1. 1 اندازه گيري تجربي حلاليت فوماريك اسيد در دي اكسيد كربن فوق بحراني و بررسي الگوهاي نظري پيش بيني حلاليت مهدي صحيحي استاد راهنما: دكتر سيد حسن قاضي عسكر استاد مشاور: دكتر حسين فرخ پور

2. 2 Historical  1869 - Discovering the Critical Point (Thomas Andrews )  1879 - Solving the inorganic salts in ethanole at high pressure ( Hannay & Hogarth )  1895 – Changing the color of Iodine in supercritical carbon dioxide (Willard )

3. 3 Supercritical Fluids  Supercritical fluids are substances above their critical temperatures and pressures, whose properties are intermediate between those of gases and liquids, and which can be controlled by both temperature and pressure.  Both Gas and liquid phases have the same densities in this range. SOLID GAS LIQUID SUPERCRITICAL FLUID Triple point Critical point Pressure (bar) 303 74 (31.1ºC) (-60ºC) 8 Temperature (K)

4. 4 SOLID GAS LIQUID SUPERCRITICAL FLUID Triple point Critical point Pressure (bar) Temperature (K) 303 74

5. 5 SOLID GAS LIQUID SUPERCRITICAL FLUID Triple point Critical point Pressure (bar) Temperature (K) 303 74

6. 6 SOLID GAS LIQUID SUPERCRITICAL FLUID Triple point Critical point Pressure (bar) Temperature (K) 303 74

7. 7 SOLID GAS LIQUID SUPERCRITICAL FLUID Triple point Critical point Pressure (bar) Temperature (K) 303 74

8. 8 Common Supercritical Fluids Carbon dioxide Tc = 31.1 °C Pc = 73.8 bar FluoroformTc = 25.9 °C Pc = 48.2 bar Water Tc = 374.0 °C Pc = 220.6 bar AmmoniaTc = 132.4 °C Pc= 113.2 bar EthaneTc = 32.2 °C Pc = 48.7 bar

9. 9 It’s critical point is in an easily reached range. At its normal Gaseous state Carbon Dioxide is an extremely bad solvent, but as a liquid it has much better solvent capabilities. Low toxicity, low reactivity & high purity at low cost. Why CO 2 ?

10. 10 Applications Extraction with supercritical fluid  Nicotine  Herbal medicine  Herbal essence  Caffeine  Herbal oil  Anti oxidants Supercritical fluid as a reaction enviroment  Synthesis of catalyst (RESS, GAC)  Making the small reactors with high performance

11. 11 The Effect of Different Factors on Solubility in SCF Pressure and Temperature

12. 12 Supercritical fluid  Polar : DimethylEther  Nonepolar : Ethane  CO 2 Sample matrices Vapor pressure Inter molecular forces

13. 13 Methods of Solubility Measurement Static Continuose

14. 14 Methods of Solubility Calculation Mass measurement Chromatography Spectrometry Methods of Sample Collection Solvent Solid phase Direct …

15. 15 Fumaric Acid Fumaric acid [(E) – 1,2 – butane dicarboxylic acid ]  Fumaric is used in plastic industry to produce its esters specially polyesters. Also the esters of this acid is used in pharmacological industry.

16. 16 The Physical Properties of Fumaric Acid Fumaric acidProperty 299-300 ◦ C 116.07 gr/mol 290 ◦ C 2.1 3.03 (in 25 ◦ C) 4.47 (in 25 ◦ C) < 0.001 Kpa (in 20 ◦ C) 1.64 gr/cm 3 (in 20 ◦ C) 4.9 gr/lit (in 20 ◦ C) melting point molecular weight boiling point pH for 0.1 M solution ( calculative ) pK a1 pK a2 vapor pressure density solubility in water

17. 17 Experimental Reagents MaterialPurityCompany Carbn dioxide> 99.5%Zam Zam Co.Ltd Ethanole> 99%Merck Chemical Co Fumaric acid> 99%Merck Chemical Co

18. 18 Apparatus and procedure :  The solubility measurements were carried out using a static apparatus. (1) imported two– position valve; (2) oven; (3) high pressure needle; (4) equilibrium cell; (5) sampling loop; (6) collection vessel; (7) 6 - port two – position switching valve

19. 19 For browsing the pressure we used the back-pressure regulator ( BPR, model BP 1580-81, Jasco ). The oven (model 6410 Plus, Jasco ) temperature was maintained within ± 0.1 ◦C The collected solutes were determined using UV-VIS spectrophotometric technique ( UV-VIS spectrophotometer model V-730, Jasco ). 750 mg of sample + glass crashed in the equilibrium cell The liquid carbon dioxide molecular filter The liquid carbon dioxide cooling coil reciprocating LC pump (model LC – 6A, Shimadzu Co. )

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23. 23 Washing Solvent Optimization

24. 24 Results and Discussion

25. 25 FT-IR Spectra of Samples Before After FT-IR

26. 26 Before After GC-MS

27. 27 Before After H-NMR

28. 28 The Amount of Sample

29. 29 The Accuracy of Results RSD 5.85±0.09 6.89±0.09 6.91±0.09 9.203%

30. 30 Solubility of Fumaric Acid in SC-CO 2

31. 31 Pressure Effect

32. 32 Temperature Effect on the Solubility of Fumaric acid in SC-CO 2

33. 33 Equation of State Dilute fluids:  Van dervals  Dieterci  Beattie-Brridgman  Redlich-Kwang  Peng-Robinson Peng-Robinson: P c,T c,ώ Z c, Density One parameter mixing rules Every property

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35. 35 Mixing Rules  Van dervals  Kwak-Mansoori  modified Kwak-Mansoori modified Kwak-Mansoori:

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37. 37 Solubility

38. 38 Fumaric acid:

39. 39 Chrastil Equation Clausius - Clapeyron

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42. 42 Conclusion  Solubilities of fumaric acid in binary system in supercritical carbon dioxide have been measured.  Mole fraction solubilities of fumaric acid in temperature of 50°C were 6.35×10-5 at pressure of 80 bar to 3.45×10-5 at pressure of 300 bar and in temperature of 80°C were 4.1×10-5 at pressure 60 bar to 0.83×10-5 at pressure 300 bar.  Disagreement of experimental and calculative data shows that the Peng– Robinson equation of state and Kwak–Mansoori mixing rules are not suitable for fumaric acid.  The solubilities are correlated with Chrastil equation and association number for fumaric acid was found as 1.226.

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