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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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