RECRYSTALLIZATION

Bettina Maria Q. Acua, Enrico Joseph C. Aguinaldo, Alyanna Patrice L. Arceo Jasmine Grace C. Asinas, Sigrid Jessa R. Bello Group 1 2G Pharmacy Organic Chemistry Laboratory

ABSTRACT
The purification method used in this experiment was recrystallization. The experiment was divided into two parts. The first part was conducted to determine which is the best recrystallizing agent, which turned out to be the water, respectively. The second part was the recrystallization. The best recrystallizing solvent was added to the crude acetanilide and was subjected to water bath to purify the crude acetanilide. The filtrate obtained was then cooled and pure acetanilide was obtained.

INTRODUCTION
Most of the organic substances when synthetically prepared or isolated from natural source are impure due to the presence of some bye-products or reactants. Before the compound can be analyzed qualitatively or quantitatively, it is necessary that it should be in a pure state. Purification is not always easy and various methods depending upon the nature of the compound and impurities are employed. Various methods used for the purification of organic compounds are based on the nature of the compound and the impurity present in it. Some of these methods are sublimation and by recrystallization. The problem with sublimation is that only those solids that can pass directly into the vapor phase without passing through the liquid phase can be purified. Therefore, solids not having this property cannot be purified and the latter method of purifying can be performedRecrystallization. Recrystallization is a technique of purifying organic solids based on solubility. It is a useful purification method for most organic compounds that are solids at room temperature. The selection of a proper solvent is the most critical part of the recrystallization procedure. Recrystallization involves dissolving the solid to be crystallized in a hot solvent or solvent mixture and then cooling the solution slowly. The dissolved solid has decreased solubility at lower temperatures and separates from the solution as it cooled. A small seed crystal is formed initially, and it then grows layer by layer. The effect of dissolving a solid and then permitting it to crystallize is that the crystals which form contain fewer impurities than the material which was originally dissolved. Successive recrystallizations can produce extremely pure crystalline samples. The purification technique crystallization is governed by the solubility of a solid in a solvent increases with increase in temperature and decrease with decreasing temperature and purification is based on differences in the solubility of the solids and impurities in a given

solvent. There are a couple of potential pitfalls in the crystallization process. If too much solvent is used to dissolve the compound in the first step, it may remain soluble even at cooler temperatures. Thus, instead of crystallizing, it will remain in solution. Another problem involves performing the crystallization too rapidly. If the hot solution is disturbed, or cooled too quickly, then solute molecules precipitate from solution, trapping impurities within the solid structure. The objectives of the performed experiment were to synthesize acetanilide by acetylation of aniline and to purify crude acetanilide product by recrystallization. The purity of the obtained pure acetanilide was ascertained by determining its melting or boiling point. Today, there are new methods of checking the purity of an organic compound which are based on different types of chromatographic and spectroscopic techniques.

EXPERIMENTAL A. Compounds tested

1. Water, hexane, methanol 2. Aniline, acetic anhydride, crude acetanilide

B. Procedure 1. Selecting Solvent

the

Best

Recrystallizing

Choosing the proper solvent is very important in recrystallization because it will help us to increase our yield. If we will use inappropriate solvent, the recrystallization process perhaps will not be that successful. One member placed a corn-grained amount of pure acetanilide into each test tubes. To the first test tube, 1 mL of water was placed. The second test tube contains 1 mL of hexane and the last one contains methanol of the same volume as the first two. The test tubes were observed at different conditions. Then subjected to water bath and cooled. The solubility of the pure acetanilide in the different solvents at varying temperature was noted.

Table 1. Compounds Used and their Structural Formula

The crystals obtained were put again in another Erlenmeyer flask and 20 mL of distilled water was added. Then, the Erlenmeyer flask was placed on top of hot plate. The solution was heated until all the crystals were dissolved.

Figure 4. Heating the solution until all crystals were dissolved on top of the hot plate. Immediately, the solution was filtered and the filtrate was collected. Filtering the hot solution was done to remove any insoluble impurity. Allowing the hot solution to cool slowly causes some of the dissolved substances to crystallize out. Crystals are well formed in slow cooling, whereas at rapid cooling, precipitation occurs.

Water

Methanol

Hexane

2. Recrystallization
Initially, 2 mL of Aniline was measured and put in an Erlenmeyer flask. One member added 20 mL of distilled water. Then, by serological pipette, 3 mL of acetic anhydride was added slowly. The proper sequence of mixing the compounds was followed.

Figure 1. The Structural Formula of Aniline

Figure 2. The Structural Formula of Acetic Anhydride The formed crystals were contaminated. Recrystallization with the best recrystallizing agent initially determined which was water was used. The solution was then cooled in an ice bath to hasten crystallization. After, cooling the solution was filtered through a wet filter paper. The crystals were dried and weighed. Crystals collected were crude acetanilide.

Figure 5. Picture of the filtrate and residue after filtration. The filtrate was cooled in running water and placed in refrigerator. During cooling and crystallization, the solution was protected from airborne contaminants by covering the opening with a parafilm.

Figure 6. Picture of Pure Acetanilide crystals after Refrigeration Figure 3. Crude Acetanilide and its Structural Formula Mother liquor refers to the solution that remains in the crystals. To reduce the amount of mother liquor, washing of crystals with cold

distilled water must be done. However, during filtration, some part of the solution was lost that resulted to reduction of the pure acetanilide. The crystals formed were obtained by adding water to the Erlenmeyer flask. Then, the solution was filtered and the pure acetanilide was pressed in-between two filter papers to absorb the water. Finally, dried pure acetanilide was weighed and its purity was tested by determining its melting point. Some factors were followed to ensure proper melting point determination like the crystals must be well-pulverized and well-packed.

solvents, cannot form a product of high purity and in good recovery yield.
Weight of Crude Acetanilide Weight of Pure Acetanilide Percentage recovery 2.4 g 0.4g 16.67%

Table 3. The weight of the crude and pure acetanilide and the percentage recovery. Given the formula for percentage recovery, we can compute the percentage of the pure acetanilide recovered from the acetanilide synthesized from the acetylation of aniline with acetic anhydride.
x 100 %

RESULTS AND DISCUSSION

The choice of solvent is perhaps the most critical step in the process of recrystallization since the correct solvent must be selected to form a product of high purity and in good recovery or yield. A solvent should satisfy certain criteria for use in recrystallization. There are different criteria for the choice of solvent. First, according to solubility property, it must be: (a) Insoluble in room temperature (b) The desired compound should be reasonably soluble in the hot solvent (c) Insoluble upon cooling. (2) The boiling point of the solvent should be low enough so that it can readily be removed from the crystals. (3) The choice of solvent must be non-reactive with solutes. (4) Dissolves most substance to be crystallized in hot solution and crystallize most of the substance when cold. (5) It should dissolve either the substance of interest or only the impurities, but not both. (6) It should yield well formed crystals of the desired substance. (6) Easy to separate the crystals using filtration. Moderately volatile, so crystals can readily be dried. Lastly, the solvent must be nontoxic, nonflammable and inexpensive.
At room temp. Insoluble Soluble Insoluble During heating Soluble Soluble Insoluble Upon cooling Insoluble Soluble Insoluble

The yielded acetanilide was 16.67% the weight of the crude acetanilide. This is the pure acetanilide synthesized from the acetylation of aniline with acetic anhydride. To calculate the percentage yield, the theoretical yield and the limiting reagent must be first identified. The limiting reagent is the reactant that is used up first in a reaction. As the name implies, it also limits the amount of product to be formed. The theoretical yield on the other hand, is the maximum yield of pure crystals that could be obtained by cooling or evaporating a given solution. Calculation of the weight of aniline and acetic anhydride:

Water Methanol Hexane

Table 2. Solubility of Pure Acetanilide in Different Compounds and Temperatures Three solvents were tested namely, distilled water, methanol and hexane respectively. Table 2 shows that water satisfied all the criteria for solubility needed for it to be called the best recrystallizing agent. On the other hand, methanol only met one criterion, that is, it must be soluble during heating while hexane met two criteria but was insoluble during heating making it inappropriate solvent for recrystallization of the experiment. Hence, acetanilide, when placed on these two

These are the amounts of the two reactants in grams calculated using their density and the volume used in the experiment. Aniline- C6H5NH2 MW= 93.13 g/mole Density=1.0217 g/mL Acetic Anhydride- C4H6O3 MW=102.09 g/mole Density= 1.082 g/mL

http://www.chem.utoronto.ca/coursenotes/CHM2 49/Recrystallization.pdf 08/19/12 http://www.chemicalland21.com/lifescience/phar /ACETANILIDE.htm 08/19/12 Figure 7. Computation of the limiting reagent. Figure 7 shows that aniline is the limiting reagent since it needed 2.96 g to react with 3 mL of acetic anhydride and at the same time, aniline will limit the amount of product to be formed. Given the formula for the Percentage yield determination: http://www.erowid.org/archive/rhodium/chemistr y/equipment/recrystallization.html 08/19/12 http://www.mesacc.edu/~timoz40351/Organic% 20Lab/235LL/235LL%20Latest%20Versions/Cryst allization/Crystallization_rev1.pdf 08/21/12

The percentage yield of the pure acetanilide is 19. 58% which was obtained from the 2-mL aniline and 3-mL acetic anhydride. Melting point determination was used to test the purity of the acetanilide obtained. Melting point is the temperature range at which the crystals start to melts and the last crystal disappear. Melting range for pure substances is =/<0.5 C. In the experiment, the melting point recorded was 113 C. Therefore, the acetanilide yield was pure.

REFERENCES
BOOKS Bayquen, Cruz, de Guia et al. (2009). Laboratory Manual in Organic Chemistry. Philippines: Quezon City. Pg 47
WEBSITES

http://oscience.info/chemistry/purification-andcharacterization-of-organiccompounds/purification-of-organic-compounds-2/ 08/19/12 http://spot.pcc.edu/~gbackes/ORGANIC/CH%20 241/Labs/The%20Crystallization%20Procedure.ht m 08/19/12 http://firstyear.chem.usyd.edu.au/prelab/e24.pdf -08/19/12