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Laura Tomlinson 091231817

Experiment C1:
Kinetics and Mechanism of Hydrolysis of Haloalkanes
21/03/2011

Abstract
The activation energy and pre-exponential factor of the hydrolysis of both
TBB and TBC were calculated from the timed conductance of the reaction
mixture. The values calculated for TBC were found to be accurate and
consistent with literature values but those calculated for TBB were not as
consistent. From this the mechanism of both the reactions were determined
to be SN1.

Introduction
To calculate the Activation energy of the two hydrolysis reactions the electrical conductance of
their solutions, when the reaction was occurring, had to be recorded. Conductance is the
measure of how easily electrons flow through a certain pathway and is the reciprocal of
resistance.
The conductance of the reaction was measured by setting up a single electrical cell. This was a
reaction vessel which contained two sealed platinum electrodes connected to a conductance
meter. For the hydrolysis reactions carried out, one of the products of the reaction was a
halogen hydron ionic species (e.g. HCl and HBr) both of which dissociated into their respective
ions in solution. As the reaction progressed the amount of these free ions in solution increased
and this in turn caused the conductance value to increase. This is because electrical current is
carried by ions in solution so the more free ions present in solution, the larger the current
created. The reason that the end point of this reaction could be calculated is because once all
the TBB/ TBC had reacted to form is hydrolysed product no more halogen hydron ionic species
were created. This caused a plateau in the conductance readings signalling the end of the
chemical reaction. The time taken for the reaction to complete was recorded and from this the
relative rate constant could be calculated.
There are two possible mechanisms that the hydrolysis reactions can undergo, S N1 and SN2.
Both are nucleophilic substitutions but vary in the amount of molecules involved in their rate
determining step. An SN1 reaction has only one molecule involved in its rate determining step
and forms an ionic intermediate. On the other hand an SN2 reaction involves two molecules in it
rate determining step and forms no intermediates. Using this knowledge we will be able to
determine the mechanism of the reactions from the concentrations of solvent used.

Theory
The rate constant (k) is a quantifiable measure of the speed of a reaction. It relates the
concentrations of the reactants and the temperature of the reaction to its speed. Concentration
was not used throughout this report but mole fraction was used instead.
Mole Fraction = moles of solute t
Moles of solution
The Arrhenius equation was used throughout this report to explain the relationship between the
rate constant and temperature and was used to calculate both the pre-exponential factor and
the Activation energy. Ea is equal to the activation energy of the reaction, A is the pre-
exponential factor, R is the gas constant and T is the absolute
temperature.
Procedure
The experiment was carried out as described in the script.
Results – Effect of solvent composition on the Rate Constant for Hydrolysis of TBC
at 25°C.

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Sample G0 Ginf kobs R2
1 0.0007 0.0335 0.0124 0.9967
2 0.00006 0.00663 0.0094 0.9971
3 0.00009 0.001957 0.0042 0.9929
4 0.0004 0.00761 0.0035 0.9591

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Mole fraction of each reaction mixture:
Mass = Density × volume
Moles = Mass
Mr
Mole Fraction = moles of solute t
Moles of solution

Sample 1 – Ethanol:
Moles = 0.79 × 0.98 = 0.017
46.07
Mole Fraction = 0.017 t= 0.01
1.66+1.92×10-4+0.017

Sample Mole Fraction kobs


1 0.010 0.0124
2 0.043 0.0094
3 0.090 0.0042
4 0.128 0.0035

The relationship between the mole fraction of ethanol and the value of kobs has a negative
correlation. As the amount of ethanol is increased the reaction speed slows. This graph
shows sample 3 as an anomalous result as its kobs value is lower than expected.

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Results – Effect of temperature on Rate constant for Hydrolysis of TBC

Temperature (°C) Temperature (°K) 1/Temperature (K-1) kobs ln kobs


21.4 294.9 3.39×10-3 0.0140 -4.27
26.8 300.3 3.33×10-3 0.0284 -3.56
31.2 304.7 3.28×10-3 0.0498 -2.99
36.8 310.3 3.22×10-3 0.0976 -2.33
40.4 313.9 3.19×10-3 0.1371 -1.99

Ln kobs = -Ea (1/Temperature) + lnA


R
y = mx + c

-Ea = -11222 lnA = 33.804


R
A = 4.796×1014 s-1
Ea = 93299.71 J mol-1
= 93.3 KJ mol-1

All points on this graph fall on the best fit line making the values for the activation energy
and pre-exponential factor accurate.

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Results – Effect of temperature on Rate constant for Hydrolysis of TBB

Temperature (°C) Temperature (°K) 1/Temperature (K-1) kobs ln kobs


2.2 275.7 3.63×10-3 0.0297 -3.52
7.4 280.9 3.56×10-3 0.0468 -3.06
12.5 286.0 3.50×10-3 0.1115 -2.19
17.3 290.8 3.44×10-3 0.1185 -2.13
22.5 296.0 3.38×10-3 0.2025 -1.60

Ln kobs = -Ea (1/Temperature) + lnA


R
y = mx + c

-Ea = -7734.4 lnA = 24.571


R
A = 4.689×1010 s-1
Ea = 930.29.71 J mol-1
= 0.93 KJ mol-1

The points on this graph do not fall directly on the best fit line which may cause some
discrepancies with the values for activation energy and pre-exponential factor.

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Discussion:
When the mole fraction of Ethanol was plotted against the observed rate constant in section
one of the above experiments a negative relationship was observed. This means that as the
concentration of ethanol increased the rate of the reaction decreased. Ethanol is not directly
involved as a reactant in the mechanism but as the volume of ethanol was increased the
volume of water used decreased. Using this knowledge, and the knowledge that water is a
reactant involved in the mechanism, we can say that as the volume of water decreased the
rate of the reaction decreased. Water is used as a source of H+ and OH- in the reaction and
is also used to stabilize any ionic intermediates formed. Ethanol is less polar and therefore
unable to stabilize any ionic intermediates formed. Ionic intermediates are only formed
during an SN1 reaction and as this reaction was dependent on the volume of water it is clear
that ionic intermediates were formed. This is sufficient evidence to state that the reaction is
an SN1 reaction.
Chemical equation:
(CH3)3CCl + H2O → (CH3)3COH + HCl
SN1 mechanism:

SN2 mechanism:

The Activation energy (Ea) is the minimum energy a molecule must possess to form its
intermediate/ transition state and then progress to the final products. For a reaction to
precede at a reasonable rate a certain percentage of molecules involved must possess that
amount of energy or above. This can be calculated using the Arrhenius equation.
The pre-exponential factor (A) is a collision frequency factor and is
used to represent the amount of times that a molecule will collide
and whether it will collide with sufficient force and the correct
orientation to cause a reaction.
The value for the activation energy calculated from the reaction of TBC was 93.3 KJ mol-1
and this is very close to the published value of 95 KJ mol-1. This slight difference in values
could be caused by a slight difference in the temperature when they were recorded. The
value calculated for the pre-exponential constant (A) was 4.796×1014 s-1 which is also quite

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close to the published value of 3.4×1014 s-1. These value differences may also be caused by
variations in recording temperature.
The value for the activation energy calculated from the reaction of TBB was 0.93KJ mol-1
and this is very different to the published value of 85KJ mol-1. This difference in values could
be caused by a variety of different factors. The water bath that the reaction was undertaken
in had to be cooled using ice cubes and this is not a very accurate way of getting a precise
temperature reading. The reaction mixture may have also not have been given enough time
to equilibrate to the required temperature before the reaction was started. As one of the
main reactants in this experiment was water the possibility of contamination of the reaction
mixture was much higher due to residues from previous washing of the equipment. This
would cause early reaction, lowering the conductance recorded and therefore the calculated
activation energy. When the suspension of TBB was added to the reaction vessel the
conductance was already being recorded (to obtain a base reading) and if the injection of
TBB took longer than expected this affected the correlation of the whole plot. This would
also affect the overall activation energy.
The value calculated for the pre-exponential constant (A) was 4.689×1010 s-1which is also
very different to the published value of 3.4×1014 s-1. These values also show a large amount
of variation and may also be caused by the factors mentioned above.
The hydrolysis of TBB has a lower activation energy value than TBC. Both of the above
reactions occur through an SN1 mechanism as they both use the same nucleophile and their
rates depend on the concentration of water. The reason for TBB having a slightly lower
activation energy is due to the variation in leaving group (Br instead of Cl). Bromine has a
much lower pKa than Cl (ten times more effective) and therefore dissociates more readily
leading to the intermediate cation by using less energy. This is the cause for the difference
in Ea.

Conclusion:
The hydrolysis reactions of both TBB and TBC occur via an S N1 mechanism. This was
shown to be true when the mole fraction of ethanol was plotted against the observed rate
constant and a negative relationship was obtained. The Activation energy for the hydrolysis
of TBC was calculated as 93.3KJ mol-1 and the pre-exponential factor at 4.796×1014 s-1.
Both were close to the published value. The values for both these factors were also
calculated for TBB and were found to be 0.93KJ mol -1 and 4.689×1010 s-1. These are very
inconsistent with the published values and could have been caused by a variety of human
and equipment errors.

Questions:
1 Is it necessary, in general, to obtain Ginf in order to obtain kobs?
Yes, the infinity value is needed in the calculation as the end point of the reaction
must be determined for the relative rate to be measured.
2 What is conductance and in what units is it measured?
Conductance is the reciprocal of resistance and is measured in Siemans. It is the
measure of the property which allows the passage of an electric current.
3 What other techniques might be used to perform this experiment?
Rate constant can also be calculated from the relationship between concentration
and reaction time. The concentration of TBB/ TBC could be varied and the
reaction timed to its end point.