Thermodynamic properties of HFC-32 (difluoromethane)

An 18-coefficient modified Benedict–Webb–Rubin equation of state of HFC-32 (difluoromethane) has been developed, based on the updated available PVT measurements, heat capacity measurements and speed of sound measurements. Correlations of vapor pressure and saturated liquid density are also presented. The correlations have been developed based on the reported experimental saturation properties data. This equation of state is effective both in the superheated gaseous phase and compressed liquid phase at pressures up to 70 MPa, densities to 1450 kg/m³, and temperatures from 150 to 475 K, respectively.     

HFC-227ea的气相pvT性质

改进了实验室原有的pvT实验台,测量了HFC-227ea气相pvT性质。膨胀法和等容法相结合,仅需一次充注,沿10条定容线测量了共80组实验数据。实验数据的温度范围为310-410K,压力最大到3．2MPa。首先对超临界410K等温线的数据进行了膨胀法分析,建立了压力和密度关系。以此为基础,获得了各条定容线的密度。建立了HFC-227ea的气相状态方程,与已发表的HFC-227ea的pvT数据进行了比较,实验数据的最大压力偏差小于0．07％,与其他人实验数据也符合良好。状态方程还能精确计算气相声速,与实验数据的最大偏差小于0．05％,说明数据和状态方程都是准确可靠的。     

Gas-phasePVT properties of 1,1,1,2,3,3-Hexafluoropropane

We have measured the gas-phasePVT properties of 1,1,1,2,3,3,-hexafluoro-propane (R-236ea), which is considered to be a promising candidate for the replacement of 1,2-dichlorotetrafluoroethane (R-114). The measurements have been performed with a Burnett apparatus over a temperature range of 340 390 K and at pressures of 0.10–2.11 MPa. The experimental uncertainties of the measurements were estimated to be within ±0.5 kPa in pressure. ±8 mK in temperature, and ±0.15% in density. A truncated virial equation of state was developed to represent thePVT data and the second virial coefficients were also derived. The saturated vapor densities were also calculated by extrapolating the gas-phase isotherms to the vapor pressures. The critical density estimated from the rectilinear diameter was compared with the experimental value. The purity of the R-236ea sample used in the present measurements was 99.9 mol%. Paper presented at the Fourth Asian Thermophysical Properties Conference, September 5–8, 1995, Tokyo, Japan.     

Vapor–Liquid Equilibrium Measurements for Binary Mixtures Containing 1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea)1

Isothermal vapor–liquid equilibrium data for two binary mixtures of alternative refrigerants were determined by using an apparatus applying recirculating vapor and liquid. The difluoromethane (HFC-32)+1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) and 1,1,1,2-tetrafluoroethane (HFC-134a)+1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) systems were studied at 298.15 and 312.65 K. The pressure and vapor and liquid compositions were measured at each temperature. The experimental data were correlated with the Peng–Robinson equation of state using the van der Waals one-fluid mixing rule. Calculated results show that this equation yields good agreement with the experimental data.     

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.     

Vapor pressures and gas-phasePVT data for 1-Chloro-1,2,2,2-tetrafluoroethane (R124)

We present new data for the vapor pressure andPVT surface of 1-chloro-1,2,2,2-lelralluoroethane (designated R124 by the refrigeration industry) in the temperature range 278–423 K. ThePVT data are for the gas phase at densities up to 1.5 times the critical density. Correlating equations are given for the vapor pressures from 220 K to the critical temperature, 395.43 K, and for thePVT surface at densities up to 2 mol · L^–1 (approximately 0.5 times the critical density). Second and third virial coefficients have been derived from thePVT measurements.     

Thermodynamic properties of 1-chloro-1,2,2,2-tetrafluoroethane (R124)

The critical temperature and pressure, vapor pressure, and PVT relations for gaseous and liquid 1-chloro-1,2,2,2-tetrafluoroethane (R124) were determined experimentally. The vapor pressure was measured in the temperature range from 278.15 K to the critical temperature. The PVT measurements were carried out using two types of volumeters in the temperature range from 278.15 to 423.15 K, at pressure up to 100 MPa. The numerical PVT data of gaseous state are fitted as a function of density to a modified Benedict-Webb-Rubin equation. The pressure-volume relations of the liquid at each temperature are correlated satisfactorily as a function of pressure by the Tait equation. The critical density and saturated vapor and liquid densities are also determined and some of the thermodynamic properties are derived from the experimental results.     

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.     

Vapor+Liquid Equilibrium Measurements and Correlation of the Binary Refrigerant Mixtures Difluoromethane (HFC-32)+1,1,1,2,3,3-Hexafluoropropane (HFC-236ea) and Pentafluoroethane (HFC-125)+1,1,1,2,3,3-Hexafluoropropane (HFC-236ea) at 288.6, 303.2, and 318.2 K

Isothermal vapor–liquid equilibria (VLE) for the binary systems of difluoromethane (HFC-32)+1,1,1,2,3,3-hexafluoropropane (HFC-236ea) and pentafluoroethane (HFC-125)+1,1,1,2,3,3-hexafluoropropane (HFC-236ea) were measured at 288.6, 303.2, and 318.2 K using an apparatus in which the vapor phase was recirculated through the liquid. The phase composition at equilibrium was measured by gas chromatography, based on calibration using gravimetrically prepared mixtures. Both systems show a slight deviation from Raoult's law. The uncertainties in pressure, temperature, and vapor- and liquid-phase composition measurements were estimated to be no more than ±1 kPa, ±0.02 K, and ±0.002 mol fraction, respectively. The data were analyzed using the Carnahan–Starling–DeSantis equation of state.     

Thermophysical Properties of Gaseous HBr and BCl3 from Speed-of-Sound Measurements

The speed of sound in gaseous hydrogen bromide (HBr) and boron trichloride (BCl₃) was measured using a highly precise acoustic resonance technique. The HBr speed-of-sound measurements span the temperature range 230 to 440 K and the pressure range from 0.05 to 1.5 MPa. The BCl₃ speed-of-sound measurements span the temperature range 290 to 460 K and the pressure range from 0.05 MPa to 0.40 MPa. The pressure range in each fluid was limited to 80% of the sample vapor pressure at each temperature. The speed-of-sound data have a relative standard uncertainty of 0.01%. The data were analyzed to obtain the ideal-gas heat capacities as a function of temperature with a relative standard uncertainty of 0.1%. The heat capacities agree with those calculated from spectroscopic data within their combined uncertainties. The speeds of sound were fitted with the virial equation of state to obtain the temperature-dependent density virial coefficients. Two virial coefficient models were employed, one based on the hard-core square-well intermolecular potential model and the second based on the hard-core Lennard–Jones intermolecular potential model. The resulting virial equations of state reproduced the speed-of-sound measurements to 0.01% and can be expected to calculate vapor densities with a relative standard uncertainty of 0.1%. Transport properties calculated from the hard-core Lennard–Jones potential model should have a relative standard uncertainty of 10% or less.     

Thermophysical Properties of Chlorine from Speed-of-Sound Measurements

The speed of sound was measured in gaseous chlorine using a highly precise acoustic resonance technique. The data span the temperature range 260 to 440 K and the pressure range 100 kPa to the lesser of 1500 kPa or 80% of the sample's vapor pressure. A small correction (0.003 to 0.06%) to the observed resonance frequencies was required to account for dispersion caused by the vibrational relaxation of chlorine. The speed-of-sound measurements have a relative standard uncertainty of 0.01%. The data were analyzed to obtain the ideal-gas heat capacity as a function of the temperature with a relative standard uncertainty of 0.1%. The reported values of C ^o _p are in agreement with those determined from spectroscopic data. The speed-of-sound data were fitted by virial equations of state to obtain the temperature dependent density virial coefficients. Two virial coefficient models were employed, one based on square-well intermolecular potentials and the second based on a hard-core Lennard–Jones intermolecular potential. The resulting virial equations reproduced the sound speed data to within 0.01% and may be used to calculate vapor densities with relative standard uncertainties of 0.1% or less.     

HFC-227ea热力性质研究进展

1,1,1,2,3,3,3-七氟丙烷(HFC-227ea)是一种很有希望的环保替代工质,其热物性研究受到了国际上的广泛关注。综述近些年来国际上对HFC-227ea热力性质的研究进展,汇总其pvT性质、饱和蒸气压、表面张力及其他热力学导出性质的实验数据发表情况,简述HFC-227ea的状态方程的研究现状。     

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.     

Measurement of the dipole moments of seven partially fluorinated hydrocarbons with a radiofrequency reentrant cavity resonator

Equilibrium dipole moments of gaseous pentafluorodimethyl ether (HFE-125), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea) 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,2,3-pentafluoropropane (HFC-245ca), 1,1,1,2,2-pentafluoropropane (HFC-245fa), and 1,1,1,2,2,3,3,4-octafluorobutane (HFC-338mccq) were obtained from the resonance frequency of a reentrant cavity at temperatures between 250 and 373K. The electronic contributions to the polarization were determined for each fluid from liquid-phase optical index of refraction measurements at 297 K.     

Viscosity of Gaseous Mixtures of HFC-125+HFC-32

This paper reports experimental results for the viscosity of gaseous mixtures of HFC-125 (pentafluoroethane)+HFC-32 (difluoromethane). The measurements were carried out with an oscillating-disk viscometer of the Maxwell type at temperatures from 298.15 to 423.15K. The viscosity was measured for three mixtures (mole fraction of HFC-125 is 0.7498, 0.4998, or 0.2475). The viscosity at normal pressure was analyzed with the extended law of corresponding states developed by Kestin et al. and the scaling parameters were obtained for unlike-pair interactions between HFC-125 and HFC-32. The modified Enskog theory developed by Vesovic and Wakeham was applied to predict the viscosity for the binary gaseous mixtures under pressure. For the calculation of the pseudo-radial distribution function in mixtures, a method based on the Carnahan–Starling equation for the radial distribution function of hard sphere mixtures is proposed.     

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.     

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.     

A Thermodynamic Property Model for Fluid-Phase Propane

A fundamental equation of state for propane (R-290), formulated in terms of the non-dimensional Helmholtz free energy, is presented. It was developed based on selected reliable measurements for pressure-volume-temperature (PVT), isochoric and isobaric heat capacities, speed of sound, and the saturation properties which were all converted to ITS-90. Supplementary input data calculated from a virial equation for the vapor-phase PVT properties at lower temperatures and other correlations for the saturated vapor pressures and saturated vapor- and liquid-densities have also been used. The present equation of state includes 19 terms in the residual part and represents most of the reliable experimental data accurately in the range of validity from 85.48 K (the triple point temperature) to 623 K, at pressures to 103 MPa, and at densities to 741 kg·m^–3. The smooth behavior of the derived thermodynamic properties in the entire fluid phase is demonstrated. In addition, graphical and statistical comparisons between experimental data and the available thermodynamic models, including the present one, showed that the present model can provide a physically sound representation of all the thermodynamic properties of engineering importance.     

Saturated Liquid Densities for 33 Binary Refrigerant Mixtures Based on the ISM Equation of State

In this work, the ISM equation of state based on statistical-mechanical perturbation theory has been extended to liquid refrigerant mixtures by using correlations of Boushehri and Mason. Three temperature-dependent parameters are needed to use the equation of state: the second virial coefficient, B₂(T), an effective van der Waals covolume, b(T), and a scaling factor, α (T). The second virial coefficients are calculated from a correlation based on the heat of vaporization, ΔH_vap, and the liquid density at the normal boiling point, ρ_nb. α(T) and b(T) can also be calculated from second virial coefficients by a scaling rule. The theory has considerable predictive power, since it permits the construction of the PVT surface from the heat of vaporization and the liquid density at the normal boiling point. The equation of state was tested on 33 liquid mixtures from 12 refrigerants. The results indicate that the liquid densities can be predicted to at most 2.8% over a wide range of temperatures, 170–369 K.     

Thermophysical Properties of Nitrogen Trifluoride, Ethylene Oxide, and Trimethyl Gallium from Speed-of-Sound Measurements

The speed of sound was measured in gaseous nitrogen trifluoride, ethylene oxide, and trimethyl gallium using a highly precise acoustic resonance technique. The measurements span the temperature range 200 to 425 K and reach pressures up to the lesser of 1500 kPa or 80% of the sample vapor pressure. The speed-of-sound measurements have a relative standard uncertainty of less than 0.01%. The data were analyzed to obtain the constant-pressure ideal-gas heat capacity C ⁰ _p as a function of temperature with a relative standard uncertainty of 0.1%. The values of C ⁰ _p are in agreement with those determined from spectro- scopic data. The speed-of-sound data were fitted by virial equations of state to obtain temperature-dependent density virial coefficients. Two virial coefficient models were employed, one based on square-well intermolecular potentials, and the second based on a hard-core Lennard-Jones intermolecular potential. The resulting virial equations reproduced the sound-speed data to within ±0.02%, and may be used to calculate vapor densities with relative standard uncertainties of 0.1% or less.