Fluid Phase Equilibria 158–160 Ž1999.

557–563

A new classification of isotherms for Gibbs adsorption of gases on

solids
M.D. Donohue ) , G.L. Aranovich
Chemical Engineering Department, The Johns Hopkins UniÕersity, 3400 North Charles Street, Baltimore, MD 21218, USA
Received 12 April 1998; accepted 25 January 1999

Abstract

A systematic analysis of adsorption behavior has been performed. The results are presented here as a new
classification of isotherms for fluidrsolid equilibria. q 1999 Elsevier Science B.V. All rights reserved.

Keywords: Gas–solid equilibria; Lattice theory; Gibbs adsorption; Classification of isotherms

1. Introduction

The first systematic attempt to interpret adsorption isotherms for gasrsolid equilibria was
introduced by S. Brunauer, L.S. Deming, W.E. Deming and E. Teller ŽBDDT. in 1940 w1x. These
authors classified isotherms into five types. The BDDT classification became the core of the modern
IUPAC classification of adsorption isotherms w2,3x. Type I isotherms characterize microporous
adsorbents. Types II and III describe adsorption on macroporous adsorbents with strong and weak
adsorbate–adsorbent interactions, respectively. Types IV and V represent adsorption isotherms with
hysteresis. Type VI has steps. The BDDT and IUPAC classifications have two deficiencies: they are
incomplete and they give the incorrect impression that adsorption isotherms are always monotonic
functions of pressure.
Here, we present a brief summary of a comprehensive analysis of adsorption behavior. This
analysis is based on experimental results, molecular simulations, and lattice theory concepts proposed
by Ono and Kondo w4x in 1960. The Ono–Kondo approach was derived to describe density gradients
at a vapor–liquid interface and it has become a classical part of molecular theory for liquid surfaces
w5x. This theory has been developed for gas–solid and liquid–solid equilibria w6–11x.

)
Corresponding author. Tel.: q1-410-516-7761; fax: q1-410-516-5510; e-mail: mdd@jhu.edu

0378-3812r99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 8 - 3 8 1 2 Ž 9 9 . 0 0 0 7 4 - 6
558 M.D. Donohue, G.L. AranoÕichr Fluid Phase Equilibria 158–160 (1999) 557–563

2. Ono–Kondo equations

Here we consider lattice theory for a one-component adsorbate with ´ being the energy of
interaction between nearest neighbors, and ´s being the energy of interaction between surface and
adsorbate molecule in the first layer. Consider taking an adsorbate molecule at a layer i and moving it
to an empty site in an infinitely distant layer. This is equivalent to the exchange of a molecule with a
vacancy w7x,
Mi q V` ™ Vi q M` Ž1.
where M is the adsorbate molecule, and V is the vacancy that it fills Ž and vice versa. . If this
exchange occurs at equilibrium, then:
D H y TD S s 0 Ž2.
where D H and D S are the enthalpy and entropy changes, and T is the absolute temperature. The
value of D S can be represented in the form:
D S s k B ln W1 y k B ln W2 Ž3.
where W1 is the number of configurations where site in the layer i is occupied by an adsorbate
molecule and the site in the infinitely distant layer is empty, and W2 is the number of configurations
where the site in the infinitely distant layer is occupied by an adsorbate molecule and site in the layer
i is empty, and k B is Boltzmann’s constant.
If the overall number of configurations for the system is W0 , then:
W1rW0 s x i Ž l y x` . Ž4.
and
W2rW0 s x`Ž l y x i . Ž5.
where x i is the fraction of sites occupied by molecules in layer i, and x` is the fraction of sites
occupied with fluid molecules in the bulk.
Substituting Eqs. Ž4. and Ž 5. into Eq. Ž 3. we obtain
D S s k BT ln x i Ž l y x` . r Ž l y x i . x` Ž6.
The change in enthalpy can be calculated by considering the number of neighboring sites that are
occupied near the surface compared to the bulk:
D H s y´ Ž z 1 x iq1 q z 2 x i q z 1 x iy1 y z x` . Ž7.
where z is the volume coordination number, z 2 is the monolayer coordination number, and
z 1 s Ž z y z 2 .r2. From Eqs. Ž2., Ž6. and Ž7. it follows that for i G 2:
ln  x i Ž l y x` . r Ž l y x 1 . x` 4 q Ž ´rk B T . z 1 Ž x iq1 y x` . q z 2 Ž x i y x` . q z 1 Ž x iy1 y x` . s 0
Ž8.
For i s 1, Eq. Ž7. must be modified to include the effect of the interface. Therefore,
D H s y´ Ž z 2 x 1 q z 1 x 2 y z x` . q ´s Ž9.
Combining Eqs. Ž 2. , Ž 6. and Ž 9. , we obtain:
ln  x 1Ž l y x` . r Ž l y x 1 . x` 4 q Ž ´rk B T .Ž z 2 x 1 q z 1 x 2 y z x` . q ´srk B T s 0 Ž 10.
 M.D. Donohue, G.L. AranoÕichr Fluid Phase Equilibria 158–160 (1999) 557–563 559

3. Analysis of adsorption isotherms

3.1. Monolayer adsorption

Eqs. Ž8. and Ž10. represent a set of coupled equations. For monolayer adsorption we have x i s x`
for i G 2. In the low concentration limit, Eq. Ž10. gives x 1 s x` expŽy´srk B T . which is Henry’s
law. When there are no adsorbate–adsorbate interactions, ´ s 0, it follows from Eq. Ž10. that
x 1 s x`rw x` q Ž1 y x` .expŽ ´srk B T .x which is analogous the Langmuir isotherm. If x` < x 1 then Eq.
Ž10. gives x 1 s x`rw x` q Ž1 y x` .expŽ ´srk B T q z 2 x 1 ´rk B T .x. This is similar to the Frumkin adsorp-
tion isotherm.

3.2. Multilayer adsorption

The Gibbs adsorption for multilayer adsorption is G Ž x`. s Ý`is1Ž x i y x` .. Calculation of isotherm
from Eqs. Ž8. and Ž10. shows that increasing ´srk BT leads to an increase in the Henry’s constant and
a convex shape of the isotherm at small densities. This is a characteristic feature of Type II and IV
isotherms in the IUPAC classification w2,3x. For small ´srk BT, the isotherm becomes concave at
small densities. This behavior is known for Type III and Type V isotherms in the IUPAC
classification. For low temperature calculations, Eqs. Ž 8. and Ž 10. exhibit steps in the isotherms
resulting from two-dimensional phase transitions. This kind of isotherm is considered Type VI in the
IUPAC classification w2,3x.

3.3. Adsorption at supercritical conditions

Fig. 1 illustrates the behavior of the Gibbs adsorption near and above the critical temperature. Fig.
1a gives theoretical predictions obtained from Eqs. Ž 8. and Ž 10. . Fig. 1b shows experimental

Fig. 1. Isotherm of the Gibbs adsorption in a wide range of conditions. Ža. Theoretical isotherms for different sets of
parameters: 1—for ´ r kT sy0.7 and ´s r kT sy5.2; 2—for ´ r kT sy2r3 and ´s r kT sy5.2; 3—for ´ r kT sy2r3
and ´s r kT sy2r3; 4—for ´ r kT sy0.6 and ´s r kT sy2r3; Žb. Experimental isotherms for ethylene on carbon black
at different temperatures: 1—263 K, 2—273 K, 3—283 K, 4—285 K, 5—288 K, 6—293 K, 7—303 K, 8—313 K, and 9
—323 K. Data from Ref. w12x.
560 M.D. Donohue, G.L. AranoÕichr Fluid Phase Equilibria 158–160 (1999) 557–563

adsorption isotherms of ethylene on carbon black for temperatures from 263 K to 323 K Ž data from
w12x.. As can be seen from Fig. 1b, adsorption isotherms for subcritical ethylene are Type II in the
IUPAC classification. However, for supercritical ethylene, the adsorption isotherms show maxima that
range from being very pronounced to rather weak. Subcritical isotherms are monotonically increasing
functions of the density. Supercritical isotherms have maxima, and at a higher density the Gibbs
adsorption goes down as the density goes up. Subcritical isotherms show a singularity at the saturation
conditions. The remnants of this singularity lead to the peak at near-critical temperatures Ž curves 2
and 3 in Fig. 1a. . Supercritical isotherms do not have steps.
Fig. 1 demonstrates the theoretical roots and experimental evidence for those types of adsorption
isotherms which are beyond the current IUPAC classification. In particular, curve 1 in Fig. 1a is for
subcritical conditions Žmean-field critical point is at ´rk BT s 2r3.. Curve 2 in Fig. 1a is at critical
conditions, and at high affinity to the surface. Curve 3 in Fig. 1a is at the same bulk conditions but for
low affinity to the surface. Curve 4 in Fig. 1a illustrates the adsorption behavior at the well
supercritical temperature and low affinity to the surface. Fig. 1b shows experimental data for
subcritical, near-critical, and supercritical conditions. As seen from Fig. 1a and b, at subcritical
conditions we have standard BET-like adsorption isotherms. However, near the critical temperature
these isotherms change dramatically to non-monotonic behavior showing sharp maxima, and further
increase in temperature leads to isotherms with smooth maxima. These types of behavior are predicted
theoretically and observed in experiment, but not included in the IUPAC classification.

4. Adsorption in pores and adsorption hysteresis

When there is adsorption in porous adsorbents, there is a limit to the number of adsorbed layers. In
slit-like pores with n layers there are two surfaces. For n G 3 equations of equilibrium can be
represented in general form:
n
ln x i Ž 1 y x` . r Ž 1 y x i . x` q Ž ´rk B T . ž Ý A i k x i y Bk x `
is1
/ q Ck ´srk B T s 0 Ž 11.

where 1 F k F n.
Eq. Ž11. indicates the possibility of having stepped isotherms for microporous adsorbents. Such
steps have been observed experimentally in high resolution measurements for argon and nitrogen on
microporous adsorbents w13x. The current IUPAC classification of adsorption isotherms w2,3x does not
include this type of behavior.
Eq. Ž11. also has multiple solutions at low temperatures. When this occurs, a particular bulk
density can be in equilibrium with two densities in adsorbed phase. However, this does not lead to
hysteresis in the adsorption isotherm. Rather, the requirement that phases in equilibrium have equal
spreading pressures results in steps in the adsorption isotherm w14x.

5. New classification of adsorption isotherms

The current IUPAC classification of adsorption behavior for gasrsolid equilibria w2,3x reflects the
ideas of Brunauer w15x based on knowledge in the 1930s–1940s. Though not stated explicitly in the
 M.D. Donohue, G.L. AranoÕichr Fluid Phase Equilibria 158–160 (1999) 557–563 561

Fig. 2. New classification of adsorption isotherms.

IUPAC publications, the IUPAC classification is limited to condensable vapors w16x. However, many
important gasrsolid systems fall outside this classification Žfor example, nitrogen, oxygen, fluorine,
hydrogen, carbon dioxide, carbon monoxide, nitric oxide, methane, ethylene, some freons at a room
temperature.. Moreover, this restriction is ambiguous because gases can be non-condensable in the
bulk, but condensable in pores of an adsorbent. In our opinion, the current IUPAC classification w2,3x
is obsolete.
Fig. 2 shows a new classification of adsorption isotherms. While general, the classification shown
in Fig. 2 is meant to be qualitative and does not show all possible details. In this classification, Type I
shows adsorption isotherms on microporous adsorbents for subcritical, near critical and supercritical
conditions. At supercritical conditions, the isotherm is not monotonic. Types II and III give adsorption
isotherms on macroporous adsorbents with strong and weak affinities, respectively. For low tempera-
tures these Types have steps, but increasing temperature transforms them into the smooth monotonic
curves which are like those in Types II and III of the IUPAC classification. However, near the critical
temperature these isotherms change dramatically to non-monotonic behavior showing sharp maxima,
and further increase in temperature leads to isotherms with smooth maxima. Types IV and V
characterize mesoporous adsorbents with strong and weak affinities, respectively. For lower tempera-
tures they show adsorption hysteresis. We also have included supercritical isotherms for mesoporous
adsorbents which are predicted by lattice theory and the logic of this classification scheme. However,
we are not aware of any experimental data showing the disappearance of hysteresis for mesoporous
systems at supercritical temperatures.

6. Discussion

Many advances have been made over the last sixty years in understanding adsorption behavior. Of
particular note are advances that have been made using density functional theory w17,18x, self-con-
sistent field theory w19x, molecular dynamics w20x, and Monte Carlo simulations w21,22x. . Here, we
have presented an analysis made by a much simpler theoretical approach. We have shown that the
562 M.D. Donohue, G.L. AranoÕichr Fluid Phase Equilibria 158–160 (1999) 557–563

Ono–Kondo model is simple, flexible with respect to various boundary conditions, and able to predict
different adsorption behavior in a systematic way.
Ono–Kondo lattice theory is able to predict all known types of adsorption behavior including steps
in the isotherms w9x, scaling behavior near saturation conditions w7x, supercritical behavior w8x, and
adsorption hysteresis w6x. By changing two energetic parameters Ženergies for adsorbate–adsorbate
and adsorbate–adsorbent interactions., one can obtain smooth or stepped multilayer adsorption
isotherms for macroporous adsorbents. By adopting appropriate boundary conditions, it is possible to
describe adsorption on microporous adsorbents w11x. The monolayer version of the theory gives all
known types of isotherms for monolayer adsorption of gases on solids w23x. Three-dimensional
equations allow one to predict adsorption on heterogeneous surfaces w10x and to analyze adsorption
hysteresis w6x.
However, it should be noted that the new classification of adsorption isotherms shown in Fig. 2 is
not based entirely on the model. Rather, we have used this simple model to organize a wide spectrum
of experimental results in a logical and systematic way. This could have been done using any of
several different approaches. Our conclusion from this analysis is that the IUPAC classification is
obsolete. In particular, experiments and calculations shown in Fig. 1 demonstrate isotherms with
maxima at supercritical conditions Žwhich is ‘forbidden’ in the framework of the current IUPAC
classification w2,3x.. Monte Carlo simulation at these conditions confirms this type of adsorption
behavior w22x. This kind of behavior is beyond the current IUPAC classification, and it is included in
the new classification shown in Fig. 2.

7. List of symbols

kB Boltzmann’s constant
M Adsorbate molecule
n Number of adsorbed layers
T Absolute temperature
V Vacancy
W0 Overall number of configurations
W1 Number of configurations where site in the layer i is occupied by an adsorbate molecule
and the site in the infinitely distant layer is empty
W2 Number of configurations where the site in the infinitely distant layer is occupied by an
adsorbate molecule and site in the layer i is empty
xi Fraction of sites occupied by molecules in layer i
x` Fraction of sites occupied with fluid molecules in the bulk
z Volume coordination number
z2 Monolayer coordination number
z1 Ž z y z 2 .r2
G Gibbs adsorption
DH Enthalpy change
DS Entropy
´ Energy of interaction between nearest neighbors
´s Energy of interaction between surface and adsorbate molecule in the first layer
 M.D. Donohue, G.L. AranoÕichr Fluid Phase Equilibria 158–160 (1999) 557–563 563

Acknowledgements

MD would like to acknowledge support by the Division of Chemical Sciences of the U.S.
Department of Energy, under Contract DE-FG02-87ER13777.

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