Fluid Phase Equilibria 191 (2001) 99109

Azeotropic and heats of mixing data for various

binary systems with diethoxymethane
Dana Constantinescu
a
, Roland Wittig
b
, J urgen Gmehling
b,
a
Institute of Physical Chemistry, I.G. Murgulescu, Romanian Academy,
Splaiul Independentei 202, Bucharest 77208, Romania
b
Universit at Oldenburg, Technische Chemie, Postfach 2503, D-26111 Oldenburg, Germany
Received 11 June 2001; accepted 10 August 2001
Abstract
Reliable azeotropic data have been measured for the binary systems ethanol +diethoxymethane, diethoxy-
methane +1-propanol, diethoxymethane +heptane, and cyclohexane +diethoxymethane with the help of a wire
band column. Additionally molar excess enthalpies (H
E
) for the binary mixtures of diethoxymethane with hexane,
1-octene, methanol and ethanol at 363.15 K have been determined with an isothermal ow calorimeter. The ex-
perimental data were compared with the results using the available ether main group of the group contribution
method Modied UNIFAC (Dortmund), which is a well-known model for the prediction of phase equilibria and
excess properties. For the description of the H
E
data a RedlichKister polynomial was also used.
The aim of this work is to supplement the available data base for acetal systems required for the introduction of a
new acetal group in the Modied UNIFAC (Dortmund) model. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Excess (properties); Vaporliquid equilibria; Group contribution method; Modied UNIFAC (Dortmund); Wire
band column; Isothermal ow calorimeter
1. Introduction
The knowledge of azeotropic points offers the most important information for the synthesis and design
of distillation processes. However, the immense amount of data [1] stored in Dortmund Data Bank (more
than 45,000 entries on azeotropic and zeotropic behavior) cannot only be used for process synthesis, e.g.
design of distillation columns, selection of the most suitable solvent for azeotropic distillation, but also
for the further development of group contribution methods and for tting reliable G
E
models parameters.
Inthe case of G
E
models [2], a preconditionfor a gooddescriptionof phase equilibria of multicomponent
systems is the determination of reliable binary interaction parameters. In chemical industry, mainly

Corresponding author. Tel.: +49-441-798-3831; fax: +49-411-798-3330.

E-mail address: gmehling@tech.chem.uni-oldenburg.de (J. Gmehling).
0378-3812/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S0378- 3812( 01) 00615- X
100 D. Constantinescu et al. / Fluid Phase Equilibria 191 (2001) 99109
vaporliquid equilibria (VLE) data are used to t the required binary parameters. However, as mentioned
in previous papers [3,4], it is recommended to t the required interaction parameters simultaneously to
all available reliable experimental data (VLE, azeotropic data, activity coefcients at innite dilution
(

), H
E
, solidliquid equilibria (SLE) of eutectic systems, etc.), since the parameters obtained by a
simultaneous t allow an improved representation of the real behavior across the whole composition and
a large temperature range.
In the Modied UNIFAC method [5,6], different types of phase equilibria and excess properties are
used for tting simultaneously the required temperature-dependent group interaction parameters. Excess
enthalpy data are of a particular signicance as supporting data at high temperature [7] and provide
the most important information about the temperature dependence, because of the direct relationship
between the partial molar excess enthalpy (H
E
i
) and the observed temperature dependence of the activity
coefcient
i
, by means of the GibbsHelmholtz relation:

ln
i
(1/T )

P,x
=
H
E
i
R
(1)
Although a large number of excess enthalpy data around room temperature are available, H
E
data at high
temperature are scarce. This paper presents excess enthalpies at high temperature.
This paper presents azeotropic data for the binarysystems ethanol +diethoxymethane, diethoxymethane
+1-propanol, diethoxymethane +heptane, and cyclohexane +diethoxymethane. For these systems, also
published azeotropic data are available. Additionally, excess enthalpies for binary mixtures of diethoxy-
methane with hexane, 1-octene, methanol and ethanol were measured. Since 95%of the published H
E
data
were measured between 283 and 323 K [8], our attention is focused to measure the required supporting
H
E
data at higher temperatures. The measurements were performed using an isothermal ow calorimeter
with a large operational range (273425 K). Enthalpies of mixing for hexane +diethoxymethane [9] and
diethoxymethane +1-octene [10] are also reported in literature, but only at T = 298.15 K. The exper-
imental azeotropic and H
E
data were compared graphically with the results predicted by the Modied
UNIFACmodel using the available ether main group. For the correlation of the H
E
data a RedlichKister
polynomial was used.
Diethoxymethane is a compound belonging to the main classes of oxaalkanes. Besides the technical
importance for these classes of substances there is also an interest to examine, in terms of Modied
UNIFAC model, vaporliquid equilibria and related thermodynamic excess functions. The intention of
this paper is to supplement the available azeotropic and H
E
data for acetal systems required for the
introduction of a acetal group in the Modied UNIFAC model.
2. Experimental section
2.1. Materials
Chemicals with high purity obtained from various suppliers prior to their use were puried by vac-
uum distillation. The purity of the compounds was carefully checked by gas chromatography (GC) and
KarlFischer titration. Besides the supplier, the chemicals together with the pure compound specication
are summarized in Table 1.
D. Constantinescu et al. / Fluid Phase Equilibria 191 (2001) 99109 101
Table 1
Suppliers, purities, water contents of the chemicals used
Compound Supplier Purity (% GC) Water content
(mass ppm)
Hexane Fluka >99.9 40
Heptane Merck >99.5 50
Cyclohexane Scharlau >99.9 10
1-Octene Acros >99.8 70
Methanol Scharlau >99.9 30
Ethanol Merck >99.9 30
1-Propanol Riedel de Ha en >99.8 50
Diethoxymethane Acros >99.5 10
2.2. Measurement of the azeotropic points
A commercially available wire band column with an electronically controlled reux ratio (supplier:
Normag, Hofheim, Germany) was used to distil the mixtures, as described earlier [1]. The reux ratio
is realized on the basis of a vapor dividing principle. For pressures below atmospheric pressure, the
desired pressure is kept constant with the help of a vacuum pump. The temperature is determined using
a resistance thermometer with an accuracy of 0.1 K and the pressure by means of a sensor (Druck
Limited, type PDCR) with an accuracy of 0.05 kPa. The accuracy of the azeotropic composition y
az
determined is approximately 0.2 mol%.
Approximately 30 cm
3
of the binary mixture with estimated azeotropic composition are distilled at
constant pressure and a small pressure drop at nearly total reux for approximately 60 min. Then the
composition of the distillate is determined analytically by GC. For all systems investigated homogeneous
pressure maximum azeotropes were obtained. To verify whether the system shows azeotropic (separation
factor
12
= 1) and not quasi-azeotropic (
12
1) behavior, the experiments were always repeated
starting with a different feed composition.
2.3. H
E
measurements
A commercially available isothermal ow calorimeter from Hart Scientic (model 7501) was used
for the excess enthalpy measurements [11]. The calorimeter consists of two solvents pumps (ISCO, LC
2600, 260 cm
3
), a thermostated ow cell, a back pressure regulator, which prevents evaporation (it is
known [12] that vaporization effects may cause considerable errors at higher temperatures) and provides
the opportunity to measure H
E
data also at higher pressures (up to 15 MPa). The ow cell, containing a
pulsed heater, a calibration heater, a Peltier cooler and a mixing tube wound around a copper cylinder
[13], is located in a stainless steel cylinder which is immersed in a thermostat.
The power per pulse can be varied between 0.05 and 20 J. The exact energy per pulse is obtained
by calibration using the energy dissipated from a precise resistor xed at the cylinder of the ow cell.
The temperature of the ow cell is maintained constant by adjusting the frequency of the pulsed heater
to balance the cooling from the Peltier cooler and the heat effect. The temperature of the liquid pumps
and the thermostat are monitored with Hart Scientic platinum resistance thermometers (model 1006
Micro-Therm) with an accuracy of 0.005 K.
102 D. Constantinescu et al. / Fluid Phase Equilibria 191 (2001) 99109
From the recorded frequency change of the pulsed heater, the ow rate, the pure component densities
and the molar mass of the components the molar excess enthalpies can be calculated using the energy
evolved per pulse. The uncertainty in H
E
is estimated to be less than 1%, as shown previously [11].
Studies of test mixtures indicated that the precision of the results was better than 1% over the whole
composition range.
3. Experimental results
The experimental azeotropic data (T, P, composition) for the investigated systems ethanol +diethoxy-
methane, diethoxymethane +1-propanol, diethoxymethane +heptane, and cyclohexane + diethoxy-
methane are given in Table 2 together with the data from literature [1420]. In all cases homogeneous
pressure maximum azeotropes were observed.
The experimental data for the acetal systems were compared with the results of the group contribution
method Modied UNIFAC (Dortmund) using the ether group. The results are shown in Figs. 14 in the
form of Ty
az
-diagrams. As can be seen, there is a good agreement between experiment and prediction
Table 2
Experimental azeotropic data for different acetal systems
System Experimental data T (K) Published data Reference
P (kPa) y
1
P (kPa) y
1
Ethanol (1) + diethoxymethane (2) 347.35 101.32 0.6081 [14]
347.35 101.32 0.6208 [15]
102.35 0.6497 348.30
95.99 0.6350 346.85
52.51 0.5765 331.00
27.48 0.5123 315.95
20.02 0.4700 309.25
Diethoxymethane (1) + 1-propanol (2) 359.85 101.32 0.7800 [16]
359.30 99.67 0.8236 [17]
99.43 0.7680 359.01
56.27 0.8367 342.29
16.82 0.9356 311.65
Diethoxymethane (1) + heptane (2) 102.30 0.9101 361.27
360.95 101.32 [18]
343.15 56.95 0.9100 [19]
35.66 0.8830 333.03
323.15 27.10 0.8950 [19]
11.21 0.8476 302.53
Cyclohexane (1) + diethoxymethane (2) 353.25 101.32 0.8580 [16]
101.39 0.8226 353.21
44.33 0.8366 328.07
14.97 0.8623 300.83
298.15 0.9000 [20]
D. Constantinescu et al. / Fluid Phase Equilibria 191 (2001) 99109 103
Fig. 1. Experimental and predicted azeotropic data for the binary system ethanol (1) +diethoxymethane (2): () from [14]; ()
from [15]; () our data; () Modied UNIFAC (Dortmund).
Fig. 2. Experimental and predicted azeotropic data for the binary system diethoxymethane (1) +1-propanol (2): () from [16];
() from [17]; () our data; () Modied UNIFAC (Dortmund).
Fig. 3. Experimental and predicted azeotropic data for the binary system diethoxymethane (1) +heptane (2): () from [19]; ()
our data; () Modied UNIFAC (Dortmund).
104 D. Constantinescu et al. / Fluid Phase Equilibria 191 (2001) 99109
Fig. 4. Experimental and predicted azeotropic data for the binary system cyclohexane (1) +diethoxymethane (2): () from [16];
() from [20]; () our data; () Modied UNIFAC (Dortmund).
for ethanol +diethoxymethane, reasonable agreement for diethoxymethane +heptane, diethoxymethane
+1-propanol and poor agreement for cyclohexane +diethoxymethane.
The ClausiusClapeyron and GibbsHelmholtz equation give the alteration of the azeotropic compo-
sition with temperature. In most cases, a correct temperature dependence is predicted, which in majority
of cases depend mainly on the slope of the vapor pressure data and only to a smaller extend on the
temperature dependence of the activity coefcient (partial molar excess enthalpies) [1].
However, to improve the results of Modied UNIFAC (Dortmund) additional measurements for the
determination of parameters for a new acetal group tted simultaneously to VLE, H
E
,

, SLE of
eutectic systems, etc. are required.
Therefore, also heat of mixing measurements for systems with diethoxymethane were performed. The
measured excess enthalpies for the binary systems of diethoxymethane with hexane, 1-octene, methanol
and ethanol at 363.15 K are listed in Table 3. The experimental data have been compared with the results
of the group contribution method Modied UNIFAC (Dortmund) using the ether group. Additionally,
the RedlichKister [21] expansion was used to correlate the results:
H
E
x
1
x
2
=
m

j
A
j
(2x
j
1)
j1
(2)
using the following objective function [22]:
F =
n

H
E
x
1
x
2

exp

H
E
x
1
x
2

calc

2
(3)
The tted RedlichKister parameters A
j
together with the root mean square deviations (RMSD) are given
in Table 4. The number of parameters used to represent the experimental data depends on the molecular
complexity of the H
E
behavior, the quality of the data, and the number of data points available. The reliable
and extensive data justify the use of ve parameters. For all studied systems, the obtained RMSDs are
within the estimated experimental error of 1% [12].
D. Constantinescu et al. / Fluid Phase Equilibria 191 (2001) 99109 105
Table 3
Excess molar enthalpies for mixtures containing diethoxymethane at 363.15 K
x
1
H
E
(J mol
1
) x
1
H
E
(J mol
1
) x
1
H
E
(J mol
1
)
Hexane (1) + diethoxymethane (2), P = 1.31 MPa
0.0479 91.8 0.3891 490.3 0.7413 393.1
0.0960 172.6 0.4387 506.5 0.7926 337.3
0.1443 249.9 0.4886 514.9 0.8441 269.9
0.1928 313.1 0.5387 511.6 0.8958 187.5
0.2415 370.1 0.5890 500.5 0.9478 95.5
0.2905 415.4 0.6395 470.3
0.3397 458.6 0.6900 437.4
Diethoxymethane (1) + 1-octene (2), P = 1.34 MPa
0.0620 54.3 0.4557 313.3 0.7903 216.9
0.1225 113.9 0.5068 319.8 0.8340 182.3
0.1814 167.7 0.5567 320.2 0.8768 141.9
0.2390 209.3 0.6055 312.8 0.9187 98.5
0.2951 246.9 0.6533 299.2 0.9598 51.4
0.3499 279.4 0.6999 279.7
0.4034 302.2 0.7456 254.3
Methanol (1) + diethoxymethane (2), P = 1.34 MPa
0.1397 828.1 0.6729 1171.0 0.9250 426.0
0.2553 1233.7 0.7163 1063.0 0.9459 240.9
0.3525 1409.8 0.7552 958.2 0.9652 153.3
0.4354 1451.9 0.7904 845.2 0.9832 69.9
0.5070 1423.4 0.8223 737.0
0.5694 1356.3 0.8514 629.7
0.6242 1271.9 0.9025 524.7
Ethanol (1) + diethoxymethane (2), P = 1.34 MPa
0.1013 710.9 0.5881 1563.3 0.8653 692.4
0.1922 1166.9 0.6367 1471.5 0.8955 550.7
0.2743 1445.7 0.6817 1367.8 0.9239 407.4
0.3487 1598.8 0.7236 1244.0 0.9507 266.1
0.4166 1662.6 0.7626 1113.4 0.9760 123.0
0.4786 1672.8 0.7991 980.0
0.5356 1633.6 0.8333 837.0
Table 4
RedlichKister-parameters
Component 1 Component 2 T (K) A
1
A
2
A
3
A
4
A
5
RMSD
a
(J mol
1
)
Hexane Diethoxymethane 363.15 2055.34 56.24 36.96 105.02 79.33 0.734
Diethoxymethane 1-Octene 363.15 1283.52 124.78 127.82 113.62 83.99 1.078
Methanol Diethoxymethane 363.15 5686.34 1376.37 1101.35 107.55 1258.72 1.155
Ethanol Diethoxymethane 363.15 6615.09 1102.18 963.79 199.58 1049.38 0.998
a
RMSD =

1
n

n
(H
E
exp
H
E
calc
)
2
.
106 D. Constantinescu et al. / Fluid Phase Equilibria 191 (2001) 99109
Fig. 5. Experimental and correlated, respectively predicted H
E
data for hexane (1) +diethoxymethane (2) at 363.15 K () our
data, and at 298.15 K () from [9]; () RedlichKister; (- - -) Modied UNIFAC (Dortmund).
In Figs. 57, the Modied UNIFAC (Dortmund) and RedlichKister results are compared with the
experimental results. As can be seen all systems show relatively symmetric endothermal behavior.
In Fig. 5, the H
E
data for the system hexane +diethoxymethane at 363.15 K are shown together with
previously published data [9] at 298.15 K. The prediction of the H
E
data at 298.15 K with Modied
Fig. 6. Experimental and correlated, respectively predicted H
E
data for diethoxymethane (1) +1-octene (2) at 363.15 K () our
data, and at 298.15 K () from [10]; () RedlichKister; (- - -) Modied UNIFAC (Dortmund).
D. Constantinescu et al. / Fluid Phase Equilibria 191 (2001) 99109 107
Fig. 7. Experimental and correlated, respectively predicted H
E
data for methanol (1) () and ethanol (1) () + diethoxymethane
(2) at 363.15 K; () RedlichKister; (- - -) Modied UNIFAC (Dortmund).
UNIFAC (Dortmund) using the ether main group is reasonably good, but for the H
E
data at 363.15 K
poor agreement is obtained.
In Fig. 6, the H
E
data for the system diethoxymethane +1-octene at 363.15 K are shown together with
published data [10] at 298.15 K. With Modied UNIFAC (Dortmund) the excess enthalpies are predicted
too low at 298.15 K, respectively too high at 363.15 K.
Fig. 7 illustrates that the excess enthalpies of the two lowest alcohols, methanol and ethanol with
diethoxymethane differ only slightly. With Modied UNIFAC (Dortmund) lower H
E
values are predicted
for both data sets.
In conclusion, it can be recognized that the predicted excess molar enthalpies with Modied UNIFAC
(Dortmund) using the existing group interaction parameters for the ether group provide poor results
for the investigated mixtures especially at high temperature. To overcome this problem, a new group
should be introduced so that the proximity effect, due to the two O atoms in acetals, can be taken into
account.
4. Conclusions
Azeotropic data for the binary systems ethanol +diethoxymethane, diethoxymethane +1-propanol,
diethoxymethane +heptane, and cyclohexane +diethoxymethane have been measured and compared
with the results of the group contribution method Modied UNIFAC (Dortmund).
Additionally, excess enthalpies were measured for the binary mixtures of diethoxymethane with hexane,
1-octene, methanol and ethanol at 363 K. The H
E
data have been compared with data using Modied
UNIFAC (Dortmund) and correlated using the RedlichKister expansion.
108 D. Constantinescu et al. / Fluid Phase Equilibria 191 (2001) 99109
Because of the proximity effect the predictions using the available ether group of the Modied
UNIFAC model provide only poor results for the acetal systems investigated. Preliminary extensive
studies have already demonstrated this effect for oxaalkanes, including linear and cyclic acetals [2329].
To overcome this problem, a new structural group for acetals will be introduced in Modied UNIFAC
(Dortmund).
The main objective within this work was to provide azeotropic and H
E
data for the introduction of
the new acetal main group. Additional phase equilibrium measurements (VLE,

, SLE of eutectic
systems) for tting temperature-dependent parameters will be carried out in the future.
List of symbols
A RedlichKister parameter
F objective function
G molar Gibbs enthalpy (J mol
1
)
GC gas chromatography
H molar enthalpy (J mol
1
)
P pressure (kPa)
R general gas constant (R = 8.3144 J mol
1
K
1
)
SLE solidliquid equilibria
T temperature (K)
VLE vaporliquid equilibria
x liquid phase composition
y vapor phase composition
Greek letters

12
separation factor
activity coefcient
Superscripts
E excess property
at innite dilution
Subscripts
1, 2, i components 1, 2, i
az at the azeotropic point
calc calculated value
exp experimental value
P at constant pressure
x at constant mole fraction
Acknowledgements
The authors thank Mr. R. B olts for his technical assistance in carrying out the calorimetric
measurements.
D. Constantinescu et al. / Fluid Phase Equilibria 191 (2001) 99109 109
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