Sorption isotherm and state diagram of grapefruit as a tool to improve

product processing and stability

M.J. Fabra, P. Talens, G. Moraga, N. Martnez-Navarrete
*
Food Technology Department, Institute of Food Engineering for Development, Universidad Politcnica de Valencia, P.O. Box 22012, 46071 Valencia, Spain
a r t i c l e i n f o
Article history:
Received 16 September 2008
Received in revised form 6 December 2008
Accepted 28 December 2008
Available online 1 January 2009
Keywords:
Glass transition temperature
Freezing temperature
Water activity
Water content
Relative humidity
Differential scanning calorimetry
Cryoscopy
a b s t r a c t
The sorption isotherm and state diagram of grapefruit have been constructed and modelled. Partially air-
dehydrated and freeze-dried grapefruit was used to obtain samples in the range of freezable and non-
freezable water content, respectively. The cooling curve and/or differential scanning calorimetry of the
samples allowed freezing and glass transition temperatures to be obtained. The sorption isotherm was
tted to the BET (Brunauer, Emmett and Teller) and GAB (GuggenheimAndersonde Boer) models
and the glass transition data to the Gordon and Taylor model. To predict the freezing curve, both general-
ized Norrish and Robinson and Stokes equations and an empirical model have been used. At water con-
tent greater than 0.19 g water/g sample, cooling the product to 31.2 C and keeping it in frozen storage
at below 50 C will ensure its maximum stability. If only non-freezable water is present in the product,
the more stable glassy state may be achieved at different temperature or water contents, which may be
predicted from the obtained state diagram.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Grapefruit is a citrus fruit which contributes to human health
with especially high amounts of ascorbic acid and bre (Peir
et al., 2006). The presence of avonoids such as naringin, narirutin
and hesperidin (Peir-Mena, 2007) is also important, as their in-
take seems to have a signicant impact on the prevention of differ-
ent kinds of cancer and cerebro and cardiovascular diseases,
mainly due to their antioxidant activity and ability to inhibit cell
proliferation (Kuo, 1996; Vanamala et al., 2006). Naringin is
responsible for the bitter taste of grapefruit, which limits its popu-
larity among consumers. Nevertheless, fresh or processed grape-
fruit may be conveniently mixed with some other foods to
formulate attractive, healthy products. In this sense, grapefruit
with different water contents, from fresh to freeze-dried, can be
considered and adequate storage conditions must be dened in or-
der to ensure the best quality when nally used.
Water activity and water content, correlated through sorption
isotherms, have been considered relevant parameters to describe
food stability. Sorption isotherms of foodstuffs are essential for
the design, modelling and optimisation of many processes such
as drying, mixing or storage. The typical shape of an isotherm re-
ects the way in which the water binds the system (Wolf et al.,
1985; Lahsasni et al., 2004). For a xed water content, the weaker
the water interactions, the greater the water activity and the prod-
uct becomes more unstable. Water activity depends on the compo-
sition, temperature and physical state of the compounds.
The physical state of food compounds is also related to the sta-
bility. It is well known that the solid state is much more stable than
the liquid one. Nevertheless, below the crystallization tempera-
ture, glassy or rubbery non-equilibrium amorphous states may
be achieved, frequently in processes with high cooling or dehydra-
tion rates and especially in highly concentrated systems. The glassy
state resembles the characteristics of the solid state, and occurs be-
low the glass transition temperature. Literature reports that foods
can be considered very stable in the glassy state, since the molec-
ular mobility is greatly reduced. In this physical state, the com-
pounds involved in deteriorative reactions take many months or
even years to diffuse over molecular distances and approach each
other to react (Slade and Levine, 1991). The rubbery state occurs
above the glass transition temperature, where molecular mobility
increases and viscosity decreases. Thus, the product becomes like
a liquid, corresponding to a more unstable state. This is also a
non-thermodynamic equilibrium state, which will evolve more
quickly over time. In both cases, they will evolve up to the corre-
sponding thermodynamic equilibrium state below the crystalliza-
tion temperature, which is the solid one. The crystallization
temperature decreases and T
g
increases when the water content
decreases. The state diagram of a food is the right tool to use to nd
out the relationships between these temperatures and the water
content, allowing the control of phase transitions in order to design
0260-8774/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2008.12.029
* Corresponding author. Tel.: +34 96 3879362; Fax: +34 96 3877369.
E-mail address: nmartin@tal.upv.es (N. Martnez-Navarrete).
Journal of Food Engineering 93 (2009) 5258
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efcient processes to obtain high quality products and also to opti-
mize storage conditions (Roos and Karel, 1991; Roos, 1995; Rah-
man, 2006).
The freeze-drying of fruits is an industrial process that allows
dried products to be obtained by the sublimation of water at low
pressure. During this process, the formation of non-equilibrium
amorphous states is usual (Roos, 1995). Several authors have
discussed the importance of the glassy-rubbery state in powder
products as it relates to collapse, stickiness, caking and re-crystal-
lization phenomena (White and Cakebread, 1966; Kasapis et al.,
2004; Ohkuma et al., 2008; Wang et al., 2008). The formation of
solute crystals will imply an increase in free water and thus in
water activity, with the consequent increase in the rate of deterio-
rative reactions. In this sense, it is very important to know the
water contentwater activityglass transition temperature rela-
tionships to determine storage temperature and relative humidity
that ensure the stability of freeze-dried products avoiding the
change from the stable glassy state to the rubbery one. In general,
foods with a glass transition temperature higher than room tem-
perature (2535 C) can be considered as stable (Aguilera et al.,
1993).
For high water content products, such as fresh or concentrated
fruit juices, frozen storage must be considered to ensure the max-
imum stability, the amount of ice formed being dependent on stor-
age temperature. As the glass transition temperature decreases
when the water content increases, in these kinds of products the
glassy state is normally not achieved at the common processing
and storage temperatures. Nevertheless, the cryoconcentration of
the liquid phase of the product during ice formation implies the in-
crease in the T
g
, that will achieve a maximum value when, due to
kinetic impediments, the maximum amount of ice crystals is
formed in the system. The glass transition temperature of the
maximally cryoconcentrated matrix is known as T
/
g
and the corre-
sponding solid content is C
/
g
. Its water content (1 C
/
g
) corresponds
to the non-freezable water of the product, which is known as W
/
g
.
From this point of view, the maximum stability in frozen products
will be achieved when the freezable water is allowed to crystallize
and the temperature remains below T
/
g
. Cryostabilization and cryo-
protection technologies are related to the possibility of increasing
T
g
or W
/
g
, respectively, by adding different solutes. For these rea-
sons, the most important aspect in these kinds of foods is to know
the temperature at which the ice begins to appear and the amount
of ice that will be formed at any temperature, as well as the T
/
g
and
W
/
g
.
The state diagram of a product over the whole range of water
content gives full information about the temperature of the differ-
ent phase transitions at any water content. Many authors have
studied state diagrams of the aqueous solutions of pure compo-
nents and model systems such as sugars (Roos and Karel, 1991).
Moreover, state diagrams have been reported for different fruits
such as grape and strawberry (S and Sereno, 1994), apple (Bai
et al., 2001; S et al., 1999), pineapple (Telis and Sobral, 2001) or
persimmon (Sobral et al., 2001) but no data have been found either
for citrus fruits in general or for grapefruit, in particular.
The aim of this work was to establish the state diagram and the
water sorption isotherm of grapefruit. This information may be
useful to optimize processing and storage conditions of different
grapefruit products that may be used in the food industry, in the
range of both freezable and non-freezable water content.
2. Materials and methods
Grapefruits (Citrus paradise var. Marsh) were purchased in a lo-
cal market and selected on the basis of a similar soluble solid con-
tent (9.6 0.2 Brix). They were peeled and homogenized with a
high-shear probe mixer (Ultra-Turrax T25, IKA). A part of the
homogenizate was partially dehydrated at three different water
content levels using a modied household oven at 3.9 m/s and
50 C (Contreras et al., 2008), in order to obtain different grapefruit
samples in the range of freezable water content. On the other hand,
the rest of the homogenizate was frozen at 40 C in an ultrafreezer
(ARC -45/87, Dycometal) at a potency of 3.2 kW. After that, it was
freeze-dried at 50 C and 10
2
Pa (Lioalfa 650, Telstar Industrial)
and conditioned at different water contents, as described below,
presumably in the range of non-freezable water content.
Fresh and partially dehydrated samples were analyzed as to
water and soluble solid content, water activity and initial freezing
point. Three replicates of each analysis were carried out. Mass frac-
tion of water was obtained by vacuum drying the sample at 60 C
to constant weight (Vacioterm, Selecta). Brix was measured in an
Abb Atago 3-T refractometer. To obtain a
w
a dew point hygrome-
ter (Aqualab CX-2, Decagon Devices) was used. The initial freezing
temperature was obtained fromthe change in the slope of the cool-
ing curve obtained using a cryostatic bath (Refrigerated Circulator
Nomenclature
a parameter in Eqs. (9) and (10) shown in Table 1
b parameter in Eqs. (9) and (10) shown in Table 1
a
w
water activity
Brix soluble solid content in the liquid phase of the product
(g soluble solids/100 g liquid phase)
C parameter in (14) shown in Table 1
C
/
g
solid content of the maximally cryoconcentrated matrix
k parameter in Eqs. (5) and (6) shown in Table 1
K parameter in (3) and (4) shown in Table 1
K
i
Norrish coefcient in (8) shown in Table 1.
T
f
initial freezing temperature (C)
T
/
m
initial melting temperature of the ice crystals surround-
ing the maximally cryoconcentrated matrix (C)
T
g
glass transition temperature (C)
T
/
g
glass transition temperature of the maximally cryocon-
centrated matrix (C)
T
g(w)
glass transition temperature of amorphous water (C)
T
g(as)
glass transition temperature of anhydrous solids (C)
w
e
equilibrium water content (g water/g dry solids)
w
o
monolayer water content (g water/g dry solids)
W
/
g
non-freezable water content (g water/g product)
x
I
(T) mass fraction of ice (g ice/g product) formed at a deter-
mined temperature T
x
s
mass fraction of soluble solids in the product (g solids/g
product)
x
w
mass fraction of water (g water/g product)
x
ccs
w
mass fraction of water in the cryoconcentrated solution
(g water/g cryoconcentrated solution) obtained when
cooling the sample to temperature T
x
0
w
initial mass fraction of water (g water/g product)
X
i
solid molar fraction
X
w
water molar fraction
z
s
mass fraction of solids in the sample liquid phase (g sol-
uble solids/g liquid phase) = Brix/100.
M.J. Fabra et al. / Journal of Food Engineering 93 (2009) 5258 53
9101, PolyScience) at 18 C. Samples were placed into a glass test
tube, immersed in the cold refrigerated bath with a thermocouple
and subjected to permanent stirring. The temperature of each sam-
ple was recorded every 5 s.
For adsorption experiments, the freeze-dried grapefruit was
placed, at 25 C, in hermetic chambers at different relative humid-
ities (RH) which were achieved by placing different saturated salt
solutions (LiCl, KCH
2
CH
3
, MgCl
2
, K
2
CO
3
, Mg(NO
3
)
2
, CuCl
2
, NaCl) in-
side them. Relative humidities ranged between 11 and 75% (Green-
span, 1977). Three replicates of about 1.5 g were placed in each
chamber. The samples were weighed periodically till a constant va-
lue was reached (assumed when the difference between two con-
secutive weights was lower than 0.001 g), thus ensuring a
w
of each
sample to be equal to the corresponding RH/100. In each equili-
brated sample, x
w
and T
g
were analyzed. To this end, equilibrated
samples (-10 mg) were placed into DSC pans (Seiko Instruments,
P/N SSC000C008), sealed and analyzed using a DSC 220 CU-
SSC5200 (Seiko Instruments). The heating rate was 5 C/min and
the temperature range varied between 100 and 100 C, depend-
ing on sample water content. The water content after the thermal
analysis was determined by drying the sample in the pans (previ-
ously holed) in a vacuum oven (<100 mm Hg) at 60 1 C until
constant weight. After drying, the pans were again thermally stud-
ied to determine the T
g
of the anhydrous sample.
T
/
g
and T
/
m
were also analyzed in triplicate by DSC. To this end, a
sample of fresh grapefruit was placed into a sealed DSC pan and
cooled from room temperature to 35 C (at 2 C/min), held at this
temperature for 30 min and then cooled to 100 C (at 10 C/min),
thus ensuring the maximum ice crystallization (Moraga et al.,
2004). Afterwards, the heating curve was registered till 40 C at a
heating rate of 5 C/min.
3. Results and discussion
3.1. Sorption isotherm
Many food products exhibit a different behaviour for adsorption
and desorption processes. Nevertheless, when a food product is
subjected to water content changes in a range that implies water
loss or gain, the use of a working isotherm, as suggested by Labu-
za (1984), may be useful to predict any drying or humidication
cycle undergone by the food. In this work, it was of interest to ob-
tain useful data over the whole water content range of grapefruit
and so, all the experimental w
e
a
w
values were considered to con-
struct the working sorption isotherm of grapefruit (Fig. 1). The
observed behaviour was typical of products with high-sugar con-
tents which adsorb relatively small amounts of water at low-water
activities but present a sharp increase in the amount of sorbed
water at higher water activities, due to the prevailing effect of sol-
ute-solvent interactions associated to sugar dissolution (Hubinger
et al., 1992; Saravacos et al., 1986; Tsami et al., 1990). Similar re-
sults have been obtained with other fruits such as pineapple (Telis
and Sobral, 2001), persimmon (Sobral et al., 2001), strawberry
(Moraga et al., 2004), guava, mango and pineapple (Hubinger
et al., 1992) or grape (Gabas et al., 1999).
Experimental sorption data were tted to GAB (Guggenheim
Andersonde Boer) (Van den Berg and Bruin, 1981) and BET (Bru-
nauer, Emmett and Teller) (Brunauer et al., 1938) models. The BET
equation (Table 1, Eq. (1)) is the only one that stems from a ther-
modynamic approach to the sorption process (Iglesias and Chirife,
1976) and the obtained parameters have a physical meaning, w
o
corresponding to the amount of water needed to surround the food
surface with just one layer of water molecules and C relating to the
heat liberated in the monolayer sorption process. The concept of
monolayer water content was found to be a reasonable guide to
various aspects of interest in dried foods, related to the limit from
which the rate of deteriorative reactions began to increase signi-
cantly. Nevertheless, this equation is not adequate at high water
activity levels, when dissolution phenomena become more impor-
tant than sorption. The GAB model (Table 1, Eq. (3)) has been suc-
cessfully used by many investigators to t sorption data over a
wide range of a
w
.
Fig. 1 shows the predicted sorption isotherm obtained from
both tted models (Table 1, Eqs. (2) and (4)). The limit for BET
model application in grapefruit was 0.68 water activity, thus indi-
cating the limit from which solutesolvent interactions become
more important in this fruit. Determination coefcients (r
2
) of
BET and GAB models were 0.913 and 0.996, respectively. The same
monolayer water content was obtained in both cases, this being
0.10 g water/g dry solids. Regarding the C parameter, it differs from
1.48 to 1.52 depending on the use of the BET or GAB model. The K
parameter of the GAB model, related to the enthalpy of water mul-
tilayer sorption, was 0.98. As deduced from the C values, the ob-
tained sorption isotherms may be classied as type III, according
to Brunauers classication (Brunauer et al., 1940) in agreement
with that found for other fruits (Lim et al., 1995; Maskan and
Ggs, 1998; Roos, 1993; Vzquez et al., 1999).
3.2. State diagram
Fig. 2 shows some experimental DSC curves obtained in sam-
ples presumably without freezable water content. Fig. 3 shows
the experimental DSC curve of the maximally cryoconcentrated
fresh grapefruit sample, allowing the evaluation of T
/
g
and T
/
m
. In
a DSC curve, a step change in the heat ow implies a change in
the heat capacity of the sample, which occurs during a glass tran-
sition. This is clearly observed in Fig. 2 for the different samples.
Fig. 3 shows a typical thermogramof a sample containing freezable
water content where, despite the glass transition, there appears an
endotherm associated to the ice melting. In this gure, two glass
transitions, one condensed to the ice melting endotherm, can be
observed. As described by Rahman (2004), this may be the result
of the formation of a solute-unfrozen water unequilibrated phase
trapped around or within the ice crystals. This phase relaxed at a
higher temperature than the bulk unfrozen phase, resulting in
the two-step glass transition. From this point of view, the T
g
at
the lowest temperature was assumed as the T
/
g
of the sample. It
was characterized at the mid point of the transition, resulting in
a value of 50.0 0.3 C. Related to the endotherm, the beginning
of the ice melting, evaluated as indicated in Fig. 3, corresponds to
T
/
m
, this being 31.2 0.9 C for grapefruit.
6
7
8
0
1
2
3
5
0 0.25 0.5 0.75 1
a
w
w
e

(
g


w
a
t
e
r
/
g

d
r
y

s
o
l
i
d
s
)

Fig. 1. Water sorption isotherm of grapefruit at 25 C. Experimental points (v) and
tted BET (x) and GAB () models.
54 M.J. Fabra et al. / Journal of Food Engineering 93 (2009) 5258
Table 2 summarizes the onset and mid-point temperatures of
the glass transition for the rest of the analyzed samples, which oc-
curred over a temperature range of 822.6 C. Midpoint T
g
was
considered as the characteristic of the glass transition (Roos,
1995). In Table 2 it stands out the T
g
of the sample with
a
w
= 0.755, which is lower than T
/
g
. This indicates the presence of
freezable water content in this sample. If a partial ice formation oc-
curred during the cooling process, the evaluated T
g
will correspond
to a sample with an unknown amount of water present in the
amorphous matrix. This fact could not be checked in this case, as
the sample was only heated up to 20 C during DSC analysis.
For this reason, the experimental T
g
value analyzed for this sample
was not considered in the study.
The T
g
x
w
data of samples without freezable water were tted
to the linearized Gordon and Taylor model (Table 1, Eq. (5)), con-
sidering T
g(w)
as 135 C (Roos, 1995). The linearized equation (Ta-
ble 1, Eq. (6)) was tted with no intercept, assuming the
experimental 42 C value as T
g(as)
, with a very close agreement be-
tween experimental and predicted values (Fig. 4). In this case, the
obtained empirical constant k value was 4.66 (R
2
= 0.980, standard
Table 1
Models used for tting the experimental data.
Model Expression Eq.
BET (Brunauer et al., 1938) we =
woCaw
(1aw)(1(C1)aw)
(1)
Linearized
aw
(1aw)we
=
1
woC

C1
woC
aw (2)
GAB (Van den Berg and Bruin, 1981) we =
woCKaw
(1Kaw)(1(C1)Kaw)
(3)
Linearized
aw
we
=
1
woCK

C2
woC
aw
K(1C)
woC
a
2
w
(4)
Gordon and Taylor (1952) Tg =
(1xw)Tg(as) kxwTg(w)
(1xw)kxw
(5)
Linearized Tg = T
g(as)
k
xw(Tg(w) Tg)
(1xw)
(6)
Robinson and Stokes (1965) log awaw = 0:004207DT
f
2:1 10
6
DT
2
f
where DT
f
= 0T
f
(7)
Generalized Norrish (Norrish, 1966) lnaw = lnXw (
P
i
K
1=2
i
X
i
)
2
(8)
Empirical Eq. based on Tchigeov (Fikiin, 1998) T
f
=
a
1
b
ln(2xw)
(9)
Linearized
1
T
=
1
a

b
a

1
ln(2xw)
(10)
Soluble solids fraction in the product xs = (
zs
1zs
)xw (11)
Mass balance to obtain mass fraction if ice x
I
(T) =
x
0
w
x
CCS
w
(T)
1x
CCS
w
(T)
(12)
-90 -70 -50 -30 -10 10 30 50 70
0.1 mW
E
n
d
o

H
e
a
t

f
l
u
x

aw=0.112
aw=0.225
aw=0.320
aw=0.432
aw=0.500
aw=0.675
Tg
T (C)
Fig. 2. DSC thermograms showing glass transition of grapefruit samples equili-
brated at different water activities.
-6
-5
-4
-3
-2
-1
-70 -50 -30 -10 10 30
T (C)
H
T g
T
m
-45
-35
-25
-15
-5
5
-70 -50 -30 -10 10 30
T (C)
H
e
a
t

f
l
u
x

(
m
W
)
H
e
a
t

f
l
u
x

(
m
W
)
Fig. 3. DSC thermogram of fresh grapefruit sample. The inner graph shows the
complete information and the outer one an amplied scale to analyze the
characteristic T
/
g
and T
/
m
of the sample.
Table 2
Values of the glass transition temperature (onset and mid point T
g
) for freeze-dried
grapefruit samples equilibrated at different water activity (a
w
) and water content
(x
w
).
a
w
x
w
(g water/g sample) Onset T
g
(C) Mid-point T
g
(C)
0 38.0 1.3 42.0 0.3
0.113 0.018 0.004 12.0 0.8 23.3 0.2
0.230 0.039 0.011 8.1 1.4 13 0.2
0.330 0.058 0.001 8.3 0.6 3.1 0.2
0.430 0.083 0.002 17.0 1.2 11.0 0.2
0.520 0.118 0.001 33.0 0.6 27.2 0.2
0.680 0.151 0.055 54.1 0.5 47.5 0.3
0.755 0.232 0.002 60.0 1.2 53.1 0.4
-140
-120
-100
-80
-60
-40
-20
0
20
40
60
0 0.25 0.5 0.75 1
x
w
(g water/g product)
T

(

C
)
Wg
Tm
Tg
Eq. (7)+(8)
Tf curve Eq. (9)
x Experimental
Eq. (5) 2p
Eq. (5) 1p Tgcurve
Experimental
Fig. 4. State diagram of grapefruit. Experimental and predicted values using the
equations described in Table 1 (freezing temperature (T
f
) curve predicted using Eqs.
(7) and (8) considering all the solutes of grapefruit; glass transition temperature
(T
g
) predicted using Eq. (5) tted with one (1p) or two (2p) parameters; T
/
g
: glass
transition temperature of maximally cryoconcentrated fruit liquid phase; T
/
m
:
melting temperature of ice crystals surrounding the maximally cryoconcentrated
fruit liquid phase; W
/
g
: non-freezable water content).
M.J. Fabra et al. / Journal of Food Engineering 93 (2009) 5258 55
error of the estimate (SE) = 4.3). When the model was tted by
estimating both T
g(as)
and k parameters these being 34.53 C and
4.11, respectively (R
2
= 0.989, SE = 3.7), a close t was also ob-
tained, except in the case of the anhydrous sample (Fig. 4). In this
case, the predicted T
g(as)
was lower than the experimental one.
From this point of view, if the value of the anhydrous sample is
needed, it is advisable to determine it experimentally. The k
parameter obtained for grapefruit was similar to that obtained
when working with other fruits such as strawberries (k = 4.14,
Moraga et al., 2004), apple (k = 3.59, Bai et al., 2001), blueberry
and blackberry (k = 4.02 and 4.12, respectively, Khallou et al.,
2000).
The experimental T
g(as)
and the k parameter obtained from the
Gordon and Taylor tted model were used to predict W
/
g
of this
product, taking into account the experimental T
/
g
value. The ob-
tained value was 0.19 g water/g maximally cryoconcentrated ma-
trix. Similar values have been reported for strawberry (Roos,
1987), apple (Bai et al., 2001) and pineapple (Telis and Sobral,
2001), these being 0.214, 0.264 and 0.220, respectively.
Fig. 5 shows, as an example, the cooling curve obtained for fresh
grapefruit and the procedure used to determine T
f
in samples with
freezable water content. In a similar way as that proposed by Rah-
man et al. (2005), T
f
was considered as the equilibrium tempera-
ture observed in the cooling curve. Table 3 shows experimental
values of water content, water activity, Brix and initial ice forma-
tion temperature of fresh and partially dehydrated samples. In the
case of T
f
x
w
relationships, no common models have been de-
scribed to t experimental data in foods. Bai et al. (2001) suggest
the use of the theoretical ClausiusClapeyron equation but it is
limited to ideal solutions. A modication of this equation was pro-
posed by Sablani et al. (2004) by introducing parameters for non-
ideal behaviour. Two different approaches have been followed in
this work to predict the freezing curve. On the one hand, the liquid
phase of grapefruit samples was considered as a solution of water,
sugars and citric acid and the classical equations used to predict
the behaviour of solutions were applied. On the other hand, an
empirical equation based on the Tchigeov model (Fikiin, 1998)
was also used.
When the liquid phase of the grapefruit is considered as a solu-
tion, the Robinson and Stokes equation (Table 1, Eq. (7)), obtained
from a thermodynamic approach to solid-liquid equilibrium, may
be useful to predict T
f
of samples with different a
w
. On the other
hand, if the predominant solutes in the liquid phase of the product
are sugars and/or citric acid, as in fruits, the Generalized Norrish
equation (Table 1, Eq. (8)) may be used to predict a
w
of samples
with known water and soluble solid content. The combined use
of both equations allows us to obtain a predicted T
f
x
w
relationship
in a product of known composition; the more that is known about
the present compounds and their ratio, the greater the exactitude
in the prediction.
In order to estimate the soluble solid composition of the liquid
phase of the product with different water contents, the following
approaches were considered. For a determined x
w
, the solid mass
fraction will be (1x
w
). The ratio of soluble to insoluble solids for
grapefruit was obtained from the experimental x
w
and Brix of
the fresh sample (Table 3). The mass fraction of soluble solids in
the product was calculated from Eq. (11) (Table 1), this being
0.093. In this way, the ratio of soluble to insoluble solids was
0.75:0.25.
As described by Peir-Mena (2007), who worked with 10 Brix
Star Ruby grapefruit samples, the main soluble solids in this fruit
are sucrose, fructose, glucose and citric acid, in mass ratios of
45.5, 21.2, 18.0 and 15.3, respectively. If the composition of the dif-
ferent soluble solids is not known, the simplest approach will be to
consider the major one present in the fruit (in this case sucrose) as
the only one. Table 3 shows predicted T
f
values for the experimen-
tally considered samples. When only the major solute (sucrose)
was considered, important differences were obtained between
experimental and predicted values. When the different soluble sol-
utes and their ratios in grapefruit were taken into account, a much
closer t between experimental and predicted T
f
was observed.
To apply the empirical procedure based on the Tchigeov model
(Table 1, Eq. (9)), experimental T
f
x
w
and T
/
m
W
/
g
data were con-
sidered and tted to the corresponding linearized equation (Table
1, Eq. (10)). The two obtained empirical parameters, a and b, were
4.427 and 0.696 (R
2
= 0.9996), respectively. The predicted values
in this case (Table 3) were also very similar to the experimental
ones, with only slightly more marked differences at the water con-
tent corresponding to W
/
g
.
Fig. 4 shows the state diagram of grapefruit, which shows
experimental and predicted T
f
and T
/
m
values over all the freezable
water content range, together with the experimental and predicted
-5
0
5
10
15
20
25
0 100 200 300 400
Time (s)
T

(

C
)
T
f
Fig. 5. Cooling curve of fresh grapefruit. The arrow indicates the initial freezing
temperature.
Table 3
Experimental (mean standard deviation) and predicted values of water content (x
w
, g water/g sample), Brix (g soluble solids/100 g liquid phase in the sample), water activity
(a
w
) and initial freezing temperature (T
f
, C) of samples considered in the study in the range of freezable water content.
Experimental values Predicted values
a
x
w
Brix a
w
T
f
(C) a
w
b
Eq. (8) T
f
b
Eq. (7) T
f
c
Eq. (7) T
f
Eq. (9)
0.876 0.003 9.6 0.2 0.993 0.003 0.9 0.1 0.991 0.91 0.60 0.89
0.839 0.002 13.2 0.2 0.987 0.002 1.2 0.2 0.988 1.23 0.82 1.21
0.712 0.004 18.0 0.2 0.975 0.004 2.5 0.1 0.975 2.61 1.80 2.52
0.647 0.002 25.0 0.3 0.964 0.003 3.3 0.1 0.966 3.54 2.50 3.38
0.190
d
31.2 0.9
e
0.754 28.78 29.50 24.05
a
Following the indicated equations (see Table 1).
b
Considering sucrose, glucose, fructose and citric acid as soluble solids of grapefruit.
c
Considering sucrose as the only soluble solid of grapefruit.
d
Water content of the maximally cryoconcentrated matrix (predicted value from Gordon and Taylor model).
e
Experimental T
/
m
value.
56 M.J. Fabra et al. / Journal of Food Engineering 93 (2009) 5258
T
g
x
w
relationships. If the water content of the product recom-
mends its frozen storage, temperatures must be maintained at be-
low T
g
to avoid ice recrystallization and improve grapefruit quality
after thawing. In this sense, and from an economic point of view,
the most desirable process will be that which allows the maximum
ice formation during cooling and the storage at temperatures be-
low T
/
g
. Nevertheless, as T
/
g
= 50

C, the use of cryostabilizers with
a high molecular weight, such as maltodextrines (Roos, 1995), may
be recommendable to increase the T
g
of the product and approxi-
mate it to that of commercial freezers.
The freezing curve of the state diagram can also be applied to
evaluate the amount of ice formed in foods according to their ini-
tial water content and the products freezing point, which is extre-
mely important in the quality preservation of frozen fruits. Fig. 6
shows the mass fraction of ice in frozen grapefruit as a function
of temperature for, both, the fresh sample (87.6% water content)
and the partially dehydrated sample (70% water content). Eq.
(12) (Table 1), deduced from the mass balances at each tempera-
ture in the curve, was used to estimate these values. To this end,
the freezing curve predicted when using Eqs. (7) and (8) was used.
In Fig. 6, the different initial ice formation temperature depend-
ing on the samples initial water content can be observed. It is also
possible to observe that the greatest amount of ice is formed at the
beginning of the freezing process and that not all the water of the
sample will be converted into ice. In fact, at 28.75 C, 84.6 and
63 g ice/100 g sample are formed in fresh and partially dehydrated
samples, respectively, which imply that 97% and 90% of the water
present in the product will be frozen. On the other hand, it can be
observed that if the fresh fruit is stored at 18 C, the amount of ice
formed at equilibrium is 82.5 g ice/100 g product (94 g ice/100 g
water) whereas only 58.5 g ice/100 g product (84 g ice/100 g
water) is formed if the sample is previously dehydrated till 70%
water content. The smaller amount of ice formed per gram of water
present in the dehydrated sample will presumably be related with
a better product quality after thawing.
When no freezable water exists in the product, it becomes more
practical to know about the T
g
x
w
relationships. Collapse and the
development of stickiness during the drying of fruit juices is prob-
ably the main technical obstacle to obtain free-owing powder and
to maintain it when handling, in order to improve its rehydration
(Karathanos et al., 1993). As described by Roos (1995), the powders
will be able to support their own weight when thermal and water
plasticizations are minimized by keeping the product temperature
below the T
g
. As can be observed in the grapefruit state diagram
(Fig. 4), the critical water content (CWC) that takes the product
from the glassy to rubbery state at room temperature (25 C) is
2.23 g water/100 g product. As the usual water content of freeze-
dried or spray-dried products ranges between 35%, there are
two possibilities to ensure powder quality: increasing the T
g
or
decreasing the storage temperature. As commented on above, add-
ing high molecular weight solutes (i.e. maltodextrins) will increase
the T
g
of the product. On the other hand, the chilling storage of
freeze-dried grapefruit at 5 C increases CWC to 5.37 g water/
100 g product (Fig. 4).
3.3. Glass transition temperature- water activity-water content
relationship
Freeze-dried products may suffer a glass transition with small
changes in temperature or water content. An increase in the water
content will occur if the powder is exposed to an atmosphere with
a RH/100 higher than its a
w
. Modelling water plasticization and
water adsorption phenomena together will allow food stability to
be predicted in various processing and storage conditions. The Gor-
don and Taylor and GAB models may be used to obtain a modied
state diagram showing depression of T
g
with increasing a
w
. From
this diagram, the critical water activity (CWA) that depresses the
T
g
below the storage temperature may be obtained. If the sorption
isotherm is also plotted in the diagram, the corresponding CWC of
the product will be obtained.
Fig. 7 shows the T
g
a
w
x
w
relationships of freeze-dried grape-
fruit in the range of non-freezable water content. In this case, if
the product is commercialized at 25 C, the CWA that takes the
product from the glassy to rubbery state is 0.140 (CWC 2.23 g
water/100 g sample). This means that storing the powder at a RH
of over 14% will lead to the rubbery state. Above these values, col-
lapse and stickiness of grapefruit powder, as well as the crystalliza-
tion of amorphous compounds, could take place, the higher the
storage temperature, the more likely it is that this will occur. From
this result, it can be deduced that the product must be adequately
packaged in a low water vapour permeability material. Knowing
how water sorption behaves at different temperatures will allow
us to analyze the convenience of, for example, the chilled storage
of dried powder.
On the other hand, the CWC at 25 C is much lower than the
monolayer moisture content obtained from the BET and GAB mod-
els, which indicates that w
o
is not a water content that assures
quality preservation during the storage of dried grapefruit, as has
been reported by Moraga et al. (2004) and Roos (1993) for
strawberry.
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
-30 -25 -20 -15 -10 -5 0
T (C)
x
I

(
g

i
c
e
/
g

s
a
m
p
l
e
)
Fig. 6. Mass fraction of ice (x
I
) in frozen grapefruit as a function of temperature.
Fresh, 87.6% water content (), and partially dehydrated, 70% water content (- - -),
fruit. Arrows indicate the amount of ice formed in each case at 18 C.
-100
-80
-60
-40
-20
0
20
40
60
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
a
w
T
g

(

C
)
0
0.05
0.1
0.15
0.2
0.25
0.3
x
w
CWA25
CWC25

(
g

w
a
t
e
r
/
g

p
r
o
d
u
c
t
)
Fig. 7. Temperature - water activity () and water activity - water content ()
relationship of grapefruit in the range of non-freezable water content. CWA: critical
water activity; CWC: critical water content.
M.J. Fabra et al. / Journal of Food Engineering 93 (2009) 5258 57
4. Conclusions
In products such as grapefruit, the freezing curve at different
water contents may be predicted by using Generalized Norrish
and Robinson & Stokes equations, although the solute composition
of the sample is needed to obtain accurate results. When this is un-
known, the proposed empirical equation based on the Tchigeov
model may also be applied and in this case some experimental
T
f
x
w
data are needed. This curve, together with the T
g
x
w
relation-
ship predicted by the Gordon and Taylor model, allows the state
diagram to be constructed, which is useful to establish the process-
ing and storage conditions that will ensure the maximum stability
of different grapefruit-products. If the water content of the product
is greater than 19.0 g water/100 g sample (a
w
= 0.687), frozen stor-
age will be recommended. In this case, cooling the sample to
31.2 C will allow the maximum ice formation and the frozen stor-
age at temperature lower than 50 0.3 C will be necessary to en-
sure the glassy state of the remaining amorphous matrix and so its
maximum stability. The partial dehydration of the sample plays a
cryoprotective role. If non-freezable water is present in the sample,
the more stable glassy state may be achieved at different temper-
ature-water content relationships. At room temperature (25 C),
the low CWA and CWC values of the product indicate how packag-
ing is needed to ensure stability. Both for freezing or freeze-drying,
strategies to increase the T
g
will improve the products stability
during storage.
Acknowledgements
The authors thank the Ministerio de Educacin y Ciencia and
the Fondo Europeo de Desarrollo Regional (FEDER) for the nancial
support throughout the project AGL2005-05994. Author M.J. Fabra
thanks Spanish Ministry of Culture and Education for a FPU grant
(AP2005-3562).
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