Chem.

2416F19
Exp. 4

Experiment 4: Distillation

Introduction

Distillation is a technique used to separate liquid mixtures, and relies on differences in vapour
pressures between compounds. In a simple distillation, a mixture of liquids is heated and the
vapours from the boiling mixture are condensed back into the liquid phase and collected. The
apparatus for a simple distillation is shown below. The mixture of liquids is placed in the stillpot,
and the vapours from the boiling mixture are passed through the stillhead where the temperature
of the vapours can be monitored with a thermometer. The vapours pass into a condenser to
condense, and the condensed liquid is passed through the receiver adaptor to collect in an
appropriate flask.

Thermometer

Stillhead Condenser
Receiver adaptor

Stillpot

Cold water out

Cold water in

Collecting flask
The apparatus above is used for simple distillations, but many other variants of distillation exist,
such as steam and vacuum distillation. Rotoevaporation is another example of distillation, but it is
used to remove liquids from mixtures and to retain non-volatile components.

Theory of distillation for pure liquids

The particles of a liquid exist in equilibrium between the liquid and gas phase. As the temperature
of this system is raised, more particles will exist in the gas phase and the vapour pressure of the
liquid increases. When the vapour pressure above a liquid is equal to the atmospheric or external
pressure, the liquid will begin to boil. Boiling corresponds to the spontaneous formation of
bubbles, or particles in the gas phase, from a liquid.

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A pure liquid will maintain a constant temperature during boiling. If more heat is added to the
boiling pure liquid, the rate at which liquid particles enter the gas phase will increase, but the
temperature of the system will not change. The boiling point of a liquid is the temperature when it
starts to boil, and is usually within a 2oC range. When the composition of the vapours passing
through a stillhead are constant, as for a distilling a pure liquid, the temperature of the vapours will
remain constant.

Heat can accumulate in liquids, and this may result in the liquid violently starting to boil. During
a distillation this can result in liquid instead of vapour passing through the stillhead into the
condenser, potentially contaminating any distillate that has been collected. Boiling chips are used
to provide spaces for bubble formation so that the heating process proceeds in a controlled manner.
Boiling chips come in a variety of forms, but all are composed of porous material, and the pores
in the boiling chips act as nucleation sites for bubble formation. Once the liquid has stopped
boiling, the boiling chips must be replaced because the pores will have become filled with the
liquid. A magnetic stirbar can also be used to ensure smooth boiling during distillation.

Theory of distillation for mixtures

Only ideal mixtures will be considered here, where an ideal mixture is a homogenous liquid
composed of two or more volatile compounds. Ideal mixtures must obey Dalton’s Law and
Raoult’s Law, and these two laws govern the boiling and composition behaviour of ideal mixtures.

Dalton’s Law states that the total pressure in a volume of a mixture of gases is equal to the sum of
partial pressures of the components of the gas, and it is depicted mathematically below where PT
is the total pressure of the mixture of gases, and PA and PB are the partial pressures of gases A and
B in the mixture. Dalton’s Law applies to a mixture of gases with any number of components.

𝑃𝑇 = 𝑃𝐴 + 𝑃𝐵

Raoult’s Law relates to homogenous mixtures of liquids, and states that the partial pressure of gas
particles due to a liquid in a homogenous mixture is related to the vapour pressure of the pure
liquid and the mole fraction of the liquid in the liquid mixture. Raoult’s Law is depicted below,
where PA is the partial pressure of gas phase particles of A of a homogenous mixture of A with
other liquids, PoA is the vapour pressure of pure liquid A, and XA is the mole fraction of liquid A
in the liquid mixture. The value of XA is simply the ratio of the moles of A in the liquid mixture
to the total number of moles of particles in the liquid phase. An example is given for a binary
mixture of liquid A and liquid B.

𝑃𝐴 = 𝑋𝐴 𝑃𝐴𝑜

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 𝐴 𝑛
𝑋𝐴 = ⁄𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 = 𝐴⁄𝑛 + 𝑛
𝐴 𝐵

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Exp. 4

𝑋𝐴 + 𝑋𝐵 = 1 𝑓𝑜𝑟 𝑎 𝑏𝑖𝑛𝑎𝑟𝑦 𝑚𝑖𝑥𝑡𝑢𝑟𝑒

Vapour pressure versus composition diagrams

A vapour pressure versus composition diagram is a useful graphical tool to follow the course of a
distillation, and its formulation directly relies on both Dalton’s Law and Raoult’s Law. Note this
diagram applies to a single temperature or standard state.
Vapour
Pressure due o
to A (PA) P B

Vapour
Pressure due
o to B (PB)
P A

0.0 1.0
Composition B
There are several points to note about this diagram for an ideal mixture of liquids A and B in
relation to Dalton’s Law and Raoult’s Law:

 Regardless of the mole fraction of B (the x-axis), the total pressure above the mixture
(PTotal) is always the sum of the partial pressures of the components of the mixture (PA +
PB = PTotal, Dalton’s Law).
 At mole fraction XB = 0 there is no B in the mixture, and therefore the mixture is actually
pure A, and the total vapour pressure above pure A is PoA, the vapour pressure of pure
liquid A (Raoult’s Law).
 At mole fraction XB = 1 the mixture is pure B and contains no A, and therefore the total
vapour pressure above pure B is PoB , the vapour pressure of pure liquid B (Raoult’s Law).
 The value of PTotal changes linearly from XB = 0 to XB = 1, and has a intercept of PoA at XB
= 0, just as predicted by substituting Raoult’s Law into Dalton’s Law:
𝑃𝑇 = 𝑃𝐴 + 𝑃𝐵 = 𝑋𝐴 𝑃𝐴𝑜 + 𝑋𝐵 𝑃𝐵𝑜 = 𝑃𝐴𝑜 + 𝑋𝐵 (𝑃𝐵𝑜 − 𝑃𝐴𝑜 )
 At XB = 0.5 the vapour phase above the mixture (described by P T) has more contribution
from the vapour pressure of the more volatile component (B).

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Exp. 4

Boiling point composition diagrams

During the distillation of an ideal mixture of liquids the composition of both the liquid and gas
phase above the liquid are constantly changing as the vapour is removed through the condenser.
This concept is depicted in a boiling point composition diagram, which is a plot of boiling
temperature versus composition of either the liquid phase or the vapour phase. An example of a
boiling point composition diagram is depicted below.

Vapour composition line

Liquid composition line

The boiling point composition diagram is consistent with Raoult’s Law. The boiling point of pure
A is indicated as 95oC when the mole fraction of A is 1, while the boiling point of B is indicated
as 65oC when the mole fraction of A is 0 (mole fraction of B is 1), and therefore B is the more
volatile, or lower boiling, component of the mixture.

If a mixture of A and B that has a mole fraction of 0.60 A is heated, the boiling point composition
diagram indicates that the liquid will boil at approximately 76 oC, and that the composition of the
vapours from the boiling mixture will contain a mole fraction of approximately 0.24 A. This
implies that the vapour above a boiling mixture is enriched in the more volatile, or lower boiling
component relative to the composition of the mixture.

Consider an experiment where a mixture of A and B of unknown composition is heated until it

boils at approximately 84oC. Observing this boiling temperature implies that the composition of
the vapour whose temperature was measured was approximately 0.46 A, and that the composition
of the boiling liquid was approximately 0.80 A.

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Exp. 4

An important aspect of a boiling point composition diagram is that during a distillation of a mixture
of liquids the vapour is constantly being removed. Since the vapour is enriched in the more volatile
component of the mixture, the boiling liquid must be enriched in the less volatile component as
the distillation progresses, and this is the key to using distillation to separate liquid mixtures.

When a mixture of two liquids is distilled using the simple setup depicted above, the temperature
of the vapours above the boiling liquid will reflect the varying composition of the vapours. When
the temperature of the vapours is plotted against the volume of condensed vapours, or distillate,
collected the plot will depict a gradual change over from the boiling point of the more volatile
liquid to the less volatile liquid, and this is depicted in the plot below.
Stillhead Temperature

Simple Distillation

Fractional Distillation

Volume of Distillate

Fractional distillation
As can be observed from the plot above, a simple distillation of an ideal mixture of two liquids
will generally not provide vapours that are only composed of one of the components of the mixture.
The greater the difference in boiling points of the two liquids, the better the separation of the two
liquids in the vapours over the boiling mixture will be.

Fractional distillation can be used to obtain better separation between the components in an ideal
mixture of two liquids. The experimental setup for a fractional distillation differs from a simple
distillation by the addition of a fractionating column between the stillpot and the stillhead.
Fractionating columns come in a variety of types, but they all include a high surface area path for
the vapours from the stillpot to travel through before they reach the stillhead. Examples of
fractionating columns are a glass tube filled with glass beads, a glass tube containing glass fingers
from the tube wall (Vigreux), and a glass tube containing a glass spiral column (Dufton).

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The fractionating column replicates a several simple distillations, although this is only a rough
representation of what actually happens. As hot vapours move up the fractionating column, some
of the vapours will condense on the large surface area of the column, and the less volatile
components are more likely to condense than the more volatile components. The condensed
vapours will run down the wall of the column and meet hot ascending vapours. The hot ascending
vapours will revapourize some of the descending condensed vapours, and the more volatile
components will be preferentially revapourized. As this cycle of condensation and revapourization
of the vapours passing through the fractionating column continues, the hot ascending vapours will
be enriched in the more volatile component of the mixture, and the less volatile component of the
mixture will condense and travel down the column to return to the stillpot as liquid. The vapours
that pass through the entire column and arrive at the stillhead will be significantly enriched in the
more volatile component of the mixture, and so will the distillate obtained by collecting the
condensed vapours. The fractionating column essentially replicates a series of simple distillations
in which the initial distillate is more enriched in the more volatile component of the mixture.

A plot of stillhead temperature versus volume of distillate collected will reflect the improved
separation over a simple distillation. The initial distillate will be almost entirely the more volatile
component, and therefore the temperature at the stillhead will reflect a pure compound with a
constant boiling point. When the stillpot becomes depleted of the more volatile component, the
composition of the vapours at the stillhead will change over to almost entirely the less volatile
component, and therefore the temperature at the stillhead will reflect a pure compound with a
constant, but higher, boiling point. An example of a temperature versus volume of distillate plot
for a fractional distillation is depicted above, and contrasted with the same plot for a simple
distillation. Using the plot for the simple distillation it is impossible to determine what volume of
the more volatile (lower boiling point) liquid was collected, whereas the volume of the distillate
for the more volatile liquid can be easily determined by observing at what volume of the
temperature of the distillate sharply increases, indicating that the stillpot has been depleted of the
more volatile liquid.

Azeotropes
Certain mixtures with specific compositions will distill in the same manner as pure liquids
(constant stillhead temperature). A common example is the azeotrope that ethanol and water form.
Ethanol has a boiling point of 78.4oC and water has a boiling point of 100oC, but a mixture of
95.6% ethanol and 4.4% water has a constant boiling point of 78.1oC, and this mixture is called a
minimum boiling azeotrope. The implication of this is that if an aqueous mixture that contains
15% ethanol is distilled, the purest distillate will only contain 95.6% ethanol. Distillation can
never produce distillate that contains over 95.6% ethanol from a mixture of ethanol and water. An
advantage of this is that pure ethanol can be used to remove traces of water from mixtures. Adding
95.6 mL of ethanol to a mixture that contains 4.4 mL of water will remove all the water at 78.1oC
if the mixture is distilled, where it would usually take a minimum of 100oC to remove all the water.

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Exp. 4

This Experiment
In this experiment each group will perform both a simple distillation and a fractional distillation
of an impure mixture of two miscible liquids. The goal of the experiment is to compare the two
distillation techniques, to identify each liquid, and to also estimate the composition of the mixture.
The possible liquids are diethyl ether, dichloromethane, acetone, ethyl acetate, water and toluene,
and the possible compositions are 1:2, 1:1 and 2:1. The stillhead temperature versus volume of
distillate for both distillations must be recorded.

Materials and equipment

Materials
Unknown mixture (20 mL), Boiling stones

Equipment
B19 50 mL RBF, Stillhead, Thermometer, Condensor, Condensor tubing, Receiver adaptor,
Dufton column (for fractional distillation), 50 mL Thermowell and controller, Lab jack, Lab stand,
Clamp and bosshead, 2 Rubber bands, 10 mL Graduated cylinder, Aluminum foil (if required).

Procedure

Setting up the distillation apparatus (either simple or fractional distillation)

1. Assemble the clean glassware in the diagram for the simple distillation. The first step is to
clamp the RBF in place with a clamp attached to a lab stand. The foot of the stand should
be directly under the RBF. Place the stillhead into the RBF.

2. Place a rubber band around each hose barb of the condenser, and attached condenser tubing
to each barb. Attach the condenser to the side arm of the stillhead, and wrap the rubber
band around the neck of the stillhead to ensure that the condenser will not fall off the
stillhead side arm. Attach the hose from the bottom of the condenser to the water tap
securely. Place the end of the hose attached to the top of the condenser in a sink in the
fumehood. Attach a bosshead to the end of the exit hose to ensure that water pressure will
not cause it to leave the sink.

3. Attach the receiver adaptor to the bottom of the condenser, and wrap the rubber band
around the nipple of the adaptor to ensure that the adaptor will not fall off the condenser.

4. Turn the water on for the condenser slowly. Only a gently flow of water is required for the
condenser; ask a demonstrator or instructor if you are not sure.

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5. Place a lab jack on the lab stand. Plug the 50 mL Thermowell into a Thermowell controller,
and plug the controller into an outlet on the fumehood. Place the Thermowell on the lab
jack, and raise the jack until the cup of the Thermowell is firmly against the RBF.

Distillation of the unknown mixture (either simple or fractional distillation)

6. Obtain 20 mL of the unknown mixture. Have a partner carefully lift up the stillhead and
attached glassware, and pour the unknown into the RBF using a funnel. Obtain a couple of
boiling chips and add these to the RBF.

a. Simple distillation: Replace the stillhead and attached glassware onto the RBF. Add
a thermometer to the neck of the stillhead.

b. Fractional distillation: Obtain a short (~8”) Dufton column (be very careful of the
glass spiral inside the column because it is not physically attached to the column ie.
it can fall out). Add the Dufton column to the RBF, and insert the stillhead into the
top of the Dufton column. Add a thermometer to the neck of the stillhead. Wrap the
Dufton column in a single layer of aluminum foil if required.

7. Use a 10 mL graduated cylinder to collect the distillate as it leaves the receiver adaptor.
Depending on your setup you may have to lower the distillation apparatus, or use a lab jack
to raise the graduated cylinder up to the receiver adaptor. Be very careful if you adjust the
height of the distillation apparatus.

8. Turn the Thermowell controller to the maximum setting and wait for the RBF contents to
boil. Turn down the controller once boiling has started, and adjust the controller as needed
to maintain a constant and gentle boil.

9. The RBF and stillhead must warm up also, so there will be a significant warming period.
The vapours can be observed rising up the stillhead as a ring of condensate around the
glassware. When the vapours reach the thermometer, the thermometer will start to indicate
an increase in temperature, and once the thermometer has warmed up the vapours will start
to pass into the condenser and form distillate.

10. When the first drop of distillate has passed through the receiver adaptor and fallen into the
graduated cylinder record the temperature from the thermometer. This temperature will
correspond to 0 mL of distillate. Record the temperature for each successive 1 mL of
distillate that collects. Adjust the controller to maintain a constant boil throughout the
distillation. When 9 mL of distillate have been collected quickly transfer the distillate to a
beaker, and continue collecting distillate in the graduated cylinder.

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11. Try to collect at least 15 mL of distillate, but obtain at least three data points at the higher
temperature plateau (±1 oC). Stop collecting distillate when no more appears and the
temperature begins to drop. Turn off the Thermowell controller, and also the water for the
condenser, and allow the glassware to cool for a few minutes.

12. When the glassware has cooled disassemble the apparatus above the stillpot. Measure the
volume of liquid that remained undistilled in the stillpot RBF by removing it with a pipette.
When switching between distillations remove any residual liquid, add fresh boiling chips
and mixture, and proceed with the distillation. After the second distillation is complete and
the residual volume has been measured, rinse all glassware with acetone. The distillate and
residue from the RBF can be put into the non-halogenated organic waste container. Boiling
chips can be put into the solid waste container. Aluminum foil can be placed in the
indicated container. Return all equipment to either your group’s locker or the common
locker.