CHM222 Laboratory Sheet: Recrystallization

Recrystallization

Learning Objectives

In this laboratory exercise, you will learn how to purify a solid organic compound, benzoic acid
from a mixture using the technique of recrystallization. You will perform a hot gravity filtration to
remove impurities and you will assess the purity of the recrystallized benzoic acid from melting
point determination data and thin layer chromatography analysis.

Background

When an organic reaction is performed that produces a solid product, the final product often
includes many impurities that simply crystallize (become a solid) along with the desired solid
product. The solid product which includes the impurities is called the crude product. The crude
product can be purified using recrystallization. Recrystallization is widely used purification
technique for solids. The procedure involves dissolving the crude product in a hot solvent and
then obtaining the solid again via crystallization when the solvent is cooled. When the solvent
cools, the impurities stay in the filtrate (liquid) and the precipitate that crystallizes is collected by
vacuum filtration. The trick is to find a solvent or solvent pair (e.g. water-ethanol) which dissolves
your solid when the solvent is hot but crystallizes (precipitates out) when the solvent is cooled.
Often, the process requires trial and error to determine the best solvent or solvent pair. The most
crucial aspect of a recrystallization is the choice of the solvent, because the solid should have
maximum solubility in the hot solvent and the minimum solubility when the solvent is cold. In some
cases, insoluble impurities are present. Do not add more than the volume necessary to dissolve
most of the compound. Insoluble impurities are removed by filtering the hot solution using gravity
filtration.

Safety and Waste Disposal

Wear safety goggles at all times. Perform TLC and recrystallization inside the hood. Cover the
containers when transporting reagents from one hood to another. Dichloromethane is a
carcinogen avoid breathing its vapors by dispensing and handling inside the hood. Dispose of any
excess dichloromethane or solvent mixture containing dichloromethane in the “Halogenated”
waste bottle located in the back bench by the window. Dispose of used Pasteur glass pipets,
“spotting” capillary tubes, and capillary melting point tubes in the red or white buckets labeled

1|Page
CHM222 Laboratory Sheet: Recrystallization

“Broken Glass”. The TLC plates can be thrown in the garbage can after use. Place all solid waste
in the appropriately labelled waste container.

Before Coming to Lab

• The reference material for this lab is found in Organic Chemistry Laboratory Techniques
by Nichols, pages pp. 140 – 144 (Figure 3.10), and pages 167, 176, 180, and 182.

• Physical Data: For this lab you will need the chemical structure, molar mass, and melting
point of benzoic acid. Also, include the boiling points of ethanol and water.

• Include prelab questions.

• Use a flow diagram for the procedure.

Prelab Questions

1. What is crystallization used for in organic chemistry (there are two reasons)?
2. What type of impurities are in the mixture you are working with today?
3. What is the impure product called?
4. What is the most crucial aspect of this technique?
5. What technique is used to remove the insoluble impurity?
6. Why is cooling slowly important?
7. Why is a minimum amount of solvent needed?
8. Why is “scratching” necessary?
9. What is done if crystallization does not take place after cooling?
10. Why does a compound “oil out”?

Procedure

1. In the hood, set a hot plate and with a 250 mL beaker half-filled with water and boil gently
(water bath for the test tubes).

2. Label three medium size test tube: 1) deionized water, 2) 50% ethanol in deionized water, and
3) 95% ethanol in deionized water (This step will test for the best solvent or solvent pair to
use in step 10. Do not use tape or a marker. Use a wax pencil to label the tubes.

3. Add the tip of a spatula full of impure benzoic acid to each of the test tubes (try to keep the
amount the same in each test tube). To each test tube add the corresponding solvent or
solvent pair. For example, test tube #1 has deionized water.

Note: Depending on the size of the spatula and the amount of sample added, you might

2|Page
CHM222 Laboratory Sheet: Recrystallization

have to add another 1 mL after you place them in the boiling water to get most of the
sample dissolved (some impurities will not dissolve in hot solvent).

4. Place the test tubes in the boiling water and as soon as most the impure benzoic acid sample
dissolves (Background: recall there is an insoluble impurity) remove the test tubes from the
water bath. Note which solvent or solvent pair dissolves more of the solid sample. Allow
them to cool for a few minutes and then place them on ice. Select the two solvents that visually
give more solid back after placing on ice.

5. Write down detailed observations!!! If a solvent pair dissolves your sample at room
temperature, then this is not the solvent pair to use. If after you place them on ice, you do not
get a fair amount of crystals this is not the solvent to choose.

6. Based on your observations choose the two solvent systems to use in the next step that will
give the purest product after recrystallization.

7. Place about 0.800 – 1.000 gram of the impure benzoic acid into a 50 mL beaker.

8. Plug a stemless funnel with a small piece of cotton and place it on top of a second small
beaker.

9. Add approximately 5 mL of solvent 1 to the beaker with the impure benzoic acid.

10. Heat to a gentle boil until most of the solid dissolve. Recall that there is an insoluble impurity
(sand) that is removed during the hot gravity filtration step. The second impurity is not soluble
in hot water therefore it will not dissolve which is okay because this is how it will be removed
(by filtering it out).

11. Filter the hot solution into a small beaker. Maintain the beakers on the hot plate while doing
filtration and add the volume in small batches to prevent crystals from forming on the cotton
plug. If crystals form, do not worry.

12. Allow the solution containing recrystallized product to cool at room temp for approximately
5 minutes then place on ice.

13. Collect the crystals via vacuum filtration. Use squirt bottle with water to remove any trailing
compound stuck to the wall of the beaker. Allow the crystals to dry under vacuum for 5 min.
Place the crystals in the oven for 15 min to dry completely. If you place them in the oven,
make sure the oven’s temp is below the melting point of benzoic acid. (Water will decrease
your melting point (false positive and you will think it is impure).

14. Repeat steps 7 – 13 using solvent 2.

15. Determine melting point ranges of pure benzoic acid, and the recrystallized products.

3|Page
 CHM222 Laboratory Sheet: Recrystallization

16. Make a 1% solution by weighing out about 0.100 g of sample and dissolve in approximately
10 mL of TLC eluent, 25% ethyl acetate 75% hexanes.

17. Perform TLC analysis for the 1% solutions. Use 25% ethyl acetate 75% hexanes as the eluent
(2.5 mL ethyl acetate and 7.5 mL hexanes). Use the short UV light to visualize the spots. Draw
actual plates with circled spots, indicate half of the spot, all measurements and annotate each
spot.

After the lab is performed, you should have the following: solvent or solvent pair selected for final
recrystallizations, detailed observations, experimental melting ranges/point for recrystallized
products and TLC analyses.
In the conclusion, discuss which solvent pair was the most appropriate for recrystallization,
compare literature and experimental melting points. Of the two solvent or solvent pairs that you
selected which one gave the purest product (based on melting points and TLC). Why do you think
one solvent or pair was better than the other? Do not forget to discuss TLC data (provide Rf
values) and does the data provide additional evidence (or not) for the purity of the recrystallized
samples. For example, if only one spot is observed on TLC but the melting range is consistent
with an impure substance provide explanations for these observations.

References

1. Wilson, B., Recrystallization, Organic Chemistry I Laboratory Manual, 2013, College of

Lake, County; Grayslake, IL.
.
2. Mohrig et al., Techniques in Organic Chemistry, 4th ed.; W.H. Freeman and
Company, 2014, pp.221-235.

4|Page