CHEM-1110 Winter 2025 Experiment 2

EXPERIMENT 2
Decomposition Kinetics of Hydrogen Peroxide

Additional Review Material

Relevant sections in the text (Tro, Fridgen, and Shaw. Can. Ed.): 13.3

Background
Kinetics is the study of rates and mechanisms of chemical reactions. The rate of a chemical reaction
describes how fast a reaction occurs. Factors such as concentration of reactants, temperature, and the
presence or absence of a catalyst can greatly influence rates of reaction. Studies of these reaction
rates are used to elucidate reaction pathways, also called mechanisms. Mechanisms describe the
series of elementary steps a given reaction takes in going from reactants to products. Consider for
example, the general reaction scheme:
2A + B → C
At the molecular level, the reaction most likely does not proceed as written. It simply
represents the overall result of a series of elementary reactions. The reactants may in fact react to
form a number of intermediate species which in turn react with each other or react with more reactant
to form the product. The existence of such intermediate species contributes to the overall rate of
reaction and may even be rate-controlling. In many reactions the rate-limiting step determines the
overall rate and the addition of more reactant has little or no effect. In other cases, changing the
concentration of any one of the reactants can dramatically affect the reaction rate.
Rates of chemical reactions are obtained by measuring a decrease in concentration of one reactant or
an increase in concentration of a product as a function of time. Thus, the rate for the above reaction
may be represented by any of the following:
𝑑[𝐴] 𝑑[𝐵] 𝑑[𝐶]
𝑟𝑎𝑡𝑒 = − = − =
2𝑑𝑡 𝑑𝑡 𝑑𝑡
(2.1)
One objective of chemical kinetics is to determine the rate law. A rate law is a statement about
how the rate of a reaction depends on the concentration of the participating species. Rate laws are
determined by analyzing one or more reactant or product as a function of time as the reaction
proceeds and then inspecting the results to determine the theoretical equation that best fits the data.
Considering only the forward reaction for the above reaction scheme, a general form of the rate law
can be written:
𝑟𝑎𝑡𝑒 = 𝑘[𝐴]𝑥 [𝐵]𝑦 (2.2)

Where [A] and [B] represent reactant concentrations, exponents 𝑥 and 𝑦 are the order of the reaction
with respect to each reactant, and 𝑘 is the rate constant for that specific reaction at a given
temperature. The overall order of the reaction is the sum of the individual exponents. It is important
to note that these values must be determined experimentally and are a reflection of the reaction
mechanism, not the stoichiometry of the reaction equation.

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Exponents in the rate law generally have values of 0, 1, or 2 which affect the rate in the following
manner:
→ If doubling the concentration of a reactant has no effect on the rate, that reactant is said to be zero
order (𝑥 or 𝑦 = 0).
→ If doubling the concentration of a reactant doubles the rate, it is said to be 1st order (𝑥 or 𝑦 = 1).
→ If doubling the concentration of a reactant quadruples the rate, it is said to the 2nd order (𝑥 or 𝑦 =2).
This experiment studies the decomposition kinetics of the iodide-catalyzed decomposition of
hydrogen peroxide (H2O2) which is thought to proceed through the following mechanisms:
1st step: H2O2(aq) + I-(aq) IO-(aq) + H2O(l)
2nd step: H2O2(aq) + IO-(aq) I-(aq) + H2O(l) + O2(g)
Overall reaction equation: 2 H2O2(aq) O2(g) + 2 H2O(l)
The method of initial rates is used to measure the initial rate of O2(g) produced in the reaction by
monitoring the change in pressure in a sealed vessel as a function of time for several different
concentrations of the reactants, H2O2, and I- (from KI). Initial rates are then converted to a rate in
terms of a decrease in H2O2 concentration (Equation 3).
𝑑[𝐻2 𝑂2 ]
𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑟𝑎𝑡𝑒 = − = 𝑘[𝐻2 𝑂2 ]𝑥 [𝐼 − ]𝑦 (2.3)
2𝑑𝑡

According to Equation (2.3), if [I-] is constant, then a plot of ln(rate) versus ln[H2O2] has a slope equal to
the order of the reaction (𝑥) and a y-intercept equal to ln(𝑘). An alternative approach, the one which
will be used in this lab, is to hypothesize the order with respect to each reactant. For the purpose of
this experiment, hypotheses will be limited to 1st and 2nd orders as described below.

To investigate the reaction order with respect to [H2O2], the I- concentration is fixed and the H2O2
concentration is varied. The hypotheses are:
→ If 𝑥 =1, a plot of initial rate (-d[H2O2]/2dt) versus [H2O2] which goes through the origin will be linear
→ If 𝑥 = 2, a plot of initial rate (-d[H2O2]/2dt) versus [H2O2]2 which goes through the origin will be
linear
→ Only one of these will be linear
Similarly, to investigate the reaction order with respect to [I-], H2O2 concentration is fixed and I-
concentration varied. The hypotheses are:
→ If 𝑦 =1, a plot of initial rate (-d[H2O2]/2dt) versus [I-] which goes through the origin will be linear
→ If 𝑦 = 2, a plot of initial rate (-d[H2O2]/2dt) versus [I-]2 which goes through the origin will be linear
→ Only one of these will be linear.
The slope of any of the above plots = 𝑘

Having determined the order of each reactant, an average rate constant can be obtained to complete
the rate law expression for this reaction: 𝑟𝑎𝑡𝑒 = 𝑘[𝐻2 𝑂2 ]𝑥 [𝐼 − ]𝑦 (2.4)

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Glassware & Equipment

• Beakers: 250, 400 mL • Retort stand
• Clamp • Test tube:18 x 150 mm (1)
• D H2O wash bottle • Vernier LabQuest interface
• Disposable pipet (4 mL) • Vernier gas pressure sensor
• Graduated cylinders:10mL(x2) • Vernier temperature probe
• 1 hole rubber stopper (#1) with tubing connected to the pressure sensor

Chemicals & Reagents

 0.15 M KI(aq) (small bottle)  10% w/w H2O2(aq)

Procedure
1. Connect a gas pressure sensor to CH1 and a temperature probe to CH2 of the LabQuest
interface. Open the LoggerPro software from the ‘LABS’ folder located on the computer desktop.
Live readings should be observed at the bottom-left of the screen.

2. Select the Data Collection button from the menu bar. Change the default Duration settings
from 900 to 200 seconds and the Sampling Rate to 1 sample/second. Select .
3. Prepare a water bath in a 400 mL beaker and maintain the temperature at 22° ± 2°. Record in
Table 2.2.
4. Use a retort stand and clamp (not shown) to secure a test tube in the water bath. (Figure 2.1)

Figure 2.1. Equipment Set-Up

Source: Advanced Chemistry with Vernier, 2nd Ed., 2007, p.12-1.

5. Obtain a bottle of 0.15 M KI and exactly 10 mL of 10 % w/w H2O2 in a 10-mL graduated cylinder.
6. In a second 10-mL graduated cylinder, combine the volume of KI and distilled water required for
your first run as indicated in Table 2.1. Add this to the test tube in the water bath.

NOTE: The GA will assign half of the class Runs 1 – 4 to determine the order with respect to [H2O2], and
the other half Runs 4 – 7, to determine the order with respect to [I-]. Class data will then be pooled to
obtain the average order with respect to each reactant.

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Table 2.1
Run mL 0.15 M KI mL water mL 10% H2O2
1 1.0 3.0 2.0
2 1.0 2.0 3.0
3 1.0 1.0 4.0
4 1.0 4.0 1.0
5 2.0 3.0 1.0
6 3.0 2.0 1.0
7 4.0 1.0 1.0
7. Draw the required volume of H2O2 into a plastic disposable pipet (The GA will demonstrate this
technique). Invert and immerse the reservoir end into the water bath. Allow 1-2 minutes for all
solutions to equilibrate to the water bath temperature.
8. Run the reaction and collect pressure data: Steps a and c should be performed by one partner
and steps b and d by the second partner.
a) Remove the rubber stopper from the test tube. Slightly loosen the test tube clamp. Hold
the test tube from the top.
b) Remove the plastic pipet from the water bath and quickly expel the contents of the plastic
pipet into the test tube.
c) Immediately replace the rubber stopper and hold it firmly in place for the duration of the
run. While holding the test tube, move the test tube up and down to mix the contents.
d) Click to start the data collection.
e) Carefully remove the stopper from the test tube when the collection period is finished.

f) Autoscale the graph, .

g) Click and drag the mouse to highlight a linear section of the pressure vs. time plot which
spans at least 100 seconds.

h) Select the linear fit button and make note of the correlation coefficient. In Table 2.2,
record the (slope of the line of best fit) which represents the initial rate of O2 gas produced
and occupied the volume of the air system* in kPa/s.

Your linear fit equation should give you a correlation coefficient close to 1. The
correlation coefficient of the regression line is a number between -1 and +1 which
measures to what extent two variables are linearly related. The closer this value to +1,
the more linear relationship between the plotted variables.

9. Discard the contents of the test tube to the waste and prepare solutions for the next Run in the
same manner as above. To collect pressure data for subsequent runs, select , followed by
[Store latest run].
______________________________________________________
*This volume includes the volume of the test tube, tubing, and sensor, minus the 6.0 mL of solution.

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Name: Date:
Lab Partner: Section:

REPORT SHEETS – EXPERIMENT 2

Decomposition Kinetics of Hydrogen Peroxide

Objectives & Purpose [3.0]

Data and Results [12.0]

Table 2.2: The Effect of [________] on the Initial Rate of Reaction

[ ] [ ]2 Initial rate (kPa/s) Initial rate

Run
(M) (M)2 (slope of O2 P. vs time) (-d[H2O2]/2dt)

(Fixed) Reactant Concentration: [ ] = ____________ Water Bath Temperature=_____

Class average value of 𝑘 =_________

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1. Calculate the concentration [ ] and [ ]2 of the ‘varied’ reactant for each Run and the
concentration of the ‘fixed’ reactant. Remember the total volume of each solution is 6.0 mL and
the density of 10% w/w H2O2 is 1.02 g/mL. Show all work below and report results in Table 2.2
(2.5)

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Name: Section:

2. For each run, convert the initial rate of O2 gas produced (kPa/s) to a rate in terms of a decrease in
H2O2 concentration (-d[H2O2]/2dt) as follows:
a. Use Boyle’s Law (P1 V1 = P2 V2) to calculate the initial rate of O2 gas produced (kPa/s) if the
O2 gas had remained in solution (6.0 mL volume) (the volume of the air system can be
assumed to be 25 mL*). (1.5)

b. Use the ideal gas law (n/V=P/RT) to calculate the initial rate of O2 gas produced (d[O2]/dt)
in mol.L-1.s-1. Where R = 8.3145 L∙kPa∙mol-1∙K-1. (1.5)

c. Finally, use Equation 2.3 to determine the rate of decomposition of H2O2 (-d[H2O2]/2dt) in
mol.L-1.s-1. (1.0)

Use back of page if more space is needed.

_______________________________________________
*This volume includes the volume of the test tube, tubing, and sensor, minus the 6.0 mL of solution.

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3. Test the hypotheses: Two graphs will be plotted. (1) ‘varied’ reactant concentrations [ ] (x-axis)
vs initial rates (-d[H2O2]/2dt).(2) reactant concentration [ ]2(x-axis) vs initial rates (-d[H2O2]/2dt)

a. Unplug the gas pressure sensor and temperature probe from the LabQuest interface.
b. Select File →New from the menu bar.
c. Enter the ‘varied’ reactant concentrations [ ], and initial rates (-d[H2O2]/2dt) into columns
X and Y, respectively.
d. Select your Graph. Choose Graph Options from Options dropped down menu …/Autoscale
from 0.
e. Obtain the equation of the line and correlation coefficient, . Record these in the space
below and close the Linear Fit dialogue box. (1.0)

f. Replace the data in column X with the square of the reactant concentration [ ]2.
g. Autoscale the graph and obtain the equation of the line and correlation coefficient. Record
these in the space below. (1.0)

h. Which one is linear? (0.5)

i. Based on the hypotheses presented at the beginning of the lab, what is the order of the
reaction with respect to that reactant? Report this on the board.
j. Based on the class data, and the hypotheses tested, what is the order with respect to each
reactant? What is the overall order of the reaction? (1.0)
𝑥 = ____ 𝑦 = ____ 𝑜𝑣𝑒𝑟𝑎𝑙𝑙 = ____

4. State the rate law expression for this reaction using the average rate constant and the order of
each reactant as determined from the class data. (2.0)

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