Isochoric p–ρ–T and Heat Capacity Cv Measurements for Ternary Refrigerant Mixtures Containing Difluoromethane (R32), Pentafluoroethane (R125), and 1,1,1,2-Tetrafluoroethane (R134a) from 200 to 400 K at Pressures to 35 MPa

The p––T relationships and constant volume heat capacity C _v were measured for ternary refrigerant mixtures by isochoric methods with gravimetric determinations of the amount of substance. Temperatures ranged from 200 to 400 K for p––T and from 203 to 345 K for C _v, while for both data types pressures extended to 35 MPa. Measurements of p––T were carried out on compressed gas and liquid samples with the following mole fraction compositions: 0.3337 R32+0.3333 R125+0.3330 R134a and 0.3808 R32+0.1798 R125+0.4394 R134a. Measurements of C _v were carried out on liquid samples for the same two compositions. Published p––T data are in good agreement with this study. For the p––T apparatus, the uncertainty is 0.03 K for temperature and is 0.01% for pressure at p>3 MPa and 0.05% at p<3 MPa. The principal source of uncertainty is the cell volume (28.5 cm³), with a standard uncertainty of 0.003 cm³. When all components of experimental uncertainty are considered, the expanded relative uncertainty (with a coverage factor k=2 and, thus, a two-standard deviation estimate) of the density measurements is estimated to be 0.05%. For the C _v calorimeter, the uncertainty of the temperature rise is 0.002 K and for the change-of-volume work it is 0.2%; the latter is the principal source of uncertainty. When all components of experimental uncertainty are considered, the expanded relative uncertainty of the heat capacity measurements is estimated to be 0.7%.     

Isochoric p-ρ-T Measurements on 1,1-Difluoroethane (R152a) from 158 to 400 K and 1,1,1-Trifluoroethane (R143a) from 166 to 400 K at Pressures to 35 MPa

The p--T relationships have been measured for 1,1-difluoroethane (R152a) and 1,1,1-trifluoroethane (R143a) by an isochoric method with gravimetric determinations of the amount of substance. Temperatures ranged from 158 to 400 K for R152a and from 166 to 400 K for R143a, while pressures were up to 35 MPa. Measurements were conducted on compressed liquid samples. Determinations of saturated liquid densities were made by extrapolating each isochore to the vapor pressure, and determining the temperature and density at the intersection. Published p--T data are in good agreement with this study. For the p--T apparatus, the uncertainty of the temperature is ±0.03 K, and for pressure it is ±0.01% at p>3 MPa and ±0.05% at p&#60;3 MPa. The principal source of uncertainty is the cell volume (28.5 cm³), which has a standard uncertainty of ±0.003 cm³. When all components of experimental uncertainty are considered, the expanded relative uncertainty (with a coverage factor k=2 and thus a two-standard deviation estimate) of the density measurements is estimated to be ±0.05%.     

Isochoric p–ρ–T Measurements for 2,2-Dichloro-1,1,1-Trifluoroethane (R123) at Temperatures from 176 to 380 K and 1-Chloro-1,2,2,2-Tetrafluoroethane (R124) from 104 to 400 K at Pressures to 35 MPa

The p––T relationships were measured for 2,2-dichloro-1,1,1-trifluoroethane (R123) and 1-chloro-1,2,2,2-tetrafluoroethane (R124) by an isochoric method with gravimetric determinations of the amount of substance. Temperatures ranged from 176 to 380 K for R123 and from 104 to 400 K for R124, while pressures extended up to 35 MPa. Measurements were conducted on compressed liquid samples. Most published p––T data are in good agreement with this study. The uncertainty is 0.03 K for temperature and 0.01% for pressure at p>3 MPa and 0.05% at p<3 MPa. The principal source of uncertainty is the cell volume (28.5 cm³), with a standard uncertainty of 0.003 cm³. When all components of experimental uncertainty are considered, the expanded relative uncertainty (with a coverage factor k=2 and, thus, a 2-SD estimate) of the density measurements is estimated to be 0.05%.     

Vapor–Liquid Critical Surface of Ternary Difluoromethane+Pentafluoroethane+1,1,1,2-Tetrafluoroethane (R-32/125/134a) Mixtures

The plane of vapor–liquid criticality for ternary refrigerant mixtures of difluoromethane (R-32)+pentafluoroethane (R-125)+1,1,1,2-tetrafluoroethane (R-134a) was determined from data on the vapor–liquid coexistence curve near the mixture critical points. The compositions (mass percentage) of the mixtures studied were 23% R-32+25% R-125+52% R-134a (R-407C), 25% R-32+15% R-125+60% R-134a (R-407E), and 20% R-32+40% R-125+40% R-134a (R-407A). The critical temperature of each mixture was determined by observation of the disappearance of the meniscus. The critical density of each mixture was determined on the basis of meniscus disappearance level and the intensity of the critical opalescence. The uncertainties of the temperature, density, and composition measurements are estimated as ±10 mK, ±5 kg·m^–3, and ±0.05%, respectively. In addition, predictive methods for the critical parameters of R-32/125/134a mixtures are discussed.     

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 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.     

Isochoric (p-π-T) measurements on liquid and gaseous air from 67 to 400 K at pressures to 35 MPa

Comprehensive isochoricp--T measurements have been carried out on liquid and gaseous air along 16 isochores at densities ranging from 2 to 32 mol · dm^–3. The air mixture has a nominal composition of 0.7813 N₂ + 0.2096 O₂ + 0.0092 Ar. Thep--T data cover a temperature range from 67 to 400 K at pressures up to 35 MPa. Comparisons with experimental results from independent sources are presented using a fundamental equation of state based. in part, on thep--T data from this study.     

Measurements of Vapor Pressures from 280 to 369 K and (p, ρ, T) Properties from 340 to 400 K at Pressures to 200 MPa for Propane

Measurements of (p, ρ, T) properties for compressed liquid propane have been obtained by means of a metal-bellows variable volumometer at temperatures from 340 to 400 K at pressures up to 200 MPa. The volume- fraction purity of the propane sample was 0.9999. The expanded uncertainties (k = 2) of temperature, pressure, and density measurements have been estimated to be less than 3 mK; 1.5 kPa ( MPa), 0.06% (7 MPa MPa), 0.1% (50 MPa MPa) , and 0.2% (p>150 MPa); and 0.11%, respectively. Four (p, ρ, T) measurements at the same temperatures and pressures as literature values have been conducted for comparisons. In addition, vapor pressures were measured at temperatures from 280 to 369 K. Furthermore, comparisons of available equations of state with the present measurements are reported.Paper presented at the 17th European Conference on Thermophysical Properties, September 5–8, 2005, Bratislava, Slovak Republic.     

Thermal-Conductivity Measurements of Aqueous Orthophosphoric Acid Solutions in the Temperature Range from (293 to 400) K and at Pressures up to 15 MPa

A new improved guarded parallel-plate thermal-conductivity cell for absolute measurements of corrosive (chemically aggressive) fluids under pressure has been developed. Using the new modified guarded parallel-plate apparatus the thermal conductivity of aqueous orthophosphoric acid solutions was measured over the temperature range from (293 to 400) K and pressures up to 15 MPa. Measurements were made for three compositions of \(\text {H}_{3}\text {PO}_{4}\) (8 mass%, 15 mass%, and 50 mass%) along three isobars of (0.101, 5, and 15) MPa. The combined expanded uncertainty of the thermal-conductivity \((\lambda )\) measurements at the 95 % confidence level with a coverage factor of \(k=2\) is estimated to be 2 %. The uncertainties of the temperature, pressure, and concentration measurements were 15 mK, 0.05 %, and 0.01 %, respectively. The temperature, concentration, and pressure dependences of the thermal conductivity of the solution were studied. The measured values of thermal conductivity were compared with the available reported data and the values calculated from various correlation and prediction models. A new wide-range correlation model (extended Jones–Dole type equation with pressure-dependent coefficients) for the \(\text {H}_{3}\text {PO}_{4}\) (aq) solution was developed using the present experimental data.     

An Experimental Study of the <Emphasis Type="Italic">pVTx</Emphasis> Properties for Binary Mixtures of HFC-32 and HFC-125 from 258 to 354 K at Pressures up to 16.9 MPa

An experimental study of the pVTx properties for binary mixtures of HFC-32 (CH₂F₂) and HFC-125 (C₂HF₅) was conducted in the range of temperatures from 258 to 354 K, pressures up to 16.9 MPa, densities from 900 to 1400 kg·m⁻³, and compositions from 0 to 1 mole fraction of HFC-32, within the uncertainties of 4.8 mK of temperatures, 1.8 kPa of pressures, 0.022% of densities, and 0.0022 mole fraction of compositions. The present results were determined with the use of a constant-volume apparatus consisting of a cylindrical vessel of approximately 173 cm³ internal volume. The available data including the present measurements are critically compared with the equation of state developed by Tillner-Roth et al., and it is found that, in the liquid region for the range of compositions from 0.1 to 0.4 mole fraction of HFC-32, this equation of state is less reliable because of the lack of experimental data. Paper presented at the Fifteenth Symposium on Thermophysical Properties, June 22–27, 2003, Boulder, Colorado, U.S.A.     

Molar Heat Capacity Cv, Vapor Pressure, and (p, ρ, T) Measurements from 92 to 350 K at Pressures to 35 MPa and a New Equation of State for Chlorotrifluoromethane (R13)

Measurements of the molar heat capacity at constant volume C _v for chlorotrifluoromethane (R13) were conducted using an adiabatic method. Temperatures ranged from 95 to 338 K, and pressures were as high as 35 MPa. Measurements of vapor pressure were made using a static technique from 250 to 302 K. Measurements of (p, , T) properties were conducted using an isochoric method; comprehensive measurements were conducted at 15 densities which varied from dilute vapor to highly compressed liquid, at temperatures from 92 to 350 K. The R13 samples were obtained from the same sample bottle whose mole fraction purity was measured at 0.9995. A test equation of state including ancillary equations was derived using the new vapor pressures and (p, , T) data in addition to similar published data. The equation of state is a modified Benedict–Webb–Rubin type with 32 adjustable coefficients. Acceptable agreement of C _v predictions with measurements was found. Published C _v(, T) data suitable for direct comparison with this study do not exist. The uncertainty of the C _v values is estimated to be less than 2.0% for vapor and 0.5% for liquid. The uncertainty of the vapor pressures is 1 kPa, and that of the density measurements is 0.1%.