Biosystems Engineering (2002) 83 (4), 423431

doi:10.1006/bioe.2002.0124, available online at http://www.idealibrary.com on

PH}Postharvest Technology

Thermodynamics of Moisture Sorption in Sesame Seed

N.A. Aviaraa; O.O. Ajibolab; U.O. Dairoc
a

Department of Agricultural Engineering, University of Maiduguri, Maiduguri, Nigeria; e-mail of corresponding author: enaviara@yahoo.com
(N.A. Aviara)
b
Department of Agricultural Engineering, Obafemi Awolowo University, Ile-Ife, Nigeria; e-mail: fajibola@oauife.edu.ng
c
Department of Agricultural Mechanisation, University of Agriculture, Abeokuta, Nigeria
(Received 10 April 2001; accepted in revised form 5 August 2002)

Experimental data on the sorption isotherms of sesame seed were used to determine the thermodynamic
functions (heat of vaporisation, spreading pressure, net integral enthalpy and entropy). The heat of
vaporisation decreased with increase in moisture content and approached the latent heat of pure water at
moisture content between 18 and 21% dry basis. The spreading pressure increased with increase in water
activity and was not signicantly affected by temperature. Net integral enthalpy decreased with increase in
moisture content, and became asymptotic as the moisture content of 12% was approached. Net integral
entropy decreased with increase in moisture content to a minimum value of 0
138 J kg1 K1 at moisture
content of about 3
7%. It then increased with moisture content to a maximum of about 0
63 J kg1 K1 at
about 12% moisture content and thereafter, remained nearly constant. # 2002 Silsoe Research Institute. Published by
Elsevier Science Ltd. All rights reserved

1. Introduction
Sesame seed (Sesamum indicum) is a highly nutritious
seed, which contains approximately 45% by weight of
oil and 25% protein. It is a good source of essential
amino acids and minerals (Weiss, 1971).
Presently, the seeds are mainly consumed as snacks in
Nigeria, but they are increasingly being processed for
vegetable oil and livestock feed. Drying is one of the
operations employed in the post-harvest processing of
sesame seed. The design of effective drying and storage
systems for the seed requires a knowledge of its energy
requirements and the state and mode of moisture
sorption within it.
Thermodynamics has been reported as one of the
three approaches used to understand the properties of
water and calculate the energy requirements of heat and
mass transfer in biological systems (Rizvi & Benado,
1984; Fasina et al., 1997, 1999). Others are the structural
approach, which describes the mechanism of hydrogen
bonding and molecular positioning obtained using
spectroscopic techniques, and the dynamic approach,
which involves the analysis of motion of water molecules
and their contribution to hydrodynamic properties of
1537-5110/02/$35.00

the system. The use of structural and dynamic

approaches is limited in biological systems application
due to limited information on the theory of the
behaviour of water associated with solid biological
materials (Rizvi & Benado, 1984). Thermodynamic
properties of food relate the concentration of water in
food to its partial pressure, which is crucial in the
analysis of heat and mass transport phenomena during
drying. They determine the end point to which food
must be dehydrated in order to achieve a stable product
with optimal moisture content, and yield a gure for the
theoretical minimum amount of energy required to
remove a given amount of water from food. The
properties also provide insight into the microstructure
associated with the food as well as the theoretical
interpretation of physical phenomena occurring at the
foodwater interface (Rizvi, 1986). Thermodynamic
functions are readily calculated from 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 (differential or
isosteric heat of sorption), free energy, integral enthalpy
and integral entropy.
423

# 2002 Silsoe Research Institute. Published by

Elsevier Science Ltd. All rights reserved

424

N.A. AVIARA ET AL.

Notation
a; b
aw
aw*
Am
A; B; C; C1 ; C2
hfg
K
L

coefcients
water activity
geometric mean water activity
area of water molecule 1
06
1019 m2
coefcients
latent heat of vaporisation of free
water, J kg1
Boltzmann constant 1
38
1023 J kg1
heat of vaporisation of water in
material, J kg1

The heat of vaporisation of moisture in a product is

the amount of energy required to change its unit mass
from liquid to vapour at a particular temperature and
water activity. Net isosteric heat is the amount of energy
by which the heat of vaporisation of moisture in a
product exceeds the latent heat of pure water. It is useful
in estimating the state of absorbed water by solid
particles, which is a measure of the physical, chemical
and microbial stability of food under storage (Labuza,
1968). The isosteric (differential) heat or heat of
vaporisation of moisture has practical use in drying
calculations and modelling energy consumption in the
drying of biomaterials. Free energy is the energy
required to transfer water molecules in the vapour state
from the interior of the solid to the solid surface or vice
versa (Fasina et al., 1997). It is useful in estimating the
heat requirements of the drying or wetting of agricultural materials and has been considered by some researchers (Sokhansanj et al., 1991) in simulation studies on
heat and mass transfer in deep bed dryers.
The integral enthalpy represents the total energy
available to do work. It provides an indication of
the binding strength of water molecules to the solid,
and has some bearings on the energy balance of drying
and freezing operations (Gal, 1975). Entropy variation
plays an important role in exergy balance (Rotstein,
1983, 1986; Tragardh, 1986) which presents valuable
information with respect to energy utilisation in food
processing: optimum theoretical energy performance,
departure from the optimum and consumption of
utilities. It is also related to the order/disorder concept
which is useful for the interpretation of such processes
as dissolution, crystallization and swelling, which
usually occur during moisture sorption by food products.
Fish (1958) studied the thermodynamics of water in
potato starch gel and noted that starch at very high
moisture content is thermodymically similar to pure
water.

M
Mm
Po
Ps
Qin
R
Sin
T
F
y

moisture content, dry basis

monolayer moisture content, dry
basis
actual water vapour pressure, Pa
saturated water vapour pressure, Pa
net integral enthalpy, J kg1
gas constant of water vapour
0
462 kJ kg1
net integral entropy, J kg1 K1
absolute temperature, K
spreading pressure, J m2
moisture ratio

Iglesias et al. (1976) studied the thermodynamics of

water vapour sorption by sugar beet root and advanced
hypothesis, which were mainly concerned with congurational modication 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.
In a previous article (Ajibola & Dairo, 1998), the
modied Halsey model was found to t best the
experimental data on sorption isotherms of sesame
seed. This paper uses the tted equation to estimate the
thermodynamic parameters related to the sorption of
moisture by sesame seed.

2. Materials and method

2.1. Determination of thermodynamic functions
2.1.1. Heat of vaporisation
The heat of vaporisation of moisture in agricultural
and food products L can be estimated by applying the
ClausiusClapeyron equation to the sorption isotherms.
The ClausiusClapeyron equation as stated by Rizvi
(1986) and Kapsalis (1987), after some mathematical
manipulations (Fasina et al., 1999), yields the equation
lnPo

L
lnPs C1
hfg

where: Po and Ps are the actual and saturated vapour

pressures, respectively, in Pa; hfg is the latent heat of
vaporisation of free water in J kg1 ; and C1 is a
constant.

THERMODYNAMICS OF MOISTURE SORPTION

The saturation vapour pressure Ps at different

temperatures can be obtained from Rogers and Mayhew
(1981) or calculated using the psychrometric relationships in ASAE (1996). The vapour pressure in the
material can be determined using the equation
Po aw Ps

The values of water activity aw can be obtained with the

moisture sorption isotherm model which best describes
the equilibrium moisture relationships of the product.
A plot of lnPo versus lnPs yields the ratio of the
heat of vaporisation in the material to the latent heat of
saturated water vapour from the slope of the straight
line obtained.
2.1.2. Net integral enthalpy and entropy
The equation for calculating net integral enthalpy can
be derived from the rst law of thermodynamics
following the procedure reported by Rizvi (1986) as


dln aw


Qin
3


d1=T

R
F

where: T is the absolute temperature in K; and F is the

spreading pressure in J m2 . A plot of lnaw versus 1=T
at constant spreading pressure yields the net integral
enthalpy from the slope. The spreading pressure, also
known as surface potential, is the surface excess free
energy or the difference between the chemical potential
of pure adsorbent and that of the adsorbent in sorption.
It acts as a second pressure (Rizvi & Benado, 1984) and
results in increase in surface tension on bare sorption
sites due to the sorbed molecules on them (Fasina et al.,
1999). Some researchers have used spreading pressure as
the driving force in developing transport models during
diffusion in porous solids (Skaar & Babiak, 1982;
Nelson, 1986), and it can be estimated using an
analytical procedure similar to the one described by
Iglesias et al. (1976) and Fasina et al. (1999) from the
relationship
Z
KT aw y
F
daw
4
Am 0 aw
where the moisture ratio y is
y

M
Mm

and where: K is the Boltzmann constant; Am is the

surface area of a water molecule in m2 ; and M is the
moisture content, dry basis. The monolayer moisture
content Mm of the product can be obtained by applying
the BET equation (Brunauer et al., 1938) to the experimental data on the equilibrium moisture relationships of

the material. The BET equation is stated as

aw
1
C2  1aw

1  aw M Mm C2
Mm C2

425

where C2 is a constant.
For the thermodynamic system, the integral entropy
Sin is given by
Qin
Sin
 R lnaw*
7
T
where aw* is the geometric mean water activity obtained
at constant spreading pressure.
2.2. Data and analysis
The thermodynamic functions related to moisture
sorption in sesame seed were determined using the
desorption equilibrium moisture content data obtained
in the temperature range of 40708C over a water
activity range of 0
50
99 using the vapour pressure
manometric (VPM) method (Ajibola & Dairo, 1998).
Four commonly used moisture sorption isotherm
models were tted to the experimental data using NLIN
(SAS, 1986), a non-linear regression analysis procedure
that minimises the sum of squares of deviations in a
series of iterative steps. The modied Halsey model
(Iglesias & Chirife, 1976a), which gave the lowest
standard error of estimate of 2
36%, was considered to
be the model that best describes the equilibrium
moisture relationships of sesame seed. The modied
Halsey equation in terms of water activity is stated as
follows:
aw expexpA BTM C

where A; B and C are coefcients.

Values of water activity at four temperatures in the
specied range and four moisture levels in the moisture
range from 6 to 22% d.b. were determined using the
modied Halsey equation, which, for sesame seed is
expressed as
aw expexp8
95  0
0124TM 2
20

Saturated water vapour pressure was obtained from

Rogers and Mayhew (1981) in the temperature range of
40708C, and the actual vapour pressure in sesame seed
at different temperatures 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 ratio of the heat
of vaporisation of moisture in the seed to the latent heat
of saturated water at different moisture contents was
determined from the slopes of the straight lines
obtained. The non-linear regression procedure in SPSS
9
0 for Windows was used to t the Gallaher (1951)

426

N.A. AVIARA ET AL.

equation to the data obtained on the ratio of heat of

vaporisation of moisture in sesame seed to the latent
heat of saturated water vapour. The Gallaher model is
stated as follows:
L=hfg 1 a expbM

10

The non-linear regression procedure required that initial

parameter estimates be chosen close to the true values.
These estimates were obtained by linearisation of Eqn
(10) through logarithmic transformation and the application of linear regression analysis. The linear leastsquares estimates were then used as the initial estimates
in the non-linear regression procedure. The values of
coefcients a and b obtained are 0
388 and 16
37 with
standard errors of 0
0045 and 0
153, respectively. The
standard error of estimate for L=hfg was 0
016.
For sesame seed, Eqn (10) becomes
L=hfg 1 0
388 exp16
37M

11

Equation (11) was used to compute the values L=hfg and

these values were plotted against moisture content.
The monolayer moisture contents of sesame seed at
different temperatures were obtained by applying Eqn
(6) to the desorption equilibrium moisture content data
for the seed in the water activity range of 0
050
45. A
plot of aw =1  aw M versus aw yielded a straight line
with slope and intercept on the Y-axis from which Mm
was calculated. The spreading pressures in the seed at
different temperatures were calculated using Eqn (4).
The value of the spreading pressure was noted to be
indeterminate at a value for water activity of 0;
therefore, the lower limit of water activity employed
was 0
05. The computed values of spreading pressure
were adjusted by adding the value corresponding to the
interval of water activity lying between 0 and 0
05,
which was calculated by assuming that a linear relationship (Henrys law) exists between aw and y within the
water activity range (Fasina et al., 1999). For the
interval of water activity between 0 and 0
05, Eqn (4)
becomes
F

KTy
Am

seed during sorption and the net integral entropy was

plotted against moisture content.

3. Results and discussion

3.1. Equilibrium moisture contentwater activity
The desorption equilibrium moisture content}water
activity data with which the thermodynamic functions
related to moisture sorption in sesame seed were
determined are presented in Table 1. As expected, the
water activity increased with increase in equilibrium
moisture content at any particular temperature and
increased with increase in temperature at a constant
equilibrium moisture content. The moisture sorption

Table 1
Desorption equilibrium moisture contents of sesame seed at
different water activities and temperatures
Temperature, 8C

Water activity

Equilibrium moisture
content, % d.b.

40

0
53
0
60
0
76
0
85
0
91
0
92
0
95
0
99

6
1
6
6
9
1
13
0
15
4
20
8
23
7
25
2

50

0
57
0
62
0
66
0
84
0
87
0
89
0
92
0
94
0
96

5
5
6
2
6
8
9
3
10
7
12
9
14
7
21
7
24
3

60

0
52
0
58
0
67
0
84
0
88
0
90
0
93
0
96
0
98

5
2
5
8
6
0
9
2
10
8
12
6
15
1
20
8
23
8

70

0
61
0
72
0
87
0
90
0
92
0
96
0
97

5
9
6
7
9
2
10
9
13
1
15
5
21
0

12

Spreading pressure was plotted against water activity at

various temperatures to establish the spreading pressure
isotherms and determine the effect of temperature on the
spreading pressure. The natural log of water activity was
plotted against the reciprocal of the absolute temperature at constant spreading pressure and the net integral
enthalpy was determined from the slope of the straight
line obtained. The net integral enthalpy was then plotted
against moisture content. Equation (7) was used to
determine the net integral entropy of moisture in sesame

THERMODYNAMICS OF MOISTURE SORPTION

isotherms of sesame seed at different temperatures

constructed using the modied Halsey model were
sigmoidal in shape (Ajibola & Dairo, 1998) and showed
marked effect of temperature.
3.2. Heat of vaporisation
The plot of lnPo versus lnPs for sesame seed at
various moisture levels are presented in Fig. 1. The
natural log of the actual vapour pressure lnPo
increased linearly with increase in the natural log of
saturated water vapour pressure lnPs and moisture
content.
The relationship existing between lnPo and lnPs at
four moisture contents}6, 10, 16 and 22% d.b., respectively}can be expressed by the following regression
equations:
lnPo 1
1415 lnPs  1
9219

13

lnPo 1
0862 lnPs  0
0594

14

lnPo 1
0371 lnPs  0
4147

15

lnPo 1
0109 lnPs  0
1308

16

427

with values for the coefcient of determination of 0
997,

0
999, 0
999and 1
000, respectively. The plot of L=hfg for
sesame seed against moisture content is shown in Fig. 2.
From this gure, it can be seen that the heat of
vaporisation of moisture in sesame seed decreased with
increase in moisture content and approached the latent
heat of pure water at a moisture content between 18 and
21% d.b. Iglesias and Chirife (1976b) explained that the
moisture level at which the heat of sorption approaches
the heat of vaporisation of water can be an indication of
the point at which water exists in the free form in the
food product. This moisture level can, therefore, be
termed the free water point. Figure 2 also shows that
the heat of vaporisation of sesame seed is lower than
that of alfalfa pellet (Fasina & Sokhansanj, 1993),
winged bean seed (Fasina et al., 1999), barley (Cenkowski et al., 1992) and barley malt (Bala & Woods,
1991) at moisture contents below 10% d.b. At moisture
contents between 10 and 20% d.b., the heat of
vaporisation of moisture in sesame seed does not have
a marked difference from that of alfalfa pellet and
winged bean seed. The differences in heat of vaporisation could be attributed to differences in composition
and structure, equilibrium moisture data and method of
its determination, environmental factors and previous

Fig. 1. Loglog plot of the actual (po) and saturated (ps) water vapour pressure for sesame seed at various moisture contents (d.b.):
*, 6%; &, 10%;  , 16%; *, 22%.

428

N.A. AVIARA ET AL.

Fig. 2. Ratio of heat of vaporisation of moisture in sesame seed to latent heat of saturated water vapour as a function of moisture
content: comparison of sesame seed *, with alfalfa pettets &, winged bean seed *, barley &, and barley malt  .

treatments. The free water point of sesame seed is,

unexpectedly, higher than that of alfalfa pellets and
winged bean seed and as expected, lower than that of
barley and barley malt.

3.3. Net integral enthalpy and entropy

The values of the monolayer moisture content of
sesame seed obtained from Eqn (6) at the temperatures
of 40, 50, 60 and 708C were 4
12, 3
94, 3
61 and 3
15%
d.b., respectively. These show that the monolayer
moisture content decreased with increase in temperature. The spreading pressure isotherms presented in
Fig. 3 show that there was little effect of temperature on
the values of the spreading pressure of sesame seed.
Similar results have been reported for winged bean seed
and gari (Fasina et al., 1999).
The variation of net integral enthalpy with moisture
content is shown in Fig. 4. The net integral enthalpy

decreased with the increase in moisture content and the

trend seemed to become asymptotic as a moisture
content of 12% was approached. Similar trends have
been reported for the enthalpy of sugar beet root, its
insoluble fraction and sucrose (Iglesias et al., 1976),
grain sorghum (Rizvi & Benado, 1983), horseradish root
(Mazza, 1980) and yellow globe onion (Mazza & Le
Maguer, 1978).
The variation of net integral entropy with moisture
content is shown in Fig. 5. Net integral entropy
decreased with increase in moisture content to a
minimum value at about 3
7% moisture content, dry
basis. It then increased with moisture content to a
maximum value at about 12% moisture content and
thereafter, remained constant. Hill and Rizvi (1982)
reported similar trend in the entropy of full fat peanut
akes, which has a lot of oil like sesame seed. However,
similar trends have also been reported for sugar beet
root (Iglesias et al., 1976), rice (Benado & Rizvi, 1985),
gari and winged bean seed (Fasina et al., 1999).

429

THERMODYNAMICS OF MOISTURE SORPTION

Fig. 3. Spreading pressure isotherms of sesame seed at different temperatures:

408C;

Fig. 4. Net integral enthalpy of sesame seed.

508C;

608C;

708C.

430

N.A. AVIARA ET AL.

Fig. 5. Net integral entropy of sesame seed.

4. Conclusions
This study determined the thermodynamic functions
associated with moisture sorption by sesame seed. The
heat of vaporisation decreased with increase in moisture
content. The monolayer moisture content decreased
with increase in temperature, while the spreading
pressure, which increased with increase in water activity,
was not signicantly affected by temperature. Net
integral enthalpy decreased with increase in moisture
content. The trend in integral enthalpy seemed to
become asymptotic as a moisture content of 12% was
approached. The net integral entropy decreased with
increase in moisture content to a minimum value at
about 3
7% moisture content. It then increased with

moisture content to a maximum value at about 12%

moisture content and, thereafter, remained constant.

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