INSTITUTO POLITECNICO NACIONAL.

ESCUELA SUPERIOR DE INGENIERIA QUIMICA E INDUSTRIAS EXTRACTIVAS ESIQIE.

Practice N.2
CHEMICAL EQUILIBRIUM HOMOGENEO IN LIQUID PHASE STUDY OF THE
STERIFICATION OF THE ACETIC ACID.
Teacher:
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TEAM MEMBERS:
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GROUP:
2IV47
INTRODUCTION.
 OVERALL OBJECTIVE.

• With this practice, the student will use the analytical titration
technique to determine the equilibrium constant through the
concept of activity for the esterification of acetic acid in a
homogeneous system.
 OBJECTIVES.

•Calculate the chemical equilibrium constants in the liquid phase

of a stratification reaction.

•Carry out the acid catalysis of the reaction of ethanol with acetic
acid to obtain an ester: ethyl acetate and verify the dependence.

•Determine the concentration ratio and equilibrium constant for an

esterification reaction.
 THEORETICAL DEVELOPMENT.

✓ The chemical equilibrium is a state of a reactant system in which

no changes are observed as time passes, despite the fact that the
reaction continues.

The chemical equilibrium is established when there are two opposite

reactions that take place simultaneously at the same rate.

→𝑽𝒊
𝒂𝑨 + 𝒃𝑩 𝒄𝑪 + 𝒅𝑫
←𝒗𝒇
𝑉𝑑 = 𝑉𝑒𝑙𝑜𝑐𝑖𝑑𝑎𝑑 𝑑𝑒 𝑓𝑜𝑟𝑚𝑎𝑐𝑖𝑜𝑛 𝑑𝑒 𝑙𝑜𝑠 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑜𝑠.
𝑉𝑖 = 𝑉𝑒𝑙𝑜𝑐𝑖𝑑𝑎𝑑 𝑑𝑒 𝑑𝑒𝑠𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑐𝑖𝑜𝑛 𝑑𝑒 𝑙𝑜𝑠 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑜𝑠.
✓ Homogeneous Balance: applies to reactions in which all reactive
species are in the same phase.

In the stratification of the acetic acid the following reaction is carried out
with the ethanol in the presence of hydrochloric acid as a catalyst,
forming ethyl acetate and water, the reaction is described.

𝐶𝐻3 𝐶𝑂𝑂𝐻 + 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 ↔𝐻𝐶𝑙 𝐶𝐻3 𝐶𝑂𝑂𝐻2 𝐶𝐻3 + 𝐻2 𝑂

TO OBTAIN THE EQUILIBRIUM CONSTANT EXPERIMENTALLY,
WE MUST START FROM THE EQUILIBRIUM CONSTANT
EQUATION.

𝑲𝟏 𝒏𝑪𝑯𝟑 𝑪𝑶𝑶𝑪𝑯𝟐 𝑪𝑯𝟑 ∗ 𝒏𝑯𝟐 𝑶

𝑲𝒆𝒒 = 𝑲𝒙 =
𝑲𝟐 𝒏𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 ∗ 𝒏𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶𝑯
 EXPERIMENTAL DEVELOPMENT.

The experimentation turns out to be simpler, consists in preparing a series of systems

of measured volumes (with a burette sufficient accuracy is obtained) of acetic acid.

a) Ethanol.
b) Ethyl acetate.
c) Water and HCl or subsequently a mixture of all components.

1. Place the mixture in a covered jar, shake it and let it sit for a week in order to carry
out the reaction until equilibrium.

2. Subsequently, take a sample (10 to 5 ml) of the system and titrate the acid present
with a previously titrated solution of NaOH (approximately 3 N). By means of a molar
balance in the equilibrium, obtain the moles of all the components based on the
titration of the sample and the physical properties of the compounds.
Balance in equilibrium;

𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 + 𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶𝑯 ↔𝑯𝑪𝒍 𝑪𝑯𝟑 𝑪𝑶𝑶𝑯𝟐 𝑪𝑯𝟑 + 𝑯𝟐 𝑶

Depending on the degree of progress (£)

𝒏𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 = 𝒏° 𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 − £

𝒏𝑯𝟐 𝑶 = 𝒏° 𝑯𝟐 𝑶 + £

𝒏𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶𝑯 = 𝒏° 𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶𝑯 − £

𝒏𝑪𝑯𝟑 𝑪𝑶𝑶𝑪𝑯𝟐 𝑪𝑯𝟑 = 𝒏° 𝑪𝑯𝟑 𝑪𝑶𝑶𝑪𝑯𝟐 𝑪𝑯𝟑 + £

𝒏𝑯𝑪𝒍 = 𝒏° 𝑯𝑪𝒍
Where the subscript n°, denotes the initial moles of the
component and the degree of progress of the reaction. Now,
since the reaction is equimolar we can express the constant
𝐾𝑥 as a function of the moles in equilibrium, instead of the
composition as

𝒏𝑪𝑯𝟑 𝑪𝑶𝑶𝑪𝑯𝟐 𝑪𝑯𝟑 ∗ 𝒏𝑯𝟐 𝑶

𝑲𝒙 =
𝒏𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 ∗ 𝒏𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶𝑯
Those of any component, fed to the system, are expressed according
to the aggregate volume and its physical properties.
𝑽𝒊 𝑷𝒊
𝒏° = (𝜹𝒊 )→𝑷𝒖𝒓𝒆𝒛𝒂
𝑷𝑴𝒊
where:
𝑉𝑖 = 𝑉𝑜𝑙𝑢𝑚𝑒𝑛 𝑎𝑔𝑟𝑒𝑔𝑎𝑑𝑜 𝑑𝑒𝑙 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡𝑒 𝑌
𝑃𝑖 = 𝐿𝑎 𝐷𝑒𝑛𝑠𝑖𝑑𝑎𝑑 𝑑𝑒𝑙 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡𝑒 𝑌
𝛿𝑖 = 𝑆𝑢 𝑓𝑟𝑎𝑐𝑐𝑖𝑜𝑛 𝑝𝑒𝑠𝑜 𝑜 𝑝𝑢𝑟𝑒𝑧𝑎 𝑑𝑒𝑙 𝑐𝑜𝑚𝑝𝑢𝑒𝑠𝑡𝑜.
𝑃𝑀𝑖 = 𝑃𝑒𝑠𝑜 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑑𝑒𝑙 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡𝑒
The degree of progress is determined with the degree; we know that
by the neutralization ratios of an acid by a base, the reactions
analyzed are;

a) Acetic acid neutralization.

𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 + 𝑵𝒂𝑶𝑯 → 𝑪𝑯𝟑 𝑪𝑶𝑶𝑵𝒂 + 𝑯𝟐 𝑶
B) HCl neutralization.
𝑯𝑪𝒍 + 𝑵𝒂𝑶𝑯 → 𝑵𝒂𝑪𝒍 + 𝑯𝟐 𝑶

So the relationship:

𝒏 = 𝑽𝑵 𝑵𝒂𝒐𝑯
 It gives us moles of acid neutralized in the sample. To obtain the
total moles of acid in the system, the ratio of the total system
volume (𝑉𝑇 ) and the sample volume (𝑉𝑚 ) is included:

𝑽𝑵𝒂𝑶𝑯 𝑵𝑵𝒂𝑶𝑯
𝒏𝑻 = 𝑽𝑻→𝑷𝒓𝒆𝒑𝒂𝒓𝒂𝒅𝒐
𝑽𝒎→𝒔𝒐𝒍,𝒂𝒍𝒊𝒄𝒖𝒐𝒕𝒂
Where:
𝑛 𝑇 = 𝑀𝑜𝑙𝑒𝑠 𝑑𝑒 𝑎𝑐𝑖𝑑𝑜 𝑝𝑟𝑒𝑠𝑒𝑛𝑡𝑒𝑠 𝑒𝑛 𝑒𝑙 𝑠𝑖𝑠𝑡𝑒𝑚𝑎.
𝑉𝑁𝑎𝑂𝐻 = 𝑉𝑜𝑙𝑢𝑚𝑒𝑛 𝑔𝑎𝑠𝑡𝑎𝑑𝑜 𝑑𝑒 𝑠𝑜𝑙𝑢𝑐𝑖𝑜𝑛 𝑑𝑒 𝑁𝑎𝑂𝐻
𝑁𝑁𝑎𝑂𝐻 = 𝑁𝑜𝑟𝑚𝑎𝑙𝑖𝑑𝑎𝑑 𝑑𝑒 𝑙𝑎 𝑠𝑜𝑙𝑢𝑐𝑖𝑜𝑛 𝑑𝑒 𝑁𝑎𝑂𝐻
Then how:

𝒏𝑻 = 𝒏𝑯𝑪𝒍 + 𝒏𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 𝒏𝑯𝑪𝒍 = 𝒏° 𝑯𝑪𝒍

𝒏𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 = 𝒏𝑻 − 𝒏𝑯𝑪𝒍
Thus:
𝜺 = 𝒏°𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 − 𝒏𝑪𝑯𝟑 𝑪𝑶𝑶𝑯
 EXPERIMENTAL RESULTS.

• Initially a series of samples were prepared with different amounts of

reagents showing the physical properties of these in Tables 2-1 and
2-2.

• Applying the experimental procedure, the systems were titrated with

a 2,999 N sodium hydroxide solution (previously assessed), after
having been at rest for a week. Those of the degree are presented
in table 2-1.
Table 2-1. Systems prepared in the study of the esterification of acetic acid
and volume.
Reagent Vol.
I II III IV V VI VII VIII IX X XI XII
(Ml)
Ac. Acético.
60 30 60 50 25 15 25 25 ---- 30 15 30

Etanol
60 60 30 25 50 25 15 25 --- 30 30 15

Acet. Etilo
--- --- --- --- --- 15 15 25 20 --- --- ---

Water
--- --- --- --- --- --- --- --- 40 --- --- ---

HCl 5 5 5 5 5 5 5 5 5 --- --- ---

NaOH
11.05 6.10 23.8 24.45 6.6 8.4 17.55 10.6 11.3 19.0 9.65 28.1
 Table 2-2 Physical properties of reagents.

Reagent. % purity is Density gr/ml P.M

weight.
Acetic acid. 99.7 1.055 60.
Ethanol 99.2 0.790 46

Ethyl acetate 99.8 0.893 88

Water 100.0 1.000 18

Hydrochloric acid 36.5 1.185 35.5

Developing the balance of matter for each system from equations (2-
12) to (2-18), the results of table 2-3 were obtained which shows the
effect of the composition on the constant 𝐾𝑥 .
Table 2-3 Results obtained from the material balance of the data in Table 2-1.
Acetic Ethanol Ethyl Water HCl Acetic Ethanol Ethyl Water 𝐊𝐱
SISTEMA
acid. acetate acid. acetate
I 1.0518 1.0222 --- 0.2090 0.0593 0.3541 0.3245 0.6977 0.9067 5.505

II 0.5259 1.0222 --- 0.2090 0.0593 0.1142 0.6104 0.4117 0.6207 3.667

III 1.0518 0.5111 --- 0.2090 0.0593 0.6174 0.0767 0.4344 0.6434 5.904

IV 0.8765 0.4259 --- 0.2090 0.0593 0.5261 0.0755 0.3504 0.5594 4.933

V 0.4383 0.8518 --- 0.2090 0.0593 0.0988 0.5123 0.3395 0.5485 3.680

VI 0.2630 0.4259 0.1519 0.2090 0.0593 0.0916 0.2545 0.3233 0.3804 5.275

VII 0.4383 0.2556 0.1519 0.2090 0.0593 0.2559 0.0732 0.3343 0.3914 6.987

VIII 0.4383 0.4259 0.2532 0.2090 0.0593 0.1945 0.1822 0.4969 0.4528 6.347

IX ---- --- 0.2026 2.4312 0.0593 0.1606 0.1606 0.0420 2.2707 3.697

X 0.5259 0.5111 --- --- 0.0593 0.3412 0.3264 0.1847 0.1847 0.307

XI 0.2630 0.5111 --- --- 0.0593 0.1300 0.3781 0.1313 0.1313 0.360

XII 0.5259 0.2556 --- --- 0.0593 0.3784 0.1081 0.1475 0.1475 0.532
 DISCUSSION OF RESULTS.
The results presented in this practice show us that in reality the value of K x is
variable with the composition, which determines that the solution behaves not
ideal, verifying the theory of points 2-1 and 2-2.

Also, it is important to specify that the influence of the catalyst on the activities of
the compounds is very clear, causing an increase in conversion, this is observed
by comparing systems I, II, III with X, XI and XII respectively.

Although it was shown that doing a more in-depth study with respect to this
influence, as evidenced by the study presented by Trimble and Richardson in
1940: equally verify more precisely, the time required in the reaction reaches
equilibrium without a catalyst.

As mentioned in the theory point, it is difficult to obtain the effect of the

composition on the activity coefficients, however, the study of this reaction in the
future can be oriented to obtain this effect and finally find experimentally the
equilibrium constant K.
CONCLUSIONS.
 ARTICLE.
➢Water fluoride removal using adsorption technique.
The management of pollutants such as fluoride is a major public problem. The geogenic fluoride in groundwater that is
used as a source of drinking water is a major concern because the fluoride content above the permitted levels is
responsible for human dental and skeletal fluorosis. Consequently, water sources that contain high levels of fluoride have
to be treated. Coagulation / precipitation, electrochemistry, electrodialysis, reverse osmosis., Adsorption and hybrid
processes that combine adsorption and dialysis are widely used defluoridation techniques. Currently, however, the
development of profitable and clean processes is desired due to strict economic restrictions and environmental policies.
The adsorption technique is possibly one of the most versatile of all defluorization techniques due to a number of
reasons, such as cost, various end uses, socio-cultural acceptance, regulatory compliance, environmental benignity and
simplicity. For this technique, the adsorption media of activated alumina, bone charcoal and clay are the most developed.
Over the past two decades, extensive research has focused on a series of alternative adsorbents, some of which exhibit
better fluoride absorption.
The performance at the same time does not alter the quality of the treated water. Studies have also

shifted to systematic modeling to approximate adsorbent design parameters. In view of this, this review

begins with a description of the paradigm changes in drinking water sources and highlights the genesis

and toxicological effects of fluoride in drinking water as a means to define the existing problem. Next, the

potential and established techniques for defluoridation are reviewed. This is closely followed with a review

of the defluoridation adsorbents recognized by the World Health Organization and those new

defluoridation adsorbents reported in the literature over the past two decades, with special reference to

drinking water. Emphasis is placed on its availability, fluoride sorption capacity and mechanisms. By

recognizing the surface as azolith as a novel sorbent, a detailed analysis of the fluoride adsorption

behavior for this sorbent is provided. Finally, the configurations of defluoridation adsorption units and the

challenges and perspectives for their implementation are briefly discussed.

 BIBLIOGRAPHY.

1. Chapter: Chapter 1 Fluoride Removal from Water Using Adsorption Technique

Book: Advances in Fluorine Science
Author: Maurice S. Onyango,Hitoki Matsuda
Publisher: Elsevier
Date: 2006.

2. https://www.mheducation.es/bcv/guide/capitulo/844816962X.pdf

3. Smith J. M., Van Ness H. C.: “Introduccion to chemical Engineering

Thermodynamica”, McCraw-Hill.Kogakussha,Third Edition 1975.