A FRACTAL ADSORPTION MODEL

R. J. Aguerre
*
, M. P. Tolaba
f
, C. Suarez
f
*
Universidad Nacional de Lujan, (CONICET)
Cruces Rutas 5 y 7, C.C 221, (6700) Lujan, Argentina.
E-mail: rojaguunlu.edu.ar
f
Departamento de Industrias, Eacultad de Ciencias Exactas y Naturales, UBA,
Ciudad Universitaria, (1428) Buenos Aires Argentina


Abstract. The developments in Iractal geometry have stimulated the theory oI
vapor sorption so that models that take into account the chaotic and polydisperse
nature oI most absorbents have substituted the simpliIied models oI solid
surIaces. An analytical isotherm equation that describes the multilayer
adsorption on Iractal surIaces with adsorbate-adsorbate interactions (measured
in terms oI Iree energy) diIIerent Irom that oI bulk liquid, was developed.
Assuming mathematical Iunctionalities Ior the variation oI the Iree energy
with the number oI the adsorbed layer, it is possible to evaluate the inIluence
oI the adsorbate-adsorbate interactions on the adsorption capacity oI solids oI
high degree oI surIace irregularity. Eor those surIaces with relatively low
degree oI irregularity, it results that the Iree energy variation with the layer
number in the multilayer region aIIects considerably the sorption capacity oI
the adsorbent, even Ior water activities lower than those corresponding to the
monolayer moisture content. II , the isotherm steeps at a 0 G
e
i
>
W
values
lower than BET equation, provoking an increase in the sorption capacity. In
this case the adsorbed molecules are more Iirmly adsorbed and structured than
liquid water. An opposite eIIect occurs when . This eIIect becomes
less marked as the surIace irregularity increases, being relevant Ior water
activities much larger than those corresponding to the monolayer value, only.
The energy interactions between adjacent adsorbate layers become less
important as the Iractal dimension oI the adsorbent increases. Eor a Iractal
surIace, the growing oI the multilayer seems to mainly controlled by the
degree oI surIace roughness characteristic oI microporous adsorbents, where
the volume and pore dimension are the true limitants to the sorption capacity.
Particularly, Ior surIaces highly roughness the growing oI the multilayer is
prevented by geometrical restrictions, and the magnitude oI the interactions
has practically no eIIect on the shape oI the isotherm. The isotherm was tested
using published experimental equilibrium data oI various water vapor-
biopolymer systems.
0 G
e
i
<

Keywords: Iractal isotherm, Iractality, adsorbate-adsorbate interactions.

*
To whom all correspondence should be addressed


1. Introduction
The developments in Iractal geometry have stimulated the theory oI vapor sorption
so that models that take into account the chaotic and polydisperse nature oI most
absorbents have substituted the simpliIied models oI solid surIaces.
The key quantity in Iractal geometry to characterize irregularities and roughness oI
a surIace is the Iractal dimension D (Eripiat et al., 1986). The value oI D, Ior a solid
surIace can vary Irom 2 to 3. The lower limit corresponds to a Ilat surIace, whereas the
upper value oI 3 corresponds to the maximum allowed complexity oI the surIace. In
porous materials, surIaces can be so irregular that geometrical concepts as elementary
as the surIace area cease to be practically meaningIul (PIeiIer et al., 1989). Concepts oI
Iractal geometry have successIully been used to treat adsorption processes and
investigate the nature oI adsorption complexes, the distribution oI active sites and
transIer in pores (Eripiat et al., 1986; Eripiat, 1990; Adler, 1990).
The experimental methods to evaluate the surIace Iractal dimension oI porous
materials have been summarized by Wang and Li (1997). The most common method is
to determine the Iractal dimension Irom adsorption data. One oI the oldest methods, the
adsorption probe method developed by PIeiIer and Avnir (1983), is based on the
dependence oI monolayer capacity on the adsorbate size.
Another approach was to include the surIace Iractal dimension in the equation Ior
adsorption isotherm. Then, the experimental isotherm is compared to the theoretical
one, being the Iractal dimension the adjustable parameter.
Isotherm equations that consider the irregularity oI the adsorbent surIace have been
Iormulated in the literature. Among them, there is a group oI the so-called BET-like
Iractal isotherms, which were derived Irom the application oI BET multilayer theory to
Iractal surIaces (PIeiIer et al., 1989; Eripiat et al., 1986: Kutarov and Kats, 1993).
Although these group oI isotherms take into account the morphology oI the surIace and
thus oI its Iractal character, they share the same shortcoming as the classical BET
equation, that is: the molecules in all layers above the Iirst are, Irom the energetic point
oI view, completely equivalent. ModiIication oI this postulate has conducted to
diIIerent isotherms.
The most used in the area oI water vapor sorption is the Anderson's equation,
known in the literature as the GAB isotherm (van den Berg, 1981). The GAB equation
consider that the state oI the adsorbed molecules above the Iirst layer is the same but
diIIerent Irom that in the liquid-like state. It is clear that an improvement oI the GAB
approach would result iI it were considered a third Iraction oI bound water analogous
to liquid water. This hypothesis would be corroborated by the studies oI Drost-Hansen
(1969) in water sorption in biopolymers, who postulated three regions in the sorbed
water, characterized by diIIerent binding energies and degree oI structuring oI the
water in each region.
The purpose oI this study is: i) to derive an isotherm equation that considers the
inIluence oI the Iractal character oI the surIace on the physical adsorption; ii) making
use oI the Iundamental principles oI BET theory, the present isotherm model will take
into account not only the adsorbate-adsorbent interaction as well as the contribution oI
this interaction Ior all layers above the Iirst; iii) to analyze the eIIect oI adsorbate-

adsorbate interaction on the shape oI Iractal isotherm; iv) to evaluate the Iitting ability
oI the present isotherm to model water vapor sorption in biopolymers.

1.1. Mathematical model
The BET equation was derived Irom a model oI an adsorption surIace divided into n
segments, having 1, 2, 3,..., i number oI layers oI adsorbed molecules. According to
this model, condensation and evaporation occurs at the top oI these segments, i.e.,
between the uncovered surIace s
o
and the Iirst layer, s'
1

|
.
|

\
|
=
RT
E
exp s' b s
P
P
a
1
1 1 0

1
(1)
where a
1
, b
1
, have the same meaning as in BET theory (Brunauer et al., 1938), E
1
is the
heat oI adsorption oI the Iirst layer, R the gas constant and T the temperature. Between
any successive layers, the equilibrium can be expressed as:
|
.
|

\
|
=
RT
E
exp s' b s'
P
P
a
i
i i 1 - i

i
(2)
Being s'
i-1
and s' at the top oI the respective i-1 and i layers.
Considering that
i
the surIaces
(
i i
a b R ln ) is the sorption entropy oI the i-layer, Eq. (2) can be
written in a more convenient, Iorm:
|
.
|

\
|
=
RT
G
- exp
s'
s'
P
P
i
1 - i
i

(3)
where is the sorption Iree energy oI the i-layer. This equation diIIers Irom the
classical BET theory in that Ior all layers above the Iirst is not considered equal
to Iree energy oI bulk water, . Assuming that the Iree energy oI sorption Ior the i-
layer diIIers Irom the Iree energy oI bulk water by a certain amount, it can be written in
general that:
i
G
i
G
L
G
e
i L i
G G G + =
e
(4)
where diIIerentiates the state oI the adsorbed molecules Irom that oI the
molecules in the pure liquid. Replacing Eq. (4) into Eq. (3), it results:
i
G
1 i
s'
i

i
s'

= (5)
where

(6)
RT
G
exp
RT
G
exp
P
P

e
i L

i
|
|
.
|

\
|
|
.
|

\
|
=
Defining
|
|
.
|

\
|
=
RT
G
exp h
e
i
i
(7)
and given that ( ) RT G exp P P
L

0
= , it results:
i w i
0
i
h a h
P
P
= = (8)

Erom Brunauer et al. (1938), it can be demonstrated that the Iraction oI surIace
occupied by 1
st
, 2
nd
, ..., i
th
layer Iollows the relation:

=
=
i
2 j
j

1
s'
i
s' (9)
Combining eqns. (8) and (9), we have
( )

=
=
i
2 j
j
h
w
a
1
s'
i
s' (10)
As s' , it results:
0 1 1
s =

= =
= =
i
2 j
j
h
i
w
a
0
C s
i
2 j
j
h
i
w
a
0
s
1
h
i
s' (11)
where ( RT
1
G exp
1
h C = = ) is the constant C oI BET theory.
In a recent work, Aguerre et al. (1996) demonstrated that Ior a Iractal surIace the
relationship between the surIaces at the top, s'
i
, and the bottom, s
i
, Ior a molecular stack
oI i-layers is:
( )
D 2
i i
1 2i s s'

= (12)
where D is the Iractal dimension; when Eq. (12) is substituted in Eq. (11) it gives:
( )

=

=
i
2 j
j
h
2 D
1 2i
i
w
a
0
C s
i
s (13)
According to the BET theory the monolayer capacity, N
m
, is:
(
(
(

=
+ + =

=
=

2 i
i
s
w
a
0
Cs
0
s

1
0 i
i
s

1
m
N (14)
where is the cross-section area oI water molecule. The total number oI molecules, N,
that Iorm the adsorbed Iilm is:
( )
(
(
(

= =

+ =

2 i 1
2
1 2
i
s
1
s

1
N
i
k
D
k (15)
It can be noticed that the Iractal dimension does not aIIect s
l
. This is so because the
adsorbed molecules in the Iirst layer are simultaneously the measurement scale oI the
adsorbent surIace area.
Einally, combining Eqns. (13), (14) and (15), it results:

( ) ( )
( )

= =

+ +

= = =

+
=


2 i
i
2 j
j
h
2 D
1 2i
i
w
a
w
a C 1
2 i
i
2 j
i
1 k
D 2
1 2k
j
h
2 D
1 2i
i
w
a
w
a C
m
N
N

(16)
Equation (16) is thereIore the isotherm equation Ior multilayer adsorption on Iractal
surIaces that takes into account the variation oI the Iree energy oI adsorption with
successive layers. It, is interesting to comment that Ior Ilat surIaces, D 2, and h
j
1
(Iree energy oI the multilayer equal to the Iree energy oI bulk water), Eq. (16) reduces
to BET equation.
Even more, iI Ior the second and higher layers the Iree energy oI the sorbed water
diIIers Irom that oI pure water in a constant amount (h k), Eq. (16) reduces to GAB
equation. On the other hand, iI the surIace oI the adsorbent behaves like a Iractal with
2 D 3 and assuming that the energy distribution in the adsorbed Iilm is the same
like in BET theory (h
j
1), the Iollowing Iractal isotherm can be obtained:
( ) ( )
( )

+ +

= =

+
=

2 i
2 D
1 2i
i
w
a
w
a C 1
2 i
i
1 k
D 2
1 2k
2 D
1 2i
i
w
a
w
a C
m
N
N
(17)
Equation (17) was plotted in Eig.1 Ior three diIIerent values oI D.

Eig.1. Adsorption isotherms calculated according to Eq.(17) Ior C 20 and 2 D 3.


This equation was derived by Aguerre et al. (1996) and can be considered as a
BET-like Iractal isotherm, together with other Iractal isotherms published in the
literature (Eripiat, 1986; PIeiIer et al., 1989).
The applicability and accuracy oI the new isotherm was evaluated using
experimental data Ior several materials obtained Irom the literature. The goodness oI
Iit was evaluated by means oI the mean relative percentage deviation modulus, E(),
deIined as:

=
P
i
p
1
i
N
pi
N
i
N
100
(%) E (18)
where and are the experimental and predicted moisture contents,
respectively, and p the number oI data. An accurate Iit oI the experimental data
corresponds to E() values below 5.
i
N
pi
N

Table 1. Parameter values and goodness oI Iit oI Eqn. (16) as applied to the
experimental isotherms oI various materials.
Material Temperature
(C)
C N
m
(dry basis)
D E
()
ReIerences
Apple pectin (s) 25 11.06 8.12 2.64 3.4 Weisser (1986)
Cellulose,
microcrystalline (a)
25 13.24 4.92 2.58 4.1 WolI et al. (1985)
Corn starch (d) 25 12.50 9.80 2.90 2.3 Hellman & Melvin
(1950)
Native manioc
starch (a)
25 15.80 9.30 2.80 1.7 Van der Berg
(1981)
Potato starch (a) 25 8.30 6.65 2.65 3.1 WolI et al. (1985)
Rough rice (d) 25 10.70 9.00 2.90 2.6 Zuritz et al. (1979)
Rough rice (d) 40 8.30 8.90 2.90 1.3 Ealabella et al.
(1992)
Sorghum (d) 20 16.40 9.60 2.90 0.9 Ealabella et al.
(1992)
Tapioca starch (d) 25 14.30 10.20 2.90 2.4 Hellman & Melvin
(1950)
Viscose yarn (d) 30 11.06 8.12 2.64 3.4 Nanri et al. (1994)
Wheat, Durum (d) 25 12.60 8.70 2.80 0.9 Day & Nelson
(1965)
Whey protein (s) 25 7.72 6.36 2.75 3.1 Weisser (1986)
a: adsorption, d: desorption, s: sorption

The parameters C, and D reported in Table 1 were determined Ior each data
set by using a nonlinear regression analysis.
m
N
The Iractal dimension resulted Irom the present analysis ranges between 2.64 to
2.90, indicating thereIore the complexity oI the diIIerent adsorbents and the Iact that
their surIaces is Iar Irom two dimensional as being closer to a three dimensional one.

Kutarov and Kats (1993) were determined Iractal values oI 2.7 Ior cellulosic
Iibers, using the isotherm model derived by PIeiIer et al. (1989). Nagai and Yano
(1990) determined the Iractal dimension oI Ireeze-dried and ethanol-treated starches
and Iound them to be in the range 2.3-3.0. Also, Peleg (1993) reported a Iractal
dimension oI up to about 2.9 Ior some proteins.

1.2. Conclusions
The change oI Iree energy among layers, Ior a Ilat surIace, aIIects considerable
the shape oI the isotherm. II , the isotherm steeps at , values lower than
BET equation, promoting an increase in the sorption capacity. In this case the
adsorbed molecules are more Iirmly retained and structured than liquid water. An
opposite eIIect occurs when .
0
e
i
G >
0 G
e
i
<
w
a
The variation oI Iree energy in the multilayer region aIIect, in a rather similar
way, the shape oI isotherms Ior Iractal and not Iractal surIaces. However, a Iractal or
rough surIace always exhibits less sorption capacity than a Ilat surIace.
The energy interactions between adjacent adsorbate layers become less important
as the Iractal dimension oI the adsorbent increases. Eor a Iractal surIace, the growing
oI the multilayer seems to mainly controlled by the degree oI surIace roughness
characteristic oI microporous adsorbents, where the volume and pore dimension are
the true limitants to the sorption capacity.
The eIIect oI the increase oI , on the sorption equilibrium is
counterbalanced by the increase oI the surIace Iractality. Particularly, Ior highly
roughness surIaces the multilayer growing is prevented by geometrical restrictions,
and the magnitude oI the interactions has practically no eIIect on the shape oI the
isotherm.
e
i
G

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