Sorptions Isotherms and Isosteric Heats of Sorption of Olive

Please cite this article in press as: Nourh` ene, B., et al.
, Sorptions isotherms and isosteric heats of sorption of olive leaves (Chemlali variety):
Experimental and mathematical investigations, Food and Bioproducts Processing (2007), doi:10.1016/j.fbp.2007.10.010
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Sorptions isotherms and isosteric heats of sorption of olive
leaves (Chemlali variety): Experimental and mathematical
investigations
Boudhrioua Nourh` ene
a,
, Bahloul Neila
a
, Kouhila Mohammed
b
, Kechaou Nabil
a
a
Groupe de Recherche en G enie des Proc ed es Agroalimentaires de lUnit e de Recherche en M ecanique des Fluides Appliqu ee et
Mod elisation, Ecole Nationale dIng enieurs de Sfax, BP W 3038, Sfax, Tunisia
b
Laboratoire dEnergie Solaire et des Plantes Aromatiques et M edicinales, Ecole Normale Sup erieure, BP 2400, Marrakech, Morocco
a r t i c l e i n f o
Article history:
Received 1 June 2007
Accepted 10 August 2007
Keywords:
Olive leaves
Gravimetric method
Mathematical treatment
Adsorption
Desorption
a b s t r a c t
Knowledge of sorption isotherms of agricultural products is necessary to control rehydra-
tion/dehydration and storage processes. The aim of this work is to determine moisture
adsorption and desorption isotherms of Tunisian olive leaves of Chemlali variety (Olea euro-
pea L.). The static gravimetric method was used to determine sorption isotherms of olive
leaves at three temperatures (40, 50 and 60
C) and in the range of water activity varying

from 0.0572 to 0.898. Eight models available in the literature were used to describe the
experimental data. The agreement betweenexperimental andcalculatedsorptionisotherms
was satisfactory (correlation coefcients and standard deviation values ranging, respec-
tively, from 0.91 to 0.99 and from 5.610
5
to 0.23). GAB and Peleg models were found
to be the best for describing the relationship between the equilibrium moisture content,
the water activity and temperature. The isosteric heats of desorption and adsorption were
determined from sorption isotherms and then correlated with corresponding equilibrium
moisture contents. The isosteric heat of desorption was higher than the isosteric heat of
adsorption and both decreased continuously with increasing of the equilibrium moisture
content.
2007 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
1. Introduction
Olive leaves are known for their therapeutic and medicinal
properties. They are used in both traditional and modern
medicine. Olive leaves are a rich natural source of polyphe-
nolic compounds which have biologic activities such as
antioxidant, antibacterial and antifungal properties (Zarzuelo,
1991). These compounds could also be used for cosmetic and
food preservation industries. Tunisian olive tree has always
been explored for harvesting olive fruit and/or extracting
olive oil. Olive leaves are not yet investigated at industrial
scale. Fresh olives leaves evolve rapidly after falling in the
ground and are always damaged by dust, insects and micro-
organisms. Studies should be performed on fresh and/or
Corresponding author.
E-mail addresses: nourhene.boudhrioua@fss.rnu.tn (B. Nourh` ene), neilabahloul@yahoo.com (B. Neila),
kouhila@hotmail.com (K. Mohammed), nabil.kechaou@enis.rnu.tn (K. Nabil).
processed olive leaves in order to dene theirs optimal storage
conditions requiredto increase their longevity before andafter
their processing. Consequently, knowledge of water sorption
isotherms of olive leaves is necessary.
Moisture sorption isotherms could be dened as the curve
presenting the variation of the equilibrium moisture content
as a function of water activity (a
w
) at a xed temperature
and appropriate environment of relative humidity. The con-
cept of water activity is a measure of the availability of water
in the product and could be further dened as the ratio of
the water vapor pressure exerted by the food material to
the vapor pressure of pure water, at the same temperature
(Labuza, 1986). Desorption and adsorption isotherms could
be established, respectively, by dehydration or rehydration
of the product at xed conditions of relative humidity and
0960-3085/$ see front matter 2007 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.fbp.2007.10.010
Please cite this article in press as: Nourh` ene, B., et al., Sorptions isotherms and isosteric heats of sorption of olive leaves (Chemlali variety):
ARTICLE IN PRESS
2 food and bi oproducts processi ng x x x ( 2 0 0 7 ) xxxxxx
Nomenclature
a
w
water activity
L
v
latent heat of vaporization of pure water
(kJ mol
1
)
Q
st
isosteric heat of sorption (kJ mol
1
)
q
st,n
net isosteric heat of sorption (kJ mol
1
)
R universal gas constant (J mol
1
K
1
)
r correlation coefcient
S standard error
T absolute temperature (K,

C)
X
eq
equilibrium moisture content (kg/kgd.b.)
X
opt
optimum moisture content (kg/kgd.b.)
temperature. According to Brunauer et al. (1938) classication
(BET classication) of sorption isotherms, based on Van der
Waals adsorption of gases on solid substrates, ve generalized
sorptionisotherms were distinguished. The sorptionisotherm
could be used for many technologic and scientic purposes. In
fact, it allows the determination of optimal conditions (tem-
perature and relative humidity) of packaging, storage and/or
air drying of the material. The equilibrium moisture content
of the product could be compared to the nal moisture con-
tent of the product dried at the same condition to judge the
stability of the processed material (Dumoulin et al., 2004).
The relationship between water activity (a
w
) and temperature
(T) at constant equilibrium moisture content is described by
moisture sorption isosters. Thermodynamic properties such
as the isosteric heats of sorption could be deduced from sorp-
tion isotherms established at two or more temperatures. The
energy required to dehydrate or rehydrate the product could
thus be determined. The isosteric heats of sorption could be
used to analyze, design different food processes and to study
moisturesolid interactions.
Mathematical models are very useful for describing and
predicting sorption isotherms at various experimental condi-
tions and so to calculate all thermodynamic properties that
could be deduced. More than 77 equations having two or
more parameters have been suggested in the literature for
mathematical investigation of experimental data of sorption
isotherms (Oswin, 1946; Halsey, 1948; Henderson, 1952; Chung
and Pfost, 1967; Chirife and Iglesias, 1978; Motarjemi, 1988;
Costa et al., 1998). These equations are theoretical, semi-
theoretical or empirical. Some equations have a dependent
temperature term and were used to reect the tempera-
ture dependency of moisture sorption isotherms. Each of the
suggested equations has some success in describing sorp-
tion isotherms for a given type of product according to the
Brunauer classication. The GABequationis consideredas the
most suitable model to be applied to many products types and
over a wide range of water activity. However, there is actually,
no perfect equation for describing sorption isotherms for all
biological materials.
The aim of this work is to establish sorption isotherms
for Tunisian olive leaves of Chemlali variety (Olea europea L.)
at three temperatures (40, 50 and 60
C). Experiments were

performedby using the static gravimetric method. Eight math-
ematical equations were chosen from the literature to t the
experimental data. The variations of the isosteric heats of
sorption of olive leaves as a function of the equilibrium mois-
ture contents were determined.
2. Material and methods
2.1. Raw material
Fresh olive leaves of Chemlali variety (Olea europea L.) were
obtained from the farm of the Olive Institute of Sfax (a
southern Tunisian country). Olive leaves were cut into paral-
lelepiped samples for sorption experiments.
2.2. Global chemical analysis
In order to characterize the olive leaves, analysis were realized
according to the Association of Ofcial Analytical Chemists
(AOAC, 1984): moisture content, by the gravimetric method at
105
C up to constant weight (24h). Total protein was deter-

mined by the Kjeldahl method. Protein was calculated using
the general factor (6.25) (El-Shurafa et al., 1982). Fat content
was determined by the Soxhlet method, using hexane as a sol-
vent. Ash content was measured by using a mufe at 550
Cup
to constant weight (4h). Carbohydrate content was estimated
by difference of mean values, i.e., 100{Sum of percentages
of moisture, ash, protein and lipids} (Al-Hooti et al., 1998;
Barminas et al., 1999).
The sample weight was measured by an analytical balance
(METTLER-TOLEDO) having a precision of 0.0001g. Moisture
content was expressed in both wet (g moisture/100g fresh
leaves) and dry basis (kgmoisture/kgd.b). Protein, fat, carbo-
hydrates andashcontents were expressedinwet basis (g/100g
fresh leaves). All analytical determinations were performed in
triplicate. Values of different parameters were expressed as
the meanstandard deviation.
2.3. Sorption isotherms experiments
Sorption isotherms of olive leaves were determined by the
gravimetric static method. Six saturated salt solutions were
prepared by dissolving an appropriate quantity of salt in dis-
tilled water (Dumoulin et al., 2004). Each salt solution was
prepared in a glass jar of 1l with an insulated lid. The jars are
immersed ina thermostated water bathadjusted to xed tem-
perature (T) for 24h to be stabilized. Each jar provides a xed
relative humidity (RH) corresponding to a xed water activity
(a
w
) for each temperature and salt concentration (Table 1).
Olive leaves samples used for both adsorption and des-
orption experiments were of 0.10.0001g. For adsorption
experiments olive leaves samples were dried 24h in an oven
at 105
C before putting them on a tripod in the glass jars.

For desorption experiments, fresh olive leaves were used. The
six jars containing olive leaves samples were put in ther-
mostated water baths adjusted to xed temperatures (40, 50
Table 1 Selected salt used for preparing saturated salt
solutions and their corresponding water activities
Salt Water activity
40
C 50
C 60
C
KOH 0.0626 0.0572 0.0549
MgCl
2
0.3159 0.3054 0.2926
K
2
CO
3
0.4230 0.4091 0.3921
NaNO
3
0.7100 0.6904 0.6735
KCl 0.8232 0.8120 0.8025
BaCl
2
0.8910 0.8823 0.8728
ARTICLE IN PRESS
food and bi oproducts processi ng x x x ( 2 0 0 7 ) xxxxxx 3
Fig. 1 Experimental apparatus used for measurements of
sorption isotherms: static gravimetric method: (1)
thermostated water bath; (2) jar containing salt; (3) sample;
(4) sample holder; (5) saturated salt solution.
and 601
C) (Fig. 1). The samples were weighed at differ-

ent times. The mass transfer between the product and the
surrounding ambient in the jar is assured by moisture vapor
diffusion. Equilibriumwas considered to be reached when the
change in samples weight did not exceed 0.0001g (ten to four-
teen days). At the equilibrium, the experiment was stopped
and the equilibrium moisture contents (X
eq
) of the samples
were measured. At the equilibrium, the water activity (a
w
) of
the olive leaves could be expressed as a functionof the relative
humidity (RH) of the atmosphere in the jar (a
w
=RH/100).
The same procedure was conducted for both adsorption
and desorption experiments at 40, 50 and 60
C and for a water

activity ranging from0.0572 to 0.898. Both adsorption and des-
orption isotherms experiments were triplicated.
2.4. Mathematical treatment
The experimental data of adsorption and desorption
isotherms were analyzed by using eight mathematical
equations chosen among the most used equations in litera-
ture (Chirife and Iglesias, 1978; BET, 1938; Henderson, 1952;
Chung and Pfost, 1967; Halsey, 1948; Oswin, 1946; Kouhila et
al., 2001, 2002, 2003; Lahsasni et al., 2003, 2004; Viswanathan
et al., 2003; Kaymak-Ertekin and Gedik, 2004; Bellagha et al.,
2005).
Table 2 recapitulates the expressions and the parameters
of the eight used models. The parameters of each model were
determined by minimizing the difference between calculated
and experimental data. The mathematical treatment was per-
formed by using a non-linear regression analysis using the
software Curve Expert 1.37. The adequacies of the equations
were evaluated by using two statistical parameters: the stan-
dard error (S), the correlation coefcient (r) and the percent
average relative deviation (P). These parameters were dened
as follows:
S =
n
exp. data
i=1
(X
eq
i
X
eq
Cali
)
2
n
exp. data
n
param
,
r =
n
exp. data
i=1
(X
eqi
X
eq
Cali
)
2
n
exp. data
i=1
(
X
eq
X
eq
i
)
2
,
and
P(%) =
100
n
n
exp. data
i=1
X
eq
cali
X
eqi
X
eqi
where X
eq
cali
is the calculated value of equilibrium moisture
content by using the tested model, X
eqi
is the experimental
value of equilibriummoisture content, n
param
is the number of
parameters of the particular model and n
exp. data
is the number
of experimental points. The arithmetic average value of the
experimental equilibriummoisture content (
X
eq
) is calculated
as follows:
X
eq
=
1
n
exp. data
n
exp. data
i=1
X
eq
i
.
2.5. Isosteric heats of sorption
The net isosteric heats of sorption (q
st
) can be calculated
by using the following correlation which is derived from the
Table 2 Mathematical models used to describe desorption and adsorption isotherms of Chemlali olive leaves
Models names Models expressions Parameters
Guggenhein, Anderson and De Boer (GAB) (Chirife
and Iglesias, 1978)
X
eq
=
CABaw
(1Baw)(1Baw+ABaw)
, where :
ln(A) = a +
b
T
; ln(B) = a +
b
T
and
ln(C) = a +
b
T
A=C
GAB
, B=K
GAB
, C=X
mGAB
BET (BET, 1938) X
eq
=
ABaw
(1aw)(1+(A1)aw)
A, B
HendersonThompson (Henderson, 1952) X
eq
=
ln(1aw)
A(T+B)
1/C
A, B, C
Modied Chung and Pfost (Chung and Pfost, 1967) X
eq
= ABln(a
w
) ln(T +B) A, B
Halsey (Halsey, 1948) X
eq
= A
B
ln(aw)
1/C
A, B, C
Oswin (Oswin, 1946) X
eq
= A
aw
1aw
B
A, B
Peleg (Chirife and Iglesias, 1978) X
eq
= Aa
B
w
+C
D
w
A, B, C, D
Adam and Shove (Chirife and Iglesias, 1978) X
eq
= A+Ba
w
+Ca
2
w
+Da
2
w
A, B, C, D
Where A, B, C and D are parameters of the equations, C
GAB
, K
GAB
and X
mGAB
are GAB parameters, T is temperature (
C), X
eq
is equilibrium
moisture content (kg/kgd.b.) and a
w
is the water activity.
ARTICLE IN PRESS
Table 3 Global chemical composition of fresh Chemlali
olive leaves
Components
a
g/100g fresh leaves
Moisture 55.50+2.40
Protein 10.70+0.08
Fat 3.40+0.30
Ash 9.20+0.10
Carbohydrates 21.20
a
Measurements in triplicate. Values of different compounds were
expressed as the meanstandard deviation.
ClausiusClapeyron equation (Tsami, 1991):
ln(a
w
) =
q
st,n
R

1
T
+Cste (1)
where a
w
, R, T and Cste are, respectively, the water activity,
the universal gas constant, the temperature and a constant.
The sorption isotherms are plotted as ln(a
w
) versus 1/T for
xed values of equilibrium moisture contents (the isosteres
curves). The net isosteric heats of sorption could be calculated
at each value of equilibrium moisture content from the slope
of the isosters curves which is equal toq
st,n
/R. It is assumed
here that q
st,n
is invariant withtemperature and continue with
the range of investigated temperature. The application of this
method requires the measurement of sorption isotherms at
more than two temperatures.
The isosteric heat of sorption (Q
st
) could be thus estimated
by adding the net isosteric heat of sorption (q
st,n
) to the latent
heat of vaporization of pure water (L
v
) (Q
st
=q
st,n
+L
v
). In this
work, the isosteric heats of desorption and adsorption were
determined from the calculated sorption isotherms by using
the best model tting experimental data. The obtained values
of the isosteric heats of sorption (Q
st
) were then correlated to
corresponding equilibriummoisture contents inorder tostudy
the magnitude of the binding energy and the availability of
polar sites to water vapor pressure as sorption proceeds.
3. Results and discussion
3.1. Global chemical composition of fresh olive leaves
The mean values of the chemical components of the fresh
olive leaves of Chemlali variety are presented in Table 3.
Mean values of different components were expressed as the
meanstandard deviation. Fresh olive leaves are intermedi-
ate moisture products: the moisture content of the leaves was
about 55.502.40% (wet basis). Protein, ash and fat contents
of the leaves were, respectively, about 10.700.08, 9.200.10
and 3.400.30%. Accordingly carbohydrate content was about
21.20%. According to this result, the olive leaves could be
considered as a rich natural source of valuable nutriments
(carbohydrates, protein and ash).
3.2. Sorption isotherms
Coefcients of variation (standard deviation100/mean
value) of the mean values of experimental equilibrium mois-
ture contents (triplicate) obtained for sorption isotherms
ranged from 1.95 to 7.00%. The experimental desorption and
adsorption isotherms obtained at 40, 50 and 60
C are shown
in Figs. 24. Sorption isotherms of olive leaves have a sig-
moid form and behave like a type II on BET classication.
Fig. 2 Desorption and adsorption isotherms of Chemlali
olive leaves obtained at 40
C. Des: desorption; Ads:

adsorption.

adsorption.

adsorption.
ARTICLE IN PRESS
Table 4 Results of tting of the desorption isotherms of Chemlali olive leaves
Models names T (
C) Parameters r S P (%)
A B C D
GAB 40 50.787 0.996 0.041 0.99 1.710
4
3.40
50 91.300 0.997 0.028 0.99 1.010
4
5.85
60 46.825 0.998 0.028 0.99 5.610
5
2.80
BET 40 287.090 0.032 0.98 0.018 20.80
50 309.316 0.028 0.99 0.009 5.20
60 50.646 0.028 0.99 0.004 2.50
Henderson 40 0.524 18.52 0.524 0.91 0.076 32.30
50 0.583 20.258 0.583 0.91 0.019 22.95
60 0.554 26.22 0.554 0.98 0.016 22.30
Modied Chung and Pfost 40 0.332 0.061 0.94 0.035 42.00
50 0.274 0.049 0.93 0.035 32.10
60 0.260 0.048 0.91 0.034 32.70
Modied Halsey 40 0.295 0.295 2.539 0.95 0.034 40.80
50 0.282 0.282 2.626 0.98 0.020 25.20
60 0.284 0.284 2.609 0.98 0.013 22.00
Oswin 40 0.084 0.545 0.99 0.014 18.60
50 0.063 0.627 0.99 0.009 14.70
60 0.059 0.665 0.99 0.007 14.30
Peleg 40 1.610 13.933 0.152 0.753 0.99 0.012 12.40
50 0.056 0.293 0.339 5.478 0.99 0.004 3.60
60 0.351 6.041 0.063 0.398 0.99 0.002 2.75
Adam and Shove 40 0.010 0.429 1.219 1.191 0.99 0.017 13.90
50 0.005 0.341 1.047 1.068 0.99 0.007 7.50
60 0.002 0.359 1.082 1.086 0.99 0.005 5.80
Increasing temperature from40 to 50
C sharply affected equi-

librium moisture content. The effect of temperature on the
sorption isotherms of olive leaves was insignicant between
50 and 60
C. In fact, for a value of water activity equal to 0.75

equilibrium moisture content of the olive leaves extrapolated
from desorption isotherms decreased from 0.152kg/kgd.b.
(at 40
C) to 0.122kg/kgd.b. (at 50
C) and to 0.118kg/kgd.b.
(at 60
C).
Table 5 Results of tting of the adsorption isotherms of Chemlali olive leaves
Models names T (
C) Parameters r S P (%)
A B C D
GAB 40 97.230 0.998 0.029 0.98 1.610
4
7.50
50 4.20 0.998 0.039 0.97 6.310
5
5.10
60 7.64 0.928 0.038 0.94 9.010
5
6.20
BET 40 64.608 0.033 0.99 0.005 6.30
50 3.506 0.040 0.99 0.005 6.50
60 21.381 0.028 0.99 0.006 13.50
Henderson 40 0.590 15.74 0.590 0.98 0.030 27.20
50 0.532 22.876 0.531 0.97 0.037 24.60
60 0.555 26.110 0.555 0.98 0.015 31.40
Modied Chung and Pfost 40 0.367 0.081 0.93 0.043 51.20
50 0.274 0.049 0.91 0.23 88.40
60 0.252 0.046 0.91 0.036 26.05
Modied Halsey 40 0.298 0.298 2.522 0.99 0.014 19.70
50 0.282 0.282 2.626 0.98 0.020 26.95
60 0.283 0.283 2.616 0.98 0.014 16.00
Oswin 40 0.063 0.725 0.99 0.010 15.10
50 0.057 0.860 0.99 0.008 15.00
60 0.059 0.662 0.99 0.008 12.20
Peleg 40 0.066 0.331 0.497 6.743 0.99 0.006 7.10
50 0.835 11.336 0.146 1.158 0.99 0.003 9.00
60 0.436 9.002 0.097 0.709 0.99 0.002 3.60
Adam and Shove 40 0.001 0.504 1.631 1.598 0.99 0.012 11.40
50 0.009 0.576 1.895 1.878 0.99 0.020 32.50
60 0.004 0.430 1.241 1.180 0.99 0.008 13.20
ARTICLE IN PRESS
Table 6a Polynomial coefcients describing dependency of Peleg parameters vs. temperature
Polynomial model parameters (a, b and c) Sorption Peleg parameters
A B C D
a Desorption 0.009 0.097 0.002 0.049
Adsorption 0.006 0.067 0.0015 2.568
b Desorption 6.032 63.016 1.492 31.651
Adsorption 3.795 43.517 0.996 13.289
c Desorption 984.53 10241 239.95 5103.4
Adsorption 615 7086.7 164.310 17.464
Table 6b Linear coefcients describing dependency of linearized GAB parameters vs. temperature
Linear model parameters (a and b) Sorption GAB parameters
A=C
GAB
B=K
GAB
C=X
mGAB
a Desorption 2.99 0.154 9.70
Adsorption 38.99 1.58 1.06
b Desorption 355.72 52.32 2007.35
Adsorption 13453.13 505.20 1425.50
The adsorption and desorption isotherms of olive leaves
obtained at 40
C did not superpose in the intermediate

range of water activity (0.30<a
w
<0.89). For a xed value of
water activity (a
w
=0.75), the equilibrium moisture content
obtained in desorption process is higher than that obtained
in adsorption process (0.152kg/kgd.b. versus 0.137kg/kg d.b).
This difference between adsorption and desorption isotherms
is largely known in literature as hysteresis phenomenon. Sev-
eral theories have been advanced to explain the phenomena
of hysteresis.
If hysteresis arises from a capillary condensation mecha-
nism, two theories explained the formof the isotherms. These
are the linkbottle theory of Kraemer (1931) and McBain (1935)
and the delayed meniscus theory of Foster (1932) and Cohan
(1938). It is assumed that there is not a single explanation to
the hysteresis phenomena in biological products. Each prod-
uct is a complex combination of various constituents which
can rise to different water-sorption capacities (Chirife and
Iglesias, 1978).
However, the experimental results of adsorption and des-
orption isotherms obtained at 50 and 60
C superposed and
there is not any signicant differences between sorption prop-
erties of olive leaves in these experimental conditions. Rao
(1942) and Kapsalis (1987) attributed changes of sorption prop-
erties, resulting in the elimination of hysteresis, to the elastic
properties of some products. They reported that modications
of the products structures under certain experimental condi-
tions cause the elimination of hysteresis due to the absence
of capillary condensation. Capillary condensation hysteresis
in the whole range of water activity, due to the fact that some-
times hysteresis is present in water activity ranges where
capillary does not.
This included that the prehistory of the sample could mod-
ify the product structure at microscopic scale and thus its
moisture sorption properties as it could be assumed for olive
leaves sorption behavior between 50 and 60
C.
The results of the non linear regression analysis of des-
orption and adsorption isotherms of olive leaves obtained at
40, 50 and 60
C are shown, respectively, in Tables 4 and 5.

The correlation coefcients of the tested models are high
(0.91r 0.99) and the standard errors vary from 5.610
5
to 0.23. The eight tested models gave satisfactory results but
the GAB and Peleg ones gave the best tting of adsorption
and desorption isotherms for all examined temperatures (40,
50 and 60
C). The corresponding correlation coefcients vary

from 0.94 and 0.99, the standard errors vary from 9.010
5
and 1.210
2
and the percent average relative deviation P is
inferior to 10%.
Comparisons between experimental and calculated (GAB
and Peleg models) data of desorption and adsorption
isotherms obtained for Chemlali olive leaves at examined tem-
peratures is shown, respectively, in Figs. 5 and 6.
GAB and Peleg models were thus retained to describe the
temperature dependency of moisture desorption and adsorp-
tion isotherms. The variations of GAB and Peleg models
parameters versus temperature were examined. Peleg model
parameters (A, B, C and D) showed polynomial (aT
2
+bT+c)
dependency with temperature; whereas the logarithm of GAB
model parameters (A, B and C) showed the known linear
dependency with temperature. The calculated coefcients
describing the temperature dependency of sorption isotherms
are recapitulated in Tables 6a and 6b. The Peleg and GAB mod-
Fig. 5 Comparison between experimental and calculated
(GAB and Peleg models) data of desorption isotherms of
Chemlali olive leaves obtained at 40, 50 and 60
C. Cal.:
calculated.
ARTICLE IN PRESS
Fig. 6 Comparison between experimental and calculated
(GAB and Peleg models) data of adsorption isotherms of
Chemlali olive leaves obtained at 40, 50 and 60
C. Cal.:
calculated.
els could thus be used to predict desorption and adsoprtion
isotherms of olive leave at any temperature ranging between
40 and 60
C.
3.3. Isosteric heats of sorption
The adjustments of the values of the isosteric heats (Q
st
) of
sorption deduced from the ClausiusClapeyron Eq. (1) versus
corresponding equilibrium moisture contents was done by
the following Eqs. ((2) and (3)) which gave the best statistical
parameters:
Q
st
= 42.00exp(0.22X
eq
) +685.75exp(103.44X
eq
) (2)
for adsorption where r =0.98 and S=2.36.
Q
st
= 43.40exp(0.07X
eq
) +277.80exp(41.30X
eq
) (3)
for desorption where r =0.99 and S=2.26.
These mathematical correlations describe satisfactorily
the variations of Q
st
versus f(X
eq
) for examined experimen-
tal conditions (r 0.98 and S2.36). These correlations could
thus be used to determine the isosteric heats of sorption of
olive leaves for the examined experimental conditions.
Fig. 7 shows a comparison between the variations of the
values of the isosteric heats of sorption deduced from the
ClausiusClapeyron equation (dots) by using GAB and Peleg
models for predicting water activity, the calculated values
(lines) by using Eqs. (2) and (3) versus equilibrium moisture
contents and the value of the heat of vaporization of pure
water vapor (L
v
, horizontal dotted line) calculated at the mean
temperature of 50
C.
The values of the isosteric heats of sorption (Q
st
) deter-
mined by using GAB and Peleg models are very close. The
isosteric heat of sorption decreases continuously with the
increase of the equilibrium moisture content. It approaches
the latent heat of vaporization of pure water vapor (L
v
) as the
moisture content increases. This observation indicates that
adsorbed water vapor on the solid matter may behave like
pure water at higher moisture contents. Chirife and Iglesias
Fig. 7 Variations of calculated and experimental values of
desorption and adsorption isosteric heats of Chemlali olive
leaves vs. equilibrium moisture content.
(1978) analyzedthe difference betweenvalues of heats of sorp-
tion (Q
st
) and that of the latent heat of vaporization (L
v
) of
pure water vapor by the fact that the energy of interaction
between sorbate molecules and sorption sites are higher than
the energy held by the sorbate molecules together inthe liquid
state.
In addition, Fig. 7 shows that at low equilibrium moisture
contents, the heat of desorption is greater than that of adsorp-
tion. Upon further sorption, the difference rapidly decreased
and disappeared at high moisture contents. Hossain et al.
(2001) and Ertekin and Sultanglu (2001) stated that the differ-
ence between adsorption and desorption heats indicates that
the energy required in the desorption process is greater than
that in the adsorption process. Iglesias and Chirife (1978) also
observed the same variations of sorption heats and reported
that there was no direct relationship between the observed
differences between adsorption and desorption heats and the
distribution of hysteresis along the sorption isotherm.
At lowequilibriummoisture contents, the heats of sorption
(Q
st
) are higher than at high equilibriummoisture contents. In
fact, at the equilibrium moisture content of 0.03kg/kgd.b. the
isosteric heat of desorption and adsorption are, respectively,
equal to 102kJ/mol (desorption) and to 95kJ/mol (adsorp-
tion) then they decrease with the increasing of equilibrium
moisture content to reach the mean value of the latent heat
of vaporization for water vapor (L
v
). The decreasing of the
heats of sorption indicates that the watersolid interactions
are strong in the range of low equilibrium moisture contents
and then they decreased with the increase in the equilibrium
moisture content (Maskan and Gogus, 1997). Tsami (1991) sug-
gested that the high values of the heats of sorption at low
equilibrium moisture contents were due to the existence of
highly active polar sites on the surface of the product, which
are covered with water molecules forming a mono-molecular
layer. Chirife and Iglesias (1978) stated that sorption occurs
rst on the most active available sites giving rise to high inter-
actionenergy. As these sites become occupied, sorptionoccurs
on the less active sites giving rise to lower heats of sorption.
The variations of isosteric heats of sorption versus equi-
librium moisture contents were similar to those observed
by other authors for many products: Ait Mohamed et al.
ARTICLE IN PRESS
(2005a,b) for sorption of Citrus reticulate leaves and Gelidium
sesquipedale, Jamali et al. (2006a,b) for Chenopodiumand Citrus
aurantium leaves, Kechaou and Maalej (2000) for desorption of
dates andbanana andWang andBrennan(1991) for desorption
and adsorption isotherms of potatoes.
4. Conclusion
The sorption isotherms of Chemlali Tunisian olive leaves were
determined at three temperatures (40, 50 and 60
C) by using
the static gravimetric method. The experimental adsorption
and desorption isotherms of olive leaves have a sigmoid forms
and display the type II on BET classication. The equilibrium
moisture content decreased with the increase of temperature.
Eight equations were chosen fromthe literature to describe
the experimental olive leaves sorption isotherms. GAB and
Peleg models were the best for describing the relationship
between the equilibrium moisture content, the water activ-
ity and temperature for both adsorption and desorption
isotherms. The isosteric heats of sorption of olive leaves vary
inversely with the amount of the sorbed moisture. Empiri-
cal equations were established to describe these variations
between 0.025 and 0.3kgmoisture/kgd.b.
Acknowledgements
This study was supported by CMPMT for a TunisianMoroccan
project (04/MT/17) on Solar Drying and Quality of Medicinal
and Aromatic Plants. The authors would like to thank Mme
KAMMOUN Naziha, researcher in the Olive Institute of Sfax
(Tunisia), who guaranteed us a regular supply of olive leaves
of Chemlali variety during this study.
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C) and in the range of water activity varying

C). Experiments were

C up to constant weight (24h). Total protein was deter-

C before putting them on a tripod in the glass jars.

C) (Fig. 1). The samples were weighed at differ-

C and for a water

C. Des: desorption; Ads:

C. Des: desorption; Ads:

C. Des: desorption; Ads:

C sharply affected equi-

C. In fact, for a value of water activity equal to 0.75

C did not superpose in the intermediate

C are shown, respectively, in Tables 4 and 5.

C). The corresponding correlation coefcients vary

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