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Recent Developments in Macroscopic Measurement of
Multicomponent Gas Adsorption Equilibria, Kinetics, and Heats
Shivaji Sircar
Ind. Eng. Chem. Res., 2007, 46 (10), 2917-2927• DOI: 10.1021/ie0601293 • Publication Date (Web): 29 August 2006
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Ind. Eng. Chem. Res. 2007, 46, 2917-2927 2917

Recent Developments in Macroscopic Measurement of Multicomponent Gas

Adsorption Equilibria, Kinetics, and Heats
Shivaji Sircar*
School of Chemical Engineering, Lehigh UniVersity, Bethlehem, PennsylVania 18015

Most practical applications of adsorption technology for gas separation and purification deal with multi-
component feed gas mixtures. The key input variables for the design and optimization of such separation
processes are the multicomponent gas adsorption equilibria, kinetics, and isosteric heats. Recent advances in
the measurement of these properties for multicomponent systems by macroscopic methods are discussed.
The isothermal isotope exchange technique for measurement of multicomponent gas equilibria and kinetics,
and micro-calorimetry for direct measurement of component isosteric heats from gas mixtures are recommended.

Introduction and heats. It is not an exhaustive summary of every experimental

technique published in the literature.
The importance of adsorption technology as a versatile tool
for separation and purification of industrial gas mixtures is well
Traditional Experimental Methods
established.1,2 Most of these separation applications share three
key characteristics: (i) the gases to be separated are multicom- Numerous experimental procedures have been used during
ponent mixtures, often containing more than two adsorbates of the last 50 years for measuring pure and multicomponent gas
different sizes, polarizabilities, and permanent polarities, (ii) the adsorption equilibrium and kinetic data. Different laboratories
solid adsorbents (crystalline or amorphous) possess a complex around the world have developed and implemented their own
network of micro-meso-porous structures, which cannot often specific techniques for this purpose. Several books on adsorption
be characterized quantitatively, and which are often energetically describe these methods in detail.3-9
heterogeneous for sorption of one or more gases, and (iii) the The majority of the published literature on gas adsorption
conditions (pressure, temperature, and gas compositions) pre- reports data for pure gas equilibrium isotherms and kinetics.
vailing inside an adsorber during a cyclic adsorptive process There is also a substantial volume of binary gas adsorption
can vary over a very large range. equilibrium data and a small volume of binary gas adsorption
The key input variables for the design of adsorptive separation kinetic data. However, most of these binary equilibrium data
processes include multicomponent gas adsorption equilibria, sets are not extensive enough to test their thermodynamic
kinetics, and heats. These three basic properties must be known consistencies.10 Multicomponent gas equilibrium and kinetic data
accurately under all conditions encountered by the adsorbers containing three or more adsorbates are sporadic.2 The excellent
during the process cycle for meeting the requirements of an monographs by Valenzuela and Myers (1989)11 and Kärger and
industrial design.2 Ruthven (1992),7 respectively, provide good compilations of
Unfortunately, there is a serious shortage of published the published equilibrium and kinetic data (mostly on zeolites).
multicomponent gas adsorption data. Reference 2 addresses the Isosteric heats of adsorption of pure gases are generally
state of the art in some detail. A common design practice is to calculated from the equilibrium isotherms at different temper-
(i) use theoretical or empirical equilibrium adsorption models atures using adsorption thermodynamics.12,13 Binary and mul-
for homogeneous or heterogeneous adsorbents to estimate the ticomponent gas adsorption heat data are emerging only
desired multicomponent equilibrium data, (ii) use empirical recently.2,66,67
kinetic models to describe adsorbate transport into the porous Pure Gas Equilibrium Isotherm and Adsorption Kinetics.
adsorbent particles by ignoring multicomponent interactions, and The frequently used methods for measurement of pure gas
(iii) assume constant isosteric heats for the components (ap- adsorption equilibria and kinetics include (a) the constant
propriate for homogeneous sorbents only) or use simplistic pressure gravimetric method, (b) the constant volume volumetric
heterogeneous equilibrium models to estimate component heats. method, (c) the variable volume piezo-metric method, and (d)
These models are often used in good faith for process design the column breakthrough method. Table 1 describes some of
after testing them with a scanty pure and binary gas adsorption the pros and cons of these methods.
database for the system of interest. Binary and Multicomponent Gas Equilibrium Isotherm
Clearly, an extensive multicomponent database is needed for and Adsorption Kinetics. The commonly used methods for
(i) seriously testing existing adsorption equilibrium, kinetics and binary and multicomponent gas adsorption equilibrium and
heat models, (ii) developing new or improved models, and (iii) kinetics are (a) the combined gravimetric-volumetric method
providing more insight into the complex phenomenon of for binary systems, (b) the constant volume volumetric method
multicomponent gas adsorption on heterogeneous adsorbents. (with continuous gas analysis) for multicomponent systems, and
The purpose of this article is to review several traditional (c) the closed-loop recycle method for adsorption of single or
and recent macroscopic experimental methods for measuring mixed adsorbates from a single or multicomponent carrier gas.
pure gas and multicomponent gas adsorption equilibria, kinetics, Table 1 lists some of the merits and demerits of these methods.
Commercially available microbalances including magnetic
* To whom correspondence should be addressed. E-mail: suspension balances are generally employed for the gravimetric Phone: 610-758-4469. Fax: 610-758-5057. methods mentioned above.14,15 The experimental setups for the
10.1021/ie0601293 CCC: $37.00 © 2007 American Chemical Society
Published on Web 08/29/2006
2918 Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007

Table 1. Pros and Cons of Traditional Experimental Methods

ad(de)sorption equilibrium ad(de)sorption kinetics
experimental methods advantages disadvantages advantages disadvantages
(a) gravimetric relatively simple, pure gas only, relatively simple, pure gas only, no control over
commercial no control over final commercial final equilibrium state,
apparatus available equilibrium state, apparatus available nonisothermal data,
difficult to repeat difficult to repeat
(b) volumetric relatively simple, no control over relatively simple, pure nonisothermal data,
pure or multi-component gas final state, or multicomponent gas complex data analysis
random data, (model dependent),
difficult to repeat, no control over final state,
needs gas analyzer difficult to repeat,
not very useful
(c) piezometric ideal for very pure gas only not useful
high-pressure data
(d) combined relatively simple, binary gas only, nonisothermal data, no control
gravimetric-volumetric no gas analysis no control over over final state,
needed for final state, complex boundary conditions
binary systems random data, for data analysis
difficult to repeat (model dependent),
not very useful
(e) column dynamic good for trace requires precise isothermal for model dependent
adsorbates in a flow rate and trace component data analysis for
bulk carrier gas, composition sorption, directly estimation of kinetic
relatively easy measurements provides column mechanism and
to repeat, constant P, T experiment dynamics mass transfer coefficients
(f) closed-loop good for multicomponent trace no control over generally isothermal for no control over
recycle adsorbates in a bulk gas, final state, trace adsorbate systems, final state,
constant P, T experiment difficult to repeat constant P, T experiment difficult to repeat

other methods are usually designed and fabricated by the cannot be verified by today’s experimental methods. Adsorption
individual research groups. thermodynamics, kinetics and column dynamics can be fully
Pure Gas Isosteric Heats. The isosteric heat of adsorption developed using GSE as the basic variable and there is no need
of a pure ideal gas i (q°i ) at pressure (P) and temperature (T) [or to estimate the actual amount adsorbed.13
at the corresponding equilibrium amount adsorbed (n°i ) and T] b. Void Volume of the System. Many methods described in
is traditionally calculated by measuring adsorption isotherms Table 1 and others require the knowledge of the void volume
at different temperatures and employing the thermodynamic of the adsorption system for estimating the transitional or
relationship [q°i (n°i ) ) RT2{δ ln P/δT}°ni].12,13 A plot of lnP equilibrium amounts adsorbed. The void volume is typically
against (1/T) at constant ni° yields a straight line with a slope measured by helium expansion into the adsorption system and
equal to (-q°i /R). by assuming that helium is not adsorbed on the adsorbent at
Multicomponent Isosteric Heats. The isosteric heat of the conditions of the test, such as low pressure and high
adsorption of component i (qi) of a multicomponent ideal gas temperature. However, it has been shown that this assumption
mixture at pressure (P), temperature (T), and gas-phase mole can cause a significant error in estimating (i) adsorption of pure
fraction (yi) [or at the corresponding equilibrium amount gases at high pressures and (ii) adsorption of weakly sorbed
adsorbed (ni) and T] is given by the thermodynamic relationship components of a gas mixture even at moderate pressures.16
[qi(ni,T) ) RT2{δ ln(Pyi)δT}ni].12,13 However, unlike in the case Protocols for measuring helium adsorption by gravimetric
of a pure gas, it is not possible to directly measure the methods have been proposed.16,17
temperature coefficient of the partial pressure (pi ) Pyi) of c. Nonisothermal Adsorption during Kinetic Tests. The
component i of a gas mixture at constant loadings (ni) of the heat of ad(de)sorption cannot generally be removed (supplied)
components of the mixture. Thermodynamic equations can be from (to) the adsorbent mass fast enough to achieve an
derived to estimate qi by measuring ni as functions of P at isothermal kinetic process unless the kinetics of sorption is
constant T and yi, as functions of yi at constant P and T, and as extremely slow. Data analysis of a nonisothermal kinetic
functions of T at constant P and yi.12,13 However, such extensive process, where the changes in the adsorbate loading and the
data are impractical to gather even for a binary system. The adsorbate temperature are large, requires a numerical solution
author is not aware of any such data set. Calorimetry is the of a nonisothermal kinetic model, which can be complex and
best choice for direct estimation of qi (i g 2) as discussed later. ambiguous.18 Consequently, differential kinetic tests, where the
There are four important fundamental issues regarding the changes in the adsorbate loading and the adsorbent temperature
data measured by the methods mentioned above and others to are deliberately kept small, have been designed and practiced
be described in the subsequent sections. for many of the test methods mentioned earlier. The differential
a. Gibbsian Surface Excess. The true thermodynamic test permits linearization of the change in the equilibrium
variable that is measured to quantify the extent of adsorption adsorbate loading due to changes in gas-phase adsorbate
of an adsorbate gas (pure or from a mixture) by all macroscopic concentration and adsorbent temperature, as well as decoupling
experimental methods is the Gibbsian surface excess (GSE) of of the effects of these two variables in data analysis. As a result,
that gas.13 The GSE is loosely called the “amount adsorbed” in analytical solutions of simultaneous mass and heat balance
the adsorption literature. Estimation of the actual amount equations describing the differential kinetic test under different
adsorbed from the GSE requires extraordinary assumptions transport mechanisms can be obtained. That simplifies data
about the structure and composition of the adsorbed phase which analysis. Examples include (i) differential constant pressure
Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007 2919

gravimetric test for adsorption of a pure gas involving different

mass transfer protocols such as a Fickian diffusion (FD) model
(neglecting or including thermal resistance within the adsorbent
particle)19,20 or linear driving force (LDF) model (neglecting
or including thermal resistance inside the adsorbent particle),21,22
(ii) differential constant pressure gravimetric test for a binary
gas mixture with mass transfer by the LDF model,23 and (iii)
differential closed-loop recycle test with mass transfer by the
LDF model.24 It is also shown that flow of gas over the
adsorbent at a moderate to high rate for removing (or supplying)
the heat of ad(de)sorption during the kinetic test may not achieve
a true isothermal process when the kinetics of sorption is
relatively fast.24,25
d. Random Nature of Data Generation. Many of the Figure 1. FRT response curves for sorption of C3H8 on 5A zeolite with
traditional methods for measurement of multicomponent equi- heat effect.
librium adsorption data do not have control over the final
equilibrium state at the end of the test. Consequently, the data mass transfer when two or more different resistances, such as
generated is often very random in nature and their use for testing external film, surface barrier, micropore diffusion, and macro-
the quality of a model and for process design is not very pore diffusion, are significant.28 Several combinations of mass
convenient. and heat transfer resistances can be used to fit the experimental
response curves.
Recently Developed Experimental Methods Figure 1 is an example of the pressure response curves
measured for adsorption of propane by 5A zeolite (P0 ) 5.6
Several new experimental methods have been developed Torr, T0 ) 363 K). The solid lines are the best fit of the
during the last two decades which can be potentially advanta- experimental data26 by a model where heat transfer, external
geous over the traditional methods. A few of these methods film, and macropore diffusion resistances are included.28 The
are briefly described below. data could be described equally well using models including
Frequency Response Technique (FRT). The most com- heat transfer, surface barrier and micropore diffusion resistances
monly used FRT method for measurement of pure gas adsorp- or heat transfer, and micropore- and macropore diffusion
tion kinetics consists of (i) equilibrating a known amount of resistances.28 The intersection of the “in phase” and the “out of
the adsorbent with a pure adsorbate gas at pressure P0 and phase” response curves at high frequency is found to be caused
temperate T0 in a closed thermostated container of volume V0, by the existence of a skin barrier or external film resistance.
(ii) differentially perturbing the system volume in a periodic Thus, it can be used to identify the existence of a surface barrier
fashion such as a sinusoidal variation (forcing function), and in the adsorbent particle.
(iii) measuring the steady-state periodic response of the system These studies have shown that the thermal effects cannot be
pressure.26-30 The response consists of an “in phase” and an ignored in the analysis of FRT data and they may seriously
“out of phase” component having the same frequency as that undermine one of the most attractive features of the technique,
of the forcing function but exhibiting different amplitudes and viz. unambiguous, identification of the mass transfer mechanism
phase angles due to the ad(de)sorption process with finite mass in the adsorbent. Simultaneous measurement of the periodic
transfer resistances. Model analysis of the response curves is changes of the adsorbent surface temperature during the FRT
then carried out to identify the correct mass transfer mechanism test may provide additional valuable information for establishing
and quantify the adsorbate mass transfer coefficient. the sorption mechanism.28,31
The most promising features of the FRT are its potential The FRT has also been used to study sorption of binary gas
ability to (i) discriminate between different mass transfer mixtures,30 where the responses of total gas pressure as well as
mechanisms due to the high sensitivity of the response curves the partial pressures of the components of the gas mixture are
to the nature of the model equations describing different measured. Development of nonisothermal models for the
mechanisms26-28 and (ii) measure relatively fast adsorption analysis of multicomponent sorption data by FRT have also been
kinetics due to the availability of pressure transducers with very initiated.31 It showed that the transport of the faster diffusing
small response times.29 component can be affected by the presence of a slower diffusing
The differential periodic changes in gas pressure and adsor- species. It is manifested by a roll-up effect on the partial pressure
bate loading, used in FRT, permits linearization of the adsorption frequency response curve.
isotherm with respect to the gas pressure and adsorbent More recently, a continuous flow-system FRT protocol was
temperature. This leads to analytical expressions for the pressure developed to facilitate the removal of the heat of adsorption
response curves, which helps data analysis. The differential FRT from the adsorbent by forced convection and, thus, maintain
test, however, does not permit isothermal data analysis, even an isothermal operation.32 The pure adsorbate gas was passed
though the adsorbent temperature changes are very small,27,28 through a thermostated adsorbent bed at P0 and T0 until the
except for the case where the kinetics of adsorption is very slow. adsorbent was equilibrated with the gas. The feed gas pressure
It has been shown that the shape of the response curve can be was then differentially perturbed in a sinusoidal wave fashion,
severely affected, such as formation of a bimodal “out of phase” and the effluent gas pressure response (same frequency as that
response curve, due to the thermal effects. This can be of the inlet gas pressure fluctuation but a different amplitude
incorrectly interpreted as a bimodal mass transfer process in and phase angle) was monitored. Various isothermal models
the adsorbent if the data were fitted by an isothermal model.27 using different kinetic mechanisms were used to fit the FRT
A theoretical FRT analysis of nonisothermal adsorption of a response curves in order to identify the mass transfer mechanism
pure gas by a bi-porous adsorbent pellet indicated that it may for sorption of pure N2 (surface barrier alone) and O2 (combined
be impossible to extract the correct mechanism of the adsorbate surface barrier and pore diffusion) on a carbon molecular sieve.
2920 Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007

Figure 3. Isotherms for adsorption of N2 + O2 binary mixture on Na-


tion under local equilibrium conditions, which can potentially

Figure 2. ZLC response curves for desorption of (a) C2H6 and (b) C4H10
from silicalite in the Henry’s law region. be achieved using a very low gas flow rate.
The intrusion of thermal effects on ZLC experiments has been
The existence of a distributed surface barrier resistance had to recognized. A model analysis shows that they can severely
be assumed in the model to improve the data fit. The study influence the shape of the ZLC response curves when the
again demonstrates the model dependency of FRT response data adsorbent particles are large.39 An analytical expression for the
analysis. response of a nonisothermal differential ZLC test, where the
purge gas adsorbate composition is slightly lower than C0, has
Zero Length Column (ZLC) Technique. The most com-
also been derived.40 The analytical solution, however, is
monly used ZLC method consists of (i) equilibrating a small
applicable only for a differential test, which allows linearization
sample of the adsorbent placed inside a thermostated tube with
of the adsorption isotherm with respect to adsorbate concentra-
an adsorbate gas at concentration C0, pressure P0, and temper-
tion and adsorbent temperature and not for a linear isotherm
ature T0, (ii) passing an inert, adsorbate-free purge gas at P0
using a nondifferential test.41
and T0 over the adsorbent at a high specific gas flow rate, and
Total Desorption (TD) Methods. Total desorption methods
(iii) monitoring the exit gas adsorbate compositions with time.
have frequently been used for measuring the adsorption
An isothermal desorption model is then used to extract the
equilibria and kinetics of pure and multicomponent gas mixtures.
adsorbate mass transfer coefficient from the effluent concentra-
The most common TD test consists of (i) flowing a pure gas or
tion profile.7,33 Analytical isothermal models have been devel-
a gas mixture (pressure ) P0, temperature ) T0, mole fraction
oped for cases where the adsorption isotherm is linear and the
of component i ) y°i ) over a packed, thermostated adsorbent
mass transfer is controlled by (i) Fickian diffusion within the
bed, containing a known amount of the adsorbent and having a
adsorbent33 and (ii) a surface barrier.34
precalibrated void volume, until equilibrium is reached, (ii)
The key advantages of the ZLC technique arise from (i) the desorbing (heating and evacuation) and transferring the entire
simplicity of the apparatus and its operation, (ii) potential content of the bed (void and adsorbed gases) to another
absence of external mass and heat transfer resistances and evacuated vessel of known volume, and (iii) measuring the final
maintenance of essentially zero adsorbate concentration at the pressure, temperature and gas composition of the mixed
surface of the adsorbent particles due to high gas flow rate desorbed gases. A simple mass balance yields the equilibrium
during the desorption process, (iii) absence of axial dispersion, amount of component i adsorbed (ni) at the initial equilibrium
and (iv) potential for measuring fast sorption kinetics. The conditions.42-47
technique has been extensively used for studying diffusion of Figure 3 shows an example of equilibrium isotherms mea-
pure hydrocarbons in the linear Henry’s law region using various sured by the TD method for adsorption of N2 + O2 binary gas
zeolite crystals.7 mixtures on Na-mordenite at three different temperatures.43 The
Figure 2 shows examples of typical ZLC response curves zeolite exhibits a thermodynamic selectivity for N2 over O2 and
for desorption of ethane and n-butane from silicalite crystals at the Langmuir model (solid lines) describes the isotherms very
various temperatures. The solid lines are a model fit of the data well.
using the Fickian diffusion mechanism.35 The same experimental protocol is carried out using a small
Extension of the ZLC method for measuring sorption kinetics amount of the adsorbent in a “differential adsorption bed”
in the nonlinear region of the adsorption isotherm has been (DAB) test for measuring adsorption kinetics.42,44-47 It consists
investigated.36 The ZLC method has also been used to estimate of (i) flowing a pure gas or a multicomponent gas mixture over
the pure gas adsorption isotherm and binary gas selectivity of the adsorbent for a specific period of time t, (ii) desorbing and
adsorption.37,38 The equilibrium measurements assume desorp- analyzing the desorbed gases in order to calculate the amount
Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007 2921

Table 2. Estimated Errors in Component Isosteric Heats of

Adsorption of a Binary Gas Mixture by the Short-cut Method
fractional estimated errors in
conditions surface coverages isosteric heats (%)
P (atm) y1 θ1 θ2 component 1 component 2
2.0 0.5 0.332 0.129 4.0 7.1
5.0 y1 f 0 0.000 0.545 6.9 11.1
0.1 0.129 0.452 7.6 12.2
0.5 0.491 0.191 10.7 16.5
0.9 0.712 0.031 13.9 21.
y1 f 1 0.755 0.000 14.8 22.2
10.0 0.5 0.584 0.227 24.5 34.2

isosteric heat of adsorption.50,51 The method consists of (i) filling

an adsorption chamber containing a known amount of the
adsorbent and having a premeasured void volume (V°, cc/g) with
a pure or a multicomponent gas mixture [amount of component
i ) (ñi)], (ii) placing the chamber inside a constant temperature
(T) bath, and (iii) measuring the subsequent equilibrium gas-
phase pressure (P) and mole fraction of component i (yi) inside
the closed chamber. The bath temperature is then systematically
Figure 4. Uptake curves for binary (a) N2 and (b) O2 mixture by a carbon changed and the corresponding equilibrium values of P and yi
molecular sieve. are measured at different values of T. For an ideal gas, the
specific equilibrium amount of component i adsorbed (ni) at
of component i adsorbed [ni(t)] at time t, and (iii) repeating the any given set of P, T, and yi can be calculated by the component
experiment using different values of time. A relatively high gas i mass balance [ñI ) ni + V°Pyi/RT]. It was argued that if the
flow rate ensures that there is no gas-phase composition gradient amount of component i in the void gas of the chamber was
across the adsorbent mass. It is also assumed that the heat of negligible compared to its amount adsorbed, [ni . V°Pyi/RT],
adsorption is removed by forced convection created by the high then [ñi ∼ ni]. Consequently, it might be assumed that the above-
gas flow rate so that the kinetic process is isothermal. Models described experiment was carried out at approximately constant
are then used to identify the transport mechanism and estimate loadings of the components of the gas mixture. Therefore, a
the component mass transfer coefficients from the kinetic data. plot of the measured data as ln(Pyi) against 1/T would be a
Figure 4 shows the fractional uptakes of O2 and N2 from a straight line with a slope equal to (-q̃i/R), where q̃i is
binary (50% N2 + 50% O2) gas mixture on a carbon molecular approximately equal to the isosteric heat of adsorption of
sieve at 263 K measured by the DAB test.47 O2 diffuses into component i (qi) at loading ni and T.
the carbon pores faster than N2, but the carbon has practically Although SIT is creative and experimentally simple, and it
no thermodynamic selectivity for either component. Conse- promises to resolve a major practical problem in estimating the
quently, the carbon exhibits a kinetic selectivity for O2 over N2 multicomponent isosteric heat of adsorption, a detailed ther-
at early times of contact, followed by displacement of some of modynamic analysis of this approach showed that the method
the adsorbed O2 by N2 at longer times, creating a maximum in would substantially under-estimate the actual values of the
the O2 uptake curve. The solid lines are the fit of the uptake isosteric heats for the following conditions.52
curves by an isothermal dual mode (surface barrier + micropore • Large specific void volume in the apparatus
diffusion) transport mechanism. • High adsorbate loading of the component
The advantages of these methods include (i) simple experi- • Adsorbate is weakly adsorbed
mental apparatus and procedure for measuring multicomponent • Adsorbent is energetically heterogeneous
adsorption equilibria and kinetics under controlled conditions Obviously, the isosteric heat of adsorption estimated by the
and (ii) potential for achieving isothermal adsorption kinetic SIT method will be identical to the actual heat if V° is negligible.
process. The second goal, however, may not be achievable However, that is not practically achievable.
unless the kinetics of adsorption is very slow.25 Table 2 shows examples of errors in estimating the component
Wicke-Kallenbach Permeation Method (WKM). The isosteric heats for adsorption of CO2 (1) + CH4 (2) binary gas
method consists of mounting a single crystal of a microporous mixture on BPL carbon at 303.1 K by the short-cut method.52
zeolite or a single particle of a porous adsorbent as a gas Pure and binary gas adsorption isotherms for this system could
permeation membrane device by embedding it in a high be adequately described by the homogeneous Langmuir model.
temperature polymer or in an epoxy matrix. Steady state It may be seen from Table 2 that the errors in the component
permeation flux of a pure or a mixed adsorbate gas is then isosteric heats by the short-cut method can be very large under
measured across the membrane by flowing the adsorbate gas at certain conditions. Another major problem is that the component
the high pressure side of the membrane and sweeping the low isosteric heats estimated by using the assumptions of the short-
pressure side of the membrane with an inert gas and continu- cut method are found to be functions of adsorbate loadings for
ously measuring the composition of the permeate gas mixture. a homogeneous adsorbent. That is incorrect and not thermody-
Effective diffusivities for the adsorbates through the porous namically feasible. Thermodynamic prescriptions to correct the
adsorbent can then be calculated by analysis of the steady-state problems associated with the short-cut method have been
flux data.48,49 formulated.52 Their applications are, however, limited to binary
Sorption Isosteric Technique (SIT) for Measurement of systems only, and they require additional measurements of
Multicomponent Gas Isosteric Heats of Adsorption. An binary gas adsorption isotherms.
approximate short-cut method, called SIT, has been used by Figure 5 shows an experimental comparison of pure gas
various authors to estimate pure and multicomponent gas isosteric heats for adsorption of O2 and N2 on CaA zeolite at
2922 Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007

Figure 5. Isosteric heats for adsorption of pure N2 and O2 on CaA zeolite.

Figure 6. Isothermal and nonisothermal fractional uptakes in a differential
test: Specific gas flow rates (cc/g/s): (a) 181.6, (b) 60.6, and (c) 20.2.
different loadings measured by SIT and calorimetry.51 The heats
measured by SIT are lower than those measured directly by
calorimetry except in the region of P f 0 (low coverage) as
discussed earlier. The specific void volume in the SIT apparatus
was 3.80 cm3/g.
Table 3 summarizes the pros and cons of the above-described,
recently developed experimental methods for measuring adsorp-
tion equilibria and kinetics. It may be noted that one of the
nagging issues with all of these methods is the nonisothermal
nature of the kinetic process, even for a differential test. This
makes data analysis difficult and even ambiguous in some cases.
One approach to resolve this problem has been to flow the
adsorbate gas over the adsorbent at a high specific flow rate
(cm3/g of adsorbent/s) so that the heat of ad(de)sorption can be Figure 7. Adsorbent temperature changes in the differential tests of Figure
removed (supplied) instantaneously by forced convection. A 6.
recent model analysis of this idea for a differential adsorption
system showed that a true isothermal kinetic process can be from inert helium by 5A zeolite at 323 K (qethane ∼ 8.8 kcal/
achieved only for (i) adsorption of a trace adsorbate from an mol).25 It was assumed that the LDF model decsribed the mass
inert gas or (ii) systems with very slow adsorption kinetics. transfer of C2H6 (k ) 0.2 s-1) into the zeolite and the change
Otherwise, the assumption of isothermal kinetic process must in the adsorbate loading during the test was only 2.8% (initial
be questioned even when the specific gas flow rate over the C2H6 loading on the zeolite ∼0.3 mmol/g). Figure 7 shows the
adsorbent is fairly high.25 Isothermal operation is practically corresponding adsorbent temperature changes [T(t) - T0] during
impossible to achieve when the adsorbate mass transfer coef- the kinetic process. These figures clearly demonstrate that (i) iso-
ficient is moderate to high. thermal sorption kinetics cannot be assumed for systems with mod-
Figure 6 compares model calculations of isothermal and non- erately large mass transfer coefficients even when the specific
isothermal fractional uptakes [f(t)] in a differential adsorption gas flow rate over the adsorbent is very high (>100 cm3/g/s)
test using different specific gas flow rates for adsorption of C2H6 and (ii) the departure from isothermal behavior is substantial

Table 3. Pros and Cons of Recently Developed Experimental Methods

ad(de)sorption equilibrium ad(de)sorption kinetics
experimental methods advantages disadvantages advantages disadvantages
(a) total desorption pure or multicomponent gas, tedious, time-consuming, pure or multicomponent gas, tedious, time-consuming, needs gas
method (TD) control over equilibrium state, needs gas analyzer control over equilibrium analyzer, isothermal nature of
easy to repeat state, easy to repeat transient process must be checked
(b) zero length simple experiment, may be non- simple experiment, pure gas only,
column method convenient for isothermal for absence of axial dispersion, convenient data analysis
(ZLC) measuring Henry’s large adsorbent convenient for measuring for Henry’s law region only,
law constant for a particles mass transfer coefficient may be non isothermal
pure gas in the Henry’s law region, for large particles
suitable for fast kinetics
(c) frequency response not useful suitable for measuring primarily pure gas kinetics,
technique (FRT) fast kinetics, potential complex model dependent
for decoupling complex data analysis, generally
kinetic mechanisms nonisothermal
(d) Wicke-Kallenbach not useful pure or multicomponent gas, difficult to prepare leak-proof
method (WKM) direct measurement adsorbent membrane,
of effective difficult in situ regeneration
diffusivity through of the adsorbent, isothermal
the adsorbent pore nature of the permeation
process must be checked
Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007 2923

Figure 8. Sorption kinetics of N2, CH4, and Kr on 4A zeolite by IET: (a) uptake curves and (b) self-diffusivities as function of fractional coverage.

even when the adsorbent temperature changes are very small components of the gas mixture. These assumptions are valid
(<0.2 °C), if the heat of adsorption is moderately large. except for very light gases such as H2. The estimation of pure
or multicomponent mass transfer coefficient of component i by
Most Recent Developments IET is based on the assumption that the transfer coefficients or
self-diffusivities of all isotope species of that component are
Two new experimental methods, which were specifically equal at any given set of P, T, and yi values.
designed for measuring multicomponent gas adsorption equi- The key advantages of the IET are listed below:
libria, kinetics and isosteric heats, have emerged during the past • There is complete control over the equilibrium state in the
decade. They circumvent most of the disadvantages of the earlier system, which is not perturbed during the experiment, and which
methods. They are briefly described below. is defined by the chosen values of the variables P, T, and yi at
Isotope Exchange Technique (IET). The isotope exchange the start of the test. This allows equilibrium and kinetic
technique can simultaneously measure pure or multicomponent measurements at any desired condition using a multicomponent
gas adsorption equilibria and kinetics in a single experiment gas mixture as opposed to random measurements by many other
without disturbing the overall adsorbed phase.53-55 methods.
The experimental protocol of the IET method is similar to • Convenient for measurement of pure and mixed gas self-
that of Quig and Rees used for measuring self-diffusion of gases diffusivities as functions of adsorbate loadings and temperature.
in zeolites.56 It consists of equilibrating an adsorbent mass in a • The ad(de)sorption process during the IET test is absolutely
closed-loop recycle system with a pure gas i at a chosen value isothermal. Thus, data interpretation is relatively simple and un-
of pressure P and temperature T or with a multicomponent gas ambiguous.
mixture of i (g2) components at a given set of P, T, and yi • The test can be repeated easily without regenerating the
values. The gas phase may contain a bulk and a trace isotope adsorbent which permits easy check of data reproducibility.
of component i (total gas-phase mole fraction of component i • The IET apparatus is relatively inexpensive and easy to
) yi). The trace isotope concentration of component i in the operate. This can be a major advantage over microscopic
gas phase is then changed without changing the total P, T, or methods to measure self-diffusivities in porous solids such as
yi, and the transient change in the concentration of the trace nuclear magnetic resonance-pulsed field gradient (NMR-PFG)
isotope is monitored until a new isotopic equilibrium state is method57-59 and nutron defraction (ND) methods7,59 or to
reached. This information can then be used to estimate the measure transport diffusivity by Fourier transform IR spec-
equilibrium amount adsorbed of component i (ni), and the self- trometry,60 all of which require expensive and complex equip-
diffusivity (Di) of the component i at the corresponding values ments, difficult sample preparation, and intricate data analysis.
of P, T, and yi, or ni and T. The experiment can then be repeated The IET, however, requires a supply of isotopes for the
by starting with another set of P, T, and yi values in order to adsorbate gases of interest and a continuous on-line analytical
generate the complete adsorption isotherm or to obtain Di as devise (such as a quadrupole mass spectrometer) for quantitative
functions of ni and T. This ability of probing a predetermined measurement of trace isotope concentrations.
multicomponent adsorbed phase with isotopes of each of the Figure 8 shows examples of uptake data measured by IET
components of the gas mixture in a series of isothermal isotope for adsorption of pure N2, CH4, and Kr by 4A zeolite at 283 K.
exchange tests without disturbing the adsorbed phase for The uptake data can be described very well by the Fickian
determining the multicomponent adsorption equilibria and diffusion mechanism (solid lines).55 Figure 8b shows that the
kinetics at any pre-chosen condition makes IET a very powerful self-diffusivities of Kr and CH4 increase with surface coverage
tool. The details of the experimental procedure and the data (much more pronounced for Kr), whereas the self-diffusivity
analysis can be found elsewhere.53 The estimation of pure or of N2 is independent of adsorbate loadings. These complex
multicomponent gas adsorption equilibria by IET is based on behaviors are caused by the closeness of the adsorbate sizes
the assumptions that (a) the pure gas adsorption isotherms of and the pore aperture of the zeolite.55
all isotope species of component i are identical and (b) the Figure 9 shows kinetic uptake data for binary gas adsorption
equilibrium selectivity of adsorption between the isotopes of of (a) N2 and O2 from air on Takeda carbon molecular sieve at
component i is unity in the presence or absence of other 303 K 53 and (b) N2 and CH4 from an equimolar mixture on
2924 Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007

Figure 9. Examples of binary gas adsorption kinetics measured by IET.

Table 4. N2 Mass Transfer Coefficients on Takeda Carbon Molecular Sieve at P f 0

mass transfer coefficients (×104 s-1)
surface barrier micropore diffusion
authors method T (K) transport resistance (ks) (km ) 15Dm /R2) ref
Qinglin, Farooq and Karimi DAB 302.1 surface barrier + ∼88.0 ∼87.0 47
micropore diffusion
Rynders, Rao And Sircar IET 303.1 surface barrier 28.0 ∞ 53
Wang, Sward And Levan Flow FRT 298.1 surface barrier ∼3.2 ∞ 32

4A zeolite at 253 K54 measured by IET. These data unambigu- of pure adsorbate i into the cell, and (c) measuring the evolved
ously showed (solid lines) that the uptake by the carbon heat (Qi) by thermopiles surrounding the cell. The experiment
molecular sieve was governed by the LDF surface barrier is then sequentially repeated by introducing a small quantity of
mechanism, whereas that by the zeolite was governed by the other pure components (j * i) of the gas mixture into the
Fickian diffusion in the zeolite micropores. calorimeter cell and measuring the corresponding heats of
Table 4 compares the results of kinetic data analysis for adsorption (Qj). The data can be directly used to estimate
adsorption of pure N2 by Takeda carbon molecular sieve isosteric heats of adsorption of a pure gas i (yi ) 1) or those
measured by IET, Flow-FRT, and DAB methods at ∼300 K. for the components of a gas mixture (i g 2) at a specific
The extrapolated mass transfer coefficient values at the limit adsorbate loading of ni at temperature T. These data can be
of zero pressure are reported in the table. The uptake by the directly used in design of adsorptive gas separation processes.
IET was isothermal by design, whereas the analysis of FRT The details of the experimental procedure and the protocol for
and DAB data assumed isothermal uptake (reasonable due to data analysis can be found elsewhere.62
slow kinetics of N2). The key advantages of using a microcalorimeter include the
It may be seen that a surface barrier resistance at the pore following:
mouths of the carbon alone was adequate to describe the N2 • Component isosteric heats of adsorption of a multicompo-
uptake data measured by IET and the FRT response curve, but nent gas mixture can be directly measured at any specific
a dual resistance (surface barrier + micropore diffusion) model adsorbate loading and temperature.
was needed to describe the data measured by DAB. The limiting • Measurement of high quality and accurate data.
N2 mass transfer coefficient evaluated from the kinetic data • Convenient for measuring pure and multicomponent iso-
measured by IET was an order of magnitude larger than that steric heats as functions of adsorbate loadings.
obtained from the analysis of the FRT data. The time constants • Indispensable tool for measuring the complex nature of
for the overall N2 mass transfer into the carbon estimated by isosteric heats on energetically heterogeneous adsorbents.
the IET and DAB methods were similar. This lack of consistent Figure 10 shows two examples of the high quality of isosteric
interpretation of kinetic transport of gases in carbon molecular heat data measured by the microcalorimeter on heterogeneous
sieves is well documented in the literature.61 adsorbents.63,64 The heat of adsorption of pure nonpolar SF6 on
Microcalorimeter for Multicomponent Isosteric Heat of a pelletized sample of silicalite (with alumina binder) remains
Adsorption. Several Tien-Calvet type heat flux microcalorim- constant (∼9.8 kcal/mol) over a very large range of coverage
eters have recently been designed for directly measuring isosteric (homogeneous behavior) and then it drops rapidly near the limit
heats of adsorption of a pure gas or those of the components of of the saturation capacity of the adsorbent. This was caused by
a gas mixture at a preselected adsorbed phase composition and the presence of the alumina binder which introduced masked
temperature.62-67 The experimental protocol consists of (a) heterogeneity for sorption of SF6.63 The heat of adsorption of
equilibrating a known mass of an adsorbent inside the calorim- pure polar CO2 on the γ-alumina is very high at zero coverage
eter cell with a gas mixture at pressure P, temperature T, and (∼20 kcal/mol), and then it continuously and rapidly decreases
gas-phase mole fraction yi (equilibrium amount of component to ∼6.5 kcal/mol as the loading increases, indicating a highly
i adsorbed ) ni), (b) slowly introducing a very small quantity heterogeneous adsorbent.63 Thus, these systems exhibit drasti-
Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007 2925

Figure 12. Isosteric heats of adsorption of CO2 on a pelletized silicalite.

Figure 10. Pure gas isosteric heats measured by micro-calorimetry at
∼32 °C.
of a practical gas separation system.68 Most of these properties
cannot be otherwise measured or estimated.

Multicomponent gas adsorption equilibria, kinetics, and
isosteric heats form the foundation of a good adsorptive process
design. Yet, published experimental data on these basic mul-
ticomponent properties are sporadic. A brief description of
several traditional and more recently developed experimental
methods for measurement of these properties is given, and their
pros and cons are discussed. Many of these methods may not
be useful or very convenient for measurement of multicompo-
nent adsorptive properties. A nagging issue is the nonisothermal
nature of the ad(de)sorption kinetic process, even for a dif-
ferential sorption test. This complicates data analysis, and often
introduces ambiguity. Another serious problem is that the data
generated is often random in nature because there is no control
Figure 11. Binary gas isosteric heats for CO2 + C2H6 on NaX zeolite by over the final equilibrium state in many of these methods. It is
calorimetry. inconvenient to use random multicomponent data for modeling
or process design. The third major problem has been the
cally different adsorption heterogeneity which can be accurately traditional absence of a reliable method for measuring accurate
characterized only by microcalorimetry. multicomponent isosteric heats.
Figure 11 shows an example of binary gas isosteric heats for Two recently developed methods circumvent many of these
adsorption of CO2 + C2H6 mixtures on NaX zeolite at ∼29 °C short comings. The isotope exchange technique provides a
measured by micro-calorimetry.66 The data were measured at a suitable method for isothermal measurement of multicomponent
constant loading of C2H6 (∼2.6 mmol/g). The CO2 isosteric heat adsorption equilibria and kinetics where the final equilibrium
from the mixture at any given CO2 loading was higher than the state is pre-chosen by design. Microcalorimetry provides an
corresponding pure gas heat, and it decreased with increasing accurate method for direct measurement of multicomponent
loading of CO2. The isosteric heat of C2H6 from the mixture, isosteric heats at any chosen condition of adsorbate loading and
on the other hand, increased with increasing CO2 loading, and temperature. A detailed evaluation of the very complex and
it was larger than that of pure the pure gas. These apparently intricate nature of pure and mixed gas isosteric heats on
complex and counter-intuitive mixed gas heat data could only heterogeneous adsorbents can be made by microcalorimetry.
be appreciated by micro-calorimetric measurements.
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