Prediction of water activity of osmotic solutions

A.M. Sereno
a,
*
, M.D. Hubinger
b
, J.F. Comesa~ na
c
, A. Correa
c
a
Department of Chemical Engineering, University of Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto, Portugal
b
Faculty of Food Engineering, University of Campinas, 13.083-970 Campinas, S. Paulo, Brazil
c
Department of Chemical Engineering, University of Vigo, Apdo. 874, 36200 Vigo, Spain
Received 1 June 2000; accepted 1 December 2000
Abstract
Models to correlate and predict water activity in aqueous solutions of single and multiple solutes, including electrolytes, relevant
for osmotic processing of foods are reviewed. During the last decade a signicant number of theoretical thermodynamic models that
are applicable to these systems have been developed and published. Though their use is still limited, their performance is in general
very good, similar to the best traditional empirical equations. Their predictive character together with built-in capabilities to work at
dierent temperatures and in some cases pressure suggests that an increased eort to their wide use should take place. It was found
that predictions of water activity in aqueous solutions may easily be made with average relative deviations of less than 2%; this value
is of the same order or in some cases less than the typical error of current instrumentation available to measure water activity. 2001
Elsevier Science Ltd. All rights reserved.
Keywords: Osmotic dehydration; Vapourliquid equilibria; Water activity; Sugars; Electrolytes; Aqueous solutions; Predictive models
1. Introduction
Osmotic treatments involve the contact of a material,
usual of vegetal or animal origin, with a concentrated
aqueous solution and include namely osmotic dehydra-
tion and solute impregnation processes. These constitute
simple food processing operations conducted at ambient
or near ambient temperature, which achieve a signicant
degree of dewatering without phase change and allowing
some degree of product formulation and even restruc-
turing.
A special mention should be made about the use of
osmotic treatments in the preparation of intermediate
moisture foods (IMF) and the so-called fourth genera-
tion or minimally processed foods. Such processes have
been also referred to as dewatering and impregnation
soaking (Raoult-Wack, Rios, Saurel, Giroux, & Guil-
bert, 1994) and are mainly being used as a pre-treatment
introduced in any conventional fruit and vegetable
processing, in order to improve quality, reduce energy
costs or even formulate nal products. Applications
have been reported for sh and certain meat products
(Collignan & Raoult-Wack, 1994; Bohuon, Collignan,
Rios, & Raoult-Wack, 1998; Sabadini, Carvalho, So-
bral, & Hubinger, 1998), as well as for fruit products,
when the correct choice of solutes and a controlled ratio
of water removal and impregnation allow to enhance
their natural avour and colour retention (Raoult-Wack
et al., 1994; Guerrero, Alzamora, & Gerschenson, 1996;
Alzamora, 1997; Forni, Sormani, Scalise, & Torregiani,
1997; Spiess & Behsnilian, 1998).
As a preliminary step to convective air drying,
several studies are found in the recent literature as well
as its inuence on nal food properties (Lenart, 1996;
Del Valle, Cuadros, & Aguilera, 1998; Sa, Figueiredo,
& Sereno, 1999; Salvatori, Andres, Chiralt, & Fito,
1999; Lewicki & Lukaszuk, 2000; Krokida, Kiranou-
dis, Maroulis, & Marinos-Kouris, 2000). The combi-
nation of osmotic dehydration to some less common
drying steps, such as microwave drying (Venkatacha-
lapathy & Raghavan, 1999) and freeze-drying (Ka-
rathanos, Anglea, & Karel, 1996) has also been
described.
Osmotic pre-treatments may be used before vacuum
frying, by immersion in solutions of high osmotic pres-
sure (Spiess & Behsnilian, 1998), the eect on mass
transfer rates of high hydrostatic pressure (HPP) pro-
cessing, previous to osmotic treatment of vegetable tis-
sues was also investigated (Rastogi & Niranjan, 1998;
Rastogi, Angersbach, & Knorr, 2000).
Journal of Food Engineering 49 (2001) 103114
www.elsevier.com/locate/jfoodeng
*
Corresponding author. Fax: +351-22-508-1440.
E-mail address: sereno@fe.up.pt (A.M. Sereno).
0260-8774/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 6 0 - 8 7 7 4 ( 0 0 ) 0 0 2 2 1 - 1
The transfer of mass, water and solutes observed
during the contact of a solid material with an osmotic
solution is due to dierences in chemical potential inside
and outside the material, usually expressed in terms of
the corresponding activity coecients. As dehydration is
the main objective of osmotic treatments, the activity of
water in both the material and the solution and its
prediction is of major importance. This relevance is
particularly emphasised when mathematical models are
used to describe the process. For cellular materials, as is
the case of most foods, water transfer takes place in the
vicinity of the cell through the semi-permeable cell
membrane (Le Maguer, 1988); again dierence of water
activity in both sides governs its physical behaviour and
mass transport.
The thermodynamic description of these osmotic so-
lutions has been the object of intense research all along
the last century, particularly those involving sugars and/
or salts. Excellent reviews of such eorts have been
written by Van den Berg and Bruin (1981) and Le Ma-
guer (1992) to mention only two papers. Most thermo-
dynamic models used to describe vapourliquid
equilibrium of osmotic solutions are based on relations
involving Gibbs free energy of the system. Of particular
interest is the excess Gibbs energy (G
E
) and for each of
the components the partial molar excess Gibbs energy
(g
E
i
), both allowing a convenient way to quantify the
deviations from ideal behaviour.
From G
E
, a large number of physical parameters may
be calculated such as water and solute activities, partial
equilibrium properties (solubility, relative volatility,
etc.) and others (Le Maguer, 1989).
The activity of water in aqueous solutions is dened
as (Prausnitz, Lichtenthaler, & Azevedo, 1986):
a
W
T; P; x c
W
T; P; x x
W

f
W
T; P; x
f
0
W
T; P
0
; x
0

; 1
where a
W
is the water activity, x
W
is the mole fraction of
water, c
W
is the activity coecient for water, f
W
; f
W
are
the fugacities of water in the system and at reference
conditions, respectively.
It is usually assumed that under normal working
conditions of ambient temperature and atmospheric
pressure, gas phases behave ideally and so the ratio of
fugacities can be taken as the ratio of partial pressures
(Reid, Prausnitz, & Poling, 1987):
f
W
f
0
W

p
W
p
0
W
; 2
where p
W
and p
0
W
are the vapour pressures of water in
the system and of pure liquid water at the same tem-
perature, respectively. Under this assumption, from
Eq. (1):
a
W

p
W
p
0
W

RH
100
; 3
where RH is the percent relative humidity of the air
layer in equilibrium with the sample. The activity coef-
cient c
W
may be calculated directly from the partial
molar excess Gibbs energy of water, g
E
W
(Prausnitz et al.,
1986):
g
E
W
RT ln c
W
; 4
and for the total molar excess Gibbs energy, g
E
:
g
E
RT

i
x
i
ln c
i
5
for an ideal solution all the activity coecients,
c
i
T; P; x, are equal to one, corresponding to an excess
Gibbs energy equal to zero.
Several approaches have been used to calculate or
estimate excess Gibbs energy in liquid solutions, in-
cluding empirical models based on solution composi-
tion, the use of equations of state extended to the
description of condensed phases and probably more
often, dierent theories developed to describe solution
structure and interactions among the chemical species.
In Table 1 the major methodological groups used by
published contributions to the prediction of water ac-
tivity of solutions are indicated.
Most of the models included in Table 1 are general in
themselves and may be used with food and related sys-
tems (Prausnitz et al., 1986; Le Maguer, 1992). The
Nomenclature
a activity
ARD average relative deviation (%)
f fugacity
G
E
Gibbs free energy (J)
g
E
molar Gibbs free energy (J mol
1
)
h molar heat of mixing (J mol
1
)
M molar mass kg mol
1

P pressure (Pa)
p partial pressure (Pa)
R gas constant
RH relative humidity (%)
RMS root mean square
T temperature (K)
x mole fraction
Greeks
c activity coecient
t
FH
i
no. of non-hydrogen atoms in molecule i
t
ki
no. of non-hydrogen atoms in group k of component i
Subscripts
i component i
W water
Superscripts
reference state
104 A.M. Sereno et al. / Journal of Food Engineering 49 (2001) 103114
diculties usually arise from the fact that as most food
systems are not well characterised both from a chemical
and structural point of view, and consequently ther-
mophysical property data required to use (and t) the
models to such systems are not available. One way to
overcome these diculties in practical applications is to
look for correlations between these thermodynamic
properties and some easy method to measure physical
properties. This approach produced a series of empirical
and semi-empirical models which provide in many cases
excellent results and constitute relevant contributions of
widespread use in the food industry (Table 2).
All the models mentioned in Tables 1 and 2 refer to
solutions, more specically aqueous solutions. A parallel
eort has been dedicated to the correlation and predic-
tion of sorption isotherms in solid foods; a large number
of equations and models used to describe and predict
water activity and sorption isotherms of food systems
containing solid phases (Van den Berg & Bruin, 1981;
Iglesias & Chirife, 1982). Such models were not included
here, as only aqueous solutions constituted the scope of
this work.
An alternative approach to the use of empirical and
semi-empirical equations consists in the application of
group contribution methods, namely ASOG (analytical
solutions of groups, Derr & Deal, 1969; Kojima &
Tochigi, 1979) and UNIFAC (UNIQUAC functional
group activity coecients, Fredenslund, Jones, &
Prausnitz, 1975; Larsen, Rasmussen, & Fredenslund,
1987). These two proposals probably constitute the only
general accessible predictive technique for water activity
of osmotic solutions. Their main advantage is to provide
a technique for a
W
prediction for complex systems
without requiring parameters for each specic com-
pound, but instead characteristic interaction parameters
for the chemical groups that constitute each molecule.
The eect in the solution of each of such chemical group
is assumed to be the same, irrespective of the molecule
where it is contained.
The ASOG method, based on the Wilson model
(Wilson, 1964), has been used for this purpose by Correa
et al. (1994), who obtained good a
W
predictions for
aqueous solutions of both sugar/polyol and sugar/urea.
Kawaguchi et al. (1981, 1982) have combined the
method with an hydration model of ionic species origi-
nated in aqueous solutions of electrolytes; later Correa
et al. (1997) have redened the groups in solution, ob-
taining improved predictions for several binary and
multicomponent salt solutions.
Attempts to predict water activity using UNIFAC
have also been extensively reported. Choudhury and Le
Maguer (1986) used this method to predict a
W
in glucose
solutions and Achard et al. (1992) described its use to
estimate activity coecients in aqueous systems con-
taining sugars and polyols; Catte et al. (1995) used the
same group typology as suggested by Correa et al.
(1994) to characterise sugars, and successfully estimated
several thermodynamic properties. Christensen et al.
(1983) and Kikic et al. (1991) applied the same model to
predict equilibria in salt solutions. Very interesting ex-
tensions to cover organic acids (Velezmoro & Meirelles,
1998), polyethylene glycol and other polyols (Ninni et
al., 1999a, 2000), aminoacids (Ninni et al., 1999b) have
been developed by Meirelles and co-workers.
Table 1
Dierent approaches to calculate G
E
and activity coecients
Empirical equations based on solution composition
Simple equations, often including semi-theoretical basis, which often produce reasonable predictions of liquidvapour and liquidliquid
equilibria; served in some cases as the basis for more complex models: Margules equation, the Wohl expansion, Van Laar equation, RedlichKister
equation, ScatchardHamer equation
Use of equations of state (EOS)
Hu, Liu, Soane, and Prausnitz (1991): use double lattice (Freed & Flory-Huggins) to calculate Helmholtz energy of mixing, used to describe
equilibrium in non-polar or slightly polar non-ideal systems
Wu, Lin, Zhu, and Mei (1969): use modied version of Pitzer (1973) virial EOS with Fowler and Guggenheim (1939) instead of the more
common DebyeHuckel contribution of long-range electrostatic forces
Simonin (1999): uses McMillanMayer theory, assuming molecules as hard bodies interacting through van der Waals short range forces; to allow
for the presence of polar molecules (alcohols) and weak electrolytes, and a volume exclusion contribution using CarnahanStarling hard sphere
EOS
Solution theories
Van der Waalsvan Laar theory: valid only for nearly ideal systems
Regular solution theory (Hildebrand, 1929; Scatchard, Hamer, & Wood, 1938): systems without interactions among polar molecules (athermal),
e.g. hydrocarbons
Debye and Huckel (1923) introduced a successful description of long-range polar and ionic forces contribution
Lattice theory due mostly to Guggenheim (1935, 1952) and Eyring and Marchi (1963)
Flory (1941, 1942) and Huggins (1942) extension of lattice theory to polymer solutions
Local-composition models, namely Wilson (1964); NRTL model of Renon and Prausnitz (1968); UNIQUAC model of Abrams and Prausnitz
(1975)
A.M. Sereno et al. / Journal of Food Engineering 49 (2001) 103114 105
These extensive and successful applications of the two
major group contribution methods to predict water ac-
tivity of osmotic solutions constitute an example, pos-
sibly one of the earliest, of the use of advanced
thermodynamic models to describe the behaviour of
food-related systems.
2. How group contribution methods work
The main principle underlying this technique is the
assumption that all chemical functional groups in solu-
tion interact with other specic groups in a similar way,
independent of the types of groups in presence and of
the specic molecules where they are contained. To use
the method the rst step consists in `breaking' the
structure of the molecule in all its basic groups, for
which interaction and individual geometric parameters
are available. Since then, the method is applied as if the
solution was made of known groups instead of unknown
molecules.
Since their development the list of identied and
well-characterised groups is increasing. Unfortunately
some of the compounds found in food-related systems
are too complex and sometimes new groups have to be
identied and characterised. This happened with sug-
ars. Sugars in aqueous solutions, both monosaccha-
rides, like glucose and fructose, and disaccharides, like
sucrose, adopt a cyclic structure made of pyranose and
furanose unit rings (Fig. 1). To successfully describe
such compounds by the ASOG method, Correa et al.
(1994) dened three new groups named GR, FR and
CPOH standing for `glucose ring', `fructose ring' and
`cyclic-polyalcohol' (OH groups linked to consecutive
carbon atoms in a cyclic sugar structure). For polyhy-
dric alcohols (e.g. glycerol, mannitol and sorbitol) a
new group POH referring to OH groups linked to
consecutive carbon atoms in a linear chain was also
adopted. A fth `group' dened was UREA for the
urea molecule, as it could not be adequately repre-
sented by a combination of available ASOG groups
(Table 3).
The method uses two specic individual group pa-
rameters t
FH
i
and t
ki
, and four interaction parameters for
each binary pair of groups. Table 4 lists the values of
these parameters for some relevant compounds.
Table 2
Models to calculate water activity in aqueous solutions relevant to food systems
1. Empirical equations
Simple early formulas applicable to the candy industry: Grover and Nicol (1940), Money and Born (1951) and Dunning, Evans, and Taylor
(1951)
Zdanovskii (1936) and Stokes and Robinson (1966) proposed independently, equivalent models, valid, respectively, for electrolytes and non-
electrolytes, whose merits were discussed in detail by Chen, Sangster, Teng, and Lenzi (1973)
Several authors attempted to correlate water activities with freezing point depression, with moderate success: Ferro-Fontan and Chirife (1981),
Lerici, Piva, and Rosa (1983) and Chen (1987)
Lin, Zhu, Mei, and Yang (1996) proposed a simplied formula with two parameters per solute and one additional per binary interaction;
Comesa~ na, Correa, and Sereno (2000) extended to sugars and salts
Roa and Tapia (1998) proposed a very simple yet reasonably successful formula with a single parameter per solute in mixed multicomponent
solutions
2. Semi-empirical equations
A rst group includes empirical approximation of deviations from Raoult's law, Caurie (1985) and the very successful model by Chen (1989,
1990), which unfortunately involves three empirical parameters per solute
Based on the identity between equilibrium relative humidity and thermo-dynamic activity, Norrish (1966), developed one of the most successful
equations applicable to non-ionic solutes; extensions were made by Chuang and Toledo (1976) and Chirife, Ferro-Fontan, and Benmergui (1980)
calculated an improved set of parameters which has been generally adopted since then
Based on the GibbsDuhem equation for multicomponent aqueous solutions, Ross (1975) proposed a simple and successful mixing rule to
predict water activity of multicomponent solutions; extensions made by Ferro-Fontan, Chirife, and Boquet (1981) and Ruegg and Blanc (1981)
3. Local composition models
WILSON model has been used in some models combined with other contributions and is the basis of ASOG group contribution method to
predict thermodynamic equilibria. Sorrentino, Voilley, and Richon (1986), used it to predict activity coecients of aroma compounds and
Kawaguchi, Kanai, Kajiwara, and Arai (1981, 1982), of electrolytes; Correa, Comesa~ na, and Sereno (1994) applied to sugar/polyol/urea; later
Correa, Comesa~ na, Correa, and Sereno (1997) applied to electrolyte solutions, introducing modications to Kawaguchi's approach
UNIQUAC model was used by Le Maguer (1981), Saravacos and Marino-Kouris (1990) and Sander, Fredenslund, and Rasmussen (1986),
combined with DebyeHuckel contribution and applied to electrolyte systems. Le Maguer (1992) proposed a building block concept to calculate
individual molecular parameters. This model is the basis of the well-known UNIFAC group contribution method; Choudhury and Le Maguer
(1986) used it with glucose solutions; Gabas and Laguerie (1992) with sugar solutions; Achard, Gros, and Dussap (1992) with sugars and polyols;
Catte, Dussap, and Gros (1995) and Peres and Macedo (1997) introduced some improvements to describe sugars; Christensen, Sander,
Fredenslund, and Rasmussen (1983) and Kikic, Fermeglia, and Rasmussen (1991) applied to electrolytes. Velezmoro and Meirelles (1998) applied
the concept to systems of organic acids; Ninni, Camargo, and Meirelles (1999a, 2000), to polyethylene glycol and other systems with polyols;
Ninni, Camargo, and Meirelles (1999b), to aminoacids
106 A.M. Sereno et al. / Journal of Food Engineering 49 (2001) 103114
3. Solutions with electrolytes
Although some of the general models included in
Tables 1 and 2 have proved to be able to describe
aqueous electrolyte solutions, this group of systems has
deserved, from the early stages, a special separate at-
tention. Eective empirical and semi-empirical equa-
tions were derived, but their contribution to the
theoretical understanding of these systems has been
minimal. Several reviews have been published during the
last 20 years, focusing particular lines of research; a
special mention about the work of Zemaitis, Clark,
Rafal, and Scrivner (1986) where much of the published
previous information including data are collected and
that of Renon (1986). Loehe and Donohue (1997) give a
list of such reviews together with a general broad view of
recent advances.
Before 1985, most of the works have been conducted
along the principles introduced by Debye and Huckel
(1923) theories and their modication by Pitzer (1973),
Bromley (1973) and Sandler (1977). In terms of new
theoretical research on electrolyte systems, modern de-
velopments follow, according to Loehe and Donohue
(1997), four major lines: (i) extensions to DebyeHuckel
theories, which assume the system to be made of
charged ions in a continuous dielectric medium, and
employ dierent forms of the PoissonBoltzman equa-
tions to calculate potential energies in the system; (ii)
perturbation theories that use a series expansion of the
Helmholtz free energy about a given reference state; (iii)
integral equation theories that include solutions of the
OrnsteinZernicke equation, namely using the spherical
approximation concept and (iv) uctuation solution or
Table 4
Values of t
FH
i
and t
ki
for some compounds considered
Compound t
FH
i
Groups: t
ki
Glucose 12 GR:6 CPOH:4 CH2:1 OH:1
Fructose 12 FR:5 CPOH:3 CH2:2 OH:2
Sucrose 23 GR:6 FR:5 CPOH:5 CH2:3
Glycerol 6 POH:3 CH2:2.8 OH:3 O:1
Urea 4 UREA:4
Water 1 H2O:1.6
Partial list of ASOG group pair parameters, including the new groups
H
2
O GR FR O CPOH CH
2
OH POH Urea
H
2
O )1.6667 )0.8312 )20.26 0.2826 0.5045 1.4318 )3.714 )0.0067 m
0.7717 1.5856 )1.2186 2.170 )2382. )280.2 )2.418 )2.186 n
GR 0.7435 0.8393 1.8119 2.014 0.3248 0.1652 )0.9060 1.0312 m
1.3432 )1.2930 )6.468 0.3987 3.473 1.5168 7.833 )4.198 n
FR )0.0377 )14.561 1.2042 0.6475 0.8477 0.7318 )1.6816 )2.126 m
)0.8764 )1.5918 0.2919 1.5562 1.6635 0.9593 2.309 )4.814 n
Fig. 1. Ring structures for sugars in aqueous solution.
Table 3
New ASOG interaction groups
POH Polyalcohol OH groups linked to consecutive carbon atoms in a linear chain
FR Fructose ring Furanose cyclic structure of fructose in water
GR Glucose ring Pyranose cyclic structure of glucose in water
CPOH Cyclic polyalcohol OH groups linked to consecutive carbon atoms in a cyclic sugar structure
UREA Urea Urea molecule
A.M. Sereno et al. / Journal of Food Engineering 49 (2001) 103114 107
KirkhoodBu theories, accounting for composition
uctuations in an open system.
From an applied engineering point of view recent
results on electrolyte systems may be divided into three
major groups (Loehe & Donohue, 1997): (i) local com-
position and hydration models, (ii) empirical and semi-
empirical equations of state for electrolyte systems and
(iii) equations for mixed electrolytes and mixed solvents.
These are summarised in Table 5.
4. Temperature eect on a
W
Dependence of activity coecient on temperature
may be expressed in terms of the excess partial molar
enthalpy or the partial molar excess heat of mixing as
(Prausnitz et al., 1986):
d ln c
i
dT
_ _
P

h
E
i
RT
2
: 6
After integration between two dierent temperatures, a
form of the well-known ClausiusClapeyron equation is
obtained:
ln
a
W

T1
a
W

T2

h
E
W
R
1
T
1
_

1
T
2
_
; 7
when h
E
W
is constant along the path T
1
to T
2
.
In spite of this elegant way of expressing temperature
dependence, some empirical equations have been pro-
posed (e.g. Scott & Bernard, 1983; Kitic, Jardim, Fav-
etto, Resnik, & Chirife, 1986), often involving a
considerable number system specic parameters.
Those models which involve local composition based
concepts (Wilson, NRTL, UNIQUAC) as well as
equations of state have explicit dependence on temper-
ature (and in some cases pressure), making this depen-
dence automatic.
5. Comparing model predictions with experimental data
As all the required information to apply the models
included in Tables 1, 2 and 5 is detailed in the original
papers and some of the indicated reviews, they will not
be reproduced here; the reader is invited to look at those
papers for such information.
Several comparative studies have been presented in
the past, most of them involving only a small group of
models. It is apparent from these studies that for many
systems of growing interest for the food industry, there
is still a very important lack of reliable experimental
data on thermophysical properties. Experimental tech-
niques to measure them are delicate and very time
consuming.
Table 5
Equations for electrolyte solutions
1. Hydration models: ionsolvent interaction is modelled as producing solvated aggregates characterised through the use of solvating numbers and
solvating energy; this approach has been applied for many years
Zdanovskii (1936) and Stokes and Robinson (1966): based on a linear relation existing between the molalities of isopiestic systems of single or
mixed solutes
Robinson and Bower (1965): use specic expressions to describe hydration and association of ions in solution
Pitzer (1973): is a virial development of G
E
in terms of molalities of the solutions; is very widely used
Meissner and Tester (1972): use a relation of mean ionic activity coecient and ionic force of the solution through a single parameter per salt
Bromley (1973): improved previous model including extended DebyeHuckel equation
Chirife et al. (1980): proposed a relation between solutions of mixed solutes and single solutes of same ttal ionic strength
Heyrovska (1989): considers the association degree and hydration number as parameters for direct correlation of equilibrium data
Schoenert (1990a,b) and subsequent work: used expressions of G
E
of hydrated and associated ions, modifying Robinson and Stokes hydration
model
2. Local composition models: model ionsolvent interaction on a local basis, trying then to generalise to the whole system
Chen, Britt, Boston, and Evans (1982) and Chen and Evans (1986): use NRTL+PitzerDebyeHuckel; good for low and moderate
concentrations of strong electrolytes
Liu, Wimby, and Gren (1989) and Liu and Gren (1991): use WILSON+DebyeHuckel contribution
Haghtalab and Vera (1991): two parameter non-random model to calculate G
E
Cardoso and O'Connel (1987): combined UNIQUAC+DebyeHuckel contribution
Kawaguchi et al. (1981, 1982) and Correa et al. (1997): use WILSON based ASOG group contribution coupled with hydration model for cations
3. Aqueous mixed electrolytes: concentrates in developing mixing rules that can be used with single solute models
Clegg and Pitzer (1992) and Lu and Maurer (1993): combine DebyeHuckel with UNIQUAC for mean ionic activity and osmotic coecient,
proposing a mixing rule for mixed systems
4. Equation of state models: used mostly to predict the behaviour at high temperature and pressures
Pitzer and Tanger (1989), Anderko and Pitzer (1993,) and Economou, Peters, and Arons (1995): equations of state able to predict phase
behaviour of electrolyte systems at high temperature
Ikonomou and Donohue (1986) and Jin and Donohue (1988a,b): introduced the associated-perturbed-anisotropic-chain theory to describe
aqueous halides between 200C and 500C
Wu et al. (1969): combine Pitzer virial equation with Fowler and Guggenheim (1939), long-range contribution
108 A.M. Sereno et al. / Journal of Food Engineering 49 (2001) 103114
The use of more recent techniques, like group con-
tribution methods or equations of state, has not yet been
the object of extensive comparative studies, justifying
thus this analysis targetting the case of osmotic solu-
tions. For such a purpose, using some of the more
successful models, predictions of water activity for two
sugar solutions (glucose and sucrose, Tables 6 and 7 and
Figs. 2 and 3), sodium chloride solution (Table 8, Fig. 4)
and two mixed solute solutions (sucrosesodium chlo-
ride and glucosesodium chloride, Tables 9 and 10 and
Figs. 5 and 6) were made and compared. These systems
are believed to be the most common solutions for os-
motic treatment processes.
The meaning of the statistical parameters ARD and
RMS in the tables is as follows:
ARD average relative deviation
1
n

n
1
a
Wi

calc
a
Wi

exp
1 a
wi

exp
100; 8
RMS root mean square

1
n

n
1
a
Wi

calc
a
Wi

exp
1 a
Wi

exp
100
_ _
2

_
:
9
6. Conclusions
Analysis of the comparative performance of dierent
predictive models for water activity has revealed that
Table 6
Prediction of water activity in glucosewater solutions
Reference Model/Equation ARD (%) RMS Experimental data
Norrish (1966) and Chirife et al.
(1980) (parameters)
Norrish (1966) 0.63 0.89 Stokes and Robinson
(1966)
Chen (1989) Chen (1989) 0.65 0.95 Stokes and Robinson
(1966)
Table 7
Prediction of water activity in sucrosewater solutions
Reference Model/Equation ARD (%) RMS Experimental data
Norrish (1966) and Chirife et al.
(1980) (parameters)
Norrish (1966) 2.8 3.9 Robinson and Stokes
(1961)
Chen (1989) Chen (1989) 2.8 3.9 Robinson and Stokes
(1961)
Lerici et al. (1983) Lerici et al. (1983) 12.7 14.5 Lerici et al. (1983)
Fig. 2. Water activity of aqueous glucose solution: experimental data
(symbols) and predictive models (lines).
Fig. 3. Water activity of aqueous sucrose solution: experimental data
(symbols) and predictive models (lines).
A.M. Sereno et al. / Journal of Food Engineering 49 (2001) 103114 109
good estimations may be obtained, not only from em-
pirical equations with parameters tted to experimental
data but also from theoretical models derived from ex-
pressions of the excess Gibbs free energy and from
equations of state.
It is somehow surprising how good the predictions
made from group contribution models are. These truly
predictive models use group interaction parameters not
necessarily calculated from data involving the compo-
nents of interest. Due to these capabilities, further eort
and testing should be devoted to this group of tech-
niques.
For practical applications of osmotic treatments, the
most widely used equations for prediction of water ac-
tivity in binary are the ones of Norrish (1966) and Ross
(1975) (see also Lopez-Malo, Palou, Welti, Corte, &
Argaiz, 1994; Guerrero et al., 1996; Alzamora, 1997;
Nieto, Salvatori, Castro, & Alzamora, 1998). Parame-
ters calculated by Chirife et al., 1980 should be preferred
for use with Norrish equation. For solutions containing
electrolytes, Pitzer (1973) and Chen (1989, 1990) equa-
Table 9
Prediction of water activity in sucrosesodium chloridewater solutions
Reference Model/Equation ARD (%) RMS Experimental data
Teng and Seow (1981) Ross (1975) 1.09 1.13 Robinson, Stokes, and Marsh (1970)
a
Chen (1990) Chen (1989) and Ross (1975) 1.25 1.41 Robinson et al. (1970)
Comesa~ na et al. (2000) Lin et al. (1996) 1.78 1.92 Robinson et al. (1970)
a
Correa et al. (1997) ASOG 2.48 3.54 Robinson et al. (1970)
a
Teng and Seow (1981) Chirife et al. (1980) 2.62 3.1 Robinson et al. (1970)
a
Teng and Seow (1981) ZdanovskiiStokesRobinson 2.99 3.3 Robinson et al. (1970)
a
Roa and Tapia (1998) Roa and Tapia (1998) 7.15 9.52 Robinson et al. (1970)
a
Chuang and Toledo (1976) Modied Norrish/Ross (1975) 14.2 16.4 Chuang and Toledo (1976)
a
As reported by Teng and Seow (1981).
Fig. 4. Water activity of aqueous sodium chloride solution: experi-
mental data (symbols) and predictive models (lines).
Table 8
Prediction of water activity in sodium chloridewater solutions
Reference Model/Equation ARD (%) RMS Experimental data
Pitzer (1973) Pitzer (1973) 0.14 0.25 Robinson and Stokes (1965)
Correa et al. (1997) ASOG 1.67 2.33 Robinson and Stokes (1965)
Chen (1989) Chen (1989) 2.8 3.9 Robinson and Stokes (1965)
Roa and Tapia (1998) Roa and Tapia (1998) 9.35 10.7 Robinson and Stokes (1965)
Table 10
Prediction of water activity in glucoseNaCl solutions
Reference Model/Equation ARD (%) RMS Experimental data
Chen (1990) Chen (1990)/Ross 1.83 2.66 Comesa~ na et al. (2000)
Comesa~ na et al. (2000) Lin et al. (1996) 1.61 2.33 Comesa~ na et al. (2000)
This work ASOG 8.4 9.3 Comesa~ na et al. (2000)
Roa and Tapia (1998) Roa and Tapia (1998) 8.9 9.7 Comesa~ na et al. (2000)
110 A.M. Sereno et al. / Journal of Food Engineering 49 (2001) 103114
tions are recommended. For water activity of multi-
component mixtures good results are obtained using
Ross (1975) equation with any of the already mentioned
single solute models. Recently Roa and Tapia (1998)
have proposed a simple equation, based on the rst-
order sum of molalities, with a reasonable predictive
accuracy.
The use of UNIFAC and ASOG models as well as
equations of state, although constituting a good and
accurate tool to estimate the activity coecients of non-
electrolyte and electrolyte mixtures, are not yet widely
used in everyday practical application of osmotic treat-
ments. The development of computer-aided tools al-
lowing a simpler manipulation of such complex models
may contribute to their popularity and should be en-
couraged.
Acknowledgements
The authors acknowledge the support of project
XI.12, Programme CYTED, and EU project FAIR-
CT96-1118 and of project XUGA 30101B98 of Xunta
de Galicia.
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