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CHEMICAL EQUILIBRIUM IN A LIQUID PHASE

PEVIE ANNE P. TENEBROSO


Department of Chemical Engineering
College of Engineering and Architecture
Cebu Institute of Technology -University
N. Bacalso Ave. Cebu City, 6000 Philippines

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The purpose of the experiment is to be able to determine the equilibrium constant of the
esterification reaction of acetic acid (CH3COOH) and ethyl alcohol (C2H5OH). Varying
quantities of the reactants were prepared. In order to reach equilibrium at a shorter time, 6 N
HCl was used as a catalyst. The Keq constant was found to be 5.93.
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1. INTRODUCTION

There are many chemical reactions that do not go to completion. The products formed
by these reactions, in turn, react to give the reactants. In other words, these chemical
reactions are reversible. In these reactions, a point is reached where the rate of formation of
the products by the forward reaction is equal to the rate of formation of the reactants by the
reverse reaction. When a reaction reaches this stage, it is said to be in chemical equilibrium.
For a general reversible reaction:

The thermodynamic equilibrium constant is defined as:

Where:

Ka = Thermodynamic equilibrium constant


aie = activity species i at equilibrium

The thermodynamic equilibrium constant Ka is constant for a given


temperature. Addition of a catalyst in a chemical reaction does not change
the value of the equilibrium constant, it merely decreases the time it takes
for the reaction to reach equilibrium. In the liquid phase, the activity, aie,
of a species i in a mixture at equilibrium is given by the product of its
equilibrium

concentration

Cie and

its

activity

coefficient

ie.

The

thermodynamic equilibrium constant can then be written as:

Where:

Kc

is

defined

equilibrium constant.

as

the

concentration

The chemical equilibrium to be studied is the esterification reaction.


C2H5OH + CH3COOH = CH3COOC2H5 + H2O
At ordinary temperatures and in the absence of a catalyst, this
reaction approaches equilibrium very slowly. Equilibrium may be attained
in a reasonable time, either by allowing the reaction mixture to stand (in
thick-walled sealed tubes) at a high temperature (about 200E C), or at
room temperature in the presence of a strong acid which acts as a
catalyst. The concentration equilibrium constant can be determined by
analyzing the equilibrium mixture.
A catalyst used was 6 N HCl to avoid the danger of an explosion of
the heated sealed tubes. The equilibrium was approached from both
directions, starting with CH3COOC2H5 and with a mixture of C2H5OH and
CH3COOH. The mixtures were placed in flasks with ground glass stoppers,
to avoid loss by volatilization.
The relatively concentrated acid, which was used as catalyst, affects
the

concentration

coefficients

of

the

equilibrium
reactants.

constant
Smaller

by
value

changing
of

the

the

activity

concentration

equilibrium constant would be obtained if the reaction were carried out in


the absence of the catalyst. It is unnecessary to thermostat the reaction
mixture, since the heat of the reaction is practically zero.
2. MATERIALS AND METHODS
2.1 Required Materials and Apparatus:
2.1.1 Apparatus
Preparation setup is composed of the following:
Large test tubes (8 pieces)
Test tube rack
10 mL pipette
Rubber stopper
Titration setup consisting of the following:
Base burette
Erlenmeyer flasks
2.1.2 Materials

Acetic acid
Distilled water
Ethanol
Ethyl acetate
1.0 N sodium hydroxide
6 N hydrochloric acid
2.2 Methods:
2.2.1 Preparing solutions for the esterification reaction of acetic acid and ethanol.
Five mL of 6 N HCl is pipetted to the eight large test tubes labelled 1-8. To
the first two tubes, 5 mL of distilled water is added. To the third and fourth tubes, 5
mL of pure ethyl acetate is added. To the fifth and sixth tubes, 3 mL of glacial
acetic acid and 2 mL of absolute ethanol are added. To the seventh and eighth
tubes, 2 mL of glacial acetic acid and 3 mL of absolute ethanol are added. Shake
test tubes occasionally to promote reaction. Allow the solutions to settle for 3-5
days.
2.2.2 Titration
A 1.0 N of sodium hydroxide is prepared and the solutions in test tubes 1-8
is placed in separate Erlenmeyer flasks. The solution is now subjected to titration
with the sodium hydroxide as the titrant. The moles of the acid and base used are
computed using the acquired data.

3. RESULTS
Table 3.1 Data table for the NaOH used in the Experiment
*Note: Vused = 25 + (Vf Vi)

Sample

Vfinal

Vinitial

Vused

4.6

0.6

28.5

3.6

0.1

28.5

33.9

0.9

58.0

33.5

0.3

58.2

21.1

1.9

44.2

27.1

7.5

44.6

19.2

4.1

40.1

15.9

0.3

40.6

Table 3.2 Data table for solutions containing pure CH3COOC2H5


*Note: x is computed as the moles of NaOH used subtracted with the moles of HCl present in the solution
x=0.02996

H2O

CH3COOC2H5

CH3COOH

C2H5OH

Initial

0.2778

0.051136

Change

-x

-x

Equilibrium

0.2478

0.021176

0.02996

0.02996

Keq=

(CH 3 COOC 2 H 5 ) ( H 2O)


(CH 3 COOH )(C 2 H 5 OH )

Keq=

( 0.021176 ) (0.2478)
=5.85
(0.02996)( 0.02996)

Table 3.3 Data table for solutions containing 3 mL CH3COOH and 2 mL C2H5OH
*Note: x is computed as the moles of NaOH used subtracted with the moles of HCl present in the solution
x=0.01662

H2O

CH3COOC2H5

CH3COOH

C2H5OH

Initial

0.2778

0.0525

0.0343

Change

-x

-x

Equilibrium

0.01662

0.29442

0.03588

0.01768

Keq=

( 0.29442 ) (0.01662)
=7.71
(0.03588)( 0.01768)

Table 3.4 Data table for solutions containing 2 mL CH3COOH and 3 mL C2H5OH
*Note: x is computed as the moles of NaOH used subtracted with the moles of HCl present in the solution
x=0.01263

H2O

CH3COOC2H5

CH3COOH

C2H5OH

Initial

0.2778

0.035

0.05152

Change

-x

-x

Equilibrium

0.01263

0.29043

0.02237

0.03889

Keq=

4. DISCUSSION

( 0.01263 ) (0.29043)
=4.22
(0.03889)(0.02237)

In the experiment, 6 N HCl catalyst was used to avoid the danger of an explosion of
the heated sealed tubes. At ordinary temperatures and in the absence of a catalyst, the reaction
in the experiment would approach to equilibrium very slowly. Equilibrium may be attained in
a reasonable time, either by allowing the reaction mixture to stand (in thick-walled sealed
tubes) at a high temperature (about 200E C), or at room temperature in the presence of a
strong acid which acts as a catalyst.
The equilibrium was approached from both directions, starting with CH3COOC2H5
and with a mixture of C2H5OH and CH3COOH. The equilibrium concentrations was
determined by using known weights of the reactants and of the standardized 6 N HCl and
titrating the total acid present in the equilibrium mixture. The mixtures were placed in flasks
with ground glass stoppers, to avoid loss by volatilization.
The data gathered in Table 3.1 is the volume of NaOH used in the experiment. Two
samples were prepared and titrated in each solution. It can be said that the volume of NaOH
used in each sample of every solution is just almost the same.
Table 3.2 is the data table for solutions containing pure CH3COOC2H5. x is
computed as the moles of NaOH used subtracted with the moles of HCl present in the
solution and is equal to 0.02996. When computed the Keq was found to 5.85.
Table 3.3 is the data table for solutions containing 3 mL CH3COOH and 2 mL
C2H5OH. x is computed as the moles of NaOH used subtracted with the moles of HCl
present in the solution and is equal to 0.01662. When computed the Keq was found to 7.71.
Table 3.4 is the data table for solutions containing 2 mL CH3COOH and 3 mL
C2H5OH. x is computed as the moles of NaOH used subtracted with the moles of HCl
present in the solution and is equal to 0.01263. When computed the Keq was found to 4.22.
The three resulting Keqs was added and its average was computed. The average Keq
was found to be 5.93.
Some of the data gathered in the tables above may be accurate and some may be not
because of some errors. Firstly, the concentrations of the prepared solutions might not be that
accurate due to limited graduation on the beakers used when preparing the solutions affecting
the volumes of the solutions. Secondly, the temperature might not be that constant due to
fluctuations. Lastly, human error. The execution of the procedures might not executed well
especially during the titration process. Though there are differences in the data gathered, the
resulting Keq is still not large enough compared to the theoretical value.
5. CONCLUSIONS

The Keq constant in the experiment is found to be 5.93 (average of the three K eq
computed above). The concentration of acid, in this case 6 M HCl, was used as catalyst
thereby altering the activity coefficients of the reactants. The catalyst affects the
concentration equilibrium constant by changing the activity coefficients of the reactants.
Smaller value of the concentration equilibrium constant would be obtained if the reaction
were carried out in the absence of the catalyst. Generally, if there was no catalyst used the K eq
would have a smaller value and the reaction to reach equilibrium take slowly.

APPENDIX
A.1 Set-up

Web References
http://www.chem.umn.edu/groups/massari/Teaching_Files.pdf
accessed on January 10,2016
http://www.brittanica.mcmaster.ca/~ayers/chem2PA3/labs/EQUILIBRIUM.pdf
accessed on January 10,2016
http://amrita.olabs.co.in/?sub=1&brch=1&sim=2&cnt=9

accessed on January 10,2016