1. NCHU-SF : Ch. 2-11 SUPERCRITICAL FLUIDS FOR SEPARATION

2. NCHU-SF : Ch. 2-12 What for do we need phase equilibrium? Design of solvent cycle (process) Objectives

3. NCHU-SF : Ch. 2-13 Solubility of the compounds Change of solubility with process conditions Capacity of the solvent Solubility of solvent in condensed phase Distribution of compounds between the phases (separation factor, selectivity) Two-phase area What do we need to know about phase equilibrium? Objectives

4. NCHU-SF : Ch. 2-14 For what type of systems (chemical compounds) do we need phase equilibrium? CO 2, C 3 H 8, H 2 O,....(gases) Paraffins, glycerides, vitamins,... Terpenes, sesquiterpenes, mono-, di-, tri-.... Objectives

5. NCHU-SF : Ch. 2-15 Extraction with Supercritical Fluids The need for phase equilibria: Solubility, K-factor, Separation factor, Two-phase region Flow scheme of gas extraction (SFE)

6. NCHU-SF : Ch. 2-16 Kennedy 1950 Solubility of quartz in water

7. NCHU-SF : Ch. 2-17 Poynting-effect Vapor pressure enhancement E.U. Franck 1956 ____ 25 o C, ------ 500 o C P 02 /P 01 VLVL

8. NCHU-SF : Ch. 2-18 Poynting-Factor System: Ethanol - Water, 343 K EthanolWater kPa 10 1.0022 1.0006 1000 1.022 1.0065 10000 1.24251.0667

9. NCHU-SF : Ch. 2-19 Density CO 2 (calc. Bender EOS)

10. NCHU-SF : Ch. 2-20 Vapour Pressure vs. Temperature

11. NCHU-SF : Ch. 2-21 Density of supoercritical Fluid responsible for solvent power (increasing with pressure, decreasing with temperature) Hydrostatic pressure enhances effective vapour pressure (Poynting effect, small) Temperature increases vapour pressure (exponentially, big effect) Influences on Solute Concentration in Gaseous Phase

12. NCHU-SF : Ch. 2-22 Solubility of Caffeine in CO 2 Gährs 1984 Ebeling, Franck 1984 Johannsen, Brunner 1994

13. NCHU-SF : Ch. 2-23 Tsekhanskaja 1964 Solubility [g/l] Solubility of Naphthalene in Ethylene

14. NCHU-SF : Ch. 2-24 Brunner 1978 Oleic acid - ethylene

15. NCHU-SF : Ch. 2-25 Solubility of oleic acid in various gases Brunner 1978

16. NCHU-SF : Ch. 2-26 Solubility of Triglycerides in sc Gases Triglycerides of palm oil Brunner 1978

17. NCHU-SF : Ch. 2-27 Solubility in sc CO 2

18. NCHU-SF : Ch. 2-28 Solubility of Xanthines in dry sc CO 2 Johannsen and Brunner 1994

19. NCHU-SF : Ch. 2-29 P,T,x-diagram of a binary system

20. NCHU-SF : Ch. 2-30 P,x-diagram ethane - heptane Kay 1938

21. NCHU-SF : Ch. 2-31 Kay 1938 T,x-diagram ethane - heptane

22. NCHU-SF : Ch. 2-32 Melting point temperature of B higher than critical temperature of A Phase equilibria of a binary system

23. NCHU-SF : Ch. 2-33 Phase equilibrium in a binary system Melting point temperature of B higher than critical temperature of A; Interrupted critical curve.

24. NCHU-SF : Ch. 2-34 P,T- projections of phase boundary lines

25. NCHU-SF : Ch. 2-35 Phase behaviour of a ternary system Temperature dependence Pressure dependence

26. NCHU-SF : Ch. 2-36 CO 2 - benzene - oleic acid

27. NCHU-SF : Ch. 2-37 Ethylene - DMF - C18 fatty acids

28. NCHU-SF : Ch. 2-38 Solubility Enhancement by a Modifier

29. NCHU-SF : Ch. 2-39 Schmitt 1984 Solubility Enhancement by Entrainer (Modifier)

30. NCHU-SF : Ch. 2-40 Gährs 1984 Solubility of Caffeine in CO 2 Influence of nitrogen

31. NCHU-SF : Ch. 2-41 Influence of propane Prausnitz, Joshi 1984 Solubility of Phenanthrene in CO 2

32. NCHU-SF : Ch. 2-42 Phase Equilibrium in a Ternary System Brunner 1983

33. NCHU-SF : Ch. 2-43 Brunner 1983 Solubility in a gas with a modifier Influence of temperature

34. NCHU-SF : Ch. 2-44 Brunner 1983 Separation Factor Influence of entrainer

35. NCHU-SF : Ch. 2-45 Influence of concentration Brunner 1983 Separation Factor

36. NCHU-SF : Ch. 2-46 Three Phase Equilibrium

37. NCHU-SF : Ch. 2-47 P,T-diagrams of Complex Mixtures

38. NCHU-SF : Ch. 2-48 Measuring Phase Equilibrium

39. NCHU-SF : Ch. 2-49 Measuring Phase Equilibrium

40. NCHU-SF : Ch. 2-50 Modeling of Phase Equilibrium with EOS HPW modification of RK-EOS

41. NCHU-SF : Ch. 2-51 Gas-Liquid Phase Equilibrium Two different ways: A = standard fugacity  i = activity coefficient: g E -models) B = fugacity coefficient: Equations of state Thermodynamic Equilibrium

42. NCHU-SF : Ch. 2-52 VLE-Calculation: With the simplification: since :  Calculation of Phase Equilibrium

43. NCHU-SF : Ch. 2-53 Low pressure High pressure Phase Equilibrium: Non Ideal Solutions

44. NCHU-SF : Ch. 2-54 P = 101 kPa Methanol - water Chloroform - acetone    = 1 Concentration dependence of separation factor

45. NCHU-SF : Ch. 2-55 Concentration dependence of separation factor

46. NCHU-SF : Ch. 2-56 T = const. VLE T = const. VLE x sf = const. x sf = solvent free concentrations in liquid phase Limiting values of the partition coefficient K Phase Equilibrium

47. NCHU-SF : Ch. 2-57 Limiting values of separation factor  Binary system i-j in a multicomponent systemAt low pressure Binär: Phase Equilibrium

48. NCHU-SF : Ch. 2-58 Murphy´s Law of Thermodynamics THINGS GET WORSE UNDER PRESSURE