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.     

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.     

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.     

Thermodynamic Properties of Gaseous Nitrous Oxide and Nitric Oxide from Speed-of-Sound Measurements

The speed of sound was measured in gaseous nitrous oxide (N₂O) and nitric oxide (NO) using an acoustic resonance technique with a relative standard uncertainty of less than 0.01%. The measurements span the temperature range 200 to 460 K at pressures up to the lesser of 1.6 MPa or 80% of the vapor pressure. The data were analyzed to obtain the constant-pressure ideal-gas heat capacity _p ⁰ as a function of temperature with a relative standard uncertainty of 0.1%. For N₂O, the values of _p ⁰ agree within 0.1% with those determined from spectroscopic data. For NO, the values of _p ⁰ differ from spectroscopic results by as much as 1.5%, which is slightly more than the combined uncertainties. 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 nearly all 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.     

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%.     

Thermophysical Properties of Gaseous Tungsten Hexafluoride from Speed-of-Sound Measurements

The speed of sound was measured in gaseous WF₆ using a highly precise acoustic resonance technique. The data span the temperature range from 290 to 420 K and the pressure range from 50 kPa to the lesser of 300 kPa or 80% of the sample's vapor pressure. At 360 K and higher temperatures, the data were corrected for a slow chemical reaction of the WF₆ within the apparatus. The speed-of-sound data have a relative standard uncertainty of 0.005%. 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%. These heat capacities are in reasonable 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 ±0.005% and may be used to calculate vapor densities with relative standard uncertainties of 0.1% or less. The hard-core Lennard–Jones potential was used to estimate the viscosity and the thermal conductivity of dilute WF₆. The predicted viscosities agree with published data to within 5% and can be extrapolated reliably to higher temperatures.     

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.     

Viscosity and Speed of Sound of Gaseous Nitrous Oxide and Nitrogen Trifluoride Measured with a Greenspan Viscometer

The viscosity and speed of sound of gaseous nitrous oxide and nitrogen trifluoride were measured using a Greenspan acoustic viscometer. The data span the temperature range 225–375 K and extend up to 3.4 MPa. The average relative uncertainty of the viscosity is 0.68% for N₂O and 1.02% for NF₃. The largest relative uncertainties were 3.09 and 1.08%, respectively. These occurred at the highest densities (1702 mol · m^-3 for N₂O and 2770 mol · m^-3 for NF₃). The major contributor to these uncertainties was the uncertainty of the thermal conductivity. The speeds of sound measured up to 3.4 MPa are fitted by a virial equation of state that predicts gas densities within the uncertainties of the equations of states available in the literature. Accurate measurements of the speed of sound in both N₂O and NF₃ have been previously reported up to 1.5 MPa. The current measurements agree with these values with maximum relative standard deviations of 0.025% for N₂O and 0.04% for NF₃.     

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.     

The Viscosity of Seven Gases Measured with a Greenspan Viscometer

The viscosity of seven gases (Ar, CH₄, C₃H₈, N₂, SF₆, CF₄, C₂F₆) was determined by interpreting frequency-response data from a Greenspan acoustic viscometer with a detailed model developed by Gillis, Mehl, and Moldover. The model contains a parameter _r that characterizes the viscous dissipation at the ends of the viscometer's duct. It was difficult to determine _r accurately from dimensional measurements; therefore, _r was adjusted to fit the viscosity of helium on the 298 K isotherm (0.6 MPa<p<3.4 MPa). This calibration was tested by additional viscosity measurements using four, well-studied, polyatomic gases (CH₄, C₂H₆, N₂, and SF₆) near 300 K and by measurements using argon in the range 293 K<T<373 K. For these gases, all of the present results agree with reference values to within ±0.5% (±0.4% in the limit of zero density). The viscosities of CF₄ and C₂F₆ were measured between 210 and 375 K and up to 3.3 MPa with average uncertainties of 0.42 and 0.55%, respectively. At the highest density studied for CF₄ (2746 molm^–3), the uncertainty increased to 1.9%; of this 1.9%, 0.63% resulted from the uncertainty of the thermal conductivity of CF₄, which other researchers estimated to be 2% of its value at zero density. As an unexpected bonus, the present Greenspan viscometer yielded values of the speed of sound that agree, within ±0.04%, with reference values.     

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.     

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.     

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.     

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.     

Surface characteristics of parylene-C films in an inductively coupled O2/CF4 gas plasma

In this article, we report the results obtained from a study carried out on the inductively coupled plasma (ICP) etching of poly-monochloro-para-xylylene (parylene-C) thin films using an O₂/CF₄ gas mixture. The effects of adding CF₄ to the O₂ plasma on the etch rates were investigated. As the CF₄ gas fraction increases up to approximately 16%, the polymer etch rate increases in the range of 277-373 nm/min. In this work, the atomic force microscopy (AFM) analysis indicated that the surface roughness was reduced by the addition of CF₄ to the O₂ plasma. Contact angle measurements showed that the surface energy decreases with increasing CF₄ fraction. At the same time, X-ray photoelectron spectroscopy (XPS) demonstrated the increase in the relative F atomic content on the surface.     

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.     

Speed of Sound in Pure Water at Temperatures between 274 and 394 K and at Pressures up to 90 MPa

A newly designed experimental apparatus has been used to measure the speed of sound u in high-purity water on nine isotherms between 274 and 394 K and at pressures up to 90 MPa. The measurement technique is based on a traditional double-reflector pulse-echo method with a single piezoceramic transducer placed at unequal distances from two stainless steel reflectors. The transit times of an acoustic pulse are measured at a high sampling rate by a digital oscilloscope. The distances between the transducer and the reflectors were obtained at ambient temperature and pressure by direct measurements with a coordinate measuring machine. The speeds of sound are subject to an overall estimated uncertainty of 0.05 %. The acoustic data were combined with available values of density ρ and isobaric heat capacity c_p along one isobar at atmospheric pressure to calculate the same quantities over the whole temperature and pressure range by means of a numerical integration technique. These results were compared with those calculated from the IAPWS-95 formulation with corresponding relative deviations which are within 0.1%. Paper presented at the Fifteenth Symposium on Thermophysical Properties, June 22–27, 2003, Boulder, Colorado, U.S.A.     

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 Equation of State for Pentafluoroethane (R-125)

We developed a fundamental equation of state for pentafluoroethane (R-125, CHF₂CF₃) which is represented in terms of a non-dimensional Helmholtz free energy. The equation has been established on the basis of selected measurements of the pressure-density-temperature relation, speed of sound, heat capacities, and saturation properties. Linear and non-linear regression analysis was employed to determine the functional form and the numerical parameters. The equation represents all the thermodynamic properties of R-125 in the liquid and gaseous phases for temperatures between the triple point and 470 K, and pressures up to 35 MPa. The uncertainties are estimated to be about ±0.05% or 0.1 kPa for the vapor pressure, ± 0.05 % for the liquid and vapor densities, about ± 1 % for the isobaric and isochoric heat capacities in the liquid, and ± 0.5 % or ± 0.02 % for the speed of sound in the liquid and vapor, respectively.     

Thermodynamic Properties of Air from 60 to 2000 K at Pressures up to 2000 MPa

A thermodynamic property formulation for standard dry air based upon experimental P––T, heat capacity, and speed of sound data and predicted values, which extends the range of prior formulations to higher pressures and temperatures, is presented. This formulation is valid for temperatures from the solidification temperature at the bubble point curve (59.75 K) to 2000 K at pressures up to 2000 MPa. In the absence of experimental air data above 873 K and 70 MPa, air properties were predicted from nitrogen data. These values were included in the fit to extend the range of the fundamental equation. Experimental shock tube measurements ensure reasonable extrapolated properties up to temperatures and pressures of 5000 K and 28 GPa. In the range from the solidification point to 873 K at pressures to 70 MPa, the estimated uncertainty of density values calculated with the fundamental equation for the vapor is ±0.1%. The uncertainty in calculated liquid densities is ±0.2%. The estimated uncertainty of calculated heat capacities is ±1% and that for calculated speed of sound values is ±0.2%. At temperatures above 873 K and 70 MPa, the estimated uncertainty of calculated density values is ±0.5%, increasing to ±1% at 2000 K and 2000 MPa.