RECRYSTALLIZATION

Serrona, M., Soriano, C.,Tolentino, S., *Vicencio, N., Yu, B. 2DPH, Faculty of Pharmacy, University of Santo Tomas

Abstract Only solids which pass directly into vapor phase without passing their liquid phase can be purified by sublimation. Solids which do not have this property are purified with the aid of recrystallization method. The method of recrystallization is a purifying technique of impure solids that uses solubility as the basis of its purification. It is a process that involves heating the organic solids, in this experiment acetenalide, in a water bath and then cooling it in an ice bath to hasten the crystallization. The mixture is filtered and then dried in which we collected the crude acetanilide. A recrystallizing agent is added in which the pure acetanilide will be collected. Know the melting point of the pure acetanilide and compare it to the theoretical melting point, a closer melting point with the theoretical melting points means that it is pure. Having a small difference of melting point and theoretical melting point determines if the substance is pure because recrystallization is based on the substances solubility. Introduction Organic compounds whether solid or liquid contain impurities and there are a lot of ways to purify these organic compounds. Different purification techniques may be applied and it depends whether the substance is solid or liquid. For liquids, distillation is one of the most common techniques of purifying. It is a process of vaporizing a sample, condensing the vapour, and then collecting the condensate in another vessel. While for solids, recrystallization is the technique being used that involves choosing a suitable solvent in which the material can be recrystallized. [1]Solubility is defined to be degree to which a substance dissolves in a solvent to make a solution. [2]. It is the factor that affects recrystallization and it is also applied in picking a suitable agent for recrystallization. Solubility tests are being made and the suitable solvent should have high solubility in hot solvent and low solubility in cold solvent. Meaning the substance should show ideal solublitiy in the solvent thus when cooling the substance recrystallizes but the impurities will not [3]. Aniline with the formula of C6H5NH2, is a colorless, oily, basic liquid organic compound. Chemically, Aniline is a primary aromatic amine whose molecule is formed by replacing one hydrogen atom of a benzene molecule with an amino group. Aniline boils at 184C; and melts at -6C. It is of great importance in the dye industry, being used as the starting substance in the manufacture of many dyes. Aniline is prepared commercially by the reduction of nitrobenzene, a product of coal tar, or by heating chlorobenzene with ammonia in the presence of a copper catalyst. [4]Acetic anhydride, with the formula of (CH3CO)2O, is commonly abbreviated as Ac2O, it is considered to be one of the simplest acid anhydrides and is a widely used reagent in organic synthesis. It is a colorless liquid that smells strongly of acetic acid, which is formed by its reaction with the moisture in the air. Acetic anhydride is produced by carbonylation of methyl acetate. Ac2O is mainly used for the acetylation of cellulose

to cellulose acetate for photographic film and other applications. It is also use in the preparation of certain drugs like Aspirin, acetyl salicylic acid, is prepared by the acetylation of salicylic acid using acetic anhydride. [5] Acetanilide is an odorless, white flake solid or crystalline powder in its pure form. It is soluble in hot water alcohol, ether, chloroform, acetone, glycerol, and benzene. It has a melting point 114C and boiling point 304 Acetanilide can be obtained by acetylation of aniline undergoes nitration at low temperature and yields highly the paranitro products. It can be used as an inhibitor of peroxides and stabilizer for cellulose ester varnishes. It is used as an intermediate for the synthesis of rubber accelerators, dyes and dye intermediate and camphor. [6] The objectives of this experiment are to synthesize acetanilide by the acetylation of aniline and to purify the crude acetanilide product by recrystallization. Materials and Methods This First, the group placed corn-grain amounts of crude acetanilide in three different test tubes. The first test tube contained distilled water, the second one contained hexane and the third one contained 95% ethanol. The test tubes were shaken and then the solubility of crude acetanilide was noted for each test tube. The test tubes were placed in a warm water bath for about 1 to 5 minutes and again the solubility of the crude acetanilide was noted. After the warm water bath, the test tubes were cooled in room temperature and the observations in its solubility were again recorded. After all this process, the best and suitable solvent for the crude acetanilide was determined. 2ml of aniline and 20 ml of distilled water were mixed in an Erlenmeyer flask.

Then, 3ml of acetic anhydride was slowly added to the mixture. After the observations regarding the mixture, the Erlenmeyer flask was placed in an ice bath to hasten crystallization. After the full formation of crystals, the mixture was filtered in a wet filter paper. The residue in the filter paper was dried until the liquid evaporated on its own. When it is completely dry the crude acetanilide was weighed and recorded. 20 ml of recrystallizing solvent was poured in the crude acetanilide and then placed in a hot plate until the solids were completely dissolved. The solution was colored thus the solution was removed from the hot plate and activated charcoal was added to the solution for the removal of impurities. After the addition of activated charcoal the solution was again heated. While it was still hot, the solution was poured to a fluted filter paper. The filter paper was pressed for the crystals inside to dry. When the crystals were completely dry, the pure acetanilide was weighed. The pure acetanilide was triturated to a fine powder and a centimeter of fine powder was placed into a capillary tube. Then, the capillary tube was placed in the oil bath and the melting point was determined. Results and Discussion The first step in recrystallization was determining the recrystalizing solvent. In the experiment three solvents were used namely hexane, 95% Ethanol and water.

Table 1: Testing for the Suitable Solvent At Room Temperature Insoluble Soluble Insoluble During Heating Soluble Soluble Upon Cooling Insoluble Soluble

Water 95% Ethanol Hexane

Insoluble Insoluble

Their results were compared. In the comparison water produced the ideal characteristics of a recrystallizing solvent which is to have a high solubility in hot solvent and a low solubility in cold solvent. Water in the experiment was insoluble in room temperature, soluble during heating and insoluble in cooling. Weight of Crude Acetanilide: 1.7 grams The reaction of aniline with acetic anhydride produced acetanilide which was crystals with some impurities. To hasten crystallization, the mixture was placed in an ice bath which could easily decrease the solubility of acetanilide. The crystals were filtered in wetted filter paper and collected. These crystals were the crude acetanilide and the residue was dried overnight until it was completely dry. The residue contained the crude acetanilide which 1.7g. Weight of Pure Acetanilide: 1.3 grams The collected crude acetanilide crystals had some small amount of impurities which could affect the weight of pure acetanilide so recrystallization should be done. Water, the recrystallizing agent, was poured into the crude acetanilide crystals until the solids were dissolved completely. The solution was placed again in a hot water bath. While the solution was in the water bath it became colored. This

was an effect of impurities. These impurities were removed by putting small amounts of activated charcoal which is a highly absorbent carbon. This was because of its property of having large surface area for absorption. Small amounts of activated charcoal should only be added because too much of it would absorb the desired substance too. The solution was again heated and while it was still hot, it was poured in a fluted filter paper. A fluted filter paper was used to increase the surface area of the filter allowing faster and more efficient filtration. The crystals were collected and dried. After the crystals dried completely, they were weighed and the weight of the pure acetanilide was 1.3 grams. To calculate the percentage yield, the theoretical yield must first be solved. The theoretical yield is the maximum yield of pure crystals that could be obtained by cooling or evaporating a given solution. On the other hand, limiting reagent is the reactant that is used up first in a reaction. The solution below would indicate the limiting reagent and the theoretical yield of the crude acetanilide and the pure acetanilide.

C6H5NH2 + (CH3CO2)O ---> C6H5-NH-COCH3 + CH3-COOH

Aniline in grams: 2ml C6H5NH2 x 1.0217 = 2.0434 g 1 ml Acetic anhydride in grams: 3 ml (CH3CO2)O x 1.082 1 ml = 3.2460 g

Identifying the limiting reagent:

2 mL of C6H5NH2 x 1.0217 g x 1 mole x 102.09 g 1mL 93.13 g 1 mole

Book: Bayquen, A., Cruz, C., de Guia, R. (2009). Laboratory Manual in Organic Chemistry. Quezon City: C&E Publishing, Inc. Websites: [1]http://firstyear.chem.usyd.edu.au/prelab/e 24.shtml [2]http://encyclopedia2.thefreedictionary.co m/solubility [3]http://www.chem.umass.edu/people/sam al/269/cryst1.pdf [4]http://www.reference.com/browse/aniline

= 2.24 g (CH3CO2)O
3 mL of (CH3CO2)O x 1.082 g x 1 mole x 93.13g 1 ml 102.09 g 1 mole

= 2.96 g C6H5NH2

Therefore the limiting reagent is aniline.

Calculating for the Percentage Yield: Actual yield = weight of pure acetanilide in the actual experiment Theoretical yield = mass of limiting reagent % Yield = Actual Yield x 100 Theoretical Yield 1.3 g 2.24 g x 100

[5]http://english.turkcebilgi.com/Acetic+anhy dride [6]http://chemicalland21.com/lifescience/pha r/ACETANILIDE.htm

% Yield =

% Yield = 58%

In conclusion, the process of recrystallization has a direct relationship with the purity of a substance. The more it undergoes the process of recrystallization, the purer the substance gets but the amount of the substance decreases. Due to the dissolution of some crystals during heating and incomplete recrystallization in the ice bath, some of the pure acetanilide were not retrieved. References