Calculation of second virial coefficients and gaseous viscosities of the refrigerants HFC-32 (CH2 F2), HFC-23 (CHF3), and HCFC-22 (CHC1F2)

The second virial coefficients of refrigerants HFC-32 (CH₂F₂), HFC-23 (CHF₃), and HCFC-22 (CHC1F₂) have been correlated on the bisis of site site model potential and have been compared with experimental results. The molecular interactions consisted of repulsion dispersion and electrostatic parts. From the site site potentials adjusted to the experimental second virial coefficients, spherically averaged potentials have been determined and a subsequent calculation of gaseous viscosity has been carried out. Agreement between measured and calculated values of second virial coellicients and gaseous viscosity is satisfactory. Calculated values of second virial coefficients and gaseous viscosity beyond available experimental data, therefore. can be assumed as a reliable extrapolation to lower and higher temperatures.     

Measurement of Speed of Sound with a Spherical Resonator: HCFC-22, HFC-152a, HFC-143a, and Propane

A spherical resonator and acoustic signal measurement apparatus have been designed and developed for measuring the speed of sound in the gaseous phase. The inner radius of the spherical resonator, being about 6.177 cm, was determined by measuring the speed of sound in gaseous argon at temperatures between 293 and 323 K and at pressures up to 200 kPa. Measurements of the speed of sound in four halogenated hydrocarbons are presented, the compounds are chlorodifluoromethane (CHClF₂ or HCFC-22), 1,1-difluoroethane (CH₃CHF₂ or HFC-152a), 1,1,1-trifluoroethane (CH₃CF₃ or HFC-143a), and propane (CH₃CH₂CH₃ or HC-290). Ideal-gas heat capacities and acoustic virial coefficients were directly deduced from the present data. The results were compared with those from other studies. In this work, the experimental uncertainties in temperature, pressure, and speed of sound are estimated to be less than ±14 mK, ±2.0 kPa, and ±0.0037%, respectively. In addition, equations for the ideal-gas isobaric specific heat capacity for HFC-152a, HFC-143a, and propane are proposed, which are applicable in temperature ranges 240 to 400 K for HFC-152a, 250 to 400 K for HFC-143a, 225 to 375 K for propane. The purities for each of the samples of HCFC-22, HFC-152a, HFC-143a, and propane are better than 99.95 mass%.     

Predicting the virial coefficients and thermodynamic properties of a multicomponent mixture with application to the ternary mixture of CH2F2+CF3CHF2+CF3CH2F

A model for estimating second and third virial coefficients, which has been used successfully to represent the behavior of pure gases and binary mixtures, was applied to a ternary mixture. An estimate for the ternary third virial coefficient.C ₁₂₃, was added to the model. Three experimentally determined binary interaction parameters were also used. The model has been applied to the ternary mixture CH₂F₂+CF₃CHF₂+CF₃CH₂F (R32+R125+R134a). The results are useful for calculating gas-phase densities, thermodynamic properties, and fugacities for phase equilibrium calculations. The use of such models leads to a considerable economy of effort in the case of multicomponent mixtures. Examples of the thermodynamic properties are given for the equimolar ternary mixture in the range from the dew-point temperature to 400 K at pressures of 0.5, 1, and 2 MPa. Calculated densities and speeds of sound are compared with new experimental values for a near-equimolar composition.     

Design of a high-pressure ebulliometer,with vapor-liquid equilibrium results for the systems CHF2 Cl + CF3 CH3 and CF3 CH2 F + CH2F2

We describe the design and operation of a new high-pressure metal ebulliometer which can operate at pressures to at least 3 MPa in the range 220–400 K. Infinite-dilution activity coefficients are presented for the system CHF₂Cl + CF₃-CH, at 275 K and for the system CF₃-CH₂F + CH₂F₂, at 260, 230, and 300 K. The Wilson activity coellicient model and a virial coefficient model are applied to these systems, and the phase equilibrium conditions are calculated. The results are shown to agree well with predicted and with published measured values. The excess enthalpy is calculated and compared with results from a Peng Robinson equation of state. Vapor densities on the dew curves are given.     

Experimental surface tensions for HFC-32, HCFC-124, HFC-125, HCFC-141b,HCFC-142b,and HFC-152a

The surface tension of six alternative refrigerants, i.e., HFC-32 (CH, F, ). HCFC-124 (CHClFCF,), HFC-125 (CHF₂CF₃). HCFC-14lb ICH,CCI,F). HCFC-142b (CH₃CCIF₂), and HFC-152a (CH₃CHF₂), has been measured in the present study. The measurements were conducted under equilibrium conditions between the liquid and its saturated vapor. The differential capillary-rise method (DORM) used two glass capillaries, with inner radii of 0.3034 ± 0.0002 and 0.5717 ±0.0002 mm, respectively. Temperatures in the range from 270 to 340 K were considered. The accuracy of surface tension measurements is estimated to be within ±0.2 mN · m^–1. The temperatures are accurate to within ±20 mK. The temperature dependence of the resultant data were successfully represented by van der Waals' correlations to within ±(1.1 mN m^–1 for each substance. Available surface tension data are compared with the present data.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

Experimental study ofPVT properties of HFC-125 (CHF2CF3)

Pressure-volume-temperature (PVT) properties and vapor pressures of HFC125 (pentafuoroethane; CHF₂CF₃) have been experimentally obtained. Vapor pressures of HFC-125 have been measured in the range of temperatures from 223 to 338 K and pressures up to 3.54 M Pa with uncertainties of 5 mK and 2.5 kPa, respectively. The vapor pressure equation for this substance was correlated based on the present data. PVT properties of HFC-125 have been determined with a constant-volume apparatus in the range of temperatures from 280 to 473 K, pressures up to 17 M Pa, and densities up to 1145 kg · m^–3 with uncertainties of 5 mK, 2.5 kPa, and 0.01%, respectively. All of the available experimentalPVT property data were compared with the equation of state correlated by Wilson et al.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

The thermal conductivity of CFC alternatives HFC-125 and HCFC-141b in the liquid phase

The liquid thermal conductivities of the CFC alternatives, HFC-125, and HCFC-141b measured by a transient hot-wire apparatus with one bare platinum wire are reported in the temperature ranges from 193 to 333 K (HFC-125, CHF₂, CF₃) and from 193 to 393 K (HCFC-141b,CCI₂F-CF₃), in the pressure ranges from 2 to 30 MPa (HFC-125) and from 0.1 to 30 MPa (HCFC-141b), respectively. The results have been estimated to have an accurancy of ±0.5%. The liquid thermal conductives obtained have been correlated by a polynomial of temperature and pressure which can represent the experimental results within the standard deviations of 0.49% for HFC-125 and 0.46% for HCFC-141b, respectively.     

Thermophysical Properties of Gaseous CF4 and C2F6 from Speed-of-Sound Measurements

A cylindrical resonator was employed to measure the sound speeds in gaseous CF₄ and C₂F₆. The CF₄ measurements span the temperature range 300 to 475 K, while the C₂F₆ measurements range from 210 to 475 K. For both gases, the pressure range was 0.1 MPa to the lesser of 1.5 MPa or 80% of the sample’s vapor pressure. Typically, the speeds of sound have a relative uncertainty of less than 0.01 % and the ideal-gas heat capacities derived from them have a relative uncertainty of less than 0.1%. The heat capacities agree with those determined from spectroscopic data. The sound speeds were fitted with the virial equation of state to obtain the temperature-dependent density virial coefficients. Two models for the virial coefficients were employed, one based on square-well potentials and the second based on a Kihara spherical-core potential. The resulting virial equations reproduce the sound-speed measurements to within 0.005 % and yield densities with relative uncertainties of 0.1% or less. The viscosity calculated from the Kihara potential is 2 to 11% less than the measured viscosity.     

Thermodynamic properties of two gaseous halogenated ethers from speed-of-sound measurements: Difluoromethoxy-difluoromethane and 2-difluoromethoxy-1,1,1-trifluoroethane

We present measurements of the speed of sound in gaseous difluoromethoxy-difluoromethane (CHF₂-O-CHF₂) and 2-difluoromethoxy-1,1,1-trifluoroethane (CF₃-CH₂-O-CHF₂). These measurements were performed in an all-metal apparatus between 255 and 384 K. We have obtained ideal-gas heat capacities and second acoustic virial coefficients from analysis of these measurements. Two methods of correlating the second acoustic virial coefficients, a square well model of the intermolecular interaction and a function due to Pitzer and Curl, are presented.     

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.     

Thermal conductivity of gaseous CFCl3 (Freon 11) and CF2Cl2 (Freon 12) and their mixtures with N2 at 292K

Thermal conductivity of the gases CFCl₃ (Freon 11), CF₂Cl₂ (Freon 12), and their binary mixtures with nitrogen have been measured at 292 K. The results for the mixtures are compared with various theoretical models, which give the thermal conductivity as a function of concentration using properties of the pure components. From the experimental results, the mutual diffusion coefficients for the two systems are calculated.     

Determination of Second Virial Coefficients and Virial Equations of R-32 (Difluoromethane) and R-125 (Pentafluoroethane) Based on Speed-of-Sound Measurements

The second virial coefficients, B, for difluoromethane (R-32, CH₂F₂) and pentafluoroethane (R-125, CF₃CHF₂) are derived from speed-of-sound data measured at temperatures from 273 to 343 K with an experimental uncertainty of ±0.0072%. Equations for the second virial coefficients were established, which are valid in the extensive temperature ranges from 200 to 400 K and from 240 to 440 K for R-32 and R-125, respectively. The equations were compared with theoretically derived second virial coefficient values by Yokozeki. A truncated virial equation of state was developed using the determined equation for the virial coefficients. The virial equation of state represents our speed-of-sound data and most of the vapor PT data measured by deVries and Tillner-Roth within ±0.01 and ±0.1%, respectively.     

Vapor–Liquid Equilibria of Alternative Refrigerants by Molecular Dynamics Simulations

Alternative refrigerants HFC-152a (CHF₂CH₃), HFC-143a (CF₃CH₃), HFC-134a (CF₃CH₂F), and HCFC-142b (CF₂ClCH₃) are modeled as a dipolar two-center Lennard–Jones fluid. Potential parameters of the model are fitted to the critical temperature and vapor–liquid equilibrium data. The required vapor–liquid equilibrium data of the model fluid are computed by the Gibbs–Duhem integration for molecular elongations L=0.505 and 0.67, and dipole moments *²=0, 2, 4, 5, 6, 7, and 8. Critical properties of the model fluid are estimated from the law of rectilinear diameter and critical scaling relation. The vapor–liquid equilibrium data are represented by Wagner equations. Comparison of the vapor–liquid equilibrium data based on the dipolar two-center Lennard–Jones fluid with data from the REFPROP database shows good-to-excellent agreement for coexisting densities and vapor pressure.     

Formation of gas hydrate or ice by direct-contact evaporation of CFC alternatives

Experiments have been made on cool storage by evaporation of HFC-134a (CH₂FCF₃) or HCFC-123 (CHCl₂CF₃) brought into direct contact with water in a crystallizer, which was incorporated into a vapour-compression refrigerator loop. The degree of supercooling before the inception of gas-hydrate formation with HFC-134a was found to be reduced by the addition of powdery alumina or zinc or the addition of a surfactant to the water, while the addition of Pseudomonas fluorescens, a strain of ice-nucleating bacteria, showed no effect. The use of HCFC-123 instead of HFC-134a resulted in the formation of slush ice only; no sign of gas-hydrate formation was recognized. The reason for this is considered to lie in the molecular size of HCFC-123.     

Relative Permittivity and Resistivity of Liquid HFC Refrigerants Under High Pressure

The static relative permittivity (dielectric constant) and the resistivity of HFC-236ea (CF₃–CHF–CHF₂) and HFC-245fa (CF₃–CH₂–CHF₂) in the liquid phase were studied at temperatures from 293 to 343 K and pressures from 0.1 to 50 MPa. The relative permittivity was measured by a concentric-cylinder-type capacitance cell with an LCR meter with an uncertainty of less than 0.1%. The resistivity was measured by a high resistance meter using plane-parallel platinum electrodes installed in a borosilicate glass syringe. It was found that the relative permittivities and the resistivities of liquid HFC-236ea and HFC-245fa at 303 K and 0.101325 MPa are about 5.13 and 6.54 and 1.5×10¹⁰ and 0.2×10¹⁰ ·cm, respectively. The relative permittivity and the resistivity increase monotonically with increasing pressure and decreasing temperature.     

Thermal conductivity of gaseous HFC-134a,HFC-143a,HCFC-141b,and HCFC-142b

The thermal conductivity of new environmentally acceptable fluorocarbons HFC-134a (CH₂FCF₃), HFC-143a (CH₃CF₃), HCFC-141b (CH₃CCl₂F), and HCFC-142b (CH₃CCl₂F) in the gaseous phase has been measured in the temperature range 293–353 K at pressures up to 4 MPa. The thermal conductivity has been measured with a coaxial-cylinder cell on a relative basis. The apparatus was calibrated with He, Ne, Ar, Kr, N₂, CH₄, and SF₆ as reference fluids. The uncertainty of the experimental data obtained is estimated to be within 2% except for the uncertainty associated with the reference thermal-conductivity values. The excess thermal conductivity has been correlated satisfactorily as a function of density.     

Mean polarizabilities and second optical and density virial coefficients of CH3OH and CCl2F2 between 300 and 355 K

Mean dipole polarizabilities ₀(, T) as well as second optical (or refractive index) virial coefficients b _R(, T) and second density virial coefficients B(T) of gaseous CH₃OH and CCl₂F₂ have been determined by precise measurements of the refractive index n(, T, p) [543 nm 633 nm, 300 K T 355 K, p<0.25 bar (CH₃OH) and p<3 bar (CCl₂F₂)]. ₀ critically compared with the few data in literature. The b _R of these gases was measured for the first time with the cyclic-expansion method. The values of ¦B¦ and b _R=3160(25) cm³ · mol^–1 measured for CH₃OH are considerably greater than the values calculated by Buckingham's statistical-mechanical expressions for a Stockmayer interaction potential. This difference is discussed by assuming dimerization via H bonds, with result H ₂ ⁰ –(28 ... 33) kJ · mol^–1 and S ₂ ⁰ –(116 133) J · mol^–1 · K^–1 for the dimerization enthalpy and entropy for standard conditions, respectively. On the other hand, Buckingham's formulae can be used with success to estimate b _R and B of CCl₂F₂.Dedicated to Prof. Dr. F. Kohler on the occasion of his 65th birthday     

Virial equation of state and ideal-gas heat capacities of pentafluoro-dimethyl ether

A virial equation of state is presented for vapor-phase pentafluoro-dimethyl ether (CF₃−O−CF₂H), a candidate alternative refrigerant known as E125. The equation of state was determined from density measurements performed with a Burnett apparatus and from speed-of-sound measurements performed with an acoustical resonator. The speed-of-sound measurements spanned the ranges 260≤T≤400 K and 0.05≤P≤1.0 MPa. The Burnett measurements covered the ranges 283≤T≤373 K and 0.25≤P≤5.0 MPa. The speed-of-sound and Burnett measurements were first analyzed separately to produce two independent virial equations of state. The equation of state from the acoustical measurements reproduced the experimental sound speeds with a fractional RMS deviation of 0.0013%. The equation of state from the Burnett measurements reproduced the experimental pressures with a fractional RMS deviation of 0.012%. Finally, an equation of state was fit to both the speed-of-sound and the Burnett measurements simultaneously. The resulting equation of state reproduced the measured sound speeds with a fractional RMS deviation of 0.0018% and the measured Burnett densities with a fractional RMS deviation of 0.019%.     

Prediction of the Vapor Pressure of Environmentally Acceptable Halocarbons1

The vapor pressure and its dependence on temperature of halocarbons for 0.002< p _R<1 have been analyzed in terms of universal behavior. Results for CFC-114, HCFC-123, HCFC-141b, HCFC-142b, HCFC-143a, HFC-23, HFC-32, HFC-134, HFC-125, HFC-134a, and HFC-152a for reduced temperatures between 0.55 and 1.0 show that the reduced vapor pressure can be expressed as a function of 1–T _R by a Padé approximant. Deviations of the correlated data from the universal function do not amount to more than ±0.06 MPa, with an average deviation of 0.025 MPa. Predictions of the saturation vapor pressures of HCFC-124, HCFC-225ca, and HCFC-225cb, which are the systems used to test the capability of this scheme, agree within 0.025 MPa, that is, within the accuracy of the corresponding states correlation. However, for HFC-236ea, the deviations are as large as –0.07 MPa. The present scheme can be used to calculate the Pitzer acentric factor, and an average value of =0.269±0.015 is obtained for all the fluids.     

Determination of the compressibility factorZ(p,T) of three methane-ethane mixtures using the dielectric constant method

The compressibility behavior of three mixtures of the CH₄ C₂ H₆, system has been investigated experimentally by means of the dielectric constant method. Precise ( ± 1 ppm) measurements of the dielectric constant () as a function of the pressure (P) along one isotherm (T) are combined with the first three dielectric virial coefficients (A,B, andC) in order to obtain accurate values of the molar density (p). The compressibility factorZ=P/( _p RT) was obtained from the measured values ofp,P, andT. The coefficientA, is determined from the measurements of as a function ofP, while the higher-order coefficients (B, andC,) are obtained by an expansion technique. We report the measured values ofZ at 295.15 K up to 12 MPa for three mixtures of CH₄-C₂-H₆ containing, respectively. 9.54, 35.3, and 75.4% (molar) of ethane. Their exact composition was determined by weighing during the mixing process. The first three dielectric virial coefficients and the mixed second dielectric virial coefficient for the CH₄,-C₂, H₆ system agree with the calculated or the literature values within the limits of uncertainties. For the mixture containing 90.46% CH₄+C₂H₆, deviations in compressibility are of the order of 0.4% from GERG.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.