Accepted Manuscript

Title: Vapor-liquid equilibria for the binary systems ethylene +

water, ethylene + ethanol, and ethanol + water, and the ternary
system ethylene + water + ethanol from Gibbs-ensemble
molecular simulation

Author: Y. Mauricio Muñoz-Muñoz Mario Llano-Restrepo

PII: S0378-3812(15)00109-0
DOI: http://dx.doi.org/doi:10.1016/j.fluid.2015.03.007
Reference: FLUID 10477

To appear in: Fluid Phase Equilibria

Received date: 15-1-2015

Revised date: 26-2-2015
Accepted date: 2-3-2015

Please cite this article as: Y.Mauricio Muñoz-Muñoz, Mario Llano-Restrepo,

Vapor-liquid equilibria for the binary systems ethylene + water, ethylene +
ethanol, and ethanol + water, and the ternary system ethylene + water
+ ethanol from Gibbs-ensemble molecular simulation, Fluid Phase Equilibria
http://dx.doi.org/10.1016/j.fluid.2015.03.007

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Vapor-liquid equilibria for the binary systems ethylene + water, ethylene +
ethanol, and ethanol + water, and the ternary system ethylene + water +
ethanol from Gibbs-ensemble molecular simulation

Y. Mauricio Muñoz-Muñoz, Mario Llano-Restrepo*mario.llano@correounivalle.edu.co

School of Chemical Engineering, Universidad del Valle, Ciudad Universitaria Melendez,

Building 336, Apartado 25360, Cali, Colombia

*
Corresponding author. Tel: + 57-2-3312935; fax: + 57-2-3392335
 2

Highlights

 We corroborated the validity of a set of Lennard-Jones plus point-charge intermolecular

potential models for ethylene, water, and ethanol.

 These models are capable of predicting the experimental VLE phase diagrams of the
binary systems ethylene + water, ethylene + ethanol, and ethanol + water.

 Molecular simulation predictions for the VLE of the ternary system ethylene + water +
ethanol are in very good agreement with predictions made by means of the PRSV2-WS-
UNIQUAC thermodynamic model.
 3

Abstract
The conceptual design of a reactive separation process for the hydration of ethylene to ethanol
requires reliable vapor-liquid equilibrium (VLE) data for the ternary system ethylene + water +
ethanol. Due to the paucity of experimental data points in the VLE phase diagrams that have
been reported for that system, molecular simulation looks appealing in order to predict such data.
In this work, the Gibbs-ensemble Monte Carlo (GEMC) method was used to calculate the VLE
of the pure components (ethylene, water, and ethanol), the binary subsystems (ethylene + water,
ethylene + ethanol, and ethanol + water), and the ternary system (ethylene + water + ethanol). A
set of previously validated Lennard-Jones plus point-charge potential models were chosen for the
pure components, and the validity of these models was corroborated from the good agreement of
the GEMC simulation results for the vapor pressure and the VLE phase diagrams of those
components with respect to calculations carried out by means of the most accurate (reference)
multiparameter equations of state currently available for ethylene, water, and ethanol. These
potential models were found to be capable of predicting the available VLE phase diagrams of the
binary subsystems: ethylene + water at 200 and 250°C, ethylene + ethanol at 150, 170, 190, 200,
and 220°C, and ethanol + water at 200, 250, 275, and 300°C. Molecular simulation predictions
for the VLE phase diagrams of the ternary system at 200°C and pressures of 30, 40, 50, 60, 80,
and 100 atm, were found to be in very good agreement with predictions previously made by use
of a thermodynamic model that combines the Peng-Robinson-Stryjek-Vera equation of state, the
Wong-Sandler mixing rules, and the UNIQUAC activity coefficient model. The agreement
between the predictions of these two independent approaches gives confidence for the
subsequent use of molecular simulation to predict the combined phase and chemical equilibrium
of the ternary system and check the validity of predictions previously made by means of the
thermodynamic model.

Keywords: Vapor-liquid equilibrium, phase diagrams, ternary systems, ethylene hydration,

petrochemical ethanol.
 4

Nomenclature

AAD average absolute deviation

ARD average relative deviation

kB Boltzmann constant
k ij interaction parameter in the Wong-Sandler mixing rule

N number of molecules

P pressure

P sat vapor pressure

q positive electric charge

q negative electric charge

T absolute temperature

U configurational energy

Greek symbols

 correction factor for the Lorentz combining rule

H v heat of vaporization
u ij characteristic energy parameter of the UNIQUAC model

U T change of total configurational energy

 energy parameter of the LJ potential model

 molar density

 size parameter of the LJ potential model

Subscripts

Coul Coulombic

LJ Lennard-Jones
 5

T total

Superscripts

real real-space contribution

recip reciprocal-space contribution

self self-interaction contribution
 6

1. Introduction

The economics of the production of petrochemical ethanol by the direct hydration of ethylene
might improve by the application of the concept of process intensification, i.e., by making the
reaction and the separation of the product (ethanol) and the reactants (ethylene and water) to
occur simultaneously in the same piece of equipment. In the intensified process, ethanol would
be produced from ethylene by means of a vapor-liquid mixed-phase hydration, by feeding
gaseous ethylene and liquid water into a reactive separation column [1].

In a previous study [1], we used a thermodynamic model that combines the Peng-Robinson-
Stryjek-Vera (PRSV2) equation of state [2, 3], the Wong-Sandler (WS) mixing rules [4], and the
UNIQUAC activity coefficient model [5] in order to correlate the available vapor-liquid
equilibrium (VLE) experimental data for the binary subsystems (ethylene + water, ethylene +
ethanol, and ethanol + water) at 200°C. From the optimum values obtained for the adjustable
parameters of the PRSV2-WS-UNIQUAC thermodynamic model, both the VLE and the
combined phase and chemical equilibrium (CPE) of the ternary system (ethylene + water +
ethanol) were predicted at 200°C and various pressures. The thermodynamic model predicts that
for many values of the ethylene to water feed mole ratio, the vapor-liquid mixed-phase hydration
of ethylene achieves equilibrium conversions much higher than those calculated for a vapor-
phase reaction that would hypothetically occur at the same conditions of temperature, pressure,
and ethylene to water feed mole ratio. Another prediction of the thermodynamic model is that the
reactive phase diagram of the ternary system exhibits a critical point at 200°C and 155 atm. Due
to the paucity of experimental data points in the VLE phase diagrams reported by Tsiklis et al.
[6] for the ternary system (in the absence of chemical reaction), it is difficult to make a direct
assessment of the validity of the predictions made by the thermodynamic model for both the VLE
and the CPE of the ternary system. However, an indirect assessment of those predictions is
 7

possible by use of another method of predictive nature and entirely independent from the
thermodynamic model, such as molecular simulation.

The Gibbs-ensemble Monte Carlo (GEMC) method of molecular simulation [7-14] has been
used widely and successfully by many authors for the computation of VLE phase diagrams of
binary and ternary systems of industrial interest. In this work, the GEMC method was carefully
implemented in order to compute the VLE of the pure components (ethylene, water, and ethanol),
the binary subsystems (ethylene + water, ethylene + ethanol, and ethanol + water), and the ternary
system (ethylene + water + ethanol). A set of previously validated Lennard-Jones plus point-
charge potential models [15-17] were chosen for ethylene, water, and ethanol. The outline of the
paper is as follows. The intermolecular potential models for the pure components are presented
in Section 2. The simulation methods are described in Section 3. In Section 4, simulation results
for the pure components are reported, discussed, and compared with calculations carried out by
means of the most accurate (reference) equations of state currently available for ethylene, water,
and ethanol [18-20]. In Section 5, simulation results for the VLE phase diagrams of the binary
subsystems are reported, discussed, and compared with both the available experimental data [21-
23] and the correlation results obtained by use of the PRSV2-WS-UNIQUAC thermodynamic
model described in our previous study [1]. In Section 6, simulation results for the VLE phase
diagrams of the ternary system are reported, discussed, and compared with the few experimental
data available [6] and, more importantly, with the predictions previously made [1] by means of
the thermodynamic model.

2. Intermolecular potential models

As explained in more detail below, the Lennard-Jones (LJ) plus point-charge intermolecular
potential models recently devised by Weitz and Potoff [15] for ethylene, Huang et al. [16] for
water, and Schnabel et al. [17] for ethanol were chosen for the present work due to their greater
accuracy relative to other models available for those components. These potential models are
planar and rigid (i.e., they have no internal degrees of freedom).
 8

The potential model for ethylene devised by Weitz and Potoff [15] comprises two LJ sites for the
methylene (CH2) united-atom groups, each site with a positive point charge q  0.85 e , where e
is the electron charge, and separated by a distance of 1.33 Å. A negative point charge
q  1.70 e is located in the middle point (center of mass, COM) between the two LJ sites. The
point charges and the distance between the CH2 groups reproduce the gas-phase quadrupole
moment of ethylene. The local coordinates and charges of the sites, and the size and energy
parameters of the LJ potential are given in Table 1. With this model, Weitz and Potoff used the
histogram-reweighting technique [14, 24] in combination with grand canonical ensemble Monte
Carlo simulations to compute the VLE of pure ethylene and the binary mixtures ethylene +
carbon dioxide, ethylene + xenon, and ethylene + n-butane. Saturated liquid densities of pure
ethylene were predicted in very close agreement with experiment whereas its vapor pressure was
reproduced with a deviation of 2%. By comparing their potential model with other two united-
atom models (NERD and TraPPE-UA) available for ethylene, Weitz and Potoff [15] found that
their proposed model yields more accurate predictions for the saturated liquid densities, vapor
pressures, critical density, and normal boiling point of ethylene. However, no predictions for the
heat of vaporization of ethylene were reported by Weitz and Potoff.

The potential model for water devised by Huang et al. [16] is an optimized version of the TIP4P
model for water proposed 30 years ago by Jorgensen et al [25]. The optimized TIP4P model by
Huang et al. comprises three point charges and one LJ site. One negative point charge (NPC)
q  0.8391 e is located at a distance of 0.20482 Å from the oxygen (O) atom, on the line
bisecting the HOH angle, and two positive point charges, each with a value q  0.41955 e , are
located on each hydrogen (H) atom. Each hydrogen atom is located at a distance of 1.1549 Å
from the oxygen atom. The only LJ site of the model is located on the oxygen atom. The local
coordinates and charges of the sites and the size and energy parameters of the LJ potential are
given in Table 1. With this model, Huang et al. used the grand equilibrium method [26] in
combination with NPT-ensemble simulations and the gradual insertion method [27, 28] to
compute the VLE of pure water and the binary systems water + ethylene oxide and water +
ethylene glycol. The vapor pressure, the saturated liquid densities, and the heat of vaporization of
pure water were reproduced with deviations of 7.2%, 1.1%, and 2.8%, respectively. By
 9

comparing their potential model with other four united-atom models (TIP4P, TIP4P-Ew, TIP4P /
2005, and SPC / E) available for water, Huang et al. [16] found that their proposed model yields
more accurate predictions for the saturated liquid densities, vapor pressures, and heat of
vaporization of water.

The potential model for ethanol devised by Schnabel et al. [17] comprises three LJ sites and three
point charges. The LJ sites are located on the methyl (CH3) and methylene (CH2) united-atom
groups, and on the oxygen atom of the hydroxyl (OH) group. Positive point charges
q  ,1  0.2556 e and q  , 2  0.44151 e are located on the CH2 group and the hydrogen atom of the

OH group, respectively. A negative charge q  0.69711 e is located on the oxygen atom of the
OH group. The CH2 group is located at a distance of 1.9842 Å from the CH3 group. The oxygen
atom of the OH group is located at a distance of 1.71581 Å from the CH2 group. The hydrogen
and oxygen atoms of the OH group are separated by a distance of 0.95053 Å. The (CH3)(CH2)O
and (CH2)OH angles are 90.950° and 106.368°, respectively. The local coordinates and charges
of the sites and the size and energy parameters of the LJ potential are given in Table 1. With this
model, Schnabel et al. used the NPT + test particle method of Möller and Fischer [29, 30] in
combination with the gradual insertion method [27, 28] to compute the VLE of pure ethanol, and
the grand equilibrium method [26] to compute the VLE of the binary system ethanol + carbon
dioxide. The vapor pressure, the saturated liquid densities, and the heat of vaporization of pure
ethanol were reproduced with deviations of 3.7%, 0.3%, and 0.9%, respectively. By comparing
their potential model with other two united-atom models (OPLS-UA and TraPPE-UA) available
for ethanol, Schnabel et al. [17] found that their proposed model yields more accurate predictions
for the saturated liquid densities, vapor pressures, and heat of vaporization of ethanol.

3. Simulation methods
In contrast to the methods used in the works by Weitz and Potoff [15], Huang et al. [16], and
Schnabel et al. [17], the Gibbs ensemble Monte Carlo (GEMC) method [7-14] was used in the
present work, in order to compute the VLE of the pure components ethylene, water, and ethanol,
the binary subsystems (ethylene + water, ethylene + ethanol, and ethanol + water) and the ternary
mixture (ethylene + water + ethanol). The canonical version (GEMC-NVT) of the GEMC method
 10

was applied to the pure components and its isothermal-isobaric version (GEMC-NPT) was
applied to the binary and ternary systems. Our two previous implementations of the GEMC
method [31, 32] were taken as the starting point to develop the computational strategies
explained in Sections 3.1 and 3.2.

There are three types of random moves for the GEMC method when dealing with rigid
molecules: translational displacement and rotation of molecules inside each of the two simulation
boxes, volume changes for the boxes, and transfer of molecules between the two boxes (i.e,
simultaneous removal and insertion moves). These moves are accepted or rejected in accordance
with a particular probability recipe that involves the calculation of the total intermolecular
potential energy change U T  U Tn  U To between the new (trial) ( U Tn ) and the old ( U To )
configurations. The probability formulas for the acceptance or rejection of the three kinds of
moves in the GEMC method have been discussed in various papers [7-14] and also in the
textbook by Frenkel and Smit [33]. The total intermolecular energy was computed as the sum of
non-electrostatic and electrostatic contributions. The non-electrostatic contribution ( U LJ ) was

calculated by means of the Lennard-Jones pair potential model and the electrostatic contribution
( U Coul ) was calculated by means of the Ewald summation method [33-37] for the Coulombic

potential, as follows:

U T  U LJ  U Coul  U LJ
trunc
 U LJ
corr
 U Coul
real
 U Coul
recip
 U Coul
self
(1)

where U LJ
trunc
is the truncated LJ potential, U LJ
corr
is the corresponding LJ long-range correction

[33, 34, 38], and U Coul

real
, U Coul
recip
, and U LJself are the real space, reciprocal space, and self-interaction

terms of the Ewald sum, respectively [33-37]. Periodic boundary conditions and the minimum
image convention, as explained in detail by Allen and Tildesley [34], were applied to the
calculation of the total intermolecular potential energy. For the rotational moves required for
water and ethanol, the orientational displacements followed the scheme [34] that chooses random
values for the Euler angles in the rotation matrix, and employs the internal coordinates of the
sites of the molecule (see Table 1) to calculate their simulation-box coordinates. For all
 11

simulations in this work, a spherical cutoff distance rc  8.5 Å was used to truncate the LJ

potential and calculate its long-range correction from the analytical expression given in Refs. [33,
34] and extended to mixtures by de Pablo and Prausnitz [38]. The value of 8.5 Å for the cutoff
distance is a compromise between the values obtained by applying the typical criterion rc  2.5

to the LJ contributions to the potentials models of ethylene, water, and ethanol (see Table 1), and
was always less than half the simulation box length so that consistency with the minimum image
convention was preserved. Since the Ewald summation method was used in the present work to
compute the Coulombic interactions between point charges, then there was no need to truncate
those interactions and, accordingly, no need either for such a long cutoff distance (e.g., 17.5 Å)
as used in other works [16, 17] for the calculation of the Coulombic interactions by truncation
and correction by means of the reaction field method.

The time-saving strategy devised by Fartaria et al. [39] was carefully implemented in the present
work to obtain a significant decrease in the computer time required for the calculation of the
Ewald sum. In that strategy, two repository matrices are used to store pairwise potential energies
like the real space term of the Ewald sum and the truncated LJ potential, which can be retrieved
when needed, thereby saving time for the calculation of the intermolecular energy associated to
trial configurations. Whenever a translational displacement or rotation of a molecule is carried
out, the only change experienced by the repository matrices is for the row and column associated
to the molecule being moved. Therefore, the change of total configurational energy is given by
the summation (over all of the other molecules) of the difference between the trial and the old
pair energies of each of those molecules and the molecule being moved. Whenever a trial
configuration is accepted, the corresponding pairwise potential energies are recorded in the
repository matrices, to be retrieved whenever needed along the simulation run. Fartaria et al. [39]
showed that time-savings of up to 52% are possible when this strategy is implemented for
molecular models comprising point charges and the Ewald sum is used to compute the
Coulombic interactions. Besides the two repository matrices already mentioned, an additional
repository matrix was used in the present work, in order to store and retrieve the complex-
variable summation [33-37] that runs over molecular sites for each reciprocal space vector,
allowing an efficient calculation of changes in the reciprocal space term of the Ewald sum.
 12

3.1 Simulation method for pure components

For the simulation of VLE for the pure components, the following five-stage strategy was
implemented. In the first stage, estimates of the saturated liquid and vapor densities of the pure
components at a specified temperature T were obtained by means of reference multiparameter
equations of state [18-20]. These equations of state were solved by means of the calculation
approach proposed by Mao et al. [40] and Shi and Mao [41] for water and steam, and extending
its application to ethylene and ethanol. In the second stage, for each phase of the pure component,
an NVT-ensemble simulation (with N  400 molecules), with the corresponding density fixed at
the value estimated from the equation of state, was carried out for a total number of
2  10 7 moves (molecular displacements and rotations), 60% of which were typically used to
equilibrate the configurational energy. In the third stage, starting from the final configuration
obtained after the NVT runs, an NPT-ensemble simulation, with the pressure fixed at the value of
the vapor pressure estimated from the equation of state, was carried out for each phase for a total
number of 3 10 7 moves (using a ratio of one box-volume change to N molecular displacements
and rotations), 60% of which were typically used to equilibrate the molecular density and the
configurational energy. In the fourth stage, starting from the final configurations obtained after
the NPT runs, a GEMC-NVT simulation was carried out for the set of two boxes (each of them
with an initial number of N  400 molecules), for a total number of at least 1 10 5 moves (using
a ratio of one volume change to 2N molecular displacements and rotations and 2N molecular
transfers between the boxes), 60% of which were typically used to equilibrate the properties
being averaged (molecular densities and configurational energies of the two phases). The
attainment of phase equilibrium was ascertained from the statistical equality of the chemical
potentials for the two phases, calculated by means of the particle insertion method, and the length
of the simulation run was extended until that equality was achieved. Since the equality of the
chemical potentials is achieved precisely by means of the transfer moves, the achievement of that
equality in the simulation runs indicates that the number of successful transfer moves was
sufficient. Statistical uncertainties associated to the GEMC-NVT ensemble-averages were
calculated by means of the method by Flyvbjerg and Petersen [42]. In the fifth stage, an
 13

additional NVT-ensemble simulation was carried out for the final vapor-phase box obtained after
the GEMC-NVT run, in order to compute the pure-component vapor pressure by means of the
method of Harismiadis et al. [43].

3.2 Simulation method for mixtures

For the simulation of VLE for the binary and ternary mixtures, the following four-stage strategy
was implemented. In the first stage, by specifying both the temperature and the pressure of the
system, estimates of the molar compositions and the densities of the coexisting phases were
obtained from a T-P flash calculation with the help of the PRSV2-WS-UNIQUAC
thermodynamic model described in our previous study [1]. In the second stage, for each phase of
the mixture, an NVT-ensemble simulation (with N  400 molecules), with the density and mole
fractions fixed at the values estimated from the thermodynamic model, was carried out for a total
number of 2  10 7 moves (molecular displacements and rotations), 60% of which were used to
equilibrate the configurational energy. In the third stage, starting from the final configuration
obtained after the NVT runs, an NPT-ensemble simulation was carried out for each phase for a
total number of 3 10 7 moves (using a ratio of one box-volume change to N molecular
displacements and rotations), 60% of which were used to equilibrate the molecular density and
the configurational energy. In the fourth stage, starting from the final configurations obtained
after the NPT runs, a GEMC-NPT simulation was carried out for the set of two boxes (each of
them with an initial number of N  400 molecules), for a total number of moves in the range
from 1 10 7 to 1.5  10 7 (using a ratio of one volume change for each box to 2N molecular
displacements and rotations and 2N molecular transfers between the boxes). Properties of the
coexisting phases were sampled every 5  10 5 moves, and running averages were recalculated
until the statistical equality for the chemical potentials of each component in the two phases was
attained. Statistical uncertainties associated to the GEMC-NPT ensemble-averages were also
calculated by means of the method by Flyvbjerg and Petersen [42]. For all VLE simulations for
the binary and ternary mixtures, the Lorentz-Berthelot combining rules were used to calculate the
size and energy parameters of the LJ potential for the unlike interactions.

4. Simulation results for the pure components

 14

By following the five-stage strategy explained in Section 3.1, pure-component VLE molecular
simulations were carried out by using the potential models of ethylene, water, and ethanol
described in Section 2. The VLE phase diagrams of the pure components were computed over the
temperature intervals [160 K, 265 K] for ethylene, [300 K, 600 K] for water, and [270 K, 493 K]
for ethanol. These phase diagrams are shown in Figs. 1-3 as graphs of absolute temperature vs.
molar density of the two phases, where the empty squares correspond to the molecular simulation
results and the solid lines correspond to the results obtained by means of the most accurate
(reference) multiparameter equations of state currently available: the equation of Smukala et al.
[18] for ethylene, the equation of Wagner and Pruß [19] for water, and the equation of Dillon and
Penoncello [20] for ethanol.

A comprehensive account of multiparameter equations of state as an accurate source of

thermodynamic property data has been given in the book by Span [44]. These equations are
regarded as fundamental equations of state because they are based on the Helmholtz free energy.
The reference character of these multiparameter equations of state is supported by the very low
deviations that are associated to the thermodynamic properties calculated from those equations.
Indeed, the reference equation of state by Smukala et al. [18] for ethylene reproduces the
experimental data for the saturated liquid and vapor densities with deviations within 0.004% and
0.02%, respectively, and the data for the vapor pressure with a deviation less than 0.01%. The
reference equation of state by Wagner and Pruß [19] for water, which is known as the IAPWS-95
formulation, reproduces the experimental data for the saturated liquid and vapor densities with
deviations within 0.0025% and 0.1%, respectively, and the data for the vapor pressure with a
deviation within 0.025%. The reference equation of state by Dillon and Penoncello [20] for
ethanol reproduces the experimental data for the saturated liquid and vapor densities with
deviations less than 0.2% and 0.5%, respectively, and the data for the vapor pressure with a
deviation less than 0.4%. These reference equations of state were compared by their proponents
[18-20] with previous equations and were found to be much more accurate.

The average relative deviation (ARD) of the simulation results for the saturated liquid densities
with respect to the values obtained from the corresponding reference equation of state is 2.5% for
 15

ethylene, 1.1% for water, and 1.8% for ethanol. An assessment of the deviation for ethylene
cannot be made because no corresponding deviation value was reported by Weitz and Potoff
[15], using the same potential model for ethylene. The deviation for water agrees perfectly with
the value (1.1%) reported by Huang et al [16], using the same potential model for water but a
different simulation method. In contrast, the deviation for ethanol (1.8%) turns out to be larger
than the value (0.3%) reported by Schnabel et al. [17], using the same potential model for ethanol
but a different simulation method.

As mentioned in Section 3.1, the vapor pressure of the pure components was computed by
applying the method of Harismiadis et al. [43] to the final vapor-phase simulation box obtained
after each GEMC-NVT simulation run. The resulting Clausius-Clapeyron diagrams (i.e. graphs of
ln P sat vs. 1 / T ) are shown in Figs. 4-6, where the emtpy squares correspond to the molecular
simulation results and the solid line corresponds to the results obtained by means of the
respective reference equation of state [18-20]. The ARD of the simulation results for the vapor
pressure with respect to the values obtained from the corresponding reference equation of state is
5.0% for ethylene, 9.6% for water, and 4.1% for ethanol. The deviation for ethylene (5.0%) turns
out to be much larger than the value (2%) reported by Weitz and Potoff [15], using the same
potential model for ethylene but a different simulation method. The deviation for water (9.6%) is
33% larger than the value (7.2%) reported by Huang et al. [16], using the same potential model
for water but a different simulation method. In contrast, the deviation for ethanol (4.1%) is just
11% larger than the value (3.7%) reported by Schnabel et al. [17], using the same potential model
for ethanol but a different simulation method.

Simulation results for the vapor pressure and the configurational energies and densities of the
coexisting phases at a given temperature were used to compute the heat of vaporization ( H v ) of

the pure components from the following thermodynamic relationship:

 1 1 
H v  (U T(V )  U T( L ) )  P sat  (V )  ( L )  (2)
  
 16

where U T(V ) and U T( L ) are the total configurational energies of the vapor and liquid phases,

respectively, and  (V ) and  ( L ) are their corresponding densities. The resulting graphs of H v

vs. T are shown in Figs. 7-9, where the emtpy squares correspond to the molecular simulation
results and the solid line corresponds to the results obtained by means of the respective reference
equation of state [18-20]. The ARD of the simulation results for the enthalpy of vaporization
with respect to the values obtained from the corresponding reference equation of state is 1.7% for
water, 4.1% for ethanol, and 12.4% for ethylene. The deviation for water (1.7%) turns out to be
39% smaller than the value (2.8%) reported by Huang et al. [16], using the same potential model
for water but a different simulation method. In contrast, the deviation for ethanol (4.1%) turns
out to be much larger than the value (0.9%) reported by Schnabel et al. [17], using the same
potential model for ethanol but a different simulation method. For ethylene, simulation results
exhibit a significant offset (by overestimation) with respect to the equation of state results (see
Fig. 7). Since the heat of vaporization was not reported by Weitz and Potoff [15] (proponents of
the potential model of ethylene), a direct assessment of the seemingly large deviation (12.4%)
obtained in the present work cannot be made. However, similarly large deviations for the heat of
vaporization predicted by other LJ plus point-charge potential models have been reported, even
when the vapor pressure and the saturated liquid densities are reproduced accurately. For
instance, Huang et al. [16] reported an ARD (with respect to the experimental data) of 13.4% for
the heat of vaporization predicted by their potential model of ethylene glycol (see Fig. 4 in Ref.
[16], in which an offset by overestimation is also shown), even though the saturated liquid
densities and vapor pressure of that substance were reproduced with acceptable accuracy by the
same potential model (see Figs. 2 and 3 in Ref. [16]).

As shown in Figs. 1-9, the statistical uncertainties (error bars) of our GEMC simulation results
are small (most of them are within or smaller than the symbol sizes). Therefore, the resulting
discrepancy for the average deviations between the present and the previous works is more likely
due to the difference between the simulation techniques used.

The good agreement of the GEMC simulation results for the vapor pressure and the VLE phase
diagrams of the pure components, with respect to calculations carried out by means of the most
 17

accurate (reference) equations of state currently available for those components, corroborates the
validity of the potential models proposed by Weitz and Potoff [15] for ethylene, Huang et al. [16]
for water, and Schnabel et al. [17] for ethanol.

5. Simulation results for the binary mixtures

By following the four-stage strategy explained in Section 3.2, binary-mixture VLE molecular
simulations were carried out by using the potential models of ethylene, water, and ethanol
described in Section 2. Isothermal VLE phase diagrams of the binary subsystems were computed
at the following temperatures: 200, 250, and 300°C for ethylene + water, 150, 170, 190, 200, and
220°C for ethylene + ethanol, and 200, 250, 275, and 300°C for ethanol + water. The resulting
phase diagrams at 200°C are shown in Figs. 10-13 as graphs of pressure vs. molar composition of
the two phases (P-xy diagrams), where the empty squares (with their respective error bars)
correspond to the molecular simulation results, the crosses correspond to the available
experimental data [21-23], and the solid lines correspond to the results obtained by means of the
PRSV2-WS-UNIQUAC thermodynamic model described in our previous study [1]. The resulting
phase diagrams at the other temperatures listed above are shown as Figs. S1-S9 in the Supporting
Information.

5.1 Results for ethylene + water

The isothermal VLE (P-xy) phase diagrams for the binary system ethylene + water are shown in
Figs. 10 and 11 at 200°C, and in Figs. S1 and S2 (in the Supporting Information) at 250 and
300°C, respectively. The parameter values reported in Table 2 were used for the calculations with
the PRSV2-WS-UNIQUAC thermodynamic model. The solid line and data points at the left side
of the diagrams correspond to the liquid phase and the solid line and data points at the right side
of the diagrams correspond to the vapor phase. The three sets of data (molecular simulation,
thermodynamic model, and experimental measurements) consistently follow the same increasing
trend for the mole fraction of ethylene as the pressure increases. At 200 and 250°C, simulation
results for the vapor phase exhibit smaller error bars and are closer to both the experimental data
and the results obtained from the thermodynamic model, as compared to the simulation results
 18

for the liquid phase. At 300°C, as the pressure increases, simulation results for the vapor phase
exhibit a monotonic deviation to the left of the corresponding experimental data (see Fig. S2),
and the simulation result for the liquid phase at 160 atm is shifted to the right, significantly. A
possible interpretation of this behavior is that simulation would be predicting a much narrower
phase envelope for ethylene + water at 300°C, which is a surprising result considering the trend
of the experimental data.

At 200°C, the average absolute deviation (AAD) of the simulation results (ensemble-averages)
for the mole fraction of ethylene with respect to the experimental values, is 0.0030 for the liquid
phase and 0.0345 for the vapor phase. At 250°C, the AAD is 0.0015 for the liquid phase and
0.0240 for the vapor phase. At 300°C, the AAD is 0.0050 for the liquid phase and 0.0919 for the
vapor phase.

Additional simulations were carried out in order to assess the effect of including a correction
factor  in the Lorentz combining rule for the energy parameter  ij of the LJ potential for unlike

interactions, so that  i , j   ( i  j )1 / 2 . By means of a simple random search, several values of the

correction factor  were tried for the simulations at 200°C and the best results were obtained
with   0.9 , for which the resulting VLE phase diagram is shown in Fig. 11. The AAD of the
simulation results for the mole fraction of ethylene at 200°C decreased from 0.0030 to 0.0017 for
the liquid phase and from 0.0345 to 0.0189 for the vapor phase, showing an improvement with
respect to the use of the default value   1.0 . This correction factor was not applied to the
simulations at 250 and 300°C.

From an overall examination of the VLE phase diagrams shown in Figs. 10, 11, and S1, it
follows that the intermolecular potential models for ethylene and water described in Section 2 are
capable of qualitatively predicting the VLE behavior of this binary system at 200 and 250°C.

5.2 Results for ethylene + ethanol

 19

The VLE phase diagrams for the binary system ethylene + ethanol are shown in Fig. 12 at 200°C
and in Figs. S3-S6 (in the Supporting Information) for temperatures of 150, 170, 190, and 220°C.
The parameter values reported in Table 2 were used for the calculations with the PRSV2-WS-
UNIQUAC thermodynamic model. Once again, the solid line and data points at the left side of
the diagrams correspond to the liquid phase and the solid line and data points at the right side of
the diagrams correspond to the vapor phase. The three sets of data (molecular simulation,
thermodynamic model, and experimental measurements) follow the same trend for the mole
fraction of ethylene as the pressure increases. At 150°C and in the middle range of pressures,
simulation results for the vapor phase exhibit larger deviations with respect to both the
experimental data and the results obtained from the thermodynamic model.

At 150°C, the average absolute deviation (AAD) of the simulation results (ensemble-averages)
for the mole fraction of ethylene with respect to the experimental values, is 0.0332 for the liquid
phase and 0.0781 for the vapor phase. At 170°C, the AAD is 0.0275 for the liquid phase and
0.0476 for the vapor phase. At 190°C, the AAD is 0.0174 for the liquid phase and 0.0196 for the
vapor phase. At 200°C, the AAD is 0.0143 for the liquid phase and 0.0189 for the vapor phase.
At 220°C, the AAD is 0.0085 for the liquid phase and 0.0156 for the vapor phase.

Even though both molecular simulations and the T-P flash calculations made with the help of the
thermodynamic model become increasingly difficult in the region near the critical point of the
binary mixture, the results associated to these two methods are in very good agreement in that
region for some of the phase diagrams, e.g., at temperatures of 170 and 220°C (Figs. S4 and S6).
The experimental critical points of this binary system were reported by Tsiklis and Kofman [22]
for each of the five values of temperature corresponding to the VLE phase diagrams shown in
Figs. 12 and S3-S6. In each of these diagrams the experimental critical point is indicated by the
highest pressure cross. At 150 and 170°C (see Figs. S3 and S4), the critical pressures predicted
from both molecular simulation and the thermodynamic model are very close to the experimental
critical pressures of 127 and 118 atm, respectively [22]. At 190 and 200°C (see Figs. S5 and 12),
the critical pressures predicted by extrapolation from the molecular simulation results are very
close to the experimental critical pressures of 105 and 98 atm, respectively [22], whereas the
 20

critical pressures predicted by means of the thermodynamic model turn out to be slightly higher
than the experimental ones. At 220°C (see Fig. S6), both molecular simulation and the
thermodynamic model predict a critical pressure about 8% higher than the experimental value of
81 atm [22].

From an overall examination of the VLE phase diagrams shown in Figs. 12 and S3-S6, it follows
that the intermolecular potential models for ethylene and ethanol described in Section 2 are
capable of qualitatively predicting the VLE behavior of this binary system.

5.3 Results for ethanol + water

The VLE phase diagrams for the binary system ethanol + water are shown in Fig. 13 at 200°C
and in Figs. S7-S9 (in the Supporting Information) for temperatures of 250, 275, and 300°C. The
parameter values reported in Table 2 were used for the calculations with the PRSV2-WS-
UNIQUAC thermodynamic model. Once again, the solid line and data points at the left side of
the diagrams correspond to the liquid phase and the solid line and data points at the right side of
the diagrams correspond to the vapor phase. The three sets of data (molecular simulation,
thermodynamic model, and experimental measurements) follow the same trend for the mole
fraction of ethanol as the pressure increases. Even though simulation results for the vapor phase
in the middle range of pressures at 200 and 250°C (Figs. 13 and S7) deviate from both the
experimental data and the results obtained from the thermodynamic model, molecular simulation
shows to be capable of making an accurate prediction of the azeotropic point of this binary
system.

At 200°C, the average absolute deviation (AAD) of the simulation results (ensemble-averages)
for the mole fraction of ethanol with respect to the experimental values, is 0.0160 for the liquid
phase and 0.0557 for the vapor phase. At 250°C, the AAD is 0.0215 for the liquid phase and
0.0254 for the vapor phase. At 275°C, the AAD is 0.0096 for the liquid phase and 0.0122 for the
vapor phase. At 300°C, the AAD is 0.0134 for the liquid phase and 0.0180 for the vapor phase.
 21

From an overall examination of the VLE phase diagrams shown in Figs. 13 and S7-S9, it follows
that the intermolecular potential models for ethanol and water described in Section 2 are capable
of qualitatively predicting the VLE behavior of this binary system.

6. Simulation results for the ternary mixture

By following the four-stage strategy explained in Section 3.2, ternary-mixture VLE molecular
simulations were carried out by using the potential models of ethylene, water, and ethanol
described in Section 2. Due to the improved results obtained for the VLE phase diagram of
ethylene + water at 200°C by the use of a correction factor   0.9 in the Lorentz combining
rule for the LJ energy parameter of unlike interactions (see Section 5.1), such correction factor
was also used in the VLE simulations of the ternary mixture. In Section 5, VLE phase diagrams
for the binary systems were computed at various temperatures, 200°C being a common value for
the three systems with regard to the availability of experimental data [21-23] and simulation
results. Due to the availability of experimental data [6] for the ternary system at 200°C as well,
the isothermal-isobaric VLE phase diagrams of the ternary system were also computed at 200°C
and at the following pressures: 30, 40, 50, 60, 80, and 100 atm. The resulting phase diagrams are
shown in Figs. 14-19, where the filled circles correspond to the molecular simulation results, the
solid lines correspond to the results obtained from the PRSV2-WS-UNIQUAC thermodynamic
model, and the triangles correspond to the few experimental data available [6].

In the ternary diagrams, the upper locus corresponds to the vapor phase at its dew point and the
lower locus corresponds to the liquid phase at its bubble-point. The two loci define the saturation
envelope for the ternary system, the two phases of which coexist in the region within the
envelope. In contrast to the few experimental data points available and included in the phase
diagrams, both the simulation and the model predictions extend over larger ranges and follow the
same trend for the dew-point and bubble-point lines of the ternary system. At pressures of 40 and
50 atm (Figs. 15 and 16), simulation results accurately match the results obtained by means of the
thermodynamic model. At 100 atm (Fig. 19), molecular simulation predicts a slightly narrower
two-phase region, indicating that the critical point of the binary mixture ethylene + ethanol at
200°C would occur at a pressure slightly below 100 atm. At that pressure, the bubble-point and
 22

dew-point lines of the ternary system would intersect the ethylene-ethanol side of the phase
diagram at the composition of that critical point. In contrast, the thermodynamic model predicts
that this critical point would occur at a pressure slightly above 100 atm. From the experimental
VLE measurements reported by Tsiklis and Kofman [22] for the binary system ethylene +
ethanol, the critical point occurs at a pressure of 98 atm at 200°C; therefore, the molecular
simulation prediction of a value slightly below 100 atm for the critical pressure at 200°C turns
out to be more accurate than the prediction made by means of the thermodynamic model (see Fig.
12).

7. Conclusions

From the good agreement of the Gibbs-ensemble Monte Carlo simulation results for the vapor
pressure and the VLE phase diagrams of ethylene, water, and ethanol with respect to calculations
carried out by means of the most accurate (reference) multiparameter equations of state currently
available for those components [18-20], we were able to corroborate the validity of a set of
previously published intermolecular potential models for ethylene [15], water [16], and ethanol
[17], which had been validated by their proponents from results obtained by means of other
simulation methods.

These potential models are capable of predicting the available VLE phase diagrams of the binary
subsystems ethylene + water [21] (at 200 and 250°C), ethylene + ethanol [22] (at 150, 170, 190,
200, and 220°C) and ethanol + water [23] (at 200, 250, 275, and 300°C). For the binary system
ethylene + water, it was shown that the use of a correction factor of 0.9 for the Lorentz
combining rule, which is close to the default value of 1.0, improves the calculated phase diagram
at 200°C by decreasing by 45% the corresponding deviations for the mole fractions of ethylene in
the vapor and liquid phases. Since for most of the simulated binary VLE phase diagrams (11
diagrams out of a total of 12) a correction factor for the Lorentz combining rule was not needed,
and the value of the correction factor used for ethylene + water at 200°C is not far from the
default value of 1.0, then it can be said that the Lorentz-Berthelot combining rules appear to be
appropriate for the three binary systems considered in the present work. This suitability of the
 23

Lorentz-Berthelot combining rules for VLE calculations from molecular simulation is in

agreement with the findings of previous works (e.g., [31, 32, 45, 46]).

Molecular simulation predictions for the VLE phase diagrams of the ternary system at 200°C and
pressures of 30, 40, 50, 60, 80, and 100 atm are in very good agreement with predictions that we
had previously made [1] by use of a thermodynamic model that combines the Peng-Robinson-
Stryjek-Vera equation of state, the Wong-Sandler mixing rules, and the UNIQUAC activity
coefficient model.

The latter agreement is encouraging for the subsequent use of molecular simulation to predict the
combined phase and chemical equilibrium of the ternary system and check the validity of
predictions that we previously made [1] by means of the thermodynamic model.

Acknowledgement

Financial support from the Colombian Administrative Department of Science, Innovation and

Technology (COLCIENCIAS), through a research assistanship for doctoral students (Y.M.

Muñoz-Muñoz), is gratefully acknowledged.
 24

References

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[22] D.S. Tsiklis, A.N. Kofman, Russ. J. Phys. Chem. 35 (1961) 549-551.
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 26

Vitae

Y. Mauricio Muñoz-Muñoz received his undergraduate degree (B.S) in chemical engineering

from Universidad Nacional de Colombia, at the Manizales campus, in 2007, and his doctoral

degree (in chemical engineering) from Universidad del Valle, Cali, Colombia, in November
2014. He is currently working as a postdoctoral researcher in the Thermodynamics and Energy

Technology research group of Professor Jadran Vrabec, at the Faculty of Mechanical Engineering

of the University of Paderborn, in Germany.

Mario Llano-Restrepo is Professor of Chemical Engineering at Universidad del Valle in Cali,

Colombia. He received his Ph.D. degree (in chemical engineering) from Rice University in 1994.
His main research interests are modeling of phase and chemical equilibria, modeling and

simulation of separation processes, and molecular simulation. In 2009, he earned a Distinguished

Professor recognition from Universidad del Valle for service and excellence in teaching since
1994. Some of the courses he has taught are chemical thermodynamics, statistical

thermodynamics, molecular simulation, chemical reaction engineering, mass transfer, separation

operations, and separation process modeling and simulation.

 27

Figure Captions

Figure 1. VLE phase diagram for ethylene. , molecular simulation results of this work; ,

calculated with the reference multiparameter equation of state of Smukala et al. [18] for ethylene.

Figure 2. VLE phase diagram for water. , molecular simulation results of this work; ,

calculated with the reference multiparameter equation of state of Wagner and Pruß [19] for

water.

Figure 3. VLE phase diagram for ethanol. , molecular simulation results of this work; ,

calculated with the reference multiparameter equation of state of Dillon and Penoncello [20] for
ethanol.

Figure 4. Clausius-Clapeyron plot for the vapor pressure of ethylene as a function of temperature.

, molecular simulation results of this work; , calculated with the reference multiparameter
equation of state of Smukala et al. [18] for ethylene.
 28

Figure 5. Clausius-Clapeyron plot for the vapor pressure of water as a function of temperature.

, molecular simulation results of this work; , calculated with the reference multiparameter
equation of state of Wagner and Pruß [19] for water.

Figure 6. Clausius-Clapeyron plot for the vapor pressure of ethanol as a function of temperature.

, molecular simulation results of this work; , calculated with the reference multiparameter
equation of state of Dillon and Penoncello [20] for ethanol.

Figure 7. Heat of vaporization for ethylene as a function of temperature. , molecular simulation

results of this work; , calculated with the reference multiparameter equation of state of

Smukala et al. [18] for ethylene.

Figure 8. Heat of vaporization for water as a function of temperature. , molecular simulation

results of this work; , calculated with the reference multiparameter equation of state of Wagner
and Pruß [19] for water.

Figure 9. Heat of vaporization for ethanol as a function of temperature. , molecular simulation

results of this work; , calculated with the reference multiparameter equation of state of Dillon

and Penoncello [20] for ethanol.

Figure 10. VLE phase diagram of ethylene (1) + water (2) at 200°C. , molecular simulation

results of this work; , calculated with the PRSV2-WS-UNIQUAC thermodynamic model; +,

experimental data of Tsiklis et al. [21].

Figure 11. VLE phase diagram of ethylene (1) + water (2) at 200°C. , molecular simulation

results of this work using a correction factor χ = 0.9 for the Lorentz combining rule; ,
 29

calculated with the PRSV2-WS-UNIQUAC thermodynamic model; +, experimental data of

Tsiklis et al. [21].

Figure 12. VLE phase diagram of ethylene (1) + ethanol (2) at 200°C. , molecular simulation

results of this work; , calculated with the PRSV2-WS-UNIQUAC thermodynamic model; +,

experimental data of Tsiklis and Kofman [22].

Figure 13. VLE phase diagram of ethanol (1) + water (2) at 200°C. , molecular simulation
results of this work; , calculated with the PRSV2-WS-UNIQUAC thermodynamic model; +,

experimental data of Barr-David and Dodge [23].

Figure 14. VLE phase diagram of ethylene + water + ethanol at 200°C and 30 atm. ●, molecular

simulation results of this work; , calculated with the PRSV2-WS-UNIQUAC thermodynamic

model; ▲, experimental data of Tsiklis et al. [6].

Figure 15. VLE phase diagram of ethylene + water + ethanol at 200°C and 40 atm. ●, molecular

simulation results of this work; , calculated with the PRSV2-WS-UNIQUAC thermodynamic

model; ▲, experimental data of Tsiklis et al. [6].

Figure 16. VLE phase diagram of ethylene + water + ethanol at 200°C and 50 atm. ●, molecular

simulation results of this work; , calculated with the PRSV2-WS-UNIQUAC thermodynamic

model; ▲, experimental data of Tsiklis et al. [6].

Figure 17. VLE phase diagram of ethylene + water + ethanol at 200°C and 60 atm. ●, molecular

simulation results of this work; , calculated with the PRSV2-WS-UNIQUAC thermodynamic

model; ▲, experimental data of Tsiklis et al. [6].
 30

Figure 18. VLE phase diagram of ethylene + water + ethanol at 200°C and 80 atm. ●, molecular

simulation results of this work; , calculated with the PRSV2-WS-UNIQUAC thermodynamic

model; ▲, experimental data of Tsiklis et al. [6].

Figure 19. VLE phase diagram of ethylene + water + ethanol at 200°C and 100 atm. ●, molecular

simulation results of this work; , calculated with the PRSV2-WS-UNIQUAC thermodynamic

model; ▲, experimental data of Tsiklis et al. [6].

Table 1
Local coordinates (x, y) and charge q of the sites, and size (  ) and energy (  ) parameters of the

LJ-site contribution to the planar (z = 0 Å) intermolecular potential models of ethylene [15],

water [16], and ethanol [17].

Potential model of ethylene [15]

Interaction site x (Å) y (Å) q (e)  (Å)  / k B (K)

CH2 0.665 0 0.85 3.72 83.0

CH2 -0.665 0 0.85 3.72 83.0

COM 0 0 -1.70 0 0

Potential model of water [16]

O 0 0 0 3.11831 208.08
H 0.7069 0.9133 0.41955 0 0

H 0.7069 -0.9133 0.41955 0 0

NPC 0.20482 0 -0.83910 0 0

Potential model of ethanol [17]

 31

CH3 0 0 0 3.6072 120.15

CH2 1.9842 0 0.25560 3.4612 86.291

O 2.0127 1.7156 -0.69711 3.1496 85.053

H 2.9290 1.9683 0.44151 0 0

Table 2

Optimum values of the adjustable parameters for the fit of the PRSV2-WS-UNIQUAC

thermodynamic model [1] to the VLE experimental data of Tsiklis et al [21] for ethylene (1) +
water (2), Tsiklis and Kofmann [22] for ethylene (1) + ethanol (3), and Barr-David and Dodge

[23] for ethanol (3) + water (2).

System (ij) T (°C) u ij / R (K) u ji / R (K) k ij

12 200 808.94 385.66 1.0181

12 250 -603.75 2007.55 1.1301

12 300 -936.45 1685.95 2.7033

13 150 394.7 94.2 0.115

13 170 306.1 100.0 0.145

13 190 350.0 100.0 0.235

13 200 420.0 100.0 0.260

13 220 155.0 65.0 0.350

32 200 23.67 369.45 0.0085

32 250 51.92 348.74 0.0003

32 275 -22.60 395.02 0.0157

32 300 -293.78 770.99 0.0737

32
 280

260

240
T/K

220

200

180

160

0 5 10 15 20

ρV , ρL / mol L-1

Figure 1
 700

600
T/K

500

400

300

0 10 20 30 40 50 60

ρV , ρL / mol L-1

Figure 2
 550

500

450
T/K

400

350

300

250
0 5 10 15 20

ρV , ρL / mol L-1

Figure 3
 4

3
/ bar)

2
sat
ln( P

-1
3.5 4.0 4.5 5.0 5.5 6.0 6.5

1000 K / T

Figure 4
 6

4
/ bar)

2
sat
ln( P

-2

-4
1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4

1000 K / T

Figure 5
 4

2
/ bar)

0
sat
ln( P

-2

-4

2.0 2.5 3.0 3.5 4.0

1000 K / T

Figure 6
 18

16

14

12
-1
∆Hv / kJ mol

10

0
160 180 200 220 240 260 280

T/K

Figure 7
 50

40
-1
∆Hv / kJ mol

30

20

10

0
300 400 500 600 700

T/K

Figure 8
 50

40
-1
∆Hv / kJ mol

30

20

10

0
250 300 350 400 450 500

T/K

Figure 9
 160 160

140 140

120 120
P / atm

P / atm
100 100

80 80

60 60

40 40

0.000 0.005 0.010 0.015 0.020 0.4 0.5 0.6 0.7 0.8 0.9 1.0

x1 y1

Figure 10
 160 160

140 140

120 120
P / atm

P / atm
100 100

80 80

60 60

40 40

0.000 0.005 0.010 0.4 0.5 0.6 0.7 0.8 0.9 1.0

x1 y1

Figure 11
 100

80
P / atm

60

40

20
0.0 0.1 0.2 0.3 0.4

x1 , y1

Figure 12
 32

30

28

26
P / atm

24

22

20

18

16

0.0 0.2 0.4 0.6 0.8 1.0

x1 , y1

Figure 13
 T = 200 [°C], P = 30 [atm]

C2H4

0.0
1.0

0.1
0.9

0.2
0.8

0.3
0.7

0.4
0.6

0.5
0.5

0.6
0.4

0.7
0.3

0.8
0.2

0.9
0.1

1.0
0.0
CH3CH2OH 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 H2O

Figure 14
 T = 200 [°C], P = 40 [atm]

C2H4

0.0
1.0

0.1
0.9

0.2
0.8

0.3
0.7

0.4
0.6

0.5
0.5

0.6
0.4

0.7
0.3

0.8
0.2

0.9
0.1

1.0
0.0
CH3CH2OH 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 H2O

Figure 15
 T = 200 [°C], P = 50 [atm]

C 2H4

0.0
1.0

0.1
0.9

0.2
0.8

0.3
0.7

0.4
0.6

0.5
0.5

0.6
0.4

0.7
0.3

0.8
0.2

0.9
0.1

1.0
0.0
CH3CH2OH 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 H2O

Figure 16
 T = 200 [°C], P = 60 [atm]

C2H4

0.0
1.0

0.1
0.9

0.2
0.8

0.3
0.7

0.4
0.6

0.5
0.5

0.6
0.4

0.7
0.3

0.8
0.2

0.9
0.1

1.0
0.0
CH3CH2OH 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 H2O

Figure 17
 T = 200 [°C], P = 80 [atm]

C2H4

0.0
1.0

0.1
0.9

0.2
0.8

0.3
0.7

0.4
0.6

0.5
0.5

0.6
0.4

0.7
0.3

0.8
0.2

0.9
0.1

1.0
0.0
CH3CH2OH 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 H2O

Figure 18
 T = 200 [°C], P = 100 [atm]

C2H4

0.0
1.0

0.1
0.9

0.2
0.8

0.3
0.7

0.4
0.6

0.5
0.5

0.6
0.4

0.7
0.3

0.8
0.2

0.9
0.1

1.0
0.0
CH3CH2OH 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 H2O

Figure 19