The Rate of Oxidation of Iodide Ion

by Hydrogen Peroxide
R. K. McALPINE
University of Michigan, Ann Arbor, Michigan

HE practice of chemistry is concerned very peroxide is present in excess, the sodium thiosulfate
T largely with the carrying out of chemical reactions will finally be used up and then the free iodine will
whereby new substances are produced from old. The accumulate in the solution. In order to recognize the
substances entering into the reaction are'known as free iodine while its concentration is still quite low, a
reagents, and the substances produced as products. little starch solution is included in one of the original
One of the factors in chemical reactions which is mixtures. Thus the solution remains colorless as long
subject to human control and manipulation is sum- as any thiosulfate is present, but as soon as this is all
marized in the Law of Mass Action. This law, in oxidized the solution turns blue.
simplified form, states that a t a given temperature the On the basis of earlier experiments a set of stock
rate of a reaction varies directly as the active mass of reagents was made up as follows:
each reagent. Practically, the active mass of a re- Sulfuric acid.. . . . . . . . . . . . . . . . . . .approximately 5N
agent is approximately identical with its concentration, Potassium iodide.. . . . . . . . . . . . . . .approximately 0.5 N
especially in dilute solutions, although with higher Sodium thiosulfate.. .. .. . . . . . . . . .approximately 0 . 0 5 N
concentrations additional factors known as activity Hydrogen peroxide (3 per cent
solution). . . . . . . . . . . . . . . . . . . . .approximately 1.8 N
coefficients may be introduced. Starch solution.. .. . . . . . . . . . . . . . .approximately 1 per cent
Although this law is referred to early and late in the
teaching of chemistry, there are relatively few exercises In later experiments 2 N HCl was used in place of the
which can be placed in the hands of students or used sulfuric acid and Superoxol (30 per cent HzOz) was
for lecture demonstration to show the experimental diluted and tried to see if the negative catalyst used to
basis of this law. Some years ago it had been observed retard the decomposition of the ordinary hydrogen
that the rate of oxidation of iodide ion by hydrogen peroxide might affect the results. No difference in
peroxide in dilute acid solution is slow enough to results was obtained.
permit the development of a clock reaction of definite An interesting experiment may be carried out to
usefulness in this connection. This winter, for a course show the diierence in rates of the two principal re-
in general chemistry for some Navy students, the actions, oxidation of I- to Izby the H202,and reduction
reaction was brought out, dusted off, and used. It of the Iz by the NaaSzOa. Place 50 ml. of distilled
worked so well that i t was investigated somewhat water in a 250-ml. Erlenmeyer flask and add about 10
further, and the results are reported in the present ml. each of the acid and the potassium iodide solutions
paper. and 4 to 5 ml. of the starch solution. Fill a buret with
In the actual experiments two reactions are involved. the sodium thiosulfate solution. Now add about 5 ml.
First, in acid solution hydrogen peroxide oxidizes of the hydrogen peroxide and swirl. The solution turns
iodide ion to free iodine a t a moderate rate, the actual blue-black almost instantly. Next run in some of the
rate being subject to control by modifying the con- sodium thiosulfate solution, with swirling, until the
centrations of all three of the reagents. Second, free solution is decolorized, plus 1 to 2 ml. excess. W u l
iodine is reduced very rapidly by sodium thiosulfate. to mix, and let stand. In a few seconds the color
A third possible reaction, which might he expected to returns. Decolorize again with the sodium thiosulfate
take place, namely, the direct oxidation of the sodium and vary the excess added. The blue-black color will
thiosulfate by the hydrogen peroxide, actually takes return again but the time required will vary with the
place so slowly that its rate is negligible as compared actual excess of thiosulfate added. This process may
with the other two. be repeated a number of times. This experiment leads
Thus it is possible to place a solution containing to the conclusion that the oxidation of the iodide ion
sodium thiosulfate and potassium iodide in one con- is taking place a t only a moderate rate, but the re-
tainer and a solution of hydrogen peroxide and sulfuric duction of the free iodine proceeds very rapidly.
acid (or hydrochloric acid) in another. The two are One of the early experiments tried was designed to
then poured together and mixed, whereupon the show that the time required for development of the
hydrogen peroxide starts oxidizing the iodide ion to blue color varied directly with the amount of thio-
free iodine. But the sodium thiosulfate reduces the sulfate used. For this, a standard oxidizing mixture
free iodine back to iodide ion as fast as it is formed. was prepared by taking 100 ml. each of hydrogen
If the quantities are adjusted so that the hydrogen peroxide and sulfuric acid, diluting to a liter, and
mixing thoroughly. Then four diierent concentra- duration of the reaction. Lumped together, they may
tions of sodium thiosulfate were prepared by measuring be considered as a "timing correction" to be subtracted
out 5, 10, 15, and 20 ml. of the stock solution, treating from the over-all times to get values actually pro-
each with 10 ml. of the potassium iodide solution and portional to the times of the reactions. With the con-
5 ml. of the starch solution, and dilut'ng to 100 ml., centrations of sodium thiosulfate varying in the ratio
followed by thorough mixing. 1:2: 3: 4, it is a simple matter to see whether a constant
In carrying out a reaction 25 ml. of the oxidizing can be subtracted from each of the recorded times
mixture was placed in a clean 8-inch test tube and 25 (10.8, 20.9, 30.9, and 40.8) to give a closer approach to
ml. of the NazSzOa-KI-starchsolution was placed in a the simple ratio. In this particular case, if each re-
second test tube, using pipets for these (and earlier) corded time is diminished by 0.8 second the ratio
measurements. A tenth-second stop watch was then becomes 1 :2.01 :3.01 :4.00.
started, the two test tubes picked up, and at the In connection with this timing correction, which is
instant the pointer reached the 30-second mark the in the nature of a catch-all for several items, it is
solutions were poured together and mixed by pouring possible to determine experimentally how much free
back and forth four times. The tube was then held iodine is required to produce a blue color of sufficient
against a white background and the watch stopped intensity to be easily recognized. Several tubes of
a t the first showing of the blue color. The time re- distilled water may be set up with a little K I and
corded is the time from the initial pouring together to starch solution in each, and then single drops of a very
the first appearance of color. Three trials were run dilute solution of iodine (0.0054 N in the case tried)
for each concentration of sodium thiosulfate and the added and mixed, and the colors noted. One drop of
average taken. The individual data are recorded in the iodine solution, corresponding to 0.035 mg. It
Table 1. produced a faint color, and two drops, or 0.07 mg., a
medium blue. Since the amount of sodium thio-
TABLE 1
RBLA~O NCONCBNTIAZION
OW (IF Na2S20sro TKYB10. APPBARAWCB
sulfate oxidized in 10 seconds required approximately
0 s co,.oa 8 mg. of free iodine, the time that elapsed between the
Relolilra Time i n Szrondr end of the reaction and the development of the blue
Conrrnlrnlianr Ratio of
of NatSz08 Id Trial 2nd Trio1 3rd Trinl Avcrona Avrrnrrr
color was 0.07/8 times 10, or approximately 0.1 second.
Further, the physiological reaction time from the
appearance of the color to the stopping of the watch
may be assessed as approximately 0.3 second. This
item could be measured experimentally with such
It is obvious that the ratio of average times is suffi- special equipment as is nsed in the laboratory in
ciently close to the ratio of concentrations to justify psychology, but it has not seemed worth while to check
the statement that the time required to produce the this matter. It does appear, however, that in the
blue color varies approximately with the amount of reaction being investigated and under the experimental
sodium thiosulfate used. In attempting to account conditions used, there is surprisingly little error involved
for the deviation on grounds other than "experimental in taking the instant of initial pouring as identical with
error," two factors in the situation may be examined. the actual first point in the time of the reaction.
One of these involves the fact that as diierent amounts Before presenting a summary of the further experi-
of sodium thiosulfate are nsed correspondingly diierent ments carried out, in which the concentrations of
amounts of hydrogen peroxide and sulfuric acid are hydrogen peroxide, iodide ion, and acid were all varied,
used up, so that the concentrations of these reagents it will be interesting to examine the constancy of the
change during the course of the reaction. This factor timing results. Fifty-two experiments have been run
is reduced to a very minor item by the relative amounts in triplicate. By comparing the first run with the
of reagents used. The actual concentrations of hydro- second, first with third, and second with the third,
gen peroxide and sulfuric acid change very little in all three checks or comparisons of times are available for
four cases. Further, the change would be proportional each run, or 156 for the 52 experiments. The variations
to the amount of sodium thiosulfate used so the ratio of of these among themselves are summarized in Table 2.
times would not be affected.
The second factor involves the relation of times
recorded to the times of the actual reactions. This
factor is more difficult to deal with. It is obvious that
the two solutions are not mixed instantly, therefore
there is some brief interval of time between the start
of pouring together and the theoretical start of the
reaction. Further, a short time must elapse beyond
the end of the reaction and the development of the
blue color, and a further time is required to stop the
watch after the color is recognized. Certain of these Total checks.. ................................ 156
Maximum variation.. ......................... 1 . 3 seconds
items are approximately constant, independent of the Average vsriafioo.. ........................... 0 . 2 8 second
 In setting up the various experiments it was found
desirable to adjust the different concentrations so that
the maximum time would not exceed one minute.
This avoided two difficulties, namely, straying atten-
tion while waiting for the end point, and decreasing
sharpness of the end point. At the other extreme, it
was necessary to use 10 to 15 seconds in order to carry
through the standard mixing and he prepared to stop
the watch. Thus, in varying the concentration of
iodide ion 5, 10, 15, and 20 ml. of the potassium iodide
solution were each treated with 10 ml. of the sodium
thiosulfate and 5 ml. of the starch solution and diluted
to 100 ml. These were then reacted separately with a
standard mixture of hydrogen peroxide and acid (100
ml. of each, diluted to a liter). For variation of
hydrogen peroxide or acid, 5-, lo-, 15. and 20-ml.
portions of one were treated with 10-ml. portions of the
other and diluted to 100 ml. These were then reacted
separately with a standard reducing mixture of sodium
thiosulfate, potassium iodide, and starch. Variations
of this last mixture were tried, all the way from 200
ml. of sodium thiosulfate plus 200 ml. of potassium
iodide solution (plus 40 ml. of starch solution) diluted
to one liter, down to 10 ml. each of sodium thiosulfate
and potassium iodide solution. I n the later experi-
ments the mixture adopted was 50 ml. of each of the
solutions, diluted to one liter and mixed.
To show the variation in the rate of the reaction with
the concentration of the various reagents, the raw tim-
ing data were converted to rates by comparing the
reciprocals of the times observed. The unit of chemical
reaction involved in each case was the liberation of
the amount of iodine necessary to use up a standard
amount of sodium thiosulfate. The longer the time
required, the slower the reaction was proceeding. Thus
the reciprocals of the times were used to compare the
rates. These data are summarized in Table 3. The
different series referred to involved such things as
shifting from sulfuric acid to hydrokhloric acid, use of
Superoxol in place of ordinary hydrogen peroxide, and
variation in the concentrations of the standard reducing
mixture. These are not discussed further.
RAT=
TABLE 3
Conernuationr studied -
nnrros sou RAW T m n o DATA(Rnrs
1:2:3:4
- 1/11
Rca~cnl
"".id Rdcr
In these raw rates it will be observed that for the
several series of experiments involving hydrogen per-
oxide and potassium iodide, the ratios are qualitatively
the same as the relative times required for oxidizing
varying amounts of sodium thiosulfate. This is suffi-
cient to indicate that the rate of oxidation of iodide
ion by hydrogen peroxide, in the acid range studied,
varies essentially as the first power of the concentration
of each of the two reagents. In the case of both
sulfuric and hydrochloric acid the effect does not
follow a simple relation. For the first two members
of series a, b, and c in the case of sulfuric acid, and
series a and b for hydrochloric acid the effect is ap-
proximately a square root relation. That is, doubling
the concentration of the acid increases the rate by
approximately the square root of 2 (1.414). However,
a fourfold increase in the concentration of the acid
produces definitely more than a twofold increase in
rate, and in series c of the hydrochloric acid studies
the concentrations were double those of series b and
a still more marked deviation toward a first power
relation is observed.
The rates considered in the last paragraph are those
obtained from the raw timing data. It is possible t o
calculate a timing correction from the experimental
data for hydrogen peroxide and potassium iodide on
the assumption that the rate is strictly a first power
effect in these two cases. Thus, by applying a correc-
tion of one second the three series for hydrogen per-
oxide become
1:2.00:2.96:4.06
1:1.96:2.88:4.00
1:1.98:3.02:3.94
In the case of potassium iodide a correction of two
seconds in series a (using 5 N sulfuric acid and ordinary
hydrogen peroxide) and 2.5 seconds for series b (using
2 N HC1 and diluted Superoxol) gives the following
ratios:
Seriesa 1:l 94:2.98:4.08
Series b 1:2.01:3.01:3.98
In conclusion, it should be noted' that there are
several anomalies in the system under study, an
anomaly being defined as an unexpected irregularity
in chemical behavior. Thus it is not a t all obvious
why hydrogen peroxide should oxidize iodide ion so
much more slowly than iodine oxidizes sodium thio-
sulfate, and it is still more difficult to understand why
hydrogen peroxide should have so little effect on such
a strong reducing agent as sodium thiosulfate which
can he oxidized so rapidly by iodine. Further, i t may
he noted that the chemical equation for the net reac-
tion being studied is written:
+
HIOl 21- + 2H+ = Is + 2H10
According to the law of mass action, if the reaction
took place directly in accordance with the equation
it would be expected that the rate would vary directly
as the first power of the concentration of hydrogen
peroxide (which it does), and as the second power of the
concentrations of both iodide ion and hydrogen ion.
The fact that it goes as the first power of the iodide
ion rather than the square has been accounted for by a
mechanism involving two reactions, one slow and one plex than the one just suggested. Some further work
fast, the fitst forming hypoiodous acid (HIO), is being done along this line.
H202 + H C+ I - = HI0 + H20
SUMMARY
and the second forming free iodine by the reaction of
the hypoiodons acid with more iodide ion, A clock reaction has been developed to show in
+
HI0 + H + + I - = I* H20
greater detail than usual the experimental basis of the
law of mass action. Only a fourfold variation in con-
The slowness of the first reaction controls the over-all centrations was investigated except in the case of
rate, and in this equation the iodide ion has a coefficient hydrogen ion, but the range can be increased con-
of one so first power effects are to be expected (or are siderably by proper adjustment of the various re-
accounted for). However, it is to be noted that the agents. In the oxidation of iodide ion by hydrogen
coefficient for hydrogen ion is also one and so fust peroxide in moderately acid solution, the rate varies
power effects would be expected in this case also. directly as the concentrations of the hydrogen peroxide
The fact that the data for variation of hydrogen ion and the iodide ion, and less than directly as the concen-
do not show first power effects indicates that under the tration of the hydrogen ion. The effect of ionic
conditions studied the mechanism must be more com- strength has not been studied.