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TABLE OF CONTENTS
I. OBJECTIVES
II. INTRODUCTION
III. PROCEDURE
IV. RESULTS
A.
B.
C.
D.
Collected Data
Sample Calculations
Graphs
Summary Table
9
11
13
15
V. DISCUSSION
15
A. General Discussion
B. Discussion Question
15
17
VI. CONCLUSION
18
REFERENCES
18
I. OBJECTIVE
This experiments attempts to determine the acid-dependent and the acid-independent rate
constant (kH and k respectively) at room temperature, as well as, the order of the reaction with
respect to H3O+ (q) and the Arrhenius activation energy (Ea) for the hydrolysis of methyl acetate
(MeOAc) into acetic acid (AcOH) and methanol (MeOH):
(1)
II. INTRODUCTION
Part of the experiment concerns measuring rate constants. While the reaction in Equation
1 occurs naturally, Ehteshami et al. (595) state the reaction is extremely slow in pure water and
thus an acid catalyst is used to increase the forward reaction rate. According to Pell (13), the
reaction is first order with respect with both MeOAc and CH3COOH, and of order q with respect
to H3O+, hence the rate law can be written as:
][
][
Where:
[X] indicates the concentration of substance X (units:
is the rate of the reaction (units:
is time (units: )
is the rate constant (units dependent on q)
q is order of the reaction with respect to H3O+ (unit-less integer)
(2)
However the rate law in Equation 2 can be simplified. The water in the equation is being
used as a solvent, which means that its concentration is not changing appreciable from the
beginning to end. Thus for dilute solutions, the concentration of water can be treated as a
constant and combined with the rate constant k to give a simplified rate law:
][
(3)
Where:
is the new acid independent rate constant and is equal to [
] (units dependent on q)
The rate law in Equation 3 can be simplified even further. Since the hydrochloric acid,
HCl, functions as catalyst, it is not consumed in the reaction, and its concentration remains
constant. The rate law is hence pseudo-first order, with the new rate constant kH:
(4)
Where:
is the acid dependent rate constant and equal to
] (units:
(5)
Where:
[
)
)
] vs
. In this case, if
, and the y-intercept is
amount that has been consumed. The initial amount can be calculated by using the molar mass
and density of MeOAc, which according to Cheremisinoff (366) is 932 g mL-1. The amount
consumed is equal to the how much AcOH is produced. Hence the moles produced of AcOH are
measured in the experiment through the titration of aliquots of the reaction mixture using 0.1 M
NaOH. The aliquot contains both the HCl and the formed AcOH, but since the concentration of
the HCl used is known, the concentration of the AcOH can be easily determined.
The experiment measures the [AcOH] for the reaction at four different concentrations for
two purposes: to get an averaged more accurate value for
q. To find the value of
and
]
[
(6)
Hence if ln(kH) is graphed against ln[H3O+], the value of the slope of that line will be q,
and the y-intercept will be ln(k).
Once the rate constants and the order with respect to the concentration of the acid is
known, it is possible to determine the Arrhenius activation energy using the integrated Arrhenius
equation as stated by Kuby (39):
(7)
Where:
is the Arhenius activation energy (units:
The value of
graph will be -
can be determined if the ln(kH) is graphed against 1/T. The slope of this
. For this end, the hydrolysis reaction was performed at three different
temperatures (25 oC, 35 oC, and 45 oC). As before, to determine the value of kH at the different
temperatures, titration was performed on aliquots collected form the reaction solution every 15
minutes, and a graph of ln[MeOAc]t vs was plotted.
Note that the aliquots taken were immediately put into ~20 mL of ice-chilled purified
water, so the reaction rate could be slowed by the lower temperature, as well as drop in
concentration.
3. When the MeOAc was added to the solution, a timer was started separately for each
reaction solution. The room temperature was also recorded, so the temperature of the reaction is
known.
4. An aliquot of 2 mL was drawn from each reaction mixture, as quickly as possible.
Successive aliquots were taken after approximately 15 minute intervals for about 90 minutes.
The time passed was recorded for each titration. The burettes were also refilled with NaOH
between each titration, so measuring the volume used of NaOH would be easier.
5. Each aliquot was placed into a chilled (using an ice bath) 50 mL Erlenmeyer flask
which already contained about 20 mL of deionized and purified water. The aliquot was then
titrated using 0.1000 M NaOH. The experiment involves a reaction between a strong acid and
base, which has a large steep change in pH around the equivalence point, hence phenolphthalein
was used as the indicator (4 drops added to the aliquot), since its pH range is 8.3-10 (Clark).
When the aliquot changed colour, the amount of NaOH used was recorded. This step was done
for each concentration of HCl, and for each aliquot.
Finding Ea for reaction
6. About 75 mL of 1.000 M HCl was measured out into three different small jars, which
were then placed in 25
, 35
, and 45
about 5 mL of MeOAc. The jars were left in the bath for 15 minutes, so they could thermally
equilibrate with the water bath.
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48 mL of the HCl solution were removed using volumetric pipettes, and mixed in a 50 mL
volumetric flask. The flask was stoppered and swirled to mix the two substances. The reaction
solution was then poured into another small jar and re-placed in to the 25
water bath.
8. Step 7 was repeated for the HCl and MeOAc in each water bath, staggering the
mixture of the MeOAc and HCl, so enough time was left between titrations to perform them
unrushed.
9. As before an aliquot of 2 mL was drawn from each reaction mixture at the different
temperatures, as quickly as possible. Successive aliquots were taken after approximately 15
minute intervals for about 90 minutes. The time passed was recorded for each titration. The
burettes were also refilled with NaOH between each titration. The titrations were performed like
in step 5.
The methods outlined in the introduction were used to find the values of all the required
parameters (k, kH, q, EA). Any changes to the procedure were made before starting the
experiment in Week 2. The changes included changing the amount of MeOAc used for each
reaction solution, and using 4 instead of 3 concentrations of HCl. Table 1 below outlines the
equipment used and their uncertainties.
IV. RESULTS
A. COLLECTED DATA
The following tables contain the titration information for each set of titrations. Tables 2-5
contain data for titrations performed at room temperature (21.9
Tables 6-8 contain data for titrations performed at varying temperatures and with 1.000 M HCl.
If data was not collected at a certain time interval, then it is marked with --. Seven aliquots
were taken to maximize the number of data points collected, while still being able to complete
the experiment within the allotted time periods.
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B. SAMPLE CALCULATIONS
The following calculation is for the reaction at room temperature (21.9 C) when 0.5 M
HCl was used in the reaction, unless otherwise stated. It was assumed volumes are additive. The
uncertainties were calculated by using the formulas provided in the Lab Manual on page 13.
Moles of NaOH needed for titration
11
)(
]
(
and 1.000 M
The values of kH,, q below are the ones that were found by graphing time vs ln[MeOAc] t.
See graphs in the next section.
[
Finding Ea
The value for -Ea/R is the slope of the 1/T vs ln(k) graph. See graph in the next section.
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C. GRAPHS
Figure 1 The time (s) is graphed against ln[MeOAc] to find the value kH (negative of slopes) at
room temperature (21.9 ) for different concentrations of HCl used: 0.5 M (green), 0.7 M
(blue), 0.9 M (red), and 1.0 M (orange).
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0
-12
-13
ln(kH)
-12.5
-13.5
y = 2.053x - 12.659
R = 0.581
-14
-14.5
Figure 2 The ln[H3O ] is graphed against ln(kH) to determine the value of k at room
temperature (21.9 ). The kH used are the ones determined from Figure 1.
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Figure 3 The time (s) is graphed against ln[MeOAc] to find the value kH (negative of slopes)
using 1.0 M HCl for different temperatures: 25 (blue), 35 (red), and 45 M (green).
0.00315
0.0032
0.00325
0.0033
0.00335
0.0034
0.00345
-11.2
-11.4
ln(k')
-11.6
-11.8
-12
y = -3350x - 1.2968
R = 0.849
-12.2
-12.4
-12.6
-12.8
-13
Figure 2 The 1/Temperature is graphed against the respective ln(k) to determine the value of
Ea/R. The temperatures used are room temperature 21.9 , 25 , 35 , and 45 .
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D. SUMMARY TABLE
Table 9 Summary of the findings of this lab: the acid dependent (k H), acid independent (k)
rate constants, order of reaction with respect to H3O+ (q), and the activation energy (Ea).
[HCl] used (M)
Temperature ( )
0.5
0.7
0.9
1.0
1.0
1.0
1.0
21.9
21.9
21.9
21.9
25
35
45
kH (s-1)
2.053
-1
27.85
V. DISCUSSION
A. GENERAL DISCUSSION
After the data was processed using the graphical and calculatory methods outlined in the
intro, the following results were found. The value for acid dependent rate constant kH (units s-1)
at room temperature (21.9
,
) was
respect to [H3O+], was 2.053, and the activation energy Ea was found to be 27.85 kJ mol-1. The
percent error for the order of the reaction was 105.3 %, from the literature value of q = 1. The
theoretical value according to Wades (146-150) the activation energy is 44.2 kJ mol-1. This
results in a percent error of 37.0 %. While the value of the activation energy is relatively close to
the literature value, the error on the order is very large. While, values for the literature rate
constants could not be found, the fact that k was similar in value to the acid catalysed kHs
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suggests the values are not very accurate. A catalysed reaction should have a higher rate
constant. The results could be improved by minimalizing various sources of error could have
caused the large inaccuracy of the results.
An obvious way to improve the results is simply to do multiple trials. As can be seen
from Figure 1, the slope, ln(kH), for 0.9 M HCl is actually greater than for 1.0 M HCl., when in
reality the relationship should be linearly increasing with the ln[H3O+]. Such inaccuracies would
especially be greatly improved by repeated trials, since they would allow for better averaged
values to be used. With that said, due to time constrains of the lab time, it would be very hard to
actually perform multiple trials in the three lab periods. Thus, other ways to improve the lab must
also be considered.
The whole lab is contingent on the concentration of MeOAc at a given time. This
concentration is itself calculated from the amount of NaOH needed to titrate an aliquot.
Therefore, the volume of NaOH required must be carefully measured. However, it was noticed
that the colour of the titrated solution was not the same shade of pink. A light shade of pink is
preferred as the equivalence point would have just occurred; however sometimes the pink deep,
suggesting too much base had been added. Adding more base than necessary would have
resulted in an over estimation of the acid in the aliquot, and thus an overestimation of the moles
consumed of MeOAc. Thus the rate measured would be higher than the actual rate, which could
be a possible reason for the high positive error in the value of q. Titration should be performed
more carefully to prevent the introductions of such errors.
A pH meter could be used instead of titration, so that the concentration of the acid in the
aliquot can be accurately determined without the human error found in titration. Alternatively, a
test run could have been done for each reaction solution at different concentrations and
16
temperatures. This would allow a pre-determination of the equivalence point, so the titrations
could be performed with more care when the volume of NaOH neared the value in the test run.
In the lab, it was assumed that the concentration of the HCl was exactly as indicated.
Since the experiment involved very small changes in concentration of MeOAc due to the slow
rate of the reaction, even small differences in the reported concentrations of HCl could
potentially lead to large results. Also the 0.7 M and 0.9 M HCl solution were created by mixing
the provided 0.5 M and 1.0 M HCl, and thus the error in mixing the right volumes might be big
enough to be relevant. A way around this problem is to titrate 50 mL of each concentration of
HCl to measure the amount of HCl in it directly.
All of the parameters of the reaction that were required to be found were determined
through the experiment. The values of the parameters however indicate they are not very
accurate. To improve the procedure and results the design changes mentioned above could be
implemented.
B. DISCUSSION QUESTIONS
1. The hydrolysis of methyl acetate is a slightly endothermic reaction, hence the
in
the following potential energy diagram is positive. The reaction occurs by the formation of two
transition states, and one intermediate.
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VI. CONCLUSION
All the parameters, that the experiment was designed to determine, were able to be found.
For concentrations of 0.5 M, 0.7 M, 0.9 M, and 1.0 M HCl solution used, the acid dependent rate
constant kH (units s-1) at a room temperature of 21.9
,
, and
were respectively
at room temperature. The reaction was of q = 2.053 order with respect to the H 3O+
The activation energy for the reaction was 27.85 kJ mol-1. The paramaters however had high
sources of error, which suggests the labs results are inaccurate.
REFERENCES
1. Ehteshami, M.; Rahimi, N.; Eftekhari, A.A.; Nasr, M.J.; Kinetic Study of Catalytic Hydrolysis
Reaction of Methyl Acetate to Acetic Acid and Methanol. Iranian Journal of Science and
Technology. 2006. 595-606.
2. Pell, Wendy; Boulanger, Maude.; CHM2330 Physical Chemistry Lab; Winter 2014.
4. Kuby, Stephens A.; A Study of Enzymes, Volume 1; CRC Press, Boca Raton, FL, 1990; p 39.
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