Experiment A: Kinetics of the Acid Catalyzed Hydrolysis of Methyl Acetate

CHM 2330: Introduction to the Molecular Properties of Matter

By: Brandi Tubman (8368919)

Partner: Zedong Yin

Demonstrator: Michael

Due Date: March 4th, 2016

Date of Submission: March 4th, 2016

Department of Chemistry

University of Ottawa
Objectives:

The objectives of this experiment were to analyze the acid-catalyzed hydrolysis of methyl

acetate to find both the acid-dependent (kH) and acid-independent (k’) rate constants at

room temperature, as well as the order of the reaction in respect to H3O+ (q) and the

Arrhenius activation energy (Ea). This was done through multiple titrations done at

regular time intervals with varying acid concentrations and temperatures.

Introduction:

The hydrolysis of methyl acetate forms acetic acid and methanol. This reaction can be

seen in the below mechanism.

(1)

The hydrolysis reaction happens very slowly when done with distilled water, but through

the addition of a chemical catalyst, the reaction can be greatly accelerated. A chemical

catalyst is a chemical that does not interfere with the reaction but contains ions that speed

up the reaction. The catalyst in this reaction works by adding hydrogen ions, which are

contained in the reactants, therefore causing the reaction to push to form more products

and favour the forward reaction. Two different concentrations of hydrochloric acid were

used during this experiment as the catalyst. Although this experiment focuses on the

hydrolysis of methyl acetate, the reaction can also be reversed to a process called

esterification. When this reaction occurs, the solution will reach equilibrium between the

forward and reverse reactions. When equilibrium is reached the reaction rate will remain

2
the same unless the conditions of the reaction are changed, such as the addition of more

reagent or a change in temperature. At equilibrium the overall reaction rate will be equal

to the difference between the rate of hydrolysis, the forward reaction, and the rate of

esterification, the reverse reaction.

Overall Reaction Rate=Rate of Hydrolysis−Rate of Esterification (2)

The objective of the experiment requires the forward reaction to be favoured, which is

done by diluting the methyl acetate with a large amount of hydrochloric acid. This means

that the rate of esterification can be ignored for the purpose of this experiment. The

overall reaction rate is then equal to the rate of hydrolysis.

Overall Reaction Rate=Rate of Hydrolysis (3)

As stated in the lab manual, the reaction is first order with respect to methyl acetate and

water, and of order q with respect to H3O+. The initial reaction rate can be written as

follows:

+¿
H 3 O¿
¿ (4)
¿
Rate=k ' [C H 3 COOC H 3 ] [ H 2 O ] ¿

In the above equation, k’ represents the acid-independent rate constant, the square

brackets indicate the molar concentration of the compound inside them, and q represents

the order of the reaction with respect to H3O+. The equation can be simplified though

because the concentration of water will change very little during the reaction of a diluted

methyl acetate solution. The simplified equation can be written as follows:

+¿
H 3 O¿
¿ (5)
¿
Rate=k ' [C H 3 COOC H 3 ] ¿

3
The concentration of the hydrochloric acid also does not change during the reaction

because it is a catalyst, and so the reaction can be even further simplified by writing it in

terms of the acid-dependent constant, kH.

+¿
H 3 O¿
¿ (6)
¿
k H =k ' ¿

Because the concentration of the hydrochloric acid, represented by H3O+ in the equation,

remains constant throughout the reaction, the reaction can be considered pseudo-first

order. The final reaction rate equation is written as follows:

Rate=k H [ C H 3 COOC H 3 ] (7)

In order to determine the value of q, various concentrations of hydrochloric acid can be

used to evaluate kH. From this the integrated form of the pseudo-first order rate law can

be found.
t
Ct =C o e−k H
(8)

In the above equation, Ct represents the molar concentration of methyl acetate at a

specific time, t, and Co represents the initial molar concentration of methyl acetate. The

initial concentration of methyl acetate can be found through a series of steps, done as

follows:

mass
ρ= (9)
volume

mass
n= (10)
molar mass

n
C o= (11)
volume

4
In the above equations ρ represents the density of methyl acetate (0.927 g/mL) and n

represents the number of moles of methyl acetate. The density of methyl acetate

multiplied with the volume of methyl acetate used (10 mL) in the reaction result in the

mass of methyl acetate. This can then be divided by the molar mass of methyl acetate

(74.08 g/mol) to find the number of moles of methyl acetate. The final step is to divide

the number of moles by the volume of methyl acetate used, where the quotient will be the

initial concentration of methyl acetate.

In order to measure the rate of hydrolysis, which can also be thought of as the rate of

disappearance of methyl acetate over time, a series of titrations can be done. A titration is

a technique done in a laboratory using a calibrated burette. This technique is typically

used to determine the unknown concentration of a solution by titrating it with a solution

of known concentration. This means that the known concentration solution is slowly

added to the unknown concentration solution until equilibrium is reached, usually

measured using a chemical indicator. The indicator used in this experiment is

phenolphthalein, a weak and colourless acid. A few drops of indicator are added to the

unknown concentration solution before the titration begins. The equilibrium of

phenolphthalein can be seen in the below mechanism.

(12)

The addition of the phenolphthalein pushes the equilibrium towards the left, leaving the

solution colourless. The known concentration solution is then slowly added, NaOH is

5
used in this experiment as a base containing OH- ions, which pushes the equilibrium

towards the right by removing the hydrogen ions from the reaction and causing the

forward reaction to be favoured. When a forward reaction is favoured the titrant will turn

a faint pink colour. Whenever the faint pink colour of the solution persists, the

equilibrium point has been reached and the titration is complete. Knowing the volume of

sodium hydroxide used in the titration allows for the volume of acetic acid to be found

using the following equation.

Volume of Acetic Acid =Volume of NaOH titrated −10 mL (13)

10 mL must be subtracted from each amount of volume NaOH titrated because 10 mL

aliquots of solution were used to titrate during the experiment. Once the volume of acetic

acid is determined, it can be used in the following equation to find the concentration of

acetic acid.

(Volume of Acetic Acid )(0.1 M )

[ C H 3 COOH ]= 10 mL
(14)

Knowing the concentration of acetic acid allows for the concentration of methyl acetate

at a specific time, t, to be determined using the following equation.

Ct =[ HCl ] −[C H 3 COOH ] (15)

Applying the natural logarithm to both sides of the integrated pseudo-first order equation,

equation (8), can then give the following linear equation.

ln ( C t ) =−k H t+C o (16)

By plotting Ct as a function of time t for two different concentrations of hydrochloric

acid, two different kH values can be determined. From the above equation it can be said

that this relationship will result in a straight line with kH as the slope of the line. Through

6
the same principle of applying the natural logarithm to both sides of the equation,

equation (6) will become the following linear equation:

+¿
H 3 O¿
¿ (17)
ln ( k H )=q ln ¿

Plotting this equation with kH as a function of ln[H3O+] yields a straight line with q as the

slope. This allows for q to be determined. Knowing q allows for the acid-independent

constant, k’, to be found using the above equation. Because equation (17) is dependent on

temperature, it can evaluated at two different temperatures and two different values of k’

can be found. Using the below equation the Arrhenius activation energy, Ea, can be

calculated.

k1
T 1−¿ T × ln
2
k2
(18)
R T1 T2
E a= ¿

In equation (18), R represents the ideal gas constant (8.314472 JK-1mol-1), k1 and k2

represent the acid-independent rate constants at temperatures T1 and T2 respectively. The

temperatures in this equation are given in Kelvins. To convert from degrees Celsius to

Kelvins the following equation can be used.

Temperature ( K ) =Temperature ( ℃ ) +273.15 (19)

Experimental Procedure:

This experiment involved three sets of titrations. The first set of titrations was performed

using a methyl acetate solution and 0.100 M sodium hydroxide. The goal was to find data

for determining the acid-dependent rate constant, kH. A 10 mL volumetric pipette was

obtained and 10 mL of methyl acetate was pipetted into a 50 mL beaker. A 100 mL

7
volumetric pipette was obtained and 100 mL of 0.5000 M hydrochloric acid was pipetted

into a 250 mL beaker. An ice bath was prepared by filling a water bath with ice and water.

A titration apparatus was set up by obtaining a 50 mL calibrated burette and properly

clamping it to a prepared system in a vertical position slightly above the surface of the lab

bench. The burette was then filled with 0.100 M sodium hydroxide and the initial burette

reading was recorded. The 10 mL sample of methyl acetate was then added to the

hydrochloric acid in the 250 mL beaker. A 10 mL aliquot of the solution was transferred,

using a 10 mL volumetric pipette, into a 125 mL beaker. A few drops of phenolphthalein

were added to the 10 mL sample. The beaker containing the solution was placed in the

prepared ice bath for 1 minute to allow for the reaction to be slowed down enough for a

titration to be performed. After 1 minute had passed the beaker was removed from the ice

bath and immediately titrated with sodium hydroxide. The methyl acetate solution was

titrated until a faint pink colour persisted. Once the titration was complete a final burette

reading was taken in order to calculate the volume of acetic acid in the aliquot, which

would also allow for the concentration of acetic acid to be solved. The titration was

repeated four more times at fifteen-minute intervals in order to determine the

concentration of acetic acid at those times, therefore following the progression of the

reaction.

The next part of the experiment was focused on finding the acid-independent rate

constant, k’. In order to do this it was necessary to perform a second set of titrations using

a mixture of methyl acetate and 1.000 M hydrochloric acid. The same procedure as

mentioned above was followed for this part of the experiment.

8
The final part of the experiment was focused on finding the Arrhenius activation energy,

Ea. This required that another set of titrations be performed using 0.5000 M hydrochloric

acid. The same procedure as the first part of the experiment was followed, with the

exception that the solution was placed in a thermostated bath at a temperature of 35

℃.

This allowed for two different k’ values to be calculated, subsequently allowing for the

Arrhenius activation energy to be solved.

The initial procedure prepared for the experiment in week 1 involved two more sets of

titrations. One set of titrations would have been done using 0.7500 M hydrochloric acid.

The second set of titrations would have been done using a solution heated to a higher

undetermined temperature. Upon realizing that only three sets of data were necessary to

calculate the desired results, it was decided to eliminate these two steps to make the lab

more efficient time-wise and in terms of materials used. The three sets of data that were

necessary to calculate the desired results were the three sets of titrations mentioned

above, namely the titration done with 0.5000 M hydrochloric acid, the titration done with

1.000 M hydrochloric acid, and the titration done with 0.5000 M hydrochloric acid at a

temperature of 35 ℃ .

The guiding questions provided a series of steps that would be important for completing

the objectives of the lab. By understanding the equations to be used in the lab, it became

easy to see what information would be needed from the lab to solve the equations.

Knowing what information needed to be found allowed for a procedure to be developed

that involved the provided materials mentioned in the lab manual as well as provided all

the necessary information to solve the equations.

9
The below table lists the uncertainties associated with the equipment used for

measurements in the lab.

Table 1: Uncertainty of Measuring Instruments

Instrument Uncertainty
10 mL Volumetric Pipette ± 0.012 mL
100 mL Volumetric Pipette ± 0.08 mL
50 mL Burette ± 0.05 mL

Results:

The following table presents the information collected and calculated from the titration

with 0.5000 M hydrochloric acid at 25 ℃ . The most important part of this table is the

natural logarithm of the concentration of methyl acetate. This information is used in

figure 1 below to determine kH by graphing the natural logarithm of the concentration of

methyl acetate as a function of time.

Table 2: Volume of NaOH titrated at end-point and concentration of acid in 10 mL

sample at fifteen-minute time intervals with 0.5000 M HCl at 25 ℃
Time Volume of Volume of Concentratio Concentratio ln[Methyl
(mins) NaOH used in Acetic Acid n of Acetic n of Methyl Acetate]
the titration in sample Acid (M) Acetate (M) (M)
(mL) (mL) ( ± 0.05 M) ( ± 0.05 M)
( ± 0.05 ( ± 0.05
mL) mL)
0 55.50 45.50 0.21 0.94 -0.06
15 60.20 50.20 0.25 0.92 -0.08
30 65.40 55.40 0.26 0.90 -0.10
45 70.90 60.90 0.28 0.88 -0.13
60 74.40 64.40 0.29 0.87 -0.14

10
 0.00
0 10 20 30 40 50 60 70
-0.02
-0.04
-0.06
f(x) = - 0x - 0.06
ln[Methyl Acetate] (M) -0.08
-0.10
-0.12
-0.14
-0.16
Time t (mins)

Figure 1: ln[Methyl Acetate] vs. Time with 0.5000 M HCl at 25 ℃

The below table presents the data collected and calculated from the titration with 1.000 M

hydrochloric acid at 25 ℃ . The important information contained in this table is the

natural logarithm of the concentration of methyl acetate, which is graphed as a function

of time in figure 2.

Table 3: Volume of NaOH titrated at end-point and concentration of acid in 10 mL

sample at fifteen-minute time intervals with 1.000 M HCl at 25 ℃
Time (mins) Volume of Volume of Concentratio Concentratio ln[Methyl
NaOH used Acetic Acid n of Acetic n of Methyl Acetate]
in the in sample Acid (M) Acetate (M) (M)
titration (mL) ( ± 0.05 M) ( ± 0.05 M)
(mL) ( ± 0.05
( ± 0.05 mL)
mL)
0 115.00 105.00 0.95 0.16 -1.83
15 120.70 110.70 1.00 0.11 -2.20
30 130.00 120.00 1.09 0.04 -3.22
45 139.20 129.20 1.17 0.02 -3.91
60 147.60 137.60 1.25 0 ---

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 12.00

10.00

8.00

6.00
ln[Methyl Acetate] (M)
4.00

2.00

0.00
0 f(x) =10 20 30 40 50 60 70
Time t (mins)

Figure 2: ln[Methyl Acetate] vs. Time with 1.000 M HCl at 25 ℃

The following table presents the data collected and calculated from the titration with

0.5000 M hydrochloric acid at 35 ℃ . The main focus of this table is the natural

logarithm of the concentration of methyl acetate, which is graphed as a function of time

in figure 3.

Table 4: Volume of NaOH titrated at end-point and concentration of acid in 10 mL

sample at fifteen-minute time intervals with 0.5000 M HCl at 35 ℃
Time (mins) Volume of Volume of Concentratio Concentratio ln[Methyl
NaOH used Acetic Acid n of Acetic n of Methyl Acetate]
in the in sample Acid (M) Acetate (M) (M)
titration (mL) ( ± 0.05 M) ( ± 0.05 M)
(mL) ( ± 0.05
( ± 0.05 mL)
mL)
0 49.50 39.50 0.18 0.96 -0.04
15 57.30 47.30 0.22 0.93 -0.07
30 66.20 56.20 0.26 0.90 -0.11
45 74.80 64.80 0.30 0.87 -0.14
60 83.50 73.50 0.33 0.83 -0.19

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 0.00
0 10 20 30 40 50 60 70
-0.02
-0.04 f(x) = - 0x - 0.04
-0.06
-0.08
ln[Methyl Acetate] (M) -0.10
-0.12
-0.14
-0.16
-0.18
-0.20
Time t (mins)

Figure 3: ln[Methyl Acetate] vs. Time with 0.5000 M HCl at 35 ℃

The following table presents the data calculated using the information collected during

the titrations of various concentrations of HCl. The information in this table can be

graphed to find the order of the reaction with respect to H3O+, q, as presented in figure 4.

The information can also be graphed to determine the Arrhenius activation energy of the

reaction, Ea, as presented in figure 5.

Table 7: Values of kH and ln(kH) for various concentrations of hydrochloric acid at 25

⁰C
Concentratio kH /min- Uncertainty ln(kH Uncertainty Slope of Activation
1
n of HCl at of kH /min-1 /min-1) of Figure 6 Energy
25 ℃ (M) ln(kH/min-1) (q) from
Figure
7(Ea)
(kJ/mol)
0.500 0.0014 ± 1.5000 x -6.57 ± 0.33 5.11 ± 44.17
10-7
1.000 0.0484 ± 1.5000 x -3.03 ± 0.33 0.05
10-7

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 0.00
-0.80 -0.70 -0.60 -0.50 -0.40 -0.30 -0.20 -0.10 0.00
-1.00

-2.00

-3.00
lnkH f(x) = 5.11x - 3.03
-4.00

-5.00

-6.00

-7.00
ln[HCl] (M)

Figure 4: lnkH vs. ln[HCl] with various concentrations of HCl at 25 ℃

0.00
296.00 298.00 300.00 302.00 304.00 306.00 308.00 310.00
-1.00
-2.00
-3.00
lnkH f(x) = 0.35x - 112.12
-4.00
-5.00
-6.00
-7.00
Temperature (K)

Figure 5: lnkH vs. Temperature with 0.5000 M HCl at various temperatures

Calculations:

Moles of NaOH:

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 [ NaOH ] × ( volume NaOH ) × ( 0.001 L )
Moles NaOH=
1mL

(0.1000 M )(10 mL)(0.001 L)

Moles NaOH= =0.001 moles NaOH
1 mL

Moles of HCl:

[ HCl ] × ( volume HCl ) × ( 0.001 L )

Moles HCl=
1 mL

( 0.5000 ) (10 mL ) ( 0.001 L )

Moles HCl= =0.005 moles HCl
1 mL

Concentration of Acetic Acid:

moles acetic acid 0.0035 mol

[ Acetic Acid ] = [ Acetic Acid ] = =0.35 M
volume acetic acid ( 10 mL ×0.001 L )

Error Calculation for the Concentration of Acetic Acid:

2 1

[( ) ] =0.05
2 2
0.1 mol 1.0 mol 0.1 mL
∆ [ Acetic Acid ] =[ Acetic Acid ]
L
X 0.1 mL +
L ) (X 0.1 mL +
10.0 mL )( 2

Initial Concentration of Methyl Acetate (Co):

ρ 10 mL Methyl Acetate 1000 mL

C o= × ×
MM 100 mL HCl 1L

(¿ 0.932 g
mL ) 10 mL 1000 mL
× × =1.29 M
74.08 g 100 mL 1L
mol

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Concentration of Methyl Acetate at Time t (Ct):

Ct =C o−[ Acetic Acid ] =1.29 M −0.35 M =0.94 M

Slopes of Graphs of Varying Concentrations of HCl (kH):

0.5000 M HCl:

k H =−slope=−(−0.0014 )=0.0014

1.000 M HCl:

k H =−slope=−(−0.0484 )=0.0484

Acid-Independent Rate Constant (k’):

+¿
H 3 O¿
ln ( k ' ) =ln ( 0.0014 )+5.11 ( 0.5000 )=−6.57+3.54=−3.03
'
ln ( k ) =ln ( k H ) +q ¿

−3.03 −1
e =0.0484 min

Arrhenius Activation Energy (Ea):

k1
T 1−¿ T × ln
k2
2 ( 8.314 J K −1 mol−1 ) ( 298.15 K ) (308.15 K ) 0.0484 min−1
¿ × ln
R T1 T2 298.15 K−308.15 K 0.0863 min−1
E a= ¿

−1 −1
Ea =44173.34 J mol =44.17 kJ mol

Discussion:

The results calculated for the acid-dependent rate constant at room temperature were

0.0014 min -1 for 0.5000 M HCl and 0.0484 min-1 for 1.000 M HCl. The value of q as

calculated in figure 4 is 5.11. The Arrhenius activation energy calculated in figure 5 is

44.17 kJmol-1. Two acid-independent rate constants, calculated using equation (17), were

used to calculate the Arrhenius activation energy. They were 0.0484 min-1 and 0.0863

16
min-1. The two acid-independent rate constants were calculated at two different

temperatures, 25 ℃ and 35 ℃ . Because two different temperatures can be used to

calculate the Arrhenius activation energy, it can be said that the rate of the reaction

depends partly on temperature. The high value of q, which represents the order of the

reaction with respect to [H3O+], means that the rate of the reaction is affected greatly by

the concentration of the acid. Both of these conclusions can be supported by the results

obtained in the lab as the rate of the reaction increased as temperature increased and as

the concentration of hydrochloric acid increased. No literature including experimentally

accepted values for q and Ea could be found, therefore the obtained results could not be

compared to anything in order to determine if the results were valid. The calculated

Arrhenius activation energy is relatively high, which means that the reaction requires a

lot of energy in order to move forward. This also complies with the previously stated

facts of the hydrolysis of methyl acetate being a very slow reaction. The high activation

energy is the reason a catalyst was added in the beginning of the experiment as a catalyst

lowers the activation energy of a reaction therefore allowing it to move forward at a

quicker rate. Without the catalyst the reaction would have an even high activation energy,

requiring even more energy, and therefore having an overall slower reaction.

There are multiple sources of error in this lab that could lead to incorrect results for the

experiment. Each piece of measuring instrument used during the reaction, namely the

burette and volumetric pipettes, has an associated uncertainty that propagate throughout

the multiple measurements taken. There is also a potential source of error in the inhibiting

of the reaction. The reaction mixture is placed in an ice bath for one minute before

titrating in an attempt to slow the reaction to a stop, but the reaction never really stops

17
and so even as the titration is being performed the reaction is still occurring. This means

that the results obtained are not an exact measurement and that will affect the entirety of

the lab. This is also why the faint pink colour of the titrated solution will fade after a

while, as the reaction has continued and the sodium hydroxide present is no longer

sufficient to keep the reaction at equilibrium. Another potential source of error is the time

taken to perform each titration. Although each titration was done at a set time interval of

fifteen minutes, the amount of time to complete each titration varies. This variation

occurs because of human error and the amount of sodium hydroxide needed, which will

increase the time of the titration by requiring the burette to be refilled. A final source of

error comes from the sodium hydroxide itself. Sodium hydroxide is a hygroscopic

compound, meaning that it will react with the moisture in the air, therefore diluting the

solution. Sodium hydroxide also reacts with the carbon dioxide in the air, which would

reduce the concentration of sodium. Sodium is also an inorganic salt, which tend to react

with sunlight and dilute the solution. Because of this reactivity of sodium hydroxide the

proper way to store the solution is in a plastic bottle away from sunlight. However, during

this experiment, sodium hydroxide was added to the burette. While the sodium hydroxide

was in the burette it was exposed to the open environment of the lab, meaning the

solution could have reacted in many ways and potentially made the solution more dilute.

A more dilute solution would mean that more sodium hydroxide was required to

complete the titration, therefore giving inaccurate results for the experiment. Despite

these potential sources of error, the objectives of the lab were completed, although it is

unknown whether the obtained results were the correct ones.

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There are several ways this lab could be improved. One improvement would be to

perform titrations at several more temperatures. This experiment was completed using

only two temperatures, 25 ℃ and 35 ℃ , which was done with the intention of

making the lab more time-efficient. Having completed the experiment it can be concluded

that having information for multiple temperatures would allow for a better analysis of the

reaction and therefore more accurate results for the desired values. Another way to

improve the lab would be to perform titrations at various concentrations of acid. As

determined, the reaction does depend on the concentration of acid. However, if more

concentrations could have been used then the relationship between the reaction progress

and the concentration of the acid could have been further analysed and more accurate

results for the acid-dependent rate constant could have been found. Even without varying

temperatures or acid concentrations, more titrations could be performed as is already

stated in the procedure. More titrations, potentially done at more frequent time intervals,

would allow for a better following of the reaction progress. The final way to improve the

lab refers back to a potential source of error. Because the sodium hydroxide is so reactive

with the environment it would useful to cover the burette to stop exposure to air and

minimize the exposure to sunlight in some way. Similarly, the reaction mixture could also

be covered to prevent the reaction from reacting with the surrounding. The less the

chemicals react with the environment, the better the results should be for the experiment.

The picture below shows a potential energy diagram for the hydrolysis of methyl acetate.

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Conclusion:

The goal of this lab was the experimentally find the order of the reaction with respect to

the concentration of the hydronium ions, both the acid-independent and acid-dependent

rate constants, and the Arrhenius activation energy value. Each of these results were

obtained throughout the experiment. The order of the reaction with respect to the

concentration of H3O+ was determined to be 5.11. The acid-independent and acid

dependent rate constants for a reaction with 1.000 M HCl at room temperature were both

0.0484 mins-1. The acid-independent and acid-dependent rate constants for a reaction with

0.5000 M HCl at room temperature were 0.0014 mins-1 and 0.0484 mins-1 respectively.

The Arrhenius activation energy of the reaction was determined to be 44.17 kJmol-1.

These values were obtained through multiple titrations using various concentrations of

hydrochloric acid and temperatures.

References:

1) Atkin, P. de Paula, J; Physical Chemistry; 9th edition. 2009

2) Bryce, D; CHM 2330 Physical Chemistry Lab Manual; 2006; pp. 13-17.

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3) Kirby, A.J; Comprehensive Chemical Kinetics Volume 10; pp 57-58

4) Phenolphthalein Equilibrium. http://acid-base-

titrations.blogspot.ca/2007/09/indicator.html (accessed March 3rd, 2016)

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