Gue Chi 2011
Gue Chi 2011
Gue Chi 2011
ORIGINAL ARTICLE
KEYWORDS Abstract Potato peel (PP) was used as a biosorbent to remove malachite green (MG) from aque-
Sorption; ous solution under various operating conditions. The effect of the experimental parameters such as
Malachite green; initial dye concentration, biosorbent dose, initial pH, stirring speed, temperature, ionic strength and
Potato peel; biosorbent particle size was investigated through a number of batch sorption experiments. The
Modeling; sorption kinetic uptake for MG by PP at various initial dye concentrations was analyzed by
Non-linear method non-linear method using pseudo-rst, pseudo-second and pseudo-nth order models. It was found
that the pseudo-nth order kinetic model was the best applicable model to describe the sorption
kinetic data and the order n of sorption reaction was calculated in the range from 0.71 to 2.71.
Three sorption isotherms namely the Langmuir, Freundlich and RedlichPeterson isotherms in
their non-linear forms were applied to the biosorption equilibrium data. Both the Langmuir and
RedlichPeterson models were found to t the sorption isotherm data well, but the Redlich
Peterson model was better. Thermodynamic parameters show that the sorption process of MG is
endothermic and more effective process at high temperatures. The results revealed that PP is very
effective for the biosorption of MG from aqueous solutions.
2011 King Saud University. Production and hosting by Elsevier B.V. All rights reserved.
Please cite this article in press as: Guechi, E.-K., Hamdaoui, O. Sorption of malachite green from aqueous solution by potato peel: Kinet-
ics and equilibrium modeling using non-linear analysis method. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.05.011
2 E.-K. Guechi, O. Hamdaoui
1 ppm for some dyes) is highly visible and aesthetically The objective of this work was to investigate the potential
unpleasant. Due to intense color they reduce sunlight transmis- of PP as a novel sorbent in the removal of the basic dye, mal-
sion into water hence affecting aquatic plants, which ultimately achite green, from aqueous solutions. Batch sorption studies
disturb aquatic ecosystem. Dye bearing efuents are character- were conducted to investigate the effects of various parameters
ized by high chemical oxygen demand, low biodegradability such initial dye concentration, biosorbent dose, pH, tempera-
and high salt content. In addition, it has been stressed recently ture, stirring speed, ionic strength and particle size on MG bio-
that color compounds such as dyes discharged from several sorption. Equilibrium isotherm and kinetic data are analyzed
industries are very harmful to aquatic life in rivers and lakes. and modeled using different models by non-linear regression
Therefore, it is necessary to reduce dye concentration in the technique.
wastewater before it is released into the environment.
Malachite green (MG), a basic dye, is most widely used 2. Materials and methods
for coloring purpose, amongst all other dyes of its category
(Crini et al., 2007). This triarylmethane dye is widely used 2.1. Biosorbent
in the aquaculture industry worldwide as a biocide as well
as in the silk, wool, cotton, leather, paper and acrylic indus- The PP used in the present study was obtained from the uni-
tries as a dye. However there are several reports describing its versity canteen. It was washed, dried, crushed and sieved to de-
hazardous and carcinogenic effects (Srivastava et al., 2004). It sired mesh size (0.51.25 mm). Finally, the obtained material
is known to be highly cytotoxic and carcinogenic to mamma- was then dried in an air circulating oven at 50 C for 7 days
lian cells and acts as a liver tumor promoter. In humans, it and stored in a desiccator until use.
may cause irritation to the respiratory tract if inhaled and
causes irritation to the gastrointestinal tract upon ingestion. 2.2. Sorbate
Contact of malachite green with the skin causes irritation
with redness and pain; upon contact with eye will lead to per- The cationic basic dye (C.I. 42000; Basic Green 4), malachite
manent injury of human eyes. It also affects the aquatic life green oxalate salt, (molecular formula C52H56N4O12, FW
and causes detrimental effects in liver, gill, kidney, intestine, 929), was obtained from Merck and used without further puri-
gonads and pituitary gonadotrophic cells (Hameed and El- cation. The structure of this dye is displayed in Fig. 1. Five
Khaiary, 2008a). Therefore, the treatment of efuent contain- hundred milligram per liter stock solution was prepared by dis-
ing such dye is of interest due to its harmful impact on solving the required amount of dye in distilled water. Working
receiving waters. solutions of the desired concentrations were obtained by suc-
Among the numerous treatment technologies developed for cessive dilutions.
the removal of dyes from industrial efuents, biosorption is
receiving increasing attention in becoming an attractive and 2.3. Analytical method
promising technology. The study of biosorption is of great
importance from an environmental point of view, as it can A well-known procedure for determining MG concentrations,
be considered as an alternative technique for removing toxic based on Beers law calibration plots, was applied using a UV
pollutants from wastewaters (Vieira and Volesky, 2000; Nouri visible spectrophotometer (Jenway 6405). The wavelength res-
and Hamdaoui, 2007). A number of low cost biosorbent have olution and the bandwidth were, respectively, 1 and 0.5 nm.
been studied in the literature for their capacity to remove MG The length of the optical path in glass cell was 1 cm. The max-
from aqueous solutions (Baek et al., 2010; Bekci et al., 2009; imum absorption wavelength was determined as equal to
Hamdaoui et al., 2008; Hameed and El-Khaiary, 2008a; Khat- 618 nm. Then, the calibration plot was constructed. The cali-
tri and Singh, 2009; Mittal, 2006; Pradeep Sekhar et al., 2009; bration was repeated ve times during the period of measure-
Sonawane and Shrivastava, 2009). Undoubtedly, agricultural ments. The linearization of this plot usually provided
waste biomass is presently one of the most challenging topics,
which is gaining stern considerations during the past several
decades. In perspective, potato peel has emerged to be an
invaluable source.
O
Potato peel (PP), agricultural and easily available waste,
N
could be an alternative for more costly wastewater treatment O
processes. Losses caused by potato peeling range from 15% OH
to 40% their amount depending on the procedure applied,
i.e. steam, abrasion or lye peeling (Scieber et al., 2001). Plants O 2
peel the potatoes as part of the production of French fries,
crisps, puree, instant potatoes and similar products. The pro-
duced waste is 90 kg per Mg of inuent potatoes and is appor- O
tioned to 50 kg of potato skins, 30 kg starch and 10 kg inert
material. The problem of the management of PP causes consid- HO
Please cite this article in press as: Guechi, E.-K., Hamdaoui, O. Sorption of malachite green from aqueous solution by potato peel: Kinet-
ics and equilibrium modeling using non-linear analysis method. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.05.011
Sorption of malachite green from aqueous solution by potato peel: Kinetics and equilibrium modeling using non-linear
determination coefcient close to 99.99%. These data were Each run of the experiments was replicated at least two
used to calculate the sorption capacity of the biosorbent. In times and the mean values were reported. The maximum stan-
most cases, a proper dilution was necessary to obtain a well dard deviation obtained for duplicate or triplicate measure-
measurable absorption. ments of the sorbed amount was 2%.
The initial concentration of MG solution was 50 mg L1 for all 3.1. Effect of operational parameters
experiments, except for those carried out to examine the effect
of the initial dye concentration. For dye removal kinetic exper- The inuence of several operational parameters such as initial
iments, the batch method was used because of its simplicity: dye concentration, sorbent dosage, pH, stirring speed, temper-
0.25 g of biosorbent was contacted with 100 mL of dye solu- ature, ionic strength and particle size on the sorption of MG
tion in a sealed ask agitated vigorously by a magnetic stirrer by PP was investigated.
using a water bath maintained at a constant temperature. The
stirring speed was kept constant at 400 rpm, except for exper- 3.1.1. Effect of initial dye concentration
iments carried out to investigate the effect of stirring speed. At The effect of initial dye concentration on the sorption of MG
predetermined intervals of time, samples of the mixture was by PP at 25 C is shown in Fig. 2. It can be observed that the
withdrawn at suitable time intervals and analyzed by a UV sorption capacity increased with time and, at some point in
visible spectrophotometer for the concentration of MG. time, reached a constant value where no more dye was re-
The experiments were performed at the pH that resulted moved from the solution. At this point, the amount of MG
from solving the dye in water (around 4) without further being sorbed by the sorbent was in a state of dynamic equilib-
adjustment, except for those conducted to examine the effect rium with the amount of MG desorbed from the sorbent. It
of solution pH. was observed that an increase in initial dye concentration leads
To study the effect of solution pH on MG sorption, 0.25 g to an increase in the sorption of MG by PP. It was observed
of PP was agitated with 100 mL of MG solution of dye concen- that the MG removal varied with varying initial dye concentra-
tration 50 mg L1 at 25 C. The experiment was conducted at tion. It was noticed that an increase in initial dye concentration
different pH values ranging from 2 to 8. The solution pH was leads to an increase in the sorption capacity of MG by PP.
adjusted using 0.1 N HCl or NaOH aqueous solutions. Agita- Equilibrium uptake increased with the increase of initial dye
tion was provided for a period which is sufcient to reach equi- concentration at the range of experimental concentration.
librium with a constant agitation speed of 400 rpm. The amount of MG sorbed at equilibrium increased from
The effect of temperature on the sorption of MG was stud- 1.64 to 10.29 mg g1 as the concentration was increased from
ied by contacting 0.25 g of sorbent with 100 mL of dye solu- 5 to 50 mg L1. The initial rate of sorption was greater for
tion of 50 mg L1 initial concentration at different higher initial MG concentration, because the resistance to
temperatures (2545 C). the dye uptake decreased as the mass transfer driving force in-
The inuence of ionic strength on the sorption of MG by creased. It is also noticed that as the initial dye concentration
PP was studied with a constant initial concentration of increased, the equilibrium removal of MG decreased. This ef-
50 mg L1, sorbent mass of 0.25 g, solution volume of fect can be explained on the basis of the dye/sorbent ratio. At
100 mL, and temperature of 25 C. The ionic strength of the
dye solution was modied using different dosages of NaCl
(0.252 g (100 mL)1).
12
In all the experiments in which the effect of stirring speed -1
5 mg L
was studied, the initial MG concentration, sorbent mass and 10 mg L
-1
Please cite this article in press as: Guechi, E.-K., Hamdaoui, O. Sorption of malachite green from aqueous solution by potato peel: Kinet-
ics and equilibrium modeling using non-linear analysis method. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.05.011
4 E.-K. Guechi, O. Hamdaoui
low dye/sorbent ratios, there are number of sorption sites in increasing sorbent dosage. Additionally, this decrease may be
PP structure. As the dye/sorbent ratio increases, sorption sites attributed to overlapping or aggregation of sorption sites
are saturated, resulting in a decrease in the sorption efciency. resulting in decrease in total sorbent surface area available to
It is also shown in Fig. 2 that the contact time needed for dye molecules and an increase in diffusion path length.
MG solutions with initial concentrations of 50 and 40 mg L1
to reach equilibrium was 210 and 180 min, respectively. For 3.1.3. Effect of initial pH
MG solution with initial concentrations in the range of 5 Fig. 4 shows the effect of pH on the sorption of MG by PP. It
30 mg L1, equilibrium time of 150 min was required. This is can be seen that the decrease in the sorption with decrease in
due to the fact that sorption sites took up the available dye mol- pH. As pH of the system decreased, the number of negatively
ecules more quickly at low concentration, but dye needed to dif- charged sorption sites decreased and the number of positively
fuse to the inner sites of the sorbent for high concentration. The charged surface sites increased, which did not favor the sorp-
kinetic results also showed that the curves of contact time are tion of positively charged dye cations due to electrostatic
single, smooth and continuous leading to equilibrium. These repulsion. Additionally, lower sorption of MG at acidic pH
curves indicate the possible monolayer coverage of dye on the is due to the presence of excess H+ ions competing with dye
surface of PP. cations for the sorption sites of PP (Hamdaoui, 2006). Similar
result was reported for the sorption of MG by rice straw-de-
3.1.2. Effect of biosorbent dose rived char (Hameed and El-Khaiary, 2008b).
The mass of sorbent was varied in the range of 0.251 g for the
removal of MG from aqueous solution by PP. In these series of 3.1.4. Effect of stirring speed
experiments, the concentration of MG in solution was xed at Agitation is a classic parameter in sorption phenomena, inu-
50 mg L1. The effect of sorbent dose on the sorption kinetics encing the distribution of the solute in the bulk solution and
of MG by the biosorbent is shown in Fig. 3. The amount of the formation of the external boundary lm. Fig. 5 shows
dye sorbed per unit mass of sorbent decreases with an increase the sorption of MG by PP at different stirring speeds ranging
in sorbent dose. The increase in sorbent dose at constant dye from 0 (without stirring) to 800 rpm. The obtained results
concentration and volume will lead to unsaturation of sorption show that the high sorption rate and capacity were obtained
sites through the sorption process. At higher PP to solute con- with a stirring speed of 400 rpm. This agitation speed assures
centration ratios, there is a fast supercial sorption onto the a good diffusion of dye cations toward biosorbent particles.
sorbent surface that produces a lower solute concentration in For the experiment conducted without agitation, it is noticed
the solution than when the sorbent to solute concentration ratio a signicant reduction of the sorption. The amount of dye
is lower. This is because a xed mass of PP can only sorb a cer- sorption increases with the increase of the stirring speed from
tain amount of dye. Therefore, the higher the sorbent dosage is, 0 to 400 rpm. When increasing the agitation speed, the diffu-
the larger the volume of efuent that a xed mass of sorbent can sion rate of dye molecules from the bulk liquid to the liquid
purify. The decrease in the amount of MG sorbed with increas- boundary layer surrounding particles became higher because
ing sorbent mass is due to the split in the ux or the concentra- of an enhancement of turbulence and a decrease of the thick-
tion gradient between solute concentrations in the solution and ness of the liquid boundary layer. Finally, the boundary layer
on the sorbent surface. Thus, with increasing sorbent dosage, became very thin and approached the laminar sublayer at high
the amount of dye sorbed by unit weight of sorbent gets agitation speeds. On the other hand, for a high stirring speed
reduced, thus causing a decrease in sorption capacity with of 800 rpm, a signicant reduction of sorption was observed.
12 16
0.25 g
0.35 g 14
10 0.5 g
0.75 g
1g 12
8
10
q (mg g )
q (mg g )
-1
-1
6 8 pH 2
pH 4
pH 6
6 pH 8
4
2
2
0 0
0 50 100 150 200 250 0 50 100 150 200 250 300 350
Time (min) Time (min)
Figure 3 Effect of sorbent dosage on the sorption of MG by PP Figure 4 Effect of initial pH on the sorption of MG by PP
(conditions: initial dye concentration = 50 mg L1; stirring (conditions: initial dye concentration = 50 mg L1; sorbent dos-
speed = 400 rpm; T = 25 C; pH 4). age = 0.25 g (100 mL)1; stirring speed = 400 rpm; T = 25 C).
Please cite this article in press as: Guechi, E.-K., Hamdaoui, O. Sorption of malachite green from aqueous solution by potato peel: Kinet-
ics and equilibrium modeling using non-linear analysis method. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.05.011
Sorption of malachite green from aqueous solution by potato peel: Kinetics and equilibrium modeling using non-linear
12
12 -1
0 g NaCl (100 mL)
-1
10 0.25 g NaCl (100 mL)
-1
2 g NaCl (100 mL)
10
8
8
q (mg g )
-1
6
q (mg g )
-1
6 25C
35C
45C 4
4
2
2
0
0 50 100 150 200 250
0
0 50 100 150 200 250 Time (min)
Time (min)
Figure 7 Effect of salt (NaCl) concentration on the sorption of
Figure 6 Effect of temperature on the sorption of MG by PP MG by PP (conditions: initial dye concentration = 50 mg L1;
(conditions: initial dye concentration = 50 mg L1; sorbent dos- sorbent dosage = 0.25 g (100 mL)1; stirring speed = 400 rpm;
age = 0.25 g (100 mL)1; stirring speed = 400 rpm; pH 4). T = 25 C; pH 4).
Please cite this article in press as: Guechi, E.-K., Hamdaoui, O. Sorption of malachite green from aqueous solution by potato peel: Kinet-
ics and equilibrium modeling using non-linear analysis method. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.05.011
6 E.-K. Guechi, O. Hamdaoui
12 12
-1
5 mg L First order
10 mg L
-1 Second order
10 10 20 mg L
-1 nth order
-1
40 mg L
-1
50 mg L
8 8
q (mg g )
q (mg g )
-1
-1
6 6
0.18-0.5 mm
4 0.5-1.25 mm 4
1.25-2 mm
2 2
0 0
0 50 100 150 200 250 0 50 100 150 200 250
Time (min) Time (min)
Figure 8 Effect of biosorbent particle size on the sorption of Figure 9 Comparison of experimental and predicted kinetics for
MG by PP (conditions: initial dye concentration = 50 mg L1; the biosorption of MG by PP at various initial dye concentrations.
sorbent dosage = 0.25 g (100 mL)1; stirring speed = 400 rpm;
T = 25 C; pH 4). tion in which the order of sorption kinetics is not preset to a
xed value. Following Liu and Shen (2008) the sorption reac-
3.2. Modeling of sorption kinetics tion order is expressed with regard to the so-called effective
concentration of the sorption sites available on the surface
Various sorption kinetic models have been used to describe the (which is a function of the amount sorbed at a given time
uptake of sorbate depending upon the time. Understanding of and equilibrium). The simplicity of such an approach leads di-
biosorption kinetics is much less than theoretical description of rectly to both the pseudo-rst and the pseudo-second order
biosorption equilibrium. The pseudo-rst order kinetic equa- equations when the order of assumed reaction is preset to 1
tion or the so-called Lagergren equation has the following for- and 2, respectively. The rate equation for this model can be
mulation (Lagergren and Sven, 1898): written as follows:
dq dq
k1 qe q 2 kn qe qn 3
dt dt
where k1 is the pseudo-rst order rate constant (min1), qe is in which kn is a constant and n is the sorption reaction order
the amount of sorbate sorbed at equilibrium (mg g1), q is with regard to the effective concentration (Liu and Shen,
the amount of sorbate on the surface of bisorbent at any time 2008). The n parameter value can be both integer and rational
t (mg g1) and t is the time (min).Ozer (2007) and Liu and non-integer numbers.If n equals 1, integrated form of Eq. (3)
Shen (2008) have proposed to treat the pseudo-second order for the boundary conditions q = 0 when t = 0 and q = q
equation as a special case of the more general rate law equa- when t = t, will give Eq. (4).
Table 1 Pseudo-rst, pseudo-second and pseudo-nth order kinetic models constants and determination coefcients for the sorption of
MG by PP.
5 mg L1 10 mg L1 20 mg L1 30 mg L1 40 mg L1 50 mg L1
Pseudo-rst order model
k1 (min1) 103 50.62 43.34 36.33 25.95 27.70 22.61
qe (mg g1) 1.64 3.27 6.10 8.02 8.72 10.20
R2 0.998 0.998 0.995 0.994 0.996 0.988
APE (%) 2.05 2.14 3.74 4.73 3.77 7.41
Pseudo-second order model
k2 (g mg1 min1) 103 37.82 15.69 6.74 3.04 3.17 2.04
qe (mg g1) 1.82 3.68 6.94 9.54 10.24 12.28
R2 0.985 0.992 0.986 0.980 0.995 0.996
APE (%) 6.73 4.30 5.25 8.12 3.18 3.43
Pseudo-nth order model
kn (min1) (mg g1)1n 103 50.62 37.67 34.25 41.03 17.26 0.26
n 1.07 1.19 1.04 0.71 1.25 2.71
qe (mg g1) 1.64 3.32 6.12 7.90 8.99 14.13
R2 0.998 0.999 0.995 0.995 0.997 0.996
APE (%) 1.86 1.34 3.67 3.38 3.22 2.49
Please cite this article in press as: Guechi, E.-K., Hamdaoui, O. Sorption of malachite green from aqueous solution by potato peel: Kinet-
ics and equilibrium modeling using non-linear analysis method. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.05.011
Sorption of malachite green from aqueous solution by potato peel: Kinetics and equilibrium modeling using non-linear
35 35
25C 35C
30 30
25 25
q (mg g )
q (mg g )
-1
-1
20 20
Experimental
e
e
Langmuir
Experimental
Freundlich
Langmuir
15 15 Redlich-Peterson
Freundlich
Redlich-Peterson
10 10
5 5
0 100 200 300 400 500 0 100 200 300 400 500
-1 -1
C (mg L ) C (mg L )
e e
35
45C
30
25
q (mg g )
-1
Experimental
e
20 Langmuir
Freundlich
Redlich-Peterson
15
10
0 100 200 300 400 500
-1
C (mg L )
e
Figure 10 Comparison between the experimental and predicted isotherms for the biosorption of MG by PP (conditions: initial dye
concentration = 50500 mg L1; sorbent dosage = 0.25 g (100 mL)1; stirring speed = 400 rpm; pH 4).
Please cite this article in press as: Guechi, E.-K., Hamdaoui, O. Sorption of malachite green from aqueous solution by potato peel: Kinet-
ics and equilibrium modeling using non-linear analysis method. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.05.011
8 E.-K. Guechi, O. Hamdaoui
method. From Fig. 9 and Table 1, it seems that the pseudo-nth can be dened as the sorption or distribution coefcient and
order model t the experimental data well and was best than represents the quantity of dye sorbed by the sorbent for a unit
the pseudo-rst and pseudo-second order equations because equilibrium concentration.The RedlichPeterson equation
of the low average percentage error values and good coef- (Redlich and Peterson, 1959) is widely used as a compromise
cients of determination. The order of sorption reaction n was between Langmuir and Freundlich systems. This model has
found to be between 0.71 and 2.71. three parameters and incorporates the advantageous signi-
cance of both models. RedlichPeterson model can be repre-
3.3. Equilibrium isotherms sented as follows:
Table 2 Langmuir, Freundlich and RedlichPeterson isotherm models constants and determination coefcients for the sorption of
MG by PP at three different temperatures.
Model Parameters
qm (mg g1) b (L mg1) 103 R2 APE (%)
Langmuir (C)
25 32.39 17.89 0.983 4.55
35 34.62 18.06 0.985 4.32
45 35.61 18.60 0.988 3.85
1 1
KF (mg1n Ln g1 ) n R2 APE (%)
Freundlich (C)
25 4.47 3.17 0.950 6.91
35 4.77 3.16 0.939 8.02
45 4.94 3.16 0.958 6.57
A (L g1) B (L mg1)b 103 b R2 APE (%)
RedlichPeterson (C)
25 0.66 28.15 0.95 0.984 4.35
35 0.62 16.96 1.00 0.985 4.32
45 0.78 33.02 0.93 0.990 3.54
Please cite this article in press as: Guechi, E.-K., Hamdaoui, O. Sorption of malachite green from aqueous solution by potato peel: Kinet-
ics and equilibrium modeling using non-linear analysis method. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.05.011
Sorption of malachite green from aqueous solution by potato peel: Kinetics and equilibrium modeling using non-linear
-24,5
-1
Please cite this article in press as: Guechi, E.-K., Hamdaoui, O. Sorption of malachite green from aqueous solution by potato peel: Kinet-
ics and equilibrium modeling using non-linear analysis method. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.05.011