Thermodynamic Properties of Air and Mixtures of Nitrogen, Argon, and Oxygen From 60 to 2000 K at Pressures to 2000 MPa

Abstract

A thermodynamic property formulation for standard dry air based upon available experimental $\mathrm{p–\rho –T,}$ heat capacity, speed of sound, and vapor–liquid equilibrium data is presented. This formulation is valid for liquid, vapor, and supercritical air at temperatures from the solidification point on the bubble-point curve (59.75 K) to 2000 K at pressures up to 2000 MPa. In the absence of reliable experimental data for air above 873 K and 70 MPa, air properties were predicted from nitrogen data in this region. These values were included in the determination of the formulation to extend the range of validity. Experimental shock tube measurements on air give an indication of the extrapolation behavior of the equation of state up to temperatures and pressures of 5000 K and 28 GPa. The available measurements of thermodynamic properties of air are summarized and analyzed. Separate ancillary equations for the calculation of dew and bubble-point pressures and densities of air are presented. In the range from the solidification point to 873 K at pressures to 70 MPa, the estimated uncertainty of density values calculated with the equation of state is 0.1%. The estimated uncertainty of calculated speed of sound values is 0.2% and that for calculated heat capacities is 1%. At temperatures above 873 K and 70 MPa, the estimated uncertainty of calculated density values is 0.5% increasing to 1.0% at 2000 K and 2000 MPa. In addition to the equation of state for standard air, a mixture model explicit in Helmholtz energy has been developed which is capable of calculating the thermodynamic properties of mixtures containing nitrogen, argon, and oxygen. This model is valid for temperatures from the solidification point on the bubble-point curve to 1000 K at pressures up to 100 MPa over all compositions. The Helmholtz energy of the mixture is the sum of the ideal gas contribution, the real gas contribution, and the contribution from mixing. The contribution from mixing is given by a single generalized equation which is applied to all mixtures used in this work. The independent variables are the reduced density and reduced temperature. The model may be used to calculate the thermodynamic properties of mixtures at various compositions including dew and bubble-point properties and critical points. It incorporates the most accurate published equation of state for each pure fluid. The mixture model may be used to calculate the properties of mixtures generally within the experimental accuracies of the available measured properties. The estimated uncertainty of calculated properties is 0.1% in density, 0.2% in the speed of sound, and 1% in heat capacities. Calculated dew and bubble-point pressures are generally accurate to within 1%.