9

EXPERIMENT 2: Recrystallization and Melting Point

Recrystallization (or Crystallization) is a technique used to purify solids. This procedure relies on the
fact that solubility increases as temperature increases (you can dissolve more sugar in hot water than in cold
water). As a hot, saturated solution cools, it becomes supersaturated and the solute precipitates (crystallizes)
out. In a recrystallization procedure, an impure (crude) solid is dissolved in a hot solvent. As this solution
is cooled, the pure product crystallizes out and the impurities stay dissolved.


General Recrystallization Procedure:

1) Choose an appropriate solvent(s)
product is very soluble in it at high temperatures
product is not soluble in it at low temperatures
impurities are either soluble at all temps or insoluble at all temps (can be filtered off)

2) Dissolve impure solid
weigh out crude solid and record its mass (also take a melting point for reference)
add a boiling chip or boiling stick (otherwise, it may "bump" and spill)
use a minimum amount of hot solvent (Add a bit, heat/swirl. Not dissolved? Add more!)
NOTE: IF YOU USE TOO MUCH SOLVENT, YOU WILL GET NO CRYSTALS!

3) ONLY IF NEEDED: Decolorize
most pure compounds are white and give colorless solutions (looks like water)
to remove color (really trace contaminants), add activated charcoal (adsorbs the impurities)

4) ONLY IF NEEDED: Gravity filter to remove insoluble materials (including charcoal!)
use fluted filter paper and a hot, stemless funnel
NOTE: IF THE SOLUTION COOLS, PRODUCT WILL CRYSTALLIZE OUT & BE LOST!
use a small amount of hot solvent to rinse flask, filter

5) Crystallize solute (Finally! This is the RECRYSTALLIZATION part!)
cool the solution slowly: hot (boiling) room temperature 0 C (put in ice water bath)
NOTE: THIS GIVES LARGE, PURE CRYSTALS & LEAVES IMPURITIES IN SOLUTION
may need to scratch glass with a stirring rod or add a seed crystal to start crystallization

6) Collect the pure crystals
quickest method is vacuum filtration (Bchner funnel, water aspirator and trap)
the impurities will stay dissolved in the solvent that is being removed (hopefully)
rinse the pure crystals with a small amount of cold solvent (don't redissolve the crystals!)
OPTIONAL: a second crop of crystals can be obtained from the filtrate (mother liquor)

7) Analyze product
let crystals dry thoroughly (ideally, this means overnight at room temperature or under vacuum)
record mass (how much of your original solid did you recover? % recovery?)
record melting point range (did you succeed in PURIFYING your solid?)


10
EXPERIMENT 2: Recrystallization and Melting Point

Melting Point is:

a constant physical property of a solid (the temperature at which it turns to a liquid)
reported in the lab as a melting point range (usually 12 C wide), not as a single temperature
used for:
1) characterization of a compound (also IR, NMR, mass spec.)
2) identification of an unknown (compare with known mp's)
3) determination of purity
If a sample of a compound contains impurities, its mp is usually
depressed (lowered) and the range is broadened. Therefore, a
narrow mp range (12 ) suggests the sample is a pure compound.


How can this fact help us in the lab?
1) take a "mixed melting point" of an unknown (if you mix two samples - typically a known
and an unknown - and the mp doesn't change, then the two samples are the same compound)
2) take a mp before and after a purification technique (like recrystallization, this week's lab)


Method for measuring a Melting Point range:
LOAD sample in a capillary (mp) tube (pack the sample down into the CLOSED end of tube)
SLOWLY HEAT the sample and closely WATCH both the crystals and the temperature
at the first sign of melting (crystals look wet), RECORD the temperature (first number of reported range)
when the last crystal melts, RECORD the temperature (second number of reported range)
for best results: use a small, well-packed sample and heat slowly to ensure even heating


Using the Melting Point Apparatus: (Mel-Temp or Thomas Hoover UniMelt)
uses a heating coil in oil (oil is stirred automatically) or a hot plate
has a light and a magnifying glass (easy to see crystals)
rate of heating is easily adjusted (voltage control)
Instructions for use:
check to make sure temperature is low before inserting mp tube
turn unit on: various switches for light, heat and stirring
adjust the voltage control to begin SLOWLY heating your sample (higher number =faster heating)
turn all switches off when done; discard mp tube in glass waste container



11

EXPERIMENT 2: Recrystallization and Melting Point

EXPERIMENTAL PROCEDURE: (refer to Zubrick text for additional details)

Recrystallization: Using a hot plate, dissolve approximately 1.0 g of impure benzoic acid in 30 35 mL of
hot water (water at or near its b.p.) in a 125 mL Erlenmeyer flask. If there is a residual amount of material
that does not dissolve upon adding a small amount of additional solvent (H
2
O), do not continue to add more
solvent; it is important to use a MINIMUM amount of solvent in a recrystallization. This material is
probably insoluble in the hot solvent and will be separated from the hot solution by gravity filtration. If
there is any such insoluble solid residue, gravity filter this hot solution through a fluted filter paper using the
apparatus shown in your laboratory textbook. Since the glass funnel you have used is much cooler than the
hot solution, cooling of the solution will occur, resulting in some crystallization of the benzoic acid in the
stem of the funnel and in the filter paper. Preheating the funnel by running a SMALL AMOUNT of hot
solvent (H
2
O) through the funnel will reduce the loss due to this crystallization. To further reduce the
amount of loss of material, do not fill the funnel with solution but rather add small portions of the hot
solution so a minimum amount of solution is in the funnel at once.

Allow the gravity-filtered hot solution to gradually cool to room temperature. As this occurs, much of the
benzoic acid will crystallize from the solvent. When the cooled solution is at or near room temperature,
cool it further in an ice-water bath. Collect the resulting crystals by vacuum filtration, using a water
aspirator and the apparatus shown in your laboratory textbook. Transfer the crystals from the filter paper to
a tared watch glass (note weight on Data sheet) and let dry thoroughly before weighing. Never weigh filter
paper along with the crystals; the filter paper will be wet. Determine the amount of benzoic acid recovered
and, based upon the initial amount you started with, determine the percent recovery.

Melting Point: Determine the melting point ranges of the impure benzoic acid and the crystallized benzoic
acid (after it is dry). Be sure to grind each sample well before introducing it into the melting point tube (you
may use a glass rod and a watch glass). Scoop a small amount of the powder into the opening of the melting
point tube and gently tap the tube on the benchtop to move the sample down to the bottom (dropping the
melting point tube through a long glass tube can also help you pack the sample). If you do not have at least
1 mm of sample, scoop another small portion and repeat. If the column of sample is over 3 mm, discard the
melting point tube and start again. Insert the packed melting point tubes into a melting point apparatus.
SLOWLY heat the sample (~1 C per minute) and record the temperature at the very first sign of melting.
Continue to watch the sample and when the sample has melted completely, record the temperature again.
EVERY MELTING POINT IS REPORTED AS A RANGE.

Waste disposal: Please discard your purified benzoic acid into the container in the hood labeled: Benzoic
Acid - Student Prep. Melting point tubes should be placed in the glass waste container.





Your complete report for this experiment should include the data page, answers to the following
questions, and a conclusion (1 page maximum. Discuss your results yield and mp. Consider: Did
the recrystallization work? How can you tell? How could you have improved your yield?). These
pages must be stapled.

12



EXPERIMENT 2: Recrystallization and Melting Point

Data Sheet Name:
Record data in INK. Day/Time of Lab:

Instructor:


Benzoic Acid Data

sample


physical appearance


melting point range

impure






pure






literature value
(cite source)


Amount of benzoic acid used initially ___________________________ g


Tare weight of watch glass ___________________________ g


Weight of watch glass +pure crystals ___________________________ g


Amount of benzoic acid recovered ___________________________ g


Percent recovery of benzoic acid (show method; include units)







Your complete report for this experiment should include the data page, answers to the following
questions, and a conclusion (1 page maximum. Discuss your results yield and mp. Consider: Did
the recrystallization work? How can you tell? How could you have improved your yield?). These
pages must be stapled.
13
EXPERIMENT 2: Recrystallization and Melting Point

Questions

Attach answers to these questions on a separate sheet along with Experiment 2 Report.

1. What are the important solubility characteristics for a solvent for crystallization of an organic solid
which is contaminated with a small amount of impurity? Remember you want to separate the desired
solid from the contaminating impurities.



2. There are many opportunities during a recrystallization to lose crystals. How could you improve your
percent recovery? Explain.



3. Why is it necessary to cool a hot, supersaturated solution SLOWLY during a recrystallization?



4. A 20 g mixture containing 95% (by weight) of A and 5% of B is recrystallized in toluene (b.p.
110C). Solubilities in g/100 mL are given below. What amount of solvent is needed to obtain pure
A and how much pure A will be recovered? Show all calculations and explain your answers. Hint:
the goal of a recrystallization is to keep ALL of the impurity dissolved at the low temperature.
Knowing that, how much solvent is needed for this example?

Temperature 20 110
Solubility A 1.5 g 10.0 g
(g/100 mL) B 0.5 g 8.0 g


5 Why do you need to heat the sample SLOWLY to record its melting point? Give at least two reasons.



6. How can a samples melting point indicate the presence of an organic impurity?