Particulate Science and Technology, 33: 264–272

Copyright # 2015 Taylor & Francis Group, LLC

ISSN: 0272-6351 print=1548-0046 online
DOI: 10.1080/02726351.2014.970310

Modeling of Water Sorption Isotherms Characteristics of

Spray-Dried Cherimoya (Annona cherimola) Purée
MARIA M. MUÑIO, EMILIA M. GUADIX, and ANTONIO GUADIX
Department of Chemical Engineering, University of Granada, Granada, Spain

Spray drying is a solution to preserve food products from spoiling and moisture adsorption isotherms of dry products can be used
to predict their shelf life during storage and distribution. Sorption isotherms of spray-dried cherimoya purée were determined using
a gravimetric method between 10 C and 50 C and water activities from 0.05 to 0.96. The data obtained were fitted to Guggenheim,
Anderson, and De Boer (GAB), GAB modified, Henderson modified, Oswin modified, Chung–Pfost modified, and Hasley
isotherms and the Henderson model best fitted experimental data. The net isosteric heat of sorption values determined using
Clausius–Clapeyron ranged from 3.04 and 0.92 kJ=mol between 5% and 30% moisture content in dry basis, respectively.
Differential entropy also decreased with moisture content. The compensation theory was applied to sorption isotherms and higher
value of isokinetic temperature than harmonic mean temperature denotes that adsorption process was enthalpy controlled and a
negative value of Gibbs free energy reflected a spontaneous process.
Keywords: Cherimoya, compensation theory, isosteric heat of sorption, isotherm, spray drying

1. Introduction the formulation of dairy products or juices. However, its

Cherimoya (Annona cherimola) is one of the finest fruits of
all the Annona species and comes from a subtropical fruit
tree indigenous to Ecuador and Peru, dating back to 1200
BC (Gupta-Elera et al. 2010), cultivated in Taiwan, Spain,
and south part of Italy. The subacid flesh is juicy, sweet, very
fragrant, and creamy white (Barreca Davide et al. 2011). It is
considered an exotic fruit of warm climates and should be
kept at low temperatures to avoid or delay post-harvest
damages. Its main disadvantage during processing is the
high susceptibility to oxidation at room temperature, which
also affects storage (Prieto et al. 2007).
One of its most interesting properties is the antioxidant
effect that makes it a usual ingredient as bioactive element
in cosmetic, pharmaceutical, and food processing industries.
Among the beneficial effects of this fruit highlight the
decrease of lipid peroxidation and the cytoprotective effects
against oxidants (Gupta et al. 2010; Barreca et al. 2011).
Other beneficial effects in health have been observed such
as anti-inflammatory and antitumorous activity in mam-
mary, pancreatic, prostatic, and colon cancer cells. It has
been used because of its antimicrobial and insecticide
properties (Amoo et al. 2008).
The high sensitiveness to external damage and the conse-
quent large amounts of discarded fruit per year have made
the production of cherimoya purée an alternative for this
fruit industry. That purée can be used as a raw material in
Address correspondence to: Maria M. Muñio, Department of
Chemical Engineering, University of Granada, 18071 Granada,
Spain. E-mail: mmunio@ugr.es
use as purée has some limitations such as browning due to
the rapid oxidation and handling difficulties due to the high
viscosity of the purée (Brito et al. 2008). Therefore, spray
drying of cherimoya purée arises as one potential solution
that can be applied to avoid the mentioned problems.
Water is one of the most important components in food
because of its influence on product characteristics and
stability. Thus, consideration of the moisture sorption
phenomena is essential for better understanding of the
drying principles (Fortes and Okos 1980). Moisture sorption
data establish the relationship between moisture concen-
tration and partial pressure or water activity. They are
important in the field of drying, mixing, packaging, and
storage of food materials (Pahlevanzadeh and Yazdani
2005). They also facilitate the determination of the process
end-point, at optimal moisture content, necessary to achieve
product stability (McMinn et al. 1999). Water activity (aw)
may be defined 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 1968).
The knowledge of sorption isotherms is extremely
important to the food industry development. They are used
for modeling drying process, design, and optimization of
drying equipment, prediction of shelf-life stability, calcu-
lation of moisture changes which may occur during storage
and selecting appropriate packaging materials (Gal 1987).
More than 75 correlations have been proposed for math-
ematical interpretation of the extensive experimental data
(Van der Berg and Bruin 1981). These authors developed
more than 200 equations theoretically, semi-theoretically,
Water Sorption Isotherms Characteristics 265

or empirically. Moisture sorption isotherm can be based on 2. Materials and Methods

monolayer model (BET model), on a multilayer and con-
densed film models (GAB, Lewicki I and Lewicki II models), 2.1 Spray Drying of Cherimoya Purée
on semi-empirical models (Ferro-Fontan, Henderson and A cherimoya preparation was obtained by mixing 150 g of
Halsey models) and on empirical models (Smith, Oswin cherimoya purée (homogenized pulp), 275 g of water, and
and Bizot models). 75 g of milk powder, to achieve a total of 500 g. The initial
According to the BET classification, food systems typi- humidity of this preparation was 74%, measured by an infra-
cally exhibit Type II or III isotherms. Starchy foods usually red moisture determination balance (A&D Weighing).
fit Type II behavior while foods rich in soluble components, For the spray drying process, a Buchi mini spray dryer
such as sugars or salts, shows Type III behavior, with low Model 190 (Flawil, Switzerland) was used. The cherimoya
moisture contents at low water activities and a sharp preparation was pumped by means of a peristaltic pump
increase in moisture at high water activities (Tsami et al. to the atomizer, and a two-fluid nozzle was used to perform
1990). The last one would be the case of spray-dried cheri- atomization with compressed air. The feed temperature and
moya pulp. But recently, the GAB model has been proposed the feed rate were 36.5 C and 8 mL=min, respectively. Cher-
by food engineers as the universal model to fit the sorption imoya purée was spray dried with an air inlet temperature of
data for all foods (Janjai et al. 2007). Lomauro et al. 155 C, which decreased during the process to 85 C. The final
(1985) reported that moisture sorption of foods can be product was cherimoya powder with 7.5% of humidity, mea-
described by more than one sorption model and GAB gives sured as mentioned above.
the best fit for more than 50% of the fruits, meats and vege-
tables analyzed.
2.2 Determination of Sorption Isotherms
Numerous studies have been made to determine sorption
isotherms of several kinds of fruits and vegetables (Sandoval A gravimetric technique was used to determine the equilib-
and Barreiro 2002; Vullioud et al. 2004; Moraes et al. 2008; rium moisture content of cherimoya powder at seven relative
Yan et al. 2008; Lemus et al. 2009; Agnieszka and Andrzej humidities (from 4% to 96% approximately) and at five tem-
2010; Corey et al. 2011). Some of them are centered in trop- peratures between 10 C and 50 C. Sulfuric acid solutions
ical fruits such as pineapple, mango, or kiwifruit (Talla et al. were used to maintain the specified relative humidity inside
2005; Moraga et al. 2006; Simal et al. 2007) but none of them the desiccators.
are focused in the study of cherimoya pulp. Cherimoya powder samples (1  0.001 g) were placed in
To evaluate sorption process and its energy requirement, previously weighted glass desiccators and dried over a plate
thermodynamic parameters can be used, like net isosteric at 55 C under vacuum and over silica gel for 2 days. Later,
heat of sorption, differential entropy, and Gibbs free energy. the samples were kept in desiccators over sulfuric acid solu-
Isokinetic theory can be also applied to that purpose. Net tions of known concentrations that provide different relative
isosteric heat of sorption can be studied as an indicator of moistures as shown in Table 1. The desiccators were placed
the state of water adsorbed by particles and it is very useful in temperature-controlled oven to get 10 C to 50 C and the
to design drying equipment because it is a measure of physi- samples were allowed to equilibrate until no significant dif-
cal, chemical, and biological storage stability. Clausius–Cla- ference in weight was detected (0.001 g). To minimize the
peyron equation was used by Talla et al. (2005) to determine atmospheric moisture sorption due to the weighting, the
net isosteric heat of sorption for banana, mango, and pine- whole process last less than 60 s.
apple and in all cases a decrease with moisture content
increasing was observed. The same behavior observed for 2.3 Sorption Isotherms
differential entropy by Simal et al. (2005) when studying
sorption properties of pineapple; differential entropy is pro- The isotherm models used to fit the data are shown in
portional to the number of available sorption sites at a spe- Table 2. The goodness of fit of the models was evaluated
cific energy level. Different expressions are proposed in
literature to determine correlation between isosteric heat of Table 1. Water activity of sulfuric acid solutions at selected
sorption and entropy with moisture content. Finally, Gibbs concentrations and temperatures (modified of Al-Muthaseb
free energy shows the affinity of sorbents for water so it can et al., 2004 and Singh et al., 2006)
be used to know if water sorption can occurs spontaneously
Water activity (aw)
in the studied product. Sulfuric acid
Isokinetic theory, also known as enthalpy–entropy com- concentration, % v=v 10 C 20 C 30 C 40 C 50 C
pensation, was applied successfully in pineapple by Simal
et al. (2007). 10 0.9554 0.9558 0.9562 0.9566 0.9570
The aims of this study were to (i) provide experimental 20 0.8779 0.8796 0.8814 0.8830 0.8848
data for the adsorption characteristics of spray-dried of 30 0.7429 0.7491 0.7549 0.7603 0.7655
cherimoya pulp, (ii) fit experimental data to different sorp- 40 0.5480 0.5599 0.5711 0.5814 0.5914
tion isotherms equations, (iii) determine net isosteric heat 50 0.3307 0.3442 0.3574 0.3703 0.3827
of sorption and differential entropy, and (iv) apply isokinetic 60 0.1471 0.1573 0.1677 0.1782 0.1887
theory to sorption process. 70 0.0377 0.0422 0.0470 0.0522 0.0575
266 Muñio et al.

Table 2. Isotherm models used for fitting experimental data

Isotherm model Mathematical expression Equation Reference

GAB Xm CK aw (1) Van den Berg and Bruin (1981)

X¼
ð1  Kaw Þð1  Kaw þ CKaw Þ
 
GAB modified Xm C Kaw (2) Jayas and Mazza (1993)
X¼  T   
ð1  Kaw Þ 1  Kaw þ CT Kaw
 b
Oswin modified aw (3) Menkov and Dinkov (1999)
X ¼ ða þ cTÞ
1  aw
 1
Henderson modified lnð1  aw Þ b (4) Thomson et al. (1968)
X¼
aðT þ cÞ
 
Chung–Pfost modified 1 ðT þ cÞ ln aw (5) Chung and Pfost (1967)
X ¼  ln
b a
 1b
Halsey a (6) Halsey (1948)
X¼
T ln aw
X: Moisture content (% dry basis); Xm: monolayer moisture value (% dry basis); T: temperature (K); C, K, a, b, c: constants.

by using two different indicators namely root mean square
error (RMSE) and coefficient of determination (R2). Both
parameters are shown in following equations:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P RT
ðXe  Xp Þ2
RMSE ¼ ; ð1Þ
N are adjustable constants; DHC and DHK are functions of
RES
R2 ¼ 1  ; ð2Þ
TES
where Xe is the experimental value, Xp is the predicted value
by models, N is the number of experimental data, RES is the
regression error sum of squares, and TES is the total error
sum of squares. The RMSE parameter is important in the
nonlinear regression processes, and the minimum the value,
the better the fitting procedure. The R2 coefficient also shows
the goodness of fit of the models but in this case, the closer
to one, the better the ability of the models to represent the
experimental data.
GAB model involves three constants that are also func-
tions of temperature. So, there are two methods of
regression analysis in that case, in the direct method the
six constants are estimated as the same time and with the
same weight by substituting secondary equations into main
isotherm equation. In the indirect method, three main con-
stants are determined and then secondary ones are esti-
mated. According to Maroulis et al. (1988), the
recommended method is the direct one, so in this work
GAB equation was studied using the direct method as other
authors (Goula et al. 2008).
The following expressions can be used to define the three
constants mentioned as a function of temperature:

DHC
C ¼ C0 exp ; ð3Þ
RT
 
DHK
K ¼ K0 exp ; ð4Þ
RT
q 
m
X ¼ Xm0 exp : ð5Þ
where R is the universal gas constant; C0, K0, Xm0, and qm
the heat of water sorption and the heat of condensation of
pure water; and T is the absolute temperature (Maroulis
et al. 1988).
Later, Jayas and Mazza (1993) included temperature
effects into GAB equation using an inverse function of the
parameter C. The resultant GAB modified equation kept
the three original parameters, as can be observed in
Table 2, so direct method was also used to fit GAB modified
isotherm.
2.4 Thermodynamic Properties
Net isosteric heat of sorption informs about the state of
water in the food product so energy needed to dry the pro-
duct can be determined (Duckworth 1972). The isosteric
heat of sorption is also known as differential enthalpy and
can be defined as the amount of energy above vaporization
water associated to sorption process (Tsami et al. 1990).
The heat mentioned can be obtained using Clausius–Cla-
peyron equation at constant moisture content and provides
that temperature has no effect on vaporization heat of pure
water and heat sorption excess (Al-Muhtaseb 2004).
@ ln aw Qst
1 ¼ ; ð6Þ
@ T X R
where T represents temperature (K), Qst is net isosteric heat
of sorption (kJ=mol), R is the universal gas constant, and aw
represents water activity.
Water Sorption Isotherms Characteristics
Gibbs–Helmholtz thermodynamic equation can be used
to calculate change in molar differential entropy and
enthalpy, and shows the relationship between change in
molar differential entropy, enthalpy, and specific entropy
as follows:
DG ¼ DH  T DS; ð7Þ
where DG is the Gibbs free energy (kJ=mol), DH represents
differential enthalpy (kJ=mol), and DS is the change in spe-
cific entropy (kJ=mol K). Gibbs free energy, for a given
moisture sorption, can be calculated as
DG ¼ RT ln aw : ð8Þ
Substituting Equations (8) into (6), the following equation is
obtained:
 
DH 1 DS
ln aw ¼  : ð9Þ
R T R
When ln aw is plotted against 1=T at constant values of
moisture content of the product, enthalpy and entropy
changes can be calculated from the slope and the intercept,
respectively.
As mentioned above, isosteric heat of sorption is sup-
posed to be independent of temperature, so more than two
temperatures should be used to approach isosteric heat
determination by the mentioned method. Empirical relation-
ships between moisture content and isosteric heat of sorp-
tion can be used and exponential expression is one of the
most employed (Goula et al. 2008).
Also, a correlation between DH and DS can be obtained
when expressing Equation (7) as follows:
DH ¼ DGb þ Tb DS; ð10Þ
where Tb represents isokinetic temperature and DGb denotes
the Gibbs free energy at Tb. So when plotting DH versus DS,
isokinetic temperature can be obtained by linear regression.
A comparison between isokinetic temperature and harmonic
mean temperature (Thm) was carried out based on a statisti-
cal test to corroborate chemical compensation theory (Krug
et al. 1976). Harmonic mean temperature was calculated as
expressed in Equation (11):
n Crossing of 30 C, 40 C, and 50 C isotherms showed an
Thm ¼ Pn  1  ; ð11Þ
1 T
where n is the number of isotherms and T the different tem-
peratures tested. The theory mentioned can be used just
when Tb differs significantly with Thm. In the other case, dis-
tribution data only shows experimental errors, but not a
chemical cause.
3. Results and Discussion
3.1 Moisture Sorption Isotherms
Experimental moisture sorption data for cherimoya puree
powder at temperature range studied (10–50 C) are shown
267
Fig. 1. Sorption isotherms of spray-dried cherimoya pulp at dif-
ferent temperatures.
in Figure 1. The isotherms followed the characteristic Type
III classification of Brunauer et al. (1940), when water is
adsorbed a monolayer or multilayers can be formed. This
is the typical shape of isotherms of products with high sugar
content as observed by Falade et al. (2004b), Pedro et al.
(2010), and Vazquez et al. (1999), in fruits such as passion
fruit pulp, different types of grapes or pineapple.
An increasing trend of moisture content of spray-dried
cherimoya at all the temperatures studied was observed
and agreed with the fact generally observed that the higher
the value of aw the higher moisture adsorbed. However,
the main reason of the shape observed in cherimoya pulp
puree can be related to sugar states during the sorption pro-
cess, as described Goulas et al. (2008) and Vidales et al.
(1995). At low water activities sugars are in crystalline form
and water can be adsorbed just to the surface –OH sites of
the sugar and it is also strongly bound to polysaccharides
pectines and proteins but at higher relative humidity crystal-
line form of sugars pass to amorphous form and moisture
content increases sharper with water activity.
The effect of temperature and water activity on moisture
content varies in function of the main composition of the
food studied. Palipane and Driscoll (1992) observed that
an increase of temperature cause moisture content decrease
but other behavior can be observed in food with high con-
tent of sugar and at higher aw (Myhara and Sablani 2001).
unusual temperature effect on isotherms above 0.85 water
activity. This fact is usual in high sugar content food, like
cherimoya; in products with low content of sugar or high
content of protein or starch no curves intersection occurs
(Roman et al. 1982; Benado and Rizvi 1985). The main
cause of the mentioned isotherm inversion is an increasing
of sugar solubility, so an endothermic dissolution of sugar
at high water activity and temperature occurs and more
water was held by the product (Ayranci et al. 1990;
Hubinger et al. 1992). The intersection point varies in
function product composition: type of sugar and sugar size
distribution (Weiser 1985) but a similar behavior was
observed when other fruits like blueberries, pineapple and
mango (Falade et al. 2004a,b; Lim et at. 1995) were studied.
268
Table 3. Estimated parameters of isotherms models for spray died cherimoya pulp and model evaluation indicators
Model Estimated parameters
GAB C0 DHC
1.01  104 13.80
GAB modified C0 DHC
3.03  104 22.85
Oswin modified a b
12.46 0.0331
Henderson modified a b
4.04  103 0.0128
Chung–Pfost modified a b
756.22 253.28
Halsey a b
463.42 0.893
Xm, Xm0 (% in dry basis), DHC, DHK, qm (kJ=mol), C0, K0, Xm0, and qm are adjustable constants, a, b, and c are empirical constants.
3.2 Evaluation of Isotherm Models
Models fitted for spray-dried cherimoya puree are shown in
Table 2. All model studied are function of temperature, even
GAB model that contains three constants that are function
of temperature according to Arrhenius equation. In Table 3
parameters for studied adsorption models are shown, along
with RMSE and R2 values.
Generally, isotherms are conducted at mild temperature
and only few researches use extreme temperatures. In order
to minimize possible errors it is necessary to take into
account the temperature effect on aw of sulfuric acid solu-
tions used to control relative humidity in chambers. In this
paper, five temperatures were assayed, increasing from
10 C until 50 C, temperature that could be reached in stor-
age chambers with no refrigeration, mainly in cherimoya
procedure regions.
RMSE and R2 values showed in Table 3 proved that
Chung–Pfost modified model was not good fitting the
experimental data. The same can be said about Halsey
model even when R2 was high enough to be considered a
good fitting. The rest of the models used presented a RMSE
around 4 for GAB model or less for the rest and R2 in all
cases was higher than 0.95, facts that proved the goodness
of fit.
Both, GAB model and GAB modified model were fitted
using a direct method, including Xm, C and K mathematical
expressions (Equations (3) to (5)) in the isotherm model and
obtaining all the parameters when fitting it, so six para-
meters were obtained. As expected, the estimation of DHC
(enthalpy difference between monolayer and multilayer
sorption) had a large positive value but lower than the ones
for vegetables (Maroulis et al. 1988). The estimation of DHK
(difference between heat of water condensation and heat of
sorption of a multimolecular layer) was also a positive value
but smaller than the previous one (Samaniego-Esguerra et al.
1991). The values of monolayer moisture value (Xm)
obtained were around 2% and 4% dry basis, respectively,
which is supposed to be the moisture content that cause
maximum maintenance of quality at a given temperature
during the longest period of time. The parameters estimated
Muñio et al.
RMSE R2
K0 DHK Xm0 qm 4.11 0.956
0.9496 0.352 1.53 0.123
K0 DHK Xm0 qm 4.39 0.953
0.9227 0.397 3.97 0.146
c 3.86 0.955
1.00
c 3.75 0.958
0.381
c 10.24 0.681
0.0927
4.94 0.926
were around or less than 10% in dry basis according to
values obtained by several authors when studying some
other tropical fruits such as plantain, mango, kiwifruit or
pineapple (Johnson and Brenan, 2000; Falade et al. 2004a;
Moraga et al. 2006; Simal et al. 2007). Nevertheless, other
Xm values higher than 10% and around 15–20% was also
found by other authors (Lahsasni et al. 2004; Talla et al.
2005; Lemus et al. 2008) for fruits.
Among the six models studied, Henderson modified gave
the best fitting, with a slightly higher R2 coefficient (0.958)
and the lowest RSM error observed. Johnson and Brennan
(2000) also observed about the isotherms studied the best fit-
ting for GAB and Henderson models when studying other
tropical fruit, plantain.
Figure 2(a–e) shows experimental data and Henderson
modified model predicted adsorption at each temperature
studied, from 10 C to 50 C. Figure 2f represents the moist-
ure content calculated by Henderson modified model versus
the experimental moisture content. It can be observed the
high correlation between both of them.
3.3 Adsorption Thermodynamic Properties
Isosteric heat of sorption was determined using Clausius–
Clapeyron equation, Equation (9), and values obtained are
shown in Figure 3.
As can be observed in Figure 3, net isosteric heat of sorp-
tion decreased when increasing moisture content. This fact
shows changes in water binding strength, at lower moisture
content there is an initial binding of water at active polar
sites and monolayer surface is formed but with the increase
of moisture content a second layer of water is formed (multi-
layer sorption) (Tsami, et al. 1990). The same behavior was
observed by other authors when studied some other tropical
fruits, like pineapple, mango, and kiwifruit (Falade et al.
2004b; Talla et al. 2005; Moraga et al. 2006).
Net isosteric heat of sorption ranged between 3.04 and
0.92 kJ=mol from lower moisture content to higher one,
respectively, from 5% to 30% in dry basis. Similar results
were obtained for pineapple slices for humidity from 20%
Water Sorption Isotherms Characteristics
Fig. 2. Experimental data (^) and Henderson modified model predicted values (—) at (a) 10 C, (b) 20 C, (c) 30 C, (d) 40 C,
(e) 50 C, and (f) experimental data (^) and calculated data predicted by Henderson modified model (—) dispersion with 10%
error (—).
to 50% (Falade et al. 2004b). It has been proven that when
fresh fruit is compared to dry one, the later showed lower
net heat of sorption than the fresh one for low humidity
ranges (Johnson and Brenan 2000). Also, adsorption or
desorption affects values of net isosteric heat of sorption,
obtaining higher values when desorption was studied (6–
14 kJ=mol) than when adsorption was developed (4–1 kJ=
mol) for dry prickly fruit (Lahsasni et al. 2004). Other
Fig. 3. Net isosteric heat of sorption of cherimoya purée in func-
tion of moisture content.
269
characteristic values for tropical fruits net isosteric heat of
sorption were around 5–2 kJ=g mol for moisture content
ranges between 10% and 20% in the case of banana (Yan
et al. 2008). The wide range of values for fruits showed in
literature denotes that net isosteric heat of sorption depends
on properties and composition of the fruit studied. Tsami
et al. (1990) studied several fruits such as currants, figs,
prunes, and apricots and obtained a value of isoteric heat
of 5 kJ=mol for currants and apricots but that value was tri-
plicated for the rest of the fruit at the same moisture content.
The same fact was observed when working with several trop-
ical fruits at moisture ranges of 15–45%, for example, pine-
apple presented isosteric heats of 2700–500 kJ=mol for
pineapple, of 1500–100 kJ=mol for banana, and of
600–100 kJ=mol for mango (Talla et al. 2005).
Several authors analyzed the variation of net isosteric
heat of sorption with moisture content and different equa-
tions can be used to represent adequately the relation. In
the case of fruits, polynomial equations of second or third
degree had been used for prickly fruit and sweetened figs
with R2 coefficients higher than 0.96 (Lahsasni et al. 2004;
Ansari et al. 2011). The relationship mentioned was also suc-
cessfully fitted by power law and exponential relations for
pineapple, banana, mango, and passion fruit (Talla et al.
2005; Simal et al. 2007; Yan et al. 2008; Pedro et al. 2010).
270
Fig. 4. Differential entropy of adsorption of cherimoya purée in
function of moisture content.
In Figure 3 experimental data and predicted data using
Equation (9) of net isosteric heat of sorption are shown:
 
X
Qst ¼ 3:845 exp R2 ¼ 0:980; ð12Þ
19:28
where Qst is the net isosteric heat of sorption (kJ=mol) and X
represents equilibrium moisture content (% dry basis). Tsami
et al. (1990) used a similar relation between moisture content
and heat of sorption and determined the values of net iso-
steric heat of sorption of the first molecule adsorbed by food
product (Qs) and characteristic moisture content of the pro-
duct when net isosteric heat of sorption have been reduced
63% (X0). In the case of cherimoya, mentioned values were,
from Equation (12), Qs ¼ 3.845 kJ=mol and X0 ¼ 19.28%.
Differential entropy values were also obtained from the
intercept of Equation (9) at different moisture content.
The results plotted in Figure 4 showed a strong dependence
on moisture content and with an exponential trend, similar
to the one observed for net isosteric heat of sorption
(Equation (13)):
DS ¼ 9  103 expð0:05X Þ; R2 ¼ 0:978: ð13Þ
Simal et al. (2007) also reported a similar behavior of differ-
ential entropy of sorption of pineapple and an exponential
Fig. 5. Net isosteric heat of sorption and differential relation-
ship for adsorption of cherimoya purée.
Muñio et al.
relation were fitted to reproduce it. Once net isosteric heat
of sorption and differential entropy were obtained, a plot
of the first one versus entropy is showed in Figure 5. Results
were fitted according to Equation (10) and as a linear corre-
lation exhibit a good fitting (R2 ¼ 0.999) for cherimoya
purée, compensation theory can be applied in this case:
DH ¼ 0:071 þ 429:3 DS: ð14Þ
In accordance with Equation (10) isokinetic temperature of
sorption resulted to be 429.3 K. When comparing the value
obtained with harmonic mean temperature also calculated
by Equation (11), 302.5 K, a significant difference was
observed, fact that reconfirms the suitability of compen-
sation theory. Also, it can be confirmed that the process is
enthalpy driven, so the process is controlled by energy inter-
actions related to chemical composition of the product
(Azura-Nieto and Beristain-Guevara 2007).
A slightly lower value for isokinetic temperature was
reached by Simal et al. (2007) in the case of pineapple and
the process was also controlled by enthalpy.
Gibbs free energy could also be determined from Equa-
tion (10). The negative value indicates that moisture adsorp-
tion of cherimoya purée was spontaneous (Apostolopoulos
and Gilbert 1990), so no external energy contribution is
needed to carry out the process.
4. Conclusions
Moisture adsorption isotherms of spray-dried cherimoya
purée exhibited typical Type III behavior. Equilibrium
moisture content increased when increasing water activity
and a sharply increase was observed from aw > 0.8. A special
characteristic of the product studied is an isotherm inversion
at 30 C, 40 C, and 50 C due to an increase of solubility of
sugar. Among the adsorption isotherms fitted, Henderson
followed by five parameters GAB and GAB modified
described better experimental data obtained within tempera-
ture range 10–50 C and water activity range 0.05 and 0.96.
Net isosteric heat of sorption calculated by Clausius–
Clapeyron equation decreased when increasing moisture con-
tent and exhibit an exponential relation with moisture content.
A linear correlation between net isosteric heat of sorption
versus differential entropy proved that compensation theory
can be applied. A higher value of isokinetic temperature
than harmonic mean temperature denotes that adsorption
process was enthalpy controlled and a negative value of
Gibbs free energy reflected a spontaneous process.
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