Technological information

Simultaneous Representation of Liquid-Vapor Equilibrium, Molar Volume and Excess Enthalpy Forero
Vol. 30 (6), 21-34 (2019)
http://dx.doi.org/10.4067/S0718-07642019000600021

Simultaneous Representation of Liquid-Vapor Equilibrium, Molar Volume and

Excess Enthalpy of Complex Mixtures by means of a Peng-Robinson Equation of
State
Luis A. Forero * and Jorge A. Velásquez
Faculty of Chemical Engineering. Bolivarian Pontifical University. AA 56000. Medellín-Colombia (e-mail:
luis.foreroga@upb.edu.co ; jorge.velasquezj@upb.edu.co )

* Author to whom the correspondence should be addressed.

Received Mar. 27, 2019; Accepted May. 24, 2019; Final version Jun. 28, 2019, Published Dec. 2019

Summary

A generalized Peng-Robinson equation of state with the Huron-Vidal mixing rules is used to simultaneously correlate liquid-vapor equilibrium, molar
volume, and excess enthalpies of polar and non-polar mixtures. The concept of homologous series is used to develop generalized expressions that
allow representing the thermodynamic properties of a mixture from the parameters of the pure substances that make it up. The following homologous
series are analyzed: ethanol + n-alkanes, butanol + n-alkanes, 2-methoxy-2-methylbutane + n-alkanes, dimethyl carbonate + n-alkanes,
2-methoxy-2-methylbutane + n-alcohols and dimethyl carbonate + n-alcohols. Generalized expressions in terms of the ratio between the critical
temperature and the critical pressure of the components of the homologous series, were developed to obtain the binary interaction parameters of a
mixture. In general, the results are acceptable and illustrate the ability of the thermodynamic model used to represent all three properties
simultaneously.

Keywords: Peng -Robinson; Huron-Vidal; EdE cubic; Enthalpy of excess; ELV; molar volume

Simultaneous Representation of Liquid-Vapor Equilibria, Molar Volume and Excess

Enthalpy of Complex Mixtures by a PengRobinson-type Equation of State

Abstract

A generalized Peng -Robinson equation of state with the Huron-Vidal mixing rules is selected to correlate vapor-liquid equilibrium, molar volume and
excess enthalpy of polar and non-polar mixtures. The concept of homologous series is used to develop generalized expressions that can be used to
describe the thermodynamic properties of a binarymixture from parameters of the pure substances. The homologous series analyzed are: ethanol +
n-alkanes, butanol + n-alkanes, 2-methoxy-2-methylbutane + n-alkanes, dimethyl carbonate + n-alkanes,

2-methoxy-2-methylbutane + n-alcohols and dimethyl carbonate + n-alcohols.

Generalized expressions to obtain the binary interaction parameters of a mixture were developed as a function of the ratio between the critical
temperature and the critical pressure of the compounds in the homologous series. In general, results are acceptable and show the ability of the
thermodynamic model to represent the three properties simultaneously.

Keywords: Peng -Robinson; Huron-Vidal; cubic EoS; excess enthalpy; VLE; molar volume

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Simultaneous Representation of Liquid-Vapor Equilibrium, Molar Volume and Excess Enthalpy Forero

INTRODUCTION

In 2017, world energy consumption reached 157,000 GWh / year with an annual growth of 2.2% (British Petroleum Company, 2018). Conventional
hydrocarbons are running out, they will be very expensive in the future and their polluting potential is increasingly unacceptable. To overcome these
problems, new fuels or additives are required (Beatrice et al., 2013; Fantozzi et al., 2016). Oxygenated fuels used as additives show great potential to
reduce pollutants in internal combustion engines. Among the most common oxygenated additives are ethanol, butanol, dimethyl carbonate (DMC), and
2-methoxy-2-methylbutane (TAME). Therefore, an accurate prediction of the phase equilibrium,

According to Kontogeorgis and Coutsikos (2012) there are few studies on the use of mixing rules of the type EdE + G AND to describe properties such as
excess enthalpy compared to studies on phase equilibrium. The main application of the cubic equations of state corresponds to the description of phase
equilibrium (Cismondi and Mollerup, 2005). However, some authors have used this type of thermodynamic model to describe the equilibrium and the
excess enthalpy simultaneously. Table 1 presents a summary of the few studies that have been carried out in this field for mixing rules of the EdE + G
type. AND.

Table 1. Main works on the simultaneous adjustment of the phase equilibrium and the excess enthalpy with rules of the
type EdE + GE.

N ° Nature of mixtures Models used Reference

water-polar
Polar-Polar PRSV-MHV1-NRTL
eleven Ohta, 1997
Polar- benzene PRSV-WS-NRTL
Acetonitrile-alkane

isopropanol-water
methanol-benzene PRSV with
4 Orbey and Sandler, 1996
benzene-cyclohexane WS, HV, LCVM, MHV2
acetone-water

carbon dioxide-alcohol
methanol-alkane
tetrahydrofuran-DMF
Escobedo-Alvarado and
8 tetrahydrofutane-cyclohexane PRSV-WS-NRTL
Sandler, 2001
DMF-cyclohexane
benzene-cyclohexane
cyclopentane-tetrachlorethylene

ethanol-cyclohexane
ethanol-tetrahydrofuran
tetrahydrofuran-cyclohexane
6 PRSV-HV-NRTL Djorjevic et al., 1999
DMF-cyclohexane
DMF-tetrahydrofuran
chloroform-tetrahydrofuran

9 alcohol-alkane PRSV-WS-Shen and Lu Shen and Lu, 1997

aromatic alkanes
10 alkane ketones VTPR-GC Ahlers and Gmehling, 2002
aromatics-ketones

4 ester-alkane VTPR-GC Collinet and Gmehling, 2005

ketone-alkane
7 alcohol-alkane UMR-GC Voutsas et al., 2006
aromatic-alkane

PRSV-MHV1-NRTL
4 dieter-alkane Šerbanović et al., 2004
PRSV-MHV2-NRTL

According to Table 1 the simultaneous adjustment has been studied for a very small quantity of mixtures. None of the authors has analyzed more than
11 mixtures and in total there are results reported for 63 mixtures. It is worth noting that in most cases the correlation of both properties has been
studied by adjusting each mixture studied. Only in the works of Gmehling (Ahlers and Gmehling, 2002; Collinet and Gmehling, 2005) and Voutsas et al.
(2006), the development of models has been included

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Simultaneous Representation of Liquid-Vapor Equilibrium, Molar Volume and Excess Enthalpy Forero

generalized through the concept of group contribution. Regarding the nature of the mixtures, a considerable amount of functional groups have not been
covered. In the field of interest of oxygenated gasoline, the results reported by Shen and Lu (1997) for alcohols with alkanes stand out. However, there
are no reports of work for mixtures of the oxygenated-alkane additive or oxygenated alcohol additive.

On the other hand, the general conclusion is that you must work with temperature-dependent parameters if you want to correlate both properties.
According to Orbey and Sanlder (1996) it is not possible to correctly predict the excess enthalpy from the equilibrium adjustment. The opposite case
does not offer good results either. The only way to get good results is by minimizing an objective function that takes into account the deviation from
equilibrium and the deviation in the excess enthalpy (Ohta, 1997; Orbey and Sandler, 1996).

The main purpose of this article is to evaluate the ability of a cubic Peng-Robinson equation of state with Huron-Vidal-NRTL mixing rules to
simultaneously represent phase equilibrium, excess enthalpies, and volumes of mixtures containing polar and nonpolar substances. As shown in recent
publications (Forero and Velásquez, 2016b; Velásquez and Forero,

2017), the selected thermodynamic model correctly describes the liquid-vapor and liquid-liquid equilibrium of mixtures of alkanes with polar compounds.
We will work with mixtures of the type oxygenated-alkano additive or oxygenated-alcohol additive, which constitutes a novelty and the results obtained
will be of interest to the oil industry. The concept of homologous series is used to develop generalized expressions that allow the prediction of different
thermodynamic properties from the parameters of the pure substances that make up a mixture.

THERMODYNAMIC MODEL

The equation of state is of the Peng-Robinson type translated in the volume that can be stated as follows (Forero and Velásquez, 2016a):

RT to
P• • (1)
v • c • bv 2 • 2 v • c • b • • c 2 • 2 cb • b 2

The parameters a, b and c of the mixture can be calculated from the Huron-Vidal mixing rules. The mixing rule used combines the strengths of the
activity models (phase equilibrium modeling of complex mixtures at low pressures) with the strengths of cubic EdEs (phase equilibrium modeling of
simple mixtures at high pressures) (Kontogeorgis and Coutsikos , 2012). The starting point for deriving most of these blending rules comes from
matching the G AND which is obtained from the cubic EDE with the G AND of the activity model at a given pressure. The Huron-Vidal mixing rules were the
first of this type (Huron and Vidal, 1979), which uses an infinite pressure as a reference. The selection of these mixing rules over other available ones is
widely discussed in another publication (Forero and Velásquez, 2016b). Using the NRTL activity model, the calculation of the parameters a, b and c of
the mixture with these rules is as follows:

NC
• •
to • b • •x i
to i
•
G AND
• (2)
•• bi 0.6232 ••
i

NC

b• • xibi (3)
i

NC

c• • xici (4)
i

• NC •
TO hee exp • • hee TOhee
••

NC • •• j
x j RT •
RT • •
••

G AND • RT •x • i
•
(5)
NC • TO ••
•
ki
i • x k exp •• • ki RT • • ••
• k
• •
•

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Simultaneous Representation of Liquid-Vapor Equilibrium, Molar Volume and Excess Enthalpy Forero

Equations (2), (3) and (4) constitute the mixing rules. Equation (5) represents the expression for G AND according to the NRTL model (Renon and
Prausnitz, 1968). The parameters of the pure substances a i, b i and c i are calculated from the temperature of the system, the critical properties (T Ci, P Ci), the
acentric factor • i and the Halm-Stiel polar factor (1967) • i using the following expressions:

P sat (6)
• i • • 1 • log
P c T r • 0.7

P sat
• i • log • 1.7 • i • 1,552 (7)
P c T r • 0.6

2 • H2i•
•
• RT Ci • • T••
to i • 0.45723553 exp • H •1 i 1 • • ••• (8)
P Ci • •
• • T Ci • •• • •
•

RT Ci
b i• 0.07779607 (9)
P Ci

c i• • v L •
• v LExperimental • T r • 0.7
• Not relocated (10)

• ci
H2i• • • ci (eleven)
• ci • 1

•
H 1• ici • 1 (12)
H2i

2• 2.8166 • 2
• ci • 1,34695 • 1.49228 • i • 1.4252 • i • 0.12039 • i i• 0.312707 • i • i (13)

• ci • • 0.37592 • 1.44144 • i • 6.20445 • i • 0.67473 • 2 i• 15,586 • 2 i• 0.70582 • i • i (14)

Equations (6) and (7) are the definitions of the acentric factor and the polar factor respectively. Equation (8) shows the calculation of a i using the alpha
function proposed by Heyen (1980). Equation (9) illustrates the calculation of b i. The translation parameter c i is calculated according to equation (10)
requiring an experimental molar volume for the liquid at T r = 0.7. Equations (11) to (14) show how to calculate the parameters of

Heyen's alpha function in terms of the acentric and polar factors. Parameters • ci Y • ci They are related to the first and second derivatives of the alpha
function evaluated at the critical temperature (Forero and Velásquez, 2016a).

MIXTURES OF INTEREST IN THE FIELD OF OXYGENATED GASOLINES

In order to express the binary interaction coefficients of the Huron-VidalNRTL mixing rules as a function of temperature, the following quadratic
expression was used for the interaction energy parameters of the NRTL model:

TOhee• to • bheeT • c hee

T2 hee (fifteen)

In equation (15), A hee represents the interaction parameters of equation (5). The coefficients a hee b hee and c hee they depend on each mix. Equation (15) is
the one suggested and used by Ahlers and Gmehling (2002) in the VTPR group contribution method. Regarding the mixtures studied, the following
homologous series were used: ethanol-alkanes, butanol-alkanes, TAME-alkanes, DMC-alkanes, TAME-alcohols and DMCalcohols. In total 26 binary
mixtures were analyzed. In the same way as for the liquid-vapor equilibrium (Forero and Velasquez, 2016b), the RT factor was chosen c / P c of the
homologous series of alkanes or alcohols to obtain generalized expressions for a hee b hee and c hee in such a way that the general expression for each
parameter is of the form:

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Simultaneous Representation of Liquid-Vapor Equilibrium, Molar Volume and Excess Enthalpy Forero

2
• RT •c • • RT •c •
p •hee
m hee • • n hee •
• or hee (16)
• P c • SH • P c • SH

In equation (16) p hee represents any of the coefficients a hee b hee or c hee from equation (15). The RT factor c / P c
is that of each member of the homologous series. This factor is proportional to the covolume b i defined in equation 9 and that allows to differentiate the
size of the molecules between the members of a homologous series. In principle, for each homologous series, 18 parameters must be estimated.
However, for each series, the possibility of working with generalized linear expressions was initially studied. In this case the

Data fitting involves the estimation of 12 parameters. For the random mix parameter ( • hee) Two types of expressions were used. For mixtures with the
alkane series, the same expression developed to describe the liquid-vapor equilibrium of mixtures of alcohols with alkanes is used (Forero and
Velásquez, 2016b). The expression used is:

• RT •c •
• 12 • • 0.065 • • 0.459 (17)
• P c • alkanes

For mixtures with the homologous series of alcohols for simplicity, the value of • hee is taken constant and equal to
0.3, since this parameter has little influence on ELV calculations in a wide range from 0.2 to 0.47 (Zhao et al., 2017). For example, for the ELV of the
ethanol-DMC mixture at 40 kPa, varying the alpha from 0.2 to 0.47 changes the DAP from 0.15% to 0.16% and for the ELV of the ethanol-TAME
mixture at 323.15 K and 333.15 K, varying the alpha of
0.2 to 0.47 changes the WTP from 0.40% to 0.21%. It is important to clarify that the DAP mentioned correspond only to the adjustment of ELV data. The
parameters of each homologous series correspond to those that minimize the following objective function:

NS ND j P i NS ND j H Ei • H Ei
• PbEdE
•• b ••
i EdE
FO • 0.8 exp • 0.2 exp (18)
i
j•1i•1
P b exp j•1i•1
H Ei
exp
j j

Equation (18) is formed by the total relative error in the bubble pressure and the excess enthalpy. The weight factors are set arbitrarily. In this case, a
value of 0.8 has been chosen for the bubble pressure error in order to give priority to the phase equilibrium over the excess enthalpy. The objective
function that has been used is similar to that used by Ohta et al. (1997). The minimization of equation (18) was performed for the 6 series studied. The
generalized expressions developed are reported in Table 2. For the three series with n-alkanes, it was found that it is sufficient to simplify equation (16)
to a linear expression. To achieve the simultaneous adjustment of the enthalpy and the bubble pressure of the DMC series with alcohols, it was
necessary to use the quadratic expression.

The results for the ELV and the excess enthalpy after adjusting each of the series analyzed are presented in Table 3. The results for the prediction of
molar volume are also included in the table. The experimental data used are available in the literature, however, given the large number of references,
these have been omitted. For the interested reader, they can be requested from the authors. For each mixture, the mean absolute deviation (DBH) is
calculated for the property of interest (Y) as defined in equation (19):

i
1 ND Y bi exp • Y bEdE 100
DAP •
ND
• i
Y b exp
(19)
i•1

In summary, the results illustrate the ability of the new EoE to represent all three properties simultaneously. The global deviations (average DBH for all
mixtures) are 0.99%, 3.85% and 0.92% for bubble pressure, excess enthalpy and molar volume respectively. The analysis of the DAPs of each property
has the following characteristics: For the ELV, the DAP in the bubble pressure is between 0.10% and 2.68%. 69% of the analyzed mixtures present a
DAP below 1.0%. On the other hand, the absolute deviation in the mole fraction of the vapor has a mean value of 0.007. For the excess enthalpy the
DBH is between 1.42% and 6.30%. In 54% of cases, the WTP has a value lower than 3.85%. The DAP in the volume is between 0.15% and 1.96%. The
DBH is less than 1. 00% for 65% of the mixes. The largest global deviation for excess enthalpy is normal and can be attributed to the inherent
weaknesses of cubic equations of state to predict enthalpies in liquid phase (Valderrama, 2003).

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Simultaneous Representation of Liquid-Vapor Equilibrium, Molar Volume and Excess Enthalpy Forero

Table 2. Generalized parameters of the new EdE for the homologous series.

•• • ) ••
•=( , • = ( •)
• • •••• ℎ •••• • • •••••••
Substance (1)

Substance (2)

to hee kJ / kmol) b hee kJ / kmol K) c hee kJ / kmol K 2)

n-alkanes C 5- C 9

to 12 • 1032 Y • 2820 b 12
• 10.5 Y • 14.7 c 12 • 0.0015 Y • 0.0292
Ethanol

to twenty-one • • 2. 3. 4 Y • 14530 b twenty-one • 6.62 Y • 127.62 c twenty-one • • 0.0304 Y • 0.1642

n-alkanes C 5- C 10

to 12 • 744 Y • 1487 b 12 • 4.0 Y • 3.6 c 12 • 0.0014 Y • 0.0076

Butanol

to twenty-one • 202 Y • 20906 b twenty-one • 2.4 Y • 166.50 c twenty-one • • 0.0126 Y • 0.2538

n-alkanes C 6- C 10

to 12 • • 30.3 Y • 986 b 12
• 7.0 Y • 17.6 c 12 • • 0.0181 Y • 0.0459
TAME

to twenty-one • • 1098 Y • 3696 b twenty-one • 2.8 Y • 11.3 c twenty-one • • 0.0007 Y • 0.0031

n-alkanes C 6- C 9

to 12 • 3928 Y • 9.5 b 12 • • 0.123 c 12 • • 0.0031 Y • 0.0079

DMC

to twenty-one • 2828 Y • 9674 b twenty-one • • 9.52 Y • 39 c twenty-one • 0.0065 Y • 0.0478

n-alcohols C 2- C 4

to 12 • • 1098 x • 920 b 12
• • 0.27 x • 0.005 c 12 • • 0.0349 x • 0.0363
TAME

to twenty-one • 140 x • 3450 b twenty-one • 0.0025 c twenty-one • 0.0007 x • 0.0011

n-alcohols C 1- C 5

2• 0.422 x • 0.189
to12• • 9190 x 2 • 18270 x • 6018 b12• 1.4 x 2 • 1.7 x • 0.5 c 12 • 0.226 x
DMC

2• 0.089 x • 0.063
totwenty-one
• • 1615 x 2 • 5431 x • 2694 b twenty-one • • 0.48 x • 0.74 c twenty-one • • 0.067 x

Figure 1 shows the DBH of each property for each of the six series studied. According to the figure, only for the alcohol-TAME series a DBH close to
2.00% is obtained in the bubble pressure. For the excess enthalpy, three of the six series have a DBH between 4.0% and 5.0%. The largest deviation
corresponds to the ethanol-alkanes series. Finally, the volume results are very good for all series. In all six cases, the WTPs are close to or below 1.0%.

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Simultaneous Representation of Liquid-Vapor Equilibrium, Molar Volume and Excess Enthalpy Forero

Table 3. Results for liquid-vapor equilibrium, excess enthalpy and volume of mixtures with the new EoE.

ELV H AND v

Substance 1 Substance 2 ND T (K) P (kPa) DAP P Dy ND T (K) DAP H AND ND T (K) DAP v

pentane 26 303 10.5-87 0.70 0.003 24 298 6.16 9 298 0.64

hexane fifty 298-333 18-107 0.81 0.006 125 283-318 4.43 9 298 0.81

ethanol heptane 92 303-343 7.8-96 0.77 0.006 40 298-318 4.49 9 298 1.11

octane 56 313-348 4.1-95 0.89 0.004 38 298-318 5.06 9 298 1.65

nonano 27 343 6.3-73 0.61 0.001 39 298-318 5.68

pentane fifteen 303 1.3-82 1.48 0.003 fifteen 298 3.52 eleven 298 0.43

hexane 56 288-333 0.4-77 1.48 0.003 28 288-298 6.22 42 298-308 0.51

butanol heptane 69 313-363 2.5-89 0.98 0.005 31 288-328 5.74 76 288-318 0.87

octane 40 308-373 2.4-73 1.23 0.016 3. 4 288-328 6.30 42 298-308 1.34

dean 42 358-388 5.1-93 0.77 0.008 56 288-298 2.74 42 298-308 1.93

hexane 26 313 19.6-37 0.34 0.001 49 298-313 1.62 18 298 0.83

heptane 26 313 12.3-19.6 0.10 0.001 18 298-313 4.97

TAME
octane 18 323 6.7-29.3 0.61 0.003 18 298-313 3.39 19 298 1.36

dean 77 308-328 0.4-35.5 1.16 twenty 298 2.57

hexane 30 339-360 101.3 0.73 0.004 36 298-318 1.98 73 293-318 0.63

heptane 30 355-369 101.3 0.42 0.005 38 298-318 1.42 58 293-318 0.79

DMC
octane 33 362-396 101.3 0.54 0.005 36 298-318 1.82 72 293-318 1.27

nonano 37 363-421 101.3 2.68 0.008 17 318 2.91 83 293-318 1.47

ethanol 54 323-333 30-59 0.82 0.007 29 298 3.60 eleven 298 0.95

propanol TAME 54 323-333 13-44 2.60 0.01 17 298 4.56 twenty-one 298 0.61

butanol 54 323-333 6-42.5 2.52 0.01 10 298 2.99

methanol 104 314-362 40-101.3 0.49 0.003 fifteen 313 4.10 24 313 0.56

ethanol 152 325-362 40-101.3 0.78 0.012 30 303-313 4.80 18 313 0.33

propanol DMC 121 335-369.7 40-101.3 0.58 0.005 30 303-313 3.23 18 313 0.15

butanol 55 337-388 40-93.32 0.86 48 288-313 3.06 Four. Five288-313 0.28

pentanol 26 364-410 101.3 1.15 0.014 fifteen 303 3.29 Four. Five288-313 0.4

Global 1370 0.99 0.0070 856 3.85 754 0.92

6
ELV HE v

4
DBH (%)

0
Et-OH-alkaneButOH-alkane TAME-alkane DMC-alkane alcohol-TAME alcohol-DMC

Fig. 1. Mean deviations from the model selected for the ELV, the excess enthalpy and the volume of mixtures of the oxygen
additive-alkane and alcohol-oxygen additive type.

To illustrate the performance of the expressions developed, Figures 2 to 4 show the results obtained for each property with some of the series worked.

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Simultaneous Representation of Liquid-Vapor Equilibrium, Molar Volume and Excess Enthalpy Forero

1 40
(to)
(b)
35
0.8
30

0.6 25

P (kPa)
Y1

twenty

0.4 fifteen

10
0.2
5

0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x1 x 1 or and 1

435
(c)
420

405

390
T (K)

375

360

3. 4. 5

330
0 0.2 0.4 0.6 0.8 1
x 1 or Y 1

Fig. 2. Results of the new EdE for the VLE of the series: (a) ■ ethanol- nC5, ▲ ethanol- nC6, ♦ ethanol- nC7, ○ ethanolnC8, ● ethanol- nC9 (b) □
TAME-nC 2 OH at 323.15 K, ○ TAME-nC 3 OH at 323.15 K (c) ○ DMC-nC 6 at 101.3 kPa, △ DMC-nC 9
at 101.3 kPa.

In Figure 2 the results for the liquid vapor equilibrium are reported. In the first case (Figure 2a) the diagram is presented and 1 vs x 1 for mixtures of the
ethanol (1) / n-alkane (2) type. It is illustrated that through simple generalized expressions the variation in azeotropic composition can be quantitatively
described as the n-alkane changes. It is observed in figure 2a that the prediction of the azeotropic points for ethanol-alkane mixtures is correct, although
the deviation cannot be calculated because the specific experimental value of the azeotropic point is not reported. The second case (Figure 2b)
corresponds to the Pxy diagram at 323.15 K for the n-alcohols-TAME series. For the ethanol (1) / TAME (2) mixture, the values calculated with the
new EdE are practically the same as those reported in the literature (see Table 3). For the mixture propanol (1) / TAME (2) it can be observed that there
is a difference between the calculated and experimental values. But nevertheless,

The third case (Figure 2c) corresponds to the Txy diagram at 101.3 kPa for the n-alcohols-DMC series. For the 2 mixtures it can be seen that the values
calculated with the proposed model are quite close to those reported experimentally (see Table 3). The results are similar to those of the
ethanol-nalkanes series, that is, Figure 2c illustrates that it is possible to describe the presence and variation of the azeotropic behavior within a
homologous series from the parameters of the pure substances.

Figure 3 shows the results for the excess enthalpy of the ethanol-n-alkanes series (Figure 3a) and the n-alcohols-DMC series (Figure 3b). The cases
reported are those that present the highest and lowest deviation according to Table 3. The results of both series show the ability of the new EoE to
describe the excess enthalpy from simple generalized expressions. For the ethanoln-alkanes series, some difference between the calculated values
and the experimental data can be observed in the zone diluted in ethanol. Similarly, for the ethanol (1) / nonane (2) mixture there is a slight
overprediction with the evaluated model. For the isotherm illustrated in Figure 3a, the mean deviation of the mixture in question is 8.67%. According to
Park et al. (2001) deviations up to 10. 0% in the excess enthalpy can be obtained when mixing alcohol (1) / alkane (2) type mixtures with an EoE of the
mesh fluid association type. On the other hand, the calculated excess enthalpies are practically the same as those reported in the literature for the
DMC-alcohols series. The results of both series show that the excess enthalpy of a binary mixture can be correctly calculated by means of a simple
cubic EDE and from parameters that depend only on the pure substances.

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Simultaneous Representation of Liquid-Vapor Equilibrium, Molar Volume and Excess Enthalpy Forero

1200 3000
(to) (b)

1000 2500

800 2000
H E ( kJ / kmol)

H E ( kJ / kmol)
600 1500

400 1000

200 500

0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x1 x1

Fig. 3. Results for the excess enthalpy of the series: (a) ◊ ethanol-nC 6 at 318.15 K, △ ethanol-nC 7 at 318.15 K, □ ethanol-nC 8 at 318.15 K, ○ ethanol-nC 9
at 318.15 K. (b) ◊ nC 1 OH-DMC at 313.15 K, △ nC 2 OH-DMC at 313.15 K, □ nC 3 OHDMC at 313.15 K, ○ nC 4 OH-DMC at 313.15 K.

With respect to molar volume, Figure 4 shows the prediction of this property for mixtures formed by DMC and the series of n-alkanes and n-alcohols
respectively. The results confirm the capacity of the new EoE to describe the molar volume of mixtures of different nature. In the two illustrated cases, it
is observed that the calculated volumes are very close to those reported in the literature. The average deviation of each series is less than 1.0%.

0.205 0.110
(b)
(to)
0.100
0.185
0.090
0.165
0.080
v (m 3/ kmol)

v (m 3/ kmol)

0.145 0.070

0.060
0.125
0.050
0.105
0.040

0.085 0.030
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x1 x1

Fig. 4. Results for the molar volume of the series: (a) ◊ DMC-nC 6 at 318.15 K, △ DMC-nC 7 at 318.15 K, □ DMC-nC 8 to
318.15 K, ○ DMC-nC 9 at 318.15 K. (b) ◊ nC 1 OH-DMC at 313.15 K, △ nC 2 OH-DMC at 313.15 K, □ nC 3 OH-DMC at 313.15 K,
○ nC 4 OH-DMC at 313.15 K, x nC 5 OH-DMC at 313.15 K.

COMPARISON WITH OTHER MODELS OF THE LITERATURE

As mentioned before, there are not many studies on the simultaneous representation of phase equilibrium and excess enthalpy. However, in the case of
alcohol-alkane mixtures there are at least two studies reported in the literature. First, Shen and Lu (1997) reported results for 9 mixes with the
Peng-Robinson-Stryjek-Vera EoE and the Wong-Sandler mixing rules. On the other hand, Park et al. (2001) adjusted the enthalpy and equilibrium of 8
alcohol-alkane mixtures with an equation of state of the entangled fluid association type. Table 4 summarizes the deviations reported in the literature
and the results obtained with the new EdE and the generalized expressions in Table 2.

In the first part, the results are presented for three mixtures with the evaluated model and the association EdE of Park et al. (2001). According to the
results, the equilibrium and the excess enthalpy are correctly described with the two models. For enthalpy, the results seem better with the new EoE.
The DAPs with the model of Park et al. (2001) are between 3.61% and 8.88%, while those of the new EdE vary between 5.20% and 6.15%. These
results show that for the analyzed mixtures, the performance of a cubic EdE with mixing rules of the EdE + G type AND it is comparable to that of a
thermodynamic model developed to describe the phenomenon of molecular association.

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Simultaneous Representation of Liquid-Vapor Equilibrium, Molar Volume and Excess Enthalpy Forero

Table 4. Comparison of the new EdE with other EdEs in the literature.

DAP P - ELV DAP H AND

Mixture East Park et al. East Park et al.

T (K) T (K)
job (2001) job (2001)

0.7 1.54 303.15 6.15 3.61 298.2

ethanol-pentane
3.25 2.01 422.6 - - -

0.4 0.47 298 5.92 8.75 283.2

ethanol-hexane
5.2 4.83 298.2

butanol-hexane 1.57 2.5 298.15 5.88 8.88 298.2

DAP P - ELV DAP H AND

Mixture East Shen and Lu East Shen and Lu

T (K) T (K)
job (1997) job (1997)

ethanol-hexane 0.9 1.91 323 5.19 1.49 298

ethanol-heptane 0.8 0.54 303 2.08 5.55 298

butanol-pentane 1.48 1.68 303 3.52 2.8 298

butanol-hexane 2.01 2.31 298 5.99 1.85 298

butanol-heptane 1.43 1.76 323 8.31 4.85 328

butanol-decane 0.84 0.83 373 5.00 0.82 288

In the second part of Table 4, two equations of state and two mixing rules of the type EdE + G are compared AND different In total six mixtures were
analyzed. The equilibrium results are practically the same for the two EdEs. The deviations reported by Shen and Lu (1997) for the excess enthalpy are
smaller than those obtained with the new EoE. Only for the ethanol (1) / heptane (2) mixture are better results obtained with the proposed model. The
difference between the two evaluated models makes sense. The results of the work of Shen and Lu (1997) correspond to the adjustment of a single
isotherm for the liquid-vapor equilibrium and another for the enthalpy of excess of each mixture. The results of the evaluated model correspond to the
generalization of each homologous series. This generalization is carried out with the aim of describing several isotherms for phase equilibrium and
excess enthalpy.

To show that the performance of the two equations is similar, the enthalpy and phase equilibrium were correlated for each mixture to the conditions
reported by Shen and Lu (1997). In Figure 5, the deviations for the excess enthalpy are presented after adjusting the data of the six mixtures in Table 4.
The results effectively show that the deviation of the evaluated model decreases when the mixtures are analyzed individually. Additionally, it can be
seen that the two models produce similar results. For four of the six mixtures analyzed, the difference between the DAPs of both models is less than
1.00%. For the ethanol (1) / heptane (2) mixture, the evaluated model is clearly superior to the EdE of Shen and Lu (1997). Finally,

In summary, it can be established that the proposed model is comparable with other models available in the literature to represent the phase equilibrium
and the enthalpy of excess complex mixtures. Despite the fact that the results may be inferior to models such as that of Shen and Lu (1997), the main
advantage of the new EoE is that it only requires knowledge of the parameters of the pure substances. Additionally, if better results are required for
some specific conditions, it is possible to adjust the model to those conditions. Finally, it is worth clarifying that the generalized expressions in Table 2
should preferably be used under the conditions used during their development (see Table 3). Orbey and Sandler (1996) showed that the predictability of
mixing rules of the EdE + G type AND at high temperatures and pressures may be unsuitable when simultaneously setting enthalpy and equilibrium data
at low temperatures. According to Ohta (1996) and Ahlers and Gmehling (2002), it is advisable to include all possible isotherms during the parameter
regression process to obtain good results over wide temperature ranges. Due to the absence of data on equilibrium and / or excess enthalpy at high
temperatures for most of the mixtures that belong to the homologous series studied, this approach was not used for the evaluated model.

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Simultaneous Representation of Liquid-Vapor Equilibrium, Molar Volume and Excess Enthalpy Forero

9
New generalized EoS
8 Shen and Lu -1997
New optimized EoS
7

6
DAP H AND(%)

0
ethanol-hexane ethanol-heptane butanol-pentane butanol-hexane butanol-heptane butanol-decane
Serie

Fig. 5. Deviations for the enthalpy of excess alcohol (1) / alkane (2) mixtures with generalized VTPRH EdE, adjusted VTPRH EdE and Shen and Lu
(1997) EdE.

On the other hand, there are results reported in the literature only for the liquid-vapor equilibrium with different thermodynamic models.

For example, Forero and Velasquez (2014) used the Patel-Teja EdE (Patel and Teja, 1981) with Wong-Sandler mixing rules (Wong and Sandler, 1992)
and the NRTL activity model developing generalized expressions for the same types. of mixtures of the present work only for the ELV. An overall
deviation for the bubble pressure of 1.09% was reported, with the maximum DAP of 2.43% for the propanol-TAME mixture and a minimum of 0.21% for
the TAME-hexane mixture. These results are similar to those reported in table 3 for the proposed model, whose global deviation is 0.99% and the
maximum and minimum DBH correspond to 2.68% and 0.1% respectively. It is important to highlight that the results of this work include the additional
adjustment of the enthalpy.

For the cases of the ethanol-alkane and butanol-alkane series, Bender et.al (2016) developed a group contribution method for the PC-SAFT model
(Gross and Sadowski, 2001) applied to ELV. They reported an overall deviation in bubble pressure of 5.02%, with the maximum DAP of 9.11% for the
butanolpentane mixture and the minimum of 2.68% for ethanol-hexane. These deviations are greater than those of the proposed model, this makes
sense since it is a group contribution method and not the adjustment of a small group of mixtures (between 3 and 5 per homologous series).

CONCLUSIONS

The evaluated equation of state can be used to simultaneously correctly represent properties such as liquid-vapor equilibrium, volume in liquid phase,
and excess enthalpy of complex mixtures made up of nonpolar and polar substances.

The results are quite good and illustrate the ability of the model to represent the three properties simultaneously for mixtures of oxygenated additives
with alkanes and alcohols. The overall deviations are 0.99%, 3.85%, and 0.92% for bubble pressure, excess enthalpy, and molar volume respectively.

The proposed model is comparable with other models available in the literature to represent the phase equilibrium and the enthalpy of excess mixtures
of oxygenated additives-alkane and oxygenated alcohol additives.

NOTATION

Symbols
a, b, c = mixing parameters of the new equation of state a i, b i, c i = parameters of substance i of the
new equation of state R = universal ideal gas constant (kJ / kmol K) T = temperature (K)

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Simultaneous Representation of Liquid-Vapor Equilibrium, Molar Volume and Excess Enthalpy Forero

P = pressure (kPa)
v = molar volume (m 3/ kmol) x i = mole fraction of substance i G E = Gibss free energy of excess (kJ / kmol) A hee = NRTL parameter related to
the interaction energies between the molecules jei (kJ / kmol) H 1i = parameter 1 of substance i for Heyen's alpha function H 2i = parameter 2
of substance i for Heyen's alpha function

• ci = parameter related to the first derivative of the alpha function at the critical temperature
• ci = parameter related to the second derivative of the alpha function at the critical temperature a hee b hee c hee = coefficients to express
A hee as a function of temperature H E = Excess molar enthalpy (kJ / kmol)

Greek letters
• ij = NRTL parameter of non-random mixing between substances i and j
• i = acentric factor of substance i
• i = polar factor of substance i

Abbreviations
EdE = equation of state
SH = homologous series
FO = objective function DMC =
dimethyl carbonate
TAME = 2-methoxy-2-methylbutane
NS = number of substances ND =
number of data
DBH = mean absolute deviation
Y = property for which you want to calculate the DBH (bubble pressure, excess enthalpy or molar volume) D = deviation

ELV = liquid-vapor equilibrium HV =

Huron-Vidal
NRTL = Non random two liquid

Super / sub indexes

c = critical conditions exp =
experimental
sat = saturation conditions
b = bubble condition
EdE = calculated with the new EdE r = reduced
conditions
L = property in liquid state

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