5896 Langmuir 1996, 12, 5896-5904

Calorimetric Heats of Adsorption and Adsorption

Isotherms. 2. O2, N2, Ar, CO2, CH4, C2H6, and SF6 on NaX,
H-ZSM-5, and Na-ZSM-5 Zeolites
J. A. Dunne,† M. Rao,‡ S. Sircar,‡ R. J. Gorte, and A. L. Myers*
Department of Chemical Engineering, University of Pennsylvania,
Philadelphia, Pennsylvania 19104

Received May 21, 1996. In Final Form: August 1, 1996X

Isosteric heats of adsorption and adsorption isotherms have been measured simultaneously in a calorimeter
for a series of gases of increasing size and magnitude of quadrupole moment (Ar, O2, N2, CH4, C2H6, SF6,
CO2) on adsorbents of varying pore structure and ion type (NaX, H-ZSM-5, Na-ZSM-5). Adsorption isotherms
have been checked for reversibility by desorption experiments. The average experimental error in loading
is (0.6%; the average uncertainty in the isosteric heat of adsorption is (0.5 kJ/mol. Heats of adsorption
of nonpolar molecules (CH4, C2H6, SF6) increase in the order NaX, silicalite, H-ZSM-5, Na-ZSM-5 at low
coverage. Heats of adsorption of nonpolar molecules are almost identical on silicalite,
H-ZSM-5, and Na-ZSM-5 at high coverage. Heats of adsorption of the quadrupolar molecule CO2 increase
in the order silicalite, H-ZSM-5, Na-ZSM-5, NaX. The electric field adjacent to Na+ sites is 6.2 V/nm, on
the basis of the difference between the heat of adsorption of CO2 in Na-ZSM-5 and the heat of adsorption
of CO2 in silicalite.

1. Introduction generally found that in zeolite X, both affinities and zero

CO2 adsorption on NaA, NaX, and NaY has been studied
extensively1-5 to determine the effect of crystal structure
and ion type on the adsorption equilibrium and energetics.
Affinities in these adsorbents increase in the order NaY,
NaX, NaA, which is explained by the presence of more
exposed ions of type III within the X cavity6 and the smaller
pore diameter of zeolite A. Other gases such as n-butane,7
aromatics,8 pentane isomers,9 alkanes,4,10-15 and perma-
nent gases10,13,15 have been studied on NaX to elucidate
the effect of the Na ion on equilibrium.
The effect of ion type has been investigated in zeolite
X for CO2,1,5,16,17 alkanes,6,18 and N2 and O2.6,19 It is
†Allied Signal, Santa Clara, CA.
‡Air Products & Chemicals, Inc., Allentown, PA.
* Person to whom correspondence should be addressed. E-mail
address: amyers@eniac.seas.upenn.edu
X Abstract published in Advance ACS Abstracts, November 1,
coverage heats increase with increasing ion charge density
(K, Na, Li) for monovalent ions; similarly, for divalent
ions Zhang et al.18 and Habgood6 report that heats increase
in the order Ba, Sr, Ca. Zhang et al.18 report that ion type
impacts upon adsorption even at high loadings.
In ZSM-5 zeolites, similar work has been carried out to
examine the effect of the Si/Al ratio upon adsorption. At
cryogenic temperatures20-22 a lower Si/Al ratio inhibits
the formation of a step in the adsorption isotherm; this
inhibition was explained by the increased electrostatic
interactions associated with higher Al content. The heat
of adsorption of benzene increased strongly with Al
content, but n-hexane was not influenced by the Si/Al
ratio.23 Ethane on ZSM-524 displayed a linear relationship
between heat of adsorption and Al content.
Varying the ion type within the ZSM-5 pores has also
been investigated by studying the adsorption of CO2 on
the Na and high-silica forms of ZSM-5.25 Alkanes have

1996. been investigated on the Na and H forms of ZSM-5;26 the

(1) Amari, D.; Lopez Cuesta, J. M.; Nguyen, N. P.; Jerrentrup, R.;
Ginoux, J. L. J. Thermal Anal. 1992, 38, 1005-1015.
(2) Avgul’, N. N.; Aristov, B. G.; Kiselev, A. V.; Kurdyukova, L. Ya.
Russ. J. Phys. Chem. 1968, 42 (10), 1424-1426.
(3) Burevski, D.; Pilchowski, K.; Bergk, K. H. Croat. Chem. Acta
1991, 64 (2), 199-205.
(4) Choudhary, V. R.; Mayadevi, S. Sep. Sci. Technol. 1993, 28 (8),
1595-1607.
(5) Vasil’eva, E. A.; Khvoschev, S. S.; Karetina, I. V. Izv. Akad. Nauk
SSSR, Ser. Khim. 1984, 9, 1942-1947.
(6) Habgood, H. W. Can. J. Chem. 1964, 42, 2340-2350.
(7) Thamm, H.; Stach, H.; Schirmer, W.; Fahlke, B. Z. Phys. Chem.
(Leipzig) 1982, 263 (3), 461-469.
(8) Ruthven, D. M.; Kaul, B. K. Ind. Eng. Chem. Res. 1993, 32, 2047-
2052.
(9) Dzhigit, O. M.; Rakhmanova, T. A. Vestn. Mosk. Univ., Ser. 2:
Khim. 1986, 41 (5), 477-482.
(10) Barrer, R. M.; Sutherland, J. W. Proc. R. Soc. Edinburgh, Sect.
A 1956, 237, 439-463.
(11) Chkhaidze, E. V., Fomkin, A. A.; Serpinskii, V. V.; Tsitsishvili,
G. V. Izv. Akad. Nauk SSSR, Ser. Khim. 1985, 5, 974-978.
(12) Dzhigit, O. M., Kiselev, A. V.; Rachmanova, T. A. Zeolites, 1984,
4, 389.
(13) Neddenreip, R. J. J. Coll. Interface Sci. 1968, 28 (2), 293-304.
(14) Rolniak, P. D.; Kobayashi, R. AIChE J. 1980, 26 (4), 616-625.
(15) Wakasugi, Y.; Ozawa, S.; Ogino, Y. J. Colloid Interface Sci. 1981,
79 (2), 399.
(16) Barrer, R. M.; Gibbons, R. M. Trans. Faraday Soc. 1965, 61,
948-961.
(17) Khvoschev, S. S.; Zverev, A. V. J. Colloid Interface Sci. 1991,
144 (2), 571-578.
heat of adsorption of propane is lower in Na-ZSM-5 than
in silicalite, in disagreement with results obtained for
ethane.24 Low-temperature studies22 found the effect of
ion type on the step in the isotherms of N2 and Ar at
cryogenic temperatures to be less important than the Si/
Al ratio.
(18) Zhang, S. K.; Talu, O.; Hayhurst, D. T. J. Phys. Chem. 1991, 95,
1722-1726.
(19) Choudhary, N. V.; Jasra, R. V.; Bhat, S. G. T. In Zeolites and
Related Microporous Materials: State of the Art; Weitkamp, J., Karge,
H. G., Pfeifer, H., Hölderich, W., Eds.; Elsevier Science: Amsterdam,
1994; Vol. 84, pp 1247-1254.
(20) Llewellyn, P. L.; Coulomb, J.-P.; Grillet, Y.; Patarin, J.; Lauter,
H.; Reichert, H.; Rouquerol, H.; Rouquerol, J. Langmuir, 1993, 9, 1846-
1851.
(21) Llewellyn, P. L.; Coulomb, J.-P.; Grillet, Y.; Patarin, J.; Lauter,
H.; Reichert, H.; Rouquerol, H.; Rouquerol, J. Langmuir, 1993, 9, 1852-
1856.
(22) Saito, A.; Foley, H. C. Microporous Mater. 1995, 3, 543-556.
(23) Lohse, U.; Thamm, H.; Noack, M.; Fahlke, B. J. J. Inclusion
Phenomena 1987, 5, 307-313.
(24) Stach, H., Fiedler, K.; Jänchen, J. J. Pure Appl. Chem. 1993, 65
(10), 2193-2200.
(25) Dubinin, M. M.; Rakhmatkariev, G. U.; Isirikyan, A. A. Izv.
Akad. Nauk SSSR, Ser. Khim. 1989, 11, 2636-2638.
(26) Bülow, M.; Schlodder, H.; Rees, L. V. C.; Richards, R. E. In New
Developments in Zeolite Science and Technology; Proceedings of the 7th
International Conference; Murakami, Y., Iijima, A., Ward, J. W., Eds.;
Elsevier Science: Amsterdam, 1986; pp 579-586.

S0743-7463(96)00496-9 CCC: $12.00 © 1996 American Chemical Society

Heats of Adsorption and Adsorption Isotherms Langmuir, Vol. 12, No. 24, 1996 5897

The energetic interaction of a series of adsorbates, polar

and nonpolar, with ion-exchanged forms of ZSM-5 has
been investigated.27-32 The heats of adsorption were
obtained from the Clapeyron equation. However, uncer-
tainties in the values of the heats are introduced by the
differentiation process inherent in the use of the Clapeyron
equation.
The calorimetric study in this paper is intended to
elucidate the energetic interaction of a series of adsorbates
of increasing size and polarity on ion-exchanged ZSM-5
adsorbents. ZSM-5 was chosen because it has a known
crystal structure33 and its properties can be compared
with previous work carried out on the high-silica form of
ZSM-5, silicalite.34 Silicalite provides a relatively non-
heterogeneous energetic environment for both polar and
nonpolar molecules and serves as a starting point for
investigating the effect of energetic heterogeneity on
equilibrium properties. Heats of adsorption of the same Figure 1. Adsorption isotherms on NaX: (9) CO2 at 31.4 °C;
series of adsorbates were measured in NaX to investigate (0) CO2 at 32.8 °C; (b) SF6 at 31.6 °C; (4) C2H6 at 32.4 °C; (2)
CH4 at 31.3 °C; (O) N2 at 32.5 °C; ([) Ar at 31.0 °C; (]) O2 at
interactions in a pore structure larger than MFI. 33.1 °C.

2. Experimental Section
Apparatus. Adsorption isotherms and heats of adsorption
were determined simultaneously in a Tian-Calvet heat flux
calorimeter constructed in house.34 The calorimeter, which is
operated inside an isothermal enclosure, consists of heat flux
meters surrounding a Pyrex cell within which adsorption occurs.
The heat flux is integrated with respect to time to calculate the
amount of heat released for a given incremental amount adsorbed.
The volumetric method is used to determine the amount adsorbed
at a given pressure and temperature. Reversibility was estab-
lished by the coincidence of adsorption and desorption points.
The reproducibility of adsorption isotherms and heats of adsorp-
tion is excellent. Errors in measured heats are on the order of
2%.
A series of adsorbates (Ar, O2, N2, CH4, C2H6, CO2, and SF6)
of increasing size and magnitude of quadrupole moment were
studied on NaX, Na-ZSM-5, and H-ZSM-5. Adsorption isotherms
were measured between 21 and 33 °C, and equilibrium pressures
ranged from 0.08-1000 Torr. Figure 2. Adsorption isotherms on NaX: (9) CO2 at 31.4 °C;
Adsorbents. The Na-ZSM-5 sample was obtained from (0) CO2 at 32.8 °C; (b) SF6 at 31.6 °C; (4) C2H6 at 32.4 °C; (2)
Chemie Uetikon AG. TPD-TGA of isopropylamine on the H+- CH4 at 31.3 °C; (O) N2 at 32.5 °C; ([) Ar at 31.0 °C; (]) O2 at
exchanged form35 gave a Si/Al ratio of 30 (or 500 µmol of Na+ ions 33.1 °C.
per gram of sample). The H+ form was produced by ion exchange
with Na-ZSM-5 in a 1 M (NH4 )2SO4 solution at 360 K, followed was also studied (6.412 mmol of Na+ ion per gram of sample).
by calcination at 770 K. This procedure was repeated to drive The crystal structure is composed of silicon or aluminum atoms
the ion exchange to completion. The pore structure of the bound tetrahedrally by oxygen atoms to form sodalite units, which
adsorbent is identical to that of silicalite (MFI structure) and in turn are connected by 6-membered rings to form large
has a three-dimensional pore network33 of straight and zig-zag supercavities of diameter 14 Å. These cavities are connected by
channels of diameters 5.4 × 5.6 and 5.1 × 5.4 Å2. Thermo- windows composed of 12-membered rings with a diameter of
gravimetric analysis of the sample gave a dehydrated weight of 8 Å. Thermogravimetric analysis of the sample yielded a
94.6% and 95.4% of the weight in air for the Na+ and H+ forms, dehydrated weight 76% of that in air.
respectively. Pore-filling experiments performed by exposure of Na-ZSM-5 and H-ZSM-5 samples were regenerated under
the sample to n-hexane vapor for 2 mins at 25 °C and a pressure vacuum (0.01-0.001 Torr) while heating from 30 to 350 °C over
of 6.44 Torr yielded a pore volume of 0.174 cc/g. a period of 12 h, followed by bakeout at 350 °C for 12 h. NaX
A commercial sample of NaX (Linde), an aluminosilicate was regenerated with an initial bakeout of 12 h under ambient
powder with a Si/Al ratio of 1.23 (Na86 [(AlO2)86(SiO2)106]‚xH2O), conditions, followed by 24 h at 110 °C, followed by bakeout at 350
°C for 12 h. Subsequent bakeouts of the sample between runs
were performed by heating for 15 h in the range from 30 to 350
(27) Choudhary, V. R.; Mayadevi, S. Sep. Sci. Technol. 1993, 28 (13
and 14), 2197-2209. °C, followed by bakeout at 350 °C for 12 h.
(28) Lamberti, C.; Bordiga, S.; Geobaldo, S.; Zecchina, A.; Otero Areán,
C. J. Chem. Phys. 1995, 103 (8), 3158-3165. 3. Results
(29) Yamazaki, T.; Watanuki, I.; Ozawa, S.; Ogino, Y. Langmuir 1988,
4, 438-443. NaX. Adsorption isotherms for polar and nonpolar
(30) Yamazaki, T.; Watanuki, I.; Ozawa, S.; Ogino, Y. Bull. Chem.
Soc. Jpn. 1988, 61, 1039-1044. adsorbates in NaX are shown in Figure 1. The equilibrium
(31) Yamazaki, T.; Katoh, M.; Ozawa, S.; Ogino, Y. Mol. Phys. 1993, pressures lie in the range from 0.1 to 1000 Torr. The
80 (2), 313-324. log-log plot of the same data in Figure 2 magnifies the
(32) Zecchina, A.; Bordiga, S.; Lamberti, C.; Spoto, G.; Carnelli, L.;
Otero Areán, C. J. Phys. Chem. 1994, 98, 9577-9582. Henry’s law regime where the slope is unity. The lighter
(33) Olson, D. H.; Kokotailo, G. T.; Lawton, S. L.; Meier, W. M. J. components CH4, N2, O2, and Ar obey Henry’s law
Phys. Chem. 1981, 85, 2238-2243. approximately at subatmospheric pressures. Affinities
(34) Dunne, J. A.; Mariwala, R.; Rao, M.; Sircar, S.; Gorte, R. J.; of NaX for the adsorbates at low loading increase in the
Myers, A. L. Langmuir, in press.
(35) Kofke, T. J. G.; Gorte, R. J.; Farneth, W. E. J. Catal. 1988, 114, order O2, Ar, N2, CH4, C2H6, SF6, CO2. However, the
34. preference of NaX for SF6 over C2H6 at low coverage
5898 Langmuir, Vol. 12, No. 24, 1996 Dunne et al.

Figure 3. Isosteric heats of adsorption on NaX: (9) CO2 at Figure 4. Adsorption isotherms on Na-ZSM-5: (9) CO2 at
31.4 °C; (0) CO2 at 32.8 °C; (b) SF6 at 31.6 °C; (4) C2H6 at 32.4 24.1 °C; (b) SF6 at 22.2 °C; (4) C2H6 at 22.6 °C; (2) CH4 at 23.3
°C; (2) CH4 at 31.3 °C (displaced to right by 1 mmol/g); (O) N2 °C; (O) N2 at 21.9 °C; ([) Ar at 23.2 °C.
at 32.5 °C.
Table 3. Isosteric Heat of Adsorption of Carbon Dioxide
Table 1. Isosteric Heat of Adsorption (kJ/mol) on NaX, at the Limit of Zero Coverage and Approximately 300 K
Na-ZSM-5, and H-ZSM-5, and Silicalite at the Limit of adsorbent Si/Al ratio qst, kJ/mol ref
Zero Coverage and Approximately 300 K
Na-ZSM-5 30 50.0 this study
qst (kJ/mol) Na-ZSM-5 30 50.0 25
adsorbate NaX Na-ZSM-5 H-ZSM-5 silicalite Na-ZSM-5 31 42.0 27
Na-ZSM-5 46.6 46.3 31
CO2 49.1 50.0 38.0 27.2 H-ZSM-5 30 38.0 this study
C2H6 27.0 38.0 33.3 31.1 H-ZSM-5 31 26.1 27
SF6 28.2 42.0 35.2 34.4 H-ZSM-5 53.8 28.8 31
N2 19.9 24.1 20.7 17.6 NaX 1.23 49.1 this study
CH4 19.2 26.5 20.9 NaX 1.34 48.1 16
Ar 12.7 18.0 15.8 NaX 1.38 47.3 2
O2 15.0 16.3 NaX 1.45 47.5 17
NaX 1.45 50 5
Table 2. Isosteric Heat of Adsorption of Ethane and
Methane at the Limit of Zero Coverage and
Approximately 300 K increase of 10 kJ/mol observed for SF6 is in good agreement
gas adsorbent Si/Al ratio qst, kJ/mol ref
with the value of 10.5 kJ/mol obtained by Barrer et al.36
For the lighter adsorbates CH4 and N2, the range of data
C2H6 Na-ZSM-5 30 38.0 this study is too small to determine the shape of the heat profile.
Na-ZSM-5 31 37.5 24
Na-ZSM-5 31 30.0 27 The isosteric heat of CO2 on NaX decreases sharply
H-ZSM-5 30 33.3 this study from 49 kJ/mol at the limit of zero loading to a plateau
H-ZSM-5 31 28.0 27 value of 36 kJ/mol. This decrease of the isosteric heat
NaX 1.23 27.0 this study with coverage is attributed to interactions of the Na+ ion
NaX 25.1 6 with the quadrupole moment of CO2; at high coverage the
NaX 1.34 25.9 10 high-energy Na+ sites become saturated and the gas-
NaX 27.0 38
CH4 Na-ZSM-5 30 26.5 this study
solid interaction energy is mainly dispersion.
Na-ZSM-5 31 21.2 27 Na-ZSM-5. Adsorption isotherms for Na-ZSM-5 are
Na-ZSM-5 23.3 30.0 29 shown in Figure 4 (linear plot) and Figure 5 (log-log plot).
H-ZSM-5 31 19.0 27 The affinity at low coverage increases in the order Ar, N2,
H-ZSM-5 23.3 23.0 29 CH4, C2H6, SF6, CO2. The isotherms for CO2, SF6, and
NaX 1.23 19.2 this study
NaX 17.6 6
C2H6 intersect at a loading of about 0.42 mmol/g. Figure
NaX 1.34 18.8 10 5 shows that the adsorptions of Ar, N2, and CH4 obey
NaX 1.3 20.1 18 Henry’s law approximately at subatmospheric pressures.
NaX 1.18 18.4 11 Isosteric heats of adsorption are plotted in Figure 6.
NaX varied 17.4 13 All of the heat profiles exhibit a decrease with loading
reverses at 150 Torr due to the lower saturation capacity below 0.5 mmol/g. At higher loadings, the heats of SF6
of SF6. CO2 in NaX has the highest affinity of the and C2H6 are nearly constant with loading. The heats of
adsorbates studied because of strong ion-quadrupole the polar adsorbates CO2 and N2 decrease markedly with
interactions.16 loading; the isosteric heat of CO2 drops from 50 kJ/mol at
Adsorption isotherms and isosteric heats of adsorption zero loading to a value of 29 kJ/mol at high loading. The
were measured simultaneously using the calorimeter heat profile for CO2 intersects the SF6 and C2H6 curves
designed for this purpose. Isosteric heats of adsorption at a loading of about 0.5 mmol/g, the same loading at
are plotted in Figure 3 as a function of loading. Values which the isotherms intersect.
of the isosteric heat extrapolated to zero loading (see Table H-ZSM-5. Adsorption isotherms for H-ZSM-5 are
1) are 28.2, 27.0, and 19.2 kJ/mol for the nonpolar shown in Figure 7 (linear plot) and Figure 8 (log-log plot).
adsorbates SF6, C2H6, and CH4, respectively. The heats The affinities increase in the order N2, CO2, C2H6, SF6.
of SF6 and C2H6 increase with coverage, indicating that
for these molecules the gas-solid interaction energy is (36) Barrer, R. M.; Reucroft, P. J. Proc. R. Soc. Edinburgh. A 1960,
fairly constant and gas-gas interactions dominate. The 258, 449-458.
Heats of Adsorption and Adsorption Isotherms Langmuir, Vol. 12, No. 24, 1996 5899

Figure 5. Adsorption isotherms on Na-ZSM-5: (9) CO2 at Figure 8. Adsorption isotherms on H-ZSM-5: (9) CO2 at 23.9
24.1 °C; (b) SF6 at 22.2 °C; (4) C2H6 at 22.6 °C; (2) CH4 at 23.3 °C; (0) CO2 at 22.5 °C; (b) SF6 at 21.7 °C; (4) C2H6 at 21.3 °C;
°C; (O) N2 at 21.9 °C; ([) Ar at 23.2 °C. (O) N2 at 21.3 °C.

Figure 6. Isosteric heats of adsorption on Na-ZSM-5: (9) CO2 Figure 9. Isosteric heats of adsorption for H-ZSM-5: (9) CO2
at 24.1 °C; (b) SF6 at 22.2 °C; (4) C2H6 at 22.6 °C; (]) C2H6 at at 23.9 °C; (0) CO2 at 22.5 °C; (b) SF6 at 21.7 °C; (4) C2H6 at
24.1 °C; (2) CH4 at 23.3 °C; (O) N2 at 21.9 °C; ([) Ar at 23.2 21.3 °C; (O) N2 at 21.3 °C.
°C.
Table 4. CO2 on NaX (0.558 g) at 32.8 °C
P, Torr n, mmol/g Qst, kJ/mol
0.08 0.0872
0.39 0.3014
1.12 0.6557 45.73
2.33 0.9947 44.63
4.61 1.3696
7.01 1.6244 41.66
12.52 2.0238 40.48
21.95 2.4473 39.06
36.24 2.8663 37.97
56.29 3.2798 37.27
85.05 3.6952 36.60
123.07 4.0787 36.60
165.92* 4.3973
171.06 4.4009 36.50
213.87 4.6179 35.74

The experimental data points for simultaneous mea-

Figure 7. Adsorption isotherms on H-ZSM-5: (9) CO2 at 23.9
°C; (0) CO2 at 22.5 °C; (b) SF6 at 21.7 °C; (4) C2H6 at 21.3 °C;
(O) N2 at 21.3 °C.
The increase in affinity corresponds with the increasing
polarizability of these molecules, so dispersion forces
dominate in H-ZSM-5.
Isosteric heats for H-ZSM-5 are plotted in Figure 9.
The profiles for the nonpolar molecules C2H6 and SF6 are
flat. The profiles for the polar molecules CO2 and N2
decrease with loading up to about 0.5 mmol/g. The CO2
profile is flat at higher coverages.
surement of amount adsorbed and isosteric heat of
adsorption are tabulated in Tables 4-23 for O2, N2, Ar,
CH4, CO2, C2H6, and SF6 gases on zeolites NaX, H-ZSM-5,
and Na-ZSM-5. Desorption points are indicated by
asterisks. The data were checked for reversibility and
reproducibility on different samples of the same adsorbent.
Error analysis yields an average experimental error of
0.6% in the loading and an average error of (0.5 kJ/mol
in the isosteric heat of adsorption. Data for the same set
of gases adsorbed on silicalite were reported previously.34
Heat Profiles of Probe Molecules in Different
Adsorbents. Comparison of profiles of heats of adsorption
5900 Langmuir, Vol. 12, No. 24, 1996 Dunne et al.

Table 5. CO2 on NaX (0.558 g) at 31.4 °C Table 9. SF6 on NaX (0.558 g) at 31.6 °C
P, Torr n, mmol/g Qst, kJ/mol P, Torr n, mmol/g Qst, kJ/mol
0.09 0.1029 2.78 0.0923
0.37 0.2903 6.59 0.2129 28.27
1.20 0.7335 45.55 11.56 0.3579 28.67
3.08 1.1877 43.93 18.40 0.5357 28.88
6.94 1.6611 41.99 27.05 0.7294 29.07
14.87 2.1764 39.92 37.89 0.9282 29.46
25.74 2.6147 38.52 53.52 1.1473 30.39
46.70 3.1537 37.27 75.37 1.3693 30.98
77.87 3.6590 36.47 114.06 1.6191 32.19
112.94 4.0440 35.93 156.89 1.7928 33.38
158.38 4.3849 35.76 228.79 1.9763 34.25
214.38 4.6742 35.82 309.99 2.1080 36.29
279.05 4.9138 35.93 398.86 2.2098 37.50
352.28 5.1148 35.85 499.15 2.2954 38.21
431.16 5.2780 36.10
455.49* 5.3343 Table 10. CH4 on NaX (0.558 g) at 31.3 °C
515.54 5.4158 36.48
P, Torr n, mmol/g Qst, kJ/mol
Table 6. C2H6 on NaX (0.558 g) at 32.4 °C 25.32 0.0240 18.85
66.89 0.0645 19.27
P, Torr n, mmol/g Qst, kJ/mol
128.48 0.1224 19.19
10.73 0.1425 27.15 193.57 0.1833 19.13
22.85 0.3008 27.07 273.72 0.2593 18.65
37.21 0.4879 27.28 366.41 0.3399 19.66
53.63 0.6997 28.10 452.18 0.4133 19.58
69.38 0.9018 28.01 547.12 0.4923 19.65
88.10 1.1333 28.35 574.75* 0.5339
108.15 1.3641 28.78 636.81 0.5759
129.69 1.5878 29.19 698.59 0.6336 19.64
154.96 1.8161 29.52
184.62 2.0410 30.10 Table 11. Ar on NaX (0.558 g) at 31.0 °C
220.94 2.2642 30.47
P, Torr n, mmol/g Qst, kJ/mol
264.83 2.4813
319.75 2.6767 32.14 46.77 0.0083 11.87
393.89* 2.8868 132.64 0.0229 12.24
393.32 2.8660 33.14 233.43 0.0398 12.73
473.98 3.0154 33.70 338.64 0.0570 12.70
475.92 3.0382 33.62 383.84* 0.0696
562.77 3.1587 33.51 447.67 0.0745 12.80
497.57 0.0864 14.60
Table 7. O2 on NaX (0.558 g) at 33.2 °C 611.20 0.1046 13.03
727.14 0.1231 11.91
P, Torr n, mmol/g Qst, kJ/mol
162.16 0.0221 13.94 Table 12. CO2 on Na-ZSM-5 (1.551 g) at 24.1 °C
259.60 0.0373 14.17
P, Torr n, mmol/g Qst, kJ/mol
364.85 0.0515 16.48
465.37 0.0656 15.71 0.10 0.0374 48.01
559.47 0.0789 16.37 0.44 0.0917 44.98
646.19* 0.0935 1.25 0.1641 43.03
656.64 0.0892 2.61 0.2336 41.54
753.55 0.1060 13.11 5.03 0.3114 38.87
8.99 0.3944 37.64
Table 8. N2 on NaX (0.558 g) at 32.5 °C 14.92 0.4822 36.02
22.48 0.5679 34.52
P, Torr n, mmol/g Qst, kJ/mol
32.15 0.6549 33.72
35.01 0.0186 19.99 46.86 0.7611 32.67
97.88 0.0527 19.91 65.53 0.8699 31.88
165.54 0.0903 18.80 83.84 0.9601 31.00
253.36 0.1399 18.45 107.92 1.0612 30.53
346.75 0.1857 19.75 135.67 1.1621 30.13
439.97 0.2322 19.59 166.78 1.2596 29.53
537.43 0.2767 20.13 198.38 1.3470 29.48
634.13 0.3268 18.31 235.14 1.4368 29.39
732.41 0.3741 18.92 275.43 1.5234 29.27
825.26 0.4226 17.60 314.69 1.5982 29.25
359.04 1.6740 29.43
for the same molecule in different adsorbents reveals the 413.73 1.7561 29.13
472.89 1.8342 28.96
degree of energetic heterogeneity and the relative im- 502.37* 1.8725
portance of electrostatic interactions compared to disper- 536.43 1.9080
sion. Figure 10 shows that isosteric heats of adsorption
of C2H6 increase in the order NaX, silicalite, H-ZSM-5, between energetic heterogeneity and adsorbate-adsor-
Na-ZSM-5. In NaX, the heat increases strongly with bate interactions for nonpolar molecules like C2H6. The
loading, indicating the dominance of adsorbate-adsorbate heat of adsorption in Na-ZSM-5 falls slightly with loading
interactions and a relatively homogeneous environment up to 0.5 mmol/g. At loadings above 0.5 mmol/g, the
for gas-solid interactions. The heat profiles above 0.5 increments in heats are about 1 kJ/mol going from silicalite
mmol/g are flat in MFI zeolites, indicating a balance to H-ZSM-5 to Na-ZSM-5.
Heats of Adsorption and Adsorption Isotherms Langmuir, Vol. 12, No. 24, 1996 5901

Table 13. C2H6 on Na-ZSM-5 (1.551 g) at 22.6 °C Table 17. N2 on Na-ZSM-5 (1.551 g) at 21.9 °C
P, Torr n, mmol/g Qst, kJ/mol P, Torr n, mmol/g Qst, kJ/mol
0.74 0.0575 36.14 0.0299 23.62
1.82 0.1208 36.45 97.94 0.0697 23.05
3.27 0.1919 35.91 185.10 0.1181 22.64
5.02 0.2659 279.22 0.1647 22.18
7.12 0.3432 34.83 364.15 0.2031 21.86
10.63 0.4519 34.42 461.02 0.2436 21.54
15.92 0.5849 34.52 559.48 0.2821 20.99
22.09 0.7135 34.30 657.01 0.3192 20.25
28.20 0.8199 34.37 756.99 0.3553 19.72
36.26 0.9352 34.26 790.15* 0.3692
46.46 1.0512 34.16 842.15 0.3854 19.30
59.50 1.1674 34.32
77.29 1.2867 34.46 Table 18. Ar on Na-ZSM-5 (1.551 g) at 23.2 °C
101.03 1.4009 34.41
P, Torr n, mmol/g Qst, kJ/mol
132.51 1.5075 34.56
180.13 1.6161 34.53 58.54 0.0198 17.60
242.97 1.7097 34.47 160.54 0.0529 17.92
320.60 1.7868 34.67 267.85 0.0863 16.78
410.40 1.8501 34.20 375.07 0.1190 17.07
510.19 1.9026 34.19 480.97 0.1503 16.94
589.75 0.1818 17.05
Table 14. C2H6 on Na-ZSM-5 (1.551 g) at 24.1 °C 599.67* 0.1858
694.18 0.2119 16.31
P, Torr n, mmol/g Qst, kJ/mol
716.74 0.2198 16.67
1.01 0.0690 37.08 808.92 0.2467 15.83
2.63 0.1543 36.46
4.63 0.2393 35.62 Table 19. CO2 on H-ZSM-5 (1.079 g) at 23.9 °C
7.03 0.3248 35.17
P, Torr n, mmol/g Qst, kJ/mol
9.75 0.4093 34.83
12.98 0.4963 34.62 4.13 0.0691 35.68
16.85 0.5864 34.53 11.59 0.1580 32.56
21.60 0.6806 34.13 23.27 0.2652 31.40
27.15 0.7743 34.12 37.42 0.3683 30.54
54.90 0.4736 29.79
Table 15. SF6 on Na-ZSM-5 (1.551 g) at 22.2 °C 73.49 0.5703 29.04
94.47 0.6656 28.70
P, Torr n, mmol/g Qst, kJ/mol
121.75 0.7747 28.58
0.60 0.0587 40.83 151.07 0.8784 28.29
1.64 0.1281 39.15 188.95 0.9961 28.23
3.40 0.2142 38.26 230.47 1.1086 28.18
6.00 0.3156 38.01 277.89 1.2204 28.17
9.34 0.4204 37.97 334.52 1.3357 28.11
13.37 0.5265 38.00 395.56 1.4430 28.32
18.44 0.6336 39.03 462.44 1.5446 28.48
24.60 0.7456 38.88 532.90 1.6378 28.19
31.79 0.8710 39.32 606.60 1.7234 27.99
41.12 0.9953 39.49 685.41 1.8045 27.81
54.17 1.1216 39.92 721.21* 1.8427
72.17 1.2438 40.03 767.63 1.8803 27.17
99.04 1.3656 40.04
134.00 1.4680 40.18 Table 20. CO2 on H-ZSM-5 (1.079 g) at 22.5 °C
182.24 1.5586 40.16
P, Torr n, mmol/g Qst, kJ/mol
226.87* 1.6174
250.85 1.6393 39.98 2.37 0.0469 36.23
5.40 0.0921 32.64
Table 16. CH4 on Na-ZSM-5 (1.551 g) at 23.3 °C 10.72 0.1581 32.26
17.13 0.2242 31.14
P, Torr n, mmol/g Qst, kJ/mol
27.08 0.3093 30.65
19.61 0.0503 27.30 42.17 0.4159 29.74
47.85 0.1083 24.79 59.06 0.5162 29.05
85.33 0.1758 24.78 82.21 0.6332 28.48
125.78 0.2405 24.37 107.73 0.7448 28.34
169.56 0.3037 23.83 140.95 0.8705 28.06
220.05 0.3696 23.78
276.16 0.4359 23.59 sorbate-adsorbate interactions. Adsorbate-adsorbate
336.11 0.5006 23.14 interactions are less prominent in MFI zeolites. The zero
396.50 0.5615 22.82 coverage heat of 42 kJ/mol in Na-ZSM-5 compared to 34.4
467.26 0.6264 23.05
541.04 0.6889 22.81
kJ/mol in silicalite can be attributed to induced electro-
618.71 0.7504 22.45 static interactions in SF6.
The comparison in Figure 12 of isosteric heats for a
The behavior of the nonpolar molecule SF6 (Figure 11) third nonpolar molecule, CH4, displays the same behavior
is similar to that of C2H6. The heats of adsorption of observed for the other nonpolar molecules (C2H6 and
SF6 increase in the order NaX, silicalite, H-ZSM-5, SF6).
Na-ZSM-5. However, the profiles for H-ZSM-5 and The heat profiles of the polar molecule CO2 are highly
silicalite almost coincide. In NaX, the heat increases sensitive to the electric field inside the zeolites, as
strongly with loading, indicating the dominance of ad- illustrated in Figure 13. At high coverage above
5902 Langmuir, Vol. 12, No. 24, 1996 Dunne et al.

Table 21. C2H6 on H-ZSM-5 (1.079 g) at 21.3 °C

P, Torr n, mmol/g Qst, kJ/mol
1.88 0.0755 33.85
3.88 0.1474
6.05 0.2169 32.80
8.32 0.2857 33.01
10.77 0.3524 32.90
14.69 0.4485 32.80
19.10 0.5429 32.77
24.13 0.6385 32.69
31.19 0.7526 32.88
39.59 0.8642 32.87
50.25 0.9781 33.24
62.90 1.0851
82.09 1.2073 33.20
107.69 1.3240 33.47
146.32 1.4443 33.48
195.47 1.5464 33.51
265.32 1.6427 33.38 Figure 10. Isosteric heats of adsorption for C2H6: (9) NaX at
348.58 1.7210 33.06 32.4 °C; (0) Na-ZSM-5 at 22.6 °C; ([) H-ZSM-5 at 21.3 °C; (])
441.25 1.7843 33.10 silicalite at 23.0 °C.
492.69* 1.8137
541.57 1.8376 32.24

Table 22. SF6 on H-ZSM-5 (1.06 g) at 21.7 °C

P, Torr n, mmol/g Qst, kJ/mol
0.64 0.0499 35.71
1.77 0.1240 34.91
3.09 0.1974 35.07
4.73 0.2736 35.23
6.47 0.3428 35.46
8.86 0.4245 35.74
13.23 0.5470 36.18
19.83 0.6915 36.14
29.77 0.8527 36.88
44.06 1.0141 37.43
64.47 1.1664 37.70
93.76 1.3031 37.79
136.36 1.4229 37.84

Table 23. N2 on H-ZSM-5 (1.06 g) at 21.3 °C

Figure 11. Isosteric heats of adsorption for SF6: (9) NaX at
P, Torr n, mmol/g Qst, kJ/mol 31.6 °C; (0) Na-ZSM-5 at 22.2 °C; ([) H-ZSM-5 at 21.7 °C; (])
84.22 0.0316 19.98 silicalite at 31.8 °C.
168.71 0.0601
267.96 0.0923 19.83
368.39 0.1235 18.50
470.29 0.1540 19.01
573.88 0.1844 18.16
691.19 0.2188 17.89
710.91* 0.2286
806.49 0.2532 16.79

1 mmol/g, the heats for the MFI zeolites merge. At low

coverage, the heats of adsorption are nearly flat for
silicalite, indicating a relatively weak electric field.
Addition of H+ and Na+ ions (ion concentration ) 0.5 mmol/
g) to the MFI structure causes a large increase in the heat
of adsorption at low loading. NaX zeolite shows a broader
distribution of high-energy sites, and the heat of adsorption
in NaX is much higher, except at zero loading, where the
heats for NaX and Na-ZSM-5 coincide.

4. Discussion
Nonpolar Adsorbate Molecules. Heats of adsorption
of nonpolar adsorbate molecules increase in the order NaX,
silicalite, H-ZSM-5, Na-ZSM-5 (see Table 1). The pores
in NaX are larger than those of the MFI type zeolites
(silicalite, H-ZSM-5, Na-ZSM-5). For a given structure,
dispersion energy increases with decreasing pore size.
Since dispersion energies dominate for nonpolar molecules,
the higher heats of adsorption in MFI zeolites (compared
to NaX) are attributed to the smaller pore size in MFI.
The increments in the heats of adsorption of the
nonpolar adsorbates in MFI zeolites are small but
Figure 13. Isosteric heats of adsorption for CO2: (9) NaX at
32.8 °C; (0) Na-ZSM-5 at 24.1 °C; ([) H-ZSM-5 at 23.9 °C; (])
silicalite at 30.1 °C.
consistent. The effect may be attributed to ion-induced
dipole interactions of the exchangeable cations (H+, Na+)
with the adsorbate molecules (CH4, C2H6, SF6 ). For a
given nonpolar molecule, the heats of adsorption in the
three MFI zeolites merge at high coverage, where sites
close to the exchangeable cations are saturated.
Results consistent with these observations have been
reported by others. Literature values for heats of adsorp-
tion at the limit of zero coverage are given in Table 2 for
Heats of Adsorption and Adsorption Isotherms
Figure 12. Isosteric heats of adsorption for CH4: (9) NaX at
31.3 °C; (0) Na-ZSM-5 at 23.3 °C; (]) silicalite at 23.1 °C.
the nonpolar gases CH4 and C2H6. Our isosteric heats for
C2H6 are in excellent agreement with previous calorimetric
data24 on Na-ZSM-5. Our isosteric heats for C2H6 and
CH4 on NaX agree within 4% with data determined by
Barrer et al.10 Heats calculated from GC data for CH4
and C2H66,13,27 seem to underpredict the heat of adsorption,
as noted previously by Habgood.6
The zero-coverage heat of CH4 is 9 kJ/mol higher in
Na-ZSM-5 than in silicalite according to Yamazaki et al.29
IR analysis showed that CH4 interacts with Na+ ions in
the zeolite, and the increase in zero-coverage heat could
be explained by ion-induced dipole interactions. Lechert
et al.37 reported a heat of adsorption for n-butane that
was higher in Na-ZSM-5 than in silicalite. The difference
in heats between silicalite and Na-ZSM-5 increased with
increasing Al content in Na-ZSM-5.
Polar Adsorbate Molecules. The sensitivity of ad-
sorptive selectivity to cation exchange has been attributed
to strong electrostatic interactions between the multipole
moments of the adsorbate molecule and the electric field
within the adsorbent. Barrer et al.39 and Kiselev et al.40
have modeled the electric field in NaX by attributing
partial charges to the sodium cations and oxygen atoms
in the zeolite cavity. The contribution of ion-quadrupole
interactions to the total gas-solid interaction energy of
CO2 was estimated to be 41% and 55% by Kiselev and
Barrer, respectively. Similarly, for N2 a value of 23% was
estimated.40
Literature values of heats of adsorption at the limit of
zero coverage for the quadrupolar gas CO2 are given in
Table 3. Our heats are in excellent agreement with
calorimetric data on Na-ZSM-525 and NaX.5 Heats
calculated from GC data predict heats lower than that
measured by calorimetry, as noted previously for the
nonpolar gases. Our heat of adsorption for CO2 is within
2% of the value obtained by Barrer et al.16
Models for adsorbents such as NaA and NaCaA have
been developed by Cohen de Lara et al.41,42 which, like
(37) Lechert, H.; Schweitzer, W. Proceedings of the Sixth International
Zeolite Conference; Olson, D., Bisio, A., Eds.; Butterworth & Co.:
Guildford, Surrey, U. K., 1983; pp 210-216.
(38) Isirikian, A. A.; Dubinin, M. M. In Academy of Sciences of the
GDR, preprints of the workshop III, Adsorption in Microporous
Adsorbents; Stach, H., Ed.; 1987, Vol. 2, p 57.
(39) Barrer, R. M.; Gibbons, R. M. Trans. Faraday Soc. 1963, 59,
2569-2582.
(40) Kiselev, A.; Du, P. Q. J. Chem. Soc., Faraday Trans. 2, 1981,
77, 1-15.
(41) Barrachin, B.; Cohen de Lara, E. J. Chem. Soc., Faraday Trans.
2 1986, 82, 1953-1966.
(42) Cohen de Lara, E.; Delaval, Y. J. Chem. Soc., Faraday Trans.
2 1978, 74, 790-797.
Langmuir, Vol. 12, No. 24, 1996 5903
those of Barrer and Kiselev, assume charges on the oxygen
atoms and nonframework ions. The model electric field
was compared to experimental data from IR spectra for
N2 and N2O and is found to be about 5 V/nm. IR spectra
were also examined29-31 in ion-exchanged forms of ZSM-5
using CO2, CH4, and N2 as probe molecules. The interac-
tions increase in intensity in the order K, Na, Li, i.e., in
the order of increasing charge-to-size ratio. Electric fields
were determined to be 3 and 4.8 V/nm in the H and Na
forms of ZSM-5, respectively, at locations close to the ions.
Using a simplified model for the ZSM-5 pore, the contri-
bution of the charge-quadrupole term to the gas-solid
potential energy was estimated to be 43%. Lamberti et
al.28 estimated the field in Na-ZSM-5 to be 6.8 V/nm using
CO as a probe molecule.
Electric Field Adjacent to Sodium Cations in Na-
ZSM-5. The heat profiles observed for CO2 can be
explained by its electrostatic interactions with the ex-
changeable cations in the zeolite. All of the atoms (Al, Si,
O) carry charges and contribute to the electric field, but
the strongest contribution to the electric field is made by
the exchangeable cations (H and Na in this study).
The zero-coverage heats of adsorption of CO2 in silicalite
and Na-ZSM-5 are 27.2 and 50.0 kJ/mol, respectively. The
difference of 22.8 kJ/mol is due to the presence of the Na+
ion in MFI. This increase in energy due to the presence
of a nonframework ion is composed of two terms: a charge-
induced dipole term (Ψq-µ) and a charge-quadrupole term
(Ψq-Θ).
The charge-induced dipole term is given by
RE2(r)
Ψq-µ ) - (1)
2
where R is the polarizability of the adsorbate molecule
and E(r) is the electric field within the cavity at position
r. From Coulomb’s law
Rq2(r)
Ψq-µ ) - (2)
2r4
where q is the positive charge on the Na+ ion located at
a distance r from the CO2 molecule. The neighboring
atoms whose charges are being neglected (mainly O)
reduce the effective charge q from that of a single positive
charge to some lower value.
The charge-quadrupole term (Ψq-Θ) is given by
qΘ(3 cos2 θ - 1)
Ψq-Θ ) (3)
2r3
where Θ is the quadrupole moment of CO2 and θ is the
orientation angle between the axis of the quadrupole
moment and a line connecting the centers of the ion and
the CO2 molecule. For this approximate calculation, the
orientation of maximum energy (θ ) 0) is assumed.
If the sum of the energies for ion-induced dipole and
ion-quadrupole interactions is 22.8 kJ/mol, then the
charge q on the Na+ cation is 1/3 of an elementary charge
and the electric field (q/r2 ) is 6.2 V/nm. This value is
within 10% of the value of 6.8 V/nm obtained by Lamberti
et al.28 Equations 2 and 3 contribute 15% and 85%,
respectively, of the total energy of 22.8 kJ/mol. This
calculation is based upon collision diameters43,44 of 1.75
and 3.8 Å for Na+ and CO2, respectively, R ) 2.594 × 10-24
(43) Bezus, A. G.; Kiselev, A.; Lopatkin, A. A.; Du, P. Q. J. Chem.
Soc., Faraday Trans. 2, 1978, 74, 367-379.
(44) Karavias, F.; Myers, A. L. Mol. Simul. 1991, 8, 23-50.
5904 Langmuir, Vol. 12, No. 24, 1996
cm3, and Θ ) -4.3 × 10-26 esu cm2. The effective charge
of 1/3 on the sodium cation could form the basis for a
simplified model of exchangeable cations in zeolites.
The charge of 1/3 of a unit charge is lower than the
value of 0.7 quoted by Lamberti et al.28 because our
calculations ignore the negative charge on the framework
oxygen atoms surrounding the cation.
On the basis of 1/3 of an elementary charge on the Na+
ion, the calculated ion-induced dipole interaction energy
for CH4 and SF6 is 3.3 and 4.5 kJ/mol, respectively. The
induced energy of exchangeable cations with nonpolar
adsorbate molecules is considerably smaller than ion-
dipole or ion-quadrupole electrostatic interactions but
still not small enough to be ignored (see Figures 10-12).
5. Conclusions
The adsorption isotherms and heats of adsorption of a
series of gases of increasing size and polarity have been
determined in a series of adsorbents of increasing pore
size and energetic heterogeneity. For quadrupolar mol-
ecules (CO2 and N2), the effect of ion type on heats of
adsorption is dramatic, with Na+ ions providing the
Dunne et al.
strongest electric field within the pore. At higher loadings
the effects are less pronounced and heats for silicalite,
H-ZSM-5, and Na-ZSM-5 coincide.
For nonpolar molecules such as SF6, C2H6, and CH4 the
effect of ion type is less dramatic but does lead to some
increased heats of adsorption at low loadings. At higher
loadings the heats for silicalite, H-ZSM-5, and Na-ZSM-5
are almost identical with a slight increase on going to the
Na+ ion-exchanged form. An increase in heat was also
observed on going from the NaX adsorbent to the MFI
pore structure. This is attributable to increased dispersion
energy in the ZSM-5 adsorbent due to the smaller pore
size.
These series of experiments highlight the importance
of adsorbate size and polarity and adsorbent heterogeneity
in determining equilibrium properties such as adsorption
isotherms and heats of adsorption.
Acknowledgment. This research was supported by
National Science Foundation Grant CTS 9213882 and by
Air Products and Chemicals, Inc.
LA960496R