Separation and Purification Technology 39 (2004) 189–200

Removal of lead from aqueous solutions by natural clinoptilolite:

equilibrium and kinetic studies
Nihal Bektaş∗ , Serdar Kara
Environmental Engineering Department, Gebze Institute of Technology, Gebze 41400, Turkey
Received in revised form 26 November 2003; accepted 2 December 2003

Abstract

In this study, the removal of lead ions from aqueous solution using natural clinoptilolite under different experimental conditions
was investigated. The effects of the initial metal concentration, agitation speed, temperature and pH on the removal efficiency of
lead were studied. Langmuir and Freundlich isotherm constants and correlation coefficients for the present system at different
conditions were calculated and compared. The equilibrium process was described well by the Langmuir isotherm model with
the maximum sorption capacity of 166 mg/g of lead on clinoptilolite.
The sorption kinetics were tested for the first order reaction, intra-particle diffusion, pseudo-first order, and pseudo-second
order reaction at different experimental conditions. The rate constants of sorption for all these kinetic models were calculated.
Good correlation coefficients were obtained for the pseudo-second order kinetic model showing that lead uptake process followed
the pseudo-second order rate expression.
© 2003 Elsevier B.V. All rights reserved.

Keywords: Lead removal; Clinoptilolite; Equilibrium isotherm; Kinetics

1. Introduction for lead in drinking water is 10 ␮g/l [3,4]. The main

The sorption of pollutants from aqueous solution
plays an important role in wastewater treatments.
Well-designed sorption processes provide high qual-
ity effluent after treatment. Lead, one of the toxic
priority pollutants, belongs to the group metals with
atomic density greater than 6 g/ml. Lead can contam-
inate the environment from anthropogenic sources as
well as natural geochemical processes. It can accu-
mulate along the food chain and is not amenable to
biological degradation [1,2]. The EC and WHO limit
∗ Corresponding author. Tel.: +90-262-7542360;
fax: +90-262-6538490.
E-mail address: nihal@gyte.edu.tr (N. Bektaş).
industrial sources for lead include metal finishing,
mining, and mineral processes, and oil refining in-
dustries as well as motor vehicles that use petrol. The
treatment of lead contaminated water is similar to that
of many metal contaminated effluents. There are sev-
eral methods for treating metal contaminant effluent
such as ion exchange, adsorption, chemical precipi-
tation, oxidation, reduction, and reverse osmosis [5].
However, many of these approaches can be less cost
effective or difficult for practical use. Especially the
main disadvantages of the sorption methods are the
high price of the adsorbents, which increases the cost
of wastewater treatment. Therefore, there is a demand
for a treatment strategy that is simple, robust, and
which addresses local sources and regulations. Zeo-

1383-5866/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2003.12.001
190 N. Bektaş , S. Kara / Separation and Purification Technology 39 (2004) 189–200
lites are known as appropriate material for removing
heavy metal ions form wastewater. Zeolites are easy
to obtain with low price as compare to the other ad-
sorbents (activated carbon, ion exchange resin etc.)
and their exchangeable ions (Na+ , Ca2+ , K+ ) are
relatively harmless. In addition, zeolite loaded with
heavy metal ions can be easily regenerated [6].
Clinoptilolite with the simplified formula (Na,K)6
Si30 Al6 O72 ·nH2 O is the most abundant natural zeo-
lite and may serve as cost effective sorbent for the
removal of lead from wastewater. Although clinop-
tilolite is commonly used as a cation exchanger, it
can be modified to increase its total organic carbon
content in order to enhance sorption of anionic and
organic compounds [7,8]. Wide-ranging research has
been conducted to characterize the ion exchange prop-
erties of clinoptilolite for the heavy metals especially
for lead [9–13]. Equilibrium isotherms are also pre-
sented for lead removal with clinoptilolite on several
type of clinoptilolite [14–19].
The study of sorption kinetics in wastewater treat-
ment is significant since it provides valuable insights
into the reaction pathways and mechanism of sorption
reactions. In addition, the kinetics describe the solute
uptake rate and the residence time at the solid–solution
interface. Numerous sorption systems have been in-
vestigated in the literature. Most of researchers have
reported the sorption kinetics as first order kinetic pro-
cesses. Ho and McKay [20] reported a literature review
of the sorption kinetic models that has been used to
describe of the use of sorbents to treat polluted aque-
ous effluents. In their work, eleven systems previously
reported as first order kinetics and one system pre-
viously reported as second order kinetics were tested
and the highest correlation coefficients were obtained
for pseudo-second order kinetic model. Therefore, in
this study for the data several kinetic models described
below were investigated to find the best-fitted model.
The goodness of fit models is expressed by the co-
efficients of determination (r2 ). A relatively high r2
value indicated that the model successfully described
the kinetics of lead sorption by the natural clinoptilo-
lite. Despite the interest in the removal and equilib-
rium studies of lead with clinoptilolite, comparatively
limited data are available in terms of lead removal ki-
netics with clinoptilolite [21–23].
The aim of this work is to study the influence of
specific parameters such as initial metal concentration,
pH, agitation speed, particle size, and temperature and
to evaluate the equilibrium isotherms and kinetic mod-
els for removal of lead from aqueous solution by nat-
ural clinoptilolite from Bigadiç, Turkey.
2. Material and methods
2.1. Sampling and characterization of clinoptilolite
Clinoptilolite samples used in this work were
obtained from Bigadiç, Turkey. All samples were
ground in a laboratory type ball-mill and washed with
distilled water in order to remove the surface dust.
X-ray diffraction (XRD) measurements were taken by
Rigaku D-max 1000 model diffractomer. As shown
in Fig. 1, mineral identification showed that the ze-
olite consisted of mainly clinoptilolite (80%). The
impurities include quartz-silica (10%), feldspar (4%),
quartz-opal (3%), and other trace of clay minerals
(3%). The BET surface area, average pore diameter
and micro-pore volume of clinoptilolite were deter-
mined using porosimetry system (AutoporeII-9220)
and are given in the Table 1. To increase cation ca-
pacity, approximately 25 g clinoptilolite and 500 ml
of 2 M NaCl solution were mixed and shaken at
175 rpm. Then the samples were re-washed and sieved
to obtain particle sizes ranging from 315 to 1600 ␮m.
The chemical composition of clinoptilolite before and
after modification as analyzed by X-ray fluorescence
(Philips PW-2404) can be seen Table 2. The theoreti-
cal ion exchange capacity was found to be 2.57 meq/g.
2.2. Batch kinetic experiments
Stock lead solutions were prepared from analytical
grade Pb(NO3 )2 using deionized water. Sorption stud-
ies of lead were investigated by batch experiments us-
ing 100 ml glass flasks. If necessary, pH was adjusted
Table 1
The physical parameters of raw clinoptilolite and modified clinop-
tilolite (MC)
Parameters Raw clinoptilolite MC
Surface area (m2 /g) 15.36 16.41
Pore diameter (␮m) 0.0170 0.0167
Micro-pore volume (ml/g) 0.2388 0.0179
 N. Bektaş , S. Kara / Separation and Purification Technology 39 (2004) 189–200 191

1200

1000
Q
C
800
C
Intensity

600

400 C
Q
C C
200 Q

0
0 10 20 30 40 50 60 70
2 theta

Fig. 1. XRD spectrum of clinoptilolite (C: clinoptilolite; Q: quartz).

using 0.1N HCl or 0.1N NaOH. A known amount of 2.3. Equilibrium experiments
adsorbent was weighed and placed in flasks contain-
ing solution at desired concentration. Then the sus- Equilibrium behaviors were obtained in terms
pensions were placed in a shaker. Final metal con- of equilibrium isotherms. The concentration of
centrations were measured in the equilibrium solution sorbed species on the sorbent the batch contact test
after separating the clinoptilolite through the filtra- was calculated using the following mass-balance
tion paper. The solutions were stored in plastic tubes equation:
with a few drops of dilute HNO3 . Perkin-Elmer model
SIMAA 6000 atomic absorption spectrometry (AAS) qe m = V(C0 − C) (1)
was used to determinate the concentrations of lead in
solutions. where, qe is the final concentration of species on
The effects of initial metal concentration (10– sorbent (mg/g or meq/g of adsorbent), C0 is the
100 mg/l), pH (2–7), agitation speed (100–225 rpm), initial concentration of species (mg/l), C is the fi-
particle size (315–1600 ␮m) and temperature (25– nal concentration of species in solution (mg/l), m
50 ◦ C) have been studied to monitor the uptake is the mass of sorbent used (g), V is the volume of
process. solution (l).
All these parameters, except, qe which were calcu-
Table 2
lated from mass-balance equation, were measured ex-
The chemical composition of raw clinoptilolite and modified perimentally. The data then can be correlated to find a
clinoptilolite (MC) suitable isotherm. The Langmuir and Freundlich equa-
Oxides (%) Raw clinoptilolite MC
tions are the most used to describe sorption equilib-
rium for wastewater treatment applications and given
SiO2 80.20 80.70 below, respectively [24].
Al2 O3 11.20 12.63
FeO 1.79 1.09
Q0 bCe
MgO 0.79 0.78 qe = (2)
CaO 3.46 1.69 (1 + bCe )
Na2 O 0.20 1.71
K2 O 2.36 1.39 qe = Kf Cn (3)
192 N. Bektaş , S. Kara / Separation and Purification Technology 39 (2004) 189–200

After mathematical transformation Eqs. (2) and (3) XA , the fractional conversion of solute, k1 and k2 are
can be written as follows: the first order rate constants.


Ce 1 1 At equilibrium conditions,
= + 0 Ce (4)
qe Q b
0 Q dCB dCA
=− =0 (7)
log qe = log Kf + n log Ce (5) dt dt
where, qe is equilibrium removal (mg metal ion/g and
clinoptilolite), Ce is equilibrium lead concentration in Kc − (CB0 /CA0 )
solution (mg/l), Q0 (mg/g) and b (l/mg) are Langmuir XAe = (8)
Ke + 1
isotherm constants, Kf and n are Freundlich isotherm
constants. where XAe is the fractional conversion of solute at
The value of Q0 gives the theoretical monolayer equilibrium and Kc is the equilibrium constant defined
capacity saturation capacity of clinoptilolite. as follows:
The equilibrium isotherms were determined by mix- CBe CB0 − CA0 XAe k1
ing 0.5 g of clinoptilolite with 50 ml lead solution in Kc = = = (9)
CAe CA0 − CA0 XAe k2
a conical flask at the desired temperature. Three sets
of isotherm plots were obtained by using six different where CBe and CAe are the equilibrium concentrations
initial pH values, four different temperature values, for solute on the sorbent and solution, respectively.
and four different particle sizes ranging. Each isotherm The rate equation in terms of equilibrium conversion
consisted of eight lead concentrations that varied from can be obtained from Eqs. (6), (8) and (9);
25 to 2500 mg/l. dXA
= (k1 + k2 )(XAe − XA ) (10)
dt
2.4. Kinetic modelling
Integration of Eq. (9) and substituting for k2 from
The chemical kinetic describes reaction pathways, Eq. (9), gives
along times to reach the equilibrium whereas chemi-


XA 1
cal equilibrium gives no information about pathways −In 1 − = k1 1 + t (11)
and reaction rates. Sorption kinetics show a large de- XAe Kc
pendence on the physical and/or chemical characteris- Thus Eq. (10) can be re-written in a different form:
tics of the sorbent material which also influences the
sorption mechanism. In order to investigate the mech- In[1 − U(t) ] = −kr t (12)
anism of sorption, various sorption models have been
used at different experimental condition for sorption where kr is the overall rate constant. Furthermore,


processes. 1
kr = k1 1 + = k1 + k2 (13)
Kc
2.4.1. First order kinetic model
A simple first order reaction model is based on a CA0 − CA XA
U(t) = = (14)
reversible reaction with equilibrium state being estab- CA0 − CA0 XAe
lished between two phases and can be expressed as
[25], where U(t) is called the fractional attainment of equi-
librium. Therefore, a plot of −In[1 − U(t) ] versus time
dCB dCA dXA
=− = CA = k1 CA − k2 CB will give a straight line and from the slope of this plot
dt dt dt k1 can be obtained.
= k1 (CA0 −CA0 XA ) − k2 (CB0 − CA XA ) (6)
where, CB (mg/g) is the concentration of solute on the 2.4.2. Pseudo-first order model
sorbent, CA (mg/l) the concentration of solute in so- This was the first equation for the sorption of liq-
lution at any time, CB0 and CA0 the initial concentra- uid/solid system based on solid capacity [26]. In most
tions of solute on sorbent and solution, respectively, cases, the pseudo-first order equation does not fit well
 N. Bektaş , S. Kara / Separation and Purification Technology 39 (2004) 189–200 193

for the whole range of contact time. This model may
be represented:
dqt
= ks (qe − qt )
dt
Eq. (15) can be integrated for following boundary con-
ditions to obtain Eq. (16). t = 0, qt = 0, t = t, qt = qt .
k1
log (qe − qt ) = log (qe ) − t (16)
2.303
where, qe is the amount of solute on the surface of the
sorbent at equilibrium, (mg/g), qt is amount of solute
on the surface of the sorbent at time t, (mg/g), k1 is
the equilibrium rate constant of pseudo-first sorption,
(1/min).
In order to obtain the rate constants, the straight line
plots of log (q1 −qt ) against t for different experimental
conditions have been analyzed.
2.4.3. Pseudo-second order
Pseudo-second order reaction model is based on
sorption equilibrium capacity may be expressed as
[20],
h = k2 qe2
where, qe is the amount of solute sorbed at equilib-
(15) rium (mg/g), k2 is the equilibrium rate constant of
pseudo-second order (g/mg min), h is the initial sorp-
tion rate (mg/g min).
These constants can be determined by plotting t/qt
against t.
2.4.4. Intra-particle diffusion model
According to the intra-particle diffusion model pro-
posed by Weber and Morris [27], the initial rate of
intra-particle diffusion can be calculated by plotting q
against t1/2 .
qt
kp = 1/2 (19)
t
where, qt is amount of solute on the surface of the
sorbent at time t, (mg/g), kp is the intra-particle rate
constant (mg/g min), t is the time (min).
3. Results and discussion

dq 3.1. Influence of process variables

= k2 (qe − qt )2 (17)
dt
After integrating Eq. (17) for following boundary 3.1.1. Effect of the initial concentration
condition and rearranging to obtain the linearized form Fig. 2 shows the effect of the initial concentration
which is shown follows: t = 0, qt = 0, t = t, qt = qt . on the retention of lead, at concentration levels ranging
from 10 to 100 mg/l. Series of experiments have been
t 1 1 carried out with a constant agitation speed of 175 rpm
=  2+ t (18)
qt k 2 qe qe and particle size of 315–500 ␮m. Fig. 2 clearly in-

10

10 mg/L
8
25 mg/L
qt (mg/g)

50 mg/L
6 100 mg/L

0
0 50 100 150 200 250 300
t (min)

Fig. 2. Effect of initial lead concentrations for removal capacity of clinoptilolite (175 rpm, 20 ◦ C, and 315–500 ␮m).
194 N. Bektaş , S. Kara / Separation and Purification Technology 39 (2004) 189–200

1,4

1,2

1
qt (mg/g)

0,8
100 rpm
0,6 150 rpm
175 rpm
0,4 225 rpm

0,2

0
0 60 120 180 240 300
t (min)

Fig. 3. Effect of agitation speed for lead removal capacity of clinoptilolite (10 mg/l, 20 ◦ C, and 315–500 ␮m).

dicates that the sorption of the lead at different con-
centrations is increased instantly at initial stages and
then keeps increasing gradually until the equilibrium
is reached and remains constant. The equilibrium time
was found to be 120 min for all the concentrations
studied.
3.1.2. Effect of the agitation speed
Fig. 3 shows the experimental results obtained from
series of experiments performed using different agita-
tion speed, ranging from 100 to 225 rpm. As shown in
Fig. 3, the uptake of lead increased with increasing ag-
itation speed. Increasing agitation speed reduced the
film boundary layer surrounding clinoptilolite parti-
cles thus increasing the external film transfer coeffi-
cient and hence the rate of uptake. The highest lead re-
moval capacity of clinoptilolite was obtained at the ag-
itation speed of 225 rpm. This partly caused by higher
speed and broken particles that were determined by
sieve analysis before and after the experiment. There-
fore, the optimal agitation speed of 175 rpm was cho-
sen to prevent the particles from be broken.
3.1.3. Effect of the particle size
Fig. 4 shows that the sorption of lead slightly in-
creased with decreasing particle size as expected that

1,2

0,8
qt (mg/g)

0,6 315-500 µm
500-800 µm
0,4 800-1000 µm
1000-1600 µm
0,2

0
0 60 120 180 240 300
t (min)

Fig. 4. Effect of particle size for lead removal capacity of clinoptilolite (10 mg/l, 175 rpm, and 20 ◦ C).
 N. Bektaş , S. Kara / Separation and Purification Technology 39 (2004) 189–200 195

11
10
9
8 25 mg/L
7
qe (mg/g)

50 mg/L
6
75 mg/L
5
100 mg/L
4
3
2
1
0
1 2 3 4 5 6 7 8 9
pH

Fig. 5. Effect of pH for lead removal capacity of clinoptilolite (175 rpm, 20 ◦ C and 0.315–500 ␮m).

is increasing surface area of clinoptilolite. As the sorp-
tion being a surface phenomenon, the smaller sorbent
sizes offered comparatively larger surface areas and
hence higher lead removal at equilibrium. For further
experiments, the 315–500 ␮m size fraction was se-
lected because of its high removal capacities as well
as easy handling.
Ion exchange plays an important role as a sorption
mechanism for lead removal process by clinoptilolite.
The measurements of outgoing Na+ ions showed that

Table 3
A comparison of the Langmuir and Freundlich sorption constants obtained at different experimental conditions
Parameters Langmuir constants Freundlich constants

Q0 b r2 n Kf r2

pH
2 71.94 0.0319 0.9977 0.3969 5.27 0.8739
3 109.89 0.0501 0.9965 0.3922 9.18 0.8964
4 117.64 0.0911 0.9994 0.4001 10.94 0.9007
5 111.11 0.0683 0.9986 0.3762 10.65 0.8893
6 108.69 0.0366 0.9935 0.3784 9.02 0.8252
7 92.59 0.0316 0.9917 0.3741 7.68 0.8187
Particle size (␮m)
315–500 144.92 0.0697 0.9962 0.4122 13.58 0.9085
500–800 138.88 0.0681 0.9974 0.3896 13.79 0.8218
800–1000 128.20 0.0545 0.9980 0.408 10.87 0.8380
1000–1600 121.95 0.0879 0.9997 0.3874 12.43 0.8619
Temparature (◦ C)
25 120.48 0.0284 0.9989 0.3751 10.30 0.8645
30 169.49 0.0193 0.9970 0.4361 10.27 0.8900
45 181.81 0.0279 0.9990 0.4263 12.96 0.8689
70 185.18 0.0352 0.9988 0.4136 15.49 0.8826
Agitation speed (rpm)
100 149.25 0.0522 0.9994 0.3309 19.10 0.8082
150 156.25 0.0531 0.9988 0.3199 21.32 0.7660
175 166.66 0.0344 0.9983 0.3416 17.27 0.9350
225 172.41 0.0351 0.9990 0.3619 16.21 0.9543
196 N. Bektaş , S. Kara / Separation and Purification Technology 39 (2004) 189–200

only about 50% of lead removal was occurred by the
ion exchange (ZC refer to clinoptilolite).
Pb2+ + 2ZC − Na ⇔ (ZC)2 − Pb + 2Na+
Therefore it can be said that the removal of lead ions
by clinoptilolite occurs by ion exchange and through
physical adsorption when pH is less than 6.0 as the
precipitation of Pb2+ ions in the form of Pb(OH)2 in-
creases after pH 6.0 [28]. After this pH value all three
mechanism may also take place in the lead removal
process by clinoptilolite.
3.1.4. Effect of the pH
The Fig. 5 illustrates the effect of pH on the re-
moval of different initials lead concentrations. The re-
moval efficiency at equilibrium has not been signifi-
cantly changed with pH. Even at very low pH value
the lead removal efficiency is still high. This is be-
cause the pH value of solution was increased during
experiments due to hydrolysis of clinoptilolite [9]. All
subsequent experiments were conducted without pH
adjustment.
3.2. Sorption isotherms
Fig. 6 shows the relationship between the amount
of lead adsorbed per unit mass of clinoptilolite (qe ,
mg/g) and its final concentration in the solution (Ce )
for four series of experiments using different initial
pH values, temperatures, particle sizes and agitation

120

100

80
qe (mg/g)

60 pH 2
pH 3
pH 4
40 pH 5
pH 6
20 pH 7
Langmuir isotherm
0
0 200 400 600 800 1000 1200 1400 1600 1800
(a) Ce (mg/L)

160

140

120

100
qe (mg/g)

80 315-500 µm
500-800 µm
60 800-1000 µm
1000-1600 µm
40
Langmuir isotherm
20

0
0 100 200 300 400 500 600 700 800 900 1000
(b) Ce (mg/L)

Fig. 6. Equilibrium isotherms for lead removal by clinoptilolite: (a) at different agitation speeds; (b) using different particle sizes; (c) at
different pH values; (d) at different temperature values.
 N. Bektaş , S. Kara / Separation and Purification Technology 39 (2004) 189–200 197

200

175

150

125
qe (mg/g)

100
20 ºC
75 30 ºC
50 40 ºC
50 ºC
25 Langmuir isotherm

0
0 200 400 600 800 1000 1200 1400 1600
(c) Ce (mg/L)

180
160
140
120
qe (mg/g)

100
80 100 rpm
150 rpm
60
175 rpm
40 225 rpm
20 Langmuir isotherm
0
0 200 400 600 800 1000 1200 1400 1600
(d) Ce (mg/L)

Fig. 6. (Continued ).

speeds. Fig. 6 clearly indicates that the sorption ca-
pacity initially increase rapidly as fluid phase concen-
tration increases. The increase in the curvature of the
isotherms, as it tends to a monolayer, as Ce values
increase considerably for the small increase in qe , is
possibly due to the less active sites being available at
the end of the sorption process and/or the difficulty
of the edge molecules in penetrating the sorbent, lead
partially covering the surface sites.
Sorption equations were obtained by experimental
data with Eqs. (4) and (5). The corresponding cor-
relation coefficients and the isotherm constants were
calculated and presented in Table 3. However clinop-
tilolite has multi ion exchange sites [29], our result
showed that the Langmuir equation represent the sorp-
tion process very well. This result is in agreement with
various researchers who used Langmuir equation to
represent lead removal by clinoptilolite [14,17,18].
Values of Q0 , which is defined as the total capac-
ity of sorbent, at different pH values, temperatures,
particle sizes, and agitation speeds have calculated
from the Langmuir plots. The maximum capacities of
clinoptilolite for lead have been calculated in range
of 111–144–185–166 mg/g. These values compare fa-
vorably with some of those reported in the literature.
The maximum sorption capacities of various type of
clinoptilolite for lead have been given in range of
73–103 mg/g [9,10,15,19].
198 N. Bektaş , S. Kara / Separation and Purification Technology 39 (2004) 189–200

3.3. Sorption kinetics
In order to predict of sorption kinetic models of lead
ions, first order, pseudo-first order and pseudo-second
order kinetic models were applied to data. The effect
of the initial lead concentrations, agitation speeds, and
particle sizes were investigated to find the best ki-
netic model. The straight-line plots of −In[1 − U(t) ]
against time were tested to obtain the first order rate
constant for different experimental conditions. For the
pseudo-first sorption rate constant, the straight line
plots of log(q1 − qt ) against time for different experi-
mental conditions were analyzed. The equilibrium rate
constants of pseudo-second order were determined by

450
400 10 mg/L
350 25 mg/L
300 50 mg/L

250 100 mg/L

t/qt

200
150

100
50
0
0 60 120 180 240 300 360 420 480
(a) t(min)

300

250

200

315-500 µm
t/qt

150
500-800 µm
100 800-1000 µm
1000-1600 µm
50

0
0 30 60 90 120 150 180 210 240 270 300
(b) t(min)

450
400
350
300
250
(t/qt)

100 rpm
200
150 rpm
150
175 rpm
100 225 rpm
50
0
0 60 120 180 240 300 360 420 480
(c) t(min)

Fig. 7. Pseudo-second order plots for lead removal using clinoptilolite: (a) different initial concentrations; (b) different particle sizes; (c)
different agitation speeds.
 N. Bektaş , S. Kara / Separation and Purification Technology 39 (2004) 189–200
Table 4
A comparison of first order, pseudo-first order, pseudo-second order kinetic and intra-particle diffusion models rate constants obtained at different experimental conditions
Parameters First order Pseudo-first order Pseudo-second order Intra-particle diffusion model

Kc k k1 k1 r2 k1 (×103 ) r2 k2 (×103 ) h qe , cal r2 k1 r2

Agitation speed (rpm)
100 64.47 −0.0128 −0.0126 0.075 0.9161 13.58 0.9558 9.12 0.0168 1.3572 0.9748 0.075 0.9161
150 74.14 −0.0104 −0.0102 0.067 0.7413 11.28 0.8784 20.33 0.0308 1.2309 0.9794 0.067 0.7413
175 86.30 −0.0137 −0.0135 0.029 0.7354 14.74 0.9118 83.28 0.1119 1.1522 0.9995 0.029 0.7354
225 104.09 −0.0048 −0.0048 0.005 0.9272 8.06 0.8693 263.6 0.3735 1.1902 0.9999 0.005 0.9272
Co (mg/l)
10 67 −0.0115 −0.0113 0.0295 0.816 10.6 0.9742 64.53 0.0853 1.1506 0.9995 0.0295 0.816
25 97.59 −0.0075 −0.0074 0.0509 0.754 2.1 0.6501 81.33 0.5063 2.495 0.9998 0.0509 0.754
50 119.23 −0.0081 −0.0080 0.0242 0.925 0.9 0.7418 203.57 3.4388 4.1100 1 0.0242 0.925
100 218.29 −0.0084 −0.0083 0.0152 0.481 2.3 0.7906 159.20 15.698 9.9300 1 0.0152 0.481
Particle size (mm)
315–500 69.97 −0.0195 −0.0192 0.0303 0.8279 14.97 0.9662 130.40 0.1698 1.1411 0.9999 0.0303 0.8279
500–800 23.58 −0.012 −0.0115 0.0272 0.7570 5.527 0.8645 132.45 0.1605 1.1008 0.9996 0.0272 0.7570
800–1000 17.73 −0.0112 −0.0106 0.0299 0.8470 12.2 0.9391 109.49 0.1275 1.0791 0.9995 0.0299 0.8470
1000–1600 12.28 −0.0093 −0.0086 0.0270 0.5932 4.83 0.8035 113.03 0.1250 1.0516 0.9995 0.0270 0.5932

199
200 N. Bektaş , S. Kara / Separation and Purification Technology 39 (2004) 189–200
plotting t/qt against t. The values of intra-particle dif-
fusion constants were also obtained from the linear
plots of qt against t1/2 using different experimental
conditions. The pseudo-second order plots are only
presented in Fig. 7. The kinetic constants and corre-
lation coefficients of all models are given in Table 4.
Good correlation coefficients were obtained for the
pseudo-second order kinetic model, which shows that
lead uptake process follows the pseudo-second order
rate expression (Fig. 7, Table 4).
4. Conclusion
Equilibrium and kinetic data for lead removal using
clinoptilolite were presented. The parameters, which
have the influence on the removal processes, were in-
vestigated. The uptake rates of lead for all concen-
trations were rapid at initial stages and then keep in-
crease gradually until the equilibrium is reached. The
sorption of lead was slightly increased with decreas-
ing particle that is increasing surface area of clinop-
tilolite. The experimental data were correlated bet-
ter by the Langmuir isotherm model. The maximum
sorption capacities at different experimental condi-
tions calculated from Langmuir plots which in range
of 111–144–185–166 mg/g. The batch sorption kinet-
ics were tested for first order reaction, intra-particle
diffusion, pseudo-first order and pseudo-second order
reaction models for the different experimental condi-
tions. The pseudo-second order kinetic reaction model
found to be the best correlation of the data for lead
removal from aqueous solution using clinoptilolite.
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