in adsorbate concentration in solidliquid interface. Thus
it shows the increase in adsorbate concentration onto the solid
phase due to the physical nature of adsorption, which occurs
during electrostatic interactions.
The DY12 and RO12 adsorption onto ZnS:Mn-NP-AC and its
dependence on the temperature at constant initial dye concentra-
tion of 15 mg/L for both dyes were studied (see Fig. S15 in the
Supplementary Data). The values of activation energy (Ea) and
sticking probability (S*) were determined from the experimental
data by using a modied Arrhenius type equation related to surface
coverage (u) as follows [27]:
S 1  u eEa =RT (21)
*
The temperature dependent sticking probability, S , varying within
the range 0 < S* < 1, is a function of the adsorbateadsorbent
system studied here. The S* value is a measure of the potential of an
adsorbate to remain on the adsorbent indenite. The following
equation obtains the surface coverage (u):
 
Ce
u 1 : (22)
C0
From the variation of ln (1  u) versus 1/T, the activation energy
and sticking probability were determined (see Fig. S16 and Table
S7 in the Supplementary Data).
As seen, the DY12 and RO12 adsorptions onto ZnS:Mn-NP-AC
increase to some extent with increasing the temperature. This
means that more efcient dye removal by adsorption onto
ZnS:Mn-NP-AC occurs at higher temperatures. This may be
 S. Hajati et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 564571
attributed to the fact that large dye ions are more mobile at higher
temperatures.
5. Conclusion
Because of the technological and fundamental importance of
dye removal from multi-solute systems, the DY12 and RO12
removal by ZnS:Mn-NP-AC was investigated. This study was
important for several reasons. First, the dyes with severe spectra
overlapping were analyzed simultaneously with high accuracy
by rst order derivative spectrophotometric analysis method in
binary mixtures. Second, ZnS:Mn-NP-AC with a shelf life of at
least one year as low cost, novel and non toxic adsorbent was
used efciently for the removal of the dyes. The high adsorption
capacity of ZnS:Mn-NP-AC was expected because of the specic
characteristics of nanoparticles including high number of
surface reactive atoms. The adsorption capacities were investi-
gated and described by the mono- and multi-component
Langmuir and Freundlich isotherm models for both single and
binary dye solutions. The isotherm constants for DY12 and RO12
dyes were determined. The monolayer coverage capacities of the
applied adsorbent were found for single solutions of DY12 and
RO12. It was found that the equilibrium uptake amounts of DY12
and RO12 onto the applied adsorbent in binary solution
considerably decrease with increasing the concentrations of
the other dye. A better agreement was found between the
adsorption equilibrium data and mono-component Langmuir
isotherm model. However, at low concentrations, the extended
Freundlich isotherm model satisfactorily predicted multi-
component adsorption equilibrium data. An endothermic and
a spontaneous nature for the adsorption of the dyes studied were
shown from thermodynamic parameters.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jiec.2013.05.015.
571
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