CHEMICAL AND BIOMOLECULAR ENGINEERING LAB /

BIOENGINEERING LAB

CH2801
BG1801

Iodine Thiosulfation

Location: N1.2 01-01

Name: _______________________________________

Matric Number: _______________________________________

Group: _______________________________________

Date of experiment: _______________________________________

Kinetics of the Persulfate-Iodine clock Reaction (linear regression)

Objectives:

The purpose of this experiment is to familiarize you with chemical kinetics by

determining the rate law (reaction orders and a rate constant of a reaction) and the
activation energy for the reaction between persulfate ion (a.k.a. peroxodisulfate ion),
, and iodide ion, using Linear Regression.

Principles:

The rate law can be written as

(1)
Reaction rate =

Where m and n are the orders with respect to and , respectively, and k is the rate
constant. Determining the rate law involves determining the values of m and n.

The temperature dependence of the rate constant is given by

(2)

Equation (2) is called the Arrhenius Equation, where A is the pre-exponential factor, E is
the activation energy with units of J/mol, T is the absolute temperature (in Kelvin), and R
is the gas constant (R= 8.3145 J K-1 mol-1). Equation (2) can also be written in the form:

(3)

According to equation (3) the activation energy can be obtained by measuring the rate
constant at several temperatures, and then plotting ln k versus 1/T.

Method:

Reaction (1) will be carried out in the presence of thiosulfate ion, S2O32- and starch. The
concentration of thiosulfate ion will be maintained at a much lower value than that of
either the persulfate ion or the iodide ion. The reactions that occur are:

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 Slow (4)
Fast (5)

Slow (6)

Reaction (4) is much slower than reaction (5), and, as a result, the I2 in formed in reaction
(4) is immediately consumed by reaction (5), and the concentration of I2 remains at a very
low value as long as thiosulfate ion is present. Once the entire thiosulfate ion is used up,
the concentration of I2 from reaction (4) increases. The presence of I2 is detected by the
formation of a blue complex resulting from the reaction of I2 with starch, reaction (6).
The rate of reaction (6) does not become significant until the concentration of I2 becomes
appreciable.

A characteristic of this reaction is that the reaction mixture remains colorless for several
minutes after the reactants are mixed. During this time both reactions (4) and (5) are
occurring. The solution remains colorless because the I2 from reaction (4) is being
consumed by reaction (5), and can’t react with the starch. As soon as the thiosulfate ion
is used up, the I2 reacts with the starch, and an abrupt and dramatic color change, from
colorless to blue, occurs.

The rate of reaction (4) is the rate of consumption of S2O82- ion. Notice that for every
S2O82- ion used up two S2O32- ions are consumed. Thus, we have:

Rate of reaction (4) = (7)

If [S2O32-]o is the initial concentration of S2O32- ion, and t is the time interval from the
start of the reaction until the solution changes color, then in equation (7),
[S2O32-] = 0 - [S2O32-]o , and if the initial concentration of S2O32- is constant then
equation (7) becomes

Rate of reaction (4) = (8)

Combining equations (1) and (8) and taking the logarithms of both sides gives:

(9)

Or
(10)

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From equation (9) we see that if we carry out two or more experiments with a constant
concentration of I- ions we will obtain

(11)

And a graph of versus will give a straight line with slope = m.

Similarly, for two or more experiments with constant concentrations of S2O82-, a graph of
versus will give a straight line with slope = n.

To obtain the activation energy, we combine equations (3) and (9):

(12)

If the concentrations of reactants are constant then equation (11) becomes:

- (13)

A graph of versus will give a straight line with slope =

Materials & Equipment

The following solutions and equipments will be provided:

A 0.100 M (NH4)2S2O8 – (Ammonium Peroxodisulfate)

B 0.100 M (NH4)2SO4 – (Ammonium Sulphate)
C 0.010 M Na2S2O3 – (Sodium Thiosulphate)
D 0.100 M KI in 0.066 M (NH4)2SO4 – (Potassium Iodide in Ammonium Sulphate)
E 1 % starch solution

1 Metal tub x1
2 Conical Flask (100ml) x 12
3 Pipette (10ml) x 4, Pasteur Pipette (3ml) x 2, Pipette filler x 2
4 De-ionized water bottle x 1
5 Thermometer x 2
6 Stop watch x 2

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Experimental procedure:

Into each of four clean, labeled 100ml conical flasks. Dispense about 100 ml of each of
the solutions A, and D; 50 ml of each of the solutions B and C. Please collect E, (starch
solution). These solutions will be used to perform the following experiments. Do not pour
any solutions back into the stock bottles. All waste can go down the carboy provided for
aqueous base.

Part 1. Observation

To a conical flask, add 2 ml of solution A, 4 drop of starch solution (note: shake well to
mix the starch solution evenly before using) and 2 ml of solution D and swirl the mixture
gently. What do you observe? Now add 4 drops of solution C. What do you observe?
Add 4 more drops of solution C, and record your observations. Continue adding more
drops of solution C until noticeable and stable change of the mixture occur, record your
observations.

Part 2. Determining the Rate Law

Fill a metal tray with room temperature tap water to create a constant temperature bath.

Measure 8 ml of solution A into a 100 ml conical flask, and add 4 drops of starch
solution. Place this conical flask in metal tray.

Measure 2 ml of solution B, 5 ml of solution C and 10 ml of solution D into a second

conical flask.

Check the temperature of the solutions in the two 100 ml conical flask with a
thermometer. Use a different thermometer for each solution. When the two solutions are
at the same temperature, record the temperature, and pour the contents of conical flask
containing solutions B, C and D into the conical flask containing solution A and the
starch. Mix by gently swirling the conical flask. Measure and record in your notebook,
the time interval from the time of mixing to the appearance of the blue color. The
volumes just described correspond to Experiment 1 in Table 1, below. Repeat the
procedure for the remaining experiments in the Table 1.

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Table 1: Solution volumes in ml
Experiment Solution A Solution B Solution C Solution D

S2O82- (NH4)2SO4 S2O32- I-

1 8 2 5 10
2 10 0 5 10
3 5 5 5 10
4 10 5 5 5
5 10 2 5 8

Part 3. Determining the Activation Energy

To determine the activation energy, the rate of the reaction will be measured at two
additional temperatures. Repeat the procedure in Part 2, using the solution volumes
corresponding to Experiment 2 in Table 1 at temperatures of about 10 oC and 40 oC.
The lower temperature can be obtained by adding ice to tap water in the metal tray. The
higher temperature can be carried out in the water baths. The two solutions must be at the
temperature of the bath before they are mixed. Again record the temperature, and the
time to the appearance of the blue color. Perform two trials at each temperature if time
permits.

Part 4. Clean Up

1. Dilute the excess reagents well with water and dump them down the carboy provided
for aqueous base.
2. Rinse the pipette thoroughly with DI water. Wash all other the glassware with soapy
water. Rinse well with tap water then with distilled water.
3. Return all glassware in the tray to its proper place.
4. Wipe your work area clean and dry.

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Appendix I: Summary of equations and calculations

Plot versus for

Experiment 1-3. The slope = m
Plot versus for Experiment 2,
4, and 5. The slope = n
Plot versus for Experiment 2, of
Part 2, and for Experiments in Part 3. The
slope = (R=8.3145 JK-1mol-1)

Appendix II: Calculations for Part 2

For each of the experiments, 1 through 5, calculate the initial concentrations in the
reaction mixture (before reaction occurs) of S2O82- and I-, and enter them in a table.
Hint: M1V1 = M2V2.

Enter your values of t and these concentrations into an MS Excel spreadsheet, and
prepare graphs of ln(1/ t) versus ln (S2O82-), for experiments with constant initial
values of (I-) (Experiments 1, 2 and 3), and of ln(1/ t) versus ln (I-) for
experiments with constant initial values of (S2O82-) (Experiments 2, 4 and 5). The
equations to be graphed in this part are summarized in Appendix I.

Use the add trendline feature to determine the slope of each graph. Right click on a data
point in the graph. Left click on add trendline. Pick linear. Click on “Options” tab.
Choose “Display equation on chart”.

Appendix III: Calculations for Part 3

For Experiment 2 of Part 2, and for each of the experiments in Part 3, enter t and
the absolute temperature into an Excel spreadsheet, and prepare a graph of ln(1/ t)
versus 1/T. The equation to be graphed in this part is in Appendix I.

Use the add trendline feature, as before, to determine the slope of the line and calculate
the activation energy.

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 Kinetics of the Persulfate-Iodine clock Reaction (linear regression) (LOG

SHEET)

Name: Group: Date:

Table 1. Sample Data Table for Part 2 (Determine the rate law)

Temperature of reactants (Temp 1):

(S2O82-), (I-),
Experiment Time of Color change
mol/L mol/L
1
2
3
4
5

Table 2. Sample Data table for Part 3 (Determine the activation energy)

Time to color change,

Temperature of Reactants t
Trial 1 Trial 2
Temp. 1 (use your data from Part 2, Exp. 2 here):
Temp. 2:
Temp. 3:

Experimental report:

1. Calculate the initial concentrations in the reaction mixture (Before reaction occurs) of
and I-, use the space below and the back of this page. Tabulate your results for
each run as shown in Log Sheet
2.Plot the graphs of versus , versus , and versus
with separate paper.
3. Answer the following questions in complete sentences.

I.Explain your observation in Part 1 of the procedure in terms of reactions (4), (5) and
(6).
II.For reaction (4), what is the order with respect to each of the reactants? What is the
rate law?
III.What is the activation energy for reaction (4)?
IV.Discuss possible sources of error in the experiments.
V.Suggest some ways to improve the experiment.