H. F.

Shurvell The Kinetics of an Ionic Reaction

Queen's University
Kingston, Canada
A physical chemistry experiment

In this experiment, the reaction between tion from linearity is expected towards the end of an ex-
hydrogen peroxide, iodide ions, and hydrogen ions is periment.
studied. By means of a very simple procedure, the The course of the reaction is followed very simply by
reaction order with respect to hydrogen peroxide is de- allowing the iodine liberated to react with a measured
termined and a rate constant obtained. quantity of standard sodium thiosulphate solution. The
The procedure can be modified easily to give the order thiosulphate has the effect of regenerating the iodide
with respect to iodide ion and other kinetic data, such as ion according to the reaction:
the rate constants involved in the overall rate equation. +
2BOsP- b = 21- + Sloe2-
These additional experiments will be outlined after the
basic experiment has been described. Since this reaction is fast, no iodine will be liberated
The first successful quantitative investigation in until the initial quantity of thiosulphate has been con-
chemical kinetics was carried out on the reaction be- sumed. At this point, because starch solution is added
tween hydrogen peroxide, iodide ions, and hydrogen ions, to the initial reaction mixture, the solution will turn
by Harcourt and Esson in 1867 (1). Many workers blue. By making further additions of thiosulphate and
have since studied the reaction and a review of the early observing successive times of appearance of the blue
work has been published (2). More recently the reac- color, the rate of the reaction with respect to the hydro-
tion has been studied bpF. Bell and co-workers (3). An gen peroxide concentration can be easily followed. It
experiment based on the reaction has been described should be noted here that while the hydrogen ion and
previously in THIS JOURNAL (4, and it appears often in iodide ion concentrations are only reduced slightly by a
textbooks and monographs on reaction kinetics (5). dilution effect during the reaction, the hydrogen ion
We should like to describe a simple modification of the concentration is also reduced by participation in the
reaction which has been used successfully for many reaction.
years a t Queen's University for elementary courses in
physical chemistry. The Experiment
The stoichiometric reaction between hydrogen perox- The student is provided with 3% HZO,, 1M KI, 3 M
ide and iodide ions in the presence of hydrogen ions is: H2S04,and 0.1 M Na2S203. A standard 0.02 M KMnOp
+
1 3 ~ 0 ~21- + 2H+ = 2H2O + 1% solution is also provided. A starch solution is freshly
prepared by making a slurry of about 10 g of soluble
The rate law consists of two independent terms which starch with 2C-30 ml of cold distilled water and pouring
suggests that the reaction can proceed by two indepen- this slurry slowly with stirring, into about 100 ml of
dent pathways (5). boiling or nearly boiling water. A clear solution should
result.
A solution of approximately 0.05 M H202is prepared
If large excesses of hydrogen ion and iodide ion are ini- by diluting 30 ml of 3y0 HzOzto 500 ml with distilled
tially present so that the concentrations of these ions re- water. This solution is standardized by pipetting 25
main essentially constant throughout the reaction, then ml into a 250 ml Erlenmeyer flask, adding a few ml of 3
eqn. (1) becomes: M BzSOa and titrating with the standard KMnOa solu-
tion until the first permanent pink coloration is ob-
d = k, [HzO,l served. The equation for this standardization reaction

-
dt is:
where 5H201 + 2Mn01- + 6H+ ZMn++ + 50>+ 8Hz0
k, = k, [I-] + k, [H+] [I-] (2) It should be noted that the 0.05 M H20zmust be freshly
Equation (2) can be tested by measuring [H20z]at prepared and standardized before each experiment,
various times and plotting t versus log [H202]. A linear because dilute solutions of hydrogen peroxide decom-
plot will indicate that the reaction is first order with re- pose on keeping.
spect to hydrogen peroxide and the slope of the graph 150 ml of distilled water are placed in a 500 ml Erlen-
will give a value for the apparent rate constant k,. meyer flask together with 20 ml of 1M KI, 10 ml of 3 M
However, because the concentrations of hydrogen ion HzSOn,2 ml of 0.1 M Na&Oa, and 5 ml of starch solu-
and iodide ion do not remain constant,' a slight devia- tion. These solutions are rnjxed by shaking and al-
lowed to reach room temperature, which should be
' I n fact the concentrat.ion of hydrogen ion diminishes more noted. Then, using a fast delivery pipet, 20 ml of the
rapidly than t,he iodide ion, as will be seen lrtter. 0.05 A4 H,O, solution are added, starting a stopwatch at
Volume 44, Number 7 0, October 1967 / 577
the start of the addition. The time at which the solu- Details of a T v ~ i c o Ex~eriment
l
tion turns hlue is recorded and a 2 ml aliquot of Na?SpOa Initial mixture ml
is added immediately. The time is recorded when the
solution turns blue again and the procedure is repeated
until about 10 additions of N&S,Oa have been made.
After the first few additions, the time intervals between
the appearance of the hlue color will become long and
further additions of N&SpOsshould be reduced to 1 ml
aliquots. Temperature 24T
From the initial volumes used and the amounts of k. 4.26 X 1 0 - 8 .w-l

N&S20aadded, the concentrations of H202remaining a t

each time may he calculated. The results are plotted in
the way described earlier, to show that the reaction is
first order with respect to hydrogen peroxide. From least squares computer program to give the best straight
the slope of the line, the rate constant kl is calculated. line of the form: y = Ax + B. The value of kl given
in the table was obtained from this calculation.
Results and Discussion The changes in [H+]and [I-] during the experiment
Details of a typical experiment are given in the table may be easily calculated. For example, initially the
and a plot o f t versus log [H202]for this experiment is concentration of iodide ion was 0.020 moles in 207 ml,
shown in Figure 1. The linearity of the plot indicates that is 0.097 moles/l. After the addition of a further 11
that the reaction is first order with respect to H202. ml of 0.1 M N&SpOathe concentration was reduced to
0.092 moles/l. This represents a reduction of 5%. On
the other hand, one mole of hydrogen ions is consumed
for each mole of Na?SZ03reacted. The initial concen-
tration of H + was 0.290 moles/l and the final concentra-
tion 0.269 moles/l, which represents a 7y0 decrease in
hydrogen ion concentration. Thus a slight deviation
from linearity of the first order plot towards the end of
an experiment is expected.
Depending on the ambient temperature and the con-
centration of the diluted HpOz,the reaction may proceed
too rapidly initially, or may terminate after only a few
additions of N&S303. In such cases, adjustments of the
initial amounts of KI, H202,and N&SpOaused may be
made to give a more satisfactory set of data.
Further Experiments
A plot o f t versus log [H20z] b r o typical experiment. The reaction order with respect to iodide ion could be
determined by a procedure similar to that described
It is perhaps instructive to give sample calculations above. In this case the hydrogen ion and hydrogen
for some points in Figure 1. The molarity of the di- peroxide concentrations should be initially in large ex-
luted H,O, solution was found to be 0.0403M in this ex- cess. Equation (1) then becomes:
periment, thus 20 ml contained 8.06 X l,0W4 moles.
The total initial volume of reaction mixture was 207 ml.
Hence the initial H,02 concentration was 3.89 X lo-'
M. We may calculate the concentration of H202
remaining at the appearance of the first blue color as
follows: the initial reaction mixture contained 2 ml of The constants kpand ka in eqn. (1) can be deduced if k,
0.1 M N&SzOa(i.e., 2 X lo-' moles). Noting that 2 is obtained for several reaction mixtures, differing
moles of N&S,Oa are equivalent to 1 mole of H202,we initially only in acid concentration (6). Then a plot of
see that 1 X moles of HP02have reacted a t the ap- kl versus [H+], when divided by [I-], should give a
pearance of the first blue color. The volume of thereac- straight line of slope ka and intercept k2.
tion mixture remains a t 207 ml, hence the concentration In this modification of the experiment, care must be
of H202has been reduced to': taken to ensure that the initial concentrations of H202
and iodide ion are constant. This is achieved by sub-
tracting the volume of 3 M H2S04used from the volume
At the appearance of the first blue color, 2 ml of thio- of water added to the initial reaction mixture, so that
snlphate were added so a t the second appearance of the the total volume is constant. All runs must, of course,
blue color a further 1.00 X lo-' moles of HpOphave be camed out a t the same temperature. This experi-
reacted and the volume has been increased to 209 ml. ment has been used successfully in our third year Physi-
Hence the concentration of H202remaining is: cal Chemistry course and rate constants in good agree-
ment with Reference (2) have been obtained.
The effect of ionic strength could be studied by adding
non-reacting salts, such as potassium chloride (3) or
The data for the experiment was fitted by means of a sodium perchlorate (6),to the reaction mixture.
578 / Journal o f Chemical Edumfion
Literature Cited (4) MCALPINE, R. K., J. CHEM.EDUC.,22,387 (1945).
(5) See for example: BENSON,5. W., "The Foundations of
(1) HARCOURT, A. G . V., AND ESSON,W., Phil. Trans. Roy. Soc., Chemical Kinetics," McGraw-Hill Book Co., New York,
157,117 (1867). 1960, pp. 23 and 33; KING,E. L.,"HOWChemical Re-
(2) LIEBHAFSKY, H. A., AND MOHM~MAD, A,, J. Am. Chem. actions Occur," W. A. Benjsmin, Ino., New York, 1964,
Soc., 55, 3977 (1933). pp. 80-82.
(3) BELL,F., GILL,R., HOLDEN, D., AND WYNNE-JONES, W. F. (6) LIEBAAFSKY, H. A,, AND A., J . P h w Chem.
MOHM~MAD,
K., J . Phys. Chem., 55,874 (1951). 38, 857 (1934).

Volume 44, Number 10, October 1967 / 579