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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


Impact Factor: 3.34 · DOI: 10.1016/S0045-6535(99)00497-X · Source: PubMed

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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-


though there are many methods for the removal of metal
Adsorption is an e€ective puri®cation and separation ions from solutions, such as chemical precipitation,
technique used in industry especially in water and complexation, solvent extraction and membrane pro-
wastewater treatments. Often, adsorption is used to re- cesses (Patterson and Minear, 1975), adsorption pro-
move pollutants or toxic materials from aqueous and cesses showed many advantages over these methods. It is
non-aqueous solutions. Heavy metals are among these quite selective, e€ective and is able to remove very low
types of materials. They result from di€erent types of levels of heavy metals from solutions.
industries such as electroplating, cadmium±nickel bat- Biological materials, that have been used extensively
teries and alloy industries (Buchauer, 1973). Heavy for studies of the sorption of heavy metals since the
metals cannot be discharged directly to the environment beginning of last decade, promised to have e€ective
due to its harmful e€ects. For example, cadmium is ir- sorption capacity and cheaper regeneration cost as
ritant to the respiratory tract. Prolonged exposure to compared to conventional sorbents, activated carbon
this metal can cause anosmia and alloy stains that and ion-exchange resins (Singh et al., 1993). For exam-
gradually appear on the necks of the teeth and copper ple, large number of microorganisms were used as sor-
may cause keratinization of the hands and soles of the bents for heavy metals (Volesky, 1990). Interest has also
feet (Sitting, 1981). Therefore, they must be decreased to 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
*
Corresponding author. leaves for the removal of Pb2‡ , Cd2‡ and Zn2‡ (Tee and
E-mail address: alasheh@just.edu.com (S. Al-Asheh). 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 (mmol/g) and b (l/mmol) are the Langmuir constants
sorption of heavy metals to these biomaterials is at- related to the sorption capacity and energy of adsorp-
tributed to their constituents which are mainly proteins, tion, respectively.
carbohydrates and phenolic compounds which contain The above model can be extended to describe a
such functional groups as carboxyl, hydroxyl and multicomponent adsorption system. In this case the
amine-groups that are responsible for the binding of Langmuir model (often called extended-Langmuir) can
metal ions (Tobin et al., 1990; Al-Asheh et al., 1998). be written as:
Most of the previous works on heavy metal bio-
qo bi Ci
sorption considered only single metals except the work qi ˆ Pi N ; …2†
done by Chong and Volesky (1995, 1996) and Carvalho 1 ‡ kˆ1 bk Ck
et al. (1995). Multicomponent isotherms of di€erent
where qi is the uptake of component i in the multicom-
metal systems were experimentally determined by Chong
ponent system and Ck …k ˆ 1; 2; . . . N ; N is the number of
and Volesky (1995, 1996) and Carvalho et al. (1995).
components) is the equilibrium concentration of each
Other researchers investigated the in¯uence of addition
component in the system and qoi and bi are Langmuir
of one metal ion at a certain concentration level on
constants. In this study the parameters qoi and bi were
uptake of other metal ions (Tobin et al., 1987; Crist et al.,
obtained from the single isotherm for each metal ion and
1992) but no attempt was done to analyze the system in
substituted in Eq. (2) to predict the uptake of particular
terms of binary sorption isotherms. Very often ions of
metal ions in the multicomponent system. It is worth-
more than one metal are available in the industrial
while to mention that the extended Langmuir model
wastewater. Therefore, it is important to understand the
gives reasonable estimates for multicomponent equilib-
behavior of this mixture in the solution and to explore
rium data as long as the qi values for each solute obtained
the e€ect of the concentration of one metal ions on the
from single isotherm model are close to each other.
uptake of other metal ions. This can be achieved by
investigating the equilibrium isotherm of multicompo-
nent systems. 2.2. Freundlich model
In this work, binary equilibrium isotherm data of
various bisolute metal ion systems were predicted using Freundlich model also considers a monomolecular
di€erent mathematical models. The parameters for these layer coverage of solute by the sorbent. However, it
models were obtained from the single metal isotherms assumes that the sorbent has a heterogeneous valance
that are based on experimental data. This work would distribution and then has di€erent anity for adsorp-
enable to extrapolate the prediction of the binary system tion. This model takes the following form for a single
if experimental data are not available for a certain level solute adsorption:
of bisolute concentrations.
q ˆ KC 1=n ; …3†

where K and 1/n are the Freundlich constants related to


2. Adsorption isotherm models the sorption capacity and sorption intensity of the sor-
bent, respectively.
In this work Langmuir, Freundlich, IAST and Sips The Freundlich model can also be extended to de-
type models were used to provide the equilibrium data. scribe multicomponent adsorption. The expressions of
q1 in binary system (Do, 1998) are
2.1. Langmuir model
n…K1 =n1 †1=n1 C1
q1 ˆ h i1ÿn ‡ DF 2 ; …4†
Langmuir isotherm model is based on the assump- …K1 =n1 †1=n1 C1 ‡ …K2 =n2 †1=n2 C2
tion that binding sites are homogeneously distributed
over the adsorbent surface. These binding sites have the where
same anity for adsorption of a single molecular layer.
This model assumes that there is no interaction between …K1 =n1 †1=n1 C1 …K2 =n2 †1=n2 C2
DF 2 ˆ…n1 ÿ n2 † h i2ÿn
adsorbed molecules. The mathematical representation of
…K1 =n1 †1=n1 C1 ‡ …K2 =n2 †1=n2 C2
this model for a single solute solution adsorption is " 
1=n1  1=n2 #
K1 K2
qo bC  ln C1 C2 ;
qˆ ; …1† n1 n2
1 ‡ bC

where q is the solute uptake per unit weight of bark


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

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- Fig. 3. Adsorption isotherm of Ni2‡ by pine bark using dif-
ferent isotherm models. 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,
Fig. 2. Adsorption isotherm of Cd2‡ by pine bark using dif- most likely because of its speci®c trend and applicability.
ferent isotherm models. 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.
models. The Package SCIENTIST was used to evaluate In Fig. 5, it is obvious that the Langmuir model is the
the parameters for these models, using the experimental most convenient model to predict the isotherm of
data for each of the three metal ions, by the non-linear Ni2‡ )Cu2‡ system. The results of Fig. 5 show that the
least square regression (Table 1). It is seen (Figs. 1±3) Sips model is very poor in predicting the Ni2‡ )Cu2‡
that the three models ®t the experimental data reason- experimental data, especially at moderate concentra-
ably well. The values of R2 , which is a measure of the tions. Although this model successfully ®tted the single
goodness-of-®t, con®rm the good representation of the isotherm data of both Ni2‡ and Cu2‡ , it failed in pre-
experimental data by these models. 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 fore, as shown in Figs. 7 and 9, except Sips model, the
system, but they are still better than the predicted by the other models can adequately be used to predict the up-
Sips model. take of Cu2‡ and Ni2‡ in the binary systems Cu2‡ )Cd2‡
For the binary system Cd2‡ )Ni2‡ , generally all of the and Cu2‡ )Ni2‡ , respectively, from the single isotherm
models except Sips showed relatively good prediction of parameters. With less accuracy, these models can be
the equilibrium data as compared to the experimental used to predict the uptake of Cd2‡ in the binary system
data especially at high concentrations (Fig. 6). Obvi- Cd2‡ )Ni2‡ because in this case there were many points
ously the Langmuir model was the closest. Nonetheless, lying far away from the 45° line rather than being dis-
the di€erence between the Langmuir model prediction tributed around this line (Fig. 8).
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- 5. Conclusions
tion of the single isotherm data of both Cd2‡ and Ni2‡
by pine bark. The validity of a single and a single-based multi-
The predicted uptake of Cu2‡ , Ni2‡ and Cd2‡ in component adsorption isotherm models in the predic-
binary systems of Cu2‡ )Cd2‡ , Cu2‡ )Ni2‡ and tion of single and binary combination of the heavy
Cd2‡ )Ni2‡ , respectively, were compared to the experi- metals Cu2‡ , Cd2‡ and Ni2‡ adsorption was assessed.
mental data, using the four mentioned models as shown Generally, most of the models used in this work showed
in Figs. 7±9. Basically, if most of the data are distributed good representation of the adsorption isotherm when
around the 45° line this indicates that the models rep- applied to individual metal ions. The multicomponent
resent well the experimental data of the system. There- 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‡ Fig. 8. Comparison between experimental data and prediction
system using di€erent types of multicomponent isotherm made by di€erent multicomponent isotherm models for
models. Cu2‡ )Ni2‡ binary system.

Fig. 7. Comparison between experimental data and prediction Fig. 9. Comparison between experimental data and prediction
made by di€erent multicomponent isotherm models for made by di€erent multicomponent isotherm models for
Cu2‡ )Cd2‡ binary system. Cd2‡ )Ni2‡ binary system.

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