Recrystallization / Filtration

Recrystallization Purification of an organic compound by dissolving a solid in a hot solvent and recrystallizing the compound by slow cooling Vacuum Filtration - Separation of the solid solute from a liquid solvent


References:
    

Slayden, et. al., Pavia Tech 11 Pavia Tech 6.2-6.3 Pavia Tech 8 Web Site:

pp. 23 - 25 pp. 679 - 684; 687 - 688; 694 pp. 614 - 615 pp. 645 - 653 (Filtration)

http//: classweb.gmu.edu/jschorni/
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Recrystallization / Filtration


Elements of the Experiment



Recrystallization


Solid compounds synthesized in the Organic laboratory usually need to be purified before final confirmation tests are performed One of the most commonly used techniques is to purify a sample by dissolving it in a suitable solvent and recrystallizing the pure compound from the saturated solution by slow cooling The purified crystals are separated from the solvent by Vacuum Filtration

Vacuum Filtration


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

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
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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 on a pre-weighed watchglass or in your pre-weighed Buckner Funnel top in your drawer until next lab session Check with instructor Determine the Melting Point Range of the dried sample
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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
Solubility B C A Temperature

The C curve is a good solvent  Solute is sparingly soluble at room temperature  Solute is very soluble at elevated temperature
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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

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
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Recrystallization / Filtration


Solvents in Decreasing Order of Polarity

          

H2O RCOOH RCONH2 ROH RNH2 RCOR RCOOR RX ROR ArH RH

- Water - Organic Acids (Acetic Acid) - Amides (N,M-dimethylformamide) - Alcohols (Methanol, Ethanol) - Amines (Triethylamine, Pyridine) - Aldehydes, Ketones (Acetone) - Esters (Ethyl Acetate) - Halides (CH2Cl2 > CHCl3 > CCl4) - Ethers (Diethylether) - Aromatics (Benzene, Toluene) - Alkanes (Hexane, Petroleum Ether)
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Recrystallization / Filtration


Filtration


Two Purposes
 

Separate Purified Solid from the Soluble Impurities in the Solution from which it was Recrystallized Remove Solid Impurities from a Liquid Gravity Vacuum Retentivity Opposite of Porosity; measure of the size of particles that can be retained on the filter paper Measure of the size of the particles than can pass through the paper
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Two Types
 

Filter Paper


Porosity

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

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Recrystallization / Filtration


Gravity Filtration Types (Con t)



Filtering Pipettes

Microscale technique used with Pasteur Pipets A piece of cotton is inserted into the top of the lower constriction Applicable Volume < 10mL

Decantation

Careful pouring of supernatant liquid into another vessel leaving solids particles behind

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Recrystallization / Filtration


Vacuum Filtration


More rapid than gravity filtration Primarily used to filter large volumes of liquid from solids, such as crystals from the Recrystallization Process Applicable Volume > 10 mL

Buchner Funnels

Hirsch Funnels

Similar, but smaller than Buchner Funnel, with sloping sides Used in Microscale techniques Applicable Volume < 10 mL

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Recrystallization / Filtration


The Experiment Two Unknown Compounds  Purpose - Purify and isolate unknowns from impurities - Identify unknowns using melting points  List of unknown compounds is found on page 25 of the Slayden lab manual  Use literature resources to find Melting Points of compounds  Use an appropriate citation resource to find the melting points of all compounds in the list  Techniques - Recrystallization / Vacuum Filtration  Equipment - 50-75 mL Erlenmeyer Flask - Hot Plate - Buchner Funnel w/filter paper - Filter Flask with Tubing - Mel-Temp Melting Point Apparatus  Reagents - Distilled Water for water soluble compound - Methanol for methanol soluble compound

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Recrystallization / Filtration


Elements of the Experiment

 

Mass of Reagents Theoretical Volume of Solvent (Water & Methanol) Required to Dissolve Samples at Boiling Point Mix solute & solvent in Erlenmeyer flask and heat to near boiling point Recrystallize Samples from solvent by slow cooling Separate recrystallized particles from solution by Vacuum Filtration, washing with cold solvent Air-Dry Samples on pre-weighed watchglass or preweighed Buckner Funnel top Determine mass of Dried Samples Compute Percent Recovery Melting Point Range
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Recrystallization / Filtration


Procedure  Obtain a vial for each of two unknown compounds:  Water soluble compound  Methanol soluble compound  Weigh each vial to the nearest 0.001 g, record the mass in the pre-lab  Indicate applicable solvent  Follow the instructions below for each compound  Empty the contents of the vial into a 50 mL Erlenmeyer flask  Reweigh the vial to the nearest 0.001 g  Use the masses of the filled and empty vial to compute the mass of the compound Note: The computation of Mass is a separate procedure
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Recrystallization / Filtration


Procedure (Con t)  Using the mass of the compound you are going to recrystallize and the data in the table on page 25 of the Slayden manual, calculate the minimal volume of solvent required to dissolve your weighed sample at the boiling point of the solvent  For each solvent use the compound with the highest solubility per 100 mL of solvent at the boiling point. Ex. Let X be the solubility of the Water Soluble compound in 100 mL of Water at boiling point (100oC) Let Y be the mass of your weighed sample Let Z be the volume of solvent needed for your sample
X Y Y = @ Z= 100 100 Z X For Benzoic Acid, X = 6.7 g / 100 mL, and a sample weighing 1.206 g Z= 1.206g 6.7 100 = 18 mL
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Recrystallization / Filtration


Procedure (Con t)


Compare your computed results with the amounts you will actually use see next step The reason for using a little more solvent than the calculation indicates is that the computed volume is sometimes insufficient to provide a suitable solvent/solid slurry for the vacuum filtration step after the recrystallization step Start with 10 mL of Distilled Water for the Water Soluble Unknown

Start with 10 mL of Methanol for the Methanol Soluble Unknown  You will notice that it may be necessary to add additional increments of solvent to effect total solution

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Recrystallization / Filtration


Procedure (Con t)  Swirl each flask gently and heat each sample to just below boiling point Note:  Water boils at 100oC and Methanol at 65oC  Do not use a Thermometer or stirring rod, just swirl the solution  Heat solution to just below the boiling point  Heat solution only as long as it takes to dissolve the sample some solid impurities may remain  If all the solid does not dissolve, add approximately 2 mL increments of solvent until it does dissolve Note: Be patient; swirl the solution frequently and give the solid time to dissolve after each addition of solvent
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Recrystallization / Filtration


Procedure (Con t)


If the flask appears to contain insoluble impurities, check with instructor, who will guide you on the following two steps Note: do not do the following two steps unless directed to do so by the instructor
 

Tilt the flask so the particles settle to the bottom Decant the hot liquid into a clean 100 mL beaker

Allow the flask or beaker to cool very slowly to room temperature Crystals of the purified solute should start to come out of solution in a few minutes

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Recrystallization / Filtration


Procedure (Con t)


When the mixture of crystals and liquid has reached room temperature observe the relative amounts of solvent and solid particles If there is sufficient crystal / solvent mixture to allow easy pouring of the solid/solution mixture into the Buckner Funnel, skip the next step Otherwise add an additional 2-3 mL of solvent and redissolve the solid particles and cool again to room temperature slowly Repeat previous step, if necessary Place the flask (or beaker) in an water bath for 1 minute

 

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Recrystallization / Filtration


Procedure (Con t)


Set up Buchner Funnel and Filter Flask for vacuum Filtration (Instructor will demonstrate)


If so directed by the instructor, pre-weigh the top of the Buckner funnel to the nearest 0.001 g Reassemble thy Buckner Funnel Place a paper filter in the funnel top and Moisten the filter paper with cold solvent Connect the rubber tubing to the vacuum flask and the vacuum apparatus on you lab bench Turn on the water to start forming the vacuum

 

 

Filter the cold solid/solution mixture, collecting crystals on filter paper

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Recrystallization / Filtration


Procedure (Con t)  Wash crystals twice with 2-3 mL cold solvent  Follow instructor directions to either:  Place the pre-weighed top of the funnel containing the crystals in the designated drawer to dry for a week; or  Transfer the dried crystals to a pre-weighed watch glass and place in drawer to dry for a week  Determine the net weight of the dried sample  Compute the percent (%) recovery of purified sample  Determine the Melting Point range of the sample  Identify the unknown compound by its melting point Note: Use literature resources to find the melting points of the compounds in the table on page 25 of the Slayden Manual
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Recrystallization / Filtration


The Report


From the Elements of the Experiment and the detailed steps, identify and setup the Procedures for this experiment. 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 The Summary section is a paragraph presentation of the results obtained in logical order
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Recrystallization / Filtration


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 results of the melting point determination

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