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CHEMICAL KINETICS: THE IODINE CLOCK REACTION

DARLENE M. ROXAS
NATIONAL INSTITUTE OF MOLECULAR BIOLOGY AND BIOTECHNOLOGY, COLLEGE OF SCIENCE
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES
DATE SUBMITTED: 10 DECEMBER 2013
DATE PERFORMED: 23 NOVEMBER 2013

ABSTRACT
In a given chemical reaction, the reaction rates are expressed and explained through chemical kinetics. The iodine-clock reaction aims
to explain concepts of reaction rate and show the effects of major factors in the reaction rates including the concentration, temperature
and presence of catalyst between persulfate and iodide ion. Five different runs with different concentrations of S 2O82- and I- were
prepared to find the reaction order of each reactant using the initial rate methods and graphical methods. The rate law established
base from the experimental data was R=k[S2O82-][I-]. Other sets of run with constant concentration were prepared under different
temperature condition: cold (50C), room temperature (29oC), and hot (50oC) and the calculated activation energy (Ea) and Arrhenius
constant (A) was 5.043 x104 J/mol and 1.639 x1010, respectively, using the Arrhenius equation. A set with constant concentration and
constant temperature was prepared and treated with CuSO 4 to test the effect of catalyst to the reaction rate. The change in
concentration, temperature and presence of catalyst showed a significant change in the reaction rates of persulfate and iodide ion.
Faulty timer and disturbed nature of solutions due to physical factors are the possible reasons of errors in the data.

rate of reaction = k[C]m

INTRODUCTION
Chemical kinetics is the study of reaction rates, the changes in
concentrations of reactants (or products) as a function of time
[1] and can be described using the formula (1) given in this
hypothetical reaction
aA bB.

rate =

[A] [B]

a t
b t
(1)

Many of the biochemical processes proceeds spontaneously


based from thermodynamics. But whether the rate of this
reaction is slow or fast is described by chemical kinetics. Take
for example an enzyme-catalyzed reaction C D, where C is
the substrate and D is the product. Kinetics relates the
concentration of the reactants to the rate of reactions. Hence,
the rate law (2) is given by using the formula

(2)
where k is the rate constant and [C] is the given molar
concentration of reactant C. The overall order of reaction can
also be obtained using the equation (X) which is the sum of the
exponents, m, of the reactants. These exponents, however,
are not related to the stoichiometric coefficients; rather it is
determined from the actual experiment. The order of the
reaction sets up the rate law that can calculate rate constants
given the molar concentrations of reactants and establish an
integrated law that can relate the change of concentrations in a
given period of time [2].
This experiment has been used as a visual representation
involving the investigation of rate expression in chemical
kinetics. The "Iodine Clock" refers to a group of reactions
which involve the mixing of two colorless solutions to produce
a solution which remains colorless for a precise amount of
time, then suddenly changes to a deep purple-blue color. The
time is controlled by the temperature and/or the concentrations

of the reactants [3]. The experiment aims to understand the


reaction mechanism of the iodine clock reaction and to
describe the rate of reaction through measuring the rate of
formation of I2 from the reaction of S2O82- and I-. The time when
all 2O82- are consumed, the rate of I2 formation can be
calculated.
To describe the kinetics of the iodine clock reaction, certain
factors that may affect the rates of reaction were observed
including the concentration of the reactions, temperature, and
the presence of catalyst. In the experiment, the reaction (3)
between persulfate, S2O8-2, and iodide, I- was studied.

S2 O8 2- + 2I - 2SO 4 2- + I 2

The solutions from table 1 are prepared under controlled


conditions: varying concentrations at constant temperature,
varying temperatures at constant molar concentration, and
presence of catalyst.
Table 1. Different runs for the effect of concentration to
reaction rates
Beaker A, mL
Beaker B (+ 3 drops of
starch solution), mL
Ru
0.2
0.2 M 0.1 M
0.1 M
4 mM
n
m KI
KCl
K2S2O8 K2SO4 Na2S2O3
1
10
0
5
5
5
2
5
5
5
5
5
3
2.5
7.5
5
5
5
4
5
5
7.5
2.5
5
5
5
5
10
0
5

rate

The
rate
of
reaction for the first condition is measured using the following
rate law (4,5) according to the rate of disappearance of S2O82-/Iand appearance of I2 / SO42-.
(4)
n

k[S2 O8 ] [I ]

(5)

To test the effect of varying temperatures with constant molar


concentrations to the rate of reactions, several sets from run 2
shown in table 1 were prepared at different temperatures: at
50oC, 15oC, and 27oC. Svante Arrhenius demonstrated that the
rate constant of chemical reactions vary with temperature in
accordance with the equation (6) that yields to varying values
of slope so we take the natural logarithm of both sides and
resulted to a linear equation (7). Plotting ln k vs 1/T gives a
linear equation (8) wherein the slope of the line (m) is equal to
-Ea/R, and y-intercept (b) is equal to ln A.

k Ae Ea /RT
(6)

ln k

E a 1
ln A
R T
(7)

y m (x ) b
(8)
where k is the rate constant, Ea is the activation energy, R is
the universal gas constant (8.314 J/mol K), T is the
temperature (K), and A is the Arrhenius constant (the fraction
of molecules with successful collision).
On the other hand, another set of run 2 was treated with
CuSO4 to compare the effect of the catalyst on the rate of the
reactions to the controlled set of run 2.

[S2 O8 2 ] [I ] [SO 42 ] [I2 ]

t
2t
2t
t

2 m

where k is the rate constant, m and n are the orders of the two
reactants obtained from the experiment using the initial rate
method and graphing ln rate vs ln [S2O82-]/[I-] to determine the
slope of the line as the order of the reaction with respect to
reactants.

The study of chemical kinetics plays a vital role in many fields


(e.g. medicine, industry, business). Knowing the rate of the
cement to solidify after a period of time can make an impact in
flow of your business. Knowing the rate of an antibiotic to react
with your body can make an impact to your health. Having said
these real life situations, chemists study the kinetics to have a
higher percentage yield of products and to avoid unwanted
reactions [4].
RESULTS AND DISCUSSION

Given the chemical reaction (3), another way of measuring the


rate of this reaction is to couple it with a much faster reaction
that consumes I2 by adding up Na2S2O3 that results to a new
chemical reaction (9).

I 2 + 2S2 O3 2 I 2 + 2S4O 6 2
(9)
The second chemical reaction consumes all I 2 immediately
after its first reaction with S2O32-. After using all S2O32-, the
starch will react with the accumulating I2 to form a greenishblue color. The time elapsed after the mixture turns blue was
used to calculate the reaction rate of persulfate and iodide ion
[5].
For a given chemical reaction, the rate of reaction can be
measured through change of concentration over time. Runs 1,
2, 3 were used to compare the rates with respect to the varying
concentration of I-. Experimentally, the reaction time (time
when the reaction turns blue) showed a significant increase as
the concentration I- decreases shown in table 2. The same is
true for the rates of Runs 2, 4, 5 where concentration of S 2O82varies. However, the obtained rates of reaction for the different
runs were not obtained using the rate law (4). Instead, the
reciprocal of the time elapsed when the mixture turns blue was
used since it will produce the same amount of I 2 over time and
is directly proportional to the rate of the reaction.
Table 2. Effect of Reactant Concentration on Reaction Rate
[S2O82-], [I-],
[S2O32-], Rxn
Rate,
M
M
M
time, s
1/s
1 0.02
0.08 0.0008
31.34
0.0319
2 0.02
0.04 0.0008
53.86
0.0186
3 0.02
0.02 0.0008
115.94
0.00863
4 0.03
0.04 0.0008
38.06
0.0263
5 0.04
0.04 0.0008
29.34
0.0341
In order to describe the reaction of the iodine clock reaction or
how does concentration of the reactants affects the reaction, a
rate law should be established. Initial rate method (see
Appendix C for Calculations) can be used to express this
equation which gives us the orders (m, n) of the reactants for
the iodine-clock rate law (5). These exponents are conformed
from experimental data obtained. The reaction order with
respect to S2O82- /I- calculated by comparing rates for different
initial concentration of the rate law of each run is m=1 and n=1,
respectively. With these values, we can establish the rate law
(10) expression for iodine-clock reactions as

R k[S2 O8 2 ][I ]
(10)
On the other hand, reaction orders can also be determined
graphically by plotting ln (rate) vs. ln (conc. of reactants).
Figure X shows the graph of ln (rate) vs. ln ([S2O82-]) with the
obtained equation y=1.145x + 0.635 and linearity value R 2
equal to 0.999. The determined value of slope is the reaction
order of S2O82- is 1.145.
Figure 1. Effect of [S2O82-] on the rate
0
-4.2 -4 -3.8 -3.6 -3.4-1-3.2
-2

ln [S2O82-]

-3
-4
-5
ln rate

The graph of ln (rate) vs ln ([I-]) was also plotted to determine


its order. Figure 2 below shows the equation of the line
y=1.049x + 1.043 with linearity value R2 of 0.989. The obtained
slope of the equation, m= 1.049, is the reaction order of I-.
Figure 2. Effect of [I-] on the rate reaction
0
-5

-4.5

-4

-3.5

-1 -3
-2

ln [I-]

-3
-4
-5
ln rate

R k[S2 O8 2 ]1.145 [I ]1.049


Based from the obtained values
of m and n from the plotted graph, another rate law (11) can
established as
(11)
Calculating the rate constants using different rate laws (10 and
12), table 3 shows the significance difference of constant, k in
different runs.
Table 3. Calculated
laws
Rate, 1/s
1
0.0319
2
0.0186
3
0.00863
4
0.0263
5
0.0341

rate and rate constants of different rate


k1*
1.994 x101
2.325 x101
2.158 x101
2.192 x101
2.131 x101

k2**
3.979 x101
4.800 x101
4.608 x101
4.267 x101
3.980 x101

The proposed mechanism of the reaction can be described by


the equation (12)
*
3
I ( aq ) S2O8 2 ( aq ) u
slow
uu
r [I...S2O8 ] ( aq )
*

Table 4. Effect
constants
Ru Temp,
n2
K
S 1 302.1
5
S2 323.1
5
S 3 278.1
5

of temperature to the reaction rate and rate


k1*

k2**

Rxn
time, s
53.86

Rate,
1/s
0.0186

23.25

48.00

9.11

0.110

137.5

283.9

197.7
9

0.0050
6

6.325

13.06

*derived from rate law R= k[S2O82-][I-]


**derived from rate law R=k[S2O82-]1.145[I-]1.049

Table above shows that the reaction time varies accordingly to


the change of temperature wherein the time when mixture
turns blue increases as the temperature increases. The rate,
which was also obtained by reciprocating the time, and the rate
constants, which were calculated based from the established
rate laws (10 & 11) also matches the increasing trend of
temperature.
In order to calculate the Ea (activation energy) and the A
(Arrhenius constant), the graph of ln k vs 1/T should be
determined. Figure 3 shows us the straight line leaning to the
right giving us the negative slope of -6065.6, which is equal to
Ea/R, and a y-intercept of 23.52, which is equal to the ln A
given by the formula (7). The activation energy calculated
using the k obtained using the rate law (10) is 5.043 x10 4 J/mol
and the Arrhenius constant, A, is 1.639 x1010.
Figure 3. Effect of Temperature on Reaction Rate based from
R= k[S2O82-][I-]

[I...S2 O8 ]3( aq ) + I u
fast
uu
r I 2( aq ) 2SO 4

(12)
where I is a reactive, unstable species, so it has a higher
energy than the products or reactants. Since I 2 appears only in
the second fast reaction based from the experiment, the
mechanisms with slow initial step correlates the rate law given
wherein the overall rate law can include only reactants (or
products).
For the second condition, temperature often has a major effect
on reaction rates given by the Arrhenius equation (7).
Preparing the sets from Run 2 with varying temperature and
constant molar concentrations, the obtained rates and rate
constants are shown in table 4.

4
1/T 2
0
0

0
ln k

On the other hand, figure 4 shows the graph of ln k vs 1/T


where k is obtained from the rate law (11). The graph gives us
a linear equation of y= -6065.6x + 24.24 with linearity R 2 of
0.971, where calculated Ea is equal to 5.043 x104 and the
Arrhenius constant equal to 3.367 x1010.
Figure 4. Effect of Temperature on Reaction Rate based from
R=k[S2O82-]1.145[I-]1.049

faster reaction time of 13.88 s than the controlled set-up with


53.86 s. The catalyst decreases the activation energy without
being consumed during the reaction. In general principle,
causes a lower Ea, thus making the rate constant larger and
reaction rate higher [6]. This is very evident with the rate
constant obtained from the two rate laws and the rate
calculated shown in table 5.

Table 5. Calculated rate and rate constants of set w/o catalyst


and set w/ CuSO4 catalyst
Run 2
Temp, K
Rxn time, s
Rate, 1/s
S1
302.15
53.86
0.0186
S4
302.15
13.88
0.0720
*derived from rate law R= k[S2O82-][I-]
**derived from rate law R=k[S2O82-]1.145[I-]1.049

6
4
1/T 2
0
0

ln k

Stated from the collision theory is that molecules must collide


with each other to react [5]. To have a higher efficiency of
collision between molecules, the proper orientation of these
reacting species should be considered. Therefore the
evaluated Arrhenius constant, A, described as the number of
collisions that must occur for the reaction to proceed in a fast
or slow phase reflects the molecular structure or orientation of
the reacting species. Meanwhile, the activation energy Ea
calculated reflects the required energy of the molecules to
react as it is one of the requirements for a reaction to continue
based from collision theory.
The fourth set of run 2 which is prepared by adding CuSO 4 that
acts as a catalyst. The reaction time of set with catalyst has

The results presented do not display any significant difference


compared to past studies. There may have a small amount of
difference but it can be accounted as errors in time and
temperature readings and other chemical or environmental
factor.
SUMMARY AND CONCLUSIONS
The reaction rates of persulfate and iodide under different
conditions: a) varying concentration, b) temperature, and c)
presence of catalyst were obtained. Effects of varying reactant
concentration affected the average reaction time affecting also
the rates of the reaction. From the given initial rates, the
reaction orders of 1 for both reactants were obtained using the
initial rate method. Graphing ln (rate) vs ln [S2O82-] gave a
linear equation of y=1.145x + 0.653 with linearity of R 2 equal to
0.999. The slope of the line determined the reaction order of
S2O82- which is 1.145. Plotting the graph of ln (rate) vs ln [I-]
showed a straight line with a linear equation of y= 1.049x +
1.043 with linearity of R2 equal to 0.989. The reaction order of Igiven by the slope of the equation is 1.049. The calculated
order of each reactant has a significant difference with the
orders obtained from the graph. Using the order obtained from
the experimental data, the rate law of the iodine clock
reactions is R= k[S2O82-][I-], while the rate law established from
the graph (x) is R= k[S2O82-]1.145[I-]1.049. The rate constant from
rate law (11) are doubled values of rate constant from rate law
(12).
On the second part where solutions are observed under
different temperature conditions, the rates of different set-ups
have varying values of rate. Following the reaction order
obtained from initial rates method, set-up under cold
temperature (at 5oC) has computed rate of 0.00506 s-1 and a

rate constant of 6.325 M-2s-1; under room temperature (at 29oC)


has a calculated rate of 0.0186 s-1 and a rate constant of 23.25
M-2s-1; and under high temperature (at 50oC) has a calculated
rate of 0.0110 s-1 and a rate constant of 137.5 M-2s-1. As
temperature increases, the rate of reaction of persulfate and
iodide ion increases along with the rate constant. Using the
Arrhenius equation (X), the computed activation energy Ea is
5.043 X104 J/mol and the Arrhenius constant computed is
1.639 x1010.

The following values may vary as many factors can affect the
chemical reaction of persulfate and iodide ion. Inaccurate timer
can be accounted as one major sources of errors as it can
have a different settings from the other types of error so a
primary and uniform timer should be used to lessen this errors.
Other factors such as thermometers can influence any great
changes especially in the temperature obtained. Proper
reading of the temperature should also be considered.

Meanwhile, there is a great change in the computed rate


constant after using the reaction order of the two reactants
obtained from the graph. Set-up under 5oC has a calculated
rate constant equal to 13.06 M-2s-1, while set-up under room
conditions has a calculated k of 48.00 M-2s-1. Set-up under high
temperature (at 50oC) has a computed rate constant equal to
283.9 M-2s-1. The Ea is also equal to 5.043 x104, while the
Arrhenius constant has increased to 3.367 x1010 after using the
reaction orders obtained from the plotted graph (X). The
Arrhenius constant and the Ea reflects the efficiency of the
orientation of the molecules during the collision and the energy
required in order the two reactants to react.

REFERENCES

Another set-up of run 2 showed an increase in the rate from


1.86 x10-2 to 7.20 x10-2 and in the rate constant from 23.25 M2 1
s to 90.00 M-2s-1 upon addition of CuSO4 as catalyst. The
calculated rate is based from the reaction order obtained from
initial rates method. Using the reaction order from the plotted
graph of ln (rate) vs. ln [S2O82-]/[I-], the computed rate constant
significantly increased from 48.00 M-2s-1 to 185.8 M-2s-1. The
results reflect the great influence of catalyst in the fast rates of
the reaction.

[6] Petrucci, Ralph H., Herring, F., etal. General Chemistry


Principles and Modern Applications. 2011. Ontario: Pearson
Canada Inc.

[1], [2], [4] Silberberg, Martin S. Principles of General


Chemistry. 2007. New York: McGraw-Hill.
[3] Bertrand, Gary L. Iodine Clock Reaction: A Simulated
Experiment.
http://web.mst.edu/~gbert/IClock/IClock.html.
Web. 07 December 2013
[5]
Chemistry
102
http://www.csun.edu/chem/documents/Kinetics.pdf.
December 2013.

Manual.
Web. 09

APPENDIX A List of Tables


Table 1. Different runs for the effect of
Table 2. Effect of Reactant Concentration on Reaction Rate
Table 3. Calculated rate and rate constants of different rate laws
Table 4. Effect of temperature to the reaction rate and rate constants
Table 5. Calculated rate and rate constants of set w/o catalyst and set w/ CuSO4 catalyst
APPENDIX B List of Figures
Figure 1. Effect of [S2O82-] on the rate
Figure 2. Effect of [I-] on the rate reaction
Figure 3. Effect of Temperature on Reaction Rate based from R= k[S2O82-][I-]
Figure 4. Effect of Temperature on Reaction Rate based from R=k[S2O82-]1.145[I-]1.049

APPENDIX C Calculations
A. Effect of Reactant Concentration on Reaction Rate
I.

Initial Rate Method (refer to Table 1)


a. Reaction order with respect to S2O82-

R 5 0.0341 s 1
[0.04]m x[I ]n

1
R 4 0.0263 s 1
[0.03]m x[I ]n
1 1.33m
m 1

[0.08]n x[S2O8 2 ]m
R 2 0.0319 s 1

2
R1 0.0186 s 1
[0.04]n x[S2 O8 2 ]m
2 = 2n
n 1
Reaction order with respect to I-

b.

II.

Rate constants from R= k[S2O82-][I-]


a) Run 1

b)

R
[S2 O8 2 ][I ]

Run 2

R
2

[S2 O8 ][I ]

R
[S2 O82 ][I ]

0.0319 s 1
=
[0.02 M][0.08 M]

0.0263 s 1
=
[0.03 M][0.04 M]

0.0186 s 1
=
[0.02 M][0.04 M]

= 1.994 x101 M 2s 1

= 2.192 x101 M 2s 1

= 2.325 x101 M 2s 1

c) Run 3

d)

Run 4

R
[S2O8 2 ][I ]

0.00863 s 1
=
[0.02 M][0.02 M]
= 2.158 x101 M 2s 1

e)

Run 5

R
[S2 O8 2 ][I ]

0.0341 s 1
=
[0.04 M][0.04 M]
= 2.131 x101 M 2s 1

III.

Rate constants from R= k[S2O82-]1.145[I-]1.049

b)

2 1.145

[S2 O8 ]

1.049

[I ]

R
[S2 O8 ]

[I ]1.049

0.0341 s 1
=
[0.02 M]1.145 [0.08 M]1.049

0.0186 s 1
=
[0.02 M]1.145 [0.04 M]1.049

= 3.979 x101 M 2.194s 1

= 4.800 x101 M 2.194s 1


b)

Run 2

c) Run 3

2 1.145

d)

R
2 1.145

[S2 O8 ]

1.049

[I ]

Run 4

R
2 1.145

[S2O8 ]

[I ]1.049

0.0263 s 1
=
[0.03 M]1.145 [0.04 M]1.049

0.00863 s 1
=
[0.02 M]1.145 [0.02 M]1.049

= 4.267 x101 M 2.194s 1

= 4.608 x101 M 2.194s 1

d) Run 5

R
[S2 O8 2 ]1.145 [I ]1.049

0.0341 s 1
=
[0.04 M]1.145 [0.04 M]1.049
= 3.980 x101 M 2.194s 1

Run 1

B. Effect of Temperature on Reaction Rate


I.

Rate constants from R= k[S2O82-][I-]


a) Run 2: Set 1

b) Run 2: Set 2

R
[S2 O8 2 ][I ]

0.0186 s 1
=
[0.02 M][0.04 M]
= 23.25 M 2s 1
k

R
[S2 O8 2 ][I ]

0.110 s 1
=
[0.02 M][0.04 M]
= 137.5 M 2s 1

R
[S2 O82 ][I ]

0.00506 s 1
=
[0.02 M][0.04 M]
= 6.325 M 2 s 1

c)

Run 2: Set 3

Rate constants from R= k[S2O82-]1.145[I-]1.049

II.

d) Run 2: Set 1

b) Run 2: Set 2

R
[S2O8 2 ]1.145[I ]1.049

R
[S2 O8 2 ]1.145 [I ]1.049

0.0186 s 1
=
[0.02 M]1.145[0.04 M]1.049

0.110 s 1
=
[0.02 M]1.145 [0.04 M]1.049

= 48.00 M 2.194s 1

= 283.9 M 2.194s1

R
2 1.145

[S2 O8 ]

[I ]1.049

0.00506 s 1
=
[0.02 M]1.145 [0.04 M]1.049
c)

= 13.06 M 2.194s 1

Run 2: Set 3

III.

ln k

Activation Energy and Arrhenius Constant

E a 1
ln A
R T

Ea
R
Ea (6065.6)(8.3145 J/mol K)

m 6065.6

Note: The calculated activation energy


from both rate laws (10 & 11) are equal.

= 50432.4 or 5.043 x10 4 J/mol

b ln A 24.24
a)

e 24.24 3.367 x1010

Arrhenius constant for rate law R= k[S2O82-][I-]

b) Arrhenius constant for rate law R= k[S2O82-]1.145[I-]1.049

b ln A 24.24

e 24.24 3.367 x1010

C. Effect of Catalyst on Reaction Rate

I.

Rate constants from R= k[S2O82-][I-]

R
[S2 O8 2 ][I ]
0.0186 s 1
[0.02 M][0.04 M]

=
a)

= 23.25 M 2s 1

w/o catalyst

R
[S2 O8 2 ][I ]

0.0720 s 1
=
[0.02 M][0.04 M]
b)

= 90.00 M 2s 1

w/ catalyst

II. Rate constants from R= k[S2O82-]1.145[I-]1.049

R
[S2 O8 2 ]1.145 [I ]1.049

0.0186 s 1
=
[0.02 M]1.145[0.04 M]1.049
a)

= 48.00 M 2.194s 1

w/o catalyst

R
[S2O8 2 ]1.145 [I ]1.049

0.0720 s 1
=
[0.02 M]1.145 [0.04 M]1.049
b)

= 185.8 M 2.194s 1

w/ catalyst