Thermochimica Acta 659 (2018) 232–241

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

A new analysis method for improving collection of vapor-liquid equilibrium T

(VLE) data of binary mixtures using differential scanning calorimetry (DSC)
⁎
Milad Ahmadi Khoshooei, Dave Sharp , Yadollah Maham, Artin Afacan, Greg Paul Dechaine
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 1H9, Canada

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

Keywords: The method specified in ASTM E1782-14 for using differential scanning calorimetry (DSC) to measure vapor
Differential scanning calorimetry pressure of liquid samples can be extended to binary mixtures to gather vapor-liquid equilibrium (VLE data). In
Vapor-liquid equilibrium previous studies, the main uncertainty was in determining the transition temperature due to evaporation of the
Binary mixtures liquid sample prior to its actual boiling point. Using lids with a pinhole on the sample pan can only mitigate the
Sample temperature
adverse effect of pre-boiling. Present work shows evaluating the second derivative of temperature difference
between the sample and reference temperature instead of the heat-flow curve eliminates the aforementioned
drawback in the result analysis. The results obtained using the proposed method were benchmarked against
published data and excellent agreement with published data indicates that this technique can be reliably used for
experimental measurement of binary VLE data. Also, the results showed to be reproducible and thermo-
dynamically consistent.

1. Introduction
Accurate vapor pressure data is critical for designing chemical
process unit operations. As such, many attempts have been made to
gather this information with high accuracy. The first attempt at such a
measurement was done in 1803 by J. Dalton using a head space method
[1]. Many methods have been applied to obtain highly accurate vapor
pressure data for different compounds. The idea to use differential
thermal analysis (DTA) instruments for determining vapor pressure
data of pure liquids was proposed by Krawetz and Tovrog [2]. Using
differential scanning calorimetry (DSC) as a differential thermal ana-
lysis instrument has been considered an appropriate method to de-
termine vapor pressure data of pure compounds [3,4].
The boiling method is the concept of using DSC for pure liquid
samples [5], and can be applied to a mixture as well. Many different
approaches have been suggested and evaluated to improve this tech-
nique for liquids. However, a quick study in the literature reveals that
DSC is rarely used for determining vapor liquid equilibrium (VLE) data
of binary mixtures [6] because of the main drawbacks of this method:
pre-boiling, deviated baseline and uncertainty in determining transition
temperature. These drawbacks are inherent to the experimental method
and originate from the analysis method.
Since the onset of using DSC for gathering vapor pressure data of
liquids, different ideas have been proposed to overcome these draw-
backs. Wiedemann [7] used thermogravimetry for gathering vapor
pressure data, combined with the Knudsen [8] effusion method and this
combination was widely used. Perkin-Elmer Corp. [9] came up with the
idea of using a pinhole in the sample container to keep the sample
unrestricted. Later, Morie et al. [10] followed the same principle;
however, no specific information regarding the size of the holes was
indicated in their publication. The diameter of the hole should be larger
than the mean free path of the generated vapors to avoid self-pressur-
izing of the pan which elevates the boiling point of the sample. There is
an on-going discussion regarding the size of the holes to obtain the most
accurate results. Tilinski and Puderbach [4] mentioned that small holes
never generated reproducible results, and larger holes usually caused
pre-evaporation. ASTM E1782-14 [11] suggests diameters in the range
of 50–350 μm in general and more specifically holes with diameters in
the range of 50–75 μm for atmospheric pressure are recommended.
However, Butrow and Seyler [12] specified that for a pressure below
5 kPa, a larger diameter size should be used as the diameter range given
in ASTM E1782 results in a sliding edge of the heat flow thermogram.
The other important parameter to control the vapor escape rate is
the heating rate. An appropriate heating rate is key to achieving iso-
thermal boiling. Several studies were done to determine the optimum
heating rate for using DSC for liquids, from which many proposed a
range of 1–10 K/min with the focus on the range of 5–10 K/min
[4,5,10,13,14]. Higher heating rates were also successfully tried by
Silva et al. [6,15] to gather equilibrium data of fatty acid ethyl esters.
The best heating rate for a sample depends on the sample size, such that

⁎
Corresponding author.
E-mail address: dave.sharp@ualberta.ca (D. Sharp).

https://doi.org/10.1016/j.tca.2017.12.010
Received 21 July 2017; Received in revised form 27 November 2017; Accepted 5 December 2017
Available online 08 December 2017
0040-6031/ © 2017 Elsevier B.V. All rights reserved.
M.A. Khoshooei et al. Thermochimica Acta 659 (2018) 232–241

Nomenclature u Standard uncertainty

x Liquid mole fraction
A Antoine equation constants in Eq. (2) y Vapor mole fraction
B Antoine equation constants in Eq. (2)
C Antoine equation constants in Eq. (2) Greek symbols
Aij Binary interaction coefficient
A'ij Adjustable parameters in Margules model α Non-randomness factor in NRTL model
ARD Average relative deviation (%) ΔP˚ Relative vapor pressure deviation from literature values
F Quality factor for pure component vapor pressure con- λij-λii Adjustable parameters in Wilson model
sistency test
gij-gii Adjustable parameters in NRTL model Subscripts/Superscripts
OF Objective function
NC Number of data points b Bubble point cal
P Pressure in kPa c Calculated
Q Quality factor for thermodynamic consistency test exp Experimental (present work)
T Temperature in K i,j Component

a larger sample mass requires a higher heating rate. Also in the case of
having a pinhole in the sample pan, the heating rate should be chosen
in such a way that it prevents diffusion of the generated vapor into the
carrier gas and keeps the diffusion rate less than vapor storage rate in
the pan. The heating rate should be high enough to avoid any gradual
pressure increase in the sample pan due to vapor generation [16]. The
method suggested in ASTM E1782-14 recommends a rate of 5 K/min for
liquid samples. It is also recommended to start a heating procedure at
least 30–40 K below the boiling range of the sample [1,11]. Other re-
searchers used inert materials [5,10] and inter diluents [17] in the
sample to control the rate of vapor scape. Also, a sample size of 1–5 μL/
run for liquid samples is suggested in ASTM E1782-14. Furthermore, an
ideal sample pan should have a small surface area-to-volume ratio and
large vapor head volume.
All aforementioned methods were employed to minimize the ad-
verse effect of pre-boiling; however, once the experiment is done and
the data is gathered, the analysis method plays a key role in getting the
most accurate boiling temperature for a liquid sample from the ther-
mogram. Since the first attempt [10], the boiling temperature has been
determined by extrapolating the onset temperature on the heat flow
curve. The onset temperature is a point at which two tangent lines
meet, one from the baseline and the other one from the sliding part of
the heat flow curve. Since the baseline always deviates from a straight
line due to pre-evaporation of the sample, one can always question the
determined onset value. Also, due to the thermal resistance of the
thermocouples the vertical edge always deviates from being perpendi-
cular to the temperature axis, which makes the traditional method for
determining onset value more questionable. All DSC equipment uses
software to determine the onset value; however, the uncertainty in
determining the onset temperature always exists. Falleiro et al. [18]
evaluated this drawback while gathering vapor pressure data of fatty
acids. Their study showed that choosing different tangent lines in some
cases made considerable differences in determining the onset value
which highlighted the adverse effect of pre-boiling on the analysis
method.
Despite this potential drawback inherited in the analysis method,
DSC is still widely used for determining vapor pressure data of pure
liquids, especially for pure organic compounds [1,4,19]. The idea of
using DSC for pure liquids can be extended to a mixture as well. It is
obvious that the analysis method would be more sensitive to the pre-
boiling in the case of a binary mixture as compared to a pure liquid.
Using DSC for binary mixtures leads to a dynamic equilibrium during
which the liquid phase and the vapor phase are always at equilibrium
but not at the same equilibrium conditions as the initial equilibrium.
However, since the rate of vapor escape is being controlled using a
combination of pans equipped with a pinhole and optimum heating
rate, it is acceptable to use the initial liquid mixture composition as the
equilibrium composition since the rate of vapor escape prior to actual
boiling point is likely negligible. However, there is still a hesitance of
using dynamic equilibrium for mixtures [20]. Also, as there is no
measurement for the vapor phase composition at equilibrium in this
method, no Gibbs-Duhem based thermodynamic consistency test can be
applied to the experimental VLE data [21,22]. However, this technique
has been used for determining vapor-liquid equilibrium (VLE) data of
binary mixtures [6,18].
In the present work, studying the sample temperature in lieu of the
heat-flow curve was evaluated to eliminate the adverse effect of pre-
boiling on the analysis method to obtain the onset temperature. Vapor
pressure data of pure water and VLE data of three well-known binary
mixtures were measured using DSC and analyzed using this novel
analysis principle. The results then were benchmarked against pub-
lished data obtained using conventional methods.
2. Experimental
2.1. Chemicals
The chemicals used in this study were methanol, isopropanol, cy-
clohexane and toluene. To have highly pure chemicals, all four pur-
chased chemicals were selected as high-performance liquid chromato-
graphy (HLPC) grade and their purities were tested using a Scion 436-
GC gas chromatograph (Bruker, Canada), equipped with

Table 1
Provenance and purities of the studied chemical compounds.

Compound CAS Registry Number Supplier Initial Purity/wt% Measured Purity/wt% Analysis Method

Methanol(b) 67−56-1 Fisher Scientific of Canada ≥99.9 99.97 GC(a)

Isopropanol(b) 67−63-0 Fisher Scientific of Canada ≥99.9 99.98 GC
Cyclohexane 110−82-7 Sigma-Aldrich ≥99.9 99.98 GC
Toluene 108−88-3 Sigma-Aldrich ≥99.9 99.97 GC

(a) Gas chromatography.

(b) Water content in methanol and isopropanol was 0.02 wt%.

233
M.A. Khoshooei et al.
30 m × 0.25 mm I.D., 0.50 μm SUPELCOWAX 10 column. No further
purification was done on the purchased chemicals. Table 1 summarizes
the provenance, purities and analysis methods of the utilized chemical
compounds in this study. The methanol/water and isopropanol/water
binary systems were prepared using ultra-distilled water, obtained from
an in-house Reverse Osmosis unit with electrical resistivity of 18.2
MΩ.cm at 298.15 K, which is in accordance with ASTM D1193-
06(2011) [23].
2.2. Equipment
2.2.1. High pressure DSC (HPSDC)
A Mettler Toledo Inc. differential scanning calorimetry (HP DSC1
model) was used for the VLE measurements. This model has the ability
to accurately measure the sample temperature as well as fast and ef-
fective cooling, two features that made it ideally suited for the intended
measurements.
2.2.2. Digital pressure transducer
Nitrogen gas was used to control the sample pressure at 101.3 kPa.
The ambient pressure was measured using a CPE 1114 Fisher Scientific
barometer. A Heise digital pressure gauge (0–10000 kPa), calibrated
with Ruska dead weight tester was used to measure the DSC chamber
pressure (calibration uncertainty of 0.26%).
2.3. Calibration of DSC
The HPDSC thermocouples were calibrated using standard samples
of Zinc and Indium at 101.3 kPa as per the instruction of the equipment
manufacturer as well as ASTM E967-08(2014) [24] and ASTM E968-
02(2014) [25]. The calibration procedure was repeated three times for
both materials. The calibration was always in agreement with the ca-
libration criteria given by the equipment manufacturer and the two
standards. The calibration results and uncertainty were in accordance is
with ASTM E967-08(2014) and ASTM E968-02(2014) and are pre-
sented in Table 2.
2.4. Sample preparation
In preparing the samples, the least volatile compound was first
added to the vial followed by the more volatile one. Compounds were
added by weight to get the desired mole fraction. As per the ASTM
E1782-14 method, the amount of liquid sample should not exceed 5 μL.
In this study, to minimize the effect of pre-evaporation of the sample,
the maximum amount of sample was used. A Mettler Toledo XS105
Dual-Range analytical balance was used for weighing the amount of
liquid sample in the pan. A Mettler Toledo Inc. sealing unit was used to
hermetically seal the pan.
2.5. Experiment
Appropriate information regarding the specifications for liquid
samples can be found in the published ASTM E1782-14 method.
However, after testing different heating rates, 10 K/min was chosen in
this study as the heating rate to diminish the pre-boiling of the liquids,
especially in case of binary mixtures. Hermetic 20 μL Mettler Toledo
aluminum pans were used. According to the precaution which must be
taken to minimize the effect of pre-boiling of the liquid, lids with a
pinhole (Mettler Toledo) were utilized which allowed the samples to be
at the same pressure as the surrounding chamber, i.e. 101.3 kPa. Each
lid had a single 50 μm hole. Nitrogen was used for maintaining the
pressure of the chamber at 101.3 kPa and no carrier gas was used due to
the necessity to keep the pressure constant. After each run, the sample
was removed from the DSC chamber once the chamber reached ambient
temperature.
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Thermochimica Acta 659 (2018) 232–241
3. Results and discussion
The primary result of the DSC measurements is a thermogram
consisting of the heat flow plotted as a function of time. The curve
includes three main features; a baseline, a peak, and the recovery phase.
Since each run starts at ambient temperature and the sample is heated
to its boiling point, the baseline deviates from the straight line due to
pre-boiling; particularly as the sample approaches the boiling point. In
other words, the baseline becomes a curve before the main peak ap-
pears. Using an appropriate pinhole size, adding more liquid sample,
and increasing the heating rate can minimize this effect but pre-boiling
is inevitable. As such, determining a precise onset value is questionable
because a slight change in the chosen point on the baseline or even on
the peak will result in a significant change in the derived boiling tem-
perature [18]. For pure compounds, the leading edge of the peak of the
heat flow diagram should be a vertical line as the temperature remains
constant during boiling. However, in the case of a mixture, the leading
edge will not be a vertical line as the liquid compositions deviates from
the initial compositions as the vapor leaves the pan during the dynamic
equilibrium. Therefore, it is not reliable to study the heat flow curve to
get the boiling point of a mixture. To overcome these potential un-
certainties in determining the boiling point of a liquid sample, a more
rigorous pseudo-analytical method for evaluating the results has been
studied. The proposed method relies on the fact that the only un-
changed parameter is the heating rate, so the temperature curve is a
straight line if there is no phase change. This also applies to both the
initial heating prior the boiling and when the pan is fully depleted. In
the case of a binary mixture, the sample temperature curve deviates the
moment it reaches the boiling point of the sample at its initial com-
position. As the vapor leaves the pan the liquid composition changes
and the slope changes until the last droplet of the liquid boils and the
sample pan is fully depleted. Fig. 1 illustrates this idea for a binary
liquid mixture. It is notable that the slope of the straight line before and
after boiling is the heating rate value. illustrates how evaluating the
sample temperature instead of heat flow curve eliminates the potential
uncertainties in the previous studies to obtain the exact boiling point of
a liquid sample. In this study, to determine the boiling point of a liquid
sample, the difference between the sample pan temperature and the
reference pan temperature has been evaluated. A very small region in
the vicinity around the deviation point is considered, which is called
the scrutinized range. To find the exact transition point, first and second
derivatives of the temperature difference between sample and reference
temperatures have been evaluated.
Fig. 2 illustrates the concept of determining the exact transition
point. The solid line in Fig. 2 is the temperature difference curve, and
the dashed line and dotted lines are the first and second derivatives of
the temperature difference curve, respectively. By definition, at the
boiling point, the slope of temperature difference curve changes.
Therefore, the desired initial boiling point is the point at which the
temperature change direction deviates. From a mathematical point of
view, that is the inflection point of the first derivate of temperature
difference, which is also a maxima or minima of the second derivative.
These derivatives were taken from the STARe software, version 9. The
accuracy of these derivatives has been examined using the raw data for
each curve.
Moreover, the accuracy of this technique is increased by replicating
each run and defining a very narrow and scrutinized scale of time near
Table 2
Temperature and heat flow calibration results for HP DSC 1 as per ASTM E967-08(2014)
[24] and ASTM E968-02(2014) [25].
Material Onset Temperature/K Heat Flow/J g−1
Indium 429.84 ± 0.11 28.45 ± 0.17
Zinc 692.43 ± 0.13 107.67 ± 0.21
M.A. Khoshooei et al. Thermochimica Acta 659 (2018) 232–241

Fig. 1. The concept of evaluating sample tempera-

ture in lieu of the heat flow/considering deviation
point as the onset value.

the deviation point. It is stated in ASTM E1782-14 that this technique Table 3
should pass the vapor pressure gathering for pure water. Therefore, the Vapor pressure/boiling temperature data of pure water at different pressures(a).
current method has been tuned with pure water using the method
Pressure/kPa BoilingTemperature/K Temperature
specified with a heating rate of 10 K/min. Table 3 shows the results for Relative Deviation%
pure water. It is notable that different heating rates were examined for Wagner and Present Study u(T)(b)/K
both pure water and the binary mixture of methanol and water. To PruB [26]
reduce the effect of pre-evaporation of the liquid, 10 K/min has been
92.9 370.91 370.97 0.07 0.0162
chosen for this study. By minimizing the pre-evaporation of the sample, 94.1 371.07 371.21 0.07 0.0377
changes to the liquid composition are minimized. Lower heating rates 101.3 373.15 373.16 0.07 0.0027
lead to gradual vapor escape which results in uncertainties in the initial 395.0 416.31 416.36 0.07 0.0120
liquid composition at the boiling temperature. The accuracy of the re- 585.0 430.99 430.98 0.07 0.0023
592.0 431.45 431.66 0.07 0.0487
sults shown in Table 3 compared to published data proves that the
791.0 443.09 442.53 0.07 0.1238
technique is valid for pure water. The absolute error is less than 0.15% 1091.0 456.85 456.44 0.07 0.0897
for low to medium pressure and less than 0.6% for higher pressures. It 1392.0 467.93 467.41 0.08 0.1111
also shows that this method is valid for a wide pressure range from 1689.0 477.15 476.35 0.10 0.1677
atmospheric up to 2 MPa. The reproducibility of this technique was also 2088.0 487.71 486.41 0.08 0.2665

examined by replicating each run three times. The maximum mean

deviations for samples in a small pressure range are shown in Table 4,
which demonstrates that the method is reproducible. The reproduci-
bility is proven as the maximum mean deviation is not higher than
0.05 K which is 0.05% of the actual boiling temperature. Therefore, the
proposed method generates highly accurate results for pure liquids and
can be used for a pressure range of 0–2 MPa.
(a) Standard uncertainty u for pressure is u(P) = 0.2 kPa.
(b) Combined standard uncertainty includes calibration uncertainty.
Since this new technique showed excellent agreement with the
published data for pure water, it can be concluded that dissolved
oxygen did not affect the results generated using this technique as water

Fig. 2. Determining the transition point of the liquid

sample using the second derivative of the sample and
reference temperature curve.

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M.A. Khoshooei et al. Thermochimica Acta 659 (2018) 232–241

Table 4 B
log P = A −
Standard deviation and standard uncertainty for pure water’s boiling point measurements C+T (1)
at different pressures(a).
The experimental VLE data were correlated by minimizing the fol-
Pressure/kPa Boiling temperature/K u(T)(b)/K Max Mean Deviation/K lowing objective function (OF) using forward-tangent Newton method:

92.9 370.97 0.07 0.01 OF = ∑i (Tcalculated − Texperimental)2

93.0 370.99 0.07 0.05 (2)
93.5 371.09 0.07 0.05
94.1 371.21 0.07 0.02 The binary interaction parameters were calculated by minimizing
101.3 373.16 0.07 0.01 the OF described above to a tolerance of 1.00 × 10−7 K2. It is notable
that there is no unique set of binary interaction parameters for a binary
(a) Standard uncertainty u for pressure is u(P) = 0.2 kPa.
mixture and these parameters vary based on the minimization method,
(b) Combined standard uncertainty includes calibration uncertainty.
tolerance, and initial guess. Tables 7, 9 and 11 show the calculated
binary interaction parameters for all binary mixtures using four dif-
always contains dissolved oxygen.
ferent activity coefficient models. These tables show how accurate each
As stated, using DSC for binary mixtures leads to a dynamic equi-
model can correlate the experimental data in terms of max and mean
librium during which the liquid phase and the vapor phase are always
temperature deviations.
at equilibrium but not at the same equilibrium conditions as the initial
equilibrium. However, since the rate of vapor escape is being controlled
3.1. Methanol-water binary mixture
using pans equipped with a pinhole and optimum heating rate, it is
acceptable to use the initial liquid mixture compositions as the equili-
For the methanol-water binary pair, all four activity coefficient
brium compositions for both the components in the mixture as the rate
models modelled the experimental data very well as the mean deviation
of vapor escape prior to actual boiling point is always negligible. As
of the temperature difference between the experimental and calculated
such, using DSC would be considered as a total pressure measurement
temperatures is less than 0.20 K in all cases. The fitted Margules curve is
type technique for determining VLE data of binary mixtures.
shown in Fig. 3. Also, this system has no azeotrope. The experimental
The proposed method was also tested using three binary mixtures:
VLE data using the proposed method in this study are in excellent
cyclohexane-toluene; methanol-water and isopropanol-water, and the
agreement with two published series of data as shown in Fig. 3. Fig. 3
results were benchmarked against published values. All the experiments
shows the T-xy curve for the system containing methanol and water.
for these binary mixtures were done at a constant pressure of 101.3 kPa.
Table 6 also gives the raw experimental T-x data for this system. The
The first binary pair contains hydrocarbons; while the other two are
binary interaction parameters for this binary pair also are shown in
aqueous mixtures containing alcohols. The cyclohexane-toluene binary
Table 7.
pair was selected to examine the accuracy of the proposed method for a
hydrocarbon–hydrocarbon mixture which has little or no non-ideality.
3.2. Isopropanol-water binary mixture
Also, these two components have a difference of 30 K in their boiling
temperatures at atmospheric pressure, which also makes it an ideal
The system containing isopropanol and water has a homogeneous
choice to see accuracy of the system according to Henry’s law. The
positive azeotrope which means the boiling point of the mixture at the
other two binary pairs were selected to be aqueous systems because of
azeotrope point is less than the boiling point of both of its pure con-
the wide range of industrial applications for aqueous systems. The other
stituents. Except for the Margules model, the other three activity
reason for selecting methanol-water system is to study the accuracy of
coefficient models correlated the experimental VLE data very well. Of
this new method for gathering VLE data of a non-ideal system. Finally,
those three, the van Laar model had the least min deviation of tem-
the isopropanol-water binary mixture was chosen to evaluate the ability
perature difference between measured temperature and calculated
of this method to accurately capture a highly non-ideal system con-
temperature. The fitted van Laar curve is shown in Fig. 4. Table 8 shows
taining an azeotrope.
the measured temperature data as well as the calculated temperature
Various activity coefficient models including Margules, Wilson, van
and vapor composition for a wide range of liquid composition. More
Laar and NRTL were explored because they are of interest when there is
data points were examined for this binary mixture to accurately capture
no information available for the vapor phase whereas using equation of
the azeotrope point. The calculated binary interaction parameters are
state models requires appropriate initial guesses for both temperature
reported in Table 9. The azeotrope point is at a liquid mole fraction of
and vapor composition for convergence. The thermodynamic modeling
xisopropanol = 0.6825 and equilibrium temperature of 353.15 K. To
was done using the bubble point measurements algorithm at constant
evaluate the accuracy of this technique, the data published by other
pressure developed by Smith et al. [27]. Once the equilibrium tem-
researchers are reported in this work. The azeotropic composition and
perature was calculated using this method, the vapor phase composi-
temperature are reported by Brujnes & Bogart [32], Wilson and Simons
tion was calculated based on the equality of fugacities between two
[33] and, Kirk and Othmer [34] to be xisopropanol = 0.6813 and
phases.
T = 353.31 K, xisopropanol = 0.6870 and T = 353.25 K, and
For thermodynamic modeling of experimental VLE data, vapor
xisopropanol = 0.6753 to 0.6813 and T = 353.45 to 353.55 K, respec-
pressure data for all pure components is necessary. The Antoine equa-
tively. Excellent agreement for the azeotrope point data with the al-
tion (Eq. (1)) was used for the vapor pressure term in thermodynamic
ready published data in the literature is observed which shows the
modeling of the experimental data [27]. The constants of the Antoine
equation were obtained from DECHEMA® Chemistry Data Series, Vol. 1,
Table 5
pt. 1, Vapor-liquid equilibrium data for aqueous-organic systems, for Antoine equation constants (A, B & C) and molar volumes of pure components (V) are
methanol-water and isopropanol water, and Vol. 1, pt. 6a, Vapor-liquid obtained from DECHEMA® Chemistry Data Series, Volume 1 [28].
equilibrium data for aliphatic hydrocarbons C4–C6, for cyclohexane-
toluene mixture [28]. The constants used in Eq. (1) are given in Table 5. Component A B/K C/K V/mL mol−1

Also, the molar volume of pure liquids used in the Wilson model was Water 7.19611 1730.63 −39.724 18.07
obtained from Appendix A of the same references given above [28]. Methanol 7.20577 1582.271 −33.424 40.73
These data are tabulated in Table 5. Isopropanol 8.00309 2010.33 −20.514 76.92
Cyclohexane 5.97626 1206.47 −50.014 108.75
Toluene 6.07567 1342.31 −53.963 106.85

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M.A. Khoshooei et al. Thermochimica Acta 659 (2018) 232–241

373 Table 7
Binary interaction parameters (A12, A21 & α) and mean and max temperature deviation
for the methanol-water system.
368

GE Model A12(a) A21(a) α Max ΔT Mean ΔT

363 Deviation/K Deviation/K

358 Margules 0.6964 0.5931 N/A 0.81 0.19

van Laar 0.6958 0.6016 N/A 0.81 0.20
353 Wilson −82.64 279.44 N/A 0.81 0.19
NRTL 27.90 163.34 0.2976 0.80 0.19
348
(a) The binary interaction parameters A12 and A21 for Margules model are dimensionless
343
and are defined as A12 = A'12/(RT) and A21 = A'21/(RT), where A'12 and A'12 are the
adjustable parameters in Margules model. The binary interaction parameters A12 and A21
for Wilson are in Kelvin and defined as: A12 = (λ12 − λ11)/R, A21 = (λ21 − λ22)/R and
338
for NRTL are also in Kelvin and defined as: A12 = (g12 − g22)/R, A21 = (g21 − g11)/R,
where R is the universal gas constant. Parameters (λij − λii) and (gji-gjj) are the adjustable
333
parameters in Wilson and NRTL models, respectively [28].
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Fig. 3. T-xy curve for the methanol-water system at P = 101.3 kPa: (○) present work T-xy
points; ( ) present work fitted Margules curve; (Δ) Fu et al. [29]; (□) Verhoeye and
Schepper [30]; (×) Gao et al. [31].

ability of current technique to capture the azeotrope point of a highly

non-ideal system such as isopropanol-water mixture.

3.3. Cyclohexane-toluene binary mixture

The last binary pair studied in this article is the cyclohexane-toluene

system. As mentioned, this mixture was chosen to evaluate the accuracy
and validity of using DSC for gathering VLE data of binary mixtures
containing hydrocarbons. Again, all the four mentioned activity coef-
ficient models were able to correlate the experimental data very well,
and in no case, did the mean deviation of the difference between cal-
culated temperature and measured temperature exceed 0.1 K. This
system does not exhibit any non-ideality as shown in Fig. 5. The ex-
perimental VLE data are shown in Table 10 and the calculated binary
interaction parameters are shown in Table 11. The calculated vapor
phase compositions are also showed in Table 10. The experimental data
are in great agreement with previously published data. This shows that
the proposed method for gathering VLE data is valid and accurate for
binary mixtures containing hydrocarbons.
3.4. Thermodynamic consistency test
Every set of experimental VLE data must be thermodynamically
consistent, in other words, the Gibbs-Duhem equation shall be satisfied
for the gathered data. Many consistency tests have been proposed in the
literature. As per the phase rule or Duhem’s Theorem for a binary
mixture, the degree of freedom is two, one of which must be an ex-
tensive variable. Since most of the published VLE data for binary
mixture are either isobaric or isothermal, either pressure or tempera-
ture is known. Hence, by measuring only one intensive variable – either
Fig. 4. T-xy curve for the isopropanol-water system at P = 101.3 kPa: (○) present work T-
xy points; ( ) present work fitted van Laar curve; (Δ) Sevgili [35]; (□) Gironi and
Lamberti [36]; (×) Lin and Tu [37]; (◊) Wilson and Simons [38]; (+) Arce et al. [39].
liquid or vapor composition for component i – the system is thermo-
dynamically known. That is, every PTx or PTy equilibrium data is in-
trinsically made consistent [22]. Once all the PTxy data is available, the
system is over-specified and as such a thermodynamic consistency test
is required to evaluate the equilibrium data set. However, for PTx and
PTy data, a quality factor can be applied both to the pure components’
vapor pressure/boiling temperature and middle points’ bubble/dew
temperature or pressure. Kang et al. [43] proposed a comprehensive
quality assessment for testing the thermodynamic consistency of a set of
VLE data. They mentioned that most of the tests are applicable only if
all set of PTxy data are experimentally measured. However, it is stated
in their publication that pure component test can be applied to PTx
data. In this test, for both components the relative deviation between
the measured vapor pressure at the boiling point and the available
vapor pressure data in the literature is calculated and the quality factor

Table 6
Experimental Temperature (T), standard uncertainty of temperature u(T) and liquid composition (x)(a) and calculated vapor composition (y) for the methanol-water system at
P = 101.3 kPa (using Margules activity coefficient model).

xMethanol Texp/K u(T)(b)/K Tcalc/K yMethanol,calc xMethanol Texp/K u(T)(b)/K Tcalc/K yMethanol,calc

0.0000 373.16 0.07 373.15 0.0000 0.3176 350.52 0.07 350.54 0.6919
0.0129 371.91 0.07 371.10 0.0829 0.4246 347.93 0.08 347.59 0.7574
0.0376 367.95 0.07 367.74 0.2087 0.5560 344.68 0.08 344.80 0.8193
0.0752 363.76 0.07 363.67 0.3452 0.7394 341.75 0.07 341.62 0.8935
0.1196 359.80 0.07 359.97 0.4555 0.8584 340.01 0.07 339.77 0.9407
0.1740 356.38 0.07 356.52 0.5485 0.8999 339.12 0.07 339.15 0.9576
0.2424 352.97 0.07 353.26 0.6290 1.0000 337.78 0.07 337.70 1.0000

(a) Standard uncertainties u are u(P) = 0.2 kPa and u(xi) = 0.0003.
(b) Combined standard uncertainty includes calibration uncertainty.

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Table 8
Experimental Temperature (T), standard uncertainty of temperature u(T) and liquid composition (x)(a) and calculated vapor composition (y) for the isopropanol-water system at
P = 101.3 kPa (using van Laar activity coefficient model).

xIsopropanol Texp/K u(T)(b)/K Tcalc/K yIsopropanol,calc xIsopropanol Texp/K u(T)(b)/K Tcalc/K yIsopropanol,calc

0.0000 373.15 0.07 373.15 0.0000 0.2621 354.22 0.07 354.18 0.5453
0.0009 372.42 0.07 372.46 0.0252 0.3447 353.97 0.07 354.07 0.5501
0.0018 371.70 0.07 371.81 0.0487 0.4445 353.61 0.07 353.80 0.5670
0.0063 368.77 0.07 369.00 0.1449 0.5560 353.28 0.07 353.52 0.6029
0.0221 362.51 0.07 362.79 0.3314 0.6329 353.16 0.07 353.42 0.6392
0.0372 359.41 0.07 359.56 0.4159 0.6781 353.15 0.07 353.43 0.6654
0.0573 357.15 0.07 357.14 0.4747 0.6868 353.17 0.07 353.44 0.6709
0.0847 355.66 0.07 355.49 0.5133 0.8037 353.47 0.07 353.80 0.7603
0.1304 354.74 0.07 354.48 0.5373 0.8909 354.11 0.07 354.41 0.8500
0.1485 354.59 0.07 354.34 0.5409 0.9420 354.72 0.07 354.94 0.9141
0.1553 354.55 0.07 354.30 0.5418 0.9685 355.13 0.07 355.27 0.9515
0.1874 354.42 0.07 354.22 0.5441 1.0000 355.71 0.07 355.71 1.0000

(a) Standard uncertainties, u are u(P) = 0.2 kPa and u(xi) = 0.0003.
(b) Combined standard uncertainty includes calibration uncertainty.

Table 9 above and the results are given in Table 12. In this study, the relative
Binary interaction parameters (A12, A21 & α) and mean and max temperature deviation deviation in vapor pressure for all the pure components is less than 0.01
for the isopropanol-water system. or 1% of the reported vapor pressure values using Antoine equation
GE Model A12(a) A21(a) α Max ΔT Mean ΔT
constant given in Table 5. Hence, the quality factor for the pure com-
Deviation/K Deviation/K ponent consistency test is equal to 1, F = 1. This indicates that the
results have the highest thermodynamic consistency from the pure
Margules 2.4408 0.7965 N/A 1.58 0.65 component test point of view. Cunico et al. [44] also used this method
van Laar 2.6872 1.1397 N/A 0.33 0.18
for testing the thermodynamic consistency of their PTx data collected
Wilson 304.77 528.33 N/A 0.67 0.35
NRTL −19.46 750.15 0.3008 0.35 0.20 using DSC. They have reported relative deviation in vapor pressure of
monocaprylin to be 7.14% and 5.11% at the pressure of 1.2 and
(a) The binary interaction parameters A12 and A21 for Margules model are dimensionless 2.5 kPa, respectively. They also reported that te ΔP° at the pressure of
and are defined as A12 = A'12/(RT) and A21 = A'21/(RT), where A'12 and A'12 are the 1.2 and 2.5 kPa to be 3.48% and 3.02% for palmitic acid and to
adjustable parameters in Margules model. The binary interaction parameters A12 and A21
be < 0.01% and 2.13 for methyl stearate. That is, the best quality factor
for Wilson are in Kelvin and defined as: A12 = (λ12 − λ11)/R, A21 = (λ21 − λ22)/R and
for NRTL are also in Kelvin and defined as: A12 = (g12 − g22)/R, A21 = (g21 − g11)/R, they achieved is F = 0.28 as per Eq. (3). This shows significant im-
where R is the universal gas constant. Parameters (λij − λii) and (gji-gjj) are the adjustable provement in VLE data gathering using the analysis method specified in
parameters in Wilson and NRTL models, respectively [28]. this study.
Cunico et al. [44] also used a modified version of the Van Ness
consistency test, which is the Qtest,1 of TDE program from NIST [37], to
381 evaluate the consistency of the intermediate points of the experimental
PTx data. However, it is notable that this modified test cannot be based
376 on the Gibbs-Duhem equation as the full set of experimental PTxy is not
available. This method associates a quality factor to an experimental
371
VLE data within 0, the lowest quality factor, and 1, the highest quality
factor. The quality factor is calculated as below:
366 1 100 NC Tiexp − Ticalc
Qtest,1 =
1 + ARD%
where ARD % =
NC
∑i Tiexp (4)
361
where, ARD% represents the average relative deviation between the
356 experimental and calculated boiling temperatures using thermo-
dynamic models and data correlation. In Eq. (4), NC is the number of
351
data points in the collected VLE data set. This methodology was also
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 used in this study to assess the quality of gathered VLE data using DSC
and results are shown in Table 13. As shown, the quality factor for all
Fig. 5. T-xy curve for the cyclohexane-toluene system at P = 101.3 kPa: (○) present work three binary pairs is very high indicating that the data are thermo-
T-xy points; ( ) present work fitted van Laar curve; (Δ) Delzenne [40]; (□) Black [41]; dynamically consistent. This is highlighted once the maximum achieved
(×) Cholinski et al. [42]; (◊) Myers [43]. quality factor using this test reported by Cunico et al. [36] is 0.893.

is calculated as below: 3.5. Method comparison with traditional onset temperature

2
F pure = , for Δ P1° and ΔP°2 ≥ 1 ;
100(Δ P1° + ΔP2°)
They mentioned that Fpure = 1, if the relative deviation of vapor
pressure for pure compounds is not greater than 0.01P°. Here ΔP° re-
presents the relative deviation between the experimental vapor pres-
sure at the boiling point and the vapor pressure value from the litera-
ture at the same boiling temperature. All three binary pairs studied in
this research were tested using the pure component test described
As stated, in all the previous studies, which used DSC for gathering
(3)
VLE data of binary mixtures, the onset temperature was considered as
the bubble point of each sample. As such, the inherent uncertainty in
determining the onset temperature using a software always existed in
those studies. Falleiro et al. [45] tried using five different points on the
deviated baseline and considered the average value as the onset tem-
perature while they were gathering vapor pressure data of ethyl esters.
However, they did not consider different tangent lines on the peak side

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Table 10
Experimental Temperature (T), standard uncertainty of temperature u(T) and liquid composition (x)(a) and calculated vapor composition (y) for the cyclohexane-toluene system at
P = 101.3 kPa (using van Laar activity coefficient model).

xCyclohexane Texp/K u(T)(b)/K Tcalc/K yCyclohexane,calc xCyclohexane Texp/K u(T)(b)/K Tcalc/K yCyclohexane,calc

0.0000 383.60 0.07 383.76 0.0000 0.5994 361.15 0.07 361.05 0.7864
0.0295 382.12 0.07 382.04 0.0761 0.6985 358.97 0.07 358.92 0.8444
0.0515 380.72 0.07 380.81 0.1283 0.8018 356.94 0.07 356.98 0.8983
0.0987 378.33 0.07 378.34 0.2287 0.9000 355.27 0.07 355.36 0.9473
0.1838 374.31 0.07 374.35 0.3781 0.9530 354.42 0.07 354.55 0.9744
0.2964 369.86 0.07 369.86 0.5293 0.9703 354.19 0.07 354.29 0.9836
0.3968 366.50 0.07 366.49 0.6330 0.9839 353.84 0.07 354.09 0.9910
0.4981 363.57 0.07 363.57 0.7171 1.0000 353.82 0.07 353.86 1.0000

(a) Standard uncertainties u are u(P) = 0.2 kPa and u(xi) = 0.0003.
(b) Combined standard uncertainty includes calibration uncertainty.

Table 11 Table 13
Binary interaction parameters (A12, A21 & α) and mean and max temperature deviation Average relative deviation (ARD) of measured and calculated temperatures and quality
for the cyclohexane-toluene system. factor assessment (Qtest,1) and for all binary mixtures using the modified Van Ness test
[44].
GE Model A12(a) A21(a) α Max ΔT Deviation/ Mean ΔT Deviation/
K K Binary Pair ARD (%) Quality Factor (Qtest,1)

Margules 0.1611 0.3253 N/A 0.27 0.10 Methanol-Water 0.0536 0.949

van Laar 0.1763 0.3713 N/A 0.25 0.08 Isopropanol-Water 0.0505 0.952
Wilson 114.23 240.03 N/A 0.25 0.08 Cyclohexane-Toluene 0.0205 0.980
NRTL 295.94 167.17 0.3364 0.26 0.09

(a) The binary interaction parameters A12 and A21 for Margules model are dimensionless
and are defined as A12 = A'12/(RT) and A21 = A'21/(RT), where A'12 and A'12 are the
adjustable parameters in Margules model. The binary interaction parameters A12 and A21
for Wilson are in Kelvin and defined as: A12 = (λ12 − λ11)/R, A21 = (λ21 − λ22)/R and
for NRTL are also in Kelvin and defined as: A12 = (g12- g22)/R, A21 = (g21 − g11)/R,
where R is the universal gas constant. Parameters (λij − λii) and (gji − gjj) are the ad-
justable parameters in Wilson and NRTL models, respectively [28].
to determine the onset value. In another study, the same method was
used for determining VLE data of fatty acids using DSC [18], however,
the tangents from the peak were not considered. In the present study,
the bubble temperatures of the aforementioned mixtures were calcu-
lated using the proposed method and the onset temperature method.
Table 14 shows the comparison of both methods at different composi-
tions for each binary mixture. There are significant differences in the
uncertainty of the onset values compared to the proposed method. The
onset method was used successfully in the past [15,45]. However, it
was used only for heavy molecules with much higher boiling tem-
perature range of the compounds. Therefore, the effect of pre-boiling
was much less in those studies. Furthermore, the previous studies
[6,15,45] used the heating rate of 15–25 K/min, which also reduces the
effect of pre-boiling. However, to assume dynamic equilibrium, such a
high heating rate cannot be used for more volatile compounds with
significantly lower boiling temperature range. It is also noteworthy that
measurements analyzed using the onset temperature approach have one
order of magnitude higher standard uncertainty compared to the
measurements using the proposed method in this study. The standard
uncertainty of the onset temperature values is in the range of those
reported by Falleiro et al. [45] and Cunico et al. [44] for similar ana-
lysis method, which further highlights the intrinsic drawback of using
onset temperature as the boiling point of a liquid sample. Therefore, the
traditional method is not as reliable as the proposed method. Figs. 3–5
show that the proposed method predicts the measured present study
data as well as literature values accurately.
4. Conclusions
The accuracy and validity of using differential scanning calorimetry
for determining vapor-liquid equilibrium data of binary mixtures was
assessed by evaluating sample temperature instead of studying the heat
flow curve. The method proved to be feasible and practical in the case
of both pure compounds as well as binary mixtures of volatile compo-
nents. Since the method covered various types of binary mixtures in-
cluding aqueous systems and non-aqueous systems, as well as a highly
non-ideal system such as the isopropanol-water mixture containing an
azeotrope, the method can be used to gather accurate VLE data of
different types of binary pairs. For the first time, the effect of pre-
boiling and sloped baseline as a result is eliminated by using the
pseudo-analytical method proposed in this study. This tackles the in-
trinsic uncertainty in determining the onset temperature in the previous
studies. Also, the results showed reproducibility and high thermo-
dynamic consistency. Two different thermodynamic consistency tests
were applied to the experimental VLE data. The results showed the
highest consistency level for the pure component test. Also, high quality
factor for the intermediate points test was observed which shows the
high level of thermodynamic consistency of the measurements.
Using DSC for determining VLE data has some important and con-
siderable advantages in comparison to the conventional methods such
as small samples (∼5 μL/run), rapid data collection (∼5–8 min/run)

Table 12
Experimental vapor pressure comparison with the literature vapor pressure values using Antoine equation [28] (Thermodynamic consistency test for pure components)(a).

Component Temperature/K u(T)/K Pressure/kPa Calculated Vapor Pressure using Antoine Equation/kPa Relative Vapor Pressure Deviation (%)

Water 373.16 0.07 101.3 101.3 0.05

Methanol 337.78 0.07 101.3 101.6 0.32
Isopropanol 355.71 0.07 101.3 101.3 < 0.01
Cyclohexane 353.82 0.07 101.3 101.2 0.12
Toluene 383.60 0.07 101.3 100.8 0.47

(a) Standard uncertainty u for pressure is u(P) = 0.2.

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Table 14
Experimental bubble temperature (Tb) measurement data comparison between traditional onset temperature analysis (Tbonset) and the analysis method proposed in this study
(Tbcurrentmethod) at P = 101.3 kPa and the standard uncertainty, u, of both the methods (u(Tbonset) and u (Tbcurrentmethod)).

Binary Mixture Composition Tbonset/K u(Tbonset)(b)/K Tbcurrentmethod/K u(Tbcurrentmethod)(b)/K

Methanol-Water xMethanol = 0.0376 366.54 0.15 367.95 0.07

xMethanol = 0.1196 358.67 0.19 359.80 0.07
xMethanol = 0.3176 349.14 0.15 350.52 0.07
xMethanol = 0.8584 339.16 0.25 340.01 0.07
xMethanol = 0.8999 337.89 0.14 339.12 0.07

Isopropanol-Water xIsopropanol = 0.0221 361.04 0.29 362.51 0.07

xIsopropanol = 0.1304 353.21 0.22 354.74 0.07
xIsopropanol = 0.6329 352.40 0.18 353.16 0.07
xIsopropanol = 0.6781 353.38 0.26 353.15 0.07
xIsopropanol = 0.6868 352.46 0.21 353.17 0.07

Cyclohexane-Toluene xCyclohexane = 0.0515 382.13 0.21 380.72 0.07

xCyclohexane = 0.1838 373.18 0.32 374.31 0.07
xCyclohexane = 0.5994 359.99 0.12 361.15 0.07
xCyclohexane = 0.8018 355.87 0.12 356.94 0.07
xCyclohexane = 0.9703 353.23 0.28 354.19 0.07

(a) Standard uncertainties u are u(P) = 0.2 kPa and u(xi) = 0.0003.
(b) Combined standard uncertainty includes calibration uncertainty.

and no dissolved gas effects. As such, using DSC combined with the
analysis method proposed in this study, can be confidently used to
gather vapor pressure data for pure compounds and VLE data for dif-
ferent kinds of binary mixtures.
Acknowledgments
This work was supported by Alberta Crop Industry Development
Fund (ACIDF) under grant number 2011C013R. Also, the authors spe-
cially thank Dr. Arno de Klerk for providing access to his laboratory
facilities and DSC machine.
References
[1] M. Casserino, D.R. Blevins, R.N. Sanders, An improved method for measuring vapor
pressure by DSC with automated pressure control, Thermochim. Acta 284 (1996)
145–152, http://dx.doi.org/10.1016/0040-6031(96)02923-1.
[2] A.A. Krawetz, T. Tovrog, Determination of vapor pressure by differential thermal
analysis, Rev. Sci. Instrum. 33 (1962) 1465–1466, http://dx.doi.org/10.1063/1.
1717805.
[3] C.G. Biliaderis, Differential scanning calorimetry in food research—a review, Food
Chem. 10 (1983) 239–265, http://dx.doi.org/10.1016/0308-8146(83)90081-X.
[4] D. Tilinski, H. Puderbach, Experiences with the use of DSC in the determination of
vapor pressure of organic compounds, J. Therm. Anal. Calorim. 35 (1989) 503–513,
http://dx.doi.org/10.1007/BF01904452.
[5] R.J. Seyler, Parameters affecting the determination of vapor pressure by differential
thermal methods, Thermochim. Acta 17 (1976) 129–136, http://dx.doi.org/10.
1016/0040-6031(76)85019-8.
[6] L.Y. Akisawa Silva, R.M. Matricarde Falleiro, A.J.A. Meirelles, M.A. Krähenbühl,
Vapor–liquid equilibrium of fatty acid ethyl esters determined using DSC,
Thermochim. Acta 512 (2011) 178–182, http://dx.doi.org/10.1016/j.tca.2010.10.
002.
[7] H.G. Wiedemann, Applications of thermogravimetry for vapor pressure determi-
nation, Thermochim. Acta 3 (1972) 355–366, http://dx.doi.org/10.1016/0040-
6031(72)87049-7.
[8] M. Knudsen, The molecular current of gases through openings and the effusion,
Ann. Phys. 29 (1909) 999–1016.
[9] Perkin-Elmer Corp., Thermal Analysis Newsletter No. 7, Norwalk (1967) 4–8.
[10] G.P. Morie, T.A. Powers, C.A. Glover, Evaluation of thermal analysis equipment for
the determination of vapor pressure and heat of vaporization, Thermochim. Acta 3
(1972) 259–269, http://dx.doi.org/10.1016/0040-6031(72)80002-9.
[11] ASTM International, ASTM E1782-14, Standard Test Method for Determining Vapor
Pressure by Thermal Analysis, West Conshohocken, PA, 2014, pp. 1–7, http://dx.
doi.org/10.1520/E1782.
[12] A.B. Butrow, R.J. Seyler, Vapor pressure by DSC: extending ASTM e 1782 below
5 kPa, Thermochim. Acta 402 (2003) 145–152, http://dx.doi.org/10.1016/S0040-
6031(02)00604-4.
[13] H.R. Kemme, S.I. Kreps, Vapor pressure determination by differential thermal
analysis, Anal. Chem. 41 (1969) 1869–1872, http://dx.doi.org/10.1021/
ac60282a004.
[14] E.M. Barrall, Precise determination of melting and boiling points by differential
thermal analysis and differential scanning calorimetry, Thermochim. Acta 5 (1973)
377–389, http://dx.doi.org/10.1016/0040-6031(73)80016-4.
[15] L.Y.A. Silva, R.M.M. Falleiro, A.J.A. Meirelles, M.A. Krähenbühl, Determination of
the vapor pressure of ethyl esters by differential scanning calorimetry, J. Chem.
Thermodyn. 43 (2011) 943–947, http://dx.doi.org/10.1016/j.jct.2011.01.017.
[16] K. Jones, R. Seyler, Differential scanning calorimetry for boiling points and vapor
pressure, NATAS Notes 26 (1994) 61–69.
[17] E.M. Barrall, R.S. Porter, J.F. Johnson, Heats of transition for nematic mesophases,
J. Phys. Chem. 68 (1964) 2810–2813, http://dx.doi.org/10.1021/j100792a011.
[18] R.M.M. Falleiro, A.J.A. Meirelles, M.A. Krähenbühl, Experimental determination of
the (vapor + liquid) equilibrium data of binary mixtures of fatty acids by differ-
ential scanning calorimetry, J. Chem. Thermodyn. 42 (2010) 70–77, http://dx.doi.
org/10.1016/j.jct.2009.07.008.
[19] M.D. Contreras, F. Girela, A. Parera, The perfection of a method for the determi-
nation of the temperature/vapour-pressure function of liquids by differential
scanning calorimetry, Thermochim. Acta 219 (1993) 167–172, http://dx.doi.org/
10.1016/0040-6031(93)80494-U.
[20] E.W. Washburn, J.W. Read, The laws of concentrated solutions. VI. The general
boiling-point law, J. Am. Chem. Soc. 41 (1919) 729–741, http://dx.doi.org/10.
1021/ja02226a004.
[21] P.T. Eubank, B.G. Lamonte, J.F. Javier Alcarado, Consistency tests for binary VLE
data, J. Chem. Eng. Data 45 (2000) 1040–1048, http://dx.doi.org/10.1021/
je9902692.
[22] H.C. Van Ness, Thermodynamics in the treatment of vapor/liquid equilibrium (VLE)
data, Pure Appl. Chem. 67 (1995) 859–872, http://dx.doi.org/10.1351/
pac199567060859.
[23] A.S.T.M. International, ASTM D1193-06(2011) Standard Specification for Reagent
Water, West Conshohocken, PA, 2011, pp. 1–6, http://dx.doi.org/10.1520/D1193-
06R11.
[24] ASTM International, ASTM E967-08(2014) Standard Test Method for Temperature
Calibration of Differential Scanning Calorimeters and Differential Thermal
Analyzers, West Conshohocken, PA, 2014, pp. 1–4, http://dx.doi.org/10.1520/
E0967.
[25] A.S.T.M. International, ASTM E968-02(2014) Standard Practice for Heat Flow
Calibration of Differential Scanning Calorimeters, West Conshohocken, PA, 2014,
pp. 1–5, http://dx.doi.org/10.1520/E0968.
[26] W. Wagner, A. Pruß, The IAPWS formulation 1995 for the thermodynamic prop-
erties of ordinary water substance for general and scientific use, J. Phys. Chem. Ref.
Data 31 (2002) 387–535, http://dx.doi.org/10.1063/1.1461829.
[27] J.C. Smith, H.C. Van Ness, M.M. Abbott, Introduction to Chemical Engineering
Thermodynamics, McGraw-Hill Book Company, New York, 2005.
[28] J. Gmehling, U. Onken, W. Arlt, P. Grenzheuser, U. Weidlich, B. Kolbe, J. Rarey,
Chemistry Data Series, Volume I Vapor-Liquid Equilibrium Data Collection,
DECHEMA, Frankfurt,G er, 1986.
[29] Y. Fu Jinyan, Wang, Ku, Hu, Studies on vapor-liquid and liquid-liquid vapor equi-
libria for the ternary system methanol-methyl methacrylate-water: (I) three binary
systems, J. Chem. Ind. Eng., 4 (1989) 1–13.
[30] L. Verhoeye, H. De Schepper, The vapour–liquid equilibria of the binary, ternary
and quaternary systems formed by acetone, methanol, propan-2-ol, and water, J.
Appl. Chem. Biotechnol. 23 (1973) 607–619, http://dx.doi.org/10.1002/jctb.
5020230807.
[31] D. Gao, H. Zhang, P. Lücking, H. Sun, J. Si, D. Zhu, H. Chen, J. Shi, Computation of
isobaric vapor-liquid equilibrium data for binary and ternary mixtures of methanol,
water, and ethanoic acid from T, p, x and HEm measurements, J. Thermodyn. 2012
(2012) 1–13, http://dx.doi.org/10.1155/2012/641251.
[32] A.S. Brunjes, M.J.P. Bogart, Vapor-liquid equilibria for commercially important
systems of organic solvents: the binary systems ethanol-n-butanol, acetone-water
and isopropanol-water, Ind. Eng. Chem. 35 (1943) 255–260, http://dx.doi.org/10.
1021/ie50398a032.

240
M.A. Khoshooei et al.
[33] A. Wilson, E.L. Simons, Vapor-liquid equilibria, Ind. Eng. Chem. 44 (1952)
2214–2219.
[34] R.D. Kirk, D.F. Othmer, second ed., Encyclopedia of Chemical Technology vol. 16,
John Wiley and Sons Inc., New York, 1968.
[35] L.M. Sevgili, A. Senol, Isobaric (vapour + liquid) equilibrium for (2-pro-
panol + water + ammonium thiocyanate): fitting the data by an empirical equa-
tion, J. Chem. Thermodyn. 38 (2006) 1539–1545, http://dx.doi.org/10.1016/j.jct.
2006.04.006.
[36] F. Gironi, L. Lamberti, Vapour-liquid equilibrium data for the water-2-propanol
system in the presence of dissolved salts, Fluid Phase Equilib. 105 (1995) 273–286,
http://dx.doi.org/10.1016/0378-3812(94)02610-D.
[37] Y.-F. Lin, C.-H. Tu, Isobaric vapor–liquid equilibria for the binary and ternary
mixtures of 2-propanol, water, and 1,3-propanediol at P = 101.3 kPa: effect of the
1,3-propanediol addition, Fluid Phase Equilib. 368 (2014) 104–111, http://dx.doi.
org/10.1016/j.fluid.2014.02.006.
[38] A. Arce, A. Arce, J. Martı́nez-Ageitos, E. Rodil, A. Soto, (Vapour + liquid) equili-
brium of (DIPE + IPA + water) at 101.32 kPa, J. Chem. Thermodyn. 35 (2003)
871–884, http://dx.doi.org/10.1016/S0021-9614(03)00018-1.
[39] A. Delzenne, Equilibre liquide-vapeur du systeme cyclohexane-toluene sous la
pression atmospherique, Bull. Soc. Chim. Fr. (1961) 295.
241
Thermochimica Acta 659 (2018) 232–241
[40] C. Black, Multicomponent vapor-liquid equilibria from binary data, Ind. Eng. Chem.
51 (1959) 211–218.
[41] J. Choliński, M. Palczewska-Tulińska, A. Szafrańska, D. Wyrzykowskastankiewicz,
A new method of parameter adjustment and diagnostic checks on gamma models
used in vapor–liquid equilibrium calculations, Chem. Eng. Sci. 36 (1981) 173–181,
http://dx.doi.org/10.1016/0009-2509(81)80061-9.
[42] H.S. Myers, Binary mixtures of naphthenes and aromatics, Ind. Eng. Chem. 48
(1956) 1104–1108, http://dx.doi.org/10.1021/ie50558a041.
[43] J.W. Kang, V. Diky, R.D. Chirico, J.W. Magee, C.D. Muzny, I. Abdulagatov,
A.F. Kazakov, M. Frenkel, Quality assessment algorithm for vapor-liquid equili-
brium data, J. Chem. Eng. Data. 55 (2010) 3631–3640, http://dx.doi.org/10.1021/
je1002169.
[44] L.P. Cunico, D.S. Damaceno, R.M. Matricarde Falleiro, B. Sarup, J. Abildskov,
R. Ceriani, R. Gani, Vapour liquid equilibria of monocaprylin plus palmitic acid or
methyl stearate at P = (1.20 and 2.50) kPa by using DSC technique, J. Chem.
Thermodyn. 91 (2015) 108–115, http://dx.doi.org/10.1016/j.jct.2015.07.033.
[45] R.M. Matricarde Falleiro, L.Y. Akisawa Silva, A.J.A. Meirelles, M.A. Krähenbühl,
Vapor pressure data for fatty acids obtained using an adaptation of the DSC tech-
nique, Thermochim. Acta 547 (2012) 6–12, http://dx.doi.org/10.1016/j.tca.2012.
07.034.