Meat Science 96 (2014) 1417–1424

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Meat Science
journal homepage: www.elsevier.com/locate/meatsci

Desorption isotherms for fresh beef: An experimental and

modeling approach
Tom Ahmat a,⁎, Denis Bruneau a, Alexis Kuitche b, Aworou Waste Aregba a
a
I2M UMR 5295, dépt TREFLE, Bordeaux, France
b
Laboratoire Energétique, ENSAI, N'Gaoundéré, Cameroon

a r t i c l e i n f o a b s t r a c t

Article history: Desorption isotherms for fresh beef were determined at 30, 40 and 50 °C by the static gravimetric method. The
Received 29 May 2013 resulting isotherms exhibited a type II sigmoid shape. The BET, GAB and Halsey models were used to fit these ex-
Received in revised form 13 December 2013 perimental data. The GAB model was most accurate for all temperatures and all levels of water activity, followed
Accepted 15 December 2013
by the BET and Halsey models. The temperature dependence of GAB constants was estimated. The isosteric heat
Available online 24 December 2013
of desorption and its evolution in relation to moisture content were calculated using Clausius–Clapeyron equa-
Keywords:
tions. The monolayer moisture content was determined using the GAB model: it decreased as the temperature
Beef increased. The density of bound water, the number of adsorption sites, the sorption surface area and the percent-
Desorption isotherms age of bound water were calculated using the Caurie equation: all these quantities decreased as the temperature
Modeling increased. The Kelvin and Halsey equations were used for calculation of pore size, which increases with an
Isosteric heat increase in moisture levels and sorption temperature.
Bound water © 2013 Elsevier Ltd. All rights reserved.
Pore size

1. Introduction product as a function of its water activity for a given temperature is

Stability of food products is closely related to their water activity. In
general, it is considered that a water activity lower than 0.6 protects
products from degradation reactions. Indeed, the growth of microor-
ganisms is inhibited and the enzymes are inactivated. The sorption
isotherms are of interest because they provide information on the
water activity of a product depending on the environment air tempera-
ture and relative humidity.
Sorption isotherms are used a great deal in food sciences and tech-
nologies, especially in the drying process, where they are important
for determining equilibrium moisture content, the moisture content at
the end of the drying process (Talla, Jannot, Nkeng, & Puiggali, 2005).
The equilibrium moisture content is an important parameter in models
used to predict changes in the moisture content of a product during the
drying process and later during storage.
For the drying process control, it is essential to have a good knowl-
edge of the ratio between equilibrium moisture content and the relative
humidity of the surrounding environment (Gal, 1983). When the mois-
ture in the product is in equilibrium with the water vapor in the air that
surrounds it, the temperature of the product is equal to that of the air
and the water vapor pressure in the product is equal to that in the air.
The water activity of the product is then equal to the relative humidity
of the air. The curve showing the equilibrium moisture content of a
⁎ Corresponding author at: I2M dépt TREFLE, Arts et Métiers ParisTech, Esplanade des
Arts et Métiers, 33405 Talence Cedex, France. Tel.: +33 5 56 84 63 80.
E-mail address: ahmat.tom@ensam.eu (T. Ahmat).
called a sorption isotherm. Desorption isotherms are obtained when a
moist product reaches its equilibrium moisture content by giving up
water into its surroundings.
Meat preservation in hot countries is difficult because of the very
perishable nature of this product. When climate conditions are unfavor-
able, the product deteriorates very quickly. Since the conditions in trop-
ical countries make use of solar energy for drying food practically
attractive, solar drying is widely used as a meat preservation method
in tropical countries where there is a variety of dried meat such as
Biltong in South Africa (Laurent, 1981), Charque in Brazil (Shimokomaki,
France, & Carvalho, 1987; Torres et al., 1994) and Kilishi in the Sahel coun-
tries (Kalilou & Zakhia, 1997). The annual consumption of dried meat in
developing countries is constantly increasing rising yearly from 10 kg
per capita in 1960 to 26 kg per capita in 2000 and will reach 36 kg per
capita in 2030 (Heinz & Hautzinger, 2007). Thus, there is need to provide
information on sorption isotherms of meat at temperatures encountered
in solar drying processes in tropical countries to have a better understand-
ing of the behavior of the product as it dries.
There have been many studies into the sorption isotherms of meat
and its by-products (Aktas & Gürses, 2005; Clemente, Bon, Benedito, &
Mulet, 2009; Comaposada, Gou, & Pakowski, 2000; Farid & Farid,
2010; Kabil, Aktaş, & Balcı, 2012; Singh, Rao, Anjaneyulu, & Patil, 2001;
Trujillo, Pei, & Tuan Pham, 2003) which have mainly covered the effect
of temperature on moisture sorption, the study of hysteresis, sorption
heat and modeling sorption curves. Some authors have shown that
experimental data from sorption isotherms can be used to determine
the isosteric sorption heat and the properties of the bound water

0309-1740/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.meatsci.2013.12.009
1418 T. Ahmat et al. / Meat Science 96 (2014) 1417–1424
(Delgado & Sun, 2002a; Mulet, Garcia-Reverter, Sanjuan, & Bon, 1999;
Singh, Rao, Anjaneyulu, & Patil, 2006). The isosteric heat of desorption
is the energy required to remove water molecules from the solid matter
of the product. It is equal to the sum of the heat of vaporization of pure
water and the net isosteric heat of desorption. This last can be deter-
mined by applying the Clausius–Clapeyron equation to desorption iso-
therms. Knowledge of the isosteric heat of sorption is an important
matter for the design of drying equipments. Clemente et al. (2009)
and Singh et al. (2006) have studied the isosteric heat of desorption of
previously frozen raw pork meat and goat meat, respectively. Kabil
et al. (2012) have studied the isosteric heat of desorption of beef for
air temperatures below 25 °C, which are temperatures not usually en-
countered in solar drying processes in tropical countries. It is therefore
necessary to provide information on isosteric heat of desorption of
beef at solar drying temperatures in order to have a more precise idea
of the energy needed for solar drying of beef in tropical countries.
Bound water is often defined as water which is so closely linked to
the other constituents of the product that its properties differ from
those of the free water. It is a relevant indicator of product stability be-
cause it does not allow the development of microorganisms or any
chemical reaction (Caurie, 1981). Rizvi (1986) suggested that tempera-
ture has an impact on the properties of bound water of food products.
Some studies deal with the effect of temperature on the properties of
bound water in meat products (Singh et al., 2001, 2006), but none of
them looks at beef meat. Therefore, studying the influence of tempera-
ture on values of monolayer moisture content, number of sorbed mono-
layers, density of sorbed water, surface area of sorbent and percent of
bound water is useful to assess changes in sorbed water as a function
of temperature.
The evaluation of pore size distribution in porous materials is also of
great importance in drying practice (Strumillo & Kudra, 1986). Some
authors state that the total sorption area, the rate and the extent of
hydration of food materials can be determined from the number, size
and surface properties of the pores in the protein matrix (Singh et al.,
2006). Furthermore, the influence of temperature on pore size has
been pointed out (Kapsalis, 1981). Singh et al. (2001, 2006) have
studied this influence of temperature on pore size, for smoked chicken
sausage and goat meat.
Sorption isotherms of beef meat at temperatures close to those
encountered in solar drying processes in tropical countries are rare.
Trujillo et al. (2003) studied desorption isotherms of lean beef in the
temperature range 5–40 °C but provide no information on the isosteric
heat of desorption and the properties of the bound water (which are
important for a better understanding of energy supply and stability of
the meat product during drying), and did not consider the temperature
dependence of the physically significant GAB model parameters.
The aim of this study is to determine and model the desorption
isotherms of fresh beef meat. Classical temperatures encountered in
solar dryers are explored (30 °C, 40 °C and 50 °C); the isosteric heat of
Fig. 1. Schematic diagram of sorption jar and sample holder used in experiments.
desorption, temperature dependence of bound water, and properties
and size of the pores are determined.
2. Material and methods
2.1. Experimental equipment
The equipment used is a temperature-controlled climate chamber
(oven) model 53L 220 °C UFB400 (Memmert GmbH, Schwabach,
Germany); this is a basic type of universal oven that includes a forced
air circulation for a total chamber volume of 53 L. The air temperature
range in this oven is from 10 °C above ambient temperature to 220 °C.
Air temperature measurement uncertainty is ± 0.5 °C. The samples
were placed in hermetically sealed jars containing salt solutions. The
jars were 11 cm in height and 10 cm in diameter (Fig. 1), in accordance
with the Spiess and Wolf (1987) recommendations. The samples were
set on a mesh, 10 mm above the surface of the liquid in order to avoid
the samples getting wet, as suggested by Trujillo et al. (2003).
2.2. Sample preparation
The beef used was bought from wholesale butchers in the local mar-
ket in the town of N'Gaoundéré in North Cameroon. Meat comes from
freshly slaughtered beef and therefore did not undergo any treatment
postmortem. The animal was Goudali Zébus, aged between 4 and
5 years old. The part of the animal that was used was the round of the
hind quarters. First the tendons and fat were trimmed from the fresh
meat. The meat was then cut along the direction of the fibers into thin
strips, 5 cm long, 3 cm wide and 3 mm thick. Fat, protein, moisture
and ash were determined using the method of AOAC (AOAC, 1997).
2.3. Determining the equilibrium moisture content of desorption
Desorption isotherms were determined by the gravimetric static
method. We used saturated saline solutions covering a relative humid-
ity interval between 5% and 84% (Table 1) (Bizot & Multon, 1978) these
solutions were prepared in hermetically sealed jars and kept in the ther-
mostatically controlled chamber. Two samples were suspended in each
jar above the saline solutions; thus they remained in an atmosphere
with stable temperature and hygrometry. The trials were carried out
for three temperature values: 30 °C, 40 °C and 50 °C. To avoid deterio-
ration of the meat, potassium sorbate has been used as a preservative
for four solutions whose water activities are greater than or equal to
50% (NaBr,CuCl2, NaCl, and KCl). Thus 25 mg of potassium sorbate
was sprinkled on each sample at a ratio of 5 mg for 1 g of the product.
This mass is removed from the final equilibrium mass. This preservative
has been recommended and used by Singh et al. (2006) in the propor-
tions indicated above and is considered having no influence on the
sorption isotherms.
 T. Ahmat et al. / Meat Science 96 (2014) 1417–1424 1419

Table 1 The parameters of the GAB model take into account the effect of tem-
Saturated saline solutions: relative humidity versus temperature (Bizot & Multon, 1978). perature (Eqs. (2), (3) and (4)). In the GAB model, the third parameter
Salts 30 C 40 C 50 C K is the energy constant related to the sorption enthalpies (Van den
Berg & Bruin, 1981). The GAB equation has been recommended by the
KOH 8.2 6.3 5.7
LiCl 11.3 11.2 11.4 European Project Group COST 90 on Physical Properties of Foods
KCH3CO2 22.5 21.6 21.6 (Wolf, Spiess, & Jung, 1985) as the fundamental equation for the charac-
MgCl2 32.8 31.6 30.5 terization of water sorption of food materials. The Halsey model
K2CO3 43 42.2 42.2
(Eq. (7)) takes account of the condensation of the water multilayer by
NaBr 57.6 53.2 50.9
CuCl2 68.5 68 65.5 considering that the potential energy of the water molecules, which in-
NaCl 75.3 74.7 74.4 tervenes in the expression of parameters a and b in Eq. (7), is inversely
KCl 84.3 82.3 81.2 proportional to the bth power of the distance to the surface of the dry
substrate (Halsey, 1948). Iglesias, Chirife, and Lombardi (1975) report-
ed that the Halsey equation has been accurately used to describe 220
Next, the samples were weighed every 24 h on digital scales precise- experimental sorption isotherms of 69 different foods in the range of
ly to 0.001 g. The equilibrium condition was considered to be reached 0.1 b aw b 0.8.
when the difference between three consecutive weights was within The equations for these models are summarized in Table 2. In this
0.001 g. The moisture content analysis was carried out by drying in table, constants a, b, C, K and W0 are parameters to be adjusted and
a conventional oven at 103 °C for 24 h, in order to determine the functions aw and W represent water activity and equilibrium moisture
equilibrium moisture content using Eq. (1). The moisture content was content respectively. In the GAB and BET models, the parameter W0
determined in triplicate and for each replicate, two samples were con- designate the monolayer moisture content, C and K denote energy
sidered. The equilibrium moisture content values were thus averages constants. GAB parameters are dependent on temperature (in Kelvin)
of six experimental values. and have the following expressions:


meq W0 ðTÞ ¼ W 0 e
0 ΔH=RT
ð2Þ
W ¼ 100  −1 ð1Þ
ma
0 ðH1 −Hm Þ=RT
CðTÞ ¼ C e ð3Þ
where meq represents the mass of the sample in equilibrium and ma the
anhydrous mass. All these pairs of readings combined together (relative 0 ðHL −Hm Þ=RT
humidity HR, equilibrium moisture content W) provide the sorption KðTÞ ¼ K e ð4Þ
isotherm curve at a given temperature.
where W′0, C′ and K′ designate the constants associated with the theo-
2.4. Presentation of the sorption isotherm models used retical parameters of the GAB model, HL the heat of condensation of
pure water, H1 the heat of total sorption of the first layer of the primary
Moisture sorption isotherms of foods can be described by more than sites, Hm the heat of total sorption of the multilayer, ΔH the partial
one sorption model (Lomauro, Bakshi, & Labuza, 1985). Since the mois- molar enthalpy of sorption and R is the ideal gas constant.
ture sorption isotherms of food materials represent the integrated hy-
groscopic properties of various constituents, and since the sorption 2.5. Method for determining parameters intervening in the sorption iso-
properties may change as a result of chemical and physical interactions therm models
induced by heating, it is difficult to have a single mathematical model,
whether theoretical or empirical, that describes accurately the sorption The adjustment parameters in the different models were estimated
isotherm in the whole range of water activity and for various types of on the basis of experimental results, by applying Newton's method to
foods (Chirife & Iglesias, 1978). Simplicity of models and physical signif- minimize the sum S of quadratic errors between the equilibrium mois-
icance of models parameters have been our guidelines for selecting ture contents obtained experimentally (Wexp) and those obtained from
sorption isotherms models. The three that we considered are: the BET the expression given by the model being considered (Wmod):
(Brunauer, Emmet, & Teller, 1938), the GAB (Anderson, 1946; de Boer,
!2
1953; Guggenheim, 1966) and the Halsey (Halsey, 1948) models Xn
W exp −W mod
(Table 2). S¼ ð8Þ
i¼1
W exp
The BET model (Eq. (8)) has been widely used and has often given i

satisfaction for water activity values aw from 0.05 to 0.45. It contains

only two parameters, the monolayer moisture content (W0) adsorbed where n represents the number of measurements carried out for a given
on the surface of the material and the energy constant (C) which is re- temperature. In our case, n = 9 corresponds to the nine saline solutions
lated to the net heat of sorption (Al-muhtaseb, Mc Minn, & Magee, used. The resolution was carried out using the Excel Solver tool from
2002). The GAB model (Eq. (6)), which is an extension of the BET Microsoft office XP 2007 for 200 iterations with a precision value of
model from two to three parameters, is the model most commonly 10−6, a tolerance value of 1% and a convergence value of 10−6.
used model for modeling isotherms for agri-food products (Talla et al., A model's acceptability in terms of description of the experimental
2005; Aktas & Gürses, 2005; Kalilou et al., 1998; Trujillo et al., 2003). values was assessed using the correlation coefficient values r2 and the
percent deviation P defined by:
Table 2 vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Sorption isotherms: presentation of available models. u " n !
u1 X W exp −W mod 2
P ¼ 100  t  ð9Þ
Model Equation Equation number n 1 W exp
Brunauer–Emmet–Teller (BET) aw
ð1−aw ÞW ¼ CW
1
0
þ ðCW
C−1Þ
0
aw (5)
Guggenheim–Anderson–Boer (GAB) W ¼ ð1−aw KÞWð1þa
0 aw CK
(6)
h i w CK−aw KÞ
Halsey aw ¼ exp −ab (7) A model was considered acceptable when its percent deviation P
W
was less than 10% (Brunauer, Deming, Deming, & Teller, 1940) and its
correlation coefficient r2 was close to 1.
1420 T. Ahmat et al. / Meat Science 96 (2014) 1417–1424

The equilibrium moisture content residuals, which are the relative The thickness of the water adsorbed layer was calculated from the
distance between each experimental value and the corresponding Halsey equation (Eq. (15)).
modeling value, defined by Eq. (10) were determined.

1=3
−5
! t ¼ 3:54  ð15Þ
lnaw
 W exp −W mod
R ¼ 100  ð10Þ
W exp
where t is the multilayer thickness in nm.
The average pore size Rp is obtained by the sum of the critical
The evolution of R⁎ as a function of water activity aw was represented radius rc, and the multilayer thickness t (Eq. (16)) (Singh et al., 2001).
for each temperature and for all the models in order to assess whether
Rp ¼ rc þ t ð16Þ
this or that model was more efficient than another in a given water
activity interval.

2.6. Determining the properties of bound water 2.8. Determining the isosteric heat of sorption

The properties of bound water that were determined for a given
temperature were the monolayer moisture content W0, the bound
water density C, the number of adsorbed monolayers N, the surface
area of sorption A and the percentage of bound water. The monolayer
moisture content was obtained from the model with the lowest percent
deviation from among the BET and GAB models (Caurie, 1981). Bound
water density C and the number of adsorption sites N were obtained
from Caurie's linear equation (Eq. (11)) obtained by minimizing the
sum of squared errors S (Eq. (8)) between the experimental equilibrium
moisture contents and those obtained from the Caurie model equation.
Isoteric heat of desorption is obtained by adding the latent heat of
vaporization to the net isosteric heat of desorption (Eq. (17)). The latter
was calculated from sorption isosteres which represent, at a constant
moisture content, the evolution of the logarithm of the water activities
as a function of the inverse of the temperature [−lnaw = f(1/T)]. The
latent heat of vaporization of pure water is considered to be tempera-
ture independent and equal to 2401 kJ/kg, that is the average heat of
vaporization of pure water at temperatures of studies (30 °C, 40 °C
and 50 °C). The equation of the desorption isosters is given by the
Clausius–Clapeyron equation (Eq. (18)):



 Q s ¼ Q sn þ Lv ð17Þ
1 2 1−aw
ln ¼ − ln ðCWo Þ þ ln ð11Þ
W N aw
d lnaw Q
¼ − sn ð18Þ
dð1=TÞ R
For each temperature, the number of adsorption sites N was de-
duced from the slope 2/N of the straight line ln(1/W) as a function of where Qs and Qsn, expressed in kJ/kg, designates the isosteric heat of
ln[(1 − aw) / aw]. The sorption surface A, expressed in m2/g, is a sorption and the net isosteric heat of sorption respectively, R is the
parameter associated with the adsorption phenomenon and defined ideal gas constant, T is the temperature in Kelvin and Lv is the pure
as follows (Caurie, 1981). water vaporization energy.
Isosters are straight lines with a slope equal to Qsn/R, from which the
V net isosteric heat of desorption Qsn can be deduced. The shape of the
A¼ ð12Þ curve Qs = f(W) shows the evolution of the isostéric heat of sorption
d
as a function of the equilibrium moisture content.

where V = [2.10−8 / (2/N)] (m3/g) and d = 3.673.10−10 (m).

3. Results and discussion
The percentage of bound water was then obtained as follow.
3.1. Average composition of beef meat
%bw ¼ W0  N ð13Þ
The average composition of the beef samples used is given in Table 3.
The values obtained are close to those of many authors (Kabil et al.,
2.7. Determining the pore size of beef meat 2012; Ockerman, 1985).

The Kelvin equation (Eq. (14)) is used for the calculation of critical 3.2. Desorption isotherms: experimental results
radius.
Fig. 2 shows the evolution in equilibrium moisture content (W) of
the fresh beef as a function of water activity (aw) for different tempera-
−2σVM
rc ¼ ð14Þ tures (30 °C, 40 °C and 50 °C). These are desorption isotherms of type II
RT ln aw
isotherms (sigmoid shape) according to the classification by Brunauer
et al. (1940). Isotherms obtained from higher temperatures are general-
where rc is the critical radius (m), σ is the surface tension (Nm−1), VM is ly below those obtained from lower temperatures. For a given water ac-
the molar volume of sorbate (m3·mol−1), R is the universal gas constant tivity, the equilibrium moisture content of the meat decreased as the
(kJ mol−1 K−1), T is the temperature (K) and aw is the water activity. temperature increased, which corroborates the results obtained by

Table 3
Sample compositions and pH.

Wet basis moisture content Dry basis moisture content Lipid (%) Fat Ash pH
(kg water/100 kg fresh meat) (kg water/100 kg dry matter)
(%) (%)

75.70 ± 0.2 305.89 ± 1.2 22.2 ± 0.5 4.3 ± 0.3 1.02 ± 0.1 5.6 ± 0.1
 T. Ahmat et al. / Meat Science 96 (2014) 1417–1424 1421

Fig. 2. Desorption curves of fresh beef (experimental results): equilibrium moisture

content as a function of water activity for different temperatures.

Fig. 3. Experimental and predicted values of equilibrium moisture content of fresh beef at
many authors, particularly for products with a high protein content using BET,GAB and Halsey models.
(Singh et al., 2001, 2006; Delgado & Sun, 2002a).

3.3. Modeling desorption isotherms
The adjustment parameters on the experimental results, the percent
deviation P (Eq. (9)) and the correlation coefficient r2 for the three
models selected to model the desorption isotherms are summarized in
Table 4. For the three models, i.e. GAB, BET and Halsey, their deviation
coefficients P were under 10%, whatever the temperature considered;
they could therefore be used to model desorption isotherms for beef.
The most efficient model was the GAB (values of P as % at 30 °C, 40 °C
and 50 °C were 3.69; 1.97 and 5.46 respectively) followed, in order, by
the BET and Halsey models. Fig. 3 shows the experimental points of
the desorption isotherms at 30 °C, 40 °C and 50 °C and their description
by the BET, GAB and Halsey models. It represents visually a good fit be-
tween the experimental values and those obtained from these models.
The GAB model describes the experimental values very well as its re-
siduals R* (Eq. (10)) are less than ±10% for all ranges of water activity
(Fig. 4). This confirms the results obtained by some authors who consid-
er that the GAB model is the most appropriate for modeling agri-food
products (Trujillo et al., 2003; Singh et al., 2006). Although some
authors state that the BET model is more effective for water activities
between 0 and 0.45 (Aktas & Gürses, 2005; Labuza, Kaanane, & Chen,
1985), it can be seen that for fresh beef, the fit of the BET model is not
better; whatever area of water activity is considered (Fig. 5). On the
other hand, the Halsey model was more effective for water activities
between 0.3 and 0.8 (Fig. 6).
It can be seen that for each temperature measurement, the monolay-
er moisture content W0 obtained from the GAB model is always slightly
higher than or equal to that obtained from the BET model, while the
energy constant C obtained from the GAB model is lower than that ob-
tained from the BET model (Table 4). The same observations have been
made by several authors (Timmermann, Chirife, & Iglesias, 2001; Duras
& Hiver, 1993). The monolayer moisture content obtained from the GAB
model at 40 °C (W0 = 0.0624) is greater than that obtained by Trujillo
et al. (2003) (W0 = 0.0527). This difference may be explained by the
method used by these authors as they accelerate the desorption equili-
bration of their samples using a very low water activity salt for the first
stage of the desorption process, as suggested by Delgado and Sun
(2002b). In both models (GAB and BET) this monolayer moisture con-
tent decreases when the operating temperature increases (Table 4).
This result is in accordance with those obtained for most agri-food prod-
ucts (Singh et al., 2006; Delgado & Sun, 2002a; Singh et al., 2001).
Concerning the multilayer water, i.e. water associated with neighboring
molecules by water–water or water–solid substrate hydrogen binding,
it is characterized by the energy constant of the GAB which ranges
from 0 to 1. A higher value of K indicates that water in the multilayer
zone is well structured and not strongly bound; a low value of K
indicates that water is not at all freezable and less strongly bound
(Timmermann et al., 2001). For our beef meat, this value varies between
0.96 and 0.99 in a 30–50 °C temperature range; this result is in agree-
ment with that obtained by Trujillo et al. (2003). Note that in the Halsey
model (Eq. (7)), the parameter b value is in the range 1.30–1.44 and de-
creases as the temperature increases; this indicates that the interaction
between the water molecules and the solid skeleton decreases when

Table 4
Parameters interfering with sorption isotherms available models: values obtained by
adjusting on experimental results.

Model Temperature Parameters

GAB W0 C K a b P (%) r2
30 0.096 29.71 0.96 – – 3.69 0.999
40 0.069 23.92 0.98 – – 1.97 0.997
50 0.056 23.79 0.99 – – 5.46 0.998
BET 30 0.088 46.39 – – – 6.15 0.997
40 0.067 25.34 – – – 5.51 0.997
50 0.056 24.12 – – – 5.57 0.998
Halsey 30 – – – 0.0602 1.4418 4.527 0.998
40 – – – 0.0487 1.3170 7.807 0.993
Fig. 4. Equilibrium moisture content residuals R* (Eq. (10)) between experimental values
50 – – – 0.03951 1.3032 7.188 0.996
and GAB model values as a function of water activity.
1422 T. Ahmat et al. / Meat Science 96 (2014) 1417–1424

Fig. 5. Equilibrium moisture content residuals R* (Eq. (10)) between experimental values
and BET model values as a function of water activity.
Fig. 7. Desorption isoster curves of fresh beef. Napierian logarithm of the water activity as a
function of temperature inverse for different equilibrium moisture content values.
the air temperature increases. This result corroborates those obtained
for other types of meat product (Singh et al., 2001, 2006).
3.5. Isosteric heat of desorption
3.4. Temperature dependence of GAB parameters
The equilibrium moisture content values we obtained for different
air temperatures from the experimental results are all smaller than
The temperature dependence of sorption phenomena can be deter-
0.5 kg/kg dry matter (Fig. 2); for that reason, these experimental curves
mined by incorporating temperature terms into sorption equations.
have been used to determine the isosteric heat (Eq. (18)) only in the
GAB equation has often been used to study effect of temperature on
range 0.1 kg/kg to 0.5 kg/kg for moisture content values. For larger
monolayer moisture. The GAB model was identified as the best fit and
moisture content values, these have been extrapolated using the
the values for the parameters included in this model (W0, C and K)
GAB model for which the parameters have been determined in the
were obtained for discrete temperature values of 30 °C, 40 °C and
last sub-section. These experimental and extrapolated desorption
50 °C by adjustment to the experimental results (Table 4). In the GAB
curves both have been used in order to plot the desorption isoster
model, these adjustment parameters are functions of temperature
curves [− lnaw = f(1/T)] (Fig. 7). The slope Qsn/R of these isosters
(Eqs. (2), (3) and (4)). For a complete identification of the GAB model,
(Eq. (18)), obtained by linear regression, is an increasing function of
the unknowns appearing in these equations (W′0, C′, K′, ΔH, H1, HL
the equilibrium moisture content. The net isosteric heat of desorption
and Hm) have been identified by introducing parameters from the
Qsn that corresponds to each moisture content has then been deduced
GAB model obtained experimentally at 30 °C, 40 °C and 50 °C in
from this slope. Fig. 8 shows the evolution of the isosteric heat of de-
Eqs. (2), (3) and (4) and researching the temperature functions that
sorption as a function of moisture content. Indeed, the isosteric heat of
minimize the correlation coefficient values r2. Thus we obtained the
desorption decreases as the moisture content increases. For small values
parameters of the GAB model dependent only on temperature (T)
of the moisture content (less than 0.2 kg/kg dry matter), this decrease is
(Eqs. (19), (20) and (21)).
very severe; the isosteric heat of desorption then progressively tends to
asymptotic that approaches the latent heat of vaporization of pure
−5 21393;4=RT
W0 ðTÞ ¼ 1:93:10 e ð19Þ water (2401 kJ/kg). This fact points out that during the drying process
a considerable amount of energy has to be supplied to remove if needed
13738;54=RT the last traces of moisture in the meat. Knowledge of the isosteric heat
CðTÞ ¼ 0:125e ð20Þ of desorption is therefore very important for good design of the drying
equipments. This result confirms those commonly observed for most
−835;13=RT of agri-food products (Clemente et al., 2009; Delgado & Sun, 2002a;
KðTÞ ¼ 1:35e ð21Þ
Igbeka & Blaisdell, 1982). To ensure the microbiological quality of the

Fig. 6. Equilibrium moisture content residuals R* (Eq. (10)) between experimental values
and Halsey model values as a function of water activity. Fig. 8. Isosteric heat of desorption as a function of equilibrium moisture content.
 T. Ahmat et al. / Meat Science 96 (2014) 1417–1424 1423

Table 5
Properties of bound water in the beef for different temperatures.

Temperature (°C) Monolayer moisture content W0 Caurie's slope 2/N Number of adsorption Density of absorbed water C % bound water Sorption surface area A
(kg water/kg dry matter) sites N (g/cm3) %bw (m2/g)

30 0.0908 0.443 4.51 2 40 123.11

40 0.0624 0.564 3.54 1.9 24 96.7
50 0.0532 0.668 2.99 1.8 16.4 81.64

meat after drying, the water activity should be lower than 0.60 (Cheftel
& Cheftel, 1977). This value corresponds to equilibrium moisture
contents between 0.2 kg/kg dry matter and 0.1 kg/kg dry matter
(Fig. 2) for air temperatures between 30 °C and 50 °C. Energy of at
least 3000 kJ/kg is therefore required to reach such water content
(Fig. 8), that is an amount of energy that is higher by about 25% when
compared with the latent heat of vaporization of pure water.
3.6. Properties of bound water
Properties of bound water which is considered as the critical mois-
ture content beyond which deteriorations can occur, was determined
at 30 °C, 40 °C and 50 °C (Table 5). Caurie's linear curves (Eq. (11)) at
30 °C, 40 °C and 50 °C (Fig. 9) show the influence of temperature on
the slopes which increase with temperature. These slopes are inversely
proportional to the number of adsorption sites N on the surface
(Eq. (11)). Thus, the number of adsorption sites N will decrease with
the temperature (Table 5). The same observations were made by
Singh et al. (2006) for the goat meat and they explained this behavior
by the deterioration of the proteins during drying.
Knowing the slopes of the Caurie's curves, we can calculate the
adsorption surface area A using Eq. (12). This sorption surface area
decreases as the temperature increases (Table 5). This indicates that
the availability of specific surface areas for hydrophilic binding decrease
with increasing temperature.
The density of bound water and the percentage of bound water de-
crease as the temperature increases (Table 5). With densities between
1.8 g/cm3 and 2 g/cm3, bound water is almost two times more dense
than pure water. The same observations have been made by Singh
et al. (2001, 2006) on smoked chicken sausage and raw goat meat.
This high density could be explained by the strong bonds of water mol-
ecules to the hydrophilic, charged and polar groups of proteins, with an
enthalpy of vaporization considerably higher than pure water. Intermo-
lecular distances are smaller than those of pure water and therefore the
intermolecular forces become greater leading to a high density (Singh
et al., 2001). The increase in air temperature reduces the intermolecular
forces, resulting in a decrease in bound water density.
3.7. Pore size of beef meat
Pore size of beef meat was obtained using Eqs. (14)–(16). The pore
size varied from 4.03 to 12.64 Å depending on the moisture content
and the sorption temperature. Generally the pores enlarged with in-
crease in moisture levels and sorption temperature (Table 6). For all
temperatures and moisture levels, the average pore size of beef was
less than 20 Å. These pores can be thus classified as microspores accord-
ing to IUPAC (International Union of Pure Applied Chemistry) classifica-
tion. Singh et al. (2006) have studied the effect of temperature on pore
size of goat meat and they obtained values between 5.11 and 13.15 Å.
They have also observed that the pore size increases with the increase
of the sorption temperature and moisture level.
4. Conclusion
Desorption isotherms for beef were determined at 30 °C, 40 °C and
50 °C to characterize dried beef meat stability and prevent microbiolog-
ical evolution of this product in this range of air temperatures. These
isotherms are type II sigmoid in shape, and, for all water activities, equi-
librium moisture contents decreased when the air temperature in-
creased. The fit of these sorption isotherms with the GAB, BET and
Halsey models leads to high performance representations, especially
for the GAB model. The isosteric heat of desorption and its evolution
with the product moisture content were estimated in order to estimate
the energy required to ensure the preservation of beef. This energy is
greater than that needed to evaporate pure water, by at least 25%. The
monolayer moisture content values for beef at different temperatures
were estimated by GAB and BET models and ranged from 0.096 to
0.056 (dry-base) for a 30 °C–50 °C temperature range. Finally, the prop-
erties of the bound water and the influence of temperature on these
properties were identified. The density of the bound water is almost
double that of pure water. The sorption surface area decreases when
the temperature increases and varies from 81.64 m2/g to 123.11 m2/g.
The pore size increases with an increase in moisture levels and sorption
temperature and varies from approximately 4 Å to 12 Å (for moisture

Table 6
Average pores size (Å) of beef meat at different temperatures.

Water content (kg water/kg dry matter) Temperature (°C)

30 40 50

0.05 4.03 4.43 4.75

0.1 5.06 6.03 6.63
0.15 6.28 7.29 7.92
0.2 7.23 8.25 8.89
0.25 8.01 9.05 9.71
0.3 8.69 9.75 10.41
0.35 9.31 10.38 11.04
0.4 9.87 10.95 11.61
0.45 10.41 11.49 12.143
Fig. 9. Caurie's linear curves for different temperature values: small squares: 30 °C;
0.5 10.91 11.99 12.64
medium squares: 40 °C; large squares: 50 °C.
1424 T. Ahmat et al. / Meat Science 96 (2014) 1417–1424

content values 0.05 and 0.5 respectively) in the 30 °C–50 °C tempera- Cheftel, J. C., & Cheftel, H. (1977). Introduction à la Biochimie et à la Technologie des
Aliments vol. 1. Collection Technique et Documentation. Paris: Lavoisier (371 pp.).
ture range. These desorption properties are useful for a better manage- Chirife, J., & Iglesias, H. A. (1978). Equations for fitting water sorption isotherms of foods:
ment of beef drying operations: they are basic requirements to achieve Part 1. A review, J Food Technology, 13, 159–174.
appropriate modeling and design of the beef drying processes. Clemente, G., Bon, J., Benedito, J., & Mulet, A. (2009). Desorption isotherms and isosteric
heat of desorption of previously frozen raw pork meat. Meat Science, 82, 413–418.
Comaposada, J., Gou, P., Pakowski, Z., & Arnau, J. (2000). Desorption isotherms for pork
Nomenclature meat at different NaCl contents and temperatures. Drying Technology, 18, 723–746.
A sorption surface (m2/g) de Boer, J. H. (1953). The dynamical character of adsorption. Oxford: Clarendon Press.
Delgado, A. E., & Sun, D. W. (2002). Desorption isotherms for cooked and cured beef and
a Halsey model parameter pork. Journal of Food Engineering, 51, 163–170.
aw water activity Delgado, A. E., & Sun, D. W. (2002). Desorption isotherms and glass transition tempera-
b Halsey model parameter ture for chicken meat. Journal of Food Engineering, 55, 1–8.
Duras, N. H., & Hiver, H. L. (1993). Adsorption of water on cereal-bread type dietary fibers.
C GAB model parameter
Journal of Food Engineering, 20, 17–43.
C′ constant associated with the parameter C of the GAB model Farid, B. C., & Farid, C. (2010). A rapid and novel approach for predicting water sorption
H1 heat of total sorption of the first layer (kJ/kg) isotherms and isosteric heats of different meat types. Meat Science, 86, 921–925.
HL heat of condensation of pure water (kJ/kg) Gal, S. (1983). The need for, and practical applications of sorption data. In R. Jowitt, F.
Escher, B. Hallstrom, W. H. F. Th. Meffert, E. L. Spiess, & G. Vos (Eds.), Physical proper-
Hm heat of total sorption of the multilayers (kJ/kg) ties of foods (pp. 13–25). London: Applied Science Publishers.
K GAB model parameter Guggenheim, E. A. (1966). Application of statistical mechanics. Oxford: Clarendon Press.
K′ constant associated with the parameter K of the GAB model Halsey, G. (1948). Physical adsorption on non-uniform surfaces. Journal of Chemistry and
Physics, 16, 931–937.
Lv pure water vaporization energy (kJ/kg) Heinz, S., & Hautzinger, P. (2007). Meat processing technology for small-to medium scale
ma anhydrous mass (kg) producers. FAO Regional Office for Asia and the Pacific (RAP), Banking.
meq equilibrium mass (kg) Igbeka, J. C., & Blaisdell, J. L. (1982). Moisture isotherms of a processed meat product—
Bologna. Journal of Food Technology, 17, 37–46.
N number of adsorption sites Iglesias, H. A., Chirife, J., & Lombardi, J. L. (1975). An equation for correlating equilibrium
P percent deviation (%) moisture content in foods. Food Technology, 10, 289–294.
Qs isosteric heat of sorption (kJ/kg) Kabil, E., Aktaş, N., & Balcı, E. (2012). Effect of sodium chloride, sodium nitrite and temper-
ature on desorption isotherms of previously frozen beef. Meat Science, 90, 932–938.
Qsn net isosteric heat of sorption (kJ/kg) Kalilou, S., Collignan, A., & Zakhia, N. (1998). Optimizing the traditional processing of beef
rc critical radius (m) into kilishi. Meat Science, 50, 21–32.
r2 correlation coefficient Kalilou, S., & Zakhia, N. (1997). Fabrication artisanale du kilishi au Niger: Optimisation du
procédé et amélioration de la qualite du produit. Séchage des produits à haute teneur
R universal gas constant (8314 kJ/kmol K)
en eau en Afrique Francophone, 21–24 avril 1997. Burkina Faso: CTA/ABAC GERES/TPA,
R* equilibrium moisture content residual Ouagadougou (12 pp.).
Rp pore radius (m) Kapsalis, J. G. (1981). Moisture sorption hysteresis. In L. B. Rockland, & G. F. Stewart (Eds.),
S sum of quadratic errors Water activity: Influences on food quality (pp. 143–178). New York: Academic Press.
Labuza, T. P., Kaanane, A., & Chen, J. Y. (1985). Effect of temperature on the moisture sorp-
t multilayer thickness (m) tion isotherms and water activity shift of two dehydrated foods. Journal of Food
T temperature (°C or K) Science, 50, 385–391.
VM molal volume of sorbate (m3·mol−1) Laurent, C. (1981). Conservation des Produits d'origine Animate en Pays Chauds. Paris: ACCT
(157 pp.).
W equilibrium moisture content (kg water/kg dry matter) Lomauro, C. J., Bakshi, A. S., & Labuza, T. P. (1985). Evaluation of food moisture sorption iso-
W0 monolayer moisture content (kg water/kg dry matter) therm equations. Part I. Fruit, vegetable and meat products. Lebensm-Wiss-Technol, 18,
W′0 constant associated with the parameter W0 of the GAB model 111–117.
Mulet, A., Garcia-Reverter, J., Sanjuan, R., & Bon, J. (1999). Sorption isosteric heat determi-
Wexp experimental equilibrium moisture content (kg water/kg dry nation by thermal analysis and sorption isotherms. Journal of Food Science, 64, 64–68.
matter) Ockerman, H. W. (1985). Quality control of post-mortem muscle tissue. Ohio: Department
Wmod modeled equilibrium moisture content (kg water/kg dry of Animal Science, The Ohio State University and The Ohio Agricultural Research
and Development Center.
matter) Rizvi, S. S. H. (1986). Thermodynamic properties of foods in dehydration. In M.A. Rao, & S.
σ surface tension (Nm−1) S. H. Rizvi (Eds.), Engineering properties of foods (pp. 133–214). New York: Marcel
ΔH partial molar enthalpy of sorption (kJ/kg) Dekker.
Shimokomaki, M., France, B.D.G. M., & Carvalho, B. C., Jr. (1987). Charque e produtos afins:
tecnologia e conservacao. UMA Revisao, Bol. SBCTA, Campinas, 21. (pp. 25–35). 1,
25–35.
Acknowledgments Singh, R. R. B., Rao, K. H., Anjaneyulu, A. S. R., & Patil, G. R. (2001). Moisture sorption prop-
erties of smoked chicken sausages from spent hen meat. Food Research International,
34, 143–148.
The authors wish to acknowledge the Islamic Development Bank Singh, R. R. B., Rao, K. H., Anjaneyulu, A. S. R., & Patil, G. R. (2006). Water desorption char-
(IDB) for its financial support. acteristics of raw goat meat: Effect of temperature. Journal of Food Engineering, 75,
228–236.
Spiess, W. E. L., & Wolf, W. (1987). Critical evaluation of methods to determine moisture
References sorption isotherms. Water activity: Theory and applications in Food (pp. 215–233).
New York: Academic Press.
Aktas, N., & Gürses, A. (2005). Moisture adsorption properties and adsorption isosteric Strumillo, C., & Kudra, T. (1986). Drying: Principles, applications and design. In R. Hughes
heat of dehydrated slices of pastirma (Turkish dry meat product). Meat Science, 71, (Ed.), Topics in chemical engineering, Vol. 3. (pp. 3–36). New York: Gordon and Breach
571–576. Science Publishers.
Al-muhtaseb, A. H., Mc Minn, W. A.M., & Magee, T. R. A. (2002). Moisture sorption isotherm Talla, A., Jannot, Y., Nkeng, G., & Puiggali, J. -R. (2005). Desorption isotherms of tropical
characteristic of food products. A reviewInstitution of Chemical Engineers, Trans IChemE, foodstuff. Application to banana, mango and pineapple. Drying Technology, 23,
Vol 80. (pp. 118–128), 118–128 Part C. 1477–1498.
Anderson, R. B. (1946). Modification of the B.E.T. equation. Journal of the American Timmermann, E. O., Chirife, J., & Iglesias, H. A. (2001). Water sorption isotherms of food
Chemical Society, 68, 686–691. and foodstuffs: BET or GAB parameters? Journal of Food Engineering, 48, 19–31.
AOAC (1997). Official method of analysis of the Association of Official Analytical Chemists Torres, E. A. F. S., Shimokomaki, M., France, B.D.G. M., Landgraf, M., Carvalho, B. C., Jr., &
International. Washington, DC: Association of Official Analytical Chemists. Santos, J. C. (1994). Parameters determining the quality of charqui, an intermediate
Bizot, H., & Multon, J. L. (1978). Méthode de référence pour la mesure de l'activité de l'eau moisture meat product. Meat Science, 38, l6.
dans les produits alimentaires. Analles de Technologie Agricole, 27(2), 441–449. Trujillo, F. T., Pei, C. Y., & Tuan Pham, Q. (2003). Moisture sorption isotherm of fresh lean
Brunauer, S., Deming, L. S., Deming, W. E., & Teller, E. (1940). On a theory of the Van der beef and external beef fat. Journal of Food Engineering, 60, 357–366.
Walls adsorption of gases. Journal of the American Chemical Society, 62, 1723–1732. Van den Berg, C., & Bruin, S. (1981). Water activity and its estimation in food systems. In L.
Brunauer, S., Emmet, P. H., & Teller, E. (1938). Adsorption of gases in multimolecular B. Rockland, & G. F. Stewart (Eds.), Water activity: Influences on food quality
layers. Journal of the American Chemical Society, 60, 309–319. (pp. 147–177). NewYork, USA: Academic Press.
Caurie, M. (1981). Derivation of full range moisture sorption isotherms. In L. B. Rockland, Wolf, W., Spiess, W. E. L., & Jung, G. (1985). Standardization of isotherm measurements
& G. F. Stewart (Eds.), Water activity: influences on food quality (pp. 63–87). New (COST-Project 90 and 90 bis). In D. Simatos, & J. L. Multon (Eds.), Properties of water
York: Academic Press. in foods (pp. 661–677). Dordrecht: Martinus Nijhoff.