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REACTION RATE AND ACTIVATION ENERGY OF THE ACIDOLYSIS OF ETHYL ACETATE

Presores Glenn Mark S. ------------------------------------------------------ December 3, 2018

Lab Partner: Virgo Cherry Lynn C.

Abstract

This experiment was conducted to determine the reaction rate constant for the
acidolysis of ethyl acetate at two temperatures (25 oC and 45 oC) and to calculate the activation
energy of the reaction from the temperature dependence of the measured rate constants.
This experiment mostly rely on hydrolysis, a chemical decomposition involving breaking of a
bond and the addition of elements of water. In this hydrolysis of ester (ethyl acetate) with an
alkali (sodium hydroxide), HCl was used as catalyst to accelerate it. Five mL of ethyl acetate
was added into reactor vessels which contains 100 mL HCl and was thoroughly mixed. At
regular time interval, 0, 10, 20, 30, 40, and 50 minutes, 5ml of each of the samples were
withdrawn into a 250ml conical flask containing 100 mL cold water, and titrated against 0.2
M NaOH solution using phenolphthalein as indicator. From the titre values, the hydrolysis
indicates that the higher the concentration the faster the rate of reaction. The rate constants
of k’1 = 8.88x10-3 min-1 at T1 = 298.15 K and k’2 = 1.31x10-2 min-1 at T2 = 318.15 K. From
these values, an activation energy of EA = 15.69 kJ/mol was obtained. Signifying that while
the rate of reaction is concentration dependent, the rate constant is not.
I. Introduction

A chemical reaction takes place when bonds of some molecules break and for some
molecules bonds are formed. During this process some molecules undergo a change in their
identity. However, according to the rules of chemistry, the total mass remains the same during
a chemical reaction. Chemical kinetics is the study of rate of reactions, rate constants,
formations of intermediates of chemical reactions, and its effect on variables. The rate of
reaction at a very basic level dictates how fast the reaction occurs. It can be a very long and
time taking reaction.
Formally, it is the rate at which the reactants disappear and the products appear. Using
the postulates of collision theory, factors that affect the rate of reaction can be explained. This
factors were already explained in the previous report. Each reaction has a definite value of
the rate constant at a particular temperature and the value of the rate constant for the same
reaction changes with temperature and the values do not depend upon the concentration of
reaction but depend upon order of reaction.
There are basically four types of reactions, namely, zero order reaction, first order
reaction, second order reaction and third order reaction. Specifically, the reaction of ethyl
acetate with sodium hydroxide yields a second order reaction. Second order reaction is such
a reaction that depends on the concentration of either a second order reactant or on the
concentrations of both first order reactants.
Acidolysis is a chemical decomposition involving breaking of a bond and the addition
of elements of acid. The use of an acid catalyst accelerates the hydrolysis. The reaction rate
is expressed in terms of chemical composition of the reacting species. The acid ester hydrolysis
is described by the equilibrium:

H3O+
CH3COOC2H5 + H2O  CH3COOH + C2H5OH Eqn. 1

The hydrolysis of an ester such as ethyl acetate in the presence of a mineral acid gives
acetic acid and ethyl alcohol. Under the given experimental conditions, equilibrium is shifted
quantitatively towards the reaction products. . The reaction velocity (rate) vR of this reaction
is given by the rate law:

𝑑𝑐𝐸
𝑣𝑅 = − = 𝑘𝑐𝐸 𝑐𝑊 𝑐𝐾 Eqn. 2
𝑑𝑡

Where k is the reaction rate constant, cE, cW, cK were the concentration of ester, water and
catalyst at time t. The rate of the reaction investigated is a function of the acid concentration
and can be controlled by it. As a result of the practical constancy of the concentrations of H2O
(stoichiometric excess) and H3O+ (catalyst), reduces to:

𝑑𝑐𝐸
− = 𝑘′𝑐𝐸 Eqn. 3
𝑑𝑡
The rate of hydrolysis thus conforms to a pseudo-first-order time rule which can be
represented by the equation:

𝑉𝑁𝑎𝑂𝐻ꚙ −𝑉𝑁𝑎𝑂𝐻0
ln = lnQ = k’t Eqn. 4
𝑉𝑁𝑎𝑂𝐻ꚙ −𝑉𝑁𝑎𝑂𝐻

The volumes of NaOH at time t0 (VNaOH; 0, neutralisation of the constant quantity of


HCl) and subsequent to complete conversion (VNaOH; ∞) are required for the evaluation. They
can either be calculated or be determined experimentally. Thus, this experiment was
conducted to determine the reaction rate constant for the acidolysis of ethyl acetate at two
(or more) temperatures and to calculate the activation energy of the reaction from the
temperature dependence of the measured rate constants.

II. Methodology

a. Materials/Apparatus and Chemicals

This experiment was made possible by the aid of the following materials/apparatus:
Hot plate, Magnetic stirrer, thermometer, Burette, Iron stand, Erlenmeyer flask with stopper,
Burette clamp, Stopwatch, pipette, aspirator, beaker (1000 mL), and wash bottle. The
chemicals used on the other hand includes 1.0 M HCl, 0.2 M NaOH, Ethyl acetate distilled
water, and Phenolphthalein indicator.

b. Procedure

The experiment was conducted in a way that 100 ml of 1 molar hydrochloric acid
solution was pipetted into an Erlenmeyer flask. The reaction vessel was then sealed with a
stopper, and was allowed to equilibrate at room temperature for 15 minutes (T1). In order to
start the reaction, 5 ml of ethyl acetate was added unto the reaction vessel. The flask was
shaken briefly and was allowed to react at room temperature. After 10 minutes, and at further
intervals of 10 minutes, 5 ml samples was taken from the flask and transferred into a wide
neck Erlenmeyer flask containing 100 ml of cold water. The cold water was known to stop the
reaction immediately. The solution was then titrated with the 0.2 M sodium hydroxide solution
with as little delay as possible using phenolphthalein as indicator. The measurement series
was stopped after a reaction time of 50 minutes. Same process was repeated as mentioned
above, this time, reaction was performed at temperature of 45 °C (T2).
III. Results and Discussion

Table 1. lnQ values for the acidolysis of ethyl acetate at 25 oC and 45 oC.

Time VNaOH0 VNaOHꚙ Concentration of NaOH = Concentration of HCl =


(min.) 0.1437 M 0.0882 M
25 oC 45 oC
Volume of lnQ Volume of lnQ
Titrant used Titrant used
(mL) (mL)
0 2.1 14.1912 0 -0.16014 0 -0.16014
10 2.1 14.1912 4.7 mL 0.242113 8.5 mL 0.753557
20 2.1 14.1912 5.0 mL 0.274232 8.5 mL 0.753557
30 2.1 14.1912 5.35 mL 0.313055 8.5 mL 0.753557
40 2.1 14.1912 5.70 mL 0.353448 8.5 mL 0.753557
50 2.1 14.1912 5.95 mL 0.383332 8.5 mL 0.753557

Rate constant is also known as specific reaction rate because the overall concentration
of each reaction was taken as one. It also dictates the speed of each reaction because the
greater the value of the rate constant, the faster the reaction is. The kinetics of the reaction
of this experiment was then studied by taking a 5 mL ethyl acetate and mixing it with a
relatively 100 mL HCl. A 5 mL aliquot of this reaction mixture was withdrawn at 10 minutes
intervals of time, mixed with cold water and was titrated against a standard 0.2 M NaOH using
phenolphthalein as indicator. The purpose of cold water here was primarily to immediately
stop the reaction.
Table 1 presents the data’s obtained during the experiment. The results indicates that
as the reaction proceeds (10 minutes interval time), the vamount of NaOH needed to
neutralize the acid (HCl present as catalyst + CH3COOH produced by hydrolysis of the ester)
progressively increases. However, this observation was only limited for 25 oC, because at 45
o
C the amount of NaOH needed to neutralize the HCl does not change after 10 minutes.
Theoretically, as the reaction proceeds, each hydroxide ion removed in the formation
of ethanol removes one molecule of ethyl acetate, being the number of moles of either OH-
or ethyl acetate removed, the concentration of the reactants decreases, thereby increasing
the amount of NaOH needed. But for the case of 45 oC, things doesn’t work well. Thus certain
error, probably personal error might be responsible for the inconsistency of the values.
The ethyl acetate in this reaction generally undergoes esterification. The rate of
esterification of ethyl acetate with acid catalyst (HCl) is proportional to the acid or hydrogen
ion concentration as well as the concentration of the ethanol and acetic acid (Eqn. 1). Thus,
the value of lnQ or the ester concentrations at specific time presented above increases as
reaction time increases. The effect of temperature on the reaction rate is given by the well-
known Arrhenius equation (EA). These factors are interrelated, and may be used to predict
optimum operational conditions for the production of a given ester if the necessary data are
available.
If we start with equal concentrations of the reactants, the concentration of NaOH can
be conveniently followed at different time intervals by withdrawing an aliquot from the
reaction mixture and determining the NaOH present in it direct or indirect titration with a
standard solution of an acid. Thus, certain lnQ values were obtained as presented in the table
above. In accordance with equation 1.4, the plot of the expression ln [(VNaOH; ∞ - VNaOH; 0 /
VNaOH; ∞ - VNaOH)] as a function of time results in a rising straight line with a slope of k’ as
shown on Figure 1.

Graphical determination of the reaction rate


constants
1 25 degrees
y = 0.0131x + 0.275
0.8 R² = 0.4286
45 degrees
0.6
Linear (25
0.4 degrees)
lnQ

0.2 Linear (45


y = 0.0088x + 0.0136 degrees)
0 R² = 0.6826
0 10 20 30 40 50 60
-0.2

-0.4
Time (min)

Figure 1. Graphic determination of the reaction rate constants for the acid hydrolysis
of ethyl acetate at two temperatures

Table 2. Determination of the reaction rate constants for the acid hydrolysis of
ethyl acetate at various temperature.

25 oC 45 oC EA
Experimental Value of k’ 0.0088 min-1 0.0131 min-1
15.69 kJ/mol
Literature Value for k’ 6.3 x 10 min (293.15 K)
-3 -1

The values for the rate constant for ethyl acetate hydrolysis at 25°C and 45°C were
given in the literature. Theoretical values at other temperatures can be deduced from a plot
of log k versus 1/T constructed from these two known values. In Table 2 are some typical
results obtained both by the experimental and literature value. Comparison was made with
theoretical values determined as described above. The linear relationships presented in Fig. 1
confirm the validity of a pseudo-first-order time rule. The slopes of the lines, which are
determined by regression analysis correspond to the rate constants of k’1 = 8.88x10-3 min-1
at T1 = 298.15 K and k’2 = 1.31x10-2 min-1 at T2 = 318.15 K. From these values, an activation
energy of EA = 15.69 kJ/mol was obtained. It can be seen that the value of k1 was somehow
close to the literature value, however, k2 was not that close compared to k1. The suspected
reason for this data was the concentration of the standardized solutions. It was expected that
the concentration of NaOH should be 0.2 M and 1.0 M for HCl. However, the concentration of
the prepared solution were actually far from the expected one. The standardized NaOH has a
concentration of 0.1437 M and HCl has 0.0882 M. Knowing that it is a concentration
dependent, certain change in the concentration will actually contribute to a drastic change in
the value of rate constant.
The constant k includes the dependence of the reaction velocity on the binding
conditions of the participating molecules, the type of reaction and the temperature. For two
molecules to react, they must not only collide, but also have a sufficient energy content. The
activation energy EA (15.69 kJ/mol) was the difference between the average energy content
prior to reaction and the energy required for reaction. The molecules obtain the energy that
is needed for activation from heat supplied, from light and from the exchange of energy when
collisions occur. Such take-up of energy activates the molecules (loosens bonds, polarisation
etc.) so that they can react. The portion of molecules with this increased energy content
increases with increasing temperature. The greater the portion of the molecules capable of
reaction, the more molecules that will react, and so the higher the reaction velocity.

IV. Conclusion

In conclusion, it can be seen from this experiment that rate of reaction is concentration
dependent while rate constant is not. Also, that the rate constant for the acidolysis of ethyl
acetate correspond to a rate constants of k’1 = 8.88x10-3 min-1 at T1 = 298.15 K and k’2 =
1.31x10-2 min-1 at T2 = 318.15 K. From these values, an activation energy of EA = 15.69 kJ/mol
was obtained.

V. References

Búcsi A., O. I. and U. D. (n.d.). Exercise 8 Kinetics of the Hydrolysis of Ethyl Acetate, 1–6.

Fall. (2011). Kinetics of the Hydrolysis of Ethyl Acetate, 4–7.

Mccormick, P. G. (n.d.). Reaction Rate of Ethyl Acetate Hydrolysis by Osdlometry.

Mukhtar, A., Shafiq, U., Mo, Q., Ha, Q., Qizilbash, M., & Ba, A. (2017). Kinetics of Alkaline
Hydrolysis of Ethyl Acetate by Conductometric Measurement Approach Over
Temperature Ranges ( 298 . 15-343 . 15K ), 4(1), 1–11.

Ohien, P. M., & Babalola, A. (2015). Reaction rate and rate constant of the hydrolysis of ethyl
acetate with sodium hydroxide, 4–7. https://doi.org/10.5251/ajsir.2015.6.1.1.4

PHYWE Systeme GmbH & Co. KG. (n.d.). Reaction rate and activation energy of the acid
hydrolysis of ethyl acetate.

PHYWE Systeme GmbH & Co. KG. (2017). Reaction rate and activation energy of the
acidolysis.