Preparation of Bromine

Preparation of Bromine

by Magpie

12/10/09 Rev2

Introduction
This procedure is for the preparation of ~25mL of Br2 using swimming pool
grade NaBr, Rooto sulfuric acid, and 35% H2O2. The yield is very near
theoretical.

The following oxidation-reduction reaction applies:

2NaBr + H2SO4 + H2O2 = Br2 + Na2SO4 + 2H2O

CAUTION
Br2 is toxic, and some excess will be vented through the port on the vacuum
adapter. Therefore this procedure must be conducted outside or in an
efficient fume hood. (Note 1)

Do not spill any Br2 on your person. It will cause nasty and long-lasting burns.

Procedure

A. Reagent Preparation
Weigh out 100g of NaBr in a beaker. Set aside.

In a 250mL beaker place 50mL of water. To the water carefully add, with
stirring, 30mL of Rooto sulfuric acid (96wt%). The beaker should be cooled in
a cold water (or ice water) bath during the addition of the acid. Set aside.

Have available 45mL of 35% H2O2 or an equivalent amount of aqueous H2O2

of a different strength.

B. Equipment Set-Up
Using a 500mL round bottom flask (RBF) as pot and a 50mL RBF as receiver,
set up for simple distillation. A pressure-equalizing addition funnel with
sufficient capacity to hold the H2O2 solution is to be attached to the top port
of the distillation adapter. All fittings are to be of ground-glass, coated with a
thin film of silicone grease, and clamped.

Ice-water is to be supplied to the condenser. The receiver is to be placed in

an ice-water bath. (The boiling point of Br2 is 59C.)

Heating is to be supplied with a 270w Glas-Col mantle (or equivalent) placed

on top of a magnetic stirrer. Place a stir-bar in the 500mL RBF pot.

C. Distillation
Temporarily remove the 500mL pot from the apparatus and add the acid
prepared above. Using a powder funnel, add, with magnetic stirring, the
weighed out NaBr. Replace the pot in the apparatus. Keep the stir bar in
operation to provide good mixing.

Connect the pressure-equalizing funnel to the top of the distillation adapter

(valve closed!). Add the H2O2 solution prepared above to the pressure
equalizing funnel and install its plug in the fill port.

Turn on the cooling water. Set the heating mantle at 60% and turn on. If using
a hood, turn on the fan.

WARNING
Be very careful when adding the hydrogen peroxide, as an uncontrollable
reaction can result if too much hydrogen peroxide is in the mixture.

When the pot has reached a temperature sufficient to support the reaction
add the H2O2 solution a few drops at a time, keeping the reaction under
control. A steady generation of Br2 will follow. The reaction is exothermic and
the heating mantle power should be turned down as the pot heats up. By not
overheating, the loss of Br2 via the vacuum adapter port will be minimized.

Continue the distillation after all the H2O2 solution has been added until the
generation of Br2 has nearly stopped. There should be ~25mL of Br2 in the
receiver.

Drying the Br2

The liquid Br2 will be wet with some water, much of it floating on the surface.
This can be removed by shaking it with con sulfuric acid in a separatory
funnel that has been pre-cooled in the freezer. The heavier bromine (sp. gr. =
3.12) is drained off the bottom of the separatory funnel.

Storage
A narrow necked glass bottle with a PTFE lined cap is suitable for storage.
Keeping it in a freezer will minimize any leakage.

Notes
1. SM forum member "not_important" has suggested that the fugitive Br2
escaping at the vacuum adapter port can be safely captured by bubbling it
into a solution of NaOH, KOH, warm Na2CO3, or warm K2CO3. For example: 3
Br2 + 6 KOH => 5 KBr + KBrO3 + 3 H2O
2. The H2SO4 is in 14% excess.
3. The H2O2 is in 8% excess.

Reference
This procedure is based on the recommendations of benzylchloride1 of the
ScienceMadness forum.

Photos
Photos will follow when available. In their stead is the following photo taken
during the production of Br2 using a less efficient procedure.

[Edited on 7-12-2009 by Magpie]