International Journal of Food Properties

ISSN: 1094-2912 (Print) 1532-2386 (Online) Journal homepage: https://www.tandfonline.com/loi/ljfp20

Temperature and Concentration Dependence of

Density of Model Liquid Foods

Roger Darros‐Barbosa , Murat O. Balaban & Arthur A. Teixeira

To cite this article: Roger Darros‐Barbosa , Murat O. Balaban & Arthur A. Teixeira (2003)
Temperature and Concentration Dependence of Density of Model Liquid Foods, International
Journal of Food Properties, 6:2, 195-214, DOI: 10.1081/JFP-120017815

To link to this article: https://doi.org/10.1081/JFP-120017815

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 INTERNATIONAL JOURNAL OF FOOD PROPERTIES
Vol. 6, No. 2, pp. 195–214, 2003

Temperature and Concentration Dependence of

Density of Model Liquid Foods

Roger Darros-Barbosa,1 Murat O. Balaban,2,* and Arthur A. Teixeira3

1
Food Engineering and Technology Department, Unesp-Paulista State University,
São José do Rio Preto, São Paulo, Brazil
2
Food Science and Human Nutrition Department and 3Agricultural and Biological
Engineering Department, University of Florida, Gainesville, Florida, USA

ABSTRACT

Density of binary solutions and combinations of sucrose, glucose, fructose, citric acid,
malic acid, pectin, and inorganic salts were measured with an oscillating tube density
meter in the temperature range from 10
to 60
C, at varying concentrations. Density
can be predicted with accuracy better than 5  105 g cm3 using predictive equations
obtained by fitting the experimental data. Available literature values agreed well with
experimental data. Relations for the excess molar volume of these solutions were
derived in terms of mole fraction and temperature. A thermodynamic model for the
volumetric analysis of multicomponent aqueous solutions containing electrolyte and
non-electrolyte compounds was also proposed. These models can be used for prediction
of density of liquid food systems, specially fruit juices and beverages, based on
composition and temperature, with high accuracy and without elaborate experi-
mental work.

Key Words: Density; Specific volume; Oscillating tube; Multicomponent aqueous

solutions; Predictive model; Excess functions.

*Correspondence: Murat O. Balaban, Food Science and Human Nutrition Department, University of
Florida, Gainesville, Florida 32611-0370, USA; E-mail: mob@gnv.fas.ufl.edu.

195

DOI: 10.1081=JFP-120017815 1094-2912 (Print); 1532-2386 (Online)

Copyright # 2003 by Marcel Dekker, Inc. www.dekker.com
196 Darros-Barbosa, Balaban, and Teixeira

INTRODUCTION

Knowledge of physical properties of food is fundamental in the design, optimization,

and control of food processes, and in quality control. The accurate measurement or
prediction of density is vital to the engineering and technological practice in the food
industry as well as in scientific research to assess and=or study of derived thermodynamic
properties and process mechanisms. For example, it is well known that sugars are
stabilizing agents for enzymes and proteins because their ability to enhance the structure
of water.[1] Thus, the data revealing the hydration behavior are desirable for better
understanding of the mechanism of protein stabilization.
The accurate prediction of physical properties of non-electrolyte (sugars and pectin),
weak electrolyte (organic acids), and electrolyte (inorganic salts) binary or multicom-
ponent aqueous solutions play a pivotal role to a number of engineering, processing and
quality control applications in the sugar, syrup, juice, beverage, chemical, and pharma-
ceutical industries. For instance, fundamental thermodynamic information is crucial to
select reaction conditions of industrial processes such as enzymatic conversion of biomass
to useful chemicals and to understand specific interactions in biomolecular recognition.
However, such data are scarce in the literature and restricted to a few discrete conditions of
temperature and concentration. Another practice is using predictive models, which often
do not consider molecular interactions. Water is assumed to be in equilibrium between a
structured low-density form and an unstructured, high-density form.[2] Changes and
abnormalities in the properties of aqueous solutions are attributed to changes in the
water structure caused by the added solute, and are temperature, pressure, composition and
concentration dependent.
Although density data are rather extensive, it becomes apparent that, when an attempt
is made to estimate the effect of temperature, concentration, different types of solutes, and
for complex systems other than pure or binary solutions on this property, additional
information would be desirable. This is especially important for accurate predictive
purposes regarding the complex composition of food systems. For multicomponent
solutions, the data required for a complete description of the thermodynamic property
changes due to mixing are much more than those required for single or binary solutions,
and it becomes impractical to try to accumulate such data. Thus, it is beneficial that such
complex data be predicted from data for the constituent binary and=or pure constituents.
The motivation that led us to explore this area was the need for physical properties
data on food systems under high pressure conditions. Based on density and specific heat
measurements at atmospheric pressure, as well as from sound velocity data as a function of
pressure and temperature, it is possible to determine the volumetric behavior (specific
volume=compressibility) of a liquid mixture as a function of pressure, temperature, and
composition, and hence to better understand the mechanisms involved in high pressure
processing. Therefore, this work is the initial step towards the measurement and modeling
of such properties under high pressures.
The objective of this study was to measure the density of model aqueous solutions and
to fit experimental data to predictive thermodynamic equations. The aqueous solutions
investigated were binary solutions and combinations of sucrose, glucose, fructose, citric
acid, malic acid, citrus pectin, and inorganic salts. The effects of concentration and
temperature were investigated. In addition, the excess molar volumes were predicted using
Density of Binary Solutions 197

Redlich–Kister[3] equation to evaluate the deviation from the ideal behavior and to
establish the relative volumetric effect of each compound on the structure of the aqueous
solution.[4–6]

MATERIALS AND METHODS

Density measurements were performed using an oscillating tube density meter model
DMA 58 from Anton Paar-GmbH (Graz, Austria) coupled to a cooling system. This
system measures the period of oscillation, which is dependent on the density of the sample.
A hollow U-shaped tube, with calibrated volume (approximately 0.7 cm3), containing the
sample is electro-magnetically excited to undamped oscillation. The calibration constants
of the instrument, which comprise the spring constant of the oscillator, the mass of the
empty tube, and the volume of the sample, can be calculated from two period measure-
ments when the oscillator is filled with substances of known density. In this case, the
instrument was calibrated with dry air and distilled, de-ionized water at the corresponding
temperature. The calibration procedure was repeated every three days at each temperature.
A semiconductor Peltier element and a resistance-based temperature sensor monitored and
controlled the temperature of both sample and tube. An external chiller (Paar Physica-
GmbH) was used for the low temperature experiments. All samples were thermally
equilibrated to a temperature slightly above the instrument set point, in order to avoid
formation of water vapor bubbles inside the oscillating tube. After introducing the samples
slowly (to avoid formation of invisible gas bubbles), using a plastic-tipped hypodermic
glass syringe, totally free of gas bubbles, time was allowed for thermal equilibrium,
typically 10–15 min. After each measurement, the oscillator was rinsed with water
and acetone repeatedly, calibration checked, and dried by a filtered flow of air from a
built-in pump.
The measurements were performed at temperatures of 10
, 20
, 40
, and 60
C. This
system provides an accuracy of 2  105 g cm3 and precision of 0.5  105 g cm3
on density measurements, and accuracy on temperature reading of 0.01
C, which could
be controlled within 0.005
C.
The accuracy of the density measurements was confirmed based on the measure-
ment of the density of pure water. Results for three such runs and literature values are
shown in Table 1. The average deviations between the three runs and from literature
values[6,7] are 2.7  105, and 4.0  105 g cm3 respectively. Thus, the measured
density of pure water for temperatures from 10
to 60
C are in good agreement with
the density values of Fine and Milleto[7] and Pruss and Wagner,[8] considered the most
accurate data for pure water.
Solutions were prepared with analytical grade reagents from Synth (>99% purity,
Diadema, SP) using distilled and deionized water (using a Mili-Q, from Millipore,
Bedford, MA), on a weight by volume of the solution, with 0.1 mg accuracy for
mass. Binary solutions of sucrose, glucose, fructose, citric pectin (Sigma, P-9135, lot
97H0580; galacturonic acid 80%, methoxy content 9%), citric acid, malic acid, KCl,
CaCl2, MgCl2, and KH2PO4 in water were prepared. The concentrations were in the range
from 1% to 65% (w=v) for sugar solutions, 0.1% to 10% (w=v) for acid solutions, 0.025%
to 2.5% (w=v) for pectin solutions, and 0.05% to 5% (w=v) for inorganic salt solutions
198 Darros-Barbosa, Balaban, and Teixeira

Table 1. Results for the calibration of the density meter with pure water.

Density of pure water (g cm3)

This work

T (
C) Run 1 Run 2 Run 3 Average  S.D. Ref.[7] Ref.[8]

10 0.99969 0.99970 0.99965 0.99968  2.6  105 0.99969 0.99970
20 0.99831 0.99833 0.99836 0.99833  2.5  105 0.99805 0.99821
30 0.99565 0.99572 0.99568 0.99568  3.5  105 0.99557 0.99565
40 0.99231 0.99230 0.99226 0.99229  2.6  105 0.99227 0.99222
50 0.98806 0.98805 0.98800 0.98804  3.2  105 0.98816 0.98803
60 0.98319 0.98319 0.98322 0.98320  1.7  105 0.98326 0.98320

(10% w=v in the case of potassium phosphate monobasic). Other combinations of these
compounds in aqueous solutions were tested for component interaction and predictive
analysis; simple carbohydrates only, carbohydrates and organic acids, and a combination
of simple sugars, organic acids, and inorganic salts. This study intended to investigate the
concentration range of interest for food science and engineering applications.

DATA ANALYSIS

Density data for each binary solution as a function of temperature and concentration
were fitted to the following model:

r ¼ ða1 þ b1 S þ c1 S 2 Þ þ T a2 þ b2 S þ c2 S 2 Þ þ T 2 ða3 þ b3 S þ c3 S 2 Þ ð1Þ

r ¼ Density of the solution (g cm3)

S ¼ Solute concentration (g solute 100 mL-solution1)
T ¼ Temperature (
C)
ai, bi, ci ¼ Regression coefficients (continuous surface in figures).
The excess molar volume for a binary mixture is defined as:

 
ðx1 M1 þ x2 M2 Þ x M xM
Vm E ¼  1 1þ 2 2 ð2Þ
r r1 r2

VmE ¼ Excess molar volume (cm3 mole1)

r ¼ Measured density of the solution (g cm3)
r1,2 ¼ Density of the pure component 1 or 2 (g cm3), literature data[9–12]
x1,2 ¼ Mol fraction of component 1 or 2
M1,2 ¼ Molecular weight of component 1 or 2.
Density of Binary Solutions 199

A two- or three-term Redlich–Kister[3] equation was applied to represent the

compositional dependence of the excess molar volume as follows:

X
3
V m E ¼ x 1 x2 Ai ðx1  x2 Þi1 ð3Þ
i¼1

The temperature dependence of the parameter Ai in Eq. (3) is assumed to follow the form:

Ai ¼ ai;0 þ ai;1 T þ ai;2 T 2 ð4Þ

The parameters ai,0, ai,1, and ai,2 were determined by fitting excess molar volume data
calculated with Eq. (2).
A thermodynamic approach to develop a multicomponent density model is described,
based on a mixing rule, and which requires fitting binary (water þ solute) density data of
the constituent compounds (adapted from Zemaitis et al.[13]). The density of a multi-
component solution made up of water plus one or more solutes, either in terms of moles or
mol fraction, is given by Eq. (5). The summation term of the denominator can be further
expanded for the water component and the solutes.
P P P
mass nM xM xi M i
r¼ ¼P i i¼P i i¼ P ð5Þ
V ni V i xi V i xw V w þ xi V i

V ¼ Solution volume, cm3

ni ¼ Moles of component i, mole
xi ¼ Mole fraction of component i
Mi ¼ Molecular weight of component i, g mole1
V̄i ¼ Partial molar volume of component i, cm3 mole1
V̄w ¼ Partial molar volume of water, cm3 mole1.

The definition of the partial molar volume is:

 
 qV
Vi ¼ ð6Þ
qni T ;P;nj6¼i

The mixing rule proposed here is based upon applying the following expressions for
the partial molar volumes of the solutes evaluated from the constituent’s binary partial
volumes [V 2;i , obtained from the binary solution, replaces V i in Eq. (5)], and a weighed
average partial molar volume of water evaluated from the constituent’s binary solution as
defined by Eq. (7). Equation (8) is then used to compute the density of a multicomponent
solution using binary data for each solute.
P
x V
V w ¼ P1;i 1;i ð7Þ
x1;i
200 Darros-Barbosa, Balaban, and Teixeira

V̄1,i ¼ Partial molar volume of water from constituent i’s binary system, cm3 mole1
x1,i ¼ Mole fraction of water from constituent i’s binary system.
P
xM
r¼ P Pi i P ð8Þ
xw ½ ðx1;i V1;i Þ= x1;i  þ xi V 2;i


V̄2,i ¼ Partial molar volume of solute i from constituent i’s binary system, cm3 mole1.
Partial molar volumes cannot be obtained directly from the solution volume [denomi-
nator of the density Eq. (8)], because it is not possible to identify the contributions made by
the solute and solvent in geometric (i.e. space occupancy) terms since both are concentration
dependent. Therefore, we estimate these contributions based upon the apparent molar
volumes given by Eq. (9) for a binary solution. This is defined as the difference between the
molar volume of the solution and the volume of pure solvent per mole of solute.

V ¼ n2 fðV2 Þ þ n1 V 1 0 ð9Þ

f(V2) ¼ Apparent molar volume of solute in a binary solution, cm3 mole1

V̄10 ¼ Molar volume of pure solvent (water) at the same T and P, cm3 mole1.
Combining Eq. (6), for a binary system (i ¼ 2), and Eq. (9), taking the derivative, and
solving for V 2;i yields:
 
S qfðV2 Þ
V 2;i ¼ fðV2 Þ þ 2 ð10Þ
M2 qðS2 =M2 Þ

By combining Eq. (9) with the definition of solution volume in terms of partial molar
volumes of the components, we obtain the partial molar volume of water in a binary
solution as a function of the apparent molar volume of solute and the molar volume of pure
solvent (water) at the same T and P.
 
ðS2 =M2 Þ2 qfðV2 Þ
V 1;i ¼ V 1 0  ð11Þ
½ðr=100Þ  ðS2 =M2 Þ qðS2 =M2 Þ

The apparent molar volume of the solute in the binary solution was determined from
our experimental density data as a function of concentration and temperature using the
following expression, derived from the definition of apparent molar volume [Eq. (9)],
expressed here in terms of solute concentration (g solute 100 mL-solution1).
 
M2 ðr  rÞ
fðV2 Þ ¼ 1 þ w 2 ð12Þ
rw S2 10

The procedure to compute the density of a multicomponent solution involved the

following steps:

(1) Determine apparent molar volume of each solute from density data of the
constituent’s binary at the specified concentration and temperature [Eq. 12)].
Density of Binary Solutions 201

(2) Determine partial molar volume of solute and water for the binary system at the
same concentration and temperature [Eqs. (10) and (11)].
(3) Compute density of the multicomponent solution using Eq. (8).

The first derivative of apparent molar volume that appears in Eqs. (10) and (11) were
evaluated analytically from the regressed coefficients of the corresponding fitted equations.
This treatment was chosen since the numerical procedure wouldn’t be feasible for non-
equally spaced values of the variables and relatively few data points were available.
In order to demonstrate the validity of the proposed thermodynamic treatment, it was
applied to our own binary density data. This thermodynamic model provided excellent
agreement to predict density of a binary aqueous solution containing either non-electrolyte
and electrolyte solutes, giving a maximum 0.01% for the standard error compared to our
experimental data.
In order to test the ability of the proposed thermodynamic model to predict density of
a multicomponent solution, experimental density data were obtained for several combina-
tions of simple carbohydrates (sucrose, glucose, and fructose) only, carbohydrates and
organic acids (citric and malic acids), and a combination of simple sugars, organic acids,
and inorganic salts (KCl, CaCl2, MgCl2, and KH2PO4) at varying concentrations and
temperatures. This analysis was then compared with additive schemes such as the one
proposed by Choi and Okos[14] based only upon on the weighted average density data of
pure components, hence not anticipating any interaction between solvent and solute
molecules.

RESULTS AND DISCUSSION

Density of binary aqueous solutions of sucrose, glucose, fructose, citric pectin, citric
acid, malic acid, KCl, CaCl2, MgCl2, and KH2PO4, as a function of temperature and
concentration, together with the surface model are presented in Figs. 1A, 1B, and 1C.
A total of 74 data points for sucrose solutions were obtained, 60 data points for glucose,
fructose, pectin, citric, and malic acid solutions, and 36 data points for salt solutions.
Literature values, where available, agreed well with experimental data (Tables 2A, 2B,
and 2C).
Density of all solutions studied showed a quadratic dependence to temperature and
concentration, but a weaker dependence to the latter. Coefficients of predictive equations
were determined by fitting the experimental data. Table 3 shows the parameters for the
predictive equations obtained by regression analysis by adjusting experimental data to the
mathematical model [Eq. (1)]. All binary solutions fitted well into the proposed model with
correlation coefficients greater than 0.999. Using these equations, the density can be
predicted with accuracy better than 5  105 g cm3. The standard errors of all fitted
predictive equations were in the range from 0.00013 to 0.00095, with p-values less than
0.01, and the residual analysis showed adequacy of the models. The densities presented in
this study are of acceptable accuracy for engineering-design calculations and describe well
the temperature and concentration dependence of the solutes investigated.
Figures 2A and 2B show the calculated average excess molar volume by applying
Redlich–Kister model along with the fitted surfaces. Table 4 presents the results for the
202 Darros-Barbosa, Balaban, and Teixeira

Figure 1A. Experimental density of binary aqueous solutions of sucrose, glucose, and fructose,
and surface model as a function of temperature and concentration.

parameters of Redlich–Kister equation for the excess molar volume. Malic acid, KH2PO4,
and pectin aqueous solutions were not tested for excess molar volume Redlich–Kister’
model since the density of the pure component was not available over the range of
concentration and temperature studied.
The analysis of the excess molar volume showed high positive deviation for all sugar
solutions, whereas the salt solutions had negative deviation in the concentration range
studied. A change of sign was observed for citric acid solutions, as a result of the
temperature effect. It is evident that the effect of temperature is not as strong as the effect
of concentration on the excess molar volume of sugar aqueous solutions in the ranges
studied.
Excess molar volume is a good indicator of non-ideality and for solute-solvent
interactions. Results indicated that at higher concentrations, as well as at higher
Density of Binary Solutions 203

Figure 1B. Experimental density of binary aqueous solutions of citric acid, malic acid, and pectin,
and surface model as a function of temperature and concentration.

temperatures, all compounds have greater deviation from ideal behavior. While non-
electrolyte compounds showed positive deviations, especially at higher concentrations,
electrolytes exhibited negative deviations. This can be interpreted by means of the
‘‘structure-forming’’ (sugars) or ‘‘structure-breaking’’ (salts) ability of the solute about
structural changes accompanying the dissolution in water. Although it is still not clear how
the combined effect of hydrophilic and hydrophobic groups, having antagonistic behavior,
affect this property since both are present in sugar molecules. Combining energetic (heat
capacity) and volumetric analysis (density) would make it possible to gain insight into the
properties of these solutions. A study on heat capacity of these solutions is presented in a
separate article.[25]
Concerning electrolyte compounds, generally the volumes of inorganic salts in aqueous
solutions are apparently smaller than the volumes in their respective crystals, due to the
contraction of the solvent by the electrostriction effect between ions and water dipoles,
204 Darros-Barbosa, Balaban, and Teixeira

Figure 1C. Experimental density of binary aqueous solutions of potassium chloride, and calcium
chloride, potassium phosphate monobasic and magnesium chloride, and surface model as a function
of temperature and concentration.

however the magnitude of electrostatic attraction depends on the particular salt, environ-
mental conditions, and the effective volumes of the salts in solution rather than in crystals.
One factor that would make this analysis more complete would be by making
measurements of density data of pure compounds as a function of temperature, which
in the present study were obtained by regression analysis from literature data using those
from few discrete temperatures, when available.
Regarding the proposed thermodynamic approach for the density analysis of multi-
component solution, the concentration dependence of the apparent molar volumes,
computed based upon density data of binary solutions at a given temperature, were
satisfactorily described by expressions of the form of Eq. (13) for sugar solutions and Eq.
(14) for organic acids and salt solutions (adapted from Conway et al.;[26] Rudan-Tasic and
Klofutar[27]). The linear parameter P? of Eq. (13) is often designated as infinite dilution
apparent molar volume; however, in the present study the high concentration range
 Table 2A. Comparison of predicted values with literature data for aqueous binary systems of sucrose, glucose, and fructose.

Density of binary aqueous solution (g cm3)

Density of Binary Solutions

Conditions Sucrose Glucose Fructose

T (
C) S (% w=v) This study Ref.[15] Ref.[16] This study Ref.[17] Ref.[18] This study Ref.[19]
15 1 1.00322 1.00297 1.00292 1.00308
15 10 1.03811 1.03774 1.03797 1.03848
15 50 1.19168 1.19028 1.18803 1.19176
20 1 1.00236 1.00208 1.00196 1.00220 1.00229
20 10 1.03692 1.03657 1.03704 1.03736 1.03723
20 50 1.19062 1.18627 1.18735 1.19046 1.19459
25 1 1.00126 1.00087 1.00080 1.00095 1.00098 1.00108
25 10 1.03554 1.03578 1.03591 1.03483 1.03483 1.03602
25 50 1.18926 1.18871 1.18651 1.16156 1.16542 1.18880
40 1 0.99662 0.99611 0.99608 0.99639
40 10 1.03030 1.03115 1.03137 1.03065
40 50 1.18338 1.18507 1.18304 1.18164
205
 206

Table 2B. Comparison of predicted values with literature data for aqueous binary systems of citric acid, malic acid, pectin, and potassium phosphate
monobasic.

Density of binary aqueous solution (g cm3)

Conditions Citric acid Malic acid KH2PO4

Pectin
T (
C) S (% w=v) This study Ref.[20] Ref.[21] This study Ref.[17] This study This study Ref.[19]
10 2.03 1.00893 1.00817 1.00649 1.01074 1.01432
10 6.27 1.02720 1.02511 1.00665 1.03814 1.04421
18 0.2 0.99948 1.00019 0.99936 0.99921 0.99938 0.99938 1.00014
18 1 1.00300 1.00314 1.00242 1.00252 1.00253 1.00231 1.00381
18 5 1.02012 1.01797 1.01761 1.01838 1.01814 1.00806 1.02721
18 10 1.04048 1.03667 1.03642 1.03670 1.03742 0.99436 1.06829
20 2.03 1.00703 1.00626 1.00481 1.01273 1.00851
20 6.25 1.02479 1.02257 1.00670 1.04243 1.03576
40 2.01 1.00072 0.99991 0.99885 1.00200 1.00652
40 6.21 1.01777 1.01547 1.00250 1.02874 1.03576
60 1.99 0.99118 0.99029 0.98952 0.99279 0.99724
60 6.16 1.00778 1.00559 0.99264 1.01875 1.02593
Darros-Barbosa, Balaban, and Teixeira
Table 2C. Comparison of predicted values with literature data for aqueous binary systems of potassium chloride, calcium chloride, and magnesium
chloride.

Density of binary aqueous solution (g cm3)

Conditions KCl CaCl2 MgCl2

T (
C) S (% w=v) This study Ref.[22] Ref.[23] This study Ref.[22] Ref.[24] This study Ref.[24]
10 0.74 1.00441 1.00461 1.00646 1.00732
10 2.03 1.01166 1.01171 1.017 1.01864 1.017
Density of Binary Solutions

10 3.68 1.02213 1.02326 1.03011 1.03166

10 6.31 1.04084 1.04146 1.052 1.04926 1.051
10 7.25 1.04915 1.04552 1.05608 1.05463
20 0.74 1.00284 1.00298 1.00414 1.00491
20 2.03 1.01057 1.01062 1.015 1.01577 1.015
20 3.67 1.02082 1.02122 1.02728 1.02886
20 6.30 1.03737 1.03788 1.050 1.04813 1.049
20 7.24 1.04417 1.04303 1.05363 1.05458
25 0.05 0.99745 0.99734 0.99717 0.99751 0.99763
25 0.25 0.99868 0.99861 0.99879 0.99919 0.99934
25 1 1.00331 1.00338 1.00483 1.00544 1.00568
25 5 1.02800 1.02813 1.03577 1.04040 1.03755
40 0.74 0.99703 0.99683 0.99765 0.99836
40 2.02 1.00508 1.00513 1.009 1.00873 1.009
40 3.65 1.01498 1.01460 1.02012 1.02181
40 6.26 1.02930 1.02969 1.043 1.04234 1.043
40 7.19 1.03460 1.03588 1.04648 1.04957
60 0.73 0.98768 0.98776 0.98864 0.98942
60 2.00 0.99521 0.99526 1.000 0.99995 1.000
60 3.61 1.00483 1.00533 1.01082 1.01272
60 6.20 1.01960 1.02005 1.034 1.03194 1.034
60 7.12 1.02539 1.02641 1.03652 1.03833
207
 208

Table 3. Density predictive equation parameters.

Aqueous a1 b1 [102 g c1 [102 cm3 g a2 b2 [102 g
C1 c2 [102 cm3 g
C1 a3 b3 [102 g
C2 c3 [102 cm3 g
C2
3 1 2 3
1 1 2 3
2
solution [g cm ] g-solute ] g-solute ] [g cm C ] g-solute ] g-solute ] [g cm C ] g-solute1] g-solute2] r2
Sucrose 1.00042 0.004056 4.058e6 2.294e6 1.332e5 2.661e7 4.646e6 1.254e7 3.043e9 0.9999
Glucose 1.00066 0.003928 3.167e6 4.926e5 4.881e7 1.865e8 4.097e6 2.629e8 1.422e10 0.9999
Fructose 1.00036 0.004050 3.751e6 1.433e5 6.598e6 1.352e7 4.503e6 1.657e8 1.428e9 0.9999
Citric acid 1.00038 0.004858 5.210e5 2.001e5 2.793e5 1.849e6 4.379e6 1.926e7 1.275e8 0.9995
Malic acid 1.00047 0.004384 2.716e5 4.141e5 1.168e5 7.486e7 4.149e6 1.442e8 2.128e8 0.9996
Pectin 1.00070 0.004480 0.00060 4.529e5 1.683e5 9.324e6 4.121e6 1.447e7 9.922e8 0.9997
KCl 1.00199 0.003826 0.000464 0.00011 0.000135 2.616e5 3.361e6 1.642e6 3.031e7 0.9990
CaCl2 1.00163 0.008977 0.00017 0.00011 4.627e5 5.879e6 3.381e6 4.883e7 6.723e8 0.9994
KH2PO4 1.00263 0.004211 0.000273 0.00013 5.395e6 6.891e7 3.147e6 1.079e7 6.952e9 0.9993
MgCl2 1.00164 0.010501 0.00047 8.444e5 0.00011 2.123e5 3.719e6 1.313e6 2.577e7 0.9998
Darros-Barbosa, Balaban, and Teixeira
Density of Binary Solutions 209

Figure 2A. Excess molar volume and Redlich–Kister surface model as a function of solute molar
fraction and temperature for solutions of sucrose, glucose, and fructose.

investigated does not allow such extrapolation; hence, it does not have any physicoche-
mical meaning.

X
n
fðV2 Þ ¼ P1 þ Pi xi ðiþ1Þ=2 ð13Þ
i¼0
     
xi xi
fðV2 Þ ¼ P1 þ P1 1  exp  þ P2 1  exp  ð14Þ
Q1 Q2

P?, P1, P2, Pi, Q1, and Q2 ¼ Regression coefficients obtained by fitting data.
Figure 3 shows the results obtained by applying the proposed thermodynamic model
to predict density of multicomponent solutions, Choi and Okos model, along with our
experimental data on selected solutions investigated in this study. The aqueous solutions
presented were combinations of simple sugars (water, 10%-sucrose, 10%-glucose, and
210 Darros-Barbosa, Balaban, and Teixeira

Figure 2B. Excess molar volume and Redlich–Kister surface model as a function of solute mole
fraction and temperature for solutions of citric acid, potassium chloride, calcium chloride, and
magnesium chloride.

10%-fructose, designated as A), simple sugars and organic acids (water, 10%-sucrose,
5%-glucose, and 2%-fructose, 1%-citric and 1%-malic acids, designated as B), and simple
sugars, organic acids, and inorganic salts (water, 5%-sucrose, 5%-glucose, and
2%-fructose, 1%-citric and 1%-malic acids, 0.5%-KCl, 0.5%-CaCl2, 0.5%-MgCl2, and
0.5%-KH2PO4, designated as C).
It can be observed that there are some improvements in the agreement of predicted
values with experimental data especially for more complex mixtures (cases B and C). On
the other hand, the volumetric behavior of solutions of simple carbohydrates does not seem
to gain significant improvement by applying the proposed model. Hence, it can be argued
that the simplicity of previous models surpasses the lack of stronger assumptions in most
applications. Rahman[5] extended Choi and Okos’ model to accommodate the effects of
porosity and interaction of phases for solid porous materials.
 Density of Binary Solutions

Table 4. Excess molar volume parameters of the Redlich–Kister equation.

Aqueous a1,0 a1,1 [cm3 a1,2 [cm3 a2,0 a2,1 [cm3 a2,2 [cm3 a3,0 a3,1 [cm3 a3,2 [cm3
3 1 1
1 1
2 3 1 1
1 1
2 3 1 1
1
solution [cm mol ] mol C ] mol C ] [cm mol ] mol C ] mol C ] [cm mol ] mol C ] mol1
C2] r2
Sucrose 45.5474 7.87670 0.12977 326.053 21.3752 0.35437 265.122 14.6490 0.24584 0.9995
Glucose 32.2295 1.39976 0.02255 6.87986 4.88596 0.07763 31.8158 4.47412 0.07213 0.9998
Fructose 47.5300 1.39878 0.02301 2.75797 4.82726 0.07818 30.1377 4.39532 0.07248 0.9999
Citric acid 162,037 17985.9 293.786 331,115 36847.6 602.280 169,169 18875.0 308.726 0.8862
KCl 691,045 189568 3811.77 1,407,710 385571 7751.22 716,890 196044 3940.22 0.9236
CaCl2 2,000,480 426717 8319.23 4,054,780 864679 16856.1 2,054,570 438015 8537.91 0.9283
MgCl2 231,2800 564570 11806.9 4,681,450 1142100 23880.2 2,368,930 577548 12074.3 0.9261
211
212 Darros-Barbosa, Balaban, and Teixeira

Figure 3. Multicomponent density models—comparison of experimental data, proposed model

and Choi and Okos model.

CONCLUSIONS

Accurate density–concentration–temperature data of binary aqueous solutions of

sucrose, glucose, fructose, citric and malic acid, pectin, and some inorganic salts were
experimentally obtained. A reliable second order equation based on temperature, and
concentration was proposed for each solution for prediction purposes of density with an
accuracy of 5  105 g cm3. The thermodynamic treatment for the analysis of multi-
component aqueous solutions containing electrolyte and non-electrolyte compounds
revealed the intricacy and complexity involved in this task. There is no simple or
straight-forward model to accommodate such complex mixtures. Highly hydrophilic
behavior of carbohydrates increases hydrogen bonds with water molecules and helps
the structure. Strong ionic dissociation of certain inorganic salts promotes breaking of the
structure due to the electrostriction effect. Hydrophobic groups and weak electrolyte
compounds have intermediate effects. The approach presented here can be successfully
applied for multicomponent solutions since large amounts of density data for a number of
binary systems are available as those investigated in this work. An increasingly complex as
well as interesting issue is to look at the combined effects of pressure in addition to those
of temperature and concentration=composition.

ACKNOWLEDGMENTS

The authors gratefully acknowledge Dr. Antonio J. A. Meirelles for allowing us to use
the Anton-Paar DMA58 densitometer in his laboratory at the Department of Food
Density of Binary Solutions 213

Engineering, State University of Campinas, SP, Brazil, and to FAPESP (The State of São
Paulo Research Foundation—97=7546-4) for financial support.

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Received March 25, 2002

Accepted July 22, 2002