Internal

Assessment: The Effect of Dimethyl Sulfoxide on the

Activation Energy of the Iodide-Catalysed Decomposition of
Hydrogen Peroxide

Candidate Name: Paul Appel
Candidate Number: 000638-0032

Dates of experiment: 12-23 October 2015
Date of submission: 18th January 2015.



























 Paul Appel: 000638-0032
Chemistry Internal Assessment

Introduction
In 1889 the Swedish scientist Svante Arrhenius introduced the term activation energy to
the scientific world.1 In chemistry activation energy stands for the minimum amount of
energy that is required to transfer particles, atoms or molecules to a state in which a
chemical transformation can occur.2 Activation energy is the energy needed to overcome
repulsions, to start breaking bonds, to deform molecules and to allow rearrangement of
atoms and electrons.3 Activation energy can be considered as the minimum amount of
energy necessary to initiate a chemical reaction (Figure 1).

Figure 1: Energy path of the reaction with the

activation energy4
The empirical determination of the
activation energy is a very common and
important experiment in chemistry and is
!!
based on Arrhenius equation 𝑘 = 𝐴𝑒 !(!") .5
Where k is the rate constant, A a constant,
Ea is the activation energy, T is the
temperature in Kelvin and R is the gas
constant. Arrhenius equation shows the
dependence of the rate constant k on
temperature.6 Rearranging the equation
! !
Reaction coordinate
𝑙𝑛𝑘 = − !! ! + 𝑙𝑛𝐴 ,
an Arrhenius plot can be created, where lnk plotted against inverse temperature results
!!
in a slope equal to ! ! .7 Lowering the activation energy means that an experiment that
normally requires substantial energetic input can be conducted with lower energy.
Saving energy is important to reactions relevant in industries processing large
quantities of materials chemically.
Usually the rate of the reaction is found by determining the change in quantity of the
reacting compounds.
𝑟𝑎𝑡𝑒 𝑇 = 𝑘 ! [𝐴]
In order to determine the activation energy the rate is measured at different
temperatures. The data is then used to create a plot of lnk versus 1/K and calculate Ea.8
During the research for my IA I discovered a method developed by William Sweeney
determining the activation energy by measuring the temperature change that occurs
during the reaction.9 I decided to use this method to investigate the effect of dimethyl
sulfoxide (DMSO) on the iodide-catalysed decomposition of hydrogen peroxide.

1 Arnold F. Holleman and Egon Wiberg, Lehrbuch Der Anorganischen Chemie [Textbook of Inorganic

Chemistry] (Berlin: De Gruyter, 1976), 169.

2 Ibid.
3 Ibid.
4 “Energy path of the reaction with the activation energy,” Accessed January 16, 2016,

https://sallyarjoon.wordpress.com/2013/04/01/enzymes/.
5 Holleman and Wilberg, Lehrbuch Der Anorganischen Chemie, 169.
6 Ibid.
7 Ibid.
8 Ibid.
9 William Sweeney et al., "Efficient Method for the Determination of the Activation Energy of the Iodide-

Catalyzed Decomposition of Hydrogen Peroxide," J. Chem. Educ. Journal of Chemical Education (2014):
1217.
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Chemistry Internal Assessment
Research Question:
How is the activation energy of the iodide-catalysed decomposition of hydrogen
peroxide affected if DMSO solutions with different concentrations are added?

Hypothesis:
Dimethylsulfoxid (DMSO) is a small polar amphilic molecule with a hydrophilic sulfoxide
group and two hydrophobic methyl groups (figure 2a). DMSO molecules are highly
associated10 and likely to occur in chain form. Like polymeric structures they are
oriented by dipole –dipole interactions (figure 2b).11

Figure 2: a) Structure of DMSO b) Association of DMSO c) Hydrogen bond water DMSO

As DMSO is a highly polar solute it forms strong hydrogen bonds with water and as a
result can break the highly organised structure of the water molecules, (figure 2c).12 The
interaction between DMSO and water seems to be even stronger than between DMSO
molecules itself.13 These characteristics of DMSO have an impact on solutes in water. In
this investigation hydrogen peroxide and potassium iodide will be dissolved in water
leading to the assumption that the DMSO will have an impact on the reaction. The
hydrogen peroxide forms hydrogen bonds with the water molecules (figure 3a) and the
potassium and iodide ions are surrounded by a hydration shell due to the ion-dipole
interaction (figure 3b). This reduces the chances of successful collisions between the
hydrogen peroxide and the iodide. The addition of DMSO appears to have an impact on
these interactions. Being no longer surrounded by a net of water, iodide and hydrogen
peroxide collisions are more likely to occur. Therefore it can be assumed that the
activation energy of the iodide-catalysed decomposition of hydrogen peroxide will
decrease with increasing DMSO concentrations added.

Figure 3: a) Hydrogen bond between H 2O and H2O2 b) Hydration shell of iodide ion

a) b)

10 Iosif I. Vaisman and Max L. Berkowitz, “Local structural order and molecular association in water-DMSO

mixtures - Molecular dynamics study,” Journal of the American Chemical society 114 (1992): 7889-7896.
11 Zhi-Wu Yu and Peter J. Quinn, “Dimethyl Sulphoxide: A Review of its Applications in Cell Biology,”

Bioscience reports 14 (1994): 260.

12 Ibid.
13 D. Martin and H.G. Hanthal, Dimethyl Sulphoxide, (New York: Van Nostrand Rheinhold,1975).
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Chemistry Internal Assessment
Method and Materials:
Method, materials, hazards and theory are adapted from Williams Sweeny’s: Efficient
method for the determination of the iodide-catalysed decomposition of hydrogen
peroxide.14
The method used in this experiment is relatively new. To understand why it is so
convenient the original method of determining the activation energy (Ea) has to be
understood. Ea is never directly measured but has to be found by determining other
values. Normally a series of experiments are completed, with each one at a different
temperature. Then a graph of ln k versus 1/T is created and the value of the slope leads
to Ea. However this method requires trials to be completed at different temperatures,
which is problematic as it significantly increases the time of the lab and can produce
flawed results due to variations in temperature.
The following method eliminates the need for conducting multiple reactions. Instead the
method focuses on collecting the heat of reaction for the iodide-catalysed decomposition
of hydrogen peroxide dissolved in DMSO. Hydrogen peroxide decomposes
exothermically to oxygen and water at room temperature.
!.
2𝐻! 𝑂! 2𝐻! 𝑂 + 𝑂! ∆𝐻 = −98.3 𝑘𝐽𝑚𝑜𝑙 .! 15
This approach is used to obtain rate data over a range of temperatures in a single run.
Since the approach requires following the reaction over time the concentration of the
H2O2 is not constant. Thus we need to know how the concentration decreases as the
reaction progresses. In the theory section I will show that this can be done relatively
easy.

Theory:
In the literature the rate equation for the decomposition of H2O2 is given as
𝑟𝑎𝑡𝑒 = 𝑘(𝑇)[𝐻! 𝑂! ][𝐼 ! ]
The decomposition of H2O2 is exothermic, i.e. the energy released as heat can be treated
as a product and used to determine the rate of the reaction.
However the following assumptions are made:
• Volume (V) and Mass (m) of the solution are constant because the evaporation of
water is negligible.
• The specific heat capacity (C) of the solution is the same for different solutions
• The reaction is adiabatic.
Now it is possible to approximate the rate at a given temperature T as the slope of a
temperature versus time curve at temperature T.
𝑑𝑇
𝑅𝑎𝑡𝑒 𝑇 = 𝑠𝑙𝑜𝑝𝑒 ! =
𝑑𝑡
≈ 𝑘(𝑇)[𝐻! 𝑂! ][𝐼 ! ]
This can be expressed by the energy Q that is released.
𝑄 = 𝐶𝑚Δ𝑇
Since all the energy comes from the reaction:
𝑑[𝐻! 𝑂! ]
𝐶𝑚𝑑𝑇 = ∆𝐻! 𝑉𝑑𝑡
𝑑𝑡
V is the volume. Hence rearranged this equation gives.
𝑑𝑇 ∆𝐻! 𝑉 𝑑 𝐻! 𝑂! 𝑑[ 𝐻! 𝑂!
=( )( ) = 𝐶′
𝑑𝑡 𝐶𝑚 𝑑𝑡 𝑑𝑡

14 William Sweeney et al., "Activation Energy," 1217-1218.
15 Ibid.
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Chemistry Internal Assessment
It should be noted the C’ will be negative as ∆H for this reaction is also negative. If the
rate is seen as –d[H2O2]/dt an expression for dT/dt can be written based on the rate of
the temperature change.
𝑑𝑇
= 𝐶′𝑘(𝑇)[𝐻! 𝑂! ][𝐼 ! ]
𝑑𝑡
The extent of depletion of hydrogen peroxide can found by the change in temperature
relative to initial and final temperature. Assuming that the reaction is perfectly adiabatic
and the reaction goes to completion the concentration of H2O2 at a certain temperature
T can be found by:
𝑇!"#$% − 𝑇
𝐻! 𝑂! ! = 𝐻! 𝑂! ! ×
𝑇!"#$% − 𝑇!"!#$%
[H2O2]T is the concentration of hydrogen peroxide at any temperature T and [H2O2]0 is
the initial concentration. Iodide is the catalyst and its concentration is expected to
remain constant. The rate at any given point in the reaction is the slope of a temperature
versus time curve at temperature T, (slopeT) which can be expressed as

𝑑𝑇
𝑅𝑎𝑡𝑒 𝑇 =
𝑑𝑡

= (𝑠𝑙𝑜𝑝𝑒! )

= −𝐶′𝑘(𝑇) 𝐻! 𝑂! [𝐼 ! ]

𝑇!"#$% − 𝑇
= −𝐶′𝑘(𝑇) 𝐻! 𝑂! ! × ×[𝐼 ! ]
𝑇!"#$% − 𝑇!"!#$%
k can now be found by regrouping the constant terms and naming them k’.
𝑇!"#$% − 𝑇
𝑠𝑙𝑜𝑝𝑒! = {𝐶 ! 𝑘 𝑇 𝐻! 𝑂! ! 𝐼 ! }×
𝑇!"#$% − 𝑇!"!#$%
𝑇!"#$% − 𝑇
= 𝑘′(𝑇)×
𝑇!"#$% − 𝑇!"!#$%
Hence rearranging the above equation:
𝑇!"#$% − 𝑇!"!#$%
𝑘′ = 𝑠𝑙𝑜𝑝𝑒! ×
𝑇!"#$% − 𝑇
To now find k’ I have to calculate the slope between two individual data points and
multiply it by the temperature change.
Material:
• 1000 ml 12% (4.0M) hydrogen peroxide
• 400ml 0.10M potassium iodide
• 200ml of 1%, 2%, 3% 4% and 5% of dimethyl sulfoxide
• 100ml beaker
• 10ml graduated measuring cylinder
• 50ml graduated measuring cylinder.
• Scientific scale (Resolution: 0.000)
• Temperature probe
• 2 styrofoam cups with lid

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Method:
1. Weigh out 30.0ml of 12% hydrogen peroxide using a 100ml beaker and a scale.
Hydrogen peroxide is assumed to have the same density as water. 30.0ml equal
30.0g.
2. Fill the hydrogen peroxide into the styrofoam cup.
3. Use a measuring cylinder to measure out 30.0ml of 1% DMSO.
4. Add the 30.0ml DMSO to the hydrogen peroxide.
5. Use a 10ml graduated cylinder measure out 4.0ml of 0.10M potassium iodide.
6. Prepare the temperature probe connect it to laptop and set up logger pro. Set the
temperature measurement to once every second. In order to increase insulation
place one styrofoam cup in another.
7. Start the measurement and record initial temperature for 30s
8. Add the potassium iodide to the hydrogen peroxide. Place the lid on the beaker
and insert the temperature prop.
9. The reaction should be measured for 25 minutes
10. Then repeat same experiment with the 2%, 3% 4% and 5% concentrations of
DMSO.

Table 1: Experimental Variables

Independent Controlled Dependent
• Concentration • Concentration of the solvent • Immediate: Temperature change
of H2O2 DMSO (1%, 2%, 3% 4% and over time
(4.0M) 5%) • Secondary (derived): Activation
• Concentration • Leading to a final energy of the iodide-catalysed
of KI (0.1M) concentration of 0.47%, 0.94%, decomposition of hydrogen peroxide
1.41%, 1.87% and 2.34% DMSO can then be calculated from the
temperature change over time.

Hazards:
• Hydrogen peroxide is toxic and should not be ingested. It should also not come in
touch with skin or cloths. It can cause skin irritation and is a strong oxidant.
• Potassium iodide is also toxic. It should not be ingested. It also causes skin
irritation and can inflict serious damage to the eyes.
• DMSO is non-toxic. However it can penetrate skin and cells by moving through
them. Care should be taken if it is mixed with other substances to avoid
substances travelling through the skin.
• The products will reach temperatures above 80C° (353K) and care should be
taken when handling the reaction.

Data Processing
Data collection will be separated into two sections. In Section 1 the data collected during
the experiments will be processed and a graph of the natural log of k (lnk) versus
inverse temperature in kelvin (1/K) will be created.
In Section 2 the Arrhenius plots of lnk vs 1/K will be used to calculate the activation
!!
energy of each individual reaction, as the slope of the Arrhenius plot is ! ! .

Section 1
During each experiment the temperature was recorded for 25 minutes (1500s) except
for the control experiment without DMSO, measured for 18 minutes. Therefore 1500
data points were collected for each experiment. The table here shows a small extract and
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 Paul Appel: 000638-0032
Chemistry Internal Assessment
will be used to show sample calculations. All calculations were completed using Google
sheets. The link to all complete tables for all experiments can be found in the Appendix.

The potassium iodide was added after 30 seconds therefore the first 30 seconds are
discarded.
Table 2&3: The quantitative data of the iodide-catalysed decomposition of hydrogen
peroxide without DMSO and 1%DMSO solution added.

Time (s) Temp (°C) ±0.01 Time (s) Temp (°C) ±0.01
30 25.90 30 25.79
31 25.84 31 25.78
32 25.88 32 25.79

33 25.86 33 25.81
897 79.89 1497 36.21

898 79.89 1498 36.22
899 79.90 1499 36.22

900 79.95 1500 36.21

Table 4: The qualitative data of the iodide-catalysed decomposition of H2O2 with 1% DMSO
solution added.
Observations Inferences
Beginning • Nothing notable about any of
• See through liquid (H2O2) combined with see the liquids.
through but slightly oily liquid (DMSO)
• KI also see through
During Experiment • Giving off of gas/ Evaporation
• Fizzing sound during initial reaction • Temperature gain- Energy is
• Beaker became hotter given out.
• Colour change, from see through to light yellow.
End • Substances have reacted but
• The final Solution is slightly yellow. maybe not fully.
• There are slight fizzing sounds coming from the
solution

Calculations

Calculating 1/T.
The temperature collected was in measured in Celsius. Therefore it will need to be
converted to Kelvin.
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑎𝑡 31𝑠 (𝐶°) = 25.84
𝑇𝑒𝑚𝑝. (𝐾) = 𝐶° + 273.2
𝑇𝑒𝑚𝑝 (𝐾) = 25.84 + 273.2
𝑇𝑒𝑚𝑝 = 299.04 𝐾
In order to plot the data in a graph the temperature (T) needs to be converted to 1/K.
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑎𝑡 31𝑠 = 299.0
1 1
=
𝑇 299.0
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Chemistry Internal Assessment
1
= 0.003344 𝐾 !!
𝑇
Graph 1: Temperature change during the iodide-catalysed decomposition of hydrogen
peroxide mixed with 1%DMSO solution.

Calculating lnk’ example:

All 0% DMSO calculations are also shown as the 0% DMSO concentration experiment
was used as a control experiment to ensure that the experiment is feasible.

lnk’ is obtained by using the data from table 1 and 2 and the formula for (slope)T:
!"#$% !"#$"%&!'%"
𝑠𝑙𝑜𝑝𝑒! = !"#$% !"#$

0%DMSO
1%DMSO
𝑇!" − 𝑇!" 𝑇!" − 𝑇!"
= =
𝑡!" − 𝑡!" 𝑡!" − 𝑡!"
25.88 − 25.84 25.79 − 25.78
= =
32 − 31 32 − 31
= 0.04000 = 0.01000

Temperature change:
𝑇!"#$% (𝐾) − 𝑇!"!#$% (𝐾)
=
𝑇!"#$% (𝐾) − 𝑇(𝐾)

79.95
− 25.90 36.21 − 25.79
= 0.9989 𝐾 = 0.9990 𝐾
79.95 − 25.84 36.21 − 25.78

k’:
𝑇!"#$% − 𝑇!"!#$%
𝑘′ = 𝑠𝑙𝑜𝑝𝑒! ×
𝑇!"#$% − 𝑇

= 0.04000×0.9989 𝐾 = 0.01000×0.9990 𝐾
= 0.03996 = 0.009990


Now that I have found k’ I can find lnk’

𝑙𝑛𝑘′ = 𝑙𝑛0.03996 𝑙𝑛𝑘′ = 𝑙𝑛0.009990
𝑙𝑛𝑘 ! = −4.606 7
𝑙𝑛𝑘′ = −3.220

 Paul Appel: 000638-0032
Chemistry Internal Assessment
Now that I have lnk’, a graph of lnk’ vs 1/T can be plotted. The data tables and these
graphs are found in the appendix.
Graph 2: Graph of lnk’ vs. 1/T during the iodide-catalysed decomposition of hydrogen
peroxide mixed with 1%DMSO solution.
















During my experiment the temperature probe was set to measure a sample every
second. As the measurement increment is so small there are many data points during
which the temperature increase is either very small or 0 resulting in a very crowded
graph. In order to have a less crowded graph and in expectation of a clearer trend I
decimated my data. Instead of plotting every data point every 20th data point was
plotted. All these graphs can be found in the Google sheets document provided in the
Appendix. Contradictory to my expectation the trends deviated and led to very high and
unrealistic activation energies (e.g. 291 kJmol.1 for 5%DMSO). Hence I decided to use my
original data for discussion in section 2.
Furthermore I analysed if the dilution of H2O2 and I- through the addition of DMSO
affected the activation energy found. Since k’ is defined as:
𝑘 ! = 𝐶 ! 𝑘 𝑇 ×[𝐼 ! ][𝐻! 𝑂! ]!
A lower starting concentration of I- and H2O2 leads to a lower k’. The addition of 30 ml
DMSO has the following affect:
34 34
𝑘 ! = −𝐶 ! 𝑘 𝑇 𝐼 ! ! × ×[𝐻! 𝑂! ]! ×
64 64
𝑘 ! = −𝐶 ! 𝑘 𝑇 ( 𝐼 ! ! ×[𝐻! 𝑂! ]! ×0.28)
Hence k’ must be divided by 0.28. As the following table (table 4) shows, the lower
starting concentration affects on the value of lnk’ but has no impact on the difference
between lnk’ values and therefore no impact on the slope of the curve versus 1/T.
Table 5: Example calculation of ∆𝒍𝒏𝒌′
k’ lnk’ lnk’ x 0.28
0.1 -2.30258 -1.02961
0.05 -2.99573 -1.72276
∆𝑙𝑛𝑘′ 0.69315 0.69315

Therefore the addition of the DMSO solution has no impact on the calculation of Ea, as
concentration does not affect activation energy.

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Chemistry Internal Assessment
Now that I was able to plot lnk’ vs 1/T I can determine the activation energy of the
reaction.
Section 2:
The slope of graph of lnk’ vs 1/T can be used to calculate an experiment value of Ea.
The slope of the graph is equal to Ea/R. For 0% and the 1% DMSO the slope is:
𝐸!
𝑠𝑙𝑜𝑝𝑒 =
𝑅
𝐸! = 𝑠𝑙𝑜𝑝𝑒×𝑅

𝐸! = −6613×−8.31 𝐸! = −13711×−8.31
𝐸! = 55000 𝐽𝑚𝑜𝑙!! 𝐸! = 114000 𝐽𝑚𝑜𝑙!!
!!
𝐸! = 55.0 𝑘𝐽𝑚𝑜𝑙 𝐸! = 114 𝑘𝐽𝑚𝑜𝑙!!

These calculations were done for all % of DMSO and the corresponding values can be
found in the appendix.
Uncertainties:
The propagation of uncertainties throughout the calculation would have been extremely
difficult due to the use of ln. Instead the iodide-catalysed decomposition of hydrogen
peroxide dissolved in 1%DMSO was repeated three times and the three values collected
were used to calculate a standard deviation (table 5).

Table 6: The activation energy of the iodide-catalysed decomposition of hydrogen peroxide
dissolved in 1%DMSO.
Experiment Try Experimental Activation Energy (kJmol.1)
1 114
2 126
3 112

!
1
𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝐷𝑒𝑣𝑖𝑎𝑡𝑖𝑜𝑛 = (𝑥! − 𝜇)!
𝑁
!!!

𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝐷𝑒𝑣𝑖𝑎𝑡𝑖𝑜𝑛 = 7.60

This value was then converted into a percentage
𝑆𝑡𝑎. 𝐷𝑒𝑣.
𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝐷𝑒𝑣𝑖𝑎𝑡𝑖𝑜𝑛 % = ×100%
𝑀𝑒𝑎𝑛
𝑆𝑡𝑎𝑛. 𝐷𝑒𝑣 % = 0.0648 ×100%
𝑆𝑡𝑎𝑛. 𝐷𝑒𝑣. % = 6.48%
This percentage was then used for error bars in Graph 3.
Evaluation

There is very little research available regarding this particular experiment conducted
hence there is no data that my results could be compared to except the activation energy
for the control experiment of the iodide-catalysed decomposition of hydrogen peroxide.

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Chemistry Internal Assessment
The literature value is 56.0kJmol.1.16 The value I obtained was 55 kJmol-1 ± 4kJmol-1
(Uncertainty determined from the Standard deviation 6.48%). The literature value lies
within my uncertainty and the uncertainty is relatively low indicating

Possible sources of systematic error:

• Insulation: Heat energy was released during the reaction. Some of this heat
energy could have escaped. To prevent this the beaker was insulated and my
measured temperatures were as accurate as possible. I used a temperature probe
that had a very small uncertainty. Furthermore the data was processed using
Logger Pro making measurements more accurate than if they were read of a
thermometer. In future I could try to use even better insulation. There are many
good insulator materials: polyurethane foam, expanded polystyrene, fibreglass,
and cork. I could also use a container with a thicker wall to make it more difficult
for heat energy to escape and therefore to make sure that no energy can escape
during the reaction.
• I prepared all solutions, except the hydrogen peroxide. There could have been
small errors or imprecise measurements in my preparations and hence the
concentration of the DMSO or the KI could have been slightly different. In order
to avoid this problem I could prepare larger quantities reducing the possible
effect.
• The volume of the solution in the DMSO experiment is larger by 30ml. This led to
a higher heat capacity of the solution. Resulting in a smaller increase in
temperature that is more difficult to measure. There is no way of avoiding this
problem.
• As observed in my qualitative data the reaction was still occurring when I
finished my data recording at 1500 seconds. This indicates that the reaction may
not have come to completion. This can also be seen in my temperature change
graph as the curve does not flatten out completely and there is no fall in
temperature. This potentially effected my calculations, as the final temperature is
too low. In order to improve this I could extend the time period over which I
collect data.
Possible sources of random error:
• The change of air temperature: The room temperature is very difficult to keep
constant this could have affected the rate of heating of the products. The quicker
the reactants heat up the steeper the curve leading to an inaccurate temperature
change measurement. To minimise the impact of this factor of random error I
insulated the reactants during the reaction using two styrofoam cups.

Conclusion:
By determining the activation energy of the iodide-catalysed decomposition of hydrogen
peroxide mixed with 1%, 2%, 3%, 4% and 5% DMSO I was able to show that DMSO has
an influence on the activation energy (see graph 3).

The assumption made in my hypothesis that the activation energy will decrease with
increasing amounts of DMSO added did not proof to be true. In all experiments with
DMSO the activation energy significantly increased compared to the set up without

16 Jan Koolman and Klaus-Heinrich Röhm, Taschenatlas der Biochemie [Pocket atlas of Biochemistry]

(Germany: Koolman/Röhm, 2003), 24.

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DMSO 55kJmol-1 and to the literature value 56kJmol-1.17 As can be seen from graph 3 the
activation energy increases with the addition of DMSO. With further increase in DMSO
there is a trend for the activation energy to fall again (see graph 4). There are some
variations around this trend.

Graph 3&4: The change in activation energy of the iodide catalysed decomposition of
hydrogen peroxide dissolved in varying concentrations of DMSO

One plausible explanation for
this phenomenon lies within the
hydrogen bonds formed in the
solution. DMSO has the ability to
form hydrogen bonds. As the
concentration of DMSO increases
the fraction of hydrogen bonds
between DMSO and hydrogen
peroxide and DMSO and water
increases. While the fraction of
water-to-water hydrogen bonds
and water-to-hydrogen peroxide
hydrogen bonds decreases.
DMSO is a strong dipole, which
results in the newly formed
hydrogen bonds to be stronger
than those between water
molecules and hydrogen
peroxide. Consequently the
DMSO bound hydrogen remains
longer in this hydrogen bond.
This effect of a solute (DMSO) on
the structure and characteristics
of water is called “Hofmeister effect”. According to Hofmeister’s concept solutes can be
18

divided in kosmotropes (water structure maker) and chaotropes (water structure

breaker). Depending on its concentration in aqueous solution, DMSO either acts as
kosmo- or chaotrope. Safford et al. found out that adding small amounts of DMSO (6%
to 10% w/w) to water enhances the order of the water structure.19 The orientation of
the water molecules caused by DMSO seems to strengthen the water-to-water hydrogen
bonds. A more recent study from Vaisman and Berkowitz (1992) describes this
enhanced water structure already at DMSO concentrations of 2% (w/w). At higher
DMSO concentrations (15% to 52% w/w) the water structure seems to be disrupted due
to the formation of the DMSO-water complexes (Figure 4). My results fit into these
research results since at lower DMSO concentrations (1%, graph 3) the activation
energy of the decomposition of hydrogen peroxide rises caused by the “rigidified” water
structure hindering My results fit into these research results since at lower DMSO

17 Ibid.
18 Kim D. Collins and Michael W. Washabaugh, “The Hofmeister effect and the behaviour of water at

interfaces,” Quarterly review of Biophysics 18 (1985): 323-422.

19G.J. Safford et al., “Neutron inelastic scattering and X-ray studies of aqueous solutions of
dimethlysulphoxide and dimethylsulphone,” Journal of Chemical Physics 50 (1969), 2140-2159.

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 Paul Appel: 000638-0032
Chemistry Internal Assessment
concentrations (1%, graph 3) the activation energy of the decomposition of hydrogen
peroxide rises caused by the “rigidified” water structure hindering collision between the
iodide and the hydrogen peroxide. The slight decrease of the activation energy at higher
DMSO concentration (3%- 5%, graph 3) could be explained by the beginning breakdown
of the whole water net and hydrogen peroxide molecules. Due to the steric constraints of
DMSO’s two methyl groups the DMSO can only form two hydrogen bonds. This means
that there is only a short-range structure of hydrogen bonds maintained but there is no
lattice structure of hydrogen bonding (Figure 4).
This may lead to higher mobility of all reaction Figure 4: DMSO-water complexes
partners including the iodide ion, making
collisions with hydrogen peroxide more likely and
the activation energy starts to decrease. It can
therefore be concluded that the amount of DMSO
added to the decomposition of hydrogen peroxide
reaction is crucial for the effect on the water
structure. The range from 0 % to 5 % might not be
high enough to reach the point were the enhanced
water structure is disrupted, leading to a higher mobility of the reaction partners,
resulting in more collisions and therefore a decrease in the activation energy.

Further experiments:
The findings of this internal assessment give rise to further possible experiments. In my
hypothesis I assumed that the addition of DMSO to the decomposition reaction of
hydrogen peroxide would lead to a decrease of the activation energy caused by the
breaking of the water net. While I did further research I learned that the concentration
of DMSO in the experiment decides if it works as a “water structure maker” or “water
structure breaker”. An enlightening experiment would be to determine the exact point at
which the activation energy of the reaction begins to drop by adding higher
concentrations of DMSO from 15% up to 52% as described in Vaisman and Berkowitz,
1992. Thereby it might be possible to show that the breakdown of the water structure
leads to a lower activation energy of the decomposition of hydrogen peroxide.
Additional the effect of an increasing volume and hence specific heat capacity could be
investigated.

Bibliography:
• Holleman, Arnold F., and Egon Wiberg. Lehrbuch Der Anorganischen Chemie [Textbook of
Inorganic Chemistry]. Berlin: De Gruyter, 2007.
• Koolman, Jan, and Klaus-Heinrich Röhm. Taschenatlas der Biochemie [Pocket atlas of
Biochemistry]. Germany: Koolman/Röhm, 2003.
• Martin, D., and H.G. Hanthal. Dimethyl Sulphoxide. New York: Van Nostrand Rheinhold,
1975.
• Sall Jary. “Energy path of the reaction with the activation energy.” Accessed January 16,
2016. https://sallyarjoon.wordpress.com/2013/04/01/enzymes/.
• Sweeney, William, James Leem, Nauman Abid and Stephen DeMeo. "Efficient Method for
the Determination of the Activation Energy of the Iodide-Catalyzed Decomposition of
Hydrogen Peroxide." J. Chem. Educ. Journal of Chemical Education (2014): 1216-1219.
• Vaisman, Iosif I., and Max L. Berkowitz. “Local structural order and molecular association
in water-DMSO mixtures - Molecular dynamics study.” Journal of the American Chemical
society 114 (1992): 7889-7896.
• Yu, Zhi-Wu, and Peter J. Quinn. “Dimethyl Sulphoxide: A Review of its Applications in Cell
Biology.” Bioscience reports 14 (1994): 259-281.

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 Paul Appel: 000638-0032
Chemistry Internal Assessment
Appendix

https://docs.google.com/spreadsheets/d/1Z30I0FrnatbCkTRiaEcrrCQT9jY5IUREpDO9
KstjqeY/edit?usp=sharing

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