Preparing Bromoalkane and

Iodoalkane

Teacher: Hassan Ezaldeen

1- Bromoalkane

Main reactions:

1) NaBr + H2SO4 → NaHSO4 + HBr

2) R-OH + HBr → R-Br + H2O

 Steps
1- Add NaBr and ethanol to the round
bottom flask (Pear shaped flask).
2- Conc. sulfuric acid (H2SO4)
is added slowly with lots of shaking
and cooling to the mixture.

Note: Care has to be taken because

a great deal of heat is produced
when the two liquids are mixed, and
there is a real risk of the ethanol
boiling and spraying concentrated
sulfuric acid around.
3- remove the water bath and heat the solution under reflux for 30-
45 mins.
(to make sure that all ethanol reacts with HBr produced)

4- Pour the mixture in a simple distillation apparatus and extract

the products.

Products (Distillate): Mixture of organic and aqueous liquids (two

layers)

Impurities in the bromoethane include:

´ hydrogen bromide.
´ bromine - from the oxidation of bromide ions by the
concentrated sulfuric acid.
´ sulfur dioxide - formed when concentrated sulfuric acid oxidizes
the bromide ions.
´ unreacted ethanol.
5- Pour the products in a separating funnel.

Notes:
• Add sodium carbonate or sodium hydrogen
carbonate to neutralize any excess acid.
(Open the Stopper at regular intervals to
prevent the build up of pressure).
• Wash the mixture with water to remove any
inorganic impurities.
• Add small amount of sodium chloride to the
mixture to increase the density of aqueous
layer (better separation)
6- Separate the organic layer (Bromoalkane) and
collect it in a dry flask.

7- Add some anhydrous calcium chloride to the

flask, shake well and leave to stand.

Notes:
• The anhydrous calcium chloride / anhydrous
sodium sulphate is a drying agent and removes
any remaining water.
• Observation: clear solution produced.
8- Filter out the drying agents by using glass wool (Less absorbent than filter
paper).

9- Redistill the organic layer (Bromoalkane) to increases the purity.

2- Iodoalkane

A) By using the same procedure for preparing bromoalkane.

Reactions:
1- H2SO4 + NaI → NaHSO4 + HI

2- R-OH + HI → R-I + H2O

Note: you can use phosphoric acid instead of sulfuric acid because it is
weaker oxidizing agent.
 B) Reacting Alcohols with phosphorus tri-iodide (PI3).

Rule: 3R-OH + PI3 → 3R-I + H3PO3

E.g.: CH3CH2OH + PI3 → CH3CH2I + H3PO3

Note: To prepare PI3:

2P + 3I2 → 2PI3

Red
phosphorus