CHEM 210

Recrystallization
 Experiment 2: Recrystallization
Lecture Outline

1. Purpose of the Experiment

2. Theory of Recrystallization
3. Selection of a Solvent
4. Characteristics of an Ideal Recrystallization Solvent
5. Mixed Solvent Recrystallization
6. General Procedure
7. Experimental Procedure
 Overview
Recrystallization is a technique used for purification of
solid organic compounds

Steps:
• Select the proper solvent.
• Dissolve the impure solid in the minimum amount of hot
solvent.
• Filter the solution while hot (decolorize if needed).
• Cool slowly.
• Collect and wash the crystals by suction filtration.
 Purpose

1. To determine the solubility of 3 organic compounds in 3

different solvents and select the best crystallizing solvent

2. To learn the technique of recrystallization for the

purification of organic compounds.

3. To use recrystallization to purify a crude sample of

acetanilide

4. To calculate the percent recovery of pure acetanilide

5. To decolorize a sample of brown sugar using charcoal.

 Theory

➢ Recrystallization is a method of purification.

➢ It involves the physical separation of contaminants

from a sample to produce the desired pure compound.

Add a solvent

Product = mixture of pure and impurities Pure Product Impurities

➢ When crystals form during a reaction or following an
extraction, impurities may become trapped within the
crystal lattice or upon the surface of the solid.

➢ Washing the crystals with cold solvent can remove

adsorbed impurities from the surface, but this process
cannot remove the trapped (occluded) impurities.

➢ To remove these impurities, recrystallize the solid

▪ redissolve the solid in hot solvent,
▪ filter off any insoluble impurities,
▪ and then cool the solution to let the material crystallize
again.
➢ In recrystallization a saturated solution is formed by carefully
adding an amount of hot solvent just necessary to dissolve a
given amount of solid.

➢ As the solution cools after its filtration, the solubility of the

solid decreases and the solid crystallizes.

➢ Unavoidably some of the solid remains dissolved in the cold

solvent so that not all the crystals dissolved originally are
recovered.
Recrystallization depends on:

➢ The differential solubility of a substance in cold and hot

solvent.
Most organic solids are more soluble in hot than in a
comparable volume of cold solvents.

➢ The selective solubility of desired substance and

impurities.
The solid and impurities should ideally have different
solubilities.
 Selection of Solvent
➢ Selection of a proper solvent is the first and most important step, it
is crucial for the successful recrystallization of an organic solid.
➢ The success of the process depends on the fact that soluble
impurities usually are present in smaller amounts than the desired
compound so that they will remain in the cooled solution
➢ The solvent (or mixed solvent) should have a steep solubility vs.
temperature curve for the solute

B
Solubility

Temperature

➢ The “C” curve is a good solvent; Solute is very soluble at elevated

temperature and significantly insoluble at low temperature
➢ Test the solvent on a small amount of the compound
• It should not dissolve the crystals at room temperature.
• It should dissolve the crystals when hot.

➢ It is an experimental trial based on:

“Like dissolves like”

Polar compounds will dissolve in polar solvents, but

not in nonpolar solvents

Nonpolar compounds will dissolve in nonpolar

solvents, but not in polar solvents
Classes of compounds
• Ionic
• Associated , H-bonds (O-H, N-H)
• Polar organic compounds
• Hydrocarbons (nonpolar)

Classes of Organic Solvents

Alcohols Most polar

Ketones
Esters
Halogenated Alkanes
Ethers
Aromatic Compounds
Alkanes Least polar
➢ Hydrocarbons and their halogen derivatives are insoluble
in water.

➢ Compounds that contain the functional groups:

OH (alcohol),
COH (aldehyde),
RCOR’ (ketone),
COOH(carboxylic acid),
CONH2 (amide)
and can form hydrogen bonding with water are soluble
in water when the ratio of the total number of carbon atoms
to these functional groups is not more than 5.
Otherwise, the solubility decreases rapidly.
 Common Recrystallization Solvents
Boling pt. °C Freezing pt. °C Miscibility with Fire
water hazard
Solvent Formula

Petroleum ether Mixture of C5H12 and 35-65 <0 – ++++

C6H14

Ether (C2H5)2O 34.6 -116 – ++++

Acetone (CH3)2CO 56.1 -95 + +++

Ligroin CnH2n+1 60-80 <0 – ++++

Chloroform CHCl3 61.3 <0 – 0

Methyl alcohol CH3OH 64.7 -98 + ++

Carbon tetrachloride CCl4 76.7 <0 – 0

Ethyl acetate CH3COOCH2CH3 77.2 -84 – ++

95% Ethyl alcohol C2H5OH 78.1 -116 + ++

Benzene C6H6 80.2 5.5 – ++++

Acetic acid CH3COOH 118.1 16.6 + +

Dimethyl formamide (CH3)2NCOH 153.0 -61 + +

Nitrobenzene C6H5NO2 210.9 5.7 – +

 Characteristics of an Ideal Recrystallization Solvent
1. Should dissolve all the compound at the boiling point of the
solvent
2. Dissolve very little or none of the compound at room
temperature
3. Have different solubilities for the compound and the impurities;
completely dissolve impurities in cold or not at all.
4. Inert towards the substance to be crystallized; should not react
chemically with it
5. Relatively low boiling (60-100oC) so that the solvent that
adheres to the crystals can be easily removed
6. Have a boiling point below the melting point of the
compound so that the compound actually dissolves , not melts
in the hot solvent
7. Upon cooling should give well defined crystals
8. Should be nonflammable, nontoxic, and relatively inexpensive.
 Mixed Solvent Recrystallization
Solvent Pair
Sometimes it happens that no solvent is found that will dissolve the
compound when hot and not when cold, in this case a solvent pair is
used.
➢ A solvent-pair consists of two miscible solvents, one in which the
compound is soluble and the other in which the compound is
insoluble.
➢ Example ethanol-water means the compound is soluble in ethanol
but insoluble in water

In a mixed solvent (S1 + S2) recrystallization

▪ The solid A is dissolved in minimum amount of boiled S1 (high
solubility), and then small amount of hot S2 (low solubility) is added
till the solution becomes turbid.
▪ If more S2 is added, crystallization starts to form.
▪ The turbidity is cleared by adding just enough amount of hot S1 till the
solution becomes clear.
▪ Then the solution is put aside till it cools down and the crystals start
forming.
 General Procedure
1. Preparation of the hot solution

Dissolve the substance in the minimum amount of boiling

solvent;
➢ add minimum amount of solvent and heat until all dissolves
➢ add a little extra solvent to compensate for evaporation of
the solvent while heating.

2. Removal of colored impurities

Add activated charcoal, charcoal removes colored impurities

by adsorption,
➢ if too much charcoal is used the compound will get
adsorbed as well and will result in loss of yield.
3. Gravity filtration of the hot solution
➢ should be done as fast as possible
➢ use a preheated short stem funnel
➢ use a fluted filter paper

Gravity filtration is used when the desired substance is in solution.

The solid (such as decolorizing charcoal or other insoluble
impurities) is collected on the filter paper and discarded. The
filtrate is collected for further use.

Short stem funnel

Flutted filter paper

4. Cooling of the hot solution ( Cool at a moderate to slow
rate)
The rate at which crystals form affect their purity.
Goal: to obtain the maximum amount of crystals with
minimum amount of impurities.
➢ Rapid cooling results in the formation of very small crystals
that adsorb impurities on their surface.
➢ Slow cooling results in the formation of large crystals in
which solution and impurities can get trapped or occluded
within the crystal lattice.
If no crystals appear (supercooling)
- Scratch the sides of the flask with a stirring rod
- Add a seed crystal (seeding).
Note: if crystals still do not appear evaporate part of the solvent
and cool again (too much solvent has been used in step 1).
5. Collection of crystals by suction filtration
➢ The solid is collected on the filter paper
➢ The filtrate is a saturated solution of the organic compound in
the solvent it is called the “mother liquor”

Suction filtration is used when the desired compound is the

solid, and it is necessary to isolate it as a dry solid.

Buchner funnel

To Vaccum

Suction flask
6. Drying of crystals.
The crystals are air dried or in the oven at a suitable
temperature.
7. Weighing of the dry solid and calculation of percent recovery.

mass of pure crystals

Percent recovery =  100
mass of impure crystals

Note: low percent recovery may be due to

➢ Using the wrong solvent
➢ Using too much solvent
➢ Incomplete crystallization (not enough time or low
temperature)
➢ Inefficient filtration technique.
 Experimental Procedure
Part A: Selection of a crystallization solvent.
1. Determine the solubility of anthracene C14H10, benzoic acid
C6H5COOH and sodium benzoate C6H5COONa in water H2O,
toluene C6H5CH3 and ligroin (mixture of hydrocarbons)
2. Based on your results select the best solvent

Compound Water Toluene Ligroin Best

Solvent
Cold Hot Cold Hot Cold Hot

Anthracene
Benzoic acid
Sodium
benzoate
Part B: Recrystallization of Acetanilide

1. Recrystallize 1 g of crude acetanilide using water as the

crystallization solvent.
2. Calculate the percentage recovery of the product.

Part C: Decolorization of brown sugar

Use charcoal to remove the colored impurities form a

sample of brown sugar.