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Cape Chemistry Unit 1 Worksheet Date ………………...

Chemical Kinetics - 1

Aim:- Experiment to determine the order of the reaction between peroxodisulphate (VII) ions and
iodide ions.

The theory of ‘clock’ reactions ILPAC Unit 5

In a typical reaction, the early part of a ‘concentration against time curve’ approximates to a straight line, as shown below

c2
concentration, c, of products

c1

O t1
t2
time
If we choose any value of c (say c1 ) which lies on this straight line, the initial rate of reaction is given by c1/t1. However,
for a value of c (say c2) beyond the straight part of the curve, the initial rate is less than c2/t2.

In clock reactions, the initial rates of a series of reactions are obtained very simply by choosing a fixed value of c for all
the reactions as that the rate = c/t. As long as c is constant, it need not necessarily be quantified, and we can take1/t as a
measure of the rate of reaction.

When an oxidizing agent is added to aqueous potassium iodide, iodine is liberated. If sodium thiosulphate is present in
the reaction mixture, it reacts with the iodine formed to give a colourless solution. When all the thiosulphate has been
used up, iodine appears and, if starch is present in the reaction mixture, a blue colour will appear. If the amount of
sodium thiosulphate is kept constant in a series of experiments in which the concentration of one of the reactants, the
temperature or the presence or absence of a catalyst is the independent variable, the time taken for the blue colour to
appear is a measure of the rate of the reaction.

The equation for the reaction of peroxidisulphate (VI) ions by iodide ions is: S2O82- (aq) + 2I–(aq) 2SO42- (aq) + I2 (aq)
The thiosulphate reacts with the iodine formed in the above reaction as in the following equation:
2S2O32-(aq) + I2 (aq) S4O62- (aq) + 2I- (aq)

At the instant that all the thiosulphate has reacted, free iodine is produced in the solution and its presence is shown by
the appearance of the black-blue colour of the iodine-starch complex, i.e. the thiosulphate ions act as a ‘monitor’
indicating the point at which a certain amount of iodine has been formed. For this reason the reaction is often
referred to as an iodine ‘clock’ reaction. In general, for a ‘clock’ reaction, Rate of reaction α 1/t where t is the time
taken to reach a specified stage.
You are provided with:-

3 -100 cm3 beakers, 1 thermometer, 0-100 oC, 5 burettes and stands, with beakers and funnel for
filling, clamps and stands, stop clock or watch, potassium peroxodisulphate (VI) solution, 0.10 mol
dm-3 K2S2O8, potassium iodide solution, 0.50 mol dm -3, KI,sodium thiosulphate solution, 0.010 mol
dm-3 Na2S2O3, starch solution, 0.2%

Procedure:-

1. Using a burette, run 25.0 cm3 of S2O82- into a 100 cm3 beaker. Add 25 cm3 of distilled water,
using a burette, stir gently to mix.

2. Using burettes, measure out 15 cm3 of each of the potassium iodide, 3 cm3 sodium
thiosulphate solutions and 2.0 cm3 of starch solution into the second 100 cm3 beaker.

3. Measure the temperature of the two solutions. Pour the contents of the second beaker into
the first, shake to mix, and start the clock.

4 When the blue colour of the starch-iodine complex appears, stop the clock and write down
the time in the Results Table.

5. Repeat the experiment using the values in the tables given below.

Results Table 1

Experiment Vol. of Vol. of Vol. of Vol. of Vol. of Time for 1/ts-1

No. S2O82-/c 3 2- 3
H2O/cm S2O3 /c KI(aq)/cm starch the colour
m3 m3 solution/cm3 blue to
appear/s
1 25 25 3 15 2 24
2 20 30 3 15 2 30
3 15 35 3 15 2 40
4 10 40 3 15 2 60
5 5 45 3 15 2 120

Results Table 2

Experiment Vol. of Vol. of Vol. of Vol. of Vol. of Time for 1/ts-1

No. S2O82-/c H2O/cm3 S2O32-/ KI(aq)/cm3 starch the blue
m3 cm3 solution/cm3 colour to
appear/s
1 15 20 3 30 2 20
2 15 25 3 25 2 24
3 15 30 3 20 2 30
4 15 35 3 15 2 40
5 15 40 3 10 2 60
Treatment of results

(a) Plot a graph of 1/t against concentration of peroxodisulphate (VII)(aq) . What conclusion
can you draw from the graph? Is there a need to consider drawing another graph? If so state
what you will do and why.

(b) Plot a graph of 1/t against concentration of iodide (aq). What conclusion can you draw from
the graph? Is there a need to consider drawing another graph? If so state what you will do
and why.

Questions

1. In the series of the experiments: (Indicate, where appropriate, separately for the first and second set of
experiments)

(i) Which variable/s was/were controlled?

(ii) Which variable/s was/were manipulated?

(iii) Which variable/s was/were responding?

2. (i) What is the order of the reaction with respect to the peroxodisulphate(VII)
ions?

(ii) What is the order of the reaction with respect to the iodide ions?

(iii) What is the overall order of the reaction?

(iv) Write the rate equation for the reaction.

3. The reaction between potassium iodide and potassium peroxodisulphate(VI), K2S2O8, in

aqueous solution proceeds according to the overall equation:

2KI(aq) + K2S2O8(aq) 2K2SO4(aq) + I2(aq)

(i) Write the above equation in ionic form.

(ii) The electrode potential values of S2O8 2-(aq), SO42-(aq) lPt and I2(aq), 2I-(aq) lPt are

+2.01 and +0.54 V respectively.

(a) Using these values justify the above reaction.

(b) Write the cell diagram of this reaction and calculate the e.m.f. of the cell.