Pressure Dependence of the Thermophysical Properties of n-Pentadecane and n-Heptadecane

The speed of sound in liquid n-pentadecane and n-heptadecane was measured using a pulse technique operating at 3 MHz. The measurements were carried out at pressures up to 150 MPa in the temperature range from 293 to 383 K. The experimental results have been used to evaluate various thermophysical properties such as density and isentropic and isothermal compressibilities up to 150 MPa with the help of additional density and heat capacity data at atmospheric pressure.     

Speed of sound in liquid R134a

The speed of sound for liquid R134a (1,1,1,2-tetrafluoroethane) has been measured along isotherms at temperatures from close to the triplee point to above the critical temperature (180–380 K) at pressures from near saturation to 70 MPa. The measurements were made by using a pulse-echo-overlap technique at 3 MHz. A rational approximant fits the data with a standard deviation of 0.45 m s⁻¹. Because the speed of sound depends on the molar volume and the adiabatic compressibility, these data may be used with density and heat capacity data to construct accurate thermodynamic property tables.     

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.     

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 and Acoustic Properties of 1,3-Dibromopropane and 1,5-Dibromopentane within the Temperature Range From 293K to 313K at Pressures up to 100MPa

This study reports new experimental data of the speed of sound in liquid 1,3-dibromopropane and 1,5-dibromopentane from 293K to 313K at pressures up to 101MPa, measured with a pulse–echo overlap method. The experimental results have been used to calculate densities, isobaric heat capacities, isobaric coefficient of thermal expansion, and isentropic and isothermal compressibilities as functions of temperature and pressure.     

Study of the Effects of Temperature and Pressure on the Thermodynamic and Acoustic Properties of 2-Methyl-1-butanol at Temperatures from 293K to 318K and Pressures up to 100MPa

The speeds of sound in 2-methyl-1-butanol were measured at temperatures from 293K to 318K and pressures up to 101MPa. The densities were measured in the same temperature range under atmospheric pressure. The isobaric specific heat capacities were measured at atmospheric pressure and temperatures from 284K to 355K. The densities, isobaric heat capacities, isobaric thermal expansions, isentropic compressibilities, isothermal compressibilities, and internal pressures as functions of temperature and pressure were calculated using the experimental speeds of sound under elevated pressures together with the densities and heat capacities at atmospheric pressure. The effects of temperature and pressure on the isobaric thermal expansion and internal pressure of 2-methyl-1-butanol are discussed and compared with those of pentan-1-ol, 2-methyl-2-butanol, and pentan-3-ol.     

Measurement of the compressibility and sound velocity of helium up to 1 GPa

By using a gas expansion technique, the density of helium has been determined at 298.15 K as a function of pressure from 100 MPa to 1 GPa. The precision of the measurements is 0.02%, while the estimated absolute accuracy is about 0.08%. The sound velocity has been measured by a phase-comparison pulseecho technique between 98 and 298 K with intervals of 25 K and at pressures up to 1 GPa, with an accuracy generally better than 0.04%. By combining pVT with velocity-of-sound data at 298 K, the adiabatic compressibility and the ratio of the specific heats are calculated. The experimental sound velocities are compared with the values, predicted from an equation of state as proposed by Hansen.     

Measurement of the compressibility and sound velocity of neon up to 1 GPa

The density of neon has been determined at 298.15 K as a function of pressure from 80 MPa to 1 GPa. The precision of the measurements is 0.03%, while the estimated absolute accuracy is between 0.05 and 0.09%. The sound velocity has been measured between 98 and 298 K with intervals of 25 K and at pressures up to 1 GPa, with an accuracy generally better than 0.06%. The adiabatic compressibility and the ratio of the specific heats are calculated by combining pVT with velocity-of-sound data at 298 K. Several equations of state are fitted to the density data at 298.15 K.Paper presented at the Tenth Symposium on Thermophysical Properties, June 20–23, 1988, Gaithersburg, Maryland, U.S.A.     

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.     

Speed of sound in saturated and compressed fluid ethane

The speed of sound in saturated and compressed fluid ethane has been measured in the temperature range 91 to 323.15 K and at pressures to 35 MPa. These data were combined with newly available PpT data to obtain the isentropic compressibility and the ratio of the specific heats. The quality of the PpT data has been examined by comparison of sound speeds calculated from these data with the measured sound speeds.     

Compressibility and sound velocity measurements on N2 up to 1 GPa

A gas expansion technique has been used to determine the pVT properties of N₂ up to 1 GPa at 298.15 K, with an accuracy of 0.08% in density, 1 mK in temperature, and 0.05%+0.2 MPa in pressure. The sound velocity has been measured by a phase-comparison pulse-echo technique between 123 and 298 K at intervals of 25 K and at pressures up to 1 GPa, with an accuracy of better than 0.02% in sound velocity, 10 mK in temperature, and 0.05%+0.2 MPa in pressure. An equation of state is presented that correlates the density data over the wide pressure range of 36–1000 MPa with maximum deviations between the calculated and the experimental densities of less than 0.05%.     

Equation of state and ideals-gas heat capacity of a gaseous mixture of 1,1,1,2-tetrafluoroethane, pentafluoroethane, and difluoromethane

We present the gas-phase equation of state and ideal-gas heat capacity of a ternary mixture (nominal molar concentration) of 1,1,1,2-tetrafluoroethane (35%), pentafluoroethane (30%), and difluoromethane (35%) for temperatures between 260 and 453 K and pressures between 0.05 and 7.7 MPa. These results were based on two very different measurement techniques. The first technique measured the gas density of the mixture in a Burnett apparatus from 313 to 453 K and from 0.2 to 7.7 MPa. The second technique deduced the gas density and ideal-gas heat capacity from high-accuracy speed-of-sound measurements in the mixture at temperatures between 260 and 400 K and at pressures between 0.05 and 1.0 MPa. The data from the two techniques were analyzed together to obtain an equation of state that reproduced the densities from the Burnett technique with a fractional RMS deviation of 0.038%, and it also reproduced the sound speeds with a fractional RMS deviation of 0.003%. Finally, the results are compared to a predictive model based on the properties of the pure fluids.     

Compressibilities of ternary mixtures C1-nC16-CO2 under pressure from ultrasonic measurements of sound speed

Speed of sound measurements have been performed on three mixtures of the ternary system methane + carbon dioxide + normal hexadecane. The systems have been investigated from 12 to 70 MPa in the temperature range from 313 to 393 K. Furthermore, these measurements have allowed the evaluation of the isothermal and the isentropic compressibilities up to 70 MPa from low pressure (<40-MPa) density data.     

Equation of State for Normal Liquid Helium-3 from 0.1 to 3.3157 K

An equation of state for normal liquid ³He has been constructed in the form of Helmholtz free energy as a function of independent parameters—temperature, and density. The equation was fitted simultaneously to the collected experimental p-ρ-T, specific heat, sound velocity, isobaric expansion coefficient and isothermal compressibility coefficient from the world’s literature to accuracies comparable with reasonable experimental errors in the measured quantities. Extensive comparisons between the equation of state and experimental data have been made by a set of deviation plots. The state equation is valid in the region for temperatures from 0.1 K to T _c = 3.3157 K, and for pressures from vapor pressures to melting pressures.     

A new equation of state for chlorodifluoromethane (R22) covering the entire fluid region from 116 K to 550 K at pressures up to 200 MPa

A new equation of state in the form of a fundamental equation explicit in the dimensionless Helmholtz free energy has been developed for chlorodifluoromethane (R 22). This equation, which contains 22 fitted coefficients, covers the entire fluid region from 116 K (triple point temperature) to 550 K at pressures up to 200 MPa. The mathematical form of the equation was determined with the help of a new method to optimize its structure. New pressure-density-temperature data in the liquid region and especially new vapour pressures and saturated liquid densities, as well as speed of sound data have been incorporated to extend the range of validity and to improve the accuracy of properties calculated with this equation beyond that of previous formulations. Independent equations are also included for the vapour pressure as well as for the saturated liquid and vapour densities. The uncertainty of the new wide-range equation of state can roughly be given as follows: ± 0.1% in density (with the exception of the critical region), ± 1% in heat capacity, ± 0.5% in speed of sound in the liquid and 0.1% in speed of sound in the gas phase. The new equation of state corresponds to the International Temperature Scale of 1990 (ITS-90).     

Thermophysical properties ofm-cresol as a function of temperture (303 to 503 K) and pressure (0.1 to 400 MPa)

Measured and derived thermophysical properties ofm-cresol are reported for pressures up to 400 MPa at temperatures from 303 to 503 K. Isobaric thermal expansivities were measured by pressure-scanning calorimetry from 303 to 503 K and 0.1 to 400 MPa. The specific volume at 353 K was determined by pycnometry at atmospheric pressure and calculated from isothermal compressibilities measured as a funtion of pressure up to 400 MPa. Specific volumes at other temperatures and pressures are calculated from isothermal compressibilities measured as a function of pressure up to 400 MPa. Specific volumes, isothermal compressibilities, thermal coefficients of pressure, and isobaric and isochoric heat capacities at pressures up to 400 MPa are derived at several temperatures. The effects of pressure on the isobaric heat capacities ofm-cresol,n-hexane, and water are compared. The effects of self-association ofm-cresol are apparent in both the thermal expansivity and the heat capacity data.     

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.     

Thermodynamic properties of the R-415A refrigerant in the vapor phase and on the condensation line

The speed of sound in the R-415A refrigerant vapor and its density and pressure on the condensation line were measured by the ultrasonic interferometer and constant-volume piezometer methods within a range of temperatures from 293 to 373 K and pressures from 0.04 to 0.5–2.45 MPa. The temperature, pressure, density and speed of sound measurement errors were ±20 mK, ±4 kPa, and ±(0.1–0.2)%, respectively. The temperature dependence of the ideal-gas heat capacity was calculated on the basis of the obtained data. The obtained results were compared with the properties calculated by the REFPROP software.     

Determination of the thermodynamic properties of liquid <Emphasis Type="Italic">n</Emphasis>-hexadecane from the measurements of the velocity of sound

The density, the isobaric expansion coefficient, the specific heats at constant pressure and constant volume, and the isothermal compressibility coefficient of liquid n-hexadecane have been calculated in the range of temperatures 298–433 K and pressures 0.1–140 MPa from the data on the velocity of sound. The coefficients of the Tate equation in the above parametric range have been determined. The table of the thermodynamic properties of n-hexadecane has been presented. Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 82, No. 1, pp. 150–156, January–February, 2009.     

A Rigorous Thermodynamic Property Model for Fluid-Phase 1,1-Difluoroethane (R-152a)

A new thermodynamic property model for the Helmholtz free energy with rational third virial coefficients for fluid-phase 1,1-difluoroethane (R-152a) was developed. The model was validated by existing experimental data for temperatures from the triple point to 450 K and pressures up to 60 MPa. Reasonable behavior of the second and third virial coefficients was confirmed from intermolecular potential models. The estimated uncertainties are 0.1% in density for the gaseous and liquid phases, 0.4% in density for the supercritical region, 0.05% in speed of sound for the gaseous phase, 2% in speed of sound for the liquid phase, and 1% in specific heat capacities for the liquid phase. From the reasonable behavior of the ideal curves and the third virial coefficients, the model can be assumed reliable in representing the thermodynamic properties not only at states with available experimental data but also at states for which no experimental data are available.