Aic 16117

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Author Manuscript
Predicting NRTL Binary Interaction Parameters from
Molecular Simulations
Ashwin Ravichandran, Rajesh Khare*, Chau-Chyun Chen*
Department of Chemical Engineering, Texas Tech University, Box 43121
Lubbock, TX 79409
Email: rajesh.khare@ttu.edu; chauchyun.chen@ttu.edu
This is the author manuscript accepted for publication and has undergone full peer review but has not been
through the copyediting, typesetting, pagination and proofreading process, which may lead to differences
between this version and the Version of record. Please cite this article as doi:10.1002/aic.16117.
This article is protected by copyright. All rights reserved.

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Abstract
A predictive approach for calculating the binary interaction parameters ( ) of the nonrandom
two liquid (NRTL) local composition model is developed, combining molecular simulations with
the two-fluid theory. The binary interaction parameters are determined for the following three
sets of model binary mixtures: water + methanol, methanol + methyl acrylate, and water +
methyl acrylate. For each binary mixture, the interaction parameters are expressed in terms of
molecular size and strength of interactions, which are in turn, calculated from molecular
simulations. We show that the binary interaction parameters determined from simulations are in
qualitative agreement with those estimated from regressing experimental data. The major factors
that determine the binary interaction parameters are outlined based on simple thermodynamic
arguments for each mixture.
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Introduction
Designing energy efficient and sustainable industrial processes requires reliable
prediction of thermodynamic and phase equilibrium properties. Molecular thermodynamic
models developed over the past several decades have been successful in quantifying vapor-
liquid, liquid-liquid, and vapor-liquid-liquid equilibria of organic mixtures1-3 and of electrolyte
systems4,5. In some cases, these models have even been applied to large molecules such as
polymers6 and biomolecules7. Most of these semi-empirical models predict the thermodynamic
properties based on the local composition of the mixture. Notable among these models are the
Wilson model8, the nonrandom two liquid (NRTL)9 model, and their variants1,10.
In a binary mixture of species and , the local composition models relate the energy
required for the formation of two types of local domains ( centered and centered domains that
are surrounded by both and molecules) to the excess Gibbs energy of the system9. In general,
the expression for local composition for an centered domain can be stated as:

=

(1)
Here and are the local mole fractions of type molecule around type molecule and type
molecule around type molecule respectively, and are the bulk mole fractions of type and
molecules, is the non-randomness factor, and is the binary interaction parameter which is
the input to these local composition models. The binary interaction parameter quantifies the
nature of molecular interaction between different chemical species in a mixture. High positive
values of τ indicate unfavorable interaction between the solute and the solvent molecules (e.g.
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interaction between hydrophilic and hydrophobic groups) while negative numbers indicate
favorable interactions (e.g. interaction between hydrophilic and polar groups)1. The non-
randomness factor is usually set to 1.0 or 0.2-0.5 for the Wilson model and the NRTL model,
respectively8,9. An expression for the local composition around a centered domain can be
written in a similar way, resulting in the interaction parameter . It must be noted that in the
local composition models, the binary interaction parameters are not symmetric, i.e. ≠ 9.
Although the expressions for the local composition in Wilson and NRTL models are
written in a semi-heuristic fashion, a rigorous interpretation of the local composition approach of
Eq. 1, is provided by the two-liquid theory11-13. Kemény and Rasmussen11, used two-liquid
theory to formulate the partition function of a binary mixture as a product of the partition
functions of two hypothetical fluid domains. The resulting partition function was used to derive
a Wilson-like expression relating the energetic interaction between the two liquids (), bulk
concentration, and the local composition. Brandani and Prauznitz14 used similar arguments to
find the probability of forming hypothetical fluid domains by solving a combinatorial problem,
thereby arriving at an expression analogous to the Wilson model. The validity of the local
composition approach has also been confirmed independently by many experimental studies,
most of which used spectroscopic techniques to measure the local compositions15-17, that were
then compared with the local fractions predicted by the NRTL model. In one such study, Phillips
and Brennecke17 measured the local composition of various mixtures of organic solvents. They
concluded that, for binaries without any specific chemical interactions (e.g. hydrogen bonding
interactions), the local compositions predicted by the NRTL model agree closely with
experiments. Owing to their simplicity in application and rigorous treatment of the underlying
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physical phenomena, local composition models are widely used in the design of industrial
processes18.
Accurate values of the binary interaction parameters are crucial for the success of these
thermodynamic models. It is customary to obtain the values of the binary interaction parameters
by fitting the model to the experimental data, which include among others, vapor pressure,
osmotic coefficients19, phase equilibrium20, solubility, and excess enthalpy data. However, the
regression based approach is not always feasible as it requires many reliable experimental data
sets to calculate the binary interaction parameters. Also, careful analysis of data uncertainty and
selection of the optimization approach are essential, as such regression problems can often result
in different values of the binary interaction parameters due to the existence of multiple local
minima21 in the parameter estimation problem.
Thus, it is desirable to predict the binary interaction parameters from first principles, as
such a technique can circumvent the problems associated with the regression based approach and
the subsequent need for availability of many reliable experimental data sets. To our knowledge,
there have been very few attempts in the literature for calculating the interaction parameters of
the activity coefficient models from a fundamental approach. Most of these approaches focus on
the parameters of the UNIQUAC model22-24, where the model parameters are determined directly
using the interaction energies of either molecular pairs22 or small clusters of molecules23.
Neiman et al.24 noted that a similar methodology can be applied for calculating the binary
interaction parameters of the NRTL model using the bulk intermolecular energy difference
between the liquid and the gas phase. They concluded that the interaction parameters obtained
using the bulk intermolecular energies cannot be used with the NRTL model to predict the phase
diagrams of binary mixtures. In another recent work by Seyf and Haghtalab,25,26 the local
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coordination number obtained by integrating the radial distribution function was used to estimate
the binary interaction parameters. However, that approach is not predictive as it requires an
adjustable parameter, the cut-off length for integrating the radial distribution function, this cut-
off length was calculated from the knowledge of the experimental activity coefficient data.
In this work, we combine two-fluid theory27 with molecular simulations to determine the
binary interaction parameters of the NRTL model. The approach we present here is purely
predictive and considers the local structural and energetic information for calculating τ. The
binary interaction parameters are calculated from the knowledge of molecular size and
interaction strength, both of which are obtained from molecular simulations. The following three
sets of binaries were chosen as model systems to validate the method proposed here: water +
methanol (fully miscible binary), methanol + methyl acrylate (micro-clusters forming binary),
water + methyl acrylate (partially miscible binary). The reason for choosing these mixtures are
two-fold; one, experimentally determined interaction parameters are available for each of these
binaries20 that can be used for validating our approach, and two, the proposed binaries exhibit a
wide range of thermodynamic characteristics (hydrophilicity/hydrophobicity, hydrogen bonding
capabilities, etc.), which serve as a stringent test for the validity of the proposed approach.
Rest of the article is organized as follows: Section II presents a brief description of the
two-fluid theory, followed by the details of the molecular dynamics (MD) simulations. The
calculated interaction parameters and their molecular significance are discussed in Section III,
followed by conclusions.
Theoretical Background and Simulation Details
Two-Fluid Theory
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Two-fluid theory of Brandani and Prausnitz14,27,28 relates the binary interaction
parameters of a Wilson-like model with the molecular size, the effective interaction strength
between different species of the mixture, and the size of the first neighbor shell. In this work, we
extend the two-fluid theory to NRTL model and apply molecular simulations to determine the
binary interaction parameters. A brief account of the two-fluid approach used in this work is
presented herein; the reader is referred to a series of articles published by Brandani and
Prausnitz14,27,28 for a detailed discussion of the approach.
To begin, consider a binary mixture of species and . Further, consider a domain in the
binary with molecule of type at the center that is locally coordinated by z molecules out of
which are of type and ( − ) are of type 11,27. The probability of arranging molecules of
type and ( − ) molecules of type , (randomly choosing them from an infinite pool of and
molecules) in a domain around a central molecule of type is:
= (2)
where is the combinatorial factor, and are the probabilities of choosing an type or a
type molecule, respectively. It must be noted that, denotes the probability of forming an
centered domain without taking into account the interaction energies between the molecules of
species and . To account for the preferential interactions between the components, the
distribution in Eq. 2 is weighted by the local potential function , which could be written as27:
− + ( − ) !

=
(3)
"# () $
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Here, %# () & is the radius of the coordination shell with molecule of type at center, is the
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molecular diameter and is the interaction strength between the components of the binary
mixture. Note that the interaction strength, is symmetric, i.e. = at a given concentration.
The interaction potential represented by the above form assumes that the local interactions are
only governed by the molecules within the first neighbor shell of the center molecule. This is the
central assumption of the local composition approaches.
The distribution function for a non-random arrangement (including specific interactions)
of a local domain is given by weighting by the Boltzmann factor:
^
()*

=
(4)
+
^
where denotes the domain distribution function of an interacting system, and + is the
normalization factor that is analogous to a local partition function, with , = 1/#/.
+ = 0

()*

(5)
12
Substituting the expression for potential from Eq. 3 into the Eq. 4 and rearranging we get:
^ 1
= ( ′) ( ′)
+
(6)
where
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,
Author Manuscript ′ =
5 6 () 7
(7)
"# $
,
′ =
5 6 7
(8)
"# () $
By definition, and are the bulk mole fractions of components and , respectively. Hence,
by construction of Eq. 7 and Eq. 8, ′ and ′ can be interpreted as the local compositions of
molecules of types and around a center molecule of type , respectively. Taking ratio of Eq. 7
and Eq. 8, one obtains:
< <
9: ; : ; =
8( ?
(9)
<
=
5
%> () &

Equation 9 is thus equivalent to the NRTL equation (Eq. 1).
Comparing the mathematical forms of Eq. 9 and Eq. 1, the binary interaction parameter
of the NRTL model can be written as:
, −

=
(10)
"# () $
Here, is the non-randomness factor. We note that a similar expression was derived by
Brandani and Prausnitz14 for calculating the interaction parameter of the Wilson model. An
equivalent expression for the interaction parameter with the molecule of type as the center of
the domain can be derived in a similar fashion:
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, −
Author Manuscript =

(11)
"# () $
Equations 10 and 11 are the basis for calculating the NRTL binary interaction parameters
from the two-fluid theory. Note that in all of the double indexed variables, consistent with the
notations of NRTL model, the second index denotes the molecule at the center of the domain. In
what follows, %# () & is denoted as # () for the sake of simplicity in text.
Calculation Methodology
The size of the molecule (), interaction strength (), and the neighbor cage radius (#)
which are required for calculating the binary interaction parameters are obtained from the short-
range structure of the mixture as determined from molecular simulations. The interaction
potential defined by the two-fluid theory (Eq. 3) is of square well type, consistent with the local
composition approach. Hence, the simulation results for short-range structure and interactions
(potential of mean force) from MD simulations should be mapped onto square well type
potential, in order to determine the binary interaction parameters. In this work, we have
followed two different approaches for evaluating , , and # from liquid structure as follows:
Approach I
The molecular diameter () of each species is calculated from the pure component radial
distribution function (RDF). For this purpose, the position of the first peak in the RDF was taken
as the molecular diameter of the pure component29 ( or ). Using these values, was
; @;
calculated as the average of pure component radii ( = ). An alternate way to obtain
A
would be to define it as the location of the first peak in the mixture RDF between components
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and . The arithmetic mean approach chosen here is consistent with the Lorentz-Berthelot
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mixing rules30 that are used in our simulations for evaluating interactions between species and
. In fact, the force field parameters were optimized using such rules. Furthermore, for mixtures
where the two components are not fully miscible, first peak in the RDF is not well defined and
hence evaluation of from the - RDF becomes difficult.
The radius of the neighbor cage (# () ) was calculated from the simulation of binary
mixtures of components and . Simulations were performed at different concentrations of the
binary mixture and the location of the first minimum in the RDF involving the molecules of
interest was taken as the cage radius. Since RDF can be defined between different groups in a
molecular system, # () was defined as the largest of the neighbor shell locations of all such group
RDFs across all concentrations (i.e. largest # () value in the system over the entire concentration
range). Such a definition for the calculation of includes, the length scale up to which the short-
range structure of the liquid extends.
Finally, the effective molecular interaction strength () was defined as the depth of the
first minimum in the potential of mean force (PMF) required for separating the given molecular
pair. Since the net interactions between molecules determine the local structure12 in a liquid
phase, was calculated from the PMF rather than using the bare pair-wise interactions. While
calculating the interaction strength, it is necessary to ensure that the solute and solvent are
homogeneously mixed. Hence, the PMF between species and was calculated in the dilute
limit of the center molecule. In the calculation of , both and were calculated from the
binary mixture that was very dilute in component . Similarly, and , that are required to
calculate , were obtained in the limit of dilute . Defining the interaction strength in the dilute
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limit of the solute also ensures that and have no contribution from the solute-solute
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interactions.
Approach II
The expression for from the two-fluid theory (Eq. 10) can be rearranged as:
()

CD () E %# & − F () G %# () & H
"# $ "# $
(12)
,
= 6 7
"# () $
Here, # () and # () denote the size of the neighbor shell with molecule of type at the center
that is surrounded by molecules of type and type , respectively. # () and # () were evaluated
from the first minimum in the RDFs for and pairs respectively and # () was then obtained as
# () = maxL# () , # () N, consistent with Approach I.
The two quantities in the square brackets in the numerator are the square well potentials
as used by Brandani and Prausnitz for the and pairs27. These were evaluated by following
the suggestion by Hirschfelder et al.31 for connecting the square well potential with the usual
Lennard-Jones (LJ) type interactions. Specifically, it was suggested that the strength of the
square well interaction should be 0.56 times the barrier height of the LJ type interaction.
Replacing the terms in the square brackets of Eq. 12 using this approach, we get:
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()
Author Manuscript , O0.56 %#

= 6 7
& − 0.56 %# () & T (13)
"# () $
The values of and required to calculate from the above expression were obtained using
the same procedure as described in Approach I, i.e. depth of the first minima in the PMF.
Molecular Simulations
The components of interest in this work are water, methanol (MeOH), and methyl
acrylate (MA). Pure component simulations of each of these species were performed to
determine the molecular diameter (). Further, to obtain the size of the neighbor cage (# () ),
three sets of binary mixtures, (water + methanol, water + methyl acrylate, and methanol + methyl
acrylate) were simulated at different concentrations of the mixtures (0.002-0.998 mole fraction of
one of the components). All simulations were carried out using the TraPPE-UA potentials for
acrylate and alcohol32,33 while the water molecules were represented by the SPC/E model34. The
TraPPE-UA force field is known to predict the phase equilibrium properties of organic liquids
with good accuracy and hence it is an appropriate choice for the present calculations.
Simulations were performed using the LAMMPS package35. One small change made in the
force field was that, while TraPPE-UA fixes the bond length values of all pairs of atoms at their
equilibrium values, we used strong harmonic constraints to represent the bond stretching
interactions, with force constants for the corresponding bonds taken from the General AMBER
Force Field (GAFF)36. TraPPE-UA force field was tested for its consistency by comparing the
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densities of the pure components and the binaries of water + MeOH and MeOH + MA with
experimental data. Overall there was a good agreement, with the simulated densities
representing the experimental data within 2% error. Most of the MD simulation systems
reported in this study consisted of approximately 9000 united atoms. However, simulations at
very low concentrations (0.002 and 0.998 mole fractions) consisted of smaller systems
containing 3000 to 6000 united atoms. Since the properties of interest here are pertaining to the
local structure of the molecular system, the chosen system sizes were considered to be sufficient
for these calculations. Simulations were performed at 303.15 K and 1 bar in the constant number
of particles, pressure, and temperature (constant NPT) ensemble using Nosé-Hoover thermostat
and barostat37. All binary simulations were carried out for a duration of 20 ns with a time step of
1 fs. The first 5 ns of the trajectory were discarded as initial equilibration period and the rest of
the trajectory was used for subsequent calculations.
The PMF between two species, which is required for obtaining the strength of the
effective interaction (), was calculated from umbrella sampling technique38. As mentioned
above, these umbrella sampling simulations were performed on dilute mixtures. The binary
mixtures that were equilibrated for 20 ns using MD simulations were used as the starting
configurations for the umbrella sampling simulations. The reaction coordinate (U) for these
calculations was chosen as the center of mass distance between the molecular pair of interest.
Harmonic biasing potential, with a spring constant of 3012.48 kJ/mol nm2 (7.2 kcal/mol Å2) 39,
was applied to restrain the molecular pair at the desired value of the reaction coordinate. The
molecules were moved towards each other starting from a distance of 1.2 nm. The size of each
umbrella sampling window was chosen as 0.03 nm, resulting in a total of 34 windows. Umbrella
sampling simulations were performed using the COLVARS module40 in LAMMPS. Under the
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biasing potential, each window was sampled for 3 ns out of which the first 2 ns were discarded
as the initial equilibration period. The last 1 ns of the trajectory at each reaction coordinate value
was used to calculate the potential of mean force using the Weighted Histogram Analysis
Method (WHAM)41, as implemented in the WHAM code from Grossfield Laboratory42. Finally,
the entropic term 2#/ln(Y) was added back43,44 and the PMF was shifted to zero at a separation
distance of 1.2 nm, to be consistent with its definition.
Data Regression
The binary interaction parameters obtained from molecular simulations were compared
with those obtained by regressing experimental data. For this purpose, values for the three
binaries studied here were determined using data regression. ASPEN Properties software,
version 8.8 was used for calculating the interaction parameters45. Vapor-liquid equilibrium,
liquid-liquid equilibrium, and azeotrope data were primarily considered for data regression. The
standard error on the regressed interaction parameters was estimated using error propagation
technique46. Further details of the regression are provided in the Supplementary Material.
Results and Discussion
Molecular Diameters
As described in the previous section, the molecular sizes were obtained from the
corresponding pure component RDFs. The effective molecular sizes () were taken from the
location of the first peak in the pure component RDF as shown in Fig. 1. Accordingly, the size
of a water molecule calculated here to be 0.267 nm (based on the water oxygen RDF) agrees well
with the value reported in a previous study47. Size of a methanol molecule was found to be 0.424
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nm in a similar fashion using the location of the first peak in the RDF between methyl groups.
The value of the effective molecular diameter of a methanol molecule was reported to be 0.42
nm by Perera et al.29 Thus, the value obtained in the current study matches with that reported in
the literature. Similarly, the size of a methyl acrylate molecule was determined to be 0.595
nm from the location of the carbonyl carbon peak.
Water (1) + Methanol (2) Binary System: Size effects determine the interaction parameter
for the completely miscible mixture
The first binary mixture studied in this work is that between water and methanol. RDFs
were determined for water + methanol mixtures over a wide range of concentrations. We
obtained # () as the size of the first neighbor shell with molecule as center from those RDFs.
Correspondingly, # (Z[\]^) was calculated as 0.534 nm and # (_]`a) as 0.597 nm. Table 1.a
summarizes the sizes of the neighbor shells with water and methanol as center. Note that the
first hydration shell with methanol as the center molecule is slightly larger than the shell with
water as the center molecule due to the difference in their molecular sizes. Also, the value of
# () does not change significantly with the concentration of the mixture. The and values
in Eqs. 10, 11, 13 were obtained from the PMF curves for the water + methanol system (see Fig.
2).
The binary interaction parameters for water + methanol mixture obtained from
simulations are listed in Table 1.b, along with the values determined from regressing
experimental data. The value of the non-randomness factor was set to 0.3 for all the calculations
(both MD and regression calculations)9. However in practice, the non-randomness factor is
usually set between 0.2-0.5 depending on the chemical mixture9. The value of was
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consistently chosen as 0.3 in this work to compare the binary interaction parameters predicted
using our method with those in the literature20 (calculated using data regression). Furthermore,
we focus on the role played by molecular sizes and interaction strength in determining the binary
interaction parameters and hence the non-randomness factor was conveniently fixed at 0.3 for all
mixtures. The uncertainty in was estimated by propagating the error46 in the interaction
strength, . As the uncertainties in the molecular and hydration shell sizes are generally small,
they were not considered in the error estimation calculation.
The binary interaction parameters estimated from molecular simulation in combination
with the two-fluid theory (using both of the proposed approaches) show reasonable agreement
with the regressed parameters, within the limits of statistical uncertainties. It can be noted that
the interaction parameters found by regressing experimental data from two different sources (this
work and literature20), differ significantly in their magnitude. This is common occurrence in
parameter estimation using data regression, where the final converged solution depends on
various factors such as the data set used in the regression, uncertainty in the data, and the
optimization algorithm which can converge to different local minima based on the initial
conditions21,48. Table 1.c shows the infinite dilution activity coefficient values of water +
methanol binary calculated using the NRTL equations with the binary interaction parameters
obtained from both MD simulations and by regressing experimental data. The uncertainties in
those values were calculated by propagating the error in the binary interaction parameters. The
values of ln (b c ) calculated using τ obtained from Approach I are in reasonable agreement with
those predicted using τ from experimental data regression, within statistical uncertainties.
However, ln (b c ) obtained from Approach II shows considerable deviation from the other
values. We attribute this observation to overprediction of Ad by Approach II. We also note that
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the values of infinite dilution activity coefficient are sensitive to the binary interaction parameter
values.
The binary interaction parameter has contributions from both local energetic and size
effects as evident from Eq. 10 and Eq. 11. It can be seen from the potential of mean force (Fig.
2) that e = |Ad − dd | < #/ (similarly, e = |dA − AA | < #/) at low (high) water fraction,
implying that there is effectively no energetic penalty for mixing water and methanol at these
concentrations. Consequently in the case of water + methanol binary, the two-fluid theory (Eq.
10 and 11) suggests that, molecular size is the dominating effect in determining the local
composition (or the preferential solvation of components) of the mixture and hence the NRTL
binary interaction parameters. The results of Chatterjee and Bagchi16 suggest a similar
conclusion that, even in the absence of specific interactions, the difference in molecular sizes can
cause preferential solvation between components.
The P-x-y diagrams and the Gibbs free energy of mixing for water + methanol system
calculated using different binary interaction parameters at 303.15 K are compared in Fig. 3. The
phase equilibrium diagrams are calculated using ASPEN Properties software, version 9.045. The
P-x-y diagram predicted using τ values obtained from MD simulations (both Approach I and
Approach II) shows reasonable agreement with that predicted using the regressed interaction
parameters. However, in this case, predictions using τ obtained from Approach I and the
regressed τ are in closer agreement. Similarly, the Gibbs free energy of mixing calculated using
τ from Approach I and regression are in good agreement (the maximum difference between these
two predictions is 0.29 kJ/mol). As discussed earlier, one of the interaction parameters
calculated using Approach II (Ad ) has a high negative value (indicating attractive interactions
between the components) and consequently, ∆jkl is overpredicted in this case.
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Methanol (1) + Methyl Acrylate (2) Binary System: Combined size and energetic effects
determine the strength of the interaction parameter
The potential of mean force curves used in the calculation of for this system are shown
in Fig. 4. Note that for this mixture methanol is designated as component 1 and methyl acrylate
as component 2. The sizes of the neighbor shells for this binary mixture are reported in Table
2.a. The binary interaction parameters and the infinite dilution activity coefficients for methanol
+ methyl acrylate mixture are shown in Table 2.b and Table 2.c, respectively. Values of these
parameters as determined using both the approaches (Approach I and Approach II) show
reasonable agreement with those calculated from regression, within the limits of statistical
uncertainties. From the magnitude of the interaction parameters (determined from both
simulation and regression), it is clear that, methyl acrylate is not preferentially solvated by either
methanol or methyl acrylate (since dA is close to zero). On the other hand, methanol is
preferentially solvated only by other methanol molecules, as can be seen from the magnitude of
Ad .
Unlike the previous case of water + methanol binary, the thermodynamics of mixing in
this case is dominated by both energetic and size effects. At low concentrations of methanol, it
was found that methanol molecules have a higher tendency to form micro-clusters. Fig. 5 shows
the cluster size distribution of methanol at 25% mole fraction along with the corresponding
RDFs. Molecular clusters, in this work were determined using distance criterion. If two
molecules are within the specified cut-off distance of each other, they are considered to belong to
the same cluster. The cut-off distance criterion for determining methanol clusters was taken to
be 0.35 nm based on the first minimum in the oxygen-oxygen RDF. As seen from Fig. 5, though
approximately 32% of the total methanol molecules present in the system are fairly dispersed in
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methyl acrylate, micro-clusters of larger sizes are also observed. Clustering of methanol can also
be confirmed from the strength of the first peak of methanol-methanol RDF (Fig. 5b). This
clustering behavior of methanol is attributed to specific hydrogen bonded interactions between
methanol molecules that are not prominent in methyl acrylate. Consequently, methanol-
methanol interaction is much stronger than methanol-methyl acrylate interaction (as seen in Fig.
4a). This unfavorable interaction between methanol and methyl acrylate leads to a large positive
value of Ad . On the contrary, the binary becomes completely miscible at high methanol
concentrations, as solvation of methyl acrylate by methanol can take place without the breakage
of the hydrogen bonded network. It can be seen from Fig. 4b that there is effectively no
energetic penalty for mixing (since e < #/) in an acrylate centered domain. Hence, according
to two-fluid theory expression, the size effects determine the local composition and thereby the
binary interaction parameter (dA ).
In order to validate the local composition as predicted by the NRTL model, we examine
the short-range structure obtained from MD simulations. The local mole fractions were
calculated from the coordination numbers which in turn were determined by integrating the RDF.
It can be seen from Fig. 6 that in general, NRTL model predicts depletion of methyl acrylate in
the vicinity of the methanol molecules (consequently enhancement of methanol around methanol
as shown in Fig. S1 of Supplementary Material), consistent with MD simulations. However, at
concentrations where there is self-association of methanol (low methanol fraction), NRTL model
over-predicts the local mole fraction of methyl acrylate around methanol. Due to clustering of
methanol molecules (as shown in Fig. 5) at low methanol fractions, there is a depletion of
acrylate molecules to distances that are beyond the second neighbor shell, i.e ∼ 0.98 nm (based
on RDF between methanol oxygen and methyl acrylate CH3, shown in Fig. 5). However, the
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local fractions predicted by NRTL are close to the bulk concentrations. The NRTL predictions
are improved as the molecules disperse well in the solution at low acrylate concentrations. Since
methanol molecules are capable of forming hydrogen bonded networks, we suggest that the
structural correlation between these molecules extends further beyond the first neighbor shell and
a simple local domain based structural representation can only capture such behavior
qualitatively. Our observation is consistent with that by Phillips and Brennecke17 who concluded
that in mixtures with specific chemical interactions, local composition values predicted by the
NRTL model do not agree with experimental measurements. Despite this observation, it is
remarkable that the NRTL model can predict the phase behavior of such binary mixtures with
good accuracy.
Fig. 7 shows the predicted phase behavior of methanol + methyl acrylate binary at 303.15
K. The P-x-y diagrams and ∆jkl calculated using different binary interaction parameters are in
reasonable agreement with each other. All the interaction parameters predict the presence of an
azeotrope in the range of 0.6-0.66 mole fraction of methanol.
Water (1) + Methyl Acrylate (2) Binary System: Repulsive interactions dominate the
thermodynamics for this partially miscible binary
Unlike the other two binary systems studied here, MD simulations suggest that water and
methyl acrylate are not miscible over most of the concentration range. In the wide range of mole
fractions studied with simulations (from 0.2% to 99.8% water mole fraction), solubility of
methyl acrylate in water (or vice versa) was observed only in the limit of infinite dilution. Water
and methyl acrylate were observed to phase separate at all other concentrations. The PMF
curves at infinite dilution of components were calculated (see Fig. 8) in order to quantify the
strength of various interactions in the binary mixture. As expected, interaction between
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molecules of the same species is much stronger than the interaction between water and methyl
acrylate in both the cases (i.e. water centered domain and MA centered domain), explaining why
the binary is thermodynamically incompatible. It must also be noted that water-water interaction
has a deeper potential minimum than water-MA and MA-MA interactions due to its ability to
form hydrogen bonds.
The interaction strength values ( and ) calculated from the PMF shown in Fig. 8 are
used to determine . Since water and acrylate phase separate at most of the concentrations
studied in the simulation, the radius of the solvation shell (# () ) was obtained from the RDF only
at concentrations where the mixture is homogeneous (i.e. at infinite dilution). The radii of the
solvation shell thus obtained are shown in Table 3.a. The values of the binary interaction
parameters obtained from these data are listed in Table 3.b. It can be seen from Fig. 8b that at
higher water concentration, water-methyl acrylate interaction does not have a potential
minimum, which is indicative of unfavorable interaction between the components. As a
consequence, the magnitude of the binary interaction parameter (dA ) calculated from molecular
simulation (using both Approach I and Approach II) is large and the value is positive, consistent
with that estimated by regressing the experimental data.
On the other hand, the binary parameter Ad calculated from simulation using Approach I
shows significant deviation from that obtained by regressing the experimental data. However,
Ad calculated from simulation using Approach II is in line with that calculated by Zuo et al.,20
but differs from the values obtained by regressing experimental data in this work. The infinite
dilution activity coefficients, P-x-y diagrams, and the Gibbs free energy of mixing of water +
methyl acrylate systems are shown in Table 3.c, Fig. 9a, and Fig. 9b respectively. The values of
ln (b c ) for methyl acrylate are reasonably consistent between the different methods used (MD
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simulation and data regression) while the infinite dilution activity coefficient of water is
significantly different. This is due to the inconsistency in the predicted value of Ad for this
mixture. Similar discrepancy is also reflected in the calculated Gibbs free energy of mixing.
The free energy of mixing predicted using MD Approach I does not exhibit two-liquid region.
On the contrary, from MD Approach II and the determined by regressing experimental data
(both this work and the work of Zuo et al.20) predict phase separation of the mixture. Similar
conclusion about the phase behavior can also be made from the P-x-y diagram shown in Fig. 9a.
Conclusions
An approach that combines two-fluid theory and molecular simulations was formulated
to predict the binary interaction parameters of the NRTL model. The approach was validated
using three binary systems: water + methanol, methanol + methyl acrylate, and water + methyl
acrylate. The binary interaction parameters were expressed as a function of molecular diameters,
radius of the neighbor-shell, and the effective interaction strength between the molecular species.
Molecular diameters and the neighbor shell size were determined from the RDFs obtained from
MD simulation of pure components and binary mixtures, respectively. Interaction strength
between the molecules was obtained from the potential of mean force which was calculated from
umbrella sampling simulations. The concept of local composition assumes that all of the
molecules in the neighbor shell of a center molecule experience the same potential, irrespective
of their position in the cage. This idea is incorporated into the two-fluid theory by considering
an interaction potential of the square well form. However, to map the net potential experienced
by a molecule (the barrier height in the PMF) onto a square well type potential, different
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methodologies have been suggested in the literature. We have used the mapping approaches
similar to that suggested by Brandani and Prausnitz27 (Approach I), and that by Hirschfelder et
al.,31 (Approach II) to calculate the binary interaction parameters. Both of the approaches
resulted in the binary interaction parameters of similar magnitude for majority of the systems
except one, indicating the robustness of our method. The technique proposed in this work is
purely predictive and requires no adjustable parameters. Such a technique, apart from providing
molecular insight into the thermodynamics of the mixtures, can also be used as a reliable method
to determine the binary interaction parameters for mixtures where experimental data are scarce
or are not available.
Overall, the binary interaction parameters predicted using molecular simulations showed
good agreement with those calculated using experimental data. Among the systems studied, the
water-methyl acrylate pair exhibits the largest disparity in terms of size and interactions and the
predicted binary interaction parameters exhibit stronger sensitivities to the approaches in
mapping molecular simulation results to two-fluid theory. The observation suggests that our
technique might need to be refined for such systems that exhibit large differences in molecular
characteristics of the two components.
The other important aspect to consider is the temperature dependence of the binary
interaction parameters which is not investigated in this work. Based on the framework proposed
here, it is rather straight forward to extend the methodology to high temperatures, given the
availability of a reliable force field over the temperature range of interest. We defer these
investigations to future work. The approach can also be extended to other complex mixtures
such as electrolyte systems.
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Acknowledgments
This work is supported by J.F Maddox Foundation and also by National Science Foundation
under the grant NSF CMMI-1335082. Computational resources provided by Chemistry
Computational Cluster (CCC) at Texas Tech University are acknowledged.
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List of Figure Captions
Figure 1. Pure component RDFs for water, methanol, and methyl acrylate showing effective
molecular sizes.
Figure 2. Potential of mean force of water + methanol system at two different concentrations
and at 303.15 K. (a) PMF around a center water molecule that is used in the calculation of τ ,
and (b) PMF around a center methanol molecule that is used in the calculation of τ . The
symbols denote the calculated PMF values and the lines represent the PMF smoothed with cubic
splines. The depths of the potential wells are marked in their corresponding colors.
Figure 3. Comparison of water + methanol binary phase behavior at 303.15 K using NRTL
equations with obtained from data regression (performed in this work) and molecular
simulations. (a) P-x-y diagram, and (b) Gibbs free energy of mixing.
Figure 4. Potential of mean force of methanol + methyl acrylate system at two different
concentrations and at 303.15 K. (a) PMF around a center methanol molecule that is used in the
calculation of τ , and (b) PMF around a center methyl acrylate molecule that is used in the
calculation of τ . The symbols denote the calculated PMF values and the lines represent the
PMF smoothed with cubic splines. The depths of the potential wells are marked in their
corresponding colors.
Figure 5. (a) Cluster size distribution of methanol at 0.25 mole fraction of methanol, and (b)
RDF of different components at 0.25 mole fraction of methanol in methanol + methyl acrylate
binary.
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Figure 6. Local mole fraction of methyl acrylate around methanol at different concentrations of
methanol. The horizontal lines are NRTL predictions using regressed parameters20.
Figure 7. Comparison of methanol + methyl acrylate binary phase behavior at 303.15 K using
NRTL equations with obtained from data regression (performed in this work) and molecular
Figure 8. Potential of mean force of water + methyl acrylate system at two different
concentrations and at 303.15 K. (a) PMF around a center water molecule that is used in the
calculation of τ , and (b) PMF around a center methyl acrylate molecule that is used in the
calculation of τ . The symbols denote the calculated PMF values and the lines represent the
PMF smoothed with cubic splines. The depths of the potential wells are marked in their
corresponding colors.
Figure 9. Comparison of water + methyl acrylate binary phase behavior at 303.15 K using
NRTL equations with obtained from data regression (performed in this work) and molecular
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Figure 1
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Figure 2.
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Figure 3.
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Figure 4.
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Figure 5.
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Figure 6.

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Figure 7.

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Figure 8.

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Figure 9.
()
(nm)
0.534
0.597

Table 1a. Neighbor Shell Size for Water + Methanol Binary Mixture
()
(nm)
0.534
0.534
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()
(nm)
0.377
0.597
Center molecule
Methanol (2)
Water (1)
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Tables
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Table 1b. Comparison of Binary Interaction Parameters for Water + Methanol System obtained
from Simulations with those Obtained from Experimental Data at 303.15 K: Non-randomness
Factor was set to 0.3 in the Calculations
Center Simulation Simulation Regression Regression20
molecule
(Approach I) (Approach II) (this work)
Water (1) -0.395±0.187 ( ) -1.287±0.369 ( ) -0.358±0.233 ( ) 0.105 ( )
Methanol (2) 0.446±0.233 ( ) 0.512±0.417 ( ) 0.976±0.368 ( ) 0.441 ( )
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Table 1c. Infinite Dilution Activity Coefficient of Water + Methanol System obtained using
NRTL Equations with τ Calculated from Simulations and from Experimental Data at 303.15 K
Center ln ( ) Simulation ln ( ) ln ( ) ln ( )
molecule Regression Regression20

(Approach I) Simulation
(this work)
(Approach II)
Water (1) -0.005 ± 0.257 -0.848 ± 0.477 0.37 ± 0.303 0.491
Methanol (2) 0.001 ± 0.331 -1.381 ± 0.86 0.577 ± 0.467 0.543
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()
(nm)
0.855
0.856
Table 2a. Neighbor Shell Size for Methanol + Methyl Acrylate Binary Mixture

()
(nm)
0.855
0.855
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()
(nm)
0.611
0.856
Methyl acrylate (2)
Center molecule
Methanol (1)
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Table 2b. Comparison of Binary Interaction Parameters for Methanol + Methyl Acrylate System
obtained from Simulations with those obtained from Experimental Data at 303.15 K: Non-
randomness Factor was Set to 0.3
molecule
Methanol (1) 1.229±0.114 ( ) 1.547±0.289 ( ) 0.838±1.141 ( ) 0.801 ( )
Methyl 0.392±0.175 ( ) 0.298±0.365 ( ) 0.456±1.257 ( ) 0.592 ( )
acrylate (2)
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Table 2c. Infinite Dilution Activity Coefficient of Methanol + Methyl Acrylate System obtained
using NRTL Equations with τ Calculated from Simulations and from Experimental Data at
303.15 K

(this work)
(Approach II)
Methanol (1) 1.578 ± 0.178 1.82 ± 0.419 1.236 ± 1.482 1.297
Methyl 1.242 ± 0.182 1.271 ± 0.378 1.108 ± 1.422 1.222
acrylate (2)
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()
(nm)
0.660
0.795

Table 3a. Neighbor Shell Size for Water + Methyl Acrylate Binary Mixture
()
(nm)
0.660
0.660
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()
(nm)
0.525
0.795
Methyl acrylate (2)
Center molecule
Water (1)
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Table 3b. Comparison of Binary Interaction Parameters for Water + Methyl Acrylate System
obtained from Simulations with those obtained from Experimental Data at 303.15 K: Non-
randomness Factor was Set to 0.3
molecule
Water (1) 0.311±0.147 ( ) 3.826±0.306 ( ) 1.084±0.014 ( ) 2.294 ( )
Methyl 2.078±0.189 ( ) 2.741±0.279 ( ) 2.687±0.056 ( ) 2.410 ( )
acrylate (2)
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Table 3c. Infinite Dilution Activity Coefficient of Water + Methyl Acrylate System obtained
using NRTL Equations with τ Calculated from Simulations and from Experimental Data at
303.15 K

(this work)
(Approach II)
Water (1) 1.425 ± 0.152 5.03 ± 0.307 2.284 ± 0.015 3.464
Methyl 2.361 ± 0.225 3.955 ± 0.279 3.47 ± 0.056 3.563
acrylate (2)
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Page 1 of 60 AIChE Journal

Ashwin Ravichandran, Rajesh Khare*, Chau-Chyun Chen*

Department of Chemical Engineering, Texas Tech University, Box 43121

Email: rajesh.khare@ttu.edu; chauchyun.chen@ttu.edu

This article is protected by copyright. All rights reserved.

arguments for each mixture.

Designing energy efficient and sustainable industrial processes requires reliable

prediction of thermodynamic and phase equilibrium properties. Molecular thermodynamic

liquid, liquid-liquid, and vapor-liquid-liquid equilibria of organic mixtures1-3 and of electrolyte

written in a semi-heuristic fashion, a rigorous interpretation of the local composition approach of

minima21 in the parameter estimation problem.

wide range of thermodynamic characteristics (hydrophilicity/hydrophobicity, hydrogen bonding

Theoretical Background and Simulation Details

Prausnitz14,27,28 for a detailed discussion of the approach.

molecules) in a domain around a central molecule of type is:

 =     (2)

−  + ( − )  !

central assumption of the local composition approaches.

The distribution function for a non-random arrangement (including specific interactions)

of a local domain is given by weighting  by the Boltzmann factor:

normalization factor that is analogous to a local partition function, with , = 1/#/.

+ = 0    

and Eq. 8, one obtains:

Equation 9 is thus equivalent to the NRTL equation (Eq. 1).

of the NRTL model can be written as:

,   −  

the domain can be derived in a similar fashion:

Author Manuscript =

hence evaluation of  from the - RDF becomes difficult.

mixtures of components and . Simulations were performed at different concentrations of the

range structure of the liquid extends.

  () 

# () = maxL# () , # () N, consistent with Approach I.

Author Manuscript , O0.56 %#

the trajectory was used for subsequent calculations.

distance of 1.2 nm, to be consistent with its definition.

Results and Discussion

nm from the location of the carbonyl carbon peak.

for the completely miscible mixture

(both MD and regression calculations)9. However in practice, the non-randomness factor is

they were not considered in the error estimation calculation.

The binary interaction parameters estimated from molecular simulation in combination

cause preferential solvation between components.

between the components) and consequently, ∆jkl is overpredicted in this case.

determine the strength of the interaction parameter

clustering behavior of methanol is attributed to specific hydrogen bonded interactions between

binary interaction parameter (dA ).

as shown in Fig. S1 of Supplementary Material), consistent with MD simulations. However, at

azeotrope in the range of 0.6-0.66 mole fraction of methanol.

thermodynamics for this partially miscible binary

strength of various interactions in the binary mixture. As expected, interaction between

form hydrogen bonds.

minimum, which is indicative of unfavorable interaction between the components. As a

with that estimated by regressing the experimental data.

MD simulation of pure components and binary mixtures, respectively. Interaction strength

or are not available.

predicted binary interaction parameters exhibit stronger sensitivities to the approaches in

characteristics of the two components.

such as electrolyte systems.

under the grant NSF CMMI-1335082. Computational resources provided by Chemistry

Computational Cluster (CCC) at Texas Tech University are acknowledged.

coefficient model. Industrial & Engineering Chemistry Research. 2004;43:8354-8362.

2. Kato R, Krummen M, Gmehling J. Measurement and correlation of vapor--liquid

Ashwin Ravichandran, Rajesh Khare, Chau-Chyun Chen

= (2)

− + ( − ) !

of a local domain is given by weighting by the Boltzmann factor:

+ = 0

, −

hence evaluation of from the - RDF becomes difficult.

mixtures of components and . Simulations were performed at different concentrations of the

()

Author Manuscript , O0.56 %#