SUPERCRITICAL PSEUDO BOILING IN CUBIC EQUATIONS OF STATE

Today, modern combustion systems and advanced cycles often reach operating pressures exceeding the working fluid's or fuel's critical pressure. While the liquid-gas coexistence line is the dominant feature in the fluid state space at low pressures, a supercritical analog to boiling, pseudo boiling, exists at supercritical pressures. Pseudo boiling is the transcritical state transition between supercritical liquid states and supercritical gaseous states, associated with peaks in heat capacity and thermal expansion. This transition occurs across a finite temperature interval. So far, the relation between the pseudo boiling line of tabulated hi-fi p-v-T data and the behavior of efficient engineering cubic equations of state (EOS) is unclear. In the present paper, we calculate the slope of the pseudo boiling line analytically from cubic equations of state. The Redlich-Kwong EOS leads to a constant value for all species, Peng-Robinson and Soave-Redlich-Kwong EOS yield a cubic dependency of the slope on the acentric factor. For more than twenty compounds with acentric factors ranging from -0.38 to 0.57 calculated slopes are compared with NIST data and vapor pressure correlations. Particularly the Peng-Robinson EOS matches reference data very well. Classical empirical values of Guggenheim or Plank & Riedel are obtained analytically. Then, pseudo boiling predictions of the Peng Robinson EOS are compared to NIST data. Deviations in transition temperature interval, and nondimensional parameters of the distributed latent heat are compared. Especially the different caloric behavior of tabulated fluid data for H-2, N-2, CO2, and H2O cannot be reproduced by the Peng Robinson EOS. These results may open the way towards new EOS with specific emphasis on Widom line and supercritical transition behavior.