Online edition for students of organic chemistry lab courses at the University of Colorado, Boulder, Dept of Chem and

Biochem. (2006)

u Experiment 1 Purication of Crude para-Anisic Acid Crystallization:

Techniques: Crystallization, Melting Point Determination (read the sections on these techniques in the Handbook for Organic Chemistry Lab). Suggested Viewing: Crystallization, available for check-out from the Stockroom.

Crystallization is the primary technique for the purication of compounds that are solids at room temperature. In the process of crystallization, molecules are deposited from a saturated solution and are selected, according to their shapes, to t into growing crystal lattices. The technique can be carried out by dissolving a compound to be puried in a hot solvent (or solvent mixture) and then allowing the solution to cool. If the solvent or solvent mixture is properly chosen, the compound has a decreased solubility at lower temperatures, and it will form crystals in the solution. The purity of a solid, and therefore the success of or need for a crystallization procedure, is determined by taking a melting point. The melting point of a solid is dened as the temperature at which a solid and its liquid are at equilibrium. Practically, this temperature isn't observed as a point but rather as a range with the lower temperature of the range noted when the rst bit of liquid is seen and the higher temperature when the sample is entirely a liquid. As described in the Handbook, a melting point range of 2.0C or less indicates that a substance is pure enough for most laboratory purposes. Since the melting point is a physical property of a compound, the melting point of a pure compound is useful in its identication. You will use crystallization to purify p-anisic acid:
H3CO CO2H p-anisic acid

1 Crystallization: Purication of Crude para-Anisic Acid

Online edition for students of organic chemistry lab courses at the University of Colorado, Boulder, Dept of Chem and Biochem. (2006)

Summary of the Steps in a Crystallization

Step 1 Dissolve impure solid in minimum amount of hot solvent. If the solution is not highly colored, and doesnt contain insoluble impurities, go to step 4. If the solution is highly colored, go to step 2. If the solution has insoluble impurities, go to step 3.

Step 2 Treat with decolorizing charcoal, then go to step 3. Step 3 Decant or gravity lter the hot solution, then go to step 4. Step 4 Allow to cool slowly, then go to step 5. Step 5 Chill on ice, then vacuum lter to isolate the crystals.

Safety Precautions Ethanol is ammable; it is also toxic if ingested. Avoid breathing ethanol vapors by carrying out all experimental operations in your student hood. Procedure Section
(1) Dissolve the Compound

Heat about 20 mL of ethanol in a small ask on a steam bath. (Have a boiling chip in the ask to ensure even boiling.) Obtain about 0.20 g of p-anisic acid from the crude p-anisic acid jar in your lab. Weigh it and record the weight to the nearest hundredth of a gram. Sometime during the lab period, determine the melting point of a sample of crude p-anisic acid. Place your weighed, crude p-anisic acid in a 25 mL Erlenmeyer ask, add a boiling chip and 5 mL of the hot ethanol. Swirl the contents of the ask and heat the solvent-solid mixture to the boiling point using the steam bath. Intermittently add small portions of hot ethanol (about 1 mL), swirl, and heat to boiling until all soluble material has dissolved. You may need to use a glass rod to break up any chunks of undissolved material.
(2) Remove Any Colored Impurities

Remove the solution from the steam bath. Your solution of p-anisic acid will probably be colored. The color, in this case, is due to an impurity which you must remove. Therefore, add about 0.10 g of pelletized Norite to the solution. Swirl and heat the

1 Crystallization: Purication of Crude para-Anisic Acid

Online edition for students of organic chemistry lab courses at the University of Colorado, Boulder, Dept of Chem and Biochem. (2006)

mixture for up to 5 min, or until the color disappears. If the solution is still colored after 5 min, add a little more Norite and repeat the process.
(3) Remove Any Insoluble Impurities

The Norite can now be considered an insoluble impurity and must be removed from the solution of dissolved p-anisic acid by transferring the liquid to another ask. This can be accomplished by one of three methods: 1 Carefully decant the clear liquid to a clean ask. 2 Transfer the clear liquid with a Pasteur pipet. 3 Hot lter the solution through uted lter paper

Method 1 decant the clear liquid from the flask with the help of a glass stir rod to hold Norite pellets

Method 2 place the pipet at the bottom of the flask and transfer the clear liquid

Whichever method you choose, keep the solution warm during the process by placing the receiving ask on your steam bath.
(4) Crystallization

Remove the Erlenmeyer ask from the steam bath and allow the solution to cool, undisturbed, at room temperature. You will probably see crystals growing in the solution after several minutes. After 15 min, cool the ask in an ice bath (whether or not crystal growth is apparent). Place your Erlenmeyer used to heat ethanol in an ice bath to chill the solvent for use in the next step.
(5) Vacuum Filtration

Isolate the crystals by vacuum ltration. Use chilled ethanol to wash the crystals. Allow the aspirator to suck air through the crystals for ve min Transfer the crystals to a tared (pre-weighed) watch glass and allow to air dry for several minutes. Usually the lter paper can be lifted from the funnel with a spatula and then the crystals can be peeled from the paper in a single mass. Determine the weight of your puried p-anisic acid.

1 Crystallization: Purication of Crude para-Anisic Acid

Online edition for students of organic chemistry lab courses at the University of Colorado, Boulder, Dept of Chem and Biochem. (2006)

Determination of Melting Point Determine the melting point of your puried p-anisic acid using either a FisherJohns hot stage or a Mel-Temp capillary melting point apparatus; directions are given in the Handbook for Organic Chemistry Lab. Wastes Ethanol Recovery Bottle: Place all your ethanol ltrates in the Ethanol Recovery Bottle in the main hood. Do not place any water or solid p-anisic acid in this bottle, as this ethanol will be recycled for use in future labs. Recovery Jar: Place your puried p-anisic acid in the Recrystallized p-Anisic acid jar in the main hood. Any left-over crude p-anisic acid should be placed back into the crude p-anisic acid jar. Dry Waste: All wet lter papers should be placed in the plastic container in the main hood. Do not leave any p-anisic acid on the wet lter paper! (Norite is okay.) Study Questions 1) A student crystallizes 5 g of a solid and isolates 3.5 g as the rst crop. He/she then isolates a second crop of 1.2 g solid from the ltrate. a) What is the percent recovery in the rst crop? b) What is the total percent recovery? 2) The solubility of acetanilide in hot and in cold water is given in the table below. What is the maximum percent recovery if 5.0 g of acetanilide is recrystallized from 100 mL of water?
solubility in 100 mL of water 5.5 g 0.53 g temperature 100C 0C

3) What effect would each of the following operations have on the success of the crystallization of p-anisic acid from ethanol? Explain your answers. a) After Norite treatment, the hot solution containing the dissolved p-anisic acid is immediately placed in an ice bath. b) After crystallization has taken place, the cold solution is vacuum ltered and product crystals are collected on a Bchner funnel, then the crystals are washed with hot ethanol. c) After isolation of the p-anisic acid crystals on a Bchner funnel, they are washed with cold diethyl ether. 4) The CRC lists the melting point for a compound as 182-183C. You observe a melting point for this same compound isolated in your experiment as 177181C.What can you conclude about the compound isolated in your experiment?

1 Crystallization: Purication of Crude para-Anisic Acid