Microporous and Mesoporous Materials 132 (2010) 401408

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Microporous and Mesoporous Materials

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Study of equilibrium and thermodynamic adsorption of a-picoline, b-picoline,

and c-picoline by Jordanian zeolites: Phillipsite and faujasite
Zahir Rawajh a,*, Hanan Al Mohammad a, Najwa Nsour b, Khalil Ibrahim c
a
Department of Natural Resources and Environment, Jordan University of Science and Technology, P.O. Box 3030, Irbid 22110, Jordan
b
Center of Environmental Studies, The Hashemite University, P.O. Box 150459, Zarqa 13115, Jordan
c
Department of Earth and Environment Science, Faculty of Natural Resources and Environment, The Hashemite University, P.O. Box 150459, Zarqa 13115, Jordan

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

Article history: In the present study the ability of phillipsite and faujasite to remove a-picoline, b-picoline, and c-picoline
Received 12 August 2009 from aqueous solution in the broad range of concentrations (1500 mg L1) was investigated. Adsorption
Received in revised form 3 March 2010 equilibrium was carried out at different initial concentrations, sorbent concentrations, and temperatures.
Accepted 20 March 2010
BrunauerEmmettTeller (BET), the HarkinsJura, the Smith, and the Halsey equations were applied to
Available online 25 March 2010
the experimental data. The data tted the BET model best. The overall adsorption of a-, b-, and c-picoline
on phillipsite and faujasite followed the order: faujasitea-picoline < phillipsitea-picoline < faujasiteb-picoline <
Keywords:
phillipsiteb-picoline < faujasitec-picoline < phillipsitec-picoline. The values of change in Gibbs free energy
Picolines
Adsorption isotherm
(DG), enthalpy (DH), and entropy (DS) were calculated. Thermodynamic study revealed that the
Thermodynamic adsorption of picolines onto phillipsite and faujasite was an exothermic process. Isosteric heat of adsorp-
Phillipsite tion was found to decrease with the increase in surface loading.
Faujasite 2010 Elsevier Inc. All rights reserved.

1. Introduction metals and ammonium [11,12]. Small organic or inorganic mole-

The a-picoline, b-picoline, and c-picoline compounds (their
synonyms are 2-methylpyridine, 3-methylpyridine, and 4-methyl-
pyridine, respectively) are pyridine derivatives and structural iso-
mers. Picolines are useful as solvents and as raw materials for
various chemical products used in the industries of polymers, tex-
tiles, fuels, agrochemicals, pharmaceuticals, and colorants [1].
Many of the pyridine derivative compounds are hazardous in nat-
ure and persist for a long time in the environment, as they are poor
substrates to indigenous microorganisms. The removal of pyridine
derivatives from waters is therefore of great importance. Various
treatment technologies have been developed for the removal of
pyridine and its derivatives from water/wastewater. These include
adsorption [1,2], biodegradation [3], ion exchange [4], ozonation
[5], and electrochemical oxidation [6].
Many investigators have studied the feasibility of using cheap
adsorbing materials such as spent-rundle shale [7], clay minerals
[8], and zeolite [9,10]. Nevertheless, none of these adsorbents has
been fully explored or utilized for the removal of pyridine derivatives
such as a-, b-, and c-picoline from waste streams [1,2]. Zeolites are
commonly used as cation exchangers, molecular sieves, adsorbents,
and catalysts [10]. The cation exchange properties of zeolites are
exploited in wastewater treatment to remove species such as heavy
* Corresponding author. Tel.: +962 2 720 1000; fax: +962 2 720 1078.
E-mail address: zahir@just.edu.jo (Z. Rawajh).
cules may be trapped within the dehydrated internal channels of
zeolites. Thus, zeolites have a wide use as molecular sieves [11]. Zeo-
lites may permit molecules to enter their network, but only if the
molecules are smaller than the diameter of their channels; large mol-
ecules will be excluded from the zeolite porous network. Zeolite-
bearing tuff deposits are found in several locations in Jordan. The
present study was undertaken to evaluate the ability of Jordanian
zeolites (faujasite and phillipsite) to adsorb pyridine derivatives.
2. Materials and methods
2.1. Adsorbents
Samples of Jordanian zeolites were collected from two different
sites in the basaltic desert in northeast and east of Jordan. The sam-
ples of zeolites were crushed and sieved to 0.61.0 mm particle
size and stored in polyethylene containers for further use. Homo-
ionic Na-zeolites were prepared using the procedure of Wingenfel-
der et al. [13]. The pretreated minerals were dried at 60 C
overnight and stored in polyethylene containers. External and
internal cation exchange capacity (ECEC and CEC) determination
followed the procedure of Ming and Dixon [14] as modied by
Haggerty and Bowman [15].
Photomicrography of the exterior surface of unloaded and
loaded zeolite was obtained by SEM (FEI Quanta 200, The Nether-
lands). XRD analysis of the natural zeolitic tuffs was carried out.

1387-1811/$ - see front matter 2010 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2010.03.019
402 Z. Rawajh et al. / Microporous and Mesoporous Materials 132 (2010) 401408

2.2. Adsorbates where qe is the amount (mg g1) of picolines adsorbed, Co and Ce are
the initial and equilibrium concentrations (mg L1) of picolines in
All the chemicals used in the study were of analytical reagent solution, V is the volume (L) of solution, and m is the mass of zeolite
grade. The adsorbates a-, b-, and c-picoline were obtained from (g).
SigmaAldrich. The physicochemical properties of picolines are
presented in Table 1. Stock solutions of the test reagents were
made by dissolving a-picoline, b-picoline, and c-picoline in double 3. Results and discussion
distilled water.
3.1. Characterization of zeolite adsorbents
2.3. Analytical measurements
The total cation exchange capacities of phillipsite and faujasite
The picolines dissolved in water were found to be stable over were 73.0 and 70.4 cmol(+) kg1 and the external cation exchange
the concentration range of 1500 mg L1 used in the study. No capacities were 15.4 and 12.0 cmol(+) kg1, respectively. The SEM
change in the picolines concentration was observed over a time photographs in Fig. 1 were taken to observe the surface morphol-
period of 24 h. The experiments were carried out in stoppered glass ogy of natural zeolites and the zeolites loaded with c-picoline. It
bottles and no loss of picolines due to their volatilization was showed possible c-picoline clusters, on occupied surfaces. X-ray
observed during the experiments and the analysis. Absorbance diffraction of the phillipsite and faujasite zeolitic tuffs are shown
measurements were made on UVvis Spectronic 601 spectropho- in Fig. 2.
tometer. The wavelengths corresponding to maximum absorbance
(kmax) of picolines were determined by scanning a standard solu- 3.2. Effect of initial concentration
tion of known concentration at different wavelengths. Absorbance
values were recorded at the wavelength of maximum absorbance The effect of the initial concentration on the adsorption of a-, b-,
i.e., 262, 263, and 255 nm (kmax), for a-, b-, and c-picoline, respec- and c-picoline by phillipsite and faujasite zeolites was investigated
tively. These wavelengths were used for preparing a calibration in the range 1500 mg L1. The percent picoline adsorption de-
curves in aqueous solutions. creased with increase in initial concentration (Fig. 3). The amount
of picolines adsorption depends on the position of methyl group at-
2.4. Batch adsorption study tached to the organic ring and followed the order a-picoline < b-
picoline < c-picoline. This may be the result of steric hindrance be-
Batch adsorption experiments were carried out with different tween the nitrogen group and the CH3 group in case of a-picoline
initial concentrations at 298 and 328 K using a water bath shaker. and b-picoline. The steric hindrance in c-picoline is less than in a-
The pH values were adjusted using HCl or NaOH before addition of and b-picolines. The steric effect associated with the methyl group
zeolite to a value of 2. An equal amount (2.5 g) of zeolite was intro- decreases the electronic effect (or, in other words, the basic charac-
duced into 100 mL bottles and 50 mL of a-, b-, and c-picoline solu- ter), in particular for a-picoline. In this connection, it should be
tion of desired concentration (1500 mg L1) were added to each noted that the couple of free electrons are located in the same
bottle and shaken for 24 h. Immediately after shaking, each sample plane as the benzene ring, which is bound to the carbon atom of
was ltered through 0.45-lm syringe lter. The ltrates were ana- the methyl group. In this group, the four substitutes (i.e., the ben-
lyzed for the concentration remaining in solution. Control samples zene ring and three hydrogen atoms) are found in a tetrahedron
with picoline solutions and without adsorbent were also included. whose center is occupied by the carbon atom. This atomic arrange-
No adsorption occurred on either glassware or ltration systems. ment thus explains the steric effect due to the methyl group [1].
The amount of adsorbed picolines by zeolite, qe (mg g1) was When the picoline concentration in the test solution was
calculated using the following equation:
1.0 mg L1, and the amount of adsorbent in the suspension was
C o  C e V 50 g L1, 81%, 91%, and 96% of the initial picoline concentration
qe 1
m was removed for a-, b- and c-picoline by phillipsite at 298 K.
Whereas, when the initial concentration was 500 mg L1, the
amount of picolines removed dropped to 25%, 46%, and 64% in
Table 1 the same order.
Physicochemical properties of picolines [16,17]. The removal percent at low concentration (1 mg L1) for a-pic-
Properties Pyridine derivatives oline, b-picoline, c-picoline by faujasite at 298 K was 73%, 83%, and
93%, respectively. While at high concentration (500 mg L1) the re-
a-picoline b-picoline c-picoline
moval percent was 20%, 37%, and 54% in the same order (Fig. 3).
Formula C6H7N C6H7N C6H7N
Molar mass 93.13 93.13 93.13
(g mol1)
3.3. Effect of sorbent mass
Density 0.946 at 20 C 0.957 at 25 C 0.956 at
(g mL1) 25 C
Boiling point 129.5 143.9 144.9 To evaluate the optimum dosage of the sorbent, different
(C) masses of faujasite were used to adsorb c-picoline in solution. Fifty
pKa 6.00 5.63 5.98 milliliters of solution containing 25 mg L1 of picoline were placed
Solubility in Freely soluble Miscible Miscible
in vials. A certain mass of sorbent (1100 g L1) was placed in each
water
Structure vial. After a contact time of 24 h, the content of picoline in the l-
N CH3 N N
trates was measured using the method mentioned above. Fig. 4
shows that an increase in the faujasite dose increased the percent-
age of picoline removal, R, from aqueous solution from 3% to 44%.
CH3 By increasing the dose of faujasite, the number of adsorption sites
available for sorbentsorbate interaction is increased, thereby
CH3 resulting in the increased percentage of picoline removal from
solution.
 Z. Rawajh et al. / Microporous and Mesoporous Materials 132 (2010) 401408 403

Fig. 1. Scanning electron micrograph of natural faujasite and phillpsite and the c-picoline loaded faujasite and phillpsite.

Faujasite
Phillipsite
Intensity

Intensity

0 10 20 30 40 50 60 0 10 20 30 40 50
2 2

Fig. 2. XRD of natural phillpsite and faujasite zeolitic tuffs.

3.4. Effect of temperature therms are S-shape. The S isotherm has an initial slope that is small
with the amount bound increasing as a semilinear function of the
Adsorption isotherms of a-, b-, and c-picoline by phillipsite and concentration. The isotherm plot is concave up until an inection
faujasite at 298 and 328 K are given in Fig. 5. The adsorption iso- point and then plateaus in some cases. This type of isotherm is ob-
404 Z. Rawajh et al. / Microporous and Mesoporous Materials 132 (2010) 401408

120 heteroporous solids [21]. Their mathematical expressions are as

Faujasite, -picoline Phillipsite, -picoline follows:
BrunauerEmmettTeller (BET):
100 Faujasite, -picoline Phillipsite, -picoline
 
Ce 1 B  1 Ce
Faujasite, -picoline Phillipsite, -picoline 2
80 C s  C e qe BQ  BQ  C s
% Adsorption

HarkinsJura:
60    
1 B 1
 log C e 3
q2e A A
40
Smith:

20 y W b  W In 1  C e 4
Halsey:
0     
0 100 200 300 400 500 600 1 1
In qe In k  In C e 5
Initial concentration (mg/L) n n
where qe is the amount of adsorbate adsorbed per unit mass of
Fig. 3. Effect of initial concentration on the removal of a-picoline, b-picoline, and c-
adsorbent at equilibrium (mg g1); Ce is the concentration of adsor-
picoline by philipsite and faujasite zeolites where: adsorbent mass: 50 g L1; pH:
2.0; temperature: 298 K. bate in solution (mg L1); Q is the maximum sorption capacity cor-
responding to complete monolayer coverage (mg g1); Cs is the
saturation concentration of the solute corresponding to monolayer
saturation mg L1, B, Q, A, Wb, W, and k are constants. The constant
50 parameters of the equations for this system were calculated by
regression analysis using the linear form of the isotherm equations.
40 The results are given in Table 2. In order to assess how accurate
each model was in representing the experimental data, the mean
Removal %

30 relative percentage deviation modulus (E%) was used:

100 X
N
jqe exp  qeth j
20 E% 6
N i1 qeexp

10 where qe exp is the experimental value, qeth is the predicted value,

0 As could be seen from Table 2, and based on the values of r2 and
0 50 100 150 200
Sorbent concentration (g/L)
Fig. 4. Effect of sorbent concentration on percent c-picoline removal by faujasite.
served when a molecule does not have a strong afnity for the sur-
face until there is a signicant amount bound, at which time, the
slope increases as the afnity for the surface increases. This occurs
because the solute molecule has modied the surface or has begun
to bind to previously bound molecules [18]. The isotherm curves
illustrate a typical two-stage adsorption process [19]:
Region 1 (Fig. 5) displays weak adsorption and thermal effects
since adsorption takes place when picolines exchange with ad-
sorbed sodium on the homoionic zeolite surfaces [20]. Region II
is marked by a sharp increase in adsorption, which is attributed
to the adsorbateadsorbate interactions which become more and
more prevalent and the isotherm is characterized by an inection
point.
and N is the number of observations.
250 the mean relative percentage deviation modulus (E%), the sorption
of a-, b-, and c-picoline onto phillipsite and faujasite at different
temperatures tted the BET model the best. It was also found that
the Halsey model showed the poorest tting for the picolines sorp-
tion. The high t of the adsorption data to the BET equation, which
represents multilayer adsorption can be explained by the existence
of a heterogeneous pore distribution in zeolites. Because isotherms
similar to type II of the S-shape describe heteroporous solids well
[22], the tting of the experimental data at a quite high concentra-
tion range to the BET isotherm may be attributed to a second
adsorption layer at these high concentrations.
In order to asses the conformity of the experimental data to the
different models used, the theoretical BrunauerEmmettTeller
(BET), the HarkinsJura, Smith and the Halsey isotherms for sorp-
tion of c-picoline onto phillipsite and faujasite at the temperature
of 25 C were plotted (Fig. 6). The experimental data showed the
best t with the theoretical BET.
3.6. Estimation of thermodynamic parameters

3.5. Modeling of adsorption isotherms The Gibbs free energy change of the adsorption process
1
DGad kJ mol is related to the adsorption equilibrium constant
The equilibrium sorption isotherm is fundamentally very cru- (Kad) by the classical vant Hoff equation [23]:
cial in the design of sorption systems. The equilibrium sorption is
DGad RT In K ad 7
usually described by an isotherm equation characterized by certain
1 1
parameters whose values express the surface properties of the sor- It is also related to the change in entropy DS (kJ mol K ) and
bent and its afnity to the sorbate. The two-parameter isotherm heat of adsorption (DH, kJ mol1) at a constant temperature as
equations selected for the treatment of the experimental data of follows:
sorption of a-, b-, and c-picoline onto phillipsite and faujasite are
DGad DH  T DS 8
BrunauerEmmettTeller (BET), HarkinsJura, Smith, and Halsey.
The equations are suitable for multilayer sorption, especially onto From the two equations, one has,
 Z. Rawajh et al. / Microporous and Mesoporous Materials 132 (2010) 401408 405

3 3
- picoline 298K phillipsite 298K phillipsite
298K faujasite
- picoline
298K faujasite
328K phillpsite
2 328K phillipsite
328K faujasite 2
qe (mg g -1 )

qe (mg g -1 )
328K faujasite

1 1

0 0
0 20 40 60 80 100 120 0 20 40 60 80 100
-1 -1
Ce (mg L ) Ce (mg L )

5
- picoline

4
qe (mg g -1 )

3
298K ph illipsite
2
298K faujasite
1 328K ph illipsite
328K faujasite
0
0 50 100 150 200
-1
Ce (mg L )

Fig. 5. Effect of temperature on the adsorption of a-, b-, and c-picoline on phillipsite and faujasite (sorbent concentration: 50 g L1, pH: 2).

Table 2
Isotherm constants for adsorption of a-, b-, and c-picoline onto phillipsite and faujasite.

Isotherm parameters Phillipsite Faujasite

298 K 328 K 298 K 328 K
a-picoline b-picoline c-picoline a-picoline b-picoline c-picoline a-picoline b-picoline c-picoline a-picoline b-picoline c-picoline
BET
Qo (mg g1) 1.85 2.38 4.59 1.10 2.240 4.18 1.09 1.19 2.32 0.64 1.14 1.27
B 11.82 22.48 30.07 3.74 5.22 9.785 8.05 15.65 23.85 2.57 3.63 6.78
r2 0.986 0.983 0.990 0.987 0.978 0.966 0.996 0.997 0.976 0.976 0.980 0.965
E% 5.5 4.68 8.89 1.13 4.44 3.23 3.97 2.91 2.22 3.11 3.03 4.80
HarkinsJura
A 6.14 16.17 85.89 2.50 10.67 52.00 4.39 5.71 39.42 1.44 3.92 17.24
B 0.33 0.29 0.20 0.25 0.12 0.20 0.79 0.80 0.59 0.79 0.85 0.67
r2 0.939 0.929 0.949 0.930 0.904 0.863 0.998 0.979 0.918 0.994 0.847 0.940
E% 8.99 7.80 9.40 2.74 5.25 8.92 7.27 9.99 9.16 4.92 3.48 5.5
Smith
W 2.58 3.42 5.84 1.60 1.51 7.75 1.08 2.71 3.06 1.08 1.08 3.07
Wb 11.96 14.03 18.86 10.14 11.59 13.31 9.31 10.99 14.40 6.32 7.95 10.89
r2 0.957 0.952 0.979 0.934 0.945 0.931 0.850 0.704 0.892 0.811 0.795 0.741
E% 13.27 23.49 24.76 10.56 12.78 11.34 16.92 19.47 15.38 9.94 12.16 7.82
Halsey
k 35.32 41.71 84.31 18.16 15.22 32.50 18.13 15.76 32.13 12.27 10.04 21.53
n 2.83 3.42 4.80 1.10 1.22 1.22 1.10 1.62 2.87 0.45 0.45 1.19
r2 0.806 0.772 0.830 0.971 0.932 0.942 0.888 0.852 0.879 0.846 0.866 0.755
E% 17.68 21.7 24.37 15.08 17.07 18.75 21.57 24.82 22.49 7.161 20.66 19.41

DH DS the slope of the linear vant Hoff plot i.e., ln Kad versus (1/T), using
In K ad
RT R the equation:
 
where T is the absolute temperature (K) and R is the universal gas d In K ad
DH  R 9
constant (8.314 J mol1 K1). Thus, DH can be determined from d1=T
406 Z. Rawajh et al. / Microporous and Mesoporous Materials 132 (2010) 401408

-picoline phillipsite -picoline faujasite

7 12
Exper data
6 Exper data
BET 10
BET
5
Smith 8 Harkins-Jura
qe (mg g )
-1

qe (mg g )
-1
4 Halsey Smith
6
3 Harkins-Jura Halsey
4
2

1 2

0 0
0 20 40 60 80 0 30 60 90
-1 -1
Ce (mg L ) Ce (mg L )

Fig. 6. Isotherms of c-picoline sorbed onto phillipsite and faujasite.

-2
phillipsite -picoline faujasite -picoline
-2.5 -picoline
-picoline
-picoline -3 -picoline
ln K ad
ln Kad

-3.5
-4

-4.5 -5
3 3.1 3.2 3.3 3.4 3 3.1 3.2 3.3 3.4
-3 -1 -3 -1
(1/T)/(10 K ) (1/T)/(10 K )

Fig. 7. vant Hoff plot of ln Kad against (1/T) for the adsorption of picolines onto phillipsite and faujasite.

This DH corresponds to the isosteric heat of adsorption (DHst,0)
with zero surface coverage (i.e., qe = 0). Kad at qe = 0 was obtained
from the intercept of the ln (qe/Ce) versus qe plot [24,25]. Fig. 7
shows the vant Hoffs plot from which the values of DH, DS,
and DG for the adsorption of a-, b-, and c-picoline onto phillipsite
and fuajasite were calculated (Table 3). It is observed that DH and
DG have negative values, and DS has positive values. The nega-
tive DH value conrms the exothermic nature of the overall-sorp-
tion process. The positive value of DS suggests increased
randomness at the solid/solution interface with an increase in
the degree of freedom of the adsorbed picolines on phillipsite
and fuajasite. The negative values of DG indicate the feasibility
and spontaneity of the adsorption process.
3.6.1. Isosteric heat of adsorption
The uniformity or heterogeneity of the surface sites of the zeo-
lites could be deduced from the isosteric heats of adsorption as a
function of the solute adsorbed using the ClausiusClapeyron
equation [25,26]. The isosteric heats of adsorption are calculated
from adsorption isotherms at two different temperatures:
R In C 2 =C 1 
DH
1=T 2  1=T 1
where DH is the isosteric heat of adsorption in kJ mol1 at a given
amount of solute adsorbed, R is the gas constant, and C1 and C2
are the equilibrium concentrations of picoline at temperatures T1
and T2. If the isosteric heat of adsorption is independent of the
amount sorbed, then the surface is homogeneous, and if it decreases
with the amount of solute adsorbed, then the surface is heteroge-
neous. The decrease in the isosteric heat of adsorption with increas-
ing adsorption loading can be due to different types of adsorption
sites or the interaction of adsorbing molecules [27].
The heat of sorption varied signicantly with loading, where it
increased at the beginning reaching a maximum corresponding
to monolayer surface coverage of zeolites by adsorbed a-, b-, and
c- picoline. Then it showed a decrease when the picoline content
increased (Fig. 8), which could be explained by considering that
the adsorption occurred initially on the most active available sites
involving high interaction energies. As these sites became occu-
pied, adsorption occurred on the less active sites that involve lower
interaction energies [28]. At low picoline content, binding is
mainly governed by interaction between the picoline molecules
and the adsorbent surface. A plausible reason for the shape of
the curves could be the differences in attractive forces between
picoline molecules and sorption sites and among picoline mole-
10
cules themselves.
 Z. Rawajh et al. / Microporous and Mesoporous Materials 132 (2010) 401408 407

Table 3
Thermodynamic parameters of a-, b-, and c-picoline adsorption onto faujasite and phillipsite.

Faujasite Phillipsite
1 1 1 1 1
qe (mg g ) DG (kJ mol ) DH (kJ mol ) DS (J mol K ) qe (mg g1) DG(kJ mol1) DH (kJ mol1) DS (J mol1 K1)
298 K 328 K 298 K 328 K
a-picoline
0.02 20.8 22.4 4.1 55.8 0.02 10.7 11.3 4.6 20.6
0.19 25.9 28.1 4.7 71.2 0.14 19.6 20.8 8.1 38.8
0.30 27.9 30.3 4.8 77.8 0.27 28.7 30.5 11.8 56.9
0.36 24.1 26.1 4.5 65.9 0.35 26.5 28.1 10.9 52.4
0.47 21.9 23.7 4.3 59.2 0.54 17.9 19.0 7.4 35.4
0.55 20.2 21.7 4.2 53.6 0.95 9.9 10.5 4.1 19.6
0.79 19.3 20.8 4.1 51.1 1.50 9.5 10.1 4.0 18.7
1.15 15.2 16.4 3.6 39.1 2.71 7.8 8.2 3.3 15.1
2.01 11.7 12.5 3.1 28.8 5.00 5.8 6.1 2.5 11.1
b-picoline
0.02 26.3 28.4 6.2 67.6 0.01 15.3 16.1 7.3 26.9
0.24 32.7 35.3 7.2 85.8 0.14 25.6 27.1 11.4 47.8
0.35 40.0 43.2 8.0 107.0 0.31 39.4 41.7 16.3 77.5
0.55 27.0 29.0 6.6 68.5 0.56 34.3 36.3 14.3 66.9
0.72 25.4 27.3 6.3 64.0 0.74 20.5 21.7 9.2 38.1
0.95 21.4 22.9 5.9 52.0 1.08 13.4 14.1 6.3 23.7
1.30 19.1 20.4 5.7 44.9 1.56 10.5 11.0 5.2 17.7
1.75 16.6 17.7 5.3 37.8 2.74 10.3 10.1 5.0 17.7
3.41 16.2 17.3 5.5 36.0 4.5 8.4 8.8 -4.3 13.7
c-picoline
0.02 49.8 53.7 11.5 128.5 0.01 27.0 28.6 11.7 51.4
0.20 54.3 58.6 12.2 141.5 0.10 39.8 42.0 17.9 73.4
0.31 60.7 65.6 12.8 160.8 0.32 46.3 48.9 20.7 86.2
0.88 33.4 35.8 9.3 80.9 0.72 36.5 38.5 16.3 67.8
1.02 29.7 31.9 8.6 70.8 0.94 29.6 31.3 12.9 56.0
1.31 25.8 27.6 8.2 59.0 1.17 18.4 19.4 7.8 35.5
1.78 21.2 22.6 7.7 45.4 1.46 16.3 17.2 6.9 31.4
2.81 20.6 21.9 7.7 43.4 1.69 13.6 14.4 5.7 26.5
5.04 17.2 18.2 7.2 33.6 2.83 12.9 13.7 5.7 24.3

14 25
-picoline -picoline
12 Faujasite Phillipsite
-picoline 20 -picoline
10 -picoline -picoline
-H (kJ/mol)

-H (kJ/mol)

8 15

6
10
4
5
2

0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
q e (mg/g) q e (mg/g)

Fig. 8. Enthalpy of sorption of a-, b-, and c-picoline onto philipsite and faujasite.

4. Conclusions concentrations indicating that the overall adsorption process was

The maximum removal of a-, b- and c-picoline by phillipsite at
298 K is 81%, 91%, and 96% in the lower concentration (1 mg L1)
and 25%, 46%, and 64% in the higher concentration range
(500 mg L1) using 50 g L1of adsorbent dose. Whereas the re-
moval percent at low concentration (1 mg L1) for a-, b-, and c-pic-
oline, by faujasite at 298 K was 73%, 83%, and 93%, respectively and
at high concentration (500 mg L1) the removal percent dropped to
20%, 37%, and 54% for the same order. The adsorption isotherms of
a-, b-, and c-picolines are pronounced S-shape. The equilibrium
loading content increased with decreasing temperature at constant
exothermic. The equilibrium sorption isotherm data could be rep-
resented by the BET isotherm equation. The isosteric heats of sorp-
tion increased with decreasing equilibrium concentrations.
Enthalpy and entropy changes were evident, with their values
decreasing with increasing loading content.
Acknowledgement
The authors thank the Deanship of Research at Jordan Univer-
sity of Science and Technology for the grant used in carrying out
this work.
408 Z. Rawajh et al. / Microporous and Mesoporous Materials 132 (2010) 401408

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