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400 350 300 250 200 150 100 d ls 3 ls -0.4 -0.2 0 s[kJKg C] 0.2 0.4 0.6 0.8 -1o -1 400 350 300 250 200 150 100 2468 -1o -1 s[kJKg C] Chapter 4 Figure 4.1 illustrates the thermodynamic features of interest in this case for siloxane D4 and water using the T –s state diagram. A typical analysis of thermodynamic cycles is presented here, whereby the cycle minimum and maximum temperature are fixed, and different working fluids are evaluated in terms of obtainable conversion efficiency and other technological aspects. Note that fixing the p p = 4.92 bar = 0.09 bar b≈ b’ a≈ a’ CR p =39.76bar max 5 3vs 2 pmin=1.01bar 64 max min max T Tmin CR T c’≈c d f g h T max 2 flash dvs e Tflash 3 h=h h=h e’ c s=s c T min 1 (a) Siloxane D4 (b) Water Figure 4.1: Comparison between the T–s thermodynamic diagram of D4 and that of water: the highlighted temperature levels, resulting from the studied application and thus common to both fluids, are Tmin = 100◦C, Tmax = 250◦C, and Tflash = 220◦C (dash-dotted black lines). CR: liquid– vapour critical point, solid-black line: saturation line enclosing the VLE region, solid-grey: isobaric lines, dashed-black: iso-enthalpy lines. Note that the scale of the specific entropy in diagram (a) is different from that in diagram (b). minimum and maximum cycle temperature results also in the specification of the minimum and maximum cycle (saturation) pressure for the considered fluid. The expansion ratio available for work extraction is thus also fixed. From these preliminary considerations, the comparison of the thermodynamic features of molec- ularly complex fluids with those of water along expansions yields interesting conclusions: I A consequence of the large complexity of the fluid molecular structure, thus of the high value of the specific heat capacity, is the so-called retrograde shape (positive slope) of the bubble line in the T –s diagram of the fluid, which helps visualizing how the expansion of the saturated vapor is inherently dry, see, e.g., Ref. [24]. This thermodynamic feature implies, contrary to what can be observed for a simple-molecule fluid like water, that for a complex organic fluid (a) Starting from saturated liquid conditions, see state c in fig. 4.1a, an isenthalpic pressure-reduction representative of a flashing process can result in the fluid being in a saturated–vapor state (process c → d, whereby qd = 1). If the pressure is further reduced, also superheated-vapour states are attainable. (b) The previous observation, applies also to an isentropic pressure-reduction process (c → e′). 92 o T [ C] o T [ C]PDF Image | New Concepts FOR Organic Rankine Cycle Power Systems
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