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Heat of Adsorption
By S. Sircar* and D. V. Cao
Separation of gas mixtures by pressure swing and thermal swing adsorption processes is an established unit operation in the
chemical industry. Mathematical simulations of these processes require precise knowledge of multicomponent gas adsorption
equilibria, kinetics, and heats for the system of interest over all conditions of pressure, temperature, gas composition and
adsorbate loading encountered by the adsorber during the separation process. Unfortunately, the published data on heats of
adsorption are often not adequate. Limited heat data are generally available for pure gas adsorption, heat data for binary gas
mixtures are rare, and heat data for mixtures containing three or more components are nonexistent.
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demonstrate the complexity of the gas-solid interactions other. This is the situation in the Henry's Law region [4,13]
between nonpolar SF6 molecules and various porous solids of the adsorption isotherm where the Gibbsian surface
of different surface polarity. The heat of adsorption of SF6 on excess of a pure gas is a linear function of pressure [nm =
the polar NaX zeolite increases with coverage indicating K(T)P]. The variable K is the Henry's Law constant. The
lateral interactions between the adsorbed molecules. The average adsorbate occupancy in a porous adsorbent is less
lateral interaction increases as the adsorbate loading in- than one molecule per pore in the Henry's Law region so
creases. The heat of adsorption of SF6 on the nonpolar that lateral interactions are absent. For example, a type A
silicalite remains practically constant over a large range of or X zeolite crystal has ~ 3.6 1026 cavities (pores) per gram
adsorbate loading indicating an energetically homogeneous and it would require an adsorbate loading of ~ 0.60
surface, and then it decreases due to weak adsorption of SF6 millimoles/gram before the average molecular population
on the alumina binder after the silicalite adsorption sites exceeds one per cavity, and lateral interactions become
are nearly saturated with SF6 [12]. The weakly polar alumina viable. For a typical zeolite, this constitutes a fractional
behaves like an energetically homogeneous surface (constant coverage (pore filling) of ~10±20 %. The same argument
heat) in the range of the data. The heats on both weakly holds for other porous crystalline or amorphous adsor-
polar carbons decrease with increasing loadings of SF6 bents.
showing that the carbons are energetically heterogeneous d. Application of Eq. (1) to the Henry's Law region for a pure
for adsorption of SF6. gas yields [4]:
2 d ln K
T
q RT (2)
dT
3 Discussion
where q* is the isosteric heat of adsorption of a pure gas in
The data show that calorimetrically measured isosteric the Henry's Law region. Eq. (2) shows that q* is not a
heats of adsorption of a pure gas as functions of adsorbate function of adsorbate loading. It is generally assumed that
loadings can be conveniently used to characterize the q* is a very weak function of T and thus, Eq. (2) can be
energetic behavior of the adsorbent surface. However, these integrated to get
properties cannot be predicated a priori. Each gas-solid pair h i
can have different characteristics and they must be experi- K
T K exp q=RT (3)
mentally evaluated. The following general remarks can,
however, be made: where K* is the integration constant. It also represents the
a. The isosteric heat of adsorption of a pure gas will be value of K at the limit of T ® ¥. Eq. (3) is found to be valid
independent of adsorbate loading for an energetically for all gas adsorption systems when K(T) can be estimated
homogeneous adsorbent. accurately from the experimental data. It can be used to
b. Lateral interactions between adsorbed molecules are extrapolate Henry's Law constants at lower temperatures
manifested by increase in isosteric heat with coverage. (difficult to measure) by measuring them at elevated
However, this effect will be important only at higher temperatures.
adsorbate loadings. e. The isosteric heat of adsorption of a pure gas on an
c. Adsorbate-adsorbate lateral interactions are expected to energetically heterogeneous adsorbent decreases with in-
be absent or negligible at very low coverages where the creasing adsorbate coverage because the higher energy
adsorbed molecules are sufficiently separated from each adsorption sites are preferentially filled at lower pressures
(thermodynamic work of adsorp-
16
tion process is higher [13]). The
16 16
(a) (b) (c) lower energy sites are preferentially
14 14 14
filled at higher pressures. These are
12 12 12 preferential behaviors. All sites
10 10 10 have some probability of being filled
8 8 8 at all pressures. For a very highly
6 6 6 heterogeneous adsorbent, the de-
crease in the isosteric heat with
st
4 4 4
increasing coverage can start at a
2 2 2 BPL Carbon
silicalite alumina PCB Carbon very low pressure and the Henry's
0 NaX Zeolite 0
0 Law region may not be experimen-
0.0 0.4 0.8 1.2 1.6 0.0 0.4 0.8 1.2 1.6 0.0 0.4 0.8 1.2 1.6 tally measurable unless the system
temperature is very high [13].
m m m
f. It has been argued that the experi-
Figure 1. Isosteric heats of adsorption of pure SF6 on (a) zeolites NaX and silicalite, (b) alumina, and (c) BPL mentally observed constancy of the
and PCB carbons at 32 C. isosteric heat of adsorption of a
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pure gas over a region of adsorbate coverage is caused by isosteric heats. Simplified models of heat of adsorption on a
the compensatory effects of lateral interactions and heterogeneous solid also justify this behavior [14].
adsorbent heterogenerity on the isosteric heat [13]. Multicomponent isosteric heats of adsorption are much
Although that is plausible, it is unlikely, because many more complex. Fig. 3(a, b) shows calorimetrically measured
different gas-solid adsorption systems having different isosteric heats for adsorption of CO2 and C2H6 from their
adsorbate sizes and polarites and different adsorbent pore binary mixtures on NaX zeolite [10]. Fig. 3a shows that the
size distributions and surface chemistries exhibit that isosteric heats of adsorption of CO2 at constant loadings of
behavior. It will be truly fortuitous that the increasing heat C2H6 decrease with increasing loadings of CO2. Fig. 3b shows
due to lateral interactions exactly matches the decreasing that the corresponding isosteric heats of adsorption of C2H6
heat due to adsorbent heterogeneity for all these very increase with increasing loadings of CO2. An interesting point
different systems. Constancy of heat of adsorption is is that the CO2 isosteric heat from the mixture at any given
presumably an indication of adsorbent homogeneity and CO2 loading is higher than that for pure CO2 at the same
lack of lateral interactions. This is particularly true at lower loading. Furthermore, the isosteric heat of adsorption of CO2
coverages. The decrease in heat at higher coverages is due increases at any given CO2 loading when the coadsorption of
to the stronger influence of adsorbent heterogeneity over C2H6 increases. Many of these results are counter-intuitive
lateral interactions, if any, in that region. The increase in and complex. They require further analysis.
heat at higher coverages is definitely due to the lateral
interactions on a homogeneous or a weakly heterogeneous
solid.
Fig. 2 shows the calorimetrically measured isosteric heat of
adsorption of pure CO2 at three different temperatures on a
pelletized silicalite sample bonded with alumina [14]. The
adsorbent exhibits pronounced heterogeneity for adsorption
of CO2. The heat in the Henry's Law limit is ~10.8 kcal/mole
and then it decreases with increased adsorbate loadings, and
finally levels off at ~ 6.5 kcal/mole at higher coverages. It was
found that the silicalite itself was homogeneous for adsorption
of CO2 but the presence of alumina binder introduced the
severe heterogeneity on the composite material [12]. How-
ever, Fig. 2 demonstrates that the isosteric heat of adsorption
is practically independent of temperature over a range of
65 C. This is a direct validation of the commonly made
assumption regarding the temperature independence of
15
14 o
Temperature, C:
Isosteric Heat of Adsorption, q (kcal/mol)
13
6
12
11 32
o
10 70
9
8
7
6
4 Figure 3. Isosteric heats of adsorption of (a) CO2 and (b) C2H6 from their binary
gas mixtures on NaX zeolite at 29 C and at constant adsorbate loadings of C2H6.
3
1 (a)
0 4 Conclusion
0.0 0.5 1.0 1.5 2.0 2.5 3.0
m
Surface Excess, n (mmol/g) Much more work is necessary to understand multicompo-
Figure 2. Isosteric heats of adsorption of pure CO2 on a pelletized silicalite nent heats of adsorption and their impact on adsorptive
sample with alumina binder at 6, 32 and 70 C. process design. Calorimetric measurements will be necessary
Chem. Eng. Technol. 25 (2002) 10, Ó 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 0930-7516/02/1010-0947 $ 17.50+.50/0 947
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to properly investigate this subject and to generate a multi- [4] S. Sircar, I&EC Res. 1999, 38, 3670.
[5] D. M. Young, A. D. Crowell, Physical Adsorption of Gases, Butter-
component heat database for theoretical modeling. worths, London 1962.
Received: March 5, 2002 [CET 1578] [6] S. Sircar, J. Chem. Soc. Faraday Trans. I. 1985, 81, 1527.
[7] S. Sircar, R. J. Mohr, C. Ristic, M. B. Rao, J. Phys. Chem. 1999, 103, 6539.
[8] J. Dunne, R. Mariwala, M. B. Rao, S. Sircar, R. J. Gorte, A. L. Myers,
Langmuir 1996, 12, 5888.
[9] J. Dunne, M. B. Rao, S. Sircar, R. J. Gorte, A. L. Myers, Langmuir 1996,
References 12, 5896.
[10] J. Dunne, M. B. Rao, S. Sircar, R. J. Gorte, A. L. Myers, Langmuir 1997,
[1] S. Sircar, Adsorption Sci. Tech. 2001, 19, 347. 13, 4333.
[2] S. Sircar, M. B. Rao, Heat of Adsorption of Pure Gas and Multi- [11] D. V. Cao, S. Sircar, Adsorption 2001, 7, 73.
component Gas Mixtures on Microporous Adsorbents, chap. 19, in [12] D. V. Cao, S. Sircar, I&EC Res. 2001, 40, 156.
Surfaces of Nanoparticles and Porous Materials (Eds: J. A. Schwarz, C. I. [13] S. Ross, J. P. Olivier, On Physical Adsorption, Interscience Publishers,
Contescu), Marcel Dekker, New York 1999, 501. New York 1964.
[3] D. G. Hartzog, S. Sircar, Adsorption 1995, 1, 133. [14] D. V. Cao, S. Sircar, Adsorption Sci. Tech. 2001, 19, 881.
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948 Ó 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 0930-7516/02/1010-0948 $ 17.50+.50/0 Chem. Eng. Technol. 25 (2002) 10