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Reading
Part I: The Recrystallization Pre-Lab Video on the orgolabs website. Zubrick Chapters
12 (The Melting Point Experiment; we use the ‘Mel-Temp’ variety) and 13
(Recrystallization). Appendix 5 of this manual.
Part II: The Distillation Pre-Lab Video on the orgolabs website. Zubrick Chapters 17
(Boiling Stones), 18 (Sources of Heat, especially heating mantle and variac), 20
(Distillation), 36 (Theory of Distillation). Yes, you must read all of them!
Summary
In this lab, you will recrystallize the organic solid that you isolated from your
unknown mixture. After recrystallizing your solid, you will identify it based on melting
point. You will also purify your organic neutral by distillation and subsequently identify
it based on its boiling point.
Introduction
Often even after organic compounds are separated from starting materials and by-
products, some impurities remain and must be removed. Two of the most common
methods of purification in organic chemistry are recrystallization (for solids) and
distillation (for liquids), both of which you will be performing today.
Part I: Recrystallization
• It should completely dissolve the desired compound when hot (usually at the boiling
point of the solvent).
• It should dissolve very little of the desired compound when cold (usually after fifteen
minutes in an ice/water bath).
• It should dissolve impurities at all temperatures or not at all.
• It should be unreactive toward the compound.
• It should dissolve the compound in a reasonable amount of solvent. Too much solvent
will make recrystallization extremely slow and the yield is likely to be low. Too little
solvent will make it difficult to filter off all of the dissolved impurities when collecting
crystals. As a rule of thumb, you might aim to find a solvent that will dissolve a gram
of compound in ~5-10 mL of solvent.
Now, how can you predict which solvent will work the best? You can’t – not with
any degree of certainty, anyway. But chemists (and chemistry students) must understand
how the structure of compounds influences their solubility. General guidelines for
predicting acid/base solubility were given in the last chapter, but while solvent extraction
relied upon those principles (you were actually carrying out acid-base reactions),
recrystallization relies upon principles of structure, polarity, and solubility.
Understanding these principles is extremely important in designing pharmaceuticals, as
solubility will determine not only the proper route of administration but also the kinetics
and metabolic fate of the drug as well. Furthermore, as water solubility decreases for a
given drug, in general its ability to cross the blood-brain barrier increases, which can be
either essential to the drug’s action or detrimental to the patient. Although it is usually
impossible to predict the exact solubility of any organic compound on sight, below we
have provided some general principles to guide your predictions:
• Only organic compounds that contain polar functional groups (e.g., hydroxyl,
carbonyl, amino) can be dissolved in water to any appreciable extent. Like dissolves
like, and the only way to make an organic compound like water is to make it
extremely polar.
• It is commonly observed that only five or fewer carbons can be rendered soluble by a
polar functional group; any more than that and the compound behaves like a nonpolar
compound.
• Branched chains or rings can increase water solubility due to a decreased surface area
– remember oil and water – hydrocarbon chains would prefer to decrease their contact
with water and vice versa.
• Compounds with multiple polar functional groups can display behavior more like
polar compounds than hydrocarbons, and they can even prevent a compound from
dissolving in organic solvents!
nonpolar hexane 69
diethyl ether 35
↓ ethyl acetate 77
methylene chloride 40
↓ acetone 56
ethanol 78
↓ methanol 65
polar water 100
Notice that all of the solvents listed above (except for water) are fairly low boiling;
this makes it relatively easy to evaporate off residual solvent after the crystals have been
collected by filtration. When using water in a recrystallization, it is often difficult to
“dry” the crystals, which can lead to melting point depression.
All of these solvents are flammable except for water, so a steam bath is the
appropriate heating device — never an open flame or a hot plate! The latter devices can
cause solvents to boil over and ignite, causing a big fireball. Use a hot plate only for
heating water.
Even when you know the structure of your compound, it can sometimes be difficult to
find a solvent that works well for recrystallizing your compound. This problem can often
be solved by using a binary mixture of solvents: if your compound dissolves quite well in
one solvent at all temperatures (hot and cold) and doesn’t dissolve in another solvent at
any temperature (hot or cold), then a mix of these solvents may provide the necessary
properties for a recrystallization (provided that the solvents are miscible). In this lab, you
will learn two methods of determining an appropriate mixed solvent system for
recrystallization.
After a solvent is selected, the compound to be recrystallized is dissolved in a
minimal amount of hot solvent, in an Erlenmeyer flask. It is crucial that you use a
minimum amount, or your compound may remain in solution when you cool it.
Safety Precautions
• Run the steam tap for 30 seconds or so before attaching it to the bath; this allows the
corrosion inhibitors and other nastiness in the pipes to clear out instead of blowing it
all into the bath.
• Let steam baths and hot plates cool down before putting them back.
• Leave hood sashes at the appropriate level. There are height locks on them for a
reason.
• Use the steam baths with only a gentle supply of steam, or it will start raining in your
hood.
• Turn off the steam when you aren’t using it.
Procedure
Testing many recrystallization solvents can take a long time and is usually more
trouble than it’s worth. A quicker method is to dissolve your compound in a hot solvent
in which it is very soluble and then “douse” or “bait” it with another solvent to reduce the
solubility. You end up recrystallizing from a mixed solvent system, but you create the
right mixture “on the fly.”
Weigh the rest of your unknown, and place it in an appropriately sized Erlenmeyer
flask (a 125 mL flask will do, unless we pass out something smaller). Based on your
results from small-scale recrystallizations, dissolve the unknown in the solvent in which
it is most soluble when hot. It is essential that you dissolve it in a minimal amount of hot
solvent. The best way to do this is to heat the solvent in a separate flask and then slowly
add the solvent to your unknown as you stir and heat it.
Collect the crystals by vacuum filtration using a Büchner funnel (don’t forget the
filter paper!) and an aspirator trap, and wash the crystals with a small amount of cold
solvent. Keep the aspirator on, draw air through the crystals for a few minutes, and fluff
them up with a spatula to accelerate the drying process as discussed before. Be patient.
Clean up your bench while you are waiting for the crystals to dry. Transfer the crystals to
a clean, dry piece of filter paper, and press them dry. Dry them in an oven if necessary.
Note the appearance of the crystals in your notebook (color, shape, etc.)
• If you have too little product to distill, simply push the thermometer down into the
flask and record the temperature at which the liquid condenses onto the thermometer.
• Use gloves when handling glass wool or else you’ll itch for a week. If you happen to
touch glass wool and your hands start to itch, go to the sink right away and scrub your
hands with cold water.
• Immediately recap anhydrous reagents (like magnesium sulfate) when finished with
them! Anhydrous means “no water” and the air alone contains enough water to ruin
many dry reagents.
Procedure
The simple distillation set up is as shown. Note that you can set up and begin this
distillation while recrystallizing (i.e. while waiting for your hot solution of pure
compound to cool). Then, once the distillation is running smoothly, you can filter and
dry your crystals and take a melting point if you have time. Multitask, but always keep
an eye on your distillation!!!
Set up a heating mantle as the heat source to distill your compound. Use a lab jack to
support it so that you can lower the heat source quickly if you need to. The heating
mantle should be plugged into a variac (never directly into an electrical outlet!) The
variac (the heavy thing with the dial) should be plugged into an electrical outlet. The
variac has an on/off switch and a control dial. The numbers on the dial measure voltage,
not temperature.
You should distill the liquid into a pre-weighed round-bottom flask. This will enable
you to obtain a yield without removing the liquid from the flask by simply weighing the
flask with the product and subtracting the mass of the flask. This is a good general policy
whether doing a distillation or removing solvent from a purified product on a rotovap. If
you remember to always do this, it will save you the pain of scraping your product out of
a round bottom after rotovapping in order to get a yield.
Place a boiling stone into the flask you will be distilling from. Be sure that your
apparatus is clamped properly before heating; the joint of the round bottom flask and the
water condenser should each be secured with a clamp. Wiggle the apparatus a bit to test
it. You’ll probably need to insulate your apparatus as shown. Glass wool underneath
aluminum foil works well. Insulate the round bottom flask neck and the distillation head,
but not the bottom of the flask. Be sure to recycle the glass wool back to the Glassware
Storage room or the white shelves.
Do not turn on the variac until your TF has checked your distillation apparatus and
given you the thumbs up to start heating. Start the variac on a low setting (like 40), and
turn up the voltage as needed (be patient, the heating mantles take a while to heat up and
you don’t want to overdo it!) A setting between 30 and 60 is usually used, though a
setting of 90 may be necessary for this lab. Never turn up a variac all the way.
In this experiment, where we have a very small amount of liquid, you will have to
shove the thermometer down to just above the boiling liquid to get an accurate boiling
point. This is not normal (usually you just leave the bulb just below the intersection of
the distillation head). Assume the highest temperature reading is the most accurate.
Once you have obtained a reading, pull the thermometer up far enough that it does not
obstruct the path of the distilling vapor (to the level of the sidearm).
Cleanup
• Wash all of your individual glassware, and return it to the dirty glassware bins.
• Return glass wool and aluminum foil to their containers.
• Remove the Tygon tubing from the condensers and return them to the common
glassware room, not the dirty glassware bins (are they made of glass?)
• Dispose of test tubes, pipets, melting point capillaries, and glass vials in the glass
waste containers.
• Dispose of leftover solids and filter paper in the solid waste buckets.
• Dispose of paper towels and gloves in the trash.
• All acetone rinses must go into recyclable acetone waste.
• Aqueous (water) and ethanolic solutions of organic chemicals go in the aqueous waste
bucket.
• Wipe off your benchtop with paper towels (water and acetone can be used if needed).
• Wash your hands well before you leave.
Pre-Lab Write-Up
Lab Write-Up
1) Why is fluted filter paper more efficient than filter paper folded into a smooth cone for
gravity filtrations?
2) Why should you use a stemless funnel for hot gravity filtrations during a
recrystallization?
3) Circle all of the following that you should not heat on a hot plate:
6) How would the following affect the percent recovery and melting point of your
unknowns?
a) too much recrystallization solvent was used.
b) the hot solution was not gravity-filtered before cooling.
c) the hot solution was gravity-filtered and immediately plunged into an ice bath.
7) How would the following affect the percent recovery and melting point of your
unknowns?
a) the crystals (after suction filtration) were washed with hot solvent.
b) the crystals were not washed at all.
c) the crystals were not allowed to fully dry during vacuum filtration.
9) How does the melting point of an impure compound compare to the literature melting
point? Briefly explain the chemical principle (in terms of structure and intermolecular
forces) behind this observation.
10) The boiling point of a liquid can likewise be affected by several factors. What effect
would each of the following changes have upon a distillation?
11) List three possible safety risks specific to this experiment. Briefly describe
precautions to address these risks.