Subatmospheric Vapor Pressures for Fluoromethane (R41), 1,1-Difluoroethane (R152a), and 1,1,1-Trifluoroethane (R143a) Evaluated from Internal-Energy Measurements

Vapor pressures were evaluated from measured internal-energy changes U ⁽²⁾ in the vapor+liquid two-phase region. The method employed a thermodynamic relationship between the derivative quantity (U ⁽²⁾/V) _T , the vapor pressure p , and its temperature derivative (p/T). This method was applied at temperatures between the triple point and the normal boiling point of three substances: fluoromethane (R41), 1,1-difluoroethane (R152a), and 1,1,1-trifluoroethane (R143a). In the case of R41, vapor pressures up to 1 MPa were calculated to validate the technique at higher pressures. For R152a, the calculated vapor pressure at the triple-point temperature differed from a direct experimental measurement by less than the claimed uncertainty (5 Pa) of the measurement. The calculated vapor pressures for R41 helped to resolve discrepancies in several published vapor pressure sources. Agreement with experimentally measured vapor pressures for R152a and for R143a near the normal boiling point (101.325 kPa) was within the experimental uncertainty of approximately 0.04 kPa (0.04%) for the published measurements.     

The vapor pressure of 1,1,1,2-tetrafluoroethane (R134a) and chlorodifluoromethane (R22)

We measured the vapor pressure of chlorodifluoromethane (commonly known as R22) at temperatures between 217.1 and 248.5 K and of 1,1,1,2-tetrafluoroethane (commonly known as R134a) in the temperature range 214.4 to 264.7 K using a comparative ebulliometer. For 1,1,1,2-tetrafluoroethane at pressures between 220.8 and 1017.7kPa (corresponding to temperatures in the range 265.6 to 313.2K), additional measurements were made with a Burnett apparatus. We have combined our results for 1,1,1,2-tetrafluoroethane with those already published from this laboratory at higher pressures to obtain a smoothing equation for the vapor pressure from 215 K to the critical temperature. For chlorodifluoromethane our results have been combined with certain published results to provide an equation for the vapor pressure at temperatures from 217 K to the critical temperature.     

New Equation for Vapor Pressures of Difluoromethane (HFC-32)

Critically evaluated experimental vapor-pressure data sets supplemented with calculated data for low-temperature region were used in the development of vapor-pressure equations. The optimum number of terms, coefficients, and exponents of the Wagner-type equation were derived by means of the Setzmann–Wagner program OPTIM based on the combination of the stepwise regression analysis and evolutionary optimization method. Equations were checked by the reduced enthalpy of vaporization criterion derived from the Clausius–Clapeyron equation and specific volume of ideal gas. An equation developed using 261 experimental data points and low-temperature data calculated by Lüddecke and Magee gives an RMS deviation of 0.102%; a second equation based on the same experimental data and low-temperature data calculated by Tillner-Roth gives an RMS deviation of 0.101% from experimental points. The triple-point pressure extrapolated to the measured temperature T _tp = 136.34 K is discussed. Comparisons with vapor pressure equations by Outcalt and McLinden, Duarte-Garza and Magee. and Kubota et al. are also given.     

Isochoric Heat Capacity Measurements for Binary Refrigerant Mixtures Containing Difluoromethane (R32), Pentafluoroethane (R125), 1,1,1,2-Tetrafluoroethane (R134a), and Trifluoroethane (R143a) from 200 to 345 K at Pressures to 35 MPa

Molar heat capacities at constant volume C _v were measured for binary refrigerant mixtures with an adiabatic calorimeter with gravimetric determinations of the amount of substance. Temperatures ranged from 200 to 345 K, while pressures extended up to 35 MPa. Measurements were conducted on liquid samples with equimolar compositions for the following binary systems: R32/R134a, R32/R125, R125/R134a, and R125/R143a. The uncertainty is 0.002 K for the temperature rise and is 0.2% for the change-of-volume work, which is the principal source of uncertainty. The expanded relative uncertainty (with a coverage factor k=2 and thus a two-standard deviation estimate) for C _v is estimated to be 0.7%.     

A nonlinear regression analysis for estimating low-temperature vapor pressures and enthalpies of vaporization applied to refrigerants

A new method is presented to extrapolate experimental vapor pressures down to the triple Point. The method involves a nonlinear regression analysis based on the Clausius Clapeyron equation and a simple relation for the enthalpy of vaporization Triple-point pressures and vapor pressures up to 0.1 0.2 MPa are estimated for R125, R32, R143a, R134a, R152a, R123, R124, and ammonia; they generally agree with available experimental data within their uncertainty, Equations for the enthalpy of vaporization which describe this property fairly well at low temperatures are obtained as a byproduct.     

Molar heat capacity at constant volume of difluoromethane (R32) and pentafluoroethane (R125) from the triple-point temperature to 345 K at pressures to 35 MPa

Molar heat capacities at constant volume (C _v) of dill uoromethane (R32) and pentalluoroethane (R125) were measured with an adiabatic calorimeter. Temperatures ranged from their triple points to 345 K, and pressures up to 35 MPa. Measurements were conducted on the liquid in equilibrium with its vapor and on compressed liquid samples. The samples were of a high purity, verified by chemical analysis of each fluid. For the samples, calorimetric results were obtained for two-phase (C _v ⁽²⁾ ), saturated liquid (C orC _x ), and singlephase (C _v) molar heat capacities. TheC data were used to estimate vapor pressures for values less than 0.3 MPa by applying a thermodynamic relationship between the saturated liquid heat capacity and the temperature derivatives of the vapor pressure. The triple-point temperature (T _tr) and the enthalpy of fusion (_fus H) were also measured for each substance. The principal sources of uncertainty are the temperature rise measurement and the change-ofvolume work adjustment. The expanded uncertainty (at the two-sigma level) forC _v is estimated to be 0.7%, forC _v ⁽²⁾ it is 0.5%, and forC it is 0.7%.     

Thermodynamic properties and vapor pressures of polar fluids from a four-parameter corresponding-states method

A recently proposed extended Lee-Kesler corresponding-states method (ELK) for polar fluids which accurately predicts compressibility factors and departure functions is considered. Tables of polar deviation functions have been generated and values of the shape/size and polar parameters for 52 polar fluids have been calculated, allowing the method to be used for quick hand calculations in addition to the previous, more accurate, computer applications. Additionally, vapor pressures of 44 pure polar fluids were computed using the full version of the ELK and the equality of the Gibbs free energy criterion for phase equilibrium. An ELK vapor pressure correlation is proposed which is essentially numerically equivalent to, but computationally simpler than, the former method. Computed vapor pressures agree with experimental values as well or better than other vapor pressure equations designed exclusively for vapor pressure prediction of polar fluids.     

PVT Measurements on tetrafluoroethane (R134a) along the vapor-liquid equilibrium boundary between 288 and 373 K and in the liquid state from the triple point to 265 K

For the investigations of the gas-liquid phase equilibria, a new apparatus has been developed capable of simultaneously determining the pressure and the liquid and vapor densities using Archimedes' principle. The relative measurement uncertainties of the liquid and vapor densities of R134a (purity, 99.999%) at 313 K are 2×10^–4 and 7×10^–4, respectively (95% confidence level). For the measurements in the liquid region along nine quasi-isochores at pressures up to 5 MPa, an isochoric apparatus was used. The relative measurement uncertainty ofpv/(RT) is less than 1×10^–3. In addition to the investigation of the (p, v, T) properties, the temperature and pressure at the triple point and the vapor pressure between the triple point and 265 K were measured. On the basis of these data, a vapor pressure correlation has been developed that reproduces the measured vapor pressures within the uncertainty of measurement. The results of our measurements are compared with a fundamental equation for R134a, which is based on the measurements of other research groups.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

Thermal conductivity andPVT measurements of pentafluoroethane (refrigerant HFC-125)

By means of the transient and steady-state coaxial cylinder methods, the thermal conductivity of pentafluoroethane was investigated at temperatures from 187 to 419 K and pressures from atmospheric to 6.0 MPa. The estimated uncertainty of the measured results is ±(2–3)%. The operation of the experimental apparatus was validated by measuring the thermal conductivity of R22 and R12. Determinations of the vapor pressure andPVT properties were carried out by a constant-volume apparatus for the temperature range 263 to 443 K, pressures up to 6 MPa, and densities from 36 to 516 kg m^–3. The uncertainties in temperature, pressure, and density are less than ±10 mK, ±0.08%, and ±0.1%, respectively.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

Molar Heat Capacity at Constant Volume of Trifluoromethane (R23) from the Triple-Point Temperature to 342 K at Pressures to 33 MPa

Molar heat capacities at constant volume (C _v) of trifluoromethane (R23) have been measured with an adiabatic calorimeter. Temperatures ranged from the triple point to 342 K, and pressures up to 33.5 MPa. Measurements were conducted on the liquid in equilibrium with its vapor and on compressed liquid and gaseous samples. The samples were of high purity, as verified by chemical analysis. Calorimetric quantities are reported for the two-phase (C ⁽²⁾ _v), saturated-liquid (C or C_x), and single-phase (C _v) molar heat capacities. The C ⁽²⁾ _v data were used to estimate vapor pressures for values less than 100 kPa by applying a thermodynamic relationship between the two-phase internal energy U ⁽²⁾ and the temperature derivatives of the vapor pressure. The triple-point temperature and the enthalpy of fusion were also measured. The principal sources of uncertainty are the temperature rise measurement and the change-of-volume work adjustment. The expanded relative uncertainty (with a coverage factor k=2 and thus a two-standard deviation estimate) is estimated to be 0.7% for C _v, 0.5% for C ⁽²⁾ _v, and 0.7% for C .     

p,V, T and derived thermodynamic data for bromobenzene at temperatures from 278 to 323 K and pressures up to 280 MPa

Experimentally determined p, V, T data are reported for bromobenzene at 278, 288, 298, 313, and 323 K, at pressures up to about 280 MPa or (at 278 and 288 K) a lower pressure slightly below the freezing pressure at the temperature of measurement. Values of the isobaric expansivity, isothermal compressibility, internal pressure, and equivalent hard-sphere diameter, derived from the p, V, T data, are presented.On leave from the Department of Chemistry, The University of Auckland, Auckland, New Zealand.     

Molar Heat Capacity at Constant Volume of 1,1-Difluoroethane (R152a) and 1,1,1-Trifluoroethane (R143a) from the Triple-Point Temperature to 345 K at Pressures to 35 MPa

Molar heat capacities at constant volume (C _v) of 1,1-difluoroethane (R152a) and 1,1,1-trifluoroethane (R143a) have been measured with an adiabatic calorimeter. Temperatures ranged from their triple points to 345 K, and pressures up to 35 MPa. Measurements were conducted on the liquid in equilibrium with its vapor and on compressed liquid samples. The samples were of high purity, verified by chemical analysis of each fluid. For the samples, calorimetric results were obtained for two-phase ((C _v ⁽²⁾ ), saturated-liquid (C or C _x ^' ), and single-phase (C _v) molar heat capacities. The C data were used to estimate vapor pressures for values less than 105 kPa by applying a thermodynamic relationship between the saturated liquid heat capacity and the temperature derivatives of the vapor pressure. The triple-point temperature and the enthalpy of fusion were also measured for each substance. The principal sources of uncertainty are the temperature rise measurement and the change-of-volume work adjustment. The expanded relative uncertainty (with a coverage factor k=2 and thus a two-standard deviation estimate) for C _v is estimated to be 0.7%, for C _v ⁽²⁾ it is 0.5%, and for C it is 0.7%.