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Predictions of binary sorption isotherms

for the sorption of heavy metals by pine
bark using single isotherm data.
Chemosphere

ARTICLE in CHEMOSPHERE · OCTOBER 2000

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 Chemosphere 41 (2000) 659±665

Predictions of binary sorption isotherms for the sorption of

heavy metals by pine bark using single isotherm data
a,*
S. Al-Asheh , F. Banat a, R. Al-Omari a, Z. Duvnjak b

a
Department of Chemical Engineering, Jordan University of Science and Technology (JUST), P.O. Box 3030, Irbid 221100, Jordan
b
Department of Chemical Engineering, University of Ottawa, Ottawa, Ont., Canada K1N 6N5
Received 7 July 1999; accepted 1 October 1999

Abstract

The adsorption of three heavy metal ions by pine bark was studied. The study was divided into two parts; single
component adsorption of the metals Cu2‡ , Cd2‡ and Ni2‡ and bisolute adsorption of the three binary systems
Cu2‡ )Cd2‡ , Cu2‡ )Ni2‡ and Cd2‡ )Ni2‡ . Extended Langmuir model, extended Freundlich model, Sips model and ideal
adsorption solution theory (IAST) models were used to predict the equilibrium uptake for Cu2‡ , Cd2‡ and Ni2‡ in the
binary diluted solutions using the single adsorption constants. The experimental data of single isotherm adsorption
process were found to follow Langmuir isotherm model with less accuracy than Freundlich and Sips models. Whereas,
the predictions of bisolute adsorption isotherms of the mentioned three systems, Cu2‡ )Cd2‡ , Cu2‡ )Ni2‡ and
Cd2‡ )Ni2‡ , showed good agreement with experimental data when using Extended-Langmuir, Extended-Freundlich and
IAST. However, the only good ®t of the Sips model was with the Cu2‡ )Cd2‡ system. Ó 2000 Published by Elsevier
Science Ltd. All rights reserved.

1. Introduction their lower levels as set by environmental agencies. Al-

Adsorption is an e€ective puri®cation and separation
technique used in industry especially in water and
wastewater treatments. Often, adsorption is used to re-
move pollutants or toxic materials from aqueous and
non-aqueous solutions. Heavy metals are among these
types of materials. They result from di€erent types of
industries such as electroplating, cadmium±nickel bat-
teries and alloy industries (Buchauer, 1973). Heavy
metals cannot be discharged directly to the environment
due to its harmful e€ects. For example, cadmium is ir-
ritant to the respiratory tract. Prolonged exposure to
this metal can cause anosmia and alloy stains that
gradually appear on the necks of the teeth and copper
may cause keratinization of the hands and soles of the
feet (Sitting, 1981). Therefore, they must be decreased to
*
Corresponding author.
E-mail address: alasheh@just.edu.com (S. Al-Asheh).
though there are many methods for the removal of metal
ions from solutions, such as chemical precipitation,
complexation, solvent extraction and membrane pro-
cesses (Patterson and Minear, 1975), adsorption pro-
cesses showed many advantages over these methods. It is
quite selective, e€ective and is able to remove very low
levels of heavy metals from solutions.
Biological materials, that have been used extensively
for studies of the sorption of heavy metals since the
beginning of last decade, promised to have e€ective
sorption capacity and cheaper regeneration cost as
compared to conventional sorbents, activated carbon
and ion-exchange resins (Singh et al., 1993). For exam-
ple, large number of microorganisms were used as sor-
bents for heavy metals (Volesky, 1990). Interest has also
risen in removing heavy metals from solutions by plant
materials, e.g., Sphagnum peat moss was used for Cu2‡
adsorption (Gardea-Torresdey et al., 1996), waste tea
leaves for the removal of Pb2‡ , Cd2‡ and Zn2‡ (Tee and
Khan, 1988) and Accacia arabica bark for the removal

0045-6535/00/$ - see front matter Ó 2000 Published by Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 9 9 ) 0 0 4 9 7 - X
660 S. Al-Asheh et al. / Chemosphere 41 (2000) 659±665
of Cr6‡ from aqueous solutions (Singh et al., 1994). The
sorption of heavy metals to these biomaterials is at-
tributed to their constituents which are mainly proteins,
carbohydrates and phenolic compounds which contain
such functional groups as carboxyl, hydroxyl and
amine-groups that are responsible for the binding of
metal ions (Tobin et al., 1990; Al-Asheh et al., 1998).
Most of the previous works on heavy metal bio-
sorption considered only single metals except the work
done by Chong and Volesky (1995, 1996) and Carvalho
et al. (1995). Multicomponent isotherms of di€erent
metal systems were experimentally determined by Chong
and Volesky (1995, 1996) and Carvalho et al. (1995).
Other researchers investigated the in¯uence of addition
of one metal ion at a certain concentration level on
uptake of other metal ions (Tobin et al., 1987; Crist et al.,
1992) but no attempt was done to analyze the system in
terms of binary sorption isotherms. Very often ions of
more than one metal are available in the industrial
wastewater. Therefore, it is important to understand the
behavior of this mixture in the solution and to explore
the e€ect of the concentration of one metal ions on the
uptake of other metal ions. This can be achieved by
investigating the equilibrium isotherm of multicompo-
nent systems.
In this work, binary equilibrium isotherm data of
various bisolute metal ion systems were predicted using
di€erent mathematical models. The parameters for these
models were obtained from the single metal isotherms
that are based on experimental data. This work would
enable to extrapolate the prediction of the binary system
if experimental data are not available for a certain level
of bisolute concentrations.
2. Adsorption isotherm models
In this work Langmuir, Freundlich, IAST and Sips
type models were used to provide the equilibrium data.
2.1. Langmuir model
Langmuir isotherm model is based on the assump-
tion that binding sites are homogeneously distributed
over the adsorbent surface. These binding sites have the
same anity for adsorption of a single molecular layer.
This model assumes that there is no interaction between
adsorbed molecules. The mathematical representation of
this model for a single solute solution adsorption is
qo bC
qˆ ; …1†
1 ‡ bC
where q is the solute uptake per unit weight of bark
(mmol/g) at the equilibrium solute concentration, in the
aqueous phase, C (mM), in the aqueous phase, qo
(mmol/g) and b (l/mmol) are the Langmuir constants
related to the sorption capacity and energy of adsorp-
tion, respectively.
The above model can be extended to describe a
multicomponent adsorption system. In this case the
Langmuir model (often called extended-Langmuir) can
be written as:
qo bi Ci
qi ˆ Pi N ; …2†
1 ‡ kˆ1 bk Ck
where qi is the uptake of component i in the multicom-
ponent system and Ck …k ˆ 1; 2; . . . N ; N is the number of
components) is the equilibrium concentration of each
component in the system and qoi and bi are Langmuir
constants. In this study the parameters qoi and bi were
obtained from the single isotherm for each metal ion and
substituted in Eq. (2) to predict the uptake of particular
metal ions in the multicomponent system. It is worth-
while to mention that the extended Langmuir model
gives reasonable estimates for multicomponent equilib-
rium data as long as the qi values for each solute obtained
from single isotherm model are close to each other.
2.2. Freundlich model
Freundlich model also considers a monomolecular
layer coverage of solute by the sorbent. However, it
assumes that the sorbent has a heterogeneous valance
distribution and then has di€erent anity for adsorp-
tion. This model takes the following form for a single
solute adsorption:
q ˆ KC 1=n ; …3†
where K and 1/n are the Freundlich constants related to
the sorption capacity and sorption intensity of the sor-
bent, respectively.
The Freundlich model can also be extended to de-
scribe multicomponent adsorption. The expressions of
q1 in binary system (Do, 1998) are
n…K1 =n1 †1=n1 C1
q1 ˆ h i1ÿn ‡ DF 2 ; …4†
…K1 =n1 †1=n1 C1 ‡ …K2 =n2 †1=n2 C2
where
…K1 =n1 †1=n1 C1 …K2 =n2 †1=n2 C2
DF 2 ˆ…n1 ÿ n2 † h i2ÿn
…K1 =n1 †1=n1 C1 ‡ …K2 =n2 †1=n2 C2
" 
1=n1  1=n2 #
K1 K2
 ln C1 C2 ;
n1 n2
n1 …K1 =n1 †1=n1 C1 ‡ n2 …K2 =n2 †1=n2 C2
nˆ :
…K1 =n1 †1=n1 C1 ‡ …K2 =n2 †1=n2 C2
 S. Al-Asheh et al. / Chemosphere 41 (2000) 659±665 661

The same expressions can be written for component 2 by
interchanging the subscripts 1 and 2. The parameters K1 ,
K2 , n1 and n2 are obtained from single adsorption iso-
therm systems using Eq. (3).
2.3. Ideal adsorbed solution theory (IAST)
The IAST is another model that can be used to
predict the multicomponent adsorption isotherms using
single solute equilibrium data. It is based on the as-
sumption that the solution is ideal, i.e., if there is not
adsorbed-adsorbent interaction. With single-solute data
described by the Freundlich isotherm, this model has
been successfully used to describe multicomponent ad-
sorption of competing compounds (Crittenden et al.,
1985). The model can be represented by the following
expression:
" PN #ni
qi jˆ1 nj qj
Ci ˆ PN ; …5†
jˆ1 qj ni Ki
where N is the number of components in the system and
n and K are the single-solute Freundlich constants.
In the case of a binary system, Eq. (5) can be written
separately for each component. These equations are to
be solved simultaneously to obtain q1 and q2 for a given
equilibrium bisolute concentrations, C1 and C2 .
Adopting the solution procedure was from Weber and
Smith (1987), Eq. (5) can be rewritten as
" PN
qi nj qj
jˆ1
F ˆ F …qi † ˆ Ci ÿ PN
jˆ1 qj ni Ki
2.4. Sips model
The Sips model is another empirical model for the
representing equilibrium adsorption data. It is a com-
bination of the Langmuir and Freundlich isotherm type
models. The Sips model takes the following form for
single solute equilibrium data:
qo …bC†1=n
qˆ : …10†
1 ‡ …bC†1=n
Unlike the other mentioned adsorption isotherm mod-
els, this model contains three parameters; qo , b and 1/n
which can be evaluated by ®tting the experimental data
to this model. The Sips model can be extended to de-
scribe the multicomponent adsorption equilibrium data.
The Sips multicomponent adsorption isotherm model
can be written in di€erent forms, one of these is
ÿ PN
1=ni ÿ1
qoi bi Ci bk Ck
kˆ1
qi ˆ ÿ PN
1=ni : …11†
1‡ kˆ1 bk Ck
In this case qoi , ni and bi are the single-solute Sips con-
stants as obtained by Eq. (10) for component in the
system. It is important to point out that even if single
component isotherm experimental data are well repre-
sented by the Sips model, Eq. (10), this does not neces-
sarily imply that Eq. (11) will give a good representation
of the multicomponent adsorption experimental data
#ni
(Do, 1998).
: …6†

3. Experimental
The roots of this equation can be obtained by means of
iterative Newton±Raphson technique, according to
Pine bark was biosorbent used in this work. This
material is widely available in many countries. The
qnew ˆ qold ÿ Jÿ1
old Fold ; …7†
sorption of Cu2‡ , Cd2‡ and Zn2‡ ions from single metal
where Jÿ1 systems, and the binary Cu2‡ )Cd2‡ , Cu2‡ )Ni2‡ and
old is the inverse of Jacobian matrix, a square
matrix with elements oFi …q†=oqk , and i and k are row and Cd2‡ )Ni2‡ systems were carried out in batch experi-
column positions in the matrix, respectively. The diag- ments. Detailed procedure and isotherm results of these
onal elements of the Jacobian matrix are given by experiments were presented elsewhere (Al-Asheh and
Duvnjak, 1998).
P n  P ni
1 nq i qi nq
ÿP ‡ P 2
q ni Ki … q† ni Ki
P 4. Results and discussion
qn2 ‰ nqŠ…ni ÿ1†
ÿ Pi ; …8†
q ‰ni Ki Šni The experimental data of the single-metal sorption
isotherms for Cu2‡ , Cd2‡ and Ni2‡ are shown in Figs. 1±
while the o€-diagonal elements are given by 3. These results indicate that an increase in the metal
P ni P ions concentration resulted in an increase in the amount
qi nq qnk ni ‰ nqŠ…ni ÿ1† of the ions adsorbed. The capacity of the bark for these
ÿ P 2 ÿ P : …9†
… q† ni Ki q ‰ni Ki Šni metals followed the order Cu2‡ > Cd2‡ > Ni2‡ .
The same ®gures show the individual metal isotherms
The above procedure was programmed using Matlab. represented by the Langmuir, Freundlich and Sips
662 S. Al-Asheh et al. / Chemosphere 41 (2000) 659±665
Fig. 1. Adsorption isotherm of Cu2‡ by pine bark using dif-
ferent isotherm models.
Fig. 2. Adsorption isotherm of Cd2‡ by pine bark using dif-
ferent isotherm models.
models. The Package SCIENTIST was used to evaluate
the parameters for these models, using the experimental
data for each of the three metal ions, by the non-linear
least square regression (Table 1). It is seen (Figs. 1±3)
that the three models ®t the experimental data reason-
ably well. The values of R2 , which is a measure of the
goodness-of-®t, con®rm the good representation of the
experimental data by these models.
Fig. 3. Adsorption isotherm of Ni2‡ by pine bark using dif-
ferent isotherm models.
Experimental data for binary adsorption for the
systems Cu2‡ )Cd2‡ , Cu2‡ )Ni2‡ and Cd2‡ )Ni2‡ are
shown in Figs. 4±6, respectively. The data are repre-
sented as mole fraction of Cu2‡ , Cd2‡ and Ni2‡ , for
Figs. 4±6, respectively, in the solid phase (pine bark
sorbent), y, versus mole fraction of these metals in the
solution, x. These ®gures also show the prediction of
binary isotherm using the four models discussed.
Fig. 4 compares the predicted data of Cu2‡ )Cd2‡
system with the experimental data. It is seen that
Langmuir, Freundlich and IAST models results in close
prediction of the isotherm of this system as compared to
experimental data. The IAST was the best in describing
the experimental data while the Sips model was the
worst. However, the predictions by all of the models
were poor at low metal concentrations. This is charac-
teristic of adsorption isotherm models, where the be-
havior of most of the models is linear at very low
concentrations. The Freundlich isotherm model was
closer to the experimental data than Langmuir isotherm,
most likely because of its speci®c trend and applicability.
The di€erent qo values of Cu2‡ and Cd2‡ could be the
reason for the deviation of the extended Langmuir
model prediction from the experimental data.
In Fig. 5, it is obvious that the Langmuir model is the
most convenient model to predict the isotherm of
Ni2‡ )Cu2‡ system. The results of Fig. 5 show that the
Sips model is very poor in predicting the Ni2‡ )Cu2‡
experimental data, especially at moderate concentra-
tions. Although this model successfully ®tted the single
isotherm data of both Ni2‡ and Cu2‡ , it failed in pre-
dicting their binary sorption isotherm. Freundlich and
 S. Al-Asheh et al. / Chemosphere 41 (2000) 659±665 663

Table 1
Model isotherm parameters for the single metal adsorption systems
Solute Langmuir model Freundlich model Sips model
o 2 2
q b R k n R qmax b n R2
Cd 0.126 5.49 0.998 0.106 0.371 0.991 0.121 5.93 1.130 0.998
Cu 0.149 5.34 0.983 0.108 0.252 0.991 0.172 3.39 0.702 0.996
Ni 0.107 1.28 0.996 0.053 0.348 0.989 0.116 1.05 0.856 0.996

Fig. 4. Prediction of binary equilibrium data of Cu2‡ )Cd2‡ Fig. 5. Prediction of binary equilibrium data of Ni2‡ )Cu2‡
system using di€erent types of multicomponent isotherm system using di€erent types of multicomponent isotherm
models. models.

IAST are poorer than Langmuir in prediction of this
system, but they are still better than the predicted by the
Sips model.
For the binary system Cd2‡ )Ni2‡ , generally all of the
models except Sips showed relatively good prediction of
the equilibrium data as compared to the experimental
data especially at high concentrations (Fig. 6). Obvi-
ously the Langmuir model was the closest. Nonetheless,
the di€erence between the Langmuir model prediction
and the other two models prediction, Freundlich and
IAST, was not that signi®cant. Again Sips model is not
recommended, even though it showed good representa-
tion of the single isotherm data of both Cd2‡ and Ni2‡
by pine bark.
The predicted uptake of Cu2‡ , Ni2‡ and Cd2‡ in
binary systems of Cu2‡ )Cd2‡ , Cu2‡ )Ni2‡ and
Cd2‡ )Ni2‡ , respectively, were compared to the experi-
mental data, using the four mentioned models as shown
in Figs. 7±9. Basically, if most of the data are distributed
around the 45° line this indicates that the models rep-
resent well the experimental data of the system. There-
fore, as shown in Figs. 7 and 9, except Sips model, the
other models can adequately be used to predict the up-
take of Cu2‡ and Ni2‡ in the binary systems Cu2‡ )Cd2‡
and Cu2‡ )Ni2‡ , respectively, from the single isotherm
parameters. With less accuracy, these models can be
used to predict the uptake of Cd2‡ in the binary system
Cd2‡ )Ni2‡ because in this case there were many points
lying far away from the 45° line rather than being dis-
tributed around this line (Fig. 8).
5. Conclusions
The validity of a single and a single-based multi-
component adsorption isotherm models in the predic-
tion of single and binary combination of the heavy
metals Cu2‡ , Cd2‡ and Ni2‡ adsorption was assessed.
Generally, most of the models used in this work showed
good representation of the adsorption isotherm when
applied to individual metal ions. The multicomponent
adsorption isotherm models of Langmuir, IAST and
664 S. Al-Asheh et al. / Chemosphere 41 (2000) 659±665
Fig. 6. Prediction of binary equilibrium data of Cd2‡ )Ni2‡
system using di€erent types of multicomponent isotherm
models.
Fig. 7. Comparison between experimental data and prediction
made by di€erent multicomponent isotherm models for
Cu2‡ )Cd2‡ binary system.
Freundlich satisfactory predicted the equilibrium data
when applied to the binary systems Cu2‡ )Cd2‡ ,
Cu2‡ )Ni2‡ and Cd2‡ )Ni2‡ . Whereas the Sips model
poorly predicted the equilibrium data of these systems.
In conclusion, when suitable multicomponent adsorp-
tion isotherm models is selected, single isotherm data
can be used to predict binary equilibrium data.
Fig. 8. Comparison between experimental data and prediction
made by di€erent multicomponent isotherm models for
Cu2‡ )Ni2‡ binary system.
Fig. 9. Comparison between experimental data and prediction
made by di€erent multicomponent isotherm models for
Cd2‡ )Ni2‡ binary system.
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