Methods for Preparing Aqueous Solutions of Chlorine

and Bromine for Halogen Displacement Reactions

Gene A. Hiegel, Miguel H. Abdala, and S. Vincent Burke
California State University. Fullerton, Fullerton. CA 92634
Donald P. Beard
Cypress High School, 9801 Valley View St., Cypress, CA 90630
Displacement reactions are commonly used to demonstrate that chlorine is more reactive or a stronger oxidizing
agent than bromine and that bromine is more reactive than
iodine. For example, bromide ion is converted into hromine
in the presence of an aqueous solution of chlorine (eq 1) and
iodide is converted into iodine in the presence of an aqueous
solution of bromine (eq 2). The hromine or iodine formed
can be concentrated for easier observation in afew drops of a
hydrocarbon solvent such as hexane.
C1,

+ 2 BrF

2 Cl-

+ Br,

(1)

The aqueous chlorine solution used for the displacement

reaction is normally prepared by bubbling chlorine gas
through water. The solubility of chlorine in water a t 25 OC is
0.092 mol/L (9.2 mmo1/100 mL or 0.65 g/100 mL).' Since
chlorine is a gas, i t is sold in expensive steel cylinders, and
because chlorine is toxic, i t is also dangerous t o use and
store.
The aqueous hromine solution used for the displacement
reaction is normally prepared by adding liquid bromine to
water. The solubility of bromine in water at 25 ' C is 0.214
mol/L (21.4 mmo1/100 mL or 3.4 g/100 mL).= Bromine i s
toxic, causes burns a n d blisters on t h e skin, and has a low
boiling point (hp 59.5 OC) and thus is dangerous to store
and handle.2
We were interested in developing alternatives to handling
and storing cylinders of chlorine gas and containers of liquid
hromine. Several alternatives using generally available
chemicals are presented.
Chlorlne Solutlons from Sodium Hypochlorlte
Sodium hypochlorite solution, available in grocery stores
as chlorine bleach, can be used to generate chlorine. In the
presence of hydrochloric acid, sodium hypochlorite is converted into chlorine and water (eq 3). An aqueous solution of
chlorine, which is useful for the displacement reaction, can
be prepared by combining 13 mL (9.2 mmol; equivalent to
0.65 g chlorine) of 5.25% sodium hypochlorite and 69 mL of
water with 18 mL (18 mmol) of 1 N HC1. Since chlorine gas
will escape, this procedure and similar procedures involving
chlorine or bromine should be carried out in a hood or outdoors.
NaOCl + 2 HCI

C1,

+ H,O + NaCl

a s trichloroisocyanuric acid because a violent reaction

could occur. The oxidizing agent should be added to the
water. Add 9 mL (9 mmol) of 1N HC1 to the mixture and stir
with a magnetic stirrer to release the chlorine and form
cyanuric acid, 2 (eq 4). All solid should dissolve in about an
hour when the reaction is complete.

A Dlrect Subslltute for Chlorine

I t is also possible to substitute a saturated aqueous solution of trichloroisocyanuric acid (solubility 0.2 g in 100 mL
water) for a chlorine solution.3 This solution will react with
bromide ion to give bromine and provide a simpler and safer
way of demonstrating the formation of hromine by means of
a stronger oxidizing agent.
Bromlne Solutlons from Sodlum Hypochlorlte
Because the displacement reaction will generate an aqueous solution of bromine from bromide ion, it can be used to
prepare the bromine solution required for the reaction with
iodide ion eliminating the need for working with liquid hromine. Addition of 30 mL (21 mmol) of 5.25% sodium hypochlorite to a solution of 4.4 g. (43 mmol) of sodium bromide
in 42 mL (42 mmol) of 1 N hydrochloric acid and 28 mL
water will give an aqueous solution of bromine of 3.4 g or
0.021 mo1/100 mL (eq 5).
2NaBr + NaOCl + 2HCI

Brp + 3NaC1 H20

(5)

Bromlne Solutions from Trlchlorolsocyanurlc Acid

Prepare a solution of 4.4 g (43 mmol) sodium bromide in
21 mL (21 mmol) 1 N hydrochloric acid and 79 mL water.
Add 1.8 g (7.7 mmol, about 90% available chlorine; equivalent to 21 mmol chlorine) of trichloroisocyanuric acid and
stir for about an hour with a magnetic stirrer (eq 6). Gravity
filtration in a hood to remove the small amount of fine solid
will give a hromine solution of about 3.4 g or 21 mmo1/100
mL water.

(3)

Chlorlne Solutlons from Trlchlorolsocyanurlc Acld

A similar procedure using trichloroisocyanuric acid (1) [or
trichloro-s-triazinetrione], a stable solid that is used as a
disinfectant in swimming pools and is available in pool supply and hardware stores, will also generate an aqueous solution of chlorine. Trichloroisocyanuric acid, 0.80 g (3.4 mmol
with about 90% available chlorine; equivalent to 9.3 mmol or
0.66 g chlorine), should be added to 91 mL water. It is not
advisable to add w a t e r to strong oxidizing agents such

Acknowledgment
Partial support was provided by the California State University Fullerton Foundation.

The Merck Index. 10th ed.; Merck: Rahway. NJ. 1983; p 294.
Merck Index. p 192.
Merck Index. p 1295.