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%.     

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.     

Sound velocity and ideal-gas specific heat of gaseous 1,1,1,2-tetrafluoroethane (R134a)

A cylindrical, variable-path acoustic interferometer operating at 156.252kHz is developed for determining ideal-gas specific heats. Results of validation measurements with argon are very satisfactory, with the maximum deviation of the speed of sound equal to 3×10^–4. The sound velocity of gaseous R134a has been measured at low temperatures and low pressures. The specific heat was then calculated from the results. The experimental results corrected for various dispersions for the sound velocity of gaseous R134a match well with an earlier publication, with a room mean square deviation of 2.56×10^–4. A new relation for the ideal-gas specific heat as a function of temperature for R134a is obtained.     

Phase Equilibria of CFC Alternative Refrigerant Mixtures: 1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea)+Difluoromethane (HFC-32), +1,1,1,2-Tetrafluoroethane (HFC-134a), and +1,1-Difluoroethane (HFC-152a)

Isothermal vapor–liquid equilibria were measured for the binary systems difluoromethane (HFC-32)+1,1,1,2,3,3,3-heptafluoropropane (HFC-22ea) and 1,1-difluoroethane (HFC-152a)+1,1,1,2,3,3,3-heptafluoropropane at 283.15 and 303.15 K and 1,1,1,2-tetrafluoroethane (HFC-134a)+1,1,1,2,3,3,3-heptafluoropropane at 303.15 and 323.15 K in an apparatus in which both phases were recirculated. The experimental data were correlated with the Peng–Robinson equation of state using the Wong–Sandler mixing rules. Azeotropic behavior has not been found in any of the three mixtures.     

Thermal Conductivity of HFC-32, HFC-125, and HFC-134a in the Solid Phase

Measurements of the thermal conductivity of HFC-32, HFC-125, and HFC-134a were carried out for the first time in both solid and liquid phases at the saturation pressure at room temperature and in the temperature ranges from 120 to 263, from 140 to 213, and from 130 to 295 K, respectively. A transient hot-wire instrument using one bare platinum wire was employed for measurements, with an uncertainty of less than ±2%. The experimental results demonstrated that the thermal conductivity of HFC-32, HFC-125, and HFC-134a in the solid phase showed a positive temperature dependence. For HFC-32 and HFC-125, there were big jumps between the solid and the liquid thermal conductivity at the melting point. But for HFC-134a, the solid and liquid thermal conductivity at the melting point is almost-continuous.     

A fundamental equation of state for 1,1-difluoroethane (HFC-152a)

A fundamental equation ofstale for HFC-152a ( 1,1-dilluorocthane) is presented covering temperatures between the triple-point temperature ( 154.56 K) and 435 K for pressures up to 311 M Pa. The equation is based on reliable (p, g, T) data in the range mentioned above. These are generally represented within ±0.1 % of density. Furthermore. experimental values of the vapor pressure, the saturated liquid density, and some isobaric heat capacities in the liquid were included during the correlation process. The new equation of state is compared with experimental data and also with the equation of state developed by Tamatsu et al. Differences between the two equations of state generally result from using different experimental input data. It is shown that the new equation of state allows an accurate calculation of various thermodynamic properties for most technical applications.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder. Colorado. U.S.A.     

Vapor–Liquid Equilibrium of HFC-32/134a And HFC-125/134a Systems

A vapor-liquid equilibrium apparatus has been developed and used to obtain data for the binary HFC-32/134a and HFC-125/134a systems. Twenty-two equilibrium data are obtained for the HFC-32/134a system over the temperature range from 258.15 to 283.15 K at 5 K intervals and the composition range from 0.2 to 0.8 liquid mole fraction. Twenty-five equilibrium data are obtained for the HFC-125/134a system over the temperature range from 263.15 to 303.15 K at 10 K intervals and the composition range from 0.18 to 0.81 liquid mole friction. These data have been tested and found to be thermodynamically consistent. Based upon the present data, the binary interaction parameters of the Carnahan-Starling-De Santis (CSD) and Redlich–Kwong–Soave (RKS) equations of state are calculated for five isotherms for the HFC-125/134a mixture and six isotherms for the HFC-32/134a mixture. The calculated results from the CSD equation are compared with data in the open literature.     

Acoustic determination of ideal-gas heat capacity and second virial coefficients of some refrigerants between 250 and 420 K

An apparatus for speed-of-sound measurements with a spherical resonator was adapted for temperatures up to 42(I K. This included new microphones with a special wiring, a pressure indicator which can be thermostatted to 420 K, and some installations to avoid temperature gradients. Calibration of the radius of the resonator with argon was extended to higher temperatures. Speed-of-sound measurements up to 420 K and 0.5 MPa were done onl,l-dilluoroethane (R152a). 1.l,l-trilluoroethane (R 143a ),l,l,l-chlorodifluoroethane (R 142b ), l,1,1,2-tetralluoroethane (R134a), and 2.2.2-trifluoroethanol. The ideal-gas heat capacities coincide with the statistical mechanical values, except for R134a, where our values as well as recent literature data are below the values calculated from spectroscopy. The reduced second virial coefficients can be interpreted in terms of the dipole moment and the angle between dipole moment and molecular axis. For the associated substance trifluoroethanol values of the third virial coefficient are given, which are appreciably negative at low temperatures.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994 Boulder, Colorado, U.S.A.     

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.     

Thermal Conductivity of Binary Refrigerant Mixtures of HFC-32/125 and HFC-32/134a in the Liquid Phase

The liquid thermal conductivity of mixtures of HFC-32/125 and HFC-32/134a was measured using the transient hot-wire apparatus in the temperature ranges from 213 to 293 K and from 193 to 313 K, respectively, in the pressure range from 2 to 30 MPa and with HFC-32 mass fractions of 0.249, 0.500, and 0.750 for each system. The uncertainty of the thermal conductivity was estimated to be ±0.7%. For practical applications, the thermal conductivity data for the two mixtures were represented by a polynomial in temperature, pressure, and mass fraction of HFC-32 with a standard deviation of 1.0%.     

模板法制备高比表面积的氟化镁及其在HFC-152a脱HF反应中的应用

镁基固体酸催化剂在含氟化学品的合成中具有优异的性能。利用模板法制备了高表面积的氟化镁,并考察了SiO₂模板剂的用量对其结构及催化性能的影响。通过N₂物理吸附、X射线衍射、NH₃-程序升温脱附、透射电镜和X射线光电子能谱等表征手段进行了表征, 以1,1-二氟乙烷(HFC-152a, CH₃CHF₂)脱HF制备氯乙烯(VF,CH₂=CHF)为探针对其催化性能进行了研究。结果表明, SiO₂模板剂用量对氟化镁的比表面积、晶粒度和酸性有较大影响。当SiO₂模板剂用量为14mol%时, 氟化镁比表面积可达304 m²/g, 是不添加SiO₂模板剂的2.5倍, 而且Mg晶粒度更小, 配位数更多。随着Mg配位数增多, MgF₂的酸性位急剧增多, 在以Lewis酸为活性位的1,1-二氟乙烷脱HF反应中, MgF₂的催化活性迅速升高。因此, 以SiO₂为模板是制备高活性MgF₂催化剂的有效方法。     

Thermodynamic properties of 1,1,1,2-tetrafluoroethane (R134a) in the critical region

A theoretically based simplified crossover model, which is capable of representing the thermodynamic properties of fluids in a large range of temperatures and densities around the critical point, is presented. The model is used to predict the thermodynamic properties of R134a in the critical region from a limited amount of available experimental information. Values for various thermodynamic properties of R134a at densities from 2 to 8 mol·L^–1 and at temperatures from 365 to 450 K are presented.     

An experimental comparison of evaporation and condensation heat transfer coefficients for HFC-134a and CFC-12

Experimental heat transfer coefficients are reported for HFC-134a and CFC-12 during in-tube single-phase flow, evaporation and condensation. These heat transfer coefficients were measured in a horizontal, smooth tube with an inner diameter of 8.0 mm and a length of 3.67 m. The refrigerant in the test-tube was heated or cooled by using water flowing through an annulus surrounding the tube. Evaporation tests were performed for a refrigerant temperature range of 5–15°C with inlet and exit qualities of 10 and 90%, respectively. For condensation tests, the refrigerant temperature ranged from 30 to 50°C, with et and exit qualities of 90 and 10%, respectively. The mass flux was varied from 125 to 400 kg m⁻² s⁻¹ for all tests. For similar mass fluxes, the evaporation and condensation heat transfer coefficients for HFC-134a were significantly higher than those of CFC-12. Specifically, HFC-134a showed a 35–45% increase over CFC-12 for evaporation and a 25–35% increase over CFC-12 for condensation.     

Measurements of PVTx Properties for Binary Mixtures of HFC-32 (CH2F2) and HFC-134a (CH2FCF3)

An experimental study of pressure–volume–temperature–composition (PVTx) properties for binary mixtures of HFC-32 and HFC-134a was conducted in the range of temperatures from 243 to 473 K, pressures up to 16.7 MPa, densities from 9.5 to 1065 kg·m^–3, and compositions from 0.39 to 0.89 mol fraction of HFC-32, with uncertainties of 8 mK, 1.7 kPa, 0.04%, and 0.001 mol fraction, respectively. A constant-volume method was used for the present measurements either with a spherical vessel approximately 270 cm³ in its inner volume or with a cylindrical vessel approximately 138cm³ in its inner volume. The present data were compared with the Piao equation of state for this substance.     

Liquid viscosities and densities of HFC-134a+glycol mixtures

Liquid viscosity and density of six binary mixtures of HFC-134a with glycols [ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (400), and polypropylene glycol (2000)] have been measured in the temperature range from 273 to 333 K. The viscosity was measured by a rolling-ball viscometer calibrated with standard liquids of viscosities and densities (JS5, JS10, JS20, and JS50). The density was measured with a glass pycnometer. The uncertainties of the measurements were estimated to be less than 3.4 % for viscosity and 0.04 % for density, respectively. An equation is given to represent the obtained viscosity values as a function of weight fraction and temperature.     

Thermal conductivity of halogenated ethanes,HFC-134a,HCFC-123, and HCFC-141b

The gaseous thermal conductivity of three CFC alternatives, HFC-134a (1,1,1,2-tetrafluoroethane), HCFC-123 (1,1-dichloro-2,2,2-trifluoroethane), and HCFC-141b (1,1-dichloro-1-fluoroethane), has been measured in the temperature ranges 273–363 K (HFC-134a) and 313–373 K (HCFC-123, HCFC-141b) at pressures up to saturation. The measurements were performed with a new improved transient hot-wire apparatus. The uncertainty of the experimental data is estimated to be within 1%. The gaseous thermal conductivity obtained in this work together with the liquid thermal-conductivity data from the literature were correlated with temperature and density by an empirical equation based on the excess thermal-conductivity concept. The equation is found to represent the experimental results with average deviations of 2.5 % for HFC-134a, 0.75% for HCFC-123, and 0.55% for HCFC-141b, respectively.     

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.     

Thermal diffusivity and ultrasonic velocity of saturated R152a

We report thermal diffusivity and ultrasonic sound velocity data for both phases of saturated diflourethane (R152a) in the temperature range from 278 K to the critical temperature. The data were obtained in thermodynamic equilibrium by applying dynamic light scattering. For both values comparison with data from literature has been made.     

A Multiparameter Thermal Conductivity Equation for 1,1-Difluoroethane (R152a) with an Optimized Functional Form

The application of an optimization technique to the available experimental data has led to the development of a new multiparameter equation λ = λ (T,ρ ) for the representation of the thermal conductivity of 1,1-difluoroethane (R152a). The region of validity of the proposed equation covers the temperature range from 220 to 460 K and pressures up to 55 MPa, including the near-critical region. The average absolute deviation of the equation with respect to the selected 939 primary data points is 1.32%. The proposed equation represents therefore a significant improvement with respect to the literature conventional equation. The density value required by the equation is calculated at the chosen temperature and pressure conditions using a high accuracy equation of state for the fluid.Paper presented at the Seventeenth European Conference on Thermophysical Properties,September 5–8, 2005, Bratislava, Slovak Republic.     

Thermodynamic Properties of Mixtures of R-32, R-125, R-134a, and R-152a

A mixture model explicit in Helmholtz energy has been developed that is capable of predicting thermodynamic properties of refrigerant mixtures containing R-32, R-125, R-134a, and R-152a. The Helmholtz energy of the mixture is the sum of the ideal gas contribution, the compressibility (or real gas) contribution, and the contribution from mixing. The contribution from mixing is given by a single equation that is applied to all mixtures used in this work. The independent variables are the density, temperature, and composition. The model may be used to calculate thermodynamic properties of mixtures, including dew and bubble point properties and critical points, generally within the experimental uncertainties of the available measured properties. It incorporates the most accurate published equation of state for each pure fluid. The estimated uncertainties of calculated properties are ±0.25% in density, ±0.5% in the speed of sound, and ±1% in heat capacities. Calculated bubble point pressures are generally accurate to within ±1%.