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International Journal of Refrigeration 28 (2005) 714–724

Phase and viscosity behaviour of refrigerant–lubricant mixtures
S.E. Quin˜ones-Cisnerosa,*, J. Garcı´ab,c, J. Ferna´ndezb,1, M.A. Monsalvoa


Department of Chemical Engineering, Technical University of Denmark, Building 229, DK-2800 Kgs. Lyngby, Denmark
Laboratorio de Propiedades Termofı´sicas, Departamento de Fı´sica Aplicada, Facultad de Fı´sica, Universidad de Santiago,
E-15782 Santiago de Compostela, Spain
Departamento de Fı´sica 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

The understanding of thermophysical properties and phase behaviour of refrigerant–lubricant oil mixtures is highly important
for the optimal design of refrigeration and air-conditioning systems. Refrigerant–lubricant mixtures, which are likely to have
strong asymmetry, can show complex phase behaviour such as closed miscibility gaps, open miscibility gaps, liquid–liquid–
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 refrigerant–lubricant 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 me´langes
Mots cle´s : Me´lange ; Frigorige`ne ; Huile ; Lubrifiant ; Proprie´te´ 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,
E-mail address: (S.E. Quin˜ones-Cisneros).
Member of IIR Commission B1.
0140-7007/$35.00 q 2004 Elsevier Ltd and IIR. All rights reserved.

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, liquid–liquid–vapour equilibrium, and even barotropic phenomena (density inversions).
Of relevance to any phase behaviour application is the
understanding of this phenomena within the global context

which is a phenomenon intrinsically link to the type of phase behaviour that asymmetric mixtures may develop [10. this is the place where most probably phase separation may occur. Refs. For example. as it follows form the classification and theoretical basis first introduced by Scott and van Konynenburg [1. 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]. After the initial work of Scott and van Konynenburg a great deal of progress in the understanding of complex phase behaviour. the extension of these studies to transport properties is not as prolific.S. [3–12] between many others. Hence.11]. polyol ester (POEs) [21–23] and alkyl benzenes (ABs) [24–29] are published in the literature. To the knowledge of the authors. Furthermore. depending on the oil miscibility within the refrigerant-rich phase. in this work the general aspects of phase and viscosity behaviour linked to the type of asymmetric molecules required in refrigerant–lubricant mixtures are discussed in the context of phase behaviour phenomenology. even with an efficient oil separator installed. butane and CO2 are also used as refrigerants and long chain paraffins can also be used as lubricants. putting aside the barotropic aspects of phase behaviour. some of which may follow from more elaborated theoretical models. Thus. good knowledge of both viscosity and phase behaviour is of a fundamental importance. / International Journal of Refrigeration 28 (2005) 714–724 715 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. Thus. due to their importance in the understanding of complex phase behaviour of asymmetric mixtures (particularly CO2 mixtures). it leaves a liquid oil film on the internal cold surface of the evaporator tubing. 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. expansion device and piping. For illustration purposes only. 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. only some phase equilibria and viscosity experimental data of hydrofluorocarbons (HFCs) refrigerants with n-alkanes [14. Certainly. because at the evaporator the temperature and the pressure are the lowest in a refrigeration cycle. quite wellunderstood (Refs. such as propane. In fact. 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. Quin˜ones-Cisneros et al.15] and HFCs or CO2 with synthetic lubricant oils of known structure such as polyalkylene glycols (PAGs) [16–20]. the classical works of Schneider should be outlined [37–39]. 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.2]. In spite of their importance. as well as other subsequent relevant applications such as supercritical extraction. [30–39] between many others). However. Thus. the phase behaviour of natural gas components. due to their unquestionable importance in the petroleum industry. paraffins and their mixtures with CO2 is extensively studied and. All of these studies are also of relevance for refrigeration since many of these components. Out of these. has been further achieved. the Peng–Robinson (PR) equation of state (EoS) [44] has been used for the phase .E. Moreover. as the refrigerant evaporates. Therefore. In the case of refrigeration cycles. condenser. 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). 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. Based on the van der Waals equation of state. even in the case of CO2 and n-alkanes. an extensive revision and modelling of the viscosity of CO2 and n-alkanes is readily available in the friction theory related works [40–43]. some related problems might also develop as a consequence of the occurring of phase separation at unforeseen places of a refrigeration cycle. part of the lubricant oil may migrate from the compressor to other parts of the system such as the evaporator.

for processes that operate around critical points. which are likely to have strong asymmetry. cubic EoS are extremely useful and well established models. the recently developed friction theory for viscosity modelling [40]. for cases operating at moderate subcritical temperatures and pressure ranges. as well as the transitional Type IV and. in spite of its popularity. Phase and viscosity behaviour Before describing in detail the models that are used in this work. this may also induced the very serious pathological problem of isotherm crossing. p Z pr C pa (1) where pr Z RT ðv K bÞ (2) a vðv C bÞ C bðv K bÞ (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. 2–5% overall absolute average deviations at moderate pressures. In addition. in conjunction with equations of state such as the cubic PR EoS. Quin˜ones-Cisneros et al. In such cases. other type of highly accurate reference EoS can be used. Alternatively. 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. 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.1. Most severely. as well as for several n-alkanes and their mixtures [56]. 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. cubic EoS of state alone [28. Cubic EoS are known for not being too accurate in the prediction of the density of dense phases showing. depending on the required accuracy. this volume translation approach has no effect in the compressibility performance of the EoS and consequently may not be sufficient for high-pressure applications.51]. as demonstrated in the work of Scott and van Konynenburg [1. If necessary. mainly refrigerants. 2.E. / International Journal of Refrigeration 28 (2005) 714–724 behaviour modelling and the friction theory [40] for the viscosity behaviour modelling. 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 refrigerant–lubricant mixtures. For this purpose.40–43. For the understanding and study of the type of phase behaviour that may develop in refrigerant–lubricant mixtures. is studied based on the predictions that follow form the PR EoS and its coupling with the friction theory. may be of value. such as systems involving CO2.45–48]. the basic Type I. between many others approaches. due to their polynomial-dominant analytical nature. are Type II and Type III phase behaviour (according to the Scott and van Konynenburg classification). Phase behaviour Of relevance to refrigerant–lubricant mixtures. not only for a qualitative description but also for the quantitative modelling of actual applications everywhere one can imagine—from basic laboratory research to large scale industrial applications. the application of a given EoS has to be carefully carried out. Thus. such as the perturbed-hard-sphere-chain EoS [57].716 S. 2. one may take advantage of simple models such as the PR EoS [11]. of course. the PR EoS is divided into a repulsive pressure term (pr) and an attractive pressure term (pa). compounds [53].2-tetrafluoroethane (HFC-134a) [55]. such as the modifications after the Benedict–Webb–Rubin (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. However. Similarly to all of the van der Waals family EoS.58. such as refrigerant–lubricant mixtures. if a temperature dependent Pe´neloux translation is applied. In fact. However. in this work the theoretical relation between phase and viscosity behaviour in asymmetric mixtures.1. such as crossover [50.59] or combined with a group contribution model for the lubricant oil [60]. it is also of relevance to mention that for actual numerical results. in optimal circumstances. Along this line.1. scaling corrections that incorporate critical exponents. even for simple cases such as methane or ethane.2]. high-pressure applications (above 100 bars) based on cubic EoS and Pe´neloux translations can show density deviations much larger than 10%. 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. Furthermore. a simple widely used method for the improvement of the density accuracy given by cubic EoS is the Pe´neloux volume translation [49]. cubic EoS cannot possible deliver a correct quantitative description of the critical region. given by: XX  pffiffiffiffiffiffiffiffi aZ xi xj ai aj 1 K kij (4) i and j . it is important to emphasize that this article is not intended for the accurate numerical modelling of any particular system. In the case of the modelling of the phase behaviour of refrigerantClubricant systems many other approaches have been studied and or proposed. between others.

i iZ1 Here. in spite of being of rather similar chemical structure. The main idea of these examples is to show how. Furthermore. the friction theory [40] (f-theory) has been applied. 2. 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. residential air conditioning or heat pump systems may work up to supercritical conditions [61– 63]. To better illustrate this. Phase and viscosity behaviour Refrigerant–lubricant mixtures may develop complex type of phase behaviour that has to be considered when designing a cooling circuit. the selected lubricant may not be substituted for another one. two simple binary mixtures have been analyzed with the PR EoS and the f-theory. depending on the type of lubricant. The (9) is used in order to enhance the accuracy of the results. 1.S. unless a phase behaviour study is thoroughly carried out. 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.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]. / International Journal of Refrigeration 28 (2005) 714–724 bZ X xi bi (5) i where. asymmetric mixtures may develop complex phase behaviour. Therefore. (†) Pure component critical point. However. a gas cooler is used in place of the conventional condenser. As an added complication. Due to the fact that a CO2 refrigeration cycle may reach supercritical conditions on the high-pressure side. This type of behaviour shows a continuous critical curve that joints both pure compounds critical points as shown in Fig.i iZ1 krr Z n X zi krr. particularly Types III phase behaviour. in addition to larger immiscibility regions. For example. The mixture viscosity has been estimated using the predictive mixing rules proposed in Ref. MWi is the molecular weight of compound i. . Quin˜ones-Cisneros et al. as in the case of CO2 with n-hexane. 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. as there may be a low-temperature liquid–liquid–vapour equilibrium region). depending on the possible amount of oil accumulation. Thus. the mixture friction coefficients kr. once a design is achieved. Viscosity behaviour To illustrate the relation between viscosity and the type of phase behaviour that refrigerant–lubricant mixtures may develop. Thus. 3. the mixture may or may not reach supercritical conditions and such a cooling circuit cannot be considered general for CO2 applications. the kappas are temperature dependent friction coefficients and pr and pa are given by the EoS. and krr are obtained by the following mixing rules kr Z n X zi kr. the parameters that have been used correspond to CO2 (refrigerant) with n-hexane (lubricant 1) and n-decane (lubricant 2). even for a closely related chemical compound. the lubricant can be trapped in unwanted places of the cooling circuit thus having a significant impact on the heat transfer characteristics. kij is a binary interaction parameter. Refrigeration processes using CO2 near critical conditions Fig. it has been shown [10. h0 represents the viscosity at the dilute gas limit. let us consider simple CO2-lubricant mixtures. 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.2. the circuit may have to be designed with an oil receiver. Pressure–temperature projection in Type I phase behaviour. Although not relevant for the discussion. ka. the lubricant oil may not be completely miscible with CO2. depending on the chosen lubricant. 1.i (7) iZ1 ka Z n X zi ka. [40].E. That is. Also.

Viscosity–pressure diagram for Type I phase behaviour at several temperatures. In this initial region multiple phase equilibria may be found. Pressure–temperature projection in Type III phase behaviour. Fig. although bounded in this illustration example. 5. including unbounded liquid–liquid immiscibility. this temperature region may be found at near ambient conditions. 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. At subcritical conditions the coexisting liquid viscosity will vary from the pure lubricant viscosity (highest viscosity point in the curve: (. 4. a low-temperature region may be considered first. Pressure–composition phase diagrams for Type I phase behaviour. as indicated in Fig. [42]. such as CO2-lubricant mixtures. when the operating temperature is above the refrigerant critical temperature. 3. (6) Subcritical liquid phase pure refrigerant viscosity. as shown in Fig. as depicted in Fig. Quin˜ones-Cisneros et al. In turn. (†) Vapour–liquid critical points of the mixture. 4. 9. the immiscible region may again extend to high pressures. 7. Within the pressure and temperature bounds shown in Fig. 9. a low viscosity vapour phase may be found coexisting with a higher viscosity liquid phase.)) to the pure liquid refrigerant viscosity (minimum viscosity point in the curve: (6)). 3. 2. .E. 1. as a consequence of the disappearance of the three coexisting phases. (. Additionally. 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. most of the lubricant will be forced into a single condensed phase with viscosity depending on the global composition of the mixture. In Type III phase behaviour. 10. The low viscosity rich in refrigerant phase may extend to substantially high pressures. As shown in Fig. As temperature is increased.) Subcritical liquid phase pure lubricant viscosity. In contrast. in the intermediate-temperature region. a low viscosity supercritical phase is likely to be found at pressures above the critical curve bound. In some cases. If the operating temperature is below the refrigerant critical temperature then. (†) Vapour-liquid critical points of the mixture. Fig. 2. where the isotherms were determined using the friction theory as in Ref. the three coexisting phases curve may rich an ending point at a liquid–vapour critical point. The implication of Type I phase behaviour in the viscosity is shown in Fig.718 S. In the intermediate-temperature region. as depicted in Fig. giving place to an intermediate-temperature region. complex phase behaviour can be found. 6 shows the strong relation between phase and viscosity Fig. as essentially the same patters are observed in the corresponding pressure–viscosity diagram. However. barotropic phenomena may also develop showing density inversion loops. 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. the unbounded liquid– liquid immiscibility may break down. the viscosity will also reflect the complexity of the phase behaviour. Fig. In contrast to simple Type I phase behaviour. the presence of liquid–liquid immiscibility. as well as liquid–liquid– vapour equilibria can be found. or even become unbounded. 8. a refrigerant–lubricant mixture may also develop complex Type III phase behaviour. Additionally. behaviour. in combination with the barotropic behaviour shown in Fig. Fig. Thus. / International Journal of Refrigeration 28 (2005) 714–724 critical curve in Type I phase behaviour corresponds to an upper bound for simple liquid–vapour equilibria Fig. as the pressure is increased.

4. 719 Fig. the barotropic phenomenon is likely to be substantially enhanced. However. 11–14 show the pressure– Fig. showing the boundary viscosity for the L1. pressure and composition intervals for CO2CAB oil mixtures.65]. (B) Liquid–liquid critical points. In order to analyze the phase behaviour of such systems. (B) Liquid–liquid critical points of the mixture. making such systems strong candidates for the development of Type III phase behaviour. liquid–liquid (L1–L2) and liquid– liquid–vapour (L1–L2–V) equilibria. L2–V). Furthermore. In the previous section. Quin˜ones-Cisneros et al. Figs. 6. In such cases. Evolution of the pressure–composition phase diagram for Type III phase behaviour in the intermediate-temperature region.S. Relevant examples Some of the synthetic lubricant candidates for CO2 refrigeration systems are the alkyl benzenes (AB) type. However. 5 may not break as in Fig. the alkyl parts of the AB oils are ramified and quite long. it appears not to be any viscosity and phase behaviour data in large temperature. most publications on thermophysical properties of this type of mixtures do not include information about the oil composition and density [64. 7. 5. Pressure–composition phase diagram for Type III phase behaviour at a T such that the liquid–liquid unbounded immiscibility breaks down. Fall and Luks [25. L2 and V phases along the coexisting curves. Additionally. Pressure–composition phase diagram for Type III phase behaviour at a T in the low-temperature region. it was shown how rather small change in the size of the molecule may completely change both phase and viscosity behaviour. 7 but rather it may extend up to temperatures substantially above the pure refrigerant critical point. the refrigerant-rich low-viscosity vapour phase may condensate into a dense low-viscosity liquid phase with adverse effects in a cooling circuit. Fig. it should be pointed out that in some cases the immiscible L1–L2 region shown in Fig. Pressure–viscosity diagram for Type III phase behaviour at T in the low-temperature region. This diagram shows liquid–vapor (L1–V. The complex phase behaviour reported by Fall and Luks can be modelled with reasonable accuracy with the PR EoS. (†) Vapour– liquid critical points.29] have reported strong similarities in the phase behaviour of the CO2Calkylbenzene homologous series and the CO2C alkane homologous series. lubricity deterioration and high cost. The lower two dashed lines in the diagram denote the liquid–liquid– vapour equilibria while the upper two dotted lines the molar density inversion points. / International Journal of Refrigeration 28 (2005) 714–724 Fig. AB oils do not have some of the drawbacks found in polyolester (POE) and polyglycol (PAG) oils as hydrolysis. 8.E. . experimental numerical data and knowledge of the structure of the lubricant is needed.

This immiscible liquid–liquid chimney extends up to high pressure without a substantial variation of its width. 12. for the van der Waals co-volume b average. the viscosity diagrams of the studied alkyl benzenes will be qualitatively similar to those shown in the previous section for Type III phase behaviour. no viscosity data has been found in the literature for this system. i.e. Also for CO2Cheptylbenzene mixtures within 231. liquid–liquid (L1 –L 2) and liquid–liquid–vapor (L1 –L2 –V) equilibria. / International Journal of Refrigeration 28 (2005) 714–724 720 Fig. (†) Vapour–liquid critical points. Fig. composition and the pressure–molar density diagrams obtained with the PR EoS at temperatures of 277. 12 shows a slight tendency for the chimney to widen with increasing pressure giving indication of an unbounded liquid–liquid coexistence region. Pressure–composition PR phase diagram for CO2C octylbenzene at 277. The liquid phase L1 has lower molar density than the liquid phase L2 richer in refrigerant. It can be observed in Fig. 11 the presence of a liquid– liquid unbounded immiscible region in the shape of a Fig.96 and 306. . 7).15 K and for CO2Chexylbenzene for all temperatures that present LLV. The chimney topology has been found in CO2C octylbenzene mixtures within 233. In these calculations.89 and 311. straight chimney. Thus. (B) Liquid–liquid critical points. (B) Liquid– liquid critical points. The dashed and dotted lines and the points have the same significance as Fig.28 K.E.77–303.96 K. Viscosity–pressure evolution for Type III phase behaviour in the intermediate-temperature region. Figs. In systems of CO2Cheptylbenzene for temperatures between 302. lij. barotropic phenomena showing a molar density inversion loop appears.45 and 309. L2–V). taking into account the relation between the phase and viscosity behaviour.72 K and CO2Coctylbenzene between 305.96 K showing liquid–vapor (L1–V. Quin˜ones-Cisneros et al. 13 and 14. 8. 11.e.32 K for CO2Coctylbenzene. (5) into a quadratic form and using an additional binary parameter.19 K and should extend beyond these ranges. bZ XX i j   bi C bj xi xj 1 K lij 2 (10) Unfortunately. the high-pressure liquid– liquid immiscibility chimney has passed the necking down region (Fig. consistent with the work Fig.S. However.40 K. Barotropic phenomena in Type III phase behaviour in the intermediate-temperature region.96–270. 10.7 to 251. when the temperature rises above the pure CO2 critical point. from 222. Fall and Luks have experimentally found mass phase inversion of L1 and L2 at about 280 K along the LLV locus of CO2Coctylbenzene. the accuracy of the PR EoS was enhanced by modifying Eq. Fig. i. Furthermore. 9. Pressure–molar density PR phase diagram of CO2C octylbenzene at 277. (†) Vapour–liquid critical points.

the mass density of liquid 1 on the LLV locus has already shifted to a higher mass density value than liquid 2. 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. . it should be remarked that the main objective of this article is not the accurate numerical modelling of any particular system. Under this perspective. of Falls and Luks. 15. Pressure–composition PR phase diagram of CO2C octylbenzene at 306. Fig.32 K. 721 Fig. (B) Liquid–liquid critical points. the mass density of liquid 1 is quite close but lower than the mass density of liquid 2. Therefore.96 K. / International Journal of Refrigeration 28 (2005) 714–724 Fig. Pressure–mass density PR phase diagram of CO2C octylbenzene at 277. Fall and Luks have further established that the liquid phases are also inverted for the LLV locus of CO2Chexylbenzene and heptylbenzene. at 306. with the corresponding coupled f-theory viscosity model. more accurate EoS should also give the barotropic and viscosity behaviour that has been discussed here. This becomes even more relevant when Type III phase behaviour is present—as it is the case in a large number of refrigerantClubricant applications. Pressure–mass density PR phase diagram of CO2C octylbenzene at 306. 14. 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.32 K. (B) Liquid–liquid critical point. Conclusions In spite of their simplicity. Pressure–molar density PR phase diagram of CO2C octylbenzene at 306. (†) Vapour–liquid critical point.32 K. (B) Liquid–liquid critical point. can also be used to prevent other Fig. 15 and 16 show how these experimental observations are also predicted quite accurately by the PR EOS. showing mass density inversion. However. a phase and viscosity study based on a correctly tuned EoS. (†) Vapour–liquid critical points. Quin˜ones-Cisneros et al. qualitatively accurate but also numerically accurate for the phase and viscosity modelling of many mixtures of industrial interest. This modelling approach has been shown to be not only Fig.32 K showing a well defined molar density inversion loop. Figs. 13.E. Furthermore. 16. Fig. 16. such as density inversions [13]. 5. (†) Vapour–liquid critical point. 15 shows that on the LLV locus. In contrast. 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 refrigerant–lubricant mixtures.S.

A. Galindo.P. Fluid Phase Equilib 28 (1986) 87–96. L. J Chem Eng Data 45 (2000) 97–103. J. Takahashi.E. Liquid–liquid–vapor phase equilibria behavior of certain binary carbon dioxideCn-alkylbenzene mixtures. van Konynenburg. holes. K. J.J. Viscosity for mixtures of HFCs and pentarythritol esters. J Chem Phys 90 (1989) 6632–6641. A. Ind Eng Chem Res 43 (2004) 1523–1529. H. A. A. K. DeVera.E. Quin˜ones-Cisneros. Tsuji. J. H. Wisniak. Polishuk. In addition. Segura. 1. Phaseequilibria behaviour of the binary systems carbon dioxide-nbutylbenzene and carbon dioxide-trans-decalin. Luks.L. Wahlstrom. Solubility of HFC-134a refrigerant in glycol-type compounds: effects of glycol structure. 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. 1999. [9] [10] [11] [12] [15] [16] [17] References [1] R. Scheidgen. Carbon dioxide–alkanols.L. Measurements and modelling.L.K. Experimental and predicted solubilities of HFC134a (1. Philos Trans A298 (1980) 495–540.10. Chem Eng Sci 56 (2001) 6485–6510.D. Simultaneous prediction of the critical and sub-critical phase behavior in mixtures using equation of state I. F. U.M. Scott. Phase and critical behavior in Type III phase diagrams. I.H. Solubility of HCFC22. Wahlstrom. Wahlstrom. D. T. as it may be caused by an inappropriate chemical selection of the refrigerant or lubricant. de Swaan Arons. Refrigeration oils and their performance properties can widely vary depending on the source and identity of the components present in the lubricant mixture.722 S. Revised viscosities for HFC134aCglycol mixtures from 273 to 333 K. A. [5] I. Van der Waals and related models for hydrocarbon mixtures. Pelt. S.J.P. A. J. Fluid Phase Equilib 134 (1997) 103–112. J Chem Eng Data 23 (1978) 45–47. H. S. I. windows. AIChE J 40 (1994) 726–737. Ferna´ndez. Global fluid phase.L. J. M.I. J. Vamling. Measurements of bubble point pressure for CO2Cdecane and CO2Clubricating oil. Garcı´a. K. C. Ferna´ndez. Comun˜as. J. L. J. A.14-tetramethylpentadecane. The solubility of HFC125. Wisniak. Tanaka. Polishuk. 26-01-0217). Dynamic viscosity for HFC-134aCpolyether mixtures up to 373. [7] G. Peters. [13] Acknowledgements [14] The authors gratefully acknowledge the financial support of the following institutions: The Danish Technical Research Council (Project No.R. high-pressure immiscibility. the Spanish Ministry of Science and Technology (Project PPQ 20023262) and Xunta de Galicia (Project PGIDIT03PXIC20608PN). Vamling. there is very little thermophysical property data available for the pure fluids used to formulate the oil. H.H. E. HFC143a and HFC152a in n-eicosane. P. Quin˜ones-Cisneros. L. Deiters. [8] U. Proceedings of the 20th international congress of refrigeration IIR/IIF. Quin˜ones-Cisneros et al. Wahlstrom. Hauk. 19–24 September. Paper no. Discuss Faraday Soc 49 (1970) 87–97. L. Luks. Hiaki. J. Riley.1. Schneider. J. Critical lines and phase equilibria in binary van der Waals mixtures. J Chem Eng Data 43 (2004) 804–814. and related effects. Barotropic phenomena in complex phase behaviour. Carbon dioxide–heavy n-alkanes. Chem Eng Sci 58 (2003) 2529–2550. Saito. n-tridecane and 2. Sydney. Theoretical examination of the global fluid phase behavior and critical phenomena in carbon dioxideCn-alkane binary mixtures.E. Kumagai. PVT behaviour and critical phenomena in carbon dioxideCnalkane binary mixtures using PC-SAFT. R. J. Vamling. Deiters. Int J Thermophys 15 (1994) 109–115. J Phys Chem B 106 (2002) 4503–4515.V. However. closed loops. J Chem Eng Data 44 (1999) 823–828. 348. Can J Chem Eng 74 (1996) 426–428. [2] P.L. S.D. Lo´pez. Wahlstrom. Scott. Solubility of HFCs in pentaerythritol tetraalkyl esters. Vamling. Weidner. L.6. Fluid Phase Equilib 219 (2004) 87–92. HFC125. van Konynenburg. barotropy.K. Can J Chem Eng 75 (1997) 544–550. A. J Phys Chem B 107 (2003) 1864–1874. [3] I. J Chem Phys 102 (1985) 3361–3375. Global phase behavior based on the simplified-perturbed hard-chain equation of state. Pegg. HFC143a and HFC152a in a pentaerythritol tetrapentanoate ester. Segura.2tetrafluoroethane) in polyethers. M. [6] A. S. Lugo. HFC134a.L. CFC114 and HFC152a in n-hexadecane.L. / International Journal of Refrigeration 28 (2005) 714–724 technical problems such as the compressor problems that may follow from diminished lubrication properties. Australia. D. Ind Eng Chem Res 39 (2000) 4646–4651. Ferna´ndez. A. . HFC134a. Systematic investigation of the phase [18] [19] [20] [21] [22] [23] [24] [25] behavior in binary fluid mixtures.1.S. T. Thermodynamic and fluid-dynamic properties of carbon dioxide with different lubricants in cooling circuits for automobile application.M. A. Blas. Urieta. J. Simultaneous prediction of the critical and sub-critical phase behavior in mixtures using equations of state II.J. Mainar. Ind Eng Chem Res 39 (2000) 4476–4480. Kohn. Calculations based on the Redilch–Kwong equation of state. Solubility of HFC32. Tiffin. Fall.J. L. Polishuk. Phys Chem Chem Phys 6 (2004) 2307–2313. Vamling. A. Segura.15 K and 140 MPa at low polyether concentration. Wisniak. Complex phase equilibrium phenomena in fluid mixtures up to 2 GPaCosolvency. Ind Eng Chem Res 43 (2004) 8345–8353. Miura-Mochida. [4] I. S. Baylaucq. Garcı´a. Carbon dioxide–n-alkanes. C. R. n-hexadecane. Tseregounis. a major problem in developing predictive methods is the identification of the components that are included in commercial lubricant blends. Boned. E. Estimation of liquid– liquid–vapor equilibria using predictive EOS models. Klante.

H.2-tetrafluoroethane (HFC-134a) up to 140 MPa. Ze´berg-Mikkelssen. Nanu.L. [36] D. [28] K. Int J Refrig 25 (2002) 1014–1024. C. 339–348.B. N. [45] S. NIST reference fluid thermodynamic and transport properties—REFPROP. [58] A. An empirical equation for thermodynamic properties of light hydrocarbons and their mixtures. T. Geana. Yokozeki.K. E. Peng.D. [32] C. Chem Ing Tech 39 (1967) 649–656.M. 72. Viscosity prediction of carbon dioxideC hydrocarbon mixtures using the friction theory.E. Ze´berg-Mikkelsen.1. J. Fluid Phase Equilib 110 (1995) 151– 156. Perturbed-hard-sphere-chain equation of state for phase equilibria of mixtures containing a refrigerant and a lubricant oil.E. [60] N. Kiselev. G. E.K. The effects of active and passive control in a transcritical CO2 vapor compression cycle. National Institute of Standards and Technology. Maruyana. J Chem Eng Data 26 (1981) 277–279. D. Phase equilibria behaviour of the systems carbon dioxideCn-dotriacontane and carbon dioxideCndocosane. Pet Sci Tech 20 (2002) 27–42. M. Poot.1. Pe´neloux. A consistent correction for Redlich-Kwong-Soave volumes. Bertucco. H.-Y. Viscosity prediction of natural gases using the friction theory. S. Ze´berg-Mikkelsen. J Chem Eng Data 29 (1984) 413–417. [53] E. Boulder. Int J Thermophys 24 (2003) 1043–1060. Marckmann. Fluid Phase Equilib 210 (2003) 21–32.H. Valencia. A.P. Ind Eng Chem Fundam 15 (1976) 59–64. Teodorescu. tetracosane and octocosane at temperatures from 323 to 473 K and pressures up to 40 MPa. Quin˜ones-Cisneros. Ze´berg-Mikkelsen. docosane. Soave. Elvassore. CO2 mit n-Octan. Robinson. 2003. and methane. Quin˜ones-Cisneros. The friction theory (f-theory) for viscosity modeling. Stenby. nTridecan und n-Hexadecan. water.H.E. Luks. Fluid Phase Equilib 8 (1982) 7–23. Modeling of gas solubility data for HFCs—lubricant oil binary systems by means of the SRK equation of state. Comun˜as. Fall. [35] D. Solubility and viscosity of refrigerant/lubricant mixtures: hydrofluorcarbon/alkylbenzene systems. J Chem Eng Data 30 (1985) 276–279. Stenby. Chem Eng Prog Symp Ser 64 (1968) 9–15. Fluid Phase Equilib 178 (2001) 1–16. Takishima. Stenby. Z. [27] W. Fluid Phase Equilib 169 (2000) 249–276.1.W. Quin˜ones-Cisneros.W. [50] S. [59] M. K.1. [38] G. Skaugen. [61] G. de Loos. W. Poot. McLinden. / International Journal of Refrigeration 28 (2005) 714–724 [26] W. C. E.B. S. Sato. Luks. Fre´ze. A cubic equation of state with group contributions for the calculation of vapor–liquid equilibria of mixtures of hydrofluorocarbons and lubricant oils. E. [31] Y. Int J Thermophys 23 (2002) 437–454.B.G.E. Accurate density and viscosity modeling of non-polar fluids based on the f-theory and a non-cubic EOS. K. S.S. High pressure phase behaviour of binary systems of refrigerants and phenylalkanes: the system 1. Viscosity prediction of hydrocarbon mixtures based on the friction theory. Quin˜ones-Cisneros. Stenby. Fluid Phase Equilib 210 (2003) 69–75.J.C. T. S. Schneider. An effective modification of the Benedict–Webb– Rubin equation of state.1. March 30–April 2. [52] M. Benedict. Boned. R. T. J. Schneider. E. Ferna´ndez.H. Fluid Phase Equilib 23 (1985) 259–267. Investigation of heat and mass . Ze´berg-Mikkelsen. 723 [44] D. J Chem Eng Data 48 (2003) 571–575. Fluid Phase Equilib 147 (1998) 7–23. Quin˜ones-Cisneros. L. S. Stenby. [34] D. D. de Loos. High pressure phase equilibria in the system 1. S.K. Fluid Phase Equilib 162 (1999) 51–82.J.E.H.H. Stenby. Poot. Gas solubilities of carbon dioxide in heavy hydrocarbons.P. Int J Thermophys 25 (2004) 1353–1366. Luks. Rauzy. Prausnitz.H. K. 7. [29] D.A. M. Int J Thermophys 22 (2001) 1057–1071. [42] C. One parameter friction theory models for viscosity.O.0 ed. Stenby. E.W. J. Kiselev. Fall.H.K. Phase behavior and critical phenomena in fluid mixtures under pressure. Schneider. Fall. Liquid–liquid–vapor immiscibility limits in carbon dioxideCn-paraffin mixtures. Y. Colorado. Viscosity modeling of light gases at supercritical conditions using the friction theory. Bertucco. [49] A. E. Lemmon.E. A new two-constant equation of state. Klein. Cubic crossover equation of state for mixtures. [57] A.I. Int J Thermophys 23 (2002) 41–55. Ind Eng Chem Res 40 (2001) 3848–3854. Solubility of refrigerants in various lubricants. E. G. D. Fall. [30] H.E. E. Fluid phase equilibria of binary n-alkanesCsqualane systems. USA.U.E.E. E. [56] S. Quin˜ones-Cisneros.E. Viscosity measurements and correlations for 1. Ind Eng Chem Res 38 (1999) 2110–2118. Proceedings of the Eurotherm seminar No. Luks. Fluid phase equilibria and ternary mixtures of supercritical carbon dioxide with tetradecanoic acid and docosane up to 43 MPa and 393 K: cosolvency effect and miscibility windows. [37] G. p. J Chem Phys 8 (1940) 334–345. Alwani. C.2-tetrafluoroethaneCphenyloctane.D. Baylaucq. Webb. Liquid–liquid–vapor phase equilibria of the binary system carbon dioxideCn-tridecane. Ferna´ndez. Ind Eng Chem Res 40 (2001) 2966–2970.J. Ze´berg-Mikkelsen. Rubin. [54] G. M. Phasengleichgewichte und kritische Erscheinungen in bina¨ren Mischsystemen bis 1500 bar. S. [51] S. Poehler. Quin˜ones-Cisneros. C. Quin˜ones-Cisneros. Fermeglia. C. Baylaucq. C. J Chem Eng Data 30 (1985) 82–88. Viscosity modeling and prediction of reservoir fluids: from natural gas to heavy oils. S. H. Paulaitis. [39] G.K.K. Schneider. J. A.K.E. Quin˜ones-Cisneros. Spain. de Loos. Boned. Takigawa. Quin˜ones-Cisneros et al. n-Undecan. [33] J. D. Horvath. K.S. Pet Sci Tech 19 (2001) 899–910. [46] C. [62] R. Chai. Ze´berg-Mikkelsen.K. Elvassore. Cubic crossover equation of state. Liquid–liquid–vapor equilibria of the binary mixtures carbon dioxideCn-pentadecylbenzene and carbon dioxideCn-nonylbenzene. [41] S. [47] C. C. 2002. Ber Bunsen-Ges Phys Chem 76 (1972) 325–331.E. [40] S.K. Fluid Phase Equilib 222–223 (2004) 255–259. Yokozeki.2-tetrafluoroethaneCheptylbenzene. S.W. Quin˜ones-Cisneros.E. [43] C. Ze´berg-Mikkelsen. E.M. Ze´berg-Mikkelsen.1. Fluid Phase Equilib 147 (1998) 181–193. W. [48] C.B. Solubility of carbon dioxide in eicosane. Tagashira. A. Franck. Fluid Phase Equilib 158–159 (1999) 183–191. Fall. [55] M.K. L. Fluid Phase Equilib 164 (1999) 157– 172. Eggers. Heim. Stenby. Lugo. Friend. A. Masuoka. Sandler. Phase equilibria in binary fluid systems of hydrocarbons with carbon dioxide. Viscosity prediction of hydrogenCnatural gas mixtures (Hythane). Ze´berg-Mikkelsen.

Valencia. 2003. 2000. July 25–28.N. D.E. Spain. Review of thermodynamic properties of refrigerantsClubricant oils. Heat transfer characteristics of CO2 and CO2-oil mixtures in cooling stage at supercritical pressure conditions. [65] K. Purdue University. Quin˜ones-Cisneros et al. [64] C. Shimaoka. Marsh. p. 355–359. / International Journal of Refrigeration 28 (2005) 714–724 transfer in a carbon dioxide refrigeration plant. Yamamoto. Kandil. Nakanishi. M. Spain. Mori. J. Henderson. . Proceedings of the IIR-Gustav Lorentzen conference on natural working fluids. Solubility. 72. viscosity. p. Seeton. Fahl.724 S. [63] K.E. 2003. Fujimoto. Proceedings of the Eurotherm seminar no. H. Onishi. S. 349–353. USA. Valencia. Proceedings of the Eurotherm seminar no. March 30–April 2. Fluid Phase Equilib 199 (2002) 319–334. J. K. March 30–April 2. N. boundary lubrication and miscibility of CO2 and synthetic lubricants. 72.