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Chapter 8 putation of the negative-Γ region, see Ref. [48] for a review. More recently Colonna and colleagues started a new project aimed at the generation and measurement of a rarefaction shock wave in a newly conceived Ludwieg-tube-type setup [47]. A siloxane fluid, D6 (dodecamethylcyclohexas- iloxane C12 H36 O6 Si6 ), has initially been selected as the working fluid. Siloxanes are especially suited for the RSW experiment because of available knowledge on their thermal stability [49], thermodynamic properties [51–54]), and their use as working fluids in thermal energy conversion systems, see, e.g., Refs. [55–57]. Few of the compounds of the siloxane family are candidate BZT fluids [58]. The design of the rarefaction shock wave experiment drove studies aimed at better identifying the thermodynamic region within which nonclassical phenomena are admissible [59], and the max- imum pressure difference and shock wave Mach number that can be expected [10]. Given that the experimental conditions are difficult to realize and that the rarefaction shock wave is expected to be weak, therefore more challenging to measure, uncertainty quantification applied to flow simulations has been preliminarily used as an aid in determining the optimal experimental conditions [60]. The present chapter is motivated by several observations about mixtures of organic fluids. Differently from mixtures of ideal gases, thermodynamic properties of dense vapours of multi- component mixtures do not scale linearly with the mole fractions of each compound, as molecular interaction among different molecules plays a major role. Typical hallmarks of non-ideal behaviour of fluids mixtures are the critical temperature, pressure and specific volume of a binary mixture, which usually differ from that of each of the constituents. The same holds for the melting point and for most thermodynamic properties. The fundamental derivative of gasdynamics Γ, being a derived thermodynamic property, is also affected by non-ideal mixing effects, as preliminarily discussed in Ref. [61]. In addition, experiments on the thermal stability of siloxane mixtures [49], and a deeper understanding on the chemistry of thermal decomposition of poly-dymethyl siloxanes [62], show that, at temperatures close to the so-called temperature stability limit, a pure siloxane un- dergoes a transformation called rearrangement, whereby small quantities of other compounds of the same family are formed. Such mixture composition remains then constant at that temperature over time. The composition of the mixture is therefore a new relevant variable in the study of BZT fluids, and, importantly, mixtures of organic fluids are also considered for applications in organic Rankine cycle (ORC) power systems [55, 63–65], one of the possible applications of nonclassical gasdynamics [39]. In the present preliminary study on mixtures as BZT fluids, siloxanes and perfluorocarbons have been considered as constituents. Suitable thermodynamic models for multi-component fluids are briefly discussed in §8.2. Their limitation in terms of accuracy of the predicted Γ values is also addressed. These models are used to estimate the boundaries of the thermodynamic region of admissibility of rarefaction shock waves, and the influence of the mixture composition. In §8.3, exemplary simulation of a supersonic flow expanding over a wedge, whereby the composition of the mixture is varied, are presented to assess the influence of the molecular composition on the gasdynamics behaviour. Concluding remarks and an outlook on future research are given in §8.4. 8.2 Admissibility Region for Rarefaction Shock Waves in Dense gas Mixtures Modelling non-ideal thermodynamic properties of fluid mixtures—including the determination of the fundamental derivative of gasdynamics Γ—requires to correctly account for the interaction be- tween different molecules, an added degree of difficulty with respect to pure-fluid thermodynamics. 206PDF Image | New Concepts FOR Organic Rankine Cycle Power Systems
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