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Nonclassical Gasdynamics of Vapour Mixtures 1.2 1.0 0.8 0.6 1.0 1.5 2.0 2.5 v/v c σ Γ<0 Γ>0 Gas phase Liquid phase Liquid-vapour critical point Two-phase region Figure 8.1: From [10]. Liquid-vapour saturation curve (—) and Γ < 0 region (shaded region) for a BZT fluid in the volume-pressure plane computed from van der Waals model under the assumption of a constant isochoric specific heat cv and for cv /R = 2000, with R gas constant. Selected isentropes (· · · ) and the critical isotherm T = Tc (− −) are also indicated. Note that the isentropes are concave down in the Γ < 0 region. The isentrope sσ is tangent to the Γ = 0 line in σ. Substances characterized by thermodynamic states featuring negative values of Γ in the dense vapour phase are called Bethe-Zel’dovich-Thompson (BZT) fluids. The region of negative Γ in the vapour phase is shown in figure 8.1 in the pressure–specific volume thermodynamic diagram of a paradigmatic BZT fluid described by the van der Waals fluid model, where the Γ = 0 line and the vapour saturation line delimit the negative-Γ region. The studies of Thompson sparked quite some interest in the following years, and many investigations expanded the theory covering several nonclassical phenomena and aspects, see, e.g., Refs. [12–20]. One of the latest developments is related to the investigation of nonclassical phenomena in the vapour-liquid critical point region of any common fluid, see Ref. [21]. Experimental evidence of nonclassical gasdynamics is available only for two-phase vapor- liquid, see Refs. [22–24], or solid-solid systems [25]. In the single-phase vapour region, only classical gasdynamics phenomena have been observed so far. Notably, in the former Soviet Union, Borisov made an attempt to experimentally prove the existence of a rarefaction shock wave (RSW), using a special shock tube [26]. The interpretation of the results of the experiments, arguably a RSW front developing in the tube, has later been confuted in the light of additional knowledge and simulation capability [9, 21, 27]. Theoretical studies [28–33], and new simulation capabilities [34–42], paved the way to a new experimental attempt in 2000 at the University of Boulder [27, 43, 44]. The failed experiment put into evidence one of the major obstacles, namely that the BZT thermodynamic region (the region comprising the states featuring negative-Γ, see figure 8.1) is very close to the thermal decomposition temperature of suitable organic fluids, which is in the range 350–400 oC. In addition, the repeatable rupture of the shock-tube diaphragm proved unattainable due to the relatively small pressure difference and the large acoustic impedance of the fluid [45–47]. Much attention has recently been devoted to the identification of BZT fluids, and to the com- 205 s > sσ Γ=0 T=T c P/P c s = sσ s < sσ Saturation curvePDF Image | New Concepts FOR Organic Rankine Cycle Power Systems
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