Physical Chemistry Lab II

CHEMICAL KINETICS:
THE HYDROLYSIS OF METHYL ACETATE

Objectives
1. To evaluate the hydrolysis of methyl acetate by studying its chemical kinetics.
2. To quantify the activation energy requirement of the reaction.
3. To determine the change in enthalpy and change in entropy of the reaction/

Apparatus
Electronic Water Bath, timer, Erlenmeyer flasks, graduated cylinders, buret, pipet,
test tubes

Reagents
Distilled water, methyl acetate, 1.0M HCl solution, standard NaOH solution,
phenolphthalein

Procedure

Note: Careful pipetting and titrating techniques are essential if good data are to be
obtained. The temperature should be controlled as precisely as possible.

1. Obtain about 50 mL methyl acetate in a large test tube and 300 mL 1.0 M HCl in
an Erlenmeyer flask. Allow these solutions to equilibrate in 25°C bath. Also
equilibrate a flask containing about 200 mL of deionized water.

2. Into a dry 250 mL Erlenmeyer flask pipet 50 mL of the HCl and 50 mL of water.
To initiate the reaction add from a pipet 10 mL of methyl acetate. Start the timer
when the pipet is half emptied. Mix the solution thoroughly and keep it in the
bath.

3. As soon as possible, withdraw a 5 mL aliquot of the reaction mixture and transfer

it to a 150 mL Erlenmeyer which contains approximately 50 mL of water. The
receiver should be pre-chilled in an ice bath to make sure that the hydrolysis is
sufficiently slowed. Note the time at which the pipet has been half emptied.

4. Titrate the diluted aliquot as soon as possible with standard NaOH using
phenolphthalein as the indicator.

5. Repeat steps 3 and 4 at 10 minute intervals for one hour and for 20 minute
intervals for another hour, if possible. Make sure that the pipet used to withdraw
each 5 mL aliquot is clean and dry.

6. At some convenient time titrate 2 or 3 aliquots of the equilibrated HCl so that the
molarity at 25°C will be known accurately.

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 Physical Chemistry Lab II

7. Repeat the above procedure using 100 mL 1.0 M HCl and 10 mL methyl acetate
as the reaction mixture. This reaction will proceed more rapidly, so aliquots
should be withdrawn at shorter intervals. Duplicate runs should be performed if
possible. An efficient student pair should be able to follow two or more properly
spaced reactions at the same time.

8. Repeat the procedure at 35°C using the reaction conditions given in step 2.
Remember that the rate will be about double that at 25°C, so aliquots will have to
be withdrawn at shorter intervals. Determine the molar concentration of the HCl
at 35°C.

Treatment of Results

1. For each aliquot calculate Ct (or a quantity proportional to Ct). (The density of
methyl acetate is 0.9273 g/mL at 25°C and 0.9141 g/mL at 35°C, and the
molecular weight is 74.08) Plot ln C t versus t for each set of data. Evaluate the
acid-dependent rate constant, kH, in seconds-1. Use the uncertainty in the slope to
evaluate the 95% confidence limits of kH.

2. From runs at 25°C with different concentrations of HCl determine the order with
respect to H3O+ and its uncertainty. Use the nearest whole-number value of q to
calculate kF’ for each run. Also obtain the uncertainty in kF’. (Assume negligible
error in q for these calculations.)

3. Evaluate Ea, ΔH°↕, and ΔS°↕ using the temperature dependence data.

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School of Chemical Engineering and Chemistry
 Physical Chemistry Lab II

Group No._________
Date:_______________________
Instructor:________________________

Name Signature
Leader: ____________________________ ______________________________
Members: ____________________________ ______________________________
____________________________ ______________________________
____________________________ ______________________________
____________________________ ______________________________

FINAL DATA SHEET

A. Determination of Hydrolysis Rate at Room Temperature and Lower

Concentration of HCl

Estimated Actual Moles of Concentratio

Time of Volume Concetration
Reaction Reaction Acetic n of Methyl
Withdrawa of NaOH of Acetic
Time, Time, Acid in Acetate Left,
l of Aliquot used, mL Acid, mol/L
min min Aliquot mol/L
0
10
20
30
40
50
60
80
100
120

Concentration of HCl is reaction mixture, mol/L = ____________________________

B. Determination of Hydrolysis Rate at Room Temperature and Higher

Concentration of HCl

Estimated Actual Moles of Concentratio

Time of Volume Concetration
Reaction Reaction Acetic n of Methyl
Withdrawa of NaOH of Acetic
Time, Time, Acid in Acetate Left,
l of Aliquot used, mL Acid, mol/L
min min Aliquot mol/L
0
10
20
30

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School of Chemical Engineering and Chemistry
 Physical Chemistry Lab II

40
50
60
80
100
120

Concentration of HCl is reaction mixture, mol/L = ____________________________

C. Determination of Hydrolysis Rate at High Temperature and Lower

Concentration of HCl

Estimated Actual Moles of Concentratio

Time of Volume Concetration
Reaction Reaction Acetic n of Methyl
Withdrawa of NaOH of Acetic
Time, Time, Acid in Acetate Left,
l of Aliquot used, mL Acid, mol/L
min min Aliquot mol/L
0
10
20
30
40
50
60
80
100
120

Concentration of HCl is reaction mixture, mol/L = _______________________

Acid-dependent rate constant at low HCl concentration = _____________________

Acid-dependent rate constant at high HCl concentration = _____________________

Order of reaction with respect to HCl concentration = _____________________

Eact of the reaction = _____________________

ΔH° of the reaction = _____________________

ΔS° of the reaction = _____________________

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School of Chemical Engineering and Chemistry