CHEM 1103 Online W2022 Experiment 7
EXPERIMENT 7
Decomposition Kinetics of Hydrogen Peroxide
Additional Review Material
• Relevant sections in the text (Chemistry for Engineering Students, 4th Ed., Brown, Holme): 11.2 –
11.4
• How to use Excel to plot a Graph; Blackboard/ Laboratory/ Techniques.
• How to use “LINEST”; Blackboard/ Laboratory/ Techniques.
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 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]
𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑟𝑎𝑡𝑒 = − = − =
2𝑑𝑡 𝑑𝑡 𝑑𝑡
(7.1)
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 see what theoretical form 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] ! [𝐵 ]"
(7.2)
Where [A] and [B] represent reactant concentrations, exponents 𝑥 and 𝑦 are the order of the reaction
with respect to reactant A and reactant B respectively, 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
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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.
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 reaction 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.
𝑑[𝐻# 𝑂# ] 𝑑[𝑂# ]
𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑟𝑎𝑡𝑒 = − = = 𝑘[𝐻# 𝑂# ]! [𝐼 $ ]"
2𝑑𝑡 𝑑𝑡
(7.3)
According to equation 7.3, 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). ln (𝑟𝑎𝑡𝑒) = 𝑥 ln [𝐻# 𝑂# ] + 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], I- concentration is fixed and the H2O2
concentration varied. The hypotheses are:
® If 𝑥 =1, a plot of initial rate (-d[H2O2]/2dt) versus [H2O2] will be linear and go through the origin with
a slope = 𝑘
® If 𝑥 = 2, a plot of initial rate (-d[H2O2]/2dt) versus [H2O2]2 will be linear and go through the origin with
a slope = 𝑘
® Only one of these plots 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-] will be linear and go through the origin with a
slope = 𝑘
® If 𝑦 = 2, a plot of initial rate (-d[H2O2]/2dt) versus [I-]2 will be linear and go through the origin with a
slope = 𝑘
® Only one of these plots will be linear
(7.4)
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Glassware & Equipment
• Beakers: 250, 400 mL • Retort stand
• Clamp • Test tube: 18 x 150 mm
• DI H2O wash bottle • Vernier LabQuest interface
• Disposable pipet (Large, 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. Power-on the LabQuest unit. Connect a temperature probe to the CH 1 port and a gas pressure
sensor to CH 2. The LabQuest App will auto-ID the connected sensors and a live reading will appear
in the Meter screen. The default setting should be in the Time Based Mode with a sample Rate of
1 sample/second for a Duration of 900 seconds.
2. Prepare a room temperature water bath in a 400 mL beaker. Record it’s temperature in Table 7.2
3. Use a retort stand and clamp (not shown) to secure a test tube in the water bath.
Figure 7.1. Equipment Set-Up
Source: Advanced Chemistry with Vernier, 2nd Ed., 2007, p.12-1.
4. Obtain a bottle of 0.15 M KI and exactly 10 mL of 10 % w/w H2O2 in a 10-mL graduated cylinder.
Label the cylinder with masking tape.
5. In a second 10-mL graduated cylinder, combine the volume of KI and distilled water required for
your first run as indicated in Table 7.1. Add this to the test tube in the water bath and close with
the rubber stopper.
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Table 7.1
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
6. Use the large (4mL) disposable pipet to draw the required volume of H2O2 (your 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.
7. Run the reaction and collect pressure data: Steps a and c would normally 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. Make
sure to keep the test tube in the water bath throughout the reaction.
d) Tap Collect to start the data collection.
e) After about 200 seconds have passed, press Stop to end data collection. Very
carefully remove the stopper from the test tube.
f) Tap and drag across the graph to highlight a linear section of the pressure vs time plot which
spans at least 100 seconds.
g) To obtain the trend line that best represents your selected data, tap “Analyze/Curve Fit” and
select “Pressure”. From the “Choose Fit” drop down menu choose “Linear”.
h) From the equation of the line record the slope 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.
_______________________________________________________________________
*
This volume includes the volume of the test tube, tubing, and sensor, minus the 6.0 mL of solution.
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8. Discard the contents of the test tube to the waste and prepare solutions for the next Run in the
same manner as above. When you are ready to start a new run, tap Collect and select
“Discard” to delete the previous run before starting the new run.
9. At the end of your last run, unplug the gas pressure sensor and temperature probe from the
LabQuest interface. You will need the LabQuest to process your data.
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Student Name: Lab Section:
REPORT SHEETS – EXPERIMENT 7
Decomposition Kinetics of Hydrogen Peroxide
Objectives & Purpose [2.0]
Data and Results [13.0]
Important: Your GA will assign you which Table to complete during the lab session.
Table 7.2: The Effect of [H2O2] 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)
KI Concentration = ____________ Water Bath Temperature =______ºC
For the linear graph, write the equation of the line, _______________________
Correlation coefficient =_________ ; Rate constant=_________; Uncertainty in 𝑘 = _________
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Name: Section:
Table 7.3: The Effect of [KI] 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)
H2O2 Concentration: [ ] = ____________ Water Bath Temperature =______ºC
For the linear graph, write the equation of the line, _______________________
Correlation coefficient =_________ ; Rate constant=_________; Uncertainty in 𝑘 = _________
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 Tables (7.2 or 7.3) [2.0]
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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. [1.0]
c. Finally, use Equation 7.3 to determine the rate of decomposition of H2O2 (-d[H2O2]/2dt) in
mol.L-1.s-1. [1.0]
___________________________________________
*
This volume includes the volume of the test tube, tubing, and sensor, minus the 6.0 mL of solution.
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Name: Section:
Important: Make sure to watch the videos listed in the in “Additional Review Material” at the
beginning of this document to learn how to use Excel and “LINEST”.
3. Test the hypotheses: [5.5]
For each reactant, use Excel to plot two graphs. (1) initial rates (-d[H2O2]/2dt) (y-axis) vs. ‘varied’
reacted concentrations [ ] (x-axis) vs. (2) initial rates (-d[H2O2]/2dt) (y-axis) vs. reactant
concentrations [ ]2 (x-axis). Make sure to label the x and y axes graphs with the right titles.
a. Which one of the two graphs is linear?
b. For the linear graph (for each varied reactant), determine the equation of the line and
correlation coefficient. Record these values in the corresponding table (7.2 or 7.3).
c. From the equation of the line, determine the value of the rate constant, k (slope of the line).
Use “LINEST” to determine the uncertainty in k and record in the Table.
d. Based on the hypotheses presented at the beginning of the lab, what is the order of the
reaction with respect to the given reactant.
4. What is the overall order of reaction if the order of the reaction with respect to other reactant is
1? [1.0]
𝑥 = ____ 𝑦 = ____ 𝑜𝑣𝑒𝑟𝑎𝑙𝑙 = ____
5. State the rate law expression for this reaction using the average rate constant and the order of
each reactant. [1.0]
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