Sound-velocity measurements for HFC-134a and HFC-152a with a spherical resonator

A spherical acoustic resonator was developed for measuring sound velocities in the gaseous phase and ideal-gas specific heats for new refrigerants. The radius of the spherical resonator, being about 5 cm, was determined by measuring sound velocities in gaseous argon at temperatures from 273 to 348 K and pressures up to 240 kPa. The measurements of 23 sound velocities in gaseous HFC-134a (1,1,1,2-tetrafluoroethane) at temperatures of 273 and 298 K and pressures from 10 to 250 kPa agree well with the measurements of Goodwin and Moldover. In addition, 92 sound velocities in gaseous HFC-152a (1,1-difluoroethane) with an accuracy of ±0.01% were measured at temperatures from 273 to 348 K and pressures up to 250 kPa. The ideal-gas specific heats as well as the second acoustic virial coefficients have been obtained for both these important alternative refrigerants. The second virial coefficients for HFC-152a derived from the present sound velocity measurements agree extremely well with the reported second virial coefficient values obtained with a Burnett apparatus.Paper dedicated to Professor Joseph Kestin.     

Second and third interaction virial coefficients of the (methane+propane) system determined from the speed of sound

The speed of sound has been measured in the binary gaseous mixture (0.85CH₄+0.15C₃H₈) along seven isotherms at temperatures between 225 and 375 K and at pressures up to 1.4 M Pa. From the measurements, second and third acoustic virial coefficients of the mixture were obtained. These results were analyzed together with values of the second and third acoustic virial coefficients of the two pure components to obtain a set of model intermolecular potential-energy functions for the methane-propane system. Nonpairwise additivity of the intermolecular forces was included in this analysis. Ordinary second and third interaction virial coefficients calculated from the model are reported, as are the second and third virial coefficients of the pure components. Gas densities calculated by means of these virial coefficients for the mixture (0.9298CH₄+0.0702C₃H₈) were found to agree with experimental values at temperatures between 280 and 330 K to within 0.02% at pressures up to 3 MPa and to within 0.08% at 4MPa.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

Ideal-gas specific heat and second virial coefficient of HFC-125 based on sound-velocity measurements

The sound velocity in gaseous pentafluoroethane (HFC-125, CF₃CHF₂) has been measured by means of a spherical acoustic resonator, Seventy-two sound-velocity values were measured with an uncertainty of ±0.01% at temperatures from 273 to 343 K and pressures from 101 to 250 kPa. The ideal-gas specific heats and the second acoustic-virial coefficients have been determined on the basis of the Sound-velocity measurements. The second virial coefficients calculated from the present sound-velocity measurements agree with literature values which were determined fromPVT measurements by means of a Burnett method.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24 1994, Boulder, Colorado, U.S.A.     

Compressed Liquid Densities and Helmholtz Energy Equation of State for Fluoroethane (R161)

In this study, compressed liquid densities of Fluoroethane (R161, CAS No. 353-36-6) were measured using a high-pressure vibrating-tube densimeter over the temperature range from (283 to 363) K with pressures up to 100 MPa. A Helmholtz energy equation of state for R161 was developed from these density measurements and other experimental thermodynamic property data from the literature. The formulation is valid for temperatures from the triple point temperature of 130 K to 420 K with pressures up to 100 MPa. The approximate uncertainties of properties calculated with the new equation of state are estimated to be 0.25 % in density, 0.2 % in saturated liquid density between 230 K and 320 K, and 0.2 % in vapor pressure below 350 K. Deviations in the critical region are higher for all properties. The extrapolation behavior of the new formulation at high temperatures and high pressures is reasonable.     

Importance of Third Virial Coefficients for Representing the Gaseous Phase Based on Measuring PVT-Properties of 1,1,1-Trifluoroethane (R143a)

For a reliable derivation of the thermodynamic properties in the gaseous phase from thermodynamic equations of state, it has been pointed out that third virial coefficients significantly affect calculations of heat capacities. Among existing equations of state including internationally accepted equations, there is a large discrepancy, sometimes more than 5%, in calculated heat-capacity values near saturation. Two different approaches have been conducted in addressing this problem. One is for providing the third virial coefficient from intermolecular-potential models based on speed-of-sound measurements with a spherical resonator, and another is for confirming the effect of the third virial coefficient on density values near saturation by measuring the density precisely with a magnetic suspension densimeter. This report is focused on the latter case, i.e., precise measurements of density for 1,1,1-trifluoroethane, R143a, near saturation and some important evidence for the necessity of considering third virial coefficients for calculating reliable thermodynamic properties in the gaseous phase.Paper presented at the Seventh Asian Thermophysical Properties Conference, August 23–28, 2004, Hefei and Huangshan, Anhui, P. R. China.     

Vapor-Phase Helmholtz Equation for HFC-227ea from Speed-of-Sound Measurements

This work presents measurements of the speed-of-sound in the vapor phase of 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea). The measurements were obtained in a stainless-steel spherical resonator with a volume of 900 cm³ at temperatures between 260 and 380 K and at pressures up to 500 kPa. Ideal-gas heat capacities and acoustic virial coefficients are directly produced from the data. A Helmholtz equation of state of high accuracy is proposed, whose parameters are directly obtained from speed-of-sound data fitting. The ideal-gas heat capacity data are fit by a functions and used when fitting the Helmholtz equation for the vapor phase. From this equation of state other thermodynamic state function are derived. Due to the high accuracy of the equation, only very precise experimental data are suitable for the model validation and only density measurements have these requirements. A very high accuracy is reached in density prediction, showing the obtained Helmholtz equation to be very reliable. The deduced vapor densities are furthermore compared with those obtained from acoustic virial coefficients with the temperature dependences calculated from hard-core square-well potentials.     

Experimental Determination of Isobaric Heat Capacities of R227 (CF<Subscript>3</Subscript>CHFCF<Subscript>3</Subscript>) from 223 to 283 K at Pressures up to 20 MPa.

A new experimental method for measuring isobaric heat capacity c_p down to 223 K at pressures up to 30 MPa was developed with the aim to study alternative refrigerants at sub-ambient temperatures and elevated pressures. The experiments are carried out in a batch mode, using a differential fluxmetric calorimeter Setaram BT-215, equipped with a customized high-pressure unit. The measurements are performed at constant pressure with a continuous scan of temperature. First, the method was tested at atmospheric pressure with methanol in the temperature range 223–283 K. The relative deviation from recommended isobaric heat capacity data in the literature is about 0.5%. Second, the measurements were performed at pressure up to 18.2 MPa with an alternative refrigerant R134a (1,1,1,2-tetrafluoroethane) of well-known heat capacity. Our results agree with representative literature values within 0.4%. New original results were obtained for refrigerant R227 (1,1,1,2,3,3,3-heptafluoropropane) in the temperature range from 223 to 283 K and at pressures of 1.1, 5, 10, 15, and 20 MPa. The consistency of our isobaric heat capacities with calorimetric values above 273 K and with pVT data reported in the literature is discussed.     

The vapor pressure of 1,1,1,2-tetrafluoroethane (R134a) and chlorodifluoromethane (R22)

We measured the vapor pressure of chlorodifluoromethane (commonly known as R22) at temperatures between 217.1 and 248.5 K and of 1,1,1,2-tetrafluoroethane (commonly known as R134a) in the temperature range 214.4 to 264.7 K using a comparative ebulliometer. For 1,1,1,2-tetrafluoroethane at pressures between 220.8 and 1017.7kPa (corresponding to temperatures in the range 265.6 to 313.2K), additional measurements were made with a Burnett apparatus. We have combined our results for 1,1,1,2-tetrafluoroethane with those already published from this laboratory at higher pressures to obtain a smoothing equation for the vapor pressure from 215 K to the critical temperature. For chlorodifluoromethane our results have been combined with certain published results to provide an equation for the vapor pressure at temperatures from 217 K to the critical temperature.     

Burnett Measurements and Virial Coefficients for the R32 + N2O System

Experimental results for the difluoromethane (R32) + nitrous oxide (N₂O) system are presented in this paper. The Burnett apparatus was calibrated using helium, and its performance was confirmed by measurements for pure N ₂O. The values of the virial coefficients for R32 were adopted from previous measurements as the same sample was used in the present study. PVTx measurements were performed for the binary R32 + N₂O system for four isotherms (303, 323, 343, and 364 K). Twenty Burnett expansions were performed in a pressure range from 5000 to 150 kPa. The second and third virial coefficients along with the cross second and third virial coefficients were derived from experimental results. Paper presented at the Seventh Asian Thermophysical Properties Conference, August 23–28, 2004, Hefei and Huangshan, Anhui, P. R. China An erratum to this article can be found at     

CO2 + R23 Binary System: Virial Coefficients Derived from Burnett Measurements

Burnett PVT measurements were performed on trifluoromethane (R23) and mixtures of R23 with carbon dioxide (CO₂). The Burnett apparatus was calibrated using helium. Fourteen expansions were performed for 5 isotherms and in a pressure range from 130 kPa to 6 MPa for R23. Second and third virial coefficients were derived from the collected data and compared with literature values; good agreement was found between them. PVTx measurements for the binary CO₂+R23 system were carried out for five isotherms (303, 313, 323, 333, and 343 K). In all, 18 runs were performed in a pressure range from 150 kPa to 5.9 MPa. The composition of the mixtures was measured with a gas chromatograph after it had been calibrated using samples prepared gravimetrically. Second and third virial coefficients for the system were derived, together with the second and third cross virial coefficients, from experimental results using virial coefficients for CO₂ from previous measurements (for the same sample as used in the present study). Samples for composition measurements were collected during the first Burnett expansion. Second virial coefficients for the system showed positive deviations from ideal values, while the third virials were negative. No previous experimental results were found for the PVTx properties of this binary system.     

Thermodynamic properties of seven gaseous halogenated hydrocarbons from acoustic measurements: CHClFCF3, CHF2 CF3, CF3 CH3, CHF2CH3, CF3CHFCHF2, CF3CH2CF3, and CHF2CF2CH2F

Measurements of the speed of sound in seven halogenated hydrocarbons are presented. The compounds in this study are 1-chloro-1,2,2,2-tetrafluoroethane (CHClFCF₃ or HCFC-124), pentafluoroethane (CHF₂ CF₃ or HFC-125), 1,1,1-trifluoroethane (CF₃CH₃ or HFC-143a), 1,1-difluoroethane (CHF₂CH₃ or HFC-152a), 1,1,1,2,3,3-hexafluoropropane (CF₃CHFCHF₂ or HFC-236ea), 1,1,1,3,3,3-hexafluoropropane (CF₃CH₂CF₃ or HFC-236fa), and 1,1,2,2,3-pentafluoropropane (CHF₂CF₂CH₂F or HFC-245ca). The measurements were performed with a cylindrical resonator at temperatures between 240 and 400 K and at pressures up to 1.0 MPa. Ideal-gas heat capacities and acoustic virial coefficients were directly deduced from the data. The ideal-gas heat capacity of HFC-125 from this work differs from spectroscopic calculations by less than 0.2% over the measurement range. The coefficients for virial equations of state were obtained from the acoustic data and hard-core square-well intermolecular potentials. Gas densities that were calculated from the virial equations of state for HCFC-124 and HFC-125 differ from independent density measurements by at most 0.15%, for the ranges of temperature and pressure over which both acoustic and Burnett data exist. The uncertainties in the derived properties for the other five compounds are comparable to those for HCFC-124 and HFC-125.     

A Rational Fundamental Equation of State for Pentafluoroethane with Theoretical and Experimental Bases

A fundamental equation of state for pentafluoroethane was established on the basis of not only assessment of the experimental data but also by introducing parameters for virial coefficients having a theoretical background in statistical thermodynamics. The equation of state has a range of validity for temperatures from the triple point up to 500 K and pressures up to 70 MPa. The estimated uncertainties of the equation are 0.1% for the vapor pressure, 0.15% in density for the saturated-liquid phase, 0.5% in density for the saturated-vapor phase, 0.1% in density for the liquid phase, 0.1% in pressure for the gaseous phase, 0.5% in density for the supercritical region, 0.01% in speed of sound for the gaseous phase, 0.9% in speed of sound for the liquid phase, 0.5% in isobaric specific heat for the liquid phase, and 1.2% in isochoric specific heat for the liquid phase. The derived specific heats in the gaseous phase are close to the values from the virial equation of state with the second and third virial coefficients derived from intermolecular potential models and precise speed-of-sound measurements.     

The dielectric constant of liquid HFC 134a and HCFC 142b

This paper presents measurements of the dielectric constant of HFC 134a and HCFC 1426, as a function of pressure and temperature, in the temperature range from 200 to 300 K and pressures up to 20 M Pa, using a direct capacitance method, The samples used had a stated purity of 99.8 and 99.9%, respectively, The values of the dielectric constant have a precision of 0.01 % and an accuracy of 0.1%, The data obtained were correlated as a function of density and pressure, The theory developed by Vedam et al,, based on the Eulerian strain. and the Kirkwood equation for the variation of modified molar polarization with temperature and density were applied to analyze the data and to obtain the dipole moment of both refrigerants in the liquid state.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

The virial coefficients of five binary mixtures of fluorinated methanes and ethanes

We have made new measurements of the gas-phasePVT surface of five binary mixtures of hydrofluorocarbons (HFCs) in a Burnett/isochoric apparatus. The components chosen all have moderate to large reduced dipole moments. We presentPVT data, derived mixture virial coefficients, cross second virial coefficients, and binary interaction parameters for these systems, and we compare the results with a recently published model for calculating second and third viral coefficients of polar gases and their mixtures. That model accounts for the polar nature of the molecules with a term containing the reduced dipole moment, _R, and it contains mixing rules for the substance-specific parameters needed to calculate the second and third cross virial coefficients. The model and data are in satisfactory agreement. and the model can be used to greatly extend the useful range of the limited set of data.     

Saturated Liquid Viscosity and Surface Tension of Alternative Refrigerants

Light scattering by thermally excited capillary waves on liquid surfaces or interfaces can be used for the investigation of viscoelastic properties of fluids. In this work, we carried out the simultaneous determination of the surface tension and the liquid kinematic viscosity of some alternative refrigerants by surface light scattering (SLS) on a gas–liquid interface. The experiments are based on a heterodyne detection scheme and signal analysis by photon correlation spectroscopy (PCS). R23 (trifluoromethane), R32 (difluoromethane), R125 (pentafluoroethane), R143a (1,1,1-trifluoroethane), R134a (1,1,1,2-tetrafluoroethane), R152a (1,1-difluoroethane), and R123 (2,2-dichloro-1,1,1-trifluoroethane) were investigated under saturation conditions over a wide temperature range, from 233 K up to the critical point. It is estimated that the uncertainty of the present surface tension data for the whole temperature range is less than ±0.2 mN·m^–1. For temperatures up to about 0.95T _c, the kinematic viscosity of the liquid phase could be obtained with an absolute accuracy of better than 2%. For the highest temperatures studied in this work, measurements for the kinematic viscosity exhibit a maximum uncertainty of about ±4%. Viscosity and surface tension data are represented by a polynomial function of temperature and by a van der Waals-type surface tension equation, respectively. The results are discussed in detail with comparison to literature data.     

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.     

Survey of Experimental Data of Thermophysical Properties for Difluoromethane (HFC-32)

A survey of experimental data for HFC-32 was prepared at the Institute of Thermomechanics in connection with planned experiments. In tabular form, surveys of thermodynamic, transport, and other property measurements, including pvT behavior, second virial coefficient, vapor pressure, saturation densities, critical parameters, heat capacities, speed of sound, thermal conductivity, viscosity, surface tension, refractive index, dielectric constant, and dipole moment, are presented. Tables include author)s) name(s), reference, year of publication, ranges of measurements, number of points, stated uncertainty, sample purity, and experimental method.     

Virial Coefficients from Burnett Measurements for the R116 + CO<Subscript>2</Subscript> System

PVTx measurements for the R116 + CO₂ system for four isotherms (283, 304, 325 and 346 K) were performed. In total, 16 runs were performed in a pressure range from 5100 to 140 kPa. Seven runs along four isotherms in a pressure range from 3400 to 280 kPa were performed for pure hexafluoroethane (R116), and the second and third virial coefficients were derived. The values of the virial coefficients for CO₂ were adopted from our previous measurements. The second and third virial coefficients along with the second and third cross-virial coefficients were derived from the mixture results. The Burnett apparatus was calibrated using helium. The experimental uncertainty in second and third virial coefficients was estimated to be within ±2 cm³· mol^–1 and ±500 cm⁶ ·mol ^–2, respectively.     

Measurements of the viscosity of refrigerants in the vapor phase

Measurements of the viscosity of refrigerants R124, R125, R134a, and R152a in the vapor phase are presented. The measurements, performed in a new vibrating-wire instrument, cover a temperature range from 273 to 333 K from about atmospheric pressure up to below the saturation pressure. The uncertainty of the reported values is estimated to be better than ±1%. Comparison with measurements of other investigators reveals a lack of reliable data in the vapor region for these compounds. Paper presented at the Fourth Asian Thermophysical Properties Conference., September 5–8, 1995, Tokyo, Japan.