Chemical Kinetics: The Iodine Clock Reaction

Experiment #2
Tanya Daher
Chemistry 113, Section 4
March 5, 2014

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I.

Introduction
The purpose of this experiment was to find the rate law (reaction orders m and n
and rate constant, k), activation energy (Ea) and frequency factor (A) for the oxidation of
iodide by hydrogen peroxide. In this experiment, two chemical reactions occur; in
reaction I, iodide is oxidized by hydrogen peroxide from the tri-iodide ion. In reaction II,
the tri-iodide ion created in reaction I reacts with thiosulfate to reproduce the iodide that
was consumed in the first reaction. The rate law will be determined using reaction I since
it is the slower of the two reactions.
Reaction I:
Reaction II:

II.

H2O2 (aq) + 3 I- (aq) + 2H+ (aq) I3-(aq) + 2 H2O (l) (slow) (1)
2 S2O32- (aq) + I3- (aq) 3 I- (aq) + S4O62- (aq)

(fast) (2)

Experimental
For visual reference 0.02 M sodium thiosulfate, 0.1 M hydrogen peroxide and 0.2 M
potassium iodide were mixed together in three different test tubes to examine the
chemical reactions between them, once they are mixed together. Six reactions were
run and each included 50-mL of potassium iodide in different volumes. Another 50mL solution was made out of buffer, sodium thiosulfate (Na2S2O3) and potato starch,
all at different volumes for each run. Every trial was run at regular room temperature
except for the last run, F, which was chilled.
I.
Qualitative Tests
6 mL of H202 solution was added to a test tube with about 6 mL of KI solution.
This mixture was then divided into three separate portions (three separate test
tubes) and one was used as a control. The control, which was left alone, had a
yellow color to it. In a second tube portion, ten drops of starch solution was
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added, which made the solution turn dark purple. To the third portion, 2 mL of
thiosulfate solution was added, along with 10 drops of starch solution, which
II.

made the solution bubbly and clear in color.

Kinetic Measurements
There were six reactions that were run, A F. In each of the six reactions, two
different graduated cylinders were made, each containing 50-mL amounts of
solutions. The first cylinder contained specific amounts of buffer, Na2S2O3,
starch, and KI (each amount was different, depending on the run). For every
run, there was always 10 mL of buffer, 10 mL of Na2S2O3 and 1 mL of starch
added (those remained at constant amounts). The only chemical solution that
changed throughout the runs was the KI solution. In specific, run A contained
5 mL of the Na2S2O3 solution, while run B contained 10 mL and runs C, D, E,
and F contained 15 mL. The second cylinder contained specific amounts of
H2O2 and diluted to the 50-mL mark with distilled water.. For runs A, B and C,
10 mL of H2O2 was added. For run D, 20-mL was added and for runs E and F
there was 40 mL of H2O2. After the two cylinders were prepared for the
specific run, they were added into a 250-mL Erlenmeyer flask. At that point,
the timer started and the flask was mixed (which contained a complete 100
mL for each run). The flask kept mixing until the solution changed color, at
that point the time and temperature was recorded. The temperatures of the
solutions in runs A through E must have agreed within 0.5 C. Run F had the
same procedures, except it was chilled in an ice bath before mixing in the
chilled 250-mL Erlenmeyer flask. The solutions in each of the 50-mL
graduated cylinders were supposed to be around 0 C and no longer changing.

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Table 1. Volumes of reactants for runs A through F.

Graduated Cylinder 1 *
Run

Buffer

A
B
C
D
E
F (chilled)

(mL)
10.0
10.0
10.0
10.0
10.0
10.0

Na2S2O3
~0.020 M
(mL)
10.00
10.00
10.00
10.00
10.00
10.00

Graduated
Starch
(mL)
1.0
1.0
1.0
1.0
1.0
1.0

KI
~0.20 M
(mL)
5.0
10.0
15.0
15.0
15.0
15.0

Cylinder 2 *
H2O2
~0.10 M
(mL)
10.0
10.0
10.0
20.0
40.0
40.0

Table 2. Temperatures (C) and times (min:sec:(1/100)sec) for runs A through F

Run
A
B
C
D
E
F (chilled)

III.

Temperature C
21.4
21.1
20.3
20.2
19.8
2.4

Time (min:sec:(1/100)sec)
14:42:39/100
8:05:18/100
5:52:16/100
2:51:58/100
1:26:09/100
4:53:72/100

Results
Part 1: Calculations of Initial Concentrations of H2O2, I-, and S2O32-

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The molarities of the solutions of H2O2, KI, and Na2S2O3 were used with Eq. 3 to
determine the various molarities of H2O2, I-, S2O32- in reactions A through F. The
molarity for each reaction is given in Table 3.
M1V1 = M2V2
Molarity of S2O32- for reaction A:
(0.02166 M)(10 mL) = M2 (100.0mL)
M2= 0.002166 M S2O32-

(3)

Table 3. The initial concentrations of H2O2, I-, and S2O32- present in reaction A
through F.
Run
A
B
C
D
E
F (chilled)

[S2O32-] (mol L-1)

0.002166
0.002166
0.002166
0.002166
0.002166
0.002166

[I-] (mol L-1)

0.01075
0.02150
0.03225
0.03225
0.03225
0.03225

[H2O2] (mol L-1)

0.01370
0.01370
0.01370
0.02740
0.05480
0.05480

Part 2: Determination of Rates of Reaction for Each Run

The rate reaction for each of the 6 runs was calculated using Eq. 4. Table
4 supplies the results for each of the rate values.
Calculation of reaction rate for reaction A:
2
S 2 O3

Rate = k [H2O2]r [I-]s =

(4)

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2
S 2 O3

Rate = k [H2O2]r [I-]s =

1
= 2

0 M 0.002166 M

(
)
882.39 s

M
s

Rate = 1.227 x 10-6

Table 4. This shows the temperature in K and time that each reaction held at the
end of each run. It also shows the calculated rate for each run and the rate
constant k for each run (That is also calculated in Part 4 of the results section).
Run
A
B
C
D
E
F (chilled)

Temperature (K)
294.55
294.25
293.45
293.35
292.95
275.55

Time (s)

Rate

Rate Constant

882.39
485.18
352.16
171.58
86.09
293.72

(mol L-1S-1)
1.227 x 10-6
2.232 x 10-6
3.075 x 10-6
6.312 x 10-6
1.258 x 10-6
3.687 x 10-6

k (M-1 S-1)
0.008331
0.007578
0.006959
0.007143
0.007118
0.002086

Part 3: Determination of the Reaction Orders with Respect to H2O2 and IRate order for iodide:

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Rate C k[ H 2O2 ]Cr [ I ]Cs

Rate A k [ H 2O2 ]rA [ I ]sA

Using Eq. 5, the rate order for iodide was calculated,

which involved the rates for runs C and A. Runs C and A were used because they
had different concentrations of I-, but the same concentrations for every other
reactant which would be disregarded at the end of the calculation.
(5)

3.075 x 10 -6 k (0.0137M ) r (0.03225M ) s

1.227 x 10 -6 k (0.0137 M ) r (0.01075M ) s

2.50611 3s

ln (2.50611)
0.836 s for [I-]
ln (3)

S=
1

Rate order for hydrogen peroxide:

Rate D k [ H 2 O2 ]rD [ I ] sD

Rate C k [ H 2 O2 ]Cr [ I ]Cs

Using Eq. 6, the rate order for hydrogen peroxide was

calculated, which involved the rates for runs D and C. Runs D and C were used
because they had different concentrations for H2O2, but the same concentrations
for every other reactant which would be disregarded at the end of the calculation.
(6)

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6.312 x 10 -6 k (0.0274M ) r (0.03225M ) s

3.075 x 10 -6 k (0.0137 M ) r (0.03225M ) s

2.052683 2 r

ln (2.052683)
1.0375 r for [H 2 O 2 ]
ln (2)

r=
1

Part 4. Determination of Rate Orders Graphically with Respect to H2O2 and

I-.
Rate Order of Iodide:
Eq. 7 was used to plot log Rate against log [I-] in a linear trend line using runs A,
B and C. The graph made using this data is known as Figure 1.
Log Rate = (logk + (r)log[H2O2]) + s(log [I-])

(7)

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Log Rate vs. Log Concentraction of Iodide

-5.3
-5.4

Log Rate (mol)/(L*sec)

-5.5
f(x) = 0.84x - 4.26
-5.6
R = 1

Log Rate (mol)/(L*sec)

Linear (Log Rate (mol)/
(L*sec))

-5.7
-5.8
-5.9
-6

Fi
gure 1. The graph represents the log rate vs. log concentrations of iodide.

Rate Order of Hydrogen Peroxide:

Eq. 8 was used to plot log Rate against log [H2O2] in a linear trend line using runs
C, D and E. The graph made using this data is known as Figure 2.
Log Rate = (logk + (s)log[I-]) + r(log [H2O2])

(8)
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Log Rate vs. Log Concentration of Hydrogen Peroxide

-2

-4.4
-1.8 -1.6 -1.4 -1.2
-4.6
-4.8

Log Rate (mol)/(L*sec)

f(x) = 1.02x - 3.62

-5
R = 1
-5.2

Log Rate (mol)/(L*sec)

Linear (Log Rate (mol)/
(L*sec))

-5.4
-5.6
Log [H202]

Figure 2. The graph represents the log rate vs. log concentrations of hydrogen
peroxide.

Part 5: Calculation of the Rate Constants and the Average Rate Constant
Eq. 9 was used to determine the rate constant of one of the six runs. The
concentrations of I- and H2O2 and the rate corresponding to the reaction run was
also used. The rate constants determined this way can be found in Table 4.
Rate Constant for Run A:

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rate
[ H 2O2 ]1[ I ]1

Rate = k [H2O2]r [I-]s

(9)

1.227 x 10 -6
(0.0137)1 (0.01075)1

k = 0.00833 M-1S-1
Table 4. This shows the temperature in K and time that each reaction held at the
end of each run. It also shows the calculated rate for each run and the rate
constant k for each run (That is also calculated in Part 4 of the results section).
Run
A
B
C
D
E
F (chilled)

Temperature (K)
294.55
294.25
293.45
293.35
292.95
275.55

Time (s)

Rate

Rate Constant

882.39
485.18
352.16
171.58
86.09
293.72

(mol L-1S-1)
1.227 x 10-6
2.232 x 10-6
3.075 x 10-6
6.312 x 10-6
1.258 x 10-6
3.687 x 10-6

k (M-1 S-1)
0.008331
0.007578
0.006959
0.007143
0.007118
0.002086

The average rate constant value and temperature for runs A through E were
determined to be 0.006796 M-1 S-1 and 293.71 K, respectively. Run F was not used
in the calculations because it would have skewed the results since it was chilled
and not conducted the same way as runs A through E.
Part 6: Determination of Activation Energy, Ea

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Eq. 10 was used to calculate the activation energy, Ea, of the experiment. Also, the
temperature values and k values were used.
Ea 1
1
KE

R TF TE
KF

ln

Ea

KE
*R
KF
1
1

TF TE

ln

Ea

(10)

0.007118 M -1S 1
* 8.3145 J mol -1 K -1
-1 1
0.002086M S
1
1

275.55K 292.95K

ln

Ea = 47.3 kJ/mol
Part 7: Determination of Frequency Factor, A
Eq. 11 and the activation energy (that was calculated in the previous part) were
used to determine the value of the frequency factor, A.

A
e

Ea
RT

k Ae

Ea
RT

(11)
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0.006796

A
e

47300 J/mol
(8.3145 J mol -1 K 1 )( 293.71K )

A = 175327 M-1 S-1 = 1750000 M-1 S-1

IV.

Error Analysis
Standard Deviation:
The standard deviation represents the uncertainty/distribution limits a significant
number. Eq. 12 represents the standard deviation equation.

x x 2 x ... x N x
N 1

1 N
xi x
N 1 i 1

(12)
The calculation of the standard deviation, of the average rate constant, was made
through Microsoft Excel. Runs A through E were used, excluding F because it would
skew the data based on its chilled temperature. The standard deviation turned out to
M -1S-1

V.

M -1S-1

be 0.000556
while the average was 0.007426
.
Discussion
If starch was omitted from the experiment, the solution color in each of the kinetic
trials would be clear and bubbly. When starch is removed it prevents the color from
turning dark purple and the sodium thiosulfate is still present.
If Na2S2O3 (sodium thiosulfate) solution was omitted from the experiment, the
solution will still turn a dark purple color. To visualize this, tests were completed in
Part 1 of the experimental section.
If the KI solution was omitted from the experiment, the solution would not change
color because the color change depends on the reaction of iodide in the KI solution,
thus the color would remain clear.
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If there was an increase in the concentration of hydrogen peroxide by 2.5, it

would cause the reaction rate to increase by 2.5 which would result in a reaction rate
value of 2.5 x 10-5 M-1 s-1. The concentration of hydrogen peroxide in the reaction is in
first order which means that an increase to the hydrogen peroxide concentration
results in an increase of the reaction rate by the same amount.
An increase in the KI concentration by 2.5 would also result in a first order
reaction. An increase of the concentration of potassium iodide by 2.5 results in the
same change in the reaction rate that the increase of the hydrogen peroxide
concentration by 2.5 increased by. The result will also be 2.5 x 10-5 M-1 s-1.
The concentration of Na2S2O3 (sodium thiosulfate) has nothing to do with the rate
determination. Thus, a change in its concentration by 2.5 will cause no change to the
reaction, which will remain at 1.0 x 10 -5 M-1S-1.
The temperature affects rates of reaction when the solution is increased. When
temperature increases the reaction becomes faster which means the reaction rate will
go up as well. In runs E and F, run E finished reacting before run F since it had a
higher temperature.
A change in the concentration of KI would change the rate of the reaction but not
the rate constant because the reaction rate would be disregarded when calculated
since it remained at a constant amount, this would result in a constant k value.
At a room temperature of 15C, the reaction rate constant, k, would decrease. This
is true since the rate constants of runs E and F showed that k decreases when
temperature decreases due to the proportionality of the temperature affecting the rate
constant.
In a pressurized vessel (with pressure larger than the atmospheric pressure), the
rate constant would not change because this reaction is not temperature dependent.

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Any possible errors would include the concentrations of H2O2 and KI remaining
constant. The iodide concentration in the potassium iodide solution regenerates itself
once it is consumed, hence the color change in the solution. The hydrogen peroxide is
not reformed after its consumption and may be limited. The experiment stays fixed in
this manner by adding extra hydrogen peroxide so the solution stays constant. It may
change/affect the results if the concentration of hydrogen peroxide changes.

VI.

Conclusion
The purpose of this experiment was to find the rate law (reaction orders m and n
and rate constant, k), activation energy (Ea) and frequency factor (A) for the
oxidation of iodide by hydrogen peroxide. The rate law was determined to be rate
= [H2O2][I-] and both of the rate orders turned out to be one. The average rate
constant runs A through E only) was 0.0067964 .000556 M-1S-1. The activation
energy (Ea) for this experiment turned out to be 47.4 kJ/mol (47300 J/mol). The
frequency factor (A) was 1750000 M-1S-1.

VII.

References
1. 0.02 M Sodium Sulfate: http://www.hazard.com/msds/f2/bjp/bjprm.html
2. 0.1 M Hydrogen Peroxide: http://www.hazard.com/msds/f2/cfz/cfzdw.html
3. 0.2 M Potassium Iodide: http://www.hazard.com/msds/f2/bkh/bkhjn.html
4. Starch Solution: http://www.hazard.com/msds/f2/blp/blpgn.html
5. Buffer: http://hazard.com/msds/f2/bzk/bzkzl.html
6. Chemistry 113: Experimental Chemistry II Laboratory Manual, (Penn State
Altoona Press: Altoona, Spring 2014) pp. 52-58

Appendix A- Safety Hazards

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1. 0.02 M Sodium Sulfate: Inhalation: breathing product dust or mist may irritate
respiratory tract. Ingestion: low toxicity but may cause irritation to the
gastrointestinal tract and purging. Skin: irritation from prolonged contact. Eyes:
may irritate or burn and cause temporary conjunctivitis.
2. 0.1 M Hydrogen Peroxide: Harmful if swallowed, inhaled or absorbed through
skin. Material is extremely destructive to tissue of the mucus membranes and
upper respiratory tract, eyes and skin. Inhalation may result in spasm,
inflammation and edema.
3. 0.2 M Potassium Iodide: Skin, eye, inhalation: irritation. Ingestion: harmful.
4. Starch Solution: Slightly irritating to the eyes and skin. Mists/aerosols may cause
irritation to upper respiratory tract.
5. Buffer: Mildly toxic by inhalation. Corrosive to skin and eyes. High
concentrations can be fatal.

Appendix B- Lab Notebook

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