Synthesis and Analysis of Organic and Inorganic Compounds (CM3102)

2017 Spring

Week 2-3: Purification of Organic Compounds

Part 1. Acid-Base Extraction, Recrystallization, & Fractional Distillation
Objectives:
1. To be able to predict the partition of a chemical mixture between organic and aqueous phases.
2. To observe the effectiveness of properly performed recrystallization.
3. To understand the advantage of fractional distillation over simple distillation.

Reference:
C. Amsterdamsky J. Chem. Educ. 1998, 75, 219220.
The experiment described in this paper consists of three purification techniques. On the first week, acid-
base extraction and recrystallization will be practiced in the laboratory. Then, simple and fractional
distillations will be performed on the second week.

Flow Chart for separation of the three-component mixture

* 3,5-Dinitrosalicylic acid will be used instead of picric acid which is explosive.

 Synthesis and Analysis of Organic and Inorganic Compounds (CM3102)
2017 Spring

Experimental Procedure:
Preparation of a bulk solution by TAs
1. A mixture of 2,2,4-trimethylpentane (isooctane, 1 L), methoxybenzene (anisole, 1 L), benzoic
acid (100 g), and 3,5-dinitrosalicylic acid (0.36 g) is prepared. 50 mL of the solution will be given to
each student. 3,5-Dinitrosalicylic acid is added as a pale yellow impurity that can indicate the
effectiveness of the recrystallization process.

Week 2: Extraction and Recrystallization of Benzoic Acid

1. The three-component mixture (50 mL) and a 10% aqueous solution of Na 2CO3 (25 mL) are placed in
a 250 mL separatory funnel. The biphasic mixture is shaken and the aqueous layer is collected in an
Erlenmeyer flask. To the remaining organic layer, a 10% aqueous solution of Na2CO3 (25 mL) is added.
The biphasic mixture is shaken and the aqueous layer is collected in the same Erlenmeyer flask.
While the biphasic mixture is shaken in a closed separatory funnel, a positive pressure can be
developed and result in an explosion. It is important to vent the separatory funnel carefully.

2. The combined aqueous layers are acidified by concentrated hydrochloric acid until the pH of the
solution reaches 1. The yellow precipitate is filtered through a filter paper using a Bchner funnel and
washed with cold water.
The pH can be checked by a standard pH paper. The vacuum(or suction) filtration should be done
properly in order to avoid the loss of solid material. A small amount of 3,5-dinitrosalicylic acid is
responsible for the yellow color.

3. The yellow solid is dissolved in a minimal amount of boiling water and the hot solution is slowly cooled
down to room temperature. The resulting white crystals are vacuum-filtered and air-dried.
The purity of the recrystallized benzoic acid can be assessed by the lack of yellow color and the melting
point(122 C).

Week 3: Separation of two-component mixture by Fractional Distillation

1. The organic layer remaining in the separatory funnel is transferred to an Erlenmeyer flask and dried
over anhydrous CaCl2. The drying agent is removed by filtration through a filter paper or a glass frit.
Anhydrous MgSO4, Na2SO4, or K2CO3 can also be employed as a drying agent. The filtrate must be
collected in a round-bottom flask, which serves as a distillation flask later.

2. The distillation flask is equipped with a simple distillation apparatus and the filtrate is roughly purified
by distillation. One fraction (A) with the head temperature below 75 C and another fraction (B) with the
head temperature above 75 C are collected.
 Synthesis and Analysis of Organic and Inorganic Compounds (CM3102)
2017 Spring

A simple distillation apparatus consists of a distillation head, a thermometer, and a receiver unit. Boiling
chips may be added in order to prevent bumping. The head temperature profile should be recorded.

* The water contents analysis can be included before/after filtration and distillation.

3. The flask containing A is equipped with a fractional distillation apparatus and A is carefully redistilled.
The forerun below 65 C and the main fraction between 65 C and 75 C are collected.
A fractional distillation apparatus includes a Vigreux column in addition to a simple distillation apparatus.

4. B is also carefully purified by fractional distillation. The forerun below 105 C and the main fraction
between 105 C and 115 C are collected.

5. The purity of each fraction is analyzed by gas chromatography.

Safety Considerations:
Volatile organic liquids are typically very flammable and should be covered as much as possible. No
laboratory chemicals should be handled without laboratory gloves. Safety goggles and a laboratory coat
should be worn at all time. All the processes should be carried out in a well-ventilated fume hood with
the sash pulled down as low as possible. Boiling water and any hot solutions should be handled with
care because bumping can cause injury and burns.

Before you come to the lab

1. Be aware of the chemical and physical properties of compounds in this experiment.

2. Read the MSDS (material safety data sheet) of all the chemicals used in this experiment.

Pre-Lab Question