EXPERIMENT 4

RECRYSTALLIZATION

I. ABSTRACT

In this experiment, an impure compound (acetanilide) was recrystallized. By observing solubility

in different conditions, it was determined that water was the best recrystallization solvent. Other
solvents were also used to recrystallize acetanilide. It was done in two ways, each solvent’s solubility
with the impure compound was tested in hot and cold temperature. During the experiment, the
importance of the steps in recrystallization was observed. The goal of the experiment was to integrate
proper techniques in recrystallization to obtain a purified organic compound from the original impure
compound.

II. INTRODUCTION

Recrystallization is the most important method for purifying solid organic compounds. It is also a
very powerful, convenient, and efficient method of purification, and it is an important industrial
technique that is still relevant in the chemical world today. For instance, the commercial purification of
sugar is done by recrystallization on an enormous scale (Williamson and Masters, 2011).

A pure, crystalline organic substance is composed of a three-dimensional array of molecules

held together primarily by London forces. These attractive forces are fairly weak; most organic solids
melt in the range between 22°C and 250°C. An impure organic solid will not have a well-defined crystal
lattice because impurities do not allow the crystalline structure to form. The goal of recrystallization is to
remove impurities from a solid to allow a perfect crystal lattice to grow (Fieser and Williamson, 1992).

There are four important concepts to consider when discussing the process of recrystallization:
solubility, saturation level, exclusion, and nucleation. Recrystallization involves dissolving the material to
be purified in an appropriate hot solvent to yield a solution (solubility). As the solvent cools, the solution
becomes saturated with respect to the solute (saturation level), which then recrystallizes. As the
perfectly regular array of a crystal is formed, impurities are excluded (exclusion), and the crystal is thus a
single pure substance. Soluble impurities remain in solution because they are not concentrated enough
to saturate the solution. Recrystallization of a solute is initiated at a point of nucleation, which can be a
seed crystal, a speck of dust, or a scratch on the wall of the test tube (Williamson and Masters, 2011).

In this experiment, criteria for choosing good recrystallization solvents will be discussed and the
selected solvent will be used in performing recrystallization techniques to purify samples.
III. MATERIALS
A. LIST OF CHEMICALS

PHYSICOCHEMIC
PREVENTIVE
CHEMICAL NAME STRUCTURE AL HAZARDS
ACTION
PROPERTIES

Obtain
MW: 135.166
special
g/mol;
Harmful if instructions
White to gray
swallowed; before use;
solid; White,
Acetanilide Causes eye do not
shining crystalline
C8H9NO irritation; breathe
leaflets or white
combustible. dust/fume/g
crystalline
as/mist/vapo
powder.
rs/spray.

MW: 78.114
g/mol; very keep away
clear colorless hazardous in from heat
liquid with a case of skin and from
petroleum-like contact any sources
Benzene odor. Less dense (irritant), of of ignition;
C6H6 than water and eye contact avoid contact
slightly soluble (irritant), of with skin; do
in water. Vapors ingestion, of not inhale
are heavier than inhalation fumes
air.

MW: 88.106 flammable;

g/mol; also cause
do not
colorless liquid severe eye
ingest; avoid
Ethyl acetate with an ether-like, irritation and
contact with
C4H8O2 fruity odor; less moderate
skin and eyes
dense than water; skin
volatile. irritation

MW: 46.069
g/mol; Flammable;
Clear and serious eye Avoid
Ethanol colorless liquid and inhalation of
CH3CH2OH with a weak, respiratory fumes
ethereal, vinous irritation.
odor.

Activated carbon charcoal that has been heated or treated to increase its adsorptive power.
Acetanilide (crude) acetanilide with all kinds of impurities
B. EXPERIMENTAL SET-UP

IV. SCHEMATIC DIAGRAM

I. TESTING SOLVENTS FOR RECRYSTALLIZATION

II. RECRYSTALLIZATION
V. DATA AND RESULTS

I. TESTING SOLVENTS FOR RECRYSTALLIZATION

Table 3.1 Testing Solubility of Solid Sample to different Solvents to varying Temperatures
Solid
Sample Solubility (Soluble or Insoluble) Appropriate Recrystallization Solvent (√  or X)
Number
Cold Hot

Water

Ethanol

Benzene

Ethyl
acetate

II. RECRYSTALLIZATION
Table 3.2 Recrystallization of Acetanilide
Steps in Procedure Observation
Dissolution of acetanilide

Addition of Activated Carbon

 Hot Gravity Filtration

Cooling to Room Temperature

Cooling in an Ice Bath

Vacuum Filtration

Table 3.3 Percentage Recovery of Recrystallized Acetanilide

Mass of crude acetanilide (g)

Mass of Petri dish (g)

Mass of ashless filter paper (g)

Mass of recrystallized acetanilide, petri dish, ashless filter paper (g)

Mass of recrystallized acetanilide (g)

Percentage Recovery (%)

VI. POST-LAB QUESTIONS AND DISCUSSION

1. What are the criteria in selecting good recrystallization solvent? Explain the importance of each
criterion.

The best recrystallization solvent will dissolve the solute when the solution is hot but not when
the solution is cold; it will either not dissolve the impurities at all or it will dissolve them very well, so
they do not recrystallize out along with the solute; it will not react with the solute; and it will be
nonflammable, nontoxic, inexpensive, and very volatile, so it can be removed from the crystals.

Consequently, a solvent should satisfy certain criteria for use in recrystallization: (a) the desired
compound should be reasonably soluble in the hot solvent, about 5 g/100 mL (5 mg/100 μL) being
satisfactory, and insoluble or nearly insoluble in the cold solvent. Note that the reference temperature
for determination of the solubility in "cold" solvent is often taken to be room temperature. This
combination of solute and solvent will allow dissolution to occur in an amount of solvent that is not
unduly large and will also permit recovery of the purified product in high yield. A solvent having this type
of solubility properties as a function of temperature would be said to have a favorable temperature
coefficient for the desired solute. (b) Conversely, the impurities should either be insoluble in the solvent
at all temperatures or must remain at least moderately soluble in the cold solvent. In other words, if the
impurities are soluble, the temperature coefficient for them must be unfavorable; otherwise the desired
product and the impurities would both crystallize simultaneously from solution. (c) The boiling point of
the solvent should be low enough so that it can readily be removed from the crystals. (d) The boiling
point of the solvent should generally be lower than the melting point of the solid being purified. (e) The
solvent should not react chemically with the substance being purified.

2. Why is using an appropriate solvent for recrystallization necessary?

Recrystallization works only if proper solvent is used. The solute must be insoluble in the solvent
at room temperature but more soluble in the solvent at higher temperature. In the experiment, a
stemless glass funnel is provided to avoid premature recrystallization because the filtrate will cool while
it passes in the stem.

3. Explain the importance of the following steps during recrystallization

a. The minimum amount of solvent is used to dissolve the solute for recrystallization.

A few drops of solvent, normally totaling no more than a milliliter are added, and the mixture is
heated to the boiling point. Additional solvent, if needed, is added dropwise using a Pasteur pipette to
the boiling mixture until the solid just dissolves. It is important to let boiling resume after each addition
so that a minimum amount of solvent is used to effect dissolution; using excessive amounts of solvent
decreases the recovery of the solute. If it necessary to perform a hot filtration, it is prudent to add an
additional 2-5% of solvent to prevent premature crystallization during this operation.

b. A fluted filter paper is used during the hot filtration step.

The most common method for the removal of insoluble solid material is gravity filtration
through fluted filter paper. This is the method of choice for removing finely divided charcoal, dust, lint,
and so on. A piece of filter paper is fluted and is then placed in a stemless funnel. The funnel is stemless
so that the saturated solution being filtered will not have a chance to cool and clog the stem with
crystals. The filter paper should fit entirely inside the rim of the funnel; it is fluted to allow rapid
filtration, with minimal surface contact of the filter to the glass funnel, since the solution to be filtered
is more likely to recrystallize on the funnel. The funnel should be warm to prevent recrystallization
from occurring in the funnel. This can be accomplished in two ways: (1) Invert the funnel over a steam
bath for a few seconds, pick up the funnel with a towel, wipe it perfectly dry, place it on top of flask B,
and then add the fluted filter paper; or (2) place the stemless funnel in the neck of flask B and allow the
solvent to reflux into the funnel, thereby warming it.

c. The solution from the hot filtration step is not immediately placed in the ice bath for cooling.

The rate of cooling determines the size of crystals. Slow cooling tends to favor fewer and larger
crystals while fast cooling tends to favor more and smaller crystals. Very large crystals are to be
avoided since they often occlude the solvent and its dissolved impurities. Very small crystals are
undesirable because it is difficult to wash them free of the solvent and the soluble impurities,
and it takes longer to dry them. This is why it is preferred to slowly cool the solution to room
temperature before putting it to ice bath for further cooling.
d. Vacuum filtration is used during the cold filtration step.

This will draw liquid from the Buchner funnel into the flask, and filter out the crystals in the
process.

e. The cold crystals are washed with water.

It is important to wash the cold crystals with water to wash off any soluble impurities it contains.
If this is not done, the soluble impurities will be deposited on the crystals when the solvent evaporates.

4. What is the function of the activated carbon?

Activated carbon is used as a decolorizing agent to remove colored minor impurities and other
resinous by-products. Activated carbons are composed of macropores and mesopores which absorbs
tannins that protects plants from insects, bacteria, and etc. In the experiment, activated carbons are
extracted out in the system to leave out the caffeine.

5. In the process, why is it necessary to cool the filtrate in an ice bath?

It is necessary to cool the filtrate in the ice bath in order to complete the recrystallization faster
because of the loss of heat. Since solubility decreases with decreasing temperature, it is a good idea to
finally cool the mixture from room temperature to 0°C (or to the freezing point of the solvent if it is
above 0°C) in a mixture of ice and water. Cooling below 0°C is not often done, since colder baths are not
so easily prepared and other problems related to the condensation of water vapor from the air in the
form of water or frost require special techniques and apparatus.

VII. CONCLUSION

On the first part of the experiment, it can be concluded that the water dissolved the solute or
compound when boiled. It was observed that an effective way of forming crystals was placing the
solution in a cold bath. On the second part, the impure compound acetanilide was successfully
recrystallized. The impurities were removed through the process of recrystallization. In this experiment,
it is important to follow the process correctly in order to obtain a pure compound from the impure
organic compound.

VIII. REFERENCES

 Skoog, D. (n.d.). Fundamentals of Analytical Chemistry (9 th ed).

 Freeman, W., et.al(n.d.). Quantitative Chemical Analysis (6 th ed).
 Masterton, W., et.al(2012). General Chemistry (1 st ed).