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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

The importance of adsorption technology as a versatile tool
for separation and purification of industrial gas mixtures is well
established.1,2 Most of these separation applications share three
key characteristics: (i) the gases to be separated are multicom-
ponent mixtures, often containing more than two adsorbates of
different sizes, polarizabilities, and permanent polarities, (ii) the
solid adsorbents (crystalline or amorphous) possess a complex
network of micro-meso-porous structures, which cannot often
be characterized quantitatively, and which are often energetically
heterogeneous for sorption of one or more gases, and (iii) the
conditions (pressure, temperature, and gas compositions) pre-
vailing inside an adsorber during a cyclic adsorptive process
can vary over a very large range.
The key input variables for the design of adsorptive separation
processes include multicomponent gas adsorption equilibria,
kinetics, and heats. These three basic properties must be known
accurately under all conditions encountered by the adsorbers
during the process cycle for meeting the requirements of an
industrial design.2
Unfortunately, there is a serious shortage of published
multicomponent gas adsorption data. Reference 2 addresses the
state of the art in some detail. A common design practice is to
(i) use theoretical or empirical equilibrium adsorption models
for homogeneous or heterogeneous adsorbents to estimate the
desired multicomponent equilibrium data, (ii) use empirical
kinetic models to describe adsorbate transport into the porous
adsorbent particles by ignoring multicomponent interactions, and
(iii) assume constant isosteric heats for the components (ap-
propriate for homogeneous sorbents only) or use simplistic
heterogeneous equilibrium models to estimate component heats.
These models are often used in good faith for process design
after testing them with a scanty pure and binary gas adsorption
database for the system of interest.
Clearly, an extensive multicomponent database is needed for
(i) seriously testing existing adsorption equilibrium, kinetics and
heat models, (ii) developing new or improved models, and (iii)
providing more insight into the complex phenomenon of
multicomponent gas adsorption on heterogeneous adsorbents.
The purpose of this article is to review several traditional
and recent macroscopic experimental methods for measuring
pure gas and multicomponent gas adsorption equilibria, kinetics,
* To whom correspondence should be addressed. E-mail:
shs3@lehigh.edu. Phone: 610-758-4469. Fax: 610-758-5057.
10.1021/ie0601293 CCC: $37.00 © 2007 American Chemical Society
Published on Web 08/29/2006
technique published in the literature.
Traditional Experimental Methods
Numerous experimental procedures have been used during
the last 50 years for measuring pure and multicomponent gas
adsorption equilibrium and kinetic data. Different laboratories
around the world have developed and implemented their own
specific techniques for this purpose. Several books on adsorption
describe these methods in detail.3-9
The majority of the published literature on gas adsorption
reports data for pure gas equilibrium isotherms and kinetics.
There is also a substantial volume of binary gas adsorption
equilibrium data and a small volume of binary gas adsorption
kinetic data. However, most of these binary equilibrium data
sets are not extensive enough to test their thermodynamic
consistencies.10 Multicomponent gas equilibrium and kinetic data
containing three or more adsorbates are sporadic.2 The excellent
monographs by Valenzuela and Myers (1989)11 and Kärger and
Ruthven (1992),7 respectively, provide good compilations of
the published equilibrium and kinetic data (mostly on zeolites).
Isosteric heats of adsorption of pure gases are generally
calculated from the equilibrium isotherms at different temper-
atures using adsorption thermodynamics.12,13 Binary and mul-
ticomponent gas adsorption heat data are emerging only
recently.2,66,67
Pure Gas Equilibrium Isotherm and Adsorption Kinetics.
The frequently used methods for measurement of pure gas
adsorption equilibria and kinetics include (a) the constant
pressure gravimetric method, (b) the constant volume volumetric
method, (c) the variable volume piezo-metric method, and (d)
the column breakthrough method. Table 1 describes some of
the pros and cons of these methods.
Binary and Multicomponent Gas Equilibrium Isotherm
and Adsorption Kinetics. The commonly used methods for
binary and multicomponent gas adsorption equilibrium and
kinetics are (a) the combined gravimetric-volumetric method
for binary systems, (b) the constant volume volumetric method
(with continuous gas analysis) for multicomponent systems, and
(c) the closed-loop recycle method for adsorption of single or
mixed adsorbates from a single or multicomponent carrier gas.
Table 1 lists some of the merits and demerits of these methods.
Commercially available microbalances including magnetic
suspension balances are generally employed for the gravimetric
methods mentioned above.14,15 The experimental setups for the
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
individual research groups.
Pure Gas Isosteric Heats. The isosteric heat of adsorption
of a pure ideal gas i (q°i ) at pressure (P) and temperature (T) [or
at the corresponding equilibrium amount adsorbed (n°i ) and T]
is traditionally calculated by measuring adsorption isotherms
at different temperatures and employing the thermodynamic
relationship [q°i (n°i ) ) RT2{δ ln P/δT}°ni].12,13 A plot of lnP
against (1/T) at constant ni° yields a straight line with a slope
equal to (-q°i /R).
Multicomponent Isosteric Heats. The isosteric heat of
adsorption of component i (qi) of a multicomponent ideal gas
mixture at pressure (P), temperature (T), and gas-phase mole
fraction (yi) [or at the corresponding equilibrium amount
adsorbed (ni) and T] is given by the thermodynamic relationship
[qi(ni,T) ) RT2{δ ln(Pyi)δT}ni].12,13 However, unlike in the case
of a pure gas, it is not possible to directly measure the
temperature coefficient of the partial pressure (pi ) Pyi) of
component i of a gas mixture at constant loadings (ni) of the
components of the mixture. Thermodynamic equations can be
derived to estimate qi by measuring ni as functions of P at
constant T and yi, as functions of yi at constant P and T, and as
functions of T at constant P and yi.12,13 However, such extensive
data are impractical to gather even for a binary system. The
author is not aware of any such data set. Calorimetry is the
best choice for direct estimation of qi (i g 2) as discussed later.
There are four important fundamental issues regarding the
data measured by the methods mentioned above and others to
be described in the subsequent sections.
a. Gibbsian Surface Excess. The true thermodynamic
variable that is measured to quantify the extent of adsorption
of an adsorbate gas (pure or from a mixture) by all macroscopic
experimental methods is the Gibbsian surface excess (GSE) of
that gas.13 The GSE is loosely called the “amount adsorbed” in
the adsorption literature. Estimation of the actual amount
adsorbed from the GSE requires extraordinary assumptions
about the structure and composition of the adsorbed phase which
cannot be verified by today’s experimental methods. Adsorption
thermodynamics, kinetics and column dynamics can be fully
developed using GSE as the basic variable and there is no need
to estimate the actual amount adsorbed.13
b. Void Volume of the System. Many methods described in
Table 1 and others require the knowledge of the void volume
of the adsorption system for estimating the transitional or
equilibrium amounts adsorbed. The void volume is typically
measured by helium expansion into the adsorption system and
by assuming that helium is not adsorbed on the adsorbent at
the conditions of the test, such as low pressure and high
temperature. However, it has been shown that this assumption
can cause a significant error in estimating (i) adsorption of pure
gases at high pressures and (ii) adsorption of weakly sorbed
components of a gas mixture even at moderate pressures.16
Protocols for measuring helium adsorption by gravimetric
methods have been proposed.16,17
c. Nonisothermal Adsorption during Kinetic Tests. The
heat of ad(de)sorption cannot generally be removed (supplied)
from (to) the adsorbent mass fast enough to achieve an
isothermal kinetic process unless the kinetics of sorption is
extremely slow. Data analysis of a nonisothermal kinetic
process, where the changes in the adsorbate loading and the
adsorbate temperature are large, requires a numerical solution
of a nonisothermal kinetic model, which can be complex and
ambiguous.18 Consequently, differential kinetic tests, where the
changes in the adsorbate loading and the adsorbent temperature
are deliberately kept small, have been designed and practiced
for many of the test methods mentioned earlier. The differential
test permits linearization of the change in the equilibrium
adsorbate loading due to changes in gas-phase adsorbate
concentration and adsorbent temperature, as well as decoupling
of the effects of these two variables in data analysis. As a result,
analytical solutions of simultaneous mass and heat balance
equations describing the differential kinetic test under different
transport mechanisms can be obtained. That simplifies data
analysis. Examples include (i) differential constant pressure

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
traditional methods for measurement of multicomponent equi-
librium adsorption data do not have control over the final
equilibrium state at the end of the test. Consequently, the data
generated is often very random in nature and their use for testing
the quality of a model and for process design is not very
convenient.
Recently Developed Experimental Methods
Several new experimental methods have been developed
during the last two decades which can be potentially advanta-
geous over the traditional methods. A few of these methods
are briefly described below.
Frequency Response Technique (FRT). The most com-
monly used FRT method for measurement of pure gas adsorp-
tion kinetics consists of (i) equilibrating a known amount of
the adsorbent with a pure adsorbate gas at pressure P0 and
temperate T0 in a closed thermostated container of volume V0,
(ii) differentially perturbing the system volume in a periodic
fashion such as a sinusoidal variation (forcing function), and
(iii) measuring the steady-state periodic response of the system
pressure.26-30 The response consists of an “in phase” and an
“out of phase” component having the same frequency as that
of the forcing function but exhibiting different amplitudes and
phase angles due to the ad(de)sorption process with finite mass
transfer resistances. Model analysis of the response curves is
then carried out to identify the correct mass transfer mechanism
and quantify the adsorbate mass transfer coefficient.
The most promising features of the FRT are its potential
ability to (i) discriminate between different mass transfer
mechanisms due to the high sensitivity of the response curves
to the nature of the model equations describing different
mechanisms26-28 and (ii) measure relatively fast adsorption
kinetics due to the availability of pressure transducers with very
small response times.29
The differential periodic changes in gas pressure and adsor-
bate loading, used in FRT, permits linearization of the adsorption
isotherm with respect to the gas pressure and adsorbent
temperature. This leads to analytical expressions for the pressure
response curves, which helps data analysis. The differential FRT
test, however, does not permit isothermal data analysis, even
though the adsorbent temperature changes are very small,27,28
except for the case where the kinetics of adsorption is very slow.
It has been shown that the shape of the response curve can be
severely affected, such as formation of a bimodal “out of phase”
response curve, due to the thermal effects. This can be
incorrectly interpreted as a bimodal mass transfer process in
the adsorbent if the data were fitted by an isothermal model.27
A theoretical FRT analysis of nonisothermal adsorption of a
pure gas by a bi-porous adsorbent pellet indicated that it may
be impossible to extract the correct mechanism of the adsorbate
Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007 2919
Figure 1. FRT response curves for sorption of C3H8 on 5A zeolite with
heat effect.
mass transfer when two or more different resistances, such as
external film, surface barrier, micropore diffusion, and macro-
pore diffusion, are significant.28 Several combinations of mass
and heat transfer resistances can be used to fit the experimental
response curves.
Figure 1 is an example of the pressure response curves
measured for adsorption of propane by 5A zeolite (P0 ) 5.6
Torr, T0 ) 363 K). The solid lines are the best fit of the
experimental data26 by a model where heat transfer, external
film, and macropore diffusion resistances are included.28 The
data could be described equally well using models including
heat transfer, surface barrier and micropore diffusion resistances
or heat transfer, and micropore- and macropore diffusion
resistances.28 The intersection of the “in phase” and the “out of
phase” response curves at high frequency is found to be caused
by the existence of a skin barrier or external film resistance.
Thus, it can be used to identify the existence of a surface barrier
in the adsorbent particle.
These studies have shown that the thermal effects cannot be
ignored in the analysis of FRT data and they may seriously
undermine one of the most attractive features of the technique,
viz. unambiguous, identification of the mass transfer mechanism
in the adsorbent. Simultaneous measurement of the periodic
changes of the adsorbent surface temperature during the FRT
test may provide additional valuable information for establishing
the sorption mechanism.28,31
The FRT has also been used to study sorption of binary gas
mixtures,30 where the responses of total gas pressure as well as
the partial pressures of the components of the gas mixture are
measured. Development of nonisothermal models for the
analysis of multicomponent sorption data by FRT have also been
initiated.31 It showed that the transport of the faster diffusing
component can be affected by the presence of a slower diffusing
species. It is manifested by a roll-up effect on the partial pressure
frequency response curve.
More recently, a continuous flow-system FRT protocol was
developed to facilitate the removal of the heat of adsorption
from the adsorbent by forced convection and, thus, maintain
an isothermal operation.32 The pure adsorbate gas was passed
through a thermostated adsorbent bed at P0 and T0 until the
adsorbent was equilibrated with the gas. The feed gas pressure
was then differentially perturbed in a sinusoidal wave fashion,
and the effluent gas pressure response (same frequency as that
of the inlet gas pressure fluctuation but a different amplitude
and phase angle) was monitored. Various isothermal models
using different kinetic mechanisms were used to fit the FRT
response curves in order to identify the mass transfer mechanism
for sorption of pure N2 (surface barrier alone) and O2 (combined
surface barrier and pore diffusion) on a carbon molecular sieve.
2920 Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007
Figure 2. ZLC response curves for desorption of (a) C2H6 and (b) C4H10
from silicalite in the Henry’s law region.
The existence of a distributed surface barrier resistance had to
be assumed in the model to improve the data fit. The study
again demonstrates the model dependency of FRT response data
analysis.
Zero Length Column (ZLC) Technique. The most com-
monly used ZLC method consists of (i) equilibrating a small
sample of the adsorbent placed inside a thermostated tube with
an adsorbate gas at concentration C0, pressure P0, and temper-
ature T0, (ii) passing an inert, adsorbate-free purge gas at P0
and T0 over the adsorbent at a high specific gas flow rate, and
(iii) monitoring the exit gas adsorbate compositions with time.
An isothermal desorption model is then used to extract the
adsorbate mass transfer coefficient from the effluent concentra-
tion profile.7,33 Analytical isothermal models have been devel-
oped for cases where the adsorption isotherm is linear and the
mass transfer is controlled by (i) Fickian diffusion within the
adsorbent33 and (ii) a surface barrier.34
The key advantages of the ZLC technique arise from (i) the
simplicity of the apparatus and its operation, (ii) potential
absence of external mass and heat transfer resistances and
maintenance of essentially zero adsorbate concentration at the
surface of the adsorbent particles due to high gas flow rate
during the desorption process, (iii) absence of axial dispersion,
and (iv) potential for measuring fast sorption kinetics. The
technique has been extensively used for studying diffusion of
pure hydrocarbons in the linear Henry’s law region using various
zeolite crystals.7
Figure 2 shows examples of typical ZLC response curves
for desorption of ethane and n-butane from silicalite crystals at
various temperatures. The solid lines are a model fit of the data
using the Fickian diffusion mechanism.35
Extension of the ZLC method for measuring sorption kinetics
in the nonlinear region of the adsorption isotherm has been
investigated.36 The ZLC method has also been used to estimate
the pure gas adsorption isotherm and binary gas selectivity of
adsorption.37,38 The equilibrium measurements assume desorp-
Figure 3. Isotherms for adsorption of N2 + O2 binary mixture on Na-
mordenite.
tion under local equilibrium conditions, which can potentially
be achieved using a very low gas flow rate.
The intrusion of thermal effects on ZLC experiments has been
recognized. A model analysis shows that they can severely
influence the shape of the ZLC response curves when the
adsorbent particles are large.39 An analytical expression for the
response of a nonisothermal differential ZLC test, where the
purge gas adsorbate composition is slightly lower than C0, has
also been derived.40 The analytical solution, however, is
applicable only for a differential test, which allows linearization
of the adsorption isotherm with respect to adsorbate concentra-
tion and adsorbent temperature and not for a linear isotherm
using a nondifferential test.41
Total Desorption (TD) Methods. Total desorption methods
have frequently been used for measuring the adsorption
equilibria and kinetics of pure and multicomponent gas mixtures.
The most common TD test consists of (i) flowing a pure gas or
a gas mixture (pressure ) P0, temperature ) T0, mole fraction
of component i ) y°i ) over a packed, thermostated adsorbent
bed, containing a known amount of the adsorbent and having a
precalibrated void volume, until equilibrium is reached, (ii)
desorbing (heating and evacuation) and transferring the entire
content of the bed (void and adsorbed gases) to another
evacuated vessel of known volume, and (iii) measuring the final
pressure, temperature and gas composition of the mixed
desorbed gases. A simple mass balance yields the equilibrium
amount of component i adsorbed (ni) at the initial equilibrium
conditions.42-47
Figure 3 shows an example of equilibrium isotherms mea-
sured by the TD method for adsorption of N2 + O2 binary gas
mixtures on Na-mordenite at three different temperatures.43 The
zeolite exhibits a thermodynamic selectivity for N2 over O2 and
the Langmuir model (solid lines) describes the isotherms very
well.
The same experimental protocol is carried out using a small
amount of the adsorbent in a “differential adsorption bed”
(DAB) test for measuring adsorption kinetics.42,44-47 It consists
of (i) flowing a pure gas or a multicomponent gas mixture over
the adsorbent for a specific period of time t, (ii) desorbing and
analyzing the desorbed gases in order to calculate the amount

Figure 4. Uptake curves for binary (a) N2 and (b) O2 mixture by a carbon
molecular sieve.
of component i adsorbed [ni(t)] at time t, and (iii) repeating the
experiment using different values of time. A relatively high gas
flow rate ensures that there is no gas-phase composition gradient
across the adsorbent mass. It is also assumed that the heat of
adsorption is removed by forced convection created by the high
gas flow rate so that the kinetic process is isothermal. Models
are then used to identify the transport mechanism and estimate
the component mass transfer coefficients from the kinetic data.
Figure 4 shows the fractional uptakes of O2 and N2 from a
binary (50% N2 + 50% O2) gas mixture on a carbon molecular
sieve at 263 K measured by the DAB test.47 O2 diffuses into
the carbon pores faster than N2, but the carbon has practically
no thermodynamic selectivity for either component. Conse-
quently, the carbon exhibits a kinetic selectivity for O2 over N2
at early times of contact, followed by displacement of some of
the adsorbed O2 by N2 at longer times, creating a maximum in
the O2 uptake curve. The solid lines are the fit of the uptake
curves by an isothermal dual mode (surface barrier + micropore
diffusion) transport mechanism.
The advantages of these methods include (i) simple experi-
mental apparatus and procedure for measuring multicomponent
adsorption equilibria and kinetics under controlled conditions
and (ii) potential for achieving isothermal adsorption kinetic
process. The second goal, however, may not be achievable
unless the kinetics of adsorption is very slow.25
Wicke-Kallenbach Permeation Method (WKM). The
method consists of mounting a single crystal of a microporous
zeolite or a single particle of a porous adsorbent as a gas
permeation membrane device by embedding it in a high
temperature polymer or in an epoxy matrix. Steady state
permeation flux of a pure or a mixed adsorbate gas is then
measured across the membrane by flowing the adsorbate gas at
the high pressure side of the membrane and sweeping the low
pressure side of the membrane with an inert gas and continu-
ously measuring the composition of the permeate gas mixture.
Effective diffusivities for the adsorbates through the porous
adsorbent can then be calculated by analysis of the steady-state
flux data.48,49
Sorption Isosteric Technique (SIT) for Measurement of
Multicomponent Gas Isosteric Heats of Adsorption. An
approximate short-cut method, called SIT, has been used by
various authors to estimate pure and multicomponent gas
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
changed and the corresponding equilibrium values of P and yi
are measured at different values of T. For an ideal gas, the
specific equilibrium amount of component i adsorbed (ni) at
any given set of P, T, and yi can be calculated by the component
i mass balance [ñI ) ni + V°Pyi/RT]. It was argued that if the
amount of component i in the void gas of the chamber was
negligible compared to its amount adsorbed, [ni . V°Pyi/RT],
then [ñi ∼ ni]. Consequently, it might be assumed that the above-
described experiment was carried out at approximately constant
loadings of the components of the gas mixture. Therefore, a
plot of the measured data as ln(Pyi) against 1/T would be a
straight line with a slope equal to (-q̃i/R), where q̃i is
approximately equal to the isosteric heat of adsorption of
component i (qi) at loading ni and T.
Although SIT is creative and experimentally simple, and it
promises to resolve a major practical problem in estimating the
multicomponent isosteric heat of adsorption, a detailed ther-
modynamic analysis of this approach showed that the method
would substantially under-estimate the actual values of the
isosteric heats for the following conditions.52
• Large specific void volume in the apparatus
• High adsorbate loading of the component
• Adsorbate is weakly adsorbed
• Adsorbent is energetically heterogeneous
Obviously, the isosteric heat of adsorption estimated by the
SIT method will be identical to the actual heat if V° is negligible.
However, that is not practically achievable.
Table 2 shows examples of errors in estimating the component
isosteric heats for adsorption of CO2 (1) + CH4 (2) binary gas
mixture on BPL carbon at 303.1 K by the short-cut method.52
Pure and binary gas adsorption isotherms for this system could
be adequately described by the homogeneous Langmuir model.
It may be seen from Table 2 that the errors in the component
isosteric heats by the short-cut method can be very large under
certain conditions. Another major problem is that the component
isosteric heats estimated by using the assumptions of the short-
cut method are found to be functions of adsorbate loadings for
a homogeneous adsorbent. That is incorrect and not thermody-
namically feasible. Thermodynamic prescriptions to correct the
problems associated with the short-cut method have been
formulated.52 Their applications are, however, limited to binary
systems only, and they require additional measurements of
binary gas adsorption isotherms.
Figure 5 shows an experimental comparison of pure 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

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
(<0.2 °C), if the heat of adsorption is moderately large.
Most Recent Developments
Two new experimental methods, which were specifically
designed for measuring multicomponent gas adsorption equi-
libria, kinetics and isosteric heats, have emerged during the past
decade. They circumvent most of the disadvantages of the earlier
methods. They are briefly described below.
Isotope Exchange Technique (IET). The isotope exchange
technique can simultaneously measure pure or multicomponent
gas adsorption equilibria and kinetics in a single experiment
without disturbing the overall adsorbed phase.53-55
The experimental protocol of the IET method is similar to
that of Quig and Rees used for measuring self-diffusion of gases
in zeolites.56 It consists of equilibrating an adsorbent mass in a
closed-loop recycle system with a pure gas i at a chosen value
of pressure P and temperature T or with a multicomponent gas
mixture of i (g2) components at a given set of P, T, and yi
values. The gas phase may contain a bulk and a trace isotope
of component i (total gas-phase mole fraction of component i
) yi). The trace isotope concentration of component i in the
gas phase is then changed without changing the total P, T, or
yi, and the transient change in the concentration of the trace
isotope is monitored until a new isotopic equilibrium state is
reached. This information can then be used to estimate the
equilibrium amount adsorbed of component i (ni), and the self-
diffusivity (Di) of the component i at the corresponding values
of P, T, and yi, or ni and T. The experiment can then be repeated
by starting with another set of P, T, and yi values in order to
generate the complete adsorption isotherm or to obtain Di as
functions of ni and T. This ability of probing a predetermined
multicomponent adsorbed phase with isotopes of each of the
components of the gas mixture in a series of isothermal isotope
exchange tests without disturbing the adsorbed phase for
determining the multicomponent adsorption equilibria and
kinetics at any pre-chosen condition makes IET a very powerful
tool. The details of the experimental procedure and the data
analysis can be found elsewhere.53 The estimation of pure or
multicomponent gas adsorption equilibria by IET is based on
the assumptions that (a) the pure gas adsorption isotherms of
all isotope species of component i are identical and (b) the
equilibrium selectivity of adsorption between the isotopes of
component i is unity in the presence or absence of other
Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007 2923
components of the gas mixture. These assumptions are valid
except for very light gases such as H2. The estimation of pure
or multicomponent mass transfer coefficient of component i by
IET is based on the assumption that the transfer coefficients or
self-diffusivities of all isotope species of that component are
equal at any given set of P, T, and yi values.
The key advantages of the IET are listed below:
• There is complete control over the equilibrium state in the
system, which is not perturbed during the experiment, and which
is defined by the chosen values of the variables P, T, and yi at
the start of the test. This allows equilibrium and kinetic
measurements at any desired condition using a multicomponent
gas mixture as opposed to random measurements by many other
methods.
• Convenient for measurement of pure and mixed gas self-
diffusivities as functions of adsorbate loadings and temperature.
• The ad(de)sorption process during the IET test is absolutely
isothermal. Thus, data interpretation is relatively simple and un-
ambiguous.
• The test can be repeated easily without regenerating the
adsorbent which permits easy check of data reproducibility.
• The IET apparatus is relatively inexpensive and easy to
operate. This can be a major advantage over microscopic
methods to measure self-diffusivities in porous solids such as
nuclear magnetic resonance-pulsed field gradient (NMR-PFG)
method57-59 and nutron defraction (ND) methods7,59 or to
measure transport diffusivity by Fourier transform IR spec-
trometry,60 all of which require expensive and complex equip-
ments, difficult sample preparation, and intricate data analysis.
The IET, however, requires a supply of isotopes for the
adsorbate gases of interest and a continuous on-line analytical
devise (such as a quadrupole mass spectrometer) for quantitative
measurement of trace isotope concentrations.
Figure 8 shows examples of uptake data measured by IET
for adsorption of pure N2, CH4, and Kr by 4A zeolite at 283 K.
The uptake data can be described very well by the Fickian
diffusion mechanism (solid lines).55 Figure 8b shows that the
self-diffusivities of Kr and CH4 increase with surface coverage
(much more pronounced for Kr), whereas the self-diffusivity
of N2 is independent of adsorbate loadings. These complex
behaviors are caused by the closeness of the adsorbate sizes
and the pore aperture of the zeolite.55
Figure 9 shows kinetic uptake data for binary gas adsorption
of (a) N2 and O2 from air on Takeda carbon molecular sieve at
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
authors method T (K)
Qinglin, Farooq and Karimi DAB 302.1
Rynders, Rao And Sircar IET 303.1
Wang, Sward And Levan Flow FRT 298.1
4A zeolite at 253 K54 measured by IET. These data unambigu-
ously showed (solid lines) that the uptake by the carbon
molecular sieve was governed by the LDF surface barrier
mechanism, whereas that by the zeolite was governed by the
Fickian diffusion in the zeolite micropores.
Table 4 compares the results of kinetic data analysis for
adsorption of pure N2 by Takeda carbon molecular sieve
measured by IET, Flow-FRT, and DAB methods at ∼300 K.
The extrapolated mass transfer coefficient values at the limit
of zero pressure are reported in the table. The uptake by the
IET was isothermal by design, whereas the analysis of FRT
and DAB data assumed isothermal uptake (reasonable due to
slow kinetics of N2).
It may be seen that a surface barrier resistance at the pore
mouths of the carbon alone was adequate to describe the N2
uptake data measured by IET and the FRT response curve, but
a dual resistance (surface barrier + micropore diffusion) model
was needed to describe the data measured by DAB. The limiting
N2 mass transfer coefficient evaluated from the kinetic data
measured by IET was an order of magnitude larger than that
obtained from the analysis of the FRT data. The time constants
for the overall N2 mass transfer into the carbon estimated by
the IET and DAB methods were similar. This lack of consistent
interpretation of kinetic transport of gases in carbon molecular
sieves is well documented in the literature.61
Microcalorimeter for Multicomponent Isosteric Heat of
Adsorption. Several Tien-Calvet type heat flux microcalorim-
eters have recently been designed for directly measuring isosteric
heats of adsorption of a pure gas or those of the components of
a gas mixture at a preselected adsorbed phase composition and
temperature.62-67 The experimental protocol consists of (a)
equilibrating a known mass of an adsorbent inside the calorim-
eter cell with a gas mixture at pressure P, temperature T, and
gas-phase mole fraction yi (equilibrium amount of component
i adsorbed ) ni), (b) slowly introducing a very small quantity
mass transfer coefficients (×104 s-1)
surface barrier micropore diffusion
transport resistance (ks) (km ) 15Dm /R2) ref
surface barrier + ∼88.0 ∼87.0 47
micropore diffusion
surface barrier 28.0 ∞ 53
surface barrier ∼3.2 ∞ 32
of pure adsorbate i into the cell, and (c) measuring the evolved
heat (Qi) by thermopiles surrounding the cell. The experiment
is then sequentially repeated by introducing a small quantity of
other pure components (j * i) of the gas mixture into the
calorimeter cell and measuring the corresponding heats of
adsorption (Qj). The data can be directly used to estimate
isosteric heats of adsorption of a pure gas i (yi ) 1) or those
for the components of a gas mixture (i g 2) at a specific
adsorbate loading of ni at temperature T. These data can be
directly used in design of adsorptive gas separation processes.
The details of the experimental procedure and the protocol for
data analysis can be found elsewhere.62
The key advantages of using a microcalorimeter include the
following:
• Component isosteric heats of adsorption of a multicompo-
nent gas mixture can be directly measured at any specific
adsorbate loading and temperature.
• Measurement of high quality and accurate data.
• Convenient for measuring pure and multicomponent iso-
steric heats as functions of adsorbate loadings.
• Indispensable tool for measuring the complex nature of
isosteric heats on energetically heterogeneous adsorbents.
Figure 10 shows two examples of the high quality of isosteric
heat data measured by the microcalorimeter on heterogeneous
adsorbents.63,64 The heat of adsorption of pure nonpolar SF6 on
a pelletized sample of silicalite (with alumina binder) remains
constant (∼9.8 kcal/mol) over a very large range of coverage
(homogeneous behavior) and then it drops rapidly near the limit
of the saturation capacity of the adsorbent. This was caused by
the presence of the alumina binder which introduced masked
heterogeneity for sorption of SF6.63 The heat of adsorption of
pure polar CO2 on the γ-alumina is very high at zero coverage
(∼20 kcal/mol), and then it continuously and rapidly decreases
to ∼6.5 kcal/mol as the loading increases, indicating a highly
heterogeneous adsorbent.63 Thus, these systems exhibit drasti-

Figure 10. Pure gas isosteric heats measured by micro-calorimetry at
∼32 °C.
Figure 11. Binary gas isosteric heats for CO2 + C2H6 on NaX zeolite by
calorimetry.
cally different adsorption heterogeneity which can be accurately
characterized only by microcalorimetry.
Figure 11 shows an example of binary gas isosteric heats for
adsorption of CO2 + C2H6 mixtures on NaX zeolite at ∼29 °C
measured by micro-calorimetry.66 The data were measured at a
constant loading of C2H6 (∼2.6 mmol/g). The CO2 isosteric heat
from the mixture at any given CO2 loading was higher than the
corresponding pure gas heat, and it decreased with increasing
loading of CO2. The isosteric heat of C2H6 from the mixture,
on the other hand, increased with increasing CO2 loading, and
it was larger than that of pure the pure gas. These apparently
complex and counter-intuitive mixed gas heat data could only
be appreciated by micro-calorimetric measurements.
The temperature coefficient of isosteric heat of adsorption
of a gas can also be evaluated by microcalorimetry. Figure 12
shows the isosteric heats of adsorption of CO2 on a pelletized
sample of silicalite as functions of CO2 loading measured at
various temperatures by calorimetry.65 It may be seen that the
isosteric heat is not a function of temperature between 6 and
70 °C for this highly heterogeneous system. The temperature
independence of isosteric heat is generally assumed for process
design. Micro-calorimetry provided a direct proof of that
assumption.
The above-cited examples demonstrate the value of micro-
calorimetry as an indispensable tool for studying the often
complex behavior of pure and multicomponent gas isosteric
heats which play a critical role in determining the performance
Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007 2925
Figure 12. Isosteric heats of adsorption of CO2 on a pelletized silicalite.
of a practical gas separation system.68 Most of these properties
cannot be otherwise measured or estimated.
Summary
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
over the final equilibrium state in many of these methods. It is
inconvenient to use random multicomponent data for modeling
or process design. The third major problem has been the
traditional absence of a reliable method for measuring accurate
multicomponent isosteric heats.
Two recently developed methods circumvent many of these
short comings. The isotope exchange technique provides a
suitable method for isothermal measurement of multicomponent
adsorption equilibria and kinetics where the final equilibrium
state is pre-chosen by design. Microcalorimetry provides an
accurate method for direct measurement of multicomponent
isosteric heats at any chosen condition of adsorbate loading and
temperature. A detailed evaluation of the very complex and
intricate nature of pure and mixed gas isosteric heats on
heterogeneous adsorbents can be made by microcalorimetry.
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ReceiVed for reView January 31, 2006
ReVised manuscript receiVed April 16, 2006
Accepted April 18, 2006
IE0601293