Review

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.

1 Introduction The term on the right-hand side of Eq. (1) is a thermo-

Separation of gas mixtures by pressure swing and thermal
swing adsorption processes is an established unit operation in
the chemical industry [1]. 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 [2,3]. The knowledge
of multicomponent heats is critical because it governs the
changes in the local adsorbent temperatures inside the
adsorber during the ad (de) sorption process which, in turn,
influence the local adsorption equilibria and kinetics, and thus,
the overall gas separation efficiency [3]. 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.
The relevant heat of adsorption of a gas (pure or from a
mixture) for design of an adsorber is the so-called ªisosteric
heat of adsorptionº which is defined by [2,4]:
" #  
H ln…Pyi †
qi ˆ ˆ ‡RT 2 (1)
nm T nm
i T;nm i adsorption for a pure gas or the components of a gas mixture
j
where qi is the isosteric heat of adsorption of component i at a
component adsorbate loading (Gibbsian surface excess) of nmi
and temperature T. The variable H is the total enthalpy of a
closed equilibrium adsorption system at temperature T, where
the gas phase has a pressure P and mole fraction yi for
component i. The equilibrium surface excess of component i at
P, T and yi is nmi.
± of adsorption of pure SF6 on (a) two microporous zeolites
[*] S. Sircar (author to whom correspondence should be addressed),
Department of Chemical Engineering, Lehigh University, 111 Research
Drive, Bethlehem, Pa, 18015, U.S.A; D. V. Cao, Air Products and
Chemicals, Inc., 7201 Hamilton Boulevard, Allentown, PA 18195, U.S.A.
dynamic relationship relating qi with P, T, yi and nmi when the
gas phase is ideal [4]. R is the gas constant. This relationship
can be conveniently used to calculate qi as a function of nmi and
T for pure gas adsorption of component i (yi =1) from the
experimentally measured adsorption isotherms (nmi vs P at
constant T) of that gas at different temperatures. Since qi is
generally a very weak function of T, a plot of [lnP] against [1/T]
at constant nmi yields a straight line with a slope equal to [qi/R]
for pure gas adsorption. Hence, qi can be easily obtained. This
procedure, however, is not very accurate (a) at higher
adsorbate loadings for most practically used microporous
adsorbents (Type I adsorption isotherms by Brunauer
classifications [5]) where the change in the isotherm slope
with pressure is very small, and (b) at very low pressures where
the isotherm measurements at lower temperatures may not be
very accurate for strongly adsorbed gases. Use of the
thermodynamic relationship given by Eq. (1) for calculation
of qi for a binary or multicomponent gas mixture is practically
impossible [6].
2 Calorimetric Measurement
Direct calorimetric measurement of isosteric heats of
can be more convenient and accurate [7]. Several Tian-Calvet
type microcalorimeters have been designed for this purpose
[7±10] and the experimental protocol and the theoretical
framework for data analysis have also been developed [7]. The
calorimeter can be used to obtain qi as a function of any chosen
values of nmi and T, both for the adsorption and the desorption
processes.
Fig. 1(a, b, c) shows examples of calorimetric isosteric heats
(NaX and silicalite), (b) one mesoporous alumina, and (c) two
micro-mesoporous activated carbons (BPL and PCB) as
functions of adsorbate loadings at 32 C [11]. These data

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 Review

demonstrate the complexity of the gas-solid interactions
between nonpolar SF6 molecules and various porous solids
of different surface polarity. The heat of adsorption of SF6 on
the polar NaX zeolite increases with coverage indicating
lateral interactions between the adsorbed molecules. The
lateral interaction increases as the adsorbate loading in-
creases. The heat of adsorption of SF6 on the nonpolar
silicalite remains practically constant over a large range of
adsorbate loading indicating an energetically homogeneous
surface, and then it decreases due to weak adsorption of SF6
on the alumina binder after the silicalite adsorption sites
are nearly saturated with SF6 [12]. The weakly polar alumina
behaves like an energetically homogeneous surface (constant
heat) in the range of the data. The heats on both weakly
polar carbons decrease with increasing loadings of SF6
showing that the carbons are energetically heterogeneous
for adsorption of SF6.
3 Discussion
The data show that calorimetrically measured isosteric
heats of adsorption of a pure gas as functions of adsorbate
loadings can be conveniently used to characterize the
energetic behavior of the adsorbent surface. However, these
properties cannot be predicated a priori. Each gas-solid pair
can have different characteristics and they must be experi-
mentally evaluated. The following general remarks can,
however, be made:
a. The isosteric heat of adsorption of a pure gas will be
independent of adsorbate loading for an energetically
homogeneous adsorbent.
b. Lateral interactions between adsorbed molecules are
manifested by increase in isosteric heat with coverage.
However, this effect will be important only at higher
adsorbate loadings.
c. Adsorbate-adsorbate lateral interactions are expected to
be absent or negligible at very low coverages where the
adsorbed molecules are sufficiently separated from each
16 16
(a) (b)
14 14
12 12
10 10
8 8
6 6
st
other. This is the situation in the Henry's Law region [4,13]
of the adsorption isotherm where the Gibbsian surface
excess of a pure gas is a linear function of pressure [nm =
K(T)P]. The variable K is the Henry's Law constant. The
average adsorbate occupancy in a porous adsorbent is less
than one molecule per pore in the Henry's Law region so
that lateral interactions are absent. For example, a type A
or X zeolite crystal has ~ 3.6 ”1026 cavities (pores) per gram
and it would require an adsorbate loading of ~ 0.60
millimoles/gram before the average molecular population
exceeds one per cavity, and lateral interactions become
viable. For a typical zeolite, this constitutes a fractional
coverage (pore filling) of ~10±20 %. The same argument
holds for other porous crystalline or amorphous adsor-
bents.
d. Application of Eq. (1) to the Henry's Law region for a pure
gas yields [4]:
 
 2 d ln K…T†
q ˆ RT (2)
dT
where q* is the isosteric heat of adsorption of a pure gas in
the Henry's Law region. Eq. (2) shows that q* is not a
function of adsorbate loading. It is generally assumed that
q* is a very weak function of T and thus, Eq. (2) can be
integrated to get
h i
K…T† ˆ K exp q=RT (3)
where K* is the integration constant. It also represents the
value of K at the limit of T ® ¥. Eq. (3) is found to be valid
for all gas adsorption systems when K(T) can be estimated
accurately from the experimental data. It can be used to
extrapolate Henry's Law constants at lower temperatures
(difficult to measure) by measuring them at elevated
temperatures.
e. The isosteric heat of adsorption of a pure gas on an
energetically heterogeneous adsorbent decreases with in-
creasing adsorbate coverage because the higher energy
adsorption sites are preferentially filled at lower pressures
(thermodynamic work of adsorp-
16
tion process is higher [13]). The
(c) lower energy sites are preferentially
14
filled at higher pressures. These are
12 preferential behaviors. All sites
10 have some probability of being filled
8 at all pressures. For a very highly
6 heterogeneous adsorbent, the de-
crease in the isosteric heat with

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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 Review

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
 Review
to properly investigate this subject and to generate a multi-
component heat database for theoretical modeling.
Received: March 5, 2002 [CET 1578]
References
[1] S. Sircar, Adsorption Sci. Tech. 2001, 19, 347.
[2] S. Sircar, M. B. Rao, Heat of Adsorption of Pure Gas and Multi-
component Gas Mixtures on Microporous Adsorbents, chap. 19, in
Surfaces of Nanoparticles and Porous Materials (Eds: J. A. Schwarz, C. I.
Contescu), Marcel Dekker, New York 1999, 501.
[3] D. G. Hartzog, S. Sircar, Adsorption 1995, 1, 133.
_______________________
948 Ó 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
[4] S. Sircar, I&EC Res. 1999, 38, 3670.
[5] D. M. Young, A. D. Crowell, Physical Adsorption of Gases, Butter-
worths, London 1962.
[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,
12, 5896.
[10] J. Dunne, M. B. Rao, S. Sircar, R. J. Gorte, A. L. Myers, Langmuir 1997,
13, 4333.
[11] D. V. Cao, S. Sircar, Adsorption 2001, 7, 73.
[12] D. V. Cao, S. Sircar, I&EC Res. 2001, 40, 156.
[13] S. Ross, J. P. Olivier, On Physical Adsorption, Interscience Publishers,
New York 1964.
[14] D. V. Cao, S. Sircar, Adsorption Sci. Tech. 2001, 19, 881.
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