Iodine Clock Reaction Mechanisms

Jack L. Lambert and Gary T. Fina

Kansas State University, Manhattan, KS 66506

The iodine clock reactions have been favorites for demon-
strations because of their sudden and vivid color changes.
They also serve as experiments in elementary chemistry lab-
oratory courses to illustrate solution kinetics.
The simple iodine clock reaction involves a reaction se-
quence that (with initial coefficients doubled for stoichio-
metric reasons) probably is
210* --
+ 2HSOJ
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time to the appearance of the blue color, which was generated
more sluggishly the lower the bisulfite concentration. No
threshold concentration could be determined.
One of the reactions prior to the formation of hypoiodous
acid is slow. As soon as the triiodide ion appears, it is seques-
tered in the starch helix, and the colorless solution turns blue.
Only triiodide, of all the iodine species, produces the blue color
with starch. (Closely similar higher polyiodides, such as Ig~
(1) and Iif (2), have been suggested as the species that produce
the blue color, but the reaction sequence would be the same.)
Given the fast sequestering reaction and the intense color of

|{2e~step)
the chromogen, production of the color appears to be almost
210a + 2HSOf instantaneous.
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+H+ (disproportionation) The “Old Nassau” modification of the iodine clock reaction
| by Alyea (3) (see Appendix for both recipes) is identical down
-
HOI + IOj -

to the production of iodide ion, which is complexed and pre-

+ HSO3 or starch (2e“ step) cipitated by mercury(II) until the mercury(II) is exhausted
j before resuming the pathway leading to the blue starch-
--I- + oxidation products polyiodide complex.
- + HOI
j(le^step)
I2 -f OH~ 2IOJ
-*- + I* (complexation) + 2HSO^
| |
Is 2IOJ + 2HSOJ
+ linear starch + H+
| |
linear starch-lj (blue helical complex) HOI+ IOa
+ HSOJ or starch I
The first two-electron reduction step to iodite is speculative,
as other iodine species may be involved, including iodine ox-
U
ides in a more complicated reaction sequence. The second
two-electron reduction—the reduction of hypoiodous acid to
iodide ion—could be accomplished by either bisulfite or the
secondary alcohol groups of the starch. Secondary alcohols
are oxidized to ketones by hypoiodite even with alcohols that
fail to give the iodoform test. Under the moderately acidic
conditions of the reaction, hypoiodous acid (Ka 2.3 X 10 u) =

would be largely undissociated. Hgl2(s) (orange) I3

In an experiment to determine if a minimum concentration (5) + starch
of bisulfite is required for the iodine clock reaction, succes- |
sively lower concentrations of bisulfite merely extended the linear starch-IJ (blue + orange =
black)

Volume 61 Number 12 December 1984 1037

Reactions (1), (2), (3), (4), and (5) take place sequentially.
Mercury(II) chloride, HgCI2, is largely undissociated in
aqueous solution (/32 Ki X K2 ® 1014), but it is complexed
=
more strongly by sulfite (/32 1023) in [FIg(SOg)2]2_ and still
~
more strongly by iodide (K |» 1013) in [Hgl]+andin precipi-
tation of Hgl2 (Ksp 10-28) (4,5). The generated iodide first
~
forms the colorless mixed iodosulfite complex, followed by
precipitation of the orange mercury!II) iodide. Alyea attrib-
uted the rapid appearance of Hgl2 to supersaturation, which
may play a part, but the bimolecular reaction of iodide with
the mercury(II) iodosulfite complex probably would be rapid
enough to account for its nearly instantaneous appearance.
When the mercury(II) has all been precipitated as Hgl2, the
extremely rapid production of triiodide produces the blue
starch-triiodide complex, and the complementary orange and
blue colors appear black. Orange and black are the school
colors of Princeton University and also of the House of Nassau
which bestowed its name on Nassau Hall at that Univer-
sity.
Bisulfite ion is a two-electron reductant and thus a transient
iodite, 107, species must be assumed. In a colorimetric method
for carbon monoxide in the parts-per-million range reported
by Lambert and Wiens (6), iodate ion is reduced in a similar
sequence by the generated, atomically dispersed, palladium
metal in the presence of leuco crystal violet at pH 3.1,
--
2[PdCl4]2-
+ 2C0 + 2H20
| lution results in the production of elemental iodide, that end
2Pd(0) + 2C02 + 4H++ 8C1"
-
+2I0J + 4H+
|
2I0J + 2H20 + 2Pd(II)
dant, 107, and a two-electron reductant. Neither iodous acid
nor iodite salts can be isolated, but their transient existence
in solution is possible.
The rate-determining slow step in the clock reactions may
involve the migration and reaction between iodite species that
have been generated by reduction of iodate by bisulfite. One
of the two two-electron reactions or the disproportionation
step in the reaction sequence that produces iodide ion must
be relatively slow, and the iodite-iodite interaction would seem
to be a likely candidate. This slow step must account for the
interval before the appearance of the blue color (iodine clock)
and a portion of the interval before the appearance of the or-
ange precipitate (Old Nassau). The interval between the ap-
pearance of the orange precipitate and the black color in the
latter is the time needed for all the mercury (II) to react with
steadily generated iodide ion. The reaction of hypoiodite with
iodide ion to produce iodine, the reaction of iodine with iodide
ion to produce polyiodide anion, the reaction of polyiodide
anion with linear starch to produce the blue helical complex,
and the interactions of mercury(II) with iodide ion all are
known or presumed to be rapid.
In the colorimetric method for carbon monoxide (including
the continuing autocatalytic reaction sequence), iodate ion
is considered to be reduced by finely dispersed palladium
metal and, subsequently, by iodide ion. The production of
hypoiodous acid is demonstrated by its specific reaction to
oxidize leuco crystal violet to crystal violet. Reduction of io-
date ion by iodide ion is inferred to explain the autocatalytic
production of crystal violet. Although it is a common obser-
vation that the reaction of iodate and iodide ions in acid so-
-
product occurs only when an excess of iodide ion is present.
When iodate ion is present in large excess, iodate apparently
is reduced to iodite, and iodide oxidized to hypoiodite, in a
simultaneous two-electron redox reaction
-

IOJ + I" + H+ -*
IOJ + HOI
+H+
|
Acknowledgment
HOI + IO7 -

Reactions contributing to the proposed explanation for the

+ HCVH+ (HCVH+ is leuco crystal violet)
| termination of carbon monoxide were part of the research
CV+ + I- + 2H+ (CV+ is crystal violet)
Evidence for the production of hypoiodous acid is observed
in the oxidation of leuco crystal violet. Only hypoiodous acid
and hypoiodite anion, of all the oxidizing species of iodine
(including elemental I2 itself) oxidize the leuco form of the
common triphenylmethane dyes at an observable rate. As the
above reaction appears to be autocatalytic to a considerable
degree, a further reaction sequence probably takes place as
the result of reduction of iodate by the generated iodide.
iodine clock reactions and colorimetric methods for the de-
supported by National Science Foundation Grant No. CHE-
7915217.
Literature Cited
(1) Gilbert, G. A., and Marriott, J. V. R., Trans, Faraday Sac,, 44,84 (1948).
(2) Thompson, J. C., and Hamori, E., J. Phys. Ckem., 75, 272 (1971).
(3) Alyea, H. N., "Armchair Chemistry. A Programmed Laboratory Manual,” TOPS-Alyea,
Princeton, NJ, 1971, Experiment 28.
(4) Sillen, L. G., and Martell, A. E., “Stability Constants of Metal-Ion Complexes,” Special
Publication No. 17, The Chemical Society, London, 1964, pp. 231, 292, 341.
(5) Sillen, L. G., and Martell, A. E., “Stability Constants of Metal-Ion Complexes,” Special
Publication No. 25, The Chemical Society, London, 1971, p. 220.
(6) Lambert, J. L., and Wiens, R. E„ Anal. Chem., 46,929 (1974).

21- --- Appendix

Recipes for the iodine clock and the “Old Nassau” reactions are as
-- + 2IO3 + 2H+
| follows:
Solution A: 15 g of potassium iodate, KIO3, per liter of solu-
2107 + 2H0I tion.
Solution B: of sodium bisulfite, NaHSOs, and 2 g of soluble
15 g
+ H+ starch per liter. Note: dissolve the starch in boiling
J
water, cool, add NaHSOs, and dilute to 11. This
3H0I + I0J -

solution deteriorates rapidly and should he pre-

+ 3HCVH+ pared fresh as needed.
| Solution C: 5.4 g of mercuric chloride, HgCl2, per liter of solu-
3CV+ + 3H+ + 3H20 + 31" -
tion.
Iodine clock reaction:
Add one volume of solution A to three volumes of water. Then with
Discussion short vigorous stirring, add one volume of solution B.
“Old Nassau" reaction:
Several assumptions must be made to explain the sequential Add one volume of solution A and one volume of solution C to one
reactions, the most important of which is the production of volume of water. Then with short vigorous stirring, add one volume
the 107 species formed by reaction of the two-electron oxi- of solution B.

1038 Journal of Chemical Education