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1.1 1.1 1.05 1.05 Nonclassical Gasdynamics of Vapour Mixtures s=s A s=s A AA 11 0.95 0.95 0.9 0.9 0.85 0.85 B 0.8 0.8 0.75 0.75 0.7 0.7 0.65 0.65 A’ P ̃ P ̃ DSL DSL B Saturation curve Saturation curve 0.5 1 1.5 2 2.5 v ̃ (a) MD6M Figure 8.5: Pre- (A) and post-expansion (B) states on the reduced P-v plane. The negative-Γ region (dashed line) and DSL are also reported. of Γ along the dew line, Γmin, decreases monotonically with increasing molecular weight and com- plexity (figure 8.4a). In addition, the extension of the BZT region in the P-T plane increases with increasing molecular weight and complexity, cf. figure 8.3a. It is remarkable that the effect of mixing, therefore of intermolecular interaction, alters the non monotone dependency of Γmin from molecular weight and complexity. Figure 8.4b shows that for binary mixtures of the siloxane fluids MDM/MD6M and MD5M/MD6M the estimated value of Γmin does not decrease monotonically with increasing average molecular complexity and weight of the mixture, similarly to what observed for the values of the critical pressure, temperature and density in table 8.1. Indeed, for both the MDM/MD6M and the MD5M/MD6M mixtures, the value of Γmin exhibits a maximum, which is at xMDM ≈ 0.75 for MDM/MD6M, and at xMD5M ≈ 0.9 for MD5M/MD6M. Notably, for the mixture MDM(0.4)/MD6M(0.6) the value of Γmin is largely different, even in sign, from the one predicted for MD4M, which is the homologous pure fluid in terms of molecular weight and complexity. This type of dependency of Γmin on molar composition is predicted also in case of mixtures of alkanes, by using reference equations of state for the calculation of thermodynamic properties. In the case presented here, the variation of Γmin with the mole fraction of a binary mixture is such that, for any given composition, Γmin is always larger than the molar-fraction averaged value of Γmin of the two pure constituents. Due to the large variety of intermolecular forces, it cannot currently be ruled out that an opposite trend can be observed for different combinations of pure fluids, namely that the mixing of two or more fluids not considered here leads to values of Γmin that are lower than those of the mixture constituents. From the knowledge of the fundamental derivative of gasdynamics in the vapour phase, the thermodynamic conditions resulting in nonclassical gasdynamics waves can be determined. The conditions for the admissibility of rarefaction shocks are given by the work of Zamfirescu and 0.5 1 1.5 2 2.5 v ̃ (b) MDM(0.05)/MD6M(0.95) 211PDF Image | New Concepts FOR Organic Rankine Cycle Power Systems
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