J. Chem.

Thermodynamics 175 (2022) 106882

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The Journal of Chemical Thermodynamics

journal homepage: www.journals.elsevier.com/the-journal-of-chemical-thermodynamics

Vapor pressure curves and isobaric vapor–liquid equilibrium for binary

systems with compounds obtained from glycerol to be used as components
of a bio-diesel mixture
Jorge Garcia-Cano a, Vicente Gomis a, b, Alicia Font a, b, *, Vincenzo Calemma c,
Alberto de Angelis c
a
Institute of Chemical Process Engineering, University of Alicante, PO Box 99, E-03080 Alicante, Spain
b
Department of Chemical Engineering, University of Alicante, PO Box 99, E-03080 Alicante, Spain
c
Eni S.p.A., Upstream & Technical Service\DR&D, Via F. Maritano 26, 20097 San Donato Milanese, Italy

A R T I C L E I N F O A B S T R A C T

Keywords: The search of new renewable fuels and the interest of finding new uses for the abundant subproducts of many
VLE industrial processes have prompt Eni S.p.A to develop a technology for producing biofuels from glycerol. One of
Vapor pressure the compounds involved in this process is 2-ethyl-4-ethoxymethyl-1,3‑dioxolane (PrEDO). In this paper their
3-ethoxy-1,2-propanediol
temperature - vapor pressure curve has been determined experimentally as well as binary vapor–liquid equi­
2-ethyl-4-methyl-1,3-dioxolane
librium data at different pressures of systems where this compound is involved.
2-ethyl-4-ethoxymethyl-1,3-dioxolane
The experimental vapor pressure data of PrEDO have been fitted with the Antoine equation. The vapor liquid
equilibrium data have been correlated and calculated with UNIFAC, UNIQUAC, NRTL and Wilson to analyze
their use when designing distillation processes.

1. Introduction diesel, whose production in 2019 has reached about 35 millions of

The long-term European strategy provides for the achievement of
Carbon Neutrality by 2050. With the goal to counteract the global
warming and keep the global temperature rise within the limits set in the
Paris agreement of December 2015, EU has enacted a series of directives
to foster the use of fuels produced by renewable sources. The most recent
RED II directive provides that the level of renewable fuels in fossil fuel
must be 14 % by 2030, while the content of the advanced biofuel has
been raised to 3.5 % [1]. In this scenario the production of advanced
biofuel is particularly important in view of applying the concept of
circular economy. Presently, gasoil from renewable resources is largely
based on production of FAME (Fatty Acid Methyl Esters) generally
known as biodiesel [2,3]. The process involves the based catalyzed re­
action of vegetable oils or fats with monoalcohols, mainly methanol. The
transesterification reaction leads to the corresponding methyl or ethyl
esters of fatty acids and glycerol as byproduct [4], being one of the main
drawbacks of these process. Around a 10 % of the total weight of FAME
produced is simultaneously generated as glycerol during the trans­
esterification process. As a consequence of the large production of bio-
tons per year, a large quantity of glycerol is available on the market [5]
that cannot be absorbed by the industry that usually employs glycerol in
their processes. The surplus of glycerol production has led to strong
reduction of the selling price [4] despite the fact that the demand is
growing [6]. The high availability and the low price make the glycerol a
good candidate for advanced biofuel production. In this scenario, Eni S.
p.A has deemed that there were the conditions to develop an advanced
biofuel process [7–9].
Both the two building blocks of the innovative biofuels are prepared
starting from glycerol: 1,2 propanediol is produced through catalytic
hydrogenation of glycerol, while the other one, 3-ethoxy-1,2-propane­
diol (3-MEP), can be obtained from glycerol after etherification using
ethanol [10]. The 1,2-propanediol reacts by means of two consecutive
acid-catalyzed reaction substeps: firstly, forming an aldehyde (1-
propanal) and water and, secondly, the aldehyde reacting with the diol
to form a cyclic acetal such as 2-ethyl-4-methyl-1,3‑dioxolane (PrDIOX)
[11].
PrDIOX reacts with a mole of 3-MEP, under acid catalysis, producing
the second componenent for biofuels: 2-ethyl-4-ethoxymethyl-

* Corresponding author at: Institute of Chemical Process Engineering, University of Alicante, PO Box 99, E-03080 Alicante, Spain.
E-mail address: alicia.font@ua.es (A. Font).

https://doi.org/10.1016/j.jct.2022.106882
Received 17 September 2021; Received in revised form 28 July 2022; Accepted 30 July 2022
Available online 3 August 2022
0021-9614/© 2022 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
J. Garcia-Cano et al. The Journal of Chemical Thermodynamics 175 (2022) 106882

Table 1
Provenance table of the compounds used.
IUPAC name CAS Other name Provider Purity (mass Purification method Water content (mass
fraction) fraction)

3-ethoxy-1,2-propanediol 1874-62- 3-MEP, 3-monoethoxy-propanediol ENI >0.99 No further <0.0005

0 purification
2-ethyl-4-ethoxymethyl-1,3- PrEDO ENI >0.99 No further <0.001
dioxolane purification
1-propanal 123–38-6 PA, n-Propanal, 1-Propanone, Acros >0.99 No further <0.001
Propanaldehyde organics purification

Purity determined by gas chromatography.

Water content determined by the Karl Fischer technique.

Figure 1. Chromatograms of the PrEDO isomers in the liquid and vapor phases in equilibria.

1,3‑dioxolane (PrEDO) [12]. These products can be used as components
of a bio-diesel mixture.
To separate these products from the reaction media using distillation
steps, the vapor–liquid equilibrium data of the systems involved are
needed. In the literature few equilibrium data are available for these
systems. For example, no data on the vapor 2-ethyl-4-ethoxymethyl-
1,3‑dioxolane (PrEDO) has been published previously nor vapor–liquid
equilibrium data of systems where this compound is involved.
The goal of this work is the experimental determination of the vapor
pressure of this latter compound and the vapor–liquid equilibrium data
of systems such as 1-propanal + 2-ethyl-4-ethoxymethyl-1,3‑dioxolane
(PA + PrEDO) and 3-ethoxy-1,2-propanediol + 2-ethyl-4-ethoxymethyl-
1,3‑dioxolane (3-MEP + PrEDO) at different pressures related with its
separation. All these systems are involved in the reactions to obtain
alkyloxide derivatives from glycerol and they need to be determined to
assess the viability of using the distillation to separate the reaction
products.
2. Experimental
2.1. Chemicals
The compounds employed were used without further purification
directly from the provider. Table 1 presents the compounds used and
their provenance. Their purity was analyzed by gas chromatography
using an Agilent 7820A gas chromatograph using the conditions
described later in the Procedure section. The water content was deter­
mined by the Karl Fischer technique using a Mettler Toledo Karl Fischer
Titrator KF 737.
The 2-ethyl-4-ethoxymethyl-1,3‑dioxolane used in this work and
provided by ENI is a mixture of two Z/E isomers with a with very similar
thermodynamical properties. The ratio of both isomers in the initial
mixture to be studied was always the same.
To study the differences in volatility of both isomers and their
possible influence in the equilibrium, samples of PrEDO were taken
during the experiment of the vapor pressure determination of pure
PrEDO, one from the liquid and one from the vapor phase. The samples
were diluted in 1-butanol and analyzed by GC/MS. Two examples of the
chromatograms of both samples are shown in figure 1 showing the two
peaks corresponding to each PrEDO isomers.
As can be seen in figure 1, the ratio of both isomers is very similar in
the two phases. The mean content of (E)-PrEDO in all the liquid samples
was 59 % with an uncertainty of 2 % obtained considering repeatability
and instrumental factors. In the phase vapor the mean content of (E)-
PrEDO was 61 % with the same uncertainty. Therefore, there is no
appreciable variation.

2
J. Garcia-Cano et al.
Furthermore, the relative volatility (α) between both isomers
calculated with the ratio of chromatographic areas (area (Z) /area (E)) is
very close to 1 (α = 1.09). As it can be calculated from the results of this
work, the mean relative volatilities of PrEDO/3-MEP (α = 9) and 1-
propanal/PrEDO (α = 250) are much higher. From the point of view
of the use of the VLE data in the design of a separation process of PrEDO
and 3-MEP or PrEDO and 1-propanal, the relative proportion of the two
PrEDO isomers in the liquid or vapor phases is not important and the
concentration differences of both isomers in both phases can be
considered negligible.
2.2. Procedure
The experimental procedure to obtain the vapor pressure of the
compounds and to obtain the vapor–liquid equilibrium data was
explained in detail in a previous paper [13]. The equipment employed
was a commercial Fischer Labodest 602 coupled to two different pres­
sure controllers. The Fischer Minitron VLE was used in the range
10–1026 mbar and the Mensor High-Speed Pneumatic Pressure
Controller model CPC3000 above that range. The apparatus is a well-
known phase equilibria determination equipment validated many
times by our research group [13–20]. Moreover, prior to the determi­
nation of new experimental data, the overall performance is checked
with known data (e.g. boiling points of water at different pressures). The
boiling point of 1-propanal was measured and was found to be 321.14 K
at 1013 mbar. This data agrees well with the more recent literature data
already published and compiled in the NIST Chemistry Webbook. The
same procedure was carried out with 3-MEP and, in this case, the boiling
point was 377.6 K at 10 mbar and 390.5 K at 20 mbar, the same results
obtained in our previous paper [13] because we have not found other
literature data.
The pure compound or the mixture to study their equilibrium is
introduced inside the equipment and heated with a quartz rod resis­
tance, at the same time the pressure is controlled to a set point for the
boiling temperature to be reached. The temperature of the vapor in
equilibrium with the liquid is measured with a Pt100 sensor, and sam­
ples from the returning liquid and vapor are collected and analyzed
using an Agilent 7820A gas chromatograph. A Supelco Analytical 6 ft ×
1/8 in × 2.1 mm SS column packed with Porapak Q was used. He at a
flow rate of 25 mL/min was used as carrier gas. The oven was main­
tained at 493.15 K while the injector and TCD were set at 513.15 K and
the FID at 523.15 K.
To minimize the reactivity of the dioxolane compounds and avoid
their oxidation during the experiments, the air inside the equipment was
removed by vacuum and the equipment refilled with helium. This step
was repeated several times to minimize the oxygen remaining inside the
equipment before any heating was performed.
The measurements of the boiling temperature were repeated four
times with new sample in each of the measurements. For each sample
several measurement sets were performed, starting by increasing the
pressure, decreasing it and repeating the cycle. After each measurement
cycle (more than 30 h at temperatures sometimes higher than 200 ◦ C)
samples from the heater and distillate were taken and analyzed by
GC–MS using the chromatographic conditions described in Figure 1. The
results were compared with those of the original sample and showed the
presence of a compound that cannot be identified by the MS database of
our equipment. The area of the chromatographic peak increased slightly
with the time and consequently indicated that PrEDO was degrading and
this new compound was been formed. Moreover, slight variations in the
measured boiling point were observed when the same sample was
heated for long time in the equipment. These differences also suggest
slight degradation and rectification of the compounds during the mea­
surements. As a result, the values selected were the ones with fresh
sample.
On the other hand, the proportion of (Z) and (E) PrEDO isomers was
studied for some liquid phase and vapor phase samples from both the
3
The Journal of Chemical Thermodynamics 175 (2022) 106882
determinations of the vapor pressure curve of PrEDO and the VLE with
other compounds. The samples were diluted in 1-butanol and analysed
by GC/MS. All the results showed proportions between isomers very
similar to those shown in Figure 1. Taking into account the uncertainty
of the concentration measurements of each isomer, it was concluded that
there was no appreciable variation in the proportion of isomers with
respect to the original sample. For these reasons, the sum of PrEDO
isomers was considered in this study. From now on, every time we refer
to component PrEDO, we are referring to the sum of both compounds.
Moreover, as reference of the content of each isomer in the mixtures,
their concentrations are calculated using the determined mean ratio
between them.
2.2.1. Standard uncertainties of pressure, temperature and composition.
Pressure. The pressure is set and controlled in the equipment. Its
uncertainty comes from the instrumental uncertainty and the pressure
fluctuations during the experiment. Moreover, there may be small
pressure differences between the point where the pressure is measured
and the zone where equilibrium occurs which is greatly affected by
constant bubbling due to boiling. This factor is not quantifiable but
could affect the uncertainty in the measurement.
The Fischer Minitron VLE (used in the range 10–1026 mbar) has an
instrumental uncertainty of 1 mbar and the Mensor High-Speed Pneu­
matic Pressure Controller model CPC3000 (used at higher pressures) has
an instrumental uncertainty of 0.5 mbar.
During the PrEDO vapor pressure determinations, the experimental
fluctuations are mainly due to the variations of pressure around the set
point in the controller. These pressure variations are at the most 0.1
mbar for the lower pressures and 1 mbar for the highest pressures. As a
result the combined uncertainty considering the instrumental (type B)
and statistical (type A) ones together with the unquantifiable uncer­
tainty due to the distance from the measurement point to the equilib­
rium chamber is 1 mbar for the lower pressures (<700 mbar) and 2 mbar
for the higher pressures.
During the VLE determinations the observed fluctuations of pressure
are higher due to the slight fluctuation in composition in the boiling
chamber. At 10 and 20 mbar the pressure ranged in a +/- 0.2 mbar
interval with a statistical uncertainty of 0.1 mbar. Combining both
instrumental and statistical error together, with the unquantifiable un­
certainty due to the distance between the measurement point and
equilibrium chamber, it gives a combined uncertainty of 1 mbar. In the
system at 1013 mbar the pressure ranged from 1011 to 1015 mbar ac­
counting for a type A uncertainty of 1 mbar. The combined uncertainty
at 1013 mbar is 2 mbar.
Temperature. Regarding the temperature, the uncertainty comes
from the instrumental uncertainty and the pressure fluctuations during
the experiment. The Pt100 sensor of the apparatus has an instrument
uncertainty of 0.1 K.
During the vapor pressure determination experiments, the temper­
ature fluctuations are +/- 0.2 K with a statistical uncertainty of 0.1 K.
The combined instrumental and statistical temperature uncertainty is
therefore of 0.2 K.
During the VLE determinations, the repeated measurement of tem­
perature fluctuations in the equilibrium still shows higher fluctuations
since some changes in the composition also occur in the distillation still,
due to the continuous recirculation of liquid and condensed vapor to the
boiling chamber.
For the PrEDO-3-MEP system the temperature fluctuations reach, for
some mixtures, up to +/- 0.8 K giving a statistical uncertainty of 0.4 K.
This uncertainty along with the instrument one, give a combined stan­
dard uncertainty of 0.5 K.
For the 1-propanal + PrEDO system, when the 1-propanal mole
fraction in the liquid phase is lower than 0.50, the variation of the
boiling temperature with the composition is very large. Any small
change in the composition in the heater produces a high fluctuation in
the boiling temperature with differences even of +/- 3 K with a
J. Garcia-Cano et al. The Journal of Chemical Thermodynamics 175 (2022) 106882

Table 2 3. Results.
Vapor pressure of the PrEDO.
T/K P/mbar 3.1. Vapor pressure
336.6 10
348.6 20 In Table 2, the boiling temperatures at different pressures for the
382.1 100 PrEDO are presented. From these data, the Antoine parameters for the
399.5 200 two compounds were fitted. The parameters issued from this correlation
420.3 400 is shown in Table 3. The experimental data are presented in figure 2
438.8 700
452.3 1013
along with the calculated vapor pressures from the Antoine equation
468.0 1500 (Table 3). It is important to note that the equation is only valid in the
480.5 2000 range 10–2000 mbar. Data extrapolations to smaller pressures using the
The contents in (E)-PrEDO and (Z)-PrEDO
equation can lead to very large relative errors.
were 0.59 and 0.41 mol fraction respectively
in the liquid phase and 0.61 and 0.39 in the 3.2. Vapor-liquid equilibrium
phase vapor. Standard uncertainty: u(com­
positions) = 0.02 mol fraction, u(T) = 0.2 K, The vapor–liquid equilibrium data of the systems 1-propanal +
u(P) = 1 mbar for pressures in the range PrEDO at 1013 mbar and 3-MEP + PrEDO at 10 and 20 mbar are pre­
10–700 mbar and 2 mbar for the highest sented in Table 4 and 5 and have been plotted in figures 3 and 4. The
pressures (1013–2000 mbar). obvious data dispersion of the experimental points in figures 3 and 4 is
produced by the combination of the uncertainties of at least three var­
iables: pressure, temperature and composition. However, only two of
Table 3
Antoine equation parameters* for PrEDO.
them are represented (temperature and composition). It is important to
notice that the pressure effect is very important. For example, consider
A B C Temperature range SD (mbar)
the equilibrium data at 10 mbar with an uncertainty of 1 mbar. Although
PrEDO 6.783 1259.2 − 118.8 336–480 1.85 the uncertainty of the temperature was estimated in only 0.5 K, a
*Antoine equation. log(P(mbar)) = A-B/(T(K) + C). pressure difference of 1 mbar could produce an additional difference in
boiling temperature of 3 K.
No azeotrope has been found for the system 1-propanal + PrEDO
system at 1013 mbar. There exists a high difference in the boiling
temperature between the two compounds (more than 120 K). Although
the Tx curve appears to be horizontal in a composition range it decreases
slightly. Consequently, the system shows a wide range of liquid com­
positions (when the concentrations are higher than 0.5 mol fraction in 1-
propanal) that boils at similar temperatures and with vapors in equi­
librium that are highly concentrated in 1-propanal (more than 0.98 in
mole fraction). Thus, the separation of 1-propanal and PrEDO could be
performed relatively easy.
On the other hand, the vapor–liquid equilibrium data of 3-MEP +
PrEDO system at 10 and 20 mbar shows a smaller difference in boiling
point temperature between the pure compounds. It is significant that the
difference in volatilities between the two compounds is small when the
mixture is poor in 3-MEP. However, the data do not show any inversion
in the relative volatility or a boiling temperature lower than that of the
pure PrEDO, the most volatile compound of this mixture. Accordingly,
this system does not possess an azeotropic behavior.
Figure 2. Vapor pressure of PrEDO at different temperatures. Vapor pressure It has not been possible to apply thermodynamic consistency tests to
calculation using the regression parameters set [Table 3]. the experimental data. Since they are isobaric equilibrium data, it is
needed to dispose of some not known thermodynamic properties such as
statistical uncertainty of 1.8 K in the 0 to 0.25 1-propanal mole fraction the heats of mixing ΔH (although they could be substituted with
range and 0.8 K in the range from 0.25 to 0.50. The combined instru­ different empirical equations to approximately evaluate the integral
mental uncertainty and that due to the fluctuations give a temperature term depending on ΔH). In addition, the vapor pressures of the pure
uncertainty of 2 K in the first range and 0.9 K in the second one. When compounds at each temperature are necessary and they have a great
the 1-propanal concentrations in the liquid phase are greater than 0.50, influence in the test results. In spite of having the Antoine equation’s
the temperature fluctuations are smaller and similar to those of the parameters of each pure compound, their applicability range is out of
system PrEDO + 3-MEP. For these concentrations the temperature un­ the temperature range. For example, consider the Antoine equation’s
certainty is 0.5 K. parameters for the 3-MEP [13] valid in the 375 K – 496 K and 10–1013
Composition. The mole fraction uncertainty is caused by several mbar ranges. The equilibrium temperatures at 10 mbar of the system 3-
factors such as the standards preparation, the chromatographic analysis, MEP + PrEDO are always smaller than 375 K even most of them smaller
the sampling method or other unknown factors. The combined standard than 340 K. At 340 K the vapor pressure of 3-MEP calculated by
uncertainty of the mole fraction is stated to be 0.008 mol fraction. extrapolation with the Antoine equation’s parameters [13] is 0.85 mbar,
more than 10 times smaller than the limit of validity of the equation (10
mbar). Consider that the value of the vapor pressure at that temperature
was 1.15 mbar, only 0.3 mbar higher than the calculated one. The ac­
tivity coefficients calculated with the two pressures would differ in a 35
%. As the activity of the components is the most important term to be
considered in the application of the consistency test, any small error in

4
J. Garcia-Cano et al. The Journal of Chemical Thermodynamics 175 (2022) 106882

Table 4
Vapor-liquid equilibrium data in mole fraction for the 1-propanal (1) + PrEDO (2) at 1013 mbar of pressure. The superscripts (E) and (Z) denote each PrEDO isomer. No
LLE was detected visually. The boiling temperature of pure 1-propanal was taken from literature [21].
(E)
T/K x1 x2 x2 x(Z)
2 y1 y2 y2 (E) y(Z)
2

452.3 0.000 1.000 0.590 0.410 0.000 1.000 0.610 0.390

435.5 0.024 0.976 0.576 0.400 0.402 0.598 0.365 0.233
434.7 0.026 0.974 0.575 0.399 0.431 0.569 0.347 0.222
429.6 0.036 0.964 0.569 0.395 0.543 0.457 0.279 0.178
422.5 0.045 0.955 0.563 0.392 0.639 0.361 0.220 0.141
421.8 0.048 0.952 0.562 0.390 0.671 0.329 0.201 0.128
420.7 0.061 0.939 0.554 0.385 0.692 0.308 0.188 0.120
403.9 0.085 0.915 0.540 0.375 0.824 0.176 0.107 0.069
397.3 0.099 0.901 0.532 0.369 0.867 0.133 0.081 0.052
396.3 0.116 0.884 0.522 0.362 0.877 0.123 0.075 0.048
382.5 0.151 0.849 0.501 0.348 0.928 0.072 0.044 0.028
370.1 0.206 0.794 0.468 0.326 0.958 0.042 0.026 0.016
365.0 0.202 0.798 0.471 0.327 0.967 0.033 0.020 0.013
359.0 0.234 0.766 0.452 0.314 0.975 0.025 0.015 0.010
353.4 0.253 0.747 0.441 0.306 0.983 0.017 0.010 0.007
336.4 0.336 0.664 0.392 0.272 0.991 0.009 0.005 0.004
322.7 0.426 0.574 0.339 0.235 0.996 0.004 0.002 0.002
321.8 0.543 0.457 0.270 0.187 0.998 0.002 0.001 0.001
321.7 0.674 0.326 0.192 0.134 0.999 0.001 0.001 0.000
321.1 1.000 0.000 0.000 0.000 1.000 0.000 0.000 0.000

Standard uncertainty: If x1 < 0.25 then u(T) = 2 K. If 0.25 < x1 < 0.5 then u(T) = 0.9 K. If x1 > 0.5 then u(T) = 0.5 K. u(P) = 2 mbar. u(x) = u(y) = 0.008.

Table 5
Vapor-liquid equilibrium data in mole fraction for the 3-MEP (1) + PrEDO (2) at 10 and 20 mbar of pressure. The superscripts (E) and (Z) denote each PrEDO isomer
The boiling temperatures of pure 3-MEP were taken from literature [13].
10 mbar
(E)
T/K x1 x2 x2 x(Z)
2 y1 y2 y2 (E) y(Z)
2

336.6 0.000 1.000 0.590 0.410 0.000 1.000 0.610 0.390

337.1 0.010 0.990 0.584 0.406 0.003 0.997 0.608 0.389
337.5 0.043 0.957 0.565 0.392 0.021 0.979 0.597 0.382
337.7 0.048 0.952 0.562 0.390 0.021 0.979 0.597 0.382
337.6 0.051 0.949 0.560 0.389 0.021 0.979 0.597 0.382
338.1 0.104 0.896 0.529 0.367 0.036 0.964 0.588 0.376
338.8 0.215 0.785 0.463 0.322 0.064 0.936 0.571 0.365
339.5 0.339 0.661 0.390 0.271 0.063 0.937 0.572 0.365
340.1 0.472 0.528 0.312 0.216 0.078 0.922 0.562 0.360
340.7 0.610 0.390 0.230 0.160 0.105 0.895 0.546 0.349
342.5 0.706 0.294 0.173 0.121 0.137 0.863 0.526 0.337
347.2 0.801 0.199 0.117 0.082 0.196 0.804 0.490 0.314
353.1 0.862 0.138 0.081 0.057 0.305 0.695 0.424 0.271
359.0 0.910 0.090 0.053 0.037 0.514 0.486 0.296 0.190
363.2 0.936 0.064 0.038 0.026 0.630 0.370 0.226 0.144
368.7 0.956 0.044 0.026 0.018 0.792 0.208 0.127 0.081
377.6 1.000 0.000 0.000 0.000 1.000 0.000 0.000 0.000

20 mbar
(E)
T/K x1 x2 x2 x(Z)
2 y1 y2 y2 (E) y(Z)
2

348.6 0.000 1.000 0.590 0.410 0.000 1.000 0.610 0.390

349.0 0.011 0.989 0.584 0.405 0.004 0.996 0.608 0.388
349.8 0.041 0.959 0.566 0.393 0.016 0.984 0.600 0.384
349.8 0.046 0.954 0.563 0.391 0.021 0.979 0.597 0.382
349.8 0.051 0.949 0.560 0.389 0.022 0.978 0.597 0.381
350.4 0.107 0.893 0.527 0.366 0.038 0.962 0.587 0.375
351.2 0.222 0.778 0.459 0.319 0.064 0.936 0.571 0.365
351.5 0.347 0.653 0.385 0.268 0.068 0.932 0.569 0.363
352.3 0.496 0.504 0.297 0.207 0.087 0.913 0.557 0.356
353.4 0.626 0.374 0.221 0.153 0.113 0.887 0.541 0.346
355.4 0.706 0.294 0.173 0.121 0.112 0.888 0.542 0.346
360.0 0.807 0.193 0.114 0.079 0.160 0.840 0.512 0.328
370.5 0.906 0.094 0.055 0.039 0.364 0.636 0.388 0.248
375.4 0.936 0.064 0.038 0.026 0.621 0.379 0.231 0.148
380.3 0.959 0.041 0.024 0.017 0.835 0.165 0.101 0.064
390.5 1.000 0.000 0.000 0.000 1.000 0.000 0.000 0.000

Standard uncertainty: u(T) = 0.5 K, u(P) = 1 mbar u(x) = u(y) = 0.008.

the pressure vapor will produce unrealistic results. Consequently, the application of consistency test to experimental data where the vapor
knowledge of the vapor pressure values is very important and this is the pressure/temperature of the compounds exceed the applicability range
main reason for not applying any consistency test for these data. The of the vapor pressure correlation (for instance the Antoine’s equation

5
J. Garcia-Cano et al. The Journal of Chemical Thermodynamics 175 (2022) 106882

Figure 3. Vapor-liquid equilibrium data of the 1-propanal + PrEDO at 1013 mbar. The boiling temperature of pure 1-propanal was taken from literature [21].

Figure 4. Vapor-liquid equilibrium data of the 3-MEP + PrEDO at 10 and 20 mbar. The boiling temperatures of pure 3-MEP were taken from literature [13].

parameters) could lead to not reliable results.
Finally, all the systems studied present a vapor–liquid equilibrium
that permits an easy separation of the compounds by means of distilla­
tion. In the case of 3-MEP + PrEDO, the mixtures with a high content in
PrEDO would be separated with a higher amount of distillation steps due
to the small difference of volatilities of both compounds. Despite this
fact, the absence of azeotrope would make this separation by distillation
feasible.
3.2.1. Thermodynamic modeling
In order to use the equilibrium data for designing purposes, it is
advisable to have a thermodynamic model that is able to reproduce
accurately the experimental data. First of all, the group contribution
model UNIFAC [22] and its successor modified UNIFAC (Dortmund)
[23] have been tested against the experimental data. To perform this
comparison, the CHEMCAD 7.0 software has been employed. The PrEDO
and 3-MEP compounds were not present in the software’s database.
Therefore, the compounds were defined in the database in function of
the UNIFAC groups forming the molecules. Accordingly, the 3-MEP was
divided into one CH, two CH2, one CH3, two OH and one CH2-O and the
PrEDO into two CH3, two CH2, one CH, two CH2-O and one CH-O. In
addition, the Antoine equation’s parameters presented in Table 3 and in
a previous paper [13] were used to characterize the new compounds. At
this point it is important to mention the temperature ranges for which
the Antoine equation’s parameters were determined: 377–496 K for 3-
MEP and 336–480 K for PrEDO. Since most of the equilibrium

6
J. Garcia-Cano et al. The Journal of Chemical Thermodynamics 175 (2022) 106882

Table 6 Regarding the relative volatilities, UNIFAC overestimates them for the 3-
Wilson equation BIPs and mean temperature and vapor composition deviations. MEP + PrEDO system, while it underestimates them for the other
i j (λij-λii)/R/K) (λ ji - λjj)/R/K) ΔT/K Δy system.
In addition to the UNIFAC calculations, other thermodynamic
1-Propanal PrEDO − 130.38 343.26 7.29 0.0132
3-MEP PrEDO 734.89 5.73 1.75 0.044 models were tested to assess their validity in reproducing the vapor­
–liquid equilibria for these systems. The Wilson, NRTL and UNIQUAC
Molar Volume (mL/mol): 1-Propanal = 73.41, PrEDO = 90.35, 3-MEP = 113.5.
models [24] were used to perform experimental data correlation to
obtain the binary interaction parameters that characterize the studied
systems. The data at all the studied pressures were correlated simulta­
Table 7
UNIQUAC equation BIPs and mean temperature and vapor composition neously. To employ the UNIQUAC model, the values of r and q of the
deviations. molecules that were not present in the database were calculated from
the Ri and Qi of the defining UNIFAC contribution groups mentioned
i j (uij-ujj)/R/K (uji-uii)/R/K ΔT/K Δy
earlier. The PrEDO has an r = 6.1253 and a q = 5.032. The correlations
1-Propanal PrEDO − 70.85 38.11 7.43 0.0135 performed in Chemcad 7.0 produced the BIPs presented in Tables 6–8.
3-MEP PrEDO − 229.53 436.23 1.76 0.0438
In figures 5 and 6 the experimental data are compared with the
calculated data using the different thermodynamic models tested at one
of the studied pressures for each system. The results at the other pres­
Table 8 sures are similar to the ones showed in the figures. All the models pro­
NRTL equation BIPs in K and mean temperature and vapor composition duce similar results, observed in the overlapping of the bubble and dew
deviations.
curves for UNIQUAC, Wilson and NRTL. The differences between
i j (gij-gjj)/R/K (gji-gii)/R /K α ΔT/K Δy experimental and calculated temperatures are important especially for
1-Propanal PrEDO 598.94 − 305.42 0.350 7.00 0.0127 the systems 1-propanal + PrEDO and 3-MEP + PrEDO.
3-MEP PrEDO − 186.28 918.06 0.319 1.79 0.0422 In order to improve the calculated deviations, we tried different
strategies: simultaneous correlation of the equilibrium data of each
system at all the different pressures or separately for each pressure; and
temperatures calculated with the different models are outside of these
parameters depending or not with temperature. None of the obtained
ranges, the calculated vapor pressures have to be determined by means
parameters improve appreciably those shown in Tables 6–8. We think
of extrapolations of the experimental temperatures-vapor pressure
that this poor adjustment of the experimental data should not be
curves of the pure compounds and can lead to not reliable results. As the
attributed merely to a lack of flexibility of the models. As mentioned
calculations were done using those Antoine parameters previously ob­
above, the vapor–liquid equilibrium temperatures are lower than those
tained the results must be used with caution.
of the experimental temperature-vapor pressure curves of the pure
Both UNIFAC models give similar results and seem not able to
compounds fitted with the Antoine’s equation. As a consequence, the
reproduce accurately the boiling temperatures of the liquid phases in
vapor pressures necessary to carry out the calculations must be obtained
any of the system studied. In case of 3-MEP + PrEDO the boiling tem­
by extrapolations of those experimental curves. This introduces un­
peratures calculated are lower than the experimental data. Nevertheless,
certainties that can lead to significant deviations in the models fittings.
in the 1-propanal + PrEDO system the calculated temperatures are
found above the experimental ones. In the same way the dew temper­
atures with UNIFAC are overestimated for the 3-MEP + PrEDO system.

Figure 5. Thermodynamic modeling of 1-propanal + PrEDO at 1013 mbar.

Figure 6. Thermodynamic modeling of 3-MEP + PrEDO at 10 mbar.

7
J. Garcia-Cano et al.
4. Conclusion
Data from the vapor pressure of 2-ethyl-4-ethoxymethyl-1,3‑dioxo­
lane (PrEDO) have been determined and fitted employing the Antoine
equation. This compound can be used as components of a bio-diesel
mixture and can be synthetized from glycerol.
In addition, vapor–liquid equilibrium data of systems such as 1-
propanal + 2-ethyl-4-ethoxymethyl-1,3‑dioxolane + (PA + PrEDO) and
3-ethoxy-1,2-propanediol + 2-ethyl-4-ethoxymethyl-1,3‑dioxolane (3-
MEP + PrEDO) have been determined at different pressures since they
are useful to assess the viability of using the distillation to separate them
during their synthesis. All the three systems studied do not present
azeotrope and could be separated by distillation. However, the vapor­
–liquid equilibrium data cannot be fitted perfectly using the usual
thermodynamic model as NRTL, Wilson, UNIQUAC or UNIFAC.
CRediT authorship contribution statement
Jorge Garcia-Cano: Methodology, Formal analysis, Investigation,
Writing – original draft. Vicente Gomis: Validation, Methodology,
Investigation, Writing – review & editing. Alicia Font: Methodology,
Data curation, Visualization, Writing – review & editing. Vincenzo
Calemma: Conceptualization, Resources, Writing – review & editing,
Funding acquisition, Project administration. Alberto de Angelis:
Conceptualization, Resources, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
Eni S.p.A. is gratefully acknowledged for the financial support.
We gratefully acknowledge G. Assanelli for the synthesis and puri­
fication of 3-ethoxy-1,2-propanediol (3-MEP) and 2-ethyl-4-ethoxy­
methyl-1,3-dioxolane (PrEDO).
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