International Journal of Refrigeration 28 (2005) 714724

www.elsevier.com/locate/ijrefrig

Phase and viscosity behaviour of refrigerantlubricant mixtures

S.E. Quinones-Cisnerosa,*, J. Garcab,c, J. Fernandezb,1, M.A. Monsalvoa
a

Department of Chemical Engineering, Technical University of Denmark, Building 229, DK-2800 Kgs. Lyngby, Denmark
Laboratorio de Propiedades Termofsicas, Departamento de Fsica Aplicada, Facultad de Fsica, Universidad de Santiago,
E-15782 Santiago de Compostela, Spain
c
Departamento de Fsica Aplicada, Facultad de Ciencias, Universidad de Vigo, E-36200 Vigo, Spain
Received 12 January 2004; received in revised form 22 November 2004; accepted 17 December 2004
Available online 2 March 2005

Abstract
The understanding of thermophysical properties and phase behaviour of refrigerantlubricant oil mixtures is highly important
for the optimal design of refrigeration and air-conditioning systems. Refrigerantlubricant mixtures, which are likely to have
strong asymmetry, can show complex phase behaviour such as closed miscibility gaps, open miscibility gaps, liquidliquid
vapour equilibrium, and even barotropic phenomena (density inversions). In fact, the type of phase behaviour that refrigerant
lubricant mixtures may show is linked to the transition between different types of phase diagrams, mainly as a function of the
molecular asymmetry. This also has a profound effect in the mixture transport properties. Thus, in this work the general aspects
of phase and viscosity behaviour linked to the type of asymmetry found in refrigerantlubricant mixtures are discussed in the
context of phase behaviour phenomenology.
q 2004 Elsevier Ltd and IIR. All rights reserved.
Keywords: Mixture; Refrigerant; Oil; Lubricant; Physical property; Phase; Viscosity

Comportement phasique et en termes de viscosite des melanges

frigorige`ne/lubrifiant
Mots cles : Melange ; Frigorige`ne ; Huile ; Lubrifiant ; Propriete physique ; Phase ; Viscosite

1. Introduction
Phase behaviour research is of great importance in
numerous areas of physical sciences due to the diversity

* Corresponding author. Address: Institute of Physical Chemistry,

University of Cologne, Luxemburger Str. 116, D-50939 Koeln,
Germany.
E-mail address: seqc@mac.com (S.E. Quinones-Cisneros).
1
Member of IIR Commission B1.
0140-7007/$35.00 q 2004 Elsevier Ltd and IIR. All rights reserved.
doi:10.1016/j.ijrefrig.2004.12.004

of possible applications. For example, in the development

of new and efficient separation techniques, in the use of
supercritical fluids as solvents in chemical processes, in
refrigeration and air-conditioning cycles, in reservoir
enhanced oil recovery, etc. Of particular importance is the
phase behaviour of asymmetric and associating molecules,
which can show complex patterns such as closed miscibility
gaps, open miscibility gaps, liquidliquidvapour equilibrium, and even barotropic phenomena (density inversions).
Of relevance to any phase behaviour application is the
understanding of this phenomena within the global context

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715

Nomenclature
a
b
h
h0
k
k
MW
p
pr
pa

attractive energy parameter (MPa cm6/gmol2)

van der Waals co-volume (cm3/gmol)
total viscosity (mPa s)
dilute gas term (mPa s)
binary interaction parameter
friction parameter (mPa s/MPa)
molecular weight (g/gmol)
pressure (MPa)
repulsive pressure term (MPa)
attractive pressure term (MPa)

of phase diagrams, as it follows form the classification and

theoretical basis first introduced by Scott and van Konynenburg [1,2]. Based on the van der Waals equation of state,
Scott and van Konynenburg classified some of the main
types of phase behaviour patterns that binary mixtures may
develop and also located the different types of phase
behaviour patterns that they found in a global parametric
space (global phase diagram). After the initial work of Scott
and van Konynenburg a great deal of progress in the
understanding of complex phase behaviour, some of which
may follow from more elaborated theoretical models, has
been further achieved, Refs. [312] between many others.
In the case of refrigeration cycles, the circulating fluid
comes into contact with the lubricant used in compressors
and some of the refrigerant may dissolve into the oil phase
giving rise to the development of complex phase behaviour.
Furthermore, the dissolved refrigerant may substantially
lower the viscosity of the oil-rich phase resulting in lower
lubrication properties and giving rise to a potential breakdown of the compressor mechanical parts. Thus, good
knowledge of both viscosity and phase behaviour is of a
fundamental importance. Moreover, depending on the oil
miscibility within the refrigerant-rich phase, even with an
efficient oil separator installed, part of the lubricant oil may
migrate from the compressor to other parts of the system
such as the evaporator, condenser, expansion device and
piping. Therefore, some related problems might also
develop as a consequence of the occurring of phase
separation at unforeseen places of a refrigeration cycle.
For example, oil accumulation may take place inside the
heat exchanger tubes reducing heat transfer capabilities and
resulting in an overall decrement of the refrigeration cycle
performance. In fact, because at the evaporator the
temperature and the pressure are the lowest in a refrigeration
cycle, this is the place where most probably phase
separation may occur. Thus, as the refrigerant evaporates,
it leaves a liquid oil film on the internal cold surface of the
evaporator tubing. Hence, for an optimal performance
design the phase and transport properties of the coexisting
phases must be understood and the viscosity has to be
adequate in order for the oil-rich condensed phase to

R
T
v
x

gas constant (cm3 MPa/(gmol K))

temperature (K)
molar volume (cm3/gmol)
molar fraction

Subscripts
a
attractive
i
component i
j
component j
r
repulsive

smoothly flow back into the compressor. These problems

may become more serious in the presence of unforeseen
barotropic behaviour that may induce a refrigerant-rich
phase denser than the lubricant-rich phase [13], which is a
phenomenon intrinsically link to the type of phase
behaviour that asymmetric mixtures may develop [10,11].
In spite of their importance, experimental and theoretical
studies involving lubricant oils of known composition and
structure and which may also include viscosity are still
scarce and further studies are necessary. To the knowledge
of the authors, only some phase equilibria and viscosity
experimental data of hydrofluorocarbons (HFCs) refrigerants with n-alkanes [14,15] and HFCs or CO2 with synthetic
lubricant oils of known structure such as polyalkylene
glycols (PAGs) [1620], polyol ester (POEs) [2123] and
alkyl benzenes (ABs) [2429] are published in the literature.
Certainly, due to their unquestionable importance in the
petroleum industry, as well as other subsequent relevant
applications such as supercritical extraction, the phase
behaviour of natural gas components, paraffins and their
mixtures with CO2 is extensively studied and, putting aside
the barotropic aspects of phase behaviour, quite wellunderstood (Refs. [3039] between many others). Out of
these, due to their importance in the understanding of
complex phase behaviour of asymmetric mixtures (particularly CO2 mixtures), the classical works of Schneider should
be outlined [3739]. All of these studies are also of
relevance for refrigeration since many of these components,
such as propane, butane and CO2 are also used as
refrigerants and long chain paraffins can also be used as
lubricants. However, even in the case of CO2 and n-alkanes,
the extension of these studies to transport properties is not as
prolific; an extensive revision and modelling of the viscosity
of CO2 and n-alkanes is readily available in the friction
theory related works [4043].
Thus, in this work the general aspects of phase and
viscosity behaviour linked to the type of asymmetric
molecules required in refrigerantlubricant mixtures are
discussed in the context of phase behaviour phenomenology. For illustration purposes only, the PengRobinson (PR)
equation of state (EoS) [44] has been used for the phase

716

S.E. Quinones-Cisneros et al. / International Journal of Refrigeration 28 (2005) 714724

behaviour modelling and the friction theory [40] for the

viscosity behaviour modelling.

2. Phase and viscosity behaviour

Before describing in detail the models that are used in
this work, it is important to emphasize that this article is not
intended for the accurate numerical modelling of any
particular system. The main objective of this work is the
theoretical understanding of the development and connection between phase and viscosity behaviour patterns that are
likely to be found in refrigerantlubricant mixtures. For this
purpose, as demonstrated in the work of Scott and van
Konynenburg [1,2], cubic EoS are extremely useful and well
established models; not only for a qualitative description but
also for the quantitative modelling of actual applications
everywhere one can imaginefrom basic laboratory
research to large scale industrial applications. In addition,
the recently developed friction theory for viscosity modelling [40], in conjunction with equations of state such as the
cubic PR EoS, has shown to also be a powerful tool for the
accurate modelling and prediction of the viscosity behaviour
of a large amount of systems [19,4043,4548], between
others. Thus, in this work the theoretical relation between
phase and viscosity behaviour in asymmetric mixtures, such
as refrigerantlubricant mixtures, is studied based on the
predictions that follow form the PR EoS and its coupling
with the friction theory.
However, it is also of relevance to mention that for actual
numerical results, depending on the required accuracy, the
application of a given EoS has to be carefully carried out.
Cubic EoS are known for not being too accurate in the
prediction of the density of dense phases showing, in
optimal circumstances, 25% overall absolute average
deviations at moderate pressures. If necessary, for cases
operating at moderate subcritical temperatures and pressure
ranges, a simple widely used method for the improvement of
the density accuracy given by cubic EoS is the Peneloux
volume translation [49]. This approach consists of a simple
translation of the frame of reference so that the volume (or
density) representation may better overlap to the experimental data. However, in spite of its popularity, this volume
translation approach has no effect in the compressibility
performance of the EoS and consequently may not be
sufficient for high-pressure applications. In fact, even for
simple cases such as methane or ethane, high-pressure
applications (above 100 bars) based on cubic EoS and
Peneloux translations can show density deviations much
larger than 10%. Most severely, if a temperature dependent
Peneloux translation is applied, this may also induced the
very serious pathological problem of isotherm crossing.
Furthermore, for processes that operate around critical
points, such as systems involving CO2, due to their
polynomial-dominant analytical nature, cubic EoS cannot
possible deliver a correct quantitative description of the

critical region. In such cases, scaling corrections that

incorporate critical exponents, such as crossover [50,51],
may be of value. Alternatively, other type of highly accurate
reference EoS can be used, such as the modifications after
the BenedictWebbRubin (BWR) EoS [52] implemented
in the National Institute of Standards and Technology
(NIST) software package (REFPROP) for the correlation of
thermodynamic and transport properties of selected pure
and mixed, mainly refrigerants, compounds [53]. Along this
line, in a related work the Soave modification of the BWR
EoS [54] has been used in conjunction with the friction
theory for the accurate density and viscosity modelling of
1,1,1,2-tetrafluoroethane (HFC-134a) [55], as well as for
several n-alkanes and their mixtures [56]. In the case of the
modelling of the phase behaviour of refrigerantClubricant
systems many other approaches have been studied and or
proposed, such as the perturbed-hard-sphere-chain EoS
[57], cubic EoS of state alone [28,58,59] or combined with a
group contribution model for the lubricant oil [60], between
many others approaches.
2.1. Phase behaviour
Of relevance to refrigerantlubricant mixtures, which are
likely to have strong asymmetry, are Type II and Type III
phase behaviour (according to the Scott and van Konynenburg classification), as well as the transitional Type IV and,
of course, the basic Type I. For the understanding and study
of the type of phase behaviour that may develop in
refrigerantlubricant mixtures, one may take advantage of
simple models such as the PR EoS [11]. This equation is
commonly used in phase equilibria correlations at low and
moderate pressures as well as in the design and simulation of
a wide variety of industrial processes. Similarly to all of the
van der Waals family EoS, the PR EoS is divided into a
repulsive pressure term (pr) and an attractive pressure term
(pa),
p Z pr C pa

(1)

where
pr Z

RT
v K b

(2)

a
vv C b C bv K b

(3)

and
pa Z

For mixtures the PR EoS has been employed in combination

with the one-parameter van der Waals quadratic mixing rule
for a and linear for b, given by:
XX

p
aZ
xi xj ai aj 1 K kij
(4)
i

and

S.E. Quinones-Cisneros et al. / International Journal of Refrigeration 28 (2005) 714724

bZ

xi bi

(5)

where, kij is a binary interaction parameter.

2.2. Viscosity behaviour
To illustrate the relation between viscosity and the type
of phase behaviour that refrigerantlubricant mixtures may
develop, the friction theory [40] (f-theory) has been applied.
The f-theory is an approach for the viscosity modelling of
fluids based on a combination between the van der Waals
balance among repulsive and attractive pressure terms and
friction concepts of classical mechanicals. The basic
structure of an f-theory model is of the form
h Z h0 C kr pr C ka pa C krr p2r

(6)

where h is the total viscosity, h0 represents the viscosity at

the dilute gas limit, the kappas are temperature dependent
friction coefficients and pr and pa are given by the EoS.
The mixture viscosity has been estimated using the
predictive mixing rules proposed in Ref. [40]. That is, the
mixture friction coefficients kr, ka, and krr are obtained by
the following mixing rules
kr Z

n
X

zi kr;i

(7)

iZ1

ka Z

n
X

zi ka;i

iZ1

krr Z

n
X

zi krr;i

iZ1

Here, a mass weighted fraction of the form

xi
zi Z
MWi0:3 MM

(8)

with
MM Z

n
X
iZ1

xi
MWi0:3

717

are of increasing interest since many applications like

vehicle air conditioning, residential air conditioning or heat
pump systems may work up to supercritical conditions [61
63]. Due to the fact that a CO2 refrigeration cycle may reach
supercritical conditions on the high-pressure side, a gas
cooler is used in place of the conventional condenser.
However, depending on the chosen lubricant, the mixture
may or may not reach supercritical conditions and such a
cooling circuit cannot be considered general for CO2
applications. As an added complication, depending on the
type of lubricant, the lubricant oil may not be completely
miscible with CO2. Thus, the lubricant can be trapped in
unwanted places of the cooling circuit thus having a
significant impact on the heat transfer characteristics.
Therefore, depending on the possible amount of oil
accumulation, the circuit may have to be designed with an
oil receiver.
Also, asymmetric mixtures may develop complex phase
behaviour, particularly Types III phase behaviour. Thus, in
addition to larger immiscibility regions, it has been shown
[10,11] that type III phase behaviour in asymmetric
mixtures is also associate with complex barotropic phenomena (density inversions) as observed by Hauk and Weidner
[13].
To better illustrate this, two simple binary mixtures have
been analyzed with the PR EoS and the f-theory. Although
not relevant for the discussion, the parameters that have
been used correspond to CO2 (refrigerant) with n-hexane
(lubricant 1) and n-decane (lubricant 2). The main idea of
these examples is to show how, in spite of being of rather
similar chemical structure, a small variation in the chosen
lubricant may develop a totally different behaviour.
Simple fluid binary mixtures are expected to develop
Type I phase diagrams (or non-intercepting Type II, as there
may be a low-temperature liquidliquidvapour equilibrium
region), as in the case of CO2 with n-hexane. This type of
behaviour shows a continuous critical curve that joints both
pure compounds critical points as shown in Fig. 1. The

(9)

is used in order to enhance the accuracy of the results; MWi

is the molecular weight of compound i.

3. Phase and viscosity behaviour

Refrigerantlubricant mixtures may develop complex
type of phase behaviour that has to be considered when
designing a cooling circuit. Furthermore, once a design is
achieved, the selected lubricant may not be substituted for
another one, even for a closely related chemical compound,
unless a phase behaviour study is thoroughly carried out. For
example, let us consider simple CO2-lubricant mixtures.
Refrigeration processes using CO2 near critical conditions

Fig. 1. Pressuretemperature projection in Type I phase behaviour.

() Pure component critical point.

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S.E. Quinones-Cisneros et al. / International Journal of Refrigeration 28 (2005) 714724

critical curve in Type I phase behaviour corresponds to an

upper bound for simple liquidvapour equilibria Fig. 2.
The implication of Type I phase behaviour in the
viscosity is shown in Fig. 3. Within the pressure and
temperature bounds shown in Fig. 1, a low viscosity vapour
phase may be found coexisting with a higher viscosity liquid
phase, where the isotherms were determined using the
friction theory as in Ref. [42]. If the operating temperature is
below the refrigerant critical temperature then, as the
pressure is increased, most of the lubricant will be forced
into a single condensed phase with viscosity depending on
the global composition of the mixture. In contrast, when the
operating temperature is above the refrigerant critical
temperature, a low viscosity supercritical phase is likely to
be found at pressures above the critical curve bound. Fig. 3
shows how the viscosity of the liquid phase evolves as
temperature increases from totally subcritical conditions to
temperatures above the pure refrigerant critical temperature.
At subcritical conditions the coexisting liquid viscosity will
vary from the pure lubricant viscosity (highest viscosity
point in the curve: (,)) to the pure liquid refrigerant
viscosity (minimum viscosity point in the curve: (6)).
In contrast to simple Type I phase behaviour, a
refrigerantlubricant mixture may also develop complex
Type III phase behaviour. This type of behaviour is mainly
characterized by the divergence of the critical curve that
originates in the heaviest compound (the pure lubricant)
critical point, as shown in Fig. 4. Additionally, the presence
of liquidliquid immiscibility, as well as liquidliquid
vapour equilibria can be found.
In Type III phase behaviour, a low-temperature region
may be considered first. This temperature can be classified
as low with respect to the lubricant critical temperature but it
may be within operating conditions for a cooling circuit Fig.
5. In this initial region multiple phase equilibria may be
found, including unbounded liquidliquid immiscibility.
Fig. 6 shows the strong relation between phase and viscosity

Fig. 2. Pressurecomposition phase diagrams for Type I phase

behaviour. () Vapourliquid critical points of the mixture.

Fig. 3. Viscositypressure diagram for Type I phase behaviour at

several temperatures. (,) Subcritical liquid phase pure lubricant
viscosity. (6) Subcritical liquid phase pure refrigerant viscosity.

behaviour, as essentially the same patters are observed in the

corresponding pressureviscosity diagram.
As temperature is increased, the unbounded liquid
liquid immiscibility may break down, as depicted in Fig. 7,
giving place to an intermediate-temperature region. In some
cases, such as CO2-lubricant mixtures, this temperature
region may be found at near ambient conditions.
In the intermediate-temperature region, complex phase
behaviour can be found. Thus, as indicated in Fig. 8, the
three coexisting phases curve may rich an ending point at a
liquidvapour critical point. In turn, as a consequence of the
disappearance of the three coexisting phases, barotropic
phenomena may also develop showing density inversion
loops, as depicted in Fig. 9. Additionally, although bounded
in this illustration example, the immiscible region may
again extend to high pressures, or even become unbounded.
As shown in Fig. 10, in the intermediate-temperature
region, the viscosity will also reflect the complexity of the
phase behaviour. The low viscosity rich in refrigerant phase
may extend to substantially high pressures. However, in
combination with the barotropic behaviour shown in Fig. 9,

Fig. 4. Pressuretemperature projection in Type III phase

behaviour. () Vapour-liquid critical points of the mixture.

S.E. Quinones-Cisneros et al. / International Journal of Refrigeration 28 (2005) 714724

Fig. 5. Pressurecomposition phase diagram for Type III phase

behaviour at a T in the low-temperature region. This diagram shows
liquidvapor (L1V, L2V), liquidliquid (L1L2) and liquid
liquidvapour (L1L2V) equilibria.

the refrigerant-rich low-viscosity vapour phase may condensate into a dense low-viscosity liquid phase with adverse
effects in a cooling circuit. Furthermore, it should be pointed
out that in some cases the immiscible L1L2 region shown in
Fig. 5 may not break as in Fig. 7 but rather it may extend up
to temperatures substantially above the pure refrigerant
critical point. In such cases, the barotropic phenomenon is
likely to be substantially enhanced.

4. Relevant examples
Some of the synthetic lubricant candidates for CO2
refrigeration systems are the alkyl benzenes (AB) type. AB
oils do not have some of the drawbacks found in polyolester
(POE) and polyglycol (PAG) oils as hydrolysis, lubricity
deterioration and high cost. In order to analyze the phase
behaviour of such systems, experimental numerical data and
knowledge of the structure of the lubricant is needed.

Fig. 6. Pressureviscosity diagram for Type III phase behaviour at T

in the low-temperature region, showing the boundary viscosity for
the L1, L2 and V phases along the coexisting curves.

719

Fig. 7. Pressurecomposition phase diagram for Type III phase

behaviour at a T such that the liquidliquid unbounded immiscibility breaks down. (B) Liquidliquid critical points of the mixture.

However, it appears not to be any viscosity and phase

behaviour data in large temperature, pressure and composition intervals for CO2CAB oil mixtures. Additionally,
most publications on thermophysical properties of this type
of mixtures do not include information about the oil
composition and density [64,65]. However, the alkyl parts
of the AB oils are ramified and quite long, making such
systems strong candidates for the development of Type III
phase behaviour.
In the previous section, it was shown how rather small
change in the size of the molecule may completely change
both phase and viscosity behaviour. Fall and Luks [25,29]
have reported strong similarities in the phase behaviour of
the CO2Calkylbenzene homologous series and the CO2C
alkane homologous series. The complex phase behaviour
reported by Fall and Luks can be modelled with reasonable
accuracy with the PR EoS. Figs. 1114 show the pressure

Fig. 8. Evolution of the pressurecomposition phase diagram for

Type III phase behaviour in the intermediate-temperature region.
The lower two dashed lines in the diagram denote the liquidliquid
vapour equilibria while the upper two dotted lines the molar density
inversion points. (B) Liquidliquid critical points. () Vapour
liquid critical points.

S.E. Quinones-Cisneros et al. / International Journal of Refrigeration 28 (2005) 714724

720

Fig. 9. Barotropic phenomena in Type III phase behaviour in the

intermediate-temperature region. (B) Liquidliquid critical points.
() Vapourliquid critical points.

composition and the pressuremolar density diagrams

obtained with the PR EoS at temperatures of 277.96 and
306.32 K for CO2Coctylbenzene. In these calculations, the
accuracy of the PR EoS was enhanced by modifying Eq. (5)
into a quadratic form and using an additional binary
parameter, lij, for the van der Waals co-volume b average,
i.e.
bZ

XX
i


 bi C bj
xi xj 1 K lij
2

(10)

Unfortunately, no viscosity data has been found in the

literature for this system. However, taking into account
the relation between the phase and viscosity behaviour, the
viscosity diagrams of the studied alkyl benzenes will be
qualitatively similar to those shown in the previous section
for Type III phase behaviour.
It can be observed in Fig. 11 the presence of a liquid
liquid unbounded immiscible region in the shape of a

Fig. 10. Viscositypressure evolution for Type III phase behaviour

in the intermediate-temperature region. The dashed and dotted lines
and the points have the same significance as Fig. 8. (B) Liquid
liquid critical points. () Vapourliquid critical points.

Fig. 11. Pressurecomposition PR phase diagram for CO2C

octylbenzene at 277.96 K showing liquidvapor (L1V, L2V),
liquidliquid (L1 L 2) and liquidliquidvapor (L1 L2 V)
equilibria.

straight chimney. This immiscible liquidliquid chimney

extends up to high pressure without a substantial variation of
its width. The chimney topology has been found in CO2C
octylbenzene mixtures within 233.77303.19 K and should
extend beyond these ranges. Also for CO2Cheptylbenzene
mixtures within 231.96270.15 K and for CO2Chexylbenzene for all temperatures that present LLV, i.e. from 222.7
to 251.40 K. Fig. 12 shows a slight tendency for the chimney
to widen with increasing pressure giving indication of an
unbounded liquidliquid coexistence region.
In systems of CO2Cheptylbenzene for temperatures
between 302.89 and 311.72 K and CO2Coctylbenzene
between 305.45 and 309.28 K, the high-pressure liquid
liquid immiscibility chimney has passed the necking down
region (Fig. 7). Furthermore, when the temperature rises
above the pure CO2 critical point, Figs. 13 and 14,
barotropic phenomena showing a molar density inversion
loop appears. Fall and Luks have experimentally found mass
phase inversion of L1 and L2 at about 280 K along the LLV
locus of CO2Coctylbenzene. Thus, consistent with the work

Fig. 12. Pressuremolar density PR phase diagram of CO2C

octylbenzene at 277.96 K. The liquid phase L1 has lower molar
density than the liquid phase L2 richer in refrigerant.

S.E. Quinones-Cisneros et al. / International Journal of Refrigeration 28 (2005) 714724

Fig. 13. Pressurecomposition PR phase diagram of CO2C

octylbenzene at 306.32 K. (B) Liquidliquid critical point. ()
Vapourliquid critical point.

of Falls and Luks, Figs. 15 and 16 show how these

experimental observations are also predicted quite accurately by the PR EOS. Fig. 15 shows that on the LLV locus,
the mass density of liquid 1 is quite close but lower than the
mass density of liquid 2. In contrast, at 306.32 K, Fig. 16,
the mass density of liquid 1 on the LLV locus has already
shifted to a higher mass density value than liquid 2. Fall and
Luks have further established that the liquid phases are also
inverted for the LLV locus of CO2Chexylbenzene and
heptylbenzene.

5. Conclusions
In spite of their simplicity, models such as the PR EoS in
combination with the f-theory can aid to a better general
understanding of the complex phase and viscosity behaviour
that may be found in refrigerantClubricant mixtures. This
modelling approach has been shown to be not only

Fig. 14. Pressuremolar density PR phase diagram of CO2C

octylbenzene at 306.32 K showing a well defined molar density
inversion loop. (B) Liquidliquid critical point. () Vapourliquid
critical point.

721

Fig. 15. Pressuremass density PR phase diagram of CO2C

octylbenzene at 277.96 K.

qualitatively accurate but also numerically accurate for the

phase and viscosity modelling of many mixtures of
industrial interest. However, it should be remarked that
the main objective of this article is not the accurate
numerical modelling of any particular system. The main
aim of this work is the global understanding of the phase and
viscosity behaviour that may develop in connection with
asymmetric systems such as refrigerantlubricant mixtures.
Under this perspective, more accurate EoS should also give
the barotropic and viscosity behaviour that has been
discussed here. Therefore, the combination of phase and
viscosity modelling techniques discussed in this work can
also represent a powerful tool for the actual design of
refrigeration cycles and the prevention of the kind of
problems that are intrinsic to this type of systems, such as
density inversions [13]. This becomes even more relevant
when Type III phase behaviour is presentas it is the case
in a large number of refrigerantClubricant applications.
Furthermore, a phase and viscosity study based on a
correctly tuned EoS, with the corresponding coupled
f-theory viscosity model, can also be used to prevent other

Fig. 16. Pressuremass density PR phase diagram of CO2C

octylbenzene at 306.32 K, showing mass density inversion. (B)
Liquidliquid critical points. () Vapourliquid critical points.

722

S.E. Quinones-Cisneros et al. / International Journal of Refrigeration 28 (2005) 714724

technical problems such as the compressor problems that

may follow from diminished lubrication properties, as it
may be caused by an inappropriate chemical selection of the
refrigerant or lubricant.
However, a major problem in developing predictive
methods is the identification of the components that are
included in commercial lubricant blends. Refrigeration oils
and their performance properties can widely vary depending
on the source and identity of the components present in the
lubricant mixture. In addition, there is very little thermophysical property data available for the pure fluids used to
formulate the oil. Such data are essential for the development and evaluation of predictive as well as correlation
models and should also be the focus of extensive future
research in this area.

[13]

Acknowledgements

[14]

The authors gratefully acknowledge the financial support

of the following institutions: The Danish Technical
Research Council (Project No. 26-01-0217), the Spanish
Ministry of Science and Technology (Project PPQ 20023262)
and
Xunta
de
Galicia
(Project
PGIDIT03PXIC20608PN).

[9]

[10]
[11]
[12]

[15]

[16]

[17]

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models for hydrocarbon mixtures, Discuss Faraday Soc 49
(1970) 8797.
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