اندازه گيری تجربی حلاليت فوماریک اسيد در دی اكسيد كربن فوق بحرانی و بررسی الگوهای نظری پيش بينی حلاليت

اندازه گيري تجربي حالليت فوماريك اسيد در دي اكسيد كربن فوق بحراني و بررسي الگوهاي نظري پيش بيني حالليت مهدي صحيحي استاد راهنما :دكتر سيد حسن قاضي عسكر استاد مشاور :دكتر حسين فرخ پور 1 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 2 carbon dioxide (Willard ) 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 Pressure (bar) Critical point 74 LIQUID Triple point 8 3 • SUPERCRITICAL FLUID • GAS 303 (31.1ºC) (-60ºC) Temperature (K) Pressure (bar) SOLID SUPERCRITICAL FLUID Critical point 74 LIQUID Triple point • GAS Temperature (K) 4 • 303 Pressure (bar) SOLID SUPERCRITICAL FLUID Critical point 74 LIQUID Triple point • GAS Temperature (K) 5 • 303 Pressure (bar) SOLID SUPERCRITICAL FLUID Critical point 74 LIQUID Triple point • GAS Temperature (K) 6 • 303 Pressure (bar) SOLID SUPERCRITICAL FLUID Critical point 74 LIQUID Triple point • GAS Temperature (K) 7 • 303 Common Supercritical Fluids Carbon dioxide Tc = 31.1 °C Fluoroform Water Ammonia Ethane 8 Tc = 25.9 °C Pc = 73.8 bar Pc = 48.2 bar Tc = 374.0 °C Pc = 220.6 bar Tc = 132.4 °C Pc= 113.2 bar Tc = 32.2 °C Pc = 48.7 bar Why CO2 ? • 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. 9 Applications Extraction with supercritical fluid Nicotine Caffeine Herbal medicine Herbal oil Herbal essence Anti oxidants Supercritical fluid as a reaction enviroment Synthesis of catalyst (RESS , GAC) Making the small reactors with high performance 10 The Effect of Different Factors on Solubility in SCF Pressure and Temperature 11 Supercritical fluid Polar : DimethylEther Nonepolar : Ethane CO 2 Sample matrices Vapor pressure Inter molecular forces 12 Methods of Solubility Measurement Static Continuose 13 Methods of Solubility Calculation Mass measurement Chromatography Spectrometry Methods of Sample Collection Solvent Solid phase Direct … 14 Fumaric Acid O OH HO O 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. 15 The Physical Properties of Fumaric Acid 16 Fumaric acid Property C◦ 299-300 melting point gr/mol 116.07 molecular weight C◦ 290 boiling point 2.1 pH for 0.1 M solution ) calculative ( )in 25 ◦C( 3.03 pKa1 )in 25 ◦C( 4.47 pKa2 Kpa (in 20◦C) 0.001 < vapor pressure gr/cm3 (in 20 ◦C) 1.64 density gr/lit (in 20 ◦C) 4.9 solubility in water Experimental Reagents 17 Material Purity Company Carbn dioxide 99.5% > Zam Zam Co.Ltd Ethanole 99% > Merck Chemical Co Fumaric acid 99% > Merck Chemical Co 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 18  750 mg of sample + glass crashed cell  The liquid carbon dioxide in the equilibrium molecular filter  The liquid carbon dioxide cooling coil reciprocating LC pump (model LC – 6A , Shimadzu Co. )  For browsing the pressure we used the back-pressure regulator ( BPR , model BP 1580-81 , Jasco ).   19 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 ). 20 21 22 Washing Solvent Optimization 23 Results and Discussion 30 Solubility (103X) 25 20 15 10 5 0 70 100 130 160 190 220 250 280 Pressure (bar) Fre n ch , 45C Ya mi n i , 35C Hig a sh i , 35C 24 Th i s wo rk, 45C Th i s wo rk, 35C Di e fe n d a ch e r, 35C Hig a sh i , 45C Fre n ch , 35C FT-IR Spectra of Samples Before FT-IR After 25 Before GC-MS After 26 Before H-NMR After 27 The Amount of Sample So l u b i l i t y (y*10^ 3) 2.5 2 1.5 1 0.5 0 0 20 40 60 80 Aci d t o g l ass rat i o (%) 28 100 120 The Accuracy of Results 3 RSD y10 5.85±0. 09 6.89±0. 09 6.91±0.0 9 29 9.203% Solubility of Fumaric Acid in SC-CO2 30 Pressure Effect Sol ubi l i t y (y*10^3) 16 14 50دXراX سانتيگXدرجه 12 80دXراX سانتيگXدرجه 10 8 6 4 2 0 0 31 100 200 Pre ssu re (b a r) 300 400 Temperature Effect on the Solubility of Fumaric acid in SC-CO2 32 Equation of State Dilute fluids: Van dervals Dieterci Redlich-Kwang Beattie-Brridgman Peng-Robinson Peng-Robinson: Pc,Tc,ώ Zc, Density One parameter mixing rules 33 Every property am RT P  V  bm V (V  bm)  bm(V  bm) a ac (Tr , ) 2 2 R Tc ac 0.4572 ( ) Pc  0.5   (Tr , )  1 F(1 Tr ) 34 2 RTc b 0.0778 ( ) Pc F 0.37464 1.54226   0.26992  2 Mixing Rules Van dervals Kwak-Mansoori modified Kwak-Mansoori modified Kwak-Mansoori: P bm   xi xj bij am   xi xj aij i i j aij  ai a j 1 kij  ai ac 1 Fi  35 a  RTdm  2 amdmRT RT  m V  bm V (V  bm)  bm(V  bm) 2 b i bij    1 3 j  bj 2 dm   xi xj dij i 1 3 3   1 l  ij    R2Tc 2    ac 0.4572  P  c   j 3  d 13  d 13  i j   dij  1 mij   2     2 acFi di  RTci Fi 0.37464 1.54226  i  0.26992 i 2 36 Solubility   V2sol  s  P2 exp   P  P2  RT    y P 2  s f2 sol  f2 gas ln i    2B  b  Z  1  ln Z  B  i m bm   P   RT  dV  RTlnZ  RTln  i      V  n  V    i  T ,V ,nj   A 2 2B   2 RT amDi  dm Ai  2 A  2 RT D  i  i amdm  2Bi  bm    Z  B 1 2   ln       Z  B 1 2  C bm       A CP R2T 2 Ai  xj aij 37 j bmP B RT   C am  dmRT  2 amdmRT Bi  x j bij j Di  xj dij j Fumaric acid: 38 Chrastil Equation A  B  C  AB C [ AB C ] K [ A][B] [C]  Gsolvation  Hsolvation LnK   qs   qs RT RT Clausius - Clapeyron Ln[ A]   Hvaporization RT  Htot  q   ln[ B]   ln[ C] ln[ AB C ] RT 39  qv  Htot  q  ( ln    ln MB   ln MC )   ln m RT ln S  ln( MATMB  MC )  Htot LnS   q   ln    ln MB   ln    ln MC RT   ln m ln( MA  MB  MC ) a ( b)  T S   m e b q   ln MB   ln    ln MC  ln( MA  MB  MC ) 40 a Htot R 41 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. 42 43