ARTICLE IN PRESS

Biosystems Engineering (2004) 87 (2), 179–190 Available online at www.sciencedirect.com

doi:10.1016/j.biosystemseng.2003.11.006
PH}Postharvest Technology

Sorption Equilibrium and Thermodynamic Characteristics of Soya Bean

N.A. Aviara1; O.O. Ajibola2; S.A. Oni2
1
Department of Agricultural Engineering, University of Maiduguri, Maiduguri, Nigeria; e-mail of corresponding author:
nddyaviara@yahoo.com
2
Department of Agricultural Engineering, Obafemi Awolowo University, Ile-Ife, Nigeria; e-mail: femiajibola@yahoo.com

(Received 2 June 2003; accepted in revised form 19 November 2003; published online 10 January 2004)

Desorption equilibrium moisture content and water activity data for soya bean (Glycine max) TGX 1440-1E
were determined using the static gravimetric method. Measurements were taken in the water activity range of
0
07–0
98 at four temperatures (40, 50, 60 and 708C). A non-linear regression programme was used to fit five
moisture sorption isotherm models [modified Henderson, modified Chung–Pfost, modified Halsey, modified
Oswin and modified Guggenheim–Anderson–de Boer (GAB)] to the experimental data. The models were
compared using the standard error of estimate, mean relative percent deviation and residual plots. The
modified Oswin model, which gave the least standard error of 1
91% and least mean relative percent deviation
of 10
15 among the five models, when equilibrium moisture content was taken as the dependent variable, was
considered to be the best for predicting the equilibrium moisture content of soya bean. The moisture sorption
isotherms of soya bean were sigmoidal in shape, of the type II and were markedly affected by temperature. The
modified Halsey model, which gave the least standard error of 0
07 and least means relative percent deviation
of 16
67, when water activity was taken as the dependent variable, was considered the best for predicting the
water activity of soya bean.
The desorption equilibrium moisture content and water activity relationships as expressed by the moisture
sorption isotherm models that best predicted the experimental data, were used to determine the
thermodynamic characteristics of soya bean. The heat of vaporisation of moisture in soya bean decreased
with increase in moisture content and approached the latent heat of pure water at a free water point of
between 20 and 22% moisture content (d.b.). The surface potential of moisture in the seed increased with
increase in water activity, but was not significantly affected by temperature. Net integral enthalpy decreased
from a value of 550 J g1 as the moisture content increased from 5
20% (d.b.). The trend became asymptotic at
a value of 80 J g1 as the moisture content of 13% (d.b.) was approached. Net integral entropy decreased with
increase in moisture content to a minimum value of –0
38 J g1 K1 at the moisture content of 11% (d.b.), and
thereafter, increased with further increase in moisture content.
# 2003 Silsoe Research Institute. All rights reserved
Published by Elsevier Ltd

1. Introduction efficient processing and storage of soya bean requires

Soya bean (Glycine max) is a highly nutritious seed
which functions both as an oil seed as well as a
proteineous seed. Its oil and protein contents range
between 13
5 and 24
2% and 29
6 and 50
3% respec-
tively (Weiss, 1983). The seed of soya bean variety TGX
1440-1E contains about 17
5% by weight of oil, 37
8%
protein, 32% carbohydrate, 9
57% fibre and 5
6% ash
and its flour, with or without oil removal, provides a
basic material for a wide range of protein foods. The
1537-5110/$30.00
that the moisture content be reduced to appropriate
levels by drying. Proper modelling and optimisation of
the drying process require a knowledge of the equili-
brium moisture content and water activity relationships
at different temperatures, the energy requirements as
well as the state and mode of moisture sorption within
the bean seed.
Several methods of determining the moisture sorption
isotherms of agricultural materials have been employed
by researchers (Roman et al., 1982). Gal (1975, 1981,
179 # 2003 Silsoe Research Institute. All rights reserved
Published by Elsevier Ltd
 ARTICLE IN PRESS
180 N.A. AVIARA ET AL.
Notation
a,b coefficients
aw water activity
awm geometric mean water activity
Am area of water molecule ( ¼ 1
06  1019 m2)
A,B,C,
C1,C2 constants
df degree of freedom on regression model
ES standard error of estimate
hfw latent heat of vaporization of free water,
J kg1
hpw heat of vaporisation of water in material,
J kg1
K Boltzmann constant ( ¼ 1
38  1023 J kg1)
M moisture content, d.b.
Mm monolayer moisture content, d.b.
1983) carried out thorough reviews of the methods and
pointed out that there are three basic techniques namely
the manometric, the gravimetric and the special
methods. Labuza et al. (1976) reported that the vapour
pressure manometric method is one of the best methods
as it measures directly the vapour pressure exerted by
moisture in grain kernels. However, the gravimetric
technique has been noted to be preferable for obtaining
complete sorption isotherms (Gal, 1981), and has
been recommended as the standard method (Speiss &
Wolf, 1987).
Equations for fitting the moisture sorption isotherms
are of special importance in many aspects of crop and
food preservation by drying. These include the predic-
tion of drying times, shelf life of the dried product in a
packaging material and equilibrium conditions after
mixing products with varying water activities (Chirife &
Iglesias, 1978). Other applications include the analytical
determination of control for undesirable chemical and
enzymatic reactions (Bone, 1987) and control of
moisture migration in multi-domain foods (Labuza &
Hyman, 2001). Moisture sorption isotherm models,
therefore, constitute an essential component of the
overall drying theory and provide information directly
useful in accurate and optimum design of drying
equipment. They are needed in the analytical determina-
tion of the thermodynamic functions related to moisture
sorption in biological materials (Iglesias et al., 1976).
Investigators have proposed and used several theoreti-
cal, semi-theoretical and empirical models to fit the
equilibrium moisture content data of food and agricul-
tural products. Chirife and Iglesias (1978) reviewed part
of these isotherm equations and presented a discussion
of 23 common models, while Van den Berg and Bruin
(1981) presented a more comprehensive list. However,
N number of data points
P mean relative deviation, %
Po actual water vapour pressure, Pa
Ps saturated water vapour pressure, Pa
Qin net integral enthalpy, J kg1
R gas constant of water vapour
( ¼ 0
462 kJ kg1)
Sin net integral entropy, J g1 K1
t temperature, 8C
T absolute temperature, K
Y measured value of quantity
Y0 value of quantity predicted by model
F surface potential, J m2
y moisture ratio
the five moisture sorption isotherm models (modified
Henderson, modified Chung–Pfost, modified Halsey,
modified Oswin and the Guggenheim–Anderson–de
Boer (GAB)) given in Table 1 have been found the
most commonly used equations. The modified Hender-
son (Thompson, 1972) and modified Chung–Pfost (Pfost
et al., 1976) equations have been adopted as the
standard models by the American Society of Agricultur-
al Engineers (ASAE) for the description of the
equilibrium moisture content–water activity data of
cereals and oil seeds (ASAE, 1996). The modified Halsey
model (Iglesias & Chirife, 1976) has been reported as the
best model for expressing the equilibrium moisture
content and water activity relationships of several
tropical crops (Ajibola, 2000) and alongside with the
modified Oswin model (Chen & Morey, 1989) has been
shown to describe the equilibrium moisture content and
water activity data of many seeds satisfactorily (Mazza
& Jayas, 1991; Jayas & Mazza, 1991). The GAB model
has been recognised as the most satisfactory theoretical
isotherm equation (Van den Berg, 1984; Weisser, 1985;
Wolf et al., 1985; Multon, 1988) and has been
recommended as the standard model for use in food
laboratories in Europe (Wolf et al., 1985) and the USA
(Lomauro et al., 1985). The GAB does not incorporate a
temperature term; therefore, the determination of the
effect of temperature using the model usually involves
the evaluation of up to six constants. Jayas and Mazza
(1993), however, developed a modified GAB model,
which incorporates the effect of temperature.
The behaviour of water and the energy requirements
of heat and mass transfer in biological systems can be
studied using the thermodynamic approach (Rizvi &
Benado, 1984). The properties involved, relate the
concentration of water in food to its partial pressure,
 ARTICLE IN PRESS
CHARACTERISTICS OF SOYA BEAN 181

Table 1
Five commonly used moisture sorption isotherm models
Name of model Equilibrium moisture content model Water activity model
h i1=C
Modified Henderson aw  1  exp½AðT þ BÞM C 
M  lnð1a
AðTþBÞ
wÞ

h i h i
Modified Chung–Pfost M  1 ðTþBÞ A
C ln  A ln aw aw  exp ðTþBÞ expðCMÞ
h i1=C
Modified Halsey ln aw aw  exp½expðA þ BTÞM C 
M  expðAþBTÞ
Modified Oswin h i1=C 1
aw aw  h iC
M  ðA þ BTÞ 1a ðAþBTÞ
w
M þ1
C    h  2  i1=2
Modified GAB AB T aw C A C A C
M  C   2þT M 1  2þT M 1 4 1T
ð1Baw Þ 1Baw þ T Baw aw   C
2B 1T

M, moisture content, % (d.b.); aw, water activity (decimal); T, absolute temperature, K; A,B and C, constants specific to
individual equations.

which is crucial in the analysis of heat and mass
transport phenomena in drying and determine the end
point to which food must be dehydrated in order to
achieve a stable product with optimal moisture content.
They also yield a figure for the theoretical minimum
amount of energy required to remove a given quantity of
water from food and provide insight into the micro-
structure associated with the food as well as the
theoretical interpretation of physical phenomena occur-
ring at the food–water interface (Rizvi, 1986). Thermo-
dynamic functions are readily calculated from moisture
sorption isotherms and this enables the thermodynamic
approach to allow the interpretation of experimental
results in accordance with the statement of theory
(Iglesias et al., 1976). The functions include heat of
vaporisation, free energy, integral enthalpy and integral
entropy, each of which has been defined by Aviara et al.
(2002).
Fish (1958) studied the thermodynamics of water in
potato starch gel and noted that starch at very high
moisture content is thermodynamically similar to pure
water. Iglesias et al. (1976) studied the thermodynamics
of water vapour sorption by sugar beet root and
advanced hypotheses, which were mainly concerned
with configurational modification of the adsorbents
during the course of sorption, to explain the values
and trends observed. Viollaz and Rovedo (1999)
determined the equilibrium moisture sorption isotherms
of starch and gluten and proposed a new method of
calculating the isosteric heat at different temperatures.
Fasina and Sokhansanj (1993) and Fasina et al. (1997,
1999) calculated the thermodynamic functions of
moisture sorption in alfalfa pellets, winged bean seed
and gari, respectively, from their moisture sorption
isotherms. Aviara and Ajibola (2000) studied the
thermodynamics of moisture sorption in plantain and
noted that the ripening of the fruit has a significant effect
on its thermodynamic properties. In a similar study,
Aviara and Ajibola (2002) found differences in the
values and trends of the thermodynamic properties of
melon seed and cassava, and attributed the differences to
chemical adsorption, structural modification of the
adsorbent, presence of oil and more polar groups in
melon seed and presence of starch in cassava.
The main aim of this study was to establish the
equilibrium moisture content and water activity data for
soya bean TGX 1440-1E. Other objectives include the
evaluation of the ability of five commonly used moisture
sorption isotherm models to fit the experimental data
and the determination of the thermodynamic functions
in relation to moisture sorption in the seed.
2. Materials and methods
2.1. Material preparation
The soya bean variety TGX 1440-1E developed at the
International Institute of Tropical Agriculture (IITA),
Ibadan, which was used in this study, was purchased at a
centre in Ile-Ife, Nigeria. The dry seeds were cleaned and
rewetted to a higher moisture content using the method
of Ezeike (1986). This involved the soaking of bulk
quantity of the seeds in clean water for a given number
of hours depending on the initial moisture level and the
final moisture content desired. The soya bean seeds at an
initial moisture content of 7
17% [dry basis (d.b.)], were
soaked in water for a period of four and half hours to
achieve the desired moisture content of up to 38%
(d.b.). At the end of soaking, the seeds were spread out
in thin layer to dry in natural air for about 8 h. They
were then sealed in polyethylene bags and stored in that
condition for a further 24 h. This enabled a stable
and uniform moisture content to be achieved. The
 ARTICLE IN PRESS
182 N.A. AVIARA ET AL.
polyethylene bags were transferred into a refrigerator at
08C and when needed for experiments, the seeds were
allowed to equilibrate in the ambient condition for six
hours.
2.2. Equilibrium moisture content determination
The desorption equilibrium moisture contents of soya
bean seed were determined at the temperatures of 40, 50,
60 and 708C over a water activity range of 0
07–0
98,
using the static gravimetric technique. Duplicate sam-
ples of seed at a moisture content of 38% (d.b.) each
weighing about 10 g were placed in specimen baskets
and placed inside glass desiccators. Saturated solutions
of sodium hydroxide, lithium chloride, calcium chloride,
magnesium chloride, manganese chloride, sodium ni-
trite, sodium nitrate, potassium chloride, barium chlor-
ide and potassium sulphate were used to maintain
constant atmosphere of relative humidity in the desic-
cators. Excess salt was maintained in each solution. The
desiccators containing salt solutions and samples of seed
were placed inside temperature controlled Gallenkamp
DV 400 ovens, which were set at 40, 50, 60 and 708C.
The oven temperatures were monitored to within
Mayhew (1981) or calculated using the psychometric
relationships in ASAE (1996). The vapour pressure of
moisture in the material can be determined using the
equation
Po ¼ aw Ps ð2Þ
The values of water activity aw can be obtained with the
moisture sorption isotherm model, which best describes
the equilibrium moisture content water activity relation-
ships of the product. A plot of ln(Po) versus ln(Ps) yields
the ratio of the heat of vaporisation of moisture in the
material to the latent heat of saturated water vapour
from the slope of the straight line obtained.
2.3.2. Net integral enthalpy and entropy
Net integral enthalpy indicates the binding strength of
water molecules to food particles and could be a
measure of the food–water affinity. The equation for
calculating net integral enthalpy has been derived from
the first law of thermodynamics following the procedure
of Rizvi (1986) as:



½@ðln aw Þ Qin
    ð3Þ
1  R
@ 
1
08C. T F
The samples were weighed daily using a Mettler PC where: Qin is the net integral enthalpy in J kg1; R is the
2000 electronic balance with an accuracy of 0
001 g. gas constant of water vapour in J kg1; T is the absolute
Equilibrium was considered to have been attained when temperature in K; and F is the surface potential
three identical consecutive measurements were obtained. (spreading pressure) in J m2. A plot of ln(aw) versus 1/
The dry matter content was produced by oven drying at T at constant surface potential yields the net integral
1038C for 72 h. The equilibrium moisture content was enthalpy from the slope of the straight line obtained. The
calculated on dry basis from the weight change and dry surface potential, can be calculated using an analytical
matter weight, and the average value at each tempera- procedure similar to the one described by Iglesias et al.
ture and water activity was determined. (1976) and Fasina et al. (1999) from the relationship:
Z
KT aw y
F¼ @aw ð4Þ
2.3. Determination of thermodynamic properties A m 0 aw
where the moisture ratio y is:
2.3.1. Heat of vaporisation
M
The heat of vaporisation of moisture in food and y¼ ð5Þ
agricultural products hpw in J kg1 can be estimated by Mm
applying the Clausius–Clapeyron equation to the sorp- and where: K is the Boltzmann constant; Am is the
tion isotherms. The Clausius–Clapeyron equation as surface area of a water molecule in m2; and M is the
stated by Rizvi (1986) and Kapsalis (1987), after some moisture content, d.b. The monolayer moisture content
mathematical manipulations (Fasina et al., 1999), yields Mm can be obtained by applying the Brunauer, Emmett
the equation and Teller (BET) equation (Brunauer et al., 1938) to the
hpw experimental data on equilibrium moisture relationships
lnðPo Þ ¼ lnðPs Þ þ C1 ð1Þ of the material. The BET equation is stated as
hfw
aw 1 ðC2  1Þaw
where: Po and Ps are actual and saturated water vapour  þ ð6Þ
pressures, respectively, in Pa; hfw is the latent heat of ð1  aw ÞM M m C2 Mm C2
vaporisation of pure water in J kg1; and C1 is a where C2 is a constant.
constant. The saturated water vapour pressure Ps at Entropy change plays an important role in the energy
different temperatures can be obtained from Rogers and and exergy analysis of food processing systems. For a
 ARTICLE IN PRESS
CHARACTERISTICS OF SOYA BEAN
thermodynamic system, the net integral entropy Sin is
given by
Qin
Sin ¼  R lnðawm Þ ð7Þ
T
where awm is the geometric mean water activity obtained
at constant surface potential.
2.4. Data and analysis
2.4.1. Moisture sorption isotherms
The experimental desorption equilibrium moisture
content data of soya bean obtained were fitted to the five
commonly used moisture sorption isotherm models
presented in Table 1, using the non-linear regression
procedure in SPSS 9
0 for Windows, which minimises
the sum of squares of deviations in a series of iterative
steps. All the models are three parameter equations,
which can be solved explicitly for equilibrium moisture
content as a function of temperature and water activity
or for water activity as a function of temperature and
equilibrium moisture content. The non-linear regression
procedure required that initial parameter estimates be
chosen close to the true values. The initial parameter
estimates were obtained by linearisation of the models
through logarithmic transformation and application of
linear regression analysis, or solving a quadratic form of
the equation in the case of the modified GAB model.
The least-squares estimates or coefficients of the terms
were used as the initial parameter estimates in the non-
linear regression procedure. Model parameters were
estimated by first taking the equilibrium moisture
content (EMC) to be the dependent variable, and
secondly, by taking the water activity aw to be the
dependent variable. The goodness of fit of each model
was evaluated using the standard error of estimate
calculated by the procedure; mean relative percent
deviation and residual plots.
The standard error of estimate is denoted by ES and
defined as
sP ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ðY  Y 0 Þ2
ES ¼ ð8Þ
df
The mean relative percent deviation P is defined as
100 X ðY  Y 0 Þ
P¼ ð9Þ
N Y
where: Y is the measured value; Y0 is the value predicted
by model; N is the number of data points; and df is the
degree of freedom on regression model.
The residual plots are plots of residuals (differences
between measured and predicted values) of EMC and aw
against measured values. A model is considered accep-
table if the residuals are uniformly scattered around the
183
horizontal value of zero showing no systematic tendency
towards a clear pattern. A model is considered better
than another if it has a lower standard error and lower
mean relative percent deviation.
2.4.2. Thermodynamic characteristics
The thermodynamic characteristics of soya bean were
analytically determined using the desorption equilibrium
moisture content data as expressed by the moisture
sorption isotherm model that best described its equili-
brium moisture content and water activity relationships.
The model, which was considered the best equation for
predicting the water activity of soya bean, was used to
determine the values of water activity. Values of water
activity were determined at the four temperatures of
40,50, 60 and 70oC, and four moisture levels in the range
of 6–22%. Saturated water vapour pressure was
obtained at each of the above temperatures from Rogers
and Mayhew (1981), and the actual vapour pressure at
each temperature was determined using Eqn (2). The
natural log of actual vapour pressure was plotted
against the natural log of saturated water vapour
pressure at the same temperature. The ln(Po) was
regressed against ln(Ps) to establish the linear relation-
ship existing between them. The ratios of the heat of
vaporisation of moisture in the seed to the latent heat of
saturated water vapour at different moisture contents
were determined from the slopes of the straight lines
obtained. Multiple regression analysis was performed to
determine the relationship existing between ln(Po),
moisture content M and temperature T of the seeds.
The non-linear regression procedure in SPSS 9
0 for
Windows was also used to fit the Gallaher (1951)
equation to the data obtained on the heat of vaporisa-
tion ratio. This equation relates the moisture content of
food and agricultural material to the ratio of the heat of
vaporisation of moisture in the product hpw to the latent
heat of saturated water vapour hfw and can be stated as
follows:
hpw
 1 þ a expðbM Þ ð10Þ
hfw
The values of coefficients a and b were obtained and
the values of hfw =hpw were computed and plotted against
moisture content.
Monolayer moisture content is a crucial parameter in
the determination of the surface potential of moisture
sorbed in food. It has been suggested (Rockland, 1969)
as a satisfactory specification for the lower limit of
moisture in dehydrated food. The monolayer moisture
contents of soya bean at different temperatures were
obtained by applying Eqn (6) to the equilibrium
moisture content data in the water activity range of
0
05–0
45. A plot of aw/[(1aw) M] versus aw yielded a
 ARTICLE IN PRESS
184 N.A. AVIARA ET AL.

straight line with slope and intercept on the Y-axis from Table 2
which Mm was calculated. The surface potentials of Desorption equilibrium moisture contents of soya bean
moisture in the seed at different temperatures were TGX1440-1E at different water activities and temperatures
calculated using Eqn (4). The value of surface potential Temperature, K Water activity Equilibrium moisture
was noted to be indeterminate at the water activity of 0; (decimal) contents, % (d.b.)
therefore, the lower limit of water activity employed was 313 0
07 8
52
0
05. The computed values of surface potential were 0
12 9
24
adjusted by adding the value corresponding to the water 0
22 10
43
activity interval between 0 and 0
05, which was 0
32 13
10
0
51 17
59
calculated by assuming that a linear relationship
0
61 19
04
(Henry’s law) exists between aw and y within the water 0
71 20
57
activity range (Fasina et al., 1999). For the above water 0
82 22
72
activity interval, Eqn (4) becomes 0
89 25
77
0
97 35
11
KTy 323 0
07 6
40
F¼ ð11Þ
Am 0
114 7
85
0
12 8
58
Surface potential was plotted against water activity at 0
314 9
12
various temperatures to establish the surface potential 0
50 10
28
(spreading pressure) isotherms and determine the effect 0
60 12
39
of temperature. The natural log of water activity was 0
70 13
09
0
81 19
44
plotted against the reciprocal of the absolute tempera- 0
89 26
30
ture at constant surface potential, and the net integral 0
96 27
96
enthalpy was determined from the slope of the straight 333 0
07 5
79
line obtained. Net integral enthalpy was then plotted 0
112 6
85
against moisture content. Equation (7) was used to 0
21 8
19
0
31 8
67
determine the net integral entropy of moisture in soya 0
50 9
97
bean during desorption and the values obtained were 0
60 10
45
plotted against moisture content. 0
70 11
53
0
80 16
75
0
88 23
05
0
95 25
98
3. Results and discussion 343 0
07 5
28
0
111 6
49
3.1. Desorption equilibrium moisture content and water 0
02 7
87
activity relationships 0
30 7
90
0
50 9
19
0
60 9
57
The experimental data on the desorption equilibrium 0
70 10
60
moisture content of soya bean at the different conditions 0
80 12
93
considered taken as the average of two readings are 0
88 17
54
presented in Table 2. As expected, the equilibrium 0
94 25
68
moisture content (EMC) increased with increase in
water activity aw at constant temperature and decreased
with increase in temperature at constant water activity.
The data were used to estimate the parameters in both that the parameter estimates obtained for the EMC
the EMC and aw models. Table 3 shows the parameter models were not the same as the corresponding
estimates for the EMC models in which the EMC is parameter estimates for the aw models. Several investi-
taken as the dependent variable, while Table 4 shows the gators (Duggal et al., 1982; Ajibola, 1986a, 1986b,
parameter estimates for water activity models in which 1986c, 1989; Ajibola & Adams, 1986; Ajibola & Dairo,
aw is taken as the dependent variable. These different 1998; Ajibola et al., 2003) have made similar observa-
analyses provide flexibility in that the user can select the tions on other crops. According to Ajibola and Dairo
model and associated parameter values that best suit the (1998), the EMC models were obtained by logarithmic
particular application. The tables also show the indices transformation of the aw models and in the non-linear
used in comparing the models namely the standard error regression analysis, the errors were assumed to be
of estimate, mean relative percent deviation and nature normally and independently distributed. This caused
of residual plots. An examination of the tables shows distortions in the models, thereby causing the
 ARTICLE IN PRESS
CHARACTERISTICS OF SOYA BEAN 185

Table 3
Estimated parameters and comparison criteria for equilibrium moisture content models (EMC) of data for soya bean
Parameter and criteria EMC models
Modified Henderson Modified Chung–Pfost Modified Halsey Modified Oswin Modified GAB
A 6
0  105 188.854 19
204 61
831 6
5246
B 292
367 299
802 0
03652 0
151 0
809
C 2
27 0
1875 3
0836 3
72 577093
9
Es% 2
3 1
96 2
0 1
907 8
622
P 15
75 14
225 12
656 10
145 21
072
Residual plot Random Random Random Random Random
A, B and C, regressions constants; Es, standard error; P, mean relative deviation, %.

Table 4
Estimated parameters and comparison criteria for water activity models of data for soya bean
Parameter and criteria Water activity models
Modified Henderson Modified Chung–Pfost Modified Halsey Modified Oswin Modified GAB
A 1
7714  105 234
945 18
605 72
481 4
02
B 307
802 303
014 0
0387 1
384 1
329
C 3
161 0
23 2
597 3
83 106329
42
Es 0
078 0
091 0
074 0
36 0
216
P 20
25 27
78 16
67 52
04 37
97
Residual plot Random Random Random Patterned Patterned
A,B and C, regressions constants; Es, standard error; P, mean relative deviation %.

corresponding model constants to take on different 40

least-squares values.
Equilibrium moisture content, % (db)

35
Using the residual plot criterion, all the five models
tested were found acceptable for predicting the EMC of 30
soya bean. However, the modified Oswin model, which
gave the least standard error of estimate and least means 25
relative percent deviation, was considered the best 20
model for predicting the equilibrium moisture content.
This was followed closely by the modified Chung–Pfost 15
and modified Halsey models. Pollio et al. (1987) had
10
reported that the Halsey model gave an excellent fit to
the water adsorption isotherms of the soya bean 5
varieties grown in Argentina with only 2
2 relative
percent deviation. For predicting the water activity, 0
0 0.2 0.4 0.6 0.8 1
three of the models namely the modified Henderson, Water activity aw (decimal)
modified Chung–Pfost and modified Halsey were found
acceptable. Out of these three, the modified Halsey Fig. 1. Predicted moisture sorption isotherms of soya bean at
model, which gave the least standard error of estimate various temperatures using the modified Oswin model and
observed data: }&, 40oC; }  ,508C; }*, 608C; }m, 708C
and least means relative percent deviation was consid-
ered the best model for predicting the water activity of
soya bean. The modified Halsey model became the
moisture sorption isotherm equation that was used in
determining the water activity for thermodynamic The desorption equilibrium moisture isotherms
analysis. In terms of the water activity, the modified of soya bean, constructed using the modified
Halsey equation for soya bean can be stated as follows: Oswin model, shown in Fig. 1, are sigmoidal in
shape, of the type II and showed marked effect of
aw  exp½expð18
605 þ 0
0387TÞM 2
597  ð12Þ temperature.
 ARTICLE IN PRESS
186
12
ln [actual water vapour pressure]
10
8 2.5
6 2
4
2 .
0 0
8.8 9 9.2 9.4 9.6 9.8 10 10.2 10.4 10.6
ln [saturated water vapour pressure]
Fig. 2. Log-log plot actual (Po) and saturated (Ps) water
vapour pressure for soya bean at various moisture contents
(d.b.): ^, 6%; &, 10%; m, 16%; &, 22%; }, regression line
3.2. Heat of vaporisation
The plot of ln(Po) versus ln(Ps) for soya bean at
various moisture levels are presented in Fig. 2. The
natural log of the actual vapour pressure ln(Po)
increased linearly with increase in the natural log of
saturated water vapour pressure ln(Ps) and moisture
content. Similar findings were reported for winged bean
seed and gari (Fasina et al., 1999), unripe and ripe
plantain (Aviara & Ajibola, 2000), melon seed and
cassava (Aviara & Ajibola, 2002), sesame seed (Aviara
et al., 2002), cowpea (Ajibola et al., 2003).
The relationship existing between ln(Po) and ln(Ps) at
four moisture contents}6%, 10%, 16% and 22% d.b.,
respectively}can be expressed by the following regres-
sion equations:
lnðPo Þ ¼ 3
9409 lnðPs Þ  32
20
lnðPo Þ ¼ 1
7854 lnðPs Þ  8
60
lnðPo Þ ¼ 1
232 lnðPs Þ  2
54
lnðPo Þ ¼ 1
1005 lnðPs Þ  1
1026
with values for the coefficient of determination of
0
9907, 0
9964, 0
9992 and 0
9998, respectively. The
relationship between ln(Ps), moisture content M and
temperature T can be expressed by the following
polynomial equation:
lnðPs Þ ¼ 5
466 þ 0
627M  7
63  103 MT þ 0
2T
ð17Þ
with a standard error of 1
0113.
A t-test of the coefficients of terms in Eqn (17) showed
that the constant and MT terms are not significant,
N.A. AVIARA ET AL.
4
.
35
Heat of vaporisation ratio
3
1.5
1
05
0
5 10 15 20 25 30 35 40 45
Moisture content, % (db)
Fig. 3. Ratio of heat of vaporisation of moisture in soya bean to
the latent heat of saturated water vapour as a function of
moisture content compared with cowpea, sesame seed, melon
seed and cassava: }^}, cowpea; }&}, sesame; }m},
melon; }  }, soya bean; } }, cassava
while the M and T terms are significant at 5 and 1%
levels, respectively.
The values of coefficients a and b in Eqn (10) obtained
were 19
3715 and 31
466 with standard errors of 3
625
and 2
917, respectively. The standard error of esti-
mate for the latent heat ratio was 0
622. For soya bean,
Eqn (10) therefore becomes
hpw
 1 þ 19
3715 expð31
466M Þ ð18Þ
hfw
The plot of the hpw =hfw for soya bean against moisture
content is shown in Fig. 3. From this figure, it can be
seen that the heat of vaporisation of moisture in soya
bean seed decreased with increase in moisture content
and attained the free water point (Aviara et al., 2002) at
moisture content between 20 and 22% d.b. Figure 3 also
shows that below the moisture content of 10% d.b.; the
ð13Þ
hpw =hfw of soya bean is higher than that of melon seed
(Aviara & Ajibola, 2002) sesame seed (Aviara et al.,
ð14Þ 2002) and cowpea (Ajibola et al., 2003) but lower than
that of cassava (Aviara & Ajibola, 2002). This could be
ð15Þ attributed to differences in the chemical composition
and structural make up of the crops. Starch and protein
ð16Þ contents play a significant role in water adsorption by
kernels and may probably have contributed more to the
differences in heat of vaporisation of moisture among
the crops.
3.3. Monolayer moisture content and surface potential
(spreading pressure) isotherms
The plot of monolayer moisture content of soya
bean as a function of temperature is presented in Fig. 4.
The monolayer moisture content decreased with in-
crease in temperature. The relationship existing
 ARTICLE IN PRESS
CHARACTERISTICS OF SOYA BEAN 187

8 effect of temperature, does not seem to be significant.

Monolayer moisture content, % (db)

Similar response has been reported for winged bean seed

7.5 and gari (Fasina et al., 1999), plantain (Aviara &
Ajibola, 2000) and sesame seed (Aviara et al., 2002).
7

6.5 3.4. Net integral enthalpy and entropy

6 The variation of net integral enthalpy with moisture

content is shown in Fig. 6. Net integral enthalpy of soya
5.5 bean decreased with increase in moisture content from a
value of 550 J g1 at moisture content of 5
2% d.b. The
5 trend became asymptotic at about 80 J g1 as the
30 40 50 60 70 moisture content of 13% d.b. was approached. Similar
Temperature, °C trends have been reported for the enthalpy of sugar beet
Fig. 4. Variation of the monolayer moisture content of soya root, its insoluble fraction and sucrose (Iglesias et al.,
bean with temperature 1976) grain sorghum (Rizvi & Benado, 1983), horse-
radish root (Mazza, 1980), yellow globe onion (Mazza &
Le Maguer, 1978), plantain (Aviara & Ajibola, 2000),
0.45 melon seed (Aviara & Ajibola, 2002), sesame seed
0.4 (Aviara et al., 2002) and cowpea (Ajibola et al., 2003).
Surface potential, Jm−2

0.35 This response may be due to the fact that as the

0.3
moisture content of the product increased, the sorptive
sites get saturated and water molecules become held to
0.25
the particles more by surface tension than by chemical
0.2
adsorption. The surface tensional forces being weaker
0.15
are then easily broken, and this results in lower integral
0.1 enthalpy.
0.05 The variation of net integral entropy with moisture
0 content is shown in Fig. 7. Net integral entropy of soya
0 0.2 0.4 0.6 0.8 1
bean decreased with increase in moisture content to a
Water activity, decimal
minimum value of –0
38 J g1 K1 at the moisture
Fig. 5. Surface potential isotherms of soya bean at different content of 11% d.b. and thereafter, increased with
temperatures: }^}, 408C; }&}, 508C; }m}, 608C; further increase in moisture content. A similar trend
} }, 708C

between the monolayer moisture content of soya bean 900

and temperature can be expressed by the following 800
equation:
Net integral enthalpy, Jg−1

700
Mm ¼ 0
0678t þ 10
101 ð19Þ 600
with a value for the coefficient of determination of 0
999, 500
where Mm is the monolayer moisture content, % (d.b.) 400
and t is temperature 8C.
300
Rizvi (1986) noted that a survey of literature data on
the effect of temperature on different dehydrated food 200
products showed that monolayer moisture content 100
decreases with increase in temperature. This behaviour 0
has been ascribed to a reduction in the number of active 2 4 6 8 10 12 14
sites due to physical and chemical changes induced by Moisture content, % (db)
temperature.
Fig. 6. Variation of the net integral enthalpy of soya bean with
The surface potential isotherms of soya bean are moisture content, compared with sesame seed, melon seed, and
shown in Fig. 5. Surface potential increased with cowpea: }^}, sesame; }&}, melon; }m}, cowpea;
increase in water activity at any temperature, but the }  }, soya bean

188
5 shape, of the type II according to the Brunauer–
4 marked effect of temperature.
Net integral entropy, Jg−1 K−1
3 isotherm models namely modified Henderson, mod-
2
1
0 the modified Oswin proved the best for predicting
2.5 7.5 12.5
−1
−2
−3 Moisture content, % (db)
Fig. 7. Variation of the net integral entropy of soya bean with
moisture content, compared with cassava and unripe plantain
with moisture content has been reported for the entropy
of full fat peanut flakes (Hill & Rizvi, 1982), rice
(Benado & Rizvi, 1985), winged been seed and gari
(Fasina et al., 1999), plantain (Aviara & Ajibola, 2000),
cassava (Aviara & Ajibola, 2002) and sesame seed
(Aviara et al., 2002). The decrease of entropy in the low
water activity range has been thought to be due to
lateral interaction in the adsorbed film caused by
restrictive effect (loss of rotational freedom) of the
adsorbed water molecules as the available sites become
saturated, and structural alteration of the adsorbing
food towards increased crystallinity (Kapsalis, 1987).
The increase in entropy after a point indicates that
newly bound water molecules were held less strongly due
to a further degree of freedom resulting from a gradual
opening and swelling of the polymeric constituents
(Bettelheim et al., 1970). Rizvi and Benado (1984) also
noted that in foods, there tend to be two opposing
entropic contributions upon moisture sorption, viz., loss
of entropy from localisation of water and increase in
entropy due to incipient solution formation, that is
structural transformations in food arising from solubi-
lisation and swelling. Any of the above phenomena or a
combination of these may have been responsible for the
response obtained in the integral entropy of soya bean.
4. Conclusions
The investigation of sorption equilibrium and ther-
modynamic characteristics of soya bean TGX 1440-1E
revealed the following.
(1) The moisture sorptions isotherms of soya bean in
the temperature range of 40–708C are sigmoidal in
ARTICLE IN PRESS
N.A. AVIARA ET AL.
Emmett–Teller (BET) classification and showed
(2) All the five commonly used moisture sorption
ified Chung–Pfost, modified Halsey, modified Oswin
and modified Guggenheim–Anderson–de Boer
(GAB) are acceptable for predicting the equilibrium
moisture content of soya bean. Of the five models,
17.5 the equilibrium moisture content and its tempera-
ture dependence.
(3) Three of the models namely the modified Hender-
son, modified Chung–Pfost and modified Halsey are
acceptable for predicting the water activity. Of these
three, the modified Halsey model proved the best for
predicting the water activity of soya bean.
(4) The heat of vaporisation of moisture in soya bean
decreased with increase in moisture content and
attained the free water point between the moisture
contents of 20 and 22% d.b.
(5) The monolayer moisture content of the seed
decreased from 7
407 to 5
37% d.b. as the tempera-
ture increased from 408C to 708C.
(6) The surface potential (spreading pressure) of moist-
ure in the seed increased with increase in water
activity and the effect of temperature was not
significant.
(7) The net integral enthalpy decreased with increase in
moisture content, and the trend became asymptotic
as the moisture level of 13
0% d.b. was approached.
(8) The net integral entropy decreased with increase in
moisture to a minimum value at the moisture
content of 11% d.b. and thereafter, increased with
a further increase in moisture content.
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