EXPERIMENT 2

RECRYSTALLIZATION & MELTING POINT DETERMINATION

PURIFICATION OF CRYSTALLINE ORGANIC COMPOUND
Organic compounds usually occur in mixtures with related compounds or are obtained
contaminated with small amounts of other products. It is necessary to study the methods by which
solid and liquid organic compounds are purified. These methods involve fractionation usually by
crystallization, sublimation, distillation and chromatographic methods.

General Principles. When the substance to be purified is a solid it is usually dissolved in a solvent
and precipitated again in a crystalline form. The substance is said to be recrystallized and the
process is one of recrystallization. This process depends on the principle that, in general, the
solubility of a solid in a solvent increase with increase in temperature and decreases with decrease
in temperature. By solubility is meant the amount of solid which will dissolve in a given amount of
solvent to give a saturated solution at a specified temperature.

The procedure involves (1) selection of a suitable solvent for recrystallization; (2) dissolving
the impure sample in a minimum amount of solvent at or near the boiling point to form a nearly
saturated solution. Colored impurities may be removed by adding a little Norit or decolorizing
(activated) carbon; (3) filtering the hot solution to remove any insoluble impurities; (4) allowing
the hot solution to cool to deposit crystals of the desired compound; (5) filtering the crystals from
the solution (called the mother liquor) and washing the crystals with a little cold solvent to remove
the mother liquor, and (6) drying the crystals to remove the last traces of solvent.

The resulting crystalline solid, after drying is tested for purity usually by a melting point
determination. The following experiment illustrates recrystallization of impure acetanilide from a
single solvent, water.

Choice of Solvent. If recrystallization is to be effective, the solvent must be properly

selected. The choice of solvent for recrystallization depends on several factors:
1. The solvent should not react with the substance to be dissolved.
2. It should dissolve an appreciable amount of the substance to be purified when hot and
should crystallize most of the substance when cold.
3. It should not dissolve the impurities readily or it may dissolve these to a small extent only
or it should dissolve the impurities readily but not the desired substance.
4. It should yield well-formed crystals of the desired substance.
5. It should be readily removable from the filtered crystals and therefore its boiling point
should be preferably within 60 100.
6. It should be relatively safe to handle (not poisonous or flammable).

Solvents suitable for recrystallizing a known compound are generally reported in the
chemical literature. The solvent cannot be chosen on the basis of theoretical considerations alone
but must be experimentally determined. If none is reported, or if the substance is a new compound,
several solvents can be tested in the following way. Place about 10 mg (a small spatula tipful) of
the substance to be purified in each of the several 10 x 75 mm test tubes, and add about 0.25 mL of
Ex. 2: Recrystallization: Purification of Crystalline Organic Compound 2
a different solvent, when cold and when heated. Also note whether abundant, well-formed crystals
are produced as the hot solution cools.

If two or more solvents appear to be equally suitable for recrystallization, the final selection
will depend upon such factors as ease of manipulation, flammability and cost.

Notes:
1. If the sample dissolved immediately in 0.25 mL of the solvent or upon slight warming,
the solvent is unsuitable. This however must be made suitable by mixing it with another solvent
where it is miscible. The sample to be purified must be very soluble in one solvent but difficultly
soluble in the other solvent.
2. If the solid does not dissolve even on heating, another 0.25 mL of the solvent is added
and heat is again applied. If the substance does not dissolve when heated, then the solid is regarded
as sparingly soluble in that solvent. Such solvent is not suited for recrystallization.
3. If the solid dissolves in the hot solvent, the test tube is cooled to determine whether
recrystallization occurs. If no crystals appear, this may be due to the absence of nuclei for crystal
growth. The tube should be scratched with a glass rod below the surface of the solution or seeded
with a few crystals. If crystals do not separate even after scratching and cooling in ice, the solvent
is unsuitable. If crystals separate, the amount of these should be noted.

Caution! Since many recrystallization solvents are flammable, do not use Bunsen burners to heat
solutions unless your instructor indicates that you should do so.

Dissolving the Solid. Once a satisfactory solvent has been selected, it is brought to its boiling point
and the solute is dissolved in the minimum amount of boiling solvent. To obtain a good recovery of
purified material, it is best to avoid using unnecessarily large volumes of solvent. This insures that
the solution, when cooled, will return the maximum possible yield of product as crystals and
minimizes the amount of crystals lost by retention in the mother liquors. In practice, 35% more
solvent than the minimum required is used so that the hot solution will not be quite saturated. This
helps to prevent separation of the crystals and clogging of the filter paper during filtration of the hot
solution.

Note: Remember that the procedure requires adding the solvent to the solid. One never
adds the solid to the solvent, since it may then be impossible to tell when the solution is saturated.

Traces of coloring matter or impurities can sometimes be removed with selective adsorbents,
such as finely divided charcoal. The amount used should be approximately 2-3 % of the weight of
the sample. Any excess will only adsorb appreciable amounts of the substance being purified,
resulting in a lower yield. Since the addition of the decolorizing carbon may cause the hot solution
to boil over*, it is important to cool the solution somewhat beforehand, and then reheat to boiling
after the addition.
Ex. 2: Recrystallization: Purification of Crystalline Organic Compound 3

FLUTED FILTER PAPER (Hot filtration set-up)

Hot Gravity Filtration. If any insoluble impurities or decolorizing carbon is present, the hot
solution is next gravity filtered through fluted filter paper in a stem-less or wide stem, heated
funnel. A stem-less or wide stem funnel avoids the possible problem of crystallization and
subsequent clogging inside the stem. A heated funnel is necessary to prevent the cooling of the hot
solution during filtration, causing crystallization in the filter. This can be accomplished by placing
the funnel at the top of an Erlenmeyer flask containing a small amount of boiling solvent. During
the filtration into the flask, the hot vapors will rise up around the funnel and heat it. A fluted filter
paper specially folded to provide the maximum possible surface area. This allows the filtration to
occur as rapidly as possible. Otherwise, when the solution cools, crystals deposit prematurely.
 Ex. 2: Recrystallization: Purification of Crystalline Organic Compound 4
Vacuum (or Suction) Filtration. Vacuum
filtration is generally used to remove soluble
impurities and solvent from the crystals of
the purified substance. A Bchner or Hirsch
funnel is fitted to a filter flask and the holes
in the funnel is covered with a disk of filter
paper moistened with some of the solvent
used for recrystallization. The filter flask is
connected to a vacuum (or water aspirator)
through a safety trap. The safety trap
prevents the reverse flow of water that may
contaminate the filtrate when aspirator is
used. In collecting crystals, suction
filtration is usually preferred over gravity
filtration because of the difference in
pressure increasing the rate of flow of liquid
through the filter. Opening the clamp or
stopcock on the trap releases the vacuum Bchner funnel (Suction/Vacuum filtration)
inside quickly and easily. The released
vacuum also makes it easier to disconnect the filter flask from the trap or the funnel. This should
be done always before turning off the water to avoid the backflow of water
For Pre-Lab Report:
Reflux. It is sometimes necessary to heat a substance in a solvent for a long time without boiling away the solvent. This can be done by attaching a vertica
Ex. 2: Recrystallization: Purification of Crystalline Organic Compound 5

1. What is a crystal and what is meant by recrystallization?

2. How does recrystallization free a substance from impurities? Explain how each step in
recrystallization contributes to the removal of impurities (colored impurities, soluble and
insoluble impurities)?
3. What must be considered in choosing a solvent for recrystallization?
4. Why must the hot filtration step be carried out quickly? Why is a fluted filter paper used
rather than an ordinary filter paper cone? Why use a stem-less funnel?
5. When is suction (vacuum) filtration useful? (Or why is vacuum filtration sometimes
preferable to ordinary gravity filtration?)
6. What is melting point? Why can it be used as an index of purity?

EXPERIMENT

In this experiment a sample of impure acetanilide (white leaflets when pure) will be recrystallized
from a chosen solvent. You will weigh the crude sample and the pure product and determine the melting
point before and after recrystallization, to illustrate the efficiency of the process.

I. Objectives:

1. To clarify the meaning of purity in the chemical sense.

2. To apply the method of recrystallization in the purification of a solid sample.
3. To recognize melting point as a physical property that can serve as an index of purity.
4. To determine the melting point of a substance using a simple apparatus.
5. To compare the melting point of a pure vs. impure sample of a substance.

II. Procedure:

(Reminder: Organic solvents are generally flammable and their vapors are toxic.
Avoid open flames and do not inhale the vapors.)
Note:
1. The impure sample will be provided by the instructor.
2. Set aside a small portion of the crude sample and determine its melting point (Part B).
1. Weigh out 1.5-g sample and place in a 100-mL round bottom flask, connect this flask to a
reflux condenser, and start a slow stream of water through the jacket of the condenser. Add
35-mL of the solvent chosen in Part A through the top of the condenser, boiling chips *, and
bring the mixture to a boil in a water bath. Adjust the Bunsen flame so that the water

** The boiling chips are inert material with small pores that provide sites where bubbles can form,
thus inducing even boiling.
Ex. 2: Recrystallization: Purification of Crystalline Organic Compound 6
refluxes steadily. Continue to heat until no more solid appears to dissolve. Then remove the
heat source, allow the flask to cool a few moments after reflux stops to avoid boil over,
remove the condenser momentarily, and add a small amount (about 0.15 g) of decolorizing
charcoal to the contents of the flask. Replace the condenser and heat the solution at reflux
for an additional 5 minutes.
2. Meanwhile, prepare a hot filtration set-up, using a fast-flow fluted filter paper and a 125-mL
Erlenmeyer flask as the receiver. Pour 15 20-mL of hot solvent through the funnel to
warm it and to wet the filter paper. Discard this solvent.

3. Remove the condenser, and using the clamp as a handle, filter the hot mixture without delay.
If particles of charcoal pass through the filter paper, return the filtrate to the round-bottom
flask, heat the solution to boiling, and filter it again through the same piece of filter paper.
4. Allow the filtrate to cool to room temperature slowly. DO NOT AGITATE THE MIXTURE.
As the filtrate cools, crystals will begin to form immediately.
5. After the mixture has cooled to room temperature, place the Erlenmeyer flask in an ice-
water bath to complete the crystallization, along with test tubes of pure solvent. If crystals
do not form, scratch the inside of the flask with a stirring rod.
6. Meanwhile, set up the vacuum filtration. Set a piece of filter paper in place, connect the
flask to the aspirator, and turn it on. Pour a little of the cold solvent through the Bchner
funnel to wet the filter paper. When crystallization is complete, filter the crystals by suction.
Wash the crystals (with the vacuum on) with the ice-cold solvent.
7. Continue the suction until no more solvent passes through the filter. Then transfer the
crystals to a piece of clean, wax paper, spread them thinly and air dry.
8. Weigh the dried product and determine its melting point (Part C). Compare the melting
point range obtained with that of the crude sample.
9. Calculate the percent recovery of pure product.
10. Turn in the purified crystals to your instructor
properly labeled.

B. Melting Point Determination

Do not add decolorizing carbon to a hot solution. If a solution is at or near its boiling point, the
addition of finely-divided carbon (which acts as thousands of boiling chips) will cause rapid boil
over.
Melting point Set-up
Ex. 2: Recrystallization: Purification of Crystalline Organic Compound 7
1. Pulverize a small amount of the sample with the aid of a clean watchglass and stirring rod.
2. Make a heap of the powder. Gently thrust the open end of a melting point tube (a glass capillary
closed at one end) into this heap.
3. Hold the tube vertically and gently tap the closed end on a hard surface.
4. Repeat steps 2 and 3 until the tube is filled to a depth of about 2 mm.
5. Pack the material by tapping the tube until the sample level inside the tube does not change.
6. Determine the melting point of the sample using the melting point apparatus.
7. Note the temperature at which the solid just begins to melt and that at which the last trace of solid
liquefies. These two figures make up the melting point range of the sample.

IV. Questions:

1. In recrystallization, the goal is to obtain a purified material with maximum recovery. What
are the effects of the operations below on (a) purity, and (b) recovery? Explain briefly.

a. In the solution step, an unnecessarily large volume of solvent is used.

b. The crystals obtained by suction filtration are allowed to dry without being washed
with cold solvent.
c. The crystals referred to in (b) are washed with hot solvent.

2. During a recrystallization, a yellow solution of a compound was treated with charcoal and the
mixture gravity filtered through fluted filter paper. When cooled, the crystals obtained were gray,
although the compound was known to be colorless. Explain what could account for the gray color
of the crystals and what you would do to obtain a colorless product.
3. (a) Explain why any impure solid couldnt just be washed in the very beginning with a cold
solvent to remove all the soluble impurities?
(b) Assuming that charcoal and sugar are the main impurities present in a sample of crude
acetanilide, explain how recrystallization from water would remove each.
4. Before packing into a capillary tube, a solid substance has to be powdered. Why is this done
on a watchglass rather than on a piece of filter paper?
5. Describe errors which may cause an observed melting point range of a PURE sample to be:
a. higher than the correct melting point
b. broad in range

References:

Introductory Organic Chemistry Laboratory Manual, Institute of Chemistry, UPLB

Landgrebe: Theory and Practice in the Organic Chemistry Laboratory
The percent recovery is calculated as follows:
The value should be less than 100%. If it is greater, your
recrystallized material is wet or impure.
Ex. 2: Recrystallization: Purification of Crystalline Organic Compound 8
USLS-COLLEGE OF ENGINEERING
Department of Chemical Engineering
CHM3E LABORATORY

EXPERIMENT 2
RECRYSTALLIZATION & MELTING POINT DETERMINATION
PURIFICATION OF CRYSTALLINE ORGANIC COMPOUND

Group No. ____

Chemist of the Day ____________________________ Date Performed: __________
Members: ________________________________ Date Submitted: __________
________________________________ Engr. Christer John Uy
________________________________ Instructor

I. Objectives:
6. To clarify the meaning of purity in the chemical sense.
7. To apply the method of recrystallization in the purification of a solid sample.
8. To recognize melting point as a physical property that can serve as an index of purity.
9. To determine the melting point of a substance using a simple apparatus.
10. To compare the melting point of a pure and impure sample of a substance.

II. Data:
Table 1. Observations on recrystallization of crude sample

Solvent: _____________________________________
Sample Description

Mixture of crude sample and solvent

Mixture after refluxing

Mixture after adding activated C

Filtrate
Hot filtration
residue
Ex. 2: Recrystallization: Purification of Crystalline Organic Compound 9

Sample Description

On bench top
Growing crystals
In ice-bath

Filtrate
Suction filtration
Residue

Air-dried crystals

Table 2. Recovery Data

Crude/Impure Sample Recrystallized Sample
Weight of container +
sample (g)
Weight of container
(g)

Weight of sample (g)

% Recovery

Table 3. Melting point data

Crude sample Purified Sample
Trial 1
Temp. when melting starts, C
Trial 2

Temp. when melting is Trial 1

completed, C Trial 2

Melting point range

Melting point of pure sample (acetanilide, literature value): 113 - 115C

Ex. 2: Recrystallization: Purification of Crystalline Organic Compound 10
III. For Pre-Lab Report:

7. What is a crystal and what is meant by recrystallization?

8. How does recrystallization free a substance from impurities? Explain how each step in
recrystallization contributes to the removal of impurities (colored impurities, soluble and
insoluble impurities)?
9. What must be considered in choosing a solvent for recrystallization?
10. Why must the hot filtration step be carried out quickly? Why is a fluted filter paper used
rather than an ordinary filter paper cone? Why use a stem-less funnel?
11. When is suction (vacuum) filtration useful? (Or why is vacuum filtration sometimes
preferable to ordinary gravity filtration?)
12. What is melting point? Why can it be used as an index of purity?

IV. Answers to Questions:

2. In recrystallization, the goal is to obtain a purified material with maximum recovery. What
are the effects of the operations below on (a) purity, and (b) recovery? Explain briefly.

d. In the solution step, an unnecessarily large volume of solvent is used.

e. The crystals obtained by suction filtration are allowed to dry without being washed
with cold solvent.
f. The crystals referred to in (b) are washed with hot solvent.

6. During a recrystallization, a yellow solution of a compound was treated with charcoal and the
mixture gravity filtered through fluted filter paper. When cooled, the crystals obtained were gray,
although the compound was known to be colorless. Explain what could account for the gray color
of the crystals and what you would do to obtain a colorless product.
7. (a) Explain why any impure solid couldnt just be washed in the very beginning with a cold
solvent to remove all the soluble impurities?
(b) Assuming that charcoal and sugar are the main impurities present in a sample of crude
acetanilide, explain how recrystallization from water would remove each.
8. Before packing into a capillary tube, a solid substance has to be powdered. Why is this done
on a watchglass rather than on a piece of filter paper?
9. Describe errors which may cause an observed melting point range of a PURE sample to be:
a. higher than the correct melting point
b. broad in range