Experiment 6

Recrystallization


Objective: The principle objective of this experiment is:
1- To select a crystallizing solvent for three different compounds.
2- To crystallize acetanilide and determine the yield and melting point of the pure
product.
3- To decolorize brown sugar.

Introduction

Organic compounds are usually more soluble in hot solvents than in cold ones. An impure
solid organic compound, when dissolved in the proper amount of an appropriate solvent at an
elevated temperature will reprecipitate when the solution is cooled. If the hot solution is filtered
before being allowed to cool, dirt, lint, or other insoluble impurities will be removed, and the
crystals that deposit in the cooled solution are usually more pure than the starting material is. The
crystals may be removed from filtrate (mother liquor) by filtration. The soluble impurities and a
small amount of the desired substance will stay in solution. This process is called
recrystallization which is frequently used for the purification of solid organic compounds. The
success of the process depends on the fact that soluble impurities usually are present in smaller
amounts than the desired compound so that the cooled solution, although saturated with respect
to the desired product, may not be saturated with the impurity. This being the case, the latter will
not precipitate from the solution. Sometimes a solution does become saturated with respect to an
impurity during the cooling process. In this event, the impurity deposits along with the desired
product and the recrystallization will have to be repeated, perhaps several times. In each
recrystallization, a small amount of the desired compound remains behind in the mother liquor.
Such loses are unavoidable if a pure product is to be obtained.

A good solvent for recrystallization has the following properties: (1) it dissolves a reasonable
amount of the organic compound at high temperatures (usually the boiling point of the solvent)
and very little at low temperature, (2) it dissolves impurities readily at low temperatures or does
not dissolve them at all, (3) it does not react with the substance being purified, (4) it has a low
boiling point so that it is readily removed from the purified product, and (5) it is cheap.
Sometimes a solvent with all of these properties cannot be found. In such instances the solvent
that most nearly approaches the ideal is selected. Alternatively one may use miscible solvent-
pairs.

The process of recrystallization often may be aided, especially when the impurities are colored,
by selectively adsorbing contaminants on activated charcoal (Norit). A small amount of charcoal
is added to the hot solution just before the filtration step. However, charcoal will adsorb not only
the impurities but also a certain amount of the desired product. It is advisable, therefore, to use a
minimum amount of charcoal.

Recrystallization is a process in which you take some crystals, dissolve them in a solvent, and
turn them back into crystals again. As noted above, the purpose is to separate the impurities from
the desired substance. The practical process of recrystallization can be described in seven steps,
as follows (the reason for each step is given in parentheses); First, choose a solvent that doesnt
dissolve the compound when cold, but does when hot, (these properties of the solvent make the
recrystallization process possible). Add hot solvent until the compound you are trying to purify
dissolves, (this makes impurities that were locked inside the impure crystals available for
removal). Add decolorizing charcoal if colored impurities are present, (the colored molecules are
adsorbed onto the surface of the charcoal). Filter the resulting solution while it is still hot, fig.
6.1, (this step separates two kinds of impurities from the substance you want). The charcoal with
the colored molecules adhering to them are trapped on the filter paper, and so are particles of
impurities that didnt dissolve in the hot solvent to begin with. Cool the solution and obtain
crystals of your desired compound, (soluble impurities will remain in solution). Perform suction
filtration to isolate the compound, fig. 6.2, (the soluble impurities and most of the
recrystallization solvent are separated from the compound you want in this step). Drying the
crystals youve isolated, (this removes the rest of your recrystallization solvent, which is an
impurity).
Here are the setups used for hot filtration and suction filtration.

Hot Filtration: The fluted filter paper in hot filtration has a large surface area, allowing for fast
filtration (before the solvent cools); it traps the charcoal and any insoluble impurities, and lets the
solvent (containing the desired compound and the soluble impurities) go through, (fig. 8.1).














Fig. 6.1 Hot filtration set-up

Suction Filtration: For the collection of the pure crystals suction filtration is applied, employing
especially designed funnels (e. g. Buchner funnel or Hirsch funnel) to effect rapid filtration and
drying of precipitates, (fig. 6.2). Further drying can be effected in an oven at a suitable
temperature.

















Fig. 6.2 Set up for suction filtration


Procedure

I. Selection of a crystallizing solvent
Determine the solubility of anthracene, benzoic acid and sodium benzoate in water, toluene and
ligroin (See procedure below). According to the results, select the best crystallization solvent for
each. Record data and observations in Tables 6.1 and 6.2.
1. Transfer, using a spatula, about 0.1 g of the finely divided solid into a test tube
(150*18mm). It is not necessary to use a balance to measure out the solids accurately.
2. Measure in a small graduated cylinder 3 mL of the solvent. Add the solvent onto the solid
dropwise with continuous shaking until a total of one mL is added. Complete dissolution
will leave a clear or transparent solution. The solution may be colored if the solid is
colored.
If the entire solid has dissolved in the 1 mL solvent at room temperature, then the solvent
is unsuitable for crystallization. Therefore nothing more has to be done with that
compound concerning this solvent.
If it is insoluble at room temperature, heat the reaction tube to the boiling point of the
solution using the heating blocks placed on top of the heating plates. Do not forget to
place digital thermometers in the heating blocks to control your temperatures. Start your
tests from the lowest boiling point solvent. If the entire solid dissolves, it can be declared
readily soluble in the hot solvent.
If it is still insoluble after a while of boiling, add more solvent in 0.5mL portions until
all of the solid dissolves at the boiling point or until a total of 3mL of solvent is present
In the cases where the solid dissolved in boiling solvent, allow the tube to cool slowly to
room temperature, undisturbed, scratching the sides of the test tube with a glass rod to
induce crystallization. In these cases, the liquid is a good crystallization solvent.
If some or the entire solid still remains insoluble in the 3mL of the solvent at its boiling
point, then the solvent is unsuitable.


II. Recrystallization of Acetanilide

Record the required data in Table 6.3.

1. Weigh 1.0 g of crude acetanilide and record data in Table 6.4. Transfer the weighed
acetanilide into a 125 mL Erlenmeyer flask and add 2-3 boiling stones. Add around 10
mL of boiling water.

2. Heat the solution on a hot plate while stirring the flask (with hand) to dissolve the solid.
If the sample does not dissolve when water boils, add more hot water in 2 mL portions
with stirring and heating until the solid dissolves in the boiling water. Note that some
impurities may not be soluble in the solvent and remain undissolved no matter how much
solvent you add. However, make sure that the dark oily material which forms is
completely dissolved. Add an additional 5 mL of water at the boiling point and filter the
hot solution through a short stem funnel, which has been previously heated by passing
boiling water through it, into an Erlenmeyer flask. Leave the solution to cool to room
temperature and then in a bath of cold water/ice for 20 minutes.

3. When the solution is cool, collect the crystals by suction filtration and wash with two
separate 3 mL portions of cold water, each time pressing the crystals firmly with an
inverted glass stopper or a cork. Transfer the crystals to a filter paper, and press them
firmly to remove water.

4. Weigh the product and determine its percentage.

5. Determine the melting point of the crude and pure acetanilide and record data in Table
6.5


III. Decolorization of Brown Sugar

This experiment demonstrates the effect of charcoal on colored impurities.
Record the required data in Table 6.6.

Dissolve 2 g of dark brown sugar in 20 mL of water. Save a small portion of the solution
for comparison purposes; add to the remainder 0.7 g of decolorizing charcoal and boil for 5
minutes. You may add 0.5 g of Filter-Cel (Celite) as a filter aid. This material helps prevent
the very fine charcoal particles from passing through the filter paper. Using a receiver, funnel
and a fluted filter paper (consult your instructor for making a fluted paper), filter the hot
solution and compare the color of the filtrate with that of the untreated material. Record your
observations.

Reference: Brewster, Unitized experiments in organic chemistry, 4
th
Ed.

Student Name______________ Date_____________

Student ID #_______________ Section___________


Experiment 6

Recrystallization

Purpose:



Data and calculations:

I. Selection of a crystallizing solvent

Table 6.1 Table of reagents

Compound

Formula M.Wt.
(g/mol)
Melting point
(C)
Boiling point
(C)






















Table 6.2 Results

Compound Water Toluene Ligroin Best solvent for
Recrystallization Cold Hot Cold Hot Cold Hot









Discussion of Results:





II. Recrystallization of Acetanilide

Table 6.3 Table of reagents

Compound

Formula M.Wt.
(g/mol)
Melting point
(C)
Boiling point
(C)







Table 6.4 Results

Structure of
acetanilide
Mass used
(g)
Mass recovered
(g)
% Recovery




Table 6.5 Melting point Determination

Acetanilide

Experimental Melting point (C)
Crude


Pure



Discussion of Results:












III. Decolorization of Brown Sugar

Table 6.6 Table of reagents

Compound

Formula M.Wt.
(g/mol)
Melting point
(C)
Boiling point
(C)













Observation:





Discussion of Results: