Journal of Food Engineering 61 (2004) 297–307

www.elsevier.com/locate/jfoodeng

Water sorption isotherms of starch powders

Part 1: mathematical description of experimental data
A.H. Al-Muhtaseb, W.A.M. McMinn, T.R.A. Magee *

Food Process Engineering Research Group, School of Chemical Engineering, QueenÕs University Belfast,
David Keir Building Stranmillis Road, Belfast, BT9 5AG, UK
Received 20 January 2003; accepted 13 April 2003

Abstract
Adsorption and desorption isotherms for potato, highly amylopectin and highly amylose starch powders were determined at 30,
45 and 60
C using a gravimetric technique. Samples were equilibrated in desiccators containing sulphuric acid solutions of known
water activity (0.05–0.95), and placed in temperature-controlled cabinets for approximately three weeks. The starch powders exhi-
bited Type II behaviour. The sorption capacity decreased with increasing temperature. The data obtained were fitted to several
models including two parameter relationships (Halsey, Oswin, Henderson, Modified-BET and Smith), three parameter equations
(GAB, Ferro-Fontan) and four parameter equation (Peleg). A non-linear least square regression program was used to evaluate the
models constants. The empirical Peleg model followed by the kinetic GAB and the semi empirical Ferro-Fontan models were found
to best represent the experimental data in the water activity range 0.05–0.95. In the range of water activity 0.35–0.95 the Smith
model was shown to give the closest fit to the experimental data.
 2003 Elsevier Ltd. All rights reserved.

Keywords: Sorption isotherm; Potato starch; Highly amylopectin starch; Highly amylose starch; Mathematical models; Hysteresis

1. Introduction In 1957, Scott termed the equilibrium relative humi-

Control of moisture content during the processing
of foods is an ancient method of preservation, and pro-
bably humankindÕs first ‘‘technology’’ for extending the
stability of foods. This is achieved by either removing,
or binding water such that the food becomes stable to
both microbial and chemical deterioration (Labuza,
1980). The most common limitation on the shelf life of
food is microbial growth, hence several preservation
processes are aimed at achieving stability of foods by
reducing the moisture content to levels below those re-
quired by micro-organisms for survival and reproduc-
tion (Aguilera & Stanley, 1999). Sorption characteristics
have, and are currently being examined in light of their
influence on the storage stability of dehydrated pro-
ducts, as well as their affect on the diffusion of water
vapour.
*
Corresponding author. Tel.: +44-(0)28-9027-4255; fax: +44-(0)28-
9038-1753.
E-mail address: r.magee@qub.ac.uk (T.R.A. Magee).
0260-8774/$ - see front matter  2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0260-8774(03)00133-X
dity, i.e. availability of water in food, water activity
(Scott, 1957). The work was widely acclaimed and led to
a rapid expansion in the use of water activity, denoted
(aw ), which is now one of the major control variables in
food preservation technology (Van den Berg & Bruin,
1981). Water activity is a term indicating the ‘‘quality’’
of the water content of food. It describes the degree of
‘‘boundness’’ of water and, hence its availability to
participate in physical, chemical, and microbiological
reactions.
The relationship between the total moisture content
and water activity of the food, over a range of values, at
a constant temperature and under equilibrium condi-
tions, yields a moisture sorption isotherm when ex-
pressed graphically. This isotherm curve can be obtained
in one of two ways; adsorption or desorption. The ad-
sorption and desorption processes are not fully rever-
sible, therefore a distinction can be made between the
isotherms by determining whether the moisture levels
within the product are increasing or decreasing.
The effect of temperature on the sorption isotherm is
of great importance given that foods are exposed to a
298 A.H. Al-Muhtaseb et al. / Journal of Food Engineering 61 (2004) 297–307
Nomenclature
A constant (dimensionless)
aw water activity
B constant (dimensionless)
C GAB model parameter (dimensionless)
c0 constant (adjusted to the temperature effect)
(dimensionless)
E mean relative percentage deviation modulus
(%)
DHc difference in enthalpy between mono-layer
and multi-layer sorption (J mol
1 )
DHk difference between the heat of condensation
of water and the heat of sorption of the multi-
layer (J mol
1 )
K GAB model parameter (dimensionless)
k0 constant (adjusted to the temperature effect)
(dimensionless)
range of temperatures during storage and processing,
and water activity changes with temperature. Tempera-
ture affects the mobility of the water molecules, and the
dynamic equilibrium between the vapour and adsorbed
phases.
In the field of water vapour sorption by a solid sor-
bent, moisture sorption hysteresis is the phenomena by
which two different paths exist between the adsorption
and desorption isotherms (Kapsalis, 1981). The effect of
hysteresis on food is important, even though it can be
relatively low in magnitude. Rizvi (1995) stated that the
extent of hysteresis is related to the nature and state of
the components in a food. It may reflect their structural
and conformational rearrangement, which alters the
accessibility of energetically favourable polar sites and
thus, may hinder the movement of moisture. Iglesias and
Chirife (1976) recognized that it is not possible to give a
single explanation of the hysteresis phenomena in foods,
due to food being a complex combination of various
constituents, which can, not only sorb water indepen-
dently but also, interact among themselves.
Water sorption isotherm equations are useful for
predicting water sorption properties of foods, although
they provide little insight into the interaction of water
and food components (Leung, 1983). Although several
mathematical models exist to describe water sorption
isotherms of food materials (Iglesias, Chirife, & Lom-
bardi, 1975), no one equation gives accurate results
throughout the whole range of water activities, or for all
types of foods. Labuza (1975) attributed this to the fact
that the water is associated with the food matrix by
different mechanisms in different water activity regions.
Models available in the literature to describe moisture
sorption isotherm can be divided into several categories;
K1 , K2 equation parameters (dimensionless)
mi experimental value
mpi predicted value
N number of experimental data
n 1 , n2 equation parameters (dimensionless)
R universal gas constant (8.314 J mol
1 K
1 )
r equation parameter (dimensionless)
T temperature (K)
X equilibrium moisture content (kg kg
1 dry
solid)
X0 mono-layer moisture content (kg kg
1 dry
solid)
a equation parameter (dimensionless)
c equation parameter (dimensionless)
h equation parameter (dimensionless)
kinetic models based on a mono-layer (Mod-BET
model), kinetic models based on a multi-layer and
condensed film (GAB model), semi-empirical (Ferro-
Fontan, Henderson and Halsey models) and empirical
models (Smith and Oswin models). The BET model
represents a fundamental milestone in the interpretation
of multi-layer sorption isotherms, particularly Types II
and III (Timmermann, 1989). Many researchers modi-
fied the BET model and the modified equation gave a
good fit up to water activity 0.9 (Aguerre, Suarez, &
Viollaz, 1989). The GAB model is considered to be the
most versatile sorption model available in the literature
and has been adopted by a group of West European
food researchers COST 90 (Bizot, 1983; Van den Berg &
Bruin, 1981). Chirife, Bouquet, Ferro-Fontan, and
Iglesias (1983) proposed the Ferro-Fontan model. Igle-
sias and Chirife (1995) reported that the Ferro-Fontan
equation accurately represented the sorption isotherm of
92 different food products. Peleg (1993) proposed a four-
parameter model and noted that the model can be used
for both sigmoidal and non-sigmoidal isotherms, and
that it fitted as well as, or better than, the GAB model.
The Smith model (1947) is useful in describing the
sorption isotherm of biological materials such as starch
and cellulose. Henderson (1952) proposed a semi-em-
pirical model for the equilibrium moisture content of
cereal grains. Chirife and Iglesias (1978) found that
Halsey and Oswin models are also versatile.
The objectives of this study were to provide reliable
experimental data for the sorption characteristics of
starch powders (potato, highly amylopectin, highly
amylose) to model the sorption isotherms using selected
equations, determine their dependence on temperature,
and examine the hysteresis phenomena.
 A.H. Al-Muhtaseb et al. / Journal of Food Engineering 61 (2004) 297–307 299

2. Materials and methods ues of sulphuric acid solutions are presented in Table 1
(Ruegg, 1980).
2.1. Experimental procedure The prepared dessicators were then placed in tem-
perature-controlled cabinets maintained at 30, 45 and
The equilibrium moisture contents of potato (80% 60 ± 1
C. The samples were allowed to equilibrate until
amylopectin, 20% amylose) (Roquette, UK), highly there was no discernible weight change, as evidenced by
amylopectin (99.2% amylopectin, 0.8% amylose) and constant weight values (±0.001 g). This involved a pe-
highly amylose (30% amylopectin, 70% amylose) riod of approximately three weeks for potato starch
(National Starch and Chemicals, UK) starch powders powder and two weeks for highly amylopectin and
were determined by a gravimetric technique, in which highly amylose powders. The total time required for
the weight was monitored discontinuously within a removal, weighing and replacing the samples in the
standard static system of thermally stabilized desicca- desiccators was approximately 30 s. This minimized the
tors. This method was recommended by the COST 90 degree of atmospheric moisture sorption during weigh-
project (Wolf, Spiess, & Jung, 1985). For adsorption a ing. Each experiment was carried out in triplicate. The
6 ± 0.001 g sample of the bone dry powder was placed in bone dry mass was determined gravimetrically by drying
a petri-dish inside a dessicator. For desorption, a in a convectional oven at 105
C for 8–10 h (AOAC,
12 ± 0.001 g sample of 1 kg kg
1 dry basis powder was 1980).
used. Each experiment was carried out in triplicate.
Sulphuric acid (Fisher Scientific, UK) solutions were
used to maintain the specified relative humidity inside 2.2. Data analysis
the desiccators. The effect of temperature and acid
concentration on the equilibrium relative humidity val- The isotherm models used to fit the data are pre-
sented in Table 2. A non-linear least square regression
analysis was used to evaluate the model parameters. To
evaluate the goodness of fit of each model, the mean
Table 1 relative percentage deviation modulus ðEÞ was used,
Water activity of sulphuric acid solutions at selected concentrations which is defined by
and temperatures
H2 SO4 Water activity (aw ) 100 X
N
jmi
mpi j
solution % (v/v) E¼ ð11Þ
30
C 45
C 60
C N i¼1 mi
5 0.9808 0.9812 0.9818
20 0.8814 0.8839 0.8882
where mi is the experimental value, mpi is the predicted
30 0.7549 0.7629 0.7711
40 0.5711 0.5866 0.5989 value, and N is the number of experimental data. The
50 0.3574 0.3765 0.3936 mean relative percentage deviation modulus ðEÞ is
60 0.1677 0.1834 0.1988 widely adopted throughout the literature, with a modu-
70 0.047 0.0548 0.0611 lus value below 10% indicative of a good fit for practical
80 0.0059 0.0077 0.0103
purposes (Lomauro, Bakshi, & Labuza, 1985).

Table 2
Isotherm equations for experimental data fitting
Model Mathematical expression
Mod-BET (Aguerre et al., 1989) X ¼ X0 Caw =½ð1
aw Þð1
C lnð1
aw ÞÞ ð1Þ
Halsey (Halsey, 1948) X ¼ ½
A=ðT ln aw Þ1=B ð2Þ
Smith (Smith, 1947) X ¼ A þ ðB logð1
aw ÞÞ ð3Þ
1=B
Henderson (Henderson, 1952) X ¼ ½
lnð1
aw Þ=A ð4Þ
Oswin (Oswin, 1946) X ¼ Aðaw =ð1
aw ÞÞB ð5Þ
1=r
Ferro-Fontan (Ferro-Fontan, Chirife, X ¼ ½c= lnða=aw Þ ð6Þ
Sancho, & Iglesias, 1982)
Guggenheim–Anderson–de Boer X ¼ X0 CKaw =½ð1
Kaw Þð1
Kaw þ CKaw Þ ð7Þ
(Van den Berg & Bruin, 1981) C ¼ c0 expðDHC =RT Þ ð8Þ
K ¼ k0 expðDHK =RT Þ ð9Þ
Peleg (Peleg, 1993) X ¼ K1 anw1 þ K2 anw2 ð10Þ
300 A.H. Al-Muhtaseb et al. / Journal of Food Engineering 61 (2004) 297–307

3. Results and discussion sents the mean value of three replications. Without
exception, the adsorption and desorption isotherms
3.1. Desorption and adsorption isotherms demonstrate an increase in equilibrium moisture con-
tent with increasing water activity, at a constant tem-
The adsorption and desorption isotherms for potato, perature. This behaviour is manifested in the form
highly amylopectin and highly amylose starch powders of a sigmoidal shaped curve, thus reflecting a Type
at 30, 45 and 60
C are shown in Figs. 1–6. The equi- II isotherm (according to BrunauerÕs classification)
librium moisture content at each water activity repre- (Brunauer, Deming, Deming, & Troller, 1940). This is in

0.4 0.4

Moisture Content (kgkg -1 DS)

Moisture Content (kgkg -1 DS)

0.3 0.3

0.2 0.2

0.1 0.1

0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Water Activity Water Activity

60°C 45°C 30°C 60°C 45°C 30°C

Fig. 1. Experimental adsorption isotherms for potato starch powder. Fig. 4. Experimental desorption isotherms for highly amylopectin
DS ¼ dry basis. powder.

0.4
0.4
Moisture Content (kgkg -1 DS)

Moisture Content (kgkg DS)

-1

0.3 0.3

0.2 0.2

0.1 0.1

0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Water Activity Water Activtiy

60°C 45°C 30°C

30°C 60°C 45°C 30°C

Fig. 2. Experimental desorption isotherms for potato starch powder. Fig. 5. Experimental adsorption isotherms for highly amylose powder.

0.4
Moisture Content (kgkg -1 DS)

0.4
Moisture Content (kgkg DS)

0.3
-1

0.3

0.2
0.2

0.1
0.1
0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0
Water Activity 0.0 0.2 0.4 0.6 0.8 1.0
30°C Water Activity
60°C 45°C
60°C 45°C 30°C
Fig. 3. Experimental adsorption isotherms for highly amylopectin
powder. Fig. 6. Experimental desorption isotherms for highly amylose powder.
 A.H. Al-Muhtaseb et al. / Journal of Food Engineering 61 (2004) 297–307 301

agreement with Van den Berg (1981) and McMinn
(1996) who observed Type II isotherm behaviour in
potato and wheat starches, and potato starch gel, res-
pectively.
Starches consist of both crystalline and amorphous
regions. The starch sorption isotherm is attributable to
hydrogen-bonding of water molecules to the available
hydroxyl groups of the substrate, i.e. those in the
amorphous regions and on the surfaces of the crystal-
lites (Urquhart, 1959). The crystalline regions typically
exhibit resistance to solvent penetration. Hence, water
affects the structure acting as a plasticizer of the amor-
phous regions. At low water activity the plasticizing
affect is very small and the mobility of the amorphous
regions is restricted. However, as the water activity in-
creases, the sorbed moisture causes a subsequent swell-
ing of the biopolymer, the degree of crystallinity
decreases, and there is an increasing availability of the
polar groups to the water molecules. Finally, the swelled
polysaccharide forms a solution.
In the low water activity range (aw < 0:25), potato
starch, Amica and Hylon 7 have approximately equal
water sorption capacities. This indicates that the star-
ches have comparable sorption surfaces. Deviations in
their sorption capacity in the higher water activity range
may, for the most part, be due to differences with respect
to the starch amorphous structure (Van den Berg, 1981).
Van den Berg (1981) suggested that the deviation in the
than the highly amylopectin and highly amylose pow-
ders, particularly in the high water activity range
aw > 0:85. In general, the effect of temperature on de-
sorption is more noticeable; an exception to this be-
haviour was found in the case of potato starch powder
at aw > 0:90.
The temperature shifts observed have an important
practical affect on the chemical and microbiological re-
actions which cause quality deterioration. An increase in
temperature causes an increase in the water activity, at
the same moisture content, which in turn causes an in-
crease in the reaction rates leading to quality deterio-
ration (Van den Berg & Bruin, 1981).
3.2. Moisture sorption hysteresis
Figs. 7–9 show the sorption isotherms obtained at 45

C for potato, highly amylopectin and highly amylose
starch powders, respectively. The graphs clearly show
that the equilibrium moisture content for desorption
is higher than for adsorption, at a particular water acti-
vity.
The hysteresis effect extends over the entire water
activity range for all samples but is most pronounced in
0.4
Moisture Content (kgkg -1 DS)

Des Ads
sorption capacity of starches is related to the glass
transition range (0:3 > aw > 0:85) where the amorphous 0.3
parts of starch start to plasticize. Urquhart (1959),
however, attributed this deviation to the differences in 0.2
the number of hydroxyl groups available. Van den Berg,
Kaper, Weldring, and Wolters (1975) stated that potato 0.1
starch has the highest water binding capacity of any
starch, because it has the lowest degree of association 0.0
between the starch molecules. 0.0 0.2 0.4 0.6 0.8 1.0
The data also indicate that the equilibrium moisture Water Activity
content decreases with increasing temperature, at a
constant water activity, thus indicating that starch be- Fig. 7. Sorption isotherms for potato starch powder at 45
C.
Ads ¼ adsorption; Des ¼ desorption.
comes less hygroscopic. This trend may be due to a re-
duction in the total number of active sites for water
binding as a result of physical and/or chemical changes
in the product induced by temperature (Mazza & 0.4
LeMaguer, 1980). Palipane and Driscoll (1992) sug-
Moisture Content (kgkg DS)

Des Ads
gested that at increased temperatures water molecules
-1

0.3
get activated to higher energy levels, causing them to
become less stable and break away from the water-
0.2
binding sites of the food material, thus decreasing the
equilibrium moisture content. As temperature varies, the
0.1
excitation of molecules, as well as the distance, and thus
attraction between molecules, varies. This causes the
amount of sorbed water to change with temperature at a 0.0
0.0 0.2 0.4 0.6 0.8 1.0
given relative humidity (Mohsenin, 1986).
Water Activity
The equilibrium moisture content of potato starch
powder exhibits a stronger temperature dependence Fig. 8. Sorption isotherms for highly amylopectin powder at 45
C.
302 A.H. Al-Muhtaseb et al. / Journal of Food Engineering 61 (2004) 297–307

Table 3
Moisture Content (kgkg -1 DS)

Des Ads Estimated values of coefficients and mean relative percentage deviation
moduli obtained for sorption models applied to experimental adsorp-
0.3
tion data for potato starch powder
Model Constants 30
C 45
C 60
C
0.2
GAB X0 0.035 0.027 0.021
C 17.6 11.8 8.19
0.1 K 0.907 0.905 0.889
E (%) 10.3 10.8 15.0
0.0 Peleg K1 0.255 0.117 0.117
0.0 0.2 0.4 0.6 0.8 1.0 K2 0.106 0.178 0.062
n1 9.92 1.12 9.11
n2 0.682 18.3 0.866
Fig. 9. Sorption isotherms for highly amylose powder at 45
C. E (%) 5.68 11.1 12.1

Ferro- c 0.022 0.014 0.020

the 0:3 < aw < 0:9 region. The magnitude of the hys- Fontan a 1.08 1.07 1.13
r 1.26 1.29 1.06
tersis loop is smaller for highly amylopectin and highly
E (%) 15.9 19.3 24.3
amylose than for potato starch. Highly amylopectin and
highly amylose structures are more strongly associated Henderson A 13.8 18.6 31.0
B 1.07 1.07 1.12
internally than that of potato starch. This may account
E (%) 22.6 15.4 8.11
for the difference in water sorption capacity, as well as
the extent of the hysteresis (Van den Berg, 1981). Oswin A 0.069 0.052 0.037
B 0.390 0.390 0.380
Highly amylose starch (30% amylopectin) shows a
E (%) 18.8 27.2 44.4
smaller hysteresis loop than the highly amylopectin
starch (99.2% amylopectin) in the range aw > 0:7. This Halsey A 0.473 0.266 0.096
B 2.23 2.23 2.33
may be due to the different structure of the starches.
E (%) 36.3 48.8 68.7
Both amylose and amylopectin are fully amorphous,
however, due to the much easier coagulation of amylose Mod-BET A 0.031 0.023 0.017
B 0.921 0.922 0.913
during the separation process of amylose and amylo-
E (%) 30.6 38.7 53.6
pectin, amylose will be more strongly internally associ-
ated than amylopectin, with its branched structure (Van Smith A 0.008 0.007 0.006
B )0.176 )0.132 )0.090
den Berg, 1981). The trend of the hysteresis phenomena
E (%) 9.17 4.51 3.49
is similar to those reported for potato by Wang and
Brennan (1991), and McMinn and Magee (1999).
Hysteresis is not fully understood, although there is
general agreement that some thermodynamically irre- throughout the entire range of water activity. The Peleg
versible processes must occur during desorption or ad- model gives E values ranging from 5.68% to 12.4%, with
sorption, or both. The most favoured theory used to average values of 9.63% for adsorption and 9.59% for
explain this thermodynamical oddity suggests that in the desorption; this compares with average E values for the
wet condition polar sites in the molecular structure GAB model of 12.0% for adsorption and 10.1% for
of the material are almost entirely satisfied by adsor- desorption. Peleg (1993), Rahman, Perera, and Thebaud
bed water. Upon drying and shrinkage, the molecules (1998) and Delgado and Da-Wen Sun (2002) reported
and their water-holding sites are drawn closely enough that the Peleg model provided a good description of the
together to satisfy each other. This reduces the water- isotherms of potato starch, peas and cured beef, re-
holding capacity of the material upon subsequent ad- spectively. Van den Berg (1984), McMinn and Magee
sorption (Mohsenin, 1986). (1999) and Timmermann, Chirife, and Iglesias (2001)
reported that the GAB model adequately represented
the sorption isotherms of potato, wheat starch, potato
3.3. Mathematical modelling and starchy materials.
In the range of water activity 0:35 < aw < 0:9, the
The parameters for the sorption models for potato, Smith model is shown to give the closest fit to the ex-
highly amylopectin and highly amylose starch powders perimental data, giving an average E value of 5.72% for
are shown in Tables 3–8, together with the mean relative adsorption. Young (1976) applied the Smith model to
percentage deviation moduli ðEÞ. adsorption and desorption isotherms of peanuts, and
Examination of the results in Tables 3 and 4 indicates concluded that the model could be used for describing
that the Peleg model best describes the experimental the isotherms provided that the water activity was above
adsorption and desorption data for potato starch 0.30.
 A.H. Al-Muhtaseb et al. / Journal of Food Engineering 61 (2004) 297–307 303

Table 4 Table 5
Estimated values of coefficients and mean relative percentage deviation Estimated values of coefficients and mean relative percentage deviation
moduli obtained for sorption models applied to experimental desorp- moduli obtained for sorption models applied to experimental adsorp-
tion data for potato starch powder tion data for highly amylose powder
Model Constants 30
C 45
C 60
C Model Constants 30
C 45
C 60
C
GAB X0 0.056 0.046 0.029 GAB X0 0.031 0.028 0.028
C 12.1 8.24 6.38 C 11.1 8.52 6.04
K 0.88 0.888 0.917 K 0.913 0.893 0.91
E (%) 12.2 10.9 7.18 E (%) 5.54 17.8 7.18
Peleg K1 0.343 0.110 0.235 Peleg K1 0.102 0.083 0.209
K2 0.096 0.283 0.100 K2 0.236 0.198 0.068
n1 3.86 0.664 10.9 n1 0.861 0.926 7.86
n2 0.473 7.53 1.00 n2 10.6 7.05 0.737
E (%) 9.24 12.4 7.14 E (%) 6.05 4.54 5.09

Ferro- c 0.270 0.056 0.029 Ferro- c 0.021 0.079 0.036

Fontan a 1.57 1.15 1.09 Fontan a 1.07 1.23 1.13
r 0.620 0.999 1.05 r 1.21 0.77 0.965
E (%) 13.4 16.7 15.1 E (%) 11.1 10.4 6.78
Henderson A 12.6 12.8 12.9 Henderson A 13.5 16.7 15.9
B 1.35 1.12 0.940 B 0.995 1.06 0.993
E (%) 17.4 18.3 17.3 E (%) 20.2 10.6 17.5

Oswin A 0.121 0.083 0.055 Oswin A 0.059 0.056 0.051

B 0.324 0.374 0.424 B 0.410 0.392 0.407
E (%) 39.9 32.0 32.7 E (%) 20.8 52.1 28.2
Halsey A 0.663 0.583 0.490 Halsey A 0.423 0.315 0.322
B 2.64 2.33 2.09 B 2.19 2.23 2.17
E (%) 52.8 49.8 55.3 E (%) 44.6 79.5 45.2
Mod-BET A 0.059 0.038 0.025 Mod-BET A 0.027 0.026 0.023
B 0.879 0.912 0.933 B 0.925 0.918 0.926
E (%) 43.7 43.8 45.3 E (%) 35.6 68.6 33.1
Smith A 0.047 0.016 )0.006 Smith A 0.0002 0.003 )0.004
B )0.225 )0.197 )0.168 B )0.168 )0.149 )0.146
E (%) 17.4 12.1 8.64 E (%) 6.49 6.34 5.41

The Halsey model least adequately represented the
experimental data, giving an average E value of 51.3%
for adsorption and 52.6% for desorption. Wang and
Brennan (1991) reported that the Halsey model was
inadequate for representing the sorption isotherms of
potato, giving an average E value of 70.4%. The Hen-
derson, Oswin and Mod-BET model failed to describe
the experimental data giving an average E value above
20%. Wang and Brennan (1991) and Menkov (2000)
reported that the Henderson model failed to describe the
sorption isotherms of potato and lentil seeds, respec-
tively.
Examination of the results for the highly amylose
starch powder (Tables 5 and 6) revealed similar obser-
vations. The Peleg model gave the best description of the
experimental data with E values ranging from 4.54% to
6.20%, and an average value of 5.23% for adsorption
and 6.05% for desorption. The GAB model provided a
good description of the data with an average E value of
6.17% for adsorption and 4.64% for desorption. The
Ferro-Fontan model gave a similar result with an av-
erage E value of 9.43% for adsorption and 5.96% for
desorption. The Smith model also adequately fitted the
results with an average E value of 6.08% for adsorption
and 4.10% for desorption, in the range 0:35 < aw < 0:9.
Once again, the Halsey model was inadequate, giving
the highest average E values of 56.4% for adsorption
and 44.2% for desorption.
As shown in Tables 5 and 6, other models were fitted
to the experimental data. On examining the E values of
the Henderson, Oswin and Mod-BET models, these
were found to be unsuitable for representation of the
results.
In the case of highly amylopectin starch powder
(Tables 7 and 8), the Ferro-Fontan model provided the
best representation of the experimental data throughout
the entire range of water activity, with an average E
value of 7.41% for adsorption and 3.59% for desorption.
Iglesias and Chirife (1995) reported that the Ferro-
Fontan equation accurately represented the sorption
isotherm of 92 different food products (starches, pro-
teins, cereals, meats, vegetables, etc.) in the range of
water activity 0.1–0.9, with only 2–4% average error in
the predicted moisture content. The GAB model was the
304 A.H. Al-Muhtaseb et al. / Journal of Food Engineering 61 (2004) 297–307

Table 6 Table 7
Estimated values of coefficients and mean relative percentage deviation Estimated values of coefficients and mean relative percentage deviation
moduli obtained for sorption models applied to experimental desorp- moduli obtained for sorption models applied to experimental adsorp-
tion data for highly amylose powder tion data for highly amylopectin powder
Model Constants 30
C 45
C 60
C Model Constants 30
C 45
C 60
C
GAB X0 0.043 0.037 0.036 GAB X0 0.032 0.032 0.027
C 10.2 7.50 5.13 C 22.2 15.3 9.86
K 0.89 0.881 0.880 K 0.888 0.882 0.887
E (%) 7.14 4.81 1.98 E (%) 6.19 9.24 6.21
Peleg K1 0.270 0.094 0.179 Peleg K1 0.193 0.097 0.139
K2 0.094 0.202 0.101 K2 0.080 0.166 0.099
n1 6.81 0.754 8.42 n1 7.51 0.777 12.1
n2 0.582 7.45 0.96 n2 0.557 8.96 1.02
E (%) 6.08 5.87 6.20 E (%) 7.40 12.9 10.5

Ferro- c 0.046 0.045 0.050 Ferro- c 0.022 0.024 0.020

Fontan a 1.14 1.16 1.18 Fontan a 1.11 1.12 1.11
r 1.06 1.00 0.932 r 1.23 1.19 1.16
E (%) 3.53 4.37 9.98 E (%) 4.52 6.8 10.9
Henderson A 13.7 17.9 18.5 Henderson A 21.2 22.9 24.5
B 1.12 1.15 1.12 B 1.19 1.20 1.15
E (%) 17.3 13.6 8.94 E (%) 17.2 13.2 12.8

Oswin A 0.078 0.065 0.059 Oswin A 0.062 0.059 0.050

B 0.374 0.368 0.374 B 0.357 0.355 0.367
E (%) 20.1 25.9 38.1 E (%) 14.2 17.8 26.2
Halsey A 0.489 0.294 0.278 Halsey A 0.216 0.197 0.163
B 2.33 2.36 2.34 B 2.42 2.44 2.38
E (%) 34.7 40.7 57.3 E (%) 26.4 28.3 40.4
Mod-BET A 0.036 0.030 0.027 Mod-BET A 0.028 0.027 0.023
B 0.911 0.908 0.911 B 0.904 0.902 0.909
E(%) 24.9 30.1 45.1 E (%) 17.4 17.8 29.8
Smith A 0.011 0.012 0.010 Smith A 0.016 0.017 0.012
B )0.189 )0.151 )0.143 B )0.135 )0.128 )0.114
E (%) 4.03 4.06 4.21 E (%) 3.89 2.95 4.43

next best with an average E value of 7.24% for adsorp-
tion and 6.17% for desorption, followed by the Peleg
model with an average E value of 10.27% for adsorption
and 6.72% for desorption. A similar observation was
found for the Smith model with an average E value of
3.76% for adsorption and 5.18% for desorption in the
range 0:35 < aw < 0:9. Once again, the Halsey, Hen-
derson, Oswin and Mod-BET models failed to ade-
quately represent the sorption isotherms.
On comparison of all the data, it can be concluded,
that the Peleg, GAB and Ferro-Fontan models provide
a good description of moisture sorption isotherms for all
materials, at all temperatures, throughout the entire
range of water activity, with the Smith model being
satisfactory in the range 0:35 < aw < 0:9. The Halsey,
Henderson, Oswin and Mod-BET models failed to
adequately describe the experimental data for all mate-
rials in the temperature range. It should be noted that,
although the Peleg and Smith models provide a good
representation of the data, this is only mathematical and
provides no indication of the nature of the sorption
process.
3.4. Guggenheim–Anderson–de Boer model
Further examination of the GAB parameters (Tables
3–8) shows that, for adsorption, the values of the mono-
layer moisture content, X0 are lower, and those of the
Guggenheim constant C are higher than for desorption.
In terms of the sorption phenomenon this means that
during adsorption although less sorption sites are
available, they have a greater binding energy, with the
multi-layer molecules deviating more from the free bulk
water (Van den Berg, 1984). Furthermore, the X0 values
for all three materials show a tendency to decrease with
an increase in temperature. This decrease in mono-layer
moisture content can be explained by considering the
structural changes in starch polymers at increased tem-
perature. The degree of hydrogen bonding in such
polymers is reduced with increasing temperature,
thereby decreasing the availability of active sites for
water binding and thus, the mono-layer moisture con-
tent (Westgate, Lee, & Ladisch, 1992).
The Guggenheim constant was also shown to de-
crease with increasing temperature, indicating the ex-
 A.H. Al-Muhtaseb et al. / Journal of Food Engineering 61 (2004) 297–307 305

Table 8 Table 9
Estimated values of coefficients and mean relative percentage deviation Characteristic GAB parameters (Eqs. (8) and (9)) for potato starch
moduli obtained for sorption models applied to experimental desorp- powder
tion data for highly amylopectin powder
c0 DHc k0 DHk
Model Constants 30
C 45
C 60
C (kJ mol
1 ) (kJ mol
1 )
GAB X0 0.041 0.041 0.034 Adsorption 0.004 21.4 0.729 0.556
C 14.59 9.13 6.79 Desorption 0.009 18.0 1.45 )1.27
K 0.902 0.881 0.89
E (%) 7.58 8.06 6.09
Peleg K1 0.284 0.097 0.200 Table 10
K2 0.109 0.225 0.073 Characteristic GAB parameters (Eqs. (8) and (9)) for highly amylo-
n1 8.32 0.671 6.84 pectin powder
n2 0.661 7.12 0.65 c0 DHc k0 DHk
E (%) 8.63 7.88 3.65 (kJ mol
1 ) (kJ mol
1 )
Ferro- c 0.034 0.045 0.045 Adsorption 0.003 22.6 0.825 0.188
Fontan a 1.10 1.15 1.16 Desorption 0.003 21.5 0.723 0.545
r 1.15 1.04 0.962
E (%) 2.82 3.41 4.53
Henderson A 12.3 16.6 18.9 Table 11
B 1.07 1.167 1.12 Characteristic GAB parameters (Eqs. (8) and (9)) for highly amylo-
E (%) 18.9 14.5 15.2 pectin powder
Oswin A 0.078 0.072 0.059 c0 DHc k0 DHk
B 0.386 0.363 0.371 (kJ mol
1 ) (kJ mol
1 )
E (%) 16.0 20.9 24.4
Adsorption 0.014 16.9 0.716 0.617
Halsey A 0.591 0.354 0.255 Desorption 0.005 19.1 0.783 0.320
B 2.26 2.40 2.36
E (%) 30.7 35.1 38.1
Mod-BET A 0.035 0.033 0.027 expected and is due to the strong exothermic interaction
B 0.918 0.905 0.911 of water vapour with the primary sorption sites of starch
E (%) 21.8 24.3 25.78 matrix. DHk represents the difference between the heat of
Smith A 0.008 0.016 0.009 condensation of water and the heat of sorption of the
B )0.20 )0.164 )0.14 multi-layer, which is expected to have a positive value
E (%) 4.64 5.53 5.38 due to the exothermic nature of moisture sorption (Van
den Berg, 1984). The relatively lower magnitudes of DHk
observed implies the presence of less firmly bound multi-
pected tendency of a decrease in binding energy for the layer molecules, at intermediary energy levels between
first adsorbed layer with increasing temperature. Such a those of mono-layer molecules and the bulk liquid. The
decrease indicates an increasingly shorter residence time small negative value of DHk , in the case of potato starch,
for the adsorbed water molecules in the first layer, with indicates that the heat of sorption of the multi-layer is
the character of the adsorption process becoming less greater than the heat of condensation of water, due to
strongly localized (Calzetta Resio, Aguerre, & Suarez, the endothermic dissolution of small molecular solutes.
1999). A clear correlation of the constant K with tem- The DHc value for adsorption is slightly higher than
perature was not observed. Van den Berg (1984) stated the value for desorption, in the case of potato and highly
that the parameters C and K incorporate the tempera- amylopectin starch, and lower in the case of highly
ture effect. C is more enthalpic while K is more entropic amylose starch. The variation in enthalpy values be-
in nature. Therefore, when describing practical iso- tween adsorption and desorption suggests a degree of
therms over limited temperature intervals, it may suffice irreversibility with respect to the water binding proper-
to incorporate the temperature effect only in C. ties of the material (McMinn & Magee, 1999).
A more detailed analysis of the GAB parameters can
provide further valuable information about adsorption
and desorption. A direct non-linear regression technique 4. Conclusions
was adopted, with Eqs. (8) and (9) being substituted into
Eq. (7). On the basis of this work the following conclusions
The results of the regression analysis are summarized can be drawn:
in Tables 9–11. DHc represents the difference in enthalpy
between mono-layer and multi-layer sorption (Van den • Potato starch, highly amylopectin and highly amylose
Berg, 1984). The large positive value calculated is as powders present Type II isotherms.
306 A.H. Al-Muhtaseb et al. / Journal of Food Engineering 61 (2004) 297–307
• Temperature affects the sorption behaviour; the equi-
librium moisture content decreases with increasing
temperature, at constant water activity.
• Hysteresis is evident over the entire range of water ac-
tivity for all materials.
• Within the temperature range investigated, the mod-
els developed by the empirical four parameter (Peleg),
the kinetic three parameter (GAB) and the semi em-
pirical three parameter Ferro-Fontan were found to
best represent the experimental data in the water ac-
tivity range 0.05–0.95; the Smith model gave the best
fit in the range 0.3–0.95.
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