CHEM 122L

General Chemistry Laboratory

Revision 2.0

Determination of the Rate Constant for an Iodine Clock Reaction

To learn about Integrated Rate Laws.

To learn how to measure a Rate Constant.
To learn about Clock Reactions.

In this laboratory exercise, we will measure the Rate Constant k for the oxidation of Iodide (I-)
by Peroxysulfate (S2O82-).
2 I-(aq) + S2O82-(aq)

I2(aq) + 2 SO42-(aq)

(Eq. 1)

In this experiment, the reaction is Clocked by a secondary Clocking reaction, which consumes
the product I2 as soon as it is produced and which triggers a color change due to the persistent
presence of I2 when the Clocking Reagent itself is completely consumed. We will use
Thiosulfate (S2O32-) as the Clocking Reagent because it can reduce the I2 back to I-:
2 S2O32-(aq) + I2(aq)

S4O62-(aq) + 2 I-(aq)

(Eq. 2)

As long as any Thiosulfate Ion is present, none of the Iodine produced in (Eq. 1) remains; it is
consumed as quickly as it is produced. (This, of course, requires that (Eq. 2) proceed very
rapidly; which is in fact the case.) As soon as the Thiosulfate is used up, Iodine will begin to
appear in the solution. The presence of Iodine is then dramatically detected because of the
formation of a Starch-Iodine molecular complex which is deep blue in color. (Actually, the
starch molecules complex with I3- which is formed by a reaction between I2 and
I-.) When the deep blue color appears the reaction is said to Clock. We can set the Clock
Point by simply adding differing amounts of Thiosulfate Ion to the reacting solution.
The Rate at which a chemical reaction proceeds is typically influenced by the concentration of
each reactant present and by the temperature of the reaction vessel. And, typically, the
relationship between the Reaction Rate and Reagent Concentration takes a simple form known as
the Rate Law:
Rate = k [A]n [B]m

(Eq. 3)

Here A and B are generic reacting Species, k is a reaction specific proportionality constant known
as the Rate Constant, and n and m are the Reaction Order. The Rate Law parameters k, n and m
must be determined experimentally.
In our case, (Eq. 1), it has been determined experimentally that the reaction kinetics is MixedSecond Order:

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Rate = k [I-] [S2O82-]

(Eq. 4)

For reasons that will become apparent, we will use a vast excess of Iodide during the reaction.
Under these conditions, the Iodide concentration [I-] will barely change over the course of the
reaction and we can say:
[I-] ~ [I-]o

(Eq. 5)

which means we can re-write our Rate Law as:

Rate = k [I-]o [S2O82-]

(Eq. 6)

This allows us to define a new Rate Constant k as:

k = k [I-]o

(Eq. 7)

And, under the experimental constraint that [I-] is very large, the Rate Law for our reaction becomes First
Order:

Rate = k [S2O82-]

(Eq. 8)

(Eq. 8) is said to be a Pseudo-First Order Rate Law with a Pseudo-First Order Rate Constant k,

because the large [I-] constraint means the reaction is only behaving as though it is first order.
Keep in mind, it is k and not k we are after. However, if we can measure k using a known Iconcentration, then we can use (Eq. 7) to determine k.
We can measure k by obtaining [S2O82-] vs. Time data and plotting this data according to the
Integrated form of the First Order Rate Law:
ln [S2O82-] = ln [S2O82-]o - k t

(Eq. 9)

The slope of this plot will yield k':

slope = - k'

(Eq. 10)

We can obtain [S2O82-] vs. Time data fairly easily by varying the amount of Thiosulfate used in
the Clocking Reaction, (Eq. 2). The amount of S2O82- remaining at the Clocking Point is related
to the amount of Thiosulfate used by the reaction stoichiometry of (Eqs. 1 and 2):

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At the Clocking Point, the number of moles of Peroxysulfate (S2O82-) which has reacted is
exactly 1/2 the number of moles of Thiosulfate (S2O32-) orginally added.
As an example, suppose we mix the following:
5mL
7mL
5mL
1mL
____
18mL

of
of
of
of

1M KI
0.2M Na2S2O3
0.15M K2S2O8
Starch Sol'n

total

Then, at the Clocking Point, when the blue Iodine-Starch complex appears:
# mmoles S2O32- added

= ( 0.2M ) x ( 0.007 L ) x ( 1000 mmole / 1 mole )

= 1.40 mmole

# mmoles S2O82- consumed

= 1.4 mmole S2O32- x ( 1 mmole I2 / 2 mmole S2O32- )

x ( 1 mmole S2O82- / 1 mmole I2 )
= 0.70 mmole

# mmole S2O82- remaining

= ( 0.15M ) x ( 0.005 L ) x ( 1000 mmole / 1 mole ) - 0.7mmole

= 0.75 mmole - 0.70 mmole
= 0.05 mmole

[S2O82-] remaining

= 0.05 mmole / 18 mL = 0.00278

ln ( [S2O82-] ) remaining

= ln ( 0.00278 )
= -5.886

Thus, by arranging for the reaction to run under Pseudo-First Order conditions, and by varying
the Clocking Reagent (Thiosulfate Ion) concentration, we can generate [S2O82-] vs time data and
thus determine first k' and then k for (Eq. 1).

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Pre-Lab Safety Questions

1.

Why are Strong Oxidizing Agents dangerous? Examine (Eq. 1) and (Eq. 2) and identify the
Oxidizing Agents. Are these Oxidizing Agents considered "Strong Oxidizing Agents"?
(You may wish to consult an SDS.)

2.

When purchased at the pharmacy, Iodine comes in the form of a tincture. What is the
Molar concentration of a typical pharmaceutical tincture? How does that compare to
Iodine concentrations we will be using in this laboratory exercise? (A rough approximation
is all that is needed here.) Should you use gloves during this exercise? Explain.

3.

What about goggles? Explain.

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Procedure
1.

Obtain 4 small beakers and label them:

Label
KI
Na2S2O3
K2S2O8
Starch
Water

Amount
~40 mL
~40 mL
~40 mL
~10 mL
~40 mL

Obtain the indicated amount of each solution.

2.

Place six 15 cm test tubes in a test tube rack. Label them 1 - 6. Add, by means of a Mohr
pipet, the amounts of the reagents listed:

Tube #

mL 1M KI

1
2
3
4
5
6

5
5
5
5
5
5

mL of 0.2M
Na2S2O3
7.0
6.5
6.0
5.0
4.0
2.0

mL Water

mL Starch

0
0.5
1.0
2.0
3.0
5.0

1
1
1
1
1
1

3.

To tube #1, add 5.0 mL of 0.15 M Potassium Peroxysulfate (S2O82-) by pipet. Record the
time to the nearest second when addition is begun. As soon as delivery is complete,
stopper the test tube and INVERT the test tube at least 5 times. (If the system is not
mixed well, only part of the solution will clock and you will have to repeat that run.)
Place this in a large beaker filled with Room Temperature water.

4.

Repeat this for test tubes #2 - #6. Start each reaction no more than one minute after the
preceding one.

5.

Record the exact time when the blue color appears; i.e., the Time at which the reaction
Clocks.

6.

Record the temperature of the Water bath.

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Data Analysis
1.

Prepare a Table of the following form and fill-in the needed Concentration values.

Tube #

mL
Na2S2O3

mmoles
S2O32added

mmoles
S2O82consumed

mmoles
S2O82remaining

[S2O82-]
remaining

ln [S2O82-]
remaining

elapsed
time

1
2
3
4
5
6

2.

Prepare a graph of ln [S2O82-] vs. Time using a software package such as Excel. Use the
software packages Linear Least Squares analysis routine to determine the Slope of the
line.

3.

Determine the Pseudo-First Order Rate Constant k for the Peroxysulfate oxidation of
Iodide.

4.

Calculate the Rate Constant k for the Peroxysulfate oxidation of Iodide; see (Eq. 7).

Note: You must provide appropriate Units of Measurement for k and k.

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Post Lab Questions

1.

Why is it important that our test tubes be placed in a Water bath? Be thorough in your
answer.

2.

In theory, we could perform a single run for this experiment and use the equation:
ln([S2O82-]) = ln([S2O82-]o) - k' t
to determine k', and hence k. Why have we gone to the trouble of performing this
experiment several times, preparing a graph of the results, and determining the slope of the
graph in order to determine k. Be specific.

3.

The chemical reaction of (Eq. 1) is written in Net Ionic form. If Potassium Ion (K+) is the
only Spectator Ion present, write the Total Molecular Equation for this reaction.

4.

Write the Lewis Structure for the Thiosulfate Ion (S2O32-) used in the Clocking reaction
(Eq. 2) . Hint: Thiosulfate is the thiol (Sulfur based) analog of Sulfate (SO42-). So, start
by working out the Lewis Structure for the Sulfate Ion.

5.

The Clocking reaction (Eq. 2) results in the Reduction of I2 to I-. Show the Sulfur is
oxidized by explicitly assigning Oxidation Sates to the S in each relevant species.