Thermodynamic properties of R32 + R134a and R125 + R32 mixtures in and beyond the critical region

A parametric crossover equation of state for pure fluids is adapted to binary mixtures. This equation incorporates scaling laws asymptotically close to the critical point and is transformed into a regular classical expansion far away from the critical point. An isomorphic generalization of the law of corresponding states is applied to the prediction of thermodynamic properties and the phase behavior of binary mixtures over a wide region around the locus of vapor-liquid critical points. A comparison is made with experimental data for pure R32, R 125 and R 134a, and for R32 + R 134a and R 125 + R32 binary mixtures. The equation of state yields a good representation of thermodynamic property data in the range of temperatures 0.8T_c(x) ≤ T ≤ 1.5T_c(x) and densities 0.35 ?_c(x) ≤ ? ≤ 1.65?_c(x).     

Liquid Thermal Conductivity of Ternary Mixtures of Difluoromethane (R32), Pentafluoroethane (R125), and 1,1,1,2-Tetrafluoroethane (R134a)1

The thermal conductivities of ternary refrigerant mixtures of difluoromethane (R32), pentafluoroethane (R125), and 1,1,1,2-tetrafluoroethane (R134a) in the liquid phase have been measured by the transient hot-wire method with one bare platinum wire. The experiments were performed in the temperature range of 233 to 323 K and in the pressure range of 2 to 20 MPa at various compositions. The measured data are correlated as a function of temperature, pressure, and composition. From the correlation, we can calculate the thermal conductivity of pure refrigerants and their binary or ternary refrigerant mixtures. The uncertainty of the measurements is estimated to be ±2%.     

Vapour-liquid equilibrium of ternary mixtures of the refrigerants R125, R143a and R134a

Apart from ternary mixtures of R32 with R125 and R134a, similar mixtures with R143a instead of R32 are discussed as alternatives to the widely used refrigerants R22 and R502. In the present work, the phase equilibrium of such ternary mixtures is described by simple cubic equations of state which are based only on experimental data for the pure substances and for a nearly equimolar mixture of every binary system.In addition to previous experimental investigations the critical properties and the saturation pressure were measured for pure R143a and for nearly equimolar mixtures of the binary systems and . The temperature ranged from −70°C up to the respective critical point. The validity of the resulting equations of state for ternary mixtures of R125, R143a and R134a is confirmed by comparison with experimental results of the vapour-liquid equilibrium for a mixture with about 17mol% of R125 and R143a, respectively, and about 66mol% of R134a.     

Thermal conductivity of R32 and its mixture with R134a

The liquid thermal conductivity of R32 (CH₂F₂) and R134a (CF₃CH₂F) was measured in the range from 223 to 323 K and from 2 to 20 MPa by the transient hot-wire method. The thermal conductivity of the R32+R134a mixture was also measured in the same range by varying the mass fraction of R32. The measured data are analyzed to obtain a correlation in terms of temperature, pressure and composition of the mixture. The uncertainty of our measurements is estimated to be within ±2%.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

The Thermal Diffusivity of the Refrigerants R32, R125, and R143a

The thermal diffusivity of the halogenated fluorocarbons R32, R125, and R143a was systematically measured in a wide region of state around the liquid-vapor critical point using dynamic light scattering as the measuring method. The experimental setup is capable of measuring in homodyne (high light intensity) or heterodyne mode (low light intensity). Especially in the vicinity of the critical point, this method is superior to other techniques since no calibration is necessary and the fluid is held in thermodynamic equilibrium. With high light-scattering intensities in the near-critical region, the uncertainty of the measurements is about 0.5% and increases to up to 5% far from the critical point. Measurements were performed in both coexisting phases, along the critical isochore, and along seven isotherms. The range of application is characterized in terms of the reduced density and pressure by 0.3 < / _c < 2 and 0.5 < p/p _c < 2.5. These limits are defined by low scattering intensities and by the mechanical limits of the apparatus due to high pressures of the fluid. The corresponding temperature range is from 300 to 390 K. When approaching the critical point, the thermal diffusivity drops by orders of magnitude and can be expressed by simple scaling laws depending on the reduced temperature difference = (T–T _c )/T _c . In addition to the thermal diffusivity, the refractive index and the critical parameters T _c , p _c are measured and presented. The density of the fluid is calculated from the refractive index using the Lorentz–Lorenz relation.     

Liquid Thermal Conductivity of Binary Mixtures of Pentafluoroethane (R125) and 1,1,1,2-Tetrafluoroethane (R134a)

Thermal conductivities of zeotropic mixtures of R125 (CF₃CHF₂) and R134a (CF₃CH₂F) in the liquid phase are reported. Thermal conductivities have been measured by a transient hot-wire method with one bare platinum wire. Measurements have been carried out in the temperature range of 233 to 323 K and in the pressure range of 2 to 20 MPa. The dependence of thermal conductivity on temperature, pressure, and composition of the binary mixture is presented. Measured thermal conductivity data are correlated as a function of temperature, pressure, and overall composition of the mixture. The uncertainty of our measurements was estimated to be better than 2%.     

Isochoric Heat Capacity Measurements for Binary Refrigerant Mixtures Containing Difluoromethane (R32), Pentafluoroethane (R125), 1,1,1,2-Tetrafluoroethane (R134a), and Trifluoroethane (R143a) from 200 to 345 K at Pressures to 35 MPa

Molar heat capacities at constant volume C _v were measured for binary refrigerant mixtures with an adiabatic calorimeter with gravimetric determinations of the amount of substance. Temperatures ranged from 200 to 345 K, while pressures extended up to 35 MPa. Measurements were conducted on liquid samples with equimolar compositions for the following binary systems: R32/R134a, R32/R125, R125/R134a, and R125/R143a. The uncertainty is 0.002 K for the temperature rise and is 0.2% for the change-of-volume work, which is the principal source of uncertainty. The expanded relative uncertainty (with a coverage factor k=2 and thus a two-standard deviation estimate) for C _v is estimated to be 0.7%.     

Nucleate boiling heat transfer coefficients of mixtures containing HFC32, HFC125, and HFC134a

Nucleate boiling heat transfer coefficients (HTCs) of binary and ternary mixtures composed of HFC32, HFC125, and HFC134a on a horizontal smooth tube of 19.0 mm outside diameter were measured. A cartridge heater was used to generate uniform heat flux on the tube. Data were taken in the order of decreasing heat flux from 80 kW m⁻² to 10 kW m⁻² with an interval of 10 kW m⁻² in the pool temperature at 7 °C. HTCs of nonazeotropic mixtures of HFC32/HFC134a, HFC125/HFC134a, and HFC32/HFC125/HFC134a showed a reduction of HTCs as much as 40% from the ideal values while the near azeotropic mixture of HFC32/HFC125 did not show the reduction. Four of the well known correlations were compared against the present data for binary mixtures. Stephan and Körner's and Schlünder's correlations yielded a good agreement with a deviation of less than 10% but they can not be easily extended to multi-component mixtures of more than three components. A new correlation was developed utilizing only the phase equilibrium data and physical properties. A regression analysis was carried out to account for the reduction of HTCs and the final correlation, which can be easily extended to multi-component mixtures of more than three components, yielded a deviation of 7% for all binary and ternary mixtures.     

Nucleate boiling heat transfer coefficients of HCFC22, HFC134a, HFC125, and HFC32 on various enhanced tubes

In this study, nucleate boiling heat transfer coefficients (HTCs) of HCFC22, HFC134a, HFC125, HFC32 were measured on a low fin, Turbo-B, and Thermoexcel-E tubes. All data were taken at the liquid pool temperature of 7 °C on horizontal tubes of 152 mm length and 18.6–18.8 mm outside diameter at heat fluxes of 10–80 kW m⁻² with an interval of 10 kW m⁻² in the decreasing order of heat flux. For a plain and low fin tubes, refrigerants with higher vapor pressures showed higher nucleate boiling HTCs consistently. This was due to the fact that the wall superheat required to activate given size cavities became smaller as pressure increased. For Turbo-B and Thermoexcel-E tubes, HFC125 showed a peculiar behavior exhibiting much reduced HTCs due to its high reduced pressure. The heat transfer enhancement ratios of the low fin, Turbo-B, and Thermoexcel-E tubes were 1.09–1.68, 1.77–5.41, 1.64–8.77 respectively in the range of heat fluxes tested.     

Equations for the Thermal Conductivity of R-32, R-125, R-134a,and R-143a

At present hydrofluorocarbons (HFCs) such as R32, R-125, R-134a, and R-143a are widely used, and it is required to obtain accurate information of thermophysical properties, especially of the thermal conductivity of HFCs. In this paper new thermal conductivity equations for R-32, R-125, R134a, and R143a are proposed, applicable over a wide range of temperature and pressure including the critical region based on existing experimental data, and the reliability of the present equations is summarized. The problem that the thermal conductivity calculated from the thermal diffusivity in the critical region differs depending on the equation of state is also discussed. Paper presented at the Sixteenth European Conference for Thermophysical Properties, September 1–4, 2002, London, United Kingdom.     

An extended corresponding states model for the thermal conductivity of refrigerants and refrigerant mixturesModèle d'états correspondants étendus pour la conductivité thermique de frigorigènes et de mélanges de frigorigènes

The extended corresponding states (ECS) model of Huber et al. (Huber, M.L., Friend, D.G., Ely, J.F. Prediction of the thermal conductivity of refrigerants and refrigerant mixtures. Fluid Phase Equilibria 1992;80:249–61) for calculating the thermal conductivity of a pure fluid or fluid mixture is modified by the introduction of a thermal conductivity shape factor which is determined from experimental data. An additional empirical correction to the traditional Eucken correlation for the dilute-gas conductivity was necessary, especially for highly polar fluids. For pure fluids, these additional factors result in significantly improved agreement between the ECS predictions and experimental data. A further modification for mixtures eliminates discontinuities at the pure component limits. The method has been applied to 11 halocarbon refrigerants, propane, ammonia, and carbon dioxide as well as mixtures of these fluids. The average absolute deviations between the calculated and experimental values ranged from 1.08 to 5.57% for the 14 pure fluids studied. Deviations for the 12 mixtures studied ranged from 2.98 to 9.40%. Deviations increase near the critical point, especially for mixtures.     

Thermal conductivity of R32 and R125 in the liquid phase at the saturation vapor pressure

The first measurements of the thermal conductivity of two refrigerants which are candidates for the replacement of those fluids currently in use are reported. Specifically, results are given for the thermal conductivity of R32 and R125 in the liquid phase along the saturation line. The measurements, which have been made by the transient hot-wire technique, extend over the temperature range from 205 to 303 K for R32 and from 225 to 306 K for R125; the results have an estimated uncertainty of ±1.0%.     

Experimental and theoretical study on flow condensation with non-azeotropic refrigerant mixtures of R32/R134a

Experiments on flow condensation have been conducted with both pure R32, R134a and their mixtures inside a tube (10 m long, 6 mm ID), with a mass flux of 131–369 kg m⁻²s⁻¹ and average condensation temperature of 23–40°C. The experimental heat transfer coefficients are compared with those predicted from correlations. The maximum mean heat transfer coefficient reduction (from a linear interpolation of the single component values) occurs at a concentration of roughly 30% R32 for the same mass flux basis, and is approximately 20% at Gr = 190 kg m⁻²s⁻¹, 16% at Gr = 300 kg m⁻²s⁻¹. Non-ideal properties of the mixture have a certain, but relatively small, influence on the degradation. Among others, temperature and concentration gradients, slip, etc. are also causes of heat transfer degradation.     

The surface tension of HFC refrigerants and mixtures

The surface tension of the refrigerants R32, R125, R134a, R143a and R152a, as well as the binary refrigerant mixtures R32-R125, R32-R134a, R125-R134a, R125-R143a, R125- R152a, R143a-R134a and R134a-R152a, and the commercially available ternary mixtures R404A and R407C was measured across the temperature range from −50 to 60°C using a measuring unit based on the capillary rise method. Different formulations for calculation of the surface tension of the binary and ternary mixtures on the basis of the surface tension of the pure refrigerants were tested. With an approach based on mass proportions in the mixture, a good correspondence between the measured and calculated values was achieved.     

Composition shift in liquid-recirculation refrigerating systems: an experimental investigation for the pure fluid R134a and the mixture R32/134aChangement de composition dans les systèmes frigorifiques à recirculation de liquide : étude expérimentale du frigorigène pur R134a et d'un mélange de R32+R134a

The ability of zeotropic mixtures with a remarkable temperature glide to operate in liquid-recirculation systems is investigated and the results of an experimental comparison between the performances of the pure fluid R134a and the zeotropic mixture R32/134a (25/75% by mass) are presented. R134a performs slightly better in the liquid-recirculation mode than in the traditional dry-expansion mode; on the other hand, liquid-recirculation configuration has a detrimental effect on the zeotropic mixture's performance. The reason for this detrimental effect is the mixture component separation which occurs at the liquid/vapor separator. The effect of this separation is investigated using gas chromatograph analysis.     

Viscosity of R134a, R32, And R125 at Saturation

This paper reports the results of the measurement of the viscosity of R134a close to the saturation line in the vapor phase. The new measurements were carried out in a vibrating-wire viscometer specially constructed for the purpose, and the results have an accuracy of ±2%. In addition, the opportunity is taken to present a reevaluation of earlier measurements along the saturation line of the viscosity of R32 and R125. Improved equations of state for these fluids are now available and can be employed to generate improved values for the viscosity.     

Equations of State for the Ozone-Safe Refrigerants R32 and R125

Equations of state for gaseous and liquid difluoromethane (R32) and pentafluoroethane (R125) were developed. The coefficients of the equations were determined using experimental density data and heat capacities c _v and c _s. The equations satisfy Maxwell's rule. The equations describe the thermodynamic properties of R32 and R125 at temperatures from 140 to 433 K and from 178 to 480 K, respectively, and at pressures up to 70 MPa within the experimental uncertainties. In particular, the root-mean-square deviations of the calculated values of density from the most reliable experimental data are equal to 0.10% for R32 and 0.12% for R125.     

Mixing rules for the specific heat capacities of several HFC-mixtures

The specific heat capacity at constant pressure (c_p) of some relevant HFCs as replacements for R12, R502 and R22 was measured. The liquids investigated are binary or ternary mixtures of R134a, R152a, R125, R32 and R143a. Empirical functional relations in polynomial forms between the temperature, specific heat capacity and concentration are established and the coefficients of the polynomial correlations are presented. These equations can be used to calculate the c_p-values for the mixtures investigated over the whole concentration range and the predicted properties generally agree with the source data to ca ± 0.1% for the pure substances. The accuracy of the measurements is better than <1% for the pure fluids and <1.5% for the mixtures. Differences between 1 and 2% can occur only at temperatures >40°C and < −50°C.     

Measurements of the thermal conductivity of liquid R32, R124, R125, and R141b

This paper reports measurements of the thermal conductivity of refrigerants R32, R124, R125, and R141b in the liquid phase. The measurements, covering a temperature range from 253 to 334 K and pressure up to 20 MPa, have been performed in a transient hotwire instrument employing two anodized tantalum wires. The uncertainty of the present thermal-conductivity data is estimated to be ±0.5%. The experimental data have been represented by polynomial functions of temperature and pressure for the purposes of interpolation. A comparison with other recent measurements is also included.     

Thermal conductivity of refrigerants R123, R134a,and R125 at low temperatures

Using a transient coaxial cylinder technique, thermal conductivities were measured for liquid 1,1,1-trifluoro-2,2-dichloroethane (refrigerant R123), 1,1,1,2-tetrafluoroethane (refrigerant R134a). and pentalluoroethane (refrigerant R 125). The uncertainty of the experimental data is estimated to be within 2–3 %. Thermal conductivities of refrigerants were measured at temperatures ranging from –114 to 20°C under pressures up to IOMPa. The apparatus was calibrated with four kinds of liquids and gases. The features of the density dependence of thermal conductivity are indicated. Existing equations for calculating the coefficient are analyzed in cases where development has been sufficient to enable comparisons to be made with experiment. Saturated-liquid thermal conductivities for R134a and R123 are compared with corresponding experimental values.