Distillation

Simple distillation is a procedure by which two liquids with different boiling points can be separated.
Simple distillation (the procedure outlined below) can be used effectively to separate liquids that have at
least fifty degrees difference in their boiling points. As the liquid being distilled is heated, the vapors that
form will be richest in the component of the mixture that boils at the lowest temperature. Purified
compounds will boil, and thus turn into vapors, over a relatively small temperature range (2 or 3°C); by
carefully watching the temperature in the distillation flask, it is possible to affect a reasonably good
separation. As distillation progresses, the concentration of the lowest boiling component will steadily
decrease. Eventually the temperature within the apparatus will begin to change; a pure compound is no
longer being distilled. The temperature will continue to increase until the boiling point of the next-lowest-
boiling compound is approached. When the temperature again stabilizes, another pure fraction of the
distillate can be collected. This fraction of distillate will be primarily the compound that boils at the second
lowest temperature. This process can be repeated until all the fractions of the original mixture have been
separated.

Figure 1. Distillation apparatus. A distillation flask with a thermometer is placed in a heating mantle and is
connected to a condenser.

Figure 2. The tubes on the condenser are attached to a water source, with the water flowing in the low
end and flowing out the high end of the condenser. The condensed vapor drips into the collection
receiver.

Basic Procedure
1. Check the calibration of the thermometer that is to be used. This can be accomplished by placing
the thermometer in an ice bath of distilled water. After the thermometer has been allowed to reach
thermal equilibrium, place it in a beaker of boiling distilled water and again allow it to reach thermal
 equilibrium. If the temperatures measured deviate from the expected values by more than two
degrees, obtain a new thermometer and check its calibration.
2. Fill the distillation flask. The flask should be no more than two thirds full because there needs to
be sufficient clearance above the surface of the liquid so that when boiling commences the liquid is not
propelled into the condenser, compromising the purity of the distillate. Boiling chips should be placed
in the distillation flask for two reasons: they will prevent superheating of the liquid being distilled and
they will cause a more controlled boil, eliminating the possibility that the liquid in the distillation flask
will bump into the condenser.

Figure 3. The thermometer is inserted in the distillation flask through a hole in the cork stopper.
The arm of the flask is inserted through a hole in the stopper of the condenser. Make sure these
stoppers are airtight, or the vapor will escape.

3. Heat the distillation flask slowly until the liquid begins to boil (see Figure 4). Vapors will begin to
rise through the neck of the distillation flask. As the vapors pass through the condenser, they will
condense and drip into the collection receiver (see Figure 5). An appropriate rate of distillation is
approximately 20 drops per minute. Distillation must occur slowly enough that all the vapors condense
to liquid in the condenser. Many organic compounds are flammable and if vapors pass through the
condenser without condensing, they may ignite as they come in contact with the heat source.

Figure 4. The distillation flask being heated in a heating mantle.

 Figure 5. The collection receiver
The vapors condense and drip from the condenser into the flask.

4. As the distillate begins to drop from the condenser, the temperature observed on the
thermometer should be changing steadily. When the temperature stabilizes, use a new receiver to
collect all the drops that form over a two to three degree range of temperature. As the temperature
begins to rise again, switch to a third collection container to collect the distillate that now is formed.
This process should be repeated; using a new receiver any time the temperature stabilizes or begins
changing, until all of the distillate has been collected in discrete fractions.
o note: All fractions of the distillate should be saved until it is shown that the desired
compound has been effectively separated by distillation.
5. Remove the heat source from the distillation flask before all of the liquid is vaporized. If all of the
liquid is distilled away, there is a danger that peroxides, which can ignite or explode, may be present in
the residue left behind. Also, when all of the liquid has evaporated, the temperature of the glass of the
filtration flask will rise very rapidly, possibly igniting whatever vapors may still be present in the
distillation flask.
1. Never distill to dryness. The residue left in the distillation flask may contain peroxides, which
could ignite or explode after all the liquid has distilled away.
2. Make sure that all joints are secured very tightly. If any vapor escapes at the connection points, it
may come into direct contact with the heat source and ignite.
3. Never heat a closed system, the increasing pressure will cause the glass to explode. If the
distillation flask has a tapered neck, the thermometer may be placed in such a way as to block to flow
of vapors up the neck of the flask; in effect creating a closed system; make sure that if using a tapered
neck flask, the thermometer is not resting in the lowest portion of the neck.
Simple distillation is effective only when separating a volatile liquid from a nonvolatile substance or when
separating two liquids that differ in boiling point by 50 degrees or more. If the liquids comprising the
mixture that is being distilled have boiling points that are closer than 50 degrees to one another, the
distillate collected will be richer in the more volatile compound but not to the degree necessary for
complete separation of the individual compounds.

The basic idea behind fractional distillation is the same as simple distillation only the process is repeated
many times. If simple distillation was performed on a mixture of liquids with similar volatilities, the resulting
distillate would be more concentrated in the more volatile compound than the original mixture but it would
still contain a significant amount of the higher boiling compound. If the distillate of this simple distillation
was distilled again, the resulting distillate would again be even more concentrated in the lower boiling
compound, but still a portion of the distillate would be the higher boiling compound. If this process is
repeated several times, a fairly pure distillate will eventually result. This, however, would take a very long
time. In fractional distillation, the vapors formed from the boiling mixture rise into the fractionating column
where they condense on the column's packing. This condensation is tantamount to a single run of simple
distillation; the condensate is more concentrated in the lower boiling compound than the mixture in the
distillation flask. As vapors continue to rise through the column, the liquid that has condensed will
revaporize. Each time this occurs the resulting vapors are more and more concentrated in the more
volatile substances. The length of the fractionating column and the material it is packed with impact the
number of times the vapors will recondense before passing into the condenser; the number of times the
column will support this is referred to as the number of theoretical plates of the column.

Since the procedures of simple distillation are so similar to those involved in fractional distillation, the
apparatus that are used in the procedures are also very similar. The only difference between the
equipment used in fractional distillation and that used in simple distillation is that with fractional distillation,
a packed fractionating column is attached to the top of the distillation flask and beneath the condenser.
This provides the surface area on which rising vapors condense, and subsequently revaporize.

The fractionating column is used to supply a temperature gradient over which the distillation can occur. In
an ideal situation, the temperature in the distillation flask would be equal to the boiling point of the mixture
of liquids and the temperature at the top of the fractionating column would be equal to the boiling point of
the lower boiling compound; all of the lower boiling compound would be distilled away before any of the
higher boiling compound. In reality, fractions of the distillate must be collected because as the distillation
proceeds, the concentration of the higher boiling compound in the distillate being collected steadily
increases. Fractions of the distillate, which are collected over a small temperature range, will be
essentially purified; several fractions should be collected as the temperature changes and these portions
of the distillate should be distilled again to amplify the purification that has already occurred.

Distillation
Distillation is the process of heating a liquid until it boils, then condensing
and collecting the resultant hot vapors. Mankind has applied the principles of
distillation for thousands of years. Distillation was probably first used by
ancient Arab chemists to isolate perfumes. Vessels with a trough on the rim
to collect distillate, called diqarus, date back to 3500 BC.

In the modern organic chemistry laboratory, distillation is a powerful tool,

both for the identification and the purification of organic compounds. The
boiling point of a compound is one of the physical properties used to identify
it. Distillation is used to purify a compound by separating it from a non-
volatile or less-volatile material. When different compounds in a mixture
have different boiling points, they separate into individual components when
the mixture is carefully distilled.

Distillation for Boiling Point Determination

The organic teaching labs employ distillation routinely, both for the
identification and the purification of organic compounds. The boiling point of
a compound, determined by distillation, is well-defined and thus is one of
the physical properties of a compound by which it can be identified.
Distillation is used to purify a compound by separating it from a non-volatile
or less-volatile material. Because different compounds often have different
boiling points, the components often separate from a mixture when the
mixture is distilled.

The boiling point is the temperature at which the vapor pressure of the liquid
phase of a compound equals the external pressure acting on the surface of
the liquid. The external pressure is usually the atmospheric pressure. For
instance, consider a liquid heated in an open flask. The vapor pressure of the
liquid will increase as the temperature of the liquid increases, and when the
vapor pressure equals the atmospheric pressure, the liquid will boil. Different
compounds boil at different temperatures because each has a different,
characteristic vapor pressure: compounds with higher vapor pressures will
boil at lower temperatures.

Boiling points are usually measured by recording the boiling point (or boiling
range) on a thermometer while performing a distillation. This method is used
whenever there is enough of the compound to perform a distillation. The
distillation method of boiling point determination measures the temperature
of the vapors above the liquid. Since these vapors are in equilibrium with the
boiling liquid, they are the same temperature as the boiling liquid. The vapor
temperature rather than the pot temperature is measured because if you put
a thermometer actually in the boiling liquid mixture, the temperature
reading would likely be higher than that of the vapors. This is because the
liquid can be superheated or contaminated with other substances, and
therefore its temperature is not an accurate measurement of the boiling
temperature.

If you are using the boiling point to identify a solid compound which you
have isolated in the lab, you will need to compare its boiling point with that
of the true compound. Boiling points are listed in various sources of scientific
data, as referenced on the Chemical Information page on this website.

If you look up the boiling point of a compound in more than one source, you
may find that the values reported differ slightly. The literature boiling point
depends on the method and ability of the technician taking the boiling point,
and also on the purity of the compound. While theoretically all boiling points
should be constant from source to source, in reality the reported boiling
points sometimes vary. Therefore, always reference the source of the
physical data which you write in your lab report.

Distillation for Compound Purification

Simple distillations are used frequently in the organic chemistry teaching
labs. They are useful in the following circumstances:
  the liquid is relatively pure to begin with (e.g., no more than 10% liquid
contaminants)
 the liquid has a non-volatile component, for example, a solid contaminant
 the liquid is contaminated by a liquid with a boiling point that differs by at
least 70°C

"Simple" distillation may be a misleading term to the beginning organic

chemistry student, since it takes a lot of practice in simple distillation to
become proficient in this technique. It is especially important to do a perfect
simple distillation when determining a boiling point for identification
purposes. You can see detailed photos of a simple distillation set-up here. Be
sure to have correct placement of the thermometer, fill the flask to the
correct level, and use a boiling chip.

Fractional Distillations
Mixtures of liquids whose boiling points are similar (separated by less than
70°C) cannot be separated by a single simple distillation. In these situations,
a fractional distillation is used. You can see photos of a fractional distillation
set-up here.

Vacuum Distillations
Vacuum distillation is distillation at a reduced pressure. Since the boiling
point of a compound is lower at a lower external pressure, the compound
will not have to be heated to as high a temperature in order for it to boil.
Vacuum distillation is used to distill compounds that have a high boiling point
or any compound which might undergo decomposition on heating at
atmospheric pressure. The vacuum is provided either by a water aspirator or
by a mechanical pump. You can see photos of a fractional distillation set-up
here. Always check for star cracks in the flasks before beginning a vacuum
distillation.