Equilibrium Constant for Hydrolysis

of Methyl Acetate

Colleen Arthur-Brewster

Chem 112L-001

Mike Fisher

Performed: October 8, 11, & 15

Due: October 24, 2019

Abstract

The purpose of this lab was to determine the equilibrium constant for methyl acetate hydrolysis (

K eq ). It is determined the concentration of acetic acid, methanol, and methyl acetate it reached

equilibrium. Measured the amount of acetic acid that was produced in the forward hydrolysis

reaction by aliquot from the equilibrium mixture. It is determined that the equilibrium constant

for hydrolysis Methyl Acetate, K eq , is 3.26(±8.09) at 23.8 ˚C with an error of 39.63% for trial

one (determined by the literature value, 5.40 [3]) and 2.92(±2.24) at 23.9 ˚C with an error of

45.98% for trial 2 (determined by the literature value, 5.40). It was determined that this
experiment we had low precision and high accuracy results, which may have been due to a

systematic error.

Introduction

In this experiment we study the hydrolysis of neat methyl acetate in 0.099 ±0.001 M HCl. This

hydrolysis reaction will occur spontaneously at room temperature and the addition of acid (HCl)

will only affect the amount of time the reaction it takes the reaction to reach equilibrium. In this

experiment the HCl is acting as a catalyst. To determine the equilibrium constant for methyl

acetate hydrolysis ( K eq ), we need to determine the concentrations of acetic acid, methanol, and

methyl acetate once the reaction has reached equilibrium. Not all chemical reactions go from

reactant to products. Some reach a state known as equilibrium where the forward reaction rate

equals the backward reaction rate. The equilibrium can be measured with a number known as the

equilibrium constant ( K eq ). The formula for determining the ( K eq ), is seen in equation 1.

[ C H 3 COOH ] [C H 3 OH ]
K eq = Equation 1
[C H 3 COOC H 3 ]

The K eq tells us how far the reactants will go to products when equilibrium is reached. The higher

the K eq the higher the concentration of products will be present in equilibrium. Using the concept

of K eq , Li et. al. studied how different particle sizes of nano-copper effected its surface

thermodynamic properties. By dissolving different particle sizes of nano-copper in sulfuric acid,

and determining the equilibrium constant at different temperatures, they were able to determine a

linear relationship between temperature and the surface tension of nono-copper [5]. Using the

principles of K eq , methyl acetate was reacted with a water and hydrochloric acid solution and
allowed to sit undisturbed for approximately 10 days, with the intention that it would reach

equilibrium. The equilibrium equation for this reaction is equation is:

C H 3 COOC H 3(aq) + H 2 O ⇌ C H 3 COOH +C H 3 OH Equation 2

Phenolphthalein was then added to the solution and it was titrated with sodium hydroxide in

order to determine the concentration of acetic acid that had formed at equilibrium the chemical

equation for the titration process are as follows:

−¿¿
+¿+C l (aq) ¿
NaO H (aq)+ HC l (aq) → H 2 O (l) + N a(aq ) Equation 3

−¿¿
+¿+C H 3 COO( aq) ¿
NaO H (aq)+ C H 3 COO H (aq ) → H 2 O(l ) + N a(aq ) Equation 4

It is assumed that the reaction had reached equilibrium on the first day of the titration, to test the

assumption we allowed the reaction to set for another approximate 48 hours and repeated the

titration process. By determining the moles of NaOH used in each aliquot, since it is a 1:1

stoichiometry, the moles of acid can be deduced. Since a known concentration of HCl was used

in the initial reaction, the moles of acetic acid were able to be determined.

Experimental

Experimental steps were followed as stated in the laboratory handout provided [1]. One week

prior to this experimental lab, prepared solution to allow the reaction to reach equilibrium.

Cleaned a 150 mL beaker with ~10 mL of 0.0975±0.0003 M HCl. Measured out ~100 mL of

0.0975±0.0003 M HCl in clean beaker. Pulled up approximately 10-15 mL of 0.0975±0.0003 M

HCl into 25.00 pipet to prepare clean pipet. Using a volumetric pipet, measured 50.00 mL of

0.0975±0.0003 M HCl into an Erlenmeyer flask. Tared the Erlenmeyer flask containing the HCl
and added 3.007 g of neat methyl acetate. Placed a stopper and wrapped top of the Erlenmeyer

flask with parafilm to allow system to reach equilibrium.

Day one of procedure we analyzed the acetic acid produced in the solution prepared one week

prior to exam. Condition the 5.00 mL pipette by filling it approximately 1/3 full of 0.221±0.006

M NaOH and disposed of solution in waste beaker. Accurately pipetted 5.00 mL of the

equilibrated solution into a clean 125 mL Erlenmeyer flask and added 3 drops of phenolphthalein

to the solution. Conditioned the burette with based used in the titration (NaOH). The burette

was then mounted to burette clamp and burette was filled to the above the zero line with and

additional NaOH, bubbles were removed from burette. The burette containing the NaOH was

drained to 0.90 mL, which was our initial burette reading. Titrated the aliquot with 0.221±0.006

M NaOH solution until a permanent faint color appeared for approximately 30 seconds.

Repeated titrations five times. Recorded the volumes of burette after each titration with the

temperature when the solutions turned a permanent pink solution. The total volume of

0.221±0.06 M NaOH used on day one was 111.35 mL and the average temperature was 23.8 ˚C.

Day two of procedure, repeated a titration on another 5.00 mL aliquots upon return to the

following lab period. All steps repeated to condition the pipette and burette. Two additional

titrations were performed. The data gathered was the initial reading of burette containing the

NaOH and the final reading after each titration. The temperature was also recorded of the

solution once the solution turned a permanent faint pink color. The total volume of 0.221±0.06

M NaOH used on day two was 37.20 mL and the average temperature was 23.9 ˚C.

Results & Discussion

After 50 mL of 0.0975±0.0003 M HCl was measured into a volumetric flask, 3.007 g of neat

methyl acetate was mixed into the solution. The flask was then stopped and wrapped in parafilm

for approximately 10 days to allow the solution to reach chemical equilibrium. The chemical

equilibrium equation is:

C H 3 COOC H 3(aq) + H 2 O ⇌ C H 3 COOH +C H 3 OH Equation 2

After ~10 days, the Methyl/HCl solution was titrated in 5 ml aliquots using 0.221±0.006 M

NaOH. The equations for this titration are:

−¿¿
+¿+C l (aq) ¿
NaO H (aq)+ HC l (aq) → H 2 O (l) + N a(aq ) Equation 3

−¿¿
+¿+C H 3 COO( aq) ¿
NaO H (aq)+ C H 3 COO H (aq ) → H 2 O(l ) + N a(aq ) Equation 4

An indicator called Phenolphthalein was added to the solutions. That was precisely 3 drops

added. An addition of NaOH was added until the Methyl/HCl solution turned a permanent faint

pink in color for approximately ~ 30 seconds. On day one, the first titration took 18.40 ml of

NaOH at 24.0 ˚C. Run 2 took 18.50 ml of NaOH at 24.0 ˚C, run 3 took 18.55 ml of NaOH at

23.75 ˚C, and run 4 took 18.65 ml of NaOH at 23.5˚C, run 5 took 18.70 ml of NaOH at 23.75˚C,

and run 6 took 18.55 ml of NaOH at 23.75˚C for the solution to produce a permanent faint pink

color. The methyl/HCl solution was stopped and wrapped in parafilm for another ~48 hours. A

second trial of titrations were completed to verify the reaction was at equilibrium when it was

titrated on the first day.

On the second day, run 1 took 18.50 ml of NaOH at 23.5 ˚C and run 2 took 18.70 ml of NaOH at

24.25˚C. Half drops of aliquot were carefully added to insure over titration did not occur. Both

runs produced a permanent faint pink colored solution.

To determine ¿ ¿), of the concentration of the reactants and product were then determined. Using

the equation 3 and 4, the number of moles of solution is to equal the number of moles of NaOH

used during the titration. First, determine the number of moles used in the 6 data runs on day

one:

0.221 M NaOH 1L
111.35 ml NaOH total· · =0.0246 mol NaOH total
1L 1000ml

To determine the moles of NaOH in each aliquot, the calculation for day one run 1 is:

18.40 ml NaOH mol∈5 ml aliquot

= =0.00407 mol NaOH ∈5 ml per aliquot
111.35ml NaOH total 0.0246 mol total

There is a 0.00407 mol of acid in the solution, because there is a 1:1 stochiometric ratio. There is

HCl in the solution, must determine the number of moles of acetic acid. To determine this by

subtracting the known number of moles of HCl in each aliquot from the number of moles of acid.

For day one and run 1 there was 0.00361 mol of acetic acid per aliquot. Because K eq is

determined by concentration, the total volume of solution was determined. Used the literature

value of the density of methyl acetate, 0.932 g/cm3[4], the volume of methyl acetate added to the

50.00 ml of 0.0975±0.0003 M HCl solution was determined:

1 ml
3.007 g methyl acetate· =3.226 ml methyl acetate
0.932 g methyl acetate

The total volume of solution was 53.226 ml. Then the equilibrium concentrations of each

compound in the aliquot were determined:

0.00361mol methyl acetate 1000 ml

· =0.154 M Methyl acetate
18.40 ml +5 ml 1L
The concentrations of acetic acid and methane and methyl acetate was included because water is

a pure liquid with an activity of 1. It is determined that the rate constant for days one and each

run was:

0.154 M acetic acid·0.154 M methane

=2.78
0.00855 M methyl acetate

The K eq for run 1 of day 1 was 2.78. Data calculations were made using Microsoft Excel for all

the runs on day one and day two. The average for both days was 3.18 (±6.71) at 23.8 ˚C with an

error of 41.9% from the literature value. It is determined that the equilibrium constant for

hydrolysis Methyl Acetate, K eq , is 3.26(±8.09) at 23.8 ˚C with an error of 39.63% for trial one

(determined by the literature value, 5.40 [3]) and 2.92(±2.24) at 23.9 ˚C with an error of 45.98%

for trial 2 (determined by the literature value, 5.40 [3]). These results were reported separate due

to the low reported ( K eq ) value. It was justified that we were precise with our measurements for

days one and two.

Conclusion

In conclusion it was assumed that the reaction was at equilibrium when the titration began. In

this experimental reaction we determine that we were precise in with our measurements and

results. The NaOH added on days one and two per aliquot were precise measurements of 111.35

mL and 37.20 mL. This experiment is repeatable and validated by comparing results with

another group in the lab by confirming the comparable ( K eq ¿ of approximately ~2.5 range. The

results of the ( K eq ) was nearly half of reported literature value of 5.40 [3]. It was determined that

the results were not accurate due to a systematic error, which was possibly due to slow aliquots

with half drop aliquots for a very faint pink solution. This experiment we had low precision
which was compared to other groups in the labs whom had the same ( K eq ) value, but determine

we had high accuracy when compared to the reported literature value. It is determined that the

equilibrium constant for hydrolysis Methyl Acetate, K eq , is 3.26(±8.09) at 23.8 ˚C with an error

of 39.63% for trial one (determined by the literature value, 5.40 [3]) and 2.92(±2.24) at 23.9 ˚C

with an error of 45.98% for trial 2 (determined by the literature value, 5.40). These results were

reported separate due to the low reported ( K eq ) value. It was justified that were precise with our

measurements for days one and two.

References

1. Experiment 6: Equilibrium constant for the Hydrolysis of Methyl Acetate. [Online]

Available https://1drv.ms/w/s!AhaCe3ey5f9igT5_dZCYQ4BfdE-X

2. Burdge, Julia and Overby, Jason. Chemistry: Atoms First, Third Edition. McGraw Hill.

Publishing 2015: p 716-763

3. International Critical Tables of Numerical Data, Vol. 7., page 139.

htttp://tinyurl.com/y7q7gd7f

4. pubchem.ncbi.nlm.nih.gov/compound/methyl_acetate

5. Li z, FuQ, Xue Y, Cui Z. Size-dependent surface thermodynamic properties of nono-

copper and its determination method by equilibrium constant. Journal of Materials

Science. 2018; 53(3):2171-2180. doi:10.1007/s10853-017-1646-9.

Appendix

*See attached Excel Spread Sheet