Kinetic Study of the Reactions between Ferric and

Iodide Ions
Christy Joy A. Retanal, Vincent S. Dagala, Carlo Manuel A. Banquerigo
Chemical Engineering Department,
Xavier University - Ateneo de Cagayan
Corrales Avenue, Cagayan de Oro, Philippines

Abstract
The experiment aims to determine the effect of ionic
strength on the rate of the ionic reaction and to determine
the rate of the reaction using the method called Iodine
clock reaction. On four separate Erlenmeyer flasks, 100
mL of 0.1 M KI, 0.01 K2S2O8, 0.001 M Na2S2O3 were
made with the exception of 1 M KNO3 ( the solvent used
is a solution of 0.001 N HCl and 1x10-5 M EDTA was
used). A starch indicator was also prepared. Na 2S2O3 was
standardized with AR grade KIO3 ; in a 250 mL E. flask,
25 mL of KIO3 was dispersed, 25mL of 2%(v/v) KI
solution and 10 mL HCl was then added, after swirling
(deep blue color develops), starch was added until the deep
blue color disappears. After preparing all necessary
solutions and reagents, a set of numbered flasks were
prepared and, following the proposed scheme, reagents
were added. Upon adding the K 2S2O8, time was noted
when the blue color disappears. The reaction of [I-] and
[S2O82-] was made and by making the volume of [I -]
constant, thus making the reaction at pseudo-first order.
The obtained value of apparent and true constant of the
reaction without the added salt KNO 3 was 6.843 x 10
and 3.421

x 103 , respectively. By obtaining the true rate

constant and ionic strength of the reaction added with KNO3,

Bronsted relation was verified. The true rate constant

increases with increasing ionic strength involving like
charged ions, thus the reaction of [I-] and [S2O82-] obeyed
the Bronsted relation. This effect is called the primary salt
effect. Also, the increasing rate constant implies in the
increasing of how fast the reaction occurs and the
deviation, due to the primary salt effect, favors the
formation of products.

Keywords: rate law, activation energy, iodine clock

reaction, kinetics,
.
I.

INTRODUCTION

In studying a chemical reaction, it is important to

consider not only the chemical properties of the reactants,
but also the conditions under which the reaction occurs,
the mechanism by which it takes place, the rate at which it
occurs, and the equilibrium toward which it proceeds.
According to the law of mass action, the rate of a chemical
reaction at a constant temperature depends only on the
concentrations of the substances that influence the rate.
The rate law is experimentally determined and can be used
to predict the relationship between the rate of a reaction
and the concentrations of reactants. The rate law is given
by:
Rate =

k [ A] a [B] b

[1]

Where A and B is the concentration and a and b is

the coefficients.
Another strategy for determining the rate law is to
use the method of initial rates. The Method of Initial Rates
involves measuring the rate of reaction, r, at very short
times before any significant changes in concentration
occur. Suppose one is studying a reaction with the
following stoichiometry:
A+2B 3C

The initial concentrations of A and B are known;

therefore, if the initial reaction rate is measured, the only
unknowns in the rate law are the rate constant, k, and the
exponents a and b. One typically measures the initial rate
for several different sets of concentrations and then
compares the initial rates. [2]
Parts A and B of this experiment are concerned
with the evaluation of exponents a and b respectively in
the rate expression. Part C is concerned with the effect of
other ions on the rate of the reaction. Thus, the objective
of this experiment is to study the kinetics of the reaction
between ferric and iodide ions then determine the order of
the reaction with respect to both ions.
The initial rate is determined by measuring the
time in seconds required for 4x 10-5 mole of

reduced to

3+
Fe to be

2+
Fe . This is indicated by adding starch

solution and a small, constant amount of

2
S 2O 3

each mixture. The following reactions then occur:

3+

2+
I3
2 Fe + 3 I
2 Fe
+

2 3 I
I3 + 2
S 2 O3

(Slow)

to

3+
Fe

I 3

3+
Fe

Rate =
I

d
d
1

2
As soon as the

any additional

I3

S 2O 3 has been consumed,

formed by the reaction between

ferric and iodide ions will react with the starch to form a
characteristic blue color. [3]
I2 + starch

blue

Note that when the blue color first appears, the

decrease in the 2 concentration of

2
S 4 O 6

(Fast)

3+

Fe from its initial

value is just equal to the initial concentration of S20{ in

Rate expression for this reaction is

the mixture. Thus the initial rate,

3+
Fe

d , is equal to
1

2
S 2O 3 i

d
,
1

B. Reaction order with respect to

where

concentration of

[ S 2O 3 ]i

is

the

initial

2
S 2O 3 and t is the time in seconds

between mixing and the appearance of the blue color. In

order to obtain reasonable reaction times, it is necessary to
use initial rate intervals that allow the

3+
Fe

concentration to decrease slightly (about 4 to 10 percent)

from its initial value. To compensate for this change, it is
suggested that the average

3+
Fe concentration during

this time interval be used in place of the initial

concentration.

II.

EXPERIMENTAL SECTION

A. Reaction order with respect to

3+

Fe

Solutions of nitric acid, potassium iodide, sodium

thiosulfate, starch,

3+

Fe and water are prepared

by adding the specified solutions of the table in

the respective beakers. The contents are swirled
and allowed to equilibriate for 10 to 15 min. The
initial temperature was recorded upon the addition
of the content of 100-mL beaker into the 25mL
beaker. The recording of time started upon the
addition and stopped in the first appearance of
color blue in the mixture. The final temperature
was measured.

This part is performed exactly the same as in part

A, except that the concentration of ferric ion is
kept constant while of the iodine is varied.
C. Effects of

2+
Fe

A solution of 0.002 M in

2+
Fe was prepared by

dissolving Fe(NH4)2(SO4)2 in 0.15 M HNO3.

The run 1 in part A was repeated by substituting
the

2+
Fe solution for the HNO3 solution.

III.

RESULTS AND DISCUSSION

Chemical kinetics is one of the fundamental aspects in a

chemical
reaction.
Chemical
kinetics
includes
investigations of how different experimental conditions
can influence the speed of a chemical reaction and yield
information about the reaction's mechanism and transition
states, as well as the construction of mathematical models
that can describe the characteristics of a chemical reaction.
[4] In the experiment, the parameters of time,
concentration and temperature were monitored to obtain
the values of rate constant, reaction rate and reaction order.
According to the law of mass action, the rate of a chemical
reaction at a constant temperature depends only on the
concentrations of the substances that influence the rate. [5]
Thus, by knowing the concentrations of [S 2O3-2],[I-], and
[Fe3+] and the time needed for the reaction, we can solve
for the rate constant, reaction rate and reaction order. Also,
by using the reactions involved:

We can express the rate law by the expression:

y = mx + b
where a is the slope and the order of reaction of the
specific reactant ion.
In this case, we are to determine the order of reaction of
the ferric ion.
First, the concentrations of [S2O3-2],[I-], and [Fe3+] in the
solution were calculated.
Table 1. Concentration of [S2O3-2],[I-], and [Fe3+] in the
Soln
Run
1
2
3
4
5
6
7
8

-2

[S2O3 ] (M)
4x10-4
4x10-4
4x10-4
4x10-4
4x10-4
4x10-4
4x10-4
4x10-4

3+

[I ] (M)
4x10-3
4x10-3
4x10-3
4x10-3
4x10-3
2x10-3
6x10-3
8x10-3

[Fe ] (M)
4x10-3
6x10-3
8x10-3
0.010
0.012
4x10-3
4x10-3
4x10-3
-2

Using the concentration of [S2O3 ] and the raw data of

time needed for the reaction, the rate of reaction can be
determined. The method of initial rates allows the values
of these orders to be found by running the reaction
multiple times under controlled conditions and measuring
the rate of the reaction in each case. All variables are held
constant from one run to the next, except for the
concentration of one reactant. The order of that reactant in
the rate law can be determined by observing how the
reaction rate varies as the concentration of that one
reactant is varied. This method is repeated for each
reactant until all the orders are determined. At that point,
the rate law can be used to find the value of the rate
constant (k) for each trial. If the temperatures are the same
for each trial, then the values of k should be the same too.
[6].
On the first five solutions, the reactant that was held
constant was iodide and the ferric ions was varied. Using
this relation, we can determine the order of reaction of
ferric ions by plotting it with the rate of reaction.
Establishing a linear relationship by the equation:

Table 2. Initial rate, log [Fe3+] and log [initial rate]

RU
N
1
2
3
4
5

Initial Rate
(mol/Ls)
5.01x10-06
6.29x10-06
8.28x10-06
9.40x10-06
1.04x10-05

log[Fe3+]

log[initial
rate]
-5.29994
-5.20126
-5.08207
-5.02694
-4.98182

-2.39794
-2.22185
-2.09691
-2.00000
-1.92082

By plotting this values, we can obtain a linear graph.

Figure 1. log [Fe3+] vs log [initial rate]
-4.8
-2.5 -2.4 -2.3 -2.2 -2.1 -2 -1.9 -1.8
-4.9
f(x) = 0.69x - 3.65

-5
-5.1

Linear ()

-5.2
-5.3
-5.4

Identifying the equation of the line which is y = 0.6898x 3.6509, and the slope obtain is 0.6898 which is relatively
close to1. Thus, we can infer that the reaction order of Fe 3+
is 1.
For the reaction order of iodide ions, the solutions from
flask 1, 6, 7, and 8 was used. The initial rates and
concentrations of iodide was shown in Table 3.
Table 3. Initial rate, log [I-] and log [initial rate]

log (Initial rate) = alog[Fe3+ or I ]0 + Constant

RU

Initial Rate

log[I-]

log[initial

N
1
6
7
8

(mol/Ls)
5.01x10-06
1.43 x10-06
7.84 x10-06
1.64 x10-06

rate]
-5.29994
-5.84528
-5.10551
-4.78533

-2.39794
-2.69897
-2.22185
-2.09691

Again, by plotting log[I-] vs log[initial rate] we can obtain

a linear graph shown in Figure 2.
Figure 2. log [I-] vs log [initial rate]
0
-2.8-2.7-2.6-2.5-2.4-2.3-2.2-2.1 -2
-1

The determined equation of the line was y =

1.6925x - 1.275 and the slope obtained was 1.6925 which
is also relatively close to 2. Thus, the reaction order of I- is
2.
Using the obtained values of initial rates and the order of
reaction of each reactant, the rate constant can be
calculated using the rate law expression:

Subtituting the values of initial rate and concentrations of

Fe3+ and I- in each run, the rate constant was identified in
each run, shown in Table 4.

Table 4. Rate Constant

4

54.4
44

64.0
63

[S2O3-2]
(M)
4.0 x10-06

[I-] (M)
4.0x10-3

[Fe3+]
(M)
4.0x10-3

Rate
(mol/Ls)
3.18x10-06

Observing the resulting value when Fe 2+ is added,

it can be observed that the reaction rate decreased. The
effect of the ion decreases the rate of reaction.

IV.

ERROR ANALYSIS

- 2

Vo= k[Fe ] [I ]

89.3
75

A. reaction rate constant or reaction rate coefficient, k,

quantifies the rate of a chemical reaction. It is the
coefficient of proportionality relating the rate of a
chemical reaction at a given temperature to the
concentration of reactant (in a unimolecular reaction) or to
the product of the concentrations of reactants.[7] In the
experiment the average rate constant obtained was 66.17.

Run

-7

54.1
67

Table 5. Rate and time of reaction using Fe(NH 4)2(SO4)2

solution.

-5
-6

58.7
5

Linear ()

-4

Ru
n

64.6
88

Now, we compare the obtained results if we added

Fe instead of HNO3 by following the same amount of
solutions in Run 1 and procedure in solving. The data are
shown on Table 5 below:

-3

3+ 1

65.5
21

2+

-2

f(x) = 1.69x - 1.27

78.
321

The errors that contributed in the inaccuracy in the results

on the experiment were: parallax error, instrumental error
is the pipette and graduate cylinders which can badly
affect the data if not read and calibrated correctly.
imprecise amount of any substance may have been added,
not mixing of the solution, delayed noting of the time of
blue color appears, variation of temperature.
V.

CONCLUSION

The experiment was successfully performed by the

students. Using the initial rate method, clock reaction, and

basic kinetic study of the reaction given, we were able to

determine the reaction order of Fe3+ and I- which is 1 and
2 respectively. The average rate constant was also
determined which gives a value of 66.17. It was also found
out that the effect of Fe2+ ion decreases the reaction rate.

1000 mL
(10 mL)

0.04 mol Fe 3+
=

REFERENCES
[1]http://chemwiki.ucdavis.edu/Core/Physical_Chemistry/Ki
netics/Rate_Laws/The_Rate_Law
[2]http://www.chm.davidson.edu/vce/kinetics/MethodOfInitia
lRates.html

=0.004 M

Concentration of S2O32-:

[3]http://ceac.atilim.edu.tr/shares/chem/files/LAB/che
%C3%B6106/CHEM%20106_EXP%204.pdf
[4] https://en.wikipedia.org/wiki/Chemical_kinetics

volume S 2032

Molarity S 2O 3 2

[S2O32-]=

[5]http://chemwiki.ucdavis.edu/Core/Physical_Chemistry/Ki
netics/Rate_Laws/The_Rate_Law
[6] Chapter 14 of Brown and LeMay on The
Kinetics of the Iodine Clock Reaction
[7]
https://en.wikipedia.org/wiki/Reaction_rate_const
ant

0.004 mol S 2 O3 2

1000 mL

(10 mL)

=0.0004 M

APPENDICES
SAMPLE CALCULATIONS

Concentration of I-

Concentration of Fe3+:
[I-]=

[Fe3+]=

volume Fe 3+

Molarity Fe 3+

volume I

Molarity I

1000 mL
(10 mL)

0.04 mol I
=

=0.004 M

Initial rate:

V0=

[ S 2O 3 ] 2+
t
1

Reaction order:

log (Initial rate) = mlog[Fe3+ or I ]0 + Constant

=(0.0004M/52.0s)x
=4.76x10-6 mol/L s

Rate constant:

y = mx + b where m = reaction order