Journal of Food Engineering 77 (2006) 194–199

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Research note

Water adsorption isotherms of texturized soy protein

A.S. Cassini a, L.D.F. Marczak a,*
, C.P.Z. Noreña b

a
Chemical Engineering Department, Federal University of Rio Grande do Sul (UFRGS), Rua Luis Englert, s/n.
Campus Central, ZIP: 90040-000 Porto Alegre, RS, Brazil
b
Institute of Food Science and Technology, Federal University of Rio Grande do Sul (UFRGS), Av. Bento Gonçalves,
9500. Campus do Vale, ZIP: 91540-000 Porto Alegre, RS, Brazil

Received 6 June 2004; received in revised form 12 May 2005; accepted 24 May 2005
Available online 9 August 2005

Abstract

Texturized soy proteins (TSP) have been used for many years as a substitute of animal protein. In recent times, TSP was used as a
functional ingredient in several food applications; its process involves a drying step. The water adsorption isotherms of TSP were
determined using the static method of saturated salt solutions at 10, 20, 30 and 40 C. The experimental data were fitted to Oswin,
Halsey, BET, GAB, Peleg and Darcy Watt models. The equilibrium moisture content at water activities up to 0.9 decreased as the
temperature was increased from 20 to 40 C. At higher water activities, the moisture content showed an inverse behavior, resulting a
crossover of the isotherms. The GAB and Peleg equation showed the best fit for the experimental curves. The total heat of sorption
of TSP increased with decreased moisture content.
 2005 Elsevier Ltd. All rights reserved.

Keywords: Texturized soy protein; Sorption isotherms; Water activity

1. Introduction At the present time, the use of TSP as meat replacer

Proteins are essential components of cells and biolog-
ical processes. They are involved in regulatory functions
and controlling intra and extracellular conditions.
Around 1950, the nutritional importance of protein
and the high content of this nutrient in the soybean (soy-
bean contains about 40% of vegetable protein) were
emphasized. On these grands, the food industry started
production of a defatted soybean flour designed for hu-
man feed. This production has increased and, nowadays,
millions of tons of defatted meal are produced world-
wide (Bunge, 2001). Given their high applicability in
the food industry, this product was processed further
into texturized, concentrated and isolated soy protein.
*
Corresponding author. Tel.: +55 51 33163304; fax: +55 51
33163277.
E-mail address: ligia@enq.ufrgs.br (L.D.F. Marczak).
in meat processed products is very common. Studies
proving the relationship of soy protein consumption to
cholesterol reduction and prevention of heart diseases
have raised the interest of the whole food industry to de-
velop soy-based products. The range of new soy protein
applications increased as well: nutritional bars, bever-
ages, cereals, biscuits, sauces, chocolates and snacks
are some examples.
The main functions of TSP in a food product may in-
clude: increase water and protein content, reduce prod-
uct cost, enhance product texture and hardness and
replace a portion of the meat to keep the original protein
content.
In the production of TSP, one of the principal steps is
the drying process, which is necessary to decrease product
moisture content until the required level. The objective of
dehydration in foods is to inhibit degradation caused
by growth of bacteria, yeasts and molds. Moreover,

0260-8774/$ - see front matter  2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2005.05.059
 A.S. Cassini et al. / Journal of Food Engineering 77 (2006) 194–199 195

undesirable biochemical reactions—which are also Table 1

responsible for reduction of product shelf life—are mini- Models for fitting the adsorption isotherms of TSP
mized by drying. Inhibition of microbiological activity is Model
achieved for water activity (aw) lower than 0.7. Depend-  B
aw
Oswin X eq ¼ A ð1Þ
ing on the product, this value means moisture (wet basis) 1  aw
between 5 and 25% (Geankoplis, 1993). !
The sorption isotherms describe the relationship be- A
Halsey aw ¼ exp ð2Þ
tween water activity (aw) and the equilibrium moisture X Beq
content of a given food at constant temperature. Indus-
try has great interest in sorption isotherms determina- ðX m Caw Þð1  ðN þ 1ÞaNw NawNþ1 Þ
tion because they provide data about the shelf life BET X eq ¼ ð3Þ
ð1  aw Þð1  ðC  1Þaw  CaNþ1w Þ
stability of a product. Beyond that, it is used in drying
to determine the final moisture. This moisture combines X m CKaw
microbiological and biochemical stability with the best GAB X eq ¼ ð4Þ
ð1  K aw Þð1  Kaw þ CKaw Þ
drying cost (McLaughlin & Magee, 1998). In addition,
isotherms give significant information to other process
steps, as packaging and storage. Peleg X eq ¼ k 1 anw1 þ k 2 anw2 ð5Þ
The use of TSP as a functional ingredient is novel and
K 1 K 2 aw K 3 K 4 aw
very few sorption data are available in literature. There- DÕarcy Watt X eq ¼ þ K 5 aw þ ð6Þ
1 þ K 1 aw 1  K 3 aw
fore, the objective of this study was to determine the
sorption isotherms of the texturized soy protein at the
temperatures of 10, 20, 30 and 40 C. The total heat of
sorption and the water surface area of TSP were also
determined.
The sorption isotherms of a given food can also be
used in the estimation of other important parameters
2. Theoretical considerations of this food: the monolayer moisture content (Xm), the
total heat of sorption (Qst) and the water surface area
Food products have a very complex composition and (S0).
theoretical predictions are not accurate. For this reason, The monolayer moisture content (Xm) is an impor-
sorption isotherms at different temperatures should be tant parameter to define physical and chemical stability
determined experimentally. of foods, since it has a direct influence on lipid oxida-
Several researches—including Ajibola, 1986; tion, enzyme activity, non-enzymatic browning, flavor
Alhamdan and Hassan, 1999; Basunia and Abe, 2001; preservation and product structure (Menkov, 2000).
Kaymak-Ertekin and Sultanoglu, 2001; Maskan and The heat of sorption (Qs), estimated by the Clausius–
Gögüs, 1997; McLaughlin and Magee, 1998; Menkov, Clapeyron equation, is used to estimate the total energy
2000; Park, Vohnikova, and Brod, 2002; Sandoval and demand during drying. The heat of sorption is a mea-
Barreiro, 2002; Saravacos, Tsiourvas, and Tsami, sure of the binding energy of absorbed water by the solid
1986; Shivahare, Arora, Ahmed, and Raghavan, 2004; materials (McLaughlin & Magee, 1998). The moisture
Tsami, Marinos-Kouris, and Maroulis, 1990—have re- content at which the total heat of sorption approaches
ported sorption data for many different food products, the heat of vaporization of pure water is often taken
but sorption isotherms of TSP are not available in as an indication of ÔboundÕ water in the foodstuff
literature. (Kaymak-Ertekin & Sultanoglu, 2001). At higher mois-
In the present study, the experimental data obtained ture contents, water is available for utilization by micro-
were fitted by two two-parameter equations, Halsey organisms as it is mechanically free in the void spaces of
(Park et al., 2002) and Oswin (Kaymak-Ertekin & the system (Fasina & Sokhansanj, 1993).
Sultanoglu, 2001), two three-parameter equations, As mentioned earlier the ‘‘net’’ isosteric heat of sorp-
BET (Park et al., 2002) and GAB (Heldman & Hartel, tion is obtained using the equation of Clausius–
2000), one four-parameter equation, Peleg, 1993, and Clapeyron,
one five-parameter equation, DÕarcy Watt (Saravacos dðln aw Þ Q
et al., 1986). Table 1 shows each model used for fitting ¼ S ð7Þ
dð1=T Þ RG
experimental curves, where Xeq and Xm are, respectively,
the equilibrium and the monolayer moisture content, in where T is the absolute temperature and RG is the uni-
kg water/kg db, aw is the water activity, in kg water/kg versal gas constant (RG = 8.319 kJ/mol K).
dry air and A, B, C, K, k1, k2, K1, K2, K3, K4, K5, N, n1 The total heat of sorption (Qst) is the sum of the
and n2 are constants of the models listed. ‘‘net’’ isosteric heat of sorption and the heat of vapori-
196 A.S. Cassini et al. / Journal of Food Engineering 77 (2006) 194–199

zation of pure water (DH0, assumed constant with tem-
perature and equal to 44.09 kJ/mol).
Qst ¼ Qs þ DH 0
The water surface area of the product (S0), given in
m2/g of solid, can be determined from monolayer mois-
ture content data and can be measured by assuming the
area of a water molecule to be 10.6 Å2, using the follow-
ing equation
1 moisture contents.
S0 ¼ X m N 0 AH2 O ¼ 3.5  103 X m ;
PMH2 O
where PMH2O is the molecular weight of water (18
g/mol), N0 is the number of Avogadro (6 · 1023 mole-
cules/mol) and AH2O is the area of a water molecule
(10.6 · 1020 m2) (Labuza, 1968).
S0 is associated with amount quantity of polymers
presents in the foodstuff (Labuza, 1968).
3. Materials and methods
The TSP used in this study were obtained from com-
mercial samples (The Solae Company Ind. e Com. de
Alimentos LTDA – Esteio, RS, Brasil). The initial mois-
ture content of the samples was about 6% (w.b.). The
samples used have the following composition: 50%
protein, 20% sugars, 0% fat, 20% fibers and 4% ashes
(Central Lab, The Solae Company).
Equilibrium moisture content curves versus water
activity at 10, 20, 30 and 40 C were obtained through
the standard gravimetric method recommended by the
COST 90 Project (Spiess & Wolf, 1983) using 10 satu-
rated salt solutions–sodium hydroxide, lithium chloride,
potassium acetate, magnesium chloride, potassium car-
bonate, potassium nitrite, sodium chloride, potassium
chloride, barium chloride and copper sulfate–with rela-
tive humidity ranging from 7 to 97%.
Two samples of about 5 g of TSP were placed on a
tripod above the saturated salt solution in each of 10
hygrostats (glass jars, 400 mL). These jars were placed
inside an air-circulating thermally-insulated tempera-
ture-controlled equipment maintained at the specified
temperature within ±0.1 C, until equilibrium had been
reached (about 20 days). To prevent microbial spoilage
The coefficient determination (R2) and the mean rela-
tive deviation modulus (MRD) were used to evaluate
ð8Þ the goodness of fit. The MRD value is given in percent-
age and may be estimated as follow:
100 X
N
jV EXP;i  V CALC;i j
MRDð%Þ ¼ ; ð10Þ
N i¼1 V EXP;i
where N is the number of experimental points and
VEXP,i and VCALC,i are the experimental and calculated
ð9Þ
A good fit must show MRD values below 10% (Park
et al., 2002).
4. Results and discussion
Fig. 1 shows the experimental curves obtained relat-
ing the equilibrium moisture content of TSP with its
water activities for all the studied temperatures. The
equilibrium moisture content at each aw represents the
mean value of tree replications.
This figure shows that, for a constant temperature,
the equilibrium moisture content of the product in-
creases with aw.
In addition, the curves of Fig. 1 were very close (prac-
tically coincident), mainly for low values of aw. This
indicates a low influence of temperature (between 10
and 40 C) in the isotherms of TSP. Sandoval and
Barreiro (2002) found a similar behavior for non-
fermented cocoa beans at 25, 30 and 35 C.
Table 2 shows the fitting constants of the models
(presented in Table 1), the correlation coefficient and
the mean relative deviation modulus.
All models presented correlation coefficients very
close to unity indicating good fit to experimental data.
However, considering the MRD index, fewer models
were fit satisfactorily.
The best fit was obtained by the models of GAB and
Peleg. The first presented the lowest MRD value for the
0.8
0.7
T = 10 ºC
Xeq (kg water/kg db)

0.6
of samples, crystalline tymol was placed in the hygro- T = 20 ºC
0.5
stats where high water activities occurred (aw > 0.7) T = 30 ºC
(Wolf, Spiess, & Jung, 1985). 0.4
T = 40 ºC
After the equilibrium had been reached, the samples 0.3
were dried using the oven method at 105 C for 24 h 0.2
(AOAC, 1990). 0.1
The fitting of selected models to experimental data was
0
carried out with a non-linear estimation software (Statis- 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
aw
tica Õ98 Edition). Regressions were repeated with various
initial estimated values above and below those calculated Fig. 1. Sorption data of TSP in the temperatures of 10, 20, 30 and
to confirm that convergence was reliable (Peleg, 1993). 40 C.
 A.S. Cassini et al. / Journal of Food Engineering 77 (2006) 194–199 197

Table 2 0.8
Results obtained from the fit of the experimental curves to the selected
0.7 T = 20 ºC (exp)
models
0.6

Xeq (kg water/kgdb)

Model Cts Temperatures T = 20 ºC (GAB)
10 C 20 C 30 C 40 C 0.5
0.4 T = 40 ºC (exp)
Oswin A 0.125 0.122 0.102 0.087
B 0.378 0.461 0.558 0.666 0.3 T = 40 ºC (GAB)
R2 0.971 0.990 0.998 0.999
MRD 23.63 15.14 11.09 16.18 0.2
0.1
Halsey A 0.020 0.024 0.031 0.024
B 1.490 1.437 1.271 1.386 0
R2 0.991 0.997 0.998 0.998 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
MRD 15.46 11.62 6.24 10.19 aw

BET Xm 0.075 0.072 0.062 0.062 Fig. 2. Fitting of the experimental data to the GAB model.
C 1.020 1.055 1.094 1.123
N 11.382 12.008 11.967 9.899
R2 0.987 0.990 0.995 0.994 (the higher the temperature, the higher the dissolution
MRD 29.73 31.93 30.60 32.44 and the higher the equilibrium moisture content)
GAB Xm 0.074 0.064 0.055 0.047 (Maskan & Gögüs, 1997).
C 5.839 10.588 8.955 30.828 Different studies reported isotherm crossover for var-
K 0.874 0.922 0.950 0.976 ious types of sugars-rich foods. Tsami et al. (1990) deter-
R2 0.995 0.998 >0.999 >0.999
mined the sorption isotherms of some dried fruits
MRD 14.70 10.61 7.99 4.02
between 15 and 60 C. The authors found that the high-
Peleg k1 0.454 0.590 0.710 0.980 er the sugars content, the lower the crossover aw. Thus,
k2 0.075 0.128 0.175 0.180
n1 4.660 7.264 10.698 13.689
since the sugars content of TSP is about 20% (with a
n2 0.191 0.490 0.861 0.830 moisture content of 0.07 kg water/kg db), the crossing
R2 >0.999 0.999 0.999 0.998 of the isotherms in a high value of aw (around 0.9) were
MRD 2.18 7.58 13.45 13.27 expected.
DÕarcy Watt K1 0.127 1.004 0.046 0.045 As stated earlier, GAB and Peleg models presented
K2 385.601 0.121 127.452 135.931 the best fit to experimental curves of TSP between 10
K3 0.263 1.008 0.917 0.960 and 40 C. The GAB model, however, is the only one
K4 76.463 0.088 0.101 0.068
that predicts the isotherm crossover and, therefore, it
K5 29.133 0.141 6.079 6.256
R2 0.999 0.997 0.999 0.999 is concluded that GAB is the best model to predict the
MRD 8.33 17.93 12.46 11.56 sorption isotherms for this type of TSP in this tempera-
ture range.
The values of monolayer moisture content of TSP
estimated with GAB model at 10, 20, 30 and 40 C
higher temperatures (30 and 40 C) and the second, for can also be observed in Table 2. TSP presented a mono-
the lower (10 and 20 C). layer moisture content of 7.4% (db) at the temperature
Furthermore, the Halsey model was also accurate at of 10 C and this value decreased with increasing tem-
high temperatures. Iglesias and Chirife (1976) indicated perature. Similar results were found by McLaughlin
the good fit of this model to the isotherms of high pro- and Magee (1998) for potatoes. Monolayer values ob-
tein foods. tained here are in the acceptable range for food prod-
The fitting of BET model to experimental data gener- ucts. Labuza (1984) indicated 10% (db) as the
ated the most elevated MRD values (above 30%) and maximum monolayer moisture content for foods.
the minor correlation coefficients; this occurs, probably, Fig. 3 shows that total heat of sorption decreases for
because the use of BET model is indicated only in the fit- increasing moisture content of TSP; this fact agrees with
ting of water activities data until 0.5. observations by many researchers (Fasina &
The fitting of GAB model to experimental data at 20 Sokhansanj, 1993), since the lower the moisture content,
and 40 C are presented in Fig. 2. A little difference be- the higher the energy required to remove water from the
tween the two curves, mainly for water activities above product.
0.5, was observed. Furthermore, a crossover of these The analysis of Fig. 3 also demonstrates that total
curves can be seen at an aw value around 0.9. heat of sorption of TSP reaches the heat of vaporization
This phenomenon is characteristic of sugar rich of pure water at a moisture content about 28% (db).
foods. Labuza (1984) found that isotherm inversion is Table 3 presents the water surface area of TSP be-
caused by microbial growth and/or the sugar dissolution tween 10 and 40 C; it was estimated using Eq. (9) and
198 A.S. Cassini et al. / Journal of Food Engineering 77 (2006) 194–199

51 Acknowledgements
50
49 The authors gratefully acknowledge Solae do Brasil
48
Ind. e Com. de Alimentos LTDA. (Esteio, RS, Brasil)
for providing the products and equipment necessary
Qst (kJ/mol)

47
for this study.
46
The authors also acknowledge Capes for providing
45 financial support.
44
43
42
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