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3uch core (AHL) Addition and Substitution Reactions:

The Reaction of Dibromine with Hex-1-ene and Heptane
Alkanes have a low reactivity compared to alkenes as the carbon-carbon and carbon-hydrogen
bonds in the alkanes are relatively strong while the alkenes contain a carbon-carbon double bond,
and this second bond is more easily broken. The ease with which dibromine1 reacts with hex-1-ene
as compared to its reaction with heptane will be investigated. Some of reactions products will be
detected qualitatively. The reaction of the halogenoalkane formed with hydroxide ions will also be
investigated. The mechanisms of the addition reactions with alkenes and the substitution reactions
with alkanes, as well as the importance of halogenoalkanes in organic synthesis, will be reviewed.
Apparatus and Chemicals
4 test tubes with screw cap, separatory funnel, ring stand, UV-lamp or sunlight, bromine water,
heptane, hex-1-ene, 0.1 mol dm-3 silver nitrate, 4 mol dm-3 sodium hydroxide, 4 mol dm-3 nitric
acid, glass stirring rod, pH-paper.
Safety
Avoid inhaling dibromine fumes as dibromine is both corrosive and toxic. Heptane and hex-1-ene
are not great for your health either.
When shaking and heating volatile liquids, pressure in the container might increase. Eliminate any
built-up pressure by lifting the stopper or opening the stopcock slightly several times in the hood
(fume cupboard).
Pre-Lab
Go to the link https://www.youtube.com/watch?v=Qlf0G9OGB-I and watch the first two minutes of
the video on how to use a separatory funnel.
Part 1. The Reaction of Bromine Water with Hex-1-ene
1. Pour approximately 2 cm3 bromine water and 2 cm3 hex-1-ene into a test tube.
2. Stopper the test tube and mix. Vent in the hood.
3. Record your observations, including the number of phases visible in the test tube and the
colors of the phases before and after mixing.
Part 2. The Reaction of Bromine Water with Heptane
1. Pour approximately 3 cm3 bromine water and 3 cm3 heptane into a separatory funnel, mix by
turning the stoppered funnel upside once, vent in the hood using the stopcock, then repeat a
few times.
2. Record your observations.
3. Place the separatory funnel near a strong light source, mixing and venting occasionally.
4. Note and explain with an equation what has happened.
5. When the reaction is finished (all the bromine has reacted), separate the aqueous phase and
the organic phase. Transfer bottom phase to a test tube and stopper (Part 3). Discard the little
portion at the phase boundary. Leave the top phase in the separatory funnel (Part 4).

1
In this experiment, bromine water, not liquid dibromine, is used for safety reasons. The reaction products will be
assumed to be those obtained when using liquid dibromine.
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3uch core (AHL) Addition and Substitution Reactions:
The Reaction of Dibromine with Hex-1-ene and Heptane
Part 3. Analysis of the Aqueous Phase
1. Using the stirring rod, transfer a few drops of the aqueous phase to pH paper. Record the
pH. Which ion have you detected?
2. Add a few drops of silver nitrate to the rest of the aqueous phase. Which reactions occurs,
i.e. which ion is detected?
Part 4. Analysis of the Organic Phase
1. To the organic phase in the separatory funnel and add 3 cm3 sodium hydroxide solution.
Shake the funnel for a few minutes, adding extra water if necessary so that the two phases
have approximately the same volume.
2. Separate the two phases.
3. Add some nitric acid to the new water phase to remove hydroxide ions, which would react
to form silver oxide if present. Then add silver nitrate solution.
4. Write the reaction equation for the reaction that occurs in the organic phase when hydroxide
ions are added.
Post-Lab
A. Why does the dibromine first react with heptane when strong light is used? What is the
IUPAC name of a possible halogenoalkane produced in this reaction?
B. Write the mechanism for the free radical substitution reaction that occurs in strong light. The
mechanism must include a description of the terms, free radical, homolytic fission,
initiation, propagation and termination.
C. What is the IUPAC name of a possible reaction product when the halogenoalkane in A
reacts with hydroxide?
D. Explain how the reaction product in A can be used to produce other types of compounds.

HL only (to be done later)

E. What is the mechanism for the electrophilic addition reaction of dibromine with hex-1-ene?
Your mechanism, in addition to using curly arrows, should include a description of the
electrophile and its induced dipole. See p. 503-504 in Brown and Ford.
F. Define the terms SN1 and SN2. Describe why tertiary halogenoalkane substitution reactions
proceed by an SN1 mechanism while primary halogenoalkane substitution reactions proceed
by an SN2 mechanism. Include a description of the terms steric hindrance and positive
inductive effect in your answer. See p. 498-501 in Brown and Ford.
G. Is the reaction producing the reaction product in C likely to proceed by an SN1 or SN2
mechanism? Why? Write the mechanism for the substitution reaction that occurs when the
halogenoalkane reacts with hydroxide. Your mechanism, in addition to using curly arrows,
should include a description of the nucleophile, heterolytic fission, and the leaving group.