vb.net barcode freeware Tovics in Phase Eauilibria in Software

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CHAPTER 14 Tovics in Phase Eauilibria
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Figure 1416 T x y diagram at constant P for a binary system exhibiting VLLE
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Figure 1417 T x y diagram for several pressures
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is reached Then condensation occurs entirely at this temperature, producing the two liquid phases represented by points C and D If one starts at an intermediate point m, the process is a combination of the two just described After the dewpoint is reached, the vapor, tracing a path along line BE, is in equilibrium with a liquid tracing a path along line B D However, at temperature T* the vapor phase is at point E All remaining condensation therefore occurs at this temperature, producing the two liquids of points C and D Figure 1416 is drawn for a single constant pressure; equilibrium phase compositions, and hence the locations of the lines, change with pressure, but the general nature of the diagram is the same over a range of pressures For most systems the species become more soluble in one another as the temperature increases, as indicated by lines C G and DH of Fig 1416 If this diagram is drawn for successively higher pressures, the corresponding three-phase equilibrium temperatures increase, and lines C G and DH extend further and further until they meet at the liquidlliquid consolute point M, as shown by Fig 1417 As the pressure increases, line C D becomes shorter and shorter (indicated in Fig 1417 by lines CrDrand C1'D"),until at point M it diminishes to a differential length For still higher pressures (P4)the temperature is above the critical-solution temperature, and there is but a single liquid phase The diagram then represents two-phase VLE, and it has the form of Fig 109(d),exhibiting a minimum-boiling azeotrope For an intermediate range of pressures, the vapor phase in equilibrium with the two liquid phases has a composition that does not lie between the compositions of the two liquids This is illustrated in Fig 1417 by the curves for P3, which terminate at A N and B" The vapor in equilibrium with the two liquids at C" and Drr is at point F In addition the system exhibits an azeotrope, as indicated at point J Not all,\systemsbehave as described in the preceding paragraphs Sometimes the upper critical-solution temperature is never attained, because a vaporlliquid critical temperature is reached first In other cases the liquid solubilities decrease with an increase in temperature In this event a lower critical-solution temperature exists, unless solid phases appear first There are also systems which exhibit both upper and lower critical-solution temperatures16
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I 6 ~ oa comprehensive discussion of binary fluid-phase behavior, see J S Rowlinson and F L Swinton, Liquids r and Liquid Mixtures, 3d ed, Butterworth Scientific, London, 1982
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145 Vapor/Liquid/Liquid Equilibrium (VLLE)
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Figure 1418 is the phase diagram drawn at constant T corresponding to the constant-P diagram of Fig 1416 On it we identify the three-phase-equilibrium pressure as P*,the threephase-equilibrium vapor composition as y;, and the compositions of the two liquid phases that contribute to the vapor/liquid/liquid equilibrium state as x r and xf The phase boundaries separating the three liquid-phase regions are nearly vertical, because pressure has only a weak influence on liquid solubilities
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Figure 1418 Pxy diagram at constant T for two partially miscible liquids
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The compositions of the vapor and liquid phases in equilibrium for partially miscible systems are calculated in the same way as for miscible systems In the regions where a single liquid is in equilibrium with its vapor, the general nature of Fig 1418 is not different in any essential way from that of Fig 108(d) Since limited miscibility implies highly nonideal behavior, any general assumption of liquid-phase ideality is excluded Even a combination of Henry's law, valid for a species at infinite dilution, and Raoult's law, valid for a species as it approaches purity, is not very useful, because each approximates actual behavior for only a very small composition range Thus G E is large, and its composition dependence is often not adequately represented by simple equations Nevertheless, the NRTL and UNIQUAC equations and the UNIFAC method (App H) provide suitable correlations for activity coefficients
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