Kai-Jane Hsu 2/10/14 1) Extraction and Recrystallization Reference: Experimental Organic Chemistry: A Miniscale and Microscale Approach, 5th

ed. by Gilbert and Martin, p. 161-164 2) Introduction An unknown mixture consisting of equal amounts of an acid, a base, and a neutral compound (1:1:1) is dissolved in ethyl acetate, an organic solvent. This mixture is to be separated into three parts using extraction, purified via recrystallization, and identified by their melting points. 3) Main Reactions and Mechanisms 1) Acid 4) Table of Reactants and Products Benzoic acid 2-methylbenzoic acid 2-chlorobenzoic acid Salicylic acid 4-nitroaniline 2-methyl-4-nitroaniline 3-nitroaniline 9-fluorenone Anthracene Fluorine Phenanthrene Hydrochloric acid Sodium hydroxide Ethyl acetate

5) Procedure (Supplement B, Supplement C) Obtain 1 g of unknown mixture. Using an Erlenmeyer flask, dissolve the mixture in 20 mL of ethyl acetate. Transfer the solution to separatory funnel. Gently shake for a minute, making sure to vent every few seconds. Set it on a ring stand to separate. Extract it sequentially with three 10-mL portions of 6 M hydrochloric acid. Combine the three aqueous acidic layers in a labeled Erlenmeyer flask. Extract the remaining organic layer in the separatory funnel with three 10mL portions of 6M NaOH. Combine the three aqueous basic layers in a labeled Erlenmeyer flask.

Transfer the organic layer into a labeled Erlenmeyer flask. Dry with Na2SO4. Cool both of the aqueous extracts in an ice-water bath. Neutralize the acidic extract with 30 mL of 6M sodium hydroxide, then add a little excess to make the solution basic to pH paper. Do the same, but with 30 mL of 6M hydrochloric acid, to the basic extract. Precipitate should form. Collect the precipitates by vacuum filtration. Wash with cold distilled water. Label. Separate the organic solution from the sodium sulfate by gravity filtration. Next, blow an air hose across the top of the container. Ethyl acetate will evaporate, leaving behind the neutral compound. After the samples have been dried, weigh each of the vials. Determine melting point of each. Recrystallization For the recrystallization, work in a group of three. Determine the best solvent for recrystallizing the acid, base, or the neutral compound. Combine all three crude acid samples; do the same for the base and neutral crude samples. Using the determined best solvent, dissolve and boil. Allow hot solution to cool slowly to room temperature. Crystals should form. Isolate crystals by vaccum filtration. Rinse purified crystals with a small amount of COLD solvent. Allow to air-dry. 6) Data and Results 7) D 8) pp. 167-171 Problem 4, 5, 22 4) Drying an organic liquid involves adding a solid drying agent that wont dissolve in an organic liquid and will absorb any aqueous liquid. Swirling or shaking the solution and its drying agent hastens the drying process because it increases the surface area between the liquid and the solid, allowing for more aqueous molecules to come into contact and bond with the drying agent. 5a) 5b)

Recrystallization solvent: 1) compound needs to be insoluble in cold solvent. 2) Compound is soluble in hot solvent 3) Impurities solubility is temperature independent Use 25mL Erlenmeyer. Add about 3-4 mL of solvent. Want to minimize volume. Heat it up, add a little bit at a time until solid just dissolves. Typical volume is 5-10 mL.

If impurity stays solid, filter.

. Recrystalize your own. Collect 1) melting point and calculate % recovery. Mass (g) / 0.333g * 100% = % recovery Jennifer Hsu (kh24855) Discussion Lab 2 Extraction and Recrystallization Extraction An extraction is a laboratory procedure used to isolate a product. An extraction can be liquid-solid, for example: extracting caffeine from coffee or tea, or liquid-liquid. A liquid-liquid extraction consists of a target compound dissolved in an original solvent (So) and an extraction solvent (Sx.) The choice of solvents is very important and must follow several rules. First, they must be immiscible. Second, the Sx should not irreversibly mix with the solute that is being extracted. Third, the Sx must be somewhat specific to the compound being extracted to improve yield. Finally, the Sx must be easily removed; otherwise, the target compound will be unfortunately stuck in the Sx. In this particular experiment, there are two ways to remove the Sx. For the neutral compound, the Sx will have a low boiling point, and therefore be easy to boil off, leaving the solute behind. For the acid and basic compounds, the Sx is removed by changing the solubility of the desired compound. Solubility is affected by temperature, pressure, polarity (ionic strength), pH, and volume. In this experiment, pH is used because of the constraints of a teaching laboratory. For example, volume is not used because 1) it would be easier to recrystallize with smaller amounts and 2) with hundreds of students, it would be a waste of chemicals. When the powder containing equal fractions of acid, base, and neutral was dissolved in ethyl acetate (the So), the solution turned brownish-yellow. After adding the Sx, the separatory funnel was gently shaken. This is done because the exchange of solute occurs at the interface of the two liquids. Shaking maximizes surface area, therefore facilitating the exchange of solute. The separatory funnel was vented every few seconds because ethyl acetate has a relatively high vapor pressure. Shaking causes pressure to build up in the funnel, and so venting prevents explosions. Extracting sequentially with three 10 mL portions of Sx is more effective than with one 30 mL portion of Sx because of the equation calculating FA (see post-lab exercise #5 in laboratory notebook.) Using HCl as the Sx extracts the base solute, while using NaOH as the Sx extracts the acid solute. This is because the acid or base has an affinity for its Sx and will leave the organic layer for it. The acid portion consists of the unknown base dissolved in HCl. The first fraction is observed to be deep yellow. The subsequent fractions became lighter in color. The lower layer is identified to be the aqueous layer since the HCl solution is more dense than ethyl acetate. It is neutralized with NaOH to change the pH of the solution, causing the base to precipitate out. It was identified to be basic with a piece of litmus paper, which turned blue. The base portion consists of the unknown acid dissolved in NaOH. The first fraction is observed to be a very light yellow. The subsequent fractions became clearer in color. Again, the lower layer is identified

to be the aqueous layer since the NaOH solution is more dense than ethyl acetate. It is neutralized with HCl to change the pH of the solution, causing the acid to precipitate out. It was identified to be acidic with a piece of litmus paper, which turned bright pink. For both acid and base portions, the amount of neutralizing solution to add was determined by M1V1 = M2V2. This equation determined the approximate amount of neutralizing solution to add, therefore reducing waste an alerting the user if something was wrong. The remaining organic layer is also conserved because it retains the neutral compound. This layer is dried with sodium sulfate to absorb any remaining aqueous solvent, then filtered so the hydrated sodium sulfate is removed. Otherwise, the sodium sulfate will be mixed in with the neutral. After vacuum filtration and air drying, the crude acid was a white crystal, the crude base was a yellow crystal, and the crude neutral was a light yellow-white crystal. The observed percent yield is 71.2% for the acid, 152.9% for the base, and 80.8% for the neutral. The crude base must contain impurities or not been fully dried because gaining mass is not possible. Recrystallization Recrystallization is a laboratory procedure used to purify solutes that can crystallize. The choice of a solvent for recrystallization is very important and must fulfill several factors. First, the compound needs to be insoluble in cold solvent. Second, the compound needs to be soluble in hot solvent. Finally, the solubility of impurities must be independent of temperature. Therefore, if the impurities are soluble, they remain in the solution; or, if they are insoluble, they are filtered out during recrystallization. The solutions must be heated to a high temperature for the solutes to dissolve. Once the solutes dissolve, the solution is quickly filtered to remove impurities. Then, the solutions are allowed to slowly cool. The speed of cooling is important because if the solution cools too quickly, impurities may be trapped in the crystals or the glassware may be stressed and break. After the solutions have cooled, the crystals are isolated via vacuum filtration. To encourage filtration, the purified crystals are rinsed in cold solvent. It is important for the solvent to be cold, or it may dissolve some of the purified crystal and reduce percent yield. The purified acid had an observed melting point of 118-120C, identifying it as benzoic acid. The purified base had an observed melting point of 145-147C, identifying it as 4-nitroaniline. Finally, the purified neutral had an observed melting point of 94-96C, identifying it as phenanthrene. As a result of this experiment, the percent yield for purified acid observed was 28.2%, for purified base was 44.7%, and for purified neutral was 26.1%. The procedure that lost the most mass was recrystallization. The loss in mass is probably because of the use of many different containers and filters in recrystallization, causing residue to be lost many times. Experimental error is also applicable. The melting points do not change significantly from those measured in the crude.