International Journal of Refrigeration 103 (2019) 145–154

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International Journal of Refrigeration

journal homepage: www.elsevier.com/locate/ijrefrig

Molecular modeling of the solubility of low global warming potential

refrigerants in polyol ester lubricants
Wael A. Fouad a,∗, Lourdes F. Vega b
a
Department of Chemical Engineering, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
b
Gas Research Center and Department of Chemical Engineering, Khalifa University, P.O. Box 127788, Abu Dhabi, United Arab Emirates

a r t i c l e i n f o a b s t r a c t

Article history: Pentaerythritol esters (PECs) act as the main precursors in polyol ester (POE) lubricants. The solubility of
Received 12 January 2019 low global warming potential (GWP) refrigerants in linear chained PECs was studied in this work using
Accepted 5 April 2019
the perturbed chain form of the statistical associating fluid theory (PC-SAFT). The effect of PEC alkyl tail
Available online 10 April 2019
length on the solubility of various refrigerants was investigated. Results showed that the solubility of HFO
Keywords: refrigerants is weakly dependent on PEC molecular structure. On contrary, the solubility of other natu-
Lubricant ral and paraffin refrigerants significantly increased with increasing the alkyl tail length. Within the SAFT
Refrigerant framework, pure component and binary interaction parameters were found to correlate linearly with PEC
Low GWP molecular weight. These correlations were used to predict the solubility of refrigerants in a predefined
PC-SAFT PEC blend through component lumping. Sensitivity analyses showed that the latter simplification could
POE adequately describe the mixture phase behavior. The proposed model was then applied to fully and accu-
rately predict the solubility of carbon dioxide in commercial POE lubricants. Results demonstrate that the
proposed model can be used as a fully predictive tool to determine the solubility of refrigerants in com-
mercial POE oils, provided that the lubricant molecular weight is known, a clear step forward developing
adequate low GWP refrigerants-lubricant pairs.
© 2019 Elsevier Ltd and IIR. All rights reserved.

Modélisation moléculaire de la solubilité des frigorigènes à faible potentiel de

réchauffement planétaire dans les lubrifiants à base d’esters de polyol

Mots-clés: Lubrifiant; Frigorigène; Faible GWP; PC-SAFT; POE

1. Introduction
Lubrication oils are commonly used in rotating equipment to
reduce friction and excessive heating due to the moving body parts
in contact. In a typical vapor compression cycle, the lubrication oil
frequently escapes the compressor and is swept along with the re-
frigerant used in the system. In this stage, the oil mist is carried
by the hot discharge gas to the condenser where it mixes with liq-
uid refrigerant and passes through the liquid line to the evaporator.
As heat is being removed from the media to be cooled, the liquid
refrigerant vaporizes leaving behind an oil film in the evaporator.
∗
Corresponding author.
E-mail address: wael.ahmed@kfupm.edu.sa (W.A. Fouad).
The latter described process does not just affect the level of lubri-
cation needed for compression, but also adds to the resistance for
heat transfer in the evaporator. Consequently, gas–oil miscibility is
one of the important criteria in selecting the proper lubricant for
a specified process (Ananthanarayanan, 2013).
Ideally, the lubricant should remain miscible with the refrig-
erant in the evaporator for complete oil return as well as for
efficient heat transfer. Historically, mineral oils were commonly
used with dichlorodifluoromethane (R-12) at low pressure systems
due to their full miscibility. However, chlorofluorocarbons (CFCs)
were phased out based on the Montreal Protocol of 1987 ow-
ing to their ozone depletion potential (ODP). Consequently, 1,1,1,2-
tetrafluoroethane (R-134a) was utilized as a replacement for R-12
but, in return, is immiscible in mineral oils. This has necessitated
the rapid development of synthetic oils that are compatible with

https://doi.org/10.1016/j.ijrefrig.2019.04.004
0140-7007/© 2019 Elsevier Ltd and IIR. All rights reserved.
146 W.A. Fouad and L.F. Vega / International Journal of Refrigeration 103 (2019) 145–154

Nomenclature

A Helmholtz free energy (J)

a2 reduced Helmholtz free energy of second-order per-
turbation expansion, Eq. (9)
a3 reduced Helmholtz free energy of third-order per-
turbation expansion, Eq. (9)
NA Avogadro’s number (particles/mol)
kB Boltzmann constant (J/K)
T temperature (K)
P pressure (Pa)
m number of segments per chain
ghs average radial distribution function of hard chain
fluid
d temperature dependent segment diameter (Å)
ɛ depth of pair potential (J)
σ segment diameter (Å)
η packing fraction
Z compressibility factor
ρ total number density of molecules (1/Å3 )
xp fraction of polar segments per chain
μ dipole moment (D)
kij binary interaction parameter
MW molecular weight, (g/mol)
x mole fraction
w mass fraction
Superscripts
id ideal gas
hc hard chain
disp dispersion
polar dipolar
hydrofluorocarbons (HFCs). POE oils were found to be miscible
with HFCs, tolerant to small amounts of CFCs and mix well with
mineral oils. Consequently, converting a system with R-12-mineral
oil pair to R-134a-POE oil pair would involve a simple straight-
forward procedure (Ananthanarayanan, 2013). Recently, the Ki-
gali Amendment to the Montreal Protocol, signed at year 2016,
has legally bound governments to phase down the production
and consumption of HFCs by year 2024. Hydrofluoroolefins (HFO)
such as trans-1,3,3,3-tetrafluoropropene (R-1234ze(E)) and 2,3,3,3-
tetrafluoropropene (R-1234yf) as well as natural refrigerants such
as isobutane (R-600a) and carbon dioxide (R-744) were recom-
mended as low global warming potential (GWP) and non-ozone
depleting alternatives for R-134a. As a result, it is critical to exam-
ine the miscibility of the currently used lubrication oils with the
newly introduced low GWP refrigerant alternatives.
Absorption properties of R-1234ze(E), R-1234yf, R-600a and R-
744 in commercial lubricant oils have been reported in the past
few years (Neto et al., 2014; Spatz, 2009; Fujitaka et al., 2010;
Bobbo et al., 2014; Lee et al., 2016; Karnaz, 2014; Leck, 2009; Bock,
2015; Fukuta et al., 2005; Neto and Barbosa, 2011; Neto and Bar-
bosa, 2010; Neto and Barbosa, 2008; Zhelezny et al., 2007; Seeton
et al., 20 0 0; Youbi-Idrissi et al., 20 03; Tsuji et al., 20 04; Bobbo et
al., 2006b; Bobbo et al., 2008a). However, the exact structures of
these studied oils, which consists of different organic compounds,
antioxidant and antiwear additives, are unknown. Therefore, it has
been extremely difficult to analyze the influence of the oil struc-
ture on the system phase behavior. In addition, the task of devel-
oping any reliable thermodynamic model to predict the phase be-
havior remains a challenging endeavor.
Owing to its superiority in modeling chains of hard or soft
(Lennard–Jones) segments with highly directional attractive forces,
the SAFT equation of state (EoS) (Chapman et al., 1988, 1989, 1990)
Fig. 1. Base chemical structure of pentaerythritol esters considered in this work.
is one of the models used to study these systems. Due to the
lack of information on structure and composition, lubricant oils
were treated as a pseudocomponents within the SAFT framework.
Huber et al. (2002) used manufacturer density data at 15.6 °C to fit
the model parameters and calculate an effective molecular weight
for six POE ISO 32/68/100 oils. The simplified SAFT equation was
then used to model the solubility of HFCs in these oils. Lucia and
Luo (2002) used gas chromatography to characterize the molecular
weight of two POE oils and fitted the SAFT parameters to satu-
rated liquid density and vapor pressure estimates calculated using
group contribution methods (Elbro et al., 1991; Nath et al., 1976).
The model was then used to describe the solubility of R-134a in
these oils. Neto and Barbosa (Neto and Barbosa, 2014, 2009) ap-
plied the PC-SAFT EoS (Gross and Sadowski, 2001; Gross and Sad-
owski, 2002) to study the solubility of R-744 in POE ISO 68 and
alkylbenzene (AB) ISO 32, as well as the solubility of R-600a in
POE ISO 7 and AB ISO 5 synthetic oils. The SAFT parameters for
oils under consideration were fitted to experimental density data
at atmospheric pressure.
To better understand the thermodynamics of these systems and
its connection to the structure of the molecules integrating the
mixtures, several research groups have recently studied the solu-
bility of refrigerants in the precursors of these commercial lubri-
cants. Many of the commercial POE oils are based on mixtures of
PEC polymers that exist in the form of linear, branch and cyclic
chains. Most of the recently measured solubility data focused on
studying the effect of varying the number of CH2 repeating units
(n) found in linear and branch chained PECs (see Fig. 1). Peng–
Robinson (PR) EoS (Peng and Robinson, 1976) and Huron-Vidal
mixing rule (Orbey and Sandler, 1995) combined with the Wil-
son excess free-energy model (Wilson, 1964) were utilized as the
primary tool for data correlation in most of these experimental
efforts. Razzouk et al. (2007) followed a different molecular ap-
proach by applying the PC-SAFT EoS to model the density of pure
compressed PECs up to 45 MPa. The SAFT parameters were deter-
mined through fitting a limited number of measured vapor pres-
sure data (below 1 Pa) as well as to saturated liquid density es-
timates obtained from Tammann–Tait correlations. The developed
PC-SAFT model was later used by Fandiño et al. (2010) to model
the solubility of R-744 in linear chained PECs.
In this work, we extend our previous efforts (Fouad and Vega,
2017, 2018a, 2018b, 2018c) on studying the molecular interactions,
properties and applications of low GWP refrigerants by model-
ing their mixtures with POE oils of different viscosity grades (ISO
32/46/68). To do so, we followed a systematic approach by first
modeling the solubility of R-1234ze(E), R-1234yf, R-600a, RE-170
and R-744 in linear chained PECs using the polar version of the PC-
SAFT equation of state (Polar PC-SAFT) (Dominik et al., 2005). We
show that the fitted binary interaction parameters (kij ) exhibit a
 W.A. Fouad and L.F. Vega / International Journal of Refrigeration 103 (2019) 145–154 147

linear dependency on PEC molecular weight. Ignoring the presence The universal model constants (a0j , a1j , a2j , b0j , b1j , b2j ) were fit-
of additives and assuming that a typical POE oil can be described ted to pure component data of n-alkanes and are tabulated in
as a binary or a ternary mixture of linear chained PECs that can Gross and Sadowski’s work (Gross and Sadowski, 2001).
be lumped into a single pseudo-component, molecular parameters Finally, the change in free energy due to dipolar interactions
including kij s could be determined using correlations developed in is calculated using the Jog and Chapman, (1999) and Jog et al.
this work and applied to fully predict the solubility of refrigerants (2001) theory based on the dipolar term of Fischer and coworkers
in POE oils. Unlike other previous efforts, the proposed model does (Saager et al., 1991; Saager and Fischer, 1992; Müller et al., 1996).
not require any oil density or solubility data fitting to achieve re- This term was obtained by dissolving all the bonds in a chain and
sults. then applying the u-expansion to the resulting mixture of polar
and nonpolar spherical segments.
2. Molecular theory a2
a polar = (9)
1 − a3 /a2
The Polar PC-SAFT EoS (Dominik et al., 2005) used in this work,
where a2 and a3 are the second- and third-order terms in the per-
written for pure components in terms of the reduced residual
turbation expansion. These terms have the following form
Helmholtz free energy (ares ), is given as the sum of a hard-chain
contribution (ahc ), a dispersion contribution (adisp ), and a dipolar 2π ρ μ4
contribution (apolar ): a2 = − 2
(mi x pi )2 2i I2 (10)
9 ( kB T ) di
A Aid μ6
ares = − = ahc + adisp + a polar (1) 5 ρ2
NA kB T NA kB T a3 = π2 3
(mi x pi )3 3i I3 (11)
162 ( kB T ) di
where NA denotes Avogadro’s number, kB is Boltzmann’s con-
stant and T is the temperature. For the hard chain contribution, In the aforementioned equations, I2 and I3 are the angular pair
Chapman et al. (1988) (1989) (1990) developed an equation of state and triplet correlation functions, x pi is the fraction of polar seg-
applicable for mixtures of hard-sphere chains comprising m seg- ments in the chain and μi is the dipole moment for component i.
ments. As shown by Jog and Chapman (1999); Jog et al. (2001), they are
related to the corresponding pure fluid integrals by
ahc = mi ahs − (mi − 1 ) ln ghs
i ( di ) (2)
I2 = I2 (η, mi ) (12)
where mi is the number of segments (or spheres forming the
chain) in a molecule of component i, ghs (di ) is the radial pair dis-
i I3 = I3 (η, mi ) (13)
tribution function at contact for segments of component i, di is the
hard sphere diameter of component i, and the superscripts hc and Detailed explanations of the different terms of the molecular
hs indicate quantities of the hard-chain and hard-sphere systems, theory have been provided in previous publications (Gross and
respectively. Sadowski, 2001; Dominik et al., 2005) and the reader is referred
Gross and Sadowski (2001) used the perturbation theory of to them for further details. Table 1 illustrates pure component pa-
Barker and Henderson (1967) to calculate the contribution to the rameters for the refrigerants considered in this work. These param-
free energy due to dispersion (van der Waals) interactions between eters were previously fitted to saturated liquid density and vapor
molecules using a Lennard–Jones perturbing potential. pressure data.
 ε  Lubricants considered in this work were modeled following
adisp = −2π ρ [I1 (η, mi )]m2i σi3
i
kB T the work of Razzouk et al. (2007) in which PECs were modeled
 ε 2 as chains of homonuclear nonpolar segments using the origi-
−π ρ miC1 [I2 (η, mi )]m2i σi3
i
(3) nal PC-SAFT equation of state. The pure component parameters
kB T for pentaerytritol tetrapentanoate (PEC5, n = 3), pentaerytritol
and tetraheptanoate (PEC7, n = 5) and pentaerytritol tetranonanoate
 −1 (PEC9, n = 7) were determined through fitting a limited number of
∂ Z hc
C1 = 1 + Z hc + ρ (4) measured vapor pressure data (below 1 Pa) as well as to saturated
∂ρ liquid densities obtained from Tammann–Tait correlations. The ob-
where σ i and ɛi donate the segment diameter and dispersion en- tained molecular parameters are illustrated in Table 2. In reference
ergy of component i respectively. The value of C1 represents the to Fig. 2, Razzouk et al. (2007) showed that parameters follow
compressibility of the hard chain fluid (Zhc ) and I1 (η, mi ) and I2 (η, a linear trend as a function of molecular weight, as it happens
mi ) are given by power series in density where the coefficients are for other regular chemical families. As a result, parameters for
functions of the chain length and the packing fraction, η pentaerythritol tetrabutanoate (PEC4, n = 2), pentaerythritol tetra-
hexanoate (PEC6, n = 4) and pentaerythritol tetraoctanoate (PEC8,

6
n = 6) were obtained through interpolation using correlations
I1 (η, mi ) = a j ( m i )η j (5) shown in Fig. 2.
j=0

3. Results and discussion


6
I2 (η, mi ) = b j (mi )η j
(6)
j=0 The aim of this work is to develop a molecular model that can
predict the solubility of low GWP refrigerants in POE oils with dif-
where the coefficients aj and bj depend on the chain length ac- ferent viscosity grades. In order to do so, the solubilities of HFOs,
cording to R-600a, RE-170 and R-744 are investigated and compared as a
mi − 1 mi − 1 mi − 2 function of PEC chain length. The dipolar nature of R-1234ze(E),
a j ( mi ) = a0 j + a1 j + a2 j (7) R-1234yf and RE-170 is explicitly modeled with the perturbation
mi mi mi
theory while the dipolar and quadrupole nature of PECs and R-744,
mi − 1 mi − 1 mi − 2 respectively, are ignored due steric hindrance. From a molecular
b j ( mi ) = b0 j + b1 j + b2 j (8)
mi mi mi point of view, the dipole moment is placed on one of the chain
148 W.A. Fouad and L.F. Vega / International Journal of Refrigeration 103 (2019) 145–154

Table 1
Pure component molecular parameters for refrigerants considered in this work.

Refrigerant MW (g mol−1 ) mi σ i (Å) ɛi /kB (K) x pi μi (D) T range (K) Ref.

R-1234ze(E) 114.042 2.811 3.369 176.935 0.33 1.44 170–380 (Fouad and Vega, 2018c)
R-1234yf 114.042 2.358 3.631 179.953 0.33 2.01 230–360 (Fouad and Vega, 2018c)
RE-170 46.068 2.009 3.434 215.980 0.50 1.30 20 0–40 0 (Dominik et al., 2005)
R-600a 58.122 2.262 3.757 216.530 113–407 (Gross and Sadowski, 2001)
R-744 44.01 2.0729 2.7852 169.21 (Gross and Sadowski, 2001)

Table 2 25%, as shown in Table 4. This would allow accurate model predic-
Pure component PC-SAFT molecular parameters for the PECs
tions at temperatures where experimental data does not exist.
considered in this work.
Fig. 4 depicts the isothermal solubility of R-1234yf in linear
PEC MW (g mol−1 ) mi σ i (Å) ɛi /kB (K) PECs as a function of temperature. Excellent agreement with ex-
PEC4 416.51 9.949 3.825 254.602 perimental data (Wang et al., 2016; Sun et al., 2017a) was achieved
PEC5 472.62 10.533 3.972 261.810 using a single temperature independent kij (see Table 3), while
PEC6 528.73 11.280 4.070 266.545 adding a temperature dependent binary parameter did not improve
PEC7 584.84 12.104 4.141 269.990
the accuracy (see Tables 3 and 4). Despite their structural isome-
PEC8 640.94 12.611 4.244 275.966
PEC9 697.05 12.893 4.364 284.830 try, R-1234yf containing systems exhibit a strong positive devia-
tion from Raoult’s law in comparison to R-1234ze(E) systems. It
can be deduced that placing all the fluorine atoms on one side of
the π -bond, as in the case of R-1234yf, leads to stronger repulsive
spheres as derived by Jog and Chapman (1999) Jog et al. (2001).
interactions between the HFO and PEC molecules. The latter also
As a result, the effective contribution to the Helmholtz free energy
explains the higher volatility (vapor pressure) exhibited by pure R-
due to dipolar interactions decreases with increasing the chain
1234yf in comparison to R-1234ze(E). Although R-1234yf showed
length. Therefore, we expect that the dipolar nature of the bulky
full miscibility across all temperatures covered in this work, the
PEC molecules would exhibit minimal influence on the phase be-
phase diagrams indicate that R-1234yf is more susceptible to phase
havior. Knowledge gained from modeling the binary mixtures will
split in comparison to R-1234ze(E). This is in line with experi-
then be used to develop a predictive model to determine the gas-
mental observations by Smith (2014) for the immiscibility of R-
POE oil miscibility behavior without the need for any fitting pa-
1234ze(E) and R-1234yf in POE ISO 32 lubricants.
rameters.
The isothermal solubilities of R-600a, RE-170 and R-744 in PEC4
as a function of temperature are shown in Fig. 5. The solubil-
3.1. Solubility of refrigerants in pentaerythritol esters ity of R-744 in PEC5, PEC7 and PEC9 were previously modeled
by Fandiño et al. (2010) using the PC-SAFT EoS. In this work,
Fig. 3 demonstrates the isothermal solubility of R-1234ze(E) in we extend previous efforts to binary systems containing PEC4,
linear chained PECs as a function of temperature. The system ex- PEC6 and PEC8, thanks to the correlations of the molecular pa-
hibits a challenging S-shape type phase diagram with slight neg- rameters provided in Fig. 2. A temperature independent kij al-
ative deviations from Raoult’s law at low to moderate HFO con- lowed to adequately correlate the experimental data (Sun et al.,
centrations and positive deviations at high HFO concentrations. It 2015b, 2016; Fedele et al., 2009; Pernechele et al., 2009; Sun et
can be seen that a satisfactory agreement with experimental data al., 2017b; Fandiño et al., 2008; Bobbo et al., 2008b; Sun et al.,
(Sun et al., 2015c; Wang et al., 2015; Sun et al., 2014b; Wang et al., 2015a, 2014a), and values are illustrated in Table 3. As expected,
2016) was achieved using a temperature independent kij for each the solubility of isobutane exhibits positive deviation from Raoult’s
PEC (see Table 3). In spite of the overall good agreement, devia- law indicating that the phase behavior is dominated by weak van
tions increase with increasing the PEC chain length; considering der Waal’s interactions. On the contrary, the solubility of RE-170
a temperature linear dependent kij reduces deviations by at least and R-744 exhibit negative deviation from Raoult’s law. Molecular

a b c

Fig. 2. Molecular parameters of the studied PECs as a linear function of their molecular weight. Filled circles (•) indicate fitted parameters while filled squares () indicate
interpolated parameters.
 W.A. Fouad and L.F. Vega / International Journal of Refrigeration 103 (2019) 145–154 149

Fig. 3. Isothermal solubility of R-1234ze(E) in (a) PEC5, (b) PEC7 and (c) PEC9 at different temperatures. Symbols represent experimental data (Sun et al., 2015c, 2014b); (−)
molecular model with temperature independent kij . See text for details.

Table 3
Temperature independent fitted binary interaction parameters for refrigerant + PEC binary mixtures.

R-1234ze(E) R-1234yf R-600a RE-170 R-744

kij AAD (%) kij AAD (%) kij AAD (%) kij AAD (%) kij AAD (%)

PEC4 −0.00629 4.466 0.0261 1.143 0.0261 1.143 −0.016 4.678 0.064 6.378
PEC5 0.00425 4.968 0.0260 1.360 0.0260 1.360 −0.0143 4.195 0.0881 4.980
PEC6 0.0126 6.098 0.0202 2.125 0.0202 2.125 −0.0082 5.993 0.089 8.490
PEC7 0.0215 6.160 0.0207 1.651 0.0207 1.651 −0.0056 4.709 0.1225 10.751
PEC8 0.0306 6.399 0.0178 2.875 0.0178 2.875 0.0 0 04 7.684 0.1119 8.597
PEC9 0.04 7.248 −0.0074 5.495 0.1329 5.850

Table 4
Regressed coefficients for calculating the temperature dependent binary in- simulations performed by Sugii et al. (2015) on the solubility of R-
teraction parameters for HFO + PEC binary mixturesa .
744 in PEC6 indicated that R-744 molecules are preferably attached
R-1234ze(E) R-1234yf to the double-bonded oxygen atoms of the PEC ester groups. More-
A × 104 B × 102 AAD (%) A × 104 B × 102 AAD (%) over, simulation results also indicated the presence of unspecific
sorption of R-744 in the alkane tail region of the PECs. The latter
PEC4 2.179 7.669 1.544 1.714 7.583 0.994
PEC5 1.500 4.347 3.172 1.494 6.332 1.308 explains the strong negative deviations from Raoult’s law shown
PEC6 1.869 4.684 3.723 2.086 7.386 1.671 in Fig. 5(b)–c). Cross association (hydrogen bonding between re-
PEC7 1.452 2.471 4.145 1.863 6.277 2.382 frigerants and PECs) and PECs long range dipolar interactions were
PEC8 1.821 2.732 4.272 1.297 3.441 2.399 not explicitly modeled in this work. Instead, these interactions are
PEC9 2.167 2.893 4.233
implicitly incorporated into the dispersion term and the binary in-
a
ki j (T ) = A · T (K )−B. teraction parameters.

a b c

Fig. 4. Isothermal solubility of R-1234yf in (a) PEC5, (b) PEC6 and (c) PEC7 at different temperatures. Symbols represent experimental data (Wang et al., 2016; Sun et al.,
2017a); (−) molecular model.
150 W.A. Fouad and L.F. Vega / International Journal of Refrigeration 103 (2019) 145–154

a b c

Fig. 5. Isothermal solubility of (a) R-600a, (b) RE-170 and (c) R-744 in PEC4 at different temperatures. Symbols represent experimental data (Sun et al., 2015b; Pernechele et
al., 2009; Sun et al., 2017b); (−) molecular model with temperature independent kij .

a b c

Fig. 6. Effect of PEC chain length on the isothermal solubility of (a) R-1234ze(E), (b) R-600a and (c) RE-170 at 313.15 and 343.15 K. Symbols represent experimental data and
solid lines represent model calculations.

a b c

Fig. 7. Comparison of refrigerant isothermal solubility in (a) PEC5, (b) PEC6 and (b) PEC7 at 313.15 K. Symbols represent experimental data and solid lines represent model
calculations.

3.2. Relationship between solubility and chemical structure
The solubility of the refrigerants considered in this work as
a function of PEC chain length is depicted in Fig. 6. It can be
seen that the solubility of R-1234ze(E) is weakly dependent on the
PEC chain length. Therefore, it would be safe to approximate the
solubility of this refrigerant in linear PEC blends using any of the
binary mixture data. In contrast, the solubility of R-600a and RE-
170 show stronger chain length dependence and increases with in-
creasing the PEC chain length. As a result, the aim should be to
increase the fraction of heavier PEC components when designing
POE lubricants for both refrigerants. Fig. 7 compares the solubility
 W.A. Fouad and L.F. Vega / International Journal of Refrigeration 103 (2019) 145–154 151

a b c d

Fig. 8. Binary interaction parameters as a linear function of PEC molecular weight. (a) R-1234ze(E), (b) R-1234yf, (c) R-600a, (d) R-744.

Table 5
Deviations by the lumped model in predicting the solubility of R-1234ze(E) in a known PEC mixture. The unlumped model
is used as a reference.

PEC blend MW (g mol−1 ) kij T = 313.15 K T = 343.15 K

AMAXD (%) AAD (%) AMAXD (%) AAD (%)

25% PEC4 + 75% PEC5 458.59 0.00117 0.427 0.214 0.359 0.186
50% PEC6 + 50% PEC5 500.68 0.00801 2.808 2.249 1.770 1.613
75% PEC9 + 25% PEC5 640.94 0.0308 2.021 0.996 1.747 0.935
25% PEC4 + 75% PEC7 542.76 0.0149 4.033 2.834 3.633 2.638
50% PEC6 + 50% PEC7 556.79 0.0171 1.309 0.970 1.188 0.906
75% PEC9 + 25% PEC7 669.00 0.0354 0.816 0.953 0.756 0.857
25% PEC4 + 75% PEC9 626.92 0.0286 4.409 2.692 3.894 2.519
50% PEC6 + 50% PEC9 612.89 0.0263 1.899 1.060 1.666 0.997
75% PEC8 + 25% PEC9 654.97 0.0331 0.744 0.665 0.673 0.605
50% PEC5 + 25% PEC7 + 25% PEC9 556.78 0.0171 4.332 2.821 3.850 2.616
25% PEC5 + 50% PEC7 + 25% PEC9 584.84 0.0217 3.277 2.193 2.927 2.046
25% PEC5 + 25% PEC7 + 50% PEC9 612.89 0.0263 3.039 1.880 2.689 1.758
50% PEC4 + 25% PEC6 + 25% PEC8 500.67 0.0080 4.799 3.150 4.289 2.919
25% PEC4 + 50% PEC6 + 25% PEC8 528.73 0.0126 3.364 2.241 3.001 2.073
25% PEC4 + 25% PEC6 + 50% PEC8 556.78 0.0171 4.287 2.903 3.825 2.687

of these refrigerants in PECs at 313.15 K. As a general trend, R-
1234yf exhibits the least solubility in POE oils while R-600a ex-
hibits the highest solubility. Interestingly, shifting to R-1234ze(E)
(the structural isomer of R-1234yf) leads to an enhancement in the
solubility. This goes back to differences in molecular interactions
explained earlier in this work. In addition, R-600a and RE-170 ex-
hibit similar solubilities up to intermediate concentrates.
3.3. Sensitivity analysis on component lumping
Information provided by manufacturers on the characteristics
of a certain lubrication oil are usually limited. In most cases, the
information available to the public includes the kinematic viscos-
ity at 40 °C, density at around 20 °C and 1 atm, pour point and
flash point. The composition analyses of these commercial oils are
usually considered proprietary information. Consequently, the de-
velopment of any predictive thermodynamic model to determine
the phase behavior of oil containing systems would be very chal-
lenging. Eychenne and Mouloungui (1998) and Niedzielski (1976)
showed that the kinematic viscosities of POE oils at 40 °C are lin-
early correlated to their molecular weights. Razzouk et al. (2007)
used the correlation by Eychenne and Mouloungui (1998) to es-
timate the molecular weight of several POE oils with viscosities
up to 32 cSt. Assuming that these commercial oils can be modeled
as single pseudo-components (lumped model), correlations shown
in Fig. 2 were used to calculate their respective SAFT parameters.
The lumped model was able to accurately predict the oil density
as a function of temperature. In this work, we extend the lumped
model application to refrigerant + oil binary mixtures. Fig. 8 de-
picts that the temperature independent kij s provided in Table 3 fol-
low a linear correlation with PEC molecular weight. Consequently,
equations shown in Figs. 2 and 8 can now be used to fully predict
the solubility of refrigerants in POE oils.
A sensitivity analysis was carried out to examine the applica-
bility of using a molecular weight dependent “lumped” model to
predict the solubility of HFO refrigerants in a predefined multicom-
ponent PEC mixture (unlumped model). Due to the lack to experi-
mental data, a set of predefined binary and ternary PEC systems
were first predicted using the molecular theory (unlumped) de-
scribed in Section 3.1. In this case, components of the PEC mixtures
were explicitly modeled, HFO-oil binary interaction parameters
were taken from Table 3 and kij values among PEC molecules were
assumed to be zero. The latter was used as a reference in Tables 5
and 6 to calculate the absolute maximum deviations (AMAXD) and
the absolute average deviations (AAD) in using the lumped model
to predict the solubility of R-1234ze(E) and R-1234yf respectively.
It can be seen that deviations between both models increase with
increasing the number of components in the mixture and decrease
with increasing the system temperature. Deviations were highest
at low HFO concentrations and remained almost constant up to in-
termediate concentrations before dramatically decreasing at high
concentrations; note, however, that deviations were lower than 5%
in all cases. Hence, the analyses indicate that the proposed lumped
model is expected to provide good predictions for gas solubility in
lubricants of unknown chemical composition.
3.4. Solubility of refrigerants in commercial POE oils – lumped model
predictions
Bobbo et al. (2006b) performed a gas-chromatographic anal-
ysis to qualitatively characterize three commercial oils, namely:
Castrol Icematic SW32, ICI Emkarate RL32S and Mobil EAL Arctic
152 W.A. Fouad and L.F. Vega / International Journal of Refrigeration 103 (2019) 145–154

Table 6
Deviations by the lumped model in predicting the solubility of R-1234yf in a known PEC mixture. The unlumped model is
used as a reference.

PEC blend MW (g mol−1 ) kij T = 313.15 K T = 343.15 K

AMAXD (%) AAD (%) AMAXD (%) AAD (%)

25% PEC4 + 75% PEC5 458.59 −0.0161 0.915 0.671 0.810 0.623
50% PEC6 + 50% PEC5 500..8 −0.0110 2.132 0.836 2.552 1.137
75% PEC8 + 25% PEC5 598.86 0.0 0 098 3.191 2.261 2.831 2.127
25% PEC4 + 75% PEC7 542.76 −0.00585 1.140 0.915 1.065 0.906
50% PEC6 + 50% PEC7 556.79 −0.00414 0.0191 0.105 0.0415 0.117
75% PEC8 + 25% PEC7 626.92 0.00440 1.474 1.123 1.315 1.060
25% PEC4 + 75% PEC8 584.83 −0.0 0 073 5.386 3.833 4.802 3.627
50% PEC6 + 50% PEC8 584.84 −0.0 0 073 2.804 1.997 2.487 1.875
50% PEC4 + 25% PEC6 + 25% PEC8 500.67 −0.0110 5.355 3.630 4.786 3.438
25% PEC4 + 50% PEC6 + 25% PEC8 528.73 −0.00755 4.080 2.811 3.638 2.655
25% PEC4 + 25% PEC6 + 50% PEC8 556.78 −0.00414 5.075 3.557 4.526 3.363

Fig. 9. Isothermal solubility (mass fraction) of R-744 in Castrol Icematic (a) SW 32, (b) SW 46 and (c) SW 68 commercial lubricant. Symbols represent experimental data
(Bobbo et al., 2008a) and solid lines represent the lumped model predictions.

Table 7 POE oils of different viscosity grades. The only discrepancy exists
Predicted molecular parameters for commercial POE oils considered in
in Fig. 9(c) where the model predicts immiscibility at a slightly
this work using correlations shown in Figs. 2 and 5.
lower R-744 composition. As discussed earlier, experiments show
POE MW (g mol−1 ) mi σ i (Å) ɛi /kB (K) kCO2−POE that other commercial oils may contain a wider spectrum of com-
SW 32 554 11.580 4.114 268.855 0.101 ponents, hence model accuracy maybe influenced. Still, results ex-
SW 46 593 12.042 4.176 272.195 0.110 hibit the applicability of using the proposed model as an efficient
SW 68 634 12.529 4.235 275.441 0.119 tool for miscibility calculations with the oil molecular weight being
the only required input.

32. Results showed that the three oils were composed of differ-
ent components and that Castol’s SW32 contained the least num-
ber of components in the mixture. A matrix assisted laser desorp-
tion ionization analysis was performed to determine the molecular
weight of the four main components found in SW32 (Bobbo et al.
(2006a)). Results indicated the presence of PEC6 or PEB6, PEC7 or
PEB7 and PEC8 or PEB8 (PEB means that the alkyl chain of the
ester is branched). It was not possible to distinguish between the
structural isomers of similar molecular weight. Further elementary
analysis (amount of C, H and O) was performed by Bobbo et al.
(2008a) to determine the molecular weights of Castrol Icematic
SW32, SW46 and SW68. Estimated molecular weights of the three
oils with different viscosity grades are reported in Table 7. Con-
sequently, available information on the constituents and molec-
ular weights of these commercial oils make them an attractive
option for examining the predictive power of the lumped model
developed in this work. Correlations shown in Figs. 2 and 8 were
used to determine the required model parameters illustrated in
Table 7. In reference to Fig. 9, the lumped model was able to
fully and accurately predict the solubility of R-744 in commercial
4. Conclusions
The solubility of low GWP refrigerants in linear chained PECs
was modeled using the PC-SAFT equation of state. Using temper-
ature independent kij s, the model was able to adequately corre-
late the VLE with the highest deviations (up to 10%) scored for
R-744 + PEC binary systems. PEC mixtures with R-1234yf showed
positive deviations from Raoult’s law due to the presence of all
the fluorine atoms on one side of the carbon double bond. The
latter creates a cloud of negative charges that leads to strong re-
pulsive interactions between the HFO and PEC molecules. On con-
trary, mixtures with R-1234ze(E), RE-170 and R-744 exhibited neg-
ative deviations from Raoult’s law due to specific association inter-
actions between the refrigerant and PEC molecules. The isothermal
solubility of HFO refrigerants was found to be weakly dependent
on the PEC alkyl tail length. As a result, binary mixture data can be
used as a good representative for the phase behavior with POE oils.
The solubility of R-600a, RE-170 and R-744 was found to increase
with increasing the PEC alkyl tail length. The opposite trend was
found for HFO refrigerants. R-600a exhibited the highest solubility
 W.A. Fouad and L.F. Vega / International Journal of Refrigeration 103 (2019) 145–154
in PECs while R-1234yf exhibited the least solubility. Molecular pa-
rameters used within the SAFT framework were found to be a lin-
ear function of PEC molecular weight. Sensitivity analyses carried
out in this work showed that lumping multicomponent PEC mix-
tures into a single pseudo-component can adequately model the
mixture phase behavior. As a result, correlations developed here
were used to predict the molecular parameters needed to compute
the solubility of R-744 in commercial lubricants of different viscos-
ity grades. Good agreement with experimental data was achieved
without the need any of fitting parameters. Results demonstrate
that the proposed model can be used as a fully predictive tool to
determine the solubility of refrigerants in commercial POE oils pro-
vided that the lubricant molecular weight is known.
Acknowledgments
W.A. Fouad acknowledges financial support for this work from
King Fahd University of Petroleum and Minerals under project
SR181017. L.F. Vega acknowledges financial support for this work
from Khalifa University under project CIRA-121.
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