RECRYSTALIZATION EXPERIMENT Experimental Objectives: At the end of this experiment you should be able to perform: 1.

determine the best solvent for the recrystallization of acetanilide and Benzophenone 2. Perform the techniques of recrystallization 3. calculate percentage yield 4. assess the purity of a compound using melting point determination Theory Recrystallization is the method of choice for purifying organic solids. This technique involves dissolving a solid in a solvent then inducing the solute to precipitate from the solution. A more pure solid should precipitate if the impurities remain dissolved in the solvent. The pure solid is collected by vacuum filtration and usually washed with a minimal amount of ice-cold solvent. All purification methods exploit some physical property of the substance. Recrystallization depends on the solubility of a solid and the fact that solubility increases with temperature. The success of any recrystallization relies on the fact that at or near the boiling point, a given recrystallization solvent will dissolve more solid than at room temperature. The result is that the crude solid can be dissolved in a small amount of boiling solvent and as the solution cools, the solubility decreases and eventually, the solid will precipitate (recrystallized) from solution. The precipitation process is called crystallization. When an organic reaction produces a compound that exists as a solid, the product may crystallize from the reaction mixture or at some point after the solvents and by-products have been removed. Frequently, this crystallized substance, the crude solid, contains impurities from the reaction mixture and must be purified. A recrystallization attempts to separate the compound from the remaining impurities which may be solvent residue, side-products and salts, or some combination of all three, hence this is a purification technique. In a typical procedure, the crude solid is dissolved in a recrystallization solvent by heating the solvent/solid mixture or by adding boiling solvent to the crude. Once the crude solid is completely dissolved, the solution is allowed to cool until the solution becomes saturated and crystals begin to form. The flask is placed in an ice bath to maximize the amount of solid that can precipitate from the solution. The recrystallized solid is then collected by vacuum filtration and washed with cold solvent. Occasionally, centrifugation is required to separate the recrystallized solid from the recrystallization solvent. In many cases, it appears that the crude solid does not dissolve completely. Adding more solvent is not always the best practice since the result may be a solution that will remain unsaturated even at lower temperatures; in other words, your compound will not precipitate. If a crude sample does not dissolve completely, it may be that some of the impurities are insoluble in the solvent being used. To separate the suspended solids, a hot filtration step is performed. To perform a hot filtration, the heterogeneous mixture is filtered quickly while still near the boiling point of the solvent to remove the undissolved solids. The filtrate should still be hot enough to keep your compound in solution. Frequently, the product may start to precipitate on the filter paper during the hot filtration step. To prevent this, the glassware is warmed by boiling a small amount (3-5 mL) of the recrystallizing solvent in a clean Erlenmeyer flask with the filter funnel sitting on top. This Erlenmeyer flask will be used to collect the filtrate. Once the glassware is hot from the solvent vapors, the undissolved solids are filtered as quickly as possible. A ready supply of boiling solvent should be on hand in case the compound begins to crystallize on the filter. Add small amounts (1-2 mL) of boiling solvent to dissolve the compound so that it passes into the filtrate. Keep in mind that you will most likely boil the filtrate to evaporate the excess solvent used to re-dissolve the product. The filtrate is then allowed to cool and the pure crystals are collected by vacuum filtration and washed on the filter.

Occasionally, a crude solid will contain colored impurities which must be separated. Activated charcoal (about the size of a pea) is added to the mixture and the contents swirled to allow the colored substance to adsorb to the surface of the charcoal. Afterwards, a hot filtration is needed to remove the charcoal. When employing a hot filtration, the simplest operation to remove suspended solids, either undissolved impurities or activated charcoal, is gravity filtration. Vacuum filtration is not used during a hot filtration because the vacuum will cool the solvent and crystallization of the product may occur. However, once recrystallization is complete, vacuum filtration is the method of choice since solvent residue is quickly removed from the pure crystals. Choosing an appropriate solvent is key to a successful recrystallization. The organic compound must have low solubility in the solvent at room temperature and moderate solubility at the boiling point. Ideally, the solubility of the impurities is greater than the organic compound at both high and low temperatures obviating the need for a hot filtration step. Quite often, a single solvent which gives suitable results cannot be identified. In such cases, the use of mixed solvents (solvent pair) is often successful. Two solvents are chosen, one which dissolves the substance readily, and another in which the solute is only sparingly soluble. Note that the two solvents must be completely miscible. The usual procedure is to dissolve the crude solid in the better solvent at its boiling point, and to add the weaker solvent drop wise until a faint cloudiness persists, indicating that the solute is starting to come out of solution. A few drops more of the better solvent are then added to put the solute back into solution, and the mixture is allowed to cool to effect crystallization. Typical solvent pairs are water and ethanol, or hexane and benzene, where the 'weaker' solvent is listed first. These mixed solvent systems are interesting -- it seems that the solubility characteristics of the better solvent dominate at higher temperatures, while the mixture behaves more like the weaker solvent at lower temperatures. A word about washing purified solids on a filter: Swirl the contents of the flask and try and get a suspension of solids then quickly pour the recrystallized material and solvent into the filter funnel. Apply vacuum just long enough to draw the solvent into the Erlenmeyer flask then remove the vacuum. The objective here is to produce wet cake of recrystallized solid of uniform thickness. Next, gently add a shallow layer of wash solvent over the wet cake, apply vacuum and draw the wash through the wet cake. Repeat washings if necessary. Vacuum filtration is preferred over gravity filtration in order to quickly separate the crystals from the solvent. As with any purification step, some loss of product is expected. After collecting the pure solid, some of the compound remains in solution in the filtrate. Using solubility data, the amount of solid lost to the filtrate can be estimated. Solubility is often reported as grams of solute per 100 mL of solvent (g/100 mL) at some temperature. Consider the example below: Sample calculations of % recovery, and solubility at high and low temperature: Solubility data for phthalic acid can be obtained from the chemical literature: 18g/100 mL H2O @ 100C 0.54 g/100 mL. @ 15C A student obtained 3.2 g of crude phthalic acid. After recrystallization and drying, 2.5 g of pure acid was obtained. The percent recovery is readily determined: 2.5/3.2 x 100% = 78% recovery

A 3.2 g sample of crude requires approximately 20 mL of water for recrystallization: 3.2 g acid (100 mL/18 g) = 17.7 mL (at the boiling point of the solvent) In this example, a student heated about 25-28 mL of solvent to boiling then added the solvent to the crude acid. After recrystallization and vacuum filtration, the volume of the filtrate was about 20 mL. The amount of product lost to the filtrate can be estimated: 20 mL 0.54 g/100 mL) = 0.108 g = 0.11 g (at low temperature of the solvent) All variables considered, about 100 mg of product will remain in the solvent. If desired, the solvent can be partially evaporated to induce more solid to precipitate. This is sometimes referred to as a second crop. If the compound is extremely valuable, a third crop may be harvested from the second filtrate. Successive amounts of product obtained in this manner are often less pure than the first crop since concentrating the filtrate solution may induce some impurities to precipitate with the desired product. Procedure PART 1: Choosing a solvent
Procedure: Test the solubility of (a) acetanilide, (b) benzophenone in each of four solvents by using the directions that follow. Record all results in a properly constructed table

I.

Preparing four test tubes for each compound a. Label four test tubes: acetone, water, ethanol, and petroleum ether b. Place 100mg of compound of interest into each test tube c. Place 2.0mL of the appropriate solvent into each test tube d. Thoroughly stir each mixture and observe if that compound is soluble or insoluble at room temperature Heat mixture(s) to a boil a. Select test tube(s) containing solvent in which acetanilide and benzophenone did not dissolve at room temperature b. Use a water bath to heat the mixture(s) Cool the mixture(s) a. Allow solvent(s) to cool at room temperature b. Place tube in ice bath for 5 minutes Choose an appropriate solvent a. Based on observations choose a solvent or solvents from which to recrystallize acetanilide and benzophenone.

II.

III.

IV.

(Example Table) Compound 1

Solvent

Acetone

Water

Ethanol

Petroleum Ether

Solubility at R.T.

Solubility near b.p. of solvent

Recrystallize on cooling?

In your discussion make sure to given the criteria, YOU need to make the final decision on which solvent or set of solvents to use to recrystallize each compound and why

PART 2: Recrystallization of Impure Compounds: A. Weigh a 1.0g sample of each impure compound of unspecified purity and place in a 125 mL Erlenmeyer flask. (Do one sample at a time) B. Place 40 ml of appropriate recrystalization solvent in a separate 100 ml beaker (single solvent recrystalization) or if using a mixed solvent system heat the solvent that made your material dissolve most readily (at room temp) in a 100 ml beaker. Most use hot plate for heating (organic solvents are very flammable). Remember the use of boiling stones. C. Add 15 ml of their appropriate hot solvent to the compound of interest (do one compound at a time). In order to dissolve the entire compound possible in the mixture (and get a near saturated solution) it may be necessary to add small quantities of additional hot solvent in 1 to 2 ml increments using a Pasteur pipette. (Estimate the approximate amount of solvent used). Swirl the flask after each addition of hot solvent. (Keep this flask warm) Do you always have to do a hot filtration? (explain in discussion)

D. Pour the hot mixture through the heated funnel apparatus (heating of funnel will be shown in class). Rinse the beaker with hot solvent Pour the rinse through the heated funnel. Use as little rinse as possible. Remember that it is important that the solution and the apparatus are hot to prevent premature formation of crystals. E. If the solution is colored after hot filtration, let solution cool to room temperature and then add approximately 60 mg of activated carbon to the Erlenmeyer flask. Reheat solution to near boiling repeat hot filtration. Make sure to record color of new filtered solution.

What is the problem of using too much activated carbon for decolourizations? (explain in discussion)

F. (single solvent system) Once the solution has been filtered place the Erlenmeyer flask containing the purified material on a paper towel and let it cool undisturbed until it reaches room temperature some crystals should have formed. Then place in the ice bath for approximately 10-15 minutes or until crystallization is complete. (You may have to induce crystallization - ask the instructor if necessary) G. If using a mixed solvent system once filtered then add bad solvent until either you reach a visible saturation point (the lucky situation, where you can see crystals or slight cloudiness beginning to form). Let cool so as to grow more crystals to room temperature then place in the ice bath for approximately 10-15 minutes or until crystallization is complete H. Assemble a Buchner funnel apparatus using double filter paper moistened with cold solvent. I. Filter the crystallized material using vacuum filtration. Small amounts of cold solvent may be used to rinse down the flask and to wash the crystals. Leave the crystals to dry using the vacuum. J. Once the crystals have vacuum dried (about 10-15 minutes) place in oven until the material is at constant mass remember the oven should be at a temperature lower than the melting point of solute. K. examine the crystals, take melting point of samples and determine the percent yield Construct a simple data summary for each sample: Mass of crude sample before recrystallization ___________ Amount of solvent used to dissolve your compound ___________ Amount of pure solid obtained after crystallization ___________ Percent recovery of your product ___________ (show your calculation!) Exercises 1. A student performed a recrystallization of phthalic acid and used 35 mL of water as solvent. Assuming no loss of solvent to evaporation, calculate the loss of product in the filtrate based on the solubility of phthalic acid. 2. A student performed a recrystallization and after the solid had dissolved, the solution was immediately placed in an ice bath. Within a few seconds, a large amount of solid formed and was collected by vacuum filtration. The percent recovery was high but the melting point of the dried solid showed that the solid was contaminated with impurities. Explain. 3. During a recrystallization, a significant amount of undissolved solids remained. The student attempted to perform a hot filtration using gravity filtration. A large amount of solid formed on the filter paper. After the filtrate was cooled in ice, and the solid collected by gravity filtration, the percent recovery was very low. Explain. 4. During a recrystallization a student boiled the mixture for over 10 minutes to dissolve the crude solid and about half of the solvent evaporated. The student noticed that the amount of solids in the mixture began to increase. Explain. 5. Since you will be doing purification by recrystallization on a routine basis for both semesters of organic chemistry, you must develop good technique. Construct a procedure (flow diagram) listing the steps for a recrystallization including a hot filtration step