Thomas S.

Briggr
and Warren C. Rauscher
Galileo High School Lux Laboratory An Oscillating Iodine Clock
1150 Francisco Street
San Francisco, California 94109

Previously reported oscillating reactions either involve edione for malonic acid. Cerium mav he used in place of
relatively faint color changes or require phenanthroline, manganese and gives higher frequency oscillations of vari-
an expensive indicat0r.l We have found an oscillating io- able amplitude. In fact. invisible oscillations in iodide
dine clock reaction that gives striking cyclic changes from occur in the absence of metal catalyst in a narrow region
colorless to gold to blue using simple reagents. This reac- of higher concentration, e.g., 0.092 M potassium iodate,
tion provides an excellent lecture demonstration and 0.069 M malonic acid, 3.24 M hydrogen peroxide, and 0.16
minht be adapted to a variety of student investipations. It M sulfuric acid.
resembles the iodate-hydrogen peroxide oscillating reac- Inasmuch as no oscillating reaction is well understood
tion of Brav.2
.. but it operates at room temperature with a t this time, little can he said of the mechanism of the os-
greater intensity. cillating iodine clock. Its similarity to the Bray reaction
The followinn mixture has been found to give the best was noted ahove. If the malonic acid is not present in the
results: 0.067 M potassium iodate, 1.2 M hydrogen perox- demonstration mixture the manganese or cerium catalyse
ide, 0.053 M perchloric acid, 0.050 M malonic acid, 0.0067 a rapid initial formation of iodine. Even this simple dem-
M manganese(I1) sulfate, and 0.01% starch. These concen- onstration of catalysis is not well known in the literature.
trations may he about 30% more dilute without degrading I t should he noted that manganese and cerium and malo-
the reaction (see figure) and an equivalent amount of sul- nic acid are part of the widely publicized Belousov oscil-
furic acid may replace the perchloric acid. Constant stir- lating reaction4 in which they interact with hromate. The
king improves the cycling but is not essential. Demonstra- malonic acid is a halogen consumer and halide producer
tion solutions are stored for extended periods in three con- in both the Belousov reaction and the oscillating iodine
tainers so that mixing equal volume$ from each gives the clock.
ahove composition. One holds the hydrogen peroxide, an- Obviously, much research is needed to elucidate these
other the iodate with mineral acid and the third the malo- oscillating reactions. We hope the spectacular nature of
nic acid, starch, and manganese. this new reaction will motivate interest in the difficult ki-
In
-~~addition to the visible fluctuations in iodine concen-
~ ~~~~~ ~
netic problems related to it. The authors patefully ac-
tration this reaction exhibits large fluctuations in the con- knowledge helpful discussions with ~ i l l i a mR.
centration of iodide ion. The blue starch complex does not
~~ ~ ~
Jollv and Robert E. Connick of the Universitv of Califor-
appear until the iodide concentration approaches its peak
value of 10-4 M during each cycle. This is in accord with
the observations of Thoma and French3 that iodide is nec-
essary for the formation of the blue complex. Starch indi-
cator fails in the Bray reaction, presumably due to a lower
concentration of iodide in the absence of malonic acid. Io-
dide oscillation is easily observed by the student by means
of a silver-silver iodide electrode immersed in the oscillat-
ing mixture. This electrode is readily made from a clean
silver wire by briefly making it the anode in a dilute io-
dide solution. For the reference electrode we recommend
the use of a calomel electrode in conjunction with a salt
bridge. A standard pH meter can he connected to these
electrodesand calibrated at one point with a M io-
dide solution. Permanent records are obtained with a
chart recorder.
Many variations of this reaction exist. We have ob-
served short-lived oscillations by substituting 2,4-pentan-

'Reviews of these reactions appear in J. CHEM. EDUC., 49, minutes

No. 50972).
2Brav.- , W. C.. J.Amer. Chem. Soc.. 43.1262(1921).
3Thoma, J. A,, and French, D., J. Amer. Chem. Soe., 82,
4144(1960).
Zhabotinskii, A. M., Dokl. Akod. Nouk. SSSR, 157,392(1964).
Oscillations produced by a solution of 0.050 M potassium iodate. 0.038 M
rnalonic acid. 0.0055 M manganese(ll) sulfate. 0.88 M hydrogen perox-
ide. 0.035 M perchloric acid, and 0.01% starch. Cycling begins when
manganese is added. The signal is produced by a silver-silver iodide
electrode.

496 / Journal of Chemical Education