CHM171L Physical Chemistry 2 Laboratory

2nd Quarter, S.Y. 2017-2018

Chemical Kinetics: The Hydrolysis of Methyl Acetate

Legaspi, Ranaye V., Lojica, Kate M., Maquiling, Kenth Roger A.1, Calderon, Edna J.2
1Students, 2Professor, Physical Chemistry 2 Laboratory, CHM171L B21, School of Chemical Engineering and Chemistry, Mapúa University,
Muralla St., Intramuros, Manila 1002, Philippines
ABSTRACT
Final Report Information
The rate of a reaction determines the speed that a chemical reaction proceeds, either
how fast a reactants is consumed or how fast a product is produced. This is often
Performed 21 October 2017 expressed by the concentration of a product or a reactant. The effect of temperature,
Submitted 28 October 2017
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
Keywords: hydrochloric acid using standard sodium chloride solution at varying temperature and
concentration condition. The main focus of this experiment is to study how the
Chemical Kinetics hydrolysis of methyl acetate forming acetic acid can determine the activation energy,
Rate of a Reaction as well as the change in entropy and enthalpy of the system using the Arrhenius
First Order Rate Equation Equation and acid-dependent rate when the titration is done in a 10 minute interval
Hydrolysis
for 60 minutes, and then 20 minute interval for another hour. Moreover, a ln
Acid-Dependent Rate
Arrhenius Equation concentration vs. time graph was plotted in order to see the relationship between the
Activation Energy concentration and the rate of reaction, to which both varies directly with each other.
Enthalpy Findings show that the hydrolysis of methyl acetate has an activation energy of
Entropy 27966.85 J/mol, an enthalpy change of 27966.85 J/mol, and an entropy change of -
93.80127 J/mol-K.

INTRODUCTION concentration; (c) temperature; (d) pressure; and

(e) the presence of catalyst (Atkins & de Paula,
Chemical kinetics is the branch of physical 2006). Through the modification of these
chemistry that concerns the study and discussion conditions, one may be able to optimize a
of chemical reactions with respect to reaction chemical reaction to meet the desired results.
rates, variables affecting the rates, formation of
intermediates, steps or mechanism of reactions A thorough understanding of chemical kinetics
among others. It as well encompasses the begins with the knowledge of the rate laws of
construction of mathematical models that could reactions, otherwise known as rate equations.
hypothetically represent the observed These equations relate chemical reaction rates
characteristics of a certain chemical reaction. with concentrations or pressures of reactants and
other constant parameters, such as the rate
The rate of reaction is loosely defined as the constant and the partial reaction orders (Chang &
change in concentration of a particular species, Goldsby, 2011). For the following hypothetical
may it be the reactant or product, per unit time or reaction,
in other terms, the rate at which the reactant
disappears or at which the product forms. It 𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
depends on various factors such as: (a) availability
of reactants and its surface are; (b) species

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the rate equation is normally written as (Armenise, Garcia-Bordeje, Valverde, Romeo, &
Monzon, 2013)
𝑟 = 𝑘[𝐴]𝑥 [𝐵]𝑦
2𝑁𝐻3 → 3𝐻2 + 𝑁2
where r is the rate of reaction, k is the rate
constant, x is the order of the reaction with respect Moving on, first order reactions are reactions
to reactant A and y is the order of reaction with whose rates depend on the concentration of only
respect to reactant B. In addition, one may also one reactant (unimolecular reactions), albeit
express the rate of a chemical reaction by multiple reactants may be present in a reaction.
obtaining the differential of one specie with Considering the same reaction as before, but now
respect to time, as shown below. first order with respect to A, the differential
equation would be
1 𝑑[𝐴] 1 𝑑[𝐵] 1 𝑑[𝐶] 1 𝑑[𝐷]
𝑟= − =− = = [𝐴] 𝑡
𝑎 𝑑𝑡 𝑏 𝑑𝑡 𝑐 𝑑𝑡 𝑑 𝑑𝑡 𝑑[𝐴]
∫ = ∫ −𝑎𝑘𝑑𝑡
The reaction rate is always positive and so the [𝐴]𝑜 [𝐴] 0
negative sign denotes that the reactants are being
consumed in the reaction, thus their amount yielding an integrated rate law of the form
decreases over time. With these equations, one 𝑙𝑛[𝐴] = 𝑙𝑛[𝐴]0 − 𝑎𝑘𝑡
can form a differential equation, in which through
evaluation, would yield to a linear relationship proposing that plotting the natural logarithm of the
between the concentration of the reactants and concentration of A against time will yield a linear
time. The various forms of the integrated rate plot whose slope is equal to –ak. An example of a
equations depend on the order of the reaction with first order reaction is the decomposition of
respect to the reactant(s) under consideration. hydrogen peroxide into water and oxygen gas.

The first of the common order of reactions is the 2𝐻2 𝑂2 → 2𝐻2 𝑂 + 𝑂2

zero order reaction, where the rate does not Furthermore, second order reactions are
depend on the concentration of any of the reactions whose rate depends on the
reactants. For the following reaction, concentration of a second order reactant or two
𝑎𝐴 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 first order reactants. For the first case, the reaction
usually goes as follows.
the differential equation would be
𝑎𝐴 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
[𝐴] 𝑡
∫ 𝑑[𝐴] = ∫ −𝑎𝑘𝑑𝑡 The rate equation would then be
[𝐴]𝑜 0
[𝐴] 𝑡
𝑑[𝐴]
which would yield the following equation upon ∫ 2
= ∫ −𝑎𝑘𝑑𝑡
evaluation: [𝐴]𝑜 [𝐴] 0

[𝐴] = [𝐴]𝑜 − 𝑎𝑘𝑡 yielding an integrated rate law of the form

The above equation suggests that plotting the 1 1

= + 𝑎𝑘𝑡
concentration of reactant A against time will give a [𝐴] [𝐴]0
linear plot with a slope of value equal to –ak. A implying that plotting the reciprocal of the
common example is the reverse Haber process concentration of reactant A against time would

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yield a linear graph with a slope equal to ak. For where

the second case, the reaction commonly proceeds
𝑘 ′ = 𝑘[𝐵]0
as follows.
and the expression is identical to the first order
𝐴 + 𝐵 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
expression shown above. A common example of
The rate equation would be reaction where pseudo-first order approximations
are effective is the hydrolysis of esters, where the
𝑑[𝐴]
− = 𝑘[𝐴][𝐵] amount of water is present at large excess (Atkins
𝑑𝑡 & de Paula, 2006).
and integration by partial fractions will give an
Another noteworthy concept under chemical
integrated rate law of
kinetics is the concept of activation energies. The
1 [𝐵]0 [𝐴] activation energy of a reaction is the minimum
ln ( ) = 𝑘𝑡 energy that must be available for a chemical
[𝐴]0 − [𝐵]0 [𝐴]0 [𝐵]
reaction to occur. The lower the activation energy
The order of reaction for a specific chemical of a reaction, the faster the reaction will occur. An
reaction is done experimentally, buy constantly equation known as the Arrhenius equation gives
monitoring the concentrations of the reactant(s) the quantitative basis of the activation energy. The
during the course of the reaction, and recording activation energy may be solved using the relation
the time it takes for that concentration to reach.
𝐸𝑎
After gathering significant data, one could 𝑘 = 𝐴𝑒 𝑅𝑇
graphically represent those data fitting unto the
aforementioned orders of reaction. The most where k is the rate constant of the reaction, A is
linear graph represents the order of the reaction. the frequency factor, or the Arrhenius constant, Ea
is the activation energy, R is the universal gas
However, for a second order reaction with two constant and T is the absolute temperature
reactants, this method may be problematic: the (Levine, 2009). Moreover, the determination of the
concentrations of the two reactants must be specific rate constant at two or more temperature
followed simultaneously, which is more difficult allows the determination of the activation energy,
and the data that are usually obtained are less Ea, enthalpy of reaction, ΔH, and entropy of
precise. A common solution to this problem is the reaction, ΔS.
pseudo-first order approximation. If the
concentration of one relative reactant remains Methyl acetate undergoes hydrolysis in water in
constant because it is supplied in great excess, its the presence of an acid as catalyst, to give
concentration can be absorbed at the expressed methanol and acetic acid, according to the
constant rate, obtaining the pseudo-first order reaction:
reaction constant, because in fact, it depends on 𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻3 + 𝐻2 𝑂 + 𝐻 +
the same concentration of only one of the two → 𝐶𝐻3 𝐶𝑂𝑂𝐻 + 𝐶𝐻3 𝑂𝐻 + 𝐻 +
reactants. If, for example, [B] remains constant,
the rate equation may be written as Although there are two molecules involved in the
reaction, the water is in such large excess that
𝑟 = 𝑘[𝐴][𝐵] = 𝑘 ′ [𝐴] only methyl acetate appears to change in
concentration. Also, the huge excess of water
prevents the reverse reaction from happening. For

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the current experiment, the kinetics of acid- used in the preparation instead of 50 mL to raise
catalyzed hydrolysis of methyl acetate was the concentration of the acid.
investigated, with a focus on the effect of varying
the concentration of the acid catalyst, HCl, on the
c.) Treatment of Results
reaction rate, and measuring the specific rate
constants at two different temperature, in order to Given that the density of methyl acetate is
compute the activation energy, enthalpy of 0.9273 g/mL at 25oC and 0.9141 g/mL at 35oC,
reaction, and the entropy. and its molecular weight is 74.08 g/mol, the initial
concentration of the methyl acetate was computed
EXPERIMENTAL SECTION
using
a.) Preparation of Reagents 𝑣𝑜𝑙𝑢𝑚𝑒 𝑥 𝑑𝑒𝑛𝑠𝑖𝑡𝑦
( )𝑀𝑒𝐴𝑐
𝑀𝑊
The following reagents were allowed to 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 [𝑀𝑒𝐴𝑐] =
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
equilibrate in 25°C bath: 50 mL methyl acetate,
300 mL of 1.0 M HCl, and 200 mL of deionized In the titration of methyl acetate using
water. Into a dry 250 mL flask, 50 mL of the HCl sodium chloride, some moles of methyl acetate is
was added with 50 mL water. 10 mL of methyl converted to acetic acid. The reaction involved in
acetate was added to initiate the reaction. A timer the conversion is
was set as half of the required volume of the
MeAC + NaOH → MeOH + H2O
methyl acetate was added, and the mixed solution
was kept in a bath. Using stoichiometry, we can say that the
mole of sodium chloride present in the reaction is
the mole of methyl acetate as well. Hence,
b.) Methodology
𝑚𝑜𝑙𝑒𝑠 𝐻𝐴𝑐 = 𝑚𝑜𝑙𝑒𝑠 𝑁𝑎𝑂𝐻 𝑢𝑠𝑒𝑑
The experiment is done in three given 𝑚𝑜𝑙𝑒𝑠 𝑁𝑎𝑂𝐻 𝑢𝑠𝑒𝑑 = 𝑐𝑜𝑛𝑐 𝑁𝑎𝑂𝐻 𝑥 𝑣𝑜𝑙𝑢𝑚𝑒 𝑁𝑎𝑂𝐻
conditions: at a room temperature and low
concentration of HCl, at a room temperature and
In order to find the concentration of the
high concentration of HCl, and at a high
acetic acid, we divide the mole of acetic acid to the
temperature and low concentration of HCl. From
total volume of the solution, which is 110 mL.
the prepared mixture, 5 mL aliquot was diluted to
Since not all methyl acetate was converted to
50 mL of water in a 150 mL Erlenmeyer flask. The
acetic acid, an amount methyl acetate was left
flask was then pre-chilled in an ice bath to ensure
after the reaction. To find the concentration of the
than the hydrolysis would be sufficiently slowed.
methyl acetate left, we have
Using standard sodium chloride and
phenolphthalein indicator, the diluted aliquot was 𝑚𝑜𝑙 𝑀𝑒𝐴𝑐 − 𝑚𝑜𝑙 𝐻𝐴𝑐
[𝑀𝑒𝐴𝑐] 𝑙𝑒𝑓𝑡 =
titrated. Another aliquots were titrated every after 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
10 minutes, and this was done for an hour. After
The hydrolysis of the methyl acetate to
then, another aliquots were titrated every after 20
water in order to form acetic acid is defined by the
minutes, done for another hour. For the
reaction
temperature and concentration conditions, 25oC
and 35oC were used, while 100 mL of HCl was MeAC + H2O → HAC + MeOH

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From this reaction, we can calculate for the 120 6.4 0.60436 0.533599
reaction rate. However, since there is a large Conc. of HCl in reaction mixture 0.4545 M
amount of excess water in the reaction and HCl Temperature Condition 25oC
acts as a catalyst, the reaction rate will only be Determination of Hydrolysis Rate at Room
Temperature and Higher Concentration of
dependent to the concentration of methyl acetate.
HCl
Hence, Reaction Vol of Conc. of Conc. of
Time, min NaOH Acetic Methyl
d MeAc 
 k ' MeAc  used, Acid, M Acetate
dt mL left, M
Acid-Dependent Rate: 0 4.4 0 0.782347
[𝑀𝑒𝐴𝑐] 10 4.7 0.06252 0.719827
−ln 20 5 0.12504 0.657307
[𝑀𝑒𝐴𝑐]𝑙𝑒𝑓𝑡
𝑘𝐻 = 30 5.3 0.18756 0.594787
𝑡
40 5.8 0.29176 0.490587
Using the Arrhenius Equation, the 50 6.1 0.35428 0.428067
reaction rate can be used to find the activation 60 6.2 0.37512 0.407227
energy. This activation energy is actually equal to 80 6.6 0.45848 0.323867
100 6.9 0.521 0.261347
the enthalpy of the reaction, which can be used to
120 6.7 0.47932 0.303027
find the change in the entropy. Conc. of HCl in reaction mixture 0.625 M
Temperature Condition 25oC
k1 H  1 1 
ln     Determination of Hydrolysis Rate at Higher
k2 R  T2 T1  Temperature and Lower Concentration of
HCl
H  G Reaction Vol of Conc. of Conc. of
S 
T Time, min NaOH Acetic Methyl
used, Acid, M Acetate
RESULTS mL left, M
0 4.0 0 1.146181
Determination of Hydrolysis Rate at Room 10 4.4 0.08336 1.062821
Temperature and Lower Concentration of 20 5.4 0.29176 0.854421
HCl 30 5.7 0.35428 0.791901
Reaction Vol of Conc. of Conc. of 40 5.5 0.3126 0.833581
Time, min NaOH Acetic Methyl 50 5.6 0.33344 0.812741
used, Acid, M Acetate 60 6.1 0.43764 0.708541
mL left, M 80 5.9 0.39596 0.750221
0 3.5 0 1.137959 100 6.3 0.47932 0.666861
10 3.8 0.06252 1.075439 120 6.5 0.521 0.625181
20 4.2 0.14588 0.992079 Conc. of HCl in reaction mixture 0.4545 M
30 4.7 0.25008 0.887879 Temperature Condition 35oC
40 5 0.3126 0.825359
50 5.2 0.35428 0.783679
60 5.5 0.4168 0.721159
80 5.8 0.47932 0.658639
100 6.1 0.54184 0.596119

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[HCl] in the reaction 0.4545 M (low)

mixture 0625 (high)
Acid-dependent rate 0.0063509 min-1
constant at low HCl
concentration
Acid-dependent rate 0.0093822 min-1
constant at high HCl
concentration
Order of reaction with FIRST ORDER
respect to HCl
concentration Figure 3. First order plot of hydrolysis at higher temperature
Activation Energy 27966.85 J/mol (35˚C) and lower concentration of HCl (0.4545 M).
Enthalpy of Reaction 27966.85 J/mol
Entropy of Reaction -93.80127 J/mol-K DISCUSSION
a. Legaspi, Ranaye V.
The hydrolysis of methyl acetate involves two
reactants, the water and the methyl acetate.
Because water is supplied in a great excess
amount, the concentration of the water in the
process is relatively constant. Hence, the rate of
the reaction depends only on the concentration of
methyl acetate, obtaining a first-order reaction rate
constant.
Changing conditions such as temperature and
Figure 1. First order plot of hydrolysis at room temperature (25˚C) concentration of one component can either
and lower concentration of HCl (0.4545 M).
increase or decrease the time needed for a
reaction to reach equilibrium. In the experiment,
aliquots of methyl acetate solutions with
hydrochloric acid and water was titrated with
sodium chloride at (a) room temperature and
lower concentration, (b) room temperature and
higher concentration, and (c) higher temperature
and lower concentration. The titration of the
aliquots occurred for one hour with 10 minute
interval for each, and then for 20 minute interval
for another one hour.
Figure 2. First order plot of hydrolysis at room temperature (25˚C)
and higher concentration of HCl (0.625 M).
For an aliquot of methyl acetate solution
containing 50 mL of HCl which was titrated at a
room temperature of 25oC, data shows that the
volume of sodium chloride required to turn the
solution into light pink increases with increasing

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time. Since the amount of sodium chloride is greater amount of acetic acid is produced with a
theoretically the amount of acetic acid formed from lesser amount of methyl acetate left. This is
the titration of methyl acetate, this means that because the hydrolysis of the methyl acetate
more and more mole of acetic acid is produced in speed up due to the presence of the catalyst and
the hydrolysis of methyl acetate as time goes by. so more amount of methyl acetate was formed
Another interpretation that can be drawn from this with the same amount of time. The acid-
is that since greater production of acetic acid in the dependent rate was also determined wherein it
reaction means that more methyl acetate is being was found out that at a greater concentration, the
converted to acetic acid, the concentration of the acid-dependent rate is also higher.
methyl acetate left decreases with increasing time.
The third part of the experiment was done with a
Taking the natural logarithm of the concentration higher temperature but of the same concentration
of methyl acetate and plotting it in a graph against as to the first part. Theoretically, atoms becomes
time, a linear behavior can be obtained. Looking more excited when heated, spreading out apart
at the trend of the graph, one can simply conclude from each other. This is because of their increased
right away that the reaction of the methyl acetate average kinetic energy which makes them to be
hydrolysis is a first-order reaction. Considering more reactive. On the same manner, it can be
that the coefficient of determination is almost a expected that the rate of reaction will increase as
maximum, this can verify that the data are to the the temperature is increased from 25oC to 35oC,
fitted regression line, indicating that the reaction is with the same linear behavior as the atoms
of a first-order. engage themselves into larger collisions.
Increasing the concentration of the hydrochloric The rate law constant of a system and
acid while maintaining the same room temperature condition can be related to the
temperature condition, the same observation and activation energy using the Arrhenius Equation.
line trends can be seen. However, one can notice The activation energy can be defined as the
that the time of the reaction becomes smaller, minimum energy needed to be present for a
indicating a speed in the reaction rate of the chemical reaction to occur. Once that the free
hydrolysis of methyl acetate compared to the first energy of a molecule overpowers the activation
state. This is due to the fact that hydrochloric acid energy, the reaction would take place.
acts as an acid catalyst in the experiment which Considering that a system has a greater
speeds up the rate of a reaction without causing temperature, the average kinetic energy could
shift in the equilibrium. When a strong acid exceed the activation energy right away, giving a
catalyst is carried in a solution, the concentration faster rate of reaction
of the hydrogen ions does not change during the
The activation energy of the system can also be
reaction. Although the production of acetic acid
defined as the change in the enthalpy of the
from the hydrolysis of methyl acetate causes a
reaction. Since the Gibb’s Free Energy can be
slight increase in the concentration of the
used to relate the enthalpy and entropy to each
hydrogen ions, this increase is almost negligible
other, the change in the entropy of the reaction,
that it gives a very small effect on the reaction rate.
considering that the Gibb’s Free Energy at
Comparing the moles of the acetic acid formed at equilibrium is zero.
a higher concentration that when the
concentration of the hydrochloride acid is lower, a

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 CHM171L Physical Chemistry 2 Laboratory
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b. Lojica, Kate Ann M. Same relationship was observed in this part with
the two previous parts. Since the temperature in
This experiment was divided into three parts, this part is higher, the rate of reaction also
which have varying conditions each. This was increases. High temperature makes the molecules
designed to assess the hydrolysis of methyl excited, resulting to its collision to each other. This
acetate through its chemical kinetics. collision results in higher kinetic energy, thus
For the first part, the hydrolysis of methyl acetate higher rate of reaction
was determined at a room temperature and low Same principles in comparing were applied for
concentration of HCl, observations were part C to determine its rate of reaction. It can be
summarized in table A. seen that first order reaction suits the best thus it
The estimated time of reaction increases, the is the order of the reaction is second order.
volume of NaOH, concentration and acetic acid Furthermore, rate constant doubled in every 10°C
increases and methyl acetate left decreases. In rise in temperature. Also, rate constant must be
addition, the volume of NaOH used was also the the same for part A and part C but due to
moles of acetic acid in the aliquot titrated. Through inaccuracies of data gathered its value were
this data observed, the rate of reaction can be different to each other.
known.
Moreover, chemical reaction like this needs
In order to determine the order of reaction, graphs energy to proceed. The minimum energy required
must be compared to each other and determine is called Activation Energy. Activation energy was
what suits the best in the tread line. However, it is computed for this experiment by the equation
very difficult to distinguish one from another. Thus, given below.
the value of R2 which was given in every graph
were compared, this value determines the linearity 𝑘3 𝐸𝑎 1 1
𝑙𝑛 = ( − )
of the graph. Based from simple observation, the 𝑘1 𝑅 𝑇3 𝑇1
order of the reaction is first order. Moreover, for The activation energy is the minimum energy that
the part B of the experiment, hydrolysis took place must be available to make the chemical reaction
at room temperature but higher concentration of happen.
HCl. Data gathered for this part was given in Table
B. Lastly, there are two other parameters in chemical
kinetics, change in enthalpy and entropy. The
Based from the given data, same correlation was change in enthalpy which is the heat of reaction is
observed as part A. However, volume of NaOH most likely same with activation energy. Entropy is
used was doubled in higher concentration of HCl defined as the state of disorder of molecules. Thus,
compared to lower concentration (part A). higher entropy means higher kinetic energy
To determine the rate of reaction for this part, resulting in higher rate of reaction as mentioned
same observations applied. Obviously, the rate of above.
reaction for this part is first. Lastly, hydrolysis in
part C was conducted at higher temperature but
lower concentration of HCl. Data obtained were
shown below, table C.

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 CHM171L Physical Chemistry 2 Laboratory
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c. Maquiling, Kenth Roger A. consequently indicates that the reaction is at first

order with respect to HCl.
Esters, such as methyl acetate, when reacted with
water, are converted to alcohol and acid as shown After determining the reaction order, the reaction
in the reaction below: was again performed and evaluated but with a
higher concentration of HCl. The same trends
𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻3 + 𝐻2 𝑂 ↔ 𝐶𝐻3 𝐶𝑂𝑂𝐻 + 𝐶𝐻3 𝑂𝐻
were observed but the concentration of methyl
The hydrolysis of this organic compound is acetate after each reaction time was found to be
reversible which means the direction of the smaller implying that the reaction occurs faster
reaction can be manipulated by the addition of with a higher concentration of the catalyst. This
reagents or adjustment of the conditions under confirms one of the implications of the collision
which the reaction is performed. However, the theory for reaction, which states that reactions are
hydrolysis of methyl acetate with excess water faster when more molecules of reactants are
occurs at relatively slow rate in neutral water. To present since there are more molecules present to
address this, the reaction is usually carried out in collide and satisfy the activation energy of the
a dilute aqueous solution in the presence of a reaction. Furthermore, as observed in the
strong acid of known concentration. In doing so, experiment, the rate constant of the reaction was
the reaction rate will solely depend on the doubled, from 0.00025152 min-1 to 0.00054047 min-1
concentration of methyl acetate due to the large when HCl concentration elevated. However, the
amount of water present in the solution that makes order of the reaction still remained as first order.
the change in its amount negligible making it
In addition, the reaction was also done at a higher
constant throughout the reaction. The rate of the
temperature, to determine the effect of increasing
reaction, however, is directly proportional with the
the temperature to the reaction, and to determine
concentration of the acid.
a second value for the rate constant at higher
For this experiment, the rate constant of the temperature. It was somehow noticed that the
hydrolysis of methyl acetate was determined at reaction still proceeded at the same rate when the
varying temperature and concentration of the acid temperature was higher, although it was
catalyst, HCl. For the first part of the experiment, hypothesized prior to performing the experiment
hydrolysis of methyl acetate was carried out at that when the temperature was increased, the
room temperature utilizing a lower concentration reaction would proceed faster. This is because
of the HCl. Data gathered showed, that as the time when the temperature is increased, the reactant
of reaction progresses the amount of NaOH, the molecules would absorb energy and will have an
titrant utilized in determining the concentration of increase in their average kinetic energies, making
the acetic acid after the estimated reaction time, them collide more frequently, and thus, achieve
increases, which meant that the concentration of the activation energy in a shorter period of time
the acetic acid produced, increases with time. compared to that when the reaction is performed
Further, when the concentration of methyl acetate at room temperature. Human errors in facilitating
remaining in the vessel was plotted against time, the reaction may have caused these deviations
the most linear plot was observed when the from the theoretical results. However, what is
natural logarithm of the concentration is the important here is that one gets the temperature-
quantity plotted against time, as indicated by the dependent rate constant to be able to quantify the
highest correlation coefficient, R2. This activation energy of the reaction. After obtaining
the rate constants at 25°C and 35°C, the

Experiment 6 | Group 6 | October 28, 2016 9 of 11

 CHM171L Physical Chemistry 2 Laboratory
2nd Quarter, S.Y. 2017-2018

activation energy of the reaction were quantified order reaction. The first two parts of the
using the modified form of the Arrhenius equation, experiment involved two different concentrations
which is shown below. of HCl. The concentration of the acid that served
as a catalyst should not affect the order of reaction
𝑘1 𝐸𝑎 1 1 therefore the rate constant obtained in part A
ln ( )= ( − )
𝑘2 𝑅 𝑇2 𝑇1 should be the same as that of part B. We were not
able to obtain same values for the rate constants
The activation energy computed is equal to the in part A and B. The reaction rate dependence of
enthalpy of the reaction. To solve for the entropy, temperature can be expressed using the
it may be assumed that the Gibbs’ Free Energy of Arrhenius equation. The third part of the
the reaction is zero, since the reaction is at experiment involved a solution of the same
equilibrium. With the equation for Gibbs’ Free concentration of HCl used in part A but a
Energy, temperature 10 degrees Celsius greater than the
temperature in part A. An increase in temperature
∆𝐺 = ∆𝐻 − 𝑇∆𝑆 increases the rate constant and hence the
since the change in the Gibbs’ Free Energy is 0, reaction rate. Low activation energy and high
temperature means small amount of energy is
the equation would be
necessary for the reaction to occur and this results
∆𝐻 = 𝑇∆𝑆 to large rate constants and therefore speeds up
the reaction.
and substituting the necessary data seen in the
tables would yield an activation energy of 27966.85 Besides the error obtained from the
J/mol and an entropy of -93.80127 J/mol-K. statistical measure of the nearness of the data
gathered to the fitted regression line, the error of
CONCLUSION AND RECOMMENDATIONS
the experiment also came from the rate constant
The objective of the experiment was obtained in part B which should be the same in
successfully achieved. By knowing the result, the part A. To perform the experiment successfully
laboratory students were able to plot the and to acquire accurate results care must be
concentration of the methyl acetate left and the observed especially when titrating and pipetting.
time of reaction. The laboratory students were
able to apply the principle of chemical kinetics in REFERENCES
the experiment. Armenise, S., Garcia-Bordeje, E., Valverde, J.,
Romeo, E., & Monzon, A. (2013). A
Based from observation, factors affecting Langmuir–Hinshelwood approach to the
the reaction rate are the concentration of kinetic modelling of catalytic ammonia
reactants, concentration of a catalyst and decomposition in an integral reactor.
temperature. As the population of reactants Physical Chemistry Chemical Physics, 13.
increase, the likelihood that they will collide
increases. A catalyst can provide a good Atkins, P., & de Paula, J. (2006). Physical
environment for a reaction to occur without Chemistry, Eighth Edition. New York City:
actually being consumed by the reaction. W. H. Freeman and Company.

According to our data, for the three parts Chang, R., & Goldsby, K. (2011). General
of the experiment, the order of the reaction with Chemistry: The Essential Concepts. New
the nearest linearity is the first order of reaction. York City, United States of America:
The hydrolysis of methyl acetate is therefore a first McGraw-Hill.

Experiment 6 | Group 6 | October 28, 2016 10 of 11

 CHM171L Physical Chemistry 2 Laboratory
2nd Quarter, S.Y. 2017-2018

Levine, I. N. (2009). Physical Chemistry, Sixth 1.6 Acid-dependent Rate Constant, kH

Edition. New York City: McGraw-Hill. −ln
[𝑀𝑒𝐴𝑐]𝑙𝑒𝑓𝑡
[𝑀𝑒𝐴𝑐]
𝑘𝐻 =
𝑡
0.8489
APPENDIX − ln 1.138
𝑘𝐻 𝑎𝑡 𝑙𝑜𝑤 𝑐𝑜𝑛𝑐 =
1. Sample Calculations 120 𝑚𝑖𝑛
1.1. Concentration of HCl = 0.0063509 min-1
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐻𝐶𝑙 𝑢𝑠𝑒𝑑
𝐶𝐻𝐶𝑙 = [𝐻𝐶𝑙] 𝑥 1.7 Activation Energy, Ea
𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑘2
𝑅𝑙𝑛
50 𝑚𝐿 𝑘1
𝐸𝑎 =
𝐶𝐻𝐶𝑙,𝑙𝑜𝑤𝑒𝑟 = [1 𝑀] 𝑥 = 𝟎. 𝟒𝟓𝟒𝟓 𝑴 1 1
110 𝑚𝐿 𝑇1 − 𝑇2
100 𝑚𝐿
𝐶𝐻𝐶𝑙,ℎ𝑖𝑔ℎ𝑒𝑟 = [1 𝑀] 𝑥 = 𝟎. 𝟔𝟐𝟓 𝑴 0.0044038
160 𝑚𝐿 8.314𝑙𝑛 0.0063509
𝐸𝑎 =
1 1
1.2 Initial Concentration of Methyl Acetate, Co −
308.15 298.15
= 𝟐𝟕𝟗𝟔𝟔. 𝟖𝟓 𝐉/𝐦𝐨𝐥
𝑣𝑜𝑙𝑢𝑚𝑒 𝑥 𝑑𝑒𝑛𝑠𝑖𝑡𝑦
( )𝑀𝑒𝐴𝑐
𝑖𝑛𝑖𝑡𝑖𝑎𝑙 [𝑀𝑒𝐴𝑐] = 𝑀𝑊 1.8 Enthalpy of Reaction, ∆H
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑔 𝐸𝑎 = ∆H = 𝟐𝟕𝟗𝟔𝟔. 𝟖𝟓 𝐉/𝐦𝐨𝐥
10 𝑚𝐿 𝑥 0.9273
𝑚𝐿
𝑔
74.08
𝑚𝑜𝑙 1.9 Entropy of Reaction, ∆S
𝑖𝑛𝑖𝑡𝑖𝑎𝑙 [𝑀𝑒𝐴𝑐] = ∆H 27966.85
0.110 𝐿 ∆S = − =−
= 𝟏. 𝟏𝟑𝟖 𝒎𝒐𝒍/𝑳 𝑇 298.15
= −𝟗𝟑. 𝟖𝟎𝟏𝟐𝟕 𝐉/𝐦𝐨𝐥 − 𝐊
1.3 Mole of Acetic Acid
𝑚𝑜𝑙𝑒𝑠 𝐻𝐴𝑐 = 𝑚𝑜𝑙𝑒𝑠 𝑁𝑎𝑂𝐻 𝑢𝑠𝑒𝑑
𝑚𝑜𝑙𝑒𝑠 𝑁𝑎𝑂𝐻 𝑢𝑠𝑒𝑑 = 𝑐𝑜𝑛𝑐 𝑁𝑎𝑂𝐻 𝑥 𝑣𝑜𝑙𝑢𝑚𝑒 𝑁𝑎𝑂𝐻
3.5 𝑚𝐿
𝑚𝑜𝑙𝑒𝑠 𝐻𝐴𝐶 = 1 𝑀 𝑁𝑎𝑂𝐻 𝑥 𝑥𝐿
1000 𝑚𝐿
= 𝟎. 𝟎𝟎𝟑𝟓 𝒎𝒐𝒍

1.4 Concentration of Acetic Acid, CAC

𝑚𝑜𝑙 𝐴𝑐𝑒𝑡𝑖𝑐 𝐴𝑐𝑖𝑑

[𝐻𝐴𝑐] =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
0.0035 𝑚𝑜𝑙
[𝐻𝐴𝑐] = = 𝟎. 𝟎𝟑𝟏𝟖 𝑴
0.110 𝐿

1.5 Concentration of Methyl Acetate left, C

𝑚𝑜𝑙 𝑀𝑒𝐴𝑐 − 𝑚𝑜𝑙 𝐻𝐴𝑐
[𝑀𝑒𝐴𝑐] 𝑙𝑒𝑓𝑡 =
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
10 𝑥 0.9273
− 0.0318
[𝑀𝑒𝐴𝑐] 𝑙𝑒𝑓𝑡 = 74.08 = 𝟎. 𝟖𝟒𝟖𝟗 𝑴
0.110

Experiment 6 | Group 6 | October 28, 2016 11 of 11