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Efficient Method For The Determination of The Acti
Efficient Method For The Determination of The Acti
pubs.acs.org/jchemeduc
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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.
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(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.
B dx.doi.org/10.1021/ed500116g | J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education Laboratory Experiment
■ CONCLUSION
Experiments that are designed to measure Ea make up a small
but important niche of the kinetics curriculum. Until now, these
Figure 1. Graph of temperature vs time: representative student data experiments have been difficult and time-consuming to perform
collected from the decomposition of 30 mL of 12% hydrogen peroxide due to the challenge of quantitatively determining reactants or
with the addition of 0.50 mL of 1.0 M KI.
products with respect to time, and the requirement that the
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experiment be repeated at one or more different temperatures.
By viewing heat as a product, and using simple equipment such
HAZARDS
as a thermometer and a styrofoam calorimeter, appropriate Ea
Hydrogen peroxide (CAS No. 7722-84-1) is toxic and should experiments can be done quickly and efficiently. Additionally,
not be ingested. Contact with skin or clothing should be the ease of data collection allows students to obtain duplicate
avoided because it is a skin irritant and strong oxidant. data sets in one laboratory session, providing an unusual
Additionally, solid potassium iodide (CAS No. 7681-11-0) is opportunity in the undergraduate laboratory for students to
toxic, particularly so if ingested. It can also cause skin irritation develop confidence in their results.
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and serious eye irritation. The solutions by the end of reaction
typically reach temperatures above 80 °C and care in the ASSOCIATED CONTENT
handling of these solutions is advised.
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*
S Supporting Information
■ REFERENCES
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(3) Nyasulu, F.; Barlag, R. Gas Pressure Monitored Iodide-Catalyzed
Decomposition Kinetics of H2O2: Initial-Rate and Integrated-Rate
Methods in the General Chemistry Lab. J. Chem. Educ. 2010, 87 (9),
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(4) Bryan, A. M.; Olafsson, P. G. Activation energy determination:
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(5) Copper, C. L.; Koubek, E. A Kinetics Experiment To
Demonstrate the Role of a Catalyst in a Chemical Reaction: A
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Figure 2. Graph of ln k′ vs 1/T: the student data from Figure 1 were (6) Shatynski, J. J.; Hanesian, D. Adiabatic Kinetic Studies of the
used to construct this plot. The slope of this plot is equal to − Ea/R Cytidine/Acetic Anhydride Reaction by Utilizing Temperature versus
and yields the experimental value Ea = 56 ± 3 kJ/mol. Time Data. Ind. Eng. Chem. Res. 1993, 32 (4), 594−599.