Laboratory Experiment

pubs.acs.org/jchemeduc

Efficient Method for the Determination of the Activation Energy of

the Iodide-Catalyzed Decomposition of Hydrogen Peroxide
William Sweeney,* James Lee, Nauman Abid, and Stephen DeMeo
Department of Chemistry, Hunter College of the City, University of New York, New York, New York 10065, United States
*
S Supporting Information

ABSTRACT: An experiment is described that determines the activation

energy (Ea) of the iodide-catalyzed decomposition reaction of hydrogen
peroxide in a much more efficient manner than previously reported in the
literature. Hydrogen peroxide, spontaneously or with a catalyst, decomposes
to oxygen and water. Because the decomposition reaction is exothermic, the
energy released as heat can be treated as a product and used to determine
the rate of reaction. Energy transferred as heat is much easier to quantify
than changes in molecular concentration because temperature can be
measured with a simple thermometer. Measuring the rate of the reaction by
monitoring the rate of change in temperature is an alternate and convenient
approach to measuring changes in the concentration of hydrogen peroxide
or the volume or pressure of oxygen produced throughout the reaction.
Because the temperature rises as the reaction progresses, reaction rate data
at a range of different temperatures can be collected by students in a single
run. The extent of reaction, and thereby the extent of depletion of the peroxide, can be approximated by the reaction temperature
relative to the initial and final temperatures. Thus, by using a simple calorimeter and collecting temperature and time data, the
activation energy can be determined from an Arrhenius plot. The procedure described for gathering experimental data is easily
completed in 30 min or less, so students have the opportunity to repeat their data two or more times within the span of a single
lab period. Empirically determining the activation energy of a given reaction is a common and important kinetics experiment in
the introductory and advanced chemistry laboratory curriculum, so this methodological innovation may have great appeal to
chemical educators.
KEYWORDS: First-Year Undergraduate/General, High School/Introductory Chemistry, Upper-Division Undergraduate,
Laboratory Instruction, Physical Chemistry, Hands-On Learning/Manipulatives, Calorimetry/Thermochemistry, Kinetics

E mpirically determining the activation energy of a given

reaction is a common and important kinetics experiment
in the introductory and advanced chemistry laboratory
curriculum.1−5 This determination is based on the Arrhenius
equation, which expresses the temperature dependence of the
rate constant k as (k = Ae−(Ea/RT)), where A is a pre-exponential
constant, Ea is the activation energy of the reaction, R is the gas
constant, and T is the temperature in Kelvin. This equation can
be restated in a more convenient form ln k = (−Ea/R)(1/T) +
ln A. For calculation of the activation energy Ea, measurement
of k at several different temperatures is required. Thus, a plot of
the natural log of the rate constant versus inverse temperature,
sometimes called an Arrhenius plot, will have a slope equal to
−Ea/R.
Because an activation energy determination calls for running
experiments at different temperatures, it is normally a time-
consuming exercise to conduct with students. To solve this
problem, the authors report a more efficient way to determine
Ea.
© XXXX American Chemical Society and
Division of Chemical Education, Inc.
■ OLD METHOD TO DETERMINE THE ACTIVATION
ENERGY
To understand the significance of this approach, one must
understand how chemistry students traditionally determine Ea.
In the lab, Ea is never measured directly but instead relies on
determining other quantities. In general, a number of
experiments are run, each at a different temperature, and a
plot of ln k versus 1/T ultimately produces a slope that leads to
the value of Ea.
Running the reaction at different temperatures is problematic
because it doubles or even triples the time of the exercise and
often produces spurious data due to the inability to control for
variations in temperature. The use of multiple temperature
baths to conduct a single kinetics experiment is often not
economically practical for chemistry departments to purchase.
A dx.doi.org/10.1021/ed500116g | J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education

■
Laboratory Experiment

NEW METHOD TO DETERMINE THE ACTIVATION Note that the value of the constant C′ will be negative because
ENERGY ΔHo for this reaction is negative. If the rate is defined as
−d[H2O2]/dt, then an expression can be written based on the
The proposed method eliminates the need for conducting
rate of temperature change
multiple reactions by exploiting the heat of reaction of the
chosen chemical reaction: the decomposition of hydrogen dT
peroxide. The relatively large and exothermic heat of reaction = −C′k(T )[H 2O2 ][I−]
dt (4)
for this reaction, in addition to the low cost of reactants and the
well-characterized mechanism for the iodide decomposition The extent of reaction, and thereby the extent of depletion of
reaction, make it an ideal choice for this approach. It has been the peroxide, can be expressed by the change in reaction
previously noted in the research literature that it is possible to temperature relative to the initial and final temperatures of the
study the kinetics of a reaction by using temperature versus reaction mixture, once again assuming that the reaction is
time data under adiabatic conditions.6 perfectly adiabatic and that the reaction goes to completion.
The decomposition of hydrogen peroxide has been used to Thus, the concentration of H2O2 remaining at a given
illustrate kinetics.3,5,7−13 Hydrogen peroxide slowly, but temperature T can be estimated as
spontaneously, decomposes exothermically to oxygen and Tfinal − T
water at room temperature. The slow reaction rate is due to [H 2O2 ]T = [H 2O2 ]0 ×
Tfinal − Tinitial (5)
its relatively large activation energy of 76 kJ/mol.14 However,
hydrogen peroxide decomposes at a much faster rate when a where [H2O2]T is the concentration of hydrogen peroxide at
catalyst is introduced. The iodide-catalyzed decomposition some temperature T during the course of the reaction, and
reaction proceeds with a heat of reaction of −98.3 kJ15 [H2O2]0 is the initial hydrogen peroxide concentration.
I−
Iodide is a catalyst rather than a reactant so its concentration
2H 2O2 → 2H 2O + O2 ΔH o = −98.3kJ (1) is assumed to be approximately constant during the course of
the reaction. The rate at a given point in the reaction is the
This approach is unique because the exothermic nature of slope of a temperature versus time curve at temperature T,
the reaction mixture is used to obtain rate data over a range of (slope)T, which can be expressed as
temperatures in a single run. Because the experimental
approach inherently requires the reaction to be followed over dT
Rate(T ) =
time, reactant concentrations are not constant. Thus, to dt
determine the rate constant from the rate as a function of = (slope)T
temperature requires knowledge of how the concentration of
hydrogen peroxide decreases as the reaction progresses. = −C′k(T )[H 2O2 ][I−]
Fortunately, as will be shown below, the concentration of Tfinal − T
reactant as a function of time can be approximated relatively = −C′k(T )[H 2O2 ]0 × × [I−]
Tfinal − Tinitial
simply.

■
(6)
THEORY An effective rate constant directly proportional to the true rate
constant can be found by grouping the constant terms and
The elementary rate equation for this reaction has been renaming as k′:
determined, and the equation for the rate-limiting step has been
shown11,16 to be rate = k(T)[H2O2][I−]. The rate of energy Tfinal − T
(slope)T = {−C′k(T ) × [I‐][H 2O2 ]0 } ×
release as heat into the solution is directly proportional to the Tfinal − Tinitial
rate of hydrogen peroxide depletion. In a well-insulated
Tfinal − T
reaction vessel Q = CmΔT, where Q is the energy released as = k′(T ) ×
heat by the reaction, C is the specific heat of the solution, m is Tfinal − Tinitial (7)
the mass of the solution, and ΔT is the rise in temperature. A
Rearranging the above equation, an effective rate constant k′ is
number of assumptions can be made that allow the quantity of
found to be
energy released as heat to be easily determined with a
thermometer. These assumptions are that the mass loss due Tfinal − Tinitial
to the loss of water saturated oxygen bubbles is negligible, that k′(T) = (slope)T ×
Tfinal − T (8)
C is constant, that no heat is generated by stirring, and that the
reaction under the conditions employed is adiabatic. This approximation will not be valid at reaction temperatures
Assuming that all of the energy generated as heat by the very close to the final temperature, where the (slope)T is
decomposition of hydrogen peroxide is contained within the approaching zero while ((Tfinal − Tinitial)/(Tfinal − T))-
calorimeter, then approaches infinity.

ΔH o
d[H 2O2]
dt
V dt = CmdT
(2)
■ EXPERIMENTAL DETAILS
Working in pairs, students combine 30.0 mL of 12% hydrogen
peroxide with 4.0 mL of 0.10 M potassium iodide in a
where V is the volume of the solution. Rearranging this styrofoam cup calorimeter. Temperature data are collected at
equation one obtains 20 s intervals using a digital thermometer until the reaction is
⎛ ΔH oV ⎞ d[H 2O2 ] d[H 2O2 ] clearly over, which takes approximately 10 to 15 min (Figure
dT
=⎜ ⎟ = C′ 1). Students are instructed to gather at least three full data sets
dt ⎝ Cm ⎠ dt dt (3) in the course of the 3 h laboratory.
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Journal of Chemical Education
Figure 1. Graph of temperature vs time: representative student data
collected from the decomposition of 30 mL of 12% hydrogen peroxide
with the addition of 0.50 mL of 1.0 M KI.
■
HAZARDS
Hydrogen peroxide (CAS No. 7722-84-1) is toxic and should
not be ingested. Contact with skin or clothing should be
avoided because it is a skin irritant and strong oxidant.
Additionally, solid potassium iodide (CAS No. 7681-11-0) is
toxic, particularly so if ingested. It can also cause skin irritation
and serious eye irritation. The solutions by the end of reaction
typically reach temperatures above 80 °C and care in the
handling of these solutions is advised.
■
RESULTS
A graph of ln k′ versus 1/T obtained using the data from Figure
1 is shown in Figure 2. The values of (slope)T of the curve in
Figure 1 were approximated using pairs of (time, temperature)
points from
Δtemperature T − T1
(slope)T = = 2
Δtime t 2 − t1
Figure 2. Graph of ln k′ vs 1/T: the student data from Figure 1 were
used to construct this plot. The slope of this plot is equal to − Ea/R
and yields the experimental value Ea = 56 ± 3 kJ/mol.
C dx.doi.org/10.1021/ed500116g | J. Chem. Educ. XXXX, XXX, XXX−XXX
Laboratory Experiment
Equation 8 can then be used to yield the numerical values of
k′(T). The slope of the plot in Figure 2 is then employed to
calculate an experimental value of Ea = 56 ± 3 kJ/mol, in good
agreement with the accepted value for the activation energy of
56.0 kJ/mol.11 Students are advised to discard the late points
where T approaches Tfinal, and consequently (Tfinal − T)
becomes small with a large relative uncertainty. Thus, the final
eight points shown in Figure 1 were not used in constructing
the graph shown in Figure 2. Students gather at least three full
data sets in the 3 h laboratory. Replication of data enhances a
student’s confidence in their results and in their understanding
of the laboratory procedure. Full details of the procedure are
found in the Supporting Information.
■ CONCLUSION
Experiments that are designed to measure Ea make up a small
but important niche of the kinetics curriculum. Until now, these
experiments have been difficult and time-consuming to perform
due to the challenge of quantitatively determining reactants or
products with respect to time, and the requirement that the
experiment be repeated at one or more different temperatures.
By viewing heat as a product, and using simple equipment such
as a thermometer and a styrofoam calorimeter, appropriate Ea
experiments can be done quickly and efficiently. Additionally,
the ease of data collection allows students to obtain duplicate
data sets in one laboratory session, providing an unusual
opportunity in the undergraduate laboratory for students to
develop confidence in their results.
■
ASSOCIATED CONTENT
*
S Supporting Information
Student handouts and instructor notes. This material is
available via the Internet at http://pubs.acs.org.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: wsweeney@hunter.cuny.edu.
Notes
The authors declare no competing financial interest.
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