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ELSEVIER Fluid Phase Equilibria 123 (1996) 71-95

Thermodynamic properties of sugars in aqueous solutions: correlation


and prediction using a modified UNIQUAC model
Antdnio M. Peres, Eug~nia A. Macedo *
Laboratory of Separation and Reaction Engineering, Faculdade de Engenharia, Rua dos Bragas, 4099 Porto Codex,
Portugal
Received 26 July 1995; accepted 19 February 1996

Abstract

A modified UNIQUAC model with linear temperature-dependent parameters is proposed to describe the
thermodynamic properties (water activity, osmotic coefficient, vapor pressure, boiling temperature, freezing
point and solubility data) of three binary systems: D-glucose/water, D-fructose/water and sucrose/water. New
UNIQUAC interaction parameters are presented, estimated using the above mentioned binary data, collected
from the literature.
Good predictions of vapor-liquid and solid-liquid equilibrium data for ternary and quaternary mixtures of
D-glucose, D-fructose, sucrose and water components are obtained.
This approach uses the symmetric convention for all the components, pure fused sugar at solution pressure
and temperature being its reference state. Therefore, it allows straightforward calculations of solid-liquid
equilibria of sugars in mixed solvents. This constitutes an important advance over the approach based on the
knowledge of the dilution enthalpy data available in the literature.

Keywords: Theory; Application; Solid-liquid equilibria; Vapor-liquid equilibria; Water; Carbohydrates

I. Introduction

Knowledge of thermodynamic properties of mixtures involving biological molecules, such as


carbohydrates, is of major interest since these molecules have a prominent and significant role in a

* Corresponding author.

0378-3812/96/$15.00 Copyright© 1996ElsevierScienceB.V. All rights reserved.


PII S0378-381 2(96)03046-4
72 A.M. Peres, E.A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95

variety of areas including biological and technological applications, like, among others, metabolic and
industrial operations yielding chemical feed stocks, and the crystallization processes of common
sugars such as D-glucose, D-fructose and sucrose. Despite their importance, it is evident that there is
an enormous lack of information in certain areas, for example the phase diagrams. Recently, Goldberg
and Tewari (1989) reported that the available literature data for aqueous systems containing sugars is
relatively scarce and sparse.
The scarcity of literature data for these kinds of systems increases the importance of the
development of correlation and prediction equations for these highly non-ideal systems of sugar and
water. In this way, some thermodynamic modeling studies have been presented in the literature: the
UNIQUAC equation (Abrams and Prausnitz, 1975) was used by Le Maguer (1992) to describe the
excess Gibbs energy and excess enthalpy of five binary aqueous carbohydrate systems; Achard et al.
(1992) used the modified UNIFAC (Larsen et al., 1987) to predict water activity, as well as boiling
temperatures and freezing points of one or more sugars in water; Abed et al. (1992) and Gabas and
Lagu6rie (1993) used the UNIFAC model (Fredenslund et al., 1977) to estimate new group interaction
parameters from binary and ternary solubility data, and to predict the solid-liquid phase equilibrium
data in ternary systems of two sugars/water at a fixed temperature (25°C or 70°C); Catt6 et al. (1994)
applied the modified UNIQUAC model (Larsen et al., 1987) to correlate eight different thermody-
namic properties (water activity, osmotic coefficient, activity coefficient, boiling temperature, freezing
point, excess enthalpy, excess Gibbs energy and solubility data) of three binary water/sugar systems
and to predict the osmotic coefficient and water activity of two sugars in aqueous solutions at 25°C.
More recently, Catt6 et al. (1995) proposed a new physical chemical model, which uses a modified
UNIFAC equation (Larsen et al., 1987), that allows carbohydrate isomers to be distinguished, and
describes some important thermodynamic properties of seven water/sugar systems. These studies,
among others, have contributed to the progress of the correlation a n d / o r prediction of several
thermodynamic properties in binary, ternary and quaternary water/sugar(s) systems.
The present work undertakes to apply a modified UNIQUAC model to describe vapor-liquid and
solid-liquid equilibria for three binary systems of sugar and water. Each binary system studied
(D-glucose/water, D-fructose/water and sucrose/water) has been correlated separately and for each
one, new UNIQUAC parameters have been estimated from binary literature data, such as water
activity, osmotic coefficients, vapor pressures, boiling and freezing temperatures and solubility data.
The approach proposed in this work contrasts with the model presented by Catt6 et al. (1994) in two
major points:
(i) Only four interaction UNIQUAC parameters (Hansen et al. (1991) temperature dependency
expression) for each sugar/water pair are used instead of the six interaction parameters used by Catt6
et al. (1994) (Larsen et al. (1987), temperature dependency expression).
(ii) The standard state for the sugar, used in this work, is taken as the pure liquid at the solution
temperature instead of the infinite dilution at the solution temperature used by Catt~ et al. (1994).
This formulation, based on the symmetric convention for all the components, allows a straightfor-
ward extension of the method for the correlation and prediction of solid-liquid equilibria in mixed
solvent systems, as already shown by Chiavone-Filho and Rasmussen (1993) for electrolyte systems
and by Peres and Macedo (1996) for the calculation of solubilities of D-glucose in ethanol/water
mixtures at 40 and 60°C. This is not the case when using the unsymmetric convention for the activity
coefficient calculations, adopted by Catt6 et al. (1994), as pointed out by Sander et al. (1986).
Therefore, the range of applicability of the proposed model is larger than that of Catt~ et al. (1994).
A.M. Peres, E.A. Macedo/ Fluid Phase Equilibria 123 (1996) 71-95 73

2. Model development

In order to describe vapor-liquid and solid-liquid equilibria for aqueous systems containing one or
more sugars, a model with a suitable temperature dependency is used: a modified molecular
UNIQUAC model. In this work, the combinatorial contribution of the UNIQUAC model is given by
the expression of the combinatorial term of the molar excess Gibbs energy proposed by Larsen et al.
(1987):

ln(yC) = ln( -~°i ) + 1 - - @i (1)


Xi Xi

where tpi is the molecular volume fraction of component i defined as:


xiRip 2
with p = -- (2)
~9i= E X j R p ' 3
J
For the residual contribution, the same linear temperature dependency for the interaction parame-
ters, as proposed by Hansen et al. (1991), is used for the binary interaction parameters of sugar/water
in accordance with:
asug/w = a°ug/w + atsug/,,,,(T - T °) (3)
where a represents the UNIQUAC interaction parameters; T is the mixture temperature; T ° is an
arbitrary reference temperature, which in this work was set equal to 298.15 K; w refers to the water
molecule, and sug refers to the sugar molecules.
In total, for each sugar/water system studied, four new interaction parameters are estimated•

3. Vapor-liquid equilibria

Since sugars are not present in the vapor phase, the vapor-liquid equilibria reduces only to the
calculation of the boiling temperature and vapor pressure of the mixture. Assuming the vapor phase
behavior as ideal gas, the basic relationship used to calculate the above mentioned properties is:
P = ywXwP ° (4)
where P is the total pressure of the system or the vapor pressure, "/w is the symmetric mole fraction
activity coefficient of water, x w is the mole fraction of water, and po is the vapor pressure of pure
water; this is calculated using the Antoine equation with the constants given by Gmehling et al. (ab
1977).
The boiling temperature of a carbohydrate-water mixture, of known composition and known total
pressure of the system, can be calculated by an iterative process using Eq. (4): knowing the
composition of the mixture (x,~) and giving an initial estimate for the boiling temperature, the
symmetric mole fraction activity coefficient of water can be calculated, by means of the modified
UNIQUAC model, and with Eq. (4) a new value for the boiling temperature can be obtained and
compared with the initial estimate; the vapor pressure of the solution ( P ) can be calculated directly
using Eq. (4), since the temperature is known.
74 A.M. Peres, E.A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95

4. Solid-liquid equilibria

In this work the description of solid-liquid equilibria involves the determination of both the
freezing point and the solubility data.

4.1. Freezing point

Assuming the freezing point depression is sufficiently small that the consequent changes in pure
liquid water and pure ice heat capacities can be neglected, the freezing point depression of a
sugar/water mixture of known composition can be calculated, iteratively, using the following
expression (Ferro Fontan and Chirife, 1981)
ln( aw) = ln( ywXw) =
= fw(1 '/
R Tn,w Tn,mix R k T,,mix R Tn,mix
/
where aw is the water activity, R is the gas constant, T,,W is the freezing point of pure water (273.15
K), Tn,mix is the freezing point of the carbohydrate/water mixtures of known composition, A Hr, w is
the enthalpy of fusion of water at Tn,W, and ACp,~ is the difference between the heat capacities of
liquid water and ice at T,,mix, assumed to be temperature-independent in the range Zn,w-Zn,mi x. The
AHf, w and ACp,w values can be calculated from the DIPPR Tables (1984), yielding the values 6002 J
mol-J and 38.03 J m o l - l K-1, respectively.

4.2. Solubility of the anhydrous solid form

In this work, an equation based on the symmetric convention for the calculation of the activity
coefficients, the pure liquid at the solution temperature being the standard state for the sugar, together
with fusion enthalpy and melting temperature data (Raemy and Schweizer, 1983; DIPPR Tables,
1984; Gabas and Lagu&ie, 1992; Roos, 1993) for the sugars studied, is used to calculate the solubility
of the anhydrous solid form in the aqueous solution. This equation can be derived from an idealized
thermodynamic cycle between the solid and liquid sugar phase states. Some assumptions are made:
(i) the solvent does not appear in the solid phase;
(ii) the difference between the heat capacities of the pure liquid and the pure solid sugars (ACp) is
a linear function of temperature between T (temperature of the mixture) and Tm (melting point of the
sugar)
A C e = AA + A B ( T - T°) (6)
where A A and A B are the parameters.
The resulting expression is:
AHf AA -- A B T ° 1 ) + AA-
ln( o x = + Tin+ 2R m]~T Tm
R
AB
+ ( r - rm) (7)
2R
A.M. Peres, E.A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95 75

where the solubility of the sugar in water is related to some thermodynamic properties of the sugar,
such as the melting temperature (Tm) and the enthalpy of fusion (AHf) at Tm.
The sugar solubility calculation procedure was as follows. The knowledge of the interaction
parameters between the different species present in the solution (sugar, water), together with their size
parameters, allow the calculation of ~/sug by means of the modified UNIQUAC model for a fixed
temperature of the solution. Knowing "Ysog,the solubility of the sugar in the water can be calculated
using Eq. (7), by means of an iterative procedure, until the equilibrium composition of the solution
used to calculate "Ysugand the equilibrium composition of the solution obtained from Eq. (7) are the
same.

5. Estimation of new UNIQUAC interaction parameters

5.1. D a t a s o u r c e s

Six kinds of experimental data (water activity, osmotic coefficient, vapor pressure, boiling
temperature, freezing point and solubility data), available in the literature, were used as the database
to estimate new UNIQUAC interaction parameters for the D-glucose/water, D-fructose/water and
sucrose/water systems. The osmotic coefficient data used in this work were, whenever possible,
recalculated from the initial isopiestic experimental ratios data using data published recently for the
osmotic coefficients of electrolytes as the standard solutions (Hamer and Wu, 1972; Clarke and Glew,
1985).
A more reliable database than that of Catt6 et al. (1994) was established since the activity
coefficient and the excess properties data of sugar solutions were not included:
(i) Contrary to Catt~ et al. (1994), the published literature data on activity coefficients (Robinson
and Stokes, 1961; Bonner and Breazeale, 1965; Miyajima et al., 1983) of D-glucose or sucrose in
water were not used because these were calculated from the same osmotic coefficients already used in
the correlations, avoiding duplication of the information.
(ii) Concerning the excess properties of sugars in aqueous solutions, like, for example, excess
enthalpy, some virial expressions have been proposed for 25°C (Savage and Wood, 1976; Barone et
al., 1981). The referred equations are obtained from the correlation of experimental data of enthalpies
of dilution of aqueous solutions of sugars (Gucker et al., 1939; Lange and Markgraf, 1950; Stroth and
Sch5nert, 1977; Barone et al., 1981; Daldrup and SchSnert, 1988). However, the proposed virial
expressions cannot reproduce satisfactorily the experimental data on enthalpies of dilution: for
D-fructose, the calculated values for the enthalpy of dilution, using the equation proposed by Barone
et al. (1981), show a deviation from the experimental values of between 7% and 32%, for more than
half of the number of experimental points; for D-glucose and sucrose, the virial equations proposed by
Savage and Wood (1976) could not be tested against the enthalpy of dilution experimental data and so
they were not used. Therefore, the excess enthalpy data available in the literature were not used to
estimate the new UNIQUAC parameters, contrary to Catt~ et al. (1994).
Moreover, the database used here contains exclusively experimental data and not calculated
properties as used by Catt6 et al. (1994).
Table 1 presents detailed information concerning the experimental data collected from the literature
and used in this work. This database is more extensive than that used by Catt~ et al. (1994): 567
76 A.M. Peres, E.A. Macedo / Fluid Phase Equilibria 123 f 1996) 71-95

Table 1
Number of data points (first row), experimental temperature (second row) and concentration in mol k g - ~ (third row) ranges
and R M S D / A A D values (fourth row), for each system and each property, used on the optimization process
Water/D-glucose Water/D-fructose Water/sucrose
Water 22 a 37 g 33 i
25°C 25°C 25°C
activity 1.24-7.24 tool k g - l 0.62-22.20 mol kg i 0.20-5.86 mol kg- t
1.12%/0.28% 1.09%/0.44% 0.96%/0.31%
Osmotic 54 b 110 m
25,37,60°C 25°C
coefficient 0.34-10.32 mol kg i n.a. 0.15-5.73 mol kg 1
0.86%/0.40% 0.63%/0.43%
Boiling 11 c 12 h 19 n
100.2-- 106.0°C 100.1-130.0°C 100.1-119.4°C
temperature 0.26-9.87 tool k g - 1 0.26-37.15 mol kg- J 0.17-26.29 mol k g - l
2.12%/0.50% 2.23%/0.60% 1.69%/0.54%
Freezing 38 d 26 i 24 o
-- 0.15 tO -- 30.0 I°C - 0.05 to - 30.40°C - 0.03 to - 4.45°C
point 1.39-12.95 mol k g - l 0.03-12.72 mol kg- 1 0.01-1.95 mol kg- i
0.90%/0.31% 1.83%/0.87% 1.44%/0.50%
Vapor 33 e
25,35,45,55,65°C
1
pressure 0.66-13.61 mol kg n.a. n.a.
1.46%/0.71%
22 f 20 j 106 p
Solubility - 12.06 to 90.8°C - 3 . 8 5 to 70°C - 3 to IO0°C
5.53- 31.21 tool k g - i 15.55-70.49 tool kg - I 5.24-14.22 tool kg - i
1.13%/0.26% 1.37%/0.38% 0.77%/0.63%
178 95 292
Total data - 12.06 to 106°C - 3.85 to 130°C - 3 to 119.4°C
0.26-31.21 mol kg-1 0.03-70.49 tool k g - i 0.01-26.29 mol kg- 1
0.48%/0.41%o 0.77%/0.56% 0.42%/0.50%

n.a., not available; a Ri~egg and Blanc (1981); b Bonner and Breazeale (1965), Stokes and Robinson (1966), Miyajima et al.
(1983); c Abderafi and Bounahmidi (1994); d Young (1957), Weast (1973); e Taylor and Rowlinson (1955); f Young
(1957), Stephen and Stephen (1963), Mullin (1972), Abed et al. (1992); g Riiegg and Blanc (1981), Correa et al. (1993),
Lerici et al. (1983); h Abderafi and Bounahmidi (1994); i Young et al. (1952), Weast (1973), Lerici et al. (1983); J Jackson
et al. (1926), Young et al. (1952), Vasfitko and Smel~k (1967), Abed et al. (1992); ~ Chuang and Toledo (1976), Rtiegg and
Blanc (1981), Lerici et al. (1983); m Robinson and Sinclair (1934), Scatchard et al. (1938), Robinson et al. (1942), Robinson
and Stokes (1961); n Leschke (1987), Abderafi and Bounahmidi (1994); o Young and Jones (1949), Weast (1973), Lerici et
al. (1983); p Young and Jones (1949), Stephen and Stephen (1963), Mullin (1972).

instead of the 342 experimental data points used by the latter (because the activity coefficient, the
e x c e s s e n t h a l p y a n d t h e e x c e s s G i b b s e n e r g y d a t a u s e d b y C a t t ~ e t al. ( 1 9 9 4 ) a r e c a l c u l a t e d a n d n o t
e x p e r i m e n t a l data).
A.M. Peres, E.A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95 77

Table 2
Structural parameters(R i and Qi) for D-glucose,D-fructose,sucrose and water
Ri Qi
D-glucose 8.1528 7.920
D-fructose 8.1529 8.004
Sucrose 14.5496 13.764
Water 0.9200 1.400

5.2. UNIQUAC parameters

The application of the modified UNIQUAC model to correlate a n d / o r predict the vapor-liquid
a n d / o r solid-liquid equilibria requires the knowledge of volume (R i) and surface area (Qi)
parameters of the sugars studied (D-glucose, D-fructose and sucrose) and water, and the interaction
parameters between the different components present in the solution.
The applied volume (R i) and surface area (Qi) parameters of D-glucose, D-fructose, sucrose and
water for the modified UNIQUAC model were calculated from the size parameters of the groups
involved in the molecules. These size parameters were taken from the UNIFAC Parameter Tables
(Fredenslund et al., 1977; Skjold-Jcrgensen et al., 1979; Gmehling et al., 1982; Macedo et al., 1983;
Tiegs et al., 1987; Hansen et al., 1991), and are given in Table 2.
Temperature-dependent UNIQUAC interaction parameters were estimated, based on an extensive,
reliable and exclusively experimental database for binary water/sugar systems including six different
kinds of data: water activity, osmotic coefficient, vapor pressure, boiling temperature, freezing point
and solubility of the anhydrous sugar in water. These data cover large temperature and concentration
ranges: from below 0°C to above 100°C, and from diluted solutions until saturation, as shown in
Table 1. For each binary system, six parameters are estimated simultaneously from all the data: four
o
temperature-dependent interaction parameters, (a~ug/w, asug/w) and (aw/sug,
. t o . t .
aw/~ug), and two tempera-
ture-dependent coefficients, A A and A B of Eq. (6). To estimate the model parameters a Hooke-Jeeves
method was used to minimize the following objective function

VneXp __ Vn calc

E V~Xp
n i (8)
Fo j = E NOE
i

where V and i represent the thermodynamic properties, superscripts calc and exp indicate calculated
values according to the model and experimental data, respectively, and NDE is the number of data
points for the property i.
The estimated temperature-dependent UNIQUAC interaction parameters obtained in this study are
listed in Table 3. As already mentioned, Table 1 presents the number of data points used, the
temperature and concentration ranges, the Root Mean Square Deviations (RMSD), and the Absolute
Average Deviations (AAD), per property and per system. This table also indicates the bibliographic
78 A.M. Peres, E.A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95

Table 3
N e w estimated U N I Q U A C interaction parameters: first row ai°j; second row atij (K)
i j
D-glucose D-fructose Sucrose Water

D-glucose 0 0 a 0 a -68.6157 b
0 0 a 0 a --0.0690 b
D-fructose 0 a 0 0 ~ --28.2892 b
0 a 0 0 ~ 1.7780 b
Sucrose 0 ~ 0 ~ 0 -89.3391 b
0 a 0 a 0 0.3280 b
Water 96.5267 b 42.3676 b 118.9952 b 0
0.2770 b -- 2.2511 b -- 0.3410 b 0

In this work, set equal to zero.


b Estimated parameters.

references for each property. The RMSD and AAD values were calculated using the following
equations

V~XO vcalc 12
-

V~Xp
RMSD =
I X 100 (9)
NDE
v e x p __ VnCalc
En VneXp
AAD= X 100 (10)
NDE

Table 4
T h e r m o d y n a m i c data for the calculation o f the solubility of D-glucose, D-fructose and s u c r o s e in w a t e r
D-glucose D-fructose Sucrose
Melting 416.15 a 381.15 a 463.15 a
temperature 423.15 b 378.15 b 458.15 b
(K) 419.15 ¢ 377.15 c 459.15 c

Fusion enthalpy 32248 a 30447 a 40391 a


(J m o l - i ) 32432 b 32428 b 41076 b
31432 ¢ 36030 c 46187 c

A A (J m o l - 1 K - l) 139.5766 a 66.7299 a 316.1153 a


AB (J tool -1 K - 2 ) 0 a 4,8296 d -1.1547 d

R o o s (1993).
b R a e m y a n d S c h w e i z e r (1983).
c G a b a s and Lagu~rie (1992).
d Parameters e s t i m a t e d in this work.
A.M. Peres, E~A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95 79

1.00

0.96 °. ~ ~ , , ~ T = 25 o C

D~
•~ 0.92
-X~~D_glucose

0.88 I~o Ducg~J:°


D glacose~ RueggandBlanc(1981t ~

o Sucrose:Lericiet al. (1983) | Sucrose


0.84 • Sucrose:ChuangandToledo(1976)/
"- Correlatedcurves )
0.80 i I , I , I a I , I , I , I ,

0 1 2 3 4 5 6 7
Sugar molality
Fig. 1. Experimentaland calculatedwater activities of D-glucose/water and sucrose/water mixtures at 25°C.

Table 4 presents thermodynamic data needed for the calculation of the solubility of D-glucose,
D-fructose and sucrose in water, such as the enthalpies of fusion and melting temperatures for the
three above mentioned sugars proposed by three different authors (Raemy and Schweizer, 1983;
Gabas and Lagu6rie, 1992; Roos, 1993) and the selected values used (values in bold) for each sugar in
the present work. Table 4 also shows that the deviations between the different enthalpy of fusion data
available in the literature are acceptable. Therefore, in this work, this kind of data was considered
reliable. The selected fusion values, for each sugar studied, were the ones that allow a better
agreement between model calculated values and the literature data. Table 4 also gives the estimated

0.95 o
T=25 C
0 . 9 0 ~
~.~ 0 . 8 5 ~
080

~ 0.75 A Rueggand Blanc (


0.70 o Correaet al. (1993) [ ~ .
o Lericiet al. (1993) [
0.65 Correlatedcurve [
0.60. . . . . . . . . . . . ' ' ' . . . .
0 2 4 6 8 10 12 14 16 18 20 22 24
D-fructose molality
Fig. 2. Experimentaland calculatedwater activities of D-fructose/water mixturesat 25°C.
80 A.M. Peres, E.A. Maeedo / Fluid Phase Equilibria 123 (1996) 71-95

122 r 37oc]
1.18 25 ° C ~ o/'~_ /

'U 1.14 oo + + 60°C


° •
1.10 •
..~
© 1.06 i" aO#'// I A Stokesand Robinson(1966): 25 °C[|
_ onnerand Breazeale(1965
1.02 I - ~ / " I + 600 CJ //

0.98
0 1 2 3 4 5 6 7 8 9 10 11
Glucose molality
Fig. 3. Experimental and calculated osmotic coefficients of D-glucose in water at 25°C, 37°C and 60°C.

values o f the temperature-dependent coefficients of Eq. (6), A A and A B, which were estimated
simultaneously with the interaction parameters.

6. R e s u l t s a n d d i s c u s s i o n

6.1. C o r r e l a t i o n r e s u l t s

The correlation results obtained with the modified U N I Q U A C model compare favorably with the
experimental data available in the literature for the binary systems studied: Table 1 shows that the

1.52 a~

//
1.44 T = 25 * o ~

.~ 1.36

1.28

.= 1.20
E° J []Robinson and Sinclair (1934)
1.12 t A Scatchard et al. (1938)
oRobinson et al. (1942)
1.04 ~ * Rob'mson and Stokes (1961)
Correlated curve
0.96 , J , I . . . . . , ,
0 1 2 3 4 5 6
Sucrose molality
Fig. 4. Experimental and calculated osmotic coefficients of sucrose in water at 25°C.
A.M. Peres, E.A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95 81

~_,
oL) 180
200 ta

Leschke (1987)
and o Abderafiand Bounahmidi (1994)
Correlated curves
1
160 . . . . Predicted curve
# i

~ 140 o

120

100 Sucrose

80 ~
0 10 20 30 40 50 60 70 80 90 100

Sugar weight percentage


Fig. 5. Experimental and calculated boiling temperatures of D-fructose/water and sucrose/water mixtures.

proposed model is able to describe the referred properties with a maximum AAD value of less than
0.90%.
In Table 5 a comparison between the RMSD and the AAD values calculated in this work and those
obtained using the approach presented by Catt~ et al. (1994), for the experimental database used here,
is given. These results show that the proposed model is able to describe the experimental data with a
similar accuracy as the Catt6 et al. (1994) model, using a smaller number of UNIQUAC interaction
parameters.
Figs. 1-10 show a comparison between the experimental literature data and the correlation results
obtained with the proposed model, for each of the six thermodynamic properties (water activity,
osmotic coefficient, vapor pressure, boiling temperature, freezing point and solubility data), taken into

125

120 o Abderafi and Bounahmidi (1994)


G Correlated curve j'
a
q--, . . . . Predicted curve ,,
.~ 115
~ ts I O

110 ,'
." 0
F-
• 105

10G

9, . . . . . . , , ,
0 10 20 30 40 50 60 70 80 90 100
D-glucose weight percentage
Fig. 6. Experimental and calculated boiling temperatures of D-glucose/water.
82 A,M. Peres, E.A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95

~ o d d od

r..)

I ,~"
.o I .,<~"

~0 ~D Cq ~ 0 ~,

O ~ ~
< • ~ ~
<

<
<

N <
e,, <

e-.

.8

.-- N 0

[- "6o
A.M. Peres, E.A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95 83

,_., -4
L;
-8
•=-
O
-12 Sucrose
=~ -16 A, A: Weast (1973) ~
"~ -2C ,, o :~ricietal.(1983) '~ '~a
ts., ta Young and Jones (1949) \ \
-24 * Young et al. (1952) \ \
-28 ~ 50rrelated-_curve . . Fructose~ ~ ta

-32 . , . , . , . , . , . , . ~ .i ,
0 10 20 30 40 50 60 70 80 90
Sugar weight percentage
Fig. 7. Experimental and calculated freezing points of D-fructose/water and sucrose/water mixtures.

account for the correlation procedure of the three binary aqueous systems studied: D-glucose/water,
D - f r u c t o s e / w a t e r and sucrose/water.
A comparison between the unsymmetric molal activity coefficients calculated using the proposed
modified U N I Q U A C model and the ones published in the literature, at the same temperatures, is
shown in Figs. 11-13, for the D - g l u c o s e / w a t e r system at 25°C and 37°C, and for the s u c r o s e / w a t e r
system at 25°C, respectively. The literature unsymmetric molal activity coefficients are calculated
from the osmotic coefficient experimental data at the same temperatures, using the following equation

• tk- 1 +
lnTsug-= fom ~~b-1
d m (11)
m

0
-g

o~ _~

-12
~ -16
.~.
~a -20
-24 [ta Young(1957) X

28 ..... \
-32
0 10 20 30 40 50 60 70 80
D-glucose weight percentage
Fig. 8. Experimental and calculated freezing points of D-glucose/water mixtures.
84 A.M. Peres, E.A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95

~" 28000
D Taylor and Robinson (1955)']
P' 24000 i

20000

160001

~ 12000
------- 45°C
", 8000
_-. 35°C
~" 4000 - - -
= ---- -- . o 25°C
> 0 i I i I , I i l. ,

0.00 0.04 0.08 0.12 0.16 0.20


Mole fraction of D-glucose
Fig. 9. Experimental and calculated vapor pressures of D-glucose/water mixtures between 25°C and 65°C.

where ~tsug is the u n s y m m e t r i c molal activity coefficient o f the sugar in the aqueous solution, + is the
osmotic coefficient, and m is the molality o f the solution. The figures show a satisfactory agreement
between the two kinds o f calculated properties.

95
A

90

85

,-,80

570

~ -- /'- Young et al. (1952)


60 Sucrose J o Young (1957)
.~ • Vas~tko and Smel~ (1967)
55 7 ~. , o Stephen and Stephen (1963)
L~-gmcose [] Mullin (1972)
50 A Abed et al. (1992)
Correlated curves
45
-20 -10 0 10 20 30 40 50 60 70 80 90 100
Temperature (° C)
Fig. 10. Sugars solubility in water: comparison between experimental data and the correlated curves.
A.M. Peres, E.A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95 85

1.5
....... Bonnerand Breazeale(1965) [
O 1.4 ........ Miyajimaet al. (1983) ] ~ "
Calculated c u r v e .!.~.-'"
1.3

1.2 "'"'" 25 o C

O e.- 1.1

1.0

i I i I , I , I , I , I , I ,
0.9
0 1 2 3 4 5 6 7 8
D-glucose molality
Fig. 11. Literatureand calculatedactivitycoefficientsof D-glucosein water at 25°C.

6.2. Prediction of ternary and quaternary system properties

The predictive capabilities of the proposed model are studied based on the available literature data
on water activity, osmotic coefficient, boiling temperature and solubility data for ternary a n d / o r
quaternary aqueous systems containing D-glucose, D-fructose a n d / o r sucrose. For the prediction
calculations of ternary and quaternary aqueous systems, in addition to the six new parameters
estimated in this work, the UNIQUAC interaction parameters between two sugars are needed. Since
they are not available in the literature and Abderafi and Bounahmidi (1994) have found that the mean
values for the sugar-sugar binary interaction parameters for the Peng-Robinson (PR) and Lee-Kesler

1.4
....... Bonnerand Breazeale(1965) [ ~ ~ . .
~ 1.3 Calculatedcurve
Calculated curve ~ . ~...-""

..-"" 37 °C
~.'~
~'~,
N~ 1.1
0 ~
~.~
~ 1.0

0.9 i I i I , I i I i I i I ,

0 1 2 3 4 5 6 7
D-glucose molality
Fig. 12. Literatureand calculatedactivity coefficientsof D-glucosein water at 37°C.
86 A.M. Peres, E.A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95

i.

"6
E

_=

e..

o
-t

,to
t~

8
e.
~f,.)
0

_'6

~D
A.M. Peres, E.A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95 87

3.0
2.8 4.... Scatchard et al. (1938)
"6= 2.6 .......~ ..... Robinsonand Stokes (1961) ~,,"
e~ Calculated curve j
....~ 2.4

y 25 °C

aa = 1.{
~ 1.4

1.0
I I i I a I i I 0 I n I
0.8
0 1 2 3 4 5 6
Sucrose molality
Fig. 13. Literature and calculated activity coefficients of sucrose in water at 25°C.
Table 7
Comparison between experimental (Abderafi and Bounahmidi, 1994) and predicted vapor-liquid equilibrium data for the
ternary system D-glucose/sucrose/water
Weight fraction Boiling temperature/K
Glucose Sucrose Experimental Predicted Relative deviation/%
0.011 0.218 374.15 373.37 0.21
0.016 0.315 375.15 373.74 0.38
0.021 0.426 376.15 374.39 0.47
0.026 0.525 377.15 375.36 0.47
0.029 0.577 378.15 376.04 0.53
0.030 0.606 378.65 376.67 0.52
0.033 0.669 380.15 378.27 0.50
0.038 0.753 381.65 382.07 0.11
0.039 0.773 380.15 383.46 0.87

Table 8
Comparison between experimental (Abderafi and Bounahmidi, 1994) and predicted vapor-liquid equilibrium data for the
ternary system D-fructose/sucrose/water
Weight fraction Boiling temperature/K
Fructose Sucrose Experimental Predicted Relative deviation/%
0.006 0.105 374.15 373.08
0.011 0.213 375.15 373.36 0.48
0.016 0.325 376.15 373.80 0.62
0.021 0.424 376.65 374.40 0.60
0.027 0.529 377.15 375.48 0.44
0.029 0.574 378.65 376.16 0.66
0.033 0.670 380.65 378.43 0.58
0.035 0.704 382.15 379.71 0.64
0.039 0.773 387.15 383.73 0.88

* Listed only for information.


88 A.M. Peres, E.A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95

Table 9
Comparison between experimental (Abderafi and Bounahmidi, 1994) and predicted vapor-liquid equilibrium data for the
ternary system D - g l u c o s e / D - f r u c t o s e / w a t e r
Weight fraction Boiling temperature/K
Glucose Fructose Experimental Predicted Relative d e v i a t i o n / %
0.024 0.024 374.15 373.02 * -
0.033 0.033 374.65 373.08 * -
0.055 0.055 376.15 373.24 0.77
0.109 0.109 376.65 373.72 0.77
0.159 0.159 377.15 374.37 0.74
0.219 0.219 378.15 375.54 0.69
0,272 0.272 379.15 377.22 0.51
0.322 0.322 381.15 379.83 0,35
0.387 0,387 388.15 386.58 0.40
0.419 0.419 393.15 393.25 0.02

* Listed only for information.

Table 10
Comparison between experimental (Abderafi and Bounahmidi, 1994) and predicted vapor-liquid equilibrium data for the
quaternary system D - g l u c o s e / D - f r u c t o s e / s u c r o s e / w a t e r
Weight fraction Boiling temperature/K
Glucose Fructose Sucrose Experimental Predicted Relative d e v i a t i o n / %
0,051 0.051 0.101 374.15 373,46 0.18
0.011 0.011 0.208 375.15 373.40 0.47
0.015 0.015 0.308 375.65 373.81 0.44
0,021 0.021 0.414 376.15 374.53 0.43
0.026 0.026 0.516 377.15 375.70 0.38
0.029 0,029 0.564 379.15 376.57 0.68
0.031 0.031 0.615 380.15 377.80 0.62
0,033 0.033 0.662 381.15 379.40 0.46
0.037 0.037 0.746 385.15 384.52 0.16
0,039 0.039 0.766 392.15 386.74 1.38

Table 11
Comparison between the mean square errors (MSE) obtained in this work and in Abderafi and Bounahmidi (1994)
System Abderafi and Bounahmidi (1994) This work
Peng-Robinson Lee-Kesler NRTL
D-glucose/water 2.13 a 25.84 a 0.40 a 0.48 a
D-fructose/water 6.79 ~ 52.70 a 12.38 a 0.90 a
Sucrose/water 2.81 a 2.77 a 7.89 a 2.18 a
D-glucose/sucrose/water 3.23 a 5.16 a 6.99 a 3.55 b
D-fructose/sucrose/water 0.44 a 4.78 a 2.78 a 5.17 b
D-glucose/D-fructose/water 0.58 a 33.33 a 12.11 a 4.33 b
D-glucose/D-fructose/sucrose/water 1.84 b 18.01 b 4.96 b 5.66 b

a Correlated results.
b Predicted results MSE = ( 1 / ( N D E - n p ) ) ~ ( T nexp - Tcalc)2.
n
A.M. Peres. E.A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95 89

70
T=70 ° C
60 "'"" ....
o 50 ..4 .

40

30 ~ ~

20 ..... Gabas and Lagu6rie (1993) "~


l~ , iTti, s w ~ r k , ' , 1, | , , , ,~.

0 10 20 30 40 50 60 70 80
Weight percentage of Glucose
Fig. 14. Comparison between predicted and experimental data for the solid-liquid phase equilibrium compositions of
D-glucose/sucrose/water mixture at 70°C.

(LK) equations of state and the NRTL model were not significantly different from zero, in this work,
they were fixed and set equal to zero.
Table 6 presents a comparison between experimental (Lilley and Sutton, 1991) and predicted
values of water activities and osmotic coefficients for D-glucose/sucrose/water mixtures at 25°C,
respectively. The model is able to predict water activities and osmotic coefficients of ternary aqueous
systems with a relative deviation percentage [equal to Kexperimental v a l u e - calculated value)/
(experimental value)l x 100] smaller than 0.055% and 0.708%, respectively, which are about the same
order of magnitude of those presented by Catt6 et al. (1994), 0.054% and 0.787% respectively, as
shown in this table.
The comparison between experimental (Abderafi and Bounahmidi, 1994) and predicted vapor-liquid
80

o T_-70oc
r~
~.~ 60 "'4

40

"3 o
N 20 Abed et 4.

0
0 10 20 30 40 50 60 70 80 90 I00
Weight percentage of Fructose
Fig. 15. Comparison between predicted and experimental data for the solid-liquid phase equilibrium compositions of
D-fructose/sucrose/water mixture at 700C.
90 A.M. Peres, E.A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95

0
0
°_
i i i i i i
¢;

e~

I i i i

~S
e- ,-d

"r~ ¢ q

e-

E
0

(5
r~ i

..d

0 .~ t"q

0 0

t~
,6
ii i
8
E
I
e,,,

i i i i E
8.
d:
e~
u

I ,,~ ¢-q
A.M. Peres, E.A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95 9

c~

J~

0
" 6 o 6 6 6 6 ~
I I I
0

>

III
o

c~

E
o

G
II

III I

o~
0

I l l l l l l l

.~ 0 I
e-,

II IIT E
8..
92 A.M. Peres, E.4. Macedo / Fluid Phase Equilibria 123 (1996) 71-95

equilibrium data for the temary and quaternary aqueous systems containing D-glucose, D-fructose
a n d / o r sucrose is given in Tables 7-10. These tables show that the proposed model is able to give a
very accurate prediction of the vapor-liquid equilibrium data (boiling temperatures) for this kind of
systems: the maximum relative percentage deviation is smaller than 0.9% for D-
glucose/sucrose/water; 0.9% for D-fructose/sucrose/water; 0.8% for D-glucose/D-fructose/water
and 1.4% for D-glucose/D-fructose/sucrose/water. Table 11 shows that the new approach is able to
describe the VLE data for the binary water/sugar systems better than the PR, LK and NRTL models
(Abderafi and Bounahmidi, 1994); for the temary and quatemary mixtures the predictions are of less
quality than those of the PR EOS but are, in general, superior to those of the LK EOS and NRTL
model.
Figs. 14 and 15 show a comparison between the predicted and experimental data available in the
literature (Abed et al., 1992) for the solid-liquid phase equilibrium compositions of D-
glucose/sucrose/water and D-fructose/sucrose/water mixtures at 70°C, respectively. They also
present a comparison with the predicted values calculated by Gabas and Lagurrie (1993), using the
UNIFAC model proposed by Abed et al. (1992). From these figures it is clear that the proposed
model is able to describe, with success, the two above-mentioned ternary systems at 70°C, and
slightly better than the model used by Abed et al. (1992). Tables 12 and 13 also demonstrate this
same conclusion.
In general, the proposed modified UNIQUAC model is able to predict very satisfactorily the
above-mentioned thermodynamic properties of ternary and quatemary aqueous systems.

7. Conclusions

A modified UNIQUAC model with linear temperature dependence is proposed to describe


thermodynamic properties of aqueous sugar solutions, such as water activity, osmotic coefficient,
vapor pressure, boiling temperature, freezing point and solubility data. New sugar/water
temperature-dependent interaction parameters are presented for D-glucose, D-fructose and sucrose.
Despite the high non-ideality of the sugar solutions, this model proves to be very satisfactory in the
correlation of vapor-liquid and solid-liquid equilibria for binary aqueous systems containing one of
these sugars. The predictive capabilities of the proposed model have been successfully tested for
vapor-liquid and solid-liquid equilibrium data of ternary and quaternary aqueous mixtures containing
D-glucose, D-fructose a n d / o r sucrose.
This approach allows the extension of the proposed method to calculations of solid-liquid
equilibria of sugars in mixed solvents, as shown by Peres and Macedo (1996).

8. List of symbols

a UNIQUAC binary interaction parameter (K); water activity


AAD average absolute deviation
Fobj objective function (Eq. (8))
m molality/mol k g - t of solvent
MSE mean square error
NDE number of data points
A.M. Peres, E.A. Macedo / Fluid Phase Equilibria 123 (1996) 71-95 93

np number of fitted parameters


P system pressure/mm Hg
O group area parameter
R group volume parameter; gas constant/J mol-~ K -
RMSD root mean square deviation
T absolute temperature/K
Tm melting temperature/K
L freezing point of pure component/K
T° arbitrary reference temperature, set equal to 298.15 K
V thermodynamic property
Xi mole fraction of i

8.1. Greek letters


,,/ activity coefficient
AA temperature-dependent parameter/J mol- 1 K -
AB temperature-dependent parameter/J mol- 1 K-2
/,c,, heat capacity/J mol- ~ K -
AHf enthalpy of fusion/J mol-1
4, osmotic coefficient
molecular volume fraction of the component i

8.2. Subscripts
i thermodynamic property i
mix mixture
n data point n
sug sugar
w water

8.3. Superscripts
calc calculated
exp experimental
* unsymmetric convention

Acknowledgements
A.M.P. wishes to acknowledge Junta Nacional de Investiga~o Cientffica e Tecnol6gica (Portugal)
for financial support. The authors are very grateful to S.P. Pinho for many valuable suggestions.

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