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An Article Submitted to

INTERNATIONAL JOURNAL OF
CHEMICAL REACTOR ENGINEERING
Kinetic and Thermodynamic Modeling of
Cd
+2
and Ni
+2
Biosorption by Raw Chicken
Feathers
Hilda E. Reynel-Avila

Guadalupe de la Rosa

Cintia K. Rojas-Mayorga

Irene Cano-Aguilera

Adrian Bonilla-Petriciolet

Universidad de Guanajuato, helizabeth 00@hotmail.com

Universidad de Guanajuato, g dela rosa@hotmail.com

Instituto Tecnologico de Aguascalientes, karymayorga@yahoo.com.mx

Universidad de Guanajuato, irene@quijote.ugto.mx

Instituto Tecnol ogico de Aguascalientes, petriciolet@hotmail.com


ISSN 1542-6580
Copyright c 2011 The Berkeley Electronic Press. All rights reserved.
Kinetic and Thermodynamic Modeling of Cd
+2
and Ni
+2
Biosorption by Raw Chicken Feathers
Hilda E. Reynel-Avila, Guadalupe de la Rosa, Cintia K. Rojas-Mayorga, Irene
Cano-Aguilera, and Adrian Bonilla-Petriciolet
Abstract
Batch experiments were performed to model kinetic and thermodynamic data
for Cd+2 and Ni+2 biosorption by raw chicken feathers (CFs) under different con-
ditions. Results indicated that Cd+2 and Ni+2 sorption onto CFs occurred on the
external surface of the biosorbent. Ion removal increased with pH, whereas both
endothermic and exothermic stages where observed depending on temperature.
Our calculated thermodynamic parameters showed that, below the temperature of
30 oC, the metal uptake of Cd+2 and Ni+2 ions may be mainly controlled by a
chemisorption process. However, for temperatures higher than 30oC, it is likely
that sorption of both metals onto CFs is caused by a combination of both physical
and chemical processes, especially for Ni+2 ions. Maximum sorption capacities
were of 0.039 (Cd+2 ) and 0.065 mmol/g (Ni+2) at pH 5 and 30

C. Using 0.1 M
HCl or CH3COOH as desorbing agents, approximately a 50% recovery for Cd+2
was achieved. The pseudo-second order and the general rate law models best t
the sorption kinetics data. The equilibrium metal uptake data was best described
by the Sips isotherm.
KEYWORDS: Chicken feathers, metal biosorption, cadmium, nickel, wastewa-
ter treatment
1

1. Introduction

Water pollution with heavy metals is one of the most severe environmental
problems worldwide (Volesky, 2001; Sarkar, 2002; Wang and Cheng, 2009).
Although heavy metals have many useful applications, their toxicity,
accumulation in the food chain, and persistence may cause serious problems
(Volesky, 2001; Sarkar, 2002). According to the International Agency for
Research on Cancer, cadmium (Cd
+2
) and nickel (Ni
+2
) are two important
carcinogenic metals, despite the latter is an essential element in low doses
(Sarkar, 2002). These metals are used in several industrial activities including
metal plating, batteries, ceramic, mining, smelting, pigments, alloys, and
welding (Sarkar, 2002; Meena et al., 2005; Padmavathy, 2008; Fan et al.,
2009). A chronic exposure to Cd
+2
and Ni
+2
may cause adverse effects such as
kidney damage, gastrointestinal injury, lung insufficiency, extreme weakness,
endocrine effects, immune system damage, and cancer (Sarkar, 2002; Meena
et al., 2005; Padmavathy, 2008).
Based on the toxicological profile of heavy metals and other pollutants,
several recommendations and regulations have been established worldwide to
improve water quality (Sarkar, 2002). In this context, the removal of heavy
metal ions from industrial wastewaters has become an important and necessary
task to protect the environment and human health. Several methods such as
ion-exchange, filtration, reverse osmosis, precipitation, coagulation, sorption,
solvent extraction and chemical oxidation-reduction have been used for heavy
metal removal from wastewaters (Volesky, 2001; Wang and Chen, 2009).
Unfortunately, some methods show technical limitations, are expensive and
ineffective when the metal concentrations are in the range of 1 100 mg/L
(Wang and Cheng, 2009). The sorption processes offer several advantages for
wastewater treatment and some are even better than other techniques due to its
effectiveness, feasibility, versatility, simplicity of design, easiness of operation
and low cost (Volesky, 2001; Doyurum and Celik, 2006; Demirbas, 2008).
A current tendency in sorption research is the use of agricultural and
industrial by-products (Demirbas, 2008; Bailey et al., 1999; Babel and
Kurniawan, 2003). This approach is competitive since these materials are
usually cheap and abundant and the costs of the removal process can be
significantly reduced as compared to those using synthetic sorbents (Volesky,
2001). Many examples of natural sorbents for wastewater treatment have been
reported in the literature and they include grape bagasse, hazelnut shells, pinus
bark, rice hulls, tea leaves, banana peels, orange, apple residues and maize
leaf, among others (Demirbas, 2008; Bailey et al., 1999; Babel and
Kurniawan, 2003). These materials contain protein, carbohydrates and
phenolic compounds with several functional groups such as carbonyl,
hydroxyl and amino, which are able to bind heavy metals (Doyurum and
Celik, 2006).
Chicken feathers (CFs) are a natural biosorbent produced in huge
quantities by the poultry industry (Banat and Al-Asheh, 2000; Barone and
1 Reynel-Avila et al.: Cd and Ni biosorption modeling on chicken feathers
Published by The Berkeley Electronic Press, 2011
2

Schmidt, 2006). CFs fibers are semi-crystalline and structured by a nano-
porous network with pores of size in the range of 0.5 to 0.10 m (Kar and
Misra, 2004). This biomass is predominantly constituted by the protein
keratin, which can be assembled into -helix (41%), -sheet (38%) and
disordered structures (21%) (Barone and Schmidt, 2006). FTIR analyses
indicate that CFs contain carboxylic groups that are capable of binding metal
ions effectively (Kar and Misra, 2004). Previous studies have shown the
potential of CFs for the sorption of several metals from aqueous media (Kar
and Misra, 2004; Al-Asheh et al., 2002; Sayed et al., 2005; De la Rosa et al.,
2008). For example, Kar and Misra (2004) tested CFs to remove different
metal ions in aqueous solutions including Ni
+2
and Cd
+2
. Ni
+2
uptake was
studied at batch conditions and pH 5 while Cd
+2
sorption studies were
performed in a solution containing five metals. On the other hand, Al-Asheh et
al. (2002), studied the uptake of Ni
+2
, Cu
+2
and Zn
+2
ions in single and binary
aqueous solutions at batch conditions and 25 C. However, to best of our
knowledge, a comprehensive evaluation and modeling of the effect of
temperature and pH on the CFs performance for Cd
+2
and Ni
+2
removal has
not been reported. The evaluation and comparison of the sorption performance
is necessary in order to properly identify the relative strengths of CFs for
wastewater treatment.
In this paper, we report new experimental data for the sorption
performance of CFs in the removal of Cd
+2
and Ni
+2
ions from aqueous
solutions. The sorption process was investigated via batch experiments. The
effect of pH, contact time and temperature were explored. Metal desorption
conditions of saturated CFs were also studied. Our kinetic and equilibrium
sorption data were fitted to several theoretical and empirical sorption models,
and the most suitable models were identified using statistical criterions.
Thermodynamic parameters of the Cd
+2
and Ni
+2
sorption process were also
calculated.

2. Materials and methods

2.1 Sorbent description

Raw CFs were obtained from a poultry processing plant. CFs were washed
with detergent and rinsed several times with deionized water. Subsequently,
they were washed with aqueous ethanol (20% v/v) in order to remove organic
residues, and then rinsed with deionized water. CFs were dried at 40 C and
the barbs were carefully cut into 0.5 cm length discarding the rachis. This
biomass was used for the sorption experiments.

2.2 Kinetic and equilibrium sorption studies

Batch sorption experiments were performed using 0.06 g of dried biomass and
15 mL of either Cd
+2
or Ni
+2
at concentrations varying from 0.09 to 1.78, and
2
3

from 0.17 to 3.41 mmol/L, respectively. These concentration ranges were used
to achieve the saturation of the sorbent and to determine the maximum
sorption capacity of CFs. Metal solutions were prepared using deionized water
and nitrate salts, and all the reagents used in the study were of analytical
grade.
In all sorption experiments, sorbent and metal solutions at the different
concentrations were mixed, placed on a temperature-controlled shaker and
allowed to interact. First, kinetic experiments were performed to establish the
equilibrium time and to study the rate of metal uptake. In these experiments,
three concentrations of Cd
+2
(0.44, 0.71, 0.89 mmol/L) and Ni
+2
(0.85, 1.36
and 1.7 mmol/L) were used and samples were taken at different times
(between 0.5 to 24 h). On the other hand, Cd
+2
and Ni
+2
isotherms data were
measured at the equilibrium time. Kinetic and isotherm tests were performed
at pHs of 2, 3, 4, and 5, and temperatures of 25, 30, and 40
o
C, in order to
determine the sorption capacity of CFs and the effect of these parameters on
Cd
+2
and Ni
+2
uptake. In all experiments, the initial pH of each metal solution
was adjusted to the required pH value by using diluted acid nitric. In addition,
before the sorption experiments, biomass was equilibrated at the desired pH by
using diluted nitric acid solutions. For metal quantification, samples were
filtered and the solution was then analyzed using a Perkin Elmer AAnalist 100
atomic absorption spectrophotometer equipped with an air-acetylene burner.
The amount of metal ion sorbed q
t
(mmol/g) at time t (h) was calculated using
equation (1)



W
V C C
q
t
t
) (
0

=
(1)


where C
0
is the initial metal concentration and C
t
is the residual metal
concentration at time t given both in mmol/L, V is the volume of metal
solution in L and W is the sorbent amount in g. All experiments were
conducted in triplicate, and the average results are reported in this study.
Reproducibility of the experiments was in general within 5%.

2.3 Desorption studies

In order to assess the possibility of recycling the spent sorbent, 0.1 M HCl and
0.1 M CH
3
COOH were selected as Cd
+2
and Ni
+2
stripping agents. The
literature indicates that these acids are effective for metal desorption in several
sorbents (Srivastava et al., 2008). These concentrations were selected since
they do not produced physical damage to the biomass. The metal-loaded
sorbent with the maximum sorption capacity was chosen for these
experiments. Briefly, the metal-loaded sorbent was separated and rinsed with
deionized water to remove any unsorbed metal. Metal desorption experiments
3 Reynel-Avila et al.: Cd and Ni biosorption modeling on chicken feathers
Published by The Berkeley Electronic Press, 2011
4

were carried out using 0.06 g of metal-loaded sorbent, previously dried (in
order to control the biomass weight), and 15 mL of the acid solution at 30 C,
which was identified as the temperature for obtaining the maximum metal
sorption in the present study. The saturated CFs and the desorbing solution
were left in contact until they reached new equilibrium (i.e., 24 h of contact
time). The final metal ion concentration in the aqueous phase was employed
for the calculation of the desorption ratio by a mass balance. All the
experiments were carried out in triplicate and the mean values standard
deviations are reported. The metal desorption ratio (DR, %) was calculated
using equation (2)


|

\
|
=
sorbed ions metal of amount
desorbed ions metal of amount
100 DR
(2)


2.4 Sorption data modelling

The modeling of sorption isotherms and kinetics provides valuable
physicochemical information for the design, optimization and control of
sorption processes as a unit operation. Several sorption equilibrium and kinetic
models with two or more parameters are available in the literature and have
been used for the data analysis of heavy metal removal from water using
natural and synthetic sorbents (Ho and McKay, 1998; Febrianto et al., 2008;
Liu and Liu, 2008). In this study, the equilibrium sorption data were fitted to
the Langmuir and Freundlich (two-parameter isotherm models) and the
RedlichPeterson and Sips isotherms (three-parameter models). With respect
to kinetic modeling, the pseudo first order, pseudo second order, Elovich and
General Rate Law models were considered. Most of these kinetic models have
two adjustable parameters. The exception is the General rate law model which
has three parameters. Table 1 provides the description and characteristics of
the kinetic and isotherm equations used in this study. For interested readers,
the theoretical basis, explanation, and derivation of applied models can be
found in the review reported by Liu and Liu (2008).
The parameters of kinetic and isotherm models have been determined
by minimizing the relative difference between the experimental and theoretical
data of sorption capacities (q
t
or q
e
) using the simulated annealing stochastic
optimization method (Bonilla-Petriciolet et al., 2005). Specifically, the
objective function used for data fitting in the non-linear regression procedure
is given by equation (3)


=
|
|

\
|
=
ndat
i i
calc i i
obj
q
q q
F
1
2
exp ,
, exp ,
(3)

4
5

where q
i,exp
and q
i,calc
are the experimental and predicted metal uptakes and
ndat is the overall number of experimental data, respectively. Note that two-
parameter kinetic and isotherms are the most commonly used models by
several researchers because of their simplicity and possibility of linearization.
Unfortunately, transformation of non-linear sorption models to linear forms
usually results in parameter estimation errors and uncertainties (Kumar and
Sivanesan, 2005). In addition, the adjustable parameters of multi-parameter
sorption models cannot be estimated by linear regression. Therefore, the
adjustable parameters of all kinetic and sorption models were calculated using
a non-linear regression analysis using a stochastic optimization method since
this approach is more reliable and offers the advantage that the error
distribution is not altered as in the case of linear data fitting technique (Kumar
and Sivanesan, 2005).

Table 1. Kinetic and isotherm equations used for data modeling of Cd
+2
and
Ni
+2
sorption on chicken feathers in aqueous solutions.
Model Equation Description
Pseudo-First order ) 1 (
1
t k
e t
e q q

=
q
e
is the theoretical metal uptake
(mmol/g) and k
1
is the rate constant
(h
-1
).
Pseudo-Second
order t q k
t k q
q
e
e
t
2
2
2
1+
=

q
e
is the theoretical metal uptake
(mmol/g) and k
2
is the rate constant
(g/mmol h).
Elovich
t k q
t
ln
1
ln
1
3
|

\
|
+ |

\
|
=


is the desorption constant (g/mmol)
and k
3
is the initial sorption rate
(mmol/g h).
General Rate Law (

=
n
e t
t k n q q
1
1
4
)) )( 1 (( 1

q
e
is the theoretical metal uptake
(mmol/g), n is the sorption rate order,
and k
4
is the rate constant (h
-1
).
Langmuir
e
e m
e
bC
bC q
q
+
=
1

q
m
is the maximum amount of
sorption (mmol/g) and b (L/mmol) is
the sorption equilibrium constant
which is related to the affinity
between the sorbent and sorbate.
Freundlich
n
e f e
C K q
1
=
K
f
(mmol
1-1/n
L
1/n
g
-1
) is an indicator
of the relative sorption capacity and n
is an affinity constant which gives an
idea of the grade of heterogeneity of
the sites.
Redlich-Peterson
g
e
e
e
BC
AC
q
+
=
1

A, B and g are the three isotherm
empirical parameters.
Sips
n
e s
n
e s s
e
C a
C a q
q
+
=
1

q
s
is the monolayer sorption capacity
(mmol/g), a
s
and n are the Sips
parameters.
5 Reynel-Avila et al.: Cd and Ni biosorption modeling on chicken feathers
Published by The Berkeley Electronic Press, 2011
6



Several statistical criterions were considered for performance
comparison of kinetic and isotherm equations. Previous studies reported the
removal of Pb using CFs (De la Rosa et al., 2008), were the coefficient of
determination (R
2
), the objective function value (F
obj
), and the mean absolute
percentage deviation (E) between calculated and experimental metal uptakes
were the criterions used to measure the goodness of the fittings, and this is
given in equation (4) where

=
ndat
i
i
calc i i
q
q q
ndat
E
1
exp ,
, exp ,
100
(4)



These statistics were accompanied by a study of the behavior of the relative
residuals in equation (5)


exp ,
, exp ,
i
calc i i
i
q
q q
e

=
(5)


3. Results and discussion

3.1 Sorption kinetics and isotherms

Figures 1 3 show the kinetics of Cd
+2
and Ni
+2
sorption on chicken feathers
at different pH values (Fig. 1), temperature (Fig. 2), and initial metal
concentration (Fig. 3). It is clear that pH strongly influences the Cd
+2
and Ni
+2

uptakes and the greatest sorption occurred at high pH as expected (Fig. 1).
Specifically, a significant increase in Cd
+2
and Ni
+2
uptakes was observed at
pH 5. However, it appears that Cd
+2
sorption is more sensitive to pH changes.
The increase in metal sorption capacity as the pH increases can be explained
by changes in the chemical nature of the metal (e.g., charge density, solubility
and degree of hydrolysis) and in the sorbent surface properties, among other
factors (Al-Asheh and Duvnajk, 1997; Meena et al., 2005). At pH below 3, the
metal sorption performance of CFs is significantly affected given that H
+
ions
compete with Cd
+2
and Ni
+2
for the active sites in CF (De la Rosa et al., 2008;
Farinella et al., 2007). It is important to note that the pH value in all
experiments was measured after equilibrium because metal solutions were not
buffered. The final pH in metal solutions after sorption process ranged from
1.9 to 5.4 for both metals and there was no physical evidence of metal
6

precipitation. Furthermore, according to speciation diagrams, Cd
are the only ionic species present in solution at pH < 6.

Figure 1. Effect of pH on Cd
conducted at a T of
Initial Cd
+2
and Ni
respectively. Data represents mean of three replicates. Error bars indicate
Figure 2 shows the effect
Ni
+2
sorption by CF. For both metals, the rise in temperature from 25 C to 30
C caused an increase in the metal uptake, indicating an endothermic sorption
Furthermore, according to speciation diagrams, Cd
are the only ionic species present in solution at pH < 6.
Effect of pH on Cd
+2
and Ni
+2
sorption by CFs. Experime
at a T of 30 C and pH values of () 2, () 3, () 4, and (
Ni
+2
concentrations were of 0.89 and 0.85 mmol/L
respectively. Data represents mean of three replicates. Error bars indicate
standard deviation.

Figure 2 shows the effect of temperature on the kinetics of Cd
sorption by CF. For both metals, the rise in temperature from 25 C to 30
C caused an increase in the metal uptake, indicating an endothermic sorption
7
Furthermore, according to speciation diagrams, Cd
+2
and Ni
+2


. Experiments were
) 4, and () 5.
0.85 mmol/L,
respectively. Data represents mean of three replicates. Error bars indicate
of temperature on the kinetics of Cd
+2
and
sorption by CF. For both metals, the rise in temperature from 25 C to 30
C caused an increase in the metal uptake, indicating an endothermic sorption
7 Reynel-Avila et al.: Cd and Ni biosorption modeling on chicken feathers
Published by The Berkeley Electronic Press, 2011
8

process at this temperature range. This increase may be attributed to the
increase in the number of active surface sites available for sorption on the
sorbent caused by the stretching of the feather fibers and the decrease in the
thickness of the boundary layer which surrounds the sorbent reducing the mass
transfer resistance (Banat and Al-Asheh, 2000; Meena et al., 2005; De la Rosa
et al., 2008). However, from 30 C to 40 C both, Cd
+2
and Ni
+2
uptake
decreased. At this temperature range, it appears that metal sorption is
exothermic.
As indicated by De la Rosa et al. (2008), this behavior could be caused
by an increased mobility of metals in solution that affects the metal binding to
active sites of CFs. It is important to note that this dual effect of temperature
on sorption performance has been also reported for the removal of Pb
+2
ions
using CFs (De la Rosa et al., 2008). This unusual behavior cannot be attributed
to experimental errors since the decrease and increase in the metal uptake is
greater than the magnitude of the uncertainty of sorption experiments (see
standard deviations reported in Figure 2).
Finally, Figure 3 shows the effect of contact time and initial metal
concentration on the sorption kinetics of Cd
+2
and Ni
+2
using CF at 30
o
C and
pH 5, which are the conditions for maximum metal removal determined in the
present investigation. As expected, the metal sorption rates show that the
sorbed amount increased with an increase in the metal concentration and
contact time. In particular, the initial metal concentration provides the
necessary force to overcome the resistance to the mass transfer, which allows
metals to pass from the solution to the particle surface and favors the
interaction between metal and sorbent enhancing the metal uptake (Al-Asheh
and Duvnjak, 1997; De la Rosa et al., 2008). Thus, there is an increase in the
mass transfer driving force caused by the increase in the Cd
+2
and Ni
+2

contents. For both metals, kinetic studies confirmed that Cd
+2
and Ni
+2
sorption onto CFs is quite rapid indicating that most of the sorption process
occurs on the external surface of the sorbent where the binding sites of CFs
that might be responsible for heavy metal removal are more accessible (Kar
and Misra, 2004). Typically, 30 90% of the metal removal occurs within the
first hours of contact time and it is evident that saturation is reached after 24 h.
This trend is similar to that obtained by other studies including our results
reported for Pb
+2
sorption using CFs (Kar and Misra, 2004; De la Rosa et al.,
2008).
In summary, kinetics results indicated that the Cd
+2
and Ni
+2
sorption
on CFs is described by the following three stages: a) a very rapid external
surface sorption, b) a gradual increase in sorption due to intraparticle
diffusion, and c) a last stage where metal sorption becomes asymptotic caused
by equilibrium between metal ions and sorbent. The data presented herein
suggest that particle diffusion is not the rate-controlling step at the tested
conditions.


8


Figure 2. Effect of T on Cd
reacted with a) 0.89 mmol/L Cd
temperatures of: () 25, (







on Cd
+2
and Ni
+2
sorption by CFs. Sorbent (0.06 g) was
a) 0.89 mmol/L Cd
+2
; and b) 0.85 mmol/L Ni
+2
at pH 5 and
) 25, () 30, and () 40 C.
9

Sorbent (0.06 g) was
at pH 5 and
9 Reynel-Avila et al.: Cd and Ni biosorption modeling on chicken feathers
Published by The Berkeley Electronic Press, 2011

Figure 3. Effect of initial metal concentration on Cd
CFs. Experiments were run at
() 0.44, () 0.71, and (
() 1.70 for Ni
+2
. Data represents mean of three replicates. Error bars indicate
standard deviation.

The results for the isotherm studies are
Ni
+2
sorption isotherms can be classified as Langmuir
correspond to a favorable sorption process. In general, the equilibrium metal
uptake ranged from 0.0005 to 0.039 mmol/g for Cd
Effect of initial metal concentration on Cd
+2
and Ni
+2

ents were run at 30 C and pH 5 at initial metal concentrations of
) 0.71, and () 0.89 mmol/L for Cd
+2
, and () 0.85, (
Data represents mean of three replicates. Error bars indicate
The results for the isotherm studies are shown in Figure 4. Cd
sorption isotherms can be classified as Langmuir-type isotherm and they
correspond to a favorable sorption process. In general, the equilibrium metal
uptake ranged from 0.0005 to 0.039 mmol/g for Cd
+2
and from 0.0005 to
10

sorption by
at initial metal concentrations of
) 0.85, () 1.36, and
Data represents mean of three replicates. Error bars indicate
shown in Figure 4. Cd
+2
and
type isotherm and they
correspond to a favorable sorption process. In general, the equilibrium metal
and from 0.0005 to
10

0.065 mmol/g for Ni
present research were of 0.039 and 0.065 mmol/g, for Cd
respectively, at the conditions of pH 5 and 30 C.


Figure 4. Isotherms for Cd
and b) Effect of Temperature, Ni
Temperature. pHs: (

The maximum sorption capacities of Cd
this study are higher than those reported for other synthetic and natural
sorbents. For example, the Cd
reported for exhausted coffee: 0.013 mmol/g,
et al., 1999), rice husk ash: 0.026 mmol/g
Moringa oleifera seeds: 0.009 mmol/g
copra meal: 0.016 mmol/g [27]. In the case of Ni
higher than clinoptilolite: 0.008 mmol/g
niger: 0.03 mmol/g [10], chitosan: 0.04 mmol/g
and appears to be competitive with respect to shelled
0.016 mmol/g (Sharma et al., 2007)
0.065 mmol/g for Ni
+2
. The maximum sorption capacities obtained in the
present research were of 0.039 and 0.065 mmol/g, for Cd
+2
respectively, at the conditions of pH 5 and 30 C.
Isotherms for Cd
+2
and Ni
+2
sorption by CFs. Cd
+2
: a) Effect of pH
and b) Effect of Temperature, Ni
+2
: c) Effect of pH and d) Effect of
() 2, () 3, () 4, and () 5. Temperatures: (
30, and () 40 C.
The maximum sorption capacities of Cd
+2
and Ni
+2
ions obtained in
this study are higher than those reported for other synthetic and natural
sorbents. For example, the Cd
+2
metal uptakes of CFs are higher than those
hausted coffee: 0.013 mmol/g, waste tea: 0.015 mmol/g
rice husk ash: 0.026 mmol/g (Srivastava et al., 2008)
seeds: 0.009 mmol/g (Sharma et al., 2007), and coconut
copra meal: 0.016 mmol/g [27]. In the case of Ni
+2
, the removal with CFs is
higher than clinoptilolite: 0.008 mmol/g (Ofojama and Ho, 2007), A
: 0.03 mmol/g [10], chitosan: 0.04 mmol/g (Babel and Kurniawan, 2003)
and appears to be competitive with respect to shelled Moringa oleifera
(Sharma et al., 2007), petiolar felt-sheath of palm: 0.12 mmol/g
11
The maximum sorption capacities obtained in the
+2
and Ni
+2
,

) Effect of pH
) Effect of pH and d) Effect of
) 25, ()
ions obtained in
this study are higher than those reported for other synthetic and natural
metal uptakes of CFs are higher than those
waste tea: 0.015 mmol/g (Bailey
(Srivastava et al., 2008), shelled
, and coconut
, the removal with CFs is
, Aspergillus
(Babel and Kurniawan, 2003),
Moringa oleifera seeds:
0.12 mmol/g
11 Reynel-Avila et al.: Cd and Ni biosorption modeling on chicken feathers
Published by The Berkeley Electronic Press, 2011
12

(Iqbal et al., 2002), and rice husk: 0.094 mmol/g (Krishnani et al., 2008). Even
when a proper comparison of sorption capacities is not completely possible
due to the broad diversity of experimental conditions including sorbent
particle size, pH, temperature, and chemical modifications, these data serve as
reference. According to our results, it can be concluded that raw CFs display
acceptable metal uptakes for Cd
+2
and Ni
+2
ions in aqueous solutions.


3.2 Thermodynamic parameters

Based on the results of the equilibrium studies, we calculated the
thermodynamic parameters for Cd
+2
and Ni
+2
sorption process. The enthalpy
change (H
0
) and entropy change (S
0
) were determined from the slope and
intercept of the plot ln K
eq
versus 1/T, or better known as vant Hoff plot,
using equation (6):

R
S
RT
H
K
eq
0 0
ln

+

= (6)


where K
eq
= C
se
/ C
e
is the distribution coefficient which was calculated from
experimental data, C
se
is the concentration of sorbed solute on sorbent at
equilibrium in mmol/L, T is temperature in Kelvin and R is universal gas
constant (8.31410
3
kJ/mol K).
Thermodynamic parameters were calculated using Eq. (6) and results
are reported in Table 2 for both metals. The positive value in enthalpy change
from 25 to 30 C for both metals suggests the endothermic nature of the
process and possible strong bonding between the metal and sorbent (Uslu and
Tanyol, 2006). Also, for this temperature increment, a positive entropy change
value reflects the affinity of the sorbent to Cd
+2
and Ni
+2
ions since there may
be an increase in randomness at the sorbent/solution interface during the
process (Uslu and Tanyol, 2006; De la Rosa et al., 2008). Table 2 shows that
enthalpy and entropy changes of Ni
+2
uptakes are higher than those obtained
for Cd
+2
suggesting a more strong metal-sorbent interaction. However, at
temperatures between 30 to 40 C, the negative enthalpy values indicate that
sorption process is exothermic for both metal ions. This suggests that there is a
weak bonding between the sorbate and sorbent surface at these operating
conditions (Febrianto et al., 2008). Also, negative entropy changes correspond
to a decrease in the degree of freedom of the sorbed metal, which could be
attributed to the ions displaying a higher level of order on the solid phase (i.e.,
biomass) compared to that in the aqueous phase, this being a result of the loss
of mobility when the ions are attached to the biomass surface (Khazali et al.,
2007). In conclusion, calculated thermodynamic parameters are in agreement
with the experimental data.
Generally, physical sorption involves an enthalpy change from 2 to 21
kJ/mol, while enthalpy change of chemisorption falls in the range of 80 200
kJ/mol (Liu and Liu, 2008). In addition, as indicated by other authors (e.g.,
12
13

Febrianto et al, 2008) if a physical sorption process is involved, a decrease of
this process with an increase in temperature should be expected. When
chemisorption is involved, it is usually favored with rises in temperature.
According to these observations and our calculated thermodynamic
parameters, the results showed that, below the temperature of 30
o
C, the metal
uptake of Cd
+2
and Ni
+2
ions may be mainly controlled by a chemisorption
process. However, for temperatures higher than 30
o
C, it is likely that sorption
of both metals onto CFs is caused by a combination of both physical and
chemical processes, especially for Ni
+2
ions. According to Kar and Misra
(2004), the physisorption process may occur by the trapping of metal ions in
the nano-porous network of CFs while chemisorption is believed to occur at
the carboxylic binding sites of CFs. These thermodynamic trends have been
also observed for Pb
+2
removal from aqueous solutions using CFs (De la Rosa
et al., 2008).

Table 2. Thermodynamic parameters for Cd
+2
and Ni
+2
sorption in aqueous
solutions using chicken feathers

T,
o
C Metal ion H
0
, kJ/mol S
0
, kJ/mol K
25 30 Cd
+2
100.86 0.32
Ni
+2
127.92 0.40
30 40 Cd
+2
-18.44 -0.07
Ni
+2
-61.19 -0.22


3.3 Data modeling

Results of kinetic and isotherm data modeling are reported in Figures 5 and 6
and Table 3. For both metals, the statistical analysis indicated that the pseudo-
second order and the General Rate Law models describe the rate of metal
uptakes better than that of pseudo first-order and Elovich kinetic equations
(see Figure 5 and Table 3). According to the literature, the pseudo-second
order model assumes that two surface sites could be occupied by one sorbate
ion (Onyango et al., 2003). Therefore, it would be expected that this model is
applicable and suitable for modeling the sorption of divalent metal ions as
Cd
+2
and Ni
+2
. On the other hand, the general rate law equation considers that
sorption reaction on the surface of the sorbent is the rate-controlling step. This
model assumes that sorption rate varies with the effective concentration of
binding sites and it is unnecessary to link the sorption kinetics to the possible
sorption mechanism because sorption process is extremely complex and
various mechanisms would be involved (Liu and Shen, 2008). This kinetic
equation establishes that it is possible the existence of mixed-order reactions
with a fractional order for their rate. Liu and Shen (2008) suggested that it is
more convenient to determine the order of sorption process using the general
rate law equation instead of using a preset-order kinetic equation. Overall,
these two models showed a mean error from 0.51 to 7.52% and high values of
13 Reynel-Avila et al.: Cd and Ni biosorption modeling on chicken feathers
Published by The Berkeley Electronic Press, 2011
14

the correlation coefficients (R
2
> 0.88) in the data modeling. Model parameters
of these kinetic expressions are given in Tables 4 and 5 for all the tested
conditions explored in the present study.

Table 3. Results of data modeling using kinetic and isotherm models for Cd
+2

and Ni
+2
sorption on chicken feathers from aqueous solutions.
Statistical analysis
Metal Model R
2
E, % F
obj

Cd
+2
Pseudo-first order 0.68 - 0.98 3.64 - 11.94 1.4710
-2
1.6510
-1

Pseudo-second order 0.88 - 0.99 1.18 - 6.13 1.7310
-3
6.5610
-2

Elovich 0.77 - 0.98 2.03 - 12.21 5.6710
-3
1.4810
-1

General rate law 0.91 - 1.00 0.61 - 7.52 4.6010
-4
9.1510
-2

Langmuir 0.13 - 0.98 5.96 - 39.55 8.5110
-2
- 3.19
Freundlich 0.20 - 0.95 6.94 - 38.90 1.0310
-1
3.13
Redlich-Peterson 0.13 - 0.96 5.96 - 38.91 8.5110
-2
- 3.13
Sips 0.96 - 0.99 4.70 - 6.94 4.6410
-2
- 0.11
Ni
+2
Pseudo-first order 0.71 - 0.98 2.14 - 8.51 4.8710
-3
7.0010
-2

Pseudo-second order 0.90 - 0.99 0.65 - 6.62 6.1910
-4
7.0910
-2

Elovich 0.73 - 0.97 2.33 - 10.65 5.9110
-3
1.2310
-1

General rate law 0.94 - 1.00 0.51 - 2.61 2.7910
-4
7.0010
-3

Langmuir 0.72 - 0.97 5.70 - 26.66 7.2910
-2
- 1.45
Freundlich 0.68 - 0.92 9.29 - 27.54 1.7010
-1
- 1.47
Redlich-Peterson 0.72 - 0.97 5.70 - 26.67 7.2910
-2
- 1.45
Sips 0.95 - 0.98 5.45 - 13.21 6.8210
-2
- 0.54



Table 3 and Figure 6 display the results for the isotherm data
modeling. Figure 6 shows that our data was better correlated to the Langmuir
and Redlich-Peterson models as compared to the Freundlich isotherm.
However, Langmuir, Freundlich and Redlich-Peterson isotherms were
incapable of fitting satisfactorily the metal uptakes at pH 2, 3 and 25 C for
Cd
+2
and at pH 2 and 25 C for Ni
+2
ions. It is clear that Sips isotherm
generally gave better fits than the rest of the isotherm equations used for
modeling both Cd
+2
and Ni
+2
sorption data. Sips isotherm is an empirical
model that incorporates the features of both Langmuir and Freundlich
isotherms (Sips, 1948). At low concentrations, the Sips model reduces to the
Freundlich isotherm while a higher concentrations it may predict a monolayer
14
15

Table 4. Parameters of the pseudo-second order model for Cd
+2
and Ni
+2

sorption kinetics using raw chicken feathers.
Metal C
0,
mmol/L T, C pH q
e
mmol/g k
2
,g/mmol h R
2
F
obj

Cd
+2
0.44 30 2 6.1010
-3
277.67 0.97 1.4510
-2

3 1.2610
-2
47.28 0.98 2.2510
-2

4 1.4710
-2
49.58 0.99 2.0910
-2

5 1.7010
-2
112.98 0.96 1.6310
-2

25 5 1.1010
-2
146.65 0.99 5.3610
-3

40 5 1.5710
-2
37.80 0.96 5.0610
-2

0.71 30 2 6.7110
-3
259.70 0.88 6.5610
-2

3 1.9310
-2
152.78 0.93 1.4010
-2

4 2.2410
-2
64.91 0.97 1.4510
-2

5 2.5310
-2
106.71 0.96 9.5210
-3

25 5 1.8710
-2
107.68 0.98 9.4010
-3

40 5 2.1910
-2
68.63 0.94 3.3710
-2

0.89 30 2 6.9710
-3
120.37 0.98 1.4810
-2

3 2.3910
-2
149.25 0.99 1.7310
-3

4 2.9610
-2
36.15 0.94 5.6410
-2

5 3.0410
-2
128.45 0.96 5.0510
-3

25 5 2.5010
-2
65.20 0.98 8.1510
-3

40 5 2.7110
-2
82.79 0.96 1.3510
-2

Ni
+2
0.85 30 2 5.4410
-3
787.76 0.90 9.7710
-3

3 7.8210
-3
283.16 0.97 9.7810
-3

4 1.5010
-2
75.39 0.97 2.4910
-2

5 1.9810
-2
52.02 0.99 8.1810
-3

25 5 1.5510
-2
37.14 0.97 7.0910
-2

40 5 1.4110
-2
61.14 0.99 9.8610
-3

1.36 30 2 8.7010
-3
287.36 0.98 6.3710
-2

3 1.2710
-2
190.41 0.98 4.5110
-3

4 2.6810
-2
328.30 0.96 1.2710
-3

5 3.9710
-2
57.50 0.96 1.2610
-2

25 5 2.9410
-2
66.39 0.98 5.1110
-3

40 5 2.5310
-2
118.30 0.98 4.7210
-3

1.70 30 2 1.0710
-2
161.06 0.98 7.5410
-3

3 1.6310
-2
221.90 0.96 7.8210
-3

4 3.6110
-2
115.55 0.97 4.1210
-3

5 4.8710
-2
72.18 0.97 5.5510
-3

25 5 4.0910
-2
54.99 0.98 5.2810
-3

40 5 3.8410
-2
137.35 0.99 6.1910
-4








15 Reynel-Avila et al.: Cd and Ni biosorption modeling on chicken feathers
Published by The Berkeley Electronic Press, 2011
16

Table 5. Parameters of the general rate law model for Cd
+2
and Ni
+2
sorption
kinetics in aqueous solution using raw chicken feathers.
Metal C
0
, mmol/L T, C pH q
e
, mmol/g k
4
, h
-1
n R
2
F
obj

Cd
+2
0.44 30 2 7.3910
-3
2.97 4.00 0.98 6.4310
-3

3 1.4810
-2
1.23 4.00 0.97 3.4410
-2

4 1.5910
-2
1.57 3.27 1.00 3.4010
-3

5 2.0610
-2
3.43 4.00 0.99 3.8910
-3

25 5 1.1410
-2
3.00 2.65 0.99 2.1610
-3

40 5 1.8510
-2
1.21 4.00 0.96 9.1510
-2

0.71 30 2 8.0710
-3
3.21 4.00 0.91 4.1710
-2

3 2.2710
-2
6.08 4.00 0.99 2.6010
-3

4 2.7210
-2
2.49 4.00 0.99 6.2610
-3

5 2.5510
-2
4.49 2.32 0.97 6.5810
-3

25 5 2.0810
-2
3.58 3.31 0.97 1.0210
-2

40 5 2.4110
-2
2.72 3.23 0.92 4.5410
-2

0.89 30 2 7.7710
-3
1.66 3.38 0.98 1.3110
-2

3 2.4210
-2
5.68 2.35 0.99 1.4710
-3

4 2.7710
-2
2.82 2.11 0.99 4.7010
-3

5 3.4410
-2
9.25 3.79 1.00 4.6010
-4

25 5 3.0210
-2
2.79 3.92 0.99 3.7210
-3

40 5 3.2310
-2
4.28 3.98 0.96 9.1210
-3

Ni
+2
0.85 30 2 6.0610
-3
10.31 3.65 0.94 6.1110
-3

3 7.9710
-3
3.85 2.48 0.97 7.0010
-3

4 1.4910
-2
2.50 2.47 0.99 3.3110
-3

5 2.4210
-2
1.79 4.00 0.99 5.4810
-3

25 5 1.6010
-2
1.48 3.09 0.99 5.1910
-3

40 5 1.5410
-2
1.74 3.27 1.00 2.5210
-3

1.36 30 2 9.5410
-3
4.53 3.20 0.97 5.6210
-3

3 1.3910
-2
4.27 3.20 0.99 1.8710
-3

4 2.8010
-2
25.00 3.09 0.99 2.7910
-4

5 3.8310
-2
4.30 1.92 1.00 3.5410
-4

25 5 3.4610
-2
3.45 3.78 1.00 1.0410
-3

40 5 2.6010
-2
4.96 2.50 0.98 3.4310
-3

1.70 30 2 1.2010
-2
3.03 3.26 0.98 5.3910
-3

3 1.8310
-2
8.16 3.69 0.98 3.8310
-3

4 3.7510
-2
7.38 2.72 0.97 4.0010
-3

5 4.7610
-2
5.48 1.89 0.99 1.1410
-3

25 5 4.0910
-2
3.96 2.29 0.99 1.7210
-3

40 5 3.9310
-2
8.79 2.53 1.00 3.1210
-4









16



Figure 5. Experimental and calculated (
chicken feathers in aqueous solutions. Kinetic model: a) Pseudo
Pseudo-second order, c) Elovich, and d) General


sorption capacity characteristic of the Langmuir isotherm. When the parameter
n in the Sips equation is equals to 1.0, this model is reduced to the Langmuir
equation. In general, the exponent value
isotherms of both Cd
+2
n was considered as an empirical adjustable parameter (i.e. no restrictions
were imposed for its values during data fitting) given that this isotherm is
empirical and n has no clearl
sorption process is affected by several factors and is complex because the
binding sites of the sorbent are not all identical; there is sorption resistance
due to geometric factors and to the affinity of sor
there are external and internal mass transfer factors that limit the sorption
capacity. As a consequence, the modeling of the sorption process may be
challenging at some operating conditions.

Experimental and calculated () Cd
+2
and () Ni
+2
uptakes by
chicken feathers in aqueous solutions. Kinetic model: a) Pseudo-first order, b)
second order, c) Elovich, and d) General Rate Law.
sorption capacity characteristic of the Langmuir isotherm. When the parameter
in the Sips equation is equals to 1.0, this model is reduced to the Langmuir
equation. In general, the exponent value n was found to be greater than 1.0 for
+2
and Ni
+2
ions (see Table 6). It is important to note that
was considered as an empirical adjustable parameter (i.e. no restrictions
were imposed for its values during data fitting) given that this isotherm is
has no clearly defined physical meaning. As stated early, the
sorption process is affected by several factors and is complex because the
binding sites of the sorbent are not all identical; there is sorption resistance
due to geometric factors and to the affinity of sorbate and sorbent. Besides,
there are external and internal mass transfer factors that limit the sorption
As a consequence, the modeling of the sorption process may be
challenging at some operating conditions.
17

uptakes by
first order, b)
Rate Law.
sorption capacity characteristic of the Langmuir isotherm. When the parameter
in the Sips equation is equals to 1.0, this model is reduced to the Langmuir
was found to be greater than 1.0 for
ions (see Table 6). It is important to note that
was considered as an empirical adjustable parameter (i.e. no restrictions
were imposed for its values during data fitting) given that this isotherm is
y defined physical meaning. As stated early, the
sorption process is affected by several factors and is complex because the
binding sites of the sorbent are not all identical; there is sorption resistance
bate and sorbent. Besides,
there are external and internal mass transfer factors that limit the sorption
As a consequence, the modeling of the sorption process may be
17 Reynel-Avila et al.: Cd and Ni biosorption modeling on chicken feathers
Published by The Berkeley Electronic Press, 2011


Figure 6. Experimental and calcu
chicken feathers in aqueous solutions. Isotherm model: a) Langmuir, b)
Freundlich, c) Redlich


Table 6. Parameters of
aqueous solution using
Metal T, C pH q
Cd
+2
30 2 7.02
3 2.9610
4 5.0710
5 1.3910
25 5 3.3010
40 5 5.8510
Ni
+2
30 2 1.3110
3 3.7710
4 8.2510
5 1.1710
25 5 8.4810
40 5 7.7110

Experimental and calculated () Cd
2+
and () Ni
2+
uptakes by
chicken feathers in aqueous solutions. Isotherm model: a) Langmuir, b)
Freundlich, c) Redlich-Peterson, and d) Sips.
. Parameters of the Sips isotherm model for Cd
+2
and Ni
+2
aqueous solution using raw chicken feathers.
q
s
, mmol/g a
s
n R
2
F
7.0210
-3
265.47 3.26 0.96 4.64
2.9610
-2
5.30 1.97 0.99 6.4910
5.0710
-2
1.25 1.20 0.97 1.0710
1.3910
-1
0.32 0.76 0.98 8.9110
3.3010
-2
3.46 2.11 0.99 7.3810
5.8510
-2
0.96 1.11 0.97 7.3010
1.3110
-2
1.37 1.96 0.98 6.8510
3.7710
-2
0.38 1.07 0.97 6.8210
8.2510
-2
0.32 1.54 0.97 2.0510
1.1710
-1
0.32 1.47 0.98 1.2810
8.4810
-2
0.34 1.72 0.96 5.3610
7.7110
-2
0.33 1.57 0.95 3.4810
18

uptakes by
chicken feathers in aqueous solutions. Isotherm model: a) Langmuir, b)
+2
sorption in
F
obj

4.6410
-2

6.4910
-2

1.0710
-1

8.9110
-2

7.3810
-2

7.3010
-2

6.8510
-2

6.8210
-2

2.0510
-1

1.2810
-1

5.3610
-1

3.4810
-1

18
19

In the absence of a theoretical model that could account for the
chemical heterogeneity of the sorbent and the simultaneous prevalence of
different sorption mechanisms, it is reasonable to use the Sips model without
any mathematical restriction for its parameters during the data fitting
procedure. In general, the performance of the isotherm equations for the metal
sorption data modeling of CFs is given by: Sips > Redlich-Peterson
Langmuir > Freundlich.

3.4 Desorption studies

Desorption studies indicated that the maximum desorption was achieved with
0.1M acetic acid for Cd
+2
with a DR of 51.7 0.9%, which is slightly higher
than that obtained for HCl (44.7 1.2%). For Ni
+2
desorption, the DR was
around 14.6 1.8% and 12.2 3.1% for both desorbing agents, respectively.
In literature, a number of desorbing agents has been tested for metal recovery
and sorbent regeneration and they include both inorganic and organic agents
such as HCl, HNO
3
, H
2
SO
4
, CH
3
COOH, EDTA, and NaOH. The performance
of these desorbing agents depends on the sorbent type, the concentration of
sorbed metals, and operating conditions (e.g., concentration of desorbing
agent, temperature, and sorbent dosage). Usually, the metal recovery
efficiencies reported in literature range from 5 to 70%, where the best
desorbing ratios are obtained especially for Cd
+2
. Therefore, our results
indicate that both HCl and CH
3
COOH solutions at low concentration are
suitable for Cd
+2
desorption but they are ineffective for desorbing Ni
+2
ions
from CFs. However, other stripping agents should be explored in order to
determine if higher recoveries are possible. It appears that there may be a
strong Ni
+2
CF interaction.
Thermodynamic parameters indicate that chemisorption process is
more predominant for Ni
+2
ions and, under these conditions, low DR would be
expected. Usually, the metal sorption process is not completely reversible
given that the metal ions may become entrapped in the nano-porous network
of the sorbent, some of the metal ions may be incorporated onto the biomass
or because of the presence of a re-sorption process. The DR obtained for Cd
+2

could mean that external surface sorption was predominant on CFs and
suggests that it is possible the sorbent regeneration, at least, for this metal.

4. Conclusions

The capacity of CFs for sorbing Cd
+2
and Ni
+2
ions was considerably
dependent on pH and temperature. The sorption capacity for both metals
exhibited a maximum at pH of 5, and temperature of 30 C. Thermodynamic
calculations suggest that Cd
+2
and Ni
+2
removal by chicken feathers may be
controlled by a chemisorption process, or by a combination of both physical
and chemical processes depending on temperature. The pseudo-second order
and general rate law models were suitable for modeling the Cd
+2
and Ni
+2

19 Reynel-Avila et al.: Cd and Ni biosorption modeling on chicken feathers
Published by The Berkeley Electronic Press, 2011
20

uptakes by CFs, whereas equilibrium sorption data were properly adjusted by
the Sips model. The desorption process of Cd
+2
is feasible using CH
3
COOH
and HCl at low concentration. However, these stripping agents were not
suitable for Ni
+2
desorption. It is convenient to study other desorption
conditions to improve the desorption ratio of both metals especially for Ni
+2
.

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