JOURNAL OF COLLOID AND INTERFACE SCIENCE 183, 57–67 (1996)
ARTICLE NO. 0518
Derivation and Application of a Jovanovic–Freundlich Isotherm Model
for Single-Component Adsorption on Heterogeneous Surfaces
IGOR QUIÑONES * AND
*Departamento de Tecnologı́a, Centro de Quı́mica Farmacéutica (CQF), Calle 200 y 21, Atabey, Playa; P.O. Box 16042, La Habana, Cuba,
C.P. 11600; and †Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996-1600 and Division of Chemical
and Analytical Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6120
Received January 16, 1996; accepted May 21, 1996
A new Jovanovic–Freundlich isotherm model is derived for de-
scribing single-component adsorption equilibria on heterogeneous
surfaces. The equation is obtained by assuming that the rate of
decrease of the fraction of the surface unoccupied by the adsorbate
molecules is proportional to a certain power of the partial pressure
of the adsorbate. The equation reduces to the Jovanovic equation
when the surface becomes homogeneous. At low pressures, the
equation reduces to the Freundlich isotherm but at high pressures,
a monolayer coverage is achieved. This model has been applied
successfully to the description of the adsorption behavior of a
series of chlorinated hydrocarbons on a microporous silicagel, at
different temperatures. The monolayer capacity and the heteroge-
neity parameter exhibit a weak temperature dependence. The third
parameter of the model decreases exponentially with increasing
temperature. The fit of the experimental data to the new model
described is shown to be better than the comparable fits to classical
isotherms used for heterogeneous surfaces. The energy distribution
function corresponding to the model for Langmuir local adsorption
behavior was derived using the Sips procedure and evaluated nu-
merically in a few selected cases. This distribution is an exponen-
tial decay. q 1996 Academic Press, Inc.
Key Words: adsorption; Freundlich isotherm; isotherm; isotherm
model; Jovanovic isotherm.
INTRODUCTION
The use of adsorption processes for large-scale separa-
tions or purifications is becoming common in industry.
The recent development of industrial-scale preparative
chromatography is contributing to further increase the im-
portance of adsorption-based processes. The design and
the optimization of an implementation of an adsorption-
based separation process require the ability to characterize
accurately the adsorption equilibria involved and their de-
pendence on the experimental conditions ( 1 ) . Although,
in principle, the competitive isotherms of all the feed com-
1
Author to whom correspondence should be sent, at the University of
Tennessee.
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GEORGES GUIOCHON† ,1
ponents are required, there are methods to derive reason-
able approximations of these competitive isotherms from
single-component isotherms. These methods allow con-
siderable reduction in the time and cost required by the
data acquisition. Their accuracy depends greatly on the
availability of accurate correlation for the single-compo-
nent isotherm data ( 1, 2 ) . However, except in rare cases
involving homogeneous surfaces ( e.g., graphitized carbon
black, zeolites ) , the single-component isotherms cannot
be calculated from first principles but must be measured.
Then arises the problem of selecting a proper isotherm
model for correlating these data ( 2 ) .
Theoretical models of single-component adsorption iso-
therms have been derived using a variety of kinetic, statisti-
cal mechanical, or thermodynamic approaches (2, 3). These
fundamental studies assume the solid surface to be homoge-
neous. Most of the adsorbents used in current practice, such
as activated carbons, silica gels, alumina, and even zeolites
exhibit surface and structural heterogeneities (3). For such
surfaces, isotherm models are derived from a fundamental
integral equation relating the experimental isotherm, the
adsorption energy distribution, and the local isotherm (3).
Independently, a number of empirical and semi-empirical
isotherm models have been suggested to account for the
adsorption behavior on heterogeneous surfaces (3). Single-
component isotherms have been derived from a differential
equation relating surface coverage and pressure. This ap-
proach was first suggested by Schmidt (4), later expanded
by Tóth (5) and Misra (6), and recently applied again by
Tóth (7). It allows the derivation of thermodynamically con-
sistent isotherms for both homogeneous and heterogeneous
surfaces.
In the present paper, we apply the latter approach to derive
a semiempirical Jovanovic–Freundlich isotherm model for
the monolayer, single-component adsorption on heteroge-
neous surfaces. We use this model to account for experimen-
tal adsorption data published recently, regarding chlorinated
hydrocarbons on silica gel, at different temperatures (8, 9),
and we compare the quality of the representation obtained
57 0021-9797/96 $18.00
Copyright q 1996 by Academic Press, Inc.
All rights of reproduction in any form reserved.
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58 QUIÑONES AND GUIOCHON

TABLE 1
Selection of Adsorption Isotherm Models

Model UÅ l(u, p) Eq. no. Ref.

Henry Kp K/(1 0 Kp) [2] (2)

Langmuir Kp/(1 / Kp) K/(1 / Kp) [3] (13)
Jovanovic 1 0 e0Kp K [4] (14)
Quadratic (Kp / K2hp2)/(1 / 2Kp / K2hp2) K(1 / 2Khp / K2hp2)/[1 / 3Kp / K2(2 / h)p2 / K3hp3] [5] (15)
Fowler Kp/(e0xu / Kp) Ku/(Kp / xu2e0xu) [6] (16)
Freundlich (ap)n an(ap)n01/[1 0 (ap)n] [7] (17)
Langmuir–Freundlich (ap)n/[1 / (ap)n] n(ap)n01/[1 / (ap)n] [8] (18)
Tóth Kp/[1 / (Kp)n]1/n K{1 0 (Kp)n[1 / (Kp)n]01}/{[1 / (Kp)n]1/n 0 Kp} [9] (5)
Misra 1 0 [1 / (k 0 1)Kp]1/(k01) K/[1 / (k 0 1)Kp] [10] (6)
Radke–Prausnitz Kp/[1 / (Kp)n] [K / (Kp)n(K 0 n)]/{[1 / (Kp)n] [1 / (Kp)n 0 Kp]} [11] (19)
2 2
Dubinin–Radushkevich e0a[ln(b/p)] 2a ln(b/p)/{ea[ln(b/p)] 0 1} [12] (20)

Note. For homogeneous-surface models, U is the local surface coverage, u; for the other models, it is the overall coverage, ut ; see Eq. [1]. K is the
Henry constant. h and x are the adsorbate–adsorbate interaction parameters. n is the heterogeneity parameter. a, b, and k are other parameters which
appear in some models.

with a variety of other theoretical and semiempirical iso-
therm models previously reported (5, 10, 11).
THEORY
An heterogeneous surface is characterized by a distribu-
tion of adsorption sites which have different adsorption ener-
gies. For homotattic sites, a local adsorption isotherm model
is assumed. This model refers to an homogeneous surface.
The experimental or global isotherm is obtained (3) by the
integral equation
(2, 3). A last approach involves the assumption of a local
and an overall isotherm model (3). It is also arbitrary, as
are the choices of the two models.
We note that Langmuir (13) had already proposed de-
scribing the adsorption on an heterogeneous surface as the
sum of a finite number of classical Langmuir isotherms (Eq.
[3], Table 1), each of them characterizing adsorption on an
homogeneous patch of surface. This, in effect, introduces a
discrete energy distribution. The biLangmuir isotherm, intro-
duced by Graham (21) and used by Laub (22) in gas chro-
matography, is a particular case of this approach. It has

*
`
q proven to be extremely successful in the description of the
ut (p) Å Å u(p, e )F( e )d e,
qs 0
where ut (p) is the overall surface coverage (excess adsorp-
tion) of the heterogeneous surface by the monolayer of ad-
sorbate, a function of the partial pressure p of the adsorbate
in the bulk, q is the amount of adsorbate adsorbed at equilib-
rium per unit amount of adsorbent, qs is the monolayer capac-
ity, u(p, e ) is the local adsorption isotherm for homottatic
sites with an adsorption energy e, and F( e ) is the adsorption
energy distribution. Equation [1] is the fundamental equation
in the theory of adsorption on heterogeneous surfaces. Be-
cause this Fredholm integral equation is ill-posed, it does
not have a unique solution (3). Attempts at the derivation
of the adsorption energy distribution from the experimental
isotherm, using numerical solutions and an assumed local
isotherm, have not led to convincing results but have demon-
strated the difficulties, usually underestimated, of collecting
proper experimental data (12). Another approach consists
in deriving closed-form integrals of Eq. [1], assuming simple
functional dependences for u(p, e ) and F( e ) and fitting ex-
perimental results to these equations in an effort to identify
the relevant parameters. A number of such solutions are
listed in Table 1. This list is by no means comprehensive
[1] adsorption of enantiomers on chiral phases (23, 24). This
result is explained by the physical nature of these interac-
tions. Both enantiomers undergo the same nonselective inter-
actions with most patches of surface, while enantioselective
interactions are highly selective, but take place in well-de-
fined sites which are localized and relatively far from each
other, ensuring the lack of adsorbate–adsorbate interactions
on the enantioselective sites. Furthermore, adsorption energ-
ies on these sites are high, so saturation is achieved at low
values of the concentration and the activity coefficients re-
main practically constant.
A significant number of overall isotherms of adsorption
on heterogeneous surfaces were originally proposed for em-
pirical or semiempirical reasons, with the sole aim of de-
scribing accurately and as simply as possible the adsorption
behavior of real systems. Examples of these models are the
Freundlich (17), the Langmuir–Freundlich (18), the Tóth
(5), the Radke–Prausnitz (19), and the Dubinin–Radush-
kevich (20) equations. These isotherm models were derived
to use Eq. [1] to calculate the adsorption energy distribution
from a combination of a local and an overall adsorption
isotherm. Most studies concerning physical adsorption on
heterogeneous surfaces were carried out using the Langmuir

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 NEW JOVANOVIC–FREUNDLICH ISOTHERM MODEL
model (13) to describe the local isotherm, i.e., the adsorption
behavior on homotattic sites (3). Many empirical equations
for the overall isotherm can be obtained with local Langmuir
behavior if an appropriate choice is made for the adsorption
energy distribution. To account for lateral adsorbate–ad-
sorbate interactions, however, the Langmuir model should
be replaced as the local isotherm in Eq. [1] by another model
which takes into account this additional source of nonideal
behavior, such as the Fowler (16), Moreau (15), or Ruthven
(2) isotherm models.
Two important overall equations are the Tóth (5) and the
UNILAN (10) models. For correlation purposes, we have
used in this work the equation of the Tóth model (5) as
applied by Valenzuela and Myers (1)
p
59
tained the following overall adsorption isotherm for a Jova-
novic local isotherm, using a g-function to characterize the
distribution of the Henry constant, K, on the heterogeneous
surface
ut (p) Å 1 0 F G r
r/p
g/1
e 0Kp , [15]
where r and g are the parameters of the energy distribution.
This model, however, has not been widely applied.
Recently, Hines et al. (11) developed an overall adsorp-
tion isotherm model in which the local isotherm is given by
the Jovanovic equation (Eq. [4], Table 1) and the energy
distribution is represented by a Morse type distribution. They
obtained the equation

F G
ut (p) Å , [13]
(b / p n) 1 / n K1K3 1 K2
ut (p) Å 1 0 0 , [16]
K3 0 K1K2 K1 / p K3 / p
where b is an adjustable parameter and n is the heterogeneity
parameter [3]. The UNILAN equation is based on a uniform where K1 , K2 , and K3 are the parameters of the energy distri-
distribution of the adsorption energies and a local Langmuir bution. K2 is usually very small. We note that if we neglect
isotherm (10). Its equation is it, Eq. [16] becomes identical with the Langmuir isotherm,
with K Å 1/K1 .
ut (p) Å
1
2n
ln F
C / pe /n
C / pe 0 n G , [14]
The derivation of adsorption isotherm equations from dif-
ferential equations has been reported for a long time. In spite
of several important papers published this century (4–7), it
where C is an adjustable parameter, which, in principle, is not a most popular approach. Initially, Schmidt (4) pro-
should be equal to 1/K, where K is the low-pressure equilib- posed a semi-empirical treatment of physical adsorption and
rium constant or Henry constant. Note that the heterogeneity derived a single-component adsorption isotherm using the
parameter, n, is a parameter of the adsorption isotherm but relationship
is also a parameter of the adsorption energy distribution (3)
and, thus, is not the same for different models. For the mod- dx
Å D(S 0 x), [17]
els which are reducible to the Langmuir model (e.g., Lang- dC
muir–Freundlich, Tóth, generalized Freundlich, Redlich–
Peterson models), n is between 0 and 1. For other models where x is the amount of component adsorbed at equilibrium,
(e.g., Freundlich, UNILAN, Dubinin) which can fit also type C is the concentration of the component in the bulk, S is the
III isotherm data, n may take negative values. For some maximum amount adsorbable, and D is a constant. Integra-
models (e.g., Freundlich, Langmuir–Freundlich, Tóth, Jova- tion of Eq. [17] gives
novic–Freundlich, Redlich–Peterson models), the surface
is homogeneous when n is equal to 1. For other models x Å S(1 0 e 0DC ). [18]
(e.g., UNILAN), the surface is homogeneous when n is
equal to 0. Later, Tóth (5) derived several adsorption isotherm models
Equations [13] and [14] reduce to the Langmuir equation using one of the equations
for values of n equal to 1 and 0, respectively. Misra (25)
used the Jovanovic model (14) to represent the local adsorp- du u
tion isotherm in the solution of Eq. [1], in combination with Å [19]
dp [ F1 ( u ) / 1]p
different energy distributions. At low pressures, or for small
values of n, the solutions reduce to the Shlygin–Frumkin du u
Å , [20]
(26) or Freundlich (17) isotherms, respectively. It seems dp [ F2 (p) / 1]p
that the use of either the Jovanovic or the Langmuir models
to account for the local behavior of the adsorbate permits where F1 ( u ) and F2 (p) are functions of the surface coverage
one to obtain similar overall isotherms for analogous energy and the adsorbate partial pressure, respectively. For example,
distributions (3). Jaroniec and Piotrowska (27) have ob- Eq. [13] was derived from Eq. [19].

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60 QUIÑONES AND GUIOCHON
Later, Misra (6) derived several other adsorption isotherm
models from the differential equation
du
Å K(1 0 u ) k , [21]
dp
where k is a constant. The general solution of Eq. [21] is Eq.
[10] (Table 1). When k § 1, certain theoretical conditions of
monomolecular adsorption are met. However, Eq. [21] is
empirical. When k assumes values of 0, 1, or 2, Eq. [21]
reduces to the Henry (2), Jovanovic (14), or Langmuir
(13) isotherms, respectively. It is worth noting the similarity
between Eq. [18] and the Jovanovic model (14), considering
the proportionality between q and x on the one hand, between
qs and S on the other. However, the concept of monolayer
adsorption was first introduced by Langmuir (13) while Eq.
[4] was originally derived by Jovanovic (14), using a kinetic
approach, and later by Jaroniec (28), using statistical ther-
modynamics.
Misra (6) considered that the functional dependence of
the variation of the surface coverage with respect to the
adsorbate partial pressure at constant temperature is given
by
du
Å K f (u ), [22]
dp
or rather, considering the proportion of uncovered surface
area,
du
Å K f * (1 0 u ). [23]
dp
Equation [21] is one of the simplest forms of Eq. [23].
Recently, Tóth (7) proposed the derivation of thermodynam-
ically consistent isotherm equations for homogeneous or het-
erogeneous surfaces from one of the differential equations
du u l ( u, p) decreases with increasing partial pressure of the
Å [24]
dp p c( u )
or
du u this aspect must be discussed for specific cases. It will be
Å , [25]
dp p f(p)
where c( u ) and f(p) are functions of the surface coverage
ratio or the partial pressure, respectively, which are derived
from an incorrect isotherm model, previously obtained em-
pirically (7). It is clear that Eqs. [19] and [20] can be
reduced to Eqs. [24] and [25], respectively. Consideration
of Eqs. [24] and [25] suggests that a more general relation-
ship is
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du
Å F( u, p), [26]
dp
where F( u, p) is a function of both the surface coverage
and the partial pressure of the adsorbent. Accordingly, we
consider the following equation
F( u, p) Å (1 0 u ) l ( u, p). [27]
This relationship can be rewritten as
0 d(1 0 u )
Å l ( u, p). [28]
(1 0 u )dp
Equation [28] was selected because l ( u, p) has a physical
meaning. It is the rate of decrease of the fraction of the
surface which is unoccupied by the adsorbate molecules.
Most of the classical isotherms can be analyzed using Eq.
[28]. The functions l ( u, p) were derived for these isotherms
on homogeneous surfaces (Henry (2), Langmuir (13), Jova-
novic (14), quadratic (15), and Fowler (16)) and on hetero-
geneous surfaces (Freundlich (17), Langmuir–Freundlich
(18), Tóth (5), Radke–Prausnitz (19), and Dubinin–Ra-
dushkevich (20)). They are listed in Table 1. Among these
equations, we can distinguish those which do not take the
adsorbate–adsorbate interactions into account (Henry,
Langmuir, and Jovanovic) and those which do (Fowler and
quadratic). We also observe that for all models which reduce
to the Henry law at low partial pressure, the L-function,
l ( u, p), tends toward K when p tends toward 0. Thus, the
limit of the L-function for low values of p (hence of u ) is
K, the low pressure equilibrium constant. This conclusion
is also obvious from Eq. [28].
Isotherms which are explicit with respect to pressure give
values of l ( u, p) which depend only on the adsorbate partial
pressure. Implicit models (e.g., the Fowler isotherm) give
values of l ( u, p) which are functions of both u and p. For
several models (Langmuir, Fowler, quadratic, and Misra),
adsorbate. However, in the case of the Jovanovic isotherm,
l ( u, p) remains constant and equal to K. For the other
isotherms, the relationship is more complex and depends on
the specific values of the parameters of these models. Thus,
analyzed later.
Consideration of the L-functions in Table 1 suggests try-
ing the following function
l ( u, p) Å an(ap) n01 , [29]
an expression which is also found in the numerator of the
Freundlich equation. On the other hand, the numerator of the
Langmuir–Freundlich equation is also similar to the RHS of
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 NEW JOVANOVIC–FREUNDLICH ISOTHERM MODEL 61
Eq. [29]. Substitution of Eq. [29] into Eq. [28] and integra- The relationship between the functions F( j ) and C( z ) is
tion gives defined as
n
ut (p) Å 1 0 e 0 ( ap ) . [30] F( ze 0ip) 0 F( ze ip)
C( z ) Å . [33]
2ip
This model can be considered as a combination of the Jova-
novic and the Freundlich isotherm models. For n Å 1, it In the version of Sips procedure considered here (3), the
reduces to the Jovanovic isotherm for homogeneous sur- position of the energy distribution function is characterized
faces. For large values of the partial pressures, ut (p) tends by a minimum adsorption energy, ea . The parameter j is
toward unity; a monolayer coverage is achieved. For low defined as
values of the partial pressures, the isotherm equation is
equivalent to the Freundlich isotherm (17). Accordingly, 1
the model cannot account for a Henry law (2) region. On jÅ1/ , [34]
ap
the other hand, the coverage ratio is given as an explicit
function of the partial pressure of the adsorbate, which is a where the constant a is the same parameter as in Eq. [30].
considerable advantage for the determination of isotherms Its temperature dependence is defined as
by the chromatographic methods of frontal analysis or pulse
on a plateau (29) or for their use in the calculation of elution a Å K 0e ea/ RT , [35]
profiles or other concentration signals at high concentrations,
under nonlinear conditions (30). Note that Eq. [30] is equiv-
where K 0 is the preexponential factor, R the ideal gas con-
alent to a cumulative Weibull distribution (42).
stant, and T the absolute temperature. The parameter z is
This new model can be used to represent experimental
defined as
data concerning adsorption isotherms on heterogeneous sur-
faces composed of several subsurfaces which are themselves
z Å e (e0 ea) / RT 0 1. [36]
heterogeneous, so the overall isotherm is the sum of several
expressions such as Eq. [30], each one written for one of
the subsurfaces. Like other models developed for the de- The relationship between the global adsorption isotherm and
the function F( j ) is given by
scription of monolayer adsorption on heterogeneous surfaces

S D
without lateral interactions, this model can, in principle, be
modified to describe monolayer, single-gas adsorption with 1
F ( j ) Å ut , [37]
lateral interactions, multilayer single-gas adsorption without a( j 0 1)
or with lateral interactions, the adsorption of multicompo-
nent gas mixtures, or the adsorption of multisolute dilute while the energy distribution function is related to the func-
solutions (3). For example, the extension of the model to tion C( z ) by
describe competitive adsorption can be accomplished using
models of the adsorbed solution theory (31) or the method C( z ) Å RTF( e ). [38]
described by Jaroniec et al. (32).
The integral equation [1] can be solved analytically with Considering Eqs. [30], [34], and [37], we see that the
respect to the energy distribution function in the particular function F( j ) for the Jovanovic–Freundlich isotherm model
case in which one assumes a Langmuir local adsorption is
isotherm and a global adsorption isotherm given by Eq. [30].
0n
The solution is derived using the procedure suggested by F( j ) Å 1 0 e 0 ( j01 ) . [39]
Sips (18, 33) and was recently summarized by Jaroniec (3).
In this case, Eq. [1] is rewritten as Combining Eqs. [33] and [39] gives the value of the func-
tion C( z ),

*
`
pK( e )
ut (p) Å F( e )d e. [31] ip01 ) 0 n 0 ip01 ) 0 n
0 1 / pK( e ) e 0(ze 0 e 0(ze
C( z ) Å . [40]
2ip
Sips (18, 33) transformed Eq. [31] into the following inte-
gral, known as the Stieltjes transform: Using Euler’s formula, Eq. [40] can be transformed into

*
` 0 ncos pn
C( z ) e 0 ( z /1 ) sin[( z / 1) 0 nsin pn]
F( j ) Å dz . [32] C( z ) Å . [41]
0 j/z p

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62 QUIÑONES AND GUIOCHON

TABLE 2 tion to compare the performance of these models in account-

Summary of the Adsorption Data Analyzed in This Study ing for these data with that of the Jovanovic–Freundlich
model (Eq. [30]). The Tóth and Unilan models were chosen
T Number of in this work because they are considered as the best all-
System Adsorbate (K) data pointse Ref.
around three-constant isotherm models for microporous ad-
1 CH3Cl 288 15 (8) sorbents and they were those selected for the systematic
2 CH3Cl 293 16 (8) correlations of the large data bank of adsorption isotherms
3 CH3Cl 298 21 (8) on heterogeneous surfaces (1). The Hines model is one of
4 CH2Cl2 288 15 (8) the most recent models for heterogeneous adsorbents which
5 CH2Cl2 293 16 (8)
6 CH2Cl2 298 15 (8) assumes that the local adsorption isotherm on homotattic
7 CHCl3 288 12 (8) sites is described by the Jovanovic model (14).
8 CHCl3 293 12 (8) The nonlinear regression analysis of the models was car-
9 CHCl3 298 11 (8) ried out using a fitting procedure based on Marquardt algo-
10 CCl4 288 12 (8) rithm (34), which minimizes the residual sum of the squares
11 CCl4 293 12 (8)
12 CCl4 298 14 (8) of the differences between the experimental data and the
13 C2H3Cl3 288 15 (9) model calculations. The estimates of the parameters present
14 C2H3Cl3 293 17 (9) in the models are given at the asymptotic 95% confidence
15 C2H3Cl3 298 18 (9) interval. Conventional use of the Fisher distribution is not
16 C2Cl4 288 15 (9) possible in this case because there is only one data point for
17 C2Cl4 293 15 (9)
18 C2Cl4 298 18 (9) each value of the partial pressure. As suggested in (35), for
each model and each set of experimental data, the Fisher
a
Number of data points in the original work plus the coordinate origin, parameter was calculated according to
minus one outlier in the case of system 2.

m 0 l ( imÅ1 (qexp,i 0 qexp ) 2

Fcalc Å , [44]
Substituting Eqs. [36] and [38] into Eq. [41] gives the final m 0 1 ( imÅ1 (qexp,i 0 qt ,i ) 2
expression for the adsorption energy distribution
F( e ) where

e 0[e
(e0 ea) /RT ] 0 ncos pn
sin{e 0 [ e
(e0 ea) /RT ] 0 n
sin pn )}
Å .
pRT
This distribution includes an exponential decay at high ad-
sorption energies and a maximum value for e Å ea which is
equal to
e 0cos pnsin[sin ( pn /e)]
F( ea ) Å . [43]
pRT
RESULTS
The adsorption data used in the present work to illustrate
the new isotherm model described above, in Eq. [30], and
to show its potential usefulness were reported by Hines et
al. (8, 9).2 These data regard the adsorption of several chlori-
nated hydrocarbons on a microporous silica gel at different
temperatures (see Table 2). The surface should be consid-
ered as heterogeneous because the heat of adsorption tends
to decrease with increasing concentration of the compounds
(8, 9). These experimental data were fitted to the Tóth (5),
UNILAN (10), and Hines (11) models of isotherm adsorp-
2
The point corresponding to the isotherm origin was added to the original
experimental data to perform the fitting of the data to the different isotherm
models used in this work.
qexp,i are the experimental values of the solid phase con-
[42] centration of the adsorbate for a given system,
qexp is the mean value of the data, qexp,i for a given system,
qt ,i is the estimate of the solid phase concentration of the
adsorbate by a given model,
l is the number of adjusted parameters in the model, and
m is the number of experimental data for a given system.
Equation [ 44 ] is different from the conventional Fisher
equation. The second factor in its RHS contains the sum
of residuals in the denominator. Thus, the higher Fcalc , the
better the model correlates the experimental data. The first
factor in the RHS of Eq. [ 44 ] decreases with increasing
number of parameters of the model. This equation allows
the comparison of models having different numbers of
parameters ( 35 ) .
Tables 3–6 summarize the results of the nonlinear regres-
sion analysis of the models evaluated in this study. These
tables report the parameter estimates, their confidence inter-
vals, and the Fisher values for each set of experimental data.
For systems 13 to 18, we calculated the average absolute
deviations (AAD) produced by the Jovanovic–Freundlich
model, in order to compare these deviations with those gen-
erated by the fit of the data to the Langmuir model (13) and
the Vacancy Solution Model based on the use of the Flory–
Huggins equation (36) for the activity coefficient reported

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 NEW JOVANOVIC–FREUNDLICH ISOTHERM MODEL 63
TABLE 3a TABLE 5a
Regression Results for the Jovanovic–Freundlich Modelb Regression Results for the UNILAN Model

System System
no. qs a 1 102 n Fcalc no. qs n c Fcalc

1 5.96 { 0.26 0.42 { 0.05 0.74 { 0.04 1517.0 1 7.4 { 1.2 1.6 { 0.9 226 { 96 531.13
2 5.77 { 0.38 0.38 { 0.06 0.77 { 0.06 850.1 2 7.1 { 1.2 1.1 { 1.1 243 { 96 460.66
3 5.46 { 0.28 0.36 { 0.05 0.80 { 0.05 852.5 3 6.8 { 0.9 1.0 { 0.9 268 { 82 538.61
4 5.26 { 0.29 2.4 { 0.4 0.66 { 0.06 401.7 4 6.3 { 1.1 2.0 { 1.1 35 { 19 164.48
5 5.12 { 0.33 2.0 { 0.4 0.71 { 0.08 239.6 5 6.0 { 1.1 1.6 { 1.3 42 { 20 119.62
6 5.02 { 0.42 1.6 { 0.4 0.70 { 0.10 152.6 6 5.9 { 1.2 1.6 { 1.6 51 { 30 82.13
7 3.67 { 0.14 8.3 { 1.3 0.60 { 0.06 439.0 7 4.0 { 0.4 2.1 { 1.0 8 { 2.7 171.22
8 3.59 { 0.17 7.2 { 1.4 0.62 { 0.07 332.8 8 4.0 { 0.5 2.0 { 1.0 9 { 3.6 151.40
9 3.51 { 0.19 5.8 { 1.2 0.65 { 0.09 229.6 9 3.9 { 0.5 1.8 { 1.4 11 { 5.1 97.88
10 2.91 { 0.072 13.0 { 1.3 0.64 { 0.04 1154.6 10 3.2 { 0.2 1.7 { 0.7 5.3 { 1.2 379.79
11 2.78 { 0.086 11.6 { 1.4 0.76 { 0.06 547.8 11 3.1 { 0.2 1.3 { 1.0 6.0 { 1.5 227.25
12 2.72 { 0.058 9.6 { 0.8 0.69 { 0.04 923.2 12 3.0 { 0.19 1.4 { 0.7 7.2 { 1.4 287.98
13 3.35 { 0.041 42 { 4.1 0.60 { 0.06 392.8 13 3.45 { 0.04 0.4 { 1.7 1.4 { 0.11 645.32
14 3.33 { 0.062 25 { 2.8 0.57 { 0.06 250.6 14 3.48 { 0.08 1.63 { 0.6 2.3 { 0.3 246.37
15 3.33 { 0.052 14 { 1.2 0.58 { 0.04 489.1 15 3.54 { 0.10 1.9 { 0.5 4.0 { 0.5 290.06
16 2.95 { 0.062 260 { 28 0.37 { 0.03 1530.0 16 3.03 { 0.06 3.4 { 0.4 0.16 { 0.015 1336.01
17 2.87 { 0.047 208 { 17 0.41 { 0.03 1638.7 17 2.97 { 0.07 3.0 { 0.4 0.22 { 0.02 928.19
18 2.76 { 0.090 144 { 24 0.48 { 0.06 160.2 18 2.9 { 0.15 2.6 { 0.8 0.35 { 0.08 106.58

a
Units: qs , mmole/g; a, (mm Hg)01, n and Fcalc , dimensionless. a
Dimensions: as in Table 3, with the addition of c, mm Hg.
b
Model equation, Eq. [30].

Table 7 reports the AAD values calculated according to

by Hines (9). The AAD were calculated according to the Eq. [45] for the selected models. Figure 1 shows the best
expression fit of the Jovanovic–Freundlich model to the adsorption data
of methyl chloride. Table 8 and Fig. 2 illustrate the tempera-
Éqexp,i 0 qt ,i É ture dependence of the parameter a in Eq. [30], according
AAD Å 100 . [45] to the linear form of Eq. [35] for the six chlorinated hydro-
qexp,i
carbons studied. Figure 3 shows the pressure dependence of
the function l ( u, p) for the Jovanovic–Freundlich (Eq.
TABLE 4a [30]) and Tóth (Eq. [13]) models in the case of chlorometh-
Regression Results for the Toth Model ane at 298 K. Figure 4 represents the energy distribution
System functions calculated according to Eq. [42] for dichlorometh-
no. qs b n Fcalc ane at 288, 293, and 298 K using the parameters of Tables 2,
3, and 8. Figure 5 shows the adsorption energy distributions
1 8.1 { 1.5 30 { 33 0.69 { 0.19 607.46 calculated according to Eq. [42] for the six chlorinated hy-
2 7.5 { 1.6 66 { 108 0.80 { 0.3 480.92
drocarbons studied at 288 K.
3 7.1 { 1.1 85 { 110 0.83 { 0.2 555.46
4 7.0 { 1.7 5 { 4.5 0.59 { 0.2 177.61
5 6.7 { 1.7 8 { 10 0.66 { 0.3 124.11 DISCUSSION
6 6.6 { 2 9 { 14 0.65 { 0.4 84.69
7 4.4 { 0.8 2 { 1.5 0.60 { 0.24 162.12
8 4.3 { 0.8 2.5 { 2 0.63 { 0.26 144.90
The results presented in Tables 3–6 show that the parame-
9 4.1 { 0.9 3.5 { 4 0.68 { 0.36 95.00 ters of the Jovanovic–Freundlich isotherm model were iden-
10 3.4 { 0.4 2.1 { 0.9 0.69 { 0.17 378.28 tified with a smaller error than those of all the other models
11 3.2 { 0.4 3.4 { 2 0.81 { 0.2 225.79 studied. The Fisher values obtained for all the systems stud-
12 3.2 { 0.3 3.4 { 1.8 0.76 { 0.18 287.39 ied are larger for the regression of the Jovanovic–Freundlich
13 3.45 { 0.06 1.4 { 0.3 0.99 { 0.13 643.86
14 3.6 { 0.15 1.4 { 0.5 0.77 { 0.14 235.90
isotherm model than for those of the Tóth and UNILAN
15 3.7 { 0.2 1.7 { 0.6 0.69 { 0.12 269.36 models, with the exception of 1,1,1-trichloroethane at 288
16 3.3 { 0.2 0.19 { 0.010 0.45 { 0.09 892.09 K, showing that the data fit better to the first than to the
17 3.2 { 0.2 0.22 { 0.018 0.49 { 0.10 560.05 other two models. Note that the fit of the data for 1,1,1-
18 3.1 { 0.4 0.29 { 0.051 0.53 { 0.18 90.17 trichloroethane at 288 K to the Tóth and UNILAN models
a
Dimensions: as in Table 3, with the addition of b, dimensionless.
is also better than their fit to Hines model. Comparison of
the results obtained with the Jovanovic–Freundlich and the

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64 QUIÑONES AND GUIOCHON

TABLE 6a
Regression Results for the Hines et al. Model

System
no. qs K1 K2 1 104 K3 Fcalc

1 6.78 { 0.03 200 { 4.5 2.9 { 1.0 01.5 { 0.7 51725

2 6.69 { 0.07 224 { 9 2.0 { 0.19 02.2 { 0.8 14943
3 6.49 { 0.06 252 { 8 1.34 { 0.15 01.9 { 0.4 10373
4 5.79 { 0.25 37 { 10 10 { 52 00.4 { 2 461
5 5.77 { 0.33 45 { 15 8 { 40 00.5 { 3 236
6 5.69 { 0.45 59 { 26 0 { 57 0.05 { 4 149
7 3.88 { 0.13 9 { 3.7 49 { 51 00.82 { 1.5 547
8 3.86 { 0.18 12 { 5.4 33 { 112 00.36 { 1.7 300
9 3.78 { 0.20 13 { 6 30 { 45 00.92 { 1.5 229
10 3.11 { 0.03 5.7 { 0.5 34 { 5 00.42 { 0.2 4813
11 3.03 { 0.09 6.6 { 1.5 12 { 9 00.22 { 0.5 564
12 2.96 { 0.05 7.9 { 1.0 13 { 7 00.25 { 0.3 1244
13 3.45 { 0.06 1.5 { 3.9 0 { 11000 0.0 { 6 600
14 3.46 { 0.06 3.5 { 2.0 0 { 590 0.00 { 0.5 350
15 3.48 { 0.04 6.0 { 1.4 0 { 150 0.00 { 0.6 942
16 2.98 { 0.05 0.04 { 0.04 023 { 29b 1.09 { 0.6 1807
17 2.91 { 0.02 0.00 { 0.04 0 { 4900b 0.81 { 0.2 5834
18 2.85 { 0.08 0.00 { 0.13 0 { 264000b 0.88 { 0.6 233

a
Dimensions: as in Table 3, with the addition of K1 , K3 , mm Hg. K2, dimensionless.
b
In this case the parameter K2 is not multiplied by 10,000.

Hines models shows that the performance of the Hines model than those reported (9) for the Langmuir model and for the
is superior for a majority of systems (1 to 3, 10, 12 to 15, Vacancy Solution Model (36). The only exception is for
17, and 18). By contrast, the values of the Fisher parameters 1,1,1-trichloroethane at 288 K. In this case, the adsorption
are close for several other systems (4 to 9, 11, and 16), data fit better to the Langmuir model. All these results dem-
indicating similar model performance. It seems that the ori- onstrate the suitability of the Jovanovic–Freundlich iso-
gin of the isotherm was not included in the initial regression therm model to correlate the adsorption data studied here.
of the data (8, 9). If we include this point in the data set, The Tóth, UNILAN, and Hines models reduce to the
however, our estimates of the parameters of the Hines iso- Henry law at low pressures, whereas the Jovanovic–Freund-
therm model differ from those reported initially (8, 9). It
should be noted that the errors associated with the parameter
estimates are higher for the Hines model, especially for K2
and K3 , than for the Jovanovic–Freundlich model. This latter
model is also simpler than the former, having three parame-
ters instead of four. The results of Table 7 show that the
AAD values are lower for the Jovanovic–Freundlich model

TABLE 7
Average Absolute Deviations Observed with the Jovanovic–
Freundlich Model (Eq. [30]), the Langmuir Model (Eq. [3] and
Ref. (9)), and the Vacancy Solution Model Based on the Flory–
Huggins Activity Coefficient Equation (VSM–FH, Ref. (9))

System
no. Eq. [30] Eq. [3] VSH–FH

13 1.22 1.06 2.05

14 1.90 2.54 3.13
15 1.52 3.21 2.18
FIG. 1. Adsorption isotherms of methyl chloride on silica gel at differ-
16 0.61 3.25 2.33
17 0.67 3.44 2.22 ent temperatures. Symbols denote experimental data from Ref. (8). Solid
18 1.88 3.87 4.47 lines were calculated with Eq. [30] using the values of the parameters
given in Table 3.

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 NEW JOVANOVIC–FREUNDLICH ISOTHERM MODEL 65
TABLE 8
Regression Results for the Temperature Dependence
of the a Parameter (Eq. [35])

Standard Regression
Adsorbate ln K0 ea error coefficient

CH3Cl 010 { 9 12 { 23 0.0178 0.988626

CH2Cl2 016 { 10 29 { 24 0.0187 0.997822
CHCl3 013 { 17 26 { 42 0.0326 0.992086
CCl4 011 { 15 21 { 38 0.0295 0.990129
C2H3Cl3 033 { 7 78 { 17 0.0130 0.999858
C2Cl4 017 { 30 43 { 71 0.0556 0.991744

lich model does not. Apparently, the experimental data avail-

able do not allow sufficient coverage of the Henry law re-
gion. The success of the Jovanovic–Freundlich model to
better correlate the data may be associated with the fact
that these data are concentrated mainly in the regions of
intermediate and high coverage ratio, so the main drawback
of the Jovanovic–Freundlich model, its inability to correctly
reproduce the Henry law region, has little influence on the
quality of the data fit observed. Besides, it is known that
any three-constant isotherm equation is unable to provide a
precise fit of the experimental data at both high and low
surface coverages (1). The fact that the Jovanovic–Freund-
lich model does not reduce to the Henry law is a drawback
which has a certain importance for a variety of reasons,
although it shares this property with other important isotherm
models widely applied to describe adsorption isotherms on
heterogeneous surfaces. Such is the case, among others, of
the Freundlich (17), Langmuir–Freundlich (18), general-
ized Freundlich (33), Marczewski–Jaroniec (37), Dubi-
nin–Radushkevich (20), Dubinin–Astakhov (38), and
FIG. 2. Temperature dependence of the parameter a of Eq. [30] for
the different adsorbates.
FIG. 3. L-functions, l ( u, p), calculated for the Tóth and the Jovanovic–
Freundlich models using the parameters of the adsorption of methyl chloride
at 298 K.
Fritz–Schlünder (39) models. None of them reduces to the
Henry law at low pressures.
The impossibility of accounting for the low partial pres-
sure, Henry law region of the isotherm is a drawback of
these isotherm models which cannot be ignored nor corrected
for single-component problems. However, there is an im-
portant application of single-components in which this diffi-
culty can be alleviated; it is the modeling of competitive
isotherms. In this case, a new approach has been recently
proposed (40), based on models of the adsorbed solution
theory. It allows ignoring single-component behavior in the
Henry law region and gives results which are as good as the
classical ones. Thus, it removes the sensitivity of adsorbed
solution theory models to the type of isotherm models used
to fit single-component equilibrium data in the Henry law
region. In compensation, the method introduces new parame-
ters that must be evaluated from binary equilibrium data,
thus eliminating the possibility of predicting multicompo-
nent equilibrium isotherms from single-component data.
This limitation is relative, however, because multicomponent
data must always be generated, as tests of the model and,
in the case of actual adsorbed solution theory models, for
correlating adsorbed phase activity coefficients (31).
In this case, there are two possibilities, either to measure
single-component isotherms down to the Henry law region or
to measure binary equilibrium under constant total pressure.
From a practical point of view, the second solution is often
better, especially when strongly adsorbed compounds are
concerned. Furthermore, the experimental methods of deter-
mination of multicomponent equilibrium isotherms for both
gas mixtures and solutions have been significantly improved
in recent years, mainly because of the availability of com-

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66 QUIÑONES AND GUIOCHON
FIG. 4. Adsorption energy distributions calculated for dichloromethane
at 288, 293, and 298 K.
puter data acquisition and processing (41). Moreover, when
data have been acquired in the Henry law region, it is possi-
ble to correlate them separately.
The importance of models that fit single-component ad-
sorption data well at high concentrations stems from the
common observation that competitive adsorption behavior
is rather unimportant at low concentrations (1) and that
the different theories now available for the calculation of
multicomponent isotherms provide good estimates at low
coverages, while no model is completely satisfactory at high
concentrations (31). Thus, high concentrations is the range
in which it is desirable to find models accounting well for
single-component data, provided that these models can be
used within the framework of the adsorbed solution theory
models.
The results of the regression analyses presented in Tables
3–6 show a slight variation (usually a decrease but, in a few
cases, an increase) of the monolayer capacity with increasing
temperature for all the compounds studied. However, the
significant error observed in the determination of this param-
eter does not allow a definitive conclusion regarding this
effect. This situation is the same as for the results previously
reported (8, 9). However, the Jovanovic–Freundlich iso-
therm gives the smallest value of all isotherm models for
the monolayer capacity.
The temperature dependence of the heterogeneity parame-
ter is not well defined, given the values of the estimates
obtained at the different temperatures and those of the errors
made. The only exception is the trend exhibited by the het-
erogeneity parameter determined from the fit of the data for
1,1,1-trichloroethane to the Tóth model. At 288 K, the value
identified is close to unity, suggesting that the Langmuir
model may correlate these data as well as more complex
models. In fact, this result was obtained previously by Hines
AID JCIS 4406 / 6g16$$$185 09-25-96 13:47:31
(9), as shown in Table 7. Nevertheless, the surface is not
homogeneous, as indicated by the decreasing trend of the
values of the isosteric heats of adsorption (9). The statistical
similarity between the values of the heterogeneity parame-
ters determined from the Jovanovic–Freundlich and the Tóth
isotherm models (see Tables 3 and 4) should be noted. The
heterogeneity parameters of the Jovanovic–Freundlich
model are nearly independent of the temperature. The tem-
perature dependence of the heterogeneity parameter is not
clearly defined and the temperature dependence of the ad-
sorption energy distribution is also small (3). Many empiri-
cal and semiempirical adsorption isotherm equations for het-
erogeneous surfaces produce adsorption energy distributions
that are temperature independent (3).
As shown in Fig. 4, there is a great similarity between
the adsorption energy distributions derived for dichlorometh-
ane at the different temperatures studied. This result obtained
with the Jovanovic–Freundlich model was also obtained by
Hines et al. (8). The values obtained for the heterogeneity
parameter of the different compounds are close. The hetero-
geneity parameter of the Jovanovic–Freundlich model
shows near independence of the nature of the compound.
This confirms that silicagel exhibits the same degree of het-
erogeneity for the majority of the chlorinated hydrocarbons
studied, in agreement with previous results regarding their
adsorption energy distribution (8). The distributions derived
in this work, using Eq. [42], are similar in shape for five
of the six compounds (Fig. 5). There is a shift along the
energy axis corresponding to the different values obtained
for ea (Table 8). This result is again similar to the one
reported previously (8). The values obtained for the hetero-
geneity parameter of tetrachloroethylene are different from
those of all the other chlorinated hydrocarbons, which may
be explained by the fact that it is the only unsaturated com-
FIG. 5. Adsorption energy distributions calculated for the six chlorohy-
drocarbons studied at 288 K.
coida AP: Colloid
 NEW JOVANOVIC–FREUNDLICH ISOTHERM MODEL 67
pound studied. The same result is derived from the analysis 5. Tóth, J., Acta Chim. Hung. 32, 31 (1962).
of the values derived from the regression of the Tóth and 6. Misra, D. N., J. Colloid Interface Sci. 79, 543 (1980).
7. Tóth, J., J. Colloid Interface Sci. 163, 299 (1994).
UNILAN models to the adsorption data of this compound. 8. Kuo, S.-L., Hines, A. L., and Dural, N. H., Sep. Sci. Technol. 26, 1077
The energy distribution calculated for this compound ac- (1991).
cording to Eq. [42] does not have the same shape as the 9. Kuo, S.-L., and Hines, A. L., J. Chem. Eng. Data 37, 1 (1992).
distributions of the other five compounds (Fig. 5). 10. Honig, J. M., and Reyerson, L. H., J. Phys. Chem. 56, 140 (1952).
The parameter a decreases exponentially with increasing 11. Hines, A. L., Kuo, S.-L., and Dural, N. H., Sep. Sci. Technol. 25, 869
(1990).
temperature, as seen in Table 8 and Fig. 2. Large values 12. Stanley, B., and Guiochon, G., Langmuir 11, 1735 (1995).
of the correlation coefficients were obtained in all cases. 13. Langmuir, I., J. Am. Chem. Soc. 40, 1361 (1918).
The standard error of the estimation ( correlation ) is small. 14. Jovanovic, D. S., Kolloid-Z.Z. Polym. 235, 1203 (1969).
However, the errors made on the estimates of K 0 and ea 15. Moreau, M., Valentin, P., Vidal-Madjar, C., Lin, B. C., and Guiochon,
are rather large because the correlations of these two pa- G., J. Colloid Interface Sci. 141, 127 (1991).
16. Fowler, R., and Guggenheim, E. A., ‘‘Statistical Thermodynamics.’’
rameters are based on the use of three experimental data Cambridge Univ. Press, Cambridge, 1965.
points, resulting in only one degree of freedom. The values 17. Freundlich, ‘‘Kapillarchemie.’’ Akademische Verlagsgesellschaft,
of K 0 are low, as expected ( 3 ) . For each compound, the Leipzig, 1922.
value of ea derived from the regression is close to the 18. Sips, R., J. Chem. Phys. 16, 490 (1948).
minimum value of the isosteric heat of adsorption ( 8, 9 ) , 19. Radke, C. J., and Prausnitz, J. M., Ind. Eng. Chem. (Fundam.) 11, 445
(1972).
as required by theory ( 3 ) . 20. Dubinin, M. M., and Radushkevich, L. V., Dokl. Akad. Nauk SSR Ser.
The L-function is plotted in Fig. 3 versus the partial pres- Khim. 55, 331 (1947).
sure of the adsorbate. It is higher for the Jovanovic–Freund- 21. Graham, D., J. Phys. Chem. 57, 665 (1953).
lich isotherm than for the Tóth isotherm within the range 22. Laub, R. J., ACS Symp. Ser. 297, 1 (1986).
studied. On the other hand, the function l ( u, p) decreases 23. Jacobson, S., Golshan-Shirazi, S., and Guiochon, G., AIChE J. 37, 836
(1991).
faster with increasing pressure for the Tóth model than for 24. Charton, F., Jacobson, S. C., and Guiochon, G., J. Chromatogr. 630,
the Jovanovic–Freundlich isotherm. At low pressures, the 21 (1993).
function tends toward a limit equal to the low pressure equi- 25. Misra, D. N., J. Colloid Interface Sci. 43, 85 (1973).
librium constant for the Tóth isotherm, while it tends toward 26. Shlygin, A., and Frumkin, A., Acta Physicochim. URSS. 3, 791 (1935).
` for the Jovanovic–Freundlich isotherm (see Eq. [29] and 27. Jaroniec, M., and Piotrowska, J., Chem. Zvesti 40, 65 (1986).
28. Jaroniec, M., Colloid Polym. Sci. 254, 601 (1976).
numerical values of a and n in Table 3). The fact that the 29. Dondi, F., Gonnord, M.-F., and Guiochon, G., J. Colloid Interface Sci.
function l ( u, p) for the Jovanovic–Freundlich model tends 62, 316 (1977).
toward infinity when the pressure tends toward 0 may be a 30. Rouchon, P., Schonauer, M., Valentin, P., Vidal-Majdar, C., and Guio-
result of the fact that this equation does not reduce to the chon, G., J. Phys. Chem. 89, 2076 (1985).
Henry law at low pressures. However, the L-function de- 31. Scholl, S., Schachtl, M., Sievers, W., Schweighart, P., and Mersmann,
A., Chem. Eng. Technol. 14, 311 (1991).
creases with increasing pressure in a similar way for both 32. Jaroniec, M., Narkiewicz, J., and Rudzinski, W., J. Colloid Interface
models. Sci. 65, 9 (1978).
33. Sips, R., J. Chem. Phys. 18, 1024 (1950).
ACKNOWLEDGMENTS 34. Marquardt, D. W., J. Soc. Appl. Math. 11, 431 (1963).
35. Ajnazarova, S. L., and Kafarov, V. V., ‘‘Metodi Optimisatsi Eksperi-
This work was supported in part by UNDP project CUB/91/001. I.Q. menta v Khimicheskoy Teknologui.’’ Vishaia Shkola, Moskva, SSSR,
thanks the Laboratoire de Génie Chimique (URA CNRS 192) of INP- 1985.
ENSIGC, Toulouse, France for support, and especially Prof. Dr. A. M. 36. Cochran, T. W., Kabel, R. L., and Danner, R. P., AIChE J. 31, 268
Wilhelm, and acknowledges Eng. René Legrà from CQF, Habana, Cuba (1985).
for his help in the preparation of computer graphs. 37. Marczewski, A. W., and Jaroniec, M., Monatsh. Chem. 114, 711
(1983).
38. Dubinin, M. M., and Astakhov, V. A., Izv. Akad. Nauk SSSR Ser. Khim.
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