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Journal of the Taiwan Institute of Chemical Engineers

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Batch adsorption of cephalexin antibiotic from aqueous solution by

walnut shell-based activated carbon
Ghadir Nazari a, Hossein Abolghasemi a,b,∗, Mohamad Esmaieli a
a
Center for Separation Processes Modeling and Nano-Computations, School of Chemical Engineering, College of Engineering, University of Tehran,
P.O. Box 11365-4563, Tehran, Iran
b
Oil and Gas Center of Excellence, University of Tehran, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: The batch adsorption experiments were investigated for the adsorption of cephalexin (CFX) antibiotic on wal-
Received 8 February 2015 nut shell activated carbon (AC). The adsorbent was prepared by chemical activation method in the presence
Revised 1 June 2015
of ZnCl2 . Several adsorption parameters including the adsorbent dosage, the initial CFX concentration, con-
Accepted 7 June 2015
tact time, temperature, and pH were studied. The adsorption isotherm was analyzed by different isotherm
Available online xxx
models. It was found that the Freundlich and Toth models provided the best fit for the experimental data for
Keywords: two and three parameter models, respectively. The maximum adsorption capacity was obtained 233.1 mg/g
Batch adsorption based on the Langmuir model. The kinetic data were well represented by pseudo-second order model. Ther-
Cephalexin antibiotic modynamics analysis showed endothermic nature of CFX adsorption on walnut shell AC under examined
Walnut shell conditions.
Chemical activation © 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Activated carbon

1. Introduction ufacture of AC. The cost of AC production significantly depends on

Drugs are synthetic or natural substance that provides signif-
icant advantages to society. The entrance of drugs into the envi-
ronment occur through various waste streams such as households,
hospitals, and pharmaceutical companies, constitutes an emerging
environmental issue that needs to be effectively addressed. Treat-
ment processes such as activated sludge [1], ozonation and biomem-
brane [2] biological filtration [3], and reverse osmosis [4] have been
applied to remove pharmaceuticals from wastewater. In this regard,
adsorption is a simple and effective process, can be used as an effi-
cient method in removal of pharmaceuticals from water and wastew-
ater. Cephalosporins are one of the most widely used antibiotics,
which are divided into four major groups based on the antimicro-
bial activity. Cephalexin (CFX) is considered as the first-generation
cephalosporin antibiotic that is used to treat a number of infections.
The adsorption of CFX, has been studied using several adsorbents like
activated carbon (AC) [5–8], multi-walled carbon nanotubes [9], ben-
tonite [10], and polymeric resins [11]. Nowadays, research has been
focused on the production of AC adsorbent because of AC high ad-
sorption properties. AC is a non-graphite form of carbon which could
be produced from any carbonaceous material. Chemical activation
and steam activation are two commonly used processes for the man-
the precursor of AC. In this regard, the production of AC has been in-
vestigated with inexpensive material such as waste potato residue,
almond shell, waste rice hulls and seaweed [12–15]. Walnut shell is
considered as a good candidate for conversion to AC due to its rela-
tively high carbon content. Besides, the initial costs are relatively low.
The aim of this study is to evaluate the performance of AC prepared
from walnut shell for the removal of CFX in the batch process. In the
present work, the influence of different parameters like adsorption
isotherm, adsorption kinetic, adsorption thermodynamic and pH ef-
fect on the CFX adsorption using walnut shell AC, were studied.
2. Materials and methods
2.1. Materials
In this study, walnut shell was used as the raw material (with
the composition of cellulose (38.7%), lignin (24.7%), hemicellulose
(18.4%), extractable material (7.5%), ash (2.6%) and moisture (8.1%)).
Zinc chloride (ZnCl2 ) was supplied by Merck Company. Cephalexin
(CFX) (supplied by LOGHMAN Pharmaceutical & Hygienic Co., Tehran,
Iran) of purity 99.8% was used as an adsorbate. Table 1 shows the
properties of CFX.

∗
2.2. Preparation and characterization of the adsorbent
Corresponding author. Tel.: +98 21 61112186; fax: +98 21 66954051.
E-mail addresses: ghadir_nazari@alumni.ut.ac.ir, ghadir_nazari@yahoo.com
(G. Nazari), hoab@ut.ac.ir, Abolghasemi.ha@gmail.com (H. Abolghasemi), Walnut shell was washed with distilled water for several times
esmaili@ut.ac.ir (M. Esmaieli). to remove dust and other inorganic impurities and dried, crushed,
http://dx.doi.org/10.1016/j.jtice.2015.06.006
1876-1070/© 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: G. Nazari et al., Batch adsorption of cephalexin antibiotic from aqueous solution by walnut shell-based activated
carbon, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.06.006
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Table 1
Properties of CFX.

Chemical structure Molecular formula Molecular weight (g/mol)

S
H

HN N OH

O
H2N O O C16 H17 N3 O4 S 347.6

and sieved to a particle size of 251–354 nm. For the production of
AC, walnut shell (5 g) was mixed to 40 mL of ZnCl2 solution at 1–1
impregnation ratio (defined by the weight ratio of ZnCl2 to walnut
shell) and was stirred for 6 h. The mixture was dried in an oven at
105° C for 24 h. Then, it was placed in a vertical stainless-steel reactor
(length 1 m and internal diameter of 1 m) under high-purity nitro-
gen (99.99%) and flow rate of 300 cm3 /min to a final temperature of
450 °C at a heating rate of 5°C/min and was kept at this temperature
for 1 h to be activated. The sample dried completely in an oven at
105 °C, and then it was washed with a 0.05 M HCl solution to remove
the residual ZnCl2 , repeatedly. Subsequently, the sample was washed
with distilled water until the pH value of the washed solution was
between 6 and 7. Finally, the resulting ACs were dried in an oven at
105 °C for 24 h, and used [16]. The yield of prepared walnut shell AC
was calculated based on the following equation:
WAC
YAC (% ) = × 100
WWS
where WAC and WWS are the weights of carbon product, and dried
pods. The textural characterization of the walnut shell AC was carried
out by N2 adsorption at 77 K. The specific surface area was calculated
from the isotherms using the Brunauer–Emmett–Teller (BET) equa-
tion. Total pore volume using nitrogen vapor adsorption data in the
relative pressure of 0.95 and average pore diameter using the Barrett,
Joyner, Halenda (BJH) equation, were determined. The FTIR spectra
of the walnut shell AC was recorded from a wavenumber of 400–
4000 cm−1 by Fourier transform infrared spectroscopy. Another an-
alyzed to investigate the morphology of the sample was obtained by
scanning electron microscopy (SEM) test.
2.3. Determination of point of zero charge (pHpzc )
The zero surface charge characteristics of the walnut shell AC were
determined using the solid addition method [17,18]. For this purpose,
60 mL of 0.1 M KNO3 solution was prepared in different flasks. Their
pH was roughly adjusted between 2 and 12 by adding either 0.1 N
HCl or NaOH and measured using pH meter. The total volume of the
solution in each flask was exactly adjusted to 50 mL by adding KNO3
solution of the same strength. The pHi of the solutions was accurately
noted. Next, 0.03 g of walnut shell AC was added to each flask and the
suspensions were placed in a shaker for 24 h and allowed to equili-
brate for 1 h. The final pH values (pHf ) of the supernatant liquid were
noted. The difference between the initial and final pH values (࢞pH)
was plotted versus the pHi . The point of intersection of the resulting
curve with the axis of abscissas, resulted in the pHpzc .
2.4. Effect of initial solution pH
The effect of initial solution pH on the CFX removal was studied in
the pH range of 1.5–8.5. The pH was adjusted by adding a few drops
of 1.0 N NaOH or 1.0 N HCl. In this study, 50 mL of a fixed initial con-
centration of CFX at different pH values was agitated with 0.03 g of
walnut shell AC adsorbent for 20 h.
2.5. Adsorption equilibrium isotherm
The adsorption of CFX on walnut shell AC adsorbent was studied
using the batch adsorption technique. The adsorption experiments
have been conducted using 50 mL of CFX solution of different initial
concentrations (100, 125, 150, 175 and 200 mg/L). The solutions were
mixed with 0.03 g walnut shell AC in 100 mL Erlenmeyer flasks. All
experiments were performed at the optimum pH (pH 6.5) by adding
0.1 M HCL and NaOH solutions. The flasks were placed in a shaker at
a constant speed of 200 rpm and 30 °C for 20 h to reach equilibrium.
Then, the samples were placed in a centrifuge for 30 min at 4000 rpm.
The concentrations of CFX at equilibrium (Ce ) were determined by
UV-2100 spectrometer at a wavelength of 263 nm. The amount of CFX
adsorbed onto walnut shell AC (qe ) can be calculated as below:
(C0 − Ce )V
qe = (2)
W
(1) where C0 and Ce (mg/L) are the initial and the equilibrium concentra-
tions of CFX, respectively. V (L) is the volume of the solution and W (g)
is the mass of the adsorbent. The optimum amount of the adsorbent
dosage was investigated using different amounts of the adsorbent
(5–40 mg) at a concentration of 100 mg/L.
2.6. Adsorption kinetics
The reaction order and rate constants are two important factors in
the design of adsorption process that are determined using adsorp-
tion kinetics. The pH values, temperature and adsorbent dosage were
identical for all of the equilibrium experiments. The amount of CFX
adsorbed on walnut shell AC can be calculated as below:
(C0 − Ct )V
qt = (3)
W
where Ct (mg/L) is the concentration of the CFX solution at time
t (min).
The standard deviations (SD) of all experimental data points were
calculated according to the equation below and the values were
shown graphically as error bars in the figures

1 N
SD = (xi − μ )2 (4)
N i=1
where N and μ are the number and the average of the experimental
data, respectively.
2.7. Adsorption thermodynamics
For determination of the thermodynamic data, such as enthalpy,
entropy and Gibbs free energy provide further information about the
thermodynamics of the system. Thermodynamic parameters for the
adsorption of CFX on walnut shell AC are determined by the following
equations:
Cs
Kc = (5)
Ce
S ◦ H ◦
ln Kc = − (6)
R RT

Please cite this article as: G. Nazari et al., Batch adsorption of cephalexin antibiotic from aqueous solution by walnut shell-based activated
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Fig. 1. SEM image of the walnut shell AC adsorbent before (a) and after (b) adsorption.

Table 2
Characteristics of the walnut shell AC.

YAC (%) Surface area (m2 /g) Total pore volume (cm3 /g) Average pore diameter (nm)

41.3 1.452e+03 7.151e–01 1.970e+00

G◦ = −RT ln Kc (7)

in the above equations R is universal gas constant, Kc is the equilib-

rium constant and T is the temperature of the system. Cs and Ce are
the adsorbate concentrations on the adsorbent surface and in the so-
lution at equilibrium, respectively.

3. Results and discussion

3.1. Yield and characteristics of the adsorbent

YAC , specific surface area, total pore volume and average pore di-
ameter of prepared AC are shown in Table 2. The SEM analysis of
walnut shell AC, before and after adsorption is illustrated in Fig. 1.
From Fig. 1, the pores of the adsorbent after adsorption, filled with
CFX molecules. For determination of bonds in the synthesized ad-
sorbent, before and after adsorption using FTIR analysis. The FTIR
spectra of walnut shell AC prepared under vacuum condition at
Fig. 2. FTIR spectra of the walnut shell AC.
400 °C in the range of 400–4000 cm−1 before and after adsorption
(Fig. 2). Fig. 2 shows that some peaks are shifted or disappeared
and some new peaks are also detected. It indicates the possible in-
volvement of those functional groups on the surface of the walnut
decrease in the CFX adsorption capacity with increasing dosage of
shell AC in the adsorption process. The FTIR results are shown in
the adsorbent is essentially due to remaining unsaturated sites dur-
Table 3 [19–21].
ing the adsorption process [19]. For the quantitative removal of CFX,
a maximum dose of 0.6 g/L of the adsorbent is required.
3.2. Effect of adsorbent dosage

The effect of adsorbent dosage on the CFX removal efficiency from
aqueous solution is shown in Fig. 3. It reveals that the removal of CFX
increases up to a certain limit (0.03 g) and then it remains almost con-
stant. An increase in the removal efficiency with adsorbent dosage
can be attributed to increase in the surface area and the availability
of more adsorption sites [17]. However, with enhancement of adsor-
bent dose, adsorption capacity decreased considerably (Fig. 4). The
3.3. Determination of point of zero charge (pHpzc )
As shown in Fig. 5, pHpzc for walnut shell AC was obtained at 6.67.
In this regard, walnut shell AC at pH values less and more than 6.67
demonstrates cationic and anionic behavior, respectively. The pHpzc
can be used to determine the quality of the relation between pH and
CFX adsorption value.

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Table 3
FTIR analysis of the walnut shell AC.

IR peak Frequency (cm−1 ) Difference Assignment

Before adsorption After adsorption

1 467 NA – O–H out-of-plane bending

2 NA 683 – O–H out-of-plane bending and C–Cl stretch (strong)
3 710 NA – –C–H bending and C–Cl stretch (strong)
4 891 NA – –C–H out-of-plane bending
5 1044 1050 –6 –C–O stretch (strong)
6 NA 1378 – –N–O stretch (strong)
7 1525 1524 +1 –N–O stretch (strong, two bonds) nitro
8 1630 NA – C=C stretching
9 1696 NA – –C=O stretch (strong) amide
10 1742 1748 −6 –C=O stretch and stretch (strong)
11 2355 2353 +2 –C≡C stretching
12 2924 2926 −2 –CH stretch (strong)
13 3451 3440 +11 –OH stretch, H-bonded
14 3742 3741 +1 –NH2 stretching
15 3853 3846 +7 NA

Fig. 3. Effect of adsorbent dose on the removal of CFX on the walnut shell AC (T = 30o C Fig. 5. Determination of the point of zero charge of the walnut shell AC.
and C0 = 100 mg/L).

Fig. 6. Effect of pH on equilibrium uptake of CFX (T = 30 o C and C0 = 150 mg/L).

Fig. 4. The effect of adsorbent dosage on the CFX removal efficiency.

tained at a pH value of 6.5. At pH values higher than 6.88, physisorp-

3.4. Effect of initial solution pH
The effect of initial solution pH on the adsorption of CFX was
studied in the pH range of 1.5–8.5 (Fig. 6). At pH values less than
2.56, physisorption is thought to dominate the adsorption process.
The reason can be the positively charged surface of the adsorbent at
pH values less than the pHpzc (6.67). The zwitterionic form of CFX
molecules is predominant at pH values ranging from 2.56 to 6.88
(Fig. 7). As the pH value increases, the concentration of negatively
charged CFX species in the solution bulk rises up. Accordingly, both
the chemi- and physisorption control the adsorption of CFX, so that
the maximum adsorption capacity approximately 219.25 mg/g is ob-
tion may be responsible for the adsorption of CFX because the surface
of walnut shell AC at pH values higher than the pHpzc (6.67) is neg-
atively charged. It should be noted that while the net surface charge
of the adsorbent may be predominantly negative or positive, some
oppositely charged surface sites can still simultaneously exist in the
adsorbent.
3.5. Adsorption equilibrium isotherm
The adsorption equilibrium isotherm of CFX on the walnut shell
AC was prepared and shown in Fig. 8. Adsorption curves have cat-
egorized based on classification proposed by Giles et al. [22]. Based

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pH 2.56 2.56 pH 6.88 pH 6.88

S S S
H H H
k a1 k a2
HN N OH HN N HN N O
O

O O
O O O O O
H3N H3N O O H2 N

CFX, cationic form CFX, zwitterionic CFX, anionic form

Fig. 7. Molecular structure of CFX and its ionic forms as a function of pH.

Table 4
Adsorption isotherm parameters of CFX.

Model Model parameters R2 AR2 RMSE

Langmuir qm = 233.1, b = 1.355 0.8328 0.8312 15.170

Freundlich KF = 155.2, n = 8.772 0.9913 0.9884 3.459
Sips Ks = 172.28, as = 11.41, qm = 1510, β s = 0.1322 0.9912 0.9824 4.272
Toth KT = 155.1, aT = 1.1 × 10– 12 , t = 1.129 0.9913 0.9884 3.459

KsCe βs
Sips model qe = (10)
1 + αsCe βs

Fig. 8. The equilibrium adsorption isotherm of CFX on the walnut shell AC.
on the Giles et al. classification, adsorption isotherms are classified
in four groups of L, S, H and C. Accordingly, isotherm curves of CFX
on the walnut shell AC demonstrate the H-type curves pattern. The
H-type curves are a special case of L-type curves and specify that
the adsorbent surface has a high affinity for adsorption the solute. The
Langmuir and Freundlich isotherm two-parameter models and the
Sips and Toth isotherm three-parameter models, were used for better
analysis the experimental isotherm data. The Langmuir model [23]
assumes monolayer adsorption (the adsorbed layer is one molecule
in thickness), and adsorbent surface is homogenous [24]. The Fre-
undlich isotherm [25] is an empirical model, can be applied to mul-
tilayer adsorption, with non-uniform distribution of adsorption heat
and affinities over the heterogeneous surface. The Sips model [26]
is a combined form of the Langmuir and Freundlich expressions de-
duced for predicting the heterogeneous adsorption systems [27]. The
Toth isotherm model [28], is another empirical equation developed
to improve the Langmuir isotherm fittings (experimental data), and
useful in explaining heterogeneous adsorption systems, which satis-
fying both low and high-end boundary of the concentration [29]. The
mathematical forms of these equations can be written as:
qm bCe
Langmuir model qe =
1 + bCe
Freundlich model qe = KFCe 1/n
KTCe
Toth model qe = (11)
(aT + Ce )1/t
where qm and qe (mg/g) is the maximum and equilibrium uptake of
CFX per unit mass of carbon, respectively. b (L/mg) is the adsorption
rate constant, KF ((mg/g).(L/mg)1/n and n are the Freundlich constants
which give a measure of adsorption capacity and intensity, respec-
tively. as (L/mg) and Ks (L/mg) are the Sips model constant and βs
is power this model. KT (mg/g), aT (mg/g) and t is the Toth model
constants. The validity of these models was evaluated by root mean
square error (RMSE) which is defined as


 n (q
e,exp − qe,cal )
2

n=1
RMSE = (12)
n
where n is the number of experimental data. The parameters, accu-
racy coefficient value, and RMSE for the adsorption of CFX on wal-
nut shell AC are presented in Table 4. It shows that the best fitting of
the experimental data for two and three-parameter isotherm mod-
els achieved by the Freundlich and Toth models, respectively. In this
study, the maximum adsorption capacity on the walnut shell AC was
obtained 233.1 mg/g based on the Langmuir isotherm model. This
value has been compared to those of CFX on different adsorbents in
Table 5 [5,6,8,11,30]. It can be seen from Table 5 that the maximum
adsorption capacity of the prepared walnut shell AC is more than
other adsorbents for the removal of CFX from aqueous solution at
mentioned conditions. Also, the comparison of adsorption capacities
for the removal of pharmaceutical compounds (like cephalexin, tetra-
cycline, amoxicillin, ciprofloxacin, etc.) from aqueous solution using
activated carbon from different precursors (such as walnut shell, lo-
tus stalk, lignin, pomegranate wood, etc.) is represented in the Table 6
[5,8,31–41]. For determining the characteristic of adsorption process,
a dimensionless constant, commonly known as separation factor (RL )
defined by Webber and Chakkravorti [42] can be correlated as
1
(8) RL = (13)
1 + bC0
where b (L/mg) refers to the Langmuir constant and C0 is defined to
(9) the adsorbate initial concentration (mg/L). In this regard, lower RL

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Table 5
The comparison of the maximum adsorption capacity of CFX onto different adsorbents.

Sorbent Activator T (K) pH T (h) Dose (g/L) qmax (mg/g) Ref.

Walnut shell AC ZnCl2 303 6.5 20 0.6 233.1 This work

Commercial-carbon Steam 298 7.0 24 1.0 230.9 [6]
Commercial-carbon Steam 298 3.0 24 1.0 222.3 [11]
Albizia lebbeck seed pods-carbon KOH 323 7.0 1.5 0.5 137.0 [5]
K2 CO3 303 7.0 1.5 0.5 118.1
Lotus stalks-carbon Cu(NO3 )2 293 8.5 60 0.4 78.1 [8]
Fe(NO3 )2 293 6.5 60 0.4 75.1
H3 PO4 293 4.5 60 0.4 66.2
Molecularly imprinted polymers – 298 7.0 3.0 1.0 39.7 [30]
Amberlite XAD7-resin – 298 3.0 24 2.0 33.0 [11]
Nonimprinted polymers – 298 8.0 3.0 1.0 17.7 [30]

Table 6
Comparison of adsorption capacities for the removal of pharmaceutical compounds from aqueous solutions
using activated carbon from different precursors.

Precursor Adsorbate Activator SBET (m2 /g) qmax (mg/g) Ref.

Lignin Tetracycline H3 PO4 931.5 475.5 [31]

Lotus stalk Norfloxacin H3 PO4 1289.1 456.6 [32]
Macadamia nut shells Tetracycline NaOH 1524.0 455.8 [33]
Pomegranate wood Amoxicillin NH4 Cl 1029.0 437.0 [34]
Lignin Ciprofloxacin H3 PO4 931.5 418.6 [31]
Cattail fiber Norfloxacin H3 PO4 907.0 310.7 [35]
Beet pulp Tetracycline Steam 821.0 288.0 [36]
Animal hairs Norfloxacin H3 PO4 382.0 285.5 [35]
Walnut shell Cephalexin ZnCl2 1452.0 233.1 This study
Siris seed pods Metronidazole KOH 1824.9 196.3 [37]
Siris seed pods Metronidazole K2 CO3 1676.2 180.7 [38]
Albizia lebbeck seed pods norfloxacin KOH 1824.9 167.0 [39]
Albizia lebbeck seed pods Cephalexin KOH 1824.9 137.0 [5]
Albizia lebbeck seed pods ciprofloxacin KOH 1824.9 131.1 [39]
Albizia lebbeck seed pods Cephalexin K2 CO3 1676.6 118.1 [5]
Lotus stalks Cephalexin H3 PO4 1031.8 66.2 [8]
Animal hairs Acetaminophen H3 PO4 382.0 61.8 [35]
Cattail fiber Acetaminophen H3 PO4 907.0 59.9 [35]
Olive waste cakes Diclofenac H3 PO4 793.0 56.2 [40]
Potato peels Pramipexole KOH – 56.0 [41]
Potato peels Dorzolamide KOH – 52.0 [41]
Olive waste cakes Naproxen H3 PO4 793.0 39.5 [40]
Peanut hulls Tetracycline Steam 829.0 28.0 [36]
Olive waste cakes Ketoprofen H3 PO4 793.0 24.7 [40]
Olive waste cakes Ibuprofen H3 PO4 793.0 12.6 [40]

concentration, RL is close to zero and adsorption reaction desire to

irreversibility.

3.6. Adsorption kinetics

Fig. (10a) shows the adsorption kinetics of CFX on walnut shell AC

for different initial concentration of 100, 125, 150, 175 and 200 mg/L
and at the optimum pH of 6.5. The equilibrium was reached af-
ter around 20 h of contact. The maximum adsorption capacities of
CFX 243.13 mg/g obtained at 200 mg/L initial concentration, 0.6 g/L
adsorbent dose and 6.5 pH values. The kinetic data were analyzed
by pseudo-first order and pseudo-second order models [43,44]. The
mathematical forms of these models were given as follows:

k1
log(qe − qt ) = log(qe ) − t (14)
Fig. 9. Plots of RL against initial concentration (C0 ). 2.303

t 1 t
= + (15)
qt k2 q2e qe
value reflects that adsorption is more favorable. In a deeper descrip-
tion, RL value indicates the adsorption nature to be either unfavor- where qe (mg/g) and qt (mg/g) are the amounts of adsorbate on the
able (RL > 1), linear (RL = 1), favorable (0 < RL < 1) or irreversible sorbents at equilibrium and time t, respectively. k1 (min−1 ) is the
(RL = 0). RL values obtained for different initial concentrations and pseudo-first-order rate constant of adsorption, while k2 (g/mg min)
indicating that the adsorption of CFX on the walnut shell AC is clas- is the rate constant of pseudo-second-order adsorption. The correla-
sified favorable process. As seen in Fig. 9, with increasing the initial tions of pseudo-first order and pseudo-second order kinetic models

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Fig. 10. The kinetics models for adsorption of CFX on the walnut shell AC: (a) experimental; (b) pseudo-first-order model; (c) pseudo-second-order model; (d) intra-particle
diffusion model (pH 6.5, T = 30 o C ).

Table 7
The comparison of results between pseudo-first order and pseudo-second-order kinetic model.

Pseudo-first-order kinetic model Pseudo-second-order kinetic model

C0 (ppm) k1 (min− 1 ) qe,cal (mg/g) R2 ࢞q (%) k2 × 104 (g/mg min) qe,cal (mg/g) R2 ࢞q (%)

100 0.004 85.541 0.978 12.365 1.896 166.6 0.999 0.385

125 0.005 106.165 0.922 11.695 1.748 200.0 0.998 0.789
150 0.004 84.268 0.968 15.910 1.481 250.0 0.999 3.579
175 0.004 102.920 0.940 14.475 1.495 250.0 0.999 1.736
200 0.003 102.003 0.924 14.984 1.720 250.0 0.999 0.729

to describe the adsorption process was further validated by the nor-
malized standard deviation, ࢞q (%), which is defined as:

[(qe,exp − qe,cal )/qe,exp ]
2
q = 100
N−1
where N, is the number of experimental data, qe,exp and qe, cal (mg/g)
are the experimental and calculated equilibrium adsorption capaci-
ties, respectively. The results of kinetics data analysis are summarized
in Table 7. The pseudo-first order model (Fig. 10b) has relatively low
R2 values for correlation of CFX adsorption kinetics data. Also, there is
a large deviation between the experimental and theoretical adsorp-
tion capacity represented by q (%), indicating a poor pseudo-first-
order model fit to the experimental data. The linear plot of t/qt versus
t (Fig. 10c) for pseudo-second-order model shows the high values of
R2 (Table 7). Moreover, the theoretical adsorption capacity values
were in agreement with the experimental adsorption capacity val-
ues for this model (Table 7). The results show that the pseudo-second
order model is the best model for representation of CFX kinetics data.
Pseudo-first order and pseudo-second order kinetics models, would
not provide any information about the penetration mechanisms. In
this regard, Weber and Morris were proposed intra-particle diffusion
model [45]. The mechanism of the particle into the adsorbent can
be determined using this model. The mathematical forms of intra-
particle diffusion model can be expressed as
qt = kid t 1/2 + I
where kid (mg/g min1/2 ) is the intra-particle diffusion rate constant,
and I (mg/g) is a constant that gives an indication of the thickness of
the boundary layer. The fitting plots of qt versus t1/2 for various ini-
tial CFX concentrations is shown in Fig. 10d. Fig. 10d shows the three
different stages proceed by surface sorption, intra-particle diffusion
(16) and a likely chemical reaction stage. The last step from mentioning
three steps is very fast and considered negligible [46]. The values of
kid and I for three stages were obtained through fitting the exper-
imental data with intra-particle equation and were summarized in
Table 8. The value of ki1 , ki2 and ki3 increased with enhancement of
the initial CFX concentration (Table 8). The driving force of diffusion
in the adsorption processes, is very important. Generally, the driving
force increases with increasing the CFX concentration in bulk solu-
tion. As a result, enhancement of the CFX concentration resulted in
an increase in driving force, which will raise the diffusion rate of the
molecular CFX in the pore [47]. The regression of qt versus t1/2 for
CFX was linear and did not pass through the origin, shows that the
boundary layer diffusion control in the adsorption process [48]. Given
the large I values of all kinetic studies indicates that the intra-particle
diffusion was involved in the adsorption process, however, is not the
sole rate-limiting step [46,49].
3.7. Adsorption thermodynamics
The effect of different temperatures on the CFX adsorption by wal-
nut shell AC has been studied at pH 6.5. Fig. 11, illustrates the linear
(17) plot of ln kc versus 1/T, where the H° and S° values are calculated
from the slope and intercept of the plot. The H°, S°, G° and kc pa-
rameters were calculated and summarized in Table 9. The G° values

Please cite this article as: G. Nazari et al., Batch adsorption of cephalexin antibiotic from aqueous solution by walnut shell-based activated
carbon, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.06.006
JID: JTICE
ARTICLE IN PRESS [m5G;July 6, 2015;11:54]

8 G. Nazari et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–9

Table 8
The results of intraparticle diffusion model.

Stage 1 Stage 2 Stage 3

C0 (ppm) k1d (g/mg min0.5 ) I (mg/g) R1 2 k2d (g/mg min0.5 ) I (mg/g) R2 2 k3d (g/mg min0.5 ) I (mg/g) R3 2

100 19.080 1.418 0.994 6.983 50.54 0.979 1.315 122.58 0.902
125 23.246 4.341 0.961 7.766 67.17 0.975 1.397 148.22 0.971
150 28.528 5.798 0.954 8.466 106.05 0.947 1.523 171.00 0.871
175 30.358 6.560 0.948 9.194 101.49 0.952 1.619 181.92 0.954
200 31.709 6.681 0.951 9.329 110.43 0.992 1.763 194.95 0.932

models provide the best fit to the experimental data for two and
three-parameter isotherm models, respectively. The adsorption ki-
netic data were well described by the pseudo-second-order model
at different initial concentrations. The equation of Weber and Mor-
ris was employed to evaluate the adsorption mechanism of CFX on
the walnut shell AC and the results indicated that the boundary
layer diffusion control the adsorption process. The thermodynamic
studies indicated that the adsorption of CFX onto walnut shell AC is
spontaneous and endothermic in nature and also the randomness at
solid/liquid interface increases with increasing temperature. Overall,
the results suggested that the walnut shell AC is an efficient adsor-
bent for application in treating cephalosporins existing in pharma-
ceuticals wastewater streams.
Fig. 11. Plots of ln KC against temperature (K−1 ).
Acknowledgments
Table 9
Thermodynamic adsorption parameters of CFX. The authors are really thankful to editor and anonymous review-
Temperature (k) Kc ࢞G° (KJ/mol) ࢞H° (kJ/mol) ࢞S° (kJ/mol) ers of the Journal of the Taiwan Institute of Chemical Engineers for
their precious comments and suggestions on this article. The authors
303.15 7.30 −4.96 would also like to acknowledge Mr. Ehsan Sadeghi Pouya and Mr.
308.15 9.57 −5.87
313.15 13.01 −6.78 50.114 0.1817
Seyed Adel Hosseini for their unwavering support.
318.15 21.02 −8.60
323.15 22.92 –9.51
References

were between –4.96 and –9.51 kJ/mol for CFX adsorption. This nega-
tive G° values indicate that a spontaneous physisorption take place
[50]. The enhancement of G° negative values with increase of tem-
perature indicates a rapid and more spontaneous at higher temper-
ature [50]. The endothermic nature of CFX sorption by walnut shell
AC confirmed by the positive values of H°. An adsorption process
is generally considered as physisorption if 8 < H° < 25 kJ/mol and
as chemi-adsorption if 83 < H° < 830 kJ/mol. When H° lied be-
tween 25 and 83 kJ/mol, both the chemi- and physisorption is re-
sponsible for the adsorption process [51]. Accordingly, we concluded
that CFX sorption by walnut shell AC (H° = +50.114 kJ/mol) is the
both chemi- and physisorption adsorption process. The positive value
of S° (Table 9) indicates an enhancement in the degree of freedom
of irregularities at the solid/liquid interface during the adsorption of
CFX on the walnut shell AC. Thus, the adsorption is favored on the
walnut shell AC [52,53].
4. Conclusion
In the present study, AC was prepared via chemical activation of
walnut shell with ZnCl2 . The walnut shell AC fabricated in our re-
search presented a remarkable yield (41.3%) and high surface area
(1452 m2 /g). In order to evaluate the adsorptive properties of wal-
nut shell AC, it was applied for the CFX removal. The optimum values
of adsorbent dosage and initial solution pH were found to be 0.6 g/L
and 6.5, respectively. The maximum adsorption capacity (qmax ) was
obtained about 233.1 mg/g, which is comparable to other adsor-
bent materials applied for the CFX removal. The results of equilib-
rium experiments indicated that the Freundlich and Toth isotherm
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