RECRYSTALLIZATION OF ACETANILIDE

Maricar Suizo, Arienne Joyce Sumague, Renz Carlo Supelana, Ivy Kristine Tan, Ana Patricia Tinio, & Marie Angelique Camille Villa

Group 8, 2E Pharmacy, Faculty of Pharmacy, University of Santo Tomas

ABSTRACT Recrystallizing of substances is important in the separation of impurities of a compound. It is also based on the principle of solubility that compounds tend to be more soluble in hot liquids than cold liquids. The objective of this experiment is to separate the pure acetanilide from its impurities and calculate the percent yield. This experiment starts with a test for the best recrystallizing solvent was performed in the following: water, methanol, and hexane. In three test tubes, pinch amount of acetanilide is placed with the solvents and it was placed in a water bath and next placed in an ice bath for it to cool. Crude Acetanilide was obtained by mixing aniline and distilled water with acetic anhydride and when it was cooled there are formation of crystals. Crude acetanilide is obtained by when the mixture was filtered and dried. The recrystallizing solvent is placed with the crude acetanilide and is placed in a water batch until it dissolves. Activated charcoal was added to remove the colored impurities. While it is hot, it is directly filtered in a fluted filter paper and then washed with distilled water. As the compound crystallizes, the pure acetanilide is obtained. The percent yield of acetanilide was 18.51%.

INTRODUCTION When substances are synthesized in the laboratory, it goes with impurities. Thus, the proponents must separate the impurity from the pure substance so that the analysis of the product is the most ideal. Recrystallization is one of the common laboratory techniques to purify the substance from its impurities. It is also known with two crystallization process and it depends on the difference of solubility in two solvents with different temperature. When an impure product is contaminated by a solid with different solubility characteristics, a solvent is chosen which will dissolve the desired compound but will not dissolve the impurity (Wigal, C. T. 2008.).

Solubility is defined in quantitative terms as the concentration of the solute in a saturated solution at a certain temperature and in qualitative terms, it may be defined as the spontaneous interaction of two or more substances to form a homogeneous molecular dispersion. (Sikarra, D. 2012.) It is one important factor that affects recrystallization which is very evident in choosing a recrystallizing solvent. The recrystallizing solvent must have an ideal behavior when it is added to crude acetanilide and it must be insoluble in room temperature; soluble in boiling temperature; lastly, insoluble in cool temperature. Thus, with the best recrystallizing solvent, the product will yield the pure crystals of the substance.

Aniline is a yellowish to brownish oily liquid with a musty fishy odor. Melting point -6C; boiling point 184C; flash point 158F. Denser than water (8.5 lb / gal) and slightly soluble in water. Its vapors are heavier than air. (6)

Figure 1.3 Structure formula of Acetanilide

Figure 1.1 Structure formula of Aniline Acetic anhydride is a clear colorless liquid with a strong odor of vinegar. It has a flash point 129F and is corrosive to metals and tissue. Its density is 9.0 lb /gal and is used to make fibers, plastics, pharmaceuticals, dyes, and explosives. The boiling point if acetic anhydride 10C and 140C and the melting point is 73C. It is an important solvent and acetylation agent. It is used for the manufacture of acetylcellulose, acetylsalicylic acid, acetanilide, nitrofurane, sulfonamides, vitamin B6. (4) Figure 1.4 Synthesis of Acetanilide The objectives of this experiment is to separate the pure acetanilide from its impurities through recrystallization. In addition, the determination of best recrystallization solvent is first done. Lastly, the percentage yield of the pure acetanilide is also considered. MATERIALS AND METHODS

Materials
The materials used are Erlenmeyer flask, test tubes, hot plate, beaker, fluted filter paper, stirring rod, glass funnel, aniline, hexane, acetic anhydride, activated charcoal, methanol and distilled water.

Figure 1.2 Structure structure of Acetic anhydride Acetanilide is an odorless, white flake solid or crystalline powder (pure form); soluble in hot water alcohol, ether, chloroform, acetone, glycerol, and benzene; melting point 114 C and boiling point 304 C; can undergo self-ignite at 545 C, but is otherwise stable under most conditions. Acetanilide which can be obtained by acetylation of aniline undergoes nitration at low temperature and yields highly the paranitro products. (5)

Methods
A. Recrystallization Solvent Determination In three test tubes, pinch amount of acetanilide is placed with the solvents, (water, hexane and methanol) and it was placed in a water bath and next placed in an ice bath for it to cool. Observe and record results. B. Production of Acetanilide Mix two milliliters of aniline and 10 milliliters of distilled water in an

Erlenmeyer flask. Slowly add three milliliters of acetic anhydride. Note for any changes. Cool in an ice bath to hasten crystallization. Filter through a wet fluted filter paper. Dry and weigh the crude acetanilide. C. Recrystallization Process Pour 20 milliliters of the recrystallizing solvent into the crude acetanilide. Heat in a water bath until all the solid dissolves. If the solution is colored, add activated charcoal. Quickly filter the solution while still hot using a fluted filter paper. Allow the filtrate to cool by placing the receiver in a beaker with water. Collect crystals. Wash with distilled water. RESULTS AND DISCUSSION A recrystallizing solvent is a solvent with the ideal solubility behavior in a given temperature. In choosing the recrystallizing solvent, the substance must be insoluble in room temperature, soluble when heated and insoluble as it is cooled. The heat capacity of the solvent must not be beyond the melting point of the substance to be crystallized. If the boiling point of the solvent is so high, the solid may melt rather than dissolve it. In addition to the boiling point, the volatility of the solvent must be considered. It must be volatile enough to be easily taken off during crystallization. Volatile solvents having low boiling point is preferable. (Pavia, D.L. 1999) Another factor is the reactivity must be low, the solvent must not react with the compound to be purified and thus, it may have contaminants.

Table 3.1 Solubility of acetanilide in different solvents At room temp. Slightly soluble Soluble Insoluble During heating Soluble Soluble Insoluble Upon cooling Insoluble Soluble Insoluble

Water Methanol Hexane

Table 3.1 shows the solubility of acetanilide in different solvents with different temperatures. The solvents used are methanol, water, and hexane. The acetanilide was slightly soluble in water at room temperature, and became soluble when it was heated and turned into insoluble when it was cooled. On the other hand, methanol gave a soluble result with acetanilide in all different temperatures. Lastly, hexane with acetanilide was insoluble in all different temperatures. Among all the solvents used, water gave the most ideal solubility for the recrystallization. Activated charcoal is added to colored acetanilide while it is heated. It is added to remove the colored impurities and it has a surface area that adsorbs dissolved organic substances. Filtration is a laboratory process used to separate the solid contaminants from the liquid filtrate. In the experiment, the group used a fluted filtrate paper to separate the pure acetanilide from the contaminants while it is hot. Using a fluted filter paper increases surface area inside the funnel and speeds the filtering process. (7) In the experiment, the activated charcoal was used

because of the orange color of the acetanilide. Melting point is the temperature at which the solid and liquid phase or forms of a substance exist in equilibrium. Oil bath was used instead of water bath because the boiling point of oil is > 100C and it is not evaporated easily. Table 3.2 Weight of Acetanilide Crude Acetanilide Pure Acetanilide 3.44 g 0.5g

Acetic Anhydride (in moles):

Percentage Yield:

In table 3.2, it was evident that before the recrystallization the crude acetanilide is 3.44 g and after it has undergone recrystallization it became 0.5 g. The percentage yield is the proportion of actual yield over the theoretical yield of the experiment. The amount of limiting reagent present at the start of a reaction determines the theoretical yield or the maximum obtainable yield. The actual yield, or the amount of product actually obtained from the reaction, is almost always less than the theoretical yield. Chemical equation for acetanilide:

The limiting reagent is 0.02mol of Aniline while the theoretical weight is 2.70g of acetanilide. Thus, 18.51% is the percentage yield of acetanilide. REFERENCE
1. Pavia, D. L., Lampman, G. M., Kriz,G. S., & Engel, R. G. (1999).Organic Laboratory Techniques: A Microscale Approarch (3rd Ed.).Harcourt College Publisher. Pg. 558-576 2. Sikarra, D. et al.(2012). Techniques for Solubility Enhancement of Poorly Soluble Drugs: An Overview. Journal of Medical Pharmaceutical and Allied Sciences. 01; 1-22 3. Wigal, C. T.(2008). Signature Labs Series: Chemistry Lab Experiments CHEM 226; Cengage Learning: Mason, OH, 2008; p 29-36 4. Acetic Anhydride (Chemical Compound), Retrieved August 2,2013,from http://www.chemicalbook.com/ChemicalProductPrope rty_EN_CB2852742.htm 5. Acetanilide (Chemical Compound), Retrieved August 2,2013,from

C6H5NH2 + (CH3CO)2O C6H5NHCOCH3 + CH3COOH Calculations

Limiting Reagent: Aniline (in moles):

=>

http://www.chemicalland21.com/lifescience/phar/ACE TANILIDE.htm 6. Aniline (Chemical Compound),Retrieved August 2,2013,from http://www.chemicalbook.com/ChemicalProductPrope rty_EN_CB7169544.htm 7. Recrystallization , Retrieved August 2 ,2013,from http://pages.towson.edu/jdiscord/www/331_lablecture s/reclablec.pdf