Journal of Food Engineering 77 (2006) 753–760

www.elsevier.com/locate/jfoodeng

Thermodynamic analysis of the sorption isotherms of pure

and blended carbohydrate polymers
C. Pérez-Alonso a, C.I. Beristain b,*, C. Lobato-Calleros c,
M.E. Rodrı́guez-Huezo d, E.J. Vernon-Carter d
a
Departamento de Ingenierı́a Quı́mica, Universidad Autónoma del Estado de México, Paseo Colón esq. Paseo Tollocan s/n Col. Residencial Colón,
CP 50120 Toluca, Estado de, Mexico
b
Instituto de Ciencias Básicas, Universidad Veracruzana, Apdo. Postal 575, Xalapa, Ver., Mexico
c
Preparatoria Agrı́cola, Universidad Autónoma Chapingo, Km 38.5 Carr. México-Texcoco, Texcoco 56230, Mexico
d
Departamentos de Ingenierı́a de Procesos e Hidráulica y Biotecnologı́a, Universidad Autónoma Metropolitana-Iztapalapa, San Rafael Atlixco 186,
Col. Vicentina, CP 09340 México, DF, Mexico

Received 11 March 2005; accepted 2 August 2005

Available online 10 October 2005

Abstract

The adsorption isotherms of gum Arabic (GA), mesquite gum (MG), and maltodextrin DE 10 (MD), and a blend of the three gums
(17%GA–66%MG–17%MD) were determined at 25, 35, and 40 °C. All isotherms were fitted using the GAB model and the thermody-
namic properties (enthalpies and entropies, differential and integral) were estimated by the Clausius–Clapeyron method. The minimum
integral entropy was considered as the point of maximum stability where strong bonds between the adsorbate and adsorbent occurred,
and water is less available and likely to participate in spoilage reactions. The point of maximum stability was found between 12.24 and
14.68 kg H2O/100 kg d.s. (corresponding to water activity, aw, of 0.32–0.57) for GA, 12.12–14.27 kg H2O/100 kg d.s. (aw = 0.33–0.55)
for MG, and 11.37–13.84 kg H2O/100 kg d.s. (aw = 0.28–0.55) for the biopolymer blend, in the temperature range studied.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: Sorption isotherms; Wall materials; Thermodynamic properties; Stability; GAB model

1. Introduction (Pszczola, 1998), such as stability against oxidation, ease

In the marketplace a great number of materials are
available that can be used for encapsulation, by spray-dry-
ing, of essential oils, flavours, colorants and vitamins,
among which gum Arabic, maltodextrins and modified
starches are prominent (Giese, 1993; Watanabe, Fang,
Minemoto, Adachi, & Matsuno, 2002). To obtain stable
encapsulated additives and flavours with good functional
properties, it is of the utmost importance to make a proper
selection of the wall materials so that they Ôfit wellÕ with
the functional properties desired in the finished product
*
Corresponding author. Fax: +52 2288 4189 32.
E-mail address: cberistain@uv.mx (C.I. Beristain).
of handling, improved solubility, controlled release and ex-
tended shelf-life.
The selection of wall materials for microencapsulation
by spray-drying has traditionally involved trial and error
procedures, in which microcapsules are initially formed
and afterwards evaluated for encapsulation efficiency, sta-
bility under different storage conditions, degree of protec-
tion provided to the core material, surface observation by
scanning microscopy, among other evaluations. These pro-
cedures involve an enormous range of conditions, are
costly and time consuming.
Matsuno and Adachi (1993) proposed a method for
screening the most suitable wall materials for lipid encapsu-
lation, that takes two steps: (1) emulsification of lipid in a
solution of wall material(s), and assessing emulsifying

0260-8774/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2005.08.002
754 C. Pérez-Alonso et al. / Journal of Food Engineering 77 (2006) 753–760
activity by particle size and distribution; and (2) determina-
tion of the rate of isothermal drying of the wall material(s),
obtaining drying curves and selecting those materials that
yield concave, upward sloping curves in which drying rate
decreases rapidly as the water content decreases (type 1
curves). Nevertheless, this method does not allow for an
effective discrimination between materials showing simi-
larly shaped drying curves.
Pérez-Alonso, Báez-González, Beristain, Vernon-
Carter, and Vizcarra-Mendoza (2003) dried isothermally
aqueous solutions of gum Arabic, mesquite gum, malto-
dextrin DE10, and their blends, and determined the ‘‘acti-
vation energy’’ required by each material, or blend, for
evaporating the entrapped moisture from their matrixes.
The higher the activation energy required for moisture
evaporation, the more suitable the biopolymer or blend
for lipid microencapsulation. These authors found that a
blend of 17%GA–66%MG–17%MD exhibited the highest
activation energy, and presumably should provide better
protection to microencapsulated lipids against oxidation
than either biopolymer on its own, or any other combina-
tion. Rodrı́guez-Huezo, Pedroza-Islas, Prado-Barragán,
Beristain, and Vernon-Carter (2004) spray-dried multiple
emulsions containing carotenoids stabilized with the bio-
polymer blend suggested by Pérez-Alonso et al. (2003),
and found that the wall material provided very good pro-
tection to the carotenoids against oxidation.
Stability is greatly influenced by the moisture sorption
characteristics of the product. The thermodynamics of
water sorption in dried foodstuffs has drawn interest be-
cause it provides a more thorough interpretation of the
sorption isotherm phenomenon and helps to understand
better the sorption mechanism (Beristain, Azuara, &
Vernon-Carter, 2002).
Thermodynamics of water sorption has been used for
explaining the behaviour and structure of water on the sur-
face and in the interior of foods (Beristain, Dı́az, Garcı́a, &
Azuara, 1994; Rizvi & Benado, 1984). Moisture sorption
isotherms are useful thermodynamic tools for determining
interactions of water and food substances, and provide
information useful for assessing food processing operations
such as drying, mixing, and storage. Sorption isotherms
can also be used to investigate structural features of a food
product, such as specific surface area, pore size distribution
and crystallinity. Such data can be used for selecting appro-
priate storage conditions, and packaging systems that opti-
mize or maximize retention of aroma, flavour, colour,
texture, nutrients and biological stability (Beristain et al.,
2002; Diosady, Rizvi, Cai, & Jagdeo, 1996; Gabas,
Menegalli, & Telis, 2000).
The thermodynamic parameters establish optimum stor-
age and stability conditions (Apostolopoulos & Gilbert,
1990). For example, a change in free energy (DG) can indi-
cate an affinity of the adsorbent (wall material) for water,
and provide a spontaneous (DG) or non-spontaneous
(+DG) criteria. Changes in enthalpy (DH) can be associated
with bonding (DH) of repulsion (+DH) forces between
water and the microcapsule wall material. Furthermore,
entropy changes (DS) can define degrees of order or disor-
der existing in the wall material–water system (Apostolop-
oulos & Gilbert, 1990).
The kinetic compensation effect has been widely ob-
served in various areas such as physics, chemistry, biology
and thermal analysis. Labuza (1980) reviewed the basis for
DS/DT compensation and described the problems that can
be encountered in applying the concept of a linear enthal-
py–entropy compensation plot in food-related reactions
such as thermal inactivation of microorganisms, protein
denaturation and ascorbic acid degradation. Ferro-Fon-
tan, Chirife, Sancho, and Iglesias (1982) suggested the exis-
tence of a linear relationship between enthalpy and entropy
for water sorption in some foods. Aguerre, Suárez, and
Viollaz (1989) applied enthalphy–entropy compensation
to derive a two parameter sorption equation which took
into account the effect of temperature on water sorption
isotherms of some food products. Beristain, Garcı́a, and
Azuara (1996) analyzed the enthalpy–entropy compensa-
tion for water adsorption in two starchy foods: potatoes
and macadamia nuts, and five dried fruits, and concluded
that the linear plot of compensation correlated well for
water adsorption in starchy and sugar-rich foods. Gabas,
Telis-Romero, and Menegalli (1999) used the isokinetic
theory for modelling the effect of temperature on water
sorption of skin and pulp of grape, and concluded that
the linear plot of compensation between (DH) and (DS)
correlated well for water desorption, which occurred by en-
thalpy-controlled mechanisms.
The objective of this work was to study the sorption
thermodynamic properties of gum Arabic, mesquite gum,
maltodextrin DE 10 and a blend of these biopolymers,
and to interpret the mechanism of the sorption process
by analysing the variations of enthalpy and entropy with
respect to moisture content for all the biopolymers.
2. Materials and methods
2.1. Raw materials
Gum Arabic (Acacia senegal) (GA) was purchased from
Industria Ragar, S.A. de C.V. (Mexico City, Mexico). Mes-
quite gum (Prosopis laevigata) (MG) was collected by hand
in the Mexican State of San Luis Potosi. Both gums were
physically in the form of tear drops, and were pulverized,
dissolved, filtered and spray-dried as outlined by Vernon-
Carter et al. (1996). Maltadex 10 (maltodextrin DE 10)
(MD) was obtained from Complementos Alimenticios
S.A. de C.V. (Naucalpan, State of Mexico, Mexico) as
spray-dried powder.
2.2. Sorption isotherms
The adsorption isotherms of GA, MG, MD and a blend
of 17%GA–66%MG–17%MD (by weight) were deter-
mined. The individual biopolymers and biopolymer blend
 C. Pérez-Alonso et al. / Journal of Food Engineering 77 (2006) 753–760
were put into Petri dishes, so that they covered completely
and homogeneously the dishes surface. The dishes were
then introduced into glass desiccators, containing P2O5 as
a desiccant, at room temperature for 3 weeks in order to
reduce to a minimum the relative humidity (2%) of the
powders. The adsorption isotherms were determined by
the gravimetric method described by Lang, McCune, and
Steinberg (1981). Approximately 1 g samples of each bio-
polymer, or biopolymer blend samples of 1.0 g ± 0.1 mg
each, were put into small glass desiccators of 10 cm diam-
eter which contained saturated solutions of different salts
that provided water activities (aw) in the range of 0.11–
0.85 (Labuza, Kaanane, & Chen, 1985). Filter paper
(Whatman No. 1), placed above the saturated salt solu-
tions, in a perforated plate used as support for the powders
and for allowing moisture transmission. Three desiccators
of each powder were placed into forced convection drying
ovens at 25, 35 and 40 (±0.1) °C. The powders were
weighed every three days (Ohaus electronic balance), and
the water activity was measured with an Aqualab water
activity meter with temperature compensation (model ser-
ies 3 TE, Decagon Devices, Inc., Pullman, WA, USA).
The moisture content of the powders was determined by
weight difference after vacuum drying (Felisa model FE
100, Mexico City, Mexico) at 60 ± 1 °C for 24 h, using
magnesium perchlorate as a desiccant. Longer drying times
did not produce sample weight decrease by more than
0.1 mg.
The Guggenheim–Anderson–De Boer (GAB) equation
is a model with three parameters that have physical mean-
ing, and is recognized as the most versatile sorption model
available for the sorption of food. It is mathematically ex-
pressed as (Rizvi, 1986):
M 0 CKaw
M¼ ð1Þ
ð1  Kaw Þð1  Kaw þ CKaw Þ
where M is the equilibrium moisture content (g water/100 g
dry solids); M0 is the monolayer water content (g water/
100 g dry solids), aw is the water activity, and C is the
Guggenheim constant, given by
ðhm  hn Þ
C ¼ c0 exp ð2Þ
RT
where c 0 is the equation constant; hm is the total heat sorp-
tion of the first layer (kJ/mol); hn is the total heat of sorp-
tion of the multilayers (J/mol); R is the universal gas
constant (kJ/mol K); T is the absolute temperature (K),
and K is the constant correcting properties of the multi-
layer molecules with respect to the bulk liquid, and given
by
ðhl  hm Þ
K ¼ k 0 exp ð3Þ
RT
where k 0 is the equation constant; hl is the heat of conden-
sation of pure water (kJ/mol).
The parameters were estimated by fitting the mathemat-
ical model to the experimental data, using non-linear
755
regression with Origin version 7 Scientific Graphing and
Analysis Software (OriginLab Corp., Northampton, MA,
USA).
Goodness of fit was evaluated using the relative percent-
age difference between the experimental and predicted val-
ues of moisture content, or mean relative deviation
modulus (E), defined by the equation (Aguerre et al.,
1989; Lomauro, Bakshi, & Labuza, 1985; McLaughlin &
Magee, 1998). It is generally assumed that a good fit is ob-
tained when E < 5%.
100 X jM i  M Ei j
E¼ ð4Þ
n Mi
where Mi is the moisture content at observation i; MEi is
the predicted moisture content at that observation and n
is the number of observations.
2.3. Thermodynamic properties
The free energy for water adsorption was calculated
using GibbÕs equation:
DG ¼ RT ln aw ð5Þ
where R is the universal gas constant (kJ/mol K); T is the
sorption temperature (K), and aw is the water activity.
2.3.1. Differential properties
The differential enthalpy changes is obtained from equi-
librium sorption data, represent the difference between the
latent heat of adsorption and the latent heat of condensa-
tion of pure water. It can be determined from the following
equation, which is derived from the Clausius–Clapeyron
equation (Rizvi, 1986):
   
o lnðp=p0 Þ o ln aw hl  H l DH dif qst
¼ ¼ ¼ ¼
oð1=TÞ M oð1=TÞ M R R R
ð6Þ
where R is the universal gas constant (kJ/mol K); T is
the absolute temperature (K); p is the equilibrium pres-
sure (N/m2); p0 is vapour pressure of pure water (N/m2);
hl is the molar differential enthalpy of water absorbed
in the wall material (kJ/mol); Hl is the partial molar
enthalpy of adsorbed water at constant temperature
and pressure (kJ/mol); qst is net isosteric heat sorption
(kJ/mol).
The differential enthalpy of sorption is nearly equal to
the isosteric heat of sorption (Mariwala & Foley, 1994):
DH dif ¼ qst  RT ð7Þ
The use of the Clausius–Clapeyron equation implies that
the moisture content of the system under consideration re-
mains constant and that the enthalpy of vaporization of
pure water (as well as the excess heat of sorption) does
not change with temperature (Rizvi, 1986).
The change in molar differential entropy of adsorption
can be calculated from Gibbs–Helmholtz equation, as used
by Beristain et al. (2002):
756 C. Pérez-Alonso et al. / Journal of Food Engineering 77 (2006) 753–760

DH dif 30
DS dif ¼ sl  S l ¼  R ln aw ð8Þ 25 ºC
  T 35 ºC
oS
where s1 ¼ oN 1
is molar differential entropy of water 25
40 ºC
T ;P
adsorbed in the wall material (kJ/mol K); Sl is molar entro-

M (kg H O/100 kg d.s.)

20
py of pure water in equilibrium with the vapour (kJ/
mol K); S is total entropy of water adsorbed in the wall
material (kJ/mol K); N1 is number of moles of water ad- 15
sorbed in the wall material; R is universal gas constant

2
(kJ/mol K); aw is water activity, and T is the absolute tem- 10
perature (K).
5
2.3.2. Integral properties
The integral molar enthalpy can be calculated using an
0
equation similar to Eq. (5), but maintaining constant the 0 0.2 0.4 0.6 0.8 1
diffusion pressure, U, constant (Hill, Emmet, & Joyner, (a) Water activity
1951):
  40
o lnðp=p0 Þ Hg  Hs 25 ºC
¼ ð9Þ
oT U RT 2 35
35 ºC
40 ºC
Rearranging Eq. (9) and taking pure water as the refer-
M (kg H2O/100 kg d.s.)
30
ence state at temperature, T:
  25
o ln aw H s  H l DH int
¼ ¼ ð10Þ 20
oð1=T Þ U R R
where Hs is integral molar enthalpy of water adsorbed of 15
the wall material (kJ/mol); DHint is molar integral enthalpy
10
(kJ/mol), and U can be found by (Nunes & Rotstein, 1991):
Z
W ap aw 5
U ¼ lap  la ¼ RT M d ln aw ð11Þ
Wv 0 0
Z aw 0 0.2 0.4 0.6 0.8 1
U ¼ a1 T M d ln aw ð12Þ (b) Water activity
0
Fig. 1. Moisture sorption isotherms: (a) gum Arabic; (b) mesquite gum.
where U is diffusion pressure, or surface potential (kJ/mol),
of the wall material; lap is chemical potential of the pure
adsorbent (kJ/mol); la is chemical potential of the adsor- and sodium caseinate (Weisser, 1985). The equilibrium
bent in the condensed phase (kJ/mol); Wap is molecular moisture content values of the biopolymers were similar
weight of the adsorbent (g/mol); Wv is molecular weight to those reported for guar gum and wheat bran (Cadden,
of water (g/mol). 1988). Moisture content is expected to decrease with
Changes in molar integral entropy can be calculated increasing temperature at a given water activity (Iglesias
using Eq. (13): & Chirife, 1982). This trend was observed for MG in the
water activity region below 0.53 (Fig. 1b) and by MD be-
ðDH int ÞT
ðDS int ÞT ¼ S s  S l ¼  R ln aw ð13Þ low 0.75. However, above this region, the opposite result
T
was observed where the moisture content decreased with
where Ss = S/N1 is integral entropy of water adsorbed in temperature from 25 to 35 °C. A similar isotherm crossing
the wall material (kJ/mol K). behaviour was also observed for whey protein (Hermasson,
1977). The opposite trend was found by GA and by the
3. Results and discussion blended polymers, where moisture content increased with
the temperature (Figs. 1a and 2b). This behaviour has been
The experimental sorption isotherms at 25, 35 and 40 °C observed by microcrystalline cellulose and by fish protein
for all the biopolymers are shown in Figs. 1 and 2. The myosin (Cadden, 1988; Das & Das, 2002). Unfortunately,
experimental data were found to agree very well with the the complex nature of the adsorption phenomena in food
GAB model. The parameters from fitting the GAB model materials makes difficult to explain this adsorption behav-
are given in Table 1. The mean relative deviation modulus iour. For biopolymers, the process not only involves
value was less than 5% at 25, 35 and 40 °C. The adsorption adsorption but also structural changes of the polymer ma-
isotherms of the biopolymers had a typical sigmoid shape trix due to swelling. The conformation and topology of the
as that shown by apple pectin, soy protein, whey protein molecule and the hydrophilic/hydrophobic sites adsorbed
 C. Pérez-Alonso et al. / Journal of Food Engineering 77 (2006) 753–760 757

30 Table 1
25 ºC Estimated parameters of the GAB equation for wall materials
35 ºC T (°C) M0 (kg H2O/100 kg d.s.) C K r2 E (%)
25
40 ºC
GA
25 8.11 15.90 0.841 0.989 4.13
M (kg H O/100 kg d.s.)

20
35 9.97 18.62 0.778 0.991 4.14
40 11.00 18.83 0.740 0.989 3.66
15 MG
2

25 8.35 7.52 0.843 0.999 3.97

10
35 7.32 8.26 0.980 0.999 2.91
40 5.72 19.34 1.0 0.999 2.22
MD
5
25 7.35 12.72 0.899 0.997 3.11
35 6.99 7.84 0.902 0.999 3.03
0 40 6.96 5.26 0.889 0.996 4.80
0 0.2 0.4 0.6 0.8 1
GA17-MG66-MD17
(a) Water activity 25 6.80 17.36 0.962 0.994 3.17
35 8.93 12.73 0.907 0.997 3.49
40 40 6.39 23.04 0.965 0.996 4.76
25 ºC GA = gum Arabic; MG = mesquite gum; MD = maltodextrin; GA17–
35 35 ºC MG66–MD17 = biopolymer blend with 17% (w/w) gum Arabic–66% (w/
40 ºC w) mesquite gum–17% (w/w) maltodextrin.
30
M (kg H2O/100 kg d.s.)

25 It is assumed that strong adsorbent–adsorbate interac-

20
15
10
5
0 Iglesias and Chirife (1982) studied more than 30 foods
0 0.2 0.4 0.6
(b) Water activity
Fig. 2. Moisture sorption isotherms: (a) maltodextrin; (b) GA17–MG66–
MD17 = biopolymer blend with 17% (w/w) gum Arabic–66% (w/w)
mesquite gum–17% (w/w) maltodextrin.
at the interface is highlighted. The effect of temperature on
the water adsorption properties for GA and MG was found
opposite. This was probably due to the protein content,
size and/or shape of the involved molecules adsorbed at
the interface. López-Franco et al. (2004) reported that mes-
quite gum and gum Arabic monolayers adsorbed at the
air–water interface showed different mechanical properties,
probably due to different adsorption mechanisms.
The value of the monolayer (M0) is of particular inter-
est, as it indicates the amount of water that is strongly ad-
sorbed to specific sites and is considered as the optimum
value at which a food is more stable. Karel (1975) reported
that M0 values for several foods fell within the range of
4–11 kg H2O/100 kg d.s. The results of this work show
M0 values in the range of 5.72–11.00 kg H2O/100 kg d.s.
M0 values increased for GA as temperature increased from
25 to 40 °C, whereas that of MG and MD decreased as
temperature increased in the same temperature range.
The biopolymer blend exhibited maximum M0 at 35 °C.
tions, which are exothermic, produce temperature lowering
and increases in C (Diosady et al., 1996). However, in this
work the value of C did not show a clear trend with tem-
perature changes. Increasing temperature from 25 to
40 °C produced a steady increase in C for GA and GM,
a steady decrease in C for MD, and showed a minimum va-
lue at 35 °C for GA17-MG66-MD17 biopolymer blend.
0.8 1 and found that in 74% of them C did not increase as tem-
perature decreased, probably due to irreversible changes
associated with temperatures such increases such as enzy-
matic reactions and protein denaturation. On the other
hand, it is possible that C lacks any physical meaning,
and that it is the result of mathematical compensation
among parameters, which occurs in any curve fitting proce-
dure. The values of C ranged between 7.84 and 23.09;
which were similar to those reported for guar gum (coarse
and fine), oat bran (selected and ground), and microcrystal-
line cellulose. The values of these food fibres ranged be-
tween 7.1 and 30.8 (Cadden, 1988).
The value of K provides a measure of the interaction of
the molecules in the multilayers with the adsorbent, and
tends to fall between the energy value of the molecules in
the monolayer and that of liquid water. When K equal 1
the multilayers have the properties of liquid water. The val-
ues of K ranged between 0.74 and 1.0; the K values found
for food fibres were in the range of 0.717–0.893 (Cadden,
1988).
The differential enthalpies (DHdif) plotted as function of
water content are presented in Fig. 3. All DHdif values were
negative within the entire water content and temperature
range considered. The enthalpy values verified the existence
of strong attractive forces in the mixing of water with the
wall materials, which apparently governed the binding of
758 C. Pérez-Alonso et al. / Journal of Food Engineering 77 (2006) 753–760
50
45 GA
MG
40
MD
35 GA17-MG66-MD17
30
-ΔHdif (kJ/mol)
25
20
15
10
5
0
-5
0 5 10 15 20 25
M (kg H2O/100 kg d.s.)
Fig. 3. Isosteric heat adsorption of water for wall materials. GA = gum
Arabic; MG = mesquite gum; MD = maltodextrin; GA17–MG66–
MD17 = biopolymer blend with 17% (w/w) gum Arabic–66% (w/w)
mesquite gum–17% (w/w) maltodextrin.
water to wall material. Wall materials may exhibit active
sites with different binding energies on their surface (Rizvi
& Benado, 1984). Thus, water molecules were sorbed pref-
erentially onto active sites with the strongest forces produc-
ing the most negative DHdif values 32, 26.3 and 36.5 kJ/mol
for GA, MG and GA17-MG66-MD17, respectively, all at
a water content of 7.5 kg H2O/100 kg d.s., approximately.
As the water content increased, water molecules pene-
trated the wall material matrix and occupied all the acces-
sible active sites. Penetration of water molecules in the wall
material matrix initiated swelling, and for the biopolymer
blend swelling was higher than for the individual gums
indicating that stronger interactions exist. The differential
enthalpy increases to a maximum with increasing moisture
content and then gradually decreases in magnitude as water
content increases. The increasing DHdif corresponds to an
endothermic process that may be associated with swelling
of the carbohydrate polymer matrix that exposes new ac-
tive sites, where new water molecules can be adsorbed by
an exothermic process that compensates the endothermic
heat. The same trend in differential enthalpy has been re-
ported for food proteins, macadamia nut and potatoes
(Beristain et al., 1996; Das & Das, 2002; Iglesias, Chirife,
& Viollaz, 1976).
The behaviour of MD was different from that shown by
GA, MG and the biopolymer blend. MD shows higher val-
ues of DHdif than the other polymers up to moisture con-
tents of around 3 kg H2O/100 kg d.s., suggesting more
active adsorption sites with higher energies. The maximum
enthalpy value indicates the covering of the strongest bind-
ing sites and greater water–solid interactions. The covering
of less active adsorption sites and the formation of multi-
layers is manifested by the decrease in enthalpy as water
content increases (Fig. 3). This probably means that MD
does not swell, or does not swell to the extent that the other
polymers do, causing MD–water interactions to be pre-
dominant at very low moisture contents, but not at high
moisture contents.
Fig. 4 shows the differential entropy as a function of
moisture content at 25 °C. Differential entropy had a min-
imum at 7.5 kg H2O/100 kg d.s. (approximately) for all the
wall materials which similar to the GAB monolayer values
(8.11 kg H2O/100 kg d.s. for GA, 8.3 kg H2O/100 kg d.s.
for MG and 6.80 kg H2O/100 kg d.s. for the biopolymer
blend). This behaviour was exhibited at 35 and 40 °C by
these powders.
GA, MG and the biopolymer blend showed a decrease
in differential entropy, reaching a minimum and then
increasing in magnitude as water content increased. This
same trend was exhibited by Granny Smith apples and
30
orange oil encapsulated with mesquite gum (Nunes &
Rotstein, 1991; Beristain et al., 2002). MD showed a con-
tinuous increase in the differential entropy up to moisture
content of 15 kg H2O/100 kg d.s., remaining practically
constant at higher moisture contents. This parameter does
not mean order or disorder of the total system. The differ-
ential entropy represents the algebraic sum of the integral
entropy at a particular hydration level plus the change of
order or disorder after new water molecules are adsorbed
by the system at the same hydration level. If the values
of moisture content corresponding to minimum integral en-
tropy and minimum differential entropy are different, this
particular hydration level at the minimum differential en-
tropy cannot be considered as the maximum stability point,
because not all available actives sites have been occupied at
that particular water content, and therefore it is possible to
obtain, after this point, lower differential changes that pro-
vide a better ordering of the water molecules adsorbed on
the food. The water content at the minimum differential en-
tropy in this case was similar to the GAB monolayer values
0.00
-0.02
-0.04
Δ Sdif (kJ/mol K)
-0.06
-0.08
GA
MG
-0.10 MD
GA17-MG66-MD17
-0.12
0 5 10 15 20 25 30
M (kg H2O/100 kgd.s.)
Fig. 4. Differential entropy as a function of moisture content for wall
materials at 25 °C. GA = gum Arabic; MG = mesquite gum; MD = mal-
todextrin; GA17–MG66–MD17 = biopolymer blend with 17% (w/w) gum
Arabic–66% (w/w) mesquite gum–17% (w/w) maltodextrin.
 C. Pérez-Alonso et al. / Journal of Food Engineering 77 (2006) 753–760
-0.04
-0.06
Δ Sint (kJ/mol K)
-0.08
-0.10
5 10 15
M (kg H2O/100kgd.s.)
Fig. 5. Integral entropy as a function of moisture content for wall
materials at 25 °C. GA = gum Arabic; MG = mesquite gum; MD = mal-
todextrin; GA17–MG66–MD17 = biopolymer blend with 17% (w/w) gum
Arabic–66% (w/w) mesquite gum–17% (w/w) maltodextrin.
because the maximum entropy change was provoked by the
water sorption on the most active sites. Monolayer value is
the saturation of polar groups corresponding to water ad-
sorbed at the most active sites.
Fig. 5 shows the variation in the integral entropy, with
moisture content at 25 °C, for the biopolymers. As the
powders adsorbed moisture the entropy diminished to a
minimum point that is considered as that of maximum sta-
bility, because it is where the water molecules achieve a
more ordered arrangement within the solid. The integral
entropy values found were 14.68 kg H2O/100 kg d.s. for
GA, 14.02 kg H2O/100 kg d.s. for MG and 13.84 kg H2O/
100 kg d.s. for the biopolymer blend. MD did not exhibit
a minimum, showing a continuous increase in integral en-
tropy with increasing moisture content. All the samples
showed the same tendencies at 35 and 40 °C. The same
trend in integral entropy vs moisture content has been re-
ported for sugar beet root, green whole coffee beans and
ethyl acetate decaffeinated beans (Beristain et al., 1994;
Iglesias et al., 1976). The minimum entropy can be inter-
preted as the moisture content of the monolayer (Hill
et al., 1951; Nunes & Rotstein, 1991). This minimum
value is expected to arise where strong bonding occurs be-
tween adsorbent and adsorbate, and therefore, where there
is less water available for spoilage reactions. It can also
be seen from Fig. 5 that the moisture content corre-
sponding to the minimum integral entropy value for gum
Arabic to achieve maximum stability was greater than
that corresponding to the GAB monolayer (8.11 kg H2O/
100 kg d.s.). The same occurred for MG (8.3 kg
H2O/100 kg d.s.) and the biopolymer blend (6.80 kg H2O/
100 kg d.s.). The biopolymer blend exhibited the lowest
minimum integral entropy, so it may be considered as a
better wall material than GA or MG.
759
Table 2
Maximum stability conditions of biopolymers
GA T (°C) GA MG GA17-MG66-MD17
MG
MD
M (kg H2O/ aw M (kg H2O/ aw M (kg H2O/ aw
GA 17- MG 66- MD 17 100 kg d.s.) 100 kg d.s.) 100 kg d.s.)
25 14.68 0.574 14.02 0.554 13.84 0.553
35 12.66 0.386 14.27 0.507 13.29 0.440
40 12.23 0.316 12.12 0.329 11.37 0.281
GA = gum Arabic; MG = mesquite gum; MD = maltodextrin; GA17–
MG66–MD17 = biopolymer blend with 17% (w/w) gum Arabic–66% (w/
w) mesquite gum–17% (w/w) maltodextrin.
The conditions for maximum stability of the biopoly-
mers shown from the thermodynamic analysis are shown
20 25 in Table 2. As can be appreciated, as temperature increases
the water activity of the powders decreases.
4. Conclusions
The GAB equation was useful for modelling moisture
sorption of gum Arabic, mesquite gum, maltodextrin and
a blend of the three biopolymers in a proportion of
17:66:17%, respectively, in a water activity range of
0.11–0.85 and at 25, 35 and 40 °C. The minimum integral
entropy is proposed as indicative of the most suitable con-
ditions for storage, with the corresponding aw being avail-
able from the isotherm; this is in the range of 0.28–0.57 for
the temperature range between 25 and 40 °C.
Acknowledgment
The authors gratefully acknowledge the financial sup-
port of the National Council for Science and Technology
of Mexico (CONACyT) through grant G33565B.
References
Aguerre, R. J., Suárez, C., & Viollaz, P. E. (1989). New BET type
multilayer sorption isotherms. Part II: Modelling water sorption in
foods. Lebensmittel-Wissenschaft u-Technologie, 22, 192–195.
Apostolopoulos, D., & Gilbert, S. G. (1990). Water sorption of coffee
solubles by frontal inverse gas chromatography: thermodynamic
considerations. Journal of Food Science, 55, 475–477.
Beristain, C. I., Azuara, E., & Vernon-Carter, E. J. (2002). Effect of water
activity on the stability to oxidation of spray-dried encapsulated
orange peel oil using mesquite gum (Prosopis juliflora) as wall material.
Journal of Food Science, 67, 206–211.
Beristain, C. I., Dı́az, R., Garcı́a, H. S., & Azuara, E. (1994). Thermo-
dynamic behavior of green whole and decaffeinated coffee beans during
adsorption. Drying Technology, 12, 1221–1233.
Beristain, C. I., Garcı́a, H. S., & Azuara, E. (1996). Enthalpy–entropy
compensation in food vapour sorption. Journal of Food Engineering,
63, 405–415.
Cadden, A. M. (1988). Moisture sorption characteristics of several food
fibers. Journal of Food Science, 53(4), 1150–1155.
Das, M., & Das, S. K. (2002). Analysis of moisture sorption characteristics
of fish protein myosin. International Journal of Food Sciences and
Technology, 37, 223–227.
Diosady, L. L., Rizvi, S. S. H., Cai, W., & Jagdeo, D. J. (1996). Moisture
sorption isotherms of canola meals, and applications to packing.
Journal of Food Science, 61, 204–208.
760 C. Pérez-Alonso et al. / Journal of Food Engineering 77 (2006) 753–760
Gabas, A. L., Telis-Romero, J., & Menegalli, F. C. (1999). Thermody-
namic models for water sorption by grape skin and pulp. Drying
Technology, 17(4–5), 961–974.
Gabas, A. L., Menegalli, F. C., & Telis, R. J. (2000). Water sorption
enthalpy–entropy compensation based on isotherms of plum skin and
pulp. Journal of Food Science, 65, 680–684.
Giese, J. (1993). Packing, storage, and delivery ingredients. Food Tech-
nology, 47(8), 54–58, 60, 62–63.
Hermasson, A. (1977). Functional properties of proteins for foods water
vapour sorption. Journal of Food Technology, 12, 177–187.
Hill, T. L., Emmet, P. H., & Joyner, L. G. (1951). Calculation of
thermodynamic functions of adsorbed molecules from adsorption
isotherm measurements: nitrogen on graphon. Journal of the American
Chemical Society, 73, 5102–5107.
Ferro-Fontan, C., Chirife, J., Sancho, E., & Iglesias, H. A. (1982).
Analysis of a model for water sorption phenomena in foods. Journal of
Food Science, 47, 1590–1594.
Iglesias, H. A., & Chirife, J. (1982). Handbook of food isotherms. New
York, USA: Academic Press.
Iglesias, H. A., Chirife, J., & Viollaz, P. (1976). Thermodynamic of water
vapor sorption by sugar beet root. Journal of Food Technology, 11,
91–101.
Karel, M. (1975). Water activity and food preservation. In M. Karel, O.
R. Fennema, & D. B. Lund (Eds.), Physical principles of food
preservation. Principles of food science, Part 2 (pp. 237–263). New
York: Marcel Dekker, Inc.
Labuza, T. P. (1980). Enthalpy–entropy compensation in food reactions.
Food Technology, 34, 67–77.
Labuza, T. P., Kaanane, A., & Chen, J. Y. (1985). Effect of temperature
on the moisture sorption isotherms and water activity shift of two
dehydrated foods. Journal of Food Science, 50, 385–391.
Lang, K. W., McCune, T. D., & Steinberg, M. P. (1981). A proximity
equilibration cell for rapid determination of sorption isotherms.
Journal of Food Science, 46, 936–938.
Lomauro, G. J., Bakshi, A. S., & Labuza, T. P. (1985). Evaluation of food
moisture sorption isotherms equations. Part I: Fruit, vegetables and
meat products. Lebensmittel- Wissenschaft u-Technologie, 18, 111–117.
López-Franco, Y. L., Valdez, M. A., Hernández, J., Calderon de la Barca,
A. M., Rinaudo, M., & Goycoolea, F. M. (2004). Macromolecuar
dimensions and mechanical properties of monolayer films of sonorean
mesquite gum. Macromolecular Biosciences, 4, 865–874.
Mariwala, R. K., & Foley, H. C. (1994). Calculation of micropore
sized in carbogenic materials from methyl chloride adsorption
isotherm. Industrial and Engineering Chemistry Research, 33,
2314–2321.
Matsuno, R., & Adachi, S. (1993). Lipid encapsulation technology—
Techniques and applications to foods. Trends in Food Science and
Technologie, 4, 256–261.
McLaughlin, C. P., & Magee, T. R. A. (1998). The determination of
sorption isotherm and the isosteric heats of sorption for potatoes.
Journal of Food Engineering, 35, 267–280.
Nunes, R. V., & Rotstein, E. (1991). Thermodynamics of the water–
foodstuff equilibrium. Drying Technology, 9, 113–117.
Pérez-Alonso, C., Báez-González, J. G., Beristain, C. I., Vernon-Carter, E.
J., & Vizcarra-Mendoza, M. G. (2003). Estimation of the activation
energy of carbohydrate polymers blends as selection criteria for the
use as wall material for spray-dried microcapsules. Carbohydrate
Polymers, 53, 197–203.
Pszczola, D. E. (1998). Encapsulated ingredients: providing the right fit.
Food Technology, 52(12), 70–72, 74–76.
Rizvi, S. S. H., & Benado, A. L. (1984). Thermodynamic properties of
dehydrated foods. Food Technology, 38(3), 83–92.
Rizvi, S. S. H. (1986). Thermodynamic properties of foods in dehydration.
In N. A. Rao & S. S. A. Rizvi (Eds.), Engineering properties of foods
(pp. 133–214). New York: Marcel Dekker, Inc.
Rodrı́guez-Huezo, M. E., Pedroza-Islas, R., Prado-Barragán, L. A.,
Beristain, C. I., & Vernon-Carter, E. J. (2004). Microencapsulation by
spray-drying of multiple emulsions containing carotenoids. Journal of
Food Science, 69, E351–E359.
Vernon-Carter, E. J., Gómez, S. A., Beristain, C. I., Mosqueira, G.,
Pedroza-Islas, R., & Moreno-Terrazas, R. C. (1996). Color degrada-
tion and coalescence kinetics of Aztec marigold oleoresin-in-water
emulsions stabilized by mesquite or arabic gums and their blends.
Journal of Texture Studies, 27, 625–641.
Watanabe, Y., Fang, X., Minemoto, Y., Adachi, S., & Matsuno, R.
(2002). Suppressive effect of saturated L-ascorbate on the oxidation of
linoleic acid encapsulated with maltodextrin or gum Arabic by spray-
drying. Journal of the Agricultural and Food Chemistry, 50, 3984–
3987.
Weisser, H. (1985). Influence of temperature on sorption equilibria. In D.
Simatos & J. L. Multon (Eds.), Properties of water in foods
(pp. 95–118). Dordrecht, Netherlands: Martinus Nijhoff Publishers.