P. C. Moews, Jr. and R.
H, Pelrucci The Oxidation of Iodide Ion
Western Reserve University
Cleveland, Ohio
by Persulfate Ion
In a recent symposium (1) sponsored
by the Division of Chemical Education, ACS, the need
for further reactions amenable to simple kinetic studies
was emphasized. More specifically it was stated (2)
that reactions are needed whose rates can be measured
readily, for which the rate equation can be determined
directly, and for which it is obvious that the rate equa-
tion and the equation for the net reaction are not re-
lated in any simple way. A kinetic experiment carried
out by large sections of freshmen at Western Reserve
University—a study of the rate of oxidation of iodide
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ion by persulfate ion—seems to fit most of these criteria.
Moreover the experiment provides for a study of the
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effect of temperature, influence of ionic strength, and
effect of a catalyst on the rate of a chemical reaction.
The reaction between persulfate ion and iodide ion
may be represented by the equation:
Ss<V- + 31- =
2S04a_ + I,-
The reaction is second order, the rate being dependent
upon the concentration of both I- and SjOg2-. Mack
and France (3) employed this reaction in a physical
chemistry experiment which clearly illustrates all of the
points mentioned in the previous paragraph. Mack
and France’s experiment, while excellent for under-
graduate physical chemistry, takes more than one
laboratory period and is somewhat involved for fresh-
men.
Evans (4) has suggested the persulfate ion-iodide ion
reaction as being ideal for a kinetic experiment in gen-
eral chemistry. Evans made use of an initial rate
method in which solutions were allowed to react until a
definite concentration of iodine, estimated visually,
was attained. A more convenient initial rate method,
first described by King and Jacobs (5), involves the re-
duction of an aliquot of sodium thiosulfate by the
iodine formed in the reaction,
S4Oe2- 4* 31“
2SiOji_ + Is-
=
When all of the Sn032~ is consumed, the liberated iodine
can be detected with starch indicator. Two recent
laboratory manuals (6, 7) describe kinetic experiments
employing this reaction. In one (6, Wilson, et al.) the
reaction is followed by titration; in the other (7,
Faigenbaum, et al.) an initial rate method similar to
that of King and Jacobs (5) is used. Our experiment
also utilizes King and Jacobs initial rate method, hut
Volume 41, Number 10, October 1964 j 549
 Table 1. The Effect of Concentration of KI and (NH4)2S2Os on the Reaction Rate (24 ± 0.5°C)'
-Column A- .-Column B -Column C-
Experi- Molarity Molarity k X 104 k X 10* k X 10*
ment t (1 mole-1 l (1 mole-1 Molarity t (1 mole-5
number (NH4)2S2Oa KI KNOs (NH4)!S04 (sec) sec -I) (see) see-5) KNOa (sec) sec-5)
0.077 0.077 21 62 21 62 21 62
0.038 0.077 0.038 44 60 51 51 0.115 42 62
0.019 0.077 0.059 91 57 114 46 0.176 81 63
0.077 0.038 0.038 42 62 46 57 0.038 42 62
0.077 0.019 0.059 79 66 93 55 0.059 79 66
All solutions contain 5 ml of 0.2% starch and 10 ml of 0.01 M NasSj03, and have a total volume of 65 ml.

differs from the experiment of Faigenbaum, et al. in that Table 2, The Effect of Temperature on the Reaction Rate”1
reaction times are short, allowing several experiments
Experi- k X 104
to be performed during a brief laboratory period. ment (1mole-5
number T (°C) /(sec) see-1)
The Experiment
6 3 189 14
7 13 88 29
The student is furnished with 0.01 M Na2S203, 0.2% 8 24 42 62
starch solution, and solid KI, IvNO,, (NH4)2S2Os, and 9 33 21 120
(NH4)2S04. A stop watch is desirable but sweep second Experiment 4, Table
“
1, Column A, repeated at four different
hand wall clocks may be substituted. The students temperatures.
prepare 0.2 M solutions of (NH4)2S208 and KI. From
these solutions they prepare 0.1 M and 0.05 M solutions studied by adding small amounts of Cu2+ to the reac-
of both (NH4)2S208 and KI by dilution. In order to tion mixture. The student is told to repeat Experiment
keep the ionic strengths constant the students are told 4 with the addition of one, two, and then three drops of
to use 0.2 M KN05 and 0.2 M (NH.,)2S04 to effect the 0.02 M Cu(N03)2. Some typical results are given in
dilutions of the 0.2 M KI and 0.2 M (NH4)2S208, respec- Table 3.
tively.
In Experiment ml of 0.2 M KI, 5 ml of 0.2%
1, 25 Interpretation of Student Data
starch solution, and a 10 ml aliquot of 0.01 M Na2S203 Rate constants can be calculated readily from the
arc mixed in a 250-ml beaker.1 Twenty-five ml of data in Table 1. We have calculated rate constants
0.2 M (NH4)2S208 is quickly added to the beaker and
using the equation
the time observed simultaneously. Stirring is com-
menced immediately. At the appearance of a blue A [82082 ]
£[S2<V-][I-]
color the elapsed time is recorded and a temperature AT(sec)
reading taken. The rate constants appear in Tables 1 and 2. A value
Experiments 2-5 are carried out in the same way as for the Arrhenius activation energy may be calculated
Experiment 1 except that the concentrations of KI or from the data in Table 2 by plotting log k versus 1/f-
(NI14)2S208 are varied. In Experiment 2, 25 ml of (°K). A linear plot is obtained from wrhich a value for
0.1 M (NH4)2S208 (the solution is also 0.1 M in (NH4}2- the activation energy, 12.4 kcal, can be derived. For
S04) is substituted for the 25 ml of 0.2 M (NH4)2S208 beginning students, however, wTe believe the determina-
used in Experiment 1. Experiment 3 uses 25 ml of tion of the order of the reaction to be a more important
0.05 M (NH4)2S208; Experiment 4, 25 ml of 0.1 M exercise than the calculation of rate constants.
KI; and Experiment 5, 25 ml of 0.05 M KI. Some The student is told that one might expect the rate
typical results are given in Table 1, Column A. law for the reaction of I- with S2(V~ to be of the form:
The influence of ionic strength on the reaction can be Rate -
fc[I-]m[S2Os2- *]«
shown by carrying out the dilution of the 0.2 M KI and
(NH4)2S208 with distilled water and repeating the sev- where the exponents in and n are small whole numbers.
eral experiments; Table 1, Column B gives some typi- The student is asked to determine the values of the
cal data. Some results obtained by maintaining the exponents in and n. The time that elapses from the
ionic strength of all solutions constant with KN03 are mixing of the reactants to the appearance of the blue
listed in Table 1, Column C. color is inversely proportional to the rate of the reaction.
The effect of temperature is shown by heating and Plots are made of reaction time versus [I-] (with
cooling the solutions before mixing them. The student [S2082-] held constant) and reaction time versus
is told to carry out Experiment 4 at two temperatures [S2Os2-] (with [I-] held constant). These plots are
below and at one temperature above room temperature.
Some typical results are listed in Table 2. Table 3. The Effect of a Catalyst on the Reaction Rate11

Finally the effect of a catalyst on the reaction can be Drops

Experiment 0.02 M
number Cu(N03)2 t (sec)
5
It may be necessary to add a drop of 0.1 M EDTA (ethylen-
diaminetetraaeetic acid) solution if the reagents or distilled 10 1 31
water contain any appreciable quantity of metal ions which act 11 2 24
12 3 19
as catalysts. Of course in such cases the addition of 0.1 M
EDTA should be omitted when studying the catalytic effect of Experiment 4, Table 1, Column A, repeated with the addition
“

Cu3+ ions. of various amounts of 0.02 M CufNOah.

550 / Journal of Chemical Education

used by the student to determine the dependence of the
reaction rate on the concentrations of both I- and
S2082- and hence the values of rn and n. Instead of a
determination of a value for the activation energy, the
profound effect of temperature on the rate of the reac-
tion is impressed upon the student. Finally the student
is asked to draw conclusions about the effect of a trace
of Cu2+ on the rate of the reaction from data like those
in Table 3.
Discussion
The reaction of S2082" with I has been investigated
-
extensively; the first kinetic study is evidently that of
Price (8) in 1898. Price concluded that the reaction is
a bimolecular one and observed that copper and iron
salts are effective catalysts. The catalytic effect of
copper and iron salts has been confirmed by other
workers (.9). The reaction between persulfate ion and
thiosulfate ion is also catalyzed by copper salts (10).
This makes an exact interpretation of the data in Table
3 somewhat difficult; but this is unimportant for the
purpose of showing the catalytic effect of trace amounts
of copper. The reaction of persulfate ion with thiosul-
fate ion in the absence of a catalyst is insignificant since
the rate of the uncatalyzed reaction is much slower than
that of the S2082_-I~ reaction (10).
It has been suggested2 that this experiment would be
more effective if it were experimentally demonstrated
that the reaction of S2082- with S2032~ does not occur
to an appreciable extent. This was done by repeating
the several experiments in Table 1, Column C, replacing
the KI with KN03. After the solutions were allowed
to stand for periods of time corresponding to those re-
ported in Table 1, Column C, they were diluted with
200 ml of cold water. A 0.005 M solution of I2 in 50%
ethanol was used to titrate the unreacted thiosulfate.
A typical set of results is: Experiments 1, 2, and 3, no
loss of thiosulfate within experimental error; Experi-
ment 4, 1% of thiosulfate consumed; Experiment 5,
3% of thiosulfate consumed. The most consistent re-
sults are observed if a drop of 0.1 M EDTA is added to
each solution prior to the addition of the (NH4)2S208
solution.
An ionic reaction such as this which involves two
negative ions has a rate which is strongly dependent
upon ionic strength; it increases with increasing ionic
strength. King and Jacobs (5) were able to interpret
rate data at low ionic strengths in terms of the Bronsted-
Debye equation,
log k =
log k0 + 2AZlZ1
Salt effects on the rates of ionic reactions at higher
ionic strengths are not well understood (11). Later
workers have been concerned with the rates of the per-
sulfate ion-iodide ion reaction at higher ionic strengths
and with the effects of temperature and solvent on the
reaction. At higher ionic strengths specific effects
have been reported (9) not interpretable in terms of the
Brousted-Debye equation or any of its modifications.
Among the studies of the reaction of SaOs2- with I~
at high ionic strengths is that of Meretoja (12). Mere-
toja studied the effect on the reaction rate of ionic
strengths varying from 0 to 2.5, KN03 being employed
! Private communication, E. L. King.
as an inert electrolyte. He found that the effect of
ionic strength could be represented with the semiem-
pirical equation,
log k -
log h + y* -
By
where the velocity constant at y
k0 is 0, A is the
=
Debye-Huckel constant, and a and B may be treated
as parameters. In view of more recent work this equa-
tion should not be expected to be generally valid.
However it should be expected to be at least approxi-
mately correct where the salt effects are largely those of
1:1 electrolytes. In fact using Meretoja’s values for
the above equation at 24 °C,
l.St- -2.992 +
,
-
0.002,
the calculated rate constants agree very well with
those determined experimentally (Table 1, Columns A
and C). The most consistent set of values for the rate
constants (Table I, Column C) are obtained when the
ionic strength is kept constant with KN03. Ammo-
nium sulfate was used in Experiments 2 and 3 (Table
1, Column A) because it allows salt effects to be ex-
plained to beginning students without the necessity of
defining ionic strength.
Conclusions
Using data for the persulfate ion-iodide ion reaction
from the literature (e.g., that of Meretoja) one can de-
vise initial rate experiments to suit various purposes.
Experiments can be designed to show the effects of
temperature, catalysts, ionic strength, and reactant
concentrations. The experiments can be devised to
take varying lengths of time depending on the accuracy
desired.
The experiment as described in this paper is brief,
and uses commonly available equipment. It is suita-
ble for a short laboratory period and also has been very
successful as a lecture demonstration experiment.
While it fits most of the requirements for a simple
undergraduate kinetic experiment the large salt effects
do add a complicating factor.
Literature Cited
(1) King, E. L., Symposium Chairman, J. Chem. Educ., 40,
573-91 (1963).
(2) Campbell, J. A., J. Chem. Educ., 40, 583 (1963).
(3) Evans, G. G., J. Chem. Educ., 29, 139 (1952).
(4) Mack, E. Jr., and France, W. G., "A Laboratory Manual
of Elementary Physical Chemistry,’’ 2nd ed., D. Van
Nostrand Company, New York, 1934, p. 179.
(5) King, C. V., and Jacobs, M. B., J. Am. Chem. Soc., 53,
1704(1931).
(6) Wilson, J. M., Newcombe, R. J., Denaro, A. R., and
Rickett, R. M. W., “Experiments in Physical Chemis-
try,” Pergamon Press, New York, 1962, p. 57.
(7) Faigenbaum, H. M., Racster, L. V., Richtol, H. H., and
Wibbri.ey, S. E., “Laboratory Manual for General
Chemistry,” John Wiley and Sons, New York, 1963, p.
73.
(8) Price, T. L., Z. physik. Chem., 27, 474 (1898).
(9) House, D. A., Chem. Rev., 62, 197 (1962).
(10) Sorum, C. H., and Edward, J. O., J. Am. Chem. Soc., 74,
1204 (1952).
(11) Davies, C. W., “Progress in Reaction Kinetics,” Pergamon
Press, New York, 1961, Vol. 1, p. 161.
(12) Meretoja, A., Ann. Acad. Set. Fennicae, Ser. A., II. Chem.
No. 24, 59 pp. (1947); C. A., 42, 2163c (1948).
Volume 41, Number 10, October 1964 / 551