J. Chem.

Thermodynamics 55 (2012) 115–123

Contents lists available at SciVerse ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Solubility and physical properties of sugars in pressurized water

Marleny D.A. Saldaña ⇑, Víctor H. Alvarez, Anupam Haldar
Department of Agricultural, Food and Nutritional Science, Faculty of Agriculture, Life and Environmental Science, University of Alberta, Edmonton, AB, Canada T6G 2P5

a r t i c l e i n f o a b s t r a c t

Article history: In this study, the solubility, density, and refractive index of glucose and lactose in water as a function of
Received 6 October 2011 temperature were measured. For solubility of sugars in pressurized water, experimental data were
Received in revised form 4 April 2012 obtained at pressures of (15 to 120) bar and temperatures of (373 to 433) K using a dynamic flow high
Accepted 19 June 2012
pressure system. Density data for aqueous sugar solutions were obtained at pressures of (1 to 300) bar
Available online 3 July 2012
and temperatures of (298 to 343) K. The refractive index of aqueous sugar solutions was obtained at
293 K and atmospheric pressure. Activity coefficient models, Van Laar and the Conductor-like Screening
Keywords:
Model-Segment Activity Coefficient (COSMO-SAC), were used to fit and predict the experimental solubil-
COSMO theory
High pressure
ity data, respectively. The results obtained showed that the solubility of both sugars in pressurized water
Modeling increase with an increase in temperature. However, with the increase of pressure from 15 bar to 120 bar,
Subcritical water the solubility of both sugars in pressurized water decreased. The Van Laar model fit the experimental
Superheated water aqueous solubility data with deviations lower than 13 and 53% for glucose and lactose, respectively.
The COSMO-SAC model predicted qualitatively the aqueous solubility of these sugars.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction
There has been great interest to use alternative solvents such as
subcritical water (sCW) to treat agricultural biomass. sCW refers to
water in the liquid phase under pressure at temperatures above its
normal boiling temperature (373.15 K) and below its critical tem-
perature (647.13 K). sCW is also known as pressurized hot water,
hot compressed water, near-critical water, superheated water or
pressurized water (PW). Then, the term PW is used in this study.
In the literature, the term sCW is sometimes confused with liquid
water (<373 K).
PW can solubilize important compounds, such as sugars. Solu-
bility data is of particular importance in the food industry, where
sugars are used as sweeteners, in the pharmaceutical industry,
where sugars are used as coatings for drug delivery systems [1–
3] and in biomass conversion processes [4–6].
A search for solubility data of sugars in PW yielded very few re-
sults, particularly for two reasons: (i) experimental difficulties for
the measurements at high temperatures and pressures, and (ii)
possible sugar degradation to aldehydes or furans at temperatures
above 553 K [7]. Most sugar solubility data in water has been re-
ported at temperatures below 373 K [8–12,14] or in binary solvent
mixtures, such as (ethanol + water) [13,14]. Then, sugars solubility
database in PW is essential.
The solubility of glucose and lactose in water was obtained up
to 335 K and reported by the US National Bureau of Standards
⇑ Corresponding author. Tel.: +1 780 492 8018; fax: +1 780 492 8914.
E-mail address: marleny@ualberta.ca (M.D.A. Saldaña).
[10] but these data are not in agreement with the ones reported
in the literature [12,15,16]. Young [12] and Mullin [16] reported
higher solubility of D-glucose (298 to 315) K in distilled water com-
pared to data reported by Zhang et al. [17], who used ultrapure
water and a semi-continuous process. Zhang et al. [17] reported
solubility of glucose, D-(+)-maltose monohydrate and D-(+)-xylose
at temperatures above the boiling temperature (298 to 456) K,
but the pressure was not reported. The differences in solubility
data could be attributed to the use of different experimental tech-
niques and the water quality used for the experiments and
analysis.
Zhang et al. [17] results show unexpectedly low sugar solubility
and char formation in the high pressure vessel, indicating degrada-
tion of sugar molecules at temperatures above 413 K with a water
flow rate below 0.5 mL  min1. The use of a low flow rate increases
the residence time and the degradation of sugars. Therefore, a flow
rate of 1 mL  min1 was used by these authors. Moreover, excess of
water up to four times the volume of water pumped into the unit
was used to prevent the excess dissolved sugar from crystallization
inside the condenser where the solution cools down to ambient
temperature (298 K).
In addition to aqueous sugar solubility data, physical properties
such as density and refractive index of aqueous sugar solutions are
essential for process design (e.g. PW extraction and reaction).
Refractive index measurement has been successfully applied as it
is easy, accurate, simple, and uses a small quantity of sample
(±0.3 mL). Refractive index measurements of aqueous sugar solu-
tions allow the determination of the composition of diluted binary
solutions [13,18] and concentrated solutions [19]. Even though

0021-9614/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jct.2012.06.016
116 M.D.A. Saldaña et al. / J. Chem. Thermodynamics 55 (2012) 115–123
Nomenclature
GE excess Gibbs free energy
DHf molar enthalpy of fusion of the solute at Ttp
p pressure
q density
T temperature
Si solubility for ith sample of a selected sugar
Sm mean solubility for the selected sugar
N number of replicates
REm excess molar refractivity of the solution
solubility, density and refractive index of aqueous sugar solutions
are important, few authors reported these data. Therefore, the
main objective of this study was to obtain solubility data of glucose
and lactose in pressurized water at (15, 80, and 120) bar. The spe-
cific objectives were: (i) to determine density and refractive index
of glucose and lactose aqueous solutions, and (ii) to predict and
correlate the solubility of these sugars in PW using the Conduc-
tor-like Screening Model-Segment Activity Ccoefficient (COSMO-
SAC) model [20] and the Van Laar model [21,22], respectively.
2. Experimental section
2.1. Materials
Sugar standards such as D-(+)-glucose (stated mass fraction pur-
ity greater than 0.999), D-(+)-lactose monohydrate (stated mass
fraction purity greater than 0.999), and lactulose (stated mass frac-
tion purity greater than 0.980) and glass beads (5 mm) were ob-
tained from Sigma–Aldrich (Oakville, ON, Canada). For all
experiments, distilled water was used.
2.2. Density and refractive index measurements
Samples for density and refractive index measurements were
prepared by weighing known masses of water and sugars into bot-
tle stoppers using a Mettler-Toledo 200 analytical balance (Colum-
bus, OH, USA), with a precision of ±1  104 g.
Densities at low and high pressures were measured using the
system set of Anton Paar DMA 5000 and Anton Paar DMA HP vibra-
tion-tube digital densimeter (St. Laurent, QC, Canada) and a high
pressure pump GILSON 307 (Guelph, ON, Canada). The DMA HP
system automatically corrects the influence of viscosity on the
measured density. The DMA 5000 densimeter uses the Anton Paar
U-tube measuring principle with a reference oscillator and a
high-precision platinum thermometer. The repeatability and the
uncertainty of the experimental measurements were lower than
±5  105 g  cm3 for the density and ±0.01 K for the temperature.
The uncertainties of the experimental pressures were ±0.05 and
±0.2 bar for pressures lower than 10 bar and for pressures higher
than 10 bar, respectively.
The density measurement of the samples was carried out by
pumping the solutions into the Anton Paar DMA 5000 unit for
atmospheric pressures and the Anton Paar DMA HP for high pres-
sures. Then, the temperature was kept constant and the pressure
was changed for each measurement. The measurements were per-
formed in triplicates.
Refractive indices were determined using an automatic refrac-
tometer Mettler-Toledo RE50D (Tokyo, Japan) with a resolution
of ±105, an uncertainty in the experimental measurements of
±2  105 and an uncertainty for the temperatures of ±0.01 K. The
refractive index measurements were determined by loading the
sample in the measuring prism of the refractometer. The refractive
Rmi molar refraction of a pure component i
nD refractive index
xi mole fraction of a pure component
MWi molecular weight of the ith component of the mixture
exp experimental
cal calculated
p(r) sigma profile
Ai total molecular cavity surface area
p(r)  Ai area-weighted sigma profile
index of samples was measured at 293.15 K and atmospheric
pressure.
Sample composition was determined by refractometric analysis
[13,18,19]. The results were compared with samples of known
composition through inverse interpolation.
2.3. Solubility of sugars in pressurized water
A dynamic flow high pressure system was used to measure the
solubility of pure sugar compounds in pressurized water. This sys-
tem, with few modifications from the previously described by
Singh and Saldaña [23], has mainly two pumps, a high pressure
vessel, heating and cooling units, and a back pressure regulator
(figure 1). The high pressure vessel with a volume of 16 mL
(20.3 cm length  1.2 cm diameter) is heated by band heaters from
Trutemp (Edmonton, AB, Canada). The temperature of the high
pressure vessel and the heater were carefully controlled by K-type
thermocouples using an Omega 619 temperature controller (Stam-
ford, CT, USA) hooked up to a computer for recording the data. A
GILSON model 305 pump with a 10SC pressure head (pump 1)
(Guelph, ON, Canada) was used to pump water into the high pres-
sure vessel from the water reservoir. Another GILSON model 307
pump (pump 2) (Guelph, ON, Canada) was used to add dilution
water to the exiting solution from the high pressure vessel to pre-
vent sugar crystallization and degradation.
To determine the solubility of pure sugar in pressurized water,
first a known amount of sugar and glass beads were loaded into the
high pressure vessel. Then, water was pumped at a specific flow
rate until achieving constant pressure and temperature. At experi-
mental conditions, a determined static holding time (equilibration
time) was used before collecting the samples every 30 s.
An experimental design based on different flow rates of pump 1
from (0.5 to 1.5) mL  min1, flow rates of pump 2 from (3 to
7) mL  min1, and static holding times from (1 to 15) min was used
to determine the optimal parameter values for the solubility exper-
iments. The experiments were carried out in triplicates, where the
standard deviation (s) for the aqueous solubility of sugars is calcu-
lated using the following equation:
2 !2 , 31=2
X
N
s¼4 Si  Sm ðN  1Þ5 ; ð1Þ
i¼1
where Si is the solubility for ith sample at a constant temperature
for a selected sugar; Sm is the mean solubility for the selected sugar
at a constant temperature, and N is the number of replicates.
2.4. Lactulose determination
A colorimetric method was used to determine the lactulose con-
tent [24] in an attempt to quantify any possible degradation prod-
uct. Lactulose is a thermal degradation product that might be
obtained after measurements of aqueous lactose solubility in PW.
 M.D.A. Saldaña et al. / J. Chem. Thermodynamics 55 (2012) 115–123 117

FIGURE 1. High pressure apparatus to measure sugar solubility in pressurized water.

Lactulose was measured by hydrolysing the PW samples under f2so

x2 ¼ ; ð5Þ
acidic conditions. Cysteine hydrochloride-tryptophan reagent was c2 f2lo
added to provide the pink chromophore on hydrolyzed lactulose
molecule, which is detected by the Jenway spectrophotometer where c2 is the activity coefficient of the solute. The ratio of fugac-
model Genova (Burlington, NJ, USA). The adsorption intensity of ities is calculated by the following thermodynamic equation
the solution was measured at 518 nm and quantified using stan- [21,22]:
dards between (5 and 150) lg of lactulose per mL of sample.      
f2so DHf T tp Dcp T tp
ln ¼ 1 þ  1  lnðT tp =TÞ
f2lo RT tp T R T
3. Theoretical approach for data analysis
pðv s0
2  v2 Þ
lo
þ ; ð6Þ
3.1. Density and refractive index RT
where R is the molar gas constant, p is the pressure, T is the absolute
sThe apparent molar volume (/V) was calculated by: temperature, Ttp is the triple-point temperature of the solute, DHf is
MW 2 q1  q the molar enthalpy of fusion of the solute at Ttp, vso lo
2 and v2 are the
/V ¼ þ ; ð2Þ molar volumes of the pure solid and the pure subcooled liquid,
q1 mq1 q
respectively, and DcP is the difference in heat capacities
P2  Dc P2 ) at Ttp. The subcooled liquid molar volume, v 2 , was
where q is the density of the mixture, q1 is the density of the sol- (Dclo so lo

vent, MW2 is the molecular weight of the sugar, and m is the molal- estimated from the modified Shah and Yaws equation [25], which
ity of the solution. uses the critical properties of the solute. The critical properties were
Refractive index (nD) data was used to calculate the excess mo- estimated using the method proposed by Alvarez and Valderrama
lar refractivity, REm , by: [26]. For any temperature, v so 2 was estimated from the subcooled li-

X
N quid molar volume v lo 2 using the correlation of Goodman et al. [27].
REm ¼ Rm  xi Rmi ; ð3Þ The activity coefficient of a solute in a solvent is calculated by
i¼1 regression or prediction models. Most of the models proposed to
predict the activity coefficient of a sugar in solvents use group con-
where Rm is the molar refraction of the solution, Rmi and xi are the
tribution methods [17,28]. Even though these methods show good
molar refraction and mole fraction of the pure component i, respec-
results for (solid + liquid) equilibria behavior, these methods can-
tively. The molar refraction is calculated by the Lorentz–Lorenz
not be used for other types of phase equilibria, such as (liquid + li-
equation:
! quid) and (vapor + liquid). Furthermore, the use of these models is
 2  PN
nD  1 i xi MW i
limited for any simulation process. Recently, the COSMO-SAC
Rm ¼ : ð4Þ activity coefficient model has been used to predict solubility of
n2D þ 2 q
compounds in solvents and to predict other phase equilibria
behavior [18,20]. A flexible model to regress solubility data is the
3.2. Solubility modeling Van Laar model reported earlier by Alvarez and Saldaña [22].
Therefore, in this study, the Van Laar model was used for the
Theory of a solid solubility in a liquid is well described some- regression of the aqueous sugar solubility data while the COS-
where else [21]. The fundamental equation of phase equilibrium MO-SAC model was used to predict the solubility data.
establishes that at a given temperature and pressure, the fugacity
(f) of the solid solute in the liquid phase (f2l ) must be equal to 3.3. COSMO-SAC model and sigma profile
the fugacity of the same component in the solid phase (f2s ). In
(liquid + solid) systems, the solid is considered as a pure compo- The COSMO-SAC model requires input of an area-weighted sig-
nent with the fugacity (f2so ). The f2so and the standard state fugacity ma (r) profile, pi(r).ACOSMOi, for each molecule i. The sigma profile,
of the liquid phase (f2lo ) depend on temperature (T) and pressure pi(r), is the probability of a segment with a specific charge density,
(P). The equation of the solute solubility (x2) in the liquid is: r. The area-weighted sigma profile is a file containing the sigma
profile pondered by the total surface area of molecule i.
118 M.D.A. Saldaña et al. / J. Chem. Thermodynamics 55 (2012) 115–123

The sigma profiles were generated from a single 3D molecular
structure by performing quantum-mechanical calculations. First,
the equilibrium molecular geometry of each molecule in three
dimensions was obtained by minimization of the molecular en-
ergy. Then, the volume of cavity (VCOSMO), area of cavity (ACOSMO)
and the total number of segments (COSMO segments) were esti-
mated from the equilibrium molecular geometry using a solvation
calculation in a perfect conductor. The calculations were conducted
using the quantum chemistry package DMol3 developed by Accel-
rys Materials Studio v4.3. The detailed settings for DMol3 (GGA/
VWN-BP functional setting) were the same used earlier by Mullins
et al. [29]. Finally, the activity coefficient of the solid in the liquid
phase was calculated with the equations previously reported
[20,29].
4. Results and discussion
4.1. Density and refractive index
Density measurements of aqueous sugar solutions at different
temperatures (298 K to 343 K), and pressures (1 bar to 300 bar)
at selected sugar compositions are presented in table 1. As ex-
pected, density increases with an increase in pressure from (1 to
300) bar and decreases with an increase in temperature from
(298 to 343) K for the systems investigated, glucose and lactose
(table 1). The experimental density obtained in this study for aque-
ous sugar solutions were compared with literature data at 1 bar, as
density values at high pressures were not found in the literature.
Then, experimental density at 1 bar and 298 K of aqueous glucose
or lactose solutions agree with values previously reported by Cer-
deiriña et al. [30] and McDonald and Turcotte [31], respectively. A
maximum difference of 0.08% and 0.4% for glucose and lactose
aqueous solutions, respectively, between density data reported in
the literature and density data reported in this study were ob-
tained at the maximum sugar concentrations reported in this
study.
Table 2 shows the refractive index and density of glucose and
lactose in aqueous solutions at 293 K and atmospheric pressure
(0.933 bar). The maxima concentration measured for both aque-
ous sugar solutions was below its saturated concentration at 293 K.
The refractive index data show a quadratic polynomial tendency
for an increase in sugar concentration. Density and refractive index
show similar values at similar mass concentrations of both sugars
(g sugar/g water). This behavior indicates similar interactions of
glucose or lactose at diluted concentrations. Density and refractive
index for aqueous sugar solutions show a different trend based on
molar concentrations (figure not shown). Therefore, density and
refractive index of these aqueous sugar solutions are not colligative
properties.
The sugar apparent molar volume and excess molar refractivity
are regarded as a sensitive structural property to understand inter-
actions in solutions. Complete data of sugar apparent molar vol-
ume are presented in the supporting information (tables S1 and
S2).
Figure 2 shows the apparent molar volume, /V, of glucose and
lactose in water at 313 K and pressures of (1 and 300) bar. The lac-
tose solutions showed high variations for the /V values, changing
from (1020 to 230) cm3  mol1 compared to the /V values ob-
tained for glucose solutions that changed from (62 to 114)
cm3  mol1. The /V increases rapidly at 1 bar for glucose concen-
trations below 0.12 g/g water (molality of 0.6) and for lactose con-
centrations below 0.012 g/g water (molality of 0.04). While at
300 bar, the /V slightly decrease with an increase on the sugar con-
centration. At high sugar concentrations, the /V values remain al-
most constant. Aqueous glucose solution and aqueous lactose
solution showed similar profiles of the /V of sugars as a function
of solution concentration (figure 2). But, the low /V values obtained

TABLE 1
Density q of aqueous sugar solutions at temperature T, pressure p and concentration c of sugar in water.

c/(g  g water1) T/K qGlucose/(g  cm3)

1 bar 100 bar 200 bar 300 bar
0.0128 298.15 1.00209 n.d. n.d. n.d.
313.15 0.99717 1.00094 1.00552 1.00925
328.15 0.99059 0.99433 0.99888 1.00275
343.15 0.98263 0.98642 0.99099 0.99501
0.1151 298.15 1.03747 n.d. n.d. n.d.
313.15 1.03203 1.03414 1.03812 1.04187
328.15 1.02550 1.02700 1.03135 1.03522
343.15 1.01818 1.01881 1.02341 1.02703
0.6732 298.15 1.17164 n.d. n.d. n.d.
313.15 1.16449 1.16740 1.16925 1.17341
328.15 1.15619 1.15099 1.15702 1.16638
343.15 1.14760 1.14189 1.14612 1.14836

qLactose/(g  cm3)
0.00102 298.15 0.99763 n.d. n.d. n.d.
313.15 0.99279 0.99641 1.00071 1.00486
328.15 0.98626 0.98976 0.99401 0.99826
343.15 0.97703 0.98210 0.98646 0.99068
0.01265 298.15 1.00171 n.d. n.d. n.d.
313.15 0.99682 0.99960 1.00403 1.00805
328.15 0.99025 0.99313 0.99697 1.00119
343.15 0.98224 0.98506 0.98976 0.99367
0.09015 298.15 1.02363 n.d. n.d. n.d.
313.15 1.01685 1.02086 1.02520 1.02902
328.15 1.00993 1.01480 1.01911 1.02278
343.15 1.00287 1.00784 1.01257 1.01624

Standard uncertainties u are u(T) = 0.01 K, u(p) = 0.05 bar for p 6 10 bar, u(p) = 0.2 for p > 10 bar, u(c) = 0.0002. n.d.: not determined. q: density, T: temperature, p: pressure c:
concentration.
 M.D.A. Saldaña et al. / J. Chem. Thermodynamics 55 (2012) 115–123 119

TABLE 2
Concentration c, refractive index nD and density q of (water + sugar) systems at 293.15 K, and atmospheric pressure po (0.933 bar).

Glucose Lactose
293
c/(g  g water 1
) n293
D
q /(g  cm 3
) c/(g  g water1) n293
D
q293/(g  cm3)
0.0000 1.33299 0.99648 0.0000 1.33299 0.99648
0.0010 1.33314 0.99905 0.00098 1.33315 0.99902
0.0029 1.33341 0.99975 0.0010 1.33316 0.99902
0.0064 1.33389 1.00104 0.0024 1.33335 0.99958
0.0103 1.33445 1.00247 0.0034 1.33350 0.99998
0.0239 1.33637 1.00742 0.0052 1.33375 1.00069
0.0433 1.33903 1.01438 0.0087 1.33420 1.00205
0.0615 1.34144 1.02080 0.0126 1.33473 1.00352
0.0771 1.34345 1.02622 0.0222 1.33603 1.00699
0.0857 1.34459 1.02917 0.0321 1.33740 1.01031
0.1190 1.34870 1.04037 0.0429 1.33881 1.01364
0.1389 1.35116 1.04689 0.0595 1.34100 1.01817
0.1638 1.35412 1.05486 0.0677 1.34207 1.02014
0.1906 1.35708 1.06322 0.0769 1.34324 1.02215
0.2512 1.36375 1.08125 0.0902 1.34498 1.02466
0.4140 1.37940 1.12374 0.1015 1.34636 1.02643
0.5160 1.38794 1.14594 0.1159 1.34791 1.02820
0.6267 1.39602 1.16618 0.1392 1.35108 1.02992

q293: density at 293.15 K, n293

D : refractive index at 293.15 K, c: concentration.
Standard uncertainties u are u(T) = 0.01 K, u(po) = 0.005, and u(c) = 0.0002.

a 120
0

110 -10
-1
Φ V/ cm .mol

100 -20
90
3

Rm E

-30
80
70 -40
60 -50
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 -60
0 1 2 3 4
b 300 Molality / mole sugar.kg water-1
-1

0
Φ V/ cm .mol

FIGURE 3. Excess molar refractivity of sugars as a function of solution concentra-

-300 tion at 293 K and 1 bar for: (s) glucose and ( ) lactose.
3

-600
-900 0.25

-1200
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.20
-1
p(σ).Area (σ) / nm 2

Molality / mole sugar.kg water

0.15
FIGURE 2. Apparent molar volume of sugars (a-glucose aqueous solution; b-lactose
aqueous solution) as a function of solution concentration at 313 K and 1 bar (red
line) or 300 bar (black dashed line). (For interpretation of the references to colour in 0.10
this figure legend, the reader is referred to the web version of this article.)

0.05

for aqueous lactose solutions indicate that their molecular

structures are more compacted than those of aqueous glucose 0.00
-2.52 -1.68 -0.84 0 0.84 1.68 2.52
solutions.
Figure 3 shows the negative excess molar refractivity of glucose σ / e nm-2
and lactose at various aqueous sugar concentrations at 293 K and
FIGURE 4. Area-weighted sigma profiles used for water ( ), glucose (– –), and
1 bar. The REm of a solution is directly proportional to the molecular lactose ( ). Due to the definition as a conductor, screening charges electrostatically
packing [32]. The negative values of the REm of sugars indicate a positive where some parts of the molecules had negative r values or vice versa.
contraction in the volume caused by attractive interactions of su-
gar–water molecules. The results also indicate that the molecular
packing of aqueous lactose solution is greater than that of aqueous 4.1.1. Area-weighted sigma profile
glucose solution (less negative excess molar refractivity value). Figure 4 compares the area-weighted sigma profiles for water,
Therefore, low values of the /V and REm for aqueous lactose solution glucose, and lactose. The area-weighted sigma profiles of these
indicate high molecular structure compactness and consequently compounds can be qualitatively divided in three main regions,
lactose solubility is less influenced by pressure at the range of tem- which are separated by vertical lines located at the cut off values
peratures studied (table 3). for hydrogen bond donor groups (rHB < 0.84 e/nm2) and hydro-
120 M.D.A. Saldaña et al. / J. Chem. Thermodynamics 55 (2012) 115–123

TABLE 3
Experimental solubility data Sb of glucose and lactose in pressurized water at pressure p and temperature T.

T/K SGlucose/(g  g water1) SLactose/(g  g water1)

p/15 bar p/80 bar p/120 bar p/15 bar p/80 bar p/120 bar
303 0.508 ± 0.031 0.411 ± 0.014 0.424 ± 0.012 0.165 ± 0.001 0.154 ± 0.001 0.144 ± <0.001
323 0.659 ± 0.013 0.520 ± 0.006 0.514 ± 0.010 0.274 ± 0.013 0.241 ± 0.001 0.244 ± 0.001
343 0.768 ± 0.017 0.632 ± 0.034 0.635 ± 0.016 0.440 ± 0.043 0.360 ± 0.001 0.341 ± 0.001
373 1.442 ± 0.200 1.201 ± 0.058 1.165 ± 0.010 0.643 ± 0.083 0.554 ± 0.006 0.527 ± 0.001
393 1.964 ± 0.193 1.613 ± 0.043 1.554 ± 0.035 0.781 ± 0.028 0.715 ± 0.007 0.711 ± 0.022
413 3.086 ± 0.405 2.313 ± 0.086 2.167 ± 0.103 0.940 ± 0.033 0.886 ± 0.071 0.841 ± 0.088
433/423a 4.239 ± 0.345 2.883 ± 0.301 2.606 ± 0.025 1.109 ± 0.036 1.014 ± 0.028 0.981 ± 0.002
a
The equilibrium temperature for lactose + water was 423 K, S: solubility, T: temperature, p: pressure.
b
S solubility mean ± standard deviation (s). Standard uncertainties u are u(T) = 0.01 K, and u(p) = 0.05 bar for p 6 10 bar, and u(p) = 0.2 for p > 10 bar.

5 a 0.8

0.7

Solubility / mole fraction

4
Solubility / g glucose.g water-1

0.6

0.5
3
0.4

2 0.3

0.2
1 0.1

0
0 300 320 340 360 380 400 420 440
290 310 330 350 370 390 410 430 450

Temperature / K b 0.25
Solubility / mole fraction

FIGURE 5. Experimental solubility of glucose in pressurized water at various 0.20

temperatures and pressures of: (e) 15 bar, (h) 80 bar, (D) 120 bar, (+) unknown
pressure [17], and () 1 bar [13]. All symbols represent mean values of solubility.
The lines are for better visualization. 0.15

0.10
1.2
0.05
Concentration / g sugar.g water-1

423 K
1.0
413 K
0.00
0.8 300 320 340 360 380 400 420 440
393 K
Temperature / K
0.6
373 K
FIGURE 7. Modeling solubility of glucose (a) and lactose (b) in pressurized water at
0.4 (15, e and 120, D) bar. Open symbols represent the mean values for each
343 K
experiment in triplicate and the lines represent the values from the COSMO-SAC
323 K model at (15, –; 120, ; and 300, ) bar.
0.2
303 K

0.0
0 2
FIGURE 6. Lactose concentration as a function of time in pressurized water at 80
bar and temperatures from (303 to 423) K. Lines represent the mean values with
standard error bars for each experimental point in triplicate.
gen bond acceptor groups (rHB > 0.84 e/nm2) [20]. For sugars, the
area-weighted sigma profiles reveal to be as broad as the area-
weighted sigma profiles of water. In addition, area-weighted sigma
profiles of these sugars are dominated by two peaks of slightly neg-
ative screening charge density at approximately r = 0.7 and
r = 0.5, as a result of polarization of –CH2– groups by the hydro-
xyl–alkyl hydrogen interactions, and oxygen atoms.
Figure 4 shows that the higher number of carbon atoms in the
molecule implies an increase of the area below each histogram of
charge densities around the non-polar area (glucose < lactose).
4 6 8 10 12 14 16 The area-weighted sigma profile with high values near the r = 0
Time / min show the predominance of repulsive interactions between polar
and non-polar segments, affecting the cohesive properties of the
molecule. The same concept can be applied to mixtures with very
different area-weighted sigma profiles. Then, the area-weighted
sigma profiles of the sugar aqueous solutions show more affinity
for (water + glucose) (high solubility) than for (water + lactose)
(low solubility), supporting the data reported in table 3. Therefore,
the qualitative solubility behavior of the sugar aqueous solutions
studied was predicted by the area-weighted sigma profile.
4.2. Solubility data
The optimal values for flow rates of the pumps and static hold-
ing time were selected to obtain reproducible solubility data and to
avoid degradation. The experimental static holding time was
 M.D.A. Saldaña et al. / J. Chem. Thermodynamics 55 (2012) 115–123 121

TABLE 4 TABLE 6
Experimental concentration c of lactulose at saturated concentrations of lactose at Estimated parameters and deviations obtained with Van Laar and the COSMO-SAC
different pressures p and temperatures T. models.

T/K c/(mg lactulose  g solution1) c p/bar Aij/(J  mol1) Aji/(J  mol1) %|Dx2|
p/15 bar p/80 bar p/120 bar Water (1) + glucose (2)
Van Laar 15 2075.2610 2034.2485 13.3
303 0.28 0.54 1.17
COSMO-SAC 183.0
323 0.31 0.44 0.78
Van Laar 80 2174.2593 2597.1733 11.2
343 0.50 1.69 1.30
COSMO-SAC 250.3
373 0.89 1.87 0.88
Van Laar 120 1476.5168 2262.7727 11.2
393 0.80 2.09 2.92
COSMO-SAC 234.2
413 0.82 2.22 2.19
423 1.55 1.31 2.30 Water (1) + lactose (2)
Van Laar 15 21.4319 266.0333 53.1
T: temperature, p: pressure, c: concentration, Standard uncertainties u are COSMO-SAC 125.2
u(T) = 0.01 K, u(p) = 0.05 bar for p 6 10 bar, u(p) = 0.2 for p > 10 bar, and u(c) = 0.03. Van Laar 80 21.9743 284.1897 51.7
COSMO-SAC 123.4
Van Laar 120 19.9819 288.9909 51.1
10 min at temperatures lower than 343 K, 5 min for temperatures COSMO-SAC 121.6

between (343 and 393) K and 1 min for temperatures over 393 K. c: activity coefficient model, p: pressure, Aij: interaction parameter,
Pump 1 used a flow rate of 1 mL  min1 and pump 2 was run at %|Dx2| = 100|xexp cal exp
2  x2 |/x2 .

flow rates from (3 to 7) mL  min1. Dilution factors from 4 (that

corresponds to 3 mL  min1) up to 8 (that corresponds to
7 mL  min1) were tested to avoid any sugar degradation/crystalli-
zation in the cooling unit. A low dilution factor of 4 resulted in low-
er glucose solubility compared to those obtained using the high
dilution factors of 6 or 8 at temperatures over 390 K. Then, the
aqueous solutions of glucose or lactose were determined at various
temperatures and three pressures.
To validate the solubility technique, experimental solubility
data for glucose in pressurized water was first determined and
compared with data reported in the literature [13,17]. As observed
in figure 5, a good agreement between data obtained for glucose
solubility in pressurized water at 15 bar in this study and that re-
ported in the literature (at 1 bar [13], and at an unknown pressure
[17] was achieved up to 410 K. Deviations can be attributed to the
different pressures used.
The reliability of the technique can be observed in figure 6 for
the binary system lactose in pressurized water at 80 bar and tem-
peratures from (303 to 423) K. Figure 6 shows aqueous sugar con-
centrations as a function of time. The plateau region of the kinetic
concentrations means that equilibrium was achieved at a constant
temperature and pressure. This concentration value was used as
the nominal aqueous sugar solubility.
Table 3 summarizes the results obtained for the solubility of
binary systems, (glucose + water) and (lactose + water), at pres-
sures of (15, 80, and 120) bar and temperatures of (303 to
423) K. Standard deviation (s) values for solubility of sugars in
pressurized water are also provided in table 3. For glucose solu-
tions, s ranged from 0.006 at 323 K/80 bar to 0.405 at 413 K/
15 bar, while for lactose solutions, s ranged from <0.001 at 303 K/
120 bar to 0.088 at 413 K/120 bar, indicating that the experimental
errors increase at high temperatures. In addition, the relative stan-
dard deviations of aqueous lactose solutions were less compared to
those of aqueous glucose solutions, indicating better reliability.
Table 3 shows an increase in solubility of 8 times at 15 bar or
6 times at 120 bar for both sugars in water as temperature in-
creases from (303 to 413) K. This could be attributed to physico-
chemical properties, such as apparent molar volume and excess
molar refractivity of glucose and lactose in water at pressurized
conditions.
The increase of apparent molar volumes of sugars in water at
high pressures (figure 2) and the negative excess molar refractivity
at high concentrations of aqueous sugar solutions (figure 3) explain
the decrease of sugar solubility in water as pressure increases. Fur-
thermore, the increase in pressure has more influence on glucose
solubility (table 3) as aqueous glucose molecular structures are less
compact (REm ¼ 33:8) compared to the aqueous lactose molecular
structures (REm ¼ 52:7) as observed in figure 3. For example, at a
constant temperature of 413 K and increasing the pressure from
(15 to 120) bar, the aqueous lactose solution solubility (table 3) de-
creased only 11% compared to a decrease of 30% for the solubility
of aqueous glucose solution.
PW is able to dissolve high amounts of sugar, mainly because of
the decrease in water polarity and the increase of enthalpy. Glu-
cose has a very low polarity; therefore, glucose–water hydrogen
bonding interactions increase [33]. A decrease in water polarity en-
ables O–H (hydroxyl-)groups of sugar to bind covalently to excess
hydronium ions (H3O+), which are stronger and more stable

TABLE 5
Properties of water and sugars used for modeling

Compound MW/ Tb/K Tc/K pc/bar n293

D
q293/ DcP/ Ttp/K DHf/ COSMO VCOSMOf 103/
(g  mol1) (g  cm3) (J  mol1  K1) (J  mol1) segmentsf nm3
Glucose 180.16 844.7b 1034.3c 49.2c 1.543d 1.520d 120.0e 423.3e 32248e 794 206.692839
Lactoseg 342.30 1289.7b 1655.7c 22.0c 1.537d 1.547d 239.0e 474.2e 75306e 1305 363.311885
Watera 18.02 373.2 647.1 220.6 1.333 0.998 51.3 273.2 6000 136 25.734540
a
From Diadem public [37].
b
Calculated by method [38].
c
Calculated by method [26].
d
Calculated by method [39].
e
From Ferreira et al. [40].
f
This study.
g 293
Monohydrate lactose. MW: molecular weight, Tb: normal boiling temperature, Tc: critical temperature, pc: critical pressure, n293
D : refractive index at 293.15 K, q : density
at 293.15 K, DcP: difference in heat capacity between liquid and solid at Ttp, Ttp: triple-point temperature, DHf: the molar enthalpy of fusion of the solute at Ttp, VCOSMO:
molecular volume calculated by the COSMO solvation model.
122 M.D.A. Saldaña et al. / J. Chem. Thermodynamics 55 (2012) 115–123

TABLE 7
Thermodynamic properties of sugar dissolution as a function of temperature T and pressure p.

T/K Glucose Lactose

1 1 1
DHsol/(kJ  mol ) DGsol/(kJ  mol ) DSsol/(J  mol ) DHsol/(kJ  mol1) DGsol/(kJ  mol1) DSsol/(J  mol1)
p/15 bar
303 11.33 7.64 12.18 15.79 11.98 12.56
323 12.87 7.48 16.69 15.79 11.43 13.49
343 14.51 7.53 20.34 15.79 10.81 14.51
373 17.16 6.43 28.77 15.79 10.61 13.88
393 19.05 5.91 33.43 15.79 10.57 13.29
413 21.04 4.96 38.91 15.79 10.49 12.82
433/423a 23.12 4.36 43.31 15.79 10.19 13.23
p/80 bar
303 11.12 8.15 9.81 16.08 12.15 12.96
323 12.64 8.08 14.10 16.08 11.77 13.35
343 14.25 8.05 18.05 16.08 11.37 13.74
373 16.85 6.93 26.59 16.08 11.06 13.47
393 18.70 6.45 31.16 16.08 10.84 13.32
413 20.65 5.74 36.09 16.08 10.69 13.05
433/423a 22.70 5.39 39.96 16.08 10.49 13.21
p/120 bar
303 9.78 8.07 5.62 16.14 12.32 12.60
323 11.11 8.11 9.29 16.14 11.73 13.63
343 12.53 8.04 13.07 16.14 11.52 13.45
373 14.81 7.01 20.90 16.14 11.21 13.22
393 16.44 6.56 25.14 16.14 10.86 13.43
413 18.16 5.93 29.60 16.14 10.86 12.78
433/423a 19.96 5.68 32.97 16.14 10.61 13.08
a
The equilibrium temperature for lactose + water was 423 K. T: temperature, p: pressure, DHsol: molar enthalpy DGsol: molar Gibbs free energy, DSsol: molar entropy.

compared to hydrogen bonds. The hydroxyl groups in glucose are
also attracted to water molecules by dipole–dipole forces. The
strength of these forces can be greater than glucose–glucose inter-
actions, facilitating its solubilisation. In addition, the high enthalpy
of the PW allows sugar crystals to break, resulting in ions that hy-
drate much rapidly as compared to normal water. The polarity of
water decreases and enthalpy of solution increases with an in-
crease in temperature at a constant pressure. These two properties
explain the increased solubility of glucose and lactose in PW by
increasing the temperature.
To further assess if any degradation of sugars in the samples at
PW conditions occurs, lactulose was quantified after measure-
ments of lactose solubility. Table 4 shows lactulose concentration
with a maximum standard deviation of 0.1 mg/g solution. There
is an increase in lactulose formation as temperature and pressure
(from (15 to 120) bar) increases. But, the maximum values ob-
tained are less than 2.3 mg lactulose/g solution, which represents
only 0.4% of the 0.981 g lactose/g water at 423 K. The literature also
shows that at 423 K, enolization of lactose occurs, resulting in 26%
of degradation [34] but a pressure of 4000 bar prevents lactose
isomerization at basic pH of 10 and 60 °C [35]. Therefore, the use
of PW in a dynamic flow high pressure system avoids degradation
of lactose.
4.2.1. Modeling
Table 5 summarizes the properties used in the thermodynamic
modeling for glucose and lactose solubility in water. The values of
VCOSMO show that the molecule of lactose is larger than that of glu-
cose in agreement with their molecular weight values.
Table 6 shows the interaction parameters, Aji, and deviations
obtained using Van Laar and COSMO-SAC models for sugar solubil-
ity in pressurized water. The experimental data and predicted re-
sults for aqueous sugar solutions from (15 to 120) bar are shown
in Figure 7. This figure also shows values of the predicted aqueous
sugar solubility at 300 bar and 15 bar, resulting in low solubility at
a high pressure (300 bar) for both systems. In this study, the pre-
dicted solubility is overestimated from two up to five orders of
magnitude with a good qualitative trend. The use of the thermody-
namic equation with the DcP term did not improve the solubility
predictions, indicating that COSMO-SAC model requires further
modifications, such as the incorporation of a term to account for
hydrogen bond interactions. However, few predictive models for
(solid + liquid) systems are reported in the literature. Therefore,
the COSMO-SAC model is still a useful qualitative predictive tool.
Table 7 shows thermodynamic properties of aqueous sugar
solutions, such as molar enthalpy (DHsol), molar Gibbs free energy
(DGsol), and molar entropy (DSsol) at different temperatures and
pressures. Thermodynamic properties of sugar solutions in pres-
surized water at different temperatures were calculated using
the equations reported previously by Queimada et al. [36], who
studied phenolic compounds dissolution in water at temperatures
of 288 K to 323 K. To calculate DHsol, DSsol, and DGsol from sugar
solubility data in pressurized water, the activity coefficient of the
sugar was assumed to be equal to one. The DHsol values increases
linearly with an increase in temperature for aqueous glucose solu-
tions, but DHsol values for aqueous lactose solutions remain almost
constant. The DHsol values of lactose solutions are not a function of
temperature. The DGsol values are positive for both binary systems
studied. The DGsol values for lactose + water are higher than those
obtained for glucose + water at all temperatures investigated at a
constant pressure. The DGsol values decrease with increasing tem-
peratures at all pressures investigated. The DSsol values for aque-
ous glucose solutions increase with an increase in temperature
but decrease with an increase in pressure. The DSsol values for
aqueous lactose solutions also slightly increase with an increase
in temperature but the effect of pressure is unclear.
4.3. Technological consequences
The use of PW allows dissolving high quantities of glucose or
lactose depending on temperature and pressure conditions. Data
obtained in this study showed that pressure can limit sugar solu-
bility in pressurized water. Properties of pure glucose, lactose
and their aqueous solutions such as molar volume and excess
 M.D.A. Saldaña et al. / J. Chem. Thermodynamics 55 (2012) 115–123
molar refractivity support the solubility data obtained. The solubil-
ity of sugars in pressurized water is important for extraction of
sugars from agricultural biomass using PW technology.
5. Conclusions
Density and refractive index properties were measured at dif-
ferent aqueous sugar concentrations. The aqueous solubility of glu-
cose and lactose were also measured using a dynamic flow
apparatus as a function of temperature and pressure. The solubility
of glucose in pressurized water was higher than that of lactose. The
area-weighted sigma profiles of glucose and lactose predicted by
the COSMO theory showed that solubility depends on the number
of methyl groups present in the sugar molecule and their interac-
tions (hydrogen bonding, and dipole–dipole forces). The solubility
of lactose or glucose in pressurized water decreased with an in-
crease in pressure due to the increase of the sugar apparent molar
volume. Density and refractive index properties showed that the
molecular structure of aqueous lactose solution is more compact
than that of glucose. In addition, lactose packing is less sensible
to pressure, resulting in small changes of its solubility in pressur-
ized water at the conditions studied.
Acknowledgments
We are grateful to Alberta Innovates-Bio Solutions and to Natu-
ral Sciences and Engineering Research Council of Canada (NSERC)
for funding this project. We are also grateful to Anton Paar Canada
for the use of the DMA HP unit for density measurements. We are
thankful for the assistance of Ms. Maria Elizabeth Campos Fuentes
with sample analysis.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jct.2012.06.016.
References
[1] R.S. Rogers, Chem. Eng. News 77 (1999) 35–41.
[2] C.S. Cummings, in: E.B. Jackson (Ed.), Manufacture of High-Boiled Sweets,
Chapman & Hall, London, England, 1995, pp. 129–168.
[3] G.B. Davis, M.A. Robinson, Curr. Opin. Drug Disc. 5 (2002) 279–288.
[4] A. Kruse, A. Gawlik, Ind. Eng. Chem. Res. 42 (2003) 267–279.
[5] Y. Yu, H. Wu, Ind. Eng. Chem. Res. 49 (2009) 10682–10690.
123
[6] C. Liu, C.E. Wyman, Ind. Eng. Chem. Res. 42 (2003) 5409–5416.
[7] S. Haghighat Khajavi, Y. Kimura, T. Oomori, R. Matsuno, S. Adachi, J. Food Eng.
68 (2005) 309–313.
[8] P. Koivistoinen, L. Hyvonen, Carbohydrate Sweetners in Food and Nutrition,
Academic Press, New York, 1980.
[9] J.B. Taylor, Trans. Faraday Soc. 53 (1957) 1198–1203.
[10] F.J. Bates, Polarimetry, Saccharimetry, and the Sugars, National Bureau of
Standards, Washington, DC, 1942.
[11] H. Stephen, T. Stephen, Solubilities of Inorganic and Organic Compounds,
MacMillan Co., New York, 1963.
[12] F.E. Young, J. Phys. Chem. 61 (1957) 616–619.
[13] L.A. Alves, J. Almeida e Silva, M. Giulietti, J. Chem. Eng. Data 52 (2007) 2166–
2170.
[14] A. Bouchard, G.W. Hofland, G.-J. Witkamp, J. Chem. Eng. Data 52 (2007) 1838–
1842.
[15] S.H. Yalkowsky, Y. He, Handbook of Aqueous Solubility Data, CRC Press, Boca
Raton, FL, 2003.
[16] J.W. Mullin, Cristallization, fourth ed., Butterworth Heinemann, Oxford, 2001.
[17] D. Zhang, F. Montanes, K. Srinivas, T. Fornari, E. Ibanez, J.W. King, Ind. Eng.
Chem. Res. 49 (2010) 6691–6698.
[18] V.H. Alvarez, S. Mattedi, M. Aznar, J. Chem. Thermodyn. 43 (2011) 895–900.
[19] F.A. Kurtz, M.A. Eliason, J. Chem. Eng. Data 24 (1979) 44–45.
[20] S.T. Lin, S.I. Sandler, Ind. Eng. Chem. Res. 41 (2002) 899–913.
[21] J.M. Prausnitz, R.N. Lichtenthaler, E. Gomez de Azevedo, Molecular
Thermodynamics of Fluid. Phase Equilibria, third ed., Prentice Hall,
Englewood Cliffs, NJ, 1999.
[22] V.H. Alvarez, M.D.A. Saldaña, Ind. Eng. Chem. Res. 50 (2011) 11396–11405.
[23] P.P. Singh, M.D.A. Saldaña, Food Res. Int. 44 (2011) 2452–2458.
[24] Z. Zhang, H. Wang, R. Yang, X. Jiang, Int. J. Food Sci. Technol. 45 (2010) 258–
264.
[25] P.N. Shah, C.L. Yaws, Chem. Eng. 83 (1976) 131–135.
[26] V.H. Alvarez, J.O. Valderrama, Alimentaria 354 (2004) 55–66.
[27] B.T. Goodman, W.V. Wilding, J.L. Oscarson, R.L. Rowley, J. Chem. Eng. Data 49
(2004) 1512–1514.
[28] A.M. Peres, E.A. Macedo, Ind. Eng. Chem. Res. 36 (1997) 2816–2820.
[29] E. Mullins, R. Oldland, Y.A. Liu, S. Wang, S.I. Sandler, C.C. Chen, M. Zwolak, K.C.
Seavey, Ind. Eng. Chem. Res. 45 (2006) 4389–4415.
[30] C.A. Cerdeiriña, E. Carballo, C.A. Tovar, L. Romani, J. Chem. Eng. Data 42 (1997)
124–127.
[31] E.J. McDonald, A.L. Turcotte, J. Res. Natl. Bur. Stand. 41 (1948) 63–68.
[32] A. Urbanczyk, W.A. Van Hook, J. Chem. Thermodyn. 28 (1996) 975–986.
[33] S.S. Zumdahl, D.J. DeCoste, in: C. Hatford (Ed.), Reactions in Aqueous Solutions,
Brooks/Cole, Belmont, CA, USA, 2009, pp. 106–203.
[34] M. Paez, I. Martonez-Castro, J. Anal. Appl. Pyrolysis. 12 (1987) 31–38.
[35] F.J. Moreno, M. Villamiel, A. Olano, J. Agric. Food Chem. 51 (2003) 1894–1896.
[36] A.J. Queimada, F.L. Mota, S.P. Pinho, E.A. Macedo, J. Phys. Chem. B 113 (2009)
3469–3476.
[37] Diadem Public 1.2, The DIPPR Information and Data Evaluation Manager, 2000.
[38] K.G. Joback, R.C. Reid, Chem. Eng. Commun. 57 (1987) 233–243.
[39] X. Cao, B.C. Hancock, N. Leyva, J. Becker, W. Yu, V. Masterson, M. Int, J. Pharm.
368 (2009) 16–23.
[40] O. Ferreira, E.A. Brignole, E.A. Macedo, Ind. Eng. Chem. Res. 42 (2003) 6212–
6222.
JCT 11-456