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R.J.B. Cruz / Chemistry 26.

1 (2015)

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Chemical Kinetics: The Iodine Clock Reaction


Reniel Joseph Cruza,*
Institute of Biology, University of the Philippines, Diliman, Quezon City 1101, Philippines

ABSTRACT
During a chemical reaction, chemical kinetics explains how fast or slow the reaction occurs and it is expressed in reaction rates. The
iodine clock reaction aids to explain this concepts. It shows how the factors like concentration, temperature, and catalysts affect the
reaction rate between the persulfate ion,

S 2 O8

and the iodine ion,

. The five runs of

S 2 O8

and

were

prepared in different concentrations to find the rate law using the initial rate methods and graphical methods. Another runs of run 2
were prepared under different temperatures, at ambient (300 K), hot (328 K), and cold (278 K) conditions to explain the effect of
temperature and catalyst on the reaction rate. Consequently, the calculated activation energy (

Ea

) and the Arrhenius constant

(A) values were solved by using the Arrhenius equation. The last set at constant concentration and constant temperature were
prepared for the addition of

CuS O4

in order to observe the effect of catalyst on reaction rate.

*Corresponding author. Mobile: 09178870880


E-mail address: renieljosephcruz@gmail.com

R.J.B. Cruz / Chemistry 26.1 (2015)

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1. Introduction
Spontaneity does not imply how fast or slow a
reaction because there are many spontaneous reactions
that are either fast or slow. Factors that affects the rate
of reaction is governed by chemical kinetics. Chemical
kinetics is the area of chemistry that is concerned about
reaction rates that deals with the speed at which
changes occur. It can be described in a reaction rate, the
change in the concentration of a reactant or product per
unit of time, Zumdahl. (2012). For example, in the
reaction of the experiment Iodine Clock Reaction is the
reaction between persulfate ion,

2
S 2 O8

iodide ion,

The variable

[B]

is the rate constant and

are the molar concentrations. The order of the

reaction can be obtained by solving for the exponents

and

. These exponents are only obtained

experimentally. Once the order of the reaction is known,


it can calculate the rate constants and establish an
integrated law for the given reaction. Zumdahl. (2012)
The Iodine Clock Reaction is an experiment which
involves the mixing of two colorless solutions to produce
a solution which remains colorless, then suddenly
changes to blue. The effect of temperature is examined
by heating and cooling the mixture. Catalysts are

CuS O4

observed through the addition of

2+ I 2
2 S O4
2+ 2 I
S 2 O8

[A]

as a

catalyst for the experiment. After the mixture turn blue,


the temperature and the time is observed in every runs.
(1)

2. Materials and Methods


500ml of chemicals at 0.2 M such as

KI ,KCl

were prepared by class. Under the same volume but


different
concentration
of
two
0.1
M

2
S2 O 8

2
S O4

Rate=

K 2 S 2 O8 , K 2 S O4

and one 4.0 mM,

Na 2 S2 O3

were also prepared. 20mL of 1% fresh starch solution


were prepared for the changing of color from colorless to
blue. The solutions were prepared in different volumes
shown in Table 1.
Table 1. The different runs for the effect of persulfate and
iodide concentrations on reaction rate.
Beaker A
Beaker B (+3 drops of
fresh starch)
Run
0.2 M
0.2 M
0.1 M
0.1 M
4.0
mM
KI
KCl
K S O K SO
2

It also relates the concentration of the reactants to the


rate of reactions. The rate law is given by using the
formula:

2
S 2 O8

R=k

(3)

Na 2 S2 O3

,
, mL
, mL
, mL
mL
, mL
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
All temperature and time were measured each run.
After the color turned blue, a stopwatch timer is used for
measuring time.
The rate of reaction for the first group was calculated
using the rate law. The order of the reaction was known
by using the initial rate method, graphing ln rate vs ln

R.J.B. Cruz / Chemistry 26.1 (2015)

S 2 O8

or ln

Runs

Ea

activation energy (

) and the Arrhenius constant

(A):

ln k =

Ea 1
+ ln A
R T

( )

(m)

the y-intercept

( b)

E a / R

is equivalent to

ln A

is equivalent to

y=mx +b

CuS O4

0.02

0.02

0.0008

361

0.00277

0.03

0.04

0.0008

105

0.00952

0.04

0.04

0.0008

60

. Since this run is

S 2 O8

0.00746

0.0167

2
S 2 O8

2
S 2 O8

R=k

increases. This

Table 2. Effect of Reactant Concentration on Reaction


Rate

affected the

(6)

Another way to determine the order of the reaction is

shown below. The unit of rate

used was 1/s, the reciprocal of seconds, in order to easily


observe the relationship between the reaction time and
reaction rate.

and

To describe the order of the reaction, one should


establish the rate law. In order to find the rate law, the
initial rate method can be used by dividing two equations
from runs that has similar concentration to solve for m
and n. In the experiment the m and n values found were
1.601 and 1.623 respectively.
(see Appendix C for
solutions)

is constant). In

is also the same in runs 1,2, and 3 in comparing different


concentrations of

87
134

reaction rate directly as it increases or decreases. The


reaction rate was also affected by the reaction time. As
reaction time decreases (fast), the reaction rate was
increased (fast).

the experiment, there was an increase in the reaction

0.0008
0.0008

From Table 2, it showed that concentration was directly


proportional to the reaction rate. Furthermore, the

In runs 2, 4, and 5 were compared for the varying

rate when the concentration of

0.0115

],M

(5)

(since

Rate,
1/s

0.02
0.02

3. Results and Discussion

2
S 2 O8

2
S 2 O3

Reactio
n time,
s

1
2

concentration of

qualitative, measurement for time is unnecessary.


All solution measurements were made using
volumetric flasks (5mL, 500mL), measuring pipettes at
10mL, and top loading balance. All mixtures were placed
in a 50 mL beaker.

concentration of

,M
0.08
0.04

and

After the color turned blue, in every run time is


measured using a stopwatch timer.
To observe the effect of catalysts, the catalyst for the
experiment was a 5mL 1 M

],M

(4)

A linear equation can be derived by plotting ln k vs


1/T where slope

2
S 2 O8

in order to determine the slope of

the line.
For the effect of temperature group from sets of run 2
were prepared by using a hot plate and an ice bath. The
temperatures were set at ambient (300 K), hot (328 K),
and cold (278 K) conditions. Since the temperatures were
give, the Arrhenius Equation is useful for solving the

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to graph ln rate vs. ln

S 2 O8

and graph ln rate vs. ln

. Figure 1 below shows that the linear equation

and coefficient of determination (

of the graph of

R.J.B. Cruz / Chemistry 26.1 (2015)

ln rate vs. ln [

2
S 2 O8

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2
S 2 O8

I
R=k

were y=0.7994x+0.0899 and

0.90, respectively. The obtained slope of the equation is


0.7994.

Figure 1. Graph of ln rate vs. ln [

S 2 O8

(7)

]
To compare the two different rate laws, Table 3 shows
the comparison of calculated rate constants using
different rate laws (6 and 7). It showed a large difference
in rate constant values (see Appendix C for calculations).
Table 3. Reaction rate and calculated rate constants of
different rate laws
Rate, 1/s
k 1 (m=0.
k 2 (m=1;

[S 2 O8 ]
ln

1
2
3
4
5

f(x) = 0.8x + 0.09


R = 0.9

ln rate

Figure 2 shows the graph of ln rate vs. ln

which

has a linear equation of y=0.9264x +1.4912 and the


coefficient of determination is 0.9513. The slope of the
equation was 0.9264.

601;
n=0.623)
0.582
0.581
0.332
0.581
0.858

0.0115
0.00746
0.00277
0.00952
0.0167

n=1)
7.1875
9.325
6.925
7.933
10.4375

The proposed mechanism of the reaction is the equation


below. (8)

( aq)
3
+ S 2 O slow [I S 2 O 8 ](aq)

I (aq)

fast I 2 (aq)+ 2 S O4 ( 8)
Figure 2. Graph of ln rate vs. ln [

3
[ I S2 O 8 ](aq)
+I

ln rate

The slowest step in a multistep reaction determines the


overall rate. Based from observations, the rate of the
initial step, the slowest step, is the same with the rate
law (3). Also, the reaction moves to a faster step, which

is step 2, because

[I ]
lnf(x)
= 0.93x + 1.49
R = 0.95

is reactive thus containing high

energy that provides enough energy to proceed to the


next step. Since the initial step occurs slowly, it has a
high activation energy. Furthermore, this mechanism fits
with the rate law because the mechanism with slow
initial step matches the rate law that includes only
reactants and it suffices the energy needed for step 2.
This main reason for the addition of

The graph of a line formed a positive slope. Deductively,


the order of the reaction is a second order reaction.

B is to consume

I2

2
S 2 O3

in beaker

from the main reaction. The starch

R.J.B. Cruz / Chemistry 26.1 (2015)

indicator will not be affected. When all the

I2

were consumed,

2
S 2 O3

ions

In order to calculate for the activation energy (


) and the Arrhenius constant (

starts to appear and reacts with

starch to turn the solution into blue. The reaction


intermediate for this experiment was

I2

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I2

because

acted neither a reactant nor a product of the

reaction. It was formed in one reaction and consumed in


the next. It was also responsible for the change of color
of the reaction mixture. To sum it up, the entire
mechanism of the reaction are to be found below.

Arrhenius constant through substituting

ln A

the slope, m=-5500.9, and


b=19.379.

J/mol and

2+ I 2

slow 2 S O 4

), the graph of ln k

vs. 1/T should be examined. Figure 3 below shows a


linear
equation
y
=
-5500.9x
+
19.379
and the coefficient of determination is 0.5433. This
values may help obtain the activation energy and

(see

Appendix

calculated values of
Mechanism:

Ea

2.697 108

Ea
,

E a / R

with

with the y-intercept,

for

and

calculations)

The

were 45,734.4826

respectively.

2+2 I

S 2 O8

Figure 3. Effect of Temperature on Reaction Rate based


from

2
2 fast 2 I +S 4 O 6

I 2 + 2 S2 O 3
I 2 +starch slow complex

S 2 O8

R=k

For the effect of temperature group, the runs were


prepared at different temperature and constant
concentrations shown in Table 4 below.
Table 4. Effect of temperature to the reaction rate and
rate constants
Set Temp, Reactio Rate, 1/s

k 1
K
n time,
k 2
s
1
300
134
0.00746
727.187
9.325
2
328
2.64
0.378
36,846.7 473.4
6
75
3
278
506.77
0.00197
192.352 2.466
5
*where m=1.601; n=1.623
**where m=1; n=1
Table 4 above shows that the temperature affected
the temperature directly. When the temperature was
increased, the reaction time for the mixture to turn blue
decreased. Since the reaction rate used is the reciprocal
of the reaction time, it would increase.

f(x) = - 5500.89x + 19.38


R = 0.54

Figure 4 shows the graph of of ln k vs. 1/T under


different rate law. The liner equation of the graph is y =
= -9652.5x + 35.191and its coefficient of determination
is 0.9359, where the calculated
J/mol and

A=1.919 10 15

Ea

is 80,250.885

R.J.B. Cruz / Chemistry 26.1 (2015)

Figure 4. Effect of Temperature on Reaction Rate based


from

2
S 2 O8

I
R=k

accounted
as
errors
in
solution
preparations,
temperature readings, or time readings. This may be
caused by human error, or environmental factors.
4. Summary and Conclusions
The different reactant concentration affected the
reaction rate. From the given initial rates, the m and n
values were 0.601 and 0.623, respectively. The
exponents were approximately to 1 and can be deduced
as a second order reaction. The graph of ln rate vs. ln [

S 2 O8

1. The other graph was ln rate vs. ln [

The effect of temperature affected the reaction rate


significantly. When the temperature was increased, the
fraction of molecules that react also increased that
caused the reaction rate to increase as well.
According to the collision theory, there must be a
redistribution of energy in order for a reaction to occur.
The activation energy is the minimum kinetic energy that
molecules must bring to their collisions for a reaction to

] showed a linear equation of

y=0.9264x

+1.4912 and its coefficient of determination was 0.9513.


The slope of the line was 0.9264 and it is approximate to

f(x) = - 9652.48x + 35.19


R = 0.94

occur. While

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, the Arrhenius constant, is the number

of collisions that must occur for a reaction to proceed at


a certain speed. The calculated values of

Ea

and

] that has a

linear equation of
From the experiment, there were factors that affect the
reaction rate. First, the different reactant concentration
affected the reaction time as well as the reaction rate. It
affected the reaction time inversely and the reaction rate
directly. Another factor that affects the reaction was
temperature. When the temperature was increased, the
reaction rate also increased. Thus, temperature affects
the rate directly. Lastly, the addition of catalyst also
affected the reaction rate significantly because it rapidly
increased the reaction rate by decreasing its activation
energy.

References
http://chemwiki.ucdavis.edu/Physical_Chemistry/Kinetics/Rate_L
aws/Reaction_Mechanisms/Reaction_Mechanisms
Aiken, G., McKnight, D.M., Harnish, R., Wershaw, R., 1996.
Geochemistry of aquatic humic substances in the Lake Fryxell
Basin, Antarctica . Biogeochemistry 34, 157188.

as the

Alberts, J.J., Takcs, M., 2004. Total luminescence spectra of IHSS


standards and reference fulvic acids, humic acids and natural
organic matter: comparison of aquatic and terrestrial source
terms. Organic Geochemistry 35, 243256. American Public
Health Association, 1998. Standard Methods for the Examination
of Water and Wastewater, 20th ed. American Public Health
Association, Washington, DC.

catalyst was observed. Since this run is qualitative, the


reaction time was not measured. The reaction time was
immediate that it occurred for about less than a minute.
The reaction was immediate because the catalyst

Anesio, A.M., Hollas, C., Granli, W., Laybourn-Perry, J., 2004.


Influence of humic substances on bacterial and viral dynamics in
freshwaters. Applied and Environmental Microbiology 70, 4848
4854.

dictates the needed energy and collisions for them

to react.
The last run which is adding of

decreased the activation energy (

CuS O 4

Ea

or the energy

required to react.
The results of this experiment did not display any
significant difference compared to the past studies.
There may be a small difference because it may be

/RJBCruz