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.     

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.     

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.     

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.     

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.     

Gaseous thermal conductivity of difluoromethane (HFC-32), pentafluoroethane (HFC-125), and their mixtures

The gaseous thermal conductivity of dilluoromethane (HFC-32). pentalluoroethane (HFC-125). and their binary mixtures was measured with a transient hot-wire apparatus in the temperature ranges 283–333 K at pressures up to saturation. The uncertainty of the data is estimated to be within I %. The thermal conductivity as a function of composition of the mixtures at constant pressure and temperature is found to have a small maximum near 0.3–0.4 mole fraction of HFC-32. The gaseous thermal-conductivity data obtained for pure HFC-32 and HFC-125 were correlated with temperature and density together with the liquid thermal-conductivity data from the literature, based on the excess thermal-conductivity concept. The composition dependence of the thermal conductivity at a constant temperature is represented with the aid of the Wassiljewa equation.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%.     

Vapor–Liquid Equilibria of CFC Alternative Refrigerant Mixtures: Trifluoromethane (HFC-23)+Difluoromethane (HFC-32), Trifluoromethane (HFC-23)+Pentafluoroethane (HFC-125), and Pentafluoroethane (HFC-125)+1,1-Difluoroethane (HFC-152a)

Isothermal vapor–liquid equilibria for three binary mixtures of CFC alternative refrigerants were determined in an equilibrium apparatus in which both phases were continuously recirculated. The pressures and vapor and liquid compositions were measured for the binary systems trifluoromethane (HFC-23)+difluoromethane (HFC-32) and trifluoromethane (HFC-23)+pentafluoroethane (HFC-125) at 283.15 and 293.15 K and pentafluoroethane (HFC-125)+1,1-difluoroethane (HFC-152a) at 293.15 K. The experimental data were correlated with the Peng–Robinson–Stryjek–Vera equation of state using the Huron–Vidal original mixing rule. Calculated results with this equation showed good agreement with the experimental data.     

HCFC-22替代制冷剂研究进展及其相关问题讨论

简要介绍制冷剂的发展历史,详细介绍相关行业中制冷剂的应用现状及我国目前在替代HCFC-22方面的工作,重点介绍若干最新备受关注的制冷剂如HFO-1234yf及其混合物、HFC-161及其混合物、HFC-32和R290等。由于这些制冷剂普遍存在的可燃性问题,本文也将介绍一些描述可燃性的参数以及相关的国际标准,并提出一些选择可燃制冷剂的注意点。     

Equations of State for Technical Applications. III. Results for Polar Fluids

New functional forms have been developed for multiparameter equations of state for non- and weakly polar fluids and for polar fluids. The resulting functional forms, which were established with an optimization algorithm which considers data sets for different fluids simultaneously, are suitable as a basis for equations of state for a broad variety of fluids. The functional forms were designed to fulfil typical demands of advanced technical application with regard to the achieved accuracy. They are numerically very stable and their substance-specific coefficients can easily be fitted to restricted data sets. In this way, a fast extension of the group of fluids for which accurate empirical equations of state are available is now possible. This article deals with the results found for the polar fluids CFC-11 (trichlorofluoromethane), CFC-12 (dichlorodifluoromethane), HCFC-22 (chlorodifluoromethane), HFC-32 (difluoromethane), CFC-113 (1,1,2-trichlorotrifluoroethane), HCFC-123 (2,2-dichloro-1,1,1-trifluoroethane), HFC-125 (pentafluoroethane), HFC-134a (1,1,1,2-tetrafluoroethane), HFC-143a (1,1,1-trifluoroethane), HFC-152a (1,1-difluoroethane), carbon dioxide, and ammonia. The substance-specific parameters of the new equations of state are given as well as statistical and graphical comparisons with experimental data. General features of the new class of equations of state such as their extrapolation behavior or their numerical stability and results for non- and weakly polar fluids have been discussed in preceding articles.     

Effect of dissolved lubricating oils on the viscosity of alternative refrigerants

The operation of refrigeration systems involves the circulation of a working fluid which is actually a mixture of refrigerant and lubricant oil. Since the viscosity of oil and that of refrigerants normally differ by up to a factor of 4, the effect of dissolved oil is very large. In order to use new alternative refrigerants, accurate information on thermophysical properties of refrigerant-oil mixtures is needed. In the present study, the viscosity of refrigerant-oil mixtures was measured for HCFC-123 + 3GSD and HFC-134a + PAG in the compressed liquid region with a falling-ball viscometer. The temperature range of the measurements was 253–333 K.     

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%.     

Formation Conditions of Clathrates Between HFC Alternative Refrigerants and Water

There are two promising candidates as alternative refrigerants for air-conditioners and heat pumps. The first is R407C, which is composed of HFC-32 (23 mass%), HFC-125 (25 mass%), and HFC-134a (52 mass%). The second is R410A, which is composed of HFC-32 (50 mass%) and HFC-125 (50 mass%). In this study, formation conditions of clathrate compounds between water and HFC alternative refrigerants such as HFC-32, HFC-125, HFC-134a, and their mixtures, R407C and R410A, were investigated. Phase diagrams of clathrates of these HFC alternative refrigerants and their mixtures were determined. From the phase diagrams, the critical decomposition temperature and the critical decomposition pressure were determined. The relationship between the critical decomposition points for the clathrates of HFC-32, HFC-125, HFC-134a, R410A, and R407C were studied. It is found that R407C and R410A form clathrate compounds with water under the evaporating temperature condition in the refrigeration cycle of air-conditioners and heat pumps.     

Saturated liquid viscosities and densities of environmentally acceptable hydrochlorofluorocarbons (HCFCs)

Measurements of saturated liquid viscosities and densities were performed on environmentally acceptable hydrochlorofluorocarbons (HCFCs), CH₃CCl₂F (HCFC-141b), CH₃CClF₂ (HCFC-142b; only for viscosity), CF₃CF₂CHCl₂ (HCFC-225ca), and CClF₂CF₂CHClF (HCFC-225cb), using a capillary viscometer and a glass pycnometer in the temperature range from 273 to 353 K. The uncertainty in the measurement of viscosity is estimated to be 5% based on the comparison of the present data with those in the literature for HCFC-141b. An equation is given to represent our saturated liquid viscosity data as a function of temperature.     

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.     

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.     

Vapor–Liquid Equilibria for the 1,1,1-Trifluoroethane (HFC-143a)+1,1,1,2-Tetrafluoroethane (HFC-134a) System

A vapor–liquid equilibrium apparatus has been developed and used to obtain data for the binary HFC-143a+HFC-134a system. Fifty-four equilibrium data are obtained for the HFC-143a+HFC-134a system over the temperature range from 263.15 to 313.15 K at 10 K intervals. The experimental data were correlated with the Carnahan–Starling–De Santis (CSD) and Peng–Robinson (PR) equations of state. Based upon the present data, the binary interaction parameters for the CSD and PR equations of state were calculated for six isotherms for the HFC-143a+HFC-134a system. The binary interaction parameters for both equations of state were fitted by a linear equation as a function of temperature. The present data were in good agreement with the calculated results from the CSD equation of state, and the deviations were less than 1.0% with the exception of two points.     

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.     

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.     

Surface Tension of 1,1,1-Trifluoroethane (HFC-143a), 1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea), and Their Binary Mixture HFC-143a/227ea

The surface tension of 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2,3,3,3-hepta-fluoropropane (HFC-227ea), and their binary mixture HFC-143a/227ea at 3 nominal mass fractions of 27.91%/72.09%, 49.44%/50.56%, and 74.11%/25.89% were measured in the temperature range from 253 to 333K using the differential capillary rise method (DCRM) under vapor-liquid equilibrium conditions. The temperature and surface tension uncertainties were estimated to be within ±10 mK and ±0.15 mNm^–1, respectively. The present data were used to develop a van der Waals-type surface tension correlation for pure HFC-143a and HFC-227ea. Correlations for pure HFC-143a and HFC-227ea were used to develop a surface tension correlation for the experimental data of the HFC-143a/227ea mixtures as a function of the mass fraction.