Organic Chemistry Laboratory Manual 1

EXPERIMENT 8 – ALIPHATIC AND AROMATIC HYDROCARBONS

Aliphatic hydrocarbons are non-aromatic organic compounds where the carbon atoms
are singly, doubly, or triply bounded to another carbon atom. They are further classified into
acyclic (linear or branched) or cyclic (ring-structured) hydrocarbons.

Alkanes are saturated aliphatic hydrocarbons wherein each carbon atom uses sp3 hybrid
orbitals and forms single bonds with hydrogen and other carbon atoms. Because carbon and
hydrogen have nearly the same electronegativity, there are no regions of high and low electron
density. Hence, alkanes are considered nonpolar compounds. They are generally inert towards
any chemical reagents, which are either electron-seeking (electrophilic) or electron-donating
(nucleophilic). Consequently, they only react through free-radical substitution. An example is the
free-radical halogenation of alkanes under UV conditions.

X2 X
X
uv

Alkenes and alkynes are unsaturated aliphatic hydrocarbons because they contain
multiple bonds. Alkenes have double bonds and its carbons atoms are sp2 hybridized while
alkynes contain triple bonds and its carbon atoms are sp hybridized.

Unsaturated aliphatic hydrocarbons are quite reactive. They have loosely held p
electrons that are available to electrophilic agents, thus they react via electrophilic addition.
Alkynes react less readily than alkenes because the p electrons are more tightly held by the
carbon nuclei making them less available to electrophilic agents.

X
slow
C C X Y C C Y

X X
fast
C C Y C C
Y

Aromatic hydrocarbons exhibit different reactivity from alkenes and alkynes in spite of
their similar unsaturated nature. This can be attributed to the special stability of their resonance-
stabilized ring. To preserve the stabilization of the ring, aromatic hydrocarbons react via
electrophilic aromatic substitution. An example is illustrated below:

FeBr3 Br
Br2 FeBr4 H

Distillation is a purification technique useful for liquid mixtures where the basis of the
separation among components of a mixture is the difference in their volatilities or boiling points.
This technique can be classified depending on its application or the type of mixture being
purified. It can be a simple distillation, fractional distillation, steam distillation and distillation
under reduced pressure. Steam distillation is a type of distillation technique used for

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separating liquids that are immiscible or slightly immiscible in water.

Limonene is a major component of volatile oils from several leaves and citrus fruits (e.g.
eucalyptus leaves, lemon grass, orange peels, among others). In this experiment, limonene will
be isolated as a pure compound, or ideally with high purity via steam distillation. In addition, the
physical and chemical properties of aliphatic (hexane and limonene) and aromatic (toluene)
hydrocarbons will be determined.

MATERIALS AND APPARATUS

Limonene Sources: Eucalyptus leaves, lemon grass, pomelo (suha), calamansi, dalanghita,
orange or ponkan

n-hexane saturated NaCl solution round bottom flask (500 mL)

limonene condenser boiling chips
toluene separatory funnel (250 mL) spatula
tert-butyl chloride Erlenmeyer flask steam bath
anhydrous Na2SO4 micro test tubes glass tubings
0.05 M Br2 in H2O AlCl3 corks
0.005 M KMnO4 solution I2 in KI aluminum foil

PROCEDURE

A. Isolation of Limonene

1. Preparation of Sample. Choose a limonene source and cut the sample at home to
save time. Keep it in a stoppered container or plastic to minimize evaporation of
essential oils.

2. Steam Distillation. Prepare a steam distillation set-up as shown in Figure 1. Collect

and weigh the sample enough to fill half of a 500 mL round bottom flask. Add 250 mL
of water into the flask and distill the mixture until you have about 100 mL of the
distillate. Do not forget to discard the first 20 drops or 1 mL of the distillate prior to
pooling the rest of the distillate.

Figure 1. Steam Distillation Set-up

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Organic Chemistry Laboratory Manual 3

Pour the distillate into a 250 mL separatory funnel. Rinse the reaction flask with cold
distilled water and add the washings to the separatory funnel. Perform liquid-liquid extraction
and allow the layers to separate. Add saturated NaCl solution dropwise then elute out the
aqueous layer and transfer the organic layer in a pre-weighed 100-mL beaker.

Dry the organic layer by adding a spatula-full of anhydrous Na2SO4. Stop adding
anhydrous Na2SO4 if the drying agent forms clumps. Determine the weight of the extracted
limonene.

B. Physical Properties of Hydrocarbons

Note the physical state, color, solubility in water and the qualitative density in water of
hexane, limonene and toluene. Record your observations.

C. Chemical Properties of Hydrocarbons

1. Place 5 drops each of hexane, limonene and toluene into separate 4” test tubes. Add 2
drops of tert-butyl chloride to each test tube. Mix thoroughly. Incline the test tubes and
place a small crystal of anhydrous AlCl3 near the test tubes’ mouth (Note: Powdery AlCl3
is no longer anhydrous). Stopper the test tubes in this position taking care that the
crystal does not fall into the solution. Allow the solution to wet the crystal and observe
the change in the color of the crystal.

2. Place 2 drops each of hexane, limonene and toluene into separate 4” test tubes. Add 1
drop 0.05 M Br2 in H2O into each test tube. Place the test tubes under direct sunlight.
Shake well and record your observations. Repeat the procedure under dark conditions.

3. Place 2 drops each of hexane, limonene and toluene into separate 4” test tubes covered
with aluminium foil. Add 1 drop of I2 in KI into each test tube. Shake well and record your
observations.

4. Place 2 drops of hexane, limonene, and toluene into separate 4” test tubes. Add 2 drops
of 0.005 M KMnO4 solution. Shake well and record your observations.

5. Place 5 drops each of hexane, limonene and toluene in separate evaporating dishes in
the fumehood. Ignite using a lighter. Observe the color and appearance (clear or sooty)
of the flame. Record your observations.

WASTE DISPOSAL

1. The aqueous solutions used for this experiment should be diluted and poured safely into
the sink.

2. Dispose the used drying agent in the trash bin or you may dissolve it in water and flush it
down the sink.

3. Dispose the chlorinated and brominated organic solvents in the halogenated organic
solvent waste jar.

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Organic Chemistry Laboratory Manual 4

REFERENCES

Ault A. 1983. Techniques and Experiments for Organic Chemistry. Allyn and Bacon,
Inc., Boston, USA.

Baum SJ, Bowsen WR, and Poulter SR. 1981. Laboratory Exercises in Organic and Biological
Chemistry. MacMillan Co., New York.

Engel R, Lampman G, Kriz G and Pavia D. 1995. Organic laboratory Techniques, A

Microscale Approach, 2nd ed. Saunders College Publishing.

Murov S and Stedjee B. 1997. Experiments in Basic Chemistry, 4th edition. John Wiley and
Sons, USA.

Organic Chemistry Group ● Institute of Chemistry ● University of the Philippines Diliman