CHEM 2155 Fundamental Organic Chemistry Laboratory

Instructor: Dr. CHAN, Ho Wai Dennis

Experiment 2: Distillation of Organic Liquids

Introduction:

Distillation is the most common method used to separate and purify liquids. The process
involves heating a liquid to its boiling point, conducting the vapors to a cooling device where
they are allowed to condense, and collecting the condensate.

General Principles
If a liquid is kept in a sealed container, some molecules escape from the liquid's surface
into the space above it. When equilibrium is established, the number of molecules escaping the
liquid equals the number of molecules in the vapor that strike the liquid surface and stick. The
molecules in the vapor also strike the walls of the container and exert a pressure, defined as the
vapor pressure of the liquid. If the temperature of the liquid is raised, a greater number of
molecules escape to the vapor phase until equilibrium is once again established; the vapor
pressure of the liquid increases with increasing temperature. The following figure shows a
typical vapor pressure-temperature curve (Figure 1).

Figure 1.
Simple Distillation
Liquids are usually purified by distillation. Simple distillation allows non-volatile impurities
(with very high boiling points) to be removed from a liquid. For example, simple distillation
works well in separating sodium chloride (b.p. 1413 °C) from water (b.p. 100 °C). The sample
is heated, allowing some of the molecules to escape from the liquid into the gas phase.
Impurities with much higher boiling points will remain in the distillation pot. As the vaporized

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sample (minus impurities) is cooled in the condenser, it returns to the liquid phase. The purified
liquid is collected in the receiver.

temperature →
B

T
C1

T
A

C2 C1
100 0% A
0 composition 100% B

Figure 2. A typical liquid-vapor composition diagram

Vacuum Distillation
Distillation at reduced pressure is especially useful in purifying sample that can easily
decompose at high temperature. If the boiling point of the sample being distilled is high (greater
than 125 C and typically greater than 150 C), one can distill the liquid at reduced pressure by
introducing a vacuum (suction) to the distillation setup (see Figure 3) such that the liquid can
be distilled at a lower temperature. Then, decomposition of the sample can hence be prevented.
The lower the pressure inside the setup, the lower the temperature of the sample being distilled,
but the lowering of the boiling point attending a reduction in pressure is much more pronounced
at low than at high pressures.

Figure 3. Macroscale apparatus for vacuum distillation

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Fractional Distillation
If simple distillation is used to separate a 50/50 mixture of cyclohexane (b. p. 80.7 °C)
and toluene (b. p. 110.6 °C), the first fraction of distillate would be mostly cyclohexane, but
some toluene would also be present. The material left in the pot would be mostly toluene. In
other words, if a mixture of two miscible liquids with different boiling points is heated to
boiling, the vapor will not have the same composition as the liquid; it will be richer in the more
volatile component. The distillate would have increasing amounts of toluene and decreasing
amounts of cyclohexane as the distillation continued.
From the composition diagram (Figure 4), a mixture of A and B with composition C1
is heated, it will boil at TC1. Reading horizontally on the graph, one sees that the vapor at TC1
will have the composition given by C2. This means that if mixture C1 were placed in a
distillation apparatus and heated to its boiling point, the vapor (and therefore the first drop of
liquid to be condensed) would have the composition C2; it would be much richer in A, the more
volatile of the two components, than was the original liquid. As the distillation proceeded, A
would be selectively removed from the liquid. The boiling point of the liquid in distillation
flask would gradually rise from TC1 to TB; at the same time, the composition of the liquid
distillate would change gradually from C1 to 100% A. How it is achieved? The composition of
the distillate would gradually change from C1 to C2 (richer in A than C1) after 1 cycle of
evaporation and condensation. When the distillate is re-evaporated, the condensate will have a
composition of C3, then C4 and so forth, etc. Eventually if the condensation-revaporization
processes continue indefinitely, it will give 100% A.

-T
temperature →

-T
C1

-T
C2

-T
C3

-T
A

|
100 C4 C3 C2 C1 0% A
0 100% B
composition
Figure 4. Liquid-Vapor Composition Diagram of Fractional Distillation

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 If a perfect separation of two components A and B is achieved during a distillation, a
plot of temperature vs volume of condensate looks like the ideal graph. All of the lower boiling
component A distills at its boiling point until it is removed from the mixture; then, the higher
boiling component B distills at its boiling point. When separating mixtures of compounds with
boiling points closer together than 10 °C, completely ideal separations are not achieved. This
is because component B has an appreciable vapor pressure at the boiling point of component
A. In a laboratory situation, one can plot the volume of distillate vs temperature of the distilling
vapor to determine how closely a distillation resembles an ideal separation (Figure 5).

Figure 5.

Fractionating column (see Figure 6) is a device

for increasing the efficiency of re-distillation processes.
It consists of a vertical column packed with some inert
materials, such as glass beads, glass helices, steel wool
or some other devices (indentations) for increasing the
surface upon where the vapor may condense. As the hot
vapors rise through the column, they condense and flow
back down the column. The condensate, as it hits the
lower, hotter portions of the column, is re-vaporized,
and the more volatile components proceed up the
column once again. If the column is efficient, this
process is repeated many times in the column, and the
distillate will consist of the lowest-boiling components
of the mixture in nearly pure form.

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 Figure 6. Macroscale Apparatus for
Simple Fractional Distillation

In this experiment, a binary mixture will be provided to you. You need to separate it
into two fractions by distillation techniques. Boiling points of common liquids that you will
encounter in an organic chemistry laboratory are listed below.

Compound Boiling point (°C)

1 Dimethylsulfoxide 189.0
2 Phenol 181.0
3 Mesitylene 164.7
4 N,N-Dimethylformamide 153.0
5 p-Xylene 138.4
6 n-Butyl acetate 126.0
7 Butan-1-ol * 117.2
8 Toluene * 110.5
9 Water 100.0
10 2,2,4-Trimethylpentane 98.5
11 Propan-1-ol * 97.2
12 3-Methylhexane 91.0
13 Propan-2-ol * 82.6
14 Cyclohexane 80.7
15 Methanol * 64.7
16 Chloroform 61.2
17 Acetone * 56.5
18 Cyclopentane 49.0
19 Dichloromethane 39.8
20 Diethyl ether 34.6

Table 1. Boiling point of water and common organic liquids at 1 atm

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Experimental:

Fractional distillation of an unknown mixture containing 2 organic liquids

1. In a well-ventilated fume hood, place 5.0 mL of an

unknown organic liquid mixture to a 5-mL long-
necked round bottom flask, also add 2 to 5 pieces of
boiling stone to the flask.
2. Get ready these items: still head, thermometer adaptor
(where a thermometer is connected), and two air
condensers.
3. Assemble the apparatus for fractional distillation as
shown.
4. Adjust the bulb of the thermometer to be placed just
below the opening into the side arm of the still head.
5. Connect an air condenser to the side arm of the still
head. Below the other end of the condenser, place a
10-mL measuring cylinder. (Note: before distillation,
add 2.00 mL mixture into this measuring cylinder.)
6. Make sure all the connections are tight. Clamp the
whole setup above a sand bath. Immerse the round-
bottom flask deep in the sand (~50% to 75% of the bulb immersed). Place the
measuring cylinder (from step 5) just under the opening of the air condenser.
7. Then, adjust the temperature setting of a hot plate to around 200 °C. When the sample
boils, adjust the heating until the distillate drops at a regular rate of about one drop per
second (or slightly more slowly). Adjust temperature settings to a higher level when
the rate of collecting liquid droplets slows down.
8. Record both the temperature and the volume of distillate at regular intervals.
Discontinue the distillation after 3.00 mL (i.e. 5.00 mL reading on the cylinder) of the
distillate has been collected or before the round bottom flask is dry.
9. Record the volume of the distillates and submit your products in a vial.
10. Plot a graph of boiling point versus volume of distillate collected.
11. From the graph, determine the boiling point of the two unknown liquids.
12. Based on the observed boiling points, decide what the two unknown liquids are.

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CHEM 2155 Fundamental Organic Chemistry Laboratory 2024 Spring
Expt 2: Distillation of Organic Liquids

Name: ______________________ Group no. __________________

Student ID: ________________ Date of experiment: __________________

Risk Assessment:

Specific Chemical Hazards

For classification of hazards, please check the Safety Data Sheet (SDS) on course website.

Hazard

Chemical
Flammable Corrosive Oxidizing Irritant Health Explosive Environmentally
hazard Toxic damaging

Acetone

Methanol

Butan-1-ol

Propan-1-ol

Propan-2-ol

Toluene

[please tick  where it is appropriate]

Declaration
I am well aware of the chemical hazard(s) of the experiment(s) to be carried out in laboratories of the
Chemistry Department.

Signature: _________________________ Date:__________________________

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