CM151L Physical Chemistry Laboratory

2nd Quarter SY 2019-2020

Chemical Kinetics: Hydrolysis of Methyl Acetate

Sanin, Carlos Lorenzo S.; Lagumbay, Alexis; Rodriguez, Edriane 1, Edna Calderon2

1Student(s), Subject/Section, School of Chemical, Biological, Material Engineering and Sciences, Mapua University; 2Professor, School of Chemical, Biological, Material
Engineering and Sciences, Mapua University

ABSTRACT
The rate of a reaction determines the speed that a chemical reaction proceeds, either how fast a reactant is consumed or how
fast a product is produced. This is often expressed by the concentration of a product or a reactant. The effect of temperature,
concentration, and catalyst in the kinetics of a chemical reaction were examined in the titration of a pre-chilled solution of methyl
acetate, deionized water, and 1 M hydrochloric acid using standard sodium chloride solution at varying temperature and
concentration condition. The main focus of this experiment is to study how the hydrolysis of methyl acetate forming acetic acid
can determine the activation energy, as well as the change in entropy and enthalpy of the system using the Arrhenius Equation
and acid-dependent rate when the titration is done in a 10 minute interval for 60 minutes, and then 20 minute interval for another
hour. Moreover, a ln concentration vs. time graph was plotted in order to see the relationship between the concentration and the
rate of reaction, to which both varies directly with each other. Findings show that the hydrolysis of methyl acetate has an
activation energy of 27966.85 J/mol, an enthalpy change of 27966.85 J/mol, and an entropy change of - 93.80127 J/mol-K.
Keywords: Chemical Kinetics, Rate of a Reaction, First Order Rate Equation, Hydrolysis, Acid-Dependent Rate, Arrhenius Equation,
Activation Energy, Enthalpy, Entropy

INTRODUCTION

Chemical kinetics is the branch of physical chemistry that
concerns the study and discussion of chemical reactions with
respect to reaction rates, variables affecting the rates,
formation of intermediates, steps or mechanism of reactions
among others. It as well encompasses the construction of
mathematical models that could hypothetically represent the
observed characteristics of a certain chemical reaction. The
rate of reaction is loosely defined as the change in
concentration of a particular species, may it be the reactant
or product, per unit time or in other terms, the rate at which
the reactant disappears or at which the product forms. It
depends on various factors such as: (a) availability of
reactants and its surface are; (b) species concentration; (c)
temperature; (d) pressure; and (e) the presence of catalyst
(Atkins & de Paula, 2006). Through the modification of these
conditions, one may be able to optimize a chemical reaction
to meet the desired results. A thorough understanding of
chemical kinetics begins with the knowledge of the rate laws
of reactions, otherwise known as rate equations. These
equations relate chemical reaction rates with concentrations
or pressures of reactants and other constant parameters,
such as the rate constant and the partial reaction orders
(Chang & Goldsby, 2011). For the following hypothetical
reaction
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
the rate equation is normally written as
r = k[A]𝑥 [B] 𝑦
where r is the rate of reaction, k is the rate constant, x is the
order of the reaction with respect to reactant A and y is the
order of reaction with respect to reactant B. In addition, one
may also express the rate of a chemical reaction by obtaining
the differential of one specie with respect to time, as shown
below.
1 𝑑[𝐴] 1 𝑑[𝐵] 1 𝑑[𝐶] 1 𝑑[𝐷]
𝑟=− =− =− =−
𝑎 𝑑𝑡 𝑏 𝑑𝑡 𝑐 𝑑𝑡 𝑑 𝑑𝑡
The reaction rate is always positive and so the negative sign
denotes that the reactants are being consumed in the
reaction, thus their amount decreases over time. With these
equations, one can form a differential equation, in which
through evaluation, would yield to a linear relationship
between the concentration of the reactants and time. The
various forms of the integrated rate equations depend on the
order of the reaction with respect to the reactant(s) under
consideration. The first of the common order of reactions is
the zero-order reaction, where the rate does not depend on
the concentration of any of the reactants. For the following
reaction,

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𝑎𝐴 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑎𝐴 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

the differential equation would be: The rate equation would then be:

𝑡 𝑡
[𝐴] [𝐴]
𝑑[𝐴]
∫ 𝑑[𝐴] = ∫ −𝑎𝑘𝑑𝑡 ∫ 2
= ∫ −𝑎𝑘𝑑𝑡
[𝐴]𝑜 [𝐴]𝑜 [𝐴]
0 0

which would yield the following equation upon evaluation: yielding an integrated rate law of the form:

[𝐴] = [𝐴]𝑜 − 𝑎𝑘𝑡 1 1

The above equation suggests that plotting the concentration
of reactant A against time will give a linear plot with a slope
of value equal to –ak. A common example is the reverse
Haber process (Armenise, Garcia-Bordeje, Valverde,
Romeo, & Monzon, 2013)
= − 𝑎𝑘𝑡
[𝐴] [𝐴]𝑜
implying that plotting the reciprocal of the concentration of
reactant A against time would yield a linear graph with a
slope equal to ak. For the second case, the reaction
commonly proceeds as follows

2𝑁𝐻3 → 3𝐻2 + 𝑁2 𝐴 + 𝐵 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

Moving on, first order reactions are reactions whose rates
depend on the concentration of only one reactant
(unimolecular reactions), albeit multiple reactants may be
present in a reaction. Considering the same reaction as
before, but now first order with respect to A, the differential
equation would be
𝑡
[𝐴]
𝑑[𝐴]
∫ = ∫ −𝑎𝑘𝑑𝑡
[𝐴]𝑜 [𝐴]
0 [𝐴]𝑜 − [𝐵]𝑜
yielding an integrated rate law of the form:
𝑙𝑛[𝐴] = 𝑙𝑛[𝐴]𝑜 − 𝑎𝑘𝑡
proposing that plotting the natural logarithm of the
concentration of A against time will yield a linear plot whose
slope is equal to –ak. An example of a first order reaction is
the decomposition of hydrogen peroxide into water and
oxygen gas.
2𝐻2 𝑂2 → 2𝐻2 𝑂 + 𝑂2
Furthermore, second order reactions are reactions whose
rate depends on the concentration of a second order reactant
or two first order reactants. For the first case, the reaction
usually goes as follows.
The rate equation would be
𝑑[𝐴]
− = 𝑘[𝐴][𝐵]
𝑑𝑡
and integration by partial fractions will give an integrated rate
law of
1 [𝐵]𝑜 [𝐴]
ln ( ) = 𝑘𝑡
[𝐴]𝑜 [𝐵]
The order of reaction for a specific chemical reaction is done
experimentally, buy constantly monitoring the concentrations
of the reactant(s) during the course of the reaction, and
recording the time it takes for that concentration to reach.
After gathering significant data, one could graphically
represent those data fitting unto the aforementioned orders
of reaction. The most linear graph represents the order of the
reaction. However, for a second order reaction with two
reactants, this method may be problematic: the
concentrations of the two reactants must be followed
simultaneously, which is more difficult and the data that are
usually obtained are less precise. A common solution to this
problem is the pseudo-first order approximation. If the
concentration of one relative reactant remains constant
because it is supplied in great excess, its concentration can
be absorbed at the expressed constant rate, obtaining the

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pseudo-first order reaction constant, because in fact, it
depends on the same concentration of only one of the two
reactants. If, for example, [B] remains constant, the rate
equation may be written as
𝑟 = 𝑘[𝐴][𝐵] = 𝑘′[𝐴]
Where:
𝑘 ′ = 𝑘[𝐵]𝑜
and the expression is identical to the first order expression
shown above. A common example of reaction where
pseudo-first order approximations are effective is the
hydrolysis of esters, where the amount of water is present at
large excess (Atkins & de Paula, 2006). Another noteworthy
concept under chemical kinetics is the concept of activation
energies. The activation energy of a reaction is the minimum
energy that must be available for a chemical reaction to
occur. The lower the activation energy of a reaction, the
faster the reaction will occur. An equation known as the
Arrhenius equation gives the quantitative basis of the
activation energy. The activation energy may be solved using
the relation
𝐸𝑎
𝑘 = 𝐴𝑒 𝑅𝑇
where k is the rate constant of the reaction, A is the
frequency factor, or the Arrhenius constant, Ea is the
activation energy, R is the universal gas constant and T is
the absolute temperature (Levine, 2009). Moreover, the
determination of the specific rate constant at two or more
temperature allows the determination of the activation
energy, Ea, enthalpy of reaction, ΔH, and entropy of reaction,
ΔS. Methyl acetate undergoes hydrolysis in water in the
presence of an acid as catalyst, to give methanol and acetic
acid, according to the reaction:
𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻3 + 𝐻2 𝑂 + 𝐻 +
→ 𝐶𝐻3 𝐶𝑂𝑂𝐻 + 𝐶𝐻3 𝑂𝐻 + 𝐻 +
Although there are two molecules involved in the reaction,
the water is in such large excess that only methyl acetate
appears to change in concentration. Also, the huge excess
of water prevents the reverse reaction from happening. For
the current experiment, the kinetics of acid catalyzed
hydrolysis of methyl acetate was investigated, with a focus
on the effect of varying the concentration of the acid catalyst,
HCl, on the reaction rate, and measuring the specific rate
Experiment 06│ Group No. 10│ January 20, 2020
constants at two different temperature, in order to compute
the activation energy, enthalpy of reaction, and the entropy.
DISCUSSION
Esters, such as methyl acetate, when reacted with water, are
converted to alcohol and acid as shown in the reaction
below:
𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻3 + 𝐻2 𝑂 ↔ 𝐶𝐻3 𝐶𝑂𝑂𝐻 + 𝐶𝐻3 𝑂𝐻
The hydrolysis of this organic compound is reversible which
means the direction of the reaction can be manipulated by
the addition of reagents or adjustment of the conditions
under which the reaction is performed. However, the
hydrolysis of methyl acetate with excess water occurs at
relatively slow rate in neutral water. To address this, the
reaction is usually carried out in a dilute aqueous solution in
the presence of a strong acid of known concentration. In
doing so, the reaction rate will solely depend on the
concentration of methyl acetate due to the large amount of
water present in the solution that makes the change in its
amount negligible making it constant throughout the reaction.
The rate of the reaction, however, is directly proportional with
the concentration of the acid. For this experiment, the rate
constant of the hydrolysis of methyl acetate was determined
at varying temperature and concentration of the acid catalyst,
HCl. For the first part of the experiment, hydrolysis of methyl
acetate was carried out at room temperature utilizing a lower
concentration of the HCl. Data gathered showed, that as the
time of reaction progresses the amount of NaOH, the titrant
utilized in determining the concentration of the acetic acid
after the estimated reaction time, increases, which meant
that the concentration of the acetic acid produced, increases
with time. Further, when the concentration of methyl acetate
remaining in the vessel was plotted against time, the most
linear plot was observed when the natural logarithm of the
concentration is the quantity plotted against time, as
indicated by the highest correlation coefficient, R2 . This
consequently indicates that the reaction is at first order with
respect to HCl.
After determining the reaction order, the reaction was again
performed and evaluated but with a higher concentration of
HCl. The same trends were observed but the concentration
of methyl acetate after each reaction time was found to be
smaller implying that the reaction occurs faster with a higher
concentration of the catalyst. This confirms one of the
implications of the collision theory for reaction, which states
that reactions are faster when more molecules of reactants
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are present since there are more molecules present to collide
and satisfy the activation energy of the reaction.
In addition, the reaction was also done at a higher
temperature, to determine the effect of increasing the
temperature to the reaction, and to determine a second value
for the rate constant at higher temperature. It was somehow
noticed that the reaction still proceeded at the same rate
when the temperature was higher, although it was
hypothesized prior to performing the experiment that when
the temperature was increased, the reaction would proceed
faster. This is because when the temperature is increased,
the reactant molecules would absorb energy and will have
an increase in their average kinetic energies, making them
collide more frequently, and thus, achieve the activation
energy in a shorter period of time compared to that when the
reaction is performed at room temperature. Human errors in
facilitating the reaction may have caused these deviations
from the theoretical results. However, what is important here
is that one gets the temperature dependent rate constant to
be able to quantify the activation energy of the reaction. After
obtaining the rate constants at 25°C and 35°C, the activation
energy of the reaction were quantified using the modified
form of the Arrhenius equation, which is shown below.
𝑘1 𝐸𝑎 1 1
ln ( ) = ( − )
𝑘2 𝑅 𝑇2 𝑇1
The activation energy computed is equal to the enthalpy of
the reaction. To solve for the entropy, it may be assumed that
the Gibbs’ Free Energy of the reaction is zero, since the
reaction is at equilibrium. With the equation for Gibbs’ Free
Energy,
∆𝐺 = ∆𝐻 − 𝑇∆S
since the change in the Gibbs’ Free Energy is 0, the equation
would be
∆𝐻 =𝑇∆S
and substituting the necessary data seen in the tables would
yield an activation energy 6752.647495 of J/mol and an
entropy -22.64849067 of J/mol-K.
CONCLUSIONS AND RECOMMENDATIONS
Experiment 06│ Group No. 10│ January 20, 2020
The objective of the experiment was successfully achieved.
By knowing the result, the laboratory students were able to
plot the concentration of the methyl acetate left and the time
of reaction. The laboratory students were able to apply the
principle of chemical kinetics in the experiment. Based from
observation, factors affecting the reaction rate are the
concentration of reactants, concentration of a catalyst and
temperature. As the population of reactants increase, the
likelihood that they will collide increases. A catalyst can
provide a good environment for a reaction to occur without
actually being consumed by the reaction. According to our
data, for the three parts of the experiment, the order of the
reaction with the nearest linearity is the first order of reaction.
The hydrolysis of methyl acetate is therefore a first order
reaction. The first two parts of the experiment involved two
different concentrations of HCl. The concentration of the acid
that served as a catalyst should not affect the order of
reaction therefore the rate constant obtained in part A should
be the same as that of part B. We were not able to obtain
same values for the rate constants in part A and B. The
reaction rate dependence of temperature can be expressed
using the Arrhenius equation. The third part of the
experiment involved a solution of the same concentration of
HCl used in part A but a temperature 10 degrees Celsius
greater than the temperature in part A. An increase in
temperature increases the rate constant and hence the
reaction rate. Low activation energy and high temperature
means small amount of energy is necessary for the reaction
to occur and this results to large rate constants and therefore
speeds up the reaction. Besides the error obtained from the
statistical measure of the nearness of the data gathered to
the fitted regression line, the error of the experiment also
came from the rate constant obtained in part B which should
be the same in part A. To perform the experiment
successfully and to acquire accurate results care must be
observed especially when titrating and pipetting.
REFERENCES
Armenise, S., Garcia-Bordeje, E., Valverde, J., Romeo, E., &
Monzon, A. (2013). A Langmuir–Hinshelwood approach to
the kinetic modelling of catalytic ammonia decomposition in
an integral reactor. Physical Chemistry Chemical Physics,
13.
Atkins, P., & de Paula, J. (2006). Physical Chemistry, Eighth
Edition. New York City: W. H. Freeman and Company.
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Chang, R., & Goldsby, K. (2011). General Chemistry: The

Essential Concepts. New York City, United States of
America: McGraw-Hill.

APPENDIX

Reaction time, Volume of NaOH used, Conc. Of Acetic Acid, Conc. Of Methyl Acetate left,
min mL M M
0 24.5 0.022272727 0.935479624
10 29.4 0.026727273 0.894983757
20 32.1 0.029181818 0.872669707
30 3.7 0.033636364 0.832173839
40 3.9 0.035454545 0.815644914
50 4 0.036363636 0.807380451
60 4.2 0.038181818 0.790851525
80 4.4 0.04 0.7743226
100 4.5 0.040909091 0.766058137
120 4.8 0.043636364 0.741264748

Determination of Hydrolysis Rate at Room Temperature and Lower Concentration of HCl

0
0 20 40 60 80 100 120 140
-0.05

-0.1
ln[MeAc]

-0.15 y = -0.0018x - 0.1062

R² = 0.9049
-0.2

-0.25

-0.3

-0.35 Time

Figure 1. First order plot of hydrolysis at room temperature (25˚C) and lower concentration of HCl (0.4545 M).

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Reaction time, Volume of NaOH used, Conc. Of Acetic Acid, Conc. Of Methyl Acetate left,
min mL M M
0 31.7 0.028818182 0.875975492
10 37.5 0.034090909 0.828041608
20 5.02 0.004563636 1.09647136
30 3.9 0.035454545 0.815644914
40 4.9 0.044545455 0.733000286
50 2.08 0.018909091 0.966058137
60 4.35 0.039545455 0.778454831
80 6 0.054545455 0.642091195
100 6.3 0.057272727 0.617297806
120 5.3 0.048181818 0.699942434

Determination of Hydrolysis Rate at Higher Temperature and Lower Concentration of HCl

-5
-5.05 0 50 100 150
-5.1
ln(mol of HAc)

-5.15
-5.2
-5.25
y = 0.0028x - 5.3507
-5.3 R² = 0.9809
-5.35
-5.4
Time

Figure 2. First order plot of hydrolysis at higher temperature (35˚C) and lower concentration of HCl (0.4545 M).

Reaction time, Volume of NaOH used, Conc. Of Acetic Acid, Conc. Of Methyl Acetate left,
min mL M M
0 4.6 0.02875 0.602659287
10 4.9 0.030625 0.590940537
20 5 0.03125 0.587034287
30 5.2 0.0325 0.579221787
40 5.4 0.03375 0.571409287
50 5.5 0.034375 0.567503037
60 5.6 0.035 0.563596787
80 6 0.0375 0.547971787
100 6.2 0.03875 0.540159287
120 6.5 0.040625 0.528440537

Determination of Hydrolysis Rate at Room Temperature and Higher Concentration of HCl

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0
0 20 40 60 80 100 120 140
-0.1

-0.2
ln[MeAc]

-0.3
y = -0.0011x - 0.5126
-0.4
R² = 0.993
-0.5

-0.6

-0.7
Time

Figure 3. First order plot of hydrolysis at room temperature (25˚C) and higher concentration of HCl (0.625 M).

[HCl] in the reaction 0.4545 M (low)

mixture 0.625 M (high)
Acid-dependent rate
constant at low HCl 0.003571948
concentration
Acid-dependent rate
constant at high HCl 0.003269732
concentration
Order of reaction with
respect to HCl First Order
concentration
Activation Energy 6752.647495
Enthalpy of Reaction 6752.647495
Entropy of Reaction -22.64849067

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