1. 1/30/2015 1 Recrystallization / Filtration Purification and Isolation of an Impure Compound by Recrystallization and Vacuum Filtration Vacuum Filtration  References: ●Slayden, et. al.,– pp. 31 – 34 ●Pavia Tech 11– pp. 662 - 680 ●Pavia Tech 6.2-6.3– pp. 598 - 608 ●Pavia Tech 8– pp. 630 - 642 (Filtration) ●Web Site: http//:mason.gmu.edu/~jschorni/

2. 1/30/2015 2 Recrystallization / Filtration Background   Recrystallization Solid organic compounds produced in the laboratory usually need to be purified The most common technique involves Recrystallizing the sample from an appropriate Solvent The Recrystallization process is a relatively slow and selective formation of crystals from a solvent Precipitation is a rapid and nonselective process; thus not used to purify samples

3. 1/30/2015 3 Recrystallization / Filtration Recrystallization (Con’t)   The Recrystallization Process Dissolve sample in a minimal amount of an appropriate solvent Sample should be insoluble in solvent at room temperature, but soluble at elevated (near boiling point) temperature If solution is colorized, it is sometimes necessary to add a decolorizing agent, such as activated charcoal (Norite) Colorized solutions are first filtered through a fluted filter or a column containing alumina or silica gel Note: Unless otherwise instructed, decolorization will not be done in this experiment 5/24/2015

4. 1/30/2015 4 Recrystallization / Filtration Recrystallization (Con’t)   The Recrystallization Process (Con’t) The hot solution is cooled slowly to allow the purified crystals to form; leaving the more soluble impurities in solution After solution and purified crystals have returned to room temperature, place the beaker in water/ice bath Collect crystals by Vacuum Filtration Rinse the crystals with small portions of cold solvent Air-Dry the crystals for a week on a pre-weighed watchglass or weighing tray in your drawer or the instructor’s drawer Determine the Melting Point Range of the purified sample

5. 1/30/2015 5 Recrystallization / Filtration Recrystallization (Con’t)   The Appropriate Solvent The solute particles are generally insoluble in cold solvent, but soluble in hot solvent The solvent (or mixed solvent) should have a steep solubility vs temperature curve for the solute The “C” curve is a good solvent  Solute is sparingly soluble at room temperature  Solute is very soluble at elevated temperature A B C Temperature Solubility

6. 1/30/2015 6 Recrystallization / Filtration Recrystallization (Con’t)   The Appropriate Solvent (Con’t) Solubility of organic compounds is a function of the polarities of both the solvent and the solute:   “Like Dissolves Like”   Polar solvents dissolve polar solutes   Nonpolar solvents dissolve nonpolar solutes The stability of the solute crystal lattice affects the solubility. The higher the melting point (higher stability), the less soluble the solute

7. 1/30/2015 7 Recrystallization / Filtration Recrystallization (Con’t)   The Appropriate Solvent (Con’t) The Boiling Point of the solvent must be less than the Melting Point of the solute   If the Boiling Point of the solvent is higher than the melting point of the solute, the solute will “Melt” instead of “Dissolving” in the solvent at the elevated temperature   Upon cooling, the “Melted” solute will “Oil” out forming an insoluble mass that is not purified The solvent should not react with the solute Compounds with functional groups that can form hydrogen bonds (-OH, -NH-, -COOH, -CONH-) will be more soluble in hydroxylic (polar) solvents such as Methanol and Water

8. 1/30/2015 8 Recrystallization / Filtration Solvents in Decreasing Order of Polarity   H 2 O- Water   RCOOH- Organic Acids (Acetic Acid)   RCONH 2 - Amides (N,M-dimethylformamide)   ROH- Alcohols (Methanol, Ethanol)   RNH 2 - Amines (Triethylamine, Pyridine)   RCOR- Aldehydes, Ketones (Acetone)   RCOOR- Esters (Ethyl Acetate)   RX- Halides (CH 2 Cl 2 > CHCl 3 > CCl 4 )   ROR- Ethers (Diethylether)   ArH- Aromatics (Benzene, Toluene)   RH- Alkanes (Hexane, Petroleum Ether)

9. 1/30/2015 9 Recrystallization / Filtration Filtration   Two Purposes Separate purified solid from the soluble impurities in the solution from which it was recrystallized Remove solid impurities remaining after recrystallizing a sample from a solvent   Two Types Gravity Vacuum   Filter Paper Porosity–Measure of the size of the particles than can pass through the paper Retentivity–Opposite of Porosity; measure of the size of particles that can be retained on the filter paper

10. 1/30/2015 10 Recrystallization / Filtration Gravity Filtration Types   Filter Cones–Folded paper filter inserted into a class funnel with stem extending into a receiving flask Applicable Volume – > 10 mL   Fluted Filters–Specially folded (many creases) filter paper inserted into a glass funnel with stem extending into a receiving flask Applicable Volume – > 10 mL

11. 1/30/2015 11 Recrystallization / Filtration Gravity Filtration Types (Con’t)   Filtering Pipettes–Microscale technique used Pasteur Pipets A piece of cotton is inserted into the top of the lower constriction Applicable Volume – < 10ml

12. 1/30/2015 12 Recrystallization / Filtration Vacuum Filtration–More rapid than gravity filtration   Buchner Funnels–Primarily used to filter large volumes of liquid from solids, such as crystals from the Recrystallization Process Applicable Volume – > 10 mL   Hirsch Funnels–Similar, but smaller than Buchner Funnel, with sloping sides Used in Microscale techniques Applicable Volume – < 10 mL

13. 1/30/2015 13 Recrystallization / Filtration Experimental Overview   This experiment will consist of 4 parts: Part A   Determination of an appropriate solvent for recrystallizing an impure sample of Fluorene Part B   Recrystallization of Fluorene from the applicable solvent Part C   Isolation of purified Fluorene by vacuum filtration Part D   Verification of compound identity by melting point

14. 1/30/2015 14 Recrystallization / Filtration Part A Determine the appropriate solvent for recrystallizing an impure sample of Fluorene   Notes: Selecting a good solvent for recrystallization requires development of a practiced and consistent technique There is no perfect procedure that is applicable to all compounds Make sure the boiling point of the solvent is less than the melting point of the sample compound The solvents to be evaluated include: Water, Methanol, and Petroleum Ether (a mixture of low- boiling alkanes, 30-60 o C)

15. 1/30/2015 15 Recrystallization / Filtration Procedure – Part A (con’t)   Set up two hot water baths: 65 o C 95 o C   Place three (3) small test tubes in a test tube rack   Place a label with a solvent name on each test tube   To each test tube add about 50 mg of Fluorene   To one of the test tubes add 0.5 ml of Petroleum Ether   Stir the mixture with a microspatula   If all (or almost all) of the Fluorene solute dissolves at room temperature, then the Petroluem Ether is probably not appropriate for recrystallizing Fluorene

16. 1/30/2015 16 Recrystallization / Filtration Procedure – Part A (con’t)   Using the 65 o C water bath, continuously insert and remove the test tube in a manner that gently heats the mixture until it just begins to boil – immediately remove the test tube from the water Note:Be careful, Methanol and Petroleum Ether reach the boiling point quickly It is essential to minimize the evaporation of the solvent   If the solid does not dissolve, add more solvent dropwise, up to a maximum of 2.0 ml   Continue the heating process

17. 1/30/2015 17 Recrystallization / Filtration Procedure – Part A (con’t)   If the solid dissolves in the Petroleum Ether, allow the mixture to cool in the test rack for a few minutes and then place the test tube in an ice/water bath for about a minute   If the crystals do not come out of solution, scratch the sides of the test tube with a glass stirring rod to induce crystallization   If the crystals still do not come out, then try reheating the solution until about a third of the solvent has evaporated   Repeat the cooling & scratching process again   If the crystals still do not come of solution, then Petroleum Ether is probably not appropriate for recrystallizing Fluorene

18. 1/30/2015 18 Recrystallization / Filtration Procedure – Part A (con’t)   If the crystals come out of solution, then Petroleum Ether is an appropriate solvent for recrystallizing Fluorene   Repeat the above process for the test tube containing the Methanol solvent using the same 65 o C water bath   Repeat the above process for the test tube containing the water solvent, but use the 100 o C water bath

19. 1/30/2015 19 Recrystallization / Filtration Procedure – Part B   Recrystallize sample of Fluorene from applicable solvent Obtain a vial containing about 1.5 g of impure Fluorene Weigh the vial containing the sample to the nearest 0.001 g Empty the contents of the vial into a clean 125 ml Erlenmyer flask Reweigh the empty vial to the nearest 0.001 g Use the masses of the filled and empty vial to compute the mass of the Fluorene sample

20. 1/30/2015 20 Recrystallization / Filtration Procedure – Part B (con’t)   Recrystallize Fluorene from Solvent (con’t) Assemble the recrystallization apparatus as show in the figure below Use the setup on the left when using water as the solvent Use the setup on the right when using low-boiling point solvents. Use only enough water in the beaker to allow the flask to sit on the bottom of the beaker

21. 1/30/2015 21 Recrystallization / Filtration Procedure – Part B (con’t)   Recrystallize Fluorene from Solvent (con’t) Place the flask containing the sample on the hot plate if using water as the solvent or in the 65 o C water bath if using Methanol or Petroleum Ether as the solvent Add enough solvent to just cover the solid in the bottom of the flask Stir gently (Do not use a Thermometer or stirring rod, just swirl the solution gently) Heat solution only as long as it takes to dissolve the sample

22. 1/30/2015 22 Recrystallization / Filtration Procedure – Part B (con’t)   Recrystallize Fluorene from Solvent (con’t) If the sample does not completely dissolve after heating for a minute or so, add additional solvent (0.5 – 1.0 ml) and continue heating Repeat this process until sample has completely dissolved Note: Do not add too much or too little solvent ● ● Allow the mixture to cool slowly to room temperature Note: the purified crystals will come out of solution as the solubility decreases with decreasing temperature. Place the cooled mixture in an ice/water bath for a minute or two

23. 1/30/2015 23 Recrystallization / Filtration Procedure – Part B (con’t)   Recrystallize Fluorene from Solvent (con’t) If the cooled recrystallized mass can not be swirled, there is insufficient liquid solvent to hold the soluble impurities, thus additional solvent must added and the sample recrystallized again If little or no crystals come out of solution, it will be necessary to evaporate some the solvent Once a suitable mixture of purified crystals and solvent have been obtained, the crystals will be separated from the solvent using vacuum filtration

24. 1/30/2015 24 Recrystallization / Filtration Procedure – Part C   Vacuum Filtration Set up Buchner Funnel and Filter Flask for Vacuum Filtration (Instructor will demonstrate) Connect the rubber tubing to the vacuum flask and the vacuum apparatus on the lab bench

25. 1/30/2015 25 Recrystallization / Filtration Procedure – Part C (con’t)   Vacuum Filtration (con’t) Turn on the water flow Place a paper filter in the Buckner Funnel top and moisten the filter paper with cold solvent to seal filter on bottom of funnel Pour the crystal/solution slurry into the funnel Rinse the flask with cold solvent to transfer all solid particles to funnel Allow the filtration to continue until no more drops of solution pass into the filter flask Wash crystals 3 times with 5 mL cold solvent

26. 1/30/2015 26 Recrystallization / Filtration Procedure – Part C (con’t)   Vacuum Filtration (con’t) Dry the Sample   Transfer the crystals to a pre-weighed labelled weighing tray   Place the sample in the instructor’s drawer and allow to dry for a week Determine the Mass of the purified sample Determine the % recovery Determine the Melting Point range of the sample Verify the compound by its melting point

27. 1/30/2015 27 Recrystallization / Filtration The Report   From the procedure description determine the number of logical procedures   A procedure is a logical collection of steps leading to a new result   If a procedure involves a calculation, the equation must be setup as part of the procedure description and the computation of the results must be presented in the “Results” section including appropriate units and precision   Create neat, readable templates for presenting the results of each procedure. Use aligned columns and tables where applicable Note: The computation for each computed result must be shown

28. 1/30/2015 28 Recrystallization / Filtration Report Notes (con’t)   The Summary section is a paragraph presentation of the results obtained in logical order   The “Analysis/Conclusion” section should comment on the following using applicable arguments and selected results:   The amount of sample recovered relative to the impact of the procedure on potential loss of sample   Verification of the purity of the recovered sample in terms of appearance and comparison of the melting point with the literature value   Discuss the reasons for any difference in the melting points between the pure and impure samples