Fluid Phase Equilibria 380 (2014) 9399

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Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid

Liquidliquid equilibria for multicomponent mixtures of

2,2-dimethyl-1,3-dioxolane with n-heptane, toluene, ethanol and
water
Alexandra Kilina, George Kuranov , Igor Pukinsky, Natalia Smirnova
Department of Chemistry, Saint Petersburg State University, Universitetsky pr., 26, 198504 St. Petersburg, Russian Federation

a r t i c l e

i n f o

Article history:
Received 14 March 2014
Received in revised form 30 July 2014
Accepted 4 August 2014
Available online 11 August 2014
Keywords:
Liquidliquid equilibria
2,2-Dimethyl-1,3-dioxolane
Multicomponent mixtures
NRTL
UNIFAC

a b s t r a c t
Liquidliquid equilibria (LLE) data are presented for two quaternary systems: 2,2-dimethyl-1,3dioxolane (DMD) + n-heptane (or toluene) + ethanol + water, and for three ternary subsystems:
DMD + ethanol + water and DMD + n-heptane (or toluene) + water. The measurements were performed at
293.15 K and atmospheric pressure. The phase diagrams show extended heterogeneous areas for ternary
systems containing n-heptane (or toluene) and water, the region going from waterhydrocarbon side
of the concentration triangle to waterDMD side. A much smaller region of immiscibility with the critical point is observed for ternary mixtures of DMD with water and ethanol. The experimental LLE data
were correlated and partly predicted applying the NRTL model. The UNIFAC interaction parameters for
CH2 O groups of dioxolane alkyl-derivatives were estimated. The model was applied to predict the LLE
diagrams for ternary DMD + n-heptane (+toluene) + water solutions and for the quaternary systems containing ethanol. Both NRTL and UNIFAC models with re-estimated parameters have provided satisfactory
results.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Systems containing polyol derivatives attract special attention
during the last years, and this is mainly due to their growing industrial applications and to good possibilities for their synthesis using
natural raw materials. Cyclic acetals and ketals (in particular, 1,3dioxolane and its derivatives) obtained by chemical modication
of ethylene glycol and glycerol are among substances of interest.
They serve as reagents or solvents in organic synthesis, are used
in production of various materials. Some cyclic acetals and ketals
are considered as perspective additives to gasoline, biofuels and
diesel fuels capable of improving the octane number, phase stability
and (or) ecological characteristics [1,2]. Alkyl-derivatives of 1,3dioxolane-4-methanol have appeared to be effective, inexpensive
and nontoxic icing inhibitors [3,4]. Practical tasks and the research
interest to specic features of the behavior of solutions containing
cyclic polyethers stimulate the studies of thermodynamic properties of such systems, and a special attention is paid to their phase
behavior.

Corresponding author. Tel.: +7 9119201277.

E-mail address: g kuranov@mail.ru (G. Kuranov).
http://dx.doi.org/10.1016/j.uid.2014.08.002
0378-3812/ 2014 Elsevier B.V. All rights reserved.

The present work is aimed at the study of the mutual solubility

of the components in two quaternary systems: DMD + ethanol + nheptane + water, DMD + ethanol + toluene + water and in the constituent binary and ternary solutions containing DMD. The study
includes both experimental measurements at 293.15 K and thermodynamic modeling of LLE for binary and multicomponent
systems by NRTL and UNIFAC models. The data obtained and the
results of model estimations can be helpful in the studies of systems
containing dioxolane derivatives.

2. On the current state of the phase equilibria studies for

liquid mixtures containing 1,3-dioxolane or its derivatives
Many experimental studies of the phase behavior and thermodynamic excess functions relate to binary mixtures of 1,3-dioxolane
or its alkyl-derivatives (2-alkyl-, 4-alkyl-, 2,2-dimethyl-1,3dioxolane) with water, alkanes, chloroalkanes, alkanols. Mixtures
of another cyclic ether 1,4-dioxane or its derivatives with various
components also attract attention. Molecules of both 1,3-dioxolane
and 1,4-dioxane have quadrupole moments but in the case of dioxolane the dipole moment is quite pronounced, and this results in
a signicant difference in thermodynamic properties of systems
containing the mentioned cyclic ethers.

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A. Kilina et al. / Fluid Phase Equilibria 380 (2014) 9399

All studied mixtures of 1,3-dioxolane with hydrocarbons [59]

show positive deviations from ideality. The data demonstrate the
effect of destruction of dipole-dipole interactions in 1,3-dioxolane
on hydrocarbon addition. Such a conclusion is supported by the
data on the enthalpy of 1,3-dioxolane and hydrocarbons mixing
[6,1013].
Binary mixtures of 1,3-dioxolane with chloroalkanes demonstrate negative (1,3-dioxolane + chloroform) or small positive
(dioxolane mixtures with isomers of chlorobutane and chloropentane) deviations from ideality [5,1416]. The character of
deviations depends on the balance of two processes: the destruction of dipoledipole interactions between dioxolane molecules
and formation of donoracceptor interactions between dissimilar
molecules.
In a number of works [5,7,9,1720] VLE was studied for
1,3-dioxolane + alkanol mixtures. In these solutions one observes
strong interactions of several types: self-association of alcohol
molecules due to hydrogen bonding, dipoledipole interactions
between 1,3-dioxolane molecules and formation of hydrogen
bonds between alcohol and dioxolane species. In systems with
light alcohols their self-association is preferred, substantial positive deviations from the ideality are observed. With the growth of
the alcohol alkyl group the formation of hydrogen bonds between
dissimilar molecules becomes more pronounced, deviations from
the ideality become lower.
Large positive deviations from ideality are observed for
1,3-dioxolane + water solutions [5,19,21,22]. The curve of the concentration dependence of the vapor pressure shows that liquid
solutions at 318.15 K are close to phase splitting. Obviously, in
1,3-dioxolane + water solutions the formation of hydrogen bonds
between dissimilar molecules cannot compensate the breaking of
hydrogen bonds between water molecules.
Multicomponent systems containing 1,3-dioxolane have been
studied much less than the binaries. The VLE data are
available for three-component mixtures of 1,3-dioxolane with
methanol + water [19], 2-propanol + 2,2,4-trimethylpentane [9],
1-butanol/2-butanol + n-hexane/cyclohexane [8,23]. In all these
systems positive deviations from ideality and azeotropy are
observed.
Aqueous solutions of alkyl-substituted dioxolanes are paid special attention. Incorporation of alkyl radicals in 1,3-dioxolane
molecules results in increased positive deviations from ideality for aqueous solutions and in the appearance of a solubility
gap. The extension of the gap at a xed temperature distinctly depends on the nature of the substituent and on its
position in dioxolane molecules. According to the data presented in [24,25] the extension of heterogeneous regions in
aqueous solutions of alkyl-substituted dioxolanes grows in the
sequence 2-methyl-1,3-dioxolane < 4-methyl-1,3-dioxolane < 2,2dimethyl-1,3-dioxolane < 2-ethyl-1,3-dioxolane.
Incorporation of hydroxyl groups in molecules of 1,3-dioxolane
derivatives changes signicantly the phase behavior of the
aqueous solutions and favors a good mutual miscibility. The
phase behavior of binary and multicomponent mixtures of
2,2-dimethyl-1,3-dioxolane-4-methanol (DMDM) with n-heptane,
ethanol and water was studied in [26]. Experiments have
shown the complete mutual miscibility of the components in
DMDM + water and DMDM + ethanol mixtures in the temperature
range 243.15313.15 K, whereas for DMDM + n-heptane mixtures
a miscibility gap was observed.
Phase equilibria modeling was performed mainly for VLE in
binary mixtures of dioxolane, some ternary mixtures being also
tried. The experimental VLE data for the binaries containing 1,3dioxolane were correlated by the Wilson, NRTL, and UNIQUAC
models [9,18,20]. For all examined mixtures the results of the correlations were satisfactory, the deviations obtained were similar

for three models tried. With the interaction parameters estimated for the binary subsystems the VLE diagram for the ternary
system 1,3-dioxolane + 2-propanol + 2,2,4-trimethylpentane was
predicted. The group contribution UNIFAC and ASOG models were
used to predict the VLE in binary mixtures of 1,3-dioxolane
and 1,4-dioxane with alcohols [18,20], and in ternary systems 1,3-dioxolane + 1-butanol + cyclohexane/n-hexane [8]. The
both models gave satisfactory results for the systems containing 1,4-dioxane, while for the mixtures containing 1,3-dioxolane
(especially for the ternaries) the UNIFAC predictions were better
than the predictions using the ASOG model. The SAFT-VR approach
has been used to predict the phase equilibria for binary mixtures
of 1,3-dioxolane and 1,4-dioxane with chlorobutane isomers [15].
A good overall agreement was obtained, but the approach failed to
predict the azeotropic behavior exhibited by some of the mixtures.
With one additional adjustable parameter introduced an adequate
description of the experimental data was achieved.
There are few studies devoted to phase equilbria modeling for
mixtures containing substituted dioxolanes. The VLE data correlation using the NRTL model was performed for binary mixtures of
4-methyl-1,3-dioxolane with methanol, propylene glycol and acetone [27]. The ability to correlate VLLE data for binary mixtures
of water with 2-methyl-1,3-dioxolane or with 2,4-dimethyl-1,3dioxolane applying the UNIQUAC model was studied in [25]. The
calculations using the UNIFAC model were performed to describe
the mutual solubility of the components in binary and multicomponent mixtures of 2,2-dimethyl-1,3-dioxolane-4-methanol
with n-heptane, ethanol and water [26]. Nevertheless, further studies are needed to optimize the phase behavior modeling for these
complex mixtures which are of applied interest (in particular, in
the search of effective additives for biofuels, as it was mentioned
above).
3. Experimental
3.1. Chemicals
Information on the source, purity, and density of the chemicals
used is presented in Table 1. Densities were measured with DM
45 Mettler Toledo vibrating-tube densimeter automatically thermostated within 0.01 K. The water content in ethanol and in DMD
was controlled by the Karl Fisher (KF) titration method (Mettler
Toledo, V20). The purity of organic solvents was estimated by the
gas chromatography (GC) method.
To get pure ethanol its aqueous ethanol recticate was subjected
to the azeotropic rectication with added benzene. Distilled water
was used in the experiments.
The densities of n-heptane, toluene, ethanol and water corresponded to the standard literature values. Characteristics of DMD
were those provided by the producers.
3.2. Procedures applied in the LLE studies
The rst step of the experimental study was to nd out in
which of the binary mixtures of DMD with n-heptane, toluene,
water and ethanol miscibility gaps exist. Visual observations
were performed in the temperature range 243.13313.15 K with
the concentration step 15 mol% and the temperature step 10
degrees for each of the compositions. The tests have shown
that the limited miscibility is observed only for DMD mixtures with water, whereas DMD + ethanol, DMD + n-heptane and
DMD + toluene binaries demonstrate the complete mutual miscibility of the components. Analogous tests were performed for
ternary systems formed by three homogeneous binary subsystems
(DMD + ethanol + n-heptane, DMD + ethanol + toluene), and the aim

A. Kilina et al. / Fluid Phase Equilibria 380 (2014) 9399

95

Table 1
Properties of the pure compounds.a
Compound

Source

Purity (mass fraction)

Purication method

Analysis method

Density (kg m3 ) (298.15 K101.3 kPa)

DMD
n-Heptane
Toluene
Ethanol
Water

Fluka
Vekton
Vekton
Vekton

>0.990
>0.998
>0.998
>0.998
>0.999

None
None
None
Azeotropic rectication
Distillation

GLC, KF
GLC
GLC
GLC, KF

Exp
944.2
683.8
866.9
789.5
998.2

Standard uncertainties (u) of the measured densities () are u() = 0.1 kg m3 .

in this case was to conrm that inside the concentration triangle

there are no closed ranges of immiscibility. For each of the ternary
systems the tests were performed for three secants of the triangle,
each of them answering the constant mass ratio of two components. No closed ranges of immiscibility were observed for the both
investigated ternary systems.
The experimental LLE studies at T = const were performed for
binary and multicomponent systems containing DMD. The study
of the systems containing both DMD and water meets difculties due to chemical interactions between the components (the
products of the reaction of hydrolysis are ethyleneglycol and acetone). The effect of the hydrolysis on the phase behavior grows
with temperature and water content, and at elevated temperatures
it becomes quite signicant. Our preliminary measurements have
shown that the effect of the hydrolysis on the composition of the
coexisting phases produced during the experiments at 293.15 K can
be neglected (at least, during the time of the studies) though it is
not so at signicantly higher temperatures. Temperature 293.15 K
was chosen for our studies of the phase behavior of the mixtures.
In the experimental LLE studies we have applied two methods. In
all cases the samples were placed into the 10 mL thermostated glass
vessel with a jacket, the temperature in the vessel being maintained
constant within 0.05 K. Mixtures under study were prepared by
weight. Compositions of the mixtures were determined with the
accuracy 0.1 mass%. A magnetic stirrer was used to stir intensively
mixtures in the vessel for attaining their equilibrium state.
The isothermal titration method was applied to determine the
LLE phase boundaries (the run of the binodal curve in the concentration triangle) for all ternary systems with miscibility gaps. In
the experiments a known amount of some liquid mixture is thermostated in the glass vessel, and the titrant is added drop by drop
under stirring until a change of the phase state is observed. Depending on the run of the binodal curve different components were used
as titrants for various parts of the curve. The resulting material balance of the substances gives the point on the binodal curve. The
accuracy of the phase boundaries determination was 0.30.5 mol%.
Errors in the mole composition may be rather high if water is used
as a titrant and its content in the saturated solutions is very low (due
to small molecular weight of water and relatively large weight of
drops). In such cases the compositions of the saturated solutions
were determined by the GC method.
Other measurements performed relate to determining the
compositions of the coexisting equilibrium liquid phases in multicomponent heterogeneous mixtures. The mixtures prepared by
weight were thermostated in the glass cell and vigorously agitated
by a magnetic stirrer for at least 1 h (it was checked in the preliminary experiments that after 15 min of intensive stirring the phase
compositions became constant). Then the sample was left quiet
during not less than 2 h to get the complete separation of the liquid
layers. After that the samples of the both phases were taken using
a syringe to analyze them.
Both in the ternaries and in the quaternary systems the analysis
of the equilibrium liquid phases was performed using a gas chromatograph (CHROMOS-GH 1000, CHROMOS limited) equipped
with a heat conductivity detector and Valco PLOT Hayesep Q

Fig. 1. The LLE phase diagram for DMD + ethanol + water system at T = 293.15 K: the
experimental binodal curve and tie-lines, and the results of modeling using the NRTL
and UNIFAC (points).

capillary column (30 m, 0.53 mm, 0.20 m). The chromatographic

calibration was based on the internal standard method, and
propanol-2 was selected as the internal standard. The oven and
detector temperatures were 443 K, the injector temperature was
493 K. The carrier gas was helium with the rate 5.0 mL min1
throughout the column. Each sample was analyzed at least three
times, and the deviations from the average value were lower than
0.5 mass%.
The results of the experimental measurements obtained by two
different methods are in a good agreement between themselves.
The experimental LLE studies were performed at temperature
293.15 K for binary and multicomponent systems containing DMD.
The information on the LLE in binary and ternary mixtures without
DMD (hydrocarbon + water, hydrocarbon + water + ethanol) was
taken from literature [28].
4. Results of the LLE measurements
The LLE data are presented below for the ternary and quaternary systems at 293.15 K. The results obtained are summarized in
Tables 24 and in Figs. 13.
4.1. DMD + ethanol + water mixtures
In two binary constituents of the ternary system (DMD + ethanol
and water + ethanol) the complete mutual miscibility of the components is observed; in the system DMD + water the components
are partly miscible, and in some concentration range two liquid
phases coexist (which become identical in the critical point). The
heterogeneous area for the ternary system is rather small (Fig. 1).
The results presented in Table 2 and Fig. 1 show that all the data
obtained are in a good agreement between themselves, and it is
worth marking that different components were used as titrants to

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A. Kilina et al. / Fluid Phase Equilibria 380 (2014) 9399

Table 2
Experimental equilibrium mole fractions xi in the saturated solutions for ternary systems; T = 293.15 K, p = 101.3 kPa (Binodal curve data).a
DMD + ethanol + water

DMD + n-heptane + water

DMD + toluene + water

xD

xE

xW

xD

xH

xW

xD

xT

xW

Organic phase
0.802
0.681
0.579
0.523
0.316

0.000
0.043
0.063
0.075
0.087

0.198
0.276
0.358
0.402
0.597

0.243*
0.478*
0.599*
0.676*
0.767*
0.786*
0.804
0.797
0.818
0.816
0.811
0.802

0.738*
0.494*
0.362*
0.273*
0.161*
0.130*
0.089
0.086
0.077
0.043
0.021
0.000

0.019*
0.028*
0.039*
0.051*
0.072*
0.084*
0.107
0.117
0.105
0.141
0.168
0.198

0.100*
0.297*
0.456*
0.562*
0.788*
0.809*
0.822*
0.802

0.892*
0.685*
0.516*
0.391*
0.096*
0.050*
0.022*
0.000

0.008*
0.018*
0.028*
0.047*
0.116*
0.141*
0.156*
0.198

Aqueous phase
0.232
0.156
0.136
0.111
0.098
0.085
0.066
0.049

0.079
0.065
0.063
0.058
0.051
0.041
0.026
0.000

0.689
0.779
0.801
0.831
0.851
0.874
0.908
0.951

0.001
0.019
0.030
0.030
0.044
0.049

0.004
0.003
0.002
0.001
0.004
0.000

0.986
0.978
0.968
0.969
0.955
0.951

0.014
0.022
0.029
0.041
0.044
0.049

0.002
0.002
0.005
0.003
0.002
0.000

0.984
0.976
0.966
0.956
0.954
0.951

Standard uncertainties (u) are u(T) = 0.1 K, u(x) = 0.001. The data were obtained by the titration method (unmarked gures) or using GC (. . .*).

determine various parts of the binodal curve. Fig. 1 and Table 3

where the compositions of the coexisting liquid phases are given
show that the distribution of ethanol between the aqueous and
organic (DMD) phases is in favor of the aqueous one.
4.2. DMD + n-heptane + water mixtures
The system is formed by homogeneous binary mixtures of DMD
with n-heptane and by two binary systems with miscibility gaps:
DMD + water and n-heptane + water. The mutual solubility of water
and heptane is very small: about 0.001 mol% of water in n-heptane
and 105 mol% of n-heptane in water [29]. The ternary system
has the wide heterogeneous region between two branches of the

binodal, each of the branches going from the water + n-heptane side
of the concentration triangle to the DMD + water side. The homogeneous area near the apex of pure water is very narrow. Near
the apex of pure n-heptane such area is quite narrow too. But this
(organic) homogeneous range is getting wider on DMD addition
and it extends along the whole n-heptane + DMD side. The LLE tielines going from some point on the organic binodal brunch to some
point on the other brunch are directed approximately to the apex
of pure water.
The LLE phase boundary was determined by titration for the
water enriched area and by the GC at low water contents (Table 2).
The compositions of equilibrium liquid phases determined by the
GC are presented in Fig. 2 and Table 3. Unfortunately, in the GC

Table 3
Experimental equilibrium mole fractions xi in the coexisting liquid phases for the ternary systems; T = 293.15 K, p = 101.3 kPa (tie-lines).a
Organic phase
DMD + ethanol + water
xD
0.802
0.775
0.732
0.718
0.652
0.544
0.444
0.416
DMD + n-heptane + water
xD
0.150
0.406
0.495
0.622
0.736
0.802
DMD + toluene + water
xD
0.100
0.297
0.456
0.562
0.788
0.802
a

Aqueous phase
xE
0.000
0.014
0.027
0.033
0.049
0.069
0.080
0.084

xW
0.198
0.211
0.241
0.249
0.299
0.387
0.476
0.500

xD
0.049
0.055
0.063
0.066
0.073
0.091
0.120
0.140

xE
0.000
0.009
0.017
0.021
0.032
0.045
0.058
0.063

xW
0.951
0.936
0.920
0.913
0.895
0.864
0.822
0.797

xH
0.844
0.574
0.475
0.338
0.197
0.000

xW
0.006
0.020
0.030
0.040
0.067
0.198

xD
0.011
0.025
0.034
0.037
0.043
0.049

xH
0.001
0.001
0.001
0.002
0.002
0.000

xW
0.988
0.974
0.965
0.961
0.955
0.951

xT
0.892
0.685
0.516
0.391
0.096
0.000

xW
0.008
0.018
0.028
0.047
0.116
0.198

xD
0.002
0.008
0.013
0.019
0.037
0.049

xT
<0.001
<0.001
<0.001
<0.001
<0.001
0.000

xW
0.998
0.992
0.987
0.981
0.963
0.951

Standard uncertainties (u) are u(T) = 0.1 K, u(x) = 0.001.

A. Kilina et al. / Fluid Phase Equilibria 380 (2014) 9399

97

Table 4
Experimental mole fractions xi in the coexisting liquid phases (tie-lines) for the quaternary systems; T = 293.15 K, p = 101.3 kPa.a
Organic phase
DMD + ethanol + n-heptane + water
xE
xD
0.284
0.063
0.197
0.033
0.131
0.307
0.192
0.047
0.081
0.358
0.050
0.354
0.173
0.076
DMD + ethanol + toluene + water
xE
xD
0.253
0.166
0.120
0.101
0.227
0.212
0.087
0.089
0.084
0.513
0.026
0.156
0.233
0.099
a

Aqueous phase
xH
0.635
0.761
0.516
0.750
0.529
0.574
0.736

xW
0.018
0.009
0.046
0.011
0.032
0.022
0.015

xD
0.072
0.025
0.162
0.044
0.085
0.044
0.078

xE
0.207
0.128
0.345
0.210
0.192
0.120
0.346

xH
0.001
<0.001
0.023
<0.001
0.001
<0.001
0.007

xW
0.720
0.847
0.470
0.746
0.722
0.836
0.569

xT
0.476
0.748
0.428
0.801
0.301
0.806
0.626

xW
0.105
0.031
0.133
0.023
0.102
0.012
0.042

xD
0.032
0.016
0.050
0.007
0.033
0.006
0.014

xE
0.184
0.224
0.261
0.184
0.079
0.070
0.130

xT
0.003
0.005
0.018
0.002
0.006
<0.001
<0.001

xW
0.781
0.755
0.671
0.807
0.882
0.924
0.856

Standard uncertainties (u) are u(T) = 0.1 K, u(x) = 0.001.

into account). All the results presented for the system are in a good
agreement between themselves.
4.3. DMD + toluene + water mixtures

Fig. 2. The LLE phase diagram for DMD + n-heptane + water system at T = 293.15 K:
the experimental binodal curve and tie-lines, and the results of modeling using the
NRTL and UNIFAC (points).

measurements the peak of n-heptane on chromatograms for some

saturated aqueous solutions with very low n-heptane concentration was indistinct. In this case the n-heptane content is marked
in Table 3 as <0.001 (the uncertainty of the analysis being taken

The system DMD + toluene + water is similar to the system

containing n-heptane. It is also formed by one homogeneous
binary system (DMD + toluene) and by two binaries with miscibility gaps (DMD + water and toluene + water). The mutual solubility
of toluene and water is higher than that of n-heptane and water,
but still it remains very low: about 0.002 mol% of water in toluene
and 104 mol% of toluene in water [29]. The both ternary systems (with n-heptane or with toluene) have the same type of the
phase diagram and each of them demonstrates the extended area
of immiscibility between two branches of the binodal, the latter
having no critical point.
The data obtained are presented in Tables 2 and 3 and Fig. 3.
In the GC measurements performed the peak of toluene on the
chromatograms for some saturated aqueous solutions (where the
toluene concentration is very low) was indistinct. Taking into
account the uncertainty of the analysis in this case we present in
Table 3 the toluene content as <0.001.
4.4. Quaternary systems
The LLE data are presented for DMD + ethanol + nheptane + water and DMD + ethanol + toluene + water quaternary
systems at 293.15 K. In the both systems three of four
ternaries (DMD + ethanol + water, DMD + hydrocarbon + water,
ethanol + hydrocarbon + water) have miscibility gaps (Fig. 4). The
compositions of the coexisting equilibrium liquid phases were
determined using the GC analysis. For each quaternary system the
measurements were performed at seven gross concentrations. The
results obtained are presented in Table 4.
5. LLE modeling

Fig. 3. The LLE phase diagram for DMD + toluene + water system at T = 293.15 K: the
experimental binodal curve and tie-lines, and the results of modeling using the NRTL
and UNIFAC (points).

Phase behavior modeling for the ternary and quaternary systems under study was carried out applying the NRTL and UNIFAC
models. NRTL model [30], despite its simplicity, can be quite useful
for the correlation of LLE data in binary systems and for making predictions of the phase behavior of multicomponent mixtures basing
on the data for the binary constituents. The predictive abilities of
the UNIFAC group contribution model [31] are much wider. The
bank of the UNIFAC parameters (the geometrical parameters of

98

A. Kilina et al. / Fluid Phase Equilibria 380 (2014) 9399

Table 5
NRTL model interaction parameters.

DMD
n-Heptane
Toluene
Ethanol
Water

DMD

n-Heptane

Toluene

Ethanol

Water

0
161.3
271.2
338.2
778.7

671.4
0

3610

384.6

2672

1534.

0
522.3

325.1
1098
1781
36.62
0

Table 6
UNIFAC group assignment in this study.
Substance

Main
group

Subgroups and
their numbers

DMD

CH2
DCH2 O
CH2
OH
CH2
ACH
ACCH3
H2 O

2 CH3 1 C
2 DCH2 O
1 CH3 1 CH2
1 OH
2 CH3 5 CH2
5 ACH
1 ACCH3
1 H2 O

Ethanol
n-Heptane
Toluene
Water

5.2. Modeling using UNIFAC

Fig. 4. The quaternary system DMD + n-heptane (or toluene) + water + ethanol and
LLE diagrams for its ternary constituents.

various chemical groups and the energy parameters of interaction between the groups) is rather extensive, the estimations of
the parameters are based mainly on the VLE data; for many groups
special parameters for LLE modeling are presented [32].

Table 6 shows how molecules of the substances studied in the

present work were divided into the main structural groups and subgroups, the latters having the same interaction energy parameters
and differing between themselves only by the geometric characteristics. For example, DMD molecule includes two ether groups
CH2 O, two methyl groups and C group:

5.1. Modeling using NRTL

According to the NRTL model each binary system is characterized by three parameters. For mixtures of components 1 and 2 the
non-randomness parameter and interaction parameters A12 and
A21 are introduced. To correlate experimental data for ternary system one needs to optimize nine parameters, but in case of limited
number of experimental tie lines this is impossible. Usually parameters are evaluated using the experimental data for binary systems.
With the known parameters for the binaries one can try to predict
the phase diagrams of multi-component systems.
To estimate parameters for DMD + water binary system we
used the experimental LLE data obtained in the present work. For
water + toluene and water + n-heptane solutions the literature data
on the mutual solubility of components in the binaries were used
[29]. For water + ethanol mixtures the estimations were based on
the experimental vaporliquid equilibrium data (T = 293.15 K) from
literature [33]. We used this pair of binary parameters from VLE
data to decrease the number of parameters estimated from ternary
data, even though it is known that local composition models (like
NRTL, UNIFAC) can not describe properly VLE and LLE behavior with
the single set of parameters.
In the binary systems DMD + ethanol, DMD + n-heptane,
DMD + toluene there are no miscibility gaps, and no VLE data
are available for them. Therefore, the binary parameters for
these systems were evaluated using the experimental tie
lines for the ternary systems DMD + ethanol + water, DMD + nheptane + water and DMD + toluene + water. For water + n-heptane
and water + toluene mixtures the value was chosen equal to
0.155 and 0.14 respectively. For all other binaries we used the
value 0.3 recommended by the authors of the NRTL model [30]
(Table 5).
The results of the LLE modeling for ternary systems are presented in Figs. 13.

The geometrical and energy parameters for most of the groups

under considerations were taken from literature [32]. But the published parameters for ether groups relate only to linear or cyclic
mono-ethers. As the rst step we tried the published values of
geometric and interaction energy parameters for ether groups
(FCH2 O) in cyclic monoether (tetrahydrofuran) [32]. However,
using the values from the published LLE set of parameters we
failed to predict immiscibility in the DMD + water system. The failure is obviously due to ignoring the intramolecular interactions
of two conjugate oxygen atoms in 1,3-dioxolane molecule and in
its alkyl derivatives. We have estimated the interaction parameters between the ether group DCH2 O in cyclic diether and other
groups using the experimental data obtained in our study. The
interaction energy parameters DCH2 O-CH2 and DCH2 O-H2 O were
evaluated basing on the experimental LLE data for DMD + water
system. The set of the interaction parameters was determined by
minimizing the differences between the experimental and the calculated mole fractions of the components over all the tie lines. The
estimated parameters are presented in Table 7 together with those
determined previously for other groups interactions [32].
Our calculations using the interaction parameters from literature together with the re-estimated DCH2 O-CH2 and DCH2 O-H2 O
parameters have given a poor prediction for the ternary
DMD + ethanol + water system. Therefore, the interaction DCH2 OOH parameters were determined according to the LLE data for the
DMD + ethanol + water system (Table 7). As is seen in Fig. 1, the

A. Kilina et al. / Fluid Phase Equilibria 380 (2014) 9399

99

Table 7
UNIFAC group interaction parameters used in this work.

CH2
ACH
ACCH2
OH
H2 O
DCH2 O
a

CH2

ACH

ACCH2

OH

H2 O

DCH2 O

0
156.5
104.4
328.2
342.4
300a

114.8
0
146.8
9.21
372.8
52.13

115.7
167.0
0
1.27
203.7
65.69

644.6
703.9
4000
0
122.4
256.1a

1300
859.4
5695
28.73
0
448.4a

187.5a
32.14
213.1
540.0a)
237.2a
0

Parameters were estimated in the present work.

calculated binodal curve is in a good agreement with the experimental data.

The estimated group interaction parameters permit to predict
with a very good accuracy the LLE in the ternary system DMD + nheptane + water (Fig. 2). The experimental data available are not
sufcient to estimate parameters of interactions between DCH2 O
and ACH, ACCH2 groups, so we used the available parameters for
FCH2 O group to predict LLE in the ternary DMD + toluene + water
system [31]. The calculated results demonstrate a good agreement
with the experimental data (Fig. 3).
Using the UNIFAC parameters from Table 6 we have made LLE
predictions for two quaternary systems under study. The grosscompositions of the mixtures tried in the calculations were the
same as in the experimental measurements. The average absolute
deviations of the calculated equilibrium compositions of the liquid
phases from the experimental mole fractions for DMD + ethanol + nheptane + water and DMD + ethanol + toluene + water mixtures are
0.031 and 0.023 respectively.
6. Conclusions
The data obtained in the present study give information on the
mutual solubilities of components in binary and multicomponent
mixtures of 2,2-dimethyl-1,3-dioxolane with water, hydrocarbon
(n-heptane or toluene) and ethanol. The interest to systems containing dioxolane derivatives is due not only to various applied
tasks but also to the desire to understand better specic features of
the behavior of cyclic ethers in solutions. The results of calculations
applying the UNIFAC model demonstrate that with the interaction
parameters for linear ethers or with those for cyclic monoether
(tetrahydrofuran) the LLE in aqueous DMD solutions at 293.15 K
cannot be predicted. In the present study new UNIFAC parameters were estimated for interactions of DMD ether groups with
water, OH and CH2 groups, the simple version of the model being
tried. With the new parameters a good representation of the LLE for
the binary and multicomponent mixtures under consideration was
achieved. The values of the parameters give evidence of some interdependence of ether groups in one cyclic molecule. Evidently such
effects should be taken into account in the case of solutions of more
complicated 1,3-dioxolane derivatives especially if they contain
additional polar groups attached. In this case a new re-estimation
of the UNIFAC parameters may be needed.
Acknowledgment
The nancial support from the St. Petersburg State University
(project No. 12.38.76.2012) is gratefully acknowledged.

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