An equation of state is presented for the thermodynamic properties of propane that is valid for temperatures from the triple point temperature (85.525 K) to 650 K and for pressures up to 1000 MPa. The formulation can be used for the calculation of all thermodynamic properties, including density, heat capacity, speed of sound, energy, and saturation properties. Comparisons to available experimental data are given that establish the accuracy of calculated properties. The approximate uncertainties of properties calculated with the new equation are 0.01 % to 0.03 % in density below 350 K, 0.5 % in heat capacities, 0.03 % in the speed of sound between (260 and 420) K, and 0.02 % in vapor pressure above 180 K. Deviations in the critical region are higher for all properties except vapor pressure.
The pÀFÀT behavior of 2,3,3,3-tetrafluoroprop-1-ene (R1234yf) was measured from T = (232 to 400) K with pressures up to 10 MPa using a two-sinker densimeter. The measurements extend from low-density vapor to compressed-liquid states, and include the extended critical region. Vapor pressures from T = (250 to 366) K were also measured. The expanded (k = 2) uncertainty in density is (56 3 10 À6 3 F þ 0.0014 kg 3 m À3 ) at near-ambient conditions, increasing to (99 3 10 À6 3 F þ 0.0014 kg 3 m À3 ) at T = 400 K and p = 10 MPa. The maximum uncertainties in temperature and pressure are 0.004 K and (51 3 10 À6 3 p þ 2.0 kPa), respectively. The analysis for density accounts for the force transmission error in the magnetic suspension coupling of the densimeter and includes corrections for vertical density gradients in the measuring cell. These data, together with other data from the literature, have been used to develop an equation of state explicit in the Helmholtz energy covering the fluid region from T = (220 to 410) K with pressures up to 30 MPa. Comparisons to experimental data, including other literature data, are given to establish the accuracy of the equation of state.
Hydrofluorocarbons, currently used as refrigerants in air-conditioning systems, are potent greenhouse gases, and their contribution to climate change is projected to increase. Future use of the hydrofluorocarbons will be phased down and, thus replacement fluids must be found. Here we show that only a few pure fluids possess the combination of chemical, environmental, thermodynamic, and safety properties necessary for a refrigerant and that these fluids are at least slightly flammable. We search for replacements by applying screening criteria to a comprehensive chemical database. For the fluids passing the thermodynamic and environmental screens (critical temperature and global warming potential), we simulate performance in small air-conditioning systems, including optimization of the heat exchangers. We show that the efficiency-versus-capacity trade-off that exists in an ideal analysis disappears when a more realistic system is considered. The maximum efficiency occurs at a relatively high volumetric refrigeration capacity, but there are few fluids in this range.
Techniques to determine and compensate for the force transmission error (FTE), including the magnetic effects of the fluid being measured, in magnetic suspension densimeters are presented. For a two-sinker densimeter, the forces on the balance are expressed for each of the weighings comprising a density determination (i.e., the two sinkers plus balance calibration and tare weights). This yields a system of four equations, which are solved for the fluid density, a balance calibration factor, a coupling factor (related to the FTE), and a quantity related to the balance tare. For a single-sinker densimeter, an in situ weighing of the sinker in vacuum compensates for the FTE of the apparatus itself. A determination of the fluid-specific effect requires measurements with two different sinkers-analogous to the two-sinker analysis, but with the measurements spread out over time. The apparatus part of the FTE is generally less than ±20 ppm. Measurements on propane, helium, neon, nitrogen, argon, toluene, and air are analyzed for the fluid-specific effect; this effect is correlated with the magnetic susceptibility of the fluid together with an apparatus constant. With this analysis, the force transmission "error" becomes an effect that can be accounted for rather than a significant source of uncertainty in density measurements carried out with magnetic suspension densimeters.
The density of liquid toluene has been measured over the temperature range −60 °C to 200 °C with pressures up to 35 MPa. A two-sinker hydrostatic-balance densimeter utilizing a magnetic suspension coupling provided an absolute determination of the density with low uncertainties. These data are the basis of NIST Standard Reference Material® 211d for liquid density over the temperature range −50 °C to 150 °C and pressure range 0.1 MPa to 30 MPa. A thorough uncertainty analysis is presented; this includes effects resulting from the experimental density determination, possible degradation of the sample due to time and exposure to high temperatures, dissolved air, uncertainties in the empirical density model, and the sample-to-sample variations in the SRM vials. Also considered is the effect of uncertainty in the temperature and pressure measurements. This SRM is intended for the calibration of industrial densimeters.
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