Recrystallization:

Purification of Solid Compounds

Pure Solid Compounds:
intermolecular forces.

Molecules

held

together

in

rigid

formations

by

Types of Intermolecular Forces?

1. Van der Waals forces
London or dispersion forces
Dipole-dipole forces
2. Hydrogen bonds
Impure Compounds? Impurities buried inside the crystalline lattice

The Process: to use a hot solvent to surround the molecules in the crystalline
lattice, allowing the heat to loosen and break apart the intermolecular forces, until
the lattice is no longer intact.

Once the lattice is gone, the impurities caught inside the lattice can dissolve into
the solvent, or float off into the solvent. Then the lattice is reformed, slowly so
as to prevent trapping the impurities back into the crystal again.

Factors to Consider:
1.
The Solvent
Cannot react with the solid that is being recrystallized
Should not dissolve the solid when cold but should dissolve the solid when
hot
Should either dissolve the impurities when cold or hot (a.k.a. soluble
impurities) or should not dissolve them when cold OR hot (a.k.a. insoluble
impurities).
Should be relatively volatile.
The boiling point of the solvent should be lower than the melting point of the
solid (to avoid oiling out).
The perfect amount of solvent forms the ideal saturated solution. Use too
little and you have a supersaturated solution and run the risk of crystals
forming too soon, before you are ready for them. Use too much solvent and
you no longer have a saturated solution.
There is no such thing as a perfect solvent.
All solvents will dissolve a solid compound to some slight extent when cold.
The more solvent you use, the more the compound will stay permanently
dissolved in the solvent, leading to lower amount recovered from the solvent.
Thus: the goal is to use the barest minimal amount of solvent.
H
N

CH3
O

Example: Acetanilide
Solubility: 1 gram per 20 mL of hot water and 0.11 grams per 20
mL of cold water

So to dissolve 2 grams of acetanilide, how much hot water do you need?

1 gram into 20 mL so 2 grams into 40 mL of hot water
If you use 40 mL of hot water and you COOL it so it is now COLD water, how much
of the acetanilide will stay dissolved?
0.11 grams remain in 20 mL so 0.22 grams remain in 40 mL of cold
water
Can you ever get back ALL of the 2 grams of acetanilide from the water?
0.22 grams will stay dissolved leaving you with only 1.78 grams MAXIMUM to
be recovered.
Use as little solvent as possible. You want a saturated solution (as close to
supersaturated as you can get!) in order to get the maximum amount of crystals to
form.
Make sure the solvent is HOT when you want to dissolve something.
2

Make sure the solvent is COLD when you DONT want the crystals to
dissolve!

2. The Hot Plate

This may sound stupid but it DOES get hot. The glassware on it also gets very
hot. Electrical cords should not be near the hotplate when it is hot, or they will
melt.
Please note that the hotplates will have two controls on them, one for heat and one
for a magnetic stirrer. Turning on the magnetic stirrer will not make it hot.
3. Boiling Stones
The glass container typically used for a recrystallization process is the Erlenmeyer
flask.
The inside of the Erlenmeyer flask is a smooth surface which will not allow vapor
bubbles to form, causing the solution to begin to superheat. At some point, a
massive vaporization will occur all at once. Your solution will explode out of the top
of your Erlenmeyer (a.k.a. bumping). This is generally not considered to be a good
thing.
The purpose of a boiling stone is to provide a rough surface on which the
liquids vapor bubbles can form. This promotes a smooth and even boiling
process.
Always add boiling stones to a cool solution. What would happen if you added it to
one you had already heated to HOT?
The solution would suddenly be able to form vapor bubbles and would do so,
frothing out the top of your flask always be sure the solution/flask is not
HOT when adding boiling stones.
How many boiling stones do you think you need to do this correctly?
Only 2 or 3 are necessary to get the job done You do not need to add 25
extra is not better Contrary to popular belief, extra boiling stones do not
make something boil faster. Heat does that.
Always use anytime you are heating liquids, unless told otherwise.
4. Activated Charcoal (a.k.a. carbon, decolorizing charcoal, decolorizing carbon,
powdered graphite, activated charcoal/carbon)
Used to remove colored impurities from a solid compound during a
recrystallization process
Colored impurities are typically molecules with large Pi electron systems. These Pi
electrons can adhere to the large surface area of the activated charcoal. Once
the impurities are clinging to the charcoal, you can then filter away both the
charcoal and the impurities.

Do not add activated charcoal to a hot solution the carbon particles will act as
thousands of tiny boiling stones and cause an eruption to occur out of your flask!
Warning: Your own molecule may (does!) have Pi electrons and therefore may also
wish to adhere to the carbon. The more you use, the lower your yield tends to be.
This is unavoidable.
5. Hot Gravity Filtration
This type of filtration is used primarily to remove insoluble impurities (those
little black floatie things that never dissolve).
We use fluted filter paper for this process. Fluted filter paper is preferred over
the standard cone because it provides a larger surface area for the solvent to
travel through quicker.
Why is quicker important?
To remove INSOLUBLE impurities, you must heat to dissolve the desired compound
AND keep it hot and dissolved as you filter out the insoluble impurities. In order
to keep it hot dissolved, the solvent must stay HOT. If the solvent starts to
cool, what will happen..?
Your crystals will begin to crystallize out in the funnel instead of staying dissolved
in the solution this will dramatically LOWER your results and cause a disaster in
your filter paper!
For this same reason, a short stem funnel is always used instead of a long stem
funnel. The longer the stem, the longer the solution must travel through it and the
more likely it will be to cool down and crystallize in the stem.
WORK FAST and keep everything HOT!!
Caution: Beware of solvent-eating filter papers!! Dry filter paper will change your
concentration as the filter paper will absorb water from your solution, resulting in
a more concentrated solution. What was once happily saturated, becomes supersaturated suddenly, and crystals start to form in the filter paper
6. Vacuum Filtrations
Used to rapidly remove liquids (the solvent) from solids (the new crystals).
Used to remove SOLUBLE impurities (those that dissolved in the hot or
cold solvent at the start of the process).
The Bchner funnel has a flat bottom with a lot of surface area exposed for
drainage of the solvent. The use of a vacuum pulls the solvent through the holes
and away from the solid crystals quickly. Very often, the crystals are left in the
Bchner funnel with the vacuum running, long after the solvent is gone, in what we
call the process of air drying.

Be sure to select the correct size filter paper for your Bchner funnel (should
easily fit inside the funnel and still cover all the holes).
If you wish, you may seat the filter paper, just be sure to use whatever solvent
you are going to be filtering, so no other form of contamination occurs.