Fluid Phase Equilibria 380 (2014) 9399

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Fluid Phase Equilibria

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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 a b s t r a c t

Article history: Liquidliquid equilibria (LLE) data are presented for two quaternary systems: 2,2-dimethyl-1,3-
Received 14 March 2014 dioxolane (DMD) + n-heptane (or toluene) + ethanol + water, and for three ternary subsystems:
Received in revised form 30 July 2014 DMD + ethanol + water and DMD + n-heptane (or toluene) + water. The measurements were performed at
Accepted 4 August 2014
293.15 K and atmospheric pressure. The phase diagrams show extended heterogeneous areas for ternary
Available online 11 August 2014
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 crit-
Keywords:
ical point is observed for ternary mixtures of DMD with water and ethanol. The experimental LLE data
Liquidliquid equilibria
2,2-Dimethyl-1,3-dioxolane
were correlated and partly predicted applying the NRTL model. The UNIFAC interaction parameters for
Multicomponent mixtures CH2 O groups of dioxolane alkyl-derivatives were estimated. The model was applied to predict the LLE
NRTL diagrams for ternary DMD + n-heptane (+toluene) + water solutions and for the quaternary systems con-
UNIFAC taining 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 indus-
trial applications and to good possibilities for their synthesis using
natural raw materials. Cyclic acetals and ketals (in particular, 1,3-
dioxolane 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 1,3-
dioxolane-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 proper-
ties 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).
The present work is aimed at the study of the mutual solubility
of the components in two quaternary systems: DMD + ethanol + n-
heptane + water, DMD + ethanol + toluene + water and in the con-
stituent binary and ternary solutions containing DMD. The study
includes both experimental measurements at 293.15 K and ther-
modynamic 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 thermo-
dynamic excess functions relate to binary mixtures of 1,3-dioxolane
or its alkyl-derivatives (2-alkyl-, 4-alkyl-, 2,2-dimethyl-1,3-
dioxolane) 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 diox-
olane the dipole moment is quite pronounced, and this results in
a signicant difference in thermodynamic properties of systems
containing the mentioned cyclic ethers.

http://dx.doi.org/10.1016/j.uid.2014.08.002
0378-3812/ 2014 Elsevier B.V. All rights reserved.
94 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 demon-
strate negative (1,3-dioxolane + chloroform) or small positive
(dioxolane mixtures with isomers of chlorobutane and chloropen-
tane) deviations from ideality [5,1416]. The character of
deviations depends on the balance of two processes: the destruc-
tion 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 posi-
tive 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 con-
centration 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 spe-
cial attention. Incorporation of alkyl radicals in 1,3-dioxolane
molecules results in increased positive deviations from ideal-
ity for aqueous solutions and in the appearance of a solubility
gap. The extension of the gap at a xed temperature dis-
tinctly depends on the nature of the substituent and on its
position in dioxolane molecules. According to the data pre-
sented 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 < 2,2-
dimethyl-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 1,3-
dioxolane were correlated by the Wilson, NRTL, and UNIQUAC
models [9,18,20]. For all examined mixtures the results of the cor-
relations were satisfactory, the deviations obtained were similar
for three models tried. With the interaction parameters esti-
mated 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 sys-
tems 1,3-dioxolane + 1-butanol + cyclohexane/n-hexane [8]. The
both models gave satisfactory results for the systems contain-
ing 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 correla-
tion using the NRTL model was performed for binary mixtures of
4-methyl-1,3-dioxolane with methanol, propylene glycol and ace-
tone [27]. The ability to correlate VLLE data for binary mixtures
of water with 2-methyl-1,3-dioxolane or with 2,4-dimethyl-1,3-
dioxolane 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 multi-
component mixtures of 2,2-dimethyl-1,3-dioxolane-4-methanol
with n-heptane, ethanol and water [26]. Nevertheless, further stud-
ies 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 ther-
mostated 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 corre-
sponded 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 mix-
tures with water, whereas DMD + ethanol, DMD + n-heptane and
DMD + toluene binaries demonstrate the complete mutual mis-
cibility 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)

Exp
DMD Fluka >0.990 None GLC, KF 944.2
n-Heptane Vekton >0.998 None GLC 683.8
Toluene Vekton >0.998 None GLC 866.9
Ethanol Vekton >0.998 Azeotropic rectication GLC, KF 789.5
Water >0.999 Distillation 998.2
a
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 compo-
nents. 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 difcul-
ties due to chemical interactions between the components (the
products of the reaction of hydrolysis are ethyleneglycol and ace-
tone). 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
Fig. 1. The LLE phase diagram for DMD + ethanol + water system at T = 293.15 K: the
was chosen for our studies of the phase behavior of the mixtures. experimental binodal curve and tie-lines, and the results of modeling using the NRTL
In the experimental LLE studies we have applied two methods. In and UNIFAC (points).
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 capillary column (30 m, 0.53 mm, 0.20 m). The chromatographic
weight. Compositions of the mixtures were determined with the calibration was based on the internal standard method, and
accuracy 0.1 mass%. A magnetic stirrer was used to stir intensively propanol-2 was selected as the internal standard. The oven and
mixtures in the vessel for attaining their equilibrium state. detector temperatures were 443 K, the injector temperature was
The isothermal titration method was applied to determine the 493 K. The carrier gas was helium with the rate 5.0 mL min1
LLE phase boundaries (the run of the binodal curve in the concen- throughout the column. Each sample was analyzed at least three
tration triangle) for all ternary systems with miscibility gaps. In times, and the deviations from the average value were lower than
the experiments a known amount of some liquid mixture is ther- 0.5 mass%.
mostated in the glass vessel, and the titrant is added drop by drop The results of the experimental measurements obtained by two
under stirring until a change of the phase state is observed. Depend- different methods are in a good agreement between themselves.
ing on the run of the binodal curve different components were used The experimental LLE studies were performed at temperature
as titrants for various parts of the curve. The resulting material bal- 293.15 K for binary and multicomponent systems containing DMD.
ance of the substances gives the point on the binodal curve. The The information on the LLE in binary and ternary mixtures without
accuracy of the phase boundaries determination was 0.30.5 mol%. DMD (hydrocarbon + water, hydrocarbon + water + ethanol) was
Errors in the mole composition may be rather high if water is used taken from literature [28].
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 4. Results of the LLE measurements
drops). In such cases the compositions of the saturated solutions
were determined by the GC method. The LLE data are presented below for the ternary and quater-
Other measurements performed relate to determining the nary systems at 293.15 K. The results obtained are summarized in
compositions of the coexisting equilibrium liquid phases in mul- Tables 24 and in Figs. 13.
ticomponent heterogeneous mixtures. The mixtures prepared by
weight were thermostated in the glass cell and vigorously agitated 4.1. DMD + ethanol + water mixtures
by a magnetic stirrer for at least 1 h (it was checked in the prelim-
inary experiments that after 15 min of intensive stirring the phase In two binary constituents of the ternary system (DMD + ethanol
compositions became constant). Then the sample was left quiet and water + ethanol) the complete mutual miscibility of the com-
during not less than 2 h to get the complete separation of the liquid ponents is observed; in the system DMD + water the components
layers. After that the samples of the both phases were taken using are partly miscible, and in some concentration range two liquid
a syringe to analyze them. phases coexist (which become identical in the critical point). The
Both in the ternaries and in the quaternary systems the analysis heterogeneous area for the ternary system is rather small (Fig. 1).
of the equilibrium liquid phases was performed using a gas chro- The results presented in Table 2 and Fig. 1 show that all the data
matograph (CHROMOS-GH 1000, CHROMOS limited) equipped obtained are in a good agreement between themselves, and it is
with a heat conductivity detector and Valco PLOT Hayesep Q worth marking that different components were used as titrants to
96 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 0.000 0.198 0.243* 0.738* 0.019* 0.100* 0.892* 0.008*
0.681 0.043 0.276 0.478* 0.494* 0.028* 0.297* 0.685* 0.018*
0.579 0.063 0.358 0.599* 0.362* 0.039* 0.456* 0.516* 0.028*
0.523 0.075 0.402 0.676* 0.273* 0.051* 0.562* 0.391* 0.047*
0.316 0.087 0.597 0.767* 0.161* 0.072* 0.788* 0.096* 0.116*
0.786* 0.130* 0.084* 0.809* 0.050* 0.141*
0.804 0.089 0.107 0.822* 0.022* 0.156*
0.797 0.086 0.117 0.802 0.000 0.198
0.818 0.077 0.105
0.816 0.043 0.141
0.811 0.021 0.168
0.802 0.000 0.198
Aqueous phase
0.232 0.079 0.689 0.001 0.004 0.986 0.014 0.002 0.984
0.156 0.065 0.779 0.019 0.003 0.978 0.022 0.002 0.976
0.136 0.063 0.801 0.030 0.002 0.968 0.029 0.005 0.966
0.111 0.058 0.831 0.030 0.001 0.969 0.041 0.003 0.956
0.098 0.051 0.851 0.044 0.004 0.955 0.044 0.002 0.954
0.085 0.041 0.874 0.049 0.000 0.951 0.049 0.000 0.951
0.066 0.026 0.908
0.049 0.000 0.951
a
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 homo-
geneous 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 tie-
lines 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 Aqueous phase

DMD + ethanol + water

xD xE xW xD xE xW
0.802 0.000 0.198 0.049 0.000 0.951
0.775 0.014 0.211 0.055 0.009 0.936
0.732 0.027 0.241 0.063 0.017 0.920
0.718 0.033 0.249 0.066 0.021 0.913
0.652 0.049 0.299 0.073 0.032 0.895
0.544 0.069 0.387 0.091 0.045 0.864
0.444 0.080 0.476 0.120 0.058 0.822
0.416 0.084 0.500 0.140 0.063 0.797
DMD + n-heptane + water
xD xH xW xD xH xW
0.150 0.844 0.006 0.011 0.001 0.988
0.406 0.574 0.020 0.025 0.001 0.974
0.495 0.475 0.030 0.034 0.001 0.965
0.622 0.338 0.040 0.037 0.002 0.961
0.736 0.197 0.067 0.043 0.002 0.955
0.802 0.000 0.198 0.049 0.000 0.951
DMD + toluene + water
xD xT xW xD xT xW
0.100 0.892 0.008 0.002 <0.001 0.998
0.297 0.685 0.018 0.008 <0.001 0.992
0.456 0.516 0.028 0.013 <0.001 0.987
0.562 0.391 0.047 0.019 <0.001 0.981
0.788 0.096 0.116 0.037 <0.001 0.963
0.802 0.000 0.198 0.049 0.000 0.951
a
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 Aqueous phase

DMD + ethanol + n-heptane + water

xD xE xH xW xD xE xH xW
0.284 0.063 0.635 0.018 0.072 0.207 0.001 0.720
0.197 0.033 0.761 0.009 0.025 0.128 <0.001 0.847
0.307 0.131 0.516 0.046 0.162 0.345 0.023 0.470
0.192 0.047 0.750 0.011 0.044 0.210 <0.001 0.746
0.358 0.081 0.529 0.032 0.085 0.192 0.001 0.722
0.354 0.050 0.574 0.022 0.044 0.120 <0.001 0.836
0.173 0.076 0.736 0.015 0.078 0.346 0.007 0.569
DMD + ethanol + toluene + water
xD xE xT xW xD xE xT xW
0.253 0.166 0.476 0.105 0.032 0.184 0.003 0.781
0.101 0.120 0.748 0.031 0.016 0.224 0.005 0.755
0.212 0.227 0.428 0.133 0.050 0.261 0.018 0.671
0.089 0.087 0.801 0.023 0.007 0.184 0.002 0.807
0.513 0.084 0.301 0.102 0.033 0.079 0.006 0.882
0.156 0.026 0.806 0.012 0.006 0.070 <0.001 0.924
0.233 0.099 0.626 0.042 0.014 0.130 <0.001 0.856
a
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

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

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 concentra-
tion was indistinct. In this case the n-heptane content is marked
in Table 3 as <0.001 (the uncertainty of the analysis being taken
containing n-heptane. It is also formed by one homogeneous
binary system (DMD + toluene) and by two binaries with miscibil-
ity 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 sys-
tems (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 + n-
heptane + 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

Phase behavior modeling for the ternary and quaternary sys-

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).
tems 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 pre-
dictions 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 0 671.4 384.6 1534. 325.1

n-Heptane 161.3 0 1098
Toluene 271.2 0 1781
Ethanol 338.2 0 36.62
Water 778.7 3610 2672 522.3 0

Table 6
UNIFAC group assignment in this study.

Substance Main Subgroups and

group their numbers

DMD CH2 2 CH3 1 C

DCH2 O 2 DCH2 O
Ethanol CH2 1 CH3 1 CH2
OH 1 OH
n-Heptane CH2 2 CH3 5 CH2
Toluene ACH 5 ACH
ACCH3 1 ACCH3
Water H2 O 1 H2 O

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 interac-
tion 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 sub-
groups, the latters having the same interaction energy parameters
and differing between themselves only by the geometric charac-
teristics. 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 character-

ized 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 sys-
tem one needs to optimize nine parameters, but in case of limited
number of experimental tie lines this is impossible. Usually param-
eters 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 + n-
heptane + 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 pre-
sented in Figs. 13.
The geometrical and energy parameters for most of the groups
under considerations were taken from literature [32]. But the pub-
lished 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 fail-
ure 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 parame-
ters 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 cal-
culated 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 litera-
ture 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 O-
OH 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

CH2 0 114.8 115.7 644.6 1300 187.5a

ACH 156.5 0 167.0 703.9 859.4 32.14
ACCH2 104.4 146.8 0 4000 5695 213.1
OH 328.2 9.21 1.27 0 28.73 540.0a)
H2 O 342.4 372.8 203.7 122.4 0 237.2a
DCH2 O 300a 52.13 65.69 256.1a 448.4a 0
a
Parameters were estimated in the present work.

calculated binodal curve is in a good agreement with the experi- References

mental data.
The estimated group interaction parameters permit to predict
with a very good accuracy the LLE in the ternary system DMD + n-
heptane + 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 gross-
compositions 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 + n-
heptane + 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 con-
taining 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 parame-
ters 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 inter-
dependence 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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