6856 Ind. Eng. Chem. Res.

2005, 44, 6856-6864

Adsorption of Nitrogen, Oxygen, and Argon in Mono-, Di-, and

Trivalent Cation-Exchanged Zeolite Mordenite
Sunil A. Peter, Jince Sebastian, and Raksh V. Jasra*
Silicates and Catalysis Discipline, Central Salt and Marine Chemicals Research Institute,
G. B. Marg Bhavnagar-364002, India

Adsorption of nitrogen, oxygen, and argon is studied in zeolite mordenite (Si/Al ) 5.5) with
mono-, di-, and trivalent Na+, Li+, K+, Cs+, Ca2+, Sr2+, Ba2+, La3+, and Ce3+ as extraframework
cations. Adsorption capacity, selectivity, and heat of adsorption show a strong dependence on
the nature as well as the extent of the extraframework cations. The cation-exchanged mordenite
samples show adsorption selectivity toward nitrogen from its mixture with oxygen or argon.
The electrostatic interaction between adsorbate molecules and the cations are largely responsible
for the observed nitrogen selectivity of the mordenite samples because nitrogen has higher
quadrupole moment than oxygen or argon. The relationships between the adsorption properties
and charge densities of extraframework cations show that the interaction of adsorbate molecules
depends not only on the cation type but also on the positions of these cations in the mordenite
structure.

Introduction capacity, selectivity, and heat of adsorption of nitrogen,

Zeolites A, X, and mordenite are used1,2 as nitrogen-
selective adsorbents in commercial pressure swing
adsorption (PSA) or vacuum swing adsorption (VSA)
processes for oxygen enrichment of air. Nitrogen ad-
sorption capacity and selectivity of these adsorbents
play a significant role in determining the efficiency/
economy of a PSA/VSA process.3 Therefore, there have
been continuous efforts to modify the adsorbents to
attain higher adsorbent productivity by enhancing the
adsorption capacity and selectivity. It was reported
earlier that the extraframework cations in the zeolite
structure4,5 are largely responsible for the nitrogen
selectivity of the zeolite. Consequently, attempts have
been made to increase the number of selective sites in
the zeolite by changing the Si/Al ratio6 or using a
combination of extraframework cations.7 Jasra et al.8-11
have reported the effects of the nature, number, and
location of extraframework cations in zeolites on the
sorption of nitrogen, oxygen, and argon in zeolites A and
X. They have also studied the effect of presorbed water
and carbon dioxide, invariably present in air, on the
sorption behavior in zeolites A8,9 and X.11 Tryburce et
al.12 have studied the effect of exchangeable cations on
the adsorption properties of sodium mordenite and also
tried to correlate the changes in pore volume measured
by nitrogen adsorption with the locations of exchanged
cations. Choudary et al.5 have studied the adsorption
of nitrogen, oxygen, and argon on mordenite-type zeolite
with different Si/Al ratios using elution gas chromatog-
raphy, and they have arrived at the conclusion that the
higher adsorption capacity for nitrogen is the result of
the presence of extraframework sodium ions in the
zeolite structure. In our study, we exchanged the
extraframework cations of Na-mordenite (Si/Al ) 5.5)
with monovalent, divalent, and trivalent cations, such
as Li+, K+, Cs+, Ca2+, Ba2+, La3+, and Ce3+, to under-
stand the effect of these cations on the adsorption
* To whom correspondence should be addressed. E-Mail:
rvjasra@csmcri.org.
10.1021/ie050128v CCC: $30.25 © 2005 American Chemical Society
Published on Web 07/21/2005
oxygen, and argon. We also fitted the pure component
isothermal data on Langmuir, Freundlich, and Lang-
muir-Freundlich isotherm models.
Experimental Section
Materials. The sodium form of the mordenite, NaMOR
(commercial name ZM-060, obtained from M/s Zeocat,
France) was used as the starting material in the powder
form. The overall and framework Si/Al ratio of this
mordenite is 5.5 and corresponds to the chemical
composition Na7.4Al7.4Si40O96 ‚27H2O. For the cation
exchange, we used the chloride salts of different cations
viz, lithium, potassium, cesium, calcium, strontium,
barium (s. d. fine- chem., Mumbai, India), lanthanum,
and cerium (Sigma-Aldrich). Ultrahigh-purity nitrogen,
oxygen, and argon (Hydrogas India Pvt. Ltd., Bombay,
India) were used in all adsorption measurements.
Cation Exchange and Characterization of Mor-
denite. Ion exchange was carried out by repeatedly
treating the mordenite powder at 353 K with a 0.1 M
salt solution (solid-to-liquid ratio 1:80) followed by
filtration and washing with a copious amount of hot
distilled water until the sample is free from the chloride
ion as determined with an AgNO3 solution. The samples
were dried overnight at 353 K in an air oven. The degree
of cation exchange of these samples was determined by
ICP-AES analysis (Perkin-Elmer Instruments, Optima
2000DV). The following terminology is used to describe
the ion-exchanged samples: the first letters show the
exchanged cation and the numbers at end show the
percentage of the sodium cation present in NaMOR
exchanged with this cation (e.g., LiNaMOR-45 means
45% of the sodium cation present in the NaMOR is
exchanged with the lithium cation).
Adsorption Measurements. The isothermal adsorp-
tion of nitrogen, oxygen, and argon on the ion-exchanged
mordenites was conducted using a static volumetric
adsorption system (Micromeritics Instrument Corpora-
tion, Model ASAP 2010) at 288.2 and 303.0 K. The
adsorption temperatures were maintained constant
 Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005 6857

Figure 1. SEM image of NaMOR.

((0.1 K) by circulating water from a constant-temper-
ature bath (Julabo F25, Germany). Prior to the adsorp-
tion measurement, the samples were activated in situ
by heating to 673 K at a rate of 1 K min-1 under vacuum
(5 × 10-3 mmHg) for 8 h.
The adsorption isotherm data was fitted in the virial
equation
ln(P/q) ) A + Bq + Cq2 + ...... (1)
where q is the volume of gas adsorbed per unit weight
of the adsorbent, P is the equilibrium pressure, and A,
B, and C are the virial coefficients. Henry’s constant,
K, was calculated as
K ) exp(-A) (2)
The selectivity of a gas A over gas B in Henry’s law
region was calculated as
KA
RA/B ) (3)
KB
The heats of adsorption data in various cation-
exchanged mordenites were calculated from adsorption
isotherms by the Clausius-Clapeyron equation4,5,13
estimated from the propagation of error method were
0.5, 0.4, and 0.4% respectively.
The measured adsorption isotherms were fitted
into three isotherm models, namely, the Langmuir,
Freundlich, and Langmuir- Freundlich equations. The
Langmuir isotherm is given by the equation2
q bP
) (6)
qm (1 + bP)
where q is the amount of gas adsorbed on the adsorbent
at equilibrium, qm is the monolayer or saturated amount
adsorbed, b is the Langmuir constant, and P is the
equilibrium pressure of the adsorbate. The quantity qmb
equals K.
The Freundlich isotherm is given by the equation21
q ) KPn (7)
where K and n are fitting parameters.
The Langmuir-Freundlich isotherm is given by the
equation2
q bPn
) (8)
qm (1 + bPn)

-∆H ) R [ ∂ ln P
∂(1/T) ]θ
(4) Results
The crystals of sodium mordenite, used as the starting
where R is the gas constant, P is the equilibrium material, are fiber shaped which is clear from the SEM
pressure at the particular coverage θ, and T is the image (LEO 1430 VP Scanning Electron Microscope)
temperature in degrees Kelvin. In the Henry’s law shown in Figure 1.
region, we could calculate the heat of adsorption as X-ray powder diffraction patterns of the cation-
exchanged samples were collected using the Philips
-∆H ) R [ ∂ ln K
∂(1/T) ] (5)
X’pert MPD system at 2θ values between 5 and 65. The
structure of the mordenite is retained after cation
exchange because the X-ray diffraction patterns of the
where K is the Henry constant. The errors in the Henry samples showed the typical peaks of mordenite at 2θ
constant, adsorption selectivity, and heat of adsorption values of 22.3, 25.7, 26.3, 27.9, and 30.8, as shown in
6858 Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005

Table 1. Nitrogen, Oxygen, and Argon Sorption

Capacities on Cation-Exchanged Mordenites at 845 mm
of Hg and 303.0 K
volume adsorbed (cc g-1)
sample N2 O2 Ar
NaMOR 17.1 5.8 6.0
LiNaMOR-45 17.2 6.4 6.5
LiNaMOR-63 21.1 7.2 6.9
LiNaMOR-76 22.6 7.2 6.8
LiNaMOR-88 21.1 7.1 6.7
KNaMOR-73 7.0 4.1 4.1
KNaMOR-97 6.7 3.7 4.0
CsNaMOR-86 3.3 2.6 2.8
CsNaMOR-95 3.2 2.6 2.8
CsNaMOR-99 3.2 2.5 2.8
CaNaMOR-64 19.7 7.2 6.5
CaNaMOR-78 17.1 6.8 6.3
CaNaMOR-87 14.5 6.2 5.5
SrNaMOR- 89 20.1 8.3 8.0
Figure 2. XRD patterns for different-cation exchanged mor- BaNaMOR-56 17.4 7.7 8.3
denites with high exchanged cation content BaNaMOR-78 17.6 9.0 9.3
BaNaMOR-93 18.8 9.5 9.6
LaNaMOR-38 14.7 5.5 5.6
LaNaMOR-59 14.3 5.5 5.8
LaNaMOR-76 14.1 5.5 5.6
CeNaMOR-49 16.5 6.2 6.3
CeNaMOR-84 14.7 5.7 5.7
CeNaMOR-98 12.4 5.5 5.4

and argon show similar adsorption capacities. The

Figure 3. (a) Equilibrium adsorption isotherms for N2, O2, and
Ar on NaMOR at 303.0 K. (b) Nitrogen adsorption isotherms on
different cation-exchanged mordenites at 303.0 K with high
exchanged cation content.
Figure 2. The XRD patterns are of mordenite samples
with a high exchanged cation content.
Adsorption Capacity. Figure 3a shows the adsorp-
tion isotherms of nitrogen, oxygen, and argon on NaMOR
at 303.0 K. The nitrogen adsorption capacity on NaMOR
is high compared to that of oxygen and argon. Oxygen
isothermal adsorption of nitrogen on different cation-
exchanged mordenites at 303.0 K is shown in Figure
3b.
The sorption capacities of different cation-exchanged
mordenites at different cation-exchange levels deter-
mined from adsorption isotherms, are given in Table 1.
From the table, it is clear that lithium-exchanged
mordenite has the highest sorption capacity for nitrogen
compared to the other cation-exchanged mordenites.
The adsorption capacity for nitrogen in lithium-
exchanged mordenite increases as the cation-exchange
level increases, but in the case of the 88% lithium-
exchanged sample, it shows some decrease in the
equilibrium nitrogen adsorption capacity compared to
the 76% lithium-exchanged mordenite.
The nitrogen sorption capacity of CaNaMOR in-
creases first with calcium exchange in NaMOR and then
decreases when the Ca2+-exchange level is higher than
78%. This is in contrast to the dependence of the
nitrogen adsorption capacity on Li+/Ca2+ exchange in
zeolites A and X, where the capacity increases with an
increase in percentage of exchange and an exponential
rise in adsorption capacity is observed in zeolite X at
higher Li+/Ca2+-exchange levels.9,10 In the case of
barium exchange, the nitrogen adsorption capacity
decreases first, compared to that of sodium, and then
increases with the cation-exchange level. Strontium-
exchanged mordenite also shows a higher nitrogen
adsorption capacity than the sodium form. The oxygen
and argon sorption capacity of barium-exchanged
mordenite is higher than that of all of the other cation-
exchanged mordenites.
Figure 4 shows the relationship between the cation
size and the sorption capacities of nitrogen at 303.0 K
in different cation-exchanged mordenites and zeolite X.
The nitrogen sorption capacities are for the samples
with highest exchanged cation content. From the figure
we can see that, for monovalent cations the adsorption
capacity for nitrogen in mordenite decreases sharply
with an increase in the size of cations. In the case of
 Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005 6859

Figure 4. Relationship between the N2 sorption capacity and the size of extraframework cation in (a) mordenite and (b) zeolite X10 at
303.0 K and 845 mm of Hg.

Table 2. Henry Constants from the Virial Equation and

Selectivity at 303.0 K
Henry constant, Ka selectivityb
sample N2 O2 Ar RN2/O2 RN2/Ar RO2/Ar
NaMOR 33.3 8.0 8.0 4.1 4.2 1.0
LiNaMOR-45 35.8 8.6 8.7 4.2 4.1 1.0
LiNaMOR-63 53.8 10.3 9.3 5.2 5.7 1.1
LiNaMOR-76 66.2 9.9 8.9 6.8 7.4 1.1
LiNaMOR-88 61.7 10.0 8.6 6.2 7.3 1.2
KNaMOR-73 10.5 5.3 5.3 2.0 2.0 1.0
KNaMOR-97 9.5 4.7 5.1 2.0 1.8 0.9
CsNaMOR-86 4.6 3.7 3.8 1.3 1.2 0.9
CsNaMOR-95 4.6 3.4 3.9 1.3 1.1 0.9
CsNaMOR-99 4.5 3.4 3.7 1.3 1.2 0.9 Figure 5. Sorption selectivity, N2/O2 at higher exchanged cation
CaNaMOR-64 94.1 12.4 11.2 7.6 8.4 1.1 content as a function of the extraframework cation charge density.
CaNaMOR-78 85.3 11.7 10.5 7.3 8.1 1.1
CaNaMOR-87 54.3 10.4 9.1 5.3 5.9 1.1 Table 3. Heat of Adsorption of N2, O2, and Ar in the
SrNaMOR-89 119.1 14.1 11.4 8.5 10.4 1.2 Henry’s Law Region
BaNaMOR-56 45.9 12.8 13.2 3.6 3.5 1.0
heat of adsorptiona charge
BaNaMOR-78 59.3 14.5 15.0 4.1 4.0 1.0
BaNaMOR-93 72.0 15.9 16.2 4.5 4.4 1.0 sample N2 O2 Ar densityb
LaNaMOR-38 30.0 7.2 7.2 4.2 4.1 1.0 NaMOR 26.7 18.5 18.3 16.9
LaNaMOR-59 31.2 7.5 7.8 4.2 4.0 1.0 LiNaMOR-45 26.1 21.9 18.4
LaNaMOR-76 30.8 7.2 7.8 4.3 4.0 0.9 LiNaMOR-63 28.8 15.8 17.2
CeNaMOR-49 38.2 9.2 9.1 4.1 4.2 1.0 LiNaMOR-76 30.8 19.1 20.9
CeNaMOR-84 33.4 8.2 7.6 4.1 4.4 1.1 LiNaMOR-88 34.0 19.9 22.1 23.6
CeNaMOR-98 28.7 7.4 7.1 3.9 4.1 1.0 KNaMOR-73 20.8 16.2 19.7
a Calcultated from the virial equation (×10-3 cc g-1 mm of KNaMOR-97 22.9 22.4 21.5 12.1
Hg-1). b Calculated using the Henry constant. CsNaMOR-86 17.3 18.3 18.8
CsNaMOR-95 18.7 18.1 18.7
CsNaMOR-99 19.3 18.0 18.4 9.5
zeolite X, the nitrogen capacity decreases exponentially CaNaMOR-64 30.8 14.5 18.0
with an increase in the size of monovalent cations. For CaNaMOR-78 32.4 16.3 18.0
divalent cations, the curve shows highest nitrogen CaNaMOR-87 37.9 23.6 23.2 32.4
capacity for the strontium ion, and for trivalent cations, SrNaMOR-89 33.0 21.7 23.6 28.4
the nitrogen sorption capacities increase with cation BaNaMOR-56 26.2 26.3 26.0
size. But, in the case of zeolite X, the nitrogen capacity BaNaMOR-78 29.5 25.3 23.6
BaNaMOR-93 30.4 24.5 23.2 23.7
decrease sharply with the size of the bivalent cation. LaNaMOR-38 29.0 22.0 20.3
These observations show that, in addition to the number LaNaMOR-59 25.1 19.1 17.4
and nature of the cations, the positions of the exchanged LaNaMOR-76 24.5 21.5 18.6 45.3
cations also play an important role in the adsorption of CeNaMOR-49 29.2 24.4 24.2
nitrogen on mordenite. CeNaMOR-84 26.9 25.6 25.0
Adsorption Selectivity. Henry’s constants and the CeNaMOR-98 31.2 26.3 27.9 46.7
selectivity of nitrogen over oxygen and argon on differ- a In kJ mol-1. b In C m-1 × 10-10.
ent cation-exchanged mordenites at different cation-
exchange levels are given in Table 2. The strontium- vations also show that, apart from charge density, the
exchanged mordenite sample has the highest value for accessible locations of the extraframework cations also
the Henry constant. The dependence of the selectivity play an important role in the selectivity of nitrogen over
of nitrogen over oxygen on charge density is shown in oxygen and argon.
Figure 5. For monovalent cations, the selectivity in- Heat of Adsorption. Table 3 shows the heat of
creases with charge density. In the case of divalent adsorption for nitrogen, oxygen, and argon on various
cations, the selectivity also increases with charge cation-exchanged mordenites in the Henry’s law region
density compared to that of sodium mordenite, and and different cation-exchange levels. Figure 6 shows the
strontium-exchanged mordenite shows highest selectiv- heat of adsorption of nitrogen on cation-exchanged
ity in the Henry’s law region. For trivalent cations, the mordenites at different cation-exchange levels. In the
selectivity decreases with charge density. These obser- case of monovalent cations, the heat of adsorption for
6860 Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005

Figure 6. Dependence of the heat of adsorption of N2 on the

extent of the extraframework cations.

Figure 8. Heat of sorption of N2 as a function of the extraframe-

work cation charge density.

Figure 7. Heat of adsorption of N2 as a function of the adsorption

capacity on different cation-exchanged mordenites.

nitrogen decreases with respect to percentage of cation

exchange, except for lithium. This may be the result of
the high charge density of lithium compared to sodium,
which in turn causes the strong interaction of the
nitrogen molecule with extraframework lithium ion. In
the divalent cation exchange, the heat of adsorption for
nitrogen increases compared to that of the sodium form,
and the calcium-exchanged mordenite shows the highest
heat of adsorption for nitrogen among the other morden-
ites. In the trivalent cation exchange, the lanthanum-
exchanged mordenite shows a decrease in the heat of
adsorption for nitrogen, and the cerium-exchanged
mordenite shows some increase in heat of adsorption
with the exchange level. Figure 7 shows the heat of
adsorption of nitrogen at different coverages on various
cation-exchanged mordenites. From the figure, it is clear
that the initial heat of adsorption of nitrogen is higher
on calcium-exchanged mordenite and lower on cesium-
exchanged mordenite. Figure 8 shows the charge den-
sity versus the heat of adsorption of nitrogen on various
cation-exchanged mordenites. In the figure, we can see
that the heat of adsorption increases with charge
density for monovalent, divalent, and trivalent cations
at different slopes.
Figure 9. (a) Mordenite framework viewed along [00l]. (b)
Discussion Framework unit cell structure of mordenite.
Interaction Energies and the Sorption Proper-
ties. The pore system of mordenite, depicted in Figure denote the positions occupied by the extraframework
9a, consists of main elliptical channels with dimensions cations as suggested by Mortier et al.14
of 6.5 × 7.0 Å, oriented along the c axis which are In a zeolite framework, SiO2 and AlO2 tetrahedra are
connected by tortuous pores of 3.4 × 4.8 Å oriented in connected by sharing oxygen atoms. Al3+ and Si4+ ions
the b direction.14 It also has side pockets in the c are buried in the tetrahedra of oxygen atoms and are
direction with dimensions 2.6 × 5.7 of Å formed by not directly exposed to sorbate molecules. Thus, the
elliptical 8 rings. The framework unit cell structure of main interactions of the adsorbate molecules in a zeolite
mordenite is shown in Figure 9b. The roman numerals structure are through lattice oxygen atoms and the
 Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005 6861

Table 4. Comparison of Heat of Adsorption of N2, O2, and Table 5. Different Cation Site Population in Mordenite
Ar on Zeolites A, X, and Mordenite Zeolite
heat of adsorption, -∆Ha site occupancies
cation zeolite N2 O2 Ar sample I II III IV VI ref
Na+ MOR 26.7 18.5 18.3 Na7.4Al7.4Si40.6O96 4.5 Na - - 2.2 Na 0.7 Na 18
Xb 18.5 12.0 11.2 Na8Al8Si40O96 4 Na - - 3 Na 1 Na 12
Ac 19.6 13.8 11.9 K8Al8Si40O96 - 4K - 3K 1K 12
Li+ MOR 34.0 19.9 22.1 K8Al8Si40O96 - 3.3 K - 3K 0.9 K 20
Xb 27.0 13.4 12.4 Cs8Al8Si40O96 4 Cs - - 2 Cs 2 Cs 12
K+ MOR 22.9 22.4 21.5 Ca3.3Al7.8Si40.2O96 1.8 Ca - 0.5 Ca 0.5 Ca 0.6 Ca 20
Xb 15.4 11.9 11.8 Ca8Al8Si40O96 (ideal) 2 Ca - 2/3 Ca 2/3 Ca 2/3 Ca 20
Cs+ MOR 19.3 18.0 18.4 Ba8Al8Si40O96 - 2 Ba 1 Ba 1 Ba - 12
Xb 14.1 12.2 12.3
Ca2+ MOR 37.9 23.6 23.2
Xb 28.8 15.3 13.5
in the mordenite structure. Hayhurst and Sefcik16 have
Ad 25.1 14.1 - proposed that in the sodium form of mordenite with a
Ba2+ MOR 30.4 24.5 23.2 low Si/Al ratio (Si/Al < 5), the side pockets are accessible
X 21.4 13.5 12.9 for nitrogen sorption from the 12-membered ring main
Sr2+ MOR 33.0 21.7 23.6 channel. However, the shape of the side pocket is such
X 25.2 13.9 13.5 that the adsorbed nitrogen molecules have restricted
a In kJ mol-1. b Ref 10. c Ref 5. d Ref 8. rotational freedom. Such restriction results in a higher
quadrupole-cation field gradient interaction leading to
extraframework cations. The various interactions con- a higher heat of sorption. A similar rotational restriction
tributing toward the total energy of physical adsorption, of adsorbed nitrogen, even in the main mordenite
Φ, include dispersion, ΦD, polarization, ΦP, field-dipole channel, has been proposed by Furuyamma and
interactions, ΦFµ, field-quadrupole interactions, ΦFQ, Nagato.17 One can expect similar rotational restrictions
close-range interactions, ΦR, and sorbate-sorbate in- for other sorbate molecules, such as oxygen. On the
teractions, ΦSP. other hand, adsorbed molecules will not have these
rotational restrictions in zeolites X and A as the
Φ ) -(ΦD - ΦR) - ΦP - ΦFµ - ΦFQ - ΦSP (9) molecules are adsorbed in the main cavity which have
diameters of 13 and 11.4 Å, respectively. The nonspecific
At low sorbate coverage, the contributions from field- interaction of the oxygen atoms of the mordenite with
dipole and sorbate-sorbate interactions are negligible sorbate molecules is expected to be higher as the
in the case of nitrogen, oxygen, and argon because they channels of mordenite are smaller (6.5 and 7.0 Å for the
are nonpolar, and the total energy of physical adsorption minor and major diameters, respectively) compared to
is given by the larger cavities of zeolites X and A. As a result, the
adsorbed molecules in mordenite will have higher
Φ ) - (ΦD - ΦR) - ΦP - ΦFQ (10) electrostatic forces as well as nonspecific interactions
with zeolitic cations, framework oxygen atoms, or both
Nitrogen, because of its higher quadrupole moment thereby explaining the observed values for the heat of
(5.0035 × 10-40 C m3) compared to those of oxygen sorption.
(0.800 × 10-40 C m3) and argon (0.0), interacts strongly Sorption Properties and Cation Locations. Be-
with the extraframework cations in the mordenite, cause the extraframework cations play an important
which is evident from the heat of adsorption data given role in the adsorption of sorbate molecules on the zeolite
in the Table 3. An argon molecule with a zero quadru- surface, it is better to consider the dependence of the
pole moment and a size similar to those of nitrogen and charge densities of these cations on the interactions of
oxygen can be presumed15 to mainly interact through the sorbate molecules with the zeolite structure. If the
dispersion and polarization forces between framework sorption properties, such as heat of adsorption, adsorp-
oxygen atoms and the sorbate molecules. Therefore, the tion selectivity, etc., are solely dependent on the charge
difference in the heat of adsorption of argon from that density, then the plots of the selectivity and heat of
of nitrogen or oxygen (Table 4) will give an idea of the sorption versus charge density would show a single
contribution of electrostatic forces to the total interac- linear relationship. But from Figures 5 and 8, it is clear
tion energy. that the trend is not like that. This means that the
Some interesting observations can be made from the sorption properties are not only dependent on charge
Table 4, which gives the comparison of heat of adsorp- density but also on the location of the cations. From
tion values of nitrogen, oxygen, and argon on different Figure 4, it is clear that for monovalent cations the
cation-exchanged mordenites with those on cation- nitrogen sorption capacity decreases with an increase
exchanged zeolites X and A. The values given in the in cation size, and for divalent and trivalent cations,
table are for the zeolite samples with higher cation the nitrogen sorption capacity increases slightly with
content. The heat of adsorption values for the three cation size. This may be the result of the reallocation
sorbates in the mordenite samples are substantially of cations in the mordenite structure during cation
higher than those of zeolites X and A. The comparison exchange. In the following section, a correlation between
of heat of adsorption values for argon on different cation- the observed sorption properties and the cation locations
exchanged mordenites with those on cation-exchanged is made.
zeolites A and X reveal that the contributions of disper- Monovalent cations. Table 5 shows the probable
sion and polarization interactions are also higher for cationic sites in mordenite structure for different cat-
cation-exchanged mordenite. These observations show ions. Devautour et al.18 reported the degree of sodium
that adsorbate molecules have higher interactions with ion occupation for each site in sodium mordenite (Si/Al
extraframework cations as well as lattice oxygen atoms ) 5.5) obtained via the thermally stimulated depolar-
6862 Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005

ization current (TSDC) method: site I contains 4.5 Table 6. Langmuir Parameters for N2 Adsorption
sodium ions, site IV contains 2.2 sodium atoms, and site Isotherms on Different Cation-Exchanged Mordenites at
288.2 and 303.0 K
VI contains 0.7 sodium atoms. They have also deter-
mined,19 using the same method, that the lithium ions, 288.2 K 303.0 K
under exchange, substitute for the sodium ions in the sample Ka bb variance Ka bb variance
same positions. But the size of lithium ion is small
NaMOR 42.900 0.932 0.002 25.255 0.584 0.001
compared to that of sodium, therefore there is an LiMOR 75.092 1.815 0.089 41.993 1.107 0.017
increase in the pore volume in mordenite structure, KMOR 11.723 0.316 0.000 7.475 0.220 0.000
which is one of the reasons for the increase in the CsMOR 5.247 0.236 0.000 3.485 0.191 0.000
sorption capacity for nitrogen in lithium-exchanged CaMOR 55.968 1.980 0.145 29.962 1.196 0.035
mordenite. In potassium-exchanged mordenite, the cat- SrMOR 96.317 3.098 0.283 61.377 2.229 0.131
BaMOR 75.118 2.381 0.109 44.927 1.531 0.035
ionic sites are II, IV, and VI. The simultaneous presence LaMOR 34.761 0.947 0.010 21.540 0.638 0.003
of two potassium ions (size 1.33 Å) at each secondary CeMOR 32.690 0.940 0.014 17.921 0.552 0.001
channel entrance (sites II and IV) makes them inacces- a In cc g-1 atm-1. b In atm-1.
sible to sorbate molecules. This can be observed from
the decrease in sorption capacities for nitrogen, oxygen, Table 7. Langmuir Parameters for O2 Adsorption
and argon on potassium-exchanged mordenite. In cesium- Isotherms on Different Cation-Exchanged Mordenites at
exchanged mordenite, the ions are located at sites I, IV, 288.2 and 303.0 K
and VI. Because of the large size of cesium ion (1.69 Å), 288.2 K 303.0 K
the cesium ions situated at the main channel cause a
sample Ka bb variance Ka bb variance
decrease in pore volume inside the main channel. This
is confirmed by the sharp decrease in the sorption NaMOR 8.875 0.144 0.000 6.045 0.148 0.000
capacities for nitrogen, oxygen, and argon on cesium- LiMOR 11.232 0.214 0.000 7.456 0.150 0.000
KMOR 5.892 0.122 0.000 3.719 0.115 0.000
exchanged mordenite. CsMOR 3.806 0.140 0.000 2.602 0.126 0.000
Bivalent and Trivalent Cations. The site occupan- CaMOR 11.557 0.379 0.002 7.327 0.283 0.001
cies of bivalent cations, viz calcium and barium, are SrMOR 15.895 0.524 0.002 10.686 0.402 0.002
shown in Table 5. In the ideal case of calcium exchange BaMOR 19.500 0.585 0.001 12.029 0.378 0.000
LaMOR 8.523 0.174 0.000 5.613 0.127 0.000
in mordenite, the calcium ions locations are as follows: CeMOR 9.062 0.184 0.000 5.609 0.133 0.000
two ions are at site I and remaining two ions are equally
distributed at sites III, IV, and VI. In these, the ions at
a In cc g-1 atm-1. b In atm-1.
site III are inaccessible to sorbate molecules, which may Table 8. Langmuir Parameters for Ar Adsorption
be the reason for the decrease in sorption capacity for Isotherms on Different Cation-Exchanged Mordenites at
nitrogen with the increase in cation exchange. In the 288.2 and 303.0 K
case of barium-exchanged mordenite, the cations occupy 288.2 K 303.0 K
sites II, III, and IV. This means that, during barium
exchange, the sodium ions present at site I are removed sample Ka bb variance Ka bb variance
and there will be some increase in the pore volume NaMOR 8.836 0.137 0.000 6.053 0.111 0.000
inside the side pockets. The observed increase in the LiMOR 10.590 0.187 0.000 6.797 0.113 0.000
KMOR 6.123 0.140 0.000 4.035 0.111 0.000
sorption capacities for oxygen and argon on barium-
CsMOR 4.192 0.147 0.000 2.877 0.123 0.000
exchanged mordenite can be explained by this phenom- CaMOR 10.102 0.323 0.001 6.003 0.197 0.000
enon. The strontium ions may occupy sites II, III, and SrMOR 14.244 0.383 0.001 9.141 0.255 0.000
IV, as in the case of barium, because strontium- BaMOR 19.419 0.612 0.002 12.326 0.394 0.000
exchanged mordenite also shows increased nitrogen LaMOR 8.758 0.176 0.000 5.763 0.126 0.000
adsorption capacity similar to that of barium-exchanged CeMOR 8.687 0.180 0.000 5.447 0.109 0.000
mordenite. There is not much data available for the a In cc g-1 atm-1. b In atm-1.
cation locations in mordenite exchanged with trivalent
cations, viz lanthanum and cerium. But the observed Table 9. Freundlich Parameters for N2 Adsorption
Isotherms on Different Cation-Exchanged Mordenites at
decrease in the sorption capacities for nitrogen on these 288.2 and 303.0 K
mordenites suggest that the cations are located at less
accessible sites such as I, II, or III. 288.2 K 303.0 K
Isothermal Models and Fittings. The adsorption sample Ka n variance Ka n variance
isotherms of nitrogen on mordenite follow the type I NaMOR 22.470 0.672 0.238 16.125 0.758 0.060
isotherm,2,21 and those of oxygen and argon are almost LiMOR 27.237 0.565 0.503 20.195 0.656 0.176
linear except for the barium- and strontium-exchanged KMOR 8.938 0.851 0.008 6.141 0.890 0.003
CsMOR 4.254 0.884 0.002 2.932 0.903 0.001
mordenites, which have higher adsorption capacities for
CaMOR 19.188 0.544 0.144 13.825 0.638 0.048
oxygen and argon compared to other cation-exchanged SrMOR 24.263 0.468 0.480 19.479 0.525 0.210
mordenites. In the type I isotherm, the amount of gas BaMOR 22.812 0.515 0.439 18.071 0.596 0.175
adsorbed increases with increasing pressure and then LaMOR 18.056 0.684 0.118 13.242 0.751 0.036
saturates at about monolayer coverage. The Langmuir CeMOR 17.035 0.685 0.089 11.612 0.775 0.026
parameters for the nitrogen, oxygen, and argon adsorp- a In cc g-1 atm-n.
tion isotherms are given in Table 6-8. Tables 9-11
show the Freundlich parameters for the nitrogen, isotherms of the experimental data and the isotherm
oxygen, and argon adsorption isotherms. Tables 12-14 model data for the adsorption of nitrogen on lithium-
shows the Langmuir-Freundlich parameters for the exchanged mordenite at 288.2 K. The Freundlich iso-
nitrogen, oxygen, and argon adsorption isotherms. The therm fails to fit exactly with the experimental data in
values given in the tables are for mordenites with higher all cases of nitrogen adsorption. The Langmuir iso-
exchanged cation content. The Figure 10 shows the therm gives a somewhat good fit, but the Langmuir-
 Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005 6863

Table 10. Freundlich Parameters for O2 Adsorption Table 14. Langmuir-Freundlich Parameters for Ar
Isotherms on Different Cation-Exchanged Mordenites at Adsorption Isotherms on Different Cation-Exchanged
288.2 and 303.0 K Mordenites at 288.2 and 303.0 K
288.2 K 303.0 K 288.2 K 303.0 K
sample Ka n variance Ka n variance sample Ka n b variance Ka n bb variance
NaMOR 7.765 0.917 0.002 5.279 0.917 0.001 NaMOR 8.918 1.006 0.147 0.000 6.076 1.003 0.115 0.000
LiMOR 9.269 0.890 0.003 6.490 0.919 0.001 LiMOR 10.536 0.997 0.181 0.000 7.090 1.027 0.161 0.000
KMOR 5.255 0.934 0.001 3.339 0.939 0.000 KMOR 6.218 1.010 0.158 0.000 4.039 1.001 0.112 0.000
CsMOR 3.346 0.926 0.000 2.314 0.933 0.000 CsMOR 4.263 1.011 0.167 0.000 2.963 1.019 0.157 0.000
CaMOR 8.405 0.824 0.003 5.722 0.861 0.001 CaMOR 8.974 0.929 0.174 0.000 5.844 0.983 0.166 0.000
SrMOR 10.488 0.782 0.016 7.643 0.813 0.004 SrMOR 13.518 0.969 0.312 0.000 9.052 0.993 0.243 0.000
BaMOR 12.379 0.767 0.031 8.762 0.828 0.009 BaMOR 17.932 0.954 0.488 0.000 11.952 0.982 0.351 0.000
LaMOR 7.274 0.908 0.002 4.984 0.931 0.001 LaMOR 8.662 0.993 0.163 0.000 5.655 0.988 0.105 0.000
CeMOR 7.665 0.903 0.001 4.957 0.928 0.001 CeMOR 8.558 0.991 0.162 0.000 5.686 1.028 0.157 0.000
a In cc g-1 atm-n. a In cc g-1 atm-n. b In atm-n.

Table 11. Freundlich Parameters for Ar Adsorption

Isotherms on Different Cation-Exchanged Mordenites at
288.2 and 303.0 K
288.2 K 303.0 K
sample Ka n variance Ka n variance
NaMOR 7.783 0.921 0.002 5.459 0.936 0.001
LiMOR 8.935 0.903 0.003 6.113 0.940 0.001
KMOR 5.376 0.925 0.001 3.636 0.939 0.000
CsMOR 3.659 0.922 0.000 2.564 0.934 0.000
CaMOR 7.656 0.845 0.002 5.021 0.898 0.001
SrMOR 10.337 0.826 0.011 7.302 0.875 0.004
BaMOR 12.125 0.759 0.031 8.878 0.823 0.010
LaMOR 7.461 0.908 0.002 5.122 0.931 0.000
CeMOR 7.375 0.906 0.002 4.919 0.942 0.001
a In cc g-1 atm-n.

Table 12. Langmuir-Freundlich Parameters for N2

Adsorption Isotherms on Different Cation-Exchanged
Mordenites at 288.2 and 303.0 K
Figure 10. Langmuir, Freundlich, and Langmuir-Freundlich
288.2 K 303.0 K isotherm fittings for nitrogen on lithium-exchanged mordenite at
288.2 K.
sample Ka n bb variance K n bb variance
NaMOR 40.838 0.971 0.838 0.001 24.447 0.980 0.532 0.000
LiMOR 56.322 0.858 1.100 0.006 35.671 0.913 0.785 0.002 for the barium- and strontium-exchanged mordenites.
KMOR 11.664 0.997 0.309 0.000 7.665 1.016 0.251 0.000 The Langmuir, Freundlich, and Langmuir-Freundlich
CsMOR 5.395 1.017 0.271 0.000 3.591 1.019 0.227 0.000
CaMOR 33.083 0.751 0.744 0.002 21.232 0.823 0.548 0.001
adsorption isotherm models fit well with the experi-
SrMOR 53.331 0.739 1.240 0.012 37.359 0.768 0.946 0.004 mental data for the oxygen and argon adsorption
BaMOR 51.242 0.820 1.288 0.008 34.346 0.864 0.926 0.003 isotherms.
LaMOR 30.315 0.925 0.694 0.001 19.513 0.944 0.482 0.000
CeMOR 27.445 0.905 0.625 0.001 16.798 0.962 0.454 0.000
Conclusion
a In cc g-1 atm-n. b In atm-n.
The lithium-exchanged mordenite shows a higher
Table 13. Langmuir-Freundlich Parameters for O2 adsorption capacity for nitrogen than the other cation-
Adsorption Isotherms on Different Cation-Exchanged
Mordenites at 288.2 and 303.0 K exchanged mordenites. The strontium-exchanged mor-
denite has the highest value for the Henry constant. The
288.2 K 303.0 K strontium-exchanged mordenite also shows a higher
sample Ka n bb variance Ka n bb variance selectivity for nitrogen over oxygen and argon in the
NaMOR 8.861 0.999 0.142 0.000 5.912 0.985 0.123 0.000 Henry’s law region.
LiMOR 10.866 0.979 0.174 0.000 7.345 0.991 0.133 0.000 There is a strong dependence of sorption properties
KMOR 5.955 1.007 0.134 0.000 3.875 1.026 0.162 0.000 studied on the nature of extraframework cations, thereby
CsMOR 3.819 1.002 0.143 0.000 2.662 1.015 0.152 0.000 reflecting that these cations form the principle sites of
CaMOR 10.040 0.917 0.197 0.000 6.729 0.948 0.178 0.000
SrMOR 14.402 0.943 0.379 0.000 9.369 0.923 0.230 0.000
interactions with the sorbate molecules. However, the
BaMOR 18.145 0.958 0.474 0.000 11.594 0.978 0.328 0.000 relationships between the adsorption properties and the
LaMOR 8.383 0.989 0.154 0.000 5.642 1.003 0.133 0.000 charge densities of the extraframework cations show
CeMOR 8.598 0.967 0.123 0.000 5.543 0.993 0.119 0.000 that the adsorbate-adsorbent interactions depend not
a In cc g-1 atm-n. b In atm-n. only on the cation charge density but also on the sites
these cations occupy in the mordenite structure.
The observed high heat of sorption in the cation-
Freundlich isotherm gives an exact fit with the experi- exchanged mordenites compared to that in cation-
mental data. This can be checked from the variance exchanged zeolites X and A is the result of the rotational
values. If a model fits exactly with the experimental restrictions of adsorbate molecules inside the smaller
data, then the variance will be zero. The adsorption cavities of mordenite, compared to the cavities of zeolites
isotherms of oxygen and argon are almost linear except X and A.
6864 Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005
Among the adsorption isotherm models studied, the
Langmuirn-Freundlich model fits all of the adsorption
isotherm data exactly.
Acknowledgment
We thank CSIR, New Delhi, for financial support in
the form of a research fellowship. We also thank to Dr.
P. K. Ghosh, Director of CSMCRI, for his support.
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Received for review February 2, 2005
Revised manuscript received June 20, 2005
Accepted June 21, 2005
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