Experiment 9

Chemical Kinetics: the reaction between

H2O2 and HI

CEM2005W
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Introduction
AIM: To study the kinetics of the reaction between H2O2 and HI.

We study the rates of the reactions for two main reasons:

- the practical importance of being able to predict how quickly a
reaction mixture will move to its equilibrium state
- to elucidate the path or mechanism by which a reaction takes
place

This practical consists of 3 parts:

- To determine the total amount of iodine which would be
liberated in infinite time
- Measure the reaction between H2O2 and HI at 25°C
Reflux apparatus
- Measure the reaction between H2O2 and HI at 35°C
Part A: Determine the total amount of iodine CEM2005W

which would be liberated in infinite time

You are asked to prepare a 1 in 10 dilution of the
H2O2 provided. Make 200 ml.

Pour 20 ml of 3M H2SO4 and 40 ml of 10% KI

solution in to a 250 ml conical (Erlenmeyer) flask
(see A in picture).

Add a few drops of Na2S2O3 dropwise from the

burette to discharge any yellow colour in the
solution caused by the oxidation of I- by
impurities. Count the drops as you will need to
know this for Part B and C. A H2O2
3M H2SO4 10% KI
Pipette 25 ml of the diluted H2O2 into the flask
and cover with a watch glass. Allow to stand for
45 minutes to complete the reaction. Titration – this is done in triplicate
Then titrate the iodine liberated with Na2S2O3, adding starch just before the endpoint (as the red
solution turns yellow). The endpoint is when the solution turns clear. Repeat this two more
times and calculate a mean titre. Let this be v0.
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Part B: Reaction of H2O2 and KI at 25 ºC
For Part B and Part C it is important that the reaction be carried out at a constant
temperature. The reactions are carried out in a water jacketed flask that ensures
the temperature remains constant.

regulator
Water jacketed flask

water circulating

stirrer water bath

Glassware and equipment used Water jacketed flask kept at constant temp
Part B: Reaction of H2O2 and KI at 25 ºC CEM2005W
Add 500 ml distilled H2O (measuring cylinder) to the reaction vessel. Start the stirrer.

Add 20 ml 3M H2S04 and 40 ml of 10% KI. Discharge the yellow colour as in Part A
with Na2S2O3 using the same number of drops.
Add 5 ml of starch solution.

Ensure the burette is filled with Na2S2O3.

Note the initial reading and record it. Run
2ml into the reaction vessel and record the
exact volume vt. The first time reading taken
after the addn of H2O2 will be the time
needed to consume this volume vt of
Na2S2O3.
water Na2S2O3 H2O2
3M H2SO4
Note the temp in the reaction vessel and 10% KI starch
ensure it remains constant at 25°C by taking
readings every minute for 5 minutes. Line up your reagents before you start
Now pipette 25 ml of H2O2 into the reaction vessel. Start the stopwatch when half
the volume has been delivered. This is time zero (t=0).
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Part B: Reaction of H2O2 and KI
at 25 ºC
Stir the solution continuously and wait for the blue colour to
appear. Note the exact time this happens. This is the time
corresponding to the first vt-value. Do not stop the clock – use
the lap function which stops the time so you can record it, but
the stopwatch continues to time in the background. Press lap
again and the display continues with the correct time.
Student A: uses the burette and
Immediately add another 2 ml of Na2S2O3 stirring all the time to reads the volume on the burette
get rid of the blue colour as quickly as possible. Note the
burette reading. Again, once the blue colour Is observed note
the time (using the lap function). This time immediately add 1
ml of Na2S2O3.

Proceed similarly for about 20 readings (adding 1 ml each screen

time).

Check temp remains constant throughout the run by reading

the thermometer after every third addition of Na2S2O3. stopwatch
Student B: uses the stopwatch and
This part will be done in pairs – one student behind the screen records times and burette readings
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Part C: Reaction of H2O2 and KI at 35 ºC
Repeat Part B but this time the temperature of the solution must be kept constant
at approximately 35 °C.

Remember to ensure that constant temperature is attained before proceeding.

Using the stopwatch

Watch the video on how to operate the stopwatch and use the lap function.
Calculations CEM2005W
The data you have collected corresponds to the amount of iodine which has been liberated by
the reaction (in terms of volume of Na2S2O3 added) at a series of times.

Therefore it is possible to determine the concentration of H2O2 at any time since 1 mole of
iodine is liberated for every mole of H2O2 destroyed.
H2O2 + 2HI ↔ I2 + 2H2O

Let initial amount of H2O2 present in the flask = a

Let the amount of H2O2 that has reacted after a time be x.

Since the volume of the liquid in the reaction vessel is large (>500 ml) compared to the
volume of Na2S2O3 added, it can be assumed that the volume remains constant throughout the
course of the experiment.

Hence, the initial conc of H2O2 is proportional to a and the concentration at time t is
proportional to a-x. It follows that the differential form of the rate expression is
dx/dt = k1 (a-x)

An alternative method of calculating the rate constant exists. If in determining the conc of
Na2S2O3 soln (Part A) it is found that v0 ml of the latter are equivalent to 25 ml H2O2 soln and if
during the kinetic measurements vt ml of Na2S2O3 have been added after a time t it follows
Results CEM2005W

Part A
Complete table – calculate the mean volume v0.

Part B and C
Complete table – time and volume results at 25°C and 35°C. Using v0 , calculate ln(v0-vt)

Draw a graph of ln(v0-vt) vs time (s) to calculate the rate constants.

Integrate the rate expression dx/dt = k1 (a-x). From this you will get an equation with your y-
axis being ln(v0-vt) and your x-axis being t. From the gradient of the plots you will be able to
calculate the rate constants k.

Use the Arrhenius equation k = Ae-Ea/RT to calculate the activation energy Ea.
Take ln of the equation and then substitute for k1 and k2 (at T1 and T2).
You will then have 2 equations: one for k1 (a) and one for k2 (b).
Subtracting (a) from (b) yields an equation that will enable you to calculate Ea (kJ/mol).
Report
i ) integrate the differential form of the rate expression and make appropriate substitutions
so as to obtain the expression in terms of vo and vt

ii) Plot ln(v0-vt) vs t at both temperatures on the same graph

iii) Evaluate the rate constants

iv) From the values of the rate constants at different temperatures, calculate the activation
energy of the reaction and show how the equation used is derived.