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An oscillating reaction

Demonstration
Bromate(V) ions are used to oxidise propane-1,3-dioic acid to CO2 in the
presence of Mn(II) ions as catalyst. The reaction mixture oscillates in
colour between red-brown & colourless with a time period of about 20
seconds.

This demonstration is fairly straightforward to set up, works reliably & is


based on the Belousov-Zhabotinsky reaction. It takes about 10 minutes
of demonstration time but rather more time to set up.
Apparatus Chemicals
For each demonstration: Con sulfuric acid 75 cm3
Eye protection: goggles malonic acid 9 g
Disposable gloves (preferably nitrile) Potassium bromate 8 g
- optional Manganese(II) sulfate-1-water
Beaker (1 dm3) 1.8 g
Magnetic stirrer (optional) Deionised / distilled water 750
Weighing boats or watch-glasses, 3 cm3
Balance, reading to 0.1 g
Con sulfuric(VI) acid, H2SO4(l)
Propane-1,3-dioic (malonic) acid, HOOCCH2COOH(s)
Potassium bromate(V), KBrO3(s)
Manganese(II) sulfate-1-water, MnSO4.H2O
The use of a magnetic stirrer is optional but highly recommended since
the use of a glass stirring rod will detract from the colour changes
occurring during the demonstration.

Procedure
Before the demonstration
a Place 750 cm3 deionised/distilled water in the beaker.
b Slowly & with stirring, add 75 cm3 con sulfuric acid carefully. The
mixture will heat up to about 50 °C.
c Allow the diluted acid to cool back to room temperature.
d Weigh out separately 9 g of malonic acid, 8 g of potassium bromate(V)
& 1.8 g of manganese(II) sulfate-1-water on weighing boats or watch-
glasses.
The demonstration
a Place the beaker of dilute sulfuric acid on a magnetic stirrer & stir the
solution fast enough for a vortex to form.
b Add the malonic acid & potassium bromate(V).
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c When these have dissolved, add the manganese(II) sulfate & observe
what happens.
d A red colour should develop immediately. This will disappear after
about one minute.
e Thereafter the colour will oscillate from red to colourless with a time
period of about 20 seconds for a complete oscillation. This will continue
with a gradually increasing time period for over 10 minutes.

Teaching notes
A stopwatch could be used to time the oscillation. The time period of 20
seconds mentioned above refers to an ambient temperature of about 20
°C. If the temperature is higher than this then the time period drops
accordingly.
The reaction will not work if tap water is used instead of deionised water.
Chloride ions, via the addition of a pinch of potassium chloride or dilute
hydrochloric acid, will immediately stop the oscillations. The use of clean
apparatus is therefore essential.
The reaction mixture can be washed down the sink with plenty of tap
water after the demonstration.
The theory of oscillating reactions is complex & not fully understood.
However, this particular process is an example of a class of processes
known as Belousov-Zhabotinsky (BZ) reactions. The overall reaction is
usually given as:
3CH2(COOH)2(aq) + 4BrO3–(aq) → 4Br–(aq) + 9CO2(g) + 6H2O(l)
The oxidation of the malonic acid by the bromate(V) ions is catalysed by
manganese(II) ions & manganese(III) ions are produced as
intermediates.
Some references claim that the red colour is due to molecular bromine
which could be produced via the following two steps:
Br–(aq) + BrO3–(aq) + 2H+(aq) → HBrO2 + HBrO(aq)
Br–(aq) + HBrO(aq) + H+(aq) → Br2(aq) + H2O(l)
However, other detailed studies of the processes occurring give a variety
of colourless bromate ions & bromic acid molecules as intermediates,
rather than bromine itself, so it is therefore possible that the red colour is
due to something else, maybe the transient existence of Mn3+ions which
are known to be red/purple in colour.
The colour oscillation is brought about by two autocatalytic steps, which
are highly complex in nature & have been the cause of several
advanced research projects over the past 30 years or so.