PRACTICE 4.

HOMOGENEUS
CHEMICAL EQUILIBRIUM IN
LIQUID FASE
Study of the esterification of acetic acid
with an alcohol and a catalyse.
Introduction

• All substances are found in a single phase

• Equilibrium constant

• Factors that alter the balance: concentration,

Pressure, temperature, catalyst
Introduction.
Objectives

1- Calculate the equilibrium constants in the liquid phase of a

reaction esterification

2- Carry out the acid catalysis of the reaction of ethanol with

acetic acid to obtain an ester (ethyl acetate)

3- Determine the concentration ratio and equilibrium constant

for an esterification reaction
Theoretical framework
Chemical equilibrium: It is a reaction that
never completes, because it occurs
simultaneously in both directions (the
reagents form products, and in turn, they
form reagents again).

Homogeneous equilibrium: Applies to

reactions in which all reactive species are in
the same phases.
 ESTERIFICATION
Esterification is the procedure by
which we can synthesize an ester. The
esteers are produced from the reaction
that takes place bethwen carboxylic
acids and alcohols. The carboxylic
acids have reactions with the alcohols
when tey’re in the presence of
reactions catalysts, which are usually a
stron acid with the proposal of forming
an ester through the removal of H2O
molecule.

CH3-COOH ( acetic acid)+ HO-CH2-CH3 ( ethanol) ↔

CH3-CO-O-CH2-CH3 (acetic ethyl) + H2O
■ The Esther are substances that have an great importance in the industry, that’s why
they sintethyze big cuantities every year, due to this importancy, a lot of studyes
have been made and diferents process to get esthers.
 MECHANISM
O

■ As for the mechanism of the chemical reactions of the

esterification, we can say that the esterification, we can say that
its reactions have a nucleophilic attack betwen the oxygen of an
alcohol and the carbon belongging to the carboxylic group. The
proton goes to the hydroxyl grupo that has the acid, which will
then be removes as water.
 Experimental development
Material
■ 8 amber jars 25 – 50 ml
■ 8 erlenmeyer flask 125 ml
■ 4 pipettes 10 ml
■ 8 glasses of precipitates 50 ml
■ 4 burettes

Chemical reagents ■ Acetato de etilo (C4H8O2)

■ Etanol (C6H6O) ■ Hidróxido de sodio (NaOH)
■ Acido acético (CH3COOH) ■ Fenolftaleína
■ Acido clorhídrico (HCl)
Experimental development
1 2 3 4 5 6 7 8
Etanol (ml) 5 5 5 2.5 7.5 5 5 5
Ac. Acetic (ml) 5 5 5 2.5 7.5 5 5 5
Ac. Clorh (ml) 2.5 2.5 ------ 2.5 2.5 ------ 5 -----
Acetato de etilo (ml) ------ 2.5 2.5 ------ ------- ------- ------ 5

𝑉𝑖 𝑚𝑙 ∗ 𝜌𝑖 ∗ 𝑝𝑢𝑟𝑒𝑧𝑎𝑖
𝑛𝑖𝑜 =
𝑃𝑀

PM (g/mol) Ρ (g/ml) Pureza (%)

Etanol 60.05 1.05 99.8
Acido acetico 46.07 0.79 99.9
Acido clorhídrico 36.46 1.19 37.0
Acetato de etilo 88.1 0.9 99.81
Experimental development
Take an aliquot from 5 to 10
ml, add 10 ml distilled water,
and title with a solution of
NaOH (3N) using as
phenolphthalein indicator.

𝑉 𝑁𝑎𝑂𝐻 ∗ 𝑁 𝑁𝑎𝑂𝐻
𝑛 𝐴𝐴𝑐 + 𝐻𝐶𝑙 = 𝑉𝑇 𝑝𝑟𝑒𝑝𝑎𝑟𝑎𝑑𝑜
𝑉 𝑎𝑙𝑖𝑐𝑢𝑜𝑡𝑎 𝑑𝑒 𝐴𝐴𝑐 + 𝐻𝐶𝑙

We get the number of moles without reacting

𝑛𝑇 𝐴𝐴𝑐 + 𝐻𝐶𝑙 = 𝑛𝐴𝐴𝑐 + 𝑛𝐻𝐶𝑙

𝑛𝐴𝐴𝑐 = 𝑛𝑇 𝐴𝐴𝑐 + 𝐻𝐶𝑙 − 𝑛𝐻𝐶𝑙

Experimental development
Degree of reaction progress
1- nfAAc = n°Aac - ξ
2- nf Etanol = n°Etanol - ξ
3- nfHCl = n°HCl
4- nfAcEt = n°AcEt + ξ
5- nfH2O = n°H2O + ξ

From the equation 1 we obtain the degree of progress (ξ)

To get the final moles of each component.
ξ = n°AAc – nfAAc

we calculate the equilibrium constant in each system

𝒏𝑨𝒄𝑬𝒕 ∗ 𝒏𝑯𝟐𝑶
𝑲𝒊 =
𝒏𝑨𝑨𝒄 ∗ 𝒏𝑬𝒕𝒂𝒏𝒐𝒍
Experimental development
We calculate the efficiency of each system

𝑛°𝐴𝑐𝐴𝑐 − 𝑛𝑓 (𝐴𝑐𝐴𝑐)
%𝐸𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑖𝑎 = 𝑥100
𝑛°𝐴𝑐𝐴𝑐

AAc Etanol Ac Et H2O HCl K Efic.

8
Results
Table 1. Inicial balance table of each system.
SYSTEM AAC ETOH AC-ET H2 O HCL
1 5 5 5
2 5 5 2.5 2.5
3 5 5 2.5
4 2.5 2.5 2.5
5 7.5 7.5 2.5
6 5 5
7 5 5 5
8 5 5 5

Table 2. Volume of NaOH spent on the titulation.

SYSTEM 1 2 3 4 5 6 7 8
VNaOh spent
Results
Calculation of the number of moles of total acid present in each system:
𝑉𝑁𝑎𝑂𝐻 ∗𝑁𝑁𝑎𝑂𝐻
𝑛𝑡(𝐴𝐴𝑐+𝐻𝐶𝑙) = …(1)
𝑉𝑎

It´s known that:

𝑛𝑡(𝐴𝐴𝑐+𝐻𝐶𝑙) = 𝑛(𝑟𝑒𝑎𝑐𝑡)𝐴𝐴𝑐 + 𝑛°𝐻𝑐𝑙 ...(2)

Clearing out from (2)

𝑛𝐴𝐴𝑐 = 𝑛𝑡(𝐴𝐴𝑐+𝐻𝐶𝑙) − 𝑛°𝐻𝐶𝑙 … (3)
Results
𝑊𝑒 𝑡𝑎𝑘𝑒 𝑡ℎ𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑝𝑟𝑜𝑔𝑟𝑒𝑠𝑠 𝑓𝑟𝑜𝑚 𝑡ℎ𝑒 𝑎𝑐𝑒𝑡𝑖𝑐 𝑎𝑐𝑖𝑑
𝑛𝑓𝐴𝐴𝑐 = 𝑛°𝐴𝐴𝑐 − 𝜀 … (4)

Clearing out from (4)

𝜀 = 𝑛°𝐴𝐴𝑐 − 𝑛𝑓𝐴𝐴𝑐 … (5)

Once we know the value of the reaction progress it’s easy to find the final number of moles
of each sustance which took part on the reaction.

Finally we could get the value of the equilibrium constant in function of the number of moles
𝑛𝐴𝑐𝐸𝑡 ∗ 𝑛𝐻2𝑂
𝐾𝑒𝑞 = … (6)
𝑛𝐴𝐴𝑐 ∗𝑛𝐸𝑡𝑂𝐻
Results
Table 3. Final balance table of each system, equilibrium constant and efficiency.
SYSTEM AAC ETOH AC-ET H2 O HCL Keq Eficiency
1
2
3
4
5
6
7
8

We´ll notice how each system that’s been made change on its concentracions regardin to his
inicial conditions. As we can see every system have acetic acid and ethanol which are our
reactives, and they’ll change into ethyl acetite.
Discussion of the results
■ The first value we’ll get is the volumen of NaOH used in the analitic technic called titulation to know the
concentration of each acid, as a result of the esterification.

■ Some of our systems have different concentration of acid, so every of them will change his value of the
degree progess.

■ We also notice if the use of a catalyst is needed or not to improve a better reaction.

■ The equilibrium constant of

■ We’ll determine efficiency of each system which will involucrate the number of moles from acetic acid at
the beginning regarding the number of moles at the end.
Conclusions

■ As a result of this practice we could expect that the use of a catalyst is important
due to it takes part on the mechanism when clorhidric acid protons the carbonyl
group.
■ Systems that have more total of acid moles will need more volume of hydroxi sodium
to titulate them.
■ We will work with a reversible reaction so experimentally the way of gettig the
equilibrium constant is by knowing tha number of moles of reactives and initial
products.
 ARTICLE
APPLICATION OF A MORDENITE MEMBRANE TO THE ESTERIFICATION OF ACETIC
ACID AND ALCOHOL USING SULFURIC ACID CATALYST
 APPLICATION OF A MORDENITE MEMBRANE TO THE
ESTERIFICATION OF ACETIC ACID AND ALCOHOL USING SULFURIC
ACID CATALYST
Esterification of acetic acid and alcohol is a classic reaction controlled by the thermodynamic
equilibrium, and the excess of one reactant or removing by-product water can be used to
overcome the equilibrium. Generally, the by-product water can be continuously removed by
distillation or co-distillation with the entrainers, which are energy consumption and harmful for
environment. As compared to the traditional distillation, the membrane reactor is more compact,
less capital intensive, giving higher conversion and selectivity separation process for the
thermodynamically and kinetically controlled esterification. Therefore, the combination of the
esterification of alcohol and carboxylic acid with inorganic and polymeric membranes membrane
separation by pervaporation or vapor permeation arrangements have been drawn much
attention in last decades.
For example, Rathod et al. used for pervaporation-assisted esterification of lactic acid and iso-
propanol by polyvinyl alcohol-polyether sulfone (PVA-PES) composite hydrophilic membrane, and
the conversion of lactic acid was increased from its equilibrium value of 51%e86%.
 REFERENCIAS

■ Mendez A.. (2013). Esterificación. Agosto 2019, de La guia Quimica Sitio web:
https://quimica.laguia2000.com/reacciones-quimicas/esterificacion
■ Anonimo. (2017). Equilibrio Homogéneo y Heterogéneo. Junio 2019, de FANDOM Sitio
web: https://equilibrio-
quimico.fandom.com/es/wiki/Equilibrio_Homog%C3%A9neo_y_Heterog%C3%A9neo
■ Mei-Hua Zhu, Zi-Jun Feng, Hai-long Hu, Xue-Mei Hua, . (Enero 2016). Application of a
mordenite membrane to the esterification of acetic acid and alcohol using sulfuric acid
catalyst*. ELSEIVIER, 1, 6. Agosto 2019, De www.sciencedirect.com Base de datos.