Survey of Organic Chemistry Laboratory Manual

Distillation
Distillation is a method of separating a mixture of liquids based on the differences in the
boiling point of the individual components. It is also used to determine the boiling point of
certain substances. The boiling point is an important property in the characterization and
identification of pure compounds. Furthermore, the boiling point range is a good measure
of a liquid’s purity.

Distillation is a very old technique, which began as early as 1810 BC in Mesopotamia. This
method was already used to produce hundreds of liters of balms, essences and incense
from natural products. In medieval times, every alchemist’s laboratory housed a distillation
apparatus called retort. Since then, it has undergone countless improvisations. Distillation
is used industrially in petroleum refining (fractional distillation) and extraction of essential
oils (steam distillation).

Simple Distillation
Simple distillation is used when the boiling points of the components in a mixture differ by
at least 25 °C or when separating liquids from non-volatile solids or oils.

thermometer

thermometer packet
still head

water condenser

water
outlet

round water receiver

bottom flask inlet adapter

receiver flask

Bunsen burner

Figure 1. Simple Distillation Setup

The pot liquid is heated in the round bottom flask until it boils. As the liquid boils, its molecules
move faster until the molecules have enough energy to break away from the intermolecular
interactions that hold them together and escape into the gas phase. The vapor emitted rises to
the still head and is then pushed into the water condenser when the still head is fully saturated
with the vapor. The vapor condenses back into a liquid inside the water condenser as the water

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flowing on the sides of the condenser absorbs the heat from the vapor. The water inlet is found
near the mouth of the receiver adapter while the water outlet is found near the still head. The
flow of water is against gravity and the flow of the vapor.

The temperature of the vapor in the still head rapidly rises until the liquid boils. As the liquid
boils, the temperature of the vapor remains constant until the liquid from which the vapor
originated is distilled. If another liquid is present in the flask, the vapor temperature will
continue to rise until the remaining liquid boils; after which, the temperature will remain
constant until that liquid is distilled.

Simple Distillation Techniques

It is highly recommended to secure the glassware with rubber bands. A rubber band around
the water outlet of the water condenser should be tied to the neck of the still head while
another rubber band around the water inlet should be tied to the neck of the receiver
adapter. This is to prevent the setup from falling apart. The round bottom flask and the
condenser must be firmly secured by clamps, which should be properly attached to stable
iron stands.

The amount of mixture in the flask must not greatly exceed two-thirds of the flask’s
volume. This is to ensure more efficient evaporation. Likewise, the amount of liquid must
not be too little.

Smooth and even boiling is important for effective distillation. In order to achieve this, the
round bottom flask is heated using a heating mantle or an oil bath; however, a water bath is
used for liquids with a boiling point of less than 90 °C. Boiling chips are also added to
facilitate even boiling, and to make sure no liquid spurts directly into the condenser. For
high-boiling compounds, an air condenser is used, or air is allowed to pass through the
water condenser jacket instead of water.

Impurities cause a deviation in the boiling points of liquids. Thus, collecting several
fractions over certain temperature ranges is required. Distillate can be collected even
before the liquid reaches its boiling point. This distillate fraction is called the forerun. A
forerun is usually collected until the temperature remains constant or when the change in
temperature is minimal. At this point, the receiving flask is replaced by a new one, which
will collect distillate over a constant temperature. When the temperature suddenly rises, a
new flask will be collecting the distillate.

Immediately put out the heat source once the flask appears dry. It may contain substances,
such as organic solids, which are explosive at high temperatures.

Fractional Distillation
Fractional distillation is used when the boiling points of the components in a mixture are
close enough that the vapor emitted is a mixture of the components, with the more volatile
component present in greater amounts.

The resulting distillate is boiled and the vapor emitted will contain a greater amount of the
more volatile component. This process is repeated until the distillate only contains the
more volatile component. This repeated condensation-vaporization is done inside a

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fractionating column, placed in between the round bottom flask and still head. A
fractionating column is simply an air condenser packed with glass beads or other inert
material that provides a high surface area where condensation-vaporization takes place. It
also provides a temperature gradient where only the more volatile component of the
mixture exists as vapor at the top while the less volatile component condenses back into a
liquid which falls back into the round bottom flask. The length and the packing of the
column affect the number of condensation-vaporization cycles that can occur. Better
separation occurs with more condensation-vaporization cycles.

It is used in the refinery of crude oil where it is separated into different hydrocarbon
fractions with different boiling points. These include petroleum gases (bp up to 20 °C),
gasoline (bp up to 150 °C), kerosene (bp up to 200 °C) and diesel (bp up to 300 °C).

Vacuum Distillation
Vacuum distillation is used for liquids with very high boiling boils. In a closed vessel,
molecules in a liquid are in equilibrium with the airspace above it. The molecules in the
airspace exert a pressure known as the vapor pressure and this increases as the
temperature increases. Boiling occurs when the vapor pressure exerted by a liquid equals
the atmospheric pressure. The molecules in a liquid exert enough force against the airspace
above them that they escape as a gas. However, for liquids with very high boiling points,
high temperatures may cause them to decompose or the temperature is too high to distill
them safely. The pressure above the liquid can be reduced using a vacuum and this in turn
reduces the temperature at which they boil.

Steam Distillation
Steam distillation is used for heat sensitive compounds that are immiscible in water. Water
is added, or steam is bubbled into the sample and heated. The presence of water or steam
keeps the temperature at a maximum of 100 °C and the high heat capacity of water
prevents the sample from overheating. Some of the heat sensitive compounds are
vaporized together with water vapor as their added vapor pressures equal atmospheric
pressure and escape as a gas. The vapor mixture is then condensed into a layer of oil and
water, which can be decanted. This process only works if the heat sensitive compound is
immiscible with water; otherwise, the resulting distillate would be a solution which cannot
be separated.

This method is used in the extraction of essential oils from herbs and flowers. The distillate
contains essential oils and water saturated with essential oils known as essential waters,
floral waters, or hydrosols. These essential waters contain water-soluble constituents of
essential oils free from lipophilic substances such as hydrocarbons, esters or ethers.

References
Most CF. Experimental Organic Chemistry. USA: Wiley & Sons; 1988.

Palleros, DR. Experimental Organic Chemistry. USA: Wiley & Sons; 1988.

World Book Encyclopedia. USA: World Book; 1994.

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Experiment 2:

Distillation of an Unknown Liquid

In this experiment, a certain colorless liquid dyed with a solid dye (methylene blue or food
color) will be distilled. The liquid is a common laboratory solvent that has no more than 6
carbon atoms.

Prelab Questions
1. What type of impurities can be removed using simple distillation?
2. What forces are involved when a liquid boils? Are bonds broken when a liquid boils?
Explain.
3. Why shouldn’t the pot mixture exceed two-thirds of the round bottom flask nor be
too little?
4. What may happen if one forgets to add boiling chips?
5. What constitutes a forerun? Why is it collected separately from the rest of the
distillate?
6. Why should the water in the condenser move against gravity?

Materials
 aluminum foil
 rubber bands
 boiling chips
 unknown liquid

Procedures
Obtain about 15 mL of the unknown solution from the stockroom technician.

TIP: Take note of the smell.

Assemble a simple distillation setup. Cover the mouth of the receiving flask with aluminum
foil to minimize the evaporation of the distillate. Punch a hole using the receiver adapter to
allow it to pass through the mouth of the flask. For very volatile compounds, an ice-water
bath is used but this is not necessary for this experiment.

TIP: Use rubber bands to secure the glassware and hold them together.

Record the volume of the unknown liquid. Remove the round bottom flask; pour in the
unknown liquid and add boiling chips. Clamp the flask back into the still head and start
distilling.

Take note of the temperature at which the forerun (first ~20 drops) was collected. Quickly
replace the receiving flask and collect another batch of distillate. Take note of the
temperature range at which the change in temperature slowed down or the temperature
remained constant. Collect a new batch of distillate when the temperature starts to rise

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rapidly. Continue heating until only a very small amount of liquid remains in the flask but do
not distill to dryness.

Measure the total amount of distillate collected but do not mix the liquids together.

Boiling Point Determination

Wash the round bottom flask and throw the residue in designated waste containers. Triple-
wash the flask with small amounts of the forerun and distill the second batch of the
distillate.

TIP: Use new boiling chips.

If the volume of pot liquid is too little, add some of the forerun or the third batch of
distillate. Distill the liquid. Collect 1-ml fractions with a 10-ml graduated cylinder receiver.
Record the temperature for each fraction and take note of the temperature at which it
remained constant. Compare this with the boiling point of common laboratory solvents and
take the other characteristics of the liquid such as the smell, viscosity, miscibility, etc. into
consideration. Submit the vial containing the distillate.

Waste Disposal
Dispose the liquid in a Non-Halogenated Waste container.

Postlab Questions
1. When does a liquid boil at temperatures above and below their expected boiling
points?
2. Why isn’t the boiling point of the second fraction in the first part of the experiment
used to determine the boiling point of the liquid?
3. Would you expect a 100% recovery in this experiment? Explain.
4. What do you expect to find in the receiving flask after distillation? How about in the
round bottom flask?
5. Based on the physical properties of the unknown, what is the identity of the
unknown liquid?
6. Is it possible to separate a mixture of n-hexane (bp: 68.7 °C) and isohexane (2-
methylpentane) (bp: 60.3 °C) using the setup used in this experiment? Explain.

References
Most CF. Experimental Organic Chemistry. USA: Wiley & Sons; 1988.

Palleros DR. Experimental Organic Chemistry. USA: Wiley & Sons; 1988.

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