Automatic fitting of binary interaction
parameters for multi-fluid
Helmholtz-energy-explicit mixture models†
Ian H. Bell∗ and Eric W. Lemmon∗
National Institute of Standards and Technology, Boulder, CO, USA
E-mail: ian.bell@nist.gov; eric.lemmon@nist.gov
Abstract
In the highest-accuracy mixture models
available today, these being the multi-fluid
Helmholtz-energy-explicit formulations, there
are a number of binary interaction parame-
ters that must be obtained through correlation
or estimation schemes. These binary interac-
tion parameters are used to shape the thermo-
dynamic surface and yield higher-fidelity pre-
dictions of various thermodynamic properties
including vapor-liquid equilibria and homoge-
neous p-v-T data, amongst others.
In this work, we have used a novel and entirely
automatic evolutionary optimization algorithm
written in the python programming language to
fit the two most important interaction parame-
ters for more than 1100 binary mixtures. This
fitting algorithm can be run on multiple proces-
sors in parallel, resulting in a reasonable total
running time for this large set of binary mix-
tures. For more than 830 of the binary pairs,
the median absolute relative error in bubble-
point pressure is less than 5%.
The source code for the fitter is provided as
†
Commercial equipment, instruments, or materials
are identified only in order to adequately specify cer-
tain procedures. In no case does such identification im-
ply recommendation or endorsement by the National
Institute of Standards and Technology, nor does it im-
ply that the products identified are necessarily the best
available for the purpose. Contribution of the National
Institute of Standards and Technology, not subject to
copyright in the US
1
supplemental data, as well as the entire set
of binary interaction parameters obtained and
comparisons with the best experimental vapor-
liquid-equilibrium data that are available.
Introduction
There are many types of mixture models avail-
able to represent the thermodynamic properties
of mixtures of fluids that cover both phase equi-
libria and homogeneous (liquid, gas, and super-
critical) states. Over the years, the mixture
models have increased in complexity and ac-
curacy, largely driven by the increasing power
of computers, which has both allowed the use
of more computationally-expensive equations of
state, as well as allowed correlators the ability
to leverage this computational power to fit more
complex equations of state.
One of the most commonly used families
of models is that of cubic equations of state.
These cubic equations are straightforward to
implement, even for mixtures, and can allow for
solution of the density as a function of temper-
ature and pressure in an explicit formulation,
even though they are expressed in the form of
pressure as a function of temperature and spe-
cific volume. These cubic equations of state can
be converted to a Helmholtz-energy-explicit for-
mulation through the use of the analysis of Bell
and Jäger 1 . Other models have also been pro-
posed, including the SAFT-based models, Lee-
Kesler-Plöcker 2 , and the non-dimensionalized
Helmholtz energy formulation utilized here.
The multi-fluid mixture property model has
seen wide application because it represents
a fundamental thermodynamic potential, and
therefore all other thermodynamic properties
can be obtained by derivatives of the Helmholtz
energy. This mixture formulation is that used
in the state-of-the-art thermophysical prop-
erty libraries REFPROP 3 , CoolProp 4 , and
TREND 5 .
Non-dimensionalized Helmholtz
energy models
REFPROP 9.1 3 is the current state-of-the-art
in mixture binary parameters; it includes inter-
action parameters for 697 mixtures, with ap-
proximately 200 of these obtained from the lit-
erature 6–13 as well as mixture interaction pa-
rameters that were fitted through the use of
in-house code. To the author’s knowledge, the
only other libraries that implement a signifi-
cant number of binary interaction parameters
for high-accuracy mixture models are the open-
source library CoolProp 5.1 4 comprising 220 bi-
nary pairs and the TREND 2.0 package from
the University of Bochum, Germany 5 , compris-
ing 210 binary pairs.
In the multi-fluid mixture model, the pressure
of the mixture can be obtained from
∂αr
 
p = ρRT 1 + δ (τ, δ) . (1)
∂δ
Other thermodynamic properties of interest
(enthalpy, entropy, etc.) can be obtained in a
similar fashion. For more information on cal-
culating other thermodynamic properties from
derivatives of the residual Helmholtz energy,
see the work of Span 14 . The Helmholtz en-
ergy is expressed in terms of the reduced density
δ = ρ/ρr (x̄) and the reciprocal reduced temper-
ature τ = Tr (x̄)/T . For further information, the
reader is directed to the coverage of the mixture
models in the literature 11–13 .
According to the most recent formulation
used in all of the state-of-the-art libraries, the
reducing parameters for the mixture (Tr and
2
vr = 1/ρr ) can be given in a common form by
N N −1 X N
X
2
X xi + xj
Yr (x̄) = xi Yc,i + 2xi xj 2 Yij
i=1 i=1 j=i+1
βY,ij xi + xj
(2)
where Y is the parameter of interest, either mo-
lar specific volume v or temperature T . The
necessary parameters are given by
Yr Yc,i βY,ij Yij
Tr Tc,i βT,ij βT,ij γT,ij (Tc,i Tc,j )0.5
 3
1 1/3 1/3
vr vc,i βv,ij β γ
8 v,ij v,ij
vc,i + v c,j
These mixture reducing equations are simply
weighting functions of the critical properties of
the pure fluids that form the mixture.
For the ij pair, there are a total of four
adjustable parameters - βT,ij , γT,ij , βv,ij , and
γv,ij . The γ parameters are symmetric (γY,ij =
γY,ji ), while the β parameters are not symmet-
ric (βY,ij = 1/βY,ji ), and thus the order of flu-
ids in the binary pair is important and must
be handled carefully when implementing this
sort of mixture model. There is additionally
an adjustable parameter Fij that is applied to
the generalized departure function as described
by Kunz and Wagner. 12 In this work, we do
not consider the departure terms because of the
paucity of experimental data for many of the
mixtures under study; a significant body of ex-
perimental data is needed to be able to fit the
departure function. Hence, the parameter Fij
in the departure term is set equal to zero.
The mixture interaction parameters βT,ij ,
γT,ij , βv,ij , and γv,ij are often obtained through
manual fitting, some deterministic optimization
routines, as well as user intervention to divide
the experimental data into training and vali-
dation sets. The culmination of all this work
is the set of binary interaction parameters in
the REFPROP 9.1 library. Figure 1 shows a
boxplot of the parameter distributions for all
binary pairs that are included in REFPROP
9.1. As can be seen in the figure, the median
value (given by the red bar inside the box), is
very nearly unity for all four of the interac-
tion parameters. Aside from γT,ij , the range
of the parameters is also quite narrow, being
quite tightly clustered around unity.
envelopes, the deformation does not result in
drastically different phase envelope shapes. Im-
portantly, modifying the interaction parame-
ters has a much more significant impact on the
bubble-point lines than on the dew-point lines.
This is important because fitting only dew point
data to obtain the interaction parameters could
yield significantly erroneous predictions for the
bubble-point data. It is largely for this rea-
son that the bubble-point data were used exclu-
sively to fit the mixture interaction parameters
in this work. Furthermore, for many mixtures,
the only data available are bubble-point mea-
surements.

Figure 1: Boxplot of the mixture interaction

parameters in the REFPROP 9.1 library (blue
box shows inter-quartile range containing 25th
to 75th percentile of the data, fliers outside this
range shown by markers, the red lines show me-
dian values).

While the work, which culminated in the

mixture interaction parameters that are im-
plemented in the REFPROP library (and the
GERG models 12,13,15 , amongst others), was
able to use the binary-specific departure func- Figure 2: Phase envelopes for an equimolar
tions to strongly shape the thermodynamic mixture of methane and ethane.
property surface, the analysis here only fits two
parameters, βT,ij and γT,ij , and sets the param-
eters βv,ij and γv,ij to 1.0. The motivation for Data collection and prepara-
fitting only these two parameters is that they
are the parameters that are the most impor- tion
tant for fitting bubble-point data, and adjust-
The values obtained for the binary interaction
ing these parameters within reasonable ranges
parameters can only be as good as the experi-
does not tend to result in significant (and unde-
mental data upon which they are based. There-
sired) deformation of the thermodynamic prop-
fore, it is of utmost importance to have as
erty surfaces.
comprehensive and complete an experimental
The significance of these parameters can be
database to draw from as possible.
seen by plotting phase envelopes for binary mix-
In this work, two large databases of ex-
tures. Phase envelopes represent the saturation
perimental vapor-liquid equilibria data were
curve (dew-point and bubble-point), including
merged into one joined database. The primary
the entire critical region, for a fixed mixture
database for this study is the database Thermo-
composition. Figure 2 shows several phase en-
DataEngine 16–18 that is developed at the Na-
velopes for an equimolar mixture of methane
tional Institute of Standards and Technology in
and ethane, demonstrating that while adjusting
Boulder, Colorado. As of publication, Ther-
the interaction parameters deforms the phase
moDataEngine includes vapor-liquid equilibria

3
data for more than 40,000 binary mixtures.
The second database of experimental data is
an internal database developed by researchers
at NIST over the last few decades.
Both ThermoDataEngine and the internal
NIST mixture property database include other
types of data, including homogeneous-phase
pressure-density-temperature (p-ρ-T ) data,
virial coefficient data, etc.
Merging the two databases required careful
reconciliation of their respective datasets. In
many cases the same dataset was present in
both databases, in which case only one copy
was retained. Furthermore, the databases were
in entirely different formats with incompatible
metadata, requiring several steps of normal-
Figure 3: Distribution of bubble-point data
ization to make the databases possible to be
from reconciled databases.
merged into one master database.
In the end, the master database of experi-
mental data was created in a form compatible
with the python package pandas, and a sepa-
Fitting Methodology
rate database of bibliographic information was As described above, the goal of the fitting pro-
generated in the BibTeX format. cedure is to arrive at the best values for βT,ij
Figure 3 shows the distribution of bubble- and γT,ij for a given binary mixture of two pure
point data in the master database, sorted fluids; this pair of optimal values represents a
by the bubble-point data available. There global minimization of the objective function
are a number of popular mixtures that have (to be defined below). The fitting of binary in-
been exceptionally well studied; in this case teraction parameters is complicated by a num-
the five mixtures with the most experimental ber of unavoidable features of the fitting pro-
bubble-point data are ethanol-water, methanol- cess:
water, nitrogen-water, benzene-cyclohexane,
and ammonia-water. On the other end of the • Modification of the interaction parame-
spectrum are comparably many mixtures for ters can cause failure of flash routines
which there is only a small amount of data that previously succeeded, or vice versa.
available, with as few as one bubble-point mea- Sometimes very small changes can cause
surement. this failure state transition, and only one
datapoint may see this transition.
• The objective function is not smooth,
making numerical partial differentiation
of the objective function with respect to
the interaction parameters difficult or im-
possible.
• A highly accurate and well constructed
equation of state must already exist for
each of the components in the mixture.
• Some of the experimental data points are
questionable or are known to be faulty,

4
 though that may not be noted as such in
the respective database.
• The experimental uncertainties are in
most cases unknown.
The overarching conclusion is therefore that
deterministic (especially derivative-based) op-
timization routines are not viable for this prob-
lem. Therefore, another method must be se-
lected that can accommodate the roughness of
the objective function, is robust to transitions
in the failure state of the flash routines, and can
conveniently arrive at the optimal values for the
parameters.
Before beginning an optimization campaign,
it is crucial to understand the shape of the ob-
jective function. Figure 4 shows a plot of the
objective function for the methane-isobutane
binary pair, as well as cross-sections A and B
cutting through the surface in the vicinity of the
minimum value of the objective function. There
is a clear minimum in the objective function
near βT,ij = 1.01, and γT,ij = 1.2. The color fill-
ing the plot is generated by interpolation of the
objective function at the gridded data points.
The objective function is not smooth due to the
random selection of experimental data points,
as demonstrated by the jagged form of the con-
tours, especially at high values of γT,ij .
In the course of this work, several opti-
mization methods were investigated, including
brute-force optimization with cubic interpola-
tion, amongst others. In the end, the most
robust and computationally efficient solution
proved to be genetic optimization. In particu-
lar, we employed the open-source DEAP python
package in this work 19 , the details of which are
described further on.
Optimization and Fitting
As described above, determination of the mix-
ture interaction parameters is a challenging
optimization problem that is not well suited
to deterministic (derivative-based) optimiza-
tion methods. For this reason, various stochas-
tic optimization routines were considered.
The use of stochastic, or evolutionary, opti-
mization routines is not a new concept. For
5
instance Schmidt and Lipson 20 used evolution-
ary optimization to distill governing physical
laws from experimental data on (simple) phys-
ical systems.
Furthermore, other stochastic optimization
methods are available, and Krink et al. 21
demonstrated that evolutionary optimization is
one of the best optimization methodologies for
noisy objective functions. They show that evo-
lutionary optimization is superior to differential
evolution for noisy optimization. This provides
further support for the optimization scheme
used here.
Fitting Process
The computational pipeline employed for this
problem is to start with a library of many
(approximately 160,000) experimental vapor-
liquid-equilibrium data points spanning more
than 1,200 binary mixtures for which reliable
equations of state are available for both com-
ponents. The current fitting methodology in-
cludes only the vapor-liquid-equilibrium data,
and more specifically, the fitting procedure is
only based on the use of bubble-point measure-
ments. All of the bubble-point data for a given
binary pair are extracted from the library into
a pair-specific subset. This subset for the se-
lected mixture forms the data source for the
fitting routines.
The optimization routine has two indepen-
dent variables, βT,ij and γT,ij . For a given
set of βT,ij and γT,ij , a handful of datapoints
(generally 5-10) are randomly selected from the
dataset for the binary pair. For each of the
selected datapoints in the handful, the bubble-
point pressure is calculated as a function of the
given bubble-point temperature and bulk mole
fraction (the mole fractions of the liquid phase
at the bubble point are equivalent to the bulk
mole fractions). The signed error vector over
these randomly selected handful of datapoints
is calculated as
p~exp − p~calc
~eS = × 100 (3)
p~exp
If a flash routine fails for one of the datapoints
forming the handful, a very large number is en-
Figure 4: Presentation of the objective function over a regular grid for the binary pair methane-
isobutane along with cross-sections cutting through the surface in the vicinity of the minimum of
the surface. The objective function surface is truncated at a value of 300.

6
tered in the appropriate location in p~calc . The
error metric for the randomly selected handful
is then simply the root-sum-of-squares
qX
ERSS = [(~eS )2 ] (4)
With the RSSE error metric for the randomly
selected handful, at least one datapoint causing
failure of a flash routine will also result in large
errors for the handful.
In order to get a representative calculation of
the error for the binary pair for a given set of
βT,ij and γT,ij , this random-selection and error-
calculation process must be carried out a num-
ber of times. In general, this process is repeated
about 100 times, each time randomly selecting
approximately 5 of the data points.
Selection of the appropriate error metric is
key when considering all the calculated values
and errors for one pair of βT,ij and γT,ij . In
general, it is quite common to use either a root-
sum-of-squares error (RSSE) or mean absolute
error (MAE) error metric. The weakness of
these error metrics is that one very large value
(for instance a failure of a flash routine entered
as a large number) can dramatically skew the
error metric. On the other hand, the use of the
median absolute error rather than either RSSE
or MAE results in an error that rejects the fail-
ures in the flash routine. So long as only a few
randomly selected handfuls contain failures of
the flash routines, the median absolute error
metric will allow the optimization algorithm to
reject these failures and keep moving towards
the optimal solution.
Thus, the base objective function that is be-
ing minimized is:
OBJ0 (βT,ij , γT,ij ) = median([ERSS,1 , ERSS,2 , . . . ])
(5)
It is necessary to further constrain the objec-
tive function to yield more reliable flash routine
evaluations. With the median error metric, if
49% of the experimental data points cause fail-
ures of the flash routines, the median error can
still be quite low since the middle value is used
when sorting the absolute error. As an exam-
ple, we might have an error array ERSS (sample
7
data for illustrative purposes) that looks like
ERSS = [1, 2, 3, 1010 , 1010 ] (6)
where 1010 are large values signifying the failure
of a flash routine. In this case, 40% of the runs
have failed, but we still yield a median error
that is 3%.
In order to “push” the optimizer back to the
best solution (trading flash routine failures for
errors in prediction of VLE data), it is necessary
to penalize solutions that have a low median er-
ror but cause a significant number of flash rou-
tine failures. To that end, the OBJ0 (βT,ij , γT,ij )
function is multiplied by a penalty function de-
fined by
F = 10ffail nfail (7)
where nfail is an integral penalty exponent (usu-
ally 2 or 3), which controls the sharpness of the
penalty and ffail is the fraction (in the range 0
to 1) of the flash routine evaluations that fail.
If none of the flash routine evaluations fail, the
penalty factor F is 1, and thus no penalty is ap-
plied. If all the flash routines fail, the F factor
is 10nfail .
Thus, the final objective function that is used
in the optimizer is given by
OBJ(βT,ij , γT,ij ) = F · OBJ0 (βT,ij , γT,ij ) (8)
Fitting Implementation
The DEAP package used (and as described
above) is a flexible set of open-source tools for
minimization of objective function(s). The em-
phasis is on evolutionary optimization, though
other optimization methodologies are also sup-
ported. As such, it is relevant to briefly de-
scribe the methodology that is used in DEAP
to arrive at the “best” solution. To begin with,
a population of individuals (sometimes referred
to as chromosomes in genetic optimization lit-
erature) is generated, each with its own fitness
associated with how well the individual predicts
the bubble-point pressures. In this case the fit-
ness is the inverse of the objective function -
the higher the fitness, the lower the objective
function, and the better the values represent
the experimental measurements.
 After having randomly generated the initial
population of individuals, a number of methods
are used to combine and mutate the population
of individuals. The primary types of operations
in the genetic optimization are:
• Mutation: Similar to spontaneous muta-
tion of genetic chromosomes in biological
systems, the individual can mutate, and
each of its parameters can be given an off-
set, where the offset is given by a Gaus-
sian distribution centered around zero.
The standard deviation of the Gaussian
distribution is used to control the spread
of the mutations, and a probabilistic pa-
rameter is applied to decide whether the
individual should mutate or not.
• Cross-over / reproduction : In cross-over
or reproduction, various models can be
applied to govern the outcome of the in-
teraction of two individuals. This is simi-
lar, in biological systems, to the resulting
offspring’s chromosomes when its parents
reproduce sexually. Various models are
available, including weighting of the par-
ent’s chromosome, or allowing for weights
that can yield chromosomes outside the
range of the parent’s chromosomes.
The extent of user involvement in running this
code is tuning the width of the Gaussian distri-
butions, and setting the probabilities of muta-
tion, cross-over, and reproduction of the indi-
viduals. Otherwise, the code is entirely auto-
matic and requires no user intervention. The
following values were used in the final version
of the fitter:
• Number of generations: 30
• Population size: 150
• Tournament selection size1 : 5
• Mutation probability: 50%
1
Tournament selection refers to the process of com-
paring a number of individuals, in randomly selected
pools, and keeping the best individual from this pool
to populate the next generation. The larger the pool
size, the greater the selection pressure - corresponding
to the aggressive selection of high-fitness individuals at
the expense of population diversity.
8
• Cross-over probability: 30%
The implementation is entirely based on
a python-based open-source framework, aside
from the use of NIST REFPROP as the prop-
erty backend to provide the bubble-point eval-
uation. All thermodynamic calls are made
through the CoolProp library, which delegates
to the REFPROP library to make the neces-
sary bubble-point calculations. The system is
constructed so that it can scale to multiple pro-
cesses in parallel. Process-level parallelization
(as opposed to thread-level parallelization) is
required as REFPROP is not thread-safe, and
multiple mixture interaction files in REFPROP
must have the interaction parameters injected
into them by the optimization routines (one
mixture file per process). Finally, the fitting
routines make heavy use of the pandas python
package for data management and data subset-
ting.
The flowchart in Figure 5 shows the way that
the optimization is divided into sub-processes,
each of which operates on a given binary mix-
ture. The master process spawns a number of
subprocesses, each of which is passed a subset
of the data for the binary pair that is being
calculated by the subprocess. In this way, the
large job is subdivided into smaller segments
that can be easily handled by one processor.
As each subprocess finishes its optimization, it
writes its data to a file and signals the master
process that it has completed, and begins to
work on the next mixture.
The source code for the fitting routines is
available as an electronic appendix, along with
sample data for one binary pair (propane + n-
decane) taken from the work of Mansfield et
al 22 . These data serve as a real-world demon-
stration of the fitting methodology.
 Master process two compositions then βT,ij was set to 1.0 and
only γT,ij was fitted.
Subset data for binary pair For more complex mixtures, adjusting γT,ij
and βT,ij does not provide enough flexibility to
Process igen = 0 properly model the vapor-liquid equilibria and
homogeneous fluid properties of the binary mix-
ture in a consistent fashion. Highly asymmetric
Generation binary mixtures (helium + water being perhaps
Get individual (βT,ij , γT,ij ) the most extreme example) further stress the
flash routines, resulting in frequent failures due
Individual j=0 to insufficiently accurate starting values. These
failures of the flash routines mean that poten-
tially high-accuracy vapor-liquid equilibria data
Get Nselect points are being rejected.
experimental points

igen = igen + 1
As a result of these challenges, the resulting
j =j+1

Calculate error vector binary interaction parameters were divided into

⃗e = f (T⃗ , z) two tiers. The first tier are mixtures for which it
is believed that the interaction parameters are
Calculate error metric
⃗ j = f (⃗e)
E
reliable and can be used for accurate predictions
of the properties of this system.
Yes In order for a binary pair to be in tier #1, the
j < Nloops following two conditions must both be met:

No • The median absolute relative error (de-

fined below) associated with the bubble-
⃗
Store individual error f (E) point data is less than 5 %.

No • Sufficient experimental data are available

Generation Full? to fit both βT,ij and γT,ij (experimental
bubble point data for at least two tem-
Yes peratures and two compositions).
Mate/Mutate/Cross
If either of the conditions is not met, the binary
pair is relegated to tier #2.
No The supplemental data associated with this
Max generation #? paper include the set of interaction parame-
ters that were obtained from the fitting proce-
Yes dure, as well as the complete set of bibliographic
STOP information associated with the data used for
each of the binary pairs.
Figure 5: Flowchart for the fitting process
Accuracy
Results The tables in the supplemental information
contain all of the mixture interaction parame-
This fitting procedure was carried out for all the ters that were fit, along with information about
mixtures for which at least one experimental the accuracy of each fit at predicting the bubble
bubble-point data point could be found in the point data. The median absolute relative error
reconciled database. If bubble-point data were
not available for at least two temperatures and

9
(MARE) parameter is defined by data that were used in the fitting process, while
   in this work, the sheer amount of experimen-
 p~exp − p~calc  tal data considered required an automatic ap-
MARE = median   × 100 (9)
 
p~exp proach. Furthermore, in many cases (the open
markers), the developers of the given pair of
The median absolute relative error is only a rel-
BIPs also fit a departure function with the mul-
evant metric in comparison to existing values
tiplication factor Fij . The reader is directed to
for the error. Here we define an improvement-
the description of the GERG model for a further
in-error term I that quantifies the improvement
discussion of the departure function. In many
compared with REFPROP
cases, two BIP parameters were fit, but the two
 parameters that were fit were either γT,ij and
 (ER  − 1)  × 100 for ER >= 1
γv,ij instead of the pair βT,ij and γT,ij used in
I= 1
 − − 1 × 100 for ER < 1 this work. Additionally, the fits in REFPROP
ER
(10) are, in some cases, also based on p-v-T , heat
where the error ratio ER is defined by capacity, speed of sound, and any other data
available for a particular binary pair.
MAREREFPROP Figure 7 shows the overall MARE distribu-
ER = (11)
MAREBell tion for all the mixtures that were fit in this
work. For nearly 1000 of the binary mixtures,
The reason for this (admittedly convoluted) the MARE is less than 10%; a 10% MARE
definition for the improvement in error is such can be considered as a sufficiently accurate rep-
that if one (but not both) of MAREREFPROP resentation of the data for many applications.
or MAREBell values is very nearly zero, the im- More than 800 of the mixtures have a MARE
provement term will neither go to zero nor infin- less than 5%. In some cases this is because there
ity. The improvement I should be interpreted was only one data point, which was fit very ac-
in this way – a value of I = 1 is a 1% decrease curately, so the MARE is an imperfect metric
in the MARE, I = −1 is a 1% increase in the for goodness-of-fit.
MARE. Basically, the more positive I is, the
better.
Figure 6 shows a plot of the MARE versus the
improvement factor I. While more than 1100
mixtures were fit in this work, REFPROP in-
cludes fitted binary interaction parameter val-
ues for 522 mixtures, and those are plotted here.
For approximately 300 of the binary mixtures,
the current fitted parameters yield an improve-
ment over the parameters in REFPROP; some
of this measured improvement is a result of
the datasets considered in the respective fitting
process. On the other hand, there are many
mixtures where the fitted parameters provide a
worse representation of the VLE data than the
use of the parameters from REFPROP.
It is challenging to draw clear conclusions
from a comparison of the resultant errors
caused by the use of the binary interaction Figure 7: Distribution of MARE for the binary
parameters (BIP) in REFPROP and those in pairs fit in this work.
this work. The BIPs in REFPROP were ob-
tained by careful curation of the experimental

10
Figure 6: Improvement I and median absolute relative error (MARE) of the bubble point pre-
dictions. The improvement I is based on the median error over all experimental bubble point
measurements. The entries in the legend correspond to the number of interaction parameters that
were fit in REFPROP 9.1. The count of mixtures with this number of parameters fit in REFPROP
9.1 is given in parenthesis.

Repeatability
Due to the stochastic nature of the fitting pro-
cess, each time the optimization is executed,
the algorithm will arrive at a different opti-
mal solution for the mixture interaction pa-
rameters βT,ij and γT,ij . Ideally, the solutions
for the optimal mixture interaction parameters
should be tightly clustered around their respec-
tive mean values. In order to demonstrate the
repeatability of the optimization outlined here,
the optimizer was run 100 times for two mix-
tures. These mixtures were selected because
they demonstrated low computational require-
Figure 8: Deviations from the mean values
ments, while also having enough bubble point
(given by overbar) for βT,ij and γT,ij for the
measurements that the same points were not
binary mixtures n-heptane + n-hexane and re-
always sampled.
frigerant R143a + refrigerant R152a over 100
Figure 8 demonstrates the results from 100
runs of the fitter. Each marker represents the
runs of the optimizer for the interaction param-
results from one execution of the fitter.
eters for these mixtures. As seen in this figure,
the largest deviation of βT,ij and γT,ij from the
mean value is less than 0.2%. In the vast major- Error evolution
ity of cases, the deviations are less than 0.05%
from the mean value. As the evolutionary algorithm works to find an
optimal solution for the interaction parameters
βT,ij and γT,ij , the error decreases in a nearly
monotonic fashion. In the case of this optimiza-
tion problem, there are sometimes steps that re-

11
sult in an increase in the error due to the experi-
mental data points that have been selected. For
instance, even if βT,ij and γT,ij are unchanged,
the error can sometimes increase due to the in-
clusion of one or more points with higher error.
Fig. 9 shows the evolution of the fitness func-
tion over the 200 repeatability tests described
above. These profiles demonstrate the char-
acteristic error evolution, that of a steep de-
crease in the error initially, followed by a near-
asymptotic behavior in the limit of an infi-
nite number of generations. For both mixtures,
most runs arrive very near their optimal value
after approximately 10 generations, and the re-
maining generations are used to refine the so-
lution. In some cases, there are local increases
in the objective function (points with worse er-
ror), but in the end, all runs arrive near the
same solution.
Figure 9: Evolution of the fitness function for
the binary mixtures n-heptane + n-hexane and
refrigerant R143a + refrigerant R152a from the
repeatability tests.
Homologous families
As a demonstration of the output of the fitting
procedure, the results for the family of n-alkane
+ n-alkane mixtures are presented for all binary
pairs where it was possible to fit both βT,ij and
γT,ij . Figure 10 presents the fitted values for
βT,ij and γT,ij . A few comments are required for
this plot. As described above, βT,ij = 1/βT,ji .
Thus the order of fluids in the binary pair is
of consequence. In order to yield a consistent
12
set of variables, the binary pair was sorted such
that the first element in the binary pair (i =
1) is that with the lower molar mass, and the
second element (j = 2) in the binary pair is that
with the higher molar mass. Furthermore, the
abscissa (x-coordinate) of the plot is the ratio
of the maximum molar mass in the binary pair
to the minimum molar mass in the binary pair.
The trend in interaction parameters for the
homologous n-alkane + n-alkane family is
nearly linear, and as a result, linear curves were
fitted to βT,ij and γT,ij as a function of the ra-
tio of molar masses. These linear correlations
can be used to yield reasonable predictions of
the interaction parameters for binary n-alkane
mixtures for which no experimental data of any
kind exist. This estimation scheme has been
applied to mixtures that include higher alkanes
and has demonstrated reasonable extrapolation
ability.
Similar exercises could be carried out for
other families of fluids. As another demonstra-
tion of the strong familial trends, the obtained
values of γT,ij are plotted for the binary pairs
containing carbon dioxide in Figure 11. This
figure demonstrates greater values of γT,ij for
greater differences in critical temperature be-
tween carbon dioxide and the other component.
Figure 11: Values of γT,ij for the carbon dioxide
family. The abcissa Tc refers to the critical tem-
perature of the other component in the mixture
with carbon dioxide. The value for water is not
included.
 Figure 10: Binary interaction parameters for the homologous n-alkane + n-alkane family
Conclusions
The binary interaction parameters βT,ij and
γT,ij have been fitted for more than 1100 mix-
tures. The improved interaction parameters
will be included in a future version of REF-
PROP. The interaction parameters are ob-
tained from an evolutionary optimization algo-
rithm based on an open-source python frame-
work. The fitting procedure conveniently scales
to large computational clusters.
Further work will entail the development of
a predictive scheme for βT,ij and γT,ij based on
information about the pure fluids forming the
mixture.
Acknowledgement The authors thank Ken
Kroenlein and Chris Muzny of the National In-
stitute of Standards and Technology who fa-
cilitated the extraction of data from Thermo-
13
DataEngine and made available computational
resources used for this study, and Marcia Hu-
ber, also of NIST, for background on genetic
optimization.
Supporting Information Available:
a) Python source code of the fitter
b) Fitted binary interaction parameters
c) Comparison with the available experimental
data
This material is available free of charge via the
Internet at http://pubs.acs.org/.
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